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Sample records for ceria solid solutions

  1. Statistical thermodynamics of non-stoichiometric ceria and ceria zirconia solid solutions.

    PubMed

    Bulfin, B; Hoffmann, L; de Oliveira, L; Knoblauch, N; Call, F; Roeb, M; Sattler, C; Schmücker, M

    2016-08-17

    The thermodynamic redox properties of ceria and ceria zirconia solid solutions are analysed with a new methodology for modelling such systems based on the statistical mechanics of lattice configurations. Experimental thermogravimetric equilibrium data obtained for small non-stoichiometry measurements are combined with literature data to cover a large range of non-stoichiometry (CeO2-δ, δ = 0.001-0.32), temperature (1073-1773 K) and oxygen partial pressure (1-10(-13) bar). A dilute species model of defect clusters , obeying the law of mass action, was sufficient to describe the system over the whole range of conditions, leading to a simple analytical equation of state for the system. This offers new physical insight into the redox properties of ceria based materials, and the theoretical methods developed should also be of great interest for other materials which exhibit continuous oxygen non-stoichiometry similar to ceria, such as perovskite oxides.

  2. The complex synthesis and solid state chemistry of ceria-lanthana solid solutions prepared via a hexamethylenetetramine precipitation

    SciTech Connect

    Fleming, P.G.; Holmes, J.D.; Otway, D.J.; Morris, M.A.

    2011-09-15

    Mixed oxide solid solutions are becoming ever more commercially important across a range of applications. However, their synthesis can be problematical. Here, we show that ceria-lanthana solid solutions can be readily prepared via simple precipitation using hexamethylenetetramine. However, the solution chemistry can be complex, which results in the precipitated particles having a complex structure and morphology. Great care must be taken in both the synthesis and characterisation to quantify the complexity of the product. Even very high heat treatments were not able to produce highly homogeneous materials and X-ray diffractions reveals the non-equilibrium form of particles prepared in this way. Unexpected crystal structures are revealed including a new metastable cubic La{sub 2}O{sub 3} phase. - Graphical abstract: The suggested mechanism for the formation of dual fluorite phase particles, where Step 1 corresponds to room temperature aging, Step 2; heating the solution to 90 deg. C, Step 3; cooling of the solution to room temperature, Step 4; calcination to 500 deg. C, Step 5; calcination to 700 deg. C and Step 6; calcination to 1300 deg. C. The terminology of e.g. La{sub 1-x}Ce{sub x}(OH){sub 3} is used to indicate the formation of a mixed oxy-hydroxy participate rather than a definitive assignment of stoichiometry. Similarly, La{sub 1-y}Ce{sub y}O{sub 2} only implies a mixed solid solution. Highlights: > Mol% of prepared Ce-La oxides did not follow that of reactant mol%. > Complex reaction pathway found to be dependent on metal solution concentrations. > At certain concentrations core shell particles were found to form. > A reaction model was produced based on cationic solubility. > Report lanthana solubility higher than previously reported in CeO{sub 2}.

  3. Application of rare earth modified Zr-based ceria-zirconia solid solution in three-way catalyst for automotive emission control.

    PubMed

    Wang, Qiuyan; Zhao, Bo; Li, Guangfeng; Zhou, Renxian

    2010-05-15

    Automotive exhaust emission is a major cause of air pollution. Three-way catalyst (TWC) which can eliminate CO, HC (hydrocarbons), and NO(x) simultaneously has been used to control exhaust emissions. Ceria-zirconia is a key component in TWC and most researchers pay attention to Ceria-Zirconia (Ce-rich) solid solution. The research presented in this paper is focused on the intrinsic structure of Ceria-Zirconia (Zr-based) solid solution and its application in TWC. A series of Ce(0.2)Zr(0.8)O(2) modified with rare earths (La, Nd, Pr, Sm, and Y) have been prepared by coprecipitation method combined with supercritical drying technique. All samples showed single tetragonal solid solution, indicating that the rare earth ion inserted into the lattice structure completely, and an approximately linearly relationship between lattice parameter a and the ionic radius of doped rare earth was observed. The catalytic performances of corresponding Pd-only catalysts were investigated in simulated exhaust gas. The presence of La, Nd, and Pr was favorable to the catalytic activity and wide air/fuel operation window. The relationship between the intrinsic structure of the Zr-based ceria-zirconia solid solution and catalytic activity was discussed in detail, which has some reference value for catalyst design and application.

  4. The effect of Nd on the properties of ceria-zirconia solid solution and the catalytic performance of its supported Pd-only three-way catalyst for gasoline engine exhaust reduction.

    PubMed

    Wang, Qiuyan; Li, Guangfeng; Zhao, Bo; Zhou, Renxian

    2011-05-15

    A series of ceria-zirconia-neodymia mixed oxides with different contents of neodymia and the supported Pd-only three-way catalysts before and after aging have been prepared and characterized. The influence of Nd doping on the structural/textural properties of ceria-zirconia (CZ) and the effect on the three-way catalytic performance are also investigated. The results demonstrate that the addition of neodymia results in the formation of ceria-zirconia-neodymia ternary solid solution (CZN) with better textural and structural properties as well as improved reducibility and redox behavior, leading to the promoted three-way catalytic activity and enlarged air/fuel operation window. The modified solid solution with 5 wt.% neodymia shows the preferable textural/structural properties considering that the capacity of foreign cation is limited in the crystal lattice of ceria-zirconia solid solution, and Pd/CZN5 shows the optimum three-way catalytic performance and wider air/fuel operation window, especially for the corresponding aged one.

  5. A Space-Charge Treatment of the Increased Concentration of Reactive Species at the Surface of a Ceria Solid Solution.

    PubMed

    Zurhelle, Alexander F; Tong, Xiaorui; Klein, Andreas; Mebane, David S; De Souza, Roger A

    2017-09-18

    We apply a space-charge theory applicable to concentrated solid solutions-Poisson-Cahn theory-to describe quantitatively as a function of temperature and oxygen partial pressure published data obtained by in situ X-ray photoelectron spectroscopy (XPS) for the concentration of Ce3+ (the reactive species) at the surface of the oxide catalyst Ce0.8Sm0.2O1.9. In contrast to previous theoretical treatments, our calculations clearly indicate that the surface is positively charged and compensated by an attendant negative space-charge zone. The high space-charge potential that develops at the surface (> 0.8 V) is demonstrated to be hardly detectable by XPS measurements because of the short extent of the space-charge layer. Our approach emphasizes the need to take into account defect interactions and to allow deviations from local charge neutrality when considering the surfaces of oxide catalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Isn't the space-charge potential in ceria-based solid electrolytes largely overestimated?

    PubMed

    Kim, Sangtae

    2016-07-20

    The effective ionic conductivity of polycrystalline solid electrolytes that conduct oxide ions or protons is known to be markedly below those of the corresponding single crystals due to substantial current obstruction across the grain boundary. Numerous studies have previously demonstrated that the ionic charge carriers deplete in the vicinity of the grain boundary to form a potential barrier at the grain boundary, which further impedes the current across the grain boundary. Hence an accurate estimation of the barrier height is essential to acquire a comprehensive and precise mechanistic picture of the ionic current in solid electrolytes. The values of the potential barrier height, i.e. equivalent to the equilibrium space-charge potential with the opposite sign, in prominent solid electrolytes such as ceria solid solutions are available in the literature and were determined exclusively from the ratio of the resistivity of the grain boundary to that of the crystal interior. Here I present the results clearly demonstrating that the resistivity ratio yields considerable overestimation of the barrier height even in relatively diluted solid solutions of ceria. These results imply that the space charge is unlikely the sole origin of the large current obstruction across the grain boundary in ceria-based solid electrolytes.

  7. Low-temperature preparation by polymeric complex solution synthesis of Cu-Gd-doped ceria cermets for solid oxide fuel cells anodes: Sinterability, microstructures and electrical properties

    NASA Astrophysics Data System (ADS)

    Tartaj, J.; Gil, V.; Moure, A.

    A homogeneous dispersion of fine CuO in a gadolinia-doped ceria (CGO) ceramic matrix by the polymeric organic complex solution method has been achieved. Highly sinterable powders were prepared by this method after calcining the precursor at 600 °C and attrition milled. The powders consist of individual particles of few tens of nanometer in size with a low agglomeration state. The isopressed compacts were sintered in air at 1000 °C and reducing in N 2 90%-H 2 10% atmosphere to form Cu-CGO cermets. The microstructures showed a uniform distribution of porous metallic Cu particles surrounded by microporous spaces. The influence of Cu content in Cu-CGO cermets on the electrode performance has been investigated in order to create the most suitable microstructure. The electrical properties of Cu-CGO cermets have been also studied using impedance spectroscopy, in the temperature range form 150 to about 700 °C in argon atmosphere. These measurements determined a high value of electrical conductivity at 700 °C, similar to that corresponded to pure metallic cupper.

  8. UV-shielding property, photocatalytic activity and photocytotoxicity of ceria colloid solutions.

    PubMed

    Zholobak, N M; Ivanov, V K; Shcherbakov, A B; Shaporev, A S; Polezhaeva, O S; Baranchikov, A Ye; Spivak, N Ya; Tretyakov, Yu D

    2011-01-10

    UV-shielding property, photocatalytic activity and cytotoxicity (including photocytotoxicity) of citrate-stabilized ceria colloid solutions were studied. It was established that UV-shielding property (namely, the sun protection factor, the critical absorption wavelength and the UVA/UVB-ratio) of ceria nanoparticles are as good as those of titanium dioxide and zinc oxide nanoparticles. It was further demonstrated that ceria nanoparticles possesses substantially lower photocatalytic activity, which additionally decreases upon decrease in ceria particle size. It was found that colloid ceria solutions are non-toxic to mouse fibroblasts (L929) and fibroblast-like cells of African Green monkey (VERO). Moreover, ceria nanoparticles are capable to protect these cells from UV-irradiation-induced damage. It was proposed that nanocrystalline ceria could be used not only as UV-blocking material, but also as prophylactic and even therapeutic compound for sunburns treatment.

  9. Solid Solutions

    NASA Astrophysics Data System (ADS)

    Lee, Go-Eun; Kim, Il-Ho; Lim, Young Soo; Seo, Won-Seon; Choi, Byeong-Jun; Hwang, Chang-Won

    2014-06-01

    Since Bi2Te3 and Bi2Se3 have the same crystal structure, they form a homogeneous solid solution. Therefore, the thermal conductivity of the solid solution can be reduced by phonon scattering. The thermoelectric figure of merit can be improved by controlling the carrier concentration through doping. In this study, Bi2Te2.85Se0.15:D m (D: dopants such as I, Cu, Ag, Ni, Zn) solid solutions were prepared by encapsulated melting and hot pressing. All specimens exhibited n-type conduction in the measured temperature range (323 K to 523 K), and their electrical conductivities decreased slightly with increasing temperature. The undoped solid solution showed a carrier concentration of 7.37 × 1019 cm-3, power factor of 2.1 mW m-1 K-1, and figure of merit of 0.56 at 323 K. The figure of merit ( ZT) was improved due to the increased power factor by I, Cu, and Ag dopings, and maximum ZT values were obtained as 0.76 at 323 K for Bi2Te2.85Se0.15:Cu0.01 and 0.90 at 423 K for Bi2Te2.85Se0.15:I0.005. However, the thermoelectric properties of Ni- and Zn-doped solid solutions were not enhanced.

  10. Nanostructured gadolinium-doped ceria microsphere synthesis from ion exchange resin: Multi-scale in-situ studies of solid solution formation

    SciTech Connect

    Caisso, Marie; Lebreton, Florent; Horlait, Denis; Neuville, Daniel R.; Dardenne, Kathy; Rothe, Jörg; Delahaye, Thibaud

    2014-10-15

    In the current nano-sized material revolution, the main limitations to a large-scale deployment of nanomaterials involve health concerns related to nano-dissemination via air. Developing new chemical routes benefiting from nano-size advantages while avoiding their hazards could overcome these limitations. Addressing this need, a chemical route leading to soft nano-particle agglomerates, i.e., macroscopic precursors presenting the ability to be decomposed into nano-sized materials, was developed and applied to Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ}. Using cerium/gadolinium-loaded ion exchange resin, the Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} solid solution formation as a function of temperature was studied in-situ through X-ray diffraction, X-ray absorption spectroscopy and Raman spectroscopy. Temperatures corresponding to the organic skeleton decomposition and to the mixed oxide crystallization were identified. An optimal heat treatment, leading to nanostructured soft agglomerates, was established. Microsphere processing capabilities were evaluated and particle size distribution measurements were recorded. A very low fracture strength was calculated, and a nanometric particle size distribution (170 nm) was determined. - Graphical abstract: The elaboration of micro-spherical precursors leading to the formation of nano-oxide soft agglomerates was studied and approved through the use of ion exchange resin loaded with cerium and gadolinium. The formation of the solid solution was followed through in-situ measurements such as XAS, XRD, Raman, TGA and DSC. Key temperatures were identified for the formation of the mixed-oxide. Following this study, the microstructure and particle size of oxide microspheres formed highlight the formation of soft nano-arrangments. - Highlights: • Soft microspherical agglomerates able to be decomposed into nano-sized materials. • In situ study of cerium/gadolinium-loaded ion exchange resin conversion in oxide. • In situ multi-scale study

  11. Nanostructured gadolinium-doped ceria microsphere synthesis from ion exchange resin: Multi-scale in-situ studies of solid solution formation

    NASA Astrophysics Data System (ADS)

    Caisso, Marie; Lebreton, Florent; Horlait, Denis; Picart, Sébastien; Martin, Philippe M.; Bès, René; Renard, Catherine; Roussel, Pascal; Neuville, Daniel R.; Dardenne, Kathy; Rothe, Jörg; Delahaye, Thibaud; Ayral, André

    2014-10-01

    In the current nano-sized material revolution, the main limitations to a large-scale deployment of nanomaterials involve health concerns related to nano-dissemination via air. Developing new chemical routes benefiting from nano-size advantages while avoiding their hazards could overcome these limitations. Addressing this need, a chemical route leading to soft nano-particle agglomerates, i.e., macroscopic precursors presenting the ability to be decomposed into nano-sized materials, was developed and applied to Ce0.8Gd0.2O2-δ. Using cerium/gadolinium-loaded ion exchange resin, the Ce0.8Gd0.2O2-δ solid solution formation as a function of temperature was studied in-situ through X-ray diffraction, X-ray absorption spectroscopy and Raman spectroscopy. Temperatures corresponding to the organic skeleton decomposition and to the mixed oxide crystallization were identified. An optimal heat treatment, leading to nanostructured soft agglomerates, was established. Microsphere processing capabilities were evaluated and particle size distribution measurements were recorded. A very low fracture strength was calculated, and a nanometric particle size distribution (170 nm) was determined.

  12. Controlled synthesis, characterization, and morphology-dependent reducibility of ceria-zirconia-yttria solid solutions with nanorod-like, microspherical, microbowknot-like, and micro-octahedral shapes.

    PubMed

    Zhang, Yujuan; Zhang, Lei; Deng, Jiguang; Dai, Hongxing; He, Hong

    2009-03-02

    By adopting the strategy of triblock copolymer (Pluronic P123) or cetyltrimethylammonium bromide (CTAB) assisted hydrothermal treatment, we fabricated cubic fluorite-type Ce(0.6)Zr(0.3)Y(0.1)O(2) (CZY) solid solution polycrystallites with various morphologies. These materials were characterized by means of techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected-area electron diffraction, X-ray photoelectron spectroscopy, thermogravimetry, laser Raman, Fourier-transfer infrared spectroscopy, hydrogen temperature-programmed reduction, and surface area measurements. It is found that the nanorod-like, microspherical, microbowknot-like, and micro-octahedral CZY particles were respectively generated hydrothermally with CTAB at 120 degrees C for 72 h and with P123 at 100, 120, and 240 degrees C for 48 h after calcination at 550 degrees C for 3 h. There was a copresence of Ce(3+) and Ce(4+) in the CZY samples that led to the formation of oxygen vacancies. We observed a good correlation of low-temperature reducibility with the morphology of the CZY samples. The reducibility of these nano- and micromaterials at low temperatures (240-550 degrees C) enhanced in the order micro-octahedral CZY < microspherical CZY < microbowknot-like CZY < nanorod-like CZY. The formation mechanism of CZY with various morphologies was discussed.

  13. Ceria-based solid catalysts for organic chemistry.

    PubMed

    Vivier, Laurence; Duprez, Daniel

    2010-06-21

    Ceria has been the subject of thorough investigations, mainly because of its use as an active component of catalytic converters for the treatment of exhaust gases. However, ceria-based catalysts have also been developed for different applications in organic chemistry. The redox and acid-base properties of ceria, either alone or in the presence of transition metals, are important parameters that allow to activate complex organic molecules and to selectively orient their transformation. Pure ceria is used in several organic reactions, such as the dehydration of alcohols, the alkylation of aromatic compounds, ketone formation, and aldolization, and in redox reactions. Ceria-supported metal catalysts allow the hydrogenation of many unsaturated compounds. They can also be used for coupling or ring-opening reactions. Cerium atoms can be added as dopants to catalytic system or impregnated onto zeolites and mesoporous catalyst materials to improve their performances. This Review demonstrates that the exceptional surface (and sometimes bulk) properties of ceria make cerium-based catalysts very effective for a broad range of organic reactions.

  14. Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

    NASA Astrophysics Data System (ADS)

    Buyukkilic, Salih

    Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations

  15. Facile synthesis and unique physicochemical properties of three-dimensionally ordered macroporous magnesium oxide, gamma-alumina, and ceria-zirconia solid solutions with crystalline mesoporous walls.

    PubMed

    Li, Huining; Zhang, Lei; Dai, Hongxing; He, Hong

    2009-05-18

    Three-dimensionally (3D) ordered macroporous (3DOM) MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) with polycrystalline mesoporous walls have been successfully fabricated with the triblock copolymer EO(106)PO(70)EO(106) (Pluronic F127) and regularly packed monodispersive polymethyl methacrylate (PMMA) microspheres as the template and magnesium, aluminum, cerium and zirconium nitrate(s), or aluminum isopropoxide as the metal source. The as-synthesized metal oxides were characterized by means of techniques such as X-ray diffraction (XRD), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), Fourier transform infrared (FT-IR), high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy/selected area electron diffraction (HRTEM/SAED), BET, carbon dioxide temperature-programmed desorption (CO(2)-TPD), and hydrogen temperature-programmed reduction (H(2)-TPR). It is shown that the as-fabricated MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples possessed single-phase polycrystalline structures and displayed a 3DOM architecture; the MgO, Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples exhibited worm-hole-like mesoporous walls, whereas the gamma-Al(2)O(3) samples exhibited 3D ordered mesoporous walls. The solvent (ethanol or water) nature and concentration, metal precursor, surfactant, and drying condition have an important impact on the pore structure and surface area of the final product. The introduction of surfactant F127 to the synthesis system could significantly enhance the surface areas of the 3DOM metal oxides. With PMMA and F127 in a 40% ethanol solution, one can generate well-arrayed 3DOM MgO with a surface area of 243 m(2)/g and 3DOM Ce(0.6)Zr(0.4)O(2) with a surface area of 100 m(2)/g; with PMMA and F127 in an ethanol-HNO(3) solution, one can obtain 3DOM gamma-Al(2)O(3)with a surface area of 145 m(2)/g. The 3DOM MgO and 3DOM gamma-Al(2)O(3) samples showed

  16. Evaluation of ceria electrolytes in solid oxide fuel cells electric power generation

    SciTech Connect

    Milliken, C.; Guruswamy, S.; Khandkar, A.

    1999-03-01

    Samaria-doped ceria solid oxide fuel cells (SOFC) single cells have demonstrated power densities >250 mW/cm{sup 2} at 700 C and stable performance for 15,000 h. Though encouraging, issues of stack performance and efficiency due to mixed conduction remain. Stacks operated on H{sub 2}/3% H{sub 2}O show approximately half the power density expected from single cells. A coupled thermal-electrochemical model which included conduction heat transfer in the solid and convection to the reactant gases was developed. The model was used to predict stack efficiencies using ceria-based SOFCs in power plant applications. Analyses indicate that ceria SOFCs may provide as high as 42% electrical efficiency when operated on humidified hydrogen fuel. These efficiencies are surprisingly high and challenge the notion that mixed conductors are unsuitable for such applications.

  17. Effect of the mineralizer solution in the hydrothermal synthesis of gadolinium-doped (10% mol Gd) ceria nanopowders.

    PubMed

    Dell'Agli, Gianfranco; Spiridigliozzi, Luca; Marocco, Antonello; Accardo, Grazia; Ferone, Claudio; Cioffi, Raffaele

    2016-05-18

    Gadolinium-doped ceria is an attractive electrolyte material for potential application in solid oxide fuel cells (SOFCs) operating at intermediate temperatures typically with 10%-20% substitution of Ce+4 by Gd+3. In particular, 10% gadolinium-doped ceria seems to have the highest values of conductivities among the other dopant compositions. Nanosized powders of gadolinium-doped ceria were prepared by hydrothermal treatment using coprecipitate as a precursor and in the presence of 3 different mineralizer solutions. The powders obtained were characterized by X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy and thermal analysis, while the electrical behavior of the corresponding pellets were ascertained by AC impedance spectroscopy. Nanocrystalline gadolinium-doped ceria powders with fluorite cubic crystal structure were obtained by hydrothermal treatment. Independent of the mineralizer used, these powders were able to produce very dense ceramics, especially when selecting an optimized sintering cycle. In contrast, the electrical behavior of the samples was influenced by the mineralizer solution, and the samples synthesized in the neutral and alkaline solutions showed higher values of electrical conductivity, in the range of temperatures of interest. By the coprecipitation method, it has been possible to synthesize nanosized gadolinium-doped cerium oxide in a fluorite structure, stable in a wide range of temperatures. Hydrothermal treatment directly on the as-synthesized coprecipitates, without any drying step, had a very positive effect on the powders, which can be sintered with a high degree of densification, especially with an optimized sintering cycle. Furthermore, the electrical behavior of these samples was very interesting, especially for the samples synthesized using neutral mineralizer solution and basic mineralizer solution.

  18. Nanocrystalline ceria coatings on solid oxide fuel cell anodes: the role of organic surfactant pretreatments on coating microstructures and sulfur tolerance

    PubMed Central

    Wu, Chieh-Chun; Tang, Ling

    2014-01-01

    Summary Treatments with organic surfactants, followed by the deposition of nanocrystalline ceria coatings from aqueous solution, were applied to anodes of solid oxide fuel cells. The cells were then operated in hydrogen/nitrogen fuel streams with H2S contents ranging from 0 to 500 ppm. Two surfactant treatments were studied: immersion in dodecanethiol, and a multi-step conversion of a siloxy-anchored alkyl bromide to a sulfonate functionality. The ceria coatings deposited after the thiol pretreatment, and on anodes with no pretreatment, were continuous and uniform, with thicknesses of 60–170 nm and 100–140 nm, respectively, and those cells exhibited better lifetime performance and sulfur tolerance compared to cells with untreated anodes and anodes with ceria coatings deposited after the sulfonate pretreatment. Possible explanations for the effects of the treatments on the structure of the coatings, and for the effects of the coatings on the performance of the cells, are discussed. PMID:25383282

  19. Enhanced Ceria Solid Electrolyte Fuel Cell Development. Reduction of Electronic Conductivity Permits use of a Solid Ceria Electrolyte in High Efficiency High Power Density Fuel Cells at Temperatures Compatible with Metallic Cell Hardware

    DTIC Science & Technology

    1990-01-01

    DTC FILE COPY DARPA ORDER 9526 lit I 0ENHANCED CERIA SOLID ELECTROLYTE FUEL CELL DEVELOPMENT Reduction of Electronic Conductivity Permits use of a...Solid Ceria Electrolyte * I’- in High Efficiency High Power Density Fuel Cells at Temperatures Compatible with Metallic Cell Hardware Prepared by D T IC...D. L. MairicleI < T International Fuel Cells D. .. Box 739 FEB 0 8 1990 195 Governors Highway D South Windsor, CT 06074 January 1990 IFCR-10824

  20. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  1. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  2. Highly efficient solid state catalysis by reconstructed (001) Ceria surface

    PubMed Central

    Solovyov, Vyacheslav F.; Ozaki, Toshinori; Atrei, Andrea; Wu, Lijun; Al-Mahboob, Abdullah; Sadowski, Jerzy T.; Tong, Xiao; Nykypanchuk, Dmytro; Li, Qiang

    2014-01-01

    Substrate engineering is a key factor in the synthesis of new complex materials. The substrate surface has to be conditioned in order to minimize the energy threshold for the formation of the desired phase or to enhance the catalytic activity of the substrate. The mechanism of the substrate activity, especially of technologically relevant oxide surfaces, is poorly understood. Here we design and synthesize several distinct and stable CeO2 (001) surface reconstructions which are used to grow epitaxial films of the high-temperature superconductor YBa2Cu3O7. The film grown on the substrate having the longest, fourfold period, reconstruction exhibits a twofold increase in performance over surfaces with shorter period reconstructions. This is explained by the crossover between the nucleation site dimensions and the period of the surface reconstruction. This result opens a new avenue for catalysis mediated solid state synthesis. PMID:24717357

  3. Highly efficient solid state catalysis by reconstructed (001) Ceria surface

    SciTech Connect

    Solovyov, VF; Ozaki, T; Atrei, A; Wu, LJ; Al-Mahboob, A; Sadowski, JT; Tong, X; Nykypanchuk, D; Li, Q

    2014-04-10

    Substrate engineering is a key factor in the synthesis of new complex materials. The substrate surface has to be conditioned in order to minimize the energy threshold for the formation of the desired phase or to enhance the catalytic activity of the substrate. The mechanism of the substrate activity, especially of technologically relevant oxide surfaces, is poorly understood. Here we design and synthesize several distinct and stable CeO2 (001) surface reconstructions which are used to grow epitaxial films of the high-temperature superconductor YBa2Cu3O7. The film grown on the substrate having the longest, fourfold period, reconstruction exhibits a twofold increase in performance over surfaces with shorter period reconstructions. This is explained by the crossover between the nucleation site dimensions and the period of the surface reconstruction. This result opens a new avenue for catalysis mediated solid state synthesis.

  4. Novel structured gadolinium doped ceria based electrolytes for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Timurkutluk, Bora; Timurkutluk, Cigdem; Mat, Mahmut D.; Kaplan, Yuksel

    Novel three-layered intermediate temperature solid oxide fuel cell (SOFC) electrolytes based on gadolinium doped ceria (GDC) are developed to suppress the electronic conductivity of GDC, to improve the mechanical properties of the cell and to minimize power loss due to mixed conductive nature of GDC. Three different electrolytes are fabricated by sandwiching thin YSZ, ScSZ and ScCeSZ between two relatively thick GDC layers. An electrolyte composed of pure GDC is also manufactured for comparison. NiO/GDC and LSCF/GDC electrodes are then coated on the electrolytes by a screen printing route. SEM results show that it is possible to obtain dense and crack free thin layers of YSZ, ScSZ and ScCeSZ between two GDC layers without delamination. Performance measurements indicate that interlayered thin electrolytes act as an electronic conduction barrier and improve open circuit voltages (OCVs) of GDC based cells.

  5. Praseodymium and gadolinium doped ceria as a cathode material for low temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Chockalingam, Rajalekshmi; Ganguli, Ashok Kumar; Basu, Suddhasatwa

    2014-03-01

    Mixed ionic electronic conducting praseodymium and gadolinium doped ceria (PrxCe0.95-xGd0.05O2-δ (0.15 ≤ x ≤ 0.40)) compositions have been studied as a cathode material for low temperature solid oxide fuel cells. Four compositions of PrxCe0.95-xGd0.05O2-δ (PCGO) have been prepared by varying the praseodymium content. Phase formation, thermal expansion, ionic conductivity, electronic conductivity, ionic transference number and electrochemical performance have been investigated. X-ray diffraction results indicate that PCGO samples crystallize in the fluorite structure, and the lattice volume decreases with increasing praseodymium content, x. The coefficient of thermal expansion increases with increasing x, and at x = 0.2 shows an optimum value of 12 × 10-6 K-1. Ionic transference number decrease while electronic conductivity increase with increasing x. It has been found that electronic contribution to the total conductivity is higher than ionic contribution for all compositions. The praseodymium doping with cerium dioxide introduces impurity bands within the ceria band gap and facilitates the electronic transition from valance band to conduction band through praseodymium impurity levels. The single cell with configuration, Pr0.2Ce0.75-xGd0.05O2-δ-Ce0.80Gd0.20O2-δ∥Ce0.80Gd0.20O2-δ∥NiO-Ce0.80Gd0.20O2-δ delivers a maximum power density of 98 mW cm-2 at 650 °C.

  6. Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

    PubMed

    Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

    2012-06-01

    Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

  7. Low-temperature ceria-electrolyte solid oxide fuel cells for efficient methanol oxidation

    NASA Astrophysics Data System (ADS)

    Meng, Xie; Zhan, Zhongliang; Liu, Xuejiao; Wu, Hao; Wang, Shaorong; Wen, Tinglian

    Low temperature anode-supported solid oxide fuel cells with thin films of samarium-doped ceria (SDC) as electrolytes, graded porous Ni-SDC anodes and composite La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF)-SDC cathodes are fabricated and tested with both hydrogen and methanol fuels. Power densities achieved with hydrogen are between 0.56 W cm -2 at 500 °C and 1.09 W cm -2 at 600 °C, and with methanol between 0.26 W cm -2 at 500 °C and 0.82 W cm -2 at 600 °C. The difference in the cell performance can be attributed to variation in the interfacial polarization resistance due to different fuel oxidation kinetics, e.g., 0.21 Ω cm 2 for methanol versus 0.10 Ω cm 2 for hydrogen at 600 °C. Further analysis suggests that the leakage current densities as high as 0.80 A cm -2 at 600 °C and 0.11 A cm -2 at 500 °C, resulting from the mixed electronic and ionic conductivity in the SDC electrolyte and thus reducing the fuel efficiency, can nonetheless help remove any carbon deposit and thereby ensure stable and coking-free operation of low temperature SOFCs in methanol fuels.

  8. Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

    PubMed

    Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

    2015-11-04

    Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Solid oxide fuel cell bi-layer anode with gadolinia-doped ceria for utilization of solid carbon fuel

    NASA Astrophysics Data System (ADS)

    Kellogg, Isaiah D.; Koylu, Umit O.; Dogan, Fatih

    Pyrolytic carbon was used as fuel in a solid oxide fuel cell (SOFC) with a yttria-stabilized zirconia (YSZ) electrolyte and a bi-layer anode composed of nickel oxide gadolinia-doped ceria (NiO-GDC) and NiO-YSZ. The common problems of bulk shrinkage and emergent porosity in the YSZ layer adjacent to the GDC/YSZ interface were avoided by using an interlayer of porous NiO-YSZ as a buffer anode layer between the electrolyte and the NiO-GDC primary anode. Cells were fabricated from commercially available component powders so that unconventional production methods suggested in the literature were avoided, that is, the necessity of glycine-nitrate combustion synthesis, specialty multicomponent oxide powders, sputtering, or chemical vapor deposition. The easily-fabricated cell was successfully utilized with hydrogen and propane fuels as well as carbon deposited on the anode during the cyclic operation with the propane. A cell of similar construction could be used in the exhaust stream of a diesel engine to capture and utilize soot for secondary power generation and decreased particulate pollution without the need for filter regeneration.

  10. Hierarchically oriented macroporous anode-supported solid oxide fuel cell with thin ceria electrolyte film.

    PubMed

    Chen, Yu; Zhang, Yanxiang; Baker, Jeffrey; Majumdar, Prasun; Yang, Zhibin; Han, Minfang; Chen, Fanglin

    2014-04-09

    Application of anode-supported solid oxide fuel cell (SOFC) with ceria based electrolyte has often been limited by high cost of electrolyte film fabrication and high electrode polarization. In this study, dense Gd0.1Ce0.9O2 (GDC) thin film electrolytes have been fabricated on hierarchically oriented macroporous NiO-GDC anodes by a combination of freeze-drying tape-casting of the NiO-GDC anode, drop-coating GDC slurry on NiO-GDC anode, and co-firing the electrolyte/anode bilayers. Using 3D X-ray microscopy and subsequent analysis, it has been determined that the NiO-GDC anode substrates have a porosity of around 42% and channel size from around 10 μm at the electrolyte side to around 20 μm at the other side of the NiO-GDC (away from the electrolyte), indicating a hierarchically oriented macroporous NiO-GDC microstructure. Such NiO-GDC microstructure shows a tortuosity factor of ∼1.3 along the thickness direction, expecting to facilitate gas diffusion in the anode during fuel cell operation. SOFCs with such Ni-GDC anode, GDC film (30 μm) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3-GDC (LSCF-GDC) cathode show significantly enhanced cell power output of 1.021 W cm(-2) at 600 °C using H2 as fuel and ambient air as oxidant. Electrochemical Impedance Spectroscopy (EIS) analysis indicates a decrease in both activation and concentration polarizations. This study has demonstrated that freeze-drying tape-casting is a very promising approach to fabricate hierarchically oriented porous substrate for SOFC and other applications.

  11. Calcium-doped ceria materials for anode of solid oxide fuel cells running on methane fuel

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Du, Yanhai

    2017-04-01

    A calcium-doped ceria with nominal compositions of Ce1-xCaxO2-δ (0.00 ≤ x ≤ 0.30) has been developed as an anode component for solid oxide fuel cells running on methane fuel. Crystal phases of Ce1-xCaxO2-δ are investigated with respect to the amount of calcium dopant. The Ce1-xCaxO2-δ shows single fluorite phase when the calcium is within 15 mol.%, and higher calcium doping levels lead to the appearance of a secondary phase (CaO). Conductivities of Ce1-xCaxO2-δ ceramics are studied by a four-probe method in air and the composition of Ce0.9Ca0.1O2-δ (x = 0.10) is found exhibiting the highest conductivity among the samples investigated in this work. Electrocatalytic properties of Ce0.9Ca0.1O2-δ are evaluated based on Ni-Ce1-xCaxO2-δ anode supported single cell running on methane fuel. At 800 °C, the single cell with Ni-Ce0.9Ca0.1O2-δ (x = 0.10) anode exhibits an optimum maximum powder density (618 mW cm-2) and good performance stability during 30 h operation in methane fuel. The promising findings substantiate the good performance of Ni-Ce0.9Ca0.1O2-δ anode for electrochemical oxidation of methane fuel.

  12. Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Mirfakhraei, Behzad

    Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately

  13. Ceria catalyst for inert-substrate-supported tubular solid oxide fuel cells running on methane fuel

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Kim, Bok-Hee; Du, Yanhai; Xu, Qing; Ahn, Byung-Guk

    2016-05-01

    A ceria catalyst is applied to an inert-substrate supported tubular single cell for direct operation on methane fuel. The tubular single cell comprises a porous yttria-stabilized zirconia (YSZ) supporter, a Ni-Ce0.8Sm0.2O1.9 anode, a YSZ/Ce0.8Sm0.2O1.9 bi-layer electrolyte, and a La0.6Sr0.4Co0.2Fe0.8O3-δ cathode. The ceria catalyst is incorporated into the porous YSZ supporter layer by a cerium nitrate impregnation. The effects of ceria on the microstructure and electrochemical performance of the tubular single cell are investigated with respect to the number of impregnations. The optimum number of impregnations is determined to be four based on the maximum power density and polarization property of the tubular single cell in hydrogen and methane fuels. At 700 °C, the tubular single cell shows similar maximum power densities of ˜260 mW cm-2 in hydrogen and methane fuels, respectively. Moreover, the ceria catalyst significantly improves the performance stability of the cell running on methane fuel. At a current density of 350 mA cm-2, the single cell shows a low degradation rate of 2.5 mV h-1 during the 13 h test in methane fuel. These results suggest the feasibility of applying the ceria catalyst to the inert-substrate supported tubular single cell for direct operation on methane fuel.

  14. Ceria and copper/ceria functional coatings for electrochemical applications: Materials preparation and characterization

    NASA Astrophysics Data System (ADS)

    Melnik, J.; Fu, X. Z.; Luo, J. L.; Sanger, A. R.; Chuang, K. T.; Yang, Q. M.

    Following preliminary investigations, two electrodeposition techniques (electrophoretic and electrolytic) were selected and adapted for deposition of doped ceria ceramic and copper/doped ceria composite coatings on Ni substrates (foil and foam). The copper/doped ceria composites have potential value as protective functional coatings for current collectors in electrochemical cells including solid oxide fuel sells (SOFC). The doped ceria ceramic coating has potential application as a porous matrix for anodes of SOFCs operating on syngas, sour gas, or hydrocarbons.

  15. Multi-scale analysis of the diffusion barrier layer of gadolinia-doped ceria in a solid oxide fuel cell operated in a stack for 3000 h

    NASA Astrophysics Data System (ADS)

    Morales, M.; Miguel-Pérez, V.; Tarancón, A.; Slodczyk, A.; Torrell, M.; Ballesteros, B.; Ouweltjes, J. P.; Bassat, J. M.; Montinaro, D.; Morata, A.

    2017-03-01

    The state-of-the-art materials for SOFCs are yttria-stabilized zirconia as electrolyte and lanthanum strontium cobalt ferrite as cathode. However, the formation of insulating phases between them requires the use of diffusion barriers, typically made of gadolinia doped ceria. The study of the stability of this layer during the fabrication and in operando is currently one of the major goals of the SOFC industry. In this work, the cation inter-diffusion at the cathode/barrier layer/electrolyte region is analysed for an anode-supported cell industrially fabricated by conventional techniques, assembled in a short-stack and tested under real operation conditions for 3000 h. A comprehensive study of this cell, and an equivalent non-operated one, is performed in order to understand the inter-diffusion mechanisms with possible effects on the final performance. The analyses evidence that the cation diffusion is occurring during the fabrication process. Despite the significant diffusion of Ce,Gd, Zr, Y and Sr cations, the formation of typically reported CGO-YSZ solid solution is not observed while the presence of isolated grains of SrZrO3 is proved. All in all, this study presents new insights into the stability of the typically employed diffusion barriers for solid oxide cells that will guide future strategies to improve their performance and durability.

  16. Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

    2017-02-01

    A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

  17. H2 and CO oxidation process at the three-phase boundary of Cu-ceria cermet anode for solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Zheng, Minghao; Wang, Shuang; Li, Mei; Xia, Changrong

    2017-03-01

    Cu-ceria cermets have been widely investigated as the anode materials for solid oxide fuel cells (SOFCs) that operated with hydrocarbon fuels. However, the anode reaction processes are not clear yet, especially those at the ceria-Cu-gas three phase boundary (3 PB). This work investigates samaria-doped ceria (SDC)-Cu-gas 3 PB reaction kinetics for the oxidation of H2 and CO, the products from hydrocarbons via external and internal reforming. Electrochemical conductivity relaxation measurement demonstrates that Cu is a synergistic catalyst that can significantly increase the reaction rate. The reaction at 3 PB contributes 81.3/66.8% of H2/CO oxidation when 5.4% SDC surface is covered with Cu particles. Combining with AC impedance analysis, elementary steps are proposed for the reaction at 3 PB. Water vapor combining to oxygen vacancy and carbon monoxide transforming to carbonate are the rate-determining steps for the oxidation of H2 and CO, respectively. Cu-SDC has shown much higher catalytic activity, i.e. about fivefold reaction rate, for the oxidation of CO than H2. In addition, Cu-SDC electrodes exhibit lower interfacial polarization resistance and lower activation energy for the electrochemical oxidation of CO than H2. Consequently, CO is easier to be oxidized than H2 when the Cu-ceria anode is fueled with syngas, the reforming product from hydrocarbons.

  18. Hardness of cubic solid solutions

    PubMed Central

    Gao, Faming

    2017-01-01

    We demonstrate that a hardening rule exists in cubic solid solutions with various combinations of ionic, covalent and metallic bonding. It is revealed that the hardening stress ∆τFcg is determined by three factors: shear modulus G, the volume fraction of solute atoms fv, and the size misfit degree δb. A simple hardening correlation in KCl-KBr solid-solution is proposed as ∆τFcg = 0.27 G. It is applied to calculate the hardening behavior of the Ag-Au, KCl-KBr, InP-GaP, TiN-TiC, HfN-HfC, TiC-NbC and ZrC-NbC solid-solution systems. The composition dependence of hardness is elucidated quantitatively. The BN-BP solid-solution system is quantitatively predicted. We find a hardening plateau region around the x = 0.55–0.85 in BNxP1−x, where BNxP1−x solid solutions are far harder than cubic BN. Because the prediction is quantitative, it sets the stage for a broad range of applications. PMID:28054659

  19. Hardness of cubic solid solutions

    NASA Astrophysics Data System (ADS)

    Gao, Faming

    2017-01-01

    We demonstrate that a hardening rule exists in cubic solid solutions with various combinations of ionic, covalent and metallic bonding. It is revealed that the hardening stress ∆τFcg is determined by three factors: shear modulus G, the volume fraction of solute atoms fv, and the size misfit degree δb. A simple hardening correlation in KCl-KBr solid-solution is proposed as ∆τFcg = 0.27 G. It is applied to calculate the hardening behavior of the Ag-Au, KCl-KBr, InP-GaP, TiN-TiC, HfN-HfC, TiC-NbC and ZrC-NbC solid-solution systems. The composition dependence of hardness is elucidated quantitatively. The BN-BP solid-solution system is quantitatively predicted. We find a hardening plateau region around the x = 0.55-0.85 in BNxP1-x, where BNxP1-x solid solutions are far harder than cubic BN. Because the prediction is quantitative, it sets the stage for a broad range of applications.

  20. Enhanced ceria solid electrolyte fuel cell development. Reduction of electronic conductivity permits use of a solid ceria electrolyte in high efficiency high power density fuel cells at temperatures compatible with metallic cell hardware

    NASA Astrophysics Data System (ADS)

    Maricle, D. L.

    1990-01-01

    The high operating temperature of zirconia based solid oxide fuel cells has been shown in many studies to have advantages for both space and terrestrial applications. The high heat rejection temperature minimizes radiator size and weight for high atmospheric and space applications. Mobile and stationary terrestrial applications take advantage of a cell temperature high enough to directly reform hydro-carbon fuels, achieving high efficiency and energy density. Government funded solid oxide fuel cell (SOFC) efforts are concentrated on the monolithic and tubular cell designs employing zirconia as the oxide ion conduction membrane. Zirconia requires an operating temperature of 1000 C to achieve adequate electrolyte conductivity. All-ceramic cell structures are used in both cases, leading to fragile, failure prone cells, and manufacturing steps which are difficult to scale up and costly. IFC's molten carbonate fuel cell development demonstrates the reliability of ductile sheet metal parts used for gas flow fields, separator plates, and frames in the 650 C temperature range. Ceria doped with gadolinium has ionic conductivity at 700 C comparable to zirconia at 1000 C. At 700 C a variety of stainless steels offer acceptable strength and oxidation resistance for use as cell hardware.

  1. STRUCTURE AND PROPERTIES OF SOLID SOLUTIONS.

    DTIC Science & Technology

    Contents: solid solution strengthening and strain aging in Ag-base Al alloys; solid solution strengthening and aging in Cu-base Al alloys; solid ... solution strengthening in NaCl-base NaBr solutions; short-range order; solid solution strength in the gold-silver system.

  2. Tuning the Thickness of Ba-Containing "Functional" Layer toward High-Performance Ceria-Based Solid Oxide Fuel Cells.

    PubMed

    Gong, Zheng; Sun, Wenping; Shan, Duo; Wu, Yusen; Liu, Wei

    2016-05-04

    Developing highly efficient ceria-based solid oxide fuel cells with high power density is still a big concern for commercial applications. In this work, a novel structured Ce0.8Sm0.2O2-δ (SDC)-based fuel cell with a bilayered anode consisting of Ni-SDC and Ni-BaZr0.1Ce0.7Y0.2O3-δ (Ni-BZCY) was designed. In addition to the catalysis function, the Ni-BZCY anode "functional" layer also provides Ba source for generating an electron-blocking layer in situ at the anode/electrolyte interface during sintering. The Ni-BZCY thickness significantly influences the quality of the electron-blocking layer and electrochemical performances of the cell. The cell with a 50 μm thick Ni-BZCY layer exhibits the best performance in terms of open circuit voltage (OCV) and peak power density (1068 mW cm(-2) at 650 °C). The results demonstrate that this cell with an optimal structure has a distinct advantage of delivering high power performance with a high efficiency at reduced temperatures.

  3. Role of the gadolinia-doped ceria interlayer in high-performance intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jung, Doh Won; Kwak, Chan; Seo, Sooyeon; Moon, Kyoung-Seok; Han, In-taek; Kim, Ju Sik

    2017-09-01

    In this study, Ba0.5Sr0.5Co0.8Fe0.1Zn0.1O3-δ (BSCFZ) is used as a cathode with anode-supported scandia-stabilized zirconia (ScSZ) as the electrolyte to achieve intermediate-temperature solid oxide fuel cells (SOFCs). A gadolinia-doped ceria (GDC) interlayer is used between the BSCFZ cathode and the ScSZ electrolyte to protect ScSZ against interfacial reaction with the Co-containing cathode. However, an unfavorable reaction occurs at the GDC/ScSZ interface when the sintering temperature of the GDC interlayer is higher than 1200 °C. Thus, the performance of anode-supported SOFCs with GDC interlayers prepared at different sintering temperatures has been evaluated using I-V measurements and AC impedance spectroscopy. The results demonstrate that the sintering temperature of the GDC interlayer should be optimized for both the reaction between the BSCFZ cathode and ScSZ electrolyte and the reaction at the GDC/ScSZ interface. A maximum power density of 0.78 W cm-2 has been achieved at 700 °C with a GDC interlayer sintered at 1200 °C. Furthermore, the cell with the optimized GDC interlayer has been shown to maintain excellent reliability with respect to load cycling and thermal cycling.

  4. Synthesis and In Situ Environmental Transmission Electron Microscopy Investigations of Ceria-Based Oxides for Solid Oxide Fuel Cell Anodes

    NASA Astrophysics Data System (ADS)

    Sharma, Vaneet

    The behavior of a solid oxide fuel cell (SOFC) cermet (ceramic-metal composite) anode under reaction conditions depends significantly on the structure, morphology and atomic scale interactions between the metal and the ceramic components. In situ environmental transmission electron microscope (ETEM) is an important tool which not only allows us to perform the basic nanoscale characterization of the anode materials, but also to observe in real-time, the dynamic changes in the anode material under near-reaction conditions. The earlier part of this dissertation is focused on the synthesis and characterization of Pr- and Gd-doped cerium oxide anode materials. A novel spray drying set-up was designed and constructed for preparing nanoparticles of these mixed-oxides and nickel oxide for anode fabrication. X-ray powder diffraction was used to investigate the crystal structure and lattice parameters of the synthesized materials. Particle size distribution, morphology and chemical composition were investigated using transmission electron microscope (TEM). The nanoparticles were found to possess pit-like defects of average size 2 nm after subjecting the spray-dried material to heat treatment at 700 °C for 2 h in air. A novel electron energy-loss spectroscopy (EELS) quantification technique for determining the Pr and Gd concentrations in the mixed oxides was developed. Nano-scale compositional heterogeneity was observed in these materials. The later part of the dissertation focuses mainly on in situ investigations of the anode materials under a H2 environment in the ETEM. Nano-scale changes in the stand-alone ceramic components of the cermet anode were first investigated. Particle size and composition of the individual nanoparticles of Pr-doped ceria (PDC) were found to affect their reducibility in H2 gas. Upon reduction, amorphization of the nanoparticles was observed and was linked to the presence of pit-like defects in the spray-dried material. Investigation of metal

  5. La2NiO4+δ infiltrated into gadolinium doped ceria as novel solid oxide fuel cell cathodes: Electrochemical performance and impedance modelling

    NASA Astrophysics Data System (ADS)

    Nicollet, C.; Flura, A.; Vibhu, V.; Rougier, A.; Bassat, J. M.; Grenier, J. C.

    2015-10-01

    This paper is devoted to the study of composite cathodes of La2NiO4+δ infiltrated into a Gd-doped ceria backbone. Porous Gd-doped ceria backbones are screen printed onto yttria-stabilized zirconia or Gd-doped ceria dense electrolytes, and infiltrated with a La and Ni nitrate solution (2:1 stoichiometry ratio). The influence of the preparation parameters on the polarization resistance, such as the concentration of the infiltration solution, the amount of infiltrated phase, the annealing temperature, the thickness of the electrode, and the nature of the electrolyte, is characterized by impedance spectroscopy performed on symmetrical cells. The optimization of these parameters results in a decrease of the polarization resistance down to 0.15 Ω cm2 at 600 °C. Using the Adler-Lane-Steele model, the modelling of the impedance diagrams leads to the determination of the ionic conductivity as well as the surface exchange rate of the infiltrated electrode.

  6. Enhanced hydrogen oxidation activity and H2S tolerance of Ni-infiltrated ceria solid oxide fuel cell anodes

    NASA Astrophysics Data System (ADS)

    Mirfakhraei, Behzad; Paulson, Scott; Thangadurai, Venkataraman; Birss, Viola

    2013-12-01

    The effect of Ni infiltration into porous Gd-doped ceria (GDC) anodes on their H2 oxidation performance, with and without added 10 ppm H2S, is reported here. Porous GDC anodes (ca. 10 μm thick) were deposited on yttria stabilized zirconia (YSZ) supports and then infiltrated with catalytic amounts of a Ni nitrate solution, followed by electrochemical testing in a 3-electrode half-cell setup at 500-800 °C. Infiltration of 3 wt.% Ni into the porous GDC anode lowered the polarization resistance by up to 85%, affecting mainly the low frequency impedance arc. When exposed to 10 ppm H2S, the Ni-infiltrated anodes exhibited a ca. 5 times higher tolerance toward sulfur poisoning compared to GDC anodes alone, also showing excellent long-term stability in 10 ppm H2S. In the presence of H2S, it is proposed that Ni, likely distributed as a nanophase, helps to maintain a clean GDC surface at the Ni/GDC interface at which the H2 oxidation reaction takes place. In turn, the GDC will readily supply oxygen anions to the adjacent Ni surfaces, thus helping to remove adsorbed sulfur.

  7. Defects clustering and ordering in di- and trivalently doped ceria

    SciTech Connect

    Li, Zhi-Peng; Mori, Toshiyuki; Zou, Jin; Drennan, John

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Defect structures in trivalently and divalently doped ceria has been elucidated. ► Dumbbell structure is a universal basic vacancy structure in fluorite oxides. ► Electrostatic attraction dominates elastic interaction in doped ceria. ► Provide a physical picture of conductivity behavior in aliovalently doped ceria. -- Abstract: The formation and growth of defect clusters in CeO{sub 2}-M{sub 2}O{sub 3} (M = La{sup 3+}, Pr{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Y{sup 3+}, Yb{sup 3+}) and CeO{sub 2}-DO (N = Cd{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, Ba{sup 2+}) binary solid solutions have been comparatively studied by atomistic simulations based on energy minimization of atomic interactions. The calculation ensemble, including both divalent and trivalent dopants, shows a similar energetic tendency for defect species (dopants and associated oxygen vacancies) to aggregate and grow. The dumbbell structure has been verified as a universal vacancy structure in oxygen deficient fluorite lattice. Nevertheless, it also demonstrates different tendencies of dopant–vacancy associations that depend on dopant valence and radius. The dopant is site-selective in trivalent defect clusters correlated with dopant size. While in divalent solid solutions, clusters adopt similar dopant–vacancy locations. Furthermore, all clusters in divalently doped ceria have stronger dopant–vacancy associations/interactions compared to those in trivalent ones. As a consequence, the correlation of the dopant size as well as valence effects on oxygen-ion conductivity has been illustrated based on an ordered defect cluster model. This study thereby offers insight into the physical picture of ionic conductivity behavior experimentally obtained in aliovalently doped ceria.

  8. Germanium-silicon solid solutions

    NASA Technical Reports Server (NTRS)

    Zemskov, V. S.; Kubasov, V. N.; Belokurova, I. N.; Titkov, A. N.; Shulpina, I. L.; Safarov, V. I.; Guseva, N. B.

    1977-01-01

    An experiment on melting and directional crystallization of an antimony (Sb) doped germanium silicon (GeSi) solid solution was designed for the Apollo-Soyuz Test Project (ASTP) to study the possibility of using zero-g conditions for obtaining solid-solution monocrystals with uniformly distributed components. Crystallization in the zero-g environment did not occur under ideal stationary growth and segregation conditions. Crystallization under zero-g conditions revealed the heterogeneous nature of Si and Sb distribution in the cross sections of crystals. The presence of the radial thermal gradient in the multipurpose furnace could be one of the reasons for such Si and Sb distribution. The structure of space-grown crystals correlates with the nature of heterogeneities of Si and Sb distribution in crystals. The type of surface morphology and the contour observed in space-grown crystals were never observed in ground-based crystals and indicate the absence of wetting of the graphitized walls of the ampoule by the melt during melting and crystallization.

  9. Growth of Solid Solution Crystals

    NASA Technical Reports Server (NTRS)

    Lehoczky, S. L.; Szofran, F. R.; Holland, L. R.

    1985-01-01

    The major objective of this program is to determine the conditions under which single crystals of solid solutions can be grown from the melt in a Bridgman configuration with a high degree of chemical homogeneity. The central aim is to assess the role of gravity in the growth process and to explore the possible advantages for growth in the absence of gravity. The alloy system being investigated is the solid solution semiconductor with x-values appropriate for infrared detector applications in Hg sub (1-x) Cd sub x Te the 8 to 14 micro m wavelength region. Both melt and Te-solvent growth are being considered. The study consists of an extensive ground-based experimental and theoretical research effort followed by flight experimentation where appropriate. Experimental facilities have been established for the purification, casting, and crystal growth of the alloy system. Facilities have been also established for the metallurgical, compositional, electric and optical characterization of the alloys. Crystals are being grown by the Bridgman-Stockbarger method and are analyzed by various experimental techniques to evaluate the effects of growth conditions on the longitudinal and radial compositional variations and defect densities in the crystals.

  10. Composite ceria-coated aerogels and methods of making the same

    DOEpatents

    Eyring, Edward M; Ernst, Richard D; Turpin, Gregory C; Dunn, Brian C

    2013-05-07

    Ceria-coated aerogels can include an aerogel support material having a stabilized ceria coating thereon. The ceria coating can be formed by solution or vapor deposition of alcogels or aerogels. Additional catalytic metal species can also be incorporated into the coating to form multi-metallic compounds having improved catalytic activity. Further, the ceria coated aerogels retain high surface areas at elevated temperatures. Thus, improvements in catalytic activity and thermal stability can be achieved using these ceria-coated composite aerogels.

  11. High performance metal-supported solid oxide fuel cells with Gd-doped ceria barrier layers

    NASA Astrophysics Data System (ADS)

    Klemensø, Trine; Nielsen, Jimmi; Blennow, Peter; Persson, Åsa H.; Stegk, Tobias; Christensen, Bjarke Holl; Sønderby, Steffen

    Metal-supported solid oxide fuel cells are believed to have commercial advantages compared to conventional anode (Ni-YSZ) supported cells, with the metal-supported cells having lower material costs, increased tolerance to mechanical and thermal stresses, and lower operational temperatures. The implementation of a metallic support has been challenged by the need to revise the cell fabrication route, as well as electrode microstructures and material choices, to compete with the energy output and stability of full ceramic cells. The metal-supported SOFC design developed at Risø DTU has been improved, and an electrochemical performance beyond the state-of-the-art anode-supported SOFC is demonstrated possible, by introducing a CGO barrier layer in combination with Sr-doped lanthanum cobalt oxide (LSC) cathode. Area specific resistances (ASR) down to 0.27 Ω cm 2, corresponding to a maximum power density of 1.14 W cm -2 at 650 °C and 0.6 V, were obtained on cells with barrier layers fabricated by magnetron sputtering. The performance is dependent on the density of the barrier layer, indicating Sr 2+ diffusion is occurring at the intermediate SOFC temperatures. The optimized design further demonstrate improved durability with steady degradation rates of 0.9% kh -1 in cell voltage for up to 3000 h galvanostatic testing at 650 °C and 0.25 A cm -2.

  12. A novel Ni/ceria-based anode for metal-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Rojek-Wöckner, Veronika A.; Opitz, Alexander K.; Brandner, Marco; Mathé, Jörg; Bram, Martin

    2016-10-01

    For optimization of ageing behavior, electrochemical performance, and sulfur tolerance of metal-supported solid oxide fuel cells a new anode concept is introduced, which is based on a Ni/GDC cermet replacing the established Ni/YSZ anodes. In the present work optimized processing parameters compatible with MSC substrates are specified by doing sintering studies on pressed bulk specimen and on real porous anode structures. The electrochemical performance of the Ni/GDC anodes was characterized by means of symmetrical electrolyte supported model-type cells. In this study, three main objectives are pursued. Firstly, the effective technical realization of the Ni/GDC concept is demonstrated. Secondly, the electrochemical behavior of Ni/GDC porous anodes is characterized by impedance spectroscopy and compared with the current standard Ni/YSZ anode. Further, a qualitative comparison of the sulfur poisoning behavior of both anode types is presented. Thirdly, preliminary results of a successful implementation of the Ni/GDC cermet into a metal-supported single cell are presented.

  13. Mesoporous NiO-samaria doped ceria for low-temperature solid oxide fuel cells.

    PubMed

    Kim, Jin-Yeop; Kim, Ji Hyeon; Choi, Hyung Wook; Kim, Kyung Hwan; Park, Sang Joon

    2014-08-01

    In order to prepare anode material for low-temperature solid oxide fuel cells (SOFCs), the mesoporous NiO-SDC was synthesized using a cationic surfactant (cetyltrimethyl-ammonium bromide; CTAB) for obtaining wide triple-phase boundary (TPB). In addition, Ni-SDC anode-supported SOFC single cells with YSZ electrolyte and LSM cathode were fabricated and the performance of single cells was evaluated at 600 °C. The microstructure of NiO-SDC was characterized by XRD, EDX, SEM, and BET, and the results showed that the mesoporous NiO-SDC with 10 nm pores could be obtained. It was found that the surface area and the electrical performance were strongly influenced by the Ni content in Ni-SDC cermets. After calcined at 600 °C, the surface area of NiO-SDC was between 90-117 m2/g at 35-45 Ni wt%, which was sufficiently high for providing large TPB in SOFC anode. The optimum Ni content for cell performance was around 45 wt% and the corresponding MPD was 0.36 W/cm2. Indeed, the mesoporous NiO-SDC cermet may be of interest for use as an anode for low-temperature SOFCs.

  14. Composite solid oxide fuel cell anode based on ceria and strontium titanate

    DOEpatents

    Marina, Olga A.; Pederson, Larry R.

    2008-12-23

    An anode and method of making the same wherein the anode consists of two separate phases, one consisting of a doped strontium titanate phase and one consisting of a doped cerium oxide phase. The strontium titanate phase consists of Sr.sub.1-xM.sub.xTiO.sub.3-.delta., where M is either yttrium (Y), scandium (Sc), or lanthanum (La), where "x" may vary typically from about 0.01 to about 0.5, and where .delta. is indicative of some degree of oxygen non-stoichiometry. A small quantity of cerium may also substitute for titanium in the strontium titanate lattice. The cerium oxide consists of N.sub.yCe.sub.1-yO.sub.2-.delta., where N is either niobium (Nb), vanadium (V), antimony (Sb) or tantalum (Ta) and where "y" may vary typically from about 0.001 to about 0.1 and wherein the ratio of Ti in said first phase to the sum of Ce and N in the second phase is between about 0.2 to about 0.75. Small quantities of strontium, yttrium, and/or lanthanum may additionally substitute into the cerium oxide lattice. The combination of these two phases results in better performance than either phase used separately as an anode for solid oxide fuel cell or other electrochemical device.

  15. Gadolinia-doped ceria mixed with alkali carbonates for solid oxide fuel cell applications: I. A thermal, structural and morphological insight

    NASA Astrophysics Data System (ADS)

    Benamira, M.; Ringuedé, A.; Albin, V.; Vannier, R.-N.; Hildebrandt, L.; Lagergren, C.; Cassir, M.

    Ceria-based composites are developed and considered as potential electrolytes for intermediate solid oxide fuel cell applications (ITSOFC). After giving a survey of the most relevant results in the literature, the structural, thermal and morphological properties of composite materials based on gadolinia-doped ceria (GDC) and alkali carbonates (Li 2CO 3-K 2CO 3 or Li 2CO 3-Na 2CO 3) are carefully examined. Thermal analyses demonstrate the stability of the composite with very low weight losses of both water and CO 2 during thermal cycling and after 168 h ageing. High-temperature and room-temperature X-ray diffraction allowed determining the precise structure of the composite and its regular and reversible evolution with the temperature. The microstructure and morphology of electrolyte pellets, as observed by scanning electron microscopy (SEM), show two-well separated phases: nanocrystals of GDC and a well-distributed carbonate phase. Finally, electrical conductivity determined by impedance spectroscopy is presented as a function of time to highlight the stability of such composites over 1500 h.

  16. Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials.

    PubMed

    Laycock, Christian J; Staniforth, John Z; Ormerod, R Mark

    2011-05-28

    tolerance of Ni/YSZ, however, in the presence of H(2)S ceria did not promote the reverse Boudouard reaction and at high temperatures carbon deposition was greater over ceria-doped Ni/YSZ. In order to further study the effects of ceria-doping, a solid oxide fuel cell (SOFC) was constructed with a ceria-doped anode cermet and its electrical performance on simulated biogas compared to hydrogen was tested. This fuel cell was subsequently ran for 1000 h on simulated biogas with no degradation in its overall electrical performance.

  17. Orientational ordering of solution derived epitaxial Gd-doped ceria nanowires induced by nanoscratching

    NASA Astrophysics Data System (ADS)

    Zabaleta, Jone; Mestres, Narcis; Abellán, Patricia; Gibert, Marta; Sandiumenge, Felip; Puig, Teresa; Obradors, Xavier

    2010-01-01

    When one-dimensional nanostructures are epitaxially grown on a substrate a key goal is to control the nanowire's position and orientation. Nanoscratching of single crystalline (001)- LaAlO3 substrates is demonstrated to be extraordinarily effective in directing the self-assembly of Ce0.9Gd0.1O2-y epitaxial nanowires grown by chemical solution deposition. The local anisotropic elastic strain field imposed by the indentation lines is responsible for the breaking of the pre-existing orientation energy degeneracy and selects the nanowires' orientation parallel to the lines to an extent that can reach 100%.

  18. The grain growth behavior of NiO in thermally-stable mesoporous gadolinium-doped ceria network for intermediate-temperature solid oxide fuel cell anode materials.

    PubMed

    Ahn, Seunghyun; Koo, Hyun; Bae, Sung-Hwan; Chang, Ikwhang; Cha, Sukwon; Yoo, Young-Sung; Park, Chan

    2014-10-01

    The grain growth behavior of NiO nano grains in mesoporous gadolinium-doped ceria (GDC) network was investigated for anode materials of intermediate-temperature solid oxide fuel cell (SOFC). Both mesoporous GDC and NiO-GDC powders were synthesized using tri-block copolymer, Pluronic F127 as a structure-directing agent, and then X-ray diffraction, N2 adsorption/desorption isotherms, thermo gravimetric analysis, field-emission scanning electron microscopy and transmission electron microscopy were used for characterization of the mesoporous structure. Mesoporous GDC synthesized using pluronic F127 triblock copolymer had ordered double mesoporous structure with an average pore size of 9.68 nm and was thermally stable up to 700 degrees C. NiO grains in the mesoporous GDC network grew to have an octahedral shape with truncated-edges, but massive NiO agglomeration occurred as the calcination temperature increases up to 850 degrees C.

  19. Intermediate-Temperature Solid-Oxide Fuel Cells with a Gadolinium-Doped Ceria Anodic Functional Layer Deposited via Radio-Frequency Sputtering.

    PubMed

    Tanveer, Waqas Hassan; Ji, Sanghoon; Yu, Wonjong; Cho, Gu Young; Lee, Yoon Ho; Cha, Suk Won

    2015-11-01

    We investigated the effects of the insertion of a gadolinium-doped ceria (GDC) anodic functional layer (AFL) on the electrochemical performance of intermediate-temperature solid-oxide fuel cells (SOFCs). Fully stabilized yttria-stabilized zirconia (YSZ) was used as an oxygen-ion-conducting and support material. Nickel-Samaria-doped ceriathin film was used as an anode material, while screen-printed lanthanum strontium magnetite served as a cathode material. In order to enhance the interfacial reaction on the anode side, a GDC-AFL with a thickness of about 140 nm, deposited via radio-frequency sputtering, was inserted into the anode-electrolyte interface. SOFCs with and without a GDC-AFL were electrochemically characterized. In an intermediate temperature range of about 700 - 800 degrees C, the application of the GDC-AFL led to an increase in the peak power density of approximately 16%.

  20. Doped Yttrium Chromite-Ceria Composite as a Redox-Stable and Sulfur-Tolerant Anode for Solid Oxide Fuel Cells

    SciTech Connect

    Yoon, Kyung J.; Coyle, Christopher A.; Marina, Olga A.

    2011-12-11

    A Ca- and Co-doped yttrium chromite (YCCC) - samaria-doped ceria (SDC) composite was studied in relation to a potential use as a solid oxide fuel cell (SOFC) anode material. Tests performed using the yttria-stabilized zirconia (YSZ) electrolyte-supported cells revealed that the electrocatalytic activity of the YCCC-SDC anode towards hydrogen oxidation at 800 C was comparable to that of the Ni-YSZ anode. In addition, the YCCC-SDC anode exhibited superior sulfur tolerant characteristics showing less than 10% increase in a polarization resistance, fully reversible, upon exposure to 20 ppm H2S at 800 C. No performance degradation was observed during multiple reduction-oxidation (redox) cycles when the anode was intentionally exposed to the air environment followed by the reduction in hydrogen. The redox tolerance of the YCCC-SDC anode was attributed to the dimensional and chemical stability of the YCCC exhibiting minimal isothermal chemical expansion upon redox cycling.

  1. Catalytic modification of Ni-Sm-doped ceria anodes with copper for direct utilization of dry methane in low-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Zhicheng; Weng, Wenjian; Cheng, Kui; Du, Piyi; Shen, Ge; Han, Gaorong

    2008-05-01

    A Cu/Ni/Sm-doped ceria (SDC) anode has been designed for direct utilization of dry methane in low-temperature anode-supported solid oxide fuel cells. The anode is prepared by the impregnation method, whereby a small amount of Cu is incorporated into the previously prepared Ni/SDC porous matrix. After reduction, Cu nanoparticles adhere to and are uniformly distributed on the surface of the Ni/SDC matrix. For the resulting Cu/Ni/SDC anode-supported cell, maximum power density of 317 mW cm-2 is achieved at 600 °C. The power density shows only ∼2% loss after 12-h operation. The results demonstrate that the Cu/Ni/SDC anode effectively suppresses carbon deposition by decreasing the Ni surface area available and the level of carbon monoxide disproportionation. This combination of effects results in very low-power density loss over the operating time.

  2. Deactivation of ceria-based SOFC anodes in methanol

    NASA Astrophysics Data System (ADS)

    Kim, Taeyoon; Ahn, Kipyung; Vohs, John M.; Gorte, Raymond J.

    The performance and stability of Cu-ceria-YSZ (yttria-stabilized zirconia) and carbon-ceria-YSZ, solid-oxide-fuel-cell (SOFC) anodes were examined in neat (100%) methanol at 973 K and compared to the performance of the same anodes in dry H 2. The presence of Cu catalyzed the decomposition of methanol, so that the initial performance of cells with Cu-ceria-YSZ anodes was similar to CO and H 2. However, with carbon-ceria-YSZ anodes, the open-circuit voltage was significantly higher and the reaction over-potential significantly lower in methanol than in H 2, suggesting that methanol is a more effective reductant of the anode three-phase boundary region. Carbon-ceria-YSZ anodes were found to undergo rapid and irreversible deactivation in methanol. Steady-state rates of methanol decomposition over ceria-YSZ were found to undergo a similar deactivation as the carbon-ceria anodes. Although no evidence for carbon deposition was observed with methanol at 973 K, the addition of steam was found to partially stabilize both anode and catalyst performance. Scanning electron microscopy (SEM) of ceria particles in YSZ showed a large change in the morphology of the ceria particles when the samples were heated in methanol, while negligible changes were observed when heating in H 2. It is suggested that the results with methanol can be explained as resulting from the very low P(O 2) that is effectively produced by having methanol in contact with ceria.

  3. Single crystals of metal solid solutions

    NASA Technical Reports Server (NTRS)

    Miller, J. F.; Austin, A. E.; Richard, N.; Griesenauer, N. M.; Moak, D. P.; Mehrabian, M. R.; Gelles, S. H.

    1974-01-01

    The following definitions were sought in the research on single crystals of metal solid solutions: (1) the influence of convection and/or gravity present during crystallization on the substructure of a metal solid solution; (2) the influence of a magnetic field applied during crystallization on the substructure of a metal solid solution; and (3) requirements for a space flight experiment to verify the results. Growth conditions for the selected silver-zinc alloy system are described, along with pertinent technical and experimental details of the project.

  4. Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers as Optical Sensors for Radicals

    PubMed Central

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Hamed, Aya; Elrasheedy, Asmaa

    2016-01-01

    This work presents a new nanocomposite of cerium oxide (ceria) nanoparticles embedded in electrospun PVA nanofibers for optical sensing of radicals in solutions. Our ceria nanoparticles are synthesized to have O-vacancies which are the receptors for the radicals extracted from peroxide in water solution. Ceria nanoparticles are embedded insitu in PVA solution and then formed as nanofibers using an electrospinning technique. The formed nanocomposite emits visible fluorescent emissions under 430 nm excitation, due to the active ceria nanoparticles with fluorescent Ce3+ ionization states. When the formed nanocomposite is in contact with peroxide solution, the fluorescence emission intensity peak has been found to be reduced with increasing concentration of peroxide or the corresponding radicals through a fluorescence quenching mechanism. The fluorescence intensity peak is found to be reduced to more than 30% of its original value at a peroxide weight concentration up to 27%. This work could be helpful in further applications of radicals sensing using a solid mat through biomedical and environmental monitoring applications. PMID:27571083

  5. Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers as Optical Sensors for Radicals.

    PubMed

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Hamed, Aya; Elrasheedy, Asmaa

    2016-08-26

    This work presents a new nanocomposite of cerium oxide (ceria) nanoparticles embedded in electrospun PVA nanofibers for optical sensing of radicals in solutions. Our ceria nanoparticles are synthesized to have O-vacancies which are the receptors for the radicals extracted from peroxide in water solution. Ceria nanoparticles are embedded insitu in PVA solution and then formed as nanofibers using an electrospinning technique. The formed nanocomposite emits visible fluorescent emissions under 430 nm excitation, due to the active ceria nanoparticles with fluorescent Ce(3+) ionization states. When the formed nanocomposite is in contact with peroxide solution, the fluorescence emission intensity peak has been found to be reduced with increasing concentration of peroxide or the corresponding radicals through a fluorescence quenching mechanism. The fluorescence intensity peak is found to be reduced to more than 30% of its original value at a peroxide weight concentration up to 27%. This work could be helpful in further applications of radicals sensing using a solid mat through biomedical and environmental monitoring applications.

  6. Solution-solid-solid mechanism: superionic conductors catalyze nanowire growth.

    PubMed

    Wang, Junli; Chen, Kangmin; Gong, Ming; Xu, Bin; Yang, Qing

    2013-09-11

    The catalytic mechanism offers an efficient tool to produce crystalline semiconductor nanowires, in which the choice, state, and structure of catalysts are active research issues of much interest. Here we report a novel solution-solid-solid (SSS) mechanism for nanowire growth catalyzed by solid-phase superionic conductor nanocrystals in low-temperature solution. The preparation of Ag2Se-catalyzed ZnSe nanowires at 100-210 °C is exampled to elucidate the SSS model, which can be extendable to grow other II-VI semiconductor (e.g., CdSe, ZnS, and CdS) nanowires by the catalysis of nanoscale superionic-phase silver or copper(I) chalcogenides (Ag2Se, Ag2S, and Cu2S). The exceptional catalytic ability of these superionic conductors originates from their structure characteristics, known for high-density vacancies and fast mobility of silver or copper(I) cations in the rigid sublattice of Se(2-) or S(2-) ions. Insights into the SSS mechanism are provided based on the formation of solid solution and the solid-state ion diffusion/transport at solid-solid interface between catalyst and nanowire.

  7. Energetics of Rare Earth Doped Uranium Oxide Solid Solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Lei

    J/mol. Since all the other doped fluorite oxides based on zirconia, hafnia, ceria, and thoria are in the oxygen deficit (oxygen vacancy formation) regime, a systematic study of these rare earth doped fluorite oxides (LnxA 1-xO2-0.5x) was made comparing experimental and computational results. A consistent trend suggested by both calorimetry and computation, was found for all oxygen vacancy containing systems (actinide and non-actinide oxide systems). Larger size mismatch between the smaller host cation (A 4+) and the larger rare earth dopant cation (Ln3+) generally produces more stable solid solutions. The energetics of these systems is the result of competition between strain energy arising from size mismatch (endothermic) and defect association (exothermic). The formation enthalpies of LnxU1-xO2-0.5x obtained from calculation are slightly positive.

  8. Study on the CO Oxidation over Ceria-Based Nanocatalysts.

    PubMed

    Piumetti, Marco; Andana, Tahrizi; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-12-01

    A series of ceria nanocatalysts have been prepared to study the structure dependency of the CO oxidation reaction. The ceria samples with well-defined nanostructures (nanocubes/Ce-NC and nanorods/Ce-NR) have been prepared using the hydrothermal method. Mesoporous ceria (Ce-MES) and ceria synthesized with solution combustion technique (Ce-SCS) have also been prepared for comparison. The lowest CO oxidation temperature has been reached by using ceria nanocubes (Ce-NC). This high activity draws immense contributions from the highly reactive (100) and (110) surfaces of the truncated nanocubes. The Ce-MES and Ce-SCS samples, despite their high surface areas, are unable to outdo the activity of Ce-NC and Ce-NR due to the abundant presence of (111) crystalline planes. This finding confirms the structure sensitivity of CO oxidation reaction catalyzed with ceria.

  9. Study on the CO Oxidation over Ceria-Based Nanocatalysts

    NASA Astrophysics Data System (ADS)

    Piumetti, Marco; Andana, Tahrizi; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-03-01

    A series of ceria nanocatalysts have been prepared to study the structure dependency of the CO oxidation reaction. The ceria samples with well-defined nanostructures (nanocubes/Ce-NC and nanorods/Ce-NR) have been prepared using the hydrothermal method. Mesoporous ceria (Ce-MES) and ceria synthesized with solution combustion technique (Ce-SCS) have also been prepared for comparison. The lowest CO oxidation temperature has been reached by using ceria nanocubes (Ce-NC). This high activity draws immense contributions from the highly reactive (100) and (110) surfaces of the truncated nanocubes. The Ce-MES and Ce-SCS samples, despite their high surface areas, are unable to outdo the activity of Ce-NC and Ce-NR due to the abundant presence of (111) crystalline planes. This finding confirms the structure sensitivity of CO oxidation reaction catalyzed with ceria.

  10. Computer simulation of concentrated solid solution strengthening

    NASA Technical Reports Server (NTRS)

    Kuo, C. T. K.; Arsenault, R. J.

    1976-01-01

    The interaction forces between a straight edge dislocation moving through a three-dimensional block containing a random array of solute atoms were determined. The yield stress at 0 K was obtained by determining the average maximum solute-dislocation interaction force that is encountered by edge dislocation, and an expression relating the yield stress to the length of the dislocation and the solute concentration is provided. The magnitude of the solid solution strengthening due to solute atoms can be determined directly from the numerical results, provided the dislocation line length that moves as a unit is specified.

  11. Synthesis of solid solutions of perovskites

    SciTech Connect

    Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.; Plaude, A.V.

    1986-03-01

    The authors carry out thermographic studies, using a derivatograph, in order to understand the nature of the processes taking place during the synthesis of solid solutions of perovskites. Based on the detailed studies on the phase transformations occurring in the charges of the PSN-PMN solid solutions and on the selection of the optimum conditions for carrying out their synthesis, the authors obtained a powder containing a minimum quantity of the undesirable pyrochlore phase and by sintering it using the hot pressing method, they produced single phase ceramic specimens containing the perovskite phase alone with a density close to the theoretical value and showing zero apparent porosity and water absorption.

  12. Radiation-Induced Reduction of Ceria in Single and Polycrystalline Thin Films

    SciTech Connect

    Kumar, Amit; Devanathan, Ramaswami; Shutthanandan, V.; Kuchibhatla, Satyanarayana V N T; Karakoti, Ajay S.; Yang, Yong; Thevuthasan, Suntharampillai; Seal, Sudipta

    2012-01-12

    Ceria (CeO{sub 2}) is a technologically important ceramic material with a wide range of neoteric applications in catalysis, solid oxide fuel cells, oxygen gas sensors, hydrogen production, and ultraviolet shielding. Recent research has revealed promising biomedical applications of ceria. Nanoparticles of ceria have been shown to protect healthy cells from radiation-induced cellular damage. The mechanisms governing the radioprotection characteristics of ceria nanoparticles are not well understood and it has been hypothesized that reversible switching between Ce{sup 4+} and Ce{sup 3+} states may enable ceria nanoparticles to mop up free radicals.

  13. Evaluation of the Effect of Sulfur on the Performance of Nickel/Gadolinium-Doped Ceria Based Solid Oxide Fuel Cell Anodes.

    PubMed

    Riegraf, Matthias; Yurkiv, Vitaliy; Costa, Rémi; Schiller, Günter; Friedrich, K Andreas

    2017-02-08

    The focus of this study is the measurement and understanding of the sulfur poisoning phenomena of Ni/gadolinium-doped ceria (CGO) based solid oxide fuel cells (SOFC). Cells with Ni/CGO10 and NiCu5/CGO40 anodes were characterized by using impedance spectroscopy at different temperatures and H2 /H2 O fuel ratios. The short-term sulfur poisoning behavior was investigated systematically at temperatures of 800-950 °C, current densities of 0-0.75 A cm(-2) , and H2 S concentrations of 1-20 ppm. A sulfur poisoning mitigation effect was observed at high current loads and temperatures. The poisoning behavior was reversible for short exposure times. It was observed that the sulfur-affected processes exhibited significantly different relaxation times that depend on the Gd content in the CGO phase. Moreover, it was demonstrated that the capacitance of Ni/CGO10 anodes is strongly dependent on the temperature and gas-phase composition, which reflects a changing Ce(3+) /Ce(4+) ratio. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

    PubMed Central

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-01-01

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode. PMID:26928192

  15. An open circuit voltage equation enabling separation of cathode and anode polarization resistances of ceria electrolyte based solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Yanxiang; Chen, Yu; Yan, Mufu

    2017-07-01

    The open circuit voltage (OCV) of solid oxide fuel cells is generally overestimated by the Nernst equation and the Wagner equation, due to the polarization losses at electrodes. Considering both the electronic conduction of electrolyte and the electrode polarization losses, we express the OCV as an implicit function of the characteristic oxygen pressure of electrolyte (p* [atm], at which the electronic and ionic conductivities are the same), and the relative polarization resistance of electrodes (rc = Rc/Ri and ra = Ra/Ri, where Ri/c/a [Ωcm2] denotes the ionic resistance of electrolyte, and the polarization resistances of cathode and anode, respectively). This equation approaches to the Wagner equation when the electrodes are highly active (rc and ra → 0), and approaches to the Nernst equation when the electrolyte is a purely ionic conductor (p* → 0). For the fuel cells whose OCV is well below the prediction of the Wagner equation, for example with thin doped ceria electrolyte, it is demonstrated that the combination of OCV and impedance spectroscopy measurements allows the determination of p*, Rc and Ra. This equation can serve as a simple yet powerful tool to study the internal losses in the cell under open circuit condition.

  16. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer.

    PubMed

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-02-29

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm(2) at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode.

  17. Slurry spin coating of thin film yttria stabilized zirconia/gadolinia doped ceria bi-layer electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Joong; Kim, Manjin; Neoh, Ke Chean; Han, Gwon Deok; Bae, Kiho; Shin, Jong Mok; Kim, Gyu-Tae; Shim, Joon Hyung

    2016-09-01

    Thin ceramic bi-layered membrane comprising yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is fabricated by the cost-effective slurry spin coating technique, and it is evaluated as an electrolyte of solid oxide fuel cells (SOFCs). It is demonstrated that the slurry spin coating method is capable of fabricating porous ceramic films by adjusting the content of ethyl-cellulose binders in the source slurry. The porous GDC layer deposited by spin coating under an optimal condition functions satisfactorily as a cathode-electrolyte interlayer in the test SOFC stack. A 2-μm-thick electrolyte membrane of the spin-coated YSZ/GDC bi-layer is successfully deposited as a dense and stable film directly on a porous NiO-YSZ anode support without any interlayers, and the SOFC produces power output over 200 mW cm-2 at 600 °C, with an open circuit voltage close to 1 V. Electrochemical impedance spectra analysis is conducted to evaluate the performance of the fuel cell components in relation with the microstructure of the spin-coated layers.

  18. Pyrolysis result of polyethylene waste as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

    NASA Astrophysics Data System (ADS)

    Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

    2017-02-01

    In this research, the result of pyrolysis on polyethylene was used as fuel for a solid oxide fuel cell (SOFC). The pyrolysis result is a liquid which consists of hydrocarbon chains. According to GC-MS analysis, the hydrocarbons mainly consist of C7 to C20 hydrocarbon chain. Then, the liquid was applied to a single cell of NSDC-L | NSDC | NSDC-L. NSDC is a composite SDC (samarium doped-ceria) with sodium carbonate. Meanwhile, NSDC-L is a composite of NSDC with LiNiCuO (LNC). NSDC and LNC were analyzed by X-ray diffraction to understand their crystal structure. The result shows that presence of carbonate did not change the crystal structure of SDC. SEM EDX analysis for fuel cell before and after being loaded with polyethylene oil to get information of element diffusion to the electrolyte. Meanwhile, the conductivity properties were investigated through impedance measurement. The presence of carbonate even increases the electrical conductivity. The single cell test with the pyrolysis result of polyethylene at 300 – 600 °C, found that the highest power density is at 600 °C with the maximum power density of 0.14 mW/cm2 and open circuit voltage of 0.4 Volt. Elemental analysis at three point spots of single cell NDSC-L |NSDC|NSDC-L found that a migration of ions was occurred during fuel operation at 300 – 600 °C.

  19. Synthesis and characterization of scandia ceria stabilized zirconia powders prepared by polymeric precursor method for integration into anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Tu, Hengyong; Liu, Xin; Yu, Qingchun

    2011-03-01

    Scandia ceria stabilized zirconia (10Sc1CeSZ) powders are synthesized by polymeric precursor method for use as the electrolyte of anode-supported solid oxide fuel cell (SOFC). The synthesized powders are characterized in terms of crystalline structure, particle shape and size distribution by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). 10Sc1CeSZ electrolyte films are deposited on green anode substrate by screen-printing method. Effects of 10Sc1CeSZ powder characteristics on sintered films are investigated regarding the integration process for application as the electrolytes in anode-supported SOFCs. It is found that the 10Sc1CeSZ films made from nano-sized powders with average size of 655 nm are very porous with many open pores. In comparison, the 10Sc1CeSZ films made from micron-sized powders with average size of 2.5 μm, which are obtained by calcination of nano-sized powders at higher temperatures, are much denser with a few closed pinholes. The cell performances are 911 mW cm-2 at the current density of 1.25 A cm-2 and 800 °C by application of Ce0.8Gd0.2O2 (CGO) barrier layer and La0.6Sr0.4CoO3 (LSC) cathode.

  20. Evaluation of the Effect of Sulfur on the Performance of Nickel/Gadolinium‐Doped Ceria Based Solid Oxide Fuel Cell Anodes

    PubMed Central

    Yurkiv, Vitaliy; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

    2016-01-01

    Abstract The focus of this study is the measurement and understanding of the sulfur poisoning phenomena of Ni/gadolinium‐doped ceria (CGO) based solid oxide fuel cells (SOFC). Cells with Ni/CGO10 and NiCu5/CGO40 anodes were characterized by using impedance spectroscopy at different temperatures and H2/H2O fuel ratios. The short‐term sulfur poisoning behavior was investigated systematically at temperatures of 800–950 °C, current densities of 0–0.75 A cm−2, and H2S concentrations of 1–20 ppm. A sulfur poisoning mitigation effect was observed at high current loads and temperatures. The poisoning behavior was reversible for short exposure times. It was observed that the sulfur‐affected processes exhibited significantly different relaxation times that depend on the Gd content in the CGO phase. Moreover, it was demonstrated that the capacitance of Ni/CGO10 anodes is strongly dependent on the temperature and gas‐phase composition, which reflects a changing Ce3+/Ce4+ ratio. PMID:27863123

  1. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

    NASA Astrophysics Data System (ADS)

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-02-01

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode.

  2. High-Solids Polyimide Precursor Solutions

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2004-01-01

    The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

  3. Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Varga, Tamas; Thevuthasan, Suntharampillai

    2014-01-21

    The mixed oxidation state (3+/4+) of ceria nanoparticles of smaller sizes make them attractive materials for their catalytic antioxidant biological properties. However the unmodified smaller ceria nanoparticles are limited in their use due to particles agglomeration and reduced surface chemical reactivity in the solutions used to disperse the nanoparticles. This work describes an effort to stabilize small ceria nanoparticles, retaining their desired activity, on a larger stable silica support. The ceria nanoparticles attached to silica was synthesized by a solution synthesis technique in which the surface functional groups of silica nanoparticles were found to be essential for the formation of smaller ceria nanoparticles. The surface chemical and vibrational spectroscopy analysis revealed cerium–silicate (Ce-O-Si) covalent bond linkage between silica and cerium oxide nanoparticles. The colloidal properties (agglomerate particle size and suspension stability) of ceria attached to silica was significantly improved due to inherent physico-chemical characteristics of silica against random collision and gravitation settling as opposed to unmodified ceria nanoparticles in solution. The bio-catalytic activity of ceria nanoparticles in the 3+ oxidation state was not found to be limited by attachment to the silica support as measured by free radical scavenging activity in different biological media conditions.

  4. Effects of some rare earth and carbonate-based co-dopants on structural and electrical properties of samarium doped ceria (SDC) electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Anwar, Mustafa; Khan, Zuhair S.; Mustafa, Kamal; Rana, Akmal

    2015-09-01

    In the present study, samarium doped ceria (SDC) and SDC-based composite with the addition of K2CO3 were prepared by co-precipitation route and effects of pH of the solution and calcination temperature on microstructure of SDC and SDC-K2CO3, respectively, were investigated. Furthermore, experimentation was performed to investigate into the ionic conductivity of pure SDC by co-doping with yttrium i.e., YSDC, XRD and SEM studies show that the crystallite size and particle size of SDC increases with the increase in pH. The SEM images of all the samples of SDC synthesized at different pH values showed the irregular shaped and dispersed particles. SDC-K2CO3 was calcined at 600∘C, 700∘C and 800∘C for 4 h and XRD results showed that crystallite size increases while lattice strain, decreases with the increase in calcination temperature and no peaks were detected for K2CO3 as it is present in an amorphous form. The ionic conductivity of the electrolytes increases with the increase in temperature and SDC-K2CO3 shows the highest value of ionic conductivity as compared to SDC and YSDC. Chemical compatibility tests were performed between the co-doped electrolyte and lithiated NiO cathode at high temperature. It revealed that the couple could be used up to the temperature of 700∘C.

  5. Gadolinium doped Ceria nanocrystals synthesized from mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rossinyol, Emma; Pellicer, Eva; Prim, Anna; Estradé, Sònia; Arbiol, Jordi; Peiró, Francesca; Cornet, Albert; Morante, Joan Ramon

    2008-02-01

    Highly crystalline and thermally stable gadolinium doped ceria (GDC) particles have been synthesized by hard template route for the first time. This oxide is being recognized as an intermediate temperature (500-700 °C) electrolyte material for applications in solid-oxide fuel cells. The GDC particles show high crystallinity and nanometric size (2.83 ± 0.05 nm in diameter) and Raman analyses confirm the formation of the solid solution instead of a CeO2 and Gd2O3 mixture. EDX and EELS studies indicate a stoichiometry coherent with the Gd0.2Ce0.8O1.9 phase. The synthesized nanometric powder is expected to be used in solid oxide fuel cells as well as in the catalytic treatment of automobile exhaust fumes.

  6. Extremely thin bilayer electrolyte for solid oxide fuel cells (SOFCs) fabricated by chemical solution deposition (CSD).

    PubMed

    Oh, Eun-Ok; Whang, Chin-Myung; Lee, Yu-Ri; Park, Sun-Young; Prasad, Dasari Hari; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Lee, Hae-Weon

    2012-07-03

    An extremely thin bilayer electrolyte consisting of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is successfully fabricated on a sintered NiO-YSZ substrate. Major processing flaws are effectively eliminated by applying local constraints to YSZ nanoparticles, and excellent open circuit voltage and cell performance are demonstrated in a solid oxide fuel cell (SOFC) at intermediate operating temperatures.

  7. Growth of Solid Solution Single Crystals

    NASA Technical Reports Server (NTRS)

    Lehoczky, Sandor L.; Szofran, Frank R.; Gillies, Donald C.; Watring, Dale A.

    1999-01-01

    The objective of the study is to establish the effects of processing semiconducting, solid solution, single crystals in a microgravity environment on the metallurgical, compositional, electrical, and optical characteristics of the crystals. The alloy system being investigated is the solid solution semiconductor Hg(1-x)Cd(x)Te, with x-values appropriate for infrared detector applications in the 8 to 14 mm wavelength region. Both melt and Te-solvent growth are being performed. The study consists of an extensive ground-based experimental and theoretical research effort followed by flight experimentation where appropriate. The ground-based portion of the investigation also includes the evaluation of the relative effectiveness of stabilizing techniques, such as applied magnetic fields, for suppressing convective flow during the melt growth of the crystals.

  8. Defect equilibria and chemical expansion in undoped and doped ceria and strontium doped lanthanum cobalt iron oxide oxygen conducting materials and their applications in solid-state electrochemical cells

    NASA Astrophysics Data System (ADS)

    Bishop, Sean R.

    Ceramic oxygen conducting materials are used in many energy-related applications from fuel reforming to electricity generation. In a typical ceramic oxygen conductor, oxygen ions are transmitted through a dense membrane via defects in the material. Hence, defects control the performance of these materials. In low oxygen partial pressure, ceria based materials become non-stoichiometric and can form defect complexes that hinder ionic conductivity. In addition, oxygen non-stoichiometry induces strain (chemical expansion) that can result in stresses for composite or constrained applications. In this dissertation the non-stoichiometry and chemical expansion behavior is reported as a function of PO2 for undoped ceria, gadolinium doped ceria (GDC) and strontium doped lanthanum cobalt iron oxide (LSCF). Undoped ceria was measured at 800°C and GDC and LSCF at 600--900°C in a wide PO2 range. It was found that defect interactions could effectively be modeled in ceria based materials using defect complex formation in a mass action formalism and the results were used to model nonlinear chemical expansion behavior. In LSCF, non-stoichiometry and chemical expansion were modeled using using metallic and semi-conductor models. A semi-conductor model with B-site small polarons best represented the measured behavior. The resulting models and parameters can be used to predict mechanical and electrical behavior of SOFC components. Surface oxygen non-stoichiometry has also been measured by comparing low surface area to high surface area samples. It was found that surface defect concentration previously ignored in the literature can result in erroneous non-stoichiometry measurements. In the latter half of this dissertation these materials are applied in SOFC and ceramic oxygen generator (COG) technology. A strategy is presented here for advanced life support systems employs a catalytic layer combined with a COG cell so that CO2 is reduced all the way to solid carbon and oxygen without

  9. Magnetic Damping of Solid Solution Semiconductor Alloys

    NASA Technical Reports Server (NTRS)

    Szofran, Frank R.; Benz, K. W.; Croell, Arne; Dold, Peter; Cobb, Sharon D.; Volz, Martin P.; Motakef, Shariar

    1999-01-01

    The objective of this study is to: (1) experimentally test the validity of the modeling predictions applicable to the magnetic damping of convective flows in electrically conductive melts as this applies to the bulk growth of solid solution semiconducting materials; and (2) assess the effectiveness of steady magnetic fields in reducing the fluid flows occurring in these materials during processing. To achieve the objectives of this investigation, we are carrying out a comprehensive program in the Bridgman and floating-zone configurations using the solid solution alloy system Ge-Si. This alloy system has been studied extensively in environments that have not simultaneously included both low gravity and an applied magnetic field. Also, all compositions have a high electrical conductivity, and the materials parameters permit reasonable growth rates. An important supporting investigation is determining the role, if any, that thermoelectromagnetic convection (TEMC) plays during growth of these materials in a magnetic field. TEMC has significant implications for the deployment of a Magnetic Damping Furnace in space. This effect will be especially important in solid solutions where the growth interface is, in general, neither isothermal nor isoconcentrational. It could be important in single melting point materials, also, if faceting takes place producing a non-isothermal interface. In conclusion, magnetic fields up to 5 Tesla are sufficient to eliminate time-dependent convection in silicon floating zones and possibly Bridgman growth of Ge-Si alloys. In both cases, steady convection appears to be more significant for mass transport than diffusion, even at 5 Tesla in the geometries used here. These results are corroborated in both growth configurations by calculations.

  10. Magnetic Damping of Solid Solution Semiconductor Alloys

    NASA Technical Reports Server (NTRS)

    Szofran, Frank R.; Benz, K. W.; Corell, Arne; Dold, Peter; Cobb, Sharon D.; Volz, Martin P.; Motakef, Shariar

    1998-01-01

    The objective of this study is to conduct the Earth-based research sufficient to successfully propose a flight experiment (1) to experimentally test the validity of the modeling predictions applicable to the magnetic damping of convective flows in conductive melts as this applies to the bulk growth of solid solution semiconducting materials in the reduced gravitational levels available in low Earth orbit and (2) to assess the effectiveness of steady magnetic fields in reducing the fluid flows occurring in these materials during space processing. To achieve the objectives of this investigation, we are carrying out a comprehensive program in the Bridgman and floating-zone configurations using the solid solution alloy system Ge-Si. This alloy system was chosen because it has been studied extensively in environments that have not simultaneously included both low gravity and an applied magnetic field. Also, all compositions have a high electrical conductivity, and the materials parameters permit high growth rates compared to many other commonly studied alloy semiconductors. An important supporting investigation is determining the role, if any, that thermoelectromagnetic convection (TEMC) plays during growth of these materials in a magnetic field. Some compositional anomalies observed by us in magnetic grown crystals can only be explained by TEMC; this has significant implications for the deployment of a Magnetic Damping Furnace in space. This effect will be especially important in solid solutions where the growth interface is, in general, neither isothermal nor isoconcentrational. It could be important in single melting point materials, also, if faceting takes place producing a non-isothermal interface.

  11. Vaporization of thoria-urania solid solution

    NASA Astrophysics Data System (ADS)

    Yamawaki, Michio; Nagasaki, Takanori; Kanno, Masayoshi

    1985-02-01

    In order to elucidate the vaporization behavior of thoria-urania solid solution, its vapor species identification and partial vapor pressure measurement have been made in a high temperature mass spectrometer. Partial vapor pressure of UO 3(g) over Th 1- yU y0 2 was observed to remarkably change with time and this behavior can be explained from the extended Blackburn's thermochemical model. Activities of U0 2(s) and Th0 2(s) in Th0 2-U0 2 show positive deviation from Raoult's law. Absolute vapor pressures of U0 2(g) and UO 3(g) over Th 1- yU y0 2 are evaluated.

  12. Lattice thermal expansion and solubility limits of neodymium-doped ceria

    NASA Astrophysics Data System (ADS)

    Zhang, Jinhua; Ke, Changming; Wu, Hongdan; Yu, Jishun; Wang, Jingran

    2016-11-01

    NdxCe1-xO2-0.5x (x=0-1.0) powders were prepared by reverse coprecipitation-calcination method and characterized by XRD. The crystal structure of product powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value. An empirical equation simulating the lattice parameter of neodymium doped ceria was established based on the experimental data. The lattice parameters of the fluorite structure solid solutions increased with extensive adoption of Nd3+, and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are higher than 13.5×10-6 °C-1 from room temperature to 1200 °C.

  13. Polypropylene oil as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

    NASA Astrophysics Data System (ADS)

    Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

    2017-03-01

    The research focusses on converting polypropylene oil as pyrolysis product of polypropylene plastic into an electricity. The converter was a direct liquid fuel-solid oxide fuel cell (SOFC) with cerium oxide based material as electrolyte. The polypropylene vapor flowed into fuel cell, in the anode side and undergo oxidation reaction, meanwhile, the Oxygen in atmosphere reduced into oxygen ion at cathode. The fuel cell test was conducted at 400 - 600 °C. According to GC-MS analysis, the polypropylene oil consist of C8 to C27 hydrocarbon chain. The XRD analysis result shows that Na2CO3 did not change the crystal structure of SDC even increases the electrical conductivity. The maximum power density is 0.079 mW.cm-2 at 773 K. The open circuite voltage is 0.77 volt. Chemical stability test by analysing the single cell at before and after fuel cell test found that ionic migration occured during fuel cell operation. It is supported by the change of elemental composition in the point position of electrolyte and at the electrolyte-electrode interface

  14. Carbon deposition behaviour in metal-infiltrated gadolinia doped ceria electrodes for simulated biogas upgrading in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Duboviks, V.; Lomberg, M.; Maher, R. C.; Cohen, L. F.; Brandon, N. P.; Offer, G. J.

    2015-10-01

    One of the attractive applications for reversible Solid Oxide Cells (SOCs) is to convert CO2 into CO via high temperature electrolysis, which is particularly important for biogas upgrading. To improve biogas utility, the CO2 component can be converted into fuel via electrolysis. A significant issue for SOC operation on biogas is carbon-induced catalyst deactivation. Nickel is widely used in SOC electrodes for reasons of cost and performance, but it has a low tolerance to carbon deposition. Two different modes of carbon formation on Ni-based electrodes are proposed in the present work based on ex-situ Raman measurements which are in agreement with previous studies. While copper is known to be resistant towards carbon formation, two significant issues have prevented its application in SOC electrodes - namely its relatively low melting temperature, inhibiting high temperature sintering, and low catalytic activity for hydrogen oxidation. In this study, the electrodes were prepared through a low temperature metal infiltration technique. Since the metal infiltration technique avoids high sintering temperatures, Cu-Ce0.9Gd0.1O2-δ (Cu-CGO) electrodes were fabricated and tested as an alternative to Ni-CGO electrodes. We demonstrate that the performance of Cu-CGO electrodes is equivalent to Ni-CGO electrodes, whilst carbon formation is fully suppressed when operated on biogas mixture.

  15. Electrical, Electrochemical, and Optical Characterization of Ceria Films

    NASA Astrophysics Data System (ADS)

    Oh, Tae-Sik

    Acceptor-doped ceria has been recognized as a promising intermediate temperature solid oxide fuel cell electrode/electrolyte material. For practical implementation of ceria as a fuel cell electrolyte and for designing model experiments for electrochemical activity, it is necessary to fabricate thin films of ceria. Here, metal-organic chemical vapor deposition was carried out in a homemade reactor to grow ceria films for further electrical, electrochemical, and optical characterization. Doped/undoped ceria films are grown on single crystalline oxide wafers with/without Pt line pattern or Pt solid layer. Deposition conditions were varied to see the effect on the resultant film property. Recently, proton conduction in nanograined polycrystalline pellets of ceria drew much interest. Thickness-mode (through-plane, z-direction) electrical measurements were made to confirm the existence of proton conductivity and investigate the nature of the conduction pathway: exposed grain surfaces and parallel grain boundaries. Columnar structure presumably favors proton conduction, and we have found measurable proton conductivity enhancement. Electrochemical property of gas-columnar ceria interface on the hydrogen electrooxidation is studied by AC impedance spectroscopy. Isothermal gas composition dependence of the electrode resistance was studied to elucidate Sm doping level effect and microstructure effect. Significantly, preferred orientation is shown to affect the gas dependence and performance of the fuel cell anode. A hypothesis is proposed to explain the origin of this behavior. Lastly, an optical transmittance based methodology was developed to obtain reference refractive index and microstructural parameters (thickness, roughness, porosity) of ceria films via subsequent fitting procedure.

  16. Plasma sprayed ceria-containing interlayer

    DOEpatents

    Schmidt, Douglas S.; Folser, George R.

    2006-01-10

    A plasma sprayed ceria-containing interlayer is provided. The interlayer has particular application in connection with a solid oxide fuel cell used within a power generation system. The fuel cell advantageously comprises an air electrode, a plasma sprayed interlayer disposed on at least a portion of the air electrode, a plasma sprayed electrolyte disposed on at least a portion of the interlayer, and a fuel electrode applied on at least a portion of the electrolyte.

  17. A correlation between the ionic conductivities and the formation enthalpies of trivalent-doped ceria at relatively low temperatures.

    PubMed

    Avila-Paredes, Hugo J; Shvareva, Tatiana; Chen, Weiqun; Navrotsky, Alexandra; Kim, Sangtae

    2009-10-14

    We report a correlation between oxygen ionic conductivity and the enthalpy of formation of trivalent-doped ceria from the component binary oxides observed at relatively low temperatures (150-275 degrees C). The bulk conductivities of La-doped ceria samples identical to those previously examined by thermochemical studies were measured as a function of La content for a direct comparison. The conductivity showed a maximum at a La concentration of 5 mol%, implying that the number of freely mobile oxygen vacancies reaches a maximum near that doping level in the temperature range of interest. The formation enthalpies previously reported by Chen and Navrotsky also show a maximum, indicating destabilization near that composition. Additional measurements show that this maximum is very pronounced and sharply peaked near that composition. These enthalpies suggest that the energetically favorable long-range interactions between the charged defects that trap the oxygen vacancies become dominant above 5 mol% doping in the CeO2-LaO1.5 solid solution. In addition, the conductivities measured from independently prepared Gd-doped ceria samples show a maximum at around 10 mol% doping below 450 degrees C as anticipated from a pronounced maximum in the formation enthalpies of the CeO2-GdO1.5 solid solution. These empirical findings confirm that the ionic conductivity of trivalent-doped ceria is strongly enough correlated with its formation enthalpy at relatively low temperatures so that information about the critical dopant concentration associated with the conductivity maximum may be gained from the formation enthalpies of the solid solutions, and vice versa. We have no direct information about this correlation at higher temperatures; both thermodynamics and conductivity maximum might change if the defect clusters dissociate to any significant extent.

  18. Interaction of Keggin anions of 12-tungstophosphoric acid with Ce(x)Zr(1-x)O2 solid solutions.

    PubMed

    Rao, G Ranga; Rajkumar, T

    2008-08-01

    The interaction of 20 wt% 12-tungstophosphoric acid with Ce(x)Zr(1-x)O(2) solid solutions has been studied by PXRD, FTIR, FT-Raman, H(2)-TPR, NH(3)-TPD, diffuse reflectance UV-vis-NIR, and (31)P MAS NMR techniques. The study indicates that the Keggin anions are attached to Lewis metal ion centres and anion vacancies on Ce(x)Zr(1-x)O(2) supports through WO terminal bonds. The Keggin units at the interface are chemically perturbed as indicated by non-intrinsic IR bands observed at 958 cm(-1) (WO(ter) bond), and 1052, 1102 cm(-1) (PO bond). NH(3)-TPD shows that the Keggin anions fixed to Lewis sites and/or oxygen ion vacancies decrease the ammonia uptake on Ce(x)Zr(1-x)O(2) solid solutions. H(2)-TPR shows modified redox behaviour of Ce(x)Zr(1-x)O(2) solid solutions due to the simultaneous reduction of ceria, decomposition of Keggin anions and the reduction of WO(3). The broadening of (31)P MAS NMR and DR-UV-vis-NIR spectra demonstrate the existence of chemical interactions between the Keggin anions and Ce(x)Zr(1-x)O(2) supports.

  19. End-Member Formulation of Solid Solutions and Reactive Transport

    SciTech Connect

    Lichtner, Peter C.

    2015-09-01

    A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed to correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.

  20. Special quasirandom structure modeling of fluorite-structured oxide solid solutions with aliovalent cation substitutions

    NASA Astrophysics Data System (ADS)

    Wolff-Goodrich, Silas; Hanken, Benjamin E.; Solomon, Jonathan M.; Asta, Mark

    2015-07-01

    The accuracy of the special quasirandom structure (SQS) approach for modeling the structure and energetics of fluorite-structured oxide solid solutions with aliovalent cation substitutions is assessed in an ionic-pair potential study of urania and ceria based systems mixed with trivalent rare-earth ions. Mixing enthalpies for SQS supercells containing 96 and 324 lattice sites were calculated using ionic pair potentials for U0.5La0.5O1.75, U0.5Y0.5O1.75, Ce0.5La0.5O1.75, Ce0.5Y0.5O1.75, and Ce0.5Gd0.5O1.75, which all have stoichiometries of pyrochlores. The SQS results were compared to benchmark values for random substitutional disorder obtained using large supercell models. The calculations show significant improvement of the mixing enthalpy for the larger 324 site SQS, which is attributed to a better description of the structural distortions, as characterized by the radial distribution functions in relaxed systems.

  1. Growth of Solid Solution Single Crystals

    NASA Technical Reports Server (NTRS)

    Lehoczky, Sandor L.; Szofran, F. R.; Gillies, Donald C.

    2001-01-01

    The solidification of a solid solution semiconductor, having a wide separation between liquidus and solidus has been extensively studied in ground based, high magnetic field and Spacelab experiments. Two alloys of mercury cadmium telluride have been studied; with 80.0 mole percent of HgTe and 84.8 mole percent of HgTe respectively, the remainder being cadmium telluride. Such alloys are extremely difficult to grow by directional solidification on earth due to high solutal and thermal density differences that give rise to fluid flow and consequent loss of interface shape and composition. Diffusion controlled growth is therefore impossible to achieve in conventional directional solidification. The ground based experiments consisted of growing crystals in several different configurations of heat pipe furnaces, NASA's Advanced Automated Directional Solidification Furnace (AADSF), and a similar furnace incorporated in a superconducting magnet capable of operating at up to 5T. The first microgravity experiment took place during the flight of STS-62 in March 1994, with the AADSF installed on the second United States Microgravity Payload (USMP-2). The alloy was solidified at 3/4 inch per day over a 9 day period, and for the first time a detailed evaluation was performed correlating composition variations to measured residual acceleration. The second flight experiment took place in the fourth United States Microgravity Payload Mission (USMP-4) in November 1997. Due to contamination of the furnace system, analysis shows that the conditions prevailing during the experiment were quite different from the requirements requested prior to the mission. The results indicate that the sample did accomplish the desired objectives.

  2. Highly CO2-Tolerant Cathode for Intermediate-Temperature Solid Oxide Fuel Cells: Samarium-Doped Ceria-Protected SrCo0.85Ta0.15O3-δ Hybrid.

    PubMed

    Li, Mengran; Zhou, Wei; Zhu, Zhonghua

    2017-01-25

    Susceptibility to CO2 is one of the major challenges for the long-term stability of the alkaline-earth-containing cathodes for intermediate-temperature solid oxide fuel cells. To alleviate the adverse effects from CO2, we incorporated samarium-stabilized ceria (SDC) into a SrCo0.85Ta0.15O3-δ (SCT15) cathode by either mechanical mixing or a wet impregnation method and evaluated their cathode performance stability in the presence of a gas mixture of 10% CO2, 21% O2, and 69% N2. We observed that the CO2 tolerance of the hybrid cathode outperforms the pure SCT15 cathode by over 5 times at 550 °C. This significant enhancement is likely attributable to the low CO2 adsorption and reactivity of the SDC protective layer, which are demonstrated through thermogravimetric analysis, energy-dispersive spectroscopy, and electrical conductivity study.

  3. Compositional Segregation in Unidirectionally Solidified Solid Solution Crystals

    NASA Technical Reports Server (NTRS)

    Wang, J. C.

    1983-01-01

    A computer program was developed to model compositional segregation in unidrectionally solidified solid-solution-semiconducting crystals. The program takes into account the variations of the interface segregation constant and solidification rate with composition. Calculations are performed for the HgCdTe solid solution system that is compared with experimental data.

  4. Combining two redox active rare earth elements for oxygen storage - electrical properties and defect chemistry of ceria-praseodymia single crystals.

    PubMed

    Michel, Kathrin; Eufinger, Jens-Peter; Ulbrich, Gregor; Lerch, Martin; Janek, Juergen; Elm, Matthias T

    2017-07-21

    Solid solutions of ceria and praseodymia are highly relevant for electrochemical applications as the incorporation of praseodymium into the ceria lattice shifts the range of mixed ionic electronic conductivity to higher oxygen partial pressures. To better understand the influence of praseodymium substitution on the transport processes and oxygen storage capacity in ceria, single crystals of ceria substituted with 14 mol% praseodymium have been investigated, obtaining the bulk properties without the influence of grain boundaries. Beside the characterization of structural changes caused by the substitution using XRD and Raman spectroscopy, the electrochemical transport properties of ceria-praseodymia single crystals are reported. Measurements of the total electrical conductivity, the ionic transference number and the non-stoichiometry of Ce0.85Pr0.14Zr0.01O2-δ were performed in an oxygen partial pressure range of -25 < lg[p(O2)/bar] < 0 at 700 °C. With praseodymium being redox active itself, higher values of oxygen deficiency and electrical conductivity than in pure ceria have been observed in the high oxygen partial pressure region, while no significant structural changes occur due to the similar ionic radii of both cations. From measurements of the impedance at different temperatures, the migration enthalpy for the electronic charge carriers has been determined. By analysing the non-stoichiometry at 700 °C using a defect chemical model it was also possible to determine the equilibrium constants of Pr and Ce reduction in Ce0.85Pr0.14Zr0.01O2-δ single crystals.

  5. Growth of Solid Solution Single Crystals

    NASA Technical Reports Server (NTRS)

    Lehoczky, Sandor L.; Szofran, F. R.; Gillies, Donald C.; Watring, D. A.

    1999-01-01

    The solidification of a solid solution semiconductor, having a wide separation between liquidus and serious has been extensively studied in ground based, high magnetic field and Spacelab experiments. Two alloys of mercury cadmium telluride have been studied; mercury cadmium telluride with 80.0 mole percent of HgTe and 84.8 mole percent respectively. These alloys are extremely difficult to grow by directional solidification on earth due to high solutal and thermal density differences that give rise to fluid flow and consequent loss of interface shape and composition. Diffusion controlled growth is therefore impossible to achieve in conventional directional solidification. The ground based experiments consisted of growing crystals in several different configurations of heat pipe furnaces, NASA's Advanced Automated Directional Solidification Furnace (AADSF), and a similar furnace incorporated in a superconducting magnet capable of operating at up to 5T. The first microgravity experiment took place during the flight of STS-62 in March 1994, with the AADSF installed on the second United States Microgravity Payload (USMP-2). The alloy was solidified at 3/4 inch per day over a 9 day period, and for the first time a detailed evaluation was performed of residual acceleration effects. The second flight experiment took place in the fourth United States Microgravity Payload Mission (USMP-4) in November 1997. Due to contamination of the furnace system by a previously processed sample, the sample was not received until May 1998, and the preliminary analysis shows that the conditions prevailing during the experiment were quite different from the requirements requested prior to the mission. Early results are indicating that the sample may not accomplish the desired objectives. As with the USMP-2 mission, the results of the ground based experiments were compared with the crystal grown in orbit under microgravity conditions. On the earth, it has been demonstrated that the

  6. Growth of Solid Solution Single Crystals

    NASA Technical Reports Server (NTRS)

    Lehoczky, Sandor L.; Szofran, F. R.; Gillies, Donald C.; Watring, D. A.

    1999-01-01

    The solidification of a solid solution semiconductor, having a wide separation between liquidus and serious has been extensively studied in ground based, high magnetic field and Spacelab experiments. Two alloys of mercury cadmium telluride have been studied; mercury cadmium telluride with 80.0 mole percent of HgTe and 84.8 mole percent respectively. These alloys are extremely difficult to grow by directional solidification on earth due to high solutal and thermal density differences that give rise to fluid flow and consequent loss of interface shape and composition. Diffusion controlled growth is therefore impossible to achieve in conventional directional solidification. The ground based experiments consisted of growing crystals in several different configurations of heat pipe furnaces, NASA's Advanced Automated Directional Solidification Furnace (AADSF), and a similar furnace incorporated in a superconducting magnet capable of operating at up to 5T. The first microgravity experiment took place during the flight of STS-62 in March 1994, with the AADSF installed on the second United States Microgravity Payload (USMP-2). The alloy was solidified at 3/4 inch per day over a 9 day period, and for the first time a detailed evaluation was performed of residual acceleration effects. The second flight experiment took place in the fourth United States Microgravity Payload Mission (USMP-4) in November 1997. Due to contamination of the furnace system by a previously processed sample, the sample was not received until May 1998, and the preliminary analysis shows that the conditions prevailing during the experiment were quite different from the requirements requested prior to the mission. Early results are indicating that the sample may not accomplish the desired objectives. As with the USMP-2 mission, the results of the ground based experiments were compared with the crystal grown in orbit under microgravity conditions. On the earth, it has been demonstrated that the

  7. Special quasirandom structures for perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Jiang, Zhijun; Nahas, Yousra; Xu, Bin; Prosandeev, Sergey; Wang, Dawei; Bellaiche, Laurent

    2016-11-01

    Special quasirandom structures (SQS) are presently generated for disordered (A‧1-x {{\\text{A}}\\prime \\prime} x )BX3 and A(B‧1-x {{\\text{B}}\\prime \\prime} x )X3 perovskite solid solutions, with x  =  1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x  =  1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained.

  8. Optimization of ionic conductivity in doped ceria

    PubMed Central

    Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

    2006-01-01

    Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

  9. Structural analysis of 5-fluorouracil and thymine solid solutions

    NASA Astrophysics Data System (ADS)

    Vogt, Frederick G.; Vena, Joseph A.; Chavda, Manisha; Clawson, Jacalyn S.; Strohmeier, Mark; Barnett, Maria E.

    2009-08-01

    Solid-state analysis with powder X-ray diffraction (PXRD), solid-state NMR (SSNMR), and other spectroscopic and physical methods can provide detailed structural information about organic and pharmaceutical cocrystals. In this study, a range of solid-state analysis methods are used to characterize co-crystallized solid solutions of 5-fluorouracil and thymine. 1H, 13C and 19F SSNMR and PXRD methods are used to study the structure and disorder present in a solid solution previously prepared by solution evaporation methods; here the solid solution is prepared over a wider stoichiometric range by solvent-drop grinding techniques. Long-range perturbations of key chemical shifts are detectable by SSNMR, indicating that the solid solution is not random. Cross-polarization and heteronuclear correlation SSNMR experiments between 1H, 13C, and 19F nuclei offer insight into the structure of this solid solution, and density functional theory (DFT) methods are applied to calculate lattice energies and NMR properties in order to understand the population of the two primary disordered sites in the crystal structure. In addition, a second solid solution of 5-fluorouracil and thymine is reported and analyzed. This solid solution, which was produced by solvent-drop grinding experiments and characterized by SSNMR and powder X-ray diffraction methods, is determined to be an isostructural phase to that of anhydrous thymine with the inclusion of 5-fluorouracil defects. A similar effect does not occur under excess 5-fluorouracil conditions; instead, phase-separated Form 1 of 5-fluorouracil and anhydrous thymine are obtained. DFT calculations are applied to offer a possible explanation for this disparity.

  10. Theoretical Study of Sulphur Interaction with Ceria

    SciTech Connect

    Baranek, Ph.; Gauthier, L.; Marrony, M.

    2007-12-26

    Sulphur-containing molecules are responsible for the poisoning of catalysts used in many chemical processes such as fuel processing for hydrogen production and for fuel cells. An option which would constitute a breakthrough in this field would be to develop sulphur tolerant catalysts. Ceria (CeO{sub 2}) is an important ceramic material exploited in a wide range of applications such as solid oxide fuel cells. Then it is important to understand its surface catalytic properties. The adsorption of S, H{sub 2}S and other S-containing compounds on different surfaces of ceria are investigated at the ab initio quantum mechanical level, by using the periodic CRYSTAL06 code. In this extended abstract, we focus on the S adsorption on the stoichiometric (111), (110) and (100) surfaces of ceria. The equilibrium lattice parameters of CeO{sub 2}, surface stabilities, and S adsorption energies have been evaluated. The calculations have been performed at the Hartree-Fock (HF), density functional theory (DFT) and hybrid levels. A good agreement between calculated, and, other theoretical and experimental various properties has been found with hybrid approximations. The role of f orbitals of Ce is commented.

  11. Solar hydrogen production using Ce1-xLixO2-δ solid solutions via a thermochemical, two-step water-splitting cycle

    NASA Astrophysics Data System (ADS)

    Meng, Qing-Long; Lee, Chong-il; Shigeta, Satoshi; Kaneko, Hiroshi; Tamaura, Yutaka

    2012-10-01

    The reactivity of Ce1-xLixO2-δ (x=0.025, 0.05, 0.075 and 0.1) solid solutions during the redox and two-step water-splitting cycles has been investigated in this work. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) patterns and field-emission scanning electron microscopy (FE-SEM) indicate that there are two reaction mechanisms in the O2-releasing step and the shift in the reaction mechanisms occurs in the O2-releasing step because of sintering at high temperatures, and a decrease in the concentration of lattice oxygen occurs as the O2-releasing step proceeds. The reaction in the O2-releasing step follows a second-order mechanism over a temperature range of 1000-1170 °C and a contracting-area model over a temperature range of 1170-1500 °C. According to direct gas mass spectroscopy (DGMS), ceria doped at 5 mol% Li exhibits the highest reactivity in the O2-releasing step during both redox cycles in air and two-step water-splitting cycles, whereas ceria doped at 2.5 mol% Li yields the highest amount of hydrogen (4.79 ml/g) in the H2-generation step during the two-step water-splitting cycles, which is higher than ceria doped with other metals. DGMS and electrochemical impedance spectroscopy (EIS) suggest that the average reaction rate in the H2-generation step is influenced by the concentration of extrinsic oxygen vacancies, and thus, the reactivity in the H2-generation step, to some degree, could be tuned by varying the concentration of extrinsic oxygen vacancies (Li content).

  12. Enhanced superhydrophilicity and thermal stability of ITO surface with patterned ceria coatings

    NASA Astrophysics Data System (ADS)

    Xue, Mingshan; Peng, Na; Li, Changquan; Ou, Junfei; Wang, Fajun; Li, Wen

    2015-02-01

    Surface wettability of solid materials is significant for both fundamental research and engineering applications. Compared with most existing fabrication methods of superhydrophilic surfaces by UV exposure or chemical modification, in this work, a superhydrophilic ceria coating on ITO substrate is developed by a fast, simple one-step method. It is found that the superhydrophilicity of ceria coatings is strongly dependent on both the patterned microstructures benefiting the capillary effect and the peculiar chemical composition of ceria inducing numerous oxygen vacancies and large surface free energy. Owing to the inherent physical stability of ceria, such a superhydrophilic ceria coating exhibits an excellently thermal stability at both room temperature and higher temperature. These results open up new avenues for the underlying applications of superhydrophilic coatings, such as heat transfer/dissipation.

  13. Formation and characterization of different ceria/silica composite materials via dispersion of ceria gel or soluble ceria precursors in silica sols.

    PubMed

    Khalil, Kamal M S; Elkabee, Leena A; Murphy, Brian

    2005-07-15

    Composite ceria/silica materials of 10 and 20% (w/w) were prepared by calcination, at 650 degrees C for 3 h, of the xerogels obtained by mixing the corresponding amount of a ceria precursor with freshly prepared sols of spherical silica particles (Stober particles) in their mother liquors. Two different ceria precursors were examined in this investigation. The first was a gel produced by the prehydrolysis of cerium(IV) isopropoxide in isopropanol medium, and the second was an aqueous solution of cerium(IV) ammonium nitrate. Different textural and morphological characteristics that developed by calcination were investigated by TGA, FTIR, XRD, SEM, and analyses of N2 adsorption isotherms. The results indicated that ceria dispersion and formation of mesoporous textural composite materials produced by the second precursor, cerium(IV) ammonium nitrate, are better than those produced by the first precursor, prehydrolyzed cerium(IV) isopropoxide. The results are discussed in terms of the effect of precursors and mixing media on nucleation and growth of ceria particles and their protection from sintering on calcination at the test temperature.

  14. Solid solution hardening of molecular crystals: tautomeric polymorphs of omeprazole.

    PubMed

    Mishra, Manish Kumar; Ramamurty, Upadrasta; Desiraju, Gautam R

    2015-02-11

    In the context of processing of molecular solids, especially pharmaceuticals, hardness is an important property that often determines the manufacturing steps employed. Through nanoindentation studies on a series of omeprazole polymorphs, in which the proportions of the 5- and 6-methoxy tautomers vary systematically, we demonstrate that solid-solution strengthening can be effectively employed to engineer the hardness of organic solids. High hardness can be attained by increasing lattice resistance to shear sliding of molecular layers during plastic deformation.

  15. Plurality of inherent states in equiatomic solid solutions

    NASA Astrophysics Data System (ADS)

    Demkowicz, M. J.

    2017-03-01

    We show that single-crystal, equiatomic solid solutions of Lennard-Jones particles have a plurality of inherent states: mechanically stable configurations with identical lattice site occupancies, yet distinct potential-energy minima. External loading triggers transitions between inherent states via localized shear transformations. A plurality of inherent states and mechanically activated transitions between them make equiatomic solid solutions an unusual form of matter: one that is crystalline like single-component metals, yet exhibits localized shear transformations like metallic glasses.

  16. Surface structure of coherently strained ceria ultrathin films

    NASA Astrophysics Data System (ADS)

    Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan; Monti, Matteo; Cao, Chuntian; El Gabaly, Farid; Chueh, William C.; Toney, Michael F.

    2016-11-01

    Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained Ce O2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a "stacks and islands" model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different Ce O2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. The successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.

  17. Surface structure of coherently strained ceria ultrathin films

    SciTech Connect

    Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan; Monti, Matteo; Cao, Chuntian; El Gabaly, Farid; Chueh, William C.; Toney, Michael F.

    2016-11-14

    Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained CeO2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a “stacks and islands” model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different CeO2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. In conclusion, the successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.

  18. Surface structure of coherently strained ceria ultrathin films

    DOE PAGES

    Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan; ...

    2016-11-14

    Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained CeO2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a “stacks and islands”more » model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different CeO2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. In conclusion, the successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.« less

  19. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Baer, Donald R.; Thevuthasan, Suntharampillai

    2012-04-25

    A new hybrid material system that consists of ceria attached silica nanoparticles has been developed. Because of the versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and antioxidant properties of ceria nanoparticles, this material system is ideally suited for biomedical applications. The silica particles of size ~50nm were synthesized by the Stöber synthesis method and ceria nanoparticles of size ~2-3nm was attached to the silica surface using a hetrocoagulation method. The presence of silanol groups on the surface of silica particles mediated homogenous nucleation of ceria which were attached to silica surface by Si-O-Ce bonding. The formations of silica-ceria hybrid nanostructures were characterized by X-photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). The HRTEM image confirms the formation of individual crystallites of ceria nanoparticles attached to the silica surface. The XPS analysis indicates that ceria nanoparticles are chemically bonded to surface of silica and possess mixture of +3 and +4 chemical states.

  20. Characterization and performance of ceria based SOFCs

    SciTech Connect

    Milliken, C.; Elangovan, S.; Khandkar, A.C.

    1995-12-31

    Alkaline earth doped ceria based electrolytes have been used for solid oxide fuel cells operating at 700 C--800 C with power densities between 250--400 mW/cm{sup 2}. Cells with stable operating characteristics have been demonstrated on H{sub 2} + 3 % H{sub 2}O/air and agree well with the theoretical model by Riess for mixed conducting electrolytes. The characterization and performance of such cells have been evaluated using a mixed-conducting electrolyte model.

  1. Analytical Solution for Isentropic Flows in Solids

    NASA Astrophysics Data System (ADS)

    Heuzé, Olivier

    2009-12-01

    In the XIXth century, Riemann gave the equations system and the exact solution for the isentropic flows in the case of the ideal gas. But to our knowledge, nothing has been done to apply it to condensed media. Many materials of practical interest, for instance metals, obey to the linear law D = c+s u, where D is the shock velocity, u the particle velocity, and c and s properties of the material. We notice that s is strongly linked to the fundamental derivative. This means that the assumption of constant fundamental derivative is useful in this case, as it was with the isentropic gamma in the Riemann solution. Then we can apply the exact Riemann solution for these materials. Although the use of the hypergeometric function is complicated in this case, we obtain a very good approximation with the development in power series.

  2. Optical sensing of peroxide using ceria nanoparticles via fluorescence quenching technique

    NASA Astrophysics Data System (ADS)

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Salah, Mohammed

    2016-07-01

    This study introduces the application of ceria nanoparticles (NPs) as an optical sensor for peroxide using fluorescence quenching technique. Our synthesized ceria NPs have the ability to adsorb peroxides via its oxygen vacancies. Ceria NPs solution with added variable concentrations of hydrogen peroxides is exposed through near-UV excitation and the detected visible fluorescent emission is found to be at ˜520 nm. The fluorescent intensity peak is found to be reduced with increasing the peroxide concentrations due to static fluorescence quenching technique. The relative intensity change of the visible fluorescent emission has been reduced to more than 50% at added peroxide concentrations up to 10 wt. %. In order to increase ceria peroxides sensing sensitivity, lanthanide elements such as samarium (Sm) are used as ceria NPs dopant. This research work could be applied further in optical sensors of radicals in biomedical engineering and environmental monitoring.

  3. Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

    SciTech Connect

    Rai, R.N.; Kant, Shiva; Reddi, R.S.B.; Ganesamoorthy, S.; Gupta, P.K.

    2016-01-15

    Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB and UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solutionSolid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.

  4. Effect of tar fractions from coal gasification on nickel-yttria stabilized zirconia and nickel-gadolinium doped ceria solid oxide fuel cell anode materials

    NASA Astrophysics Data System (ADS)

    Lorente, E.; Berrueco, C.; Millan, M.; Brandon, N. P.

    2013-11-01

    The allowable tar content in gasification syngas is one of the key questions for the exploitation of the full potential of fuel cell concepts with integrated gasification systems. A better understanding of the interaction between tars and the SOFC anodes which leads to carbon formation and deposition is needed in order to design systems where the extent of gas cleaning operations is minimized. Model tar compounds (toluene, benzene, naphthalene) have been used in experimental studies to represent those arising from biomass/coal gasification. However, the use of toluene as a model tar overestimates the negative impact of a real gasification tar on SOFC anode degradation associated with carbon formation. In the present work, the effect of a gasification tar and its distillation fractions on two commercially available fuel cell anodes, Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium doped ceria), is reported. A higher impact of the lighter tar fractions was observed, in terms of more carbon formation on the anodes, in comparison with the whole tar sample. The characterization of the recovered tars after contact with the anode materials revealed a shift towards a heavier molecular weight distribution, reinforcing the view that these fractions have reacted on the anode.

  5. Samarium doped ceria-(Li/Na) 2CO 3 composite electrolyte and its electrochemical properties in low temperature solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Di, Jing; Chen, Mingming; Wang, Chengyang; Zheng, Jiaming; Fan, Liangdong; Zhu, Bin

    A composite of samarium doped ceria (SDC) and a binary carbonate eutectic (52 mol% Li 2CO 3/48 mol% Na 2CO 3) is investigated with respect to its morphology, conductivity and fuel cell performances. The morphology study shows the composition could prevent SDC particles from agglomeration. The conductivity is measured under air, argon and hydrogen, respectively. A sharp increase in conductivity occurs under all the atmospheres, which relates to the superionic phase transition in the interface phases between SDC and carbonates. Single cells with the composite electrolyte are fabricated by a uniaxial die-press method using NiO/electrolyte as anode and lithiated NiO/electrolyte as cathode. The cell shows a maximum power density of 590 mW cm -2 at 600 °C, using hydrogen as the fuel and air as the oxidant. Unlike that of cells based on pure oxygen ionic conductor or pure protonic conductor, the open circuit voltage of the SDC-carbonate based fuel cell decreases with an increase in water content of either anodic or cathodic inlet gas, indicating the electrolyte is a co-ionic (H +/O 2-) conductor. The results also exhibit that oxygen ionic conductivity contributes to the major part of the whole conductivity under fuel cell circumstances.

  6. High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Garcia-Garcia, F. J.; Beltrán, A. M.; Yubero, F.; González-Elipe, A. R.; Lambert, R. M.

    2017-09-01

    Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable Isbnd V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work.

  7. Ceria-based SOFC development

    SciTech Connect

    Doshi, R.; Krumpelt, M.

    1996-02-01

    The advantages of lowering the operating temperature of solid oxide fuel cells have led to efforts to develop fuel cells based on electrolytes like ceria which have a higher conductivity than zirconia. Lowering the operating temperature, however, causes increased electrode polarization. The currently used cathode material for higher temperature operation, lanthanum manganite, is inadequate for operation below 650--700{degrees}C. Therefore, to develop fuel cells for operation at 500{degrees}C, new electrode materials need to be. developed. It is recognized that the cathode performance requires the most improvement due to significantly slower oxygen reduction kinetics and/or oxygen diffusion kinetics through the electrode. In fact, for fuel cells made with thin electrolytes, the cathode accounts for up to 90% of the total voltage loss under load. Results on fuel cell tests in methanol and hydrogen and on new cathode materials are reported here. The results on new cathode materials are compared with known material properties, like nonstoichiometry and oxygen diffusion coefficients.

  8. Highly sensitive and robust peroxidase-like activity of porous nanorods of ceria and their application for breast cancer detection.

    PubMed

    Tian, Zhimin; Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhou, Xuemei; Qu, Yongquan

    2015-08-01

    Porous nanorods of ceria (PN-Ceria), a novel ceria nanostructure with a large surface area and a high surface Ce(3+) fraction, exhibited strong intrinsic peroxidase activity toward a classical peroxidase substrate in the presence of H2O2. Peroxidase-like activity of ceria originated from surface Ce(3+) species as the catalytic center, thereby explaining the high performance of PN-Ceria as an artificial enzyme mimicking peroxidase. Compared with the natural enzyme horseradish peroxidase (HRP), PN-Ceria showed several advantages such as low cost, easy storage, high sensitivity, and, prominently, chemical and catalytic stability under harsh conditions. Importantly, the enzymatic activity of PN-Ceria remained nearly constant and stable over a wide range of temperature and pH values, ensuring the accuracy and reliability of measurements of its peroxidase-like activity. A PN-Ceria based novel diagnostic system was developed for breast cancer detection with a higher sensitivity than the standard HRP detection system. Our work has laid a solid foundation for the development of PN-Ceria as a novel diagnostic tool for clinical use.

  9. Alloy softening in binary iron solid solutions

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.; Witzke, W. R.

    1976-01-01

    An investigation was conducted to determine softening and hardening behavior in 19 binary iron-alloy systems. Microhardness tests were conducted at four temperatures in the range 77 to 411 K. Alloy softening was exhibited by 17 of the 19 alloy systems. Alloy softening observed in 15 of the alloy systems was attributed to an intrinsic mechanism, believed to be lowering of the Peierls (lattice friction) stress. Softening and hardening rates could be correlated with the atomic radius ratio of solute to iron. Softening observed in two other systems was attributed to an extrinsic mechanism, believed to be associated with scavenging of interstitial impurities.

  10. Efficient and Color-Tunable Oxyfluoride Solid Solution Phosphors for Solid-State White Lighting

    SciTech Connect

    Im, Won Bin; George, Nathan; Kurzman, Joshua; Brinkley, Stuart; Mikhailovsky, Alexander; Hu, Jerry; Chmelka, Bradley F.; DenBaars, Steven P.; Seshadri, Ram

    2012-09-06

    A solid solution strategy helps increase the efficiency of Ce{sup 3+} oxyfluoride phosphors for solid-state white lighting. The use of a phosphor-capping architecture provides additional light extraction. The accompanying image displays electroluminescence spectra from a 434-nm InGaN LED phosphor that has been capped with the oxyfluoride phosphor.

  11. The interaction of biomass gasification syngas components with tar in a solid oxide fuel cell and operational conditions to mitigate carbon deposition on nickel-gadolinium doped ceria anodes

    NASA Astrophysics Data System (ADS)

    Mermelstein, J.; Millan, M.; Brandon, N. P.

    The combination of biomass gasification with solid oxide fuel cells (SOFCs) is gaining increasing interest as an efficient and environmentally benign method of producing electricity and heat. However, tars in the gas stream arising from the gasification of biomass material can deposit carbon on the SOFC anode, having detrimental effects to the life cycle and operational characteristics of the fuel cell. This work examines the impact of biomass gasification syngas components combined with benzene as a model tar, on carbon formation on Ni/CGO (gadolinium-doped ceria) SOFC anodes. Thermodynamic calculations suggest that SOFCs operating at temperatures > 750 °C are not susceptible to carbon deposition from a typical biomass gasification syngas containing 15 g m -3 benzene. However, intermediate temperature SOFCs operating at temperatures < 650 °C require threshold current densities well above what is technologically achievable to inhibit the effects of carbon deposition. SOFC anodes have been shown to withstand tar levels of 2-15 g m -3 benzene at 765 °C for 3 h at a current density of 300 mA cm -2, with negligible impact on the electrochemical performance of the anode. Furthermore, no carbon could be detected on the anode at this current density when benzene levels were <5 g m -3.

  12. Forces between hydrophobic solids in concentrated aqueous salt solution.

    PubMed

    Mastropietro, Dean J; Ducker, William A

    2012-03-09

    Much research has focused on the discovery and description of long-ranged forces between hydrophobic solids immersed in water. Here we show that the force between high contact-angle solids in concentrated salt solution (1 M KCl) agrees very well with van der Waals forces calculated from Lifshitz theory for separations greater than 5 nm. The hydrophobic solids are octadecyltrichlorosilane-coated glass, with an advancing contact angle of 108°. Thus, in 1 M salt solution, it is unnecessary to invoke the presence of a hydrophobic force at separations greater than 5 nm. Through measurement in salt solution, we avoid the necessity of accounting for large electrostatic forces that frequently occur in pure water and may obscure resolution of other forces.

  13. Alloy softening in binary iron solid solutions

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.; Witzke, W. R.

    1976-01-01

    An experimental study was conducted to determine whether alloy softening in Fe alloys is dependent on electron concentration and to provide a direct comparison of alloy softening and hardening in several binary Fe alloy systems having the same processing history. Alloy additions to Fe included the elements in the Periods 4-6 and the Groups IV-VIII with the exception of technetium. A total of 19 alloy systems was investigated, and hardness testing was the primary means of evaluation. Testing was carried out at four temperatures over a homologous temperature range of 0.043-0.227 times the absolute melting temperature of unalloyed Fe. Major conclusions are that the atomic radius ratio of solute-to-Fe is the key factor in controlling low-temperature hardness of the binary Fe alloys and that alloy softening rates at 77 K and alloy hardening rates at 411 K are correlated with this atomic radius ratio for 15 of the binary alloy systems. Mechanisms of alloy softening and hardening are proposed.

  14. Functionally graded doped lanthanum cobalt ferrite and ceria-based composite interlayers for advancing the performance stability in solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Ghosh, Koyel Banerjee; Mukhopadhyay, Jayanta; Basu, Rajendra N.

    2016-10-01

    Functionally graded composite interlayer based on 50% of La0.54Sr0.4Co0.2Fe0.8O3-δ and 50% of La0.54Sr0.4Fe0.2Co0.8O3-δ (CF-1) and cobalt and gadolinium doped ceria (CoCGO) is synthesized varying the mass ratio as CF-1:CoCGO = 80:20(L80-C20), 50:50(L50-C50) and 20:80(L20-C80). Detail study using impedance spectroscopy of symmetrical cell fabricated with CoCGO as electrolyte reveals the lowest electrode polarization 0.04 Ω cm2 at 800 °C for L80-C20 composite. Electrode and ohmic polarization is also evaluated configuring the symmetric cell as CF-1/L80-C20||CoCGO||L80-C20/CF-1. Symmetric cell with varying composition of the composite interlayer (L80-C20/L50-C50/L20-C80||CoCGO||L20-C80/L50-C50/L80-C20) shows considerably low electrode polarization of 0.067 Ω cm2 at 800 °C with activation energy 1.19 eV. Electrochemical performances evaluated using single cell configuration Ni-YSZ||YSZ||CoCGO/L20-C80/L50-C50/L80-C20/CF-1 shows power density as high as 2.03 W cm-2 at 800 °C at 0.7 V. Addition of composite interlayers increases the stability significantly and the voltage degradation is found negligible (0.9%) for first 300 h at a constant load of 0.5 A cm-2 which is further increased to 2.9% for next 300 h. The cell stability is clinically correlated with layer wise elemental 'Sr' mapping in the applied quad interlayers.

  15. Design principles for radiation-resistant solid solutions

    NASA Astrophysics Data System (ADS)

    Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

    2017-05-01

    We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

  16. Ozonation of bezafibrate over ceria and ceria supported on carbon materials.

    PubMed

    Gonçalves, Alexandra G; Órfão, José J M; Pereira, Manuel Fernando R

    2015-01-01

    Two catalysts containing ceria dispersed on the surface of multi-walled carbon nanotubes and activated carbon were investigated as ozonation catalysts for the mineralization of bezafibrate (BZF). The results were compared with those obtained in the absence of the catalyst and in the presence of the parent carbon materials, as well as in the presence of ceria (CeO2). Carbon materials containing ceria showed an interesting catalytic effect. Both materials enhanced the mineralization of BZF relatively to single ozonation and ozonation catalysed by the corresponding carbon materials. In the catalytic ozonation with these materials, both surface and bulk reactions are supposed to occur. The BZF ozonation catalysed by CeO2 leaded to the highest mineralization degrees, indicating that the reaction mechanism followed in the presence of CeO2 (free radical oxidation in solution) leads to the formation of intermediates more easily degradable, mainly after 120 min of reaction. Some primary products and refractory final oxidation compounds in single and catalytic ozonation of BZF were followed. The original chlorine present on the BZF molecule is completely converted to chloride anion and part of the nitrogen is mainly converted to NO3- along with smaller amounts of NO2- and NH4+. Microtox tests revealed that simultaneous use of ozone and CeO2 originated lower acute toxicity.

  17. Suppression of vacancy cluster growth in concentrated solid solution alloys

    SciTech Connect

    Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; Bei, Hongbin; Weber, William J.; Zhang, Yanwen

    2016-12-13

    Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solution alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.

  18. KNH2-KH: a metal amide-hydride solid solution.

    PubMed

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

  19. Brazing method produces solid-solution bond between refractory metals

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Brazing two refractory metals by diffusion bonding minimizes distortion and avoids excessive grain growth in the metals. This method requires the selection of an interface metal that forms intermediate low-melting eutectics or solid solutions with the metals to be brazed.

  20. Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

    DTIC Science & Technology

    1989-02-15

    studies suggested that RAINH phase separation from the liquid polycarbosilane might be avoided by carrying out the pyrolyses at elevated temperatures, where... Pyrolyses Involving [Aethvl 2AMN21 3 In the last few months of this program, an alternative route to SiC/AlN solid solutions was discovered which obviates the

  1. On the solution of a lubrication problem with particulate solids

    NASA Technical Reports Server (NTRS)

    Dai, F.; Khonsari, M. M.

    1991-01-01

    The lubrication characteristic of a fluid with solid particles is studied using the continuum theory of mixtures. The governing equations are formulated and appropriate boundary conditions are introduced for an arbitrary-shaped lubricant film thickness. As a special case, closed-form analytical perturbation solutions for pressure and shear stress are obtained for a mixture of a conventional oil and solid particles with small values of solid-volume fraction sheared in the clearance space of an infinitely long slider bearing. It is found that when compared with a pure fluid, the mixture of the fluid and solid generates a higher pressure and therefore a higher load-carrying capacity with the added advantage of a reduction in the coefficient of friction.

  2. Deep eutectic-solvothermal synthesis of nanostructured ceria

    PubMed Central

    Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

    2017-01-01

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents. PMID:28120829

  3. Deep eutectic-solvothermal synthesis of nanostructured ceria

    NASA Astrophysics Data System (ADS)

    Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

    2017-01-01

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents.

  4. Deep eutectic-solvothermal synthesis of nanostructured ceria.

    PubMed

    Hammond, Oliver S; Edler, Karen J; Bowron, Daniel T; Torrente-Murciano, Laura

    2017-01-25

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents.

  5. Phosphate modified ceria as a Brønsted acidic/redox multifunctional catalyst

    DOE PAGES

    Nelson, Nicholas C.; Wang, Zhuoran; Naik, Pranjali; ...

    2017-01-06

    Deposition of trimethylphosphate onto ceria followed by thermal treatment resulted in the formation of surface phosphates with retention of the ceria fluorite structure. The structural and chemical properties of the phosphate-functionalized ceria were studied using 31P solid-state NMR, XPS, zeta titration, ammonia thermal desorption, pyridine adsorption, and model reactions. The introduction of phosphates generated Brønsted acid sites and decreased the number of Lewis acid sites on the surface. The relative amount of Lewis and Brønsted acids can be controlled by the amount of trimethylphosphate used in the synthesis. Upon deposition of Pd, the multifunctional material showed enhanced activity for themore » hydrogenolysis of eugenol and guaiacol compared to Pd on the unmodified ceria support. As a result, this was attributed to the cooperativity between the Lewis acid sites, which activate the substrate for dearomatization, and the redox/Brønsted acid properties, which catalyze hydrogenolysis.« less

  6. Comparison Between Simulated And Experimental Au-ion Profiles Implanted in nanocrystalline ceria

    SciTech Connect

    Moll, Sandra J.; Zhang, Yanwen; Zhu, Zihua; Edmondson, Philip D.; Namavar, Fereydoon; Weber, William J.

    2013-07-15

    Radiation response of nanocrystalline ceria films deposited on a silicon substrate was investigated under a 3-MeV Au-ion irradiation at 300 K. A uniform grain growth cross the ceria films is observed and effective densification of the ceria thin films occurs during irradiation. The Au ion profiling was measured by secondary ion mass spectrometry (SIMS) and compared to the Au ion distribution predicted by the Stopping and Range of Ions in Solids (SRIM) code. It is observed that the Au-ion penetration depth is underestimated in comparison with the SIMS measurements. An overestimation of the electronic stopping power for heavy incident ions in the SRIM program may account for the discrepancies between the calculations and the SIMS experimental results. This work presents an approach to compensate the overestimation of the electronic stopping powers in the SRIM program by adjusting the nanocrystalline ceria target density to better predict the ion implantation profile.

  7. Comparison between simulated and experimental Au-ion profiles implanted in nanocrystalline ceria

    SciTech Connect

    Moll, Sandra; Zhang, Yanwen; Zhu, Zihua; Edmondson, Dr. Philip; Namavar, Fereydoon; Weber, William J

    2013-01-01

    Radiation response of nanocrystalline ceria films deposited on a silicon substrate was investigated under a 3-MeV Au-ion irradiation at 300 K. A uniform grain growth cross the ceria films is observed and effective densification of the ceria thin films occurs during irradiation. The Au ion profiling was measured by secondary ion mass spectrometry (SIMS) and compared to the Au ion distribution predicted by the Stopping and Range of Ions in Solids (SRIM) code. It is observed that the Au-ion penetration depth is underestimated in comparison with the SIMS measurements. An overestimation of the electronic stopping power for heavy incident ions in the SRIM program may account for the discrepancies between the calculations and the SIMS experimental results. This work presents an approach to compensate the overestimation of the electronic stopping powers in the SRIM program by adjusting the nanocrystalline ceria target density to better predict the ion implantation profile.

  8. Modification of solid oxide fuel cell anodes with cerium oxide coatings

    NASA Astrophysics Data System (ADS)

    Tang, Ling

    A priority for research in solid oxide fuel cells (SOFCs) is to develop cells that can maintain adequate performance in sulfur-containing fuel streams. There has been evidence that cerium oxide in the anode or electrolyte is associated with sulfur tolerance of the cell, but the mechanism underlying this effect is not well understood. The objective of the present research is to show that the porous cermet SOFC anodes can be coated with cerium oxide films, so that the cell performance can be evaluated as a function of the anode structure and the microstructure of the film. Three types of anodes---Ni/yttria-stabilized zirconia (YSZ), Ni/gadolinia-doped ceria (GDC), and Ni/GDC with GDC interlayer were infiltrated with an aqueous solution to deposit nanocrystalline ceria films. The cells were then tested in hydrogen/nitrogen fuel containing hydrogen sulfide at levels up to 500 ppm. Modification of the anodes with thiol-terminated and trichlorosilane-terminated surfactants was explored. Different ceria film morphology was achieved for each surface treatment. In the cells that underwent performance testing, the thiol treatment promoted ceria film deposition, while the sulfonate treatment suppressed ceria deposition. Uniform ceria films up to 100 nm thick could be deposited in 48 h. Results on cell testing conditions, e.g. current, time, and H2S exposure were related to different anode structures and ceria coating morphologies. In general, the Ni/GDC anodes showed better performance than the Ni/YSZ anode. The introduction of ceria films often resulted in higher cell current and longer testing time, including operation under H2S exposure. Post-testing characterization revealed that, for some anodes, microstructure changes such as coarsening of Ni in the anode, migration of Ni to the anode surface, and depletion of Ni occurred. These changes in microstructure were irreversible and might account for permanent loss of cell performance. The presence of ceria films delayed these

  9. Characterization of ceria-based SOFCs

    SciTech Connect

    Doshi, R.; Routbort, J.; Krumpelt, M.

    1996-12-31

    Solid Oxide Fuel Cells (SOFCs) operating at low temperatures (500-700{degrees}C) offer many advantages over the conventional zirconia-based fuel cells operating at higher temperatures. Reduced operating temperatures result in: (1) Application of metallic interconnects with reduced oxidation problems (2) Reduced time for start-up and lower energy consumption to reach operating temperatures (3) Increased thermal cycle ability for the cell structure due to lower thermal stresses of expansion mismatches. While this type of fuel cell may be applied to stationary applications, mobile applications require the ability for rapid start-up and frequent thermal cycling. Ceria-based fuel cells are currently being developed in the U.K. at Imperial College, Netherlands at ECN, and U.S.A. at Ceramatec. The cells in each case are made from a doped ceria electrolyte and a La{sub 1-x}Sr{sub x}Co{sub 1-y}Fe{sub y}O{sub 3} cathode.

  10. Suppression of vacancy cluster growth in concentrated solid solution alloys

    DOE PAGES

    Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

    2016-12-13

    Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

  11. Improved performance of a symmetrical solid oxide fuel cell by swapping the roles of doped ceria and La0.6Sr1.4MnO4+δ in the electrode

    NASA Astrophysics Data System (ADS)

    Shen, Jian; Yang, Guangming; Zhang, Zhenbao; Tadé, Moses O.; Zhou, Wei; Shao, Zongping

    2017-02-01

    Symmetrical solid oxide fuel cells (SSOFCs) show many advantageous features as compared with conventional cells with nickel cermet anode and oxide cathode. A K2NiF4-type layer-structured oxide, La0.6Sr1.4MnO4+δ (LSMO4), was reported to be a potential electrode for SSOFCs, and the modification of LSMO4 surface with samaria-doped ceria (SDC) and NiO was found to be the key in improving performance. In this study, the swapping of roles for SDC and LSMO4 in electrodes of SSOFCs is exploited, i.e., SDC is applied as the scaffold and LSMO4 as the surface modifier. Different from pristine LSMO4, the impregnated LSMO4 demonstrates amorphous phase. Compared to NiO-SDC impregnated LSMO4, NiO-LSMO4/SDC electrodes show a superior cathodic performance with an area specific resistance of 0.1 Ω cm2 at 700 °C. Under optimized conditions, maximum power densities of 714 and 108 mW cm-2 at 800 °C are achieved for an electrolyte-supported symmetrical single cell with a NiO-LSMO4/SDC electrode operating with hydrogen and methane, respectively. The difference in performance of the electrodes built by swapping the role and function of the SDC and LSMO4 phases is discussed, and a possible mechanism responsible for such different behaviours in cell power outputs via the impregnation of LSMO4 (NiO)+SDC electrodes is proposed.

  12. Measurement of oxygen chemical potential in Gd 2O 3-doped ceria-Y 2O 3-stabilized zirconia bi-layer electrolyte, anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Lim, Hyung-Tae; Virkar, Anil V.

    Solid oxide fuel cells (SOFC) were fabricated with gadolinia-doped ceria (GDC)-yttria stabilized zirconia (YSZ), thin bi-layer electrolytes supported on Ni + YSZ anodes. The GDC and YSZ layer thicknesses were 45 μm, and ∼5 μm, respectively. Two types of cells were made; YSZ layer between anode and GDC (GDC/YSZ) and YSZ layer between cathode and GDC (YSZ/GDC). Two platinum reference electrodes were embedded within the GDC layer. Cells were tested at 650 °C with hydrogen as fuel and air as oxidant. Electric potentials between embedded reference electrodes and anode and between cathode and anode were measured at open circuit, short circuit and under load. The electric potential was nearly constant through GDC in the cathode/YSZ/GDC/anode cells. By contrast, it varied monotonically through GDC in the cathode/GDC/YSZ/anode cells. Estimates of oxygen chemical potential, μO2 , variation through GDC were made. μO2 within the GDC layer in the cathode/GDC/YSZ/anode cell decreased as the current was increased. By contrast, μO2 within the GDC layer in the cathode/YSZ/GDC/anode cell increased as the current was increased. The cathode/YSZ/GDC/anode cell exhibited maximum power density of ∼0.52 W cm -2 at 650 °C while the cathode/GDC/YSZ/anode cell exhibited maximum power density of ∼0.14 W cm -2 for the same total electrolyte thickness.

  13. Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm-2 at 550 °C

    NASA Astrophysics Data System (ADS)

    Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

    2014-06-01

    Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm-2 at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm-2. Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

  14. Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

    PubMed

    Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

    2014-06-04

    Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

  15. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Feng, Qinzhong; Zhang, Zhiyong; Ma, Yuhui; He, Xiao; Zhao, Yuliang; Chai, Zhifang

    2012-01-01

    The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (Δ H 0 , Δ S 0 , and Δ G 0 ) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment.

  16. Surface segregation in Ni(W) solid solution

    NASA Astrophysics Data System (ADS)

    Sagie, Eyal; Polak, Micha

    2000-07-01

    The surface composition of Ni-7%W solid solution equilibrated under UHV in the range 750-1100 K was determined by means of quantitative Auger electron spectroscopy. Only part of the excess tungsten accumulated at the sputter-cleaned surface dissolved upon subsequent annealing, and from the temperature dependence of the residual W equilibrium concentration, quantified for two different in-depth distribution models, segregation enthalpies and excess entropies are derived. The observed tungsten surface segregation tendency indicates dominance of elastic strain release over weakened interatomic bonding driving forces in this solid solution. Tungsten segregation levels are relatively low because of the small net energetic driving force, and due to a suppressing excess entropy effect. Adsorption of oxygen on the alloy surfaces enhances W segregation at elevated temperatures due to preferential WO interactions.

  17. Interdiffusion in Ternary Magnesium Solid Solutions of Aluminum and Zinc

    SciTech Connect

    Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; Sohn, Yong Ho

    2016-01-11

    Al and Zn are two of the most common alloying elements in commercial Mg alloys, which can improve the physical properties through solid solution strengthening and precipitation hardening. Diffusion plays a key role in the kinetics of these and other microstructural design relevant to Mg-alloy development. However, there is a lack of multicomponent diffusion data available for Mg alloys. Through solid-to-solid diffusion couples, diffusional interactions of Al and Zn in ternary Mg solid-solution at 400° and 450 °C were examined by an extension of the Boltzmann-Matano analysis based on Onsager s formalism. Concentration profiles of Mg-Al-Zn ternary alloys were determined by electron probe microanalysis, and analyzed to determine the ternary interdiffusion coefficients as a function of composition. Zn was determined to interdiffuse the fastest, followed by Mg and Al. Appreciable diffusional interactions among Mg, Al, and Zn were observed by variations in sign and magnitude of cross interdiffusion coefficients. In particular, Zn was found to significantly influence the interdiffusion of Mg and Al significantly: the and ternary cross interdiffusion coefficients were both negative, and large in magnitude, in comparison to and , respectively. Al and Mg were observed influence the interdiffusion of Mg and Al, respectively, with positive and interdiffusion coefficients, but their influence on the Zn interdiffusion was negligible.

  18. Interdiffusion in Ternary Magnesium Solid Solutions of Aluminum and Zinc

    DOE PAGES

    Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; ...

    2016-01-11

    Al and Zn are two of the most common alloying elements in commercial Mg alloys, which can improve the physical properties through solid solution strengthening and precipitation hardening. Diffusion plays a key role in the kinetics of these and other microstructural design relevant to Mg-alloy development. However, there is a lack of multicomponent diffusion data available for Mg alloys. Through solid-to-solid diffusion couples, diffusional interactions of Al and Zn in ternary Mg solid-solution at 400° and 450 °C were examined by an extension of the Boltzmann-Matano analysis based on Onsager s formalism. Concentration profiles of Mg-Al-Zn ternary alloys were determinedmore » by electron probe microanalysis, and analyzed to determine the ternary interdiffusion coefficients as a function of composition. Zn was determined to interdiffuse the fastest, followed by Mg and Al. Appreciable diffusional interactions among Mg, Al, and Zn were observed by variations in sign and magnitude of cross interdiffusion coefficients. In particular, Zn was found to significantly influence the interdiffusion of Mg and Al significantly: the and ternary cross interdiffusion coefficients were both negative, and large in magnitude, in comparison to and , respectively. Al and Mg were observed influence the interdiffusion of Mg and Al, respectively, with positive and interdiffusion coefficients, but their influence on the Zn interdiffusion was negligible.« less

  19. Evaluation of experimental parameters for growth of homogeneous solid solutions

    NASA Astrophysics Data System (ADS)

    Scheel, Hans J.; Swendsen, Robert H.

    2001-12-01

    In this paper, we discuss the experimental conditions required to grow large two-component crystals from homogeneous solid solutions. Building on the work of Burton, Prim, and Slichter and that of Van Erk, we are able to establish that the concentration fluctuations for diffusion-limited growth are rather insensitive to hydrodynamic fluctuations. This enables a crystal grower to take advantage of forced convection to optimize growth rates without aggravating the striation problem.

  20. Solid-State and Solution Characterization of Myricetin.

    PubMed

    Franklin, Stephen J; Myrdal, Paul B

    2015-12-01

    Myricetin (MYR) is a natural compound that has been investigated as a chemopreventative agent. MYR has been shown to suppresses ultraviolet B (UVB)-induced cyclooxygenase-2 (COX-2) protein expression and reduce the incidence of UVB-induced skin tumors in mice. Despite MYR's promise as a therapeutic agent, minimal information is available to guide the progression of formulations designed for future drug development. Here, data is presented describing the solid-state and solution characterization of MYR. Investigation into the solid-state properties of MYR identified four different crystal forms, two hydrates (MYR I and MYR II) and two metastable forms (MYR IA and MYR IIA). From solubility studies, it was evident that all forms are very insoluble (<5 μg/ml) in pure water. MYR I was found to be the most stable form at 23, 35, and 56°C. Stability determination indicated that MYR undergoes rapid apparent first-order degradation under basic pH conditions, and that degradation was influenced by buffer species. Apparent first-order degradation was also seen when MYR was introduced to an oxidizing solution. Improved stability was achieved after introducing 0.1% antioxidants to the solution. MYR was found to have good stability following exposure to ultraviolet radiation (UVR), which is a consideration for topical applications. Finally, a partitioning study indicated that MYR possess a log P of 2.94 which, along with its solid-state properties, contributes to its poor aqueous solubility. Both the solid-state properties and solution stability of MYR are important to consider when developing future formulations.

  1. Characteristics of photosensors based on solid solutions of AII BVIcompounds

    NASA Astrophysics Data System (ADS)

    Lubegin, Gennady V.; Gusliannikov, Vladimir V.

    1999-10-01

    In the work there are submitted the results of the research of photosensors on a base of solid solutions of A(superscript II)B(superscript VI) compounds for measurement and control of intensity of low-level light in narrow areas of spectrum. The basic principles of technological process of manufacturing of injection photo diodes are described. The results of measurements of voltage-current characteristics and spectral characteristics of photo diodes, received in laboratory technological process with the various contents of cadmy and zinc in ZnCd(subscript 1-x)S(subscript x) solid solutions, and also sulfur and selen in CdS(subscript 1-x)Se(subscript x) solid solutions are submitted. The investigation results have shown, that photosensors work at low positive bias voltage, do not require cooling, have high sensitivity in a maximum and narrow selectivity. In CdS(subscript 1-x)Se(subscript x)- photosensors the photosensitive protecting coverage of transparent films on the base of As(subscript 2)S(subscript 3) compounds is applied. The opportunity of creation of a wide discrete range of photo diodes with the sensitivity in range from near ultraviolet up to near infrared area of spectrum is shown.

  2. Solid-solution nanocrystallite formation by high-energy milling.

    PubMed

    Kwon, Hanjung; Jung, Suna; Cho, Sung-Wook; Kil, Dae-Sup; Roh, Ki-Min; Lim, Jae-Won

    2013-09-01

    Solid-solution nanocrystalline powders were prepared by the high-energy milling of Ti alloys with graphite. The B1 structure (NaCl-like structure) phases, (Ti, Cr)C and (Ti, Al)C, were formed during the milling process of Ti-Cr + graphite and Ti-Al + graphite, and the synthetic procedures were investigated in terms of the phase evolution from XRD data. The (Ti, Al)C phase was obtained after milling for 20 hr at BPR = 40:1 (under a more severe condition), while the (Ti, Cr)C phase formed after milling for 20 hr at BPR = 20:1 (a relatively soft condition). The difference in the tendency to create a solid solution with Ti in the B1 structure caused a difference in the synthetic behavior of (Ti, Al)C and (Ti, Cr)C. In other words, (Ti, Cr)C is formed earlier than (Ti, Al)C during milling because the atomic size of Cr (0.166 nm) is similar to that of Ti (0.176 nm), which leads to the straightforward formation of the solid-solution (Ti, Cr)C as compared to when (Ti, Al)C is used. As a result, the crystallite size of the (Ti, Al)C phase (2-3 nm) synthesized at a later stage becomes smaller than that of the (Ti, Cr)C phase (5 10 nm) formed at an earlier stage during milling.

  3. Effects of different precursors on size and optical properties of ceria nanoparticles prepared by microwave-assisted method

    SciTech Connect

    Samiee, Sara; Goharshadi, Elaheh K.

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer A rapid and efficient microwave method was applied for synthesis of nano ceria. Black-Right-Pointing-Pointer Changing precursor has great effects on optical properties and size of nano ceria. Black-Right-Pointing-Pointer Fabrication of ceria nanoparticles using Ce{sup 4+} salts leads to better results. Black-Right-Pointing-Pointer Band gap energies of ceria nanoparticles were evaluated by UV-vis spectroscopy. -- Abstract: Cerium oxide, ceria (CeO{sub 2}), is one of the favourable nanoparticles (NPs) that possesses many remarkable properties so that it can be used in medicine, chemistry, environment, energy, information, industry, and so on. In this study, the crystalline ceria NPs were successfully prepared by an efficient microwave-assisted heating technique from an aqueous solution using different cerium salts (Ce(IV) and Ce(III) salts). The products were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), FTIR spectroscopy, Raman spectroscopy, and UV-vis absorption spectroscopy. The results revealed that changing the precursor led to great effects on size, band gap energy, and the reaction time of preparing the ceria NPs. The significant feature of this manuscript is that the effects of different precursors on the structural and optical properties of ceria NPs were investigated for the first time. The average particle size of different samples was below 8 nm.

  4. Flow-based solution-liquid-solid nanowire synthesis

    NASA Astrophysics Data System (ADS)

    Laocharoensuk, Rawiwan; Palaniappan, Kumaranand; Smith, Nickolaus A.; Dickerson, Robert M.; Werder, Donald J.; Baldwin, Jon K.; Hollingsworth, Jennifer A.

    2013-09-01

    Discovered almost two decades ago, the solution-liquid-solid (SLS) method for semiconductor nanowire synthesis has proven to be an important route to high-quality, single-crystalline anisotropic nanomaterials. In execution, the SLS technique is similar to colloidal quantum-dot synthesis in that it entails the injection of chemical precursors into a hot surfactant solution, but mechanistically it is considered the solution-phase analogue to vapour-liquid-solid (VLS) growth. Both SLS and VLS methods make use of molten metal nanoparticles to catalyse the nucleation and elongation of single-crystalline nanowires. Significantly, however, the methods differ in how chemical precursors are introduced to the metal catalysts. In SLS, precursors are added in a one-off fashion in a flask, whereas in VLS they are carried by a flow of gas through the reaction chamber, and by-products are removed similarly. The ability to dynamically control the introduction of reactants and removal of by-products in VLS synthesis has enabled a degree of synthetic control not possible with SLS growth. We show here that SLS synthesis can be transformed into a continuous technique using a microfluidic reactor. The resulting flow-based SLS (`flow-SLS') platform allows us to slow down the synthesis of nanowires and capture mechanistic details concerning their growth in the solution phase, as well as synthesize technologically relevant axially heterostructured semiconductor nanowires, while maintaining the propensity of SLS for accessing ultrasmall diameters below 10 nm.

  5. Extended Hansen approach: calculating partial solubility parameters of solid solutes.

    PubMed

    Wu, P L; Beerbower, A; Martin, A

    1982-11-01

    A multiple linear regression method, known as the extended Hansen solubility approach, was used to estimate the partial solubility parameters, delta d, delta p, and delta h for crystalline solutes. The method is useful, since organic compounds may decompose near their melting points, and it is not possible, to determine solubility parameters for these solid compounds by the methods used for liquid solvents. The method gives good partial and total solubility parameters for naphthalene; with related compounds, less satisfactory results were obtained. At least three conditions, pertaining to the regression equation and the solvent systems, must be met in order to obtain reasonable solute solubility parameters. In addition to providing partial solubility parameters, the regression equations afford a calculation of solute solubility in both polar and nonpolar solvents.

  6. Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

    PubMed

    Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

    2007-01-01

    The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

  7. Multiparametric dissolution of thorium-cerium dioxide solid solutions.

    PubMed

    Claparede, Laurent; Clavier, Nicolas; Dacheux, Nicolas; Mesbah, Adel; Martinez, Julien; Szenknect, Stéphanie; Moisy, Philippe

    2011-11-21

    The dissolution of Th(1-x)Ce(x)O(2) solid solutions samples prepared by thermal conversion of oxalate precursors was studied by varying independently several parameters (such as chemical composition, leachate acidity, leaching temperature, firing temperature, and crystallization state). The relative effects of these parameters on the normalized dissolution rate were examined. Either the obtained partial order related to the proton activity (n = 0.50 ± 0.01) or the activation energy (E(A) = 57 ± 6 kJ.mol(-1)) suggested that the dissolution was mainly driven by surface reactions occurring at the solid/liquid interface. Conversely to that observed for Th(1-x)U(x)O(2) and Ce(1-x)Nd(x)O(2-x/2) solid solutions, the chemical composition did not induce strong modifications of the chemical durability of the leached samples. While the initial normalized dissolution rate slightly depended on the elimination of crystal defects for firing temperatures below 800 °C, it was mainly independent of the crystallite size (T ≥ 900 °C). The role of crystal defects (then that of preparation conditions) appeared thus important to consider since they contributed to modifications of the normalized dissolution rates of the same order of magnitude than that of the leachate acidity.

  8. Crystallization in solid solution-aqueous solution systems: Thermodynamic and kinetic approaches

    SciTech Connect

    Shtukenberg, A. G. Punin, Yu. O.; Azimov, P. Ya.

    2010-03-15

    A new phenomenological approach is proposed to describe the crystallization kinetics in solid solution-aqueous solution binary systems. The phase diagrams, equilibria, and quasie-quilibria are considered within this approach. The crystallization kinetics near the true equilibrium and the crystallization features at large deviations from equilibrium are discussed on this basis. Special attention is paid to possible interactions in a solution with a seed crystal placed in it. In particular, the interactions leading to the seed's crystal growth or dissolution and to a possible exchange or metasomatic reactions are considered. In addition, the effect of the generated mismatch stress on the crystal growth rate and composition is analyzed.

  9. Interfacial Free Energy of Cu-Co Solid Solutions

    NASA Astrophysics Data System (ADS)

    Zhevnenko, S. N.

    2013-06-01

    The surface energies of Cu-Co solid solutions in hydrogen atmosphere were measured. The measurements were performed on pure copper and copper alloys containing 0.45, 0.7, 1.4, 2.25, 2.50, and 2.8 at. pct Co and 4.1 at. pct Co for the temperature range 1245 K to 1349 K (972 °C to 1076 °C). The experiments were conducted using the zero creep method for 18 mcm foils. The modified method allowed " in situ" determining of the surface energy. It was shown that the surface energy increases as the concentration increases up to 1.4 at. pct Co and then decreases. Such extreme behavior was obtained by the direct method for the first time in a solid metallic system.

  10. Grain Size Hardening Effects in Mg-Gd Solid Solutions

    NASA Astrophysics Data System (ADS)

    Nagarajan, Devarajan; Cáceres, Carlos H.; Griffiths, John R.

    2016-11-01

    Pure Mg and alloys with 0.4, 1.3, and 3.8 at. pct Gd were cast with grain sizes between 700 and 35 µm and tested in tension and compression after solid solution heat treatment and quenching. The grain structure of the castings was random, that is, there was no preferred orientation, unlike the situation in extrusions and forgings usually reported in the literature. The results are compared to earlier work on Mg-Zn alloys. A tension-compression asymmetry in which the yield strength in compression is less than in tension was observed in pure Mg but was reversed for the concentrated alloys. The Hall-Petch stress intensity factor, k, first increased then decreased with the amount of Gd in solution. It is noted that defining the friction stress by extrapolating the data to infinite grain size should be treated with caution in Mg and its alloys: nevertheless, a rationale involving solid solution softening/hardening and twinning is offered for the observed values of the friction stress. The reversion of the tension-compression asymmetry is explained by the operation of { {10bar{1}1} } (contraction) twinning in the concentrated alloys in place of { {10bar{1}2} } (extension) twinning in pure Mg and the dilute alloys. It is argued that the activation of { {10bar{1}1} } twinning in the more concentrated alloys accounts for their lower k-value.

  11. Room-Temperature Tensile Behavior of Oriented Tungsten Single Crystals with Rhenium in Dilute Solid Solution

    DTIC Science & Technology

    1966-01-01

    SINGLE CRYSTALS WITH RHENIUM IN DILUTE SOLID SOLUTION Sby M. Garfinkle Lewis Research Center Cleveland, Ohio 20060516196 NATIONAL AERONAUTICS AND...WITH RHENIUM IN DILUTE SOLID SOLUTION By M. Garfinkle Lewis Research Center Cleveland, Ohio NATIONAL AERONAUTICS AND SPACE ADMINISTRATION For sale by...ORIENTED TUNGSTEN SINGLE CRYSTALS WITH RHENIUM IN DILUTE SOLID SOLUTION * by M. Garfinkle Lewis Research Center SUMMARY Tungsten single crystals

  12. Incubational domain characterization in lightly doped ceria

    SciTech Connect

    Li Zhipeng; Mori, Toshiyuki; John Auchterlonie, Graeme; Zou Jin; Drennan, John

    2012-08-15

    Microstructures of both Gd- and Y-doped ceria with different doping level (i.e., 10 at% and 25 at%) have been comprehensively characterized by means of high resolution transmission electron microscopy and selected area electron diffraction. Coherent nano-sized domains can be widely observed in heavily doped ceria. Nevertheless, it was found that a large amount of dislocations actually exist in lightly doped ceria instead of heavily doped ones. Furthermore, incubational domains can be detected in lightly doped ceria, with dislocations located at the interfaces. The interactions between such linear dislocations and dopant defects have been simulated accordingly. As a consequence, the formation mechanism of incubational domains is rationalized in terms of the interaction between intrinsic dislocations of doped ceria and dopant defects. This study offers the insights into the initial state and related mechanism of the formation of nano-sized domains, which have been widely observed in heavily rare-earth-doped ceria in recent years. - Graphical abstract: Interactions between dislocations and dopants lead to incubational domain formation in lightly doped ceria. Highlights: Black-Right-Pointing-Pointer Microstructures were characterized in both heavily and light Gd-/Y-doped ceria. Black-Right-Pointing-Pointer Dislocations are existed in lightly doped ceria rather than heavily doped one. Black-Right-Pointing-Pointer Interactions between dislocations and dopant defects were simulated. Black-Right-Pointing-Pointer Formation of dislocation associated incubational domain is rationalized.

  13. REVIEWS OF TOPICAL PROBLEMS: Diffusive decomposition of solid solutions

    NASA Astrophysics Data System (ADS)

    Slezov, V. V.; Sagalovich, V. V.

    1987-01-01

    The present status of the theory of the late stage of diffusive decomposition of multicomponent solid solutions, owing to diffusive interaction of macrodefects, is reviewed. Methods for solving the systems of equations describing the decomposition process are analyzed. The evolution of the critical dimensions of precipitates and the transformation of an arbitrary distribution function into a universal function for different mechanisms of mass transfer are studied in detail. The conditions for coexistence of phases in the presence of decomposition of multicomponent systems are examined. The results of the theory are compared with experiment.

  14. Diffusion of Chromium in Alpha Cobalt-Chromium Solid Solutions

    NASA Technical Reports Server (NTRS)

    Weeton, John W

    1951-01-01

    Diffusion of chromium in cobalt-chromium solid solutions was investigated in the range 0 to 40 atomic percent at temperatures of 1360 degrees, 1300 degrees, 1150 degrees, and 10000 degrees c. The diffusion coefficients were found to be relatively constant within the composition range covered by each specimen. The activation heat of diffusion was determined to be 63,000 calories per mole. This value agrees closely with the value of 63,400 calories per mole calculated by means of the Dushman-Langmuir equation.

  15. Influence of correlation effects on radiation damage in solid solutions

    NASA Astrophysics Data System (ADS)

    Petrenko, P. V.; Kulish, N. P.; Mel'nikova, N. A.; Grabovskii, Yu. E.

    2016-09-01

    The influence of correlation effects due to thermodynamic interaction of alloy components on segregation processes upon radiation treatment has been analyzed. The analysis has been performed for 53 metallic solid solutions. It has been shown that the short-range order in alloys causes a redistribution of flows of radiation defects and changes the mechanism of their annihilation, which in a certain temperature range is responsible for the high resistance of alloys to radiation swelling. The presence of two maxima in the curve of the temperature dependence of swelling for austenitic nickel-chromium alloys is associated with the existence therein of different types of short-range order at different temperatures.

  16. METHOD FOR PREPARING URANIUM MONOCARBIDE-PLUTONIUM MONOCARBIDE SOLID SOLUTION

    DOEpatents

    Ogard, A.E.; Leary, J.A.; Maraman, W.J.

    1963-03-19

    A method is given for preparing solid solutions of uranium monocarbide- plutonium monocarbide. In this method, the powder form of uranium dioxide, plutonium dioxide, and graphite are mixed in a ratio determined by the equation: xUO/sub 2/ + yPuO/sub 2/ + (2+z)C yields UxPu/sub y/C/sub z/ +2CO, where x + y equ al 1.0 and z is greater than 0.9 but less than 1.0. The resulting mixture is compacted and heated in a vacuum at a temperature of 1850 deg C. (AEC)

  17. Temperature dependence of nucleation rate in a binary solid solution

    NASA Astrophysics Data System (ADS)

    Wang, H. Y.; Philippe, T.; Duguay, S.; Blavette, D.

    2012-12-01

    The influence of regression (partial dissolution) effects on the temperature dependence of nucleation rate in a binary solid solution has been studied theoretically. The results of the analysis are compared with the predictions of the simplest Volmer-Weber theory. Regression effects are shown to have a strong influence on the shape of the curve of nucleation rate versus temperature. The temperature TM at which the maximum rate of nucleation occurs is found to be lowered, particularly for low interfacial energy (coherent precipitation) and high-mobility species (e.g. interstitial atoms).

  18. Features of luminescence of liquid and solid solutions of dibenzopyrenequinnone

    SciTech Connect

    Nurmukhametov, R.N.; Baskakova, Z.M.; Khachatorova, G.T.; Mil'khiker, P.D.

    1986-01-01

    This paper reports on a study of the fluorescence characteristics of DBPQ in liquid and solid media with various polarities. The absorption, fluorescence, and fluorescence excitation spectra of the dye are investigated in a series of solvents and polymeric matrices. In liquid solutions, no new fluorescence band appears. The unusual fluorescence properties of DBPQ can be attributed to inversion of closely positioned energy levels of the S..pi pi..* and Tn..pi..* states under the influence of the medium and on the ability of the dye molecules to be photoreduced to the leuco form.

  19. A Thermodynamic Investigation of the Redox Properties of Ceria-Titania Mixed Oxides

    SciTech Connect

    Zhou,G.; Hanson, J.; Gorte, R.

    2008-01-01

    Ceria-titania solutions with compositions of Ce0.9Ti0.1O2 and Ce0.8Ti0.2O2 were prepared by the citric-acid (Pechini) method and characterized using X-ray diffraction (XRD) for structure, coulometric titration for redox thermodynamics, and water-gas-shift (WGS) reaction rates. Following calcination at 973 K, XRD suggests that the mixed oxides exist as single phase, fluorite structures, although there was no significant change in the lattice parameter compared to pure ceria. The mixed oxides are shown to be significantly more reducible than bulk ceria, with enthalpies for re-oxidation being approximately -500 kJ/mol O2, compared to -760 kJ/mol O2 for bulk ceria. However, WGS rates over 1 wt% Pd supported on ceria, Ce0.8Ti0.2O2, and Ce0.8Zr0.2O2 were nearly the same. For calcination at 1323 K, the mixed oxides separated into ceria and titania phases, as indicated by both the XRD and thermodynamic results.

  20. Thermal Conductivity in Nanocrystalline Ceria Thin Films

    SciTech Connect

    Marat Khafizov; In-Wook Park; Aleksandr Chernatynskiy; Lingfeng He; Jianliang Lin; John J. Moore; David Swank; Thomas Lillo; Simon R. Phillpot; Anter El-Azab; David H. Hurley

    2014-02-01

    The thermal conductivity of nanocrystalline ceria films grown by unbalanced magnetron sputtering is determined as a function of temperature using laser-based modulated thermoreflectance. The films exhibit significantly reduced conductivity compared with stoichiometric bulk CeO2. A variety of microstructure imaging techniques including X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron analysis, and electron energy loss spectroscopy indicate that the thermal conductivity is influenced by grain boundaries, dislocations, and oxygen vacancies. The temperature dependence of the thermal conductivity is analyzed using an analytical solution of the Boltzmann transport equation. The conclusion of this study is that oxygen vacancies pose a smaller impediment to thermal transport when they segregate along grain boundaries.

  1. Electronic origin of solid solution softening in bcc molybdenum alloys.

    PubMed

    Medvedeva, N I; Gornostyrev, Yu N; Freeman, A J

    2005-04-08

    The intrinsic mechanism of solid solution softening in bcc molybdenum alloys due to 5d transition metal additions is investigated on the basis of ab initio electronic-structure calculations that model the effect of alloying elements on the generalized stacking fault (GSF) energies. We demonstrate that additions with an excess of electrons (Re, Os, Ir, and Pt) lead to a decrease in the GSF energy and those with a lack of electrons (Hf and Ta) to its sharp increase. Using the generalized Peierls-Nabarro model for a nonplanar core, we associate the local reduction of the GSF energy with an enhancement of double kink nucleation and an increase of the dislocation mobility, and we reveal the electronic reasons for the observed dependence of the solution softening on the atomic number of the addition.

  2. Enhanced ionic conductivity in Gd-doped ceria and (Li/Na)2SO4 composite electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Yao, Chuangang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Liu, Xiliang; Meng, Fanzhi; Wu, Xiaojie; Meng, Jian

    2015-11-01

    A series of novel composite electrolytes based on 20 mol% Gd doped CeO2 with varying amounts of (Li/Na)2SO4 have been synthesized. X-ray diffraction, thermogravimetry and differential scanning calorimetry, scanning electron microscope and transmission electron microscope were applied to characterize the phase components and microstructures of the composite electrolytes. Their ionic conductivities were determined by AC impedance spectroscopy. It has been found that the optimum sintering temperature and sulphate content for the composite electrolyte is 870 °C and 20 wt% (Li/Na)2SO4, respectively. Above 550 °C, a sharp increase in conductivity occurred, which can be interpreted as superionic phase transitions in the interface phases between GDC and sulphates. Both the high ionic conductivities above the transition temperature, 0.191, 0.298 and 0.372 S cm-1 at 550, 650 and 750 °C respectively, and low activation energy (0.303 eV) highlight composite GDC-20 wt% (Li/Na)2SO4 a promising electrolyte candidate for application in intermediate temperature solid oxide fuel cells.

  3. Kinetics of the cellular decomposition of supersaturated solid solutions

    NASA Astrophysics Data System (ADS)

    Ivanov, M. A.; Naumuk, A. Yu.

    2014-09-01

    A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

  4. Irradiation-induced composition patterns in binary solid solutions

    SciTech Connect

    Dubey, Santosh; El-Azab, Anter

    2013-09-28

    A theoretical/computational model for the irradiation-driven compositional instabilities in binary solid solutions has been developed. The model is suitable for investigating the behavior of structural alloys and metallic nuclear fuels in a reactor environment as well as the response of alloy thin films to ion beam irradiation. The model is based on a set of reaction-diffusion equations for the dynamics of vacancies, interstitials, and lattice atoms under irradiation. The dynamics of these species includes the stochastic generation of defects by collision cascades as well as the defect reactions and diffusion. The atomic fluxes in this model are derived based on the transitions of lattice defects. The set of reaction-diffusion equations are stiff, hence a stiffly stable method, also known as the Gear method, has been used to numerically approximate the equations. For the Cu-Au alloy in the solid solution regime, the model results demonstrate the formation of compositional patterns under high-temperature particle irradiation, with Fourier space properties (Fourier spectrum, average wavelength, and wavevector) depending on the cascade damage characteristics, average composition, and irradiation temperature.

  5. Formation of solid solutions between racemic and enantiomeric citalopram oxalate.

    PubMed

    de Diego, Heidi Lopez; Bond, Andrew D; Dancer, Robert James

    2011-05-01

    The X-ray powder diffractograms of racemic citalopram oxalate and (S)-citalopram oxalate are very similar, but the melting point of the racemate is higher than that of the pure enantiomer. The higher melting point indicates that the racemate is a racemic compound, rather than a conglomerate. The crystal structure of the enantiomer contains two molecules of (S)-citalopram in the asymmetric unit. The conformation of the two molecules is different but they approximate mirror images of each other if the aromatic groups are interchanged. The crystal structure of the racemate is essentially isostructural with that of the enantiomer, having almost the same cell parameters but containing a crystallographic inversion centre that is not retained in the enantiomer structure. The closely-comparable crystal structures permit solid solutions to be formed between racemic and enantiomeric citalopram oxalate. Phase diagrams of the (R)-citalopram and (S)-citalopram oxalate system are constructed, and they show that solid solutions are formed at all ratios of the two enantiomers.

  6. Isomorphism and solid solutions among Ag- and Au-selenides

    SciTech Connect

    Palyanova, Galina A.; Seryotkin, Yurii V.; Kokh, Konstantin A.; Bakakin, Vladimir V.

    2016-09-15

    Au-Ag selenides were synthesized by heating stoichiometric mixtures of elementary substances of initial compositions Ag{sub 2−x}Au{sub x}Se with a step of x=0.25 (0≤x≤2) to 1050 °C and annealing at 500 °C. Scanning electron microscopy, optical microscopy, electron microprobe analysis and X-ray powder diffraction methods have been applied to study synthesized samples. Results of studies of synthesized products revealed the existence of three solid solutions with limited isomorphism Ag↔Au: naumannite Ag{sub 2}Se – Ag{sub 1.94}Au{sub 0.06}Se, fischesserite Ag{sub 3}AuSe{sub 2} - Ag{sub 3.2}Au{sub 0.8}Se{sub 2} and gold selenide AuSe - Au{sub 0.94}Ag{sub 0.06}Se. Solid solutions and AgAuSe phases were added to the phase diagram of Ag-Au-Se system. Crystal-chemical interpretation of Ag-Au isomorphism in selenides was made on the basis of structural features of fischesserite, naumannite, and AuSe. - Highlights: • Au-Ag selenides were synthesized. • Limited Ag-Au isomorphism in the selenides is affected by structural features. • Some new phases were introduced to the phase diagram Ag-Au-Se.

  7. Solid-solution semiconductor nanowires in pseudobinary systems.

    PubMed

    Liu, Baodan; Bando, Yoshio; Liu, Lizhao; Zhao, Jijun; Masanori, Mitome; Jiang, Xin; Golberg, Dmitri

    2013-01-09

    Pseudobinary solid-solution semiconductor nanowires made of (GaP)(1-x)(ZnS)(x), (ZnS)(1-x)(GaP)(x) and (GaN)(1-x)(ZnO)(x) were synthesized based on an elaborative compositional, structural, and synthetic designs. Using analytical high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS), we confirmed that the structure uniformity and a lattice match between the two constituting binary components play the key roles in the formation of quaternary solid-solution nanostructures. Electrical transport measurements on individual GaP and (GaP)(1-x)(ZnS)(x) nanowires indicated that a slight invasion of ZnS in the GaP host could lead to the abrupt resistance increase, resulting in the semiconductor-to-insulator transition. The method proposed here may be extended to the rational synthesis of many other multicomponent nanosystems with tunable and intriguing optoelectronic properties for specific applications.

  8. Zn₃P₂-Zn₃As₂ solid solution nanowires.

    PubMed

    Im, Hyung Soon; Park, Kidong; Jang, Dong Myung; Jung, Chan Su; Park, Jeunghee; Yoo, Seung Jo; Kim, Jin-Gyu

    2015-02-11

    Semiconductor alloy nanowires (NWs) have recently attracted considerable attention for applications in optoelectronic nanodevices because of many notable properties, including band gap tunability. Zinc phosphide (Zn3P2) and zinc arsenide (Zn3As2) belong to a unique pseudocubic tetragonal system, but their solid solution has rarely been studied. Here In this study, we synthesized composition-tuned Zn3(P1-xAsx)2 NWs with different crystal structures by controlling the growth conditions during chemical vapor deposition. A first type of synthesized NWs were single-crystalline and grew uniformly along the [110] direction (in a cubic unit cell) over the entire compositional range (0 ≤ x ≤ 1) explored. The use of an indium source enabled the growth of a second type of NWs, with remarkable cubic-hexagonal polytypic twinned superlattice and bicrystalline structures. The growth direction of the Zn3P2 and Zn3As2 NWs was also switched to [111] and [112], respectively. These structural changes are attributable to the Zn-depleted indium catalytic nanoparticles which favor the growth of hexagonal phases. The formation of a solid solution at all compositions allowed the continuous tuning of the band gap (1.0-1.5 eV). Photocurrent measurements were performed on individual NWs by fabricating photodetector devices; the single-crystalline NWs with [110] growth direction exhibit a higher photoconversion efficiency compared to the twinned crystalline NWs with [111] or [112] growth direction.

  9. Isomorphism and solid solutions among Ag- and Au-selenides

    NASA Astrophysics Data System (ADS)

    Palyanova, Galina A.; Seryotkin, Yurii V.; Kokh, Konstantin A.; Bakakin, Vladimir V.

    2016-09-01

    Au-Ag selenides were synthesized by heating stoichiometric mixtures of elementary substances of initial compositions Ag2-xAuxSe with a step of x=0.25 (0≤x≤2) to 1050 °C and annealing at 500 °C. Scanning electron microscopy, optical microscopy, electron microprobe analysis and X-ray powder diffraction methods have been applied to study synthesized samples. Results of studies of synthesized products revealed the existence of three solid solutions with limited isomorphism Ag↔Au: naumannite Ag2Se - Ag1.94Au0.06Se, fischesserite Ag3AuSe2 - Ag3.2Au0.8Se2 and gold selenide AuSe - Au0.94Ag0.06Se. Solid solutions and AgAuSe phases were added to the phase diagram of Ag-Au-Se system. Crystal-chemical interpretation of Ag-Au isomorphism in selenides was made on the basis of structural features of fischesserite, naumannite, and AuSe.

  10. Comparison of ceria nanoparticle concentrations in effluent from chemical mechanical polishing of silicon dioxide.

    PubMed

    Zazzera, Larry; Mader, Brian; Ellefson, Mark; Eldridge, Jess; Loper, Steve; Zabasajja, John; Qian, Julie

    2014-11-18

    This work measured and compared the effluent from the chemical mechanical polishing (CMP) of silicon dioxide using ceria slurry and ceria fixed abrasive. CMP waste streams were tested for total solids, cerium, silicon, and 6 nm to 20 μm diameter particles. The concentration of cerium and total solids in the effluent were very different for the two polishes studied. The fixed abrasive polish produced 94% less CeO2 emissions per SiO2 removed. The higher ceria levels in the slurry effluent are associated with 99-279 nm particles, and attributed to ceria abrasive. The lower concentration of ceria in the effluent from the fixed abrasive process is due to the lower wear rate of mineral from the fixed abrasive, compared to the more environmentally mobile mineral in the slurry. These results support the "bonded" nature of the abrasive particles in fixed abrasive polishing and are relevant to sustainability strategies that seek to reduce particle emissions in surface conditioning technology.

  11. Performance studies of copper-iron/ceria-yttria stabilized zirconia anode for electro-oxidation of butane in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kaur, Gurpreet; Basu, Suddhasatwa

    2013-11-01

    Addition of second metal to Cu is useful for electro-oxidation of hydrocarbons in solid oxide fuel cells (SOFC). In this work, electro-catalysts based on Cu-Fe bimetallic anode for use of both H2 and n-C4H10 in SOFC is prepared by wet impregnation method into a porous CeO2-YSZ matrix. The prepared Cu-Fe/CeO2-YSZ anodes are then characterized by thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), elemental dispersive X-ray (EDX) and scanning electron microscopy (SEM). Carbonaceous deposits formed on Cu-Fe/CeO2-YSZ anodes after exposure to n-C4H10 are studied using a combination of i-V characteristics and TGA measurements. It is observed that the addition of Fe to Cu in CeO2-YSZ cermet anode enhance the performance in H2 and n-C4H10 fuels. The performance of cell having molar ratio of Cu-Fe of 1:1 in Cu-Fe/CeO2-YSZ anode shows power density of 240 mW cm-2 and 260 mW cm-2 in n-C4H10 and in H2 after n-C4H10 flow at 800 °C. The i-V curve shows that the conductivity of the anode improves after exposure to n-C4H10. No apparent degradation in performance is observed after n-C4H10 flow except for carbon fibre formation indicating Cu-Fe bimetallic is worth considering as an anode for direct butane SOFC.

  12. Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

    NASA Astrophysics Data System (ADS)

    Rai, R. N.; Kant, Shiva; Reddi, R. S. B.; Ganesamoorthy, S.; Gupta, P. K.

    2016-01-01

    Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB and UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal.

  13. Creep Behavior of Solid Solution Strengthened Y3Al5O12

    DTIC Science & Technology

    2007-11-02

    DATES COVERED Final Technical Report 15 Feb 97 to 29 Aug 97 4. TITLE AND SUBTITLE Creep Behavior of Solid Solution Strengthened Y3A15012 6...Final Report Title: Creep Behavior of Solid Solution Strengthened Y3AI5012 Award Number: F49620-97-1-0097 For the period of: 2/14/97-8/31/97...been investigated at present in these oxides is through the formation of solid solution alloys. For the case of oxides two different possible solid

  14. Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

    USGS Publications Warehouse

    Glynn, P.D.; Reardon, E.J.; Plummer, L.N.; Busenberg, E.

    1990-01-01

    Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

  15. Effect of unsintered gadolinium-doped ceria buffer layer on performance of metal-supported solid oxide fuel cells using unsintered barium strontium cobalt ferrite cathode

    NASA Astrophysics Data System (ADS)

    Kim, Yu-Mi; Kim-Lohsoontorn, Pattaraporn; Bae, Joongmyeon

    In this study, a Gd 0.1Ce 0.9O 1.95 (GDC) buffer layer and a Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ (BSCF) cathode, fabricated without pre-sintering, are investigated (unsintered GDC and unsintered BSCF). The effect of the unsintered GDC buffer layer, including the thickness of the layer, on the performance of solid oxide fuel cells (SOFCs) using an unsintered BSCF cathode is studied. The maximum power density of the metal-supported SOFC using an unsintered BSCF cathode without a buffer layer is 0.81 W cm -2, which is measured after 2 h of operation (97% H 2 and 3% H 2O at the anode and ambient air at the cathode), and it significantly decreases to 0.63 W cm -2 after 50 h. At a relatively low temperature of 800 °C, SrZrO 3 and BaZrO 3, arising from interaction between BSCF and yttria-stabilized zirconia (YSZ), are detected after 50 h. Introducing a GDC interlayer between the cathode and electrolyte significantly increases the durability of the cell performance, supporting over 1000 h of cell usage with an unsintered GDC buffer layer. Comparable performance is obtained from the anode-supported cell when using an unsintered BSCF cathode with an unsintered GDC buffer layer (0.75 W cm -2) and sintered GDC buffer layer (0.82 W cm -2). When a sintered BSCF cathode is used, however, the performance increases to 1.23 W cm -2. The adhesion between the BSCF cathode and the cell can be enhanced by an unsintered GDC buffer layer, but an increase in the layer thickness (1-6 μm) increases the area specific resistance (ASR) of the cell, and the overly thick buffer layer causes delamination of the BSCF cathode. Finally, the maximum power densities of the metal-supported SOFC using an unsintered BSCF cathode and unsintered GDC buffer layer are 0.78, 0.64, 0.45 and 0.31 W cm -2 at 850, 800, 750 and 700 °C, respectively.

  16. Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

    PubMed

    Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

    2015-01-01

    The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

  17. Stable high conductivity ceria/bismuth oxide bilayered electrolytes

    SciTech Connect

    Wachsman, E.D.; Jayaweera, P.; Jiang, N.; Lowe, D.M.; Pound, B.G.

    1997-01-01

    The authors have developed a high conductivity bilayered ceria/bismuth oxide anolyte/electrolyte that uses the Po{sub 2} gradient to obtain stability at the anolyte-electrolyte interface and reduced electronic conduction due to the electrolyte region. Results in terms of solid oxide fuel cell (SOFC) performance and stability are presented. These results include a 90 to 160 mV increase in open-circuit potential, depending on temperature, with the bilayered structure as compared to SOFCs fabricated from a single ceria layer. An open-circuit potential of >1.0 V was obtained at 500 C with the bilayered structure. This increase in open-circuit potential is obtained without any measurable increase in cell resistance and is stable for over 1,400 h of testing, under both open-circuit and maximum power conditions. Moreover, SOFCs fabricated from the bilayered structure result in a 33% greater power density as compared to cells with a single ceria electrolyte layer.

  18. Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria-Zirconia Nanocrystals.

    PubMed

    Curran, Christopher D; Lu, Li; Jia, Yue; Kiely, Christopher J; Berger, Bryan W; McIntosh, Steven

    2017-02-21

    Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2-x) and ceria-zirconia (Ce1-yZryO2-x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a single enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.

  19. Lattice Strain Defects in a Ceria Nanolayer

    PubMed Central

    2016-01-01

    An ultrathin two-dimensional CeO2 (ceria) phase on a Cu(110) surface has been fabricated and fully characterized by high-resolution scanning tunneling microscopy, photoelectron spectroscopy, and density functional theory. The atomic lattice structure of the ceria/Cu(110) system is revealed as a hexagonal CeO2(111)-type monolayer separated from the Cu(110) surface by a partly disordered Cu–O intercalated buffer layer. The epitaxial coupling of the two-dimensional ceria overlayer to the Cu(110)-O surface leads to a nanoscopic stripe pattern, which creates defect regions of quasi-periodic lattice distortions. The symmetry and lattice mismatch at the interface is clarified to be responsible for the topographic stripe geometry and the related anisotropic strain defect regions at the ceria surface. This ceria monolayer is in a fully oxidized and thermodynamically stable state. PMID:26988695

  20. Lattice Strain Defects in a Ceria Nanolayer.

    PubMed

    Ma, Liying; Doudin, Nassar; Surnev, Svetlozar; Barcaro, Giovanni; Sementa, Luca; Fortunelli, Alessandro; Netzer, Falko P

    2016-04-07

    An ultrathin two-dimensional CeO2 (ceria) phase on a Cu(110) surface has been fabricated and fully characterized by high-resolution scanning tunneling microscopy, photoelectron spectroscopy, and density functional theory. The atomic lattice structure of the ceria/Cu(110) system is revealed as a hexagonal CeO2(111)-type monolayer separated from the Cu(110) surface by a partly disordered Cu-O intercalated buffer layer. The epitaxial coupling of the two-dimensional ceria overlayer to the Cu(110)-O surface leads to a nanoscopic stripe pattern, which creates defect regions of quasi-periodic lattice distortions. The symmetry and lattice mismatch at the interface is clarified to be responsible for the topographic stripe geometry and the related anisotropic strain defect regions at the ceria surface. This ceria monolayer is in a fully oxidized and thermodynamically stable state.

  1. Environment-mediated structure, surface redox activity and reactivity of ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Sayle, Thi X. T.; Molinari, Marco; Das, Soumen; Bhatta, Umananda M.; Möbus, Günter; Parker, Stephen C.; Seal, Sudipta; Sayle, Dean C.

    2013-06-01

    Nanomaterials, with potential application as bio-medicinal agents, exploit the chemical properties of a solid, with the ability to be transported (like a molecule) to a variety of bodily compartments. However, the chemical environment can change significantly the structure and hence properties of a nanomaterial. Accordingly, its surface reactivity is critically dependent upon the nature of the (biological) environment in which it resides. Here, we use Molecular Dynamics (MD) simulation, Density Functional Theory (DFT) and aberration corrected TEM to predict and rationalise differences in structure and hence surface reactivity of ceria nanoparticles in different environments. In particular we calculate reactivity `fingerprints' for unreduced and reduced ceria nanoparticles immersed in water and in vacuum. Our simulations predict higher activities of ceria nanoparticles, towards oxygen release, when immersed in water because the water quenches the coordinative unsaturation of surface ions. Conversely, in vacuum, surface ions relax into the body of the nanoparticle to relieve coordinative unsaturation, which increases the energy barriers associated with oxygen release. Our simulations also reveal that reduced ceria nanoparticles are more active towards surface oxygen release compared to unreduced nanoceria. In parallel, experiment is used to explore the activities of ceria nanoparticles that have suffered a change in environment. In particular, we compare the ability of ceria nanoparticles, in an aqueous environment, to scavenge superoxide radicals compared to the same batch of nanoparticles, which have first been dried and then rehydrated. The latter show a distinct reduction in activity, which we correlate to a change in the redox chemistry associated with moving between different environments. The reactivity of ceria nanoparticles is therefore not only environment dependent, but is also influenced by the transport pathway or history required to reach the particular

  2. Environment-mediated structure, surface redox activity and reactivity of ceria nanoparticles.

    PubMed

    Sayle, Thi X T; Molinari, Marco; Das, Soumen; Bhatta, Umananda M; Möbus, Günter; Parker, Stephen C; Seal, Sudipta; Sayle, Dean C

    2013-07-07

    Nanomaterials, with potential application as bio-medicinal agents, exploit the chemical properties of a solid, with the ability to be transported (like a molecule) to a variety of bodily compartments. However, the chemical environment can change significantly the structure and hence properties of a nanomaterial. Accordingly, its surface reactivity is critically dependent upon the nature of the (biological) environment in which it resides. Here, we use Molecular Dynamics (MD) simulation, Density Functional Theory (DFT) and aberration corrected TEM to predict and rationalise differences in structure and hence surface reactivity of ceria nanoparticles in different environments. In particular we calculate reactivity 'fingerprints' for unreduced and reduced ceria nanoparticles immersed in water and in vacuum. Our simulations predict higher activities of ceria nanoparticles, towards oxygen release, when immersed in water because the water quenches the coordinative unsaturation of surface ions. Conversely, in vacuum, surface ions relax into the body of the nanoparticle to relieve coordinative unsaturation, which increases the energy barriers associated with oxygen release. Our simulations also reveal that reduced ceria nanoparticles are more active towards surface oxygen release compared to unreduced nanoceria. In parallel, experiment is used to explore the activities of ceria nanoparticles that have suffered a change in environment. In particular, we compare the ability of ceria nanoparticles, in an aqueous environment, to scavenge superoxide radicals compared to the same batch of nanoparticles, which have first been dried and then rehydrated. The latter show a distinct reduction in activity, which we correlate to a change in the redox chemistry associated with moving between different environments. The reactivity of ceria nanoparticles is therefore not only environment dependent, but is also influenced by the transport pathway or history required to reach the particular

  3. Solid state and solution nitrate photochemistry: photochemical evolution of the solid state lattice.

    PubMed

    Asher, Sanford A; Tuschel, David D; Vargson, Todd A; Wang, Luling; Geib, Steven J

    2011-05-05

    We examined the deep UV 229 nm photochemistry of NaNO(3) in solution and in the solid state. In aqueous solution excitation within the deep UV NO(3)¯ strong π → π* transition causes the photochemical reaction NO(3)¯ → NO(2)¯ + O·. We used UV resonance Raman spectroscopy to examine the photon dose dependence of the NO(2)¯ band intensities and measure a photochemical quantum yield of 0.04 at pH 6.5. We also examined the response of solid NaNO(3) samples to 229 nm excitation and also observe formation of NO(2)¯. The quantum yield is much smaller at ∼10(-8). The solid state NaNO(3) photochemistry phenomena appear complex by showing a significant dependence on the UV excitation flux and dose. At low flux/dose conditions NO(2)¯ resonance Raman bands appear, accompanied by perturbed NO(3)¯ bands, indicating stress in the NaNO(3) lattice. Higher flux/dose conditions show less lattice perturbation but SEM shows surface eruptions that alleviate the stress induced by the photochemistry. Higher flux/dose measurements cause cratering and destruction of the NaNO(3) surface as the surface layers are converted to NO(2)¯. Modest laser excitation UV beams excavate surface layers in the solid NaNO(3) samples. At the lowest incident fluxes a pressure buildup competes with effusion to reach a steady state giving rise to perturbed NO(3)¯ bands. Increased fluxes result in pressures that cause the sample to erupt, relieving the pressure.

  4. High electrochemical activity of the oxide phase in model ceria-Pt and ceria-Ni composite anodes.

    PubMed

    Chueh, William C; Hao, Yong; Jung, WooChul; Haile, Sossina M

    2011-12-04

    Fuel cells, and in particular solid-oxide fuel cells (SOFCs), enable high-efficiency conversion of chemical fuels into useful electrical energy and, as such, are expected to play a major role in a sustainable-energy future. A key step in the fuel-cell energy-conversion process is the electro-oxidation of the fuel at the anode. There has been increasing evidence in recent years that the presence of CeO(2)-based oxides (ceria) in the anodes of SOFCs with oxygen-ion-conducting electrolytes significantly lowers the activation overpotential for hydrogen oxidation. Most of these studies, however, employ porous, composite electrode structures with ill-defined geometry and uncontrolled interfacial properties. Accordingly, the means by which electrocatalysis is enhanced has remained unclear. Here we demonstrate unambiguously, through the use of ceria-metal structures with well-defined geometries and interfaces, that the near-equilibrium H(2) oxidation reaction pathway is dominated by electrocatalysis at the oxide/gas interface with minimal contributions from the oxide/metal/gas triple-phase boundaries, even for structures with reaction-site densities approaching those of commercial SOFCs. This insight points towards ceria nanostructuring as a route to enhanced activity, rather than the traditional paradigm of metal-catalyst nanostructuring.

  5. Enhanced ionic conductivity of co-doped ceria-carbonate nano composite electrolyte material for LT-SOFCs

    NASA Astrophysics Data System (ADS)

    Venkataramana, Kasarapu; Madhuri, Chittimadula; Reddy, C. Vishnuvardhan

    2017-05-01

    Co-doped ceria Ce0.8Sm0.1Y0.12-δ and co-doped ceria-carbonate nano composite Ce0.8Sm0.1Y0.1O2-δ - (Na-K)2CO3 used as electrolytes in low temperature solid oxide fuel cells (LT-SOFCs) were synthesized. Structural and morphological studies were characterized by XRD and SEM. Electrical conductivity measurements were carried out by using Impedance Spectroscopy in the temperature range of 100 to 500°C. It was observed that the co-doped ceria-carbonate Nano composite material exhibited high ionic conductivity than that of co-doped ceria making it useful as promising electrolyte material for LT-SOFCs.

  6. A solid dielectric gated graphene nanosensor in electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Yibo; Wang, Cheng; Petrone, Nicholas; Yu, Jaeeun; Nuckolls, Colin; Hone, James; Lin, Qiao

    2015-03-01

    This letter presents a graphene field effect transistor (GFET) nanosensor that, with a solid gate provided by a high-κ dielectric, allows analyte detection in liquid media at low gate voltages. The gate is embedded within the sensor and thus is isolated from a sample solution, offering a high level of integration and miniaturization and eliminating errors caused by the liquid disturbance, desirable for both in vitro and in vivo applications. We demonstrate that the GFET nanosensor can be used to measure pH changes in a range of 5.3-9.3. Based on the experimental observations and quantitative analysis, the charging of an electrical double layer capacitor is found to be the major mechanism of pH sensing.

  7. Production of C59N:C60 solid solution

    NASA Astrophysics Data System (ADS)

    Fülöp, Ferenc; Rockenbauer, Antal; Simon, Ferenc; Pekker, Sándor; Korecz, László; Garaj, Slaven; Jánossy, András

    2001-10-01

    We describe a simple way to produce large quantities of solid solutions of monomer C59N in pure C60 using an electric gas discharge tube. Typical concentrations are 10-5 to 10-4 C59N with respect to C60. The 14N and several 13C hyperfine constants were measured by ESR. These are a sensitive test for electronic structure calculations of the monomer. As the temperature is raised towards the sc to fcc structural transition at 261 K, the ESR spectrum motionally narrows and the activation energy for reorientation is measured. The rotational dynamics of the C59N monomer between 130 and 600 K parallels that of C60 in the bulk thus interactions between C59N and C60 are surprisingly weak.

  8. Dielectric properties of the multicomponent PZT-type solid solution

    NASA Astrophysics Data System (ADS)

    Bochenek, Dariusz; Niemiec, Przemysław; Adamczyk, Małgorzata; Machnik, Zbigniew; Dercz, Grzegorz

    2015-10-01

    In this paper the multicomponent PZT-type solid solution doped by barium, calcium, strontium, bismuth and germanium with composition: Pb0.975Ba0.01Ca0.01Sr0.005(Zr0.52Ti0.48)O3 + 1.4 wt.% Bi2O3 + 0.3 wt.% GeO obtained by hot uniaxial pressing method is described. The results of structural, dielectric, ferroelectric and electromechanical studies of these ceramics are presented. It has been stated that introduction to the basic composition PZT admixtures of the barium, calcium, strontium, bismuth and germanium has a positive effect on the electro-physic parameters of obtained ceramic samples. This material has good microstructure, with high value of the dielectric permittivity (with the high temperature of phase transition) as well as low dielectric losses. It allows considering this material as elements for low frequency and high temperature electromechanical transducers.

  9. Nucleation of the diamond phase in aluminium-solid solutions

    NASA Technical Reports Server (NTRS)

    Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.

    1993-01-01

    Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

  10. Lattice thermal conductivity of nanograined half-Heusler solid solutions

    SciTech Connect

    Geng, Huiyuan Meng, Xianfu; Zhang, Hao; Zhang, Jian

    2014-05-19

    We report a phenomenological model of atomic weight, lattice constant, temperature, and grain size to calculate the high-temperature lattice thermal conductivity of nanograined solid solutions. The theoretical treatment developed here is reasonably consistent with the experimental results of n-type MNiSn and p-type MCoSb alloys, where M is the combination of Hf, Zr, and Ti. For disordered half-Heusler alloys with moderated grain sizes, we predict that the reduction in lattice thermal conductivity due to grain boundary scattering is independent of the scattering parameter, which characterizes the phonon scattering cross section of point defects. In addition, the lattice thermal conductivity falls off with temperature as T{sup –1∕2} around the Debye temperature.

  11. A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO2 mitigation.

    PubMed

    Chueh, William C; Haile, Sossina M

    2010-07-28

    We present a comprehensive thermodynamic and kinetic analysis of the suitability of cerium oxide (ceria) for thermochemical fuel production. Both portions of the two-step cycle, (i) oxygen release from the oxide at 1773 and 1873 K under inert atmosphere, and (ii) hydrogen release upon hydrolysis at 1073 K, are examined theoretically as well as experimentally. We observe gravimetric fuel productivity that is in quantitative agreement with equilibrium, thermogravimetric studies of ceria. Despite the non-stoichiometric nature of the redox cycle, in which only a portion of the cerium atoms change their oxidation state, the fuel productivity of 8.5-11.8 ml of H(2) per gram of ceria is competitive with that of other solid-state thermochemical cycles currently under investigation. The fuel production rate, which is also highly attractive, at a rate of 4.6-6.2 ml of H(2) per minute per gram of ceria, is found to be limited by a surface-reaction step rather than by ambipolar bulk diffusion of oxygen through the solid ceria. An evaluation of the thermodynamic efficiency of the ceria-based thermochemical cycle suggests that, even in the absence of heat recovery, solar-to-fuel conversion efficiencies of 16 to 19 per cent can be achieved, assuming a suitable method for obtaining an inert atmosphere for the oxygen release step.

  12. Crystal-chemical features of the solid solutions

    SciTech Connect

    Titov, V.V.; Kesler, Ya.A.; Gordeev, I.V.; Mozhaev, A.P.

    1988-04-01

    The unusual magnetic properties of the solid solutions of CuCr/sub 2/S/sub 4/ in Cu/sub 0.5/Mo/sub 0.5/Cr/sub 2/S/sub 4/ (M = Al, Ga, In) are closely related to the crystal chemistry of these compounds. Specimens for structural investigation were obtained by solid-phase synthesis in evacuated quartz capsules. X-ray phase analysis of all the compounds was made by the powder method in a DRON-1 diffractometer with Cu K..cap alpha.. filtered radiation. The experimental confirmation of the ordering of the cations in the tetrahedral sublattice of the investigated spinels was obtained by the authors from their IR absorption spectra taken in the range 400-33 cm/sup /minus/1/. The presence of seven intense absorption bands in the spectra of the specimens indicates that these materials belong to the space group F/anti/43m, i.e., that there is ordering in the A sublattice. Their investigation led them to the conclusion that in a number of cases the vibrational spectra of the crystals are more sensitive in the investigation of atomic ordering than the spectra of x-ray and neutron diffraction, in agreement with the theoretical predictions.

  13. Purification of uranothorite solid solutions from polyphase systems

    NASA Astrophysics Data System (ADS)

    Clavier, Nicolas; Szenknect, Stéphanie; Costin, Dan Tiberiu; Mesbah, Adel; Ravaux, Johann; Poinssot, Christophe; Dacheux, Nicolas

    2013-10-01

    The mineral coffinite, nominally USiO4, and associated Th1-xUxSiO4 uranothorite solid solutions are of great interest from a geochemical point of view and in the case of the direct storage of spent nuclear fuels. Nevertheless, they clearly exhibit a lack in the evaluation of their thermodynamic data, mainly because of the difficulties linked with their preparation as pure phases. This paper thus presents physical and chemical methods aiming to separate uranothorite solid solutions from oxide additional phases such as amorphous SiO2 and nanometric crystallized Th1-yUyO2. The repetition of centrifugation steps envisaged in first place was rapidly dropped due to poor recovery yields, to the benefit of successive washings in acid then basic media. Under both static and dynamic flow rates (i.e. low or high rate of leachate renewal), ICP-AES (Inductively Coupled Plasma - Atomic Emission Spectroscopy) analyses revealed the systematic elimination of Th1-yUyO2 in acid media and of SiO2 in basic media. Nevertheless, two successive steps were always needed to reach pure samples. On this basis, a first cycle performed in static conditions was chosen to eliminate the major part of the accessory phases while a second one, in dynamic conditions, allowed the elimination of the residual impurities. The complete purification of the samples was finally evidenced through the characterization of the samples by the means of PXRD (Powder X-Ray Diffraction), SEM (Scanning Electron Microscopy) observations and X-EDS (X-Ray Energy Dispersive Spectroscopy) analyses.

  14. Thermal expansion of solid solutions in apatite binary systems

    SciTech Connect

    Knyazev, Alexander V.; Bulanov, Evgeny N. Korokin, Vitaly Zh.

    2015-01-15

    Graphical abstract: Thermal dependencies of volume thermal expansion parameter for with thermal expansion diagrams for Pb{sub 5}(PO{sub 4}){sub 3}F{sub x}Cl{sub 1−x}. - Highlights: • Solid solutions in three apatitic binary systems were investigated via HT-XRD. • Thermal expansion coefficients of solid solutions in the systems were calculated. • Features of the thermal deformation of the apatites were described. • Termoroentgenography is a sensitive method for the investigation of isomorphism. - Abstract: High-temperature insitu X-ray diffraction was used to investigate isomorphism and the thermal expansion of apatite-structured compounds in three binary systems in the entire temperature range of the existence of its hexagonal modifications. Most of the studied compounds are highly expandable (α{sub l} > 8 × 10{sup 6} (K{sup −1})). In Pb{sub 5}(PO{sub 4}){sub 3}F–Pb{sub 5}(PO{sub 4}){sub 3}Cl system, volume thermal expansion coefficient is independence from the composition at 573 K. In Pb{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(VO{sub 4}){sub 3}Cl, the compound with equimolar ratio of substituted atoms has constant volume thermal expansion coefficient in temperature range 298–973 K. Ca{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(PO{sub 4}){sub 3}Cl system is characterized by the most thermal sensitive composition, in which there is an equal ratio of isomorphic substituted atoms.

  15. The effect of solute distribution on the strain rate sensitivity of solid solutions

    NASA Astrophysics Data System (ADS)

    Xu, Zhijie

    Several aspects of the physics of the interaction of mobile solute atoms and dislocations in dilute solid solution alloys are studied in this thesis. Solute is added to pure metals in order to improve their strength. Alloying also leads to a number of other effects, some of which are undesirable. For example, it leads to reduced ductility and may cause plastic instabilities. Both of these limit material formability. Here, understanding is added regarding the physical basis of these phenomena. Reduced formability is associated with the occurrence of plastic instabilities which are caused either by low strain hardening or by low (negative) strain rate sensitivity (SRS). The current study is focused on the second effect. The strain rate sensitivity has an instantaneous component (always positive), which is associated with the thermally activated motion of dislocations, and a transient component (which may be either positive or negative), which is associated with the correlated motion of dislocations and solute. Negative SRS results when the transient component is sufficiently negative and is presumably due to clustering of solute at dislocations. The study has a multiscale nature. On the nanoscale, the formation of solute clusters at stationary dislocation cores is studied using Monte Carlo simulations and EAM potentials in an Al-Mg alloy. The size of the thermodynamically stable cluster and the binding energy of the dislocation to its cluster are evaluated as a function of the average solute concentration and temperature. Such data enter all existing constitutive models of DSA. On the mesoscale, we investigate how solute structures (concentration fluctuations) defined on longer length scales affect dislocation motion and hence the strain rate sensitivity of the material. This investigation is performed using 2D dislocation dynamics simulations. On the macroscopic scale, parametric constitutive modeling is used to investigate the effect of mesoscopic solute structures

  16. Enhanced structural and electrical properties due to the effect of co-doping ceria electrolyte

    NASA Astrophysics Data System (ADS)

    Sandhya, K.; Chitra Priya N., S.; Aswathy P., K.; Rajendran, Deepthi N.; Thappily, Praveen

    2017-06-01

    In the present investigation, ceria co-doped with samarium and antimony has been prepared by the citrate reaction method. The FTIR pattern shows the extent of ceria content by Ce-O peaks with the effect of codoping. XRD pattern exhibits single phase structure with lattice parameter of 5.475Å. SEM images show surface morphology improved by the process of codoping at reduced sintering temperature. Electrical measurement of the sample reveals ionic conduction mechanism with higher grain conductivity at 750°C. The results of the analysis show that the codoped samples have better structural and electrical properties for usage as a solid electrolyte for IT-SOFC.

  17. Thermochemical compatibility between selected (La,Sr)(Co,Fe,Ni)O 3 cathodes and rare earth doped ceria electrolytes

    NASA Astrophysics Data System (ADS)

    Zając, Wojciech; Świerczek, Konrad; Molenda, Janina

    In this paper the results of thermal expansion coefficient measurements of different singly and doubly doped ceria electrolytes, together with results for selected cathode materials from (La,Sr)(Co,Fe,Ni)O 3 system are given. A high temperature chemical stability of the cathode-electrolyte interface was measured on 1:1 wt. mixtures of previously characterized ceria and perovskite powders. The samples were heated at 800, 1000 or at 1200 °C in air for 6 or 100 h. Chemical reactivity investigations were conducted using XRD with Rietveld analysis. For all heated samples the crystal structure of both components were preserved. However, their lattice parameters evolved to a different extent, suggesting the existence of cation exchange. A formation of the solid state solution between Ce 1- xRE xO 2- x/2 and La(Co,Fe,Ni)O 3- δ was found, with mobile La cation. On the basis of the obtained results a qualitative mechanism of the observed reaction was proposed.

  18. From cerium oxycarbonate to nanostructured ceria: Relations between synthesis, thermal process and morphologies

    NASA Astrophysics Data System (ADS)

    Bakiz, Bahcine; Guinneton, Frédéric; Dallas, Jean-Pierre; Villain, Sylvie; Gavarri, Jean-Raymond

    2008-06-01

    Nanostructured cerium dioxide rods and powders were synthesized via two sol-gel routes, respectively at 200 °C, and in room conditions without any thermal treatment. The initial solution involved nitrates, urea and polyvinyl-pyrrolidine in aqueous medium. In a first step, we synthesized cerium oxycarbonate by heating the solution at 80 °C: crystalline grains of (Ce 3+) 2O(CO 3) 2, H 2O phase were obtained in the form of elongated crystalline spindles (5-10 μm long). Thermal decomposition of these spindle-like crystals gave rise to smaller elongated rods of nanostructured ceria. A second sol-gel route allowed obtaining nanosized ceria, after NH 4OH addition and without any heating process. X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses allowed characterizing the oxycarbonate polycrystalline samples and the two types of nanocrystalline ceria phases.

  19. Crystalline structure of ceria particles controlled by the oxygen partial pressure and STI CMP performances.

    PubMed

    Kim, Ye-Hwan; Kim, Sang-Kyun; Kim, Namsoo; Park, Jea-Gun; Paik, Ungyu

    2008-09-01

    The effect of the crystalline structures of nano-sized ceria particles on shallow trench isolation (STI) chemical mechanical planarization (CMP) performance was investigated. The ceria particles were synthesized via a solid-state displacement reaction method, and their crystalline structure was controlled by regulating the oxygen partial pressure at the reaction site on the precursor. The crystalline structures of ceria particles were analyzed by the high-resolution TEM nano-beam diffraction pattern. In a calcination process with a high oxygen concentration, the synthesized ceria particles had a cubic fluorite structure (CeO(2)), because of the decarbonation of the cerium precursor. However, a low oxygen concentration results in a hexagonal phase cerium oxide (Ce(2)O(3)) rather than the cubic phase due to the insufficient oxidation of Ce(3+) to Ce(4+). In the STI CMP evaluation, the ceria slurry prepared with the cubic CeO(2) shows enhanced performances of the oxide-to-nitride removal selectivity.

  20. Mechanical characterization of hydroxyapatite, thermoelectric materials and doped ceria

    NASA Astrophysics Data System (ADS)

    Fan, Xiaofeng

    For a variety of applications of brittle ceramic materials, porosity plays a critical role structurally and/or functionally, such as in engineered bone scaffolds, thermoelectric materials and in solid oxide fuel cells. The presence of porosity will affect the mechanical properties, which are essential to the design and application of porous brittle materials. In this study, the mechanical property versus microstructure relations for bioceramics, thermoelectric (TE) materials and solid oxide fuel cells were investigated. For the bioceramic material hydroxyapatite (HA), the Young's modulus was measured using resonant ultrasound spectroscopy (RUS) as a function of (i) porosity and (ii) microcracking damage state. The fracture strength was measured as a function of porosity using biaxial flexure testing, and the distribution of the fracture strength was studied by Weibull analysis. For the natural mineral tetrahedrite based solid solution thermoelectric material (Cu10Zn2As4S13 - Cu 12Sb4S13), the elastic moduli, hardness and fracture toughness were studied as a function of (i) composition and (ii) ball milling time. For ZiNiSn, a thermoelectric half-Heusler compound, the elastic modulus---porosity and hardness---porosity relations were examined. For the solid oxide fuel cell material, gadolina doped ceria (GDC), the elastic moduli including Young's modulus, shear modulus, bulk modulus and Poisson's ratio were measured by RUS as a function of porosity. The hardness was evaluated by Vickers indentation technique as a function of porosity. The results of the mechanical property versus microstructure relations obtained in this study are of great importance for the design and fabrication of reliable components with service life and a safety factor. The Weibull modulus, which is a measure of the scatter in fracture strength, is the gauge of the mechanical reliability. The elastic moduli and Poisson's ratio are needed in analytical or numerical models of the thermal and

  1. Investigation of Propellant and Explosive Solid Solution Systems II X-Ray Studies

    DTIC Science & Technology

    1978-03-01

    A\\Yj* ^\\C/*^ ^ 1 tatf AD 7t ott w AD-E400 125 TECHNICAL REPORT ARLCD-TR-77066 INVESTIGATION OF PROPELLANT AND EXPLOSIVE SOLID SOLUTION SYSTEMS...Report ARLCD-TR-77066 2. GOVT ACCESSION NO. *. TITLE (and Subtitle) INVESTIGATION OF PROPELLANT AND EXPLOSIVE SOLID SOLUTION SYSTEMS II X-RAY...Interplanar spacings and x-ray diffraction 9 intensities of AP, KP and their physical mixtures and solid solutions 4 X-ray data of 3 AN: KP solid solution and

  2. ON THE THERMODYNAMICS OF SOLID INTRUSION SOLUTIONS WITH BODY-CENTERED CUBIC LATTICE

    DTIC Science & Technology

    THE PROPERTIES OF AN ELASTICALLY DEFORMED SOLID INTRUSION SOLUTION WITH BODY - CENTERED CUBIC LATTICE, UNBALANCED WITH RESPECT TO ENERGETICALLY DIFFERENT POSITIONS OF THE ATOMS OF THE DISSOLVED SUBSTANCE.

  3. Thermal Expansion of Fluorapatite-Chlorapatite Solid Solutions

    NASA Astrophysics Data System (ADS)

    Hovis, Guy; Abraham, Tony; Hudacek, William; Wildermuth, Sarah; Scott, Brian; Altomare, Caitlin; Medford, Aaron; Conlon, Maricate; Morris, Matthew; Leaman, Amanda; Almer, Christine; Tomaino, Gary; Harlov, Daniel

    2015-04-01

    X-ray powder diffraction experiments have been performed on fifteen fluorapatite-chlorapatite solid solutions synthesized and chemically characterized at the GeoForschungsZentrum - Potsdam (Hovis and Harlov, 2010; Schettler, Gottschalk, and Harlov, 2011), as well as two natural near-end-member samples, from room temperature to ~900 °C at 50 to 75 °C intervals. NIST 640a Si was employed as an internal standard; data from Parrish (1953) were used to determine Si peak positions at elevated temperatures. Unit-cell parameters calculated using the software of Holland and Redfern (1997) result in volume-temperature (V-T) plots that are linear or slightly concave up (V plotted as the vertical axis) over the T range investigated. Relations for the "a" and "c" unit-cell dimensions with T for these hexagonal minerals are nearly linear, but as with V, commonly improved by quadratic fits to the data. Coefficients of thermal expansion for volume (αV ), calculated as (1/V0°C) x (ΔV/ΔT) based on linear V-T relationships, mostly fall within the range 42 ± 2 x 10-6 deg-1 and show no obvious dependence on composition. Thermal expansion coefficients for individual unit-cell axes, however, do show clear relationships to composition, αa increasing from ~9.5 to ~13.5 x 10-6 deg-1 and αc decreasing from ~19.5 to ~13 x 10-6 deg-1 from the Cl to the F end member. Clearly, a compensating structural relationship accounts for the observed relationships. Such compositional dependence was not seen in the thermal expansion data for F-OH apatite solid solutions (Hovis, Scott, Altomare, Leaman, Morris, and Tomaino, American Mineralogist, in press). This difference can be explained by the similar sizes of F- and (OH)- versus the much greater size contrast between F- and Cl-. Sincere thanks to the National Science Foundation for support of this work, which has provided numerous research experiences for Lafayette College undergraduates. Thanks also to the Earth Sciences Department, University

  4. Thermal Expansion of Fluorapatite-Chlorapatite Solid Solutions

    NASA Astrophysics Data System (ADS)

    Hovis, G. L.; Abraham, T.; Hudacek, W.; Wildermuth, S.; Scott, B.; Altomare, C.; Medford, A.; Conlon, M.; Morris, M.; Leaman, A.; Almer, C.; Tomaino, G.; Harlov, D. E.

    2014-12-01

    X-ray powder diffraction experiments have been performed on fifteen fluorapatite-chlorapatite solid solutions synthesized and chemically characterized at the GeoForschungsZentrum - Potsdam (Hovis and Harlov, 2010; Schettler, Gottschalk, and Harlov, 2011), as well as two natural near-end-member samples, from room temperature to ~900 °C at 50 to 75 °C intervals. NIST 640a Si was employed as an internal standard; data from Parrish (1953) were used to determine Si peak positions at elevated temperatures. Unit-cell parameters calculated using the software of Holland and Redfern (1997) result in volume-temperature (V-T) plots that are linear or slightly concave up (V plotted as the vertical axis) over the T range investigated. Relations for the "a" and "c" unit-cell dimensions with T for these hexagonal minerals are nearly linear but, as with V, commonly improved by quadratic fits to the data. Coefficients of thermal expansion for volume (αV), calculated as (1/V0°C) x (ΔV/ΔT) based on linear V-T relationships, mostly fall within the range 42 ± 2 x 10-6 deg-1 and show no obvious dependence on composition. Thermal expansion coefficients for individual unit-cell axes, however, do show clear relationships to composition, αa increasing from ~9.5 to ~13.5 x 10-6 deg-1 and αc decreasing from ~19.5 to ~13 x 10-6 deg-1 from the Cl to the F end member. Clearly, a compensating structural relationship accounts for the observed relationships. Such compositional dependence was not seen in the thermal expansion data for F-OH apatite solid solutions (Hovis, Scott, Altomare, Leaman, Morris, and Tomaino, American Mineralogist, in press). This difference can be explained by the similar sizes of F- and (OH)- versus the much greater size contrast between F- and Cl-. Sincere thanks to the National Science Foundation for support of this work, which has provided numerous research experiences for Lafayette College undergraduates. Thanks also to the Earth Sciences Department, University

  5. Stability region of the liebermannite-lingunite solid solution

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Irifune, T.; Ohfuji, H.; Shinmei, T.; DU, W.

    2015-12-01

    Aluminosilicate hollandite, with the chemical formula of (K,Na)AlSi3O8, is a potential host mineral of K and Na in the deep Earth [1,2]. The Na hollandite end member is called lingunite, and the K hollandite end member was named liebermannite recently. Phase relations in the system KAlSi3O8-NaAlSi3O8 under conditions of the Earth mantle transition zone and uppermost lower mantle [3,4] are essential to understanding the behavior of the liebermannite-lingunite solid solution under high pressure and high temperature, however, it is still not clear whether or not the end members can form complete solid solutions with the hollandite structure under some conditions. Previous high pressure experiments obtained the K hollandite with the limited Na content up to 50 mol % [3,4], while the Na-rich hollandite with the Na content of about 80 mol % was discovered in some meteorites [5,6]. Here we report our successful synthesis of the Na-rich hollandite with the Na content of 78 mol % at 22 GPa, 2273 K, the same condition under which the Na-rich hollandite found in the meteorite was inferred to be formed during the shock event [5]. Phase relations around 22 GPa at 1873 and 2273 K determined by our experiments indicate the solubility of NaAlSi3O8 in K hollandite is sensitive to both pressure and temperature, especially around the pressure corresponding to the dissociation of jadeite into the calcium ferrite type NaAlSiO4and stishovite, and there may be a stability region for the Na hollandite end member at temperatures slightly higher than 2273 K. Our improved phase relations provide a reasonable access to estimate the composition of hollandite in the Earth's interior and a supportive evidence to interpret the formation of the Na-rich hollandite found in meteorites via phase equilibria. [1] Irifune T., Ringwood A.E. and Hibberson W.O. (1994) Earth Planet. Sci. Lett. 126: 351-368. [2] Ishii T., Kojitani H. and Akaogi M. (2012) Earth Planet. Sci. Lett. 357-358: 34-41. [3] Yagi A

  6. Preparation and characterization of ceria-zirconia ceramics using a sol-gel process

    SciTech Connect

    Zhu Bin |; Xia Changrong; Luo Xiaoguang; Meng Guangyao

    1997-10-01

    Both powder and thin film CeO{sub 2}-ZrO{sub 2} ceramic materials have been successfully prepared via a sol-gel process. In this process, Zr and Ce hydroxide-mixed sols were prepared by hydrolysis of Zr oxychloride and Ce nitrate. The thin films were coated on glass or alumina plates and also alumina tubes by a spin- or dip-coating procedure. The structure and phase of the powder or thin-film CeO{sub 2}-ZrO{sub 2} have been characterized by X-ray diffraction (XRD). Electrical properties were measured by means of complex impedance analyses. The cyclic voltammogram measurements were performed for the ITO glass-supported CeO{sub 2}-ZrO{sub 2} thin films. Powder CeO{sub 2}-ZrO{sub 2} solid solutions having the tetragonal polymorph of zirconia are obtained for ceria contents up to 50 mol%, whereas for a ceria content more than 50 mol%, the CeO{sub 2}-ZrO{sub 2} is stabilized in the cubic fluorite structure. The thin-film CeO{sub 2}-ZrO{sub 2} usually has a cubic structural characteristic. Both powder and thin-film CeO{sub 2}-ZrO{sub 2} materials are nanostructured with an average grain size of 10 nm, and they have shown very different electrical properties. The CeO{sub 2}-ZrO{sub 2} thin films have great potential for applications in various electrochemical or optoionic devices, such as fuel cells, electrochromic devices, and so forth.

  7. Surface characterization of acidic ceria-zirconia prepared by direct sulfation

    NASA Astrophysics Data System (ADS)

    Azambre, B.; Zenboury, L.; Weber, J. V.; Burg, P.

    2010-05-01

    Acidic ceria-zirconia (SCZ) solid acid catalysts with a nominal surface density of ca 2 SO 42-/nm 2 were prepared by a simple route consisting in soaking high specific surface area Ce xZr 1- xO 2 (with x = 0.21 and 0.69) mixed oxides solutions in 0.5 M sulphuric acid. Characterizations by TPD-MS, TP-DRIFTS and FT-Raman revealed that most of surface structures generated by sulfation are stable at least up to 700 °C under inert atmosphere and consist mainly as isolated sulfates located on defects or crystal planes and to a lesser extent as polysulfates. Investigations by pyridine adsorption/desorption have stated that: SCZ possess both strong Brønsted (B) and Lewis (L) acid sites, some of them being presumably superacidic; the B/L site ratio was found to be more dependent on the temperature and hydration degree than on the composition of the ceria-zirconia. By contrast, the reactivity of the parent Ce xZr 1- xO 2 materials towards pyridine is mostly driven by redox properties resulting in the formation of Py-oxide with the participation of Lewis acid sites of moderate strength ( cus Ce x+ and Zr x+ cations). Basicity studies by CO 2 adsorption/desorption reveal that SCZ surfaces are solely acidic whereas the number and strength of Lewis basic sites increases with the Ce content for the parent Ce xZr 1- xO 2 materials.

  8. Sustainable solutions for solid waste management in Southeast Asian countries.

    PubMed

    Ngoc, Uyen Nguyen; Schnitzer, Hans

    2009-06-01

    Human activities generate waste and the amounts tend to increase as the demand for quality of life increases. Today's rate in the Southeast Asian Nations (ASEANs) is alarming, posing a challenge to governments regarding environmental pollution in the recent years. The expectation is that eventually waste treatment and waste prevention approaches will develop towards sustainable waste management solutions. This expectation is for instance reflected in the term 'zero emission systems'. The concept of zero emissions can be applied successfully with today's technical possibilities in the agro-based processing industry. First, the state-of-the-art of waste management in Southeast Asian countries will be outlined in this paper, followed by waste generation rates, sources, and composition, as well as future trends of waste. Further on, solutions for solid waste management will be reviewed in the discussions of sustainable waste management. The paper emphasizes the concept of waste prevention through utilization of all wastes as process inputs, leading to the possibility of creating an ecosystem in a loop of materials. Also, a case study, focusing on the citrus processing industry, is displayed to illustrate the application of the aggregated material input-output model in a widespread processing industry in ASEAN. The model can be shown as a closed cluster, which permits an identification of opportunities for reducing environmental impacts at the process level in the food processing industry. Throughout the discussion in this paper, the utilization of renewable energy and economic aspects are considered to adapt to environmental and economic issues and the aim of eco-efficiency. Additionally, the opportunities and constraints of waste management will be discussed.

  9. Sustainable solutions for solid waste management in Southeast Asian countries

    SciTech Connect

    Uyen Nguyen Ngoc Schnitzer, Hans

    2009-06-15

    Human activities generate waste and the amounts tend to increase as the demand for quality of life increases. Today's rate in the Southeast Asian Nations (ASEANs) is alarming, posing a challenge to governments regarding environmental pollution in the recent years. The expectation is that eventually waste treatment and waste prevention approaches will develop towards sustainable waste management solutions. This expectation is for instance reflected in the term 'zero emission systems'. The concept of zero emissions can be applied successfully with today's technical possibilities in the agro-based processing industry. First, the state-of-the-art of waste management in Southeast Asian countries will be outlined in this paper, followed by waste generation rates, sources, and composition, as well as future trends of waste. Further on, solutions for solid waste management will be reviewed in the discussions of sustainable waste management. The paper emphasizes the concept of waste prevention through utilization of all wastes as process inputs, leading to the possibility of creating an ecosystem in a loop of materials. Also, a case study, focusing on the citrus processing industry, is displayed to illustrate the application of the aggregated material input-output model in a widespread processing industry in ASEAN. The model can be shown as a closed cluster, which permits an identification of opportunities for reducing environmental impacts at the process level in the food processing industry. Throughout the discussion in this paper, the utilization of renewable energy and economic aspects are considered to adapt to environmental and economic issues and the aim of eco-efficiency. Additionally, the opportunities and constraints of waste management will be discussed.

  10. Study of fluorescence quenching in aluminum-doped ceria nanoparticles: potential molecular probe for dissolved oxygen.

    PubMed

    Shehata, N; Meehan, K; Leber, D

    2013-05-01

    This work investigates a novel usage of aluminum-doped ceria nanoparticles (ADC-NPs), as the molecular probe in optical fluorescence quenching for sensing the dissolved oxygen (DO). Cerium oxide (ceria) nanoparticles can be considered one of the most unique nanomaterials that are being studied today due to the diffusion and reactivity of oxygen vacancies in ceria, which contributes to its high oxygen storage capability. Aluminum can be considered a promising dopant to increase the oxygen ionic conductivity in ceria nanoparticles which can improve the sensitivity of ceria nanoparticles to DO. The fluorescence intensity of ADC-NPs, synthesized via chemical precipitation, is found to have a strong inverse relationship with the DO concentration in aqueous solutions. Stern-Volmer constant of ADC-NPs at room temperature is determined to be 454.6 M(-1), which indicates that ADC-NPs have a promising sensitivity to dissolved oxygen, compared to many presently used fluorophores. In addition, Stern-Volmer constant is found to have a relatively small dependence on temperature between 25 °C to 50 °C, which shows excellent thermal stability of ADC-NPs sensitivity. Our work suggests that ADC-NPs, at 6 nm, are the smallest diameter DO molecular probes between the currently used optical DO sensors composed of different nanostructures. This investigation can improve the performance of fluorescence-quenching DO sensors for industrial and environmental applications.

  11. Extended solid solutions and coherent transformations in nanoscale olivine cathodes.

    PubMed

    Ravnsbæk, D B; Xiang, K; Xing, W; Borkiewicz, O J; Wiaderek, K M; Gionet, P; Chapman, K W; Chupas, P J; Chiang, Y-M

    2014-03-12

    Nanoparticle LiFePO4, the basis for an entire class of high power Li-ion batteries, has recently been shown to exist in binary lithiated/delithiated states at intermediate states of charge. The Mn-bearing version, LiMn(y)Fe(1-y)PO4, exhibits even higher rate capability as a lithium battery cathode than LiFePO4 of comparable particle size. To gain insight into the cause(s) of this desirable performance, the electrochemically driven phase transformation during battery charge and discharge of nanoscale LiMn0.4Fe0.6PO4 of three different average particle sizes, 52, 106, and 152 nm, is investigated by operando synchrotron radiation powder X-ray diffraction. In stark contrast to the binary lithiation states of pure LiFePO4 revealed in recent investigations, the formations of metastable solid solutions covering a remarkable wide compositional range, including while in two-phase coexistence, are observed. Detailed analysis correlates this behavior with small elastic misfits between phases compared to either pure LiFePO4 or LiMnPO4. On the basis of time- and state-of-charge dependence of the olivine structure parameters, we propose a coherent transformation mechanism. These findings illustrate a second, completely different phase transformation mode for pure well-ordered nanoscale olivines compared to the well-studied case of LiFePO4.

  12. Structure and thermodynamics of Cr-Fe hydroxide solid solutions

    NASA Astrophysics Data System (ADS)

    Guo, X.; Daemen, L.; Liu, N.; Wu, D.; Boukhalfa, H.; Migdissov, A. A.; Sun, C.; Navrotsky, A.; Roback, R. C.; Reimus, P. W.; Xu, H.

    2016-12-01

    Cr(VI) in the form of CrO42- is a pollutant species in soils and groundwater that poses health and environmental issues. Natural remediation processes include reduction of Cr(VI) to Cr(III). Via electron exchange with naturally abundant Fe-bearing minerals, which leads to the formation of Cr(III)-Fe(III) hydroxides. Because these phases are largely X-ray amorphous, their structural characteristics have not been well determined. In this work, we synthesized five samples with different Fe/Cr ratios, and we used synchrotron X-rays to obtain high-resolution diffraction (XRD) and absorption spectroscopy (XAS) data to study both their long range and local structural characteristics. In addition, infrared spectroscopy was conducted to obtain OH bonding information. Our results indicate that the crystallinity of these samples decreases systematically with increasing Fe/Cr ratio and that the Fe-rich samples may contain oxyhydroxides. Thermogravimetry (TG) and differential scanning calorimetry (DSC) coupled with mass spectrometry (MS) data indicate that these oxyhydrides contain about 15 - 33 wt. % water/OH- and a water contents decrease with increasing Fe/Cr ratio. Finally, the enthalpies of formation of this solid solution are all endothermic, suggesting the instability of these hydroxides relative to their corresponding oxides. These comprehensive structural and thermodynamic analyses yield fundamental parameters for understanding the behavior of Cr-Fe hydroxides/oxyhydroxides in the environment.

  13. Magnetic properties of Co-Cu metastable solid solution alloys

    NASA Astrophysics Data System (ADS)

    Fan, Xu; Mashimo, Tsutomu; Huang, Xinsheng; Kagayama, Tomoko; Chiba, Akira; Koyama, Keiichi; Motokawa, Mitsuhiro

    2004-03-01

    Metastable solid solution alloy powders and bulk alloys in the cobalt(Co)-copper(Cu) (10 90 mol % Co) system, which is an almost immiscible system at the ambient state, were prepared by mechanical alloying (MA) and shock compression. All MA-treated powders showed the x-ray diffraction patterns of a single phase of fcc structure. The lattice parameter increases with Cu concentration and is fundamentally on the line with Vegard’s law. The magnetization curves of CoxCu100-x (x=20 80) metastable bulk alloys at room temperature showed ferromagnetism, while the one of Co10Cu90 system showed paramagnetism. The saturation magnetic moment (Ms) curve versus electron numbers per atom at 0 K was found to be similar to the Slater-Pauling curves of other transition-metal binary systems and decreased with increasing Cu concentration and approached zero at about 28.8 electrons per atom. The magnetoresistance ratio at room temperature increased with Cu content in the ferromagnetic region, while the one of the paramagnetic Co10Cu90 alloy was negligibly small.

  14. Relaxor-based solid solutions for piezoelectric and electrostrictive applications

    NASA Astrophysics Data System (ADS)

    Alberta, Edward F.

    This thesis explores the dielectric, piezoelectric, and electrostrictive properties of a number of relaxor ferroelectric-based solid solution systems. The components of these solid solution systems have a variety of characteristics ranging from normal- to relaxor- to anti-ferroelectric. Some of the relaxor end-members investigated were Pb(In1/2Nb1/2)O3 [PIN], Pb(In1/2Ta1/2)O3 [PIT], Pb(Sc 1/2Nb1/2)O3 [PSN], Pb(Ni1/3Nb 2/3)O3 [PNN], Pb(Mg1/3Nb2/3)O 3 [PMN], and Pb(Zn1/3Nb2/3)O3 [PZN]. Several of these systems have Curie temperatures [Tc] that are among the highest known for MPB compositions. Some examples are PIN-0.38PT with a Tc of 319°C, PIT-0.38PT with a Tc of 248°C, and PSN 0.42PT with a Tc of 254°C. While these are slightly lower that those of typically found in PZT, the temperature dependence of the piezoelectric properties was found to be minimal. The electromechanical coupling coefficients were largely unchanged upon heating to as high as 150°C. This is approximately equal to the Tc of PMN-PT and PZN-PT and significantly exceeds the generally accepted maximum operating temperature for these materials. Many of the materials studied were found to have very large electromechanical coupling factors and produce extraordinarily high field-induced strains. Both PSN-0.42PT and PNN-0.15PZ-0.34PT were found to produce strain levels of ˜0.30% under unipolar drive with limited hysteresis. Peak-to-peak strain levels of as much as 0.60% were possible under bipolar drive conditions. Both of these MPB compositions had very large piezoelectric properties, with the slightly larger values of d33 = 810pC/N, kp = 0.69, kt = 0.56, and k33 = 0.80 occurring in PNN-PZ-PT. Each of the MPB compositions studied has features that can be exploited for specific applications. The combination of high Tc and coercive field found in both PIN-PT and Bi(Ni1/2T1/2)O3 -PT should allow these materials to be used at high drive levels and/or at high temperatures. The high strain, low hysteresis

  15. Solidification and crystal growth of solid solution semiconducting alloys

    NASA Technical Reports Server (NTRS)

    Lehoczky, S. L.; Szofran, F. R.

    1984-01-01

    Problems associated with the solidification and crytal growth of solid-solution semiconducting alloy crystals in a terrestrial environment are described. A detailed description is given of the results for the growth of mercury cadmium telluride (HgCdTe) alloy crystals by directional solidification, because of their considerable technological importance. A series of HgCdTe alloy crystals are grown from pseudobinary melts by a vertical Bridgman method using a wide range of growth rates and thermal conditions. Precision measurements are performed to establish compositional profiles for the crystals. The compositional variations are related to compositional variations in the melts that can result from two-dimensional diffusion or density gradient driven flow effects ahead of the growth interface. These effects are discussed in terms of the alloy phase equilibrium properties, the recent high temperature thermophysical data for the alloys and the highly unusual heat transfer characteristics of the alloy/ampule/furnace system that may readily lead to double diffusive convective flows in a gravitational environment.

  16. Vacancy diffusion in magnetite-hercynite solid solution

    NASA Astrophysics Data System (ADS)

    Yamauchi, Shigeru; Nakamura, Akio; Shimizu, Toshiaki; Fueki, Kazuo

    1983-11-01

    To extend the chemical relaxation technique to ternary oxide systems, theoretical analysis was made to obtain an expression for the chemical diffusion coefficient in terms of the vacancy diffusion coefficient. An equation, D˜ = [ {C O}/{(C 1 + C 2) }] D v( {1}/{2})( {∂ ln P( O2) }/{∂ ln C v}) , was derived. This is similar to the one for the binary oxide system. Chemical relaxation experiments were made on the magnetite-hercynite solid solutions, (Fe 1- yAl y) 3-δO 4 with y = 0.0, 0.067, 0.133, and 0.20, at temperatures between 1300 and 1400°C. The vacancy diffusion coefficient decreased remarkably with an increase in y. The activation energy was found to be 20.8 ± 3.7, 33.5 ± 4.2, 50.4 ± 3.6, and 66.3 ± 4.5 kcal/mole for y = 0.0, 0.067, 0.133, and 0.20, respectively. A strong dependence on y was also found. The dependence of the vacancy diffusion coefficient on y was interpreted to indicate that the jump frequency of cation vacancies is decreased by the introduction of aluminium ion.

  17. Solid state lighting for the developing world: the only solution

    NASA Astrophysics Data System (ADS)

    Peon, Rudolfo; Doluweera, Ganesh; Platonova, Inna; Irvine-Halliday, Dave; Irvine-Halliday, Gregor

    2005-09-01

    Approximately two billion people, one third of humanity still has no access to electricity, and thus relies on fuel-based lighting, a dangerous alternative of last resort that is unhealthy, expensive, and offers very poor levels of illumination. This lack of light makes it difficult to perform most evening activities including studies by children and adults alike and therefore represents a significant barrier to human development. Over the past five years The Light Up The World Foundation (LUTW) has pioneered the use of the white light emitting diode (WLED) as an alternative home lighting solution, bringing clean, affordable light to thousands of non-electrified homes around the world. The information presented herein is intended to increase awareness of the enormous potential possessed by this emergent technology, "Solid State Lighting" (SSL), to improve the quality of life of millions of people around the world. The feasibility of its implementation is demonstrated with results from comprehensive field experience and laboratory research work. The mutual economic, social and environmental benefits for both stakeholders and SSL suppliers are discussed. Strategies conducive to the dissemination of this technology throughout the developing world are also presented.

  18. Solidification and crystal growth of solid solution semiconducting alloys

    NASA Technical Reports Server (NTRS)

    Lehoczky, S. L.; Szofran, F. R.

    1984-01-01

    Problems associated with the solidification and crytal growth of solid-solution semiconducting alloy crystals in a terrestrial environment are described. A detailed description is given of the results for the growth of mercury cadmium telluride (HgCdTe) alloy crystals by directional solidification, because of their considerable technological importance. A series of HgCdTe alloy crystals are grown from pseudobinary melts by a vertical Bridgman method using a wide range of growth rates and thermal conditions. Precision measurements are performed to establish compositional profiles for the crystals. The compositional variations are related to compositional variations in the melts that can result from two-dimensional diffusion or density gradient driven flow effects ahead of the growth interface. These effects are discussed in terms of the alloy phase equilibrium properties, the recent high temperature thermophysical data for the alloys and the highly unusual heat transfer characteristics of the alloy/ampule/furnace system that may readily lead to double diffusive convective flows in a gravitational environment.

  19. Intrinsic luminescence centers in scandia, yttria, and their solid solutions

    NASA Astrophysics Data System (ADS)

    Solomonov, V. V.; Spirina, A. V.; Spirin, A. V.; Paranin, S. N.

    2016-11-01

    Pulsed cathodoluminescence (PCL) of Y2O3 and Sc2O3 powders, as well as of ceramic samples of binary (11 mol % Sc2O3-ZrO2 and 10 mol % Y2O3-ZrO2) and ternary ( xSc2O3-(10-x)Y2O3-ZrO2) ( x = 5, 6, 7, 8 mol %) solid solutions are studied in the range of 300-850 nm at room temperature. In Y2O3 and Sc2O3, series of strong narrow luminescence bands emitted by surface bound radicals ...0 ...0 >-Y= O and ...0 ...0 >-Sc= O are found. The PCL spectra of xSc2O3-(10-x)Y2O3-ZrO2 ceramic samples showed the same series of narrow bands at 543, 551, 555, 572, 583, 594, 614, and 639 nm as the yttrium oxide spectra. The existence of these luminescence bands, which correspond to the emission of the ...0 ...0 >-Y= O radical, and the absence of the emission lines of the ...0 ...0 >-Sc= O radical indicate that yttrium ions, due to their larger radius, are the first that are displaced to the surface of crystallites in these systems, which is accompanied by the formation of the second phase in subsurface layers.

  20. Optical sensing of peroxide using ceria nanoparticles via fluorescence quenching technique

    NASA Astrophysics Data System (ADS)

    Shehata, N.; Samir, E.; Gaballah, S.

    2016-04-01

    This study introduces the application of small ceria nanoparticles (NPs) as optical sensor for peroxide using fluorescence quenching technique. Our synthesized ceria nanoparticles have the ability to adsorb peroxides via its oxygen vacancies. Ceria nanoparticles (NPs) solution with added variable concentrations of hydrogen peroxides is exposed through near UV excitation and the detected visible fluorescent emission is found to be at 520nm, with reduced peak intensity peaks with increasing the peroxide concentrations due to static fluorescence quenching technique. The relative intensity change of the visible fluorescent emission has been reduced to more than 50% at added peroxide concentrations up to 10 wt.%. This research work could be applied further in optical sensors of radicals in biomedical engineering and environmental monitoring.

  1. Bounds to Hardening by Solid Solution, Precipitation and Short Range Order in Mg Binary Alloys

    NASA Astrophysics Data System (ADS)

    Cáceres, C. H.; Abaspour, Saeideh

    Miedema's coordinates are used to rank 4 model binary alloys considering the respective values of enthalpy of formation and the tendency to developing random solid solution, precipitation, short range order (SRO) and intermetallic compounds. The terminal solid solubility generally increases whereas the tendency to order decreases with decreasing heat of formation, and hardening by near-random solid solution and/or precipitation is expected to be dominant for solutes with low tendency to order, such as Al. For solutes with an intermediate tendency to order, hence solubility, such as Zn, or to form compounds, such as Gd, SRO is predicted to dominate the hardening. For solutes whose very large heat of formation leads to very high melting point intermetallics forming congruently, such as Sb, the terminal solid solubility is too low for any solute based hardening to be feasible. Implicancies for alloy design and selection regarding solute or precipitation hardening, SRO and creep resistance are discussed.

  2. Alloying Solid Solution Strengthening of Fe-Ga Alloys: A First-Principle Study

    DTIC Science & Technology

    2006-01-01

    effect from alloying additions of Nb, Mo, V, Cr and Co in cubic solid solution of Fe-Ga alloys. Mayer bond order "BO" values were used to evaluate the...that transition metal Nb achieves the best strengthening effect in Fe-Ga alloys. The solid solution strengthening follows a trend from larger to

  3. The behavior of Gliclazide in solution and in the solid state: a case of organic compound presenting a solid-solution structure.

    PubMed

    Santa María, Dolores; Claramunt, Rosa M; Alkorta, Ibon; Elguero, José

    2009-06-01

    The structure of the hypoglycemic agent Gliclazide has been studied by (1)H, (13)C, and (15)N NMR in solution (CDCl(3) and DMSO-d(6)) and in the solid state. In the solid state, the compound crystallizes as an EZ isomer without dynamic properties. In CDCl(3) solution, the structure is still EZ but with a slow nitrogen inversion about the pyrrolidine nitrogen: two invertomers have been observed and characterized. In DMSO-d(6), the rate is faster and only averaged signals were observed. GIAO calculated absolute shieldings were used to confirm the nature of the observed species. In the solid state, Gliclazide presents the phenomenon of solid-solution with two disordered conformations present in the crystal at a 90:10 ratio.

  4. Investigation of droplet collisions for solutions with different solids content

    NASA Astrophysics Data System (ADS)

    Kuschel, Matthias; Sommerfeld, Martin

    2013-02-01

    The collision behaviour of droplets and the collision outcome are investigated for high viscous polymer solutions. For that purpose, two droplet chains produced by piezoelectric droplet generators are directed towards each other at a certain angle so that individual droplet pairs collide. For recording the collision event, one double-image and one high-speed CCD camera were used. One camera is positioned perpendicular to the collision plane recording the outcome of the collision, and the second camera is aligned parallel to the collision plane to assure that the droplet chains are exactly in one plane. A new approach for tracking droplets in combination with an extended particle tracking velocimetry algorithm has been developed. Time-resolved series of pictures were used to analyse the dynamics of droplet collisions. The three different water soluble substances were saccharose and 1-Ethenyl-2-pyrrolidone (PVP) with different molecular weights (K17, K30). The solvent was demineralised water. The solids contents ranged from 20 to 60 %, 5 to 25 % and 5 to 35 %, yielding dynamic viscosities in the range of 2-60 mPa s. Results were collected for different pairs of impact angles and Weber numbers in order to establish common collision maps for characterising the outcomes. Here, relative velocities between 0.5 and 4 m/s and impact parameters in the interval from 0 to 1 for equal-sized droplets (Δ = 1) have been investigated. Additionally, satellite formation will be discussed exemplarily for K30. A comparison with common models of different authors (Ashgriz and Poo in J Fluid Mech 221:183-204, 1990; Estrade et al. in Int J Heat Fluid Flow 20:486-491, 1999) mainly derived for low viscous droplets revealed that the upper limit of their validity is given by an Ohnesorge number of Oh = 0.115 and a capillary number of Ca = 0.577. For higher values of these non-dimensional parameters and hence higher dynamic viscosities, these models are unable to predict correctly the

  5. Solid solution, phase separation, and cathodoluminescence of GaP-ZnS nanostructures.

    PubMed

    Liu, Baodan; Bando, Yoshio; Dierre, Benjamin; Sekiguchi, Takashi; Golberg, Dmitri; Jiang, Xin

    2013-09-25

    Quaternary solid-solution nanowires made of GaP and ZnS have been synthesized through well-designed synthetic routines. The as-synthesized GaP-ZnS solid-solution nanowires exhibit decent crystallinity with the GaP phase as the host, while a large amount of twin structural defects are observed in ZnS-rich nanowires. Cathodoluminescence studies showed that GaP-rich solid-solution nanowires have a strong visible emission centered at 600 nm and the ZnS-rich solid-solution nanowires exhibited a weak emission peak in the UV range and a broad band in the range 400-600 nm. The formation mechanism, processes, and optical emissions of GaP-ZnS solid-solution nanowires were discussed in detail.

  6. Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

    NASA Astrophysics Data System (ADS)

    Menon, Sumithra Sivadas; Anitha, R.; Gupta, Bhavana; Baskar, K.; Singh, Shubra

    2016-05-01

    GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

  7. Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

    SciTech Connect

    Menon, Sumithra Sivadas; Anitha, R.; Baskar, K.; Singh, Shubra; Gupta, Bhavana

    2016-05-23

    GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

  8. Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573-1773 K temperature range.

    PubMed

    Takacs, M; Scheffe, J R; Steinfeld, A

    2015-03-28

    This work encompasses the thermodynamic characterization and critical evaluation of Zr(4+) doped ceria, a promising redox material for the two-step solar thermochemical splitting of H2O and CO2 to H2 and CO. As a case study, we experimentally examine 5 mol% Zr(4+) doped ceria and present oxygen nonstoichiometry measurements at elevated temperatures ranging from 1573 K to 1773 K and oxygen partial pressures ranging from 4.50 × 10(-3) atm to 2.3 × 10(-4) atm, yielding higher reduction extents compared to those of pure ceria under all conditions investigated, especially at the lower temperature range and at higher pO2. In contrast to pure ceria, a simple ideal solution model accounting for the formation of isolated oxygen vacancies and localized electrons accurately describes the defect chemistry. Thermodynamic properties are determined, namely: partial molar enthalpy, entropy, and Gibbs free energy. In general, partial molar enthalpy and entropy values of Zr(4+) doped ceria are lower. The equilibrium hydrogen yields are subsequently extracted as a function of the redox conditions for dopant concentrations as high as 20%. Although reduction extents increase greatly with dopant concentration, the oxidation of Zr(4+) doped ceria is thermodynamically less favorable compared to pure ceria. This leads to substantially larger temperature swings between reduction and oxidation steps, ultimately resulting in lower theoretical solar energy conversion efficiencies compared to ceria under most conditions. In effect, these results point to the importance of considering oxidation thermodynamics in addition to reduction when screening potential redox materials.

  9. Solid-solution aqueous-solution equilibria: thermodynamic theory and representation

    USGS Publications Warehouse

    Glynn, P.D.; Reardon, E.J.

    1990-01-01

    Thorstenson and Plummer's (1977) "stoichiometric saturation' model is reviewed, and a general relation between stoichiometric saturation Kss constants and excess free energies of mixing is derived for a binary solid-solution B1-xCxA: GE = RT[ln Kss - xln(xKCA) - (l-x)ln((l-x)KBA)]. This equation allows a suitable excess free energy function, such as Guggenheim's (1937) sub-regular function, to be fitted from experimentally determined Kss constants. Solid-phase free energies and component activity-coefficients can then be determined from one or two fitted parameters and from the endmember solubility products KBA and KCA. A general form of Lippmann's (1977,1980) "solutus equation is derived from an examination of Lippmann's (1977,1980) "total solubility product' model. Lippmann's ??II or "total solubility product' variable is used to represent graphically not only thermodynamic equilibrium states and primary saturation states but also stoichiometric saturation and pure phase saturation states. -from Authors

  10. Improved Oxidase Mimetic Activity by Praseodymium Incorporation into Ceria Nanocubes.

    PubMed

    Jiang, Lei; Fernandez-Garcia, Susana; Tinoco, Miguel; Yan, Zhaoxia; Xue, Qi; Blanco, Ginesa; Calvino, Jose J; Hungria, Ana B; Chen, Xiaowei

    2017-06-07

    Ceria nanocubes (NC) modified with increasing concentrations of praseodymium (5, 10, 15, and 20 mol %) have been successfully synthesized by a hydrothermal method. The as-synthesized Pr-modified ceria nanocubes exhibit an enhanced oxidase-like activity on the organic dye TMB within a wide range of concentrations and durations. The oxidase activity increases with increasing Pr amounts in Pr-modified ceria nanocubes within the investigated concentration range. Meanwhile, these Pr-modified ceria nanocubes also show higher reducibility than pure ceria nanocubes. The kinetics of their oxidase mimetic activity is fitted with the Michaelis-Menten equation. A mechanism has been proposed on how the Pr incorporation could affect the energy level of the bands in ceria and hence facilitate the TMB oxidation reaction. The presence of Pr(3+) species on the surface also contributes to the increasing activity of the Pr-modified ceria nanocubes present higher oxidase activity than pure ceria nanocubes.

  11. Continuum Modeling of Mixed Conductors: a Study of Ceria

    NASA Astrophysics Data System (ADS)

    Ciucci, Francesco

    In this thesis we have derived a new way to analyze the impedance response of mixed conducting materials for use in solid oxide fuel cells (SOFCs), with the main focus on anodic materials, in particular cerium oxides. First we have analyzed the impact of mixed conductivity coupled to electrocatalytic behavior in the linear time-independent domain for a thick ceria sample. We have derived that, for a promising fuel cell material, Samarium Doped Ceria, chemical reactions are the determining component of the polarization resistance. As a second step we have extended the previous model to the time-dependent case, where we focused on single harmonic excitation, the impedance spectroscopy conditions. We extended the model to the case where some input diffusivities are spatially nonuniform. For instance we considered the case where diffusivities change significantly in the vicinity of the electrocatalytic region. As a third and final step we use to model to capture the two dimensional behavior of mixed conducting thin films, where the electronic motion from one side of the sample to the other is impeded. Such conditions are similar to those encountered in fuel cells where an electrolyte conducting exclusively oxygen ions is placed between the anode and the cathode. The framework developed was also extended to study a popular cathodic material, Lanthanum Manganite. The model is used to give unprecedented insight in SOFC polarization resistance analysis of mixed conductors. It helps elucidate rigorously rate determining steps and to address the interplay of diffusion with diffusion losses. Electrochemical surface losses dominate for most experimental conditions of Samarium Doped Ceria and they are shown to be strongly dependent on geometry.

  12. Solid lipid nanoparticles suspension versus commercial solutions for dermal delivery of minoxidil.

    PubMed

    Padois, Karine; Cantiéni, Céline; Bertholle, Valérie; Bardel, Claire; Pirot, Fabrice; Falson, Françoise

    2011-09-15

    Solid lipid nanoparticles have been reported as possible carrier for skin drug delivery. Solid lipid nanoparticles are produced from biocompatible and biodegradable lipids. Solid lipid nanoparticles made of semi-synthetic triglycerides stabilized with a mixture of polysorbate and sorbitan oleate were loaded with 5% of minoxidil. The prepared systems were characterized for particle size, pH and drug content. Ex vivo skin penetration studies were performed using Franz-type glass diffusion cells and pig ear skin. Ex vivo skin corrosion studies were realized with a method derived from the Corrositex(®) test. Solid lipid nanoparticles suspensions were compared to commercial solutions in terms of skin penetration and skin corrosion. Solid lipid nanoparticles suspensions have been shown as efficient as commercial solutions for skin penetration; and were non-corrosive while commercial solutions presented a corrosive potential. Solid lipid nanoparticles suspensions would constitute a promising formulation for hair loss treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Evolution of mixed surfactant aggregates in solutions and at solid/solution interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Rui

    Surfactant systems have been widely used in such as enhanced oil recovery, waste treatment and metallurgy, etc., in order to solve the problem of global energy crisis, to remove the pollutants and to generate novel energy resources. Almost all surfactant systems are invariably mixtures due to beneficial and economic considerations. The sizes and shapes of aggregates in solutions and at solid/solution interfaces become important, since the nanostructures of mixed aggregates determine solution and adsorption properties. A major hurdle in science is the lack of information on the type of complexes and aggregates formed by mixtures and the lack of techniques for deriving such information. Using techniques such as analytical ultracentrifuge, small angle neutron scattering, surface tension, fluorescence, cryo-TEM, light scattering and ultrafiltration, the nanostructures of aggregates of sugar based n-dodecyl-beta-D-maltoside (DM) and nonionic pentaethyleneglycol monododecyl ether or nonyl phenol ethoxylated decyl ether (NP-10) and their mixtures have been investigated to prove the hypothesis that the aggregation behavior is linked to packing of the surfactant governed by the molecular interactions as well as the molecular structures. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and its mixtures with n-dodecyl-beta-D-maltoside while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions, in good agreement with those from small angle neutron scattering, cryo-TEM, light scattering and ultrafiltration. Type I micelles were primary micelles at cmc while type II micelles were elongated micelles. On the other hand, the nanostructures of mixed surface aggregates have been quantitatively predicted for the first time using a modified packing index. As a continuation of the Somasundaran-Fuersteneau adsorption model, a

  14. Magnetic behavior of solid Ar-O2 solutions

    SciTech Connect

    Prisk, Timothy R.; Sokol, P. E.

    2015-08-12

    Solid molecular oxygen presents an interesting example of a low-temperature crystal which exists within several different magnetic phases. When solid solutions of argon and oxygen are formed with molar concentrations of oxygen between 60 and 80 %, a new structural and magnetic phase, known as the δ-phase, appears at low temperatures. In order to investigate the nature of the δ-phase, we carried out SQUID magnetometry measurements solid argon-oxygen solutions made up of 74 % oxygen and 26 % argon. In particular, we performed measurements of the magnetic susceptibility of the solid solutions over complete temperature cycles and isothermally as a function of time. Altogether, the experimental data demonstrate that that the δ-phase is not an equilibrium thermodynamic state of the solid solutions, but is instead only a metastable state.

  15. Kinetic analysis for formation of Cd1-xZnxSe solid-solution nanocrystals.

    PubMed

    Sung, Yun-Mo; Lee, Yong-Ji; Park, Kyung-Soo

    2006-07-19

    Kinetic analysis on the nanocrystal solid-solution formation was performed by heat treating CdSe/ZnSe core/shell nanocrystals, synthesized via a typical TOP/TOPO approach, at different temperatures for different time periods. X-ray diffraction (XRD) peak shifts in Cd1-xZnxSe cores according to the solid-solution treatments were monitored and used for the estimation of the lattice parameter change. The degree of solid-solution formation was determined considering the compositional variation in Cd1-xZnxSe cores, which was obtained from the Vegard's law. The degree of solid-solution formation (x) was applied to Jander analysis, and an Arrhenius-type plot was produced using the slopes of Jander plots. The activation energy for solid-solution formation was determined as approximately 152 kJ/mol, which evidently indicates that the diffusion of Zn2+ ions in the CdSe-ZnSe system is the governing mechanism for the Cd1-xZnxSe solid-solution formation. The Jander equation to predict the solid-solution formation kinetics for the CdSe/ZnSe core/shell systems was completed using the reaction rate constant (k).

  16. Synthesis of the bismuth oxyhalide solid solutions with tunable band gap and photocatalytic activities.

    PubMed

    Ren, Kuaixia; Liu, Jie; Liang, Jie; Zhang, Kun; Zheng, Xiao; Luo, Hongde; Huang, Yunbo; Liu, Pujun; Yu, Xibin

    2013-07-14

    Three series of BiOM(x)R(1-x) (M, R = Cl, Br, I) solid solutions were systematically synthesized through a low-temperature precipitation. These solid solutions were characterized by XRD, FESEM, TEM, EDS, UV-vis spectra, nitrogen sorption/desorption, and PL. The tunable band gaps of the as-prepared solid solutions were realized via only changing the molar ratio of two halide ions. Meanwhile, the influence of citric acid in the formations of controllable morphological structures was discussed to study the growth mechanism of solid solutions. The photocatalytic activities of the bismuth oxyhalide solid solutions have also been investigated by the degradation of Rhodamine-B (RhB) under visible light irradiation. The optimized solid solutions possess higher photocatalytic activity than pure ones [BiOM (M = Cl, Br, I)] due to the broadened range of visible light response and the reduced recombination rate of electron-holes pairs. The results show that the synthesis of BiOM(x)R(1-x) (M, R = Cl, Br, I) solid solutions have profound significance for the design of the novel photocatalyst materials.

  17. Analysis of solid solutions stability in scheelite-type molybdates and tungstates

    SciTech Connect

    Zhuravlev, V.D.; Reznitskikh, O.G.; Velikodnyi, Yu.A.; Patrusheva, T.A.; Sivtsova, O.V.

    2011-10-15

    Mutual solubility of bivalent metal molybdates and tungstates with scheelite structure was theoretically estimated by calculating formation enthalpies and the maximal decomposition temperatures of solid solutions at different temperatures. The theoretical stability of continuous solid solutions in binary systems of bivalent metal molybdates and tungstates was found to be higher than reported literature data. After cooling down continuous substitution solid solution should remain in following systems: CaMoO{sub 4}-CdMoO{sub 4}, SrMoO{sub 4}-MMoO{sub 4} (M=Ba, Pb), BaMoO{sub 4}-PbMoO{sub 4}, SrWO{sub 4}-MWO{sub 4} (M=Ca, Pb), and BaWO{sub 4}-PbWO{sub 4}. There is a probability that at room temperature in systems CaMoO{sub 4}-SrMoO{sub 4,} CaWO{sub 4}-PbWO{sub 4}, and BaWO{sub 4}-SrWO{sub 4} the single homogeneity region may decompose to limited solid solutions. It was shown experimentally that a continuous series of scheelite-structure solid solutions M{sub 1-x}M{sup I}{sub x}TO{sub 4} can be formed via citrate synthesis at temperatures below 500 deg. S. - Graphical abstract: Calculated boundaries of solid solutions in BaWO{sub 4}-CaWO{sub 4} (1) and PbMoO{sub 4}-CaMoO{sub 4} (2) systems. Highlights: > Stability of solid solutions molybdates and tungstates has been investigated. > The ionic model for isovalent substitutions was used. > In 'polyhedral substitution model' enthalphies of mixing were calculated. > Most of the examined series of solid solutions is stable at room temperatures. > Solid solutions M{sub 1-x}M{sup I}{sub x}Mo(W)O{sub 4} (x=0-1) were formed via citrate synthesis below 500 S.

  18. Investigation of compositional segregation during unidirectional solidification of solid solution semiconducting alloys

    NASA Technical Reports Server (NTRS)

    Wang, J. C.

    1982-01-01

    Compositional segregation of solid solution semiconducting alloys in the radial direction during unidirectional solidification was investigated by calculating the effect of a curved solid liquid interface on solute concentration at the interface on the solid. The formulation is similar to that given by Coriell, Boisvert, Rehm, and Sekerka except that a more realistic cylindrical coordinate system which is moving with the interface is used. Analytical results were obtained for very small and very large values of beta with beta = VR/D, where V is the velocity of solidification, R the radius of the specimen, and D the diffusivity of solute in the liquid. For both very small and very large beta, the solute concentration at the interface in the solid C(si) approaches C(o) (original solute concentration) i.e., the deviation is minimal. The maximum deviation of C(si) from C(o) occurs for some intermediate value of beta.

  19. Oxygen vacancy migration in ceria and Pr-doped ceria: a DFT+U study.

    PubMed

    Dholabhai, Pratik P; Adams, James B; Crozier, Peter; Sharma, Renu

    2010-03-07

    Oxygen vacancy formation and migration in ceria (CeO(2)) is central to its performance as an ionic conductor. It has been observed that ceria doped with suitable aliovalent cationic dopants improves its ionic conductivity. To investigate this phenomenon, we present total energy calculations within the framework of density functional theory to study oxygen vacancy migration in ceria and Pr-doped ceria (PDC). We report activation energies for oxygen vacancy formation and migration in undoped ceria and for different migration pathways in PDC. The activation energy value for oxygen vacancy migration in undoped ceria was found to be in reasonable agreement with the available experimental and theoretical results. Conductivity values for reduced undoped ceria calculated using theoretical activation energy and attempt frequency were found in reasonably good agreement with the experimental data. For PDC, oxygen vacancy formation and migration were investigated at first, second, and third nearest neighbor positions to a Pr ion. The second nearest neighbor site is found to be the most favorable vacancy formation site. Vacancy migration between first, second, and third nearest neighbors was calculated (nine possible jumps), with activation energies ranging from 0.41 to 0.78 eV for first-nearest-neighbor jumps. Overall, the presence of Pr significantly affects vacancy formation and migration, in a complex manner requiring the investigation of many different migration events. We propose a relationship illuminating the role of additional dopants toward lowering the activation energy for vacancy migration in PDC.

  20. Al and Zn Impurity Diffusion in Binary and Ternary Magnesium Solid-Solutions

    SciTech Connect

    Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; Sohn, Yong Ho

    2014-01-01

    Magnesium alloys are considered for implementation into structural components where energy-efficiency and light-weighting are important. Two of the most common alloying elements in magnesium alloys are Aluminum and Zinc. The present work examines impurity diffusion coefficients of Al and Zn in Mg(Zn) and Mg(Al) binary solid solutions, respectively. Experimental investigation is carried out with ternary diffusion couples with polycrystalline alloys. Concentration profiles were measured by electron microprobe micro-analysis and the impurity diffusion coefficients were determined by the Hall Method. Results of Al and Zn impurity diffusion in Mg solid solutions are reported, and examined as a function of composition of Mg solid solution.

  1. The Effect of Hydrogen on the Solid Solution Strengthening and Softening of Nickel.

    DTIC Science & Technology

    1981-11-01

    Afl-A108 654e ILLINOIS UNIV AT URBANA DEPT OF METALLURGY AND MININS--ETC F/6 11/6 THE EFFECT OF HYDROGEN ON THE SOLID SOLUTION STRFNSTNFNING ANfl...RESOLUTION TEST CHART NATIONAL HUR[AU OF STANDARDS 1963 A, " , ..... . .... .. i ....... .. .. . t , LEVEL THE EFFECT OF HYDROGEN ON THE SOLID SOLUTION STRENGTHENING...Availability Codes IIAvail and/or Dist Special THE EFFECT OF HYDROGEN ON THE SOLID SOLUTION STRENGTHENING AND SOFTENING OF NICKEL J. Eastman, F. Heuhaum, T

  2. Existence of multi crystallographic phase in BNT-BTO solid solution near morphotropic phase boundary (MPB)

    NASA Astrophysics Data System (ADS)

    Pradhan, Lagen kumr; Pandey, Rabichandra; Kar, Manoranjan

    2017-05-01

    Lead free Bismuth sodium titanate (BNT) base solid solutions are focusing intensively due to their potential applications as an alternative for Pb-base compounds. In this work, Solid solutions of BNT and barium titanate [(1-x) BNT + x BTO with x=0.00, 0.06, 1.00] have been prepared via conventional solid state route by using the planetary ball mill method. Crystallinity of the samples characterized by XRD and various structural parameters are calculated by employing Rietveld refinement technique. The distinct peak (002/200) splitting around 460 to 470 confirmed the presence of both rhombohedral and tetragonal phase in the solid solution. Dielectric constant of the solid solution near the morphotropic phase boundary (x= 0.06) is significantly enhanced as compared to BNT and BTO. The electrical conductivity of the solid solution was found to reduce w.r.t to BNT. The above results indicate the possible application of BNT-BTO solid solution near MPB in the field of energy storage.

  3. Is Steam an Oxidant or a Reductant for Nickel/Doped-Ceria Cermets?

    PubMed

    Papaefthimiou, Vasiliki; Niakolas, Dimitris K; Paloukis, Fotios; Dintzer, Thierry; Zafeiratos, Spyridon

    2017-01-04

    Nickel/doped-ceria composites are promising electrocatalysts for solid-oxide fuel and electrolysis cells. Very often steam is present in the feedstock of the cells, frequently mixed with other gases, such as hydrogen or CO2 . An increase in the steam concentration in the feed mixture is considered accountable for the electrode oxidation and the deactivation of the device. However, direct experimental evidence of the steam interaction with nickel/doped-ceria composites, with adequate surface specificity, are lacking. Herein we explore in situ the surface state of nickel/gadolinium-doped ceria (NiGDC) under O2 , H2 , and H2 O environments by using near-ambient-pressure X-ray photoelectron and absorption spectroscopies. Changes in the surface oxidation state and composition of NiGDC in response to the ambient gas are observed. It is revealed that, in the mbar pressure regime and at intermediate temperature conditions (500-700 °C), steam acts as an oxidant for nickel but has a dual oxidant/reductant function for doped ceria.

  4. Surface Faceting and Reconstruction of Ceria Nanoparticles.

    PubMed

    Yang, Chengwu; Yu, Xiaojuan; Heißler, Stefan; Nefedov, Alexei; Colussi, Sara; Llorca, Jordi; Trovarelli, Alessandro; Wang, Yuemin; Wöll, Christof

    2017-01-02

    The surface atomic arrangement of metal oxides determines their physical and chemical properties, and the ability to control and optimize structural parameters is of crucial importance for many applications, in particular in heterogeneous catalysis and photocatalysis. Whereas the structures of macroscopic single crystals can be determined with established methods, for nanoparticles (NPs), this is a challenging task. Herein, we describe the use of CO as a probe molecule to determine the structure of the surfaces exposed by rod-shaped ceria NPs. After calibrating the CO stretching frequencies using results obtained for different ceria single-crystal surfaces, we found that the rod-shaped NPs actually restructure and expose {111} nanofacets. This finding has important consequences for understanding the controversial surface chemistry of these catalytically highly active ceria NPs and paves the way for the predictive, rational design of catalytic materials at the nanoscale.

  5. Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy

    NASA Astrophysics Data System (ADS)

    Zhang, F. X.; Zhao, Shijun; Jin, Ke; Xue, H.; Velisa, G.; Bei, H.; Huang, R.; Ko, J. Y. P.; Pagan, D. C.; Neuefeind, J. C.; Weber, W. J.; Zhang, Yanwen

    2017-05-01

    Multielement solid solution alloys are intrinsically disordered on the atomic scale, and many of their advanced properties originate from the local structural characteristics. The local structure of a NiCoCr solid solution alloy is measured with x-ray or neutron total scattering and extended x-ray absorption fine structure (EXAFS) techniques. The atomic pair distribution function analysis does not exhibit an observable structural distortion. However, an EXAFS analysis suggests that the Cr atoms are favorably bonded with Ni and Co in the solid solution alloys. This short-range order (SRO) may make an important contribution to the low values of the electrical and thermal conductivities of the Cr-alloyed solid solutions. In addition, an EXAFS analysis of Ni ion irradiated samples reveals that the degree of SRO in NiCoCr alloys is enhanced after irradiation.

  6. Synthesis of (U,Zr)C solid solutions under exothermic conditions. Revision

    SciTech Connect

    Wang, Lily L.; Moore, H.G.; Gladson, J.W.

    1993-10-01

    The reactions of forming (U,Zr)C solid solutions from their elemental components or similarly less stable reactants such as UC{sub 2} are strongly exothermic due to the high stability of these solid solutions. A simple approach of utilizing this heat of formation energy to assist the solid solution reaction process is intimately mix the less stable reactant powders and pressed them into compact; the compact is then heated to the ignition temperature of the reaction. The feasibility of this reaction method to synthesize (U,Zr) solid solutions has been demonstrated in this study. The preliminary results also show that both the initial composition and the heating rate have a significant effect on the nature of the reaction process. As expected the degree of powder mixing was also found to affect the completeness of the reaction.

  7. Infrared Spectra of Simple Inorganic Ion Pairs in Solid Solution: A Physical Inorganic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Miller, Philip J.; Tong, William G.

    1980-01-01

    Presents a physical inorganic experiment in which large single crystals of the alkali halides doped with divalent ion impurities are prepared easily. Demonstrates the ion pairing of inorganic ions in solid solution. (CS)

  8. THE ROLE OF ELECTRON CONFIGURATION ON PROPERTIES IN DILUTE SOLID SOLUTION ALLOYS

    DTIC Science & Technology

    THE ROLE OF ELECTRON CONFIGURATION ON THE PROPERTIES OF DILUTE SOLID SOLUTION ALLOYS IS DISCUSSED IN TERMS OF THE EFFECT OF DILUTE IMPURITIES ON THE RECRYSTALLIZATION CHARACTERISTICS OF PURE METALLIC ELEMENTS.

  9. Infrared Spectra of Simple Inorganic Ion Pairs in Solid Solution: A Physical Inorganic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Miller, Philip J.; Tong, William G.

    1980-01-01

    Presents a physical inorganic experiment in which large single crystals of the alkali halides doped with divalent ion impurities are prepared easily. Demonstrates the ion pairing of inorganic ions in solid solution. (CS)

  10. Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

    SciTech Connect

    Hernandez, W.Y.; Laguna, O.H.; Centeno, M.A.; Odriozola, J.A.

    2011-11-15

    Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. - Graphical abstract: In this work, Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. Highlights: > Lanthanide doped ceria as catalytic supports for CO oxidation reaction. > A higher concentration of oxygen vacancies promotes a higher catalytic activity. > Eu-doped ceria shows

  11. Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

    NASA Astrophysics Data System (ADS)

    Hernández, W. Y.; Laguna, O. H.; Centeno, M. A.; Odriozola, J. A.

    2011-11-01

    Ce 0.9M0.1O 2- δ mixed oxides ( M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO 2 (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F2g Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce 4+/Ce 3+. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO 2, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area.

  12. Planet Patrol. An Educational Unit on Solid Waste Solutions for Grades 4-6.

    ERIC Educational Resources Information Center

    Shively, Patti J.; And Others

    This educational unit on solid waste solutions is intended to convey to students an understanding of the four methods of solid waste handling, in priority order, as recommended by the Environmental Protection Agency: (1) reduction in the volume of waste produced; (2) recycling and composting; (3) waste combustion, i.e., incineration of waste; and…

  13. Planet Patrol. An Educational Unit on Solid Waste Solutions for Grades 4-6.

    ERIC Educational Resources Information Center

    Shively, Patti J.; And Others

    This educational unit on solid waste solutions is intended to convey to students an understanding of the four methods of solid waste handling, in priority order, as recommended by the Environmental Protection Agency: (1) reduction in the volume of waste produced; (2) recycling and composting; (3) waste combustion, i.e., incineration of waste; and…

  14. CoSb3-IrSb3 solid solutions: preparation and characterization

    NASA Astrophysics Data System (ADS)

    Borshchevsky, Alex; Fleurial, Jean-Pierre; Allevato, Eugene; Caillat, Thierry

    1994-08-01

    The binary antimonide compounds of the skutterudite family have a good potential for thermoelectric applications as recent results at the Jet Propulsion Laboratory (JPL) have shown. However, the room temperature thermal conductivity of these materials is about 10 Wm-1K-1 with an estimated 80% contribution from the lattice. To achieve maximum ZT values, the lattice thermal conductivity needs to be lowered. Because the lattice thermal conductivity of solid solutions can substantially decrease due to the addition of point defect phonon scattering (all state of the art thermoelectric materials are solid solutions), a study of the formation of solid solutions between the antimonide skutterudite compounds is of interest. The existence of CoP3-CoAs3 and CoAs3-CoSb3 solid solutions was already reported in the literature. The preparation and characterization of both p-type and n-type CoSb3-IrSb3 solid solutions by several techniques is reviewed in this paper. The homogeneity of the samples and the existence of solid solutions were investigated using mass density measurements, X-ray diffractometry, microprobe analysis and optical microscopy. The thermal conductivity, the electrical resistivity, and the Hall mobility were measured from 25 to 500 °C. Experimental results showed that solid solutions were successfully formed in a wide range of compositions. Some immiscibility was observed but may be due to the preparation conditions. The changes in the thermoelectric properties indicated the influence of a strong point defect scattering, resulting in large decreases in Hall mobility and thermal conductivity. The potential for high ZT values in CoSb3-IrSb3 solid solutions is discussed.

  15. Effect of Er, Gd, and Nd Co-Dopants on the Properties of Sm-Doped Ceria Electrolyte for IT-SOFC

    NASA Astrophysics Data System (ADS)

    Arabacı, Aliye

    2017-05-01

    Doped ceria electrolytes of Ce0.8Sm0.20O1.90 (SDC), Ce0.8Er0.08Sm0.12O1.90 (ESDC), Ce0.8Gd0.08Sm0.12O1.90 (GSDC), and Ce0.8Nd0.08Sm0.12O1.90 (NSDC) were prepared by a citric-nitrate combustion process. The thermal decomposition of the precursor was investigated by simultaneous thermogravimetric analysis and differential thermal analysis experiments. The phase structure of the calcined and sintered powders was characterized by X-ray diffraction analysis. All of the samples were fluorite-type ceria-based solid solutions. The calcined and sintered powders were also characterized by Fourier transform infrared spectroscopy. Scanning electron microscopy was used to characterize the samples after calcination and sintering. A relative density over 95 percent of the theoretical density was achieved after the sintering process. Electrical conductivities of the sintered samples were measured using the impedance spectra method. The highest ionic conductivity value was found to be 5.28 × 10-2 S cm-1 at 1023 K (750 °C) for GSDC sintered at 1673 K (1400 °C) for 6 hours.

  16. Effect of Er, Gd, and Nd Co-Dopants on the Properties of Sm-Doped Ceria Electrolyte for IT-SOFC

    NASA Astrophysics Data System (ADS)

    Arabacı, Aliye

    2017-02-01

    Doped ceria electrolytes of Ce0.8Sm0.20O1.90 (SDC), Ce0.8Er0.08Sm0.12O1.90 (ESDC), Ce0.8Gd0.08Sm0.12O1.90 (GSDC), and Ce0.8Nd0.08Sm0.12O1.90 (NSDC) were prepared by a citric-nitrate combustion process. The thermal decomposition of the precursor was investigated by simultaneous thermogravimetric analysis and differential thermal analysis experiments. The phase structure of the calcined and sintered powders was characterized by X-ray diffraction analysis. All of the samples were fluorite-type ceria-based solid solutions. The calcined and sintered powders were also characterized by Fourier transform infrared spectroscopy. Scanning electron microscopy was used to characterize the samples after calcination and sintering. A relative density over 95 percent of the theoretical density was achieved after the sintering process. Electrical conductivities of the sintered samples were measured using the impedance spectra method. The highest ionic conductivity value was found to be 5.28 × 10-2 S cm-1 at 1023 K (750 °C) for GSDC sintered at 1673 K (1400 °C) for 6 hours.

  17. CoSb(sub 3)-IrSb(sub 3)Solid Solutions: Preparations and Characterization

    NASA Technical Reports Server (NTRS)

    Borshchevsky, Alex; Fleuial, Jean-Pierre; Allevato, Eugene; Caillat, Thierry

    1994-01-01

    The binary antimonide compounds of the skutterudite family have a good potential for thermoelectric applications as recent results at JPL have shown. However, the room temperature thermal conductivity of these materials is about 10 Wm(sup -1)K(sup -1) with an 80 % contribution from the lattice. To achieve maximum ZT values, the lattice thermal conductivity needs to be lowered. Because the lattice thermal conductivity of solid solutions can substantially decrease due to the addition of point defect phonon scattering (all state-of-the-art thermoelectric materials are solid solutions), a study of the formation of solid solutions between the antimonide skutterudite compounds is of interest. The preparation and characterization of both p-type and n-type CoSb(sub 3)-IrSb(sub 3) solid solutions by several techniques is reviewed in this paper. Experimental results showed that solid solutions were successfully formed in a wide range of compositions. The changes in the thermoelectric properties indicated the influence of a strong point defect scattering, resulting in large decreases in Hall mobility and thermal conductivity. The potential for high ZT values in CoSb(sub 3)-IrSb(sub 3) solid solutions is discussed.

  18. Superficial composition in binary solid solutions A(B): Drastic effect of pure element surface tensions

    NASA Astrophysics Data System (ADS)

    Rolland, A.; Aufray, B.

    1985-10-01

    This paper deals with a comparative study of surface segragation of Pb and Ni respectively from Ag(Pb)(111) and Ag(Ni)(111) solid solutions. A high level of segregation of the solute is observed for both systems characterized by very low solute solubility. However, the superficial composition strongly depends on the relative surface tensions of the pure elements: the solute atoms are strictly on superficial sites when γ solute is smaller than γ solvent; in contrast uppermost layer consists purely of solvent when γ solute is greater than γ solvent. Two schematic distributions in close proximity to the surface are proposed in the last case.

  19. Electrochemical properties of ceria-based intermediate temperature solid oxide fuel cell using microwave heat-treated La0.1Sr0.9Co0.8Fe0.2O3-δ as a cathode

    NASA Astrophysics Data System (ADS)

    Choi, M.-B.; Lee, K.-T.; Yoon, H.-S.; Jeon, S.-Y.; Wachsman, E. D.; Song, S.-J.

    2012-12-01

    The temperature dependence of the chemical diffusion coefficient and the surface exchange coefficient of LSCF1982 is successfully determined from the D.C. conductivity relaxation in the temperature range of 500 ≤ T/°C ≤ 700 and an oxygen partial pressure of 0.21 atm. The kinetic values of chemical diffusion coefficient (D˜) and surface exchange coefficient (k) are 1.85 × 10-5 cm2 s-1 and 2.42 × 10-4 cm s-1 at 650 °C, respectively. The electrochemical properties of La0.1Sr0.9Co0.8Fe0.2O3-δ (LSCF1982) as a cathode for ceria based IT-SOFC are successfully characterized by I-V performance measurement and electrochemical impedance spectroscopy (EIS) in terms of cathode microstructure effects by using microwave heat treatment. The cell with microwave heat-treated cathode shows the higher performance than conventional heat treated cathode. At 650 °C the open circuit potential (OCP) and maximum power density are respectively 0.753 V and 1.79 W cm-2 under 150 sccm of wet hydrogen and air gas flow conditions, and the ohmic and electrode area specific resistance (ASR) are 0.037 and 0.014 Ω cm2, respectively.

  20. A density functional study of defect migration in gadolinium doped ceria.

    PubMed

    Dholabhai, Pratik P; Adams, James B; Crozier, Peter; Sharma, Renu

    2010-07-28

    Oxygen ion conductivity of doped ceria is observed to be two-three orders of magnitude higher than yttria stabilized zirconia, the most widely used solid electrolyte material at temperatures below 600 degrees C. Gadolinium doped ceria (GDC) is known to be one of the most promising solid electrolyte materials for operation of solid oxide fuel cells below 600 degrees C. To understand the atomic defect migration in GDC, we have used total energy calculations within the framework of density functional theory to follow oxygen vacancy migration in GDC. We report activation energies for various oxygen vacancy migration pathways in GDC. Oxygen vacancy formation and migration were evaluated for first, second, and third nearest neighbor positions to a Gd(3+) ion. Due to the comparable ionic radii of Gd(3+) and host Ce(4+) ions, the first nearest neighbor site with respect to the dopant cation is found to be the most favorable oxygen vacancy formation site. The migration pathway where the vacancy migrates from a second to first nearest neighbor is found to be most favorable. The calculated activation energies for oxygen vacancy migration in GDC are compared against the reported measured and calculated values from the literature. This work will provide a foundation for the development of a kinetic lattice Monte Carlo model for vacancy diffusion in GDC, which will improve the understanding of oxygen ion conductivity in doped ceria.

  1. Solid-solute phase equilibria in aqueous solution: VII. A re-interpretation of magnesian calcite stabilities

    NASA Astrophysics Data System (ADS)

    Königsberger, Erich; Gamsjäger, Heinz

    1992-11-01

    It is proposed to model magnesian calcites thermodynamically as dilute solid solutions of MgCO 3 in CaCO 3 according to the Unified Interaction Parameter Formalism ( BALE and PELTON, Met. Trans. A21A, 1997-2002, 1990). In this case both stoichiometric saturation and precipitation data of synthetic magnesian calcites taken from literature can consistently be explained.

  2. Oversolubility in the microvicinity of solid-solution interfaces.

    PubMed

    Bergonzi, Isabelle; Mercury, Lionel; Simon, Patrick; Jamme, Frédéric; Shmulovich, Kirill

    2016-06-01

    Water-solid interactions at the macroscopic level (beyond tens of nanometers) are often viewed as the coexistence of two bulk phases with a sharp interface in many areas spanning from biology to (geo)chemistry and various technological fields (membranes, microfluidics, coatings, etc.). Here we present experimental evidence indicating that such a view may be a significant oversimplification. High-resolution infrared and Raman experiments were performed in a 60 × 20 μm(2) quartz cavity, synthetically created and initially filled with demineralized water. The IR mapping (3 × 3 μm(2) beam size) performed using the SOLEIL synchrotron radiation source displays two important features: (i) the presence of a dangling free-OH component, a signature of hydrophobic inner walls; (ii) a shift of the OH-stretching band which essentially makes the 3200 cm(-1) sub-band predominate over the usual main component at around 3400 cm(-1). Raman maps confirmed these signatures (though less marked than IR's) and afforded a refined spatial distribution of this interfacial signal. This spatial resolution, statistically treated, results in a puzzling image of a 1-3 μm thick marked-liquid layer along the entire liquid-solid interface. The common view is then challenged by this strong evidence that a μm-thick layer analogous to an interphase forms at the solid-liquid interface. The thermodynamic counterpart of the vibrational shifts amounts to around +1 kJ mol(-1) at the interface with a rapidly decreasing signature towards the cavity centre, meaning that vicinal water may form a reactive layer, of micrometer thickness, expected to have an elevated melting point, a depressed boiling temperature, and enhanced solvent properties.

  3. Control of molecular rotor rotational frequencies in porous coordination polymers using a solid-solution approach.

    PubMed

    Inukai, Munehiro; Fukushima, Tomohiro; Hijikata, Yuh; Ogiwara, Naoki; Horike, Satoshi; Kitagawa, Susumu

    2015-09-30

    Rational design to control the dynamics of molecular rotors in crystalline solids is of interest because it offers advanced materials with precisely tuned functionality. Herein, we describe the control of the rotational frequency of rotors in flexible porous coordination polymers (PCPs) using a solid-solution approach. Solid-solutions of the flexible PCPs [{Zn(5-nitroisophthalate)x(5-methoxyisophthalate)1-x(deuterated 4,4'-bipyridyl)}(DMF·MeOH)]n allow continuous modulation of cell volume by changing the solid-solution ratio x. Variation of the isostructures provides continuous changes in the local environment around the molecular rotors (pyridyl rings of the 4,4'-bipyridyl group), leading to the control of the rotational frequency without the need to vary the temperature.

  4. High-temperature temporal stability of selected oxidizers as solids and in aqueous solutions. Interim report

    SciTech Connect

    Pellenbarg, R.E.; Smiroldo

    1986-08-08

    Various potential decontamination agents were examined as solids and in aqueous solutions for long-term stability at high temperatures. The following oxidizers were assayed iodometrically: the hypochlorite salts of calcium and lithium, sodium dischloroisocyanurate (PACE) and the preoxygen compounds sodium perborate, sodium peroxydisulfate, sodium percarbonate, and magnesium monoperoxyphthalate (H-48). The inorganic peroxide solids and the solid sodium dischloroisoyanurate were stable at 80 C, while the organic peroxide solids and the hypochlorite salts deteriorated markedly within 72 hours. In freshwater solutions of 0.01 N or less, the inorganic hypochlorite and peroxide salts decomposed slowly at 60 c. Conversely, the sodium dischloroisocyanurate, magnesium monoperoxyphthalate, and sodium percarbonate solutions exhibited near complete decomposition in 24 hours.

  5. Strain Engineering Defect Concentrations in Reduced Ceria for Improved Electro-Catalytic Performance

    DTIC Science & Technology

    2014-06-30

    oxygen surface exchange coefficient ( ), equilibrium oxygen vacancy concentration ( ), and catalytic activity ( ), of gadolinium doped ceria (GDC...by producing gadolinium doped ceria thick films and then measuring them under low atmospheres (where ceria becomes reduced). Unfortunately as shown

  6. On the structure of vanadia supported on ceria nanoshapes

    SciTech Connect

    Wu, Zili; Li, Meijun; Overbury, Steven {Steve} H

    2012-01-01

    Vanadia supported on ceria nanocrystals with defined surface planes, i.e., ceria nanoshapes including rods, cubes and octahedra were successfully synthesized. The effect of surface structure of these ceria nanoshapes on the structure of surface vanadia species as well as the formation of CeVO4 was investigated in details via in situ visible and UV Raman spectroscopy. The surface vanadia species on ceria nanoshapes evolve from monomeric vanadia to dimeric, trimeric, polymeric vanadia, and eventually crystalline V2O5 and CeVO4 as a function of vanadia loading. As expected, the nanoshaped ceria provides a rather homogeneous platform for anchoring vanadia, especially at low vanadia loading leading to only monomeric species, in contrast to the co-existence of different vanadia species on polycrystalline ceria even at extremely low vanadia loading. The formation of CeVO4 from the reaction between surface vanadia species and ceria was compared on the three ceria nanoshapes with similar surface vanadia density. It was found that both the surface structure and amount of defect sites of the ceria nanoshapes play major roles in the production of CeVO4. The easiest formation of CeVO4 on ceria rods is attributed to the lowest surface oxygen vacancy formation energy and the largest amount of defect sites available on the rods surface.

  7. Precipitation in Al–Mg solid solution prepared by solidification under high pressure

    SciTech Connect

    Jie, J.C.; Wang, H.W.; Zou, C.M.; Wei, Z.J.; Li, T.J.

    2014-01-15

    The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solution appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.

  8. Ab initio identified design principles of solid-solution strengthening in Al.

    PubMed

    Ma, Duancheng; Friák, Martin; von Pezold, Johann; Raabe, Dierk; Neugebauer, Jörg

    2013-04-01

    Solid-solution strengthening in six Al-X binary systems is investigated using first-principle methods. The volumetric mismatch parameter and the solubility enthalpy per solute were calculated. We derive three rules for designing solid-solution strengthened alloys: (i) the solubility enthalpy per solute is related to the volumetric mismatch by a power law; (ii) for each annealing temperature, there exists an optimal solute-volume mismatch to achieve maximum strength; and (iii) the strengthening potential of high volumetric mismatch solutes is severely limited by their low solubility. Our results thus show that the thermodynamic properties of the system (here Al-X alloys) set clear upper bounds to the achievable strengthening effects owing to the reduced solubility with increasing volume mismatch.

  9. Characterization of Cu, Ag and Pt added La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ and gadolinia-doped ceria as solid oxide fuel cell electrodes by temperature-programmed techniques

    NASA Astrophysics Data System (ADS)

    Huang, Ta-Jen; Shen, Xian-De; Chou, Chien-Liang

    Cu, Ag and Pt added La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ (LSCF) and gadolinia-doped ceria (GDC) were analyzed by the temperature-programmed techniques for their characteristics as either the cathode or the anode of the solid oxide fuel cells (SOFCs). Temperature-programmed oxidation using CO 2 was used to characterize the cathode materials while temperature-programmed reduction (TPR) using H 2 and TPR using CO were used to characterize the anode materials. These techniques can offer an easy screening of the materials as the SOFC electrodes. The effects of adding Cu, Ag and Pt to LSCF for the cathodic reduction activity and the anodic oxidation activity are different-Cu > Ag > Pt for reduction and Pt > Cu > Ag for oxidation. The CO oxidation activities are higher than the H 2 oxidation activities. Adding GDC to LSCF can increase both reduction and oxidation activities. The LSCF-GDC composite has a maximum activity for either reduction or oxidation when LSCF/GDC is 2 in weight.

  10. Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy

    DOE PAGES

    Zhang, F. X.; Zhao, Shijun; Jin, Ke; ...

    2017-05-19

    Multi-element solid solution alloys are intrinsically disordered on the atomic scale, and many of their advanced properties originate from the unique local structural characteristics. We measured the local structure of a NiCoCr solid solution alloy with X-ray/neutron total scattering and extended X-ray absorption fine structure (EXAFS) techniques. The atomic pair distribution function analysis (PDF) did not exhibit distinct structural distortion. But, EXAFS analysis suggested that the Cr atoms are favorably bonded with Ni and Co in the solid solution alloys. This short-range order (SRO) plays a role in the distinct low values of electrical and thermal conductivities in Ni-based solidmore » solution alloys when Cr is incorporated. Both the long-range and local structures of the NiCoCr alloy upon Ni ion irradiation were studied and an irradiation-induced enhancement of SRO was found.« less

  11. Hierarchically nanoporous ceria nanoparticles with a high-surface area: synthesis, characterization, and their catalytic activity.

    PubMed

    Ge, Jiechao; Zhong, Liangshu; Zhuo, Linhai; Tang, Bo; Song, Weiguo

    2011-01-01

    A redox route based on ethylene glycol mediated process was developed to synthesize hierarchically nanoporpous ceria nanoparticles (ceria HNPNPs). The synthesized ceria HNPNPs are composed of building blocks fabricated with cubic ceria nanocrystals of several nanometers in diameter. Scanning electron microscopy was performed to investigate the evolution process of ceria precursor, and a two-step growth process was suggested for the morphology evolution. The synthesized ceria HNPNPs exhibit high surface area, which lead to high catalytic activity for CO oxidation.

  12. Colloidal quantum dot solids for solution-processed solar cells

    NASA Astrophysics Data System (ADS)

    Yuan, Mingjian; Liu, Mengxia; Sargent, Edward H.

    2016-03-01

    Solution-processed photovoltaic technologies represent a promising way to reduce the cost and increase the efficiency of solar energy harvesting. Among these, colloidal semiconductor quantum dot photovoltaics have the advantage of a spectrally tuneable infrared bandgap, which enables use in multi-junction cells, as well as the benefit of generating and harvesting multiple charge carrier pairs per absorbed photon. Here we review recent progress in colloidal quantum dot photovoltaics, focusing on three fronts. First, we examine strategies to manage the abundant surfaces of quantum dots, strategies that have led to progress in the removal of electronic trap states. Second, we consider new device architectures that have improved device performance to certified efficiencies of 10.6%. Third, we focus on progress in solution-phase chemical processing, such as spray-coating and centrifugal casting, which has led to the demonstration of manufacturing-ready process technologies.

  13. Surface Defects Enhanced Visible Light Photocatalytic H2 Production for Zn-Cd-S Solid Solution.

    PubMed

    Zhang, Xiaoyan; Zhao, Zhao; Zhang, Wanwan; Zhang, Guoqiang; Qu, Dan; Miao, Xiang; Sun, Shaorui; Sun, Zaicheng

    2016-02-10

    In order to investigate the defect effect on photocatalytic performance of the visible light photocatalyst, Zn-Cd-S solid solution with surface defects is prepared in the hydrazine hydrate. X-ray photoelectron spectra and photoluminescence results confirm the existence of defects, such as sulfur vacancies, interstitial metal, and Zn and Cd in the low valence state on the top surface of solid solutions. The surface defects can be effectively removed by treating with sulfur vapor. The solid solution with surface defect exhibits a narrower band gap, wider light absorption range, and better photocatalytic perfomance. The optimized solid solution with defects exhibits 571 μmol h(-1) for 50 mg photocatalyst without loading Pt as cocatalyst under visible light irradiation, which is fourfold better than that of sulfur vapor treated samples. The wavelength dependence of photocatalytic activity discloses that the enhancement happens at each wavelength within the whole absorption range. The theoretical calculation shows that the surface defects induce the conduction band minimum and valence band maximum shift downward and upward, respectively. This constructs a type I junction between bulk and surface of solid solution, which promotes the migration of photogenerated charges toward the surface of nanostructure and leads to enhanced photocatalytic activity. Thus a new method to construct highly efficient visible light photocatalysts is opened.

  14. Organic solid solution composed of two structurally similar porphyrins for organic solar cells.

    PubMed

    Zhen, Yonggang; Tanaka, Hideyuki; Harano, Koji; Okada, Satoshi; Matsuo, Yutaka; Nakamura, Eiichi

    2015-02-18

    A solid solution of a 75:25 mixture of tetrabenzoporphyrin (BP) and dichloroacenaphtho[q]tribenzo[b,g,l]porphyrin (CABP) forms when they are generated in a matrix of (dimethyl(o-anisyl)silylmethyl)(dimethylphenylsilylmethyl)[60]fullerene. This solid solution provides structural and optoelectronic properties entirely different from those of either pristine compounds or a mixture at other blending ratios. The use of this BP:CABP solid solution for organic solar cell (OSC) devices resulted in a power conversion efficiency (PCE) value higher by 16 and 300% than the PCE values obtained for the devices using the single donor BP and CABP, respectively, in a planar heterojunction architecture. This increase originates largely from the increase in short circuit current density, and hence by enhanced charge carrier separation at the donor/acceptor interface, which was probably caused by suitable energy level for the solid solution state, where electronic coupling between the two porphyrins occurred. The results suggest that physical and chemical modulation in solid solution is beneficial as an operationally simple method to enhance OSC performance.

  15. Solid Solution Effects on the MgAl2O4 System

    SciTech Connect

    O'Hara, Kelley; Smith, Jeffrey D; Hemrick, James Gordon

    2009-01-01

    Phase relations between the binaries MgAl2O4-ZnAl2O4 and MgAl2O4-MgGa2O4 were studied. Stoichiometric MgAl2O4 spinel can be formed in the laboratory through a coprecipitation method. Complete solid solution formation in the MgAl2O4-MgGa2O4 system was confirmed through X-ray diffraction (XRD) analysis. XRD analysis of the MgAl2O4-ZnAl2O4 system did not confirm solid solution due to the similar lattice parameters of the two end points, however, previous studies have shown that complete solid solution does form. Thermal conductivity data is pending and will be included in the presentation. Based on previous experimentation and open literature, it is suspected that thermal conductivity will be decreased with the addition of solid solution. With increased amounts of disruption to the lattice from solid solution it is also theorized that the temperature at which the mean free path still impacts thermal conductivity could be increased.

  16. Bubble-solid interactions in water and electrolyte solutions.

    PubMed

    Pushkarova, Rada A; Horn, Roger G

    2008-08-19

    Surface forces between an air bubble and a flat mica surface immersed in aqueous electrolyte solutions have been investigated using a modified surface force apparatus. An analysis of the deformation of the air bubble with respect to the mutual position of the bubble and the mica surface, the capillary pressure, and the disjoining pressure allows the air-liquid surface electrical potential to be determined. The experiments show that a long-range, double-layer repulsion acts between the mica (which is negatively charged) and an air bubble in water and in various electrolyte solutions at low concentration, thereby indicating that the air bubble surface is negatively charged. However, there is clear evidence that charge regulation occurs at the air-water interface to maintain a constant surface potential, and as a result of this, the charge at this interface changes from negative to positive as the bubble approaches the mica surface. Because of the attraction that arises as a result of the charge reversal, a finite force is required to separate the bubble from the mica, though the mica remains wetted by the aqueous phase. At the low concentrations investigated, the potential on the gas-liquid interface is independent of the electrolyte type within experimental uncertainty.

  17. Template engaged synthesis of hollow ceria-based composites

    NASA Astrophysics Data System (ADS)

    Chen, Guozhu; Rosei, Federico; Ma, Dongling

    2015-03-01

    Hollow ceria-based composites, which consist of noble metal nanoparticles or metal oxides as a secondary component, are being studied extensively for potential applications in heterogeneous catalysis. This is due to their unique features, which exhibit the advantages of a hollow structure (e.g. high surface area and low weight), and also integrate the properties of ceria and noble metals/metal oxides. More importantly, the synergistic effect between constituents in hollow ceria-based composites has been demonstrated in various catalytic reactions. In this feature article, we summarize the state-of-the-art in the synthesis of hollow ceria-based composites, including traditional hard-templates and more recently, sacrificial-template engaged strategies, highlighting the key role of selected templates in the formation of hollow composites. In addition, the catalytic applications of hollow ceria-based composites are briefly surveyed. Finally, challenges and perspectives on future advances of hollow ceria-based composites are outlined.

  18. Template engaged synthesis of hollow ceria-based composites.

    PubMed

    Chen, Guozhu; Rosei, Federico; Ma, Dongling

    2015-03-19

    Hollow ceria-based composites, which consist of noble metal nanoparticles or metal oxides as a secondary component, are being studied extensively for potential applications in heterogeneous catalysis. This is due to their unique features, which exhibit the advantages of a hollow structure (e.g. high surface area and low weight), and also integrate the properties of ceria and noble metals/metal oxides. More importantly, the synergistic effect between constituents in hollow ceria-based composites has been demonstrated in various catalytic reactions. In this feature article, we summarize the state-of-the-art in the synthesis of hollow ceria-based composites, including traditional hard-templates and more recently, sacrificial-template engaged strategies, highlighting the key role of selected templates in the formation of hollow composites. In addition, the catalytic applications of hollow ceria-based composites are briefly surveyed. Finally, challenges and perspectives on future advances of hollow ceria-based composites are outlined.

  19. Characterization of mesoporosity in ceria particles using electron microscopy.

    PubMed

    Shih, Shao-Ju; Herrero, Pilar Rodrigo; Li, Guoqiang; Chen, Chin-Yi; Lozano-Perez, Sergio

    2011-02-01

    The geometry and three-dimensional (3D) morphology of the ceria particles synthesized by spray pyrolysis (SP) from two different precursors--cerium acetate hydrate and cerium nitrate hydrate (CeA and CeN ceria particles)--were characterized by transmission electron microscopy and electron tomography. Results were compared with surface area measurements, confirming that the surface area of CeA ceria particles is twice as large as that of CeN ceria particles. This result was supported by 3D microstructural observations, which have revealed that CeA ceria particles contain open pores (connected to surfaces) and closed pores (embedded in particles), while CeN ceria particles only contained closed pores. This experimental result suggests that the type of porosity is controlled by the precursors and could be related to their melting temperature during the heating process in SP.

  20. Surface stabilized nanosized Ce(x)Zr(1-x)O(2) solid solutions over SiO(2): characterization by XRD, Raman, and HREM techniques.

    PubMed

    Reddy, Benjaram M; Lakshmanan, Pandian; Khan, Ataullah; Loridant, Stéphane; López-Cartes, Carlos; Rojas, Teresa C; Fernandez, Asunción

    2005-07-21

    Ce(x)Zr(1)(-)(x)O(2) solid solutions deposited over silica surface were investigated by X-ray diffraction (XRD), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques in order to understand the role of silica support and the temperature stability of these composite oxides. For the purpose of comparison, an unsupported Ce(x)Zr(1)(-)(x)O(2) was also synthesized and subjected to characterization by various techniques. The Ce(x)Zr(1)(-)(x)O(2)/SiO(2) (CZ/S) (1:1:2 mole ratio based on oxides) was synthesized by depositing Ce(x)Zr(1)(-)(x)O(2) solid solution over a colloidal SiO(2) support by a deposition precipitation method and unsupported Ce(x)Zr(1)(-)(x)O(2) (CZ) (1:1 mole ratio based on oxides) was prepared by a coprecipitation procedure, and the obtained catalysts were subjected to thermal treatments from 773 to 1073 K. The XRD measurements disclose the presence of cubic phases with the composition Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) in CZ samples, while CZ/S samples possess Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), and Ce(0.5)Zr(0.5)O(2) in different proportions. The crystallinity of these phases increased with increasing calcination temperature. The cell a parameter estimations indicate contraction of ceria lattice due to the incorporation of zirconium cations into the CeO(2) unit cell. Raman measurements indicate the presence of oxygen vacancies, lattice defects, and displacement of oxygen ions from their normal lattice positions in both the series of samples. The HREM results reveal, in the case of CZ/S samples, a well-dispersed nanosized Ce-Zr-oxides over the surface of amorphous SiO(2). The structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic geometry and exhibit high thermal stability. Oxygen storage capacity measurements by a thermogravimetric method reveal a substantial enhancement in the oxygen

  1. Solid-liquid Phase Equilibria of U(VI) in NaCl Solutions

    NASA Astrophysics Data System (ADS)

    Díaz Arocas, P.; Grambow, B.

    1998-01-01

    Solid-liquid phase equilibria and equilibrium phase relationships of U(VI) in up to 5 m NaCl solutions were studied by analyzing the precipitation process in initially oversaturated solutions at different pH values. Comparison to corresponding behavior in NaClO 4 media is made. Solid precipitates and solution concentrations of U were characterized as a function of time and pH. In NaClO 4 media schoepite (UO 3·2H 2O) was found to be the stable phase between pH 4 and 6. By contrast, in NaCl media, sodium polyuranates formed. For a given NaCl concentration and pH, differences in the solubility concentration of about 3 orders of magnitude were observed, as attributed to metastability with respect to crystallinity and Na/U ratio of the precipitates. Average solubility constants log K° soere calculated for schoepite (log K° so = 5.37 ± 0.25) and for Na 0.33UO 3.16·2H 2O (log K° so = 7.13 ± 0.15). Based on these data and together with a critical review of literature data on schoepite and polyuranates a solid solution model is developed, describing composition and phase transformation of Na-polyuranates as a function of the activity ratio Na/H in solution. Solid solution formation is rationalized within the structural context of uranyl mineral sheet structure topologies and interlayer water properties.

  2. Soil solid-phase controls lead activity in soil solution.

    PubMed

    Badawy, S H; Helal, M I D; Chaudri, A M; Lawlor, K; McGrath, S P

    2002-01-01

    Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P < 0.01 and R2 = -0.89, P < 0.01, respectively). It could be predicted in soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.

  3. Influence of gadolinium doping on the structure and defects of ceria under fuel cell operating temperature

    NASA Astrophysics Data System (ADS)

    Acharya, S. A.; Gaikwad, V. M.; Sathe, V.; Kulkarni, S. K.

    2014-03-01

    Correlation between atomic positional shift, oxygen vacancy defects, and oxide ion conductivity in doped ceria system has been established in the gadolinium doped ceria system from X-ray diffraction (XRD) and Raman spectroscopy study at operating temperature (300-600 °C) of Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC). High temperature XRD data are used to quantify atomic positional shift from mean position with temperature. The Raman spectroscopy study shows additional vibration modes related to ordering of defect spaces (GdCe'-Vo••)* and (2GdCe'-Vo••)x generated due to association of oxygen vacancies and reduced cerium or dopant cations site (Gd3+), which disappear at 450 °C; indicating oxygen vacancies dissociation from the defect complex. The experimental evidences of cation-anion positional shifting and oxygen vacancies dissociation from defect complex in the IT-SOFC operating temperature are discussed to correlate with activation energy for ionic conductivity.

  4. Creating single-atom Pt-ceria catalysts by surface step decoration

    PubMed Central

    Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii; Tran, Nguyen-Dung; Negreiros, Fabio R.; Vorokhta, Mykhailo; Skála, Tomáš; Matolínová, Iva; Mysliveček, Josef; Matolín, Vladimír; Fabris, Stefano

    2016-01-01

    Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces—monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt2+ ions in planar PtO4 moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt2+ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts. PMID:26908356

  5. Creating single-atom Pt-ceria catalysts by surface step decoration

    NASA Astrophysics Data System (ADS)

    Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii; Tran, Nguyen-Dung; Negreiros, Fabio R.; Vorokhta, Mykhailo; Skála, Tomáš; Matolínová, Iva; Mysliveček, Josef; Matolín, Vladimír; Fabris, Stefano

    2016-02-01

    Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces--monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt2+ ions in planar PtO4 moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt2+ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts.

  6. Charge distribution and local structure of americium-bearing thorium oxide solid solutions.

    PubMed

    Carvajal-Nunez, U; Prieur, D; Vitova, T; Somers, J

    2012-11-05

    The electronical and structural properties of Th(0.80)Am(0.20)O(2-x) materials have been studied by the coupling of X-ray diffraction and X-ray absorption spectroscopy techniques. A substoichiometric fluorite Th(IV)(0.80)Am(III)(0.20)O(1.90) solid solution is found following sintering in moisturized Ar-H(2). In contrast, heating of this sample in air leads to a nondefective fluorite Th(IV)(0.80)Am(IV)(0.20)O(2.00) solid solution. The structures of these solid solution compounds were fully characterized by assessing the interatomic distances, the coordination numbers, and the structural disorder. The effect of the sintering atmosphere on these crystallographical parameters and on the cation valences has been determined and the capability of ThO(2) to accommodate tri- and tetravalent actinides in the fluorite structure assessed.

  7. Visualization of the atomic structure of solid solutions with the NaCl structure

    NASA Astrophysics Data System (ADS)

    Babanov, Yu. A.; Ponomarev, D. A.; Ustinov, V. V.

    2015-04-01

    It has been shown how an atomic cluster for a solid solution with a rock salt structure can be constructed using the Pauling model. Simulation has been performed for 343000 ions of Ni x Zn1 - x O3 ( x = 0, 0.3, 0.5, 0.7, 1.0) oxide substitutional solid solutions. Coordinates of all cluster ions are obtained and distribution functions of ion pairs (Ni-O, Ni-Ni, Ni-Zn, Zn-Zn, Zn-O, O-O) are constructed as functions of distance. The shape of the normal distribution indicates the existence of bounded chaos in the system of oxide solid solutions. The width of the Gaussian distribution function is determined by the difference of metal ionic radii. The results are in agreement with both X-ray diffraction and EXAFS spectroscopy data.

  8. Existence of fluorite-type solid solutions in alkali metal-uranium-oxygen systems

    NASA Astrophysics Data System (ADS)

    Sali, S. K.; Sampath, S.; Venugopal, V.

    1996-09-01

    The solubilities of Li 2O and Na 2O in UO 2 + x have been established for the first time. They form cubic solid solutions, Li yU 1 - yO 2 + x and Na yU 1 - yO 2 + x ( y = 0-0.2 and x ⪋ 0). The lattice parameters of these solid solutions can be expressed, respectively, as a function of x and y: a0(nm) = 0.54704 - 0.0104x - 0.0495y and a0(nm) = 0.54704 - 0.0102 x - 0.0345 y. Oxidation of these solid solutions in air up to 773 K gave cubic MO 2 + x and the kinetics of oxidation was found to be controlled by oxygen chemical diffusion similar to oxidation of UO 2.

  9. Isotope Labeling for Solution and Solid-State NMR Spectroscopy of Membrane Proteins

    PubMed Central

    Verardi, Raffaello; Traaseth, Nathaniel J.; Masterson, Larry R.; Vostrikov, Vitaly V.; Veglia, Gianluigi

    2013-01-01

    In this chapter, we summarize the isotopic labeling strategies used to obtain high-quality solution and solid-state NMR spectra of biological samples, with emphasis on integral membrane proteins (IMPs). While solution NMR is used to study IMPs under fast tumbling conditions, such as in the presence of detergent micelles or isotropic bicelles, solid-state NMR is used to study the structure and orientation of IMPs in lipid vesicles and bilayers. In spite of the tremendous progress in biomolecular NMR spectroscopy, the homogeneity and overall quality of the sample is still a substantial obstacle to overcome. Isotopic labeling is a major avenue to simplify overlapped spectra by either diluting the NMR active nuclei or allowing the resonances to be separated in multiple dimensions. In the following we will discuss isotopic labeling approaches that have been successfully used in the study of IMPs by solution and solid-state NMR spectroscopy. PMID:23076578

  10. Mechanosynthesis and structural characterization of nanocrystalline Ce{sub 1–x}Y{sub x}O{sub 2–δ} (x=0.1–0.35) solid solutions

    SciTech Connect

    Fabián, Martin; Antić, Bratislav; Girman, Vladimír; Vučinić-Vasić, Milica; Kremenović, Aleksandar; Suzuki, Shigeru; Hahn, Horst; Šepelák, Vladimír

    2015-10-15

    A series of nanostructured fluorite-type Ce{sub 1–x}Y{sub x}O{sub 2–δ} (0≤x≤0.35) solid solutions, prepared via high-energy milling of the CeO{sub 2}/Y{sub 2}O{sub 3} mixtures, are investigated by XRD, HR-TEM, EDS and Raman spectroscopy. For the first time, complementary information on both the long-range and short-range structural features of mechanosynthesized Ce{sub 1–x}Y{sub x}O{sub 2–δ}, obtained by Rietveld analysis of XRD data and Raman spectroscopy, is provided. The lattice parameters of the as-prepared solid solutions decrease with increasing yttrium content. Rietveld refinements of the XRD data reveal increase in microstrains in the host ceria lattice as a consequence of yttrium incorporation. Raman spectra are directly affected by the presence of oxygen vacancies; their existence is evidenced by the presence of vibration modes at ~560 and ~600 cm{sup –1}. The detailed spectroscopic investigations enable us to separate extrinsic and intrinsic origin of oxygen vacancies. It is demonstrated that mechanosynthesis can be successfully employed in the one-step preparation of nanocrystalline Ce{sub 1–x}Y{sub x}O{sub 2–δ} solid solutions. - Graphical abstract: Mechanosynthesis of nanocrystalline Ce{sub 1–x}Y{sub x}O{sub 2–δ} (x=0.1–0.35) solid solutions. - Highlights: • One-step mechanosynthesis of nanoscale Ce{sub 1–x}Y{sub x}O{sub 2–δ} (0≤x≤0.35) solid solutions. • Complementary information on the long-range and short-range structural features of mechanosynthesized Ce{sub 1–x}Y{sub x}O{sub 2–δ} is provided. • Structural variations as a response to the yttrium doping. • Separation of extrinsic and intrinsic origin of the induced oxygen vacancies.

  11. Crystal Chemistry of MgAl2O4 Spinel Solid Solution

    NASA Astrophysics Data System (ADS)

    Yoshiasa, Akira; Maekawa, Hidemi; Sugiyama, Kazumasa

    Considerable efforts have been devoted to the structural studies of spinel group minerals or type compounds because of their importance as constituents of the Earth’s crust and mantle. Despite their simple structures, many spinel type compounds exhibit complex disordering phenomena involving the mixing of cation on two sites, which have important consequences for both thermodynamic and physical properties. The cation distributions and the structural variation in MgAl2-xGaxO4 solid-solution have been clarified using 27Al MAS NMR measurements and single crystal X-ray diffraction. The determined local distance in the solid solution corresponds with the bond distance expected from the effective ionic radii except Al-O distance in the tetrahedral site. We have revealed that the Al-O distance in the tetrahedral site in spinel solid solution is about 0.15 Å longer than the expected value. Boron is the same group element as Al and Ga and its ionic radius is considerably small. Single crystals of MgAl2-xBxO4 spinel were synthesized under high pressure and high temperature. The maximum content of boron was about x = 0.13 at 1273 K and 11 GPa. The smallest B ion occupies the octahedral site in top priority in the spinel solid solution of the Mg-Al-B systems. The B3+ ions can replace considerably bigger Al3+ ion under pressure. These spinel solid-solutions are largely disordered crystals. Only the positional shifts of oxygen ion have been relaxing the disorder in the solid solution.

  12. Catalytic properties of nanoscale iron-doped zirconia solid-solution aerogels.

    PubMed

    Chen, Lifang; Hu, Juncheng; Richards, Ryan M

    2008-05-16

    Nanoscale iron-doped zirconia solid-solution aerogels are prepared via a simple ethanol thermal route using zirconyl nitrate and iron nitrate as starting materials, followed by a supercritical fluid drying process. Structural characteristics are investigated by means of powder X-ray diffraction (XRD), thermal analyses (TG/DTA), N(2) adsorption measurements and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results show that the resulting iron-doped solid solutions are metastable tetragonal zirconia which exhibit excellent dispersibility and high solubility of iron oxide. Further, when the Fe:(Fe+Zr) ratio x is lower than 0.10, all of the Fe(3+) ions can be incorporated into ZrO(2) by substituting Zr(4+) to form Zr(1-) (x)Fe(x)O(y) solid solutions. Moreover, for the first time, an additional hydroxyl group band that is not present in pure ZrO(2) is observed by DRIFTS for the Zr(Fe)O(2) solid solution. This is direct evidence of Fe(3+) ions incorporated into ZrO(2). These Zr(1-) (x)Fe(x)O(y) solid solutions are excellent catalysts for the solvent-free aerobic oxidation of n-hexadecane using air as the oxidant under ambient conditions. The Zr(0.8)Fe(0.2)O(y) solid-solution catalyst demonstrates the best catalytic properties, with the conversion of n-hexadecane reaching 36.2 % with 48 % selectivity for ketones and 24 % selectivity for alcohols and it can be recycled five times without significant loss of activity.

  13. Structural investigations of (La,Pu)PO4 monazite solid solutions: XRD and XAFS study

    NASA Astrophysics Data System (ADS)

    Arinicheva, Yulia; Popa, Karin; Scheinost, Andreas C.; Rossberg, André; Dieste-Blanco, Oliver; Raison, Philippe; Cambriani, Andrea; Somers, Joseph; Bosbach, Dirk; Neumeier, Stefan

    2017-09-01

    A solid state method was used to synthesize La1-xPuxPO4 (x = 0.01, 0.05, 0.10, 0.15, (0.5)) solid solutions with monazite structure. XRD measurements of the compounds with x = 0.50 revealed the formation of two phases: (La,Pu)PO4-monazite and a cubic phase (PuO2). Pure-phase La1-xPuxPO4-monazite solid solutions were obtained for materials with x = 0.00-0.15 and confirmed by a linear dependence of the lattice parameters on composition according to Vegard's law. X-ray absorption spectroscopy (XAS) analysis at the Pu-LIII and La-LIII edges confirmed the +III valence state of plutonium in the monazite solid solutions. The local environment of Pu is PuPO4-like along the solid solution series, except for the longest fitted cation-cation distance, which may be an indication of cluster formation consisting of a few Pu-atoms in the La-Pu-monazite lattice.

  14. Ferroelectromagnetic solid solutions on the base piezoelectric ceramic materials for components of micromechatronics

    NASA Astrophysics Data System (ADS)

    Bochenek, Dariusz; Zachariasz, Radosław; Niemiec, Przemysław; Ilczuk, Jan; Bartkowska, Joanna; Brzezińska, Dagmara

    2016-10-01

    In the presented work, a ferroelectromagnetic solid solutions based on PZT and ferrite powders have been obtained. The main aim of combination of ferroelectric and magnetic powders was to obtain material showing both electric and magnetic properties. Ferroelectric ceramic powder (in amount of 90%) was based on the doped PZT type solid solution while magnetic component was nickel-zinc ferrite Ni1-xZnxFe2O4 (in amount of 10%). The synthesis of components of ferroelectromagnetic solid solutions was performed using the solid phase sintering. Final densification of synthesized powder has been done using free sintering. The aim of the work was to obtain and examine in the first multicomponent PZT type ceramics admixed with chromium with the following chemical composition Pb0.94Sr0.06(Zr0.46Ti0.54)O3+0.25 at% Cr2O3 and next ferroelectromagnetic solid solution based on a PZT type ferroelectric powder (Pb0.94Sr0.06(Zr0.46Ti0.54)O3+0.25 at% Cr2O3) and nickel-zinc ferrite (Ni0.64Zn0.36Fe2O4), from the point of view of their mechanical and electric properties, such as: electric permittivity, ε; dielectric loss, tanδ; mechanical losses, Q-1; and Young modulus, E.

  15. Thermodynamics of Co-B-H ternary solid solutions

    SciTech Connect

    Ko, C.; McLellan, R.B. . Dept. of Mechanical Engineering and Materials Science)

    1992-01-01

    This paper reports on solubility isobars for h in Co-B binary solvents containing up to 0.1 at %B determined in the temperature range 920-1430 K. The solubility data yield values for the partial molar thermodynamic functions of the dissolved H-atoms which manifest a strong long-range H-B repulsive interactions. Boron dissolves interstitially in Pd and effects, relative to other interstitial solutes, a large dilation in the host metal lattice. In a recent study of the Pd-B-H system it was found that at B-content up to {approximately}15 at % the partial enthalpy of H-interstitials {bar H}{sub i}{sup V{minus}j{minus}i} was increased by the presence of the B atoms. As the B-content increases, {bar H}{sub i} decreases rapidly due to the formation of distorted lattice sites associated with B-B pairs, but the initial increase in {bar H}{sub i} is a somewhat unexpected result since, at low B-contents, it would be expected tht Pd-H interactions would predominantly determine {bar H}{sub i} and simple elastic considerations would lead to a decrease in {bar H}{sub i} with increasing B-content.

  16. Exciton mobility edge in CdS 1-xSe x solid solutions

    NASA Astrophysics Data System (ADS)

    Permogorov, S.; Reznitsky, A.; Verbin, S.; Lysenko, V.

    1983-07-01

    Low temperature emission spectra of localized excitons in CdS 1-xSe x solid solutions under the monochromatic excitation with tunable laser have been studied. It has been found that the luminescence of localized excitons has a high degree of linear polarization with respect to the polarization direction of exciting light. This polarization reflects the "hidden" anisotropy of macroscopically isotropic localized exciton system and strongly depends on the frequency of exciting light. Study of this dependence has permitted for the first time a determination of position of the "mobility edge" for exciton migration in disordered semiconductor solid solution.

  17. Modeling of phase decomposition of supersaturated solid solutions using the free-energy density functional method

    NASA Astrophysics Data System (ADS)

    L'vov, P. E.; Svetukhin, V. V.; Maslov, K. S.

    2016-08-01

    The nucleation and growth of particles of the second phase in a one-dimensional binary alloy is considered based on the Cahn-Hilliard equation with allowance for fluctuations. Using the results of modeling, it is shown that the second phase is occupied by the mechanism of solid solution decomposition, which involves simultaneous processes of the fluctuational nucleation of the second phase, diffusion-type growth of precipitations, and absorption of small clusters by coarse ones at the coalescence stage. Composition fluctuations are among the main factors influencing the distribution of solid solution phases.

  18. Reusable and specific proton transfer signalling by inorganic cyanide in solution and solid phase.

    PubMed

    Kaloo, Masood Ayoub; Sankar, Jeyaraman

    2015-10-04

    A highly specific cyanide mediated proton transfer signalling (PTS) is exhibited by a simple diaminomalenonitrile (DAMN) derivative 1. By virtue of the functional groups on it, the chromophore offered a rigid anchoring on a silica surface via a simple dip method, while retaining the recognition behaviour. The PTS triggered a prompt dual-modal display i.e., chromogenic and fluorogenic. The signal readout can be visualized even in micromolar concentrations. It is noteworthy that PTS can be reversed in both solution and solid phases. The remarkable sensitivity of 1 to detect CN(-) from the solution and solid phase envisages a pivotal step towards field-usable sensing.

  19. Structural and magnetic properties of mechanically alloyed Co 20Cu 80 solid solution

    NASA Astrophysics Data System (ADS)

    Yoo, Y. G.; Yang, D. S.; Yu, S. C.; Kim, W. T.; M. Lee, J.

    1999-08-01

    Microstructural change during the mechanical alloying of Co 20Cu 80 has been studied by X-ray diffractometry (XRD) and extended X-ray absorption fine structure (EXAFS) techniques. EXAFS analysis shows clearly the formation of supersaturated Co 20Cu 80 solid solution with FCC crystal structure during mechanical alloying, which is in good agreement with XRD analysis. Magnetic properties also have been studied by SQUID magnetometer from 4 to 290 K. The supersaturated Co 20Cu 80 solid solution shows wide distribution in Co cluster size due to the continuous blocking of Co cluster as a function of temperature.

  20. A solid state and solution NMR study of the tautomerism in hydroxyquinoline carboxylic acids.

    PubMed

    Gudat, Dietrich; Nycz, Jacek E; Polanski, Jaroslaw

    2008-01-01

    Some hydroxyquinoline carboxylic acids and their conjugate acids and bases were characterized by 13C and 15N NMR spectroscopy in solution and in the solid state. Differences in 13C and, in particular, 15N chemical shift patterns allow to distinguish between individual tautomers and confirm the presence of zwitterionic species in the solid state. Solution NMR spectra in dimethyl sulfoxide (DMSO) show effects resulting as a consequence of dynamic exchange and suggest the presence of an equilibrium mixture of hydroxyquinoline carboxylic acid and zwitterionic hydroxyquinolinium carboxylate tautomers.

  1. Magnetism and Solid Solution Effects in NiAI (40% AI) Alloys

    SciTech Connect

    Liu, Chain T; Fu, Chong Long; Chisholm, Matthew F; Thompson, James R; Krcmar, Maja; Wang, Xun-Li

    2007-01-01

    The solid solution effects of ternary additions of transition elements in intermetallic Ni-40% Al were investigated by both experimental studies and theoretical calculations. Co solute atoms when sitting at Ni sublattice sites do not affect the lattice parameter and hardening behavior of Ni-40Al. On the other hand, Fe, Mn, and Cr solutes, which are mainly on Al sublattice sites, substantially expand the lattice parameter and produce an unusual solid solution softening effect. First-principles calculations predict that these solute atoms with large unfilled d-band electrons develop large magnetic moments and effectively expand the lattice parameter when occupying Al sublattice sites. The theoretical predictions were verified by both electron loss-energy spectroscopy (EELS) analyses and magnetic susceptibility measurements. The observed softening behavior can be explained quantitatively by the replacement of Ni anti-site defects (potent hardeners) by Fe, Mn, and Cr anti-site defects with smaller atom size mismatch between solute and Al atoms. This study has led to the identification of magnetic interaction as an important physical parameter affecting the solid solution hardening in intermetallic alloys containing transition elements.

  2. Activities of the components in a spinel solid solution of the Fe-Al-O system

    NASA Astrophysics Data System (ADS)

    Lykasov, A. A.; Kimyashev, A. A.

    2011-09-01

    The conditions of the equilibrium between the Fe3O4-FeAl2O4 solution and wustite are determined by measuring the EMF of galvanic cells containing a solid electrolyte, and the activities of the components in the Fe3O4-FeAl2O4 solution are calculated by treating the results of the experiment on the equilibrium between the spinel solution and wustite. Their properties are found to be different from those of ideal solutions at temperatures of 1000-1300 K. A significant positive deviation from the Raoult's law is believed to indicate the tendency of the solution to decompose. The experimental data are treated in terms of the theory of regular solutions, assuming the energy of mixing to be a function of temperature only. The critical temperature of decomposition for the Fe3O4-FeAl2O4 solution is found to be 1084 K.

  3. Study for recycling of ceria-based glass polishing powder

    SciTech Connect

    Kato, Kazuhiro; Yoshioka, Toshiaki; Okuwaki, Akitsugu

    2000-04-01

    The recycling of ceria-based glass polishing powder by alkali treatment was investigated. Major impurities in the waste, a SiO{sub 2} component from fine glass powder and an Al{sub 2}O{sub 3} component from coagulating agents, could be removed easily at 50--60 C in a 4 mol/kg NaOH solution within 1 h. These impurities react with NaOH to precipitate as zeolite at higher temperature. Thus, it is expected that a recycling process which can regenerate polishing powder and convert SiO{sub 2} and Al{sub 2}O{sub 3} components into zeolite can be designed.

  4. Morphological Control and Characterization of Monodispersed Ceria Particles

    SciTech Connect

    Minamidate, Y.; Yin, S.; Devaraju, M. K.; Sato, T.

    2010-11-24

    The morphological control of cerium oxide particles was carried out by a homogeneous precipitation followed by calcination in air at 400 deg. C. The effects of pre-aging temperature, aging time and precipitation reagents on the morphologies of final products were investigated. When urea was used as a precipitation reagent, monodispersed spherical and flake-like cerium carbonate hydroxide precursor was precipitated in the solution at 90 deg. C for 2 h after pre-aging at 25 deg. C - 50 deg. C for 24-72 h. On the other hand, monodispersed nanosize rod-like cerium hydroxide particles were obtained using triethanolamine as precipitation reagent. Ceria particles with the same morphologies and slightly smaller particle size than those of as-prepared cerium precursor could be obtained after calcination in air at 400 deg. C. Physical-chemical characteristics of the monodispersed cerium oxide particles were evaluated.

  5. Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer

    SciTech Connect

    Tseng, Chih Heng; Paul, Brian; Chang, Chih-hung; Engelhard, Mark H.

    2013-01-01

    Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a micro-scale T-mixer. Findings show that the method of mixing is important in the ceria precipitation process. In batch mixing and deposition, disintegration and agglomeration dominates the deposited film. In T-mixing and deposition, more uniform nanorod particles are attainable. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)3 precipates to oxygen, yielding hydroxide precipates in place of CeO2 precipitates. Advantages of the micro-scale T-mixing approach include shorter mixing times, better control of nanoparticle shape and less agglomeration.

  6. Photophysical and photocatalytic properties of Ca(1-x)BixVxMo(1-x)O4 solid solutions.

    PubMed

    Yao, Weifeng; Ye, Jinhua

    2006-06-15

    New solid solutions with the composition of Ca(1-x)BixVxMo(1-x)O4 prepared by a solid-state method were found as novel photocatalysts with enhanced activity for O(2) evolution from aqueous solutions containing sacrificial reagent AgNO3 under visible-light irradiation (>420 nm). The obtained solid solutions crystallized in tetragonal crystal structures, except one of the end compounds, BiVO4, which crystallized in monoclinic structures. The diffuse reflection spectra of the solid solutions shift monotonically to a long wavelength as the ratio of Bi (V) ions to Ca (Mo) ions increases in the solid solution. The band structure and the dependence of the photocatalytic properties were discussed in relation to the solid-solution compositions and photophysical properties.

  7. The concentration effect at nonisothermal nucleation under conditions of solid-solution heating

    NASA Astrophysics Data System (ADS)

    Ashkalunin, A. L.; Valov, P. M.; Derkacheva, O. Yu.; Leiman, V. I.; Maksimov, V. M.

    2017-06-01

    The influence of the heating rate of a solid solution up to the temperature of isothermal annealing on the distribution of CuCl particles by radii has been studied using the example of a solid solution of CuCl in glass. The study of changes in the distribution of particle radii in the CuCl phase has been performed using exciton-thermal analysis. It has been found that, with slow (60 min) heating of the sample to 650°C, the concentration of nucleates in the CuCl phase first increases rapidly and, then, the concentration decreases. The decrease in concentration is explained by the rapid growth of the critical radius with temperature and depletion of the solution. As follows from numerical simulation, the nucleation in a solution of CuCl in glass under conditions of slow heating is in good agreement with the experimental data.

  8. The Effect of Exposed Facets of Ceria to the Nickel Species in Nickel-Ceria Catalysts and Their Performance in a NO + CO Reaction.

    PubMed

    Tang, Ke; Liu, Wei; Li, Jing; Guo, Jinxin; Zhang, Jingcai; Wang, Shuping; Niu, Shengli; Yang, Yanzhao

    2015-12-09

    CeO2 rods with {110} facets and cubes with {100} facets were utilized as catalyst supports to probe the effect of crystallographic facets on the nickel species and the structure-dependent catalytic performance. Various analysis methods (ex and in situ XRD, TEM, Raman, XPS, TPR, TPD) were used to investigate the structural forms of the catalysts, and these results indicated that the deposition of nickel species resulted in the formation of two main active types of the catalyst components: NiO strongly or weakly interacted with the surface and Ni-Ce-O solid solution. Notably, the states and distribution ratio of nickel species were related to the shape of CeO2. It was found that CeO2 rods had more active sites to coordinate with nickel species to form a strong interaction with NiO on the surface and a more stable construction when compared to cubes. Furthermore, the nickel-ceria catalysts with rod shape were more active towards NO oxidation with complete conversion below 191 °C, but for cube shape, complete conversion occurred above 229 °C (e.g., for nickel loading of ∼5%, the complete conversion temperature was 154 °C for the rod shape and 229 °C for the cube shape). On the basis of the analysis of the catalysts structure, the superior catalytic activity was due to a combination of surface structures of NiO (mainly strongly interacting with the surface) and nickel ions Ni(2+) in the Ni-Ce-O bulk phase.

  9. First-principles investigation of solute-hydrogen interaction in a α-Ti solid solution

    NASA Astrophysics Data System (ADS)

    Hu, Q. M.; Xu, D. S.; Yang, R.; Li, D.; Wu, W. T.

    2002-08-01

    In this paper, a first-principles method is used to calculate the interaction energy between substitutional solute atoms and hydrogen in α-Ti. The results show that simple metal (SM) solute atoms are repulsive to H and therefore are detraps for H, whereas transition metal (TM) solute atoms, with smaller sizes than that of the host atoms, attract H and provide traps for H. The relationship between the interaction energy and lattice distortion as well as the electronic structure is investigated. The SM-H and TM-H interactions are dominated by different factors. The repulsive interaction between SM atoms and H is mainly due to the hybridization between the electrons of SM atoms and H when they are close to each other. The interaction between the TM solutes and H is attributable to the atomic size effect, and can be described satisfactorily by Matsumoto's strain field relaxation model. From the solute-H interaction energy and available measured terminal solubility of hydrogen (TSH), the relationship between the solute trapping of hydrogen and TSH in α-Ti is discussed. No coherent relationship is found between the theoretical hydrogen trapping effect and the experimental TSH in α-Ti alloys.

  10. REMOVAL OF SOLIDS FROM HIGHLY ENRICHED URANIUM SOLUTIONS USING THE H-CANYON CENTRIFUGE

    SciTech Connect

    Rudisill, T; Fernando Fondeur, F

    2009-01-15

    Prior to the dissolution of Pu-containing materials in HB-Line, highly enriched uranium (HEU) solutions stored in Tanks 11.1 and 12.2 of H-Canyon must be transferred to provide storage space. The proposed plan is to centrifuge the solutions to remove solids which may present downstream criticality concerns or cause operational problems with the 1st Cycle solvent extraction due to the formation of stable emulsions. An evaluation of the efficiency of the H-Canyon centrifuge concluded that a sufficient amount (> 90%) of the solids in the Tank 11.1 and 12.2 solutions will be removed to prevent any problems. We based this conclusion on the particle size distribution of the solids isolated from samples of the solutions and the calculation of particle settling times in the centrifuge. The particle size distributions were calculated from images generated by scanning electron microscopy (SEM). The mean particle diameters for the distributions were 1-3 {micro}m. A significant fraction (30-50%) of the particles had diameters which were < 1 {micro}m; however, the mass of these solids is insignificant (< 1% of the total solids mass) when compared to particles with larger diameters. It is also probable that the number of submicron particles was overestimated by the software used to generate the particle distribution due to the morphology of the filter paper used to isolate the solids. The settling times calculated for the H-Canyon centrifuge showed that particles with diameters less than 1 to 0.5 {micro}m will not have sufficient time to settle. For this reason, we recommend the use of a gelatin strike to coagulate the submicron particles and facilitate their removal from the solution; although we have no experimental basis to estimate the level of improvement. Incomplete removal of particles with diameters < 1 {micro}m should not cause problems during purification of the HEU in the 1st Cycle solvent extraction. Particles with diameters > 1 {micro}m account for > 99% of the

  11. Synthesis and Non-isothermal Carbothermic Reduction of FeTiO3-Fe2O3 Solid Solution Systems

    NASA Astrophysics Data System (ADS)

    Liu, Yiran; Zhang, Jianliang; Xing, Xiangdong; Liu, Zhengjian; Liu, Xingle; Li, Naiyao; Shen, Yansong

    2017-10-01

    To investigate the carbothermic reduction behaviors of xFeTiO3·(1 - x)Fe2O3 solid solutions, the solid solutions with different x values were synthesized and used in the corresponding reactions. With an increase in x, the temperature pertaining to the onset of carbothermic reduction increased, while the rate of reduction of the solid solutions, α, decreased. The lattice parameters calculated from XRD patterns indicated that the solid solution with a higher x led to a larger lattice distortion. The non-isothermal kinetics were calculated, and an average activation energy E value of 3.0 × 102 kJ/mol was obtained.

  12. Interdiffusion and impurity diffusion in polycrystalline Mg solid solution with Al or Zn

    SciTech Connect

    Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; Sohn, Yong Ho

    2014-01-01

    Interdiffusion and impurity diffusion in Mg binary solid solutions, Mg(Al) and Mg(Zn) were investigated at temperatures ranging from 623 to 723 K. Interdiffusion coef cients were determined via the Boltzmann Matano Method using solid-to-solid diffusion couples assembled with polycrystalline Mg and Mg(Al) or Mg(Zn) solid solutions. In addition, the Hall method was employed to extrapolate the impurity diffusion coef cients of Al and Zn in pure polycrystalline Mg. For all diffusion couples, electron micro-probe analysis was utilized for the measurement of concentration pro les. The interdiffusion coef cient in Mg(Zn) was higher than that of Mg(Al) by an order of magnitude. Additionally, the interdiffusion coef cient increased signi cantly as a function of Al content in Mg(Al) solid solution, but very little with Zn content in Mg(Zn) solid solution. The activation energy and pre-exponential factor for the average effective interdiffusion coef cient in Mg(Al) solid solution were determined to be 186.8 ( 0.9) kJ/mol and 7.69 x 10-1 ( 1.80 x 10-1) m2/s, respectively, while those determined for Mg(Zn) solid solution were 139.5 ( 4.0) kJ/mol and 1.48 x 10-3 ( 1.13 x 10-3) m2/s. In Mg, the Zn impurity diffusion coef cient was an order of magnitude higher than the Al impurity diffusion coef cient. The activation energy and pre-exponential factor for diffusion of Al impurity in Mg were determined to be 139.3 ( 14.8) kJ/mol and 6.25 x 10-5 ( 5.37 x 10-4) m2/s, respectively, while those for diffusion of Zn impurity in Mg were determined to be 118.6 ( 6.3) kJ/mol and 2.90 x 10-5 ( 4.41 x 10-5) m2/s.

  13. Preparation and Analysis of Solid Solutions in the Potassium Perchlorate-Permanganate System.

    ERIC Educational Resources Information Center

    Johnson, Garrett K.

    1979-01-01

    Describes an experiment, designed for and tested in an advanced inorganic laboratory methods course for college seniors and graduate students, that prepares and analyzes several samples in the nearly ideal potassium perchlorate-permanganate solid solution series. The results are accounted for by a theoretical treatment based upon aqueous…

  14. Damage accumulation in ion-irradiated Ni-based concentrated solid-solution alloys

    DOE PAGES

    Ullah, Mohammad W.; Aidhy, Dilpuneet S.; Zhang, Yanwen; ...

    2016-03-05

    We investigate Irradiation-induced damage accumulation in Ni0.8Fe0.2 and Ni0.8Cr0.2 alloys by using molecular dynamics simulations to assess possible enhanced radiation-resistance in these face-centered cubic (fcc), single-phase, concentrated solid-solution alloys, as compared with pure fcc Ni.

  15. Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

    PubMed

    Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

    2017-06-15

    Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Thermal transport properties of halide solid solutions: Experiments vs equilibrium molecular dynamics

    NASA Astrophysics Data System (ADS)

    Gheribi, Aïmen E.; Salanne, Mathieu; Chartrand, Patrice

    2015-03-01

    The composition dependence of thermal transport properties of the (Na,K)Cl rocksalt solid solution is investigated through equilibrium molecular dynamics (EMD) simulations in the entire range of composition and the results are compared with experiments published in recent work [Gheribi et al., J. Chem. phys. 141, 104508 (2014)]. The thermal diffusivity of the (Na,K)Cl solid solution has been measured from 473 K to 823 K using the laser flash technique, and the thermal conductivity was deduced from critically assessed data of heat capacity and density. The thermal conductivity was also predicted at 900 K in the entire range of composition by a series of EMD simulations in both NPT and NVT statistical ensembles using the Green-Kubo theory. The aim of the present paper is to provide an objective analysis of the capability of EMD simulations in predicting the composition dependence of the thermal transport properties of halide solid solutions. According to the Klemens-Callaway [P. G. Klemens, Phys. Rev. 119, 507 (1960) and J. Callaway and H. C. von Bayer, Phys. Rev. 120, 1149 (1960)] theory, the thermal conductivity degradation of the solid solution is explained by mass and strain field fluctuations upon the phonon scattering cross section. A rigorous analysis of the consistency between the theoretical approach and the EMD simulations is discussed in detail.

  17. Preparation and Analysis of Solid Solutions in the Potassium Perchlorate-Permanganate System.

    ERIC Educational Resources Information Center

    Johnson, Garrett K.

    1979-01-01

    Describes an experiment, designed for and tested in an advanced inorganic laboratory methods course for college seniors and graduate students, that prepares and analyzes several samples in the nearly ideal potassium perchlorate-permanganate solid solution series. The results are accounted for by a theoretical treatment based upon aqueous…

  18. Exact Solution of the Two-Level System and the Einstein Solid in the Microcanonical Formalism

    ERIC Educational Resources Information Center

    Bertoldi, Dalia S.; Bringa, Eduardo M.; Miranda, E. N.

    2011-01-01

    The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In…

  19. Magnetic properties of solid solutions based on UFe 10Si 2

    NASA Astrophysics Data System (ADS)

    Homma, Y.; Andreev, A. V.; Shiokawa, Y.; Miyashita, J.

    2002-04-01

    Magnetization of interstitial (UFe 10Si 2C x) and substitution (U 1- xR xFe 10Si 2, R=Nd, Er) solid solutions based on UFe 10Si 2 has been studied as a function of magnetic field and temperature on aligned powders. The results point to the considerable contribution of the U sublattice to the magnetic anisotropy.

  20. Linear structural evolution induced tunable photoluminescence in clinopyroxene solid-solution phosphors.

    PubMed

    Xia, Zhiguo; Zhang, Yuanyuan; Molokeev, Maxim S; Atuchin, Victor V; Luo, Yi

    2013-11-22

    Clinopyroxenes along the Jervisite (NaScSi2O6)-Diopside (CaMgSi2O6) join have been studied, and a solid-solution of the type (Na(1-x)Ca(x))(Sc(1-x)Mg(x))Si2O6 has been identified in the full range of 0 ≤ x ≤ 1. The powder X-ray patterns of all the phases indicate a structural similarity to the end compounds and show smooth variation of structural parameters with composition. The linear structural evolution of iso-structural (Na(1-x)Ca(x))(Sc(1-x)Mg(x))Si2O6 solid-solutions obeying Vegard's rule has also been examined and verified by high resolution transmission electron microscopy (HRTEM). The continuous solid-solutions show the same structural type, therefore the photoluminescence spectra of Eu(2+) doped samples possess the superposition of spectral features from blue-emitting component (CaMgSi2O6:Eu(2+)) and yellow-emitting one (NaScSi2O6:Eu(2+)). This indicates that the spectroscopic properties of (Na(1-x)Ca(x))(Sc(1-x)Mg(x))Si2O6 clinopyroxene solid-solutions are in direct relations with structural parameters, and it is helpful for designing color-tunable photoluminescence with predetermined parameters.

  1. Thermal expansion of TRU nitride solid solutions as fuel materials for transmutation of minor actinides

    NASA Astrophysics Data System (ADS)

    Takano, Masahide; Akabori, Mitsuo; Arai, Yasuo; Minato, Kazuo

    2009-06-01

    The lattice thermal expansion of the transuranium nitride solid solutions was measured to investigate the composition dependence. The single-phase solid solution samples of (Np 0.55Am 0.45)N, (Pu 0.59Am 0.41)N, (Np 0.21Pu 0.52Am 0.22Cm 0.05)N and (Pu 0.21Am 0.18Zr 0.61)N were prepared by carbothermic nitridation of the respective transuranium dioxides and nitridation of Zr metal through hydride. The lattice parameters were measured by the high temperature X-ray diffraction method from room temperature up to 1478 K. The linear thermal expansion of each sample was determined as a function of temperature. The average thermal expansion coefficients over the temperature range of 293-1273 K for the solid solution samples were 10.1, 11.5, 10.8 and 8.8 × 10 -6 K -1, respectively. Comparison of these values with those for the constituent nitrides showed that the average thermal expansion coefficients of the solid solution samples could be approximated by the linear mixture rule within the error of 2-3%.

  2. Exact Solution of the Two-Level System and the Einstein Solid in the Microcanonical Formalism

    ERIC Educational Resources Information Center

    Bertoldi, Dalia S.; Bringa, Eduardo M.; Miranda, E. N.

    2011-01-01

    The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In…

  3. Thermal transport properties of halide solid solutions: Experiments vs equilibrium molecular dynamics

    SciTech Connect

    Gheribi, Aïmen E. Chartrand, Patrice; Salanne, Mathieu

    2015-03-28

    The composition dependence of thermal transport properties of the (Na,K)Cl rocksalt solid solution is investigated through equilibrium molecular dynamics (EMD) simulations in the entire range of composition and the results are compared with experiments published in recent work [Gheribi et al., J. Chem. phys. 141, 104508 (2014)]. The thermal diffusivity of the (Na,K)Cl solid solution has been measured from 473 K to 823 K using the laser flash technique, and the thermal conductivity was deduced from critically assessed data of heat capacity and density. The thermal conductivity was also predicted at 900 K in the entire range of composition by a series of EMD simulations in both NPT and NVT statistical ensembles using the Green-Kubo theory. The aim of the present paper is to provide an objective analysis of the capability of EMD simulations in predicting the composition dependence of the thermal transport properties of halide solid solutions. According to the Klemens-Callaway [P. G. Klemens, Phys. Rev. 119, 507 (1960) and J. Callaway and H. C. von Bayer, Phys. Rev. 120, 1149 (1960)] theory, the thermal conductivity degradation of the solid solution is explained by mass and strain field fluctuations upon the phonon scattering cross section. A rigorous analysis of the consistency between the theoretical approach and the EMD simulations is discussed in detail.

  4. The synthesis and chemical durability of Nd-doped single-phase zirconolite solid solutions

    NASA Astrophysics Data System (ADS)

    Cai, Xin; Teng, Yuancheng; Wu, Lang; Zhang, Kuibao; Huang, Yi

    2016-10-01

    Nd-doped single-phase zirconolite solid solutions was synthesized by solid-state reaction and following two steps of acid treatment. The phase composition, microstructure, and chemical durability of the zirconolite solid solutions were investigated. About 15 at% Nd was successfully stabilized into the zirconolite. The element mapping images of Ca, Zr, Nd and Ti show that all the elements are almost distributed homogeneously in the zirconolite waste forms. Product Consistency Test (PCT) was conducted under different pH values (pH = 5, 7 and 9) to evaluate the chemical durability of the Nd-doped zirconolite waste forms. The normalized element release rate of Ca (LRCa) in pH = 5 medium is higher than that of pH = 7 and 9, while the LRNd value remains almost unchanged under different pH values. The LRNd value is as low as 10-5 g m-2 d-1 after 42 days.

  5. Hydrogen-storage properties of solid-solution alloys of immiscible neighboring elements with Pd.

    PubMed

    Kusada, Kohei; Yamauchi, Miho; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Kubota, Yoshiki

    2010-11-17

    Rh and Ag are the elements neighboring Pd, which is well known as a hydrogen-storage metal. Although Rh and Ag do not possess hydrogen-storage properties, can Ag-Rh alloys actually store hydrogen? Ag-Rh solid-solution alloys have not been explored in the past because they do not mix with each other at the atomic level, even in the liquid phase. We have used the chemical reduction method to obtain such Ag-Rh alloys, and XRD and STEM-EDX give clear evidence that the alloys mixed at the atomic level. From the measurements of hydrogen pressure-composition isotherms and solid-state (2)H NMR, we have revealed that Ag-Rh solid-solution alloys absorb hydrogen, and the total amount of hydrogen absorbed reached a maximum at the ratio of Ag:Rh = 50:50, where the electronic structure is expected to be similar to that of Pd.

  6. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    SciTech Connect

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; Belianinov, Alex

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.

  7. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    DOE PAGES

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; ...

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less

  8. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    SciTech Connect

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; Belianinov, Alex

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.

  9. Fuel reforming and electrical performance studies in intermediate temperature ceria-gadolinia-based SOFCs

    NASA Astrophysics Data System (ADS)

    Livermore, Stephanie J. A.; Cotton, John W.; Ormerod, R. Mark

    The methane reforming and carbon deposition characteristics of two nickel/ceria-gadolinia cermet anodes have been studied over the temperature range 550-700°C, for use in intermediate temperature ceria-gadolinia (CGO)-based solid oxide fuel cells (SOFCs), using conventional catalytic methods and temperature-programmed spectroscopy. The electrical performance and durability of planar CGO-based SOFCs with a 280-μm-thick CGO electrolyte, screen printed cathode and different screen printed nickel/CGO cermet anodes have been studied over the temperature range 500-650°C. Temperature-programmed reduction has been used to study the reduction characteristics of the anodes, and indicates the presence of "bulk" NiO particles and smaller NiO particles in intimate contact with the ceria. Both anodes show good activity towards methane steam reforming with methane activation occurring at temperatures as low as 210°C; steady-state steam reforming of methane was observed using a methane-rich mixture at 650°C, with 20% methane conversion. Post-reaction temperature-programmed oxidation has been used to determine the amount of carbon deposited during reforming and the strength of its interaction with the anode.

  10. Controlled synthesis of ceria nanoparticles for the design of nanohybrids.

    PubMed

    Nguyen, Thanh-Dinh; Dinh, Cao-Thang; Mrabet, Driss; Tran-Thi, Minh-Nguyet; Do, Trong-On

    2013-03-15

    Ceria nanoparticles were synthesized from reaction mixture of cerium nitrate/hexamethylenediamine/water-ethylene glycol. Lamellar, particle-aggregated array, platelet, rice, cube, quasi-sphere shapes of the ceria nanoparticles can be controlled by tuning reaction parameters (reagent concentration, reagent components, pH, and reaction conditions). Studies on shape-dependent catalysis of the bare ceria samples toward CO oxidation indicated that the cube-shaped ceria nanoparticles show better catalytic activity than the nanospheres and the commercial micropowders. As capped by hexamethylenediamine (HEA) molecules, amine-functionalized ceria nanoparticles act as platforms for depositing copper particles to produce efficient Cu/CeO(2) hybrid nanocatalysts for CO conversion. Coupling of the copper clusters with the HEA-capped ceria nanocubes was achieved with the Cu contents up to 15 wt.%. The Cu/CeO(2) nanohybrids show an enhanced catalytic efficiency of low temperature CO conversion. This could be due to high exposure of the reactive {100} facets in the ceria nanocubes and interfacial copper-ceria interactions.

  11. Different routes towards oscillatory zoning in the growth of solid solutions.

    PubMed

    Lubashevsky, Ihor; Mues, Tanja; Heuer, Andreas

    2008-10-01

    Oscillatory zoning, i.e., self-formation of spatial quasiperiodic oscillations in the composition of solid growing from aqueous solution, is analyzed theoretically. Keeping in mind systems like (Ba,Sr)SO4 , we propose a one-dimensional model that takes into account the nonideality of the solid solution and the system asymmetry, in particular, reflecting itself in different solubilities for such systems. Based on a linear stability analysis, different parameter regions can be identified. Even an ideal solution with a sufficiently large asymmetry can display oscillatory zoning. Numerical simulations complement the linear stability analysis as well as the qualitative consideration of the instability development and reveal the nature of the limit cycles.

  12. Direct oxidation of waste vegetable oil in solid-oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, Z. F.; Kumar, R.; Thakur, S. T.; Rudnick, L. R.; Schobert, H.; Lvov, S. N.

    Solid-oxide fuel cells with ceria, ceria-Cu, and ceria-Rh anode were demonstrated to generate stable electric power with waste vegetable oil through direct oxidation of the fuel. The only pre-treatment to the fuel was a filtration to remove particulates. The performance of the fuel cell was stable over 100 h for the waste vegetable oil without dilution. The generated power was up to 0.25 W cm -2 for ceria-Rh fuel cell. This compares favorably with previously studied hydrocarbon fuels including jet fuels and Pennsylvania crude oil.

  13. Mitochondria-Targeting Ceria Nanoparticles as Antioxidants for Alzheimer's Disease.

    PubMed

    Kwon, Hyek Jin; Cha, Moon-Yong; Kim, Dokyoon; Kim, Dong Kyu; Soh, Min; Shin, Kwangsoo; Hyeon, Taeghwan; Mook-Jung, Inhee

    2016-02-23

    Mitochondrial oxidative stress is a key pathologic factor in neurodegenerative diseases, including Alzheimer's disease. Abnormal generation of reactive oxygen species (ROS), resulting from mitochondrial dysfunction, can lead to neuronal cell death. Ceria (CeO2) nanoparticles are known to function as strong and recyclable ROS scavengers by shuttling between Ce(3+) and Ce(4+) oxidation states. Consequently, targeting ceria nanoparticles selectively to mitochondria might be a promising therapeutic approach for neurodegenerative diseases. Here, we report the design and synthesis of triphenylphosphonium-conjugated ceria nanoparticles that localize to mitochondria and suppress neuronal death in a 5XFAD transgenic Alzheimer's disease mouse model. The triphenylphosphonium-conjugated ceria nanoparticles mitigate reactive gliosis and morphological mitochondria damage observed in these mice. Altogether, our data indicate that the triphenylphosphonium-conjugated ceria nanoparticles are a potential therapeutic candidate for mitochondrial oxidative stress in Alzheimer's disease.

  14. Soot combustion over Ce1-xFexO2-δ and CeO2/Fe2O3 catalysts: Roles of solid solution and interfacial interactions in the mixed oxides

    NASA Astrophysics Data System (ADS)

    Li, Hongcheng; Li, Kongzhai; Wang, Hua; Zhu, Xing; Wei, Yonggang; Yan, Dongxia; Cheng, Xianming; Zhai, Kang

    2016-12-01

    Two series of CeO2-Fe2O3 catalysts (CeO2-based and Fe2O3-supported oxides) with varying composition were synthesized by a hydrothermal method and characterized using various techniques. The comparison on the activity and thermal stability of different catalysts for low-temperature soot oxidation was also performed. The presence of both Ce-Fe-O solid solution and CeO2-Fe2O3 interaction were observed over the two types of catalysts. The oxygen vacancy in the solid solution is the crucial active site to facilitating the soot combustion over the CeO2-based samples. Small CeO2 nanoparticles are well dispersed on the Fe2O3-supported catalysts, which results in the formation of Fe-O-Ce species due to the strong CeO2-Fe2O3 interaction. The Fe-O-Ce species could achieve the coupling of the Ce4+-Ce3+ and Fe3+-Fe2+ couples in the CeO2-Fe2O3 interface, which is also identified as an active species for catalytic soot oxidation. The concentration of oxygen vacancy is closely related to the content of iron in ceria lattice, while the formation of Fe-O-Ce species strongly relies on the particle size of CeO2. It is also found that the oxygen vacancy is more active than the Fe-O-Ce species for soot oxidation, but it is very easy to decompose at high temperature, resulting in obvious deactivation of catalysts. By contrast, the Fe-O-Ce species is very stable under high-temperature treatments. For the fresh samples, the CeO2-based and Fe2O3-supported catalysts showed comparable catalytic activity. After long term aging at 800 °C, the loss on activity over the CeO2-based catalyst (Ce-Fe-O solid solution) is much higher than that over the Fe2O3-supported sample. The Fe2O3-supported catalysts are more suitable for practical application than the Ce-Fe-O solid solution.

  15. Ultraviolet resonance Raman spectroscopy of explosives in solution and the solid state.

    PubMed

    Emmons, Erik D; Tripathi, Ashish; Guicheteau, Jason A; Fountain, Augustus W; Christesen, Steven D

    2013-05-23

    Resonance Raman cross sections of common explosives have been measured by use of excitation wavelengths in the deep-UV from 229 to 262 nm. These measurements were performed both in solution and in the native solid state for comparison. While measurements of UV Raman cross sections in solution with an internal standard are straightforward and commonly found in the literature, measurements on the solid phase are rare. This is due to the difficulty in preparing a solid sample in which the molecules of the internal standard and absorbing analyte/explosive experience the same laser intensity. This requires producing solid samples that are mixtures of strongly absorbing explosives and an internal standard transparent at the UV wavelengths used. For the solid-state measurements, it is necessary to use nanostructured mixtures of the explosive and the internal standard in order to avoid this bias due to the strong UV absorption of the explosive. In this study we used a facile spray-drying technique where the analyte of interest was codeposited with the nonresonant standard onto an aluminum-coated microscope slide. The generated resonance enhancement profiles and quantitative UV-vis absorption spectra were then used to plot the relative Raman return as a function of excitation wavelength and particle size.

  16. Thermodynamic considerations in solid adsorption of bound solutes for patient support in liver failure.

    PubMed

    Patzer, John F

    2008-07-01

    New detoxification modes of treatment for liver failure that use solid adsorbents to remove toxins bound to albumin in the patient bloodstream are entering clinical evaluations, frequently in head-to-head competition. While generally effective in reducing toxin concentration beyond that obtainable by conventional dialysis procedures, the solid adsorbent processes are largely the result of heuristic development. Understanding the principles and limitations inherent in competitive toxin binding, albumin versus solid adsorbent, will enhance the design process and, possibly, improve detoxification performance. An equilibrium thermodynamic analysis is presented for both the molecular adsorbent recirculating system (MARS) and fractionated plasma separation, adsorption, and dialysis system (Prometheus), two advanced systems with distinctly different operating modes but with similar equilibrium limitations. The Prometheus analysis also applies to two newer approaches: sorbent suspension reactor and microsphere-based detoxification system. Primary results from the thermodynamic analysis are that: (i) the solute-albumin binding constant is of minor importance to equilibrium once it exceeds about 10(5) L/mol; (ii) the Prometheus approach requires larger solid adsorbent columns than calculated by adsorbent solute capacity alone; and (iii) the albumin-containing recycle stream in the MARS approach is a major reservoir of removed toxin. A survey of published results indicates that MARS is operating under mass transfer control dictated by solute-albumin equilibrium in the recycle stream, and Prometheus is approaching equilibrium limits under current clinical protocols.

  17. Thermodynamic Considerations in Solid Adsorption of Bound Solutes for Patient Support in Liver Failure

    PubMed Central

    Patzer, John F.

    2008-01-01

    New detoxification modes of treatment for liver failure that use solid adsorbents to remove toxins bound to albumin in the patient bloodstream are entering clinical evaluations, frequently in head-to-head competition. While generally effective in reducing toxin concentration beyond that obtainable by conventional dialysis procedures, the solid adsorbent processes are largely the result of heuristic development. Understanding the principles and limitations inherent in competitive toxin binding, albumin versus solid adsorbent, will enhance the design process and, possibly, improve detoxification performance. An equilibrium thermodynamic analysis is presented for both the Molecular Adsorbent Recirculating System (MARS) and Fractionated Plasma Separation, Adsorption, and Dialysis System (Prometheus), two advanced systems with distinctly different operating modes but with similar equilibrium limitations. The Prometheus analysis also applies to two newer approaches: sorbent suspension reactor (SSR) and microspheres-based detoxification system (MDS). Primary results from the thermodynamic analysis are that: (1) the solute-albumin binding constant is of minor importance to equilibrium once it exceeds about 105 L mol−1; (2) the Prometheus approach requires larger solid adsorbent columns than calculated by adsorbent solute capacity alone; and (3) the albumin-containing recycle stream in the MARS approach is a major reservoir of removed toxin. A survey of published results indicates that MARS is operating under mass transfer control dictated by solute-albumin equilibrium in the recycle stream and Prometheus is approaching equilibrium limits under current clinical protocols. PMID:18638303

  18. Biocompatibility evaluation of porous ceria foams for orthopedic tissue engineering.

    PubMed

    Ball, Jordan P; Mound, Brittnee A; Monsalve, Adam G; Nino, Juan C; Allen, Josephine B

    2015-01-01

    Ceria ceramics have the unique ability to protect cells from free radical-induced damage, making them materials of interest for biomedical applications. To expand upon the understanding of the potential of ceria as a biomaterial, porous ceria, fabricated via direct foaming, was investigated to assess its biocompatibility and its ability to scavenge free radicals. A mouse osteoblast (7F2) cell line was cultured with the ceria foams to determine the extent of the foams' toxicity. Toxicity assessments indicate that mouse osteoblasts cultured directly on the ceria scaffold for 72 h did not show a significant (p > 0.05) increase in toxicity, but rather show comparable toxicity to cells cultured on porous 45S5 Bioglass. The in vitro inflammatory response elicited from porous ceria foams was measured as a function of tumor necrosis factor alpha (TNF-α) secreted from a human monocytic leukemia cell line. Results indicate that the ceria foams do not cause a significant inflammatory response, eliciting a response of 27.1 ± 7.1 pg mL(-1) of TNF-α compared to 36.3 ± 5.8 pg mL(-1) from cells on Bioglass, and 20.1 ± 2.9 pg mL(-1) from untreated cells. Finally, we report cellular toxicity in response to free radicals from tert-butyl hydroperoxide with and without foamed ceria. Our preliminary results show that the foamed ceria is able to decrease the toxic effect of induced oxidative stress. Collectively, this study demonstrates that foamed ceria scaffolds do not activate an inflammatory response, and show potential free radical scavenging ability, thus they have promise as an orthopedic biomaterial.

  19. INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

    NASA Astrophysics Data System (ADS)

    Nakwaski, W.

    1988-11-01

    An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

  20. Study of Decomposition of a Highly Supersaturated Solid Solution of a Granulated Alloy, Al-1, 5Cr-1, 5Zr,

    DTIC Science & Technology

    The mechanism and kinetics of decomposition of a highly supersaturated solid solution in an alloy is of importance in stating the proper technology...that during annealing up to 250 C, there is a great density of dislocations. A hypothesis is presented concerning the structural changes occurring at heating the highly supersaturated solid solution of this alloy.

  1. Thermodynamics and solubility of (UxNp1-x) O2(am) solid solution in the carbonate system

    SciTech Connect

    Rai, Dhanpat; Hess, Nancy J.; Yui, Mikazu; Felmy, Andrew R.; Moore, D. A.

    2004-12-31

    SUMMARY-The formation of a solid solution can significantly affect the solubility of a minor component. The objectives of this study were to determine the nature of U(IV) and Np(IV) solid solutions and their thermodynamic properties. For this purpose...

  2. Uncertainties associated with lacking data for predictions of solid-solution partitioning of metals in soil.

    PubMed

    Le, T T Yen; Hendriks, A Jan

    2014-08-15

    Soil properties, i.e., pH and contents of soil organic matter (SOM), dissolved organic carbon (DOC), clay, oxides, and reactive metals, are required inputs to both mechanistic and empirical modeling in assessing metal solid-solution partitioning. Several of these properties are rarely measured in site-specific risk assessment. We compared the uncertainties induced by lacking data on these soil properties in estimating metal soil solution concentrations. The predictions by the Orchestra framework were more sensitive to lacking soil property data than the predictions by the transfer functions. The deviations between soil solution concentrations of Cd, Ni, Zn, Ba, and Co estimated with measured SOM and those estimated with generic SOM by the Orchestra framework were about 10 times larger than the deviations in the predictions by the transfer functions. High uncertainties were induced by lacking data in assessing solid-solution partitioning of oxy-anions like As, Mo, Sb, Se, and V. Deviations associated with lacking data in predicting soil solution concentrations of these metals by the Orchestra framework reached three-to-six orders of magnitude. The solid-solution partitioning of metal cations was strongly influenced by pH and contents of organic matter, oxides, and reactive metals. Deviations of more than two orders of magnitude were frequently observed between the estimates of soil solution concentrations with the generic values of these properties and the estimates based on the measured data. Reliable information on these properties is preferred to be included in the assessment by either the Orchestra framework or transfer functions.

  3. Size evolution and surface characterization of solid-state nanopores in different aqueous solutions.

    PubMed

    Li, Qingtao; Zhao, Qing; Lu, Bo; Zhang, Hengbin; Liu, Song; Tang, Zhipeng; Qu, Lijia; Zhu, Rui; Zhang, Jingmin; You, Liping; Yang, Fuhua; Yu, Dapeng

    2012-03-07

    The stability and surface evolution of solid-state nanopores in aqueous solutions are extremely important since they would get immersed in solutions during DNA translocation experiment for DNA analyses. In this work, we systematically studied the size evolution of SiN nanopores in ethanol, deionized water and potassium chloride (KCl) solutions by careful surface characterization and composition analyses using a transmission electron microscope. Surprisingly, we found that nanopores closed up completely in ethanol in an hour and showed a 30% and 20% size decrease in deionized water and KCl solutions, respectively. Strong evidence of surface oxidation was found by composition analyses in the nanopore area. Nanopore size evolution was strongly dependent on initial pore size and solution pH value. In pH = 13 KCl solution, SiN nanopores were observed to increase in size instead of decrease. The results not only provide useful information for DNA detection based on solid-state nanopores, but can also guide design and application of other nanodevices exposed to electrolyte-solvent systems such as cell-on-a-chip devices and biosensors.

  4. On the difference of equilibrium constants of DNA hybridization in bulk solution and at the solid-solution interface.

    PubMed

    Oliviero, Giulio; Federici, Stefania; Colombi, Paolo; Bergese, Paolo

    2011-01-01

    The origin of the difference between the equilibrium (affinity) constants of ligand-receptor binding in bulk solution and at a solid-solution interface is discussed in terms of Gibbsian interfacial thermodynamics. It results that the difference is determined by the surface work that the ligand-receptor interaction spends to accommodate surface binding, and in turn that the value of the surface equilibrium constant (strongly) depends on the surface that confines the event. This framework consistently describes a wide set of experimental observations of DNA surface hybridization, correctly predicting that within the surface work window for DNA hybridization, that ranges from -90 to 75 kJ mol(-1), the ratio between surface and bulk equilibrium constants ranges from 10(-16) to 10(13), spanning 29 orders of magnitude.

  5. Structural, vibrational, and thermochemical properties of the monazite-type solid solution La1-xPrxPO4

    NASA Astrophysics Data System (ADS)

    Hirsch, A.; Kegler, P.; Alencar, I.; Ruiz-Fuertes, J.; Shelyug, A.; Peters, L.; Schreinemachers, C.; Neumann, A.; Neumeier, S.; Liermann, H.-P.; Navrotsky, A.; Roth, G.

    2017-01-01

    The monazite-type solid solution La1-xPrxPO4 was synthesized by solid-state reaction and extensively investigated using electron microprobe and thermogravimetric analyses, differential scanning and high-temperature oxide melt solution calorimetry, powder X-ray diffraction, infrared and Raman spectroscopy. Lattice parameters and Ln-O bond lengths show a decrease with increasing Pr content. A small excess volume is observed for the solid solution. IR spectra of the solid solution members present no detectable differences, while a blue shift of the PO4-related modes is seen in the Raman data. This shift can be attributed to the lanthanide contraction. Within errors, calorimetry data show no systematic deviation from an ideal behavior, though one might interpret the data as an indication of a slightly asymmetric mixture. All data indicate that deviations from ideality of the solid solution - if present - are very small.

  6. A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

    PubMed

    Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

    2004-07-21

    The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

  7. Thermodynamic properties of carbon in b.c.c. and f.c.c. iron-silicon-carbon solid solutions.

    NASA Technical Reports Server (NTRS)

    Chraska, P.; Mclellan, R. B.

    1971-01-01

    The equilibrium between hydrogen-methane gas mixtures and Fe-Si-C solid solutions has been investigated both as a function of temperature and carburizing gas composition. The thermodynamic properties of the carbon atoms in both b.c.c. and f.c.c. solid solution have been derived from the equilibrium measurements. The results found have been compared with those of earlier investigations and with the predictions of recent theoretical models on ternary solid solutions containing both substitutional and interstitial solute atoms.

  8. Thermodynamic analysis of the concentration profiles of epitaxial layers of nonideal solid solutions

    SciTech Connect

    Kazakov, A.I.; Kishmar, I.N.; Mokritskii, V.A.; Yakubovskii, M.V.

    1988-03-01

    Based on thermodynamic analysis employing the quasiregular approach a mathematical model of the process of equilibrium crystallization of nonideal three-component solid solutions of compounds of the type A/sup III/B/sup V/ from a restricted volume of a solution in a melt was constructed. This model enables calculation of the distribution of the components over the thickness of the epitaxial layer for low rates of cooling of the solution in a melt. The computer calculations of the concentration profiles of the epitaxial layers of Ga/sub 1-x/Al/sub x/ agreed well with the experimental data for thicknesses of the epitaxial layers up to 20 ..mu..m. For high rates of cooling the mass transfer in the volume of the solution in a melt must be taken into account.

  9. Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State.

    PubMed

    Reddy, G N Manjunatha; Huqi, Aida; Iuga, Dinu; Sakurai, Satoshi; Marsh, Andrew; Davis, Jeffery T; Masiero, Stefano; Brown, Steven P

    2017-02-16

    The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet-based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H⋅⋅⋅N and N-H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D (1) H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible-further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K(+) , Sr(2+) ) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Kinetic and thermodynamic studies of the dissolution of thoria-urania solid solutions

    NASA Astrophysics Data System (ADS)

    Heisbourg, G.; Hubert, S.; Dacheux, N.; Purans, J.

    2004-10-01

    The dissolution of Th 1- xU xO 2 was investigated through leaching experiments combined with X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses. These experiments were performed in acidic and in oxidizing conditions (nitric solutions), for several compositions of solid solutions ranging from x = 0.24 to 0.81. Static sequential experiments in acidic media performed at room temperature confirmed that higher concentration of uranium in the solid solution leads to higher release of uranium in the leachate whatever the pH. The normalized dissolution rate in oxidizing media is increasing all the more the content of uranium is increases in the mixed oxide. While for Th enriched solids, kinetic parameters remain similar to that of ThO 2, in the case of uranium enriched solids, a drastic change is observed, and kinetic parameters are similar to that of UO 2 ones. For x > 0.50, the saturation is reached in the leachate after 100 days. XPS and EXAFS analysis on leached samples pointed out an oxidation of U(IV) at the surface for x < 0.5, and in the bulk for x > 0.5. Enrichment in Th is also observed at the surface of the solid, indicating the formation of a protective layer of hydrated thorium oxide, or hydroxide. Finally, the solubility product of secondary phase was determined. The values obtained are in good agreement with that of ThO 2, Th(OH) 4 and ThO 2, xH 2O reported in the literature.

  11. A combined analytical solution for Chemical Exchange Saturation Transfer and semi-solid Magnetization Transfer

    PubMed Central

    Zaiss, Moritz; Zu, Zhongliang; Xu, Junzhong; Schuenke, Patrick; Gochberg, Daniel F.; Gore, John C.; Ladd, Mark E.; Bachert, Peter

    2015-01-01

    Off-resonant radiofrequency irradiation in tissue indirectly lowers the water signal by saturation transfer processes: On the one hand, there are selective chemical exchange saturation transfer (CEST) effects originating from exchanging endogenous protons resonating a few ppm from water; on the other hand, there is the broad semi-solid magnetization transfer (MT) originating from immobile protons associated with the tissue matrix with kHz line-widths. Recently it was shown that endogenous CEST contrasts can be strongly affected by the MT background so that corrections are needed to derive accurate estimates of CEST effects. Herein we show that a full analytical solution of the underlying Bloch-McConnell equations for both MT and CEST provides insights into their interaction and suggests a simple means to isolate their effects. The presented analytical solution, based on the eigenspace solution of the Bloch-McConnell equations, extends previous treatments by allowing arbitrary line-shapes for the semi-solid MT effects and simultaneously describing multiple CEST pools in the presence of a large MT pool for arbitrary irradiation. The structure of the model indicates that semi-solid MT and CEST effects basically add up inversely in determining the steady-state Z-spectrum, as previously shown for direct saturation and CEST effects. Implications for existing previous CEST analyses in the presence of a semi-solid MT are studied and discussed. It turns out that to accurately quantify CEST contrast, a good reference Z-value, the observed longitudinal relaxation rate of water, and the semi-solid MT pool size fraction, must all be known. PMID:25504828

  12. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    PubMed Central

    Zhang, Yanwen; Stocks, G. Malcolm; Jin, Ke; Lu, Chenyang; Bei, Hongbin; Sales, Brian C.; Wang, Lumin; Béland, Laurent K.; Stoller, Roger E.; Samolyuk, German D.; Caro, Magdalena; Caro, Alfredo; Weber, William J.

    2015-01-01

    A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications. PMID:26507943

  13. Point defect concentrations and solid solution hardening in NiAl with Fe additions

    SciTech Connect

    Pike, L.M.; Chang, Y.A.; Liu, C.T.

    1997-08-01

    The solid solution hardening behavior exhibited when Fe is added to NiAl is investigated. This is an interesting problem to consider since the ternary Fe additions may choose to occupy either the Ni or the Al sublattice, affecting the hardness at differing rates. Moreover, the addition of Fe may affect the concentrations of other point defects such as vacancies and Ni anti-sites. As a result, unusual effects ranging from rapid hardening to solid solution softening are observed. Alloys with varying amounts of Fe were prepared in Ni-rich (40 at. % Al) and stoichiometric (50 at. % Al) compositions. Vacancy concentrations were measured using lattice parameter and density measurements. The site occupancy of Fe was determined using ALCHEMI. Using these two techniques the site occupancies of all species could be uniquely determined. Significant differences in the defect concentrations as well as the hardening behavior were encountered between the Ni-rich and stoichiometric regimes.

  14. Physicochemical and photoelectric properties of cadmium hexathio- and hexaselenogermanate crystals and solid solutions derived from them

    SciTech Connect

    Motrya, S.F.; Tkachenko, V.I.; Chereshnya, V.M.; Kikineshi, A.A.; Semrad, E.E.

    1987-03-01

    Single crystals of Cd/sub 4/GeS/sub 6/, Cd/sub 4/GeSe/sub 6/, and the derived solid solutions have been synthesized and grown. Investigation of physicochemical and photoelectric properties of the alloys showed the existence in the Cd/sub 4/GeS/sub 6/-Cd/sub 4/GeSe/sub 6/ system of a continuous series of solid solutions. The specific resistance and the photosensitivity of the alloys fall with increasing selenium content. For polycrystalline Cd/sub 4/GeS/sub 6/ and Cd/sub 4/GeSe/sub 6/, the average low-temperature heat capacity was determined, and the standard entropy, enthalpy, and entropy of formation were calculated.

  15. Effect of shear stress in ferroelectric solid solutions with coexisting phases

    NASA Astrophysics Data System (ADS)

    Lu, Xiaoyan; Zhang, Hangbo; Zheng, Limei; Cao, Wenwu

    2017-08-01

    One common feature of ferroelectric solid solutions with large piezoelectricity is the coexistence of two or more phases. Due to the strain mismatch among coexisting phases, adaptive structures near the interfaces or domain walls develop to maintain the atomic coherency. Shear stresses commonly exist, especially when the domain size is small. The effect of shear stresses on phase morphology in Pb(Zr1-xTix)O3 solid solutions with compositions within the morphotropic phase boundary region was studied within the framework of Landau phenomenological theory. Our results show that the coexisting rhombohedral (R) and tetragonal (T) phases can be modified to form stable or metastable R-like and/or T-like monoclinic phases under shear stresses. Large stresses may also induce first order or second order phase transitions.

  16. Accelerated exploration of multi-principal element alloys with solid solution phases

    NASA Astrophysics Data System (ADS)

    Senkov, O. N.; Miller, J. D.; Miracle, D. B.; Woodward, C.

    2015-03-01

    Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge—how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs—that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction.

  17. Accelerated exploration of multi-principal element alloys with solid solution phases.

    PubMed

    Senkov, O N; Miller, J D; Miracle, D B; Woodward, C

    2015-03-05

    Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge--how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs--that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction.

  18. Possible bcc → sc phase transitions in Ca-Sr solid solutions under pressure

    NASA Astrophysics Data System (ADS)

    Pozhivatenko, V. V.

    2017-08-01

    The first-principles calculations of thermodynamic characteristics of bcc and sc structures of Ca1- x Sr x solid solutions have been carried out. Taking into account insufficient accuracy of such calculations, for the description of phase transitions, the known experimental data on bcc and sc structures of calcium and strontium have been used to determine parameters for the calculation of Ca1- x Sr x properties using linear interpolation. The possibility of the occurrence of bcc-sc structural phase transitions in Ca1- x Sr x ( x = 0.0625, 0.125, 0.25, 0.5, 0.75) solid solutions and their characteristics under different pressures have been investigated.

  19. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    SciTech Connect

    Zhang, Yanwen; Stocks, George Malcolm; Jin, Ke; Lu, Chenyang; Bei, Hongbin; Sales, Brian C.; Wang, Lumin; Béland, Laurent K.; Stoller, Roger E.; Samolyuk, German D.; Caro, Magdalena; Caro, Alfredo; Weber, William J.

    2015-10-28

    A long-standing objective in materials research is to understand how energy is dissipated in both the electronic and atomic subsystems in irradiated materials, and how related non-equilibrium processes may affect defect dynamics and microstructure evolution. Here we show that alloy complexity in concentrated solid solution alloys having both an increasing number of principal elements and altered concentrations of specific elements can lead to substantial reduction in the electron mean free path and thermal conductivity, which has a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Enhanced radiation resistance with increasing complexity from pure nickel to binary and to more complex quaternary solid solutions is observed under ion irradiation up to an average damage level of 1 displacement per atom. Understanding how materials properties can be tailored by alloy complexity and their influence on defect dynamics may pave the way for new principles for the design of radiation tolerant structural alloys.

  20. Structure and magnetic properties of metastable Co-Cu solid solution nanowire arrays fabricated by electrodeposition

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Li, Fashen; Wang, Ying; Song, Lijing

    2006-08-01

    Nanowire arrays of the metastable Cox Cu1-x (0.20 x 0.85) solid solution system which can not be obtained by equilibrium methods, were prepared by electrodeposition in pores of anodic aluminum oxide (AAO) template, and subsequently annealed at different temperatures. The as-deposited samples all show single phase of fcc structure, and lattice parameters decrease with the increase of Co content and fundamentally accord with Vegard's law. The phase transition with heat treatment was investigated by X-ray diffraction and differential thermal analysis (DTA) which further confirmed the formation of solid solution. With Co content increasing, the coercivity along nanowire axis for as-deposited samples increases, but it decreases for the annealed samples at 700 °C. This phenomenon was explained considering the interaction of Co particles through Cu in nanowires after phase separation.

  1. Flexible, Luminescent Metal-Organic Frameworks Showing Synergistic Solid-Solution Effects on Porosity and Sensitivity.

    PubMed

    Liu, Si-Yang; Zhou, Dong-Dong; He, Chun-Ting; Liao, Pei-Qin; Cheng, Xiao-Ning; Xu, Yan-Tong; Ye, Jia-Wen; Zhang, Jie-Peng; Chen, Xiao-Ming

    2016-12-23

    Mixing molecular building blocks in the solid solution manner is a valuable strategy to obtain structures and properties in between the isostructural parent metal-organic frameworks (MOFs). We report nonlinear/synergistic solid-solution effects using highly related yet non-isostructural, phosphorescent Cu(I) triazolate frameworks as parent phases. Near the phase boundaries associated with conformational diversity and ligand heterogeneity, the porosity (+150 %) and optical O2 sensitivity (410 times, limit of detection 0.07 ppm) can be drastically improved from the best-performing parent MOFs and even exceeds the records hold by precious-metal complexes (3 ppm) and C70 (0.2 ppm).

  2. Isomorphism and solid solution as shown by an accurate high-resolution diffraction experiment.

    PubMed

    Poulain, Agnieszka; Kubicki, Maciej; Lecomte, Claude

    2014-12-01

    High-resolution crystal structure determination and spherical and multipolar refinement enabled an organic solid solution of 1-(4'-chlorophenyl)-2-methyl-4-nitro-1H-imidazole-5-carbonitrile and 5-bromo-1-(4'-chlorophenyl)-2-methyl-4-nitro-1H-imidazole to be found, which would not normally be revealed using only standard resolution data (ca 0.8 Å), as the disordered part is only visible at high resolution. Therefore, this new structure would have been reported as just another polymorphic form, even more reasonably as isostructural with other derivatives. To the best of our knowledge this is the first example of organic solid solution modelled via charge density Hansen-Coppens formalism and analysed by means of quantum theory of atoms in molecules (QTAIM) theory.

  3. Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions.

    PubMed

    Aguirre-Díaz, Lina María; Gándara, Felipe; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2015-05-20

    The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOFs with general formula [InxGa1-x(O2C2H4)0.5(hfipbb)] were prepared by the combination of Ga and In. They are isostructural with their monometal counterparts, synthesized with Al, Ga, and In. Differences in their behavior as heterogeneous catalysts in the three-component, one pot Strecker reaction illustrate the potential of solid solution MOFs to provide the ability to address the various stages involved in the reaction mechanism.

  4. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys.

    PubMed

    Zhang, Yanwen; Stocks, G Malcolm; Jin, Ke; Lu, Chenyang; Bei, Hongbin; Sales, Brian C; Wang, Lumin; Béland, Laurent K; Stoller, Roger E; Samolyuk, German D; Caro, Magdalena; Caro, Alfredo; Weber, William J

    2015-10-28

    A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications.

  5. Accelerated exploration of multi-principal element alloys with solid solution phases

    PubMed Central

    Senkov, O.N.; Miller, J.D.; Miracle, D.B.; Woodward, C.

    2015-01-01

    Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge—how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs—that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction. PMID:25739749

  6. Solution-Liquid-Solid Synthesis of Hexagonal Nickel Selenide Nanowire Arrays with a Nonmetal Catalyst.

    PubMed

    Xu, Kun; Ding, Hui; Jia, Kaicheng; Lu, Xiuli; Chen, Pengzuo; Zhou, Tianpei; Cheng, Han; Liu, Si; Wu, Changzheng; Xie, Yi

    2016-01-26

    Inorganic nanowire arrays hold great promise for next-generation energy storage and conversion devices. Understanding the growth mechanism of nanowire arrays is of considerable interest for expanding the range of applications. Herein, we report the solution-liquid-solid (SLS) synthesis of hexagonal nickel selenide nanowires by using a nonmetal molecular crystal (selenium) as catalyst, which successfully brings SLS into the realm of conventional low-temperature solution synthesis. As a proof-of-concept application, the NiSe nanowire array was used as a catalyst for electrochemical water oxidation. This approach offers a new possibility to design arrays of inorganic nanowires.

  7. Photoinduced processes in solid polymer solutions of dyes in an interference field of laser radiation

    SciTech Connect

    Sizykh, A G; Tarakanova, E A

    1998-12-31

    An investigation was made of the relationships governing the photochemical mechanism of formation of light-induced gratings in solid polymer solutions of a dye with a high quantum yield of the triplet states. The combined analysis of the results of real and numerical experiments was made for a solution of eosin K in gelatin. The protonation rate constant of the dye was measured and the dependence of the diffraction efficiency on the duration of irradiation was explained taking diffusion of the dye into account. A method was proposed for determination of the duffusion coefficient in a spatially modified interference field of the laser radiation. The diffusion coefficients were found. (nonlinear optical phenomena)

  8. Preparation of Li2S-P2S5 solid electrolyte from N-methylformamide solution and application for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Teragawa, Shingo; Aso, Keigo; Tadanaga, Kiyoharu; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2014-02-01

    Electrode-solid electrolyte composite materials for all-solid-state lithium batteries were prepared by coating of the Li2S-P2S5 solid electrolyte onto LiCoO2 particles using a N-methylformamide (NMF) solution of 80Li2S·20P2S5 (mol%) solid electrolyte. SEM and EDX analysis showed that the Li2S-P2S5 solid electrolyte was uniformly coated on LiCoO2 particles. The all-solid-state cell using the LiCoO2 particles coated with the solid electrolyte showed higher charge-discharge capacity than the cells using uncoated LiCoO2 particles.

  9. Solution-Processed Ambipolar Organic Thin-Film Transistors by Blending p- and n-Type Semiconductors: Solid Solution versus Microphase Separation.

    PubMed

    Xu, Xiaomin; Xiao, Ting; Gu, Xiao; Yang, Xuejin; Kershaw, Stephen V; Zhao, Ni; Xu, Jianbin; Miao, Qian

    2015-12-30

    Here, we report solid solution of p- and n-type organic semiconductors as a new type of p-n blend for solution-processed ambipolar organic thin film transistors (OTFTs). This study compares the solid-solution films of silylethynylated tetraazapentacene 1 (acceptor) and silylethynylated pentacene 2 (donor) with the microphase-separated films of 1 and 3, a heptagon-embedded analogue of 2. It is found that the solid solutions of (1)x(2)1-x function as ambipolar semiconductors, whose hole and electron mobilities are tunable by varying the ratio of 1 and 2 in the solid solution. The OTFTs of (1)0.5(2)0.5 exhibit relatively balanced hole and electron mobilities comparable to the highest values as reported for ambipolar OTFTs of stoichiometric donor-acceptor cocrystals and microphase-separated p-n bulk heterojunctions. The solid solution of (1)0.5(2)0.5 and the microphase-separated blend of 1:3 (0.5:0.5) in OTFTs exhibit different responses to light in terms of absorption and photoeffect of OTFTs because the donor and acceptor are mixed at molecular level with π-π stacking in the solid solution.

  10. Synthesis of nanocrystalline yttria doped ceria powder by urea-formaldehyde polymer gel auto-combustion process

    SciTech Connect

    Biswas, M.; Prabhakaran, K. . E-mail: kp2952002@yahoo.co.uk; Gokhale, N.M.; Sharma, S.C.

    2007-04-12

    Nanocrystalline yttria doped ceria powder has been prepared by auto-combustion of a transparent gel formed by heating an aqueous acidic solution containing methylol urea, urea, cerium(III) nitrate and yttrium(III) nitrate. The TGA and DSC studies showed the combustion reaction of the gel initiated at 225 deg. C and completed within a short period of time. XRD spectrum of the combustion product reveals the formation of phase pure cubic yttria doped ceria during the combustion process. Loose agglomerate of yttria doped ceria particle obtained by the combustion reaction could be easily deagglomerated by planetary ball milling and the powder obtained contains particles in the size range of 0.05-3.3 {mu}m with D {sub 50} value of 0.13 {mu}m. The powder particles are aggregate of nanocrystallites with a wide size range of 14-105 nm. Pellets prepared by pressing the yttria doped ceria powder sintered to 95.2% TD at 1400 deg. C.

  11. Shape-controlled ceria-based nanostructures for catalysis applications.

    PubMed

    Qiao, Zhen-An; Wu, Zili; Dai, Sheng

    2013-10-01

    Among oxide catalysts, ceria is a technologically important material because of its wide applications as a promoter in three-way catalysts for the elimination of toxic exhaust gases, low-temperature water-gas-shift reaction, oxygen sensors, oxygen permeation membrane systems, and fuel cells. The catalytic activities of cerium oxide are highly dependent on interfacial structures and nanocrystal morphologies. This Minireview highlights the recent progress in the research of ceria nanoshapes as both catalysts and catalyst supports, including the synthesis, structure characterization, catalytic properties, surface chemistry, as well as reaction mechanisms. Insights from in situ spectroscopy study and theoretical modeling of nanostructured ceria-based materials have shed light on the origin of the ceria shape effect. It is suggested that the surface structure of ceria controls the catalytic activity and selectivity through structure-dependent surface-site geometry, surface vacancy formation energy, defect sites, and coordinatively unsaturated sites on ceria. The morphology-dependent catalysis in ceria has offered a new strategy to finely tune the catalytic activity and selectivity through shape control without altering the catalyst composition. A brief summary and an outlook on this research field will be presented at the end.

  12. Pulmonary toxicity of ceria nanoparticles in mice after intratracheal instillation.

    PubMed

    Xue, Lingxi; He, Xiao; Li, Yuanyuan; Qu, Meihua; Zhang, Zhiyong

    2013-10-01

    Ceria nanoparticles (nano-ceria) are widely used for various applications such as catalytic converters for automobile exhaust, ultraviolet absorber, and electrolyte in fuel cells. Their potential impacts on the environment and human health have also drawn people's attention. The present study was designed to explore the pulmonary toxicity of nano-ceria in mice after an acute intratracheal instillation. CD-1 mice were exposed to 0.04, 0.4, 4 and 40 microg nano-ceria (corresponding to 10, 100, 1000 and 10000 times of the maximum exposure dose, respectively) and sacrificed at 1, 7, and 28 d post-exposure. Lung injury was assessed by bronchoalveolar ravage fluid (BALF) analysis, cell counts, biochemical analysis of lung homogenate, and histopathology. Cell differential analysis of the BALF show that the numbers of neutrophils and lymphocytes increased significantly in the mice exposed to 40 microg nano-ceria at 1 d after instillation, and returned to control levels by 7 d. The lactate dehydrogenate activity in the BALF from the 40 microg group increased significantly during the whole experimental period. Pathological changes were only found in the lung tissues from the mice of 40 microg nano-ceria group. The changes were most obvious by 7 d post-exposure, and returned to normal by 28 d. No other changes were found. The results of the present study suggest that exposure to nano-ceria at the current levels in the ambient air may not cause respiratory toxicity.

  13. Uptake and distribution of ceria nanoparticles in cucumber plants.

    PubMed

    Zhang, Zhiyong; He, Xiao; Zhang, Haifeng; Ma, Yuhui; Zhang, Peng; Ding, Yayun; Zhao, Yuliang

    2011-08-01

    The presence and release of nanoparticles (NPs) into the environment have important implications for human health and the environment. A critical aspect of the risk assessment of nanoparticles is to understand the interactions of manufactured nanoparticles with plants. In this study, the uptake and distribution characteristics of two types of ceria nanoparticles with sizes of ca. 7 nm and 25 nm in cucumber plants were investigated using a radiotracer method and other techniques. With increasing concentration of the nanoparticles, concentration dependent absorption by the plant roots was noticed, but the majority of the particles only loosely adhered to the root surface. The seedlings treated with 7 nm ceria particles showed significantly higher ceria contents in both roots and shoots than those exposed to 25 nm ceria particles at all test concentrations (2, 20, and 200 mg L(-1)). Only very limited amounts of ceria nanoparticles could be transferred from the roots to shoots because the entry of nanoparticles into the roots was difficult. However, the results of tissue distributions of ceria nanoparticles in the plants and two dimensional distributions of the particles in the leaves imply that once they have entered into the vascular cylinder, ceria nanoparticles could move smoothly to the end of the vascular bundle along with water flow. To the best of our knowledge, this is the first detailed study of uptake and distribution of metal oxide nanoparticles in plants.

  14. Investigation of Self-Organized Nanoheterostructure Properties in InGaAsP Solid Solutions

    DTIC Science & Technology

    1998-06-01

    UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP012787 TITLE: Investigation of Self-Organized Nanoheterostructure ... nanoheterostructure properties in InGaAsP solid solutions I S. Tarasov, 1. N. Arsent’ev, N. A. Bert, L. S. Vavilova, V.A. Kapitonov, A. V. Murashova...organized InGaAsP nanoheterostructures grown on InP and GaAs substrates have been investigated by photoluminescence and transmission electron microscopy

  15. Molecular tectonics: crystal engineering of mixed valence Fe(II)/Fe(III) solid solutions.

    PubMed

    Dechambenoit, Pierre; Ferlay, Sylvie; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2010-02-14

    Based on isostructurality between crystals formed upon combining the dicationic tecton 2 with either M(3)Fe(III)(CN)(6) or M(4)Fe(II)(CN)(6) (M = Cs), a rare example of an H-bonded mixed valence Fe(ii)-Fe(iii) solid solution ((Cs(2)2(3)-[Fe(II)(CN)(6)](2))(0.83)(2(3)-[Fe(III)(CN)(6)](2))(0.17))) and curious necklace-like composite crystals were generated.

  16. Saturation magnetization in supersaturated solid solution of Co-Cu alloy

    NASA Astrophysics Data System (ADS)

    Yuasa, Motohiro; Kajikawa, Kota; Hakamada, Masataka; Mabuchi, Mamoru

    2009-10-01

    The magnetovolume effect has been investigated using a supersaturated solid solution of a Co-19 at. %Cu alloy processed by electrodeposition. The enhanced saturation magnetization of the Co-Cu alloy was attributed to both metastable fcc Co and lattice expansion. The density functional theory using the CASTEP code revealed that an enhanced magnetic moment due to the magnetovolume effect is obtained in fcc Co, but not in hcp Co.

  17. A novel quaternary solid solution photo-absorber material for photoelectrochemical hydrogen generation.

    PubMed

    Hong, Tiantian; Liu, Zhifeng; Yan, Weiguo; Wang, Bo; Zhang, Xueqi; Liu, Junqi; Wang, Junkai; Han, Jianhua

    2015-09-14

    We report a novel quaternary solid solution (Ag-Cu-Sb-S or ACSS) serving as a photo-absorber material in the photoelectrochemical field for the first time, and ZnO/ACSS nanoarrays exhibited a photocurrent density of 4.45 mA cm(-2). The research indicates that ZnO/ACSS composite structures have enormous potential in PEC hydrogen generation systems.

  18. Damage accumulation in ion-irradiated Ni-based concentrated solid-solution alloys

    SciTech Connect

    Ullah, Mohammad W.; Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.

    2016-01-01

    We investigate Irradiation-induced damage accumulation in Ni0.8Fe0.2 and Ni0.8Cr0.2 alloys by using molecular dynamics simulations to assess possible enhanced radiation-resistance in these face-centered cubic (fcc), single-phase, concentrated solid-solution alloys, as compared with pure fcc Ni.

  19. Mixed Valence in Conjugated Anion Radicals. Solution and Solid State Studies

    DTIC Science & Technology

    1991-05-24

    voltammetry was performed using a BAS-100 electrochemical analyzer. Bulk electrolyses were performed with a Princeton Applied Research (PAR) model 173...interactions. i-w. W), According to this approach, model compounds are prepared which, when studied in I-M solution, mimic the intramolecular properties of...the synthetic metal. The model V" - compound is then incorporated into a solid in order to compare its properties with that - of the synthetic metal

  20. Properties of solid solutions, doped film, and nanocomposite structures based on zinc oxide

    NASA Astrophysics Data System (ADS)

    Lashkarev, G. V.; Shtepliuk, I. I.; Ievtushenko, A. I.; Khyzhun, O. Y.; Kartuzov, V. V.; Ovsiannikova, L. I.; Karpyna, V. A.; Myroniuk, D. V.; Khomyak, V. V.; Tkach, V. N.; Timofeeva, I. I.; Popovich, V. I.; Dranchuk, N. V.; Khranovskyy, V. D.; Demydiuk, P. V.

    2015-02-01

    A study of the properties of materials based on the wide bandgap zinc oxide semiconductor, which are promising for application in optoelectronics, photovoltaics and nanoplasmonics. The structural and optical properties of solid solution Zn1-xCdxO films with different cadmium content, are studied. The samples are grown using magnetron sputtering on sapphire backing. Low-temperature photoluminescence spectra revealed emission peaks associated with radiative recombination processes in those areas of the film that have varying amounts of cadmium. X-ray phase analysis showed the presence of a cadmium oxide cubic phase in these films. Theoretical studies of the solid solution thermodynamic properties allowed for a qualitative interpretation of the observed experimental phenomena. It is established that the growth of the homogeneous solid solution film is possible only at high temperatures, whereas regions of inhomogeneous composition can be narrowed through elastic deformation, caused by the mismatch of the film-backing lattice constants. The driving forces of the spinodal decomposition of the Zn1-xCdxO system are identified. Fullerene-like clusters of Znn-xCdxOn are used to calculate the bandgap and the cohesive energy of ZnCdO solid solutions. The properties of transparent conductive ZnO films, doped with Group III donor impurities (Al, Ga, In), are examined. It is shown that oxygen vacancies are responsible for the hole trap centers in the zinc oxide photoconductivity process. We also examine the photoluminescence properties of metal-ZnO nanocomposite structures, caused by surface plasmons.

  1. X-ray diffraction study of gold nitride films: Observation of a solid solution phase

    NASA Astrophysics Data System (ADS)

    Alves, L.; Hase, T. P. A.; Hunt, M. R. C.; Brieva, A. C.; Šiller, L.

    2008-12-01

    The structure of nitride containing gold films produced by reactive ion sputtering and nitrogen plasma etching is investigated using x-ray photoelectron spectroscopy and x-ray diffraction. It is found that gold nitride is a solid solution of nitrogen atoms dissolved in a fcc gold matrix. Differences between the strain and lattice parameters of gold and gold nitride films were observed and are explained by interstitial nitrogen present in the latter.

  2. Precipitation of Ordered Phases in Metallic Solid Solutions: A Synergistic Clustering and Ordering Process (Preprint)

    DTIC Science & Technology

    2011-07-01

    of such concurrent clustering and ordering processes in metallic solid solutions including Fe-Al [4], Ni-Al [5,6], Ni-Ti [7,8], and Cu -Ti [9,10...ordering reaction to take place. The proposition is that since the Cu -15Ni-8Sn alloy composition cannot undergo congruent ordering, spinodal...interpretation of their results. For example, Wendt and Hassan noted from [14] that in samples of the quenched alloy that have been briefly aged

  3. Experimental and theoretical investigation of Cr1-xScxN solid solutions for thermoelectrics

    NASA Astrophysics Data System (ADS)

    Kerdsongpanya, Sit; Sun, Bo; Eriksson, Fredrik; Jensen, Jens; Lu, Jun; Koh, Yee Kan; Nong, Ngo Van; Balke, Benjamin; Alling, Björn; Eklund, Per

    2016-12-01

    The ScN- and CrN-based transition-metal nitrides have recently emerged as a novel and unexpected class of materials for thermoelectrics. These materials constitute well-defined model systems for investigating mixing thermodynamics, phase stability, and band structure aiming for property tailoring. Here, we demonstrate an approach to tailor their thermoelectric properties by solid solutions. The trends in mixing thermodynamics and densities-of-states (DOS) of rocksalt-Cr1-xScxN solid solutions (0 ≤ x ≤ 1) are investigated by first-principles calculations, and Cr1-xScxN thin films are synthesized by magnetron sputtering. Pure CrN exhibits a high power factor, 1.7 × 10-3 W m-1 K-2 at 720 K, enabled by a high electron concentration thermally activated from N vacancies. Disordered rocksalt-Cr1-xScxN solid solutions are thermodynamically stable, and calculated DOS suggest the possibility for power-factor improvement by Sc3d orbital delocalization on Cr3d electrons giving decreasing electrical resistivity, while localized Cr3d orbitals with a large DOS slope may yield an improved Seebeck coefficient. Sc-rich solid solutions show a large improvement in power factor compared to pure ScN, and all films have power factors above that expected from the rule-of-mixture. These results corroborate the theoretical predictions and enable tailoring and understanding of structure-transport-property correlations of Cr1-xScxN.

  4. Mechanisms of release of silicon from solution and from a solid gold matrix

    SciTech Connect

    Hinds, M.; Styris, D.L.; Brown, G.N.

    1994-12-31

    It has been found that silicon can be determined directly in gold by solid sampling GFAAS with aqueous standards for calibration. Peak shapes for silicon from both aqueous standards and solid samples are similar and do not exhibit tailing that one would expect from an analyte occluded in a metal matrix. Experiments with silicon dried onto the surface of a gold sample confirm that silicon is on the surface prior to atomization. This can be explained by the analyte migrating to the surface via the convective cells induced by the temperature gradients in the sample in the early stages of the atomization cycle. Silicon originating from aqueous solutions does not have to migrate through a matrix and therefore is more readily atomized. Despite this, the temporal differences between silicon absorbance from solution and solid samples are not that dissimilar. One possible explanation is that the kinetics for silicon transport through the gold are quite fast and that once at the surface the rate of atomization is similar to that of the aqueous solution.

  5. Fe–Ni solid solutions in nano-size dimensions: Effect of hydrogen annealing

    SciTech Connect

    Kumar, Asheesh; Meena, S.S.; Banerjee, S.; Sudarsan, V.; Yusuf, S.M.

    2016-02-15

    Highlights: • Fe–Ni solid solution with nano-size dimensions were prepared and characterized. • Both as prepared and hydrogenated solid solutions have FCC structure of Ni. • Paramagnetic and ferromagnetic domains coexist in these samples. - Abstract: Nanoparticles of Ni{sub 0.50}Fe{sub 0.50} and Ni{sub 0.75}Fe{sub 0.25} alloys were prepared by chemical reduction in ethylene glycol medium. XRD and {sup 57}Fe Mössbauer studies have confirmed the formation of Fe–Ni solid solution in nano-size dimensions with FCC structure. These samples consist of both ferromagnetic and paramagnetic domains which have been attributed to the coexistence of large and small particles as confirmed by atomic force microscopic (AFM) and {sup 57}Fe Mössbauer spectroscopic studies. Improved extent of Fe–Fe exchange interaction existing in Ni{sub 0.50}Fe{sub 0.50} alloy compared to Ni{sub 0.75}Fe{sub 0.25} alloy explains the observed increase in the relative extent of ferromagnetic domains compared to paramagnetic domains in the former sample. Increase in the relative extent of ferromagnetic domains for hydrogenated alloys is due to increase in particle size brought about by the high temperature activation prior to hydrogenation.

  6. Controls of carbonate mineralogy and solid-solution of Mg in calcite: evidence from spelean systems

    SciTech Connect

    Gonzalez, L.A.; Lohmann, K.C.

    1985-01-01

    Precipitation of carbonate minerals in spelean systems occurs under a wide range of fluid chemistry, Mg-Ca ratios, alkalinities, pH and temperatures; thus, spelean systems provide ideal settings to determine factors controlling the mineralogy of precipitated carbonates and solid-solution of Mg in calcite. Cave waters and actively-precipitating carbonate speleothems were collected from Carlsbad Caverns National Park, New Mexico and the Mammoth-Flint Cave System, Kentucky. Carbonate mineralogy of precipitated phases was determined by x-ray diffraction, and major and minor element composition of waters and accompanying minerals were determined by Atomic Absorption Spectrophotometry. Results demonstrate that at a constant CO3 concentration the precipitation threshold for calcite to aragonite is controlled dominantly by the Mg/Ca ratio of the ambient fluid. Aragonite precipitation is favored by high Mg/Ca ratios. Conversely, with increasing CO3 concentration at constant fluid Mg/Ca ratios, calcite is preferentially precipitated. Solid-solution of Mg in calcite is positively correlated with both increased Mg/Ca ratios and CO3 concentrations. These data suggest that Mg contents of calcite can not be defined solely in terms of a homogeneous distribution coefficient. Rather, Mg concentrations can be also be affected by the CO3 concentration and degree of calcite saturation, suggesting that the rate of crystal growth also plays and important role in Mg solid-solution in calcites.

  7. Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

    USGS Publications Warehouse

    Tesoriero, A.J.; Pankow, J.F.

    1996-01-01

    Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

  8. Hydrothermal synthesis of pollucite, analcime and their solid solutions and analysis of their properties

    NASA Astrophysics Data System (ADS)

    Jing, Zhenzi; Cai, Kunchuan; Li, Yan; Fan, Junjie; Zhang, Yi; Miao, Jiajun; Chen, Yuqian; Jin, Fangming

    2017-05-01

    Pollucite, as a perfect long-term potential host for radioactive Cs immobilization, barely exists in pure form naturally but in an isomorphism form between pollucite and analcime due to coexistence of Cs and Na. Pollucite could be hydrothermally synthesized with Cs-polluted soil or clay minerals which contain Cs and Na, and it is necessary to study the properties of the synthesis if Cs and Na contained. Pure pollucite, analcime and their solid solutions were hydrothermally synthesized with chemicals, and it was found that the most formed pollucite analcime solid solutions with Cs/(Cs + Na) ratios of 2/6-5/6 had very similar properties in mineral composition, morphology and size, structural water (Cs cations) and coordination environment to pollucite. This also suggests that even coexistence of Cs and Na in nature, pollucite favors to form due to site preference for Cs over Na, which leads to the property and the structure of the most solid solutions similar to that of pollucite.

  9. Local structure in the disordered solid solution of cis- and trans-perinones.

    PubMed

    Teteruk, Jaroslav L; Glinnemann, Jürgen; Heyse, Winfried; Johansson, Kristoffer E; van de Streek, Jacco; Schmidt, Martin U

    2016-06-01

    The cis- and trans-isomers of the polycyclic aromatic compound perinone, C26H12N4O2, form a solid solution (Vat Red 14). This solid solution is isotypic to the crystal structures of cis-perinone (Pigment Red 194) and trans-perinone (Pigment Orange 34) and exhibits a combined positional and orientational disorder: In the crystal, each molecular position is occupied by either a cis- or trans-perinone molecule, both of which have two possible molecular orientations. The structure of cis-perinone exhibits a twofold orientational disorder, whereas the structure of trans-perinone is ordered. The crystal structure of the solid solution was determined by single-crystal X-ray analysis. Extensive lattice-energy minimizations with force-field and DFT-D methods were carried out on combinatorially complete sets of ordered models. For the disordered systems, local structures were calculated, including preferred local arrangements, ordering lengths, and probabilities for the arrangement of neighbouring molecules. The superposition of the atomic positions of all energetically favourable calculated models corresponds well with the experimentally determined crystal structures, explaining not only the atomic positions, but also the site occupancies and anisotropic displacement parameters.

  10. Solid Solution Photocatalyst with Spontaneous Polarization Exhibiting Low Recombination Toward Efficient CO2 Photoreduction.

    PubMed

    Zhou, Peng; Wang, Xin; Yan, Shicheng; Zou, Zhigang

    2016-08-23

    Decreasing the recombination of photogenerated carriers is a major challenge for efficiently converting solar energy into chemical energy by photocatalysis. Here, we have demonstrated that growth of a polar GaN:ZnO solid solution single crystal along its polarization axis is beneficial to efficient separation of photogenerated carriers, owing to the periodic potential barriers and wells generated from the periodically positive and negative atom arrangements in crystal structure. Local charge imbalance caused by replacing Ga(3+) with Zn(2+) leads to a polarization vector in the {0 0 0 1} planes of GaN:ZnO solid solution, thus forming a 1 D electron transport path along [2 1‾  1‾  0] in the {0 0 0 1} planes of GaN:ZnO solid solution to decrease recombination. Shorting the hole-transport distance by synthesizing porous nanoplates can further decrease recombination under the polarization field and improve the performance of polar photocatalyst in photoreduction of CO2 into CH4 .

  11. CSBB-ConeExclusion, adapting structure based solution virtual screening to libraries on solid support.

    PubMed

    Shave, Steven; Auer, Manfred

    2013-12-23

    Combinatorial chemical libraries produced on solid support offer fast and cost-effective access to a large number of unique compounds. If such libraries are screened directly on-bead, the speed at which chemical space can be explored by chemists is much greater than that addressable using solution based synthesis and screening methods. Solution based screening has a large supporting body of software such as structure-based virtual screening tools which enable the prediction of protein-ligand complexes. Use of these techniques to predict the protein bound complexes of compounds synthesized on solid support neglects to take into account the conjugation site on the small molecule ligand. This may invalidate predicted binding modes, the linker may be clashing with protein atoms. We present CSBB-ConeExclusion, a methodology and computer program which provides a measure of the applicability of solution dockings to solid support. Output is given in the form of statistics for each docking pose, a unique 2D visualization method which can be used to determine applicability at a glance, and automatically generated PyMol scripts allowing visualization of protein atom incursion into a defined exclusion volume. CSBB-ConeExclusion is then exemplarically used to determine the optimum attachment point for a purine library targeting cyclin-dependent kinase 2 CDK2.

  12. Synthesis of complex metal oxides using hydroxide, cyanide, and nitrate solid solution precursors

    NASA Astrophysics Data System (ADS)

    Vidyasagar, K.; Gopalakrishnan, J.; Rao, C. N. R.

    1985-06-01

    Precursor solid solutions provide convenient routes for preparing complex metal oxides. Hydroxide solid solutions of the general formula Ln1- xMx(OH) 3 (where Ln = La or Nd and M = Al, Cr, Fe, Co, or Ni) and La 1- x- yM' xM″ y(OH) 3 (where M' = Ni and M″ = Co or Cu) crystallize in the rare earth trihydroxide structure and can be decomposed at relatively low temperatures to yield complex metal oxides. Several oxides of the type LaNiO 3, NdNiO 3, LaNi 1- xCo xO 3, and LaNi 1- xCu xO 3 have been prepared by the hydroxide precursor route. Thermal decomposition of cyanide precursors of the type Ln[ M1- xM' x(CN) 6] · 5H 2O and Ln1- xLn' x[ M(CN) 6] · 5H 2O yields the quaternary oxides which are not readily made by ceramic methods. Nitrate solid solution precursors of the type Ba 1- xPb x(NO 3) 2, Sr 1- xPb x(NO 3) 2, and BaSrPb(NO 3) 6 have been used for preparing several interesting oxides such as BaPbO 3, Ba 2PbO 4, and BaSrPbO 4.

  13. Characterizing SiC-AlN semiconductor solid solutions with indirect and direct bandgaps

    NASA Astrophysics Data System (ADS)

    Dallaeva, Dinara; Ramazanov, Shikhgasan; Ramazanov, Gusejn; Akhmedov, Ramazan; Tománek, Pavel

    2015-01-01

    The objective of the study is to characterize the dependence of the optical properties of solid solutions of silicon carbide and aluminum nitride on composition. Even small differences in composition provide manipulation of band gap features over a wide range. Data for this paper were collected by X-ray diffraction, photoluminescence and absorption spectroscopy. The evolution of the observed optical properties as a result of compositional changes were studied. X-ray studies confirm the presence of a(SiC)1-x(AlN)x solid solution. Investigation of absorption spectra shows the optical band gap of the sample with composition (SiC)0,88(AlN)0,12 is 3.5eV, and 4.24 eV for the (SiC)0,36(AlN)0,64 solid solution. The photoluminescence spectra demonstrate the strong dependence of the spectra on composition x. The experimental results are in agreement with theory. These data demonstrate the optimization of optical properties for particular optoelectronic applications by varying the (SiC)1-x(AlN)xcomposition.

  14. Influence of the activation conditions on the elimination of residual impurities on ceria-zirconia mixed oxides

    NASA Astrophysics Data System (ADS)

    Daturi, M.; Binet, C.; Lavalley, J. C.; Vidal, H.; Kaspar, J.; Graziani, M.; Blanchard, G.

    1998-10-01

    A series of samples belonging to the ceria-zirconia solid solution has been investigated from the point of view of surface impurities, via TPO/TPD and FTIR spectroscopy. Species likely due either to the precursors or to atmospheric contamination have been taken into account and their stability has been studied following two different thermal treatments. A complete cleaning treatment is proposed in order to obtain powders of satisfactory quality for catalytic purposes. Les impuretés superficielles contenues dans une série d'oxydes mixtes cérine- zircone ont été étudiées par TPO/TPD et spectroscopie infrarouge. Les impuretés provenant soit des précurseurs soit de la contamination atmosphérique (carbonates) ont été identifiées et leur stabilité thermique a été étudiée en fonction de différents traitements thermiques. Une méthode thermique de purification est proposée afin d'obtenir des poudres de qualité suffisante pour les applications catalytiques.

  15. A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent.

    PubMed

    Waysbort, Daniel; McGarvey, David J; Creasy, William R; Morrissey, Kevin M; Hendrickson, David M; Durst, H Dupont

    2009-01-30

    A decontamination system for chemical warfare agents was developed and tested that combines a liquid decontamination reagent solution with solid sorbent particles. The components have fewer safety and environmental concerns than traditional chlorine bleach-based products or highly caustic solutions. The liquid solution, based on Decon Greentrade mark, has hydrogen peroxide and a carbonate buffer as active ingredients. The best solid sorbents were found to be a copolymer of ethylene glycol dimethacrylate and n-lauryl methacrylate (Polytrap 6603 Adsorber); or an allyl methacrylate cross-linked polymer (Poly-Pore E200 Adsorber). These solids are human and environmentally friendly and are commonly used in cosmetics. The decontaminant system was tested for reactivity with pinacolyl methylphosphonofluoridate (Soman, GD), bis(2-chloroethyl)sulfide (Mustard, HD), and S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothioate (VX) by using NMR Spectroscopy. Molybdate ion (MoO(4)(-2)) was added to the decontaminant to catalyze the oxidation of HD. The molybdate ion provided a color change from pink to white when the oxidizing capacity of the system was exhausted. The decontaminant was effective for ratios of agent to decontaminant of up to 1:50 for VX (t(1/2) < or = 4 min), 1:10 for HD (t(1/2) < 2 min with molybdate), and 1:10 for GD (t(1/2) < 2 min). The vapor concentrations of GD above the dry sorbent and the sorbent with decontamination solution were measured to show that the sorbent decreased the vapor concentration of GD. The E200 sorbent had the additional advantage of absorbing aqueous decontamination solution without the addition of an organic co-solvent such as isopropanol, but the rate depended strongly on mixing for HD.

  16. High temperature structural study of Gd-doped ceria by synchrotron X-ray diffraction (673 K ≤ T ≤ 1073 K).

    PubMed

    Artini, Cristina; Pani, Marcella; Lausi, Andrea; Masini, Roberto; Costa, Giorgio A

    2014-10-06

    The crystallographic features of Gd-doped ceria were investigated at the operating temperature of solid oxides fuel cells, where these materials are used as solid electrolytes. (Ce(1-x)Gd(x))O(2-x/2) samples (x = 0.1, 0.3, 0.5, 0.7) were prepared by coprecipitation of mixed oxalates, treated at 1473 K in air, and analyzed by synchrotron X-ray diffraction in the temperature range 673 K ≤ T ≤ 1073 K at the Elettra synchrotron radiation facility located in Trieste, Italy. In the whole temperature span a boundary was found at x ∼ 0.2 between a CeO2-based solid solution (for x ≤ 0.2) and a structure where Gd2O3 microdomains grow within the CeO2 matrix, taking advantage of the similarity between Gd(3+) and Ce(4+) sizes; the existence of the boundary at x ∼ 0.2 was confirmed also by measurements of ionic conductivity performed by impedance spectroscopy. Similar to what observed at room temperature, the trend of the cell parameter shows the presence of a maximum; with increasing temperature, the composition corresponding to the maximum moves toward lower Gd content. This evidence can be explained by analyzing the behavior of the coefficient of thermal expansion as a function of composition.

  17. Structures in solid state and solution of dimethoxy curcuminoids: regioselective bromination and chlorination

    PubMed Central

    2013-01-01

    Background Several papers described the structure of curcumin and some other derivatives in solid and in solution. In the crystal structure of curcumin, the enol H atom is located symmetrically between both oxygen atoms of the enolone fragment with an O···O distance of 2.455 Å, which is characteristic for symmetrical H-bonds. In the solution, the geometry of the enolone fragment is attributed to the inherent disorder of the local environment, which solvates one of the basic sites better than the other, stabilizing one tautomer over the other. In this paper, how the position of methoxy groups in dimethoxy curcuminoids influence the conformation of molecules and how the halogen atoms change it when they are bonded at α-position in keto-enol part of molecules is described. Results Six isomers of dimethoxy curcuminoids were prepared. Conformations in solid state, which were determined by X-ray single crystallography and 1H MAS and 13C CPMAS NMR measurements, depend on the position of methoxy groups in curcuminoid molecules. In solution, a fast equilibrium between both keto-enol forms exists. A theoretical calculation finding shows that the position of methoxy groups changes the energy of HOMO and LUMO. An efficient protocol for the highly regioselective bromination and chlorination leading to α-halogenated product has been developed. All α-halogenated compounds are present mainly in cis keto-enol form. Conclusions The structures in solid state of dimethoxy curcuminoids depend on the position of methoxy groups. The NMR data of crystalline solid samples of 3,4-diOCH3 derivative, XRD measurements and X-ray structures lead us to the conclusion that polymorphism exists in solids. The same conclusion can be done for 3,5-diOCH3 derivative. In solution, dimethoxy curcuminoids are present in the forms that can be described as the coexistence of two equivalent tautomers being in fast equilibrium. The position of methoxy groups has a small influence on the enolic hydrogen

  18. Role of Associated Defects in Oxygen Ion Conduction and Surface Exchange Reaction for Epitaxial Samaria-Doped Ceria Thin Films as Catalytic Coatings.

    PubMed

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Belianinov, Alex; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V; Rupp, Jennifer L M; Aruta, Carmela

    2016-06-15

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications.

  19. Differences in physical chemistry and dissolution rate of solid particle aerosols from solution pressurised inhalers.

    PubMed

    Buttini, Francesca; Miozzi, Michele; Balducci, Anna Giulia; Royall, Paul G; Brambilla, Gaetano; Colombo, Paolo; Bettini, Ruggero; Forbes, Ben

    2014-04-25

    Solution composition alters the dynamics of beclomethasone diproprionate (BDP) particle formation from droplets emitted by pressurised metered dose inhalers (pMDIs). The hypothesis that differences in inhaler solutions result in different solid particle physical chemistry was tested using a suite of complementary calorimetric techniques. The atomisation of BDP-ethanol solutions from commercial HFA-pMDI produced aerodynamically-equivalent solid particle aerosols. However, differences in particle physico-chemistry (morphology and solvate/clathrate formation) were detected by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and supported by hot stage microscopy (HSM). Increasing the ethanol content of the formulation from 8 to 12% (w/w), which retards the evaporation of propellant and slows the increase in droplet surface viscosity, enhanced the likelihood of particles drying with a smooth surface. The dissolution rate of BDP from the 12% (w/w) ethanol formulation-derived particles (63% dissolved over 120 min) was reduced compared to the 8% (w/w) ethanol formulation-derived particles (86% dissolved over 120 min). The addition of 0.01% (w/w) formoterol fumarate or 1.3% (w/w) glycerol to the inhaler solution modified the particles and reduced the BDP dissolution rate further to 34% and 16% dissolved in 120 min, respectively. These data provide evidence that therapeutic aerosols from apparently similar inhaler products, including those with similar aerodynamic performance, may behave non-equivalently after deposition in the lungs. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Study of solid-solution hardening in binary aluminium-based alloys

    NASA Astrophysics Data System (ADS)

    Draissia, Mohamed; Debili, Mohamed-Yacine

    2005-09-01

    Solid-solution formation in binary aluminium-based alloys is due essentially to the combined effects of the size and valence of solvent and solute atoms, as expected by the four Hume-Rothery rules. The lattice parameter of aluminium in the solid solution of the sputtered Al-Fe films is [Al-a (Å)=4.052-6.6×10-3Y]. The increasing and decreasing evolution of the lattice parameter of copper [Cu-a (Å)=3.612+1.8×10-3Z] and aluminium [Al-a (Å)=4.048-1.6×10-3X] in the sputtered Al-1.8 to 92.5 at. % Cu films is a result of the difference in size between the aluminium and copper atoms. The low solubility of copper in aluminium (<1.8 at % Cu) is due to the valences of solvent and solute atoms in contrast with other sputtered films prepared under similar conditions, such as Al-Mg (20 at. % Mg), Al-Ti (27 at. % Ti), Al-Cr (5at. % Cr) and Al-Fe (5.5 at. % Fe) where the solubility is due to the difference in size.

  1. Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

    NASA Astrophysics Data System (ADS)

    Schuler, Thomas; Nastar, Maylise

    2016-06-01

    We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

  2. Energetics of a uranothorite (Th1–xUxSiO4) solid solution

    DOE PAGES

    Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

    2016-10-11

    High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO4)x–(ThSiO4)1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumes of mixing, coupled with stronglymore » exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

  3. Structural investigations of aroylhydrazones derived from nicotinic acid hydrazide in solid state and in solution

    NASA Astrophysics Data System (ADS)

    Galić, Nives; Brođanac, Ivan; Kontrec, Darko; Miljanić, Snežana

    2013-04-01

    Structural forms of aroylhydrazones derived from nicotinic acid hydrazide have been studied in the solid state by FT-IR spectroscopy and in solution by NMR, UV-Vis and ATR spectroscopy. The studied compounds were N'-benzylidene-3-pyridinecarbohydrazide (1), N'-(2,4-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N'-(5-chloro-2-hydroxyphenylmethylidene)-3-pyridinecarbohydrazide (3), and N'-(3,5-dichloro-2-hydroxymethoxyphenylmethylidene)-3-pyridinecarbohydrazide (4). The compound 1 adopted the most stable ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd ) in the solid state as well as in various organic solvents. In mixtures of organic solvents with water the UV-Vis and ATR spectra implied intermolecular hydrogen bonding of 1 with water molecules. The presence of both tautomeric forms I and II (form II, sbnd COHdbnd Nsbnd Ndbnd Csbnd ) was proposed for the solid substance and highly concentrated solutions of 2, whereas form I was detected as the predominant one in diluted solutions. For compounds 3 and 4 a coexistence of forms I and III (form III, sbnd COsbnd NHsbnd NHsbnd Cdbnd Csbnd COsbnd ) was noticed in the solid state and in polar protic organic solvents. The conversion to form III was induced by increasing the water content in the solvent mixtures. This process was the most pronounced for compound 4. When exposed to daylight, an appearance of a new band was observed during time in the UV-Vis spectrum of 4 in organic solvent/water 1/1 mixtures, which implied that tautomeric interconversion was most likely followed by E/Z isomerisation.

  4. Efficient screening of 2D molecular polymorphs at the solution-solid interface

    NASA Astrophysics Data System (ADS)

    Lee, Shern-Long; Adisoejoso, Jinne; Fang, Yuan; Tahara, Kazukuni; Tobe, Yoshito; Mali, Kunal S.; de Feyter, Steven

    2015-03-01

    Formation of multiple polymorphs during two-dimensional (2D) crystallization of organic molecules is more of a routine occurrence than rarity. Although such diverse crystalline structures provide exciting possibilities for studying crystal engineering in 2D, predicting the occurrence of polymorphs for a given building block is often non-trivial. Moreover, there is scarcity of methods that can experimentally verify the presence of such crystalline polymorphs in a straightforward fashion. Here we demonstrate a relatively simple experimental approach for screening of 2D polymorphs formed at the solution-solid interface. The strategy involves use of solution flow produced by contacting a piece of tissue paper to the sample to generate a lateral density gradient along the substrate surface. In situ generation of such gradient allows rapid discovery and nanoscale separation of multiple 2D polymorphs in a single experiment. The concept is demonstrated using three structurally different building blocks that differ in terms of intermolecular interactions responsible for 2D crystal formation. The method described here represents a powerful tool for efficient screening of 2D polymorphs formed at the solution-solid interface.Formation of multiple polymorphs during two-dimensional (2D) crystallization of organic molecules is more of a routine occurrence than rarity. Although such diverse crystalline structures provide exciting possibilities for studying crystal engineering in 2D, predicting the occurrence of polymorphs for a given building block is often non-trivial. Moreover, there is scarcity of methods that can experimentally verify the presence of such crystalline polymorphs in a straightforward fashion. Here we demonstrate a relatively simple experimental approach for screening of 2D polymorphs formed at the solution-solid interface. The strategy involves use of solution flow produced by contacting a piece of tissue paper to the sample to generate a lateral density

  5. Exploring hardness enhancement in superhard tungsten tetraboride-based solid solutions using radial X-ray diffraction

    SciTech Connect

    Xie, Miao; Mohammadi, Reza; Turner, Christopher L.; Kaner, Richard B.; Kavner, Abby; Tolbert, Sarah H.

    2015-07-29

    In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

  6. Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

    DOE PAGES

    An, Zhinan; Jia, Haoling; Wu, Yueying; ...

    2015-05-04

    The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.

  7. Crystallographic and Optical Characteristics of Thin Films of Cu2ZnSn(SxSe1- x)4 Solid Solutions

    NASA Astrophysics Data System (ADS)

    Sheleg, A. U.; Hurtavy, V. G.; Mudryi, A. V.; Zhivulko, V. D.; Valakh, M. Ya.; Yuhimchuk, V. A.; Babichuk, I. S.; Xie, H.; Saucedo, E.

    2014-11-01

    Results of x-ray diffraction and optical studies of thin films of Cu2ZnSn(SxSe1-x)4 solid solutions were presented. Unit-cell constants a and c of Cu2ZnSn(SxSe1-x)4 were determined as functions of composition. It was shown that a and c decreased linearly with increasing S concentration. Optical transmission and photoluminescence spectra of thin films of Cu2ZnSn(SxSe1-x) solid solutions were measured. Absorption coefficients and band-gap energies were determined as functions of the solid-solution composition.

  8. Exploring hardness enhancement in superhard tungsten tetraboride-based solid solutions using radial X-ray diffraction

    SciTech Connect

    Xie, Miao; Turner, Christopher L.; Mohammadi, Reza; Kaner, Richard B. E-mail: akavner@ucla.edu Tolbert, Sarah H. E-mail: akavner@ucla.edu; Kavner, Abby E-mail: akavner@ucla.edu

    2015-07-27

    In this work, we explore the hardening mechanisms in WB{sub 4}-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under non-hydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB{sub 4} solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

  9. Exploring hardness enhancement in superhard tungsten tetraboride-based solid solutions using radial X-ray diffraction

    DOE PAGES

    Xie, Miao; Mohammadi, Reza; Turner, Christopher L.; ...

    2015-07-29

    In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

  10. BixLa1-xVO4 solid solutions: tuning of electronic properties via stoichiometry modifications

    NASA Astrophysics Data System (ADS)

    Kwolek, Przemysław; Pilarczyk, Kacper; Tokarski, Tomasz; Lewandowska, Kornelia; Szaciłowski, Konrad

    2014-01-01

    BixLa1-xVO4 solid solutions were obtained in the form of fine powder via a microwave-assisted hydrothermal route. The presence of a solid solution in the studied system was confirmed using X-ray diffraction (XRD) and optical spectroscopy techniques. Pure BiVO4 and LaVO4 were obtained in the monoclinic form, whereas solid solutions in the tetragonal, zircon-type structure. The optical band gap dependence on the composition of the solid solution is parabolic, thus there is a possibility to tune this parameter in a wide concentration range, from 2.4 to 4.0 eV. An absorption coefficient maximum is also concentration-dependent, possibly, due to the structural disorder of the samples. Solid solutions with Bi3+ concentration between 11.94 and 32.57 at.% exhibit intense, green luminescence. This indicates the presence of Bi-originated electronic states within the band gap. The value of the conduction band edge potential, measured by both electrochemical impedance spectroscopy and work function measurements, is concentration-independent. Moreover, solid solutions exhibit a photoelectrochemical photocurrent switching effect, thus they may be promising materials for molecular electronics and as dioxygen activators.BixLa1-xVO4 solid solutions were obtained in the form of fine powder via a microwave-assisted hydrothermal route. The presence of a solid solution in the studied system was confirmed using X-ray diffraction (XRD) and optical spectroscopy techniques. Pure BiVO4 and LaVO4 were obtained in the monoclinic form, whereas solid solutions in the tetragonal, zircon-type structure. The optical band gap dependence on the composition of the solid solution is parabolic, thus there is a possibility to tune this parameter in a wide concentration range, from 2.4 to 4.0 eV. An absorption coefficient maximum is also concentration-dependent, possibly, due to the structural disorder of the samples. Solid solutions with Bi3+ concentration between 11.94 and 32.57 at.% exhibit intense

  11. The solution and solid state stability and excipient compatibility of parthenolide in feverfew.

    PubMed

    Jin, Ping; Madieh, Shadi; Augsburger, Larry L

    2007-12-14

    The objectives of this research were to evaluate the stability of parthenolide in feverfew solution state and powdered feverfew (solid state), and explore the compatibility between commonly used excipients and parthenolide in feverfew. Feverfew extract solution was diluted with different pH buffers to study the solution stability of parthenolide in feverfew. Powdered feverfew extract was stored under 40 degrees C/0% approximately 75% relative humidities (RH) or 31% RH/5~50 degrees C to study the influence of temperature and relative humidity on the stability of parthenolide in feverfew solid state. Binary mixtures of feverfew powered extract and different excipients were stored at 50 degrees C/ 75% RH for excipient compatibility evaluation. The degradation of parthenolide in feverfew solution appears to fit a typical first-order reaction. Parthenolide is comparatively stable when the environmental pH is in the range of 5 to 7, becoming unstable when pH is less than 3 or more than 7. Parthenolide degradation in feverfew in the solid state does not fit any obvious reaction model. Moisture content and temperature both play important roles affecting the degradation rate. After 6 months of storage, parthenolide in feverfew remains constant at 5 degrees C/31% RH. However, approximately 40% parthenolide in feverfew can be degraded if stored at 50 degrees C/31% RH. When the moisture changed from 0% to 75% RH, the degradation of parthenolide in feverfew increased from 18% to 32% after 6-month storage under 40 degrees C. Parthenolide in feverfew exhibits good compatibility with commonly used excipients under stressed conditions in a 3-week screening study.

  12. Nanocrystalline gadolinium doped ceria: combustion synthesis and electrical characterization.

    PubMed

    Dutta, Atanu; Patra, Saheli; Bedekar, Vinila; Tyagi, A K; Basu, R N

    2009-05-01

    Twenty mol% gadolinium doped ceria powders were prepared by citrate-nitrate combustion synthesis technique. Two different sources of cerium viz. cerium nitrate and ammonium ceric nitrate were used in different oxidant-to-fuel ratios. The crystallite size of the synthesized powders ranged 5-27 nm was obtained depending on the preparation conditions with average particle size in the range 0.64-1.26 microm. Although, the powders were found to be agglomerated in nature, these powders were highly sinter-active as they showed very high sintered density (> or = 95%) when sintered at 1250 degrees C having grain size in the range of 200-500 nm. The electrical conductivity was found to depend on the temperature with two distinct regimes at a transition point of 350 degrees C. The grain boundary showed a significant role in the total conductivity with its activation energy dependent on the material preparation conditions. The activation energy of total conduction was found to be significantly low (-0.5 eV) in the temperature range of 400-700 degrees C, this property is unique for application as an electrolyte for solid oxide fuel cell operating in the low temperature range. It was found that a fuel-deficient combustion reaction using cerium nitrate as the oxidant yielded the best quality powder which showed a maximum electrical conductivity of -1.74 x 10(-2) S/cm at 600 degrees C.

  13. Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

    NASA Technical Reports Server (NTRS)

    Adler, Stuart B.

    2009-01-01

    Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod

  14. Luminescence properties of the Ca-alpha-sialon:Eu solid solution

    NASA Astrophysics Data System (ADS)

    Pawlik, Tomasz; Michalik, Daniel; Sopicka-Lizer, Malgorzata; Lisiecki, Radosław; Adamczyk, Barbara; Pławecki, Materusz; Mieszczak, Łukasz; Walerczyk, Wiktoria

    2016-09-01

    The Ca,Eu-α-sialon powders with the mixed solid solution composition have been manufactured via the solid-state reaction process in flowing nitrogen in a graphite furnace at a relatively low temperature of 1650 °C without an external overpressure. XRD data with Rielveld refinement and XPS measurements were used for characterization of the lattice constants and the surface chemical composition. The monophase Ca-Eu-α-sialon was obtained with the nominal composition of Eu0.048Ca0.702Si7.75Al2.25O0.75N15.25. The highest emission intensity in a yellow-orange region at 590 nm and quantum efficiency of 66% was found for this pure Ca,Eu-α-sialon. Estimation of m,n values from the lattice constant and EDS results showed a small deviation from the nominal composition of designed α-sialon. XPS results demonstrated significant changes of the chemical composition in the oxidized surface of phosphor particles. Possible reasons of emission redshift and relationship between the actual solid solution composition and luminescence properties are discussed in terms of simultaneous presence of Eu2+ and Eu3+ ions in the sialon crystal lattice and residual oxynitride glass.

  15. Long-term behavior of refractory thorium-plutonium dioxide solid solutions

    NASA Astrophysics Data System (ADS)

    Claparede, Laurent; Guigue, Mireille; Jouan, Gauthier; Nadah, Nassima; Dacheux, Nicolas; Moisy, Philippe

    2017-01-01

    The long-term behavior of Th0.87Pu0.13O2 was examined in nitric acid concentrations. The normalized dissolution rates after 3380 days, range from (1.4 ± 0.2) × 10-6 g m-2 d-1 in 5 M HNO3 down to (3.2 ± 0.4) × 10-8 g m-2 d-1 in 10-3 M HNO3, which confirms the high chemical durability of this solid solution. The amounts of plutonium measured in solution lead to 0.9% and 2.1% of dissolved solid in 1 M and 5 M HNO3, respectively. In such conditions, the time required to reach the full dissolution of the material varies from 430 years (5 M HNO3) to 18,000 years (10-3 M HNO3). Moreover, the partial order related to the proton activity (n = 0.45 ± 0.03) suggests that the dissolution is mainly driven by surface reactions occurring at the solid/liquid interface. The characterization of the leached samples by SEM shows small microstructural modifications (i.e. detachment of crystallites) and the absence of neoformed phase while from PXRD, the unit cell parameter and crystallite size are not significantly affected.

  16. B-site substituted solid solutions on the base of sodium-bismuth titanate

    NASA Astrophysics Data System (ADS)

    Ishchuk, V. M.; Gusakova, L. G.; Kisel, N. G.; Kuzenko, D. V.; Spiridonov, N. A.; Sobolev, V. L.

    The paper presents results of studies of the formation of phases during the solid-state synthesis in the [(Na0.5Bi0.5)0.80Ba0.20](Ti1-yBy)O3 system of solid solutions with B-site substitutions. The substitutions by zirconium, tin and ion complexes (In0.5Nb0.5) and (Fe0.5Nb0.5) have been studied. It has been found that the synthesis is a multi-step process associated with the formation of a number of intermediate phases (depending on the compositions and calcination temperatures). Single-phase solid solutions have been produced at the calcination temperatures in the interval 1000-1100∘C. An increase in the substituting ions concentration leads to a linear increase of the crystal cell size. At the same time, the tolerance factor gets reduced boosting the stability of the antiferroelectric phase as compared to that of the ferroelectric phase.

  17. Phase Pattern of Barium Strontium Titanate System and Dielectric Responses of Its Solid Solutions

    NASA Astrophysics Data System (ADS)

    Sadykov, Kh. A.; Verbenko, I. A.; Reznichenko, L. A.; Pavelko, A. A.; Shilkina, L. A.; Konstantinov, G. M.; Abubakarov, A. G.; Shevtsova, S. I.; Pavlenko, A. V.; Khasbulatov, S. V.

    2017-04-01

    Samples of solid solutions of the system Ba1- x Sr x TiO3 (0 ≤ x ≤1.0) are produced by solid-phase synthesis followed by sintering using conventional ceramic technology. Their crystal structure and grain structure are studied at room temperature and dielectric properties - in a wide range of external influences (temperature and frequency of the alternating electric field). Based on these results, the state diagram of the system is constructed including three single-phase fields with different-symmetry (tetragonal, pseudocubic, and cubic) and two morphotropic fields with coexistence of the tetragonal and pseudocubic, pseudocubic and cubic phases. Peculiarities of the grain landscape associated with the formation of morphotropic areas and melting of barium hydroxide are revealed. The dependence of the dielectric properties of solid solutions on their crystal-chemical specifics and position in the phase diagram of the system is demonstrated. A conclusion is made about the possibility of using the compositions with x = 0.2 to create materials with high dielectric constants promising for applications in microelectronics.

  18. Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts

    DOE PAGES

    Tang, Wan Si; Yoshida, Koji; Soloninin, Alexei V.; ...

    2016-09-01

    Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing 'geometric frustration' via the mixing of two different closo-polyborate anions, namely, 1-CB9H10- and CB11H12-, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambient to high temperatures. Finally,more » this result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.« less

  19. Supramolecular stabilization of metastable tautomers in solution and the solid state.

    PubMed

    Juribašić, Marina; Bregović, Nikola; Stilinović, Vladimir; Tomišić, Vladislav; Cindrić, Marina; Sket, Primož; Plavec, Janez; Rubčić, Mirta; Užarević, Krunoslav

    2014-12-22

    This work presents a successful application of a recently reported supramolecular strategy for stabilization of metastable tautomers in cocrystals to monocomponent, non-heterocyclic, tautomeric solids. Quantum-chemical computations and solution studies show that the investigated Schiff base molecule, derived from 3-methoxysalicylaldehyde and 2-amino-3-hydroxypyridine (ap), is far more stable as the enol tautomer. In the solid state, however, in all three obtained polymorphic forms it exists solely as the keto tautomer, in each case stabilized by an unexpected hydrogen-bonding pattern. Computations have shown that hydrogen bonding of the investigated Schiff base with suitable molecules shifts the tautomeric equilibrium to the less stable keto form. The extremes to which supramolecular stabilization can lead are demonstrated by the two polymorphs of molecular complexes of the Schiff base with ap. The molecules of both constituents of molecular complexes are present as metastable tautomers (keto anion and protonated pyridine, respectively), which stabilize each other through a very strong hydrogen bond. All the obtained solid forms proved stable in various solid-state and solvent-mediated methods used to establish their relative thermodynamic stabilities and possible interconversion conditions.

  20. Diode-pumped all-solid state lasers: solutions for scientific, biomedical, and industrial applications

    NASA Astrophysics Data System (ADS)

    Agnesi, Antoniangelo; Reali, Giancarlo C.

    1998-07-01

    Referring to the work carried out in our laboratory, we review low-medium power diode pumped all solid state laser systems for scientific, bio-medical and industrial applications. Side- and end-pumping are discussed and compared for such a laser systems. End-pumped scheme is mainly exploited in this report. Coupling solutions and cavity design are described emphasizing energy deposition and extraction optimization, thermal lens effects, beam quality control and longitudinal mode control. Both cw- and quasi-cw-pumped lasers are considered, operating either in continuous wave, passive Q-switching, and mode-locking regimes. Intracavity and extracavity harmonic generation, optical parametric generation and short pulse generation are among the aims of these all-solid-state sources: some result of these applications are reported.

  1. Modelling of solid polymer and direct methanol fuel cells: Phenomenological equations and analytical solutions

    NASA Astrophysics Data System (ADS)

    Kauranen, P. S.

    1993-04-01

    In the solid state concept of a direct methanol fuel cell (DMFC), methanol is directly oxidized at the anode of a solid polymer electrolyte fuel cell (SPEFC). Mathematical modelling of the transport and reaction phenomena within the electrodes and the electrolyte membrane is needed in order to get a closer insight into the operation of the fuel cell. In the work, macro-homogenous porous electrode and dilute solution theories are used to derive the phenomenological equations describing the transport and reaction mechanisms in a SPEFC single cell. The equations are first derived for a conventional H2/air SPEFC, and then extended for a DMFC. The basic model is derived in a one dimensional form in which it is assumed that species transport take place only in the direction crossing the cell sandwich. In addition, two dimensional descriptions of the catalyst layer are reviewed.

  2. Optical characterization of CdSe quantum dots with metal chalcogenide ligands in solutions and solids

    NASA Astrophysics Data System (ADS)

    Zhang, Y. Q.; Cao, X. A.

    2011-07-01

    The exchange of the original organic ligands of colloidal CdSe core and CdSe/CdS/ZnS core/multishell quantum dots (QDs) with inorganic metal chalcogenide ligands (SnS44-) resulted in carrier delocalization in solutions and enhanced inter-QD electronic coupling in solids, as inferred from peak redshift and broadening of the absorption and photoluminescence (PL) spectra. The SnS4-capped QDs retained strong excitonic absorption but suffered significant PL quenching. Mild thermal treatment below 350 °C transformed the SnS4 ligands into a more conductive phase, leading to stronger coupling yet complete PL quenching. These findings suggest that QD solids with metal chalcogenide ligands may have high quantum yields of photocurrent generation and can be used as functional blocks in thin-film solar cells for efficient solar energy conversion.

  3. Multivalent-Counterion-Induced Surfactant Multilayer Formation at Hydrophobic and Hydrophilic Solid-Solution Interfaces.

    PubMed

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun; Xu, Hui; Tucker, Ian M; Petkov, Jordan T; Sivia, Devinderjit S

    2015-06-23

    Surface multilayer formation from the anionic-nonionic surfactant mixture of sodium dodecyl dioxyethylene sulfate, SLES, and monododecyl dodecaethylene glycol, C12E12, by the addition of multivalent Al(3+) counterions at the solid-solution interface is observed and characterized by neutron reflectivity, NR. The ability to form surface multilayer structures on hydrophobic and hydrophilic silica and cellulose surfaces is demonstrated. The surface multilayer formation is more pronounced and more well developed on the hydrophilic and hydrophobic silica surfaces than on the hydrophilic and hydrophobic cellulose surfaces. The less well developed multilayer formation on the cellulose surfaces is attributed to the greater surface inhomogeneities of the cellulose surface which partially inhibit lateral coherence and growth of the multilayer domains at the surface. The surface multilayer formation is associated with extreme wetting properties and offers the potential for the manipulation of the solid surfaces for enhanced adsorption and control of the wetting behavior.

  4. Joule-Thomson Inversion in Vapor-Liquid-Solid Solution Systems

    NASA Astrophysics Data System (ADS)

    Nichita, Dan Vladimir; Pauly, Jerome; Daridon, Jean-Luc

    2009-07-01

    Solid phase precipitation can greatly affect thermal effects in isenthalpic expansions; wax precipitation may occur in natural hydrocarbon systems in the range of operating conditions, the wax appearance temperature being significantly higher (as high as 350 K) for hyperbaric fluids. Recently, methods for calculating the Joule-Thomson inversion curve (JTIC) for two-phase mixtures, and for three-phase vapor-liquid-multisolid systems have been proposed. In this study, an approach for calculating the JTIC for the vapor-liquid-solid solution systems is presented. The JTIC is located by tracking extrema and angular points of enthalpy departure variations versus pressure at isothermal conditions. The proposed method is applied to several complex synthetic and naturally occurring hydrocarbon systems. The JTIC can exhibit several distinct branches (which may lie within two- or three-phase regions or follow phase boundaries), multiple inversion temperatures at fixed pressure, as well as multiple inversion pressures at given temperature.

  5. Solution- and solid-phase oligosaccharide synthesis using glucosyl iodides: a comparative study.

    PubMed

    Lam, Son N; Gervay-Hague, Jacquelyn

    2002-11-19

    Glycosyl iodide donors have been used in both solid- and solution-phase syntheses yielding alpha-(1 --> 6)-linked glucosyl oligomers in highly efficient protocols. While the solid-phase strategy offers advantages in terms of ease of purification, it requires a total of 7.5 equiv of donor and approximately 12 h to complete the incorporation of one monosaccharide unit. In contrast, solution-phase methods require only 2.5 equiv of donor and 2-3 h reaction time per glycosylation. Moreover, since the reactions are virtually quantitative (> 90%) column chromatography of the material is facile. The overall advantages of solution-phase oligosaccharide synthesis were further illustrated in the convergent synthesis of a hexamer (methoxycarbonylmethyl 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6)-tetrakis-(2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6))-2,3,4-tri-O-benzyl-1-thio-alpha-D-glucopyranoside) that was constructed from dimer donor iodides in a two-plus-two and a two-plus-four fashion.

  6. Ruthenium complexes of substituted hydrazine: new solution- and solid-state binding modes.

    PubMed

    Dabb, Serin L; Messerle, Barbara A; Otting, Gottfried; Wagler, Jörg; Willis, Anthony

    2008-01-01

    The methylhydrazine complex [Ru(NH(2)NHMe)(PyP)(2)]Cl(BPh(4)) (PyP=1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh(4))(2). The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)(NH(2)NHMe)]Cl(BPh(4)) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with (15)N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH(2) group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH(2)NRR')]OSO(2)CF(3) (in which R=H, R'=Ph, R=R'=Me and NRR'=NC(5)H(10)) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(OSO(2)CF(3))(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.

  7. Microstructural and Electrical Characterization of Barium Strontium Titanate-Based Solid Solution Thin Films Deposited on Ceramic Substrates by Pulsed Laser Deposition

    DTIC Science & Technology

    2003-04-03

    Strontium Titanate-Based Solid Solution Thin Films Deposited on Ceramic Substrates by Pulsed Laser Deposition DISTRIBUTION: Approved for public...Society H2.4 Microstructural and Electrical Characterization of Barium Strontium Titanate- based Solid Solution Thin Films Deposited on Ceramic...investigated and report the microstructural and electrical characterization of selected barium strontium titanate-based solid solution thin films

  8. One-Dimensional Ceria as Catalyst for the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Han, W.; Wen, W; Hanson, J; Teng, X; Marinkovic, N; Rodriguez, J

    2009-01-01

    Synchrotron-based in situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to study pure ceria and Pd-loaded ceria nanotubes and nanorods (1D-ceria) as catalysts for the water-gas shift (WGS) reaction. While bulk ceria is very poor as WGS catalysts, pure 1D-ceria displayed catalytic activity at a temperature as low as 300 C. The reduction of the pure 1D-ceria in pure hydrogen started at 150 C, which is a much lower temperature than those previously reported for the reduction of 3D ceria nanoparticles. This low reduction temperature reflects the novel morphology of the oxide systems and may be responsible for the low-temperature WGS catalytic activity seen for the 1D-ceria. Pd-loaded 1D ceria displayed significant WGS activity starting at 200 C. During pretreatment in H{sub 2}, the ceria lattice parameter increased significantly around 60 C, which indicates that Pd-oxygen interactions may facilitate the reduction of Pd-loaded 1D-ceria. Pd and ceria both participate in the formation of the active sites for the catalytic reactions. The low-temperature hydrogen pretreatment results in higher WGS activity for Pd-loaded 1D-ceria.

  9. Nano-ceria pre-infiltration improves La0.6Sr0.4Co0.8Fe0.2O3-x infiltrated Solid Oxide Fuel Cell cathode performance

    NASA Astrophysics Data System (ADS)

    Burye, Theodore E.; Nicholas, Jason D.

    2015-12-01

    Here, scanning electron microscopy, X-ray diffraction, and thermo-gravimetric analysis experiments show that the pre-infiltration of Ce0.9Gd0.1O1.95 (GDC) nano-particles reduces the average size of La0.6Sr0.4Co0.8Fe0.2O3-x (LSCF) produced from the subsequent infiltration of precursor nitrate solutions containing the surfactant Triton X-100 or the chelating agent citric acid. In contrast, GDC pre-infiltration has no effect on the average size of LSCF particles produced from precursor solutions containing only lanthanum, strontium, cobalt, and iron nitrate. Consistent with the observed particle size trends, electrochemical impedance spectroscopy measurements show that GDC pre-infiltration improves the performance of Triton X-100 Derived (TXD) LSCF-GDC cathodes and Citric Acid Derived (CAD) LSCF-GDC cathodes, but has no effect on the performance of Pure Nitrate Derived (PND) LSCF-GDC cathodes. In particular, TXD LSCF-GDC cathodes with more than ∼5 vol% of GDC pre-infiltration display average LSCF particle sizes of 21 nm and open-circuit polarization resistance values of 0.10 Ωcm2 at 540 °C, compared to 48 nm and 640 °C without GDC pre-infiltration. Results suggest that this 100 °C reduction in cathode operating temperature is caused solely by LSCF particle size reductions. 7.4 vol% GDC pre-infiltrated TXD LSCF-GDC cathodes also display lower 540 °C degradation rates than conventionally infiltrated PND LSCF-GDC cathodes.

  10. Converting ceria polyhedral nanoparticles into single-crystal nanospheres.

    PubMed

    Feng, Xiangdong; Sayle, Dean C; Wang, Zhong Lin; Paras, M Sharon; Santora, Brian; Sutorik, Anthony C; Sayle, Thi X T; Yang, Yi; Ding, Yong; Wang, Xudong; Her, Yie-Shein

    2006-06-09

    Ceria nanoparticles are one of the key abrasive materials for chemical-mechanical planarization of advanced integrated circuits. However, ceria nanoparticles synthesized by existing techniques are irregularly faceted, and they scratch the silicon wafers and increase defect concentrations. We developed an approach for large-scale synthesis of single-crystal ceria nanospheres that can reduce the polishing defects by 80% and increase the silica removal rate by 50%, facilitating precise and reliable mass-manufacturing of chips for nanoelectronics. We doped the ceria system with titanium, using flame temperatures that facilitate crystallization of the ceria yet retain the titania in a molten state. In conjunction with molecular dynamics simulation, we show that under these conditions, the inner ceria core evolves in a single-crystal spherical shape without faceting, because throughout the crystallization it is completely encapsulated by a molten 1- to 2-nanometer shell of titania that, in liquid state, minimizes the surface energy. The principle demonstrated here could be applied to other oxide systems.

  11. Adhesion and Atomic Structures of Gold on Ceria Nanostructures: The Role of Surface Structure and Oxidation State of Ceria Supports.

    PubMed

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Ding, Kunlun; Yang, Xiaoyun; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-08-12

    We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts.

  12. Leaching heavy metals in municipal solid waste incinerator fly ash with chelator/biosurfactant mixed solution.

    PubMed

    Xu, Ying; Chen, Yu

    2015-07-01

    The chelator [S,S]-ethylene diamine disuccinic acid, citric acid, and biosurfactant saponin are selected as leaching agents. In this study, the leaching effect of saponin mixed with either ethylene diamine disuccinic acid or citric acid on the levels of copper, zinc, lead, and cadmium in municipal solid waste incinerator fly ash is investigated. Results indicate that saponin separately mixed with ethylene diamine disuccinic acid and citric acid exhibits a synergistic solubilisation effect on copper, zinc, lead, and cadmium leaching from fly ash. However, saponin and ethylene diamine disuccinic acid mixed solution exhibits a synergistic solubilisation effect that is superior to that of a saponin and citric acid mixed solution. The extraction rate of heavy metal in fly ash leached with a saponin and chelator mixed solution is related to the pH of the leaching solution, and the optimal range of the pH is suggested to be approximately neutral. After leaching with a saponin and chelator mixed solution, copper, zinc, lead, and cadmium contents significantly decreased (p < 0.05) in the extractable or acid-soluble and reducible fractions. By adopting the proposed approach, the leaching concentrations of copper, zinc, lead, and cadmium in treated fly ash are in accordance with Standard for Pollution Control on the Security Landfill Site for Hazardous Wastes GB18598-2001.

  13. Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

    DOEpatents

    Sugama, Toshifumi

    1993-01-01

    Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

  14. Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

    DOEpatents

    Sugama, Toshifumi

    1992-01-01

    Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

  15. Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

    DOEpatents

    Toshifumi Sugama.

    1993-04-06

    Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR)[sub n] (wherein M is Ti, Zr, Ge or Al; R is CH[sub 3], C[sub 2]H[sub 5] or C[sub 3]H[sub 7]; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., < 1,000 C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

  16. Multifunctional imidazobenzothiadiazole probe displaying solvatofluorochromism and ability to form ion-pair complexes in solid state and in solution.

    PubMed

    Alfonso, María; Fernández, Israel; Tárraga, Alberto; Molina, Pedro

    2015-05-15

    Fluorescent solid 5-pyridylimidazobenzothiadiazole displays a remarkable solvatofluorochromism and with Zn(AcO)2 and Cd(AcO)2, either in solution or under solvent-free conditions, forms ion-pair complexes that in the solid state can be discriminated and separated by fluorescence measurements and selective extraction with diethyl ether or chloroform.

  17. Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

    PubMed

    de Julián Fernández, C; Mattei, G; Paz, E; Novak, R L; Cavigli, L; Bogani, L; Palomares, F J; Mazzoldi, P; Caneschi, A

    2010-04-23

    Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

  18. SOLID SOLUTION CARBIDES ARE THE KEY FUELS FOR FUTURE NUCLEAR THERMAL PROPULSION

    NASA Technical Reports Server (NTRS)

    Panda, Binayak; Hickman, Robert R.; Shah, Sandeep

    2005-01-01

    Nuclear thermal propulsion uses nuclear energy to directly heat a propellant (such as liquid hydrogen) to generate thrust for space transportation. In the 1960 s, the early Rover/Nuclear Engine for Rocket Propulsion Application (NERVA) program showed very encouraging test results for space nuclear propulsion but, in recent years, fuel research has been dismal. With NASA s renewed interest in long-term space exploration, fuel researchers are now revisiting the RoverMERVA findings, which indicated several problems with such fuels (such as erosion, chemical reaction of the fuel with propellant, fuel cracking, and cladding issues) that must be addressed. It is also well known that the higher the temperature reached by a propellant, the larger the thrust generated from the same weight of propellant. Better use of fuel and propellant requires development of fuels capable of reaching very high temperatures. Carbides have the highest melting points of any known material. Efforts are underway to develop carbide mixtures and solid solutions that contain uranium carbide, in order to achieve very high fuel temperatures. Binary solid solution carbides (U, Zr)C have proven to be very effective in this regard. Ternary carbides such as (U, Zr, X) carbides (where X represents Nb, Ta, W, and Hf) also hold great promise as fuel material, since the carbide mixtures in solid solution generate a very hard and tough compact material. This paper highlights past experience with early fuel materials and bi-carbides, technical problems associated with consolidation of the ingredients, and current techniques being developed to consolidate ternary carbides as fuel materials.

  19. Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles

    NASA Astrophysics Data System (ADS)

    de Julián Fernández, C.; Mattei, G.; Paz, E.; Novak, R. L.; Cavigli, L.; Bogani, L.; Palomares, F. J.; Mazzoldi, P.; Caneschi, A.

    2010-04-01

    Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO2 matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

  20. A New Thermodynamic Parameter to Predict Formation of Solid Solution or Intermetallic Phases in High Entropy Alloys (Postprint)

    DTIC Science & Technology

    2015-11-02

    AFRL-RX-WP-JA-2016-0345 A NEW THERMODYNAMIC PARAMETER TO PREDICT FORMATION OF SOLID SOLUTION OR INTERMETALLIC PHASES IN HIGH ENTROPY...Interim 22 September 2014 – 21 September 2015 4. TITLE AND SUBTITLE A NEW THERMODYNAMIC PARAMETER TO PREDICT FORMATION OF SOLID SOLUTION OR...simple thermodynamic criterion is proposed to predict the presence or absence of equilibrium intermetallic phases in a high entropy alloy at a given

  1. Ab Initio Calculations and Synthesis of Sc2InC-Y2InC Solid Solution

    DTIC Science & Technology

    2010-02-03

    tribological materials. It will study a solid solution of this fascinating new class of nanolaminated materials using both theoretical and experimental means...Sc2InC-Y2InC solid solution using ab initio calculations and 2) to synthesize Sc2InC-Y2InC thin films using magnetron sputtering and to determine the correlation between composition, structure, and mechanical properties thereof.

  2. PZT-like structural phase transitions in the BiFeO3-KNbO3 solid solution.

    PubMed

    Lennox, Robert C; Taylor, Daniel D; Vera Stimpson, Laura J; Stenning, Gavin B G; Jura, Marek; Price, Mark C; Rodriguez, Efrain E; Arnold, Donna C

    2015-06-21

    Despite the high prominence of the perovskites BiFeO(3) and KNbO(3) the solid solution between the two has received little attention. We report a detailed neutron and synchrotron X-ray powder diffraction, and Raman spectroscopy study which demonstrates an R3c→P4mm→Amm2 series of structural phase transitions similar to that exhibited by the PbZrO(3)-PbTiO(3) solid solution.

  3. Thermodynamic study of solid solutions in the SnTe-AgSbTe2 system by means of EMF with solid electrolyte Ag4RbI5

    NASA Astrophysics Data System (ADS)

    Mashadieva, L. F.; Yusibov, Yu. A.; Kevser, Dzh.; Babanly, M. B.

    2017-09-01

    The results from studying the SnTe-AgSbTe2 system by means of EMF with the solid electrolyte Ag4RbI5 in the temperature range of 300-430 K are presented. The formation of a wide (≥80 mol % of AgSbTe2) region of solid solutions based on SnTe is confirmed. Partial thermodynamic functions Δ G̅, Δ H̅, and Δ S̅ of silver in alloys are calculated from the equations for the EMF temperature dependences. Based on the literature data regarding solid-phase equilibria in the Ag2Te-SnTe-Sb2Te3-Te system, potential-determining reactions are identified that allow us to calculate the standard thermodynamic formation functions and standard entropies of solid solutions (2SnTe) x (AgSbTe2)1- x ( x = 0.2, 0.4, 0.6, 0.8, and 0.9).

  4. Solution chemistry effects on orthophosphate adsorption by cationized solid wood residues

    Treesearch

    K.G. Karthikeyan; Mandla A. Tshabalala; D. Wang; M. Kalbasi

    2004-01-01

    Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to- sorbent ratio (=0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4 2-; 0.08-250 mM...

  5. Reversible pressure-induced structure changes in turbostratic BN-C solid solutions.

    PubMed

    Solozhenko, Vladimir L; Kurakevych, Oleksandr O

    2005-10-01

    The results obtained by Rietveld analysis and numerical modeling of B-C-N layered clusters with various types of lattice defects explain the evolution of diffraction patterns of turbostratic graphite-like BN-C solid solutions which are experimentally observed at room temperature at pressures up to 30 GPa. Above 20 GPa a reversible diffusionless transformation of the initial turbostratic structure takes place, giving a high-pressure phase formed by close-packed buckled layers having a diamond-like structure.

  6. Methods of deoxygenating metals having oxygen dissolved therein in a solid solution

    DOEpatents

    Zhang, Ying; Fang, Zhigang Zak; Sun, Pei; Xia, Yang; Zhou, Chengshang

    2017-06-06

    A method of deoxygenating metal can include forming a mixture of: a metal having oxygen dissolved therein in a solid solution, at least one of metallic magnesium and magnesium hydride, and a magnesium-containing salt. The mixture can be heated at a deoxygenation temperature for a period of time under a hydrogen-containing atmosphere to form a deoxygenated metal. The deoxygenated metal can then be cooled. The deoxygenated metal can optionally be subjected to leaching to remove by-products, followed by washing and drying to produce a final deoxygenated metal.

  7. Direct observation of {beta}-TaH phase precipitation in tantalum{endash}hydrogen solid solution

    SciTech Connect

    Chen, C.L.; Zhou, D.S.; Mitchell, T.E.; Ye, H.Q.

    1996-07-01

    An ordered {beta}-Ta{sub 2}H tantalum hydride precipitate and a disordered {alpha}-Ta{endash}H solid solution matrix have been observed directly by field ion microscopy and analyzed by atom probe analysis. The ordered and disordered field ion images have been explained by the electronic transition rate in the theory of field ionization. On the other hand, we found surprisingly that the field evaporation voltage dramatically decreased to approximately one half of its original evaporation voltage as the evaporation of the precipitate moves toward the phase boundary, which may due to the effects of the interface energy. {copyright} {ital 1996 American Vacuum Society}

  8. Solid-Solution Alloying of Immiscible Ru and Cu with Enhanced CO Oxidation Activity.

    PubMed

    Huang, Bo; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Matsumura, Syo; Nishida, Yoshihide; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Kitagawa, Hiroshi

    2017-03-24

    We report on novel solid-solution alloy nanoparticles (NPs) of Ru and Cu that are completely immiscible even above melting point in bulk phase. Powder X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray measurements demonstrated that Ru and Cu atoms were homogeneously distributed in the alloy NPs. Ru0.5Cu0.5 NPs demonstrated higher CO oxidation activity than fcc-Ru NPs, which are known as one of the best monometallic CO oxidation catalysts.

  9. NMR in Chevrel-phase solid solution Mo 6Se 8- xTe x

    NASA Astrophysics Data System (ADS)

    Hamard, C.; Le Floch, M.; Peña, O.; Wojakowski, A.

    1999-01-01

    The Mo 6Se 8-Mo 6Te 8 solid solution was studied by X-ray diffraction, magnetic susceptibility and 77Se and 125Te NMR. Dynamic studies show that substitution occurs differently when Se replaces Te in Mo 6Te 8 than when Te replaces Se in Mo 6Se 8. Selenium first fills the high-symmetry sites and then it becomes statistically distributed on the 6f positions of the R3¯ symmetry. In the second case, Te occupies randomly the 8 X sites of the Mo 6X 8 structure, creating large perturbations of the 125Te NMR spectra over the whole range of x.

  10. Synthesis of dental enamel-like hydroxyapatite through solution mediated solid-state conversion.

    PubMed

    Zhang, Junling; Jiang, Dongliang; Zhang, Jingxian; Lin, Qingling; Huang, Zhengren

    2010-03-02

    An ordered dental enamel-like structure of hydroxyapatite (HAp) was achieved through a solution mediated solid-state conversion process with organic phosphate surfactant and gelatin as the mediating agent. Transmission electron microscopy (TEM) tests demonstrated uniform sizes in the obtained apatite nanorods which arranged in parallel to each other along the c-axis and formed organized microarchitectural units over 10 microm in size. The sizes of the synthetic hydroxyapatite nanorods were similar to that observed in enamel from human teeth. The formation and regulation of the orientation and size of HAp nanorods might lead to a better understanding of the biomineralization process for the preparation of high performance biomaterials.

  11. Synthesis and characterization of the LDH hydrotalcite-pyroaurite solid-solution series

    SciTech Connect

    Rozov, K.; Berner, U.; Taviot-Gueho, C.; Leroux, F.; Renaudin, G.; Kulik, D.; Diamond, L.W.

    2010-08-15

    A layered double hydroxide (LDH) hydrotalcite-pyroaurite solid-solution series Mg{sub 3}(Al{sub x}Fe{sub 1-x})(CO{sub 3}){sub 0.5}(OH){sub 8} with 1 - x = 0.0, 0.1...1.0 was prepared by co-precipitation at 23 {+-} 2 {sup o}C and pH = 11.40 {+-} 0.03. The compositions of the solids and the reaction solutions were determined using ICP-OES (Mg, Al, Fe, and Na) and TGA techniques (CO{sub 3}{sup 2-}, OH{sup -}, and H{sub 2}O). Powder X-ray diffraction was employed for phase identification and determination of the unit cell parameters a{sub o} and c{sub o} from peak profile analysis. The parameter a{sub o} = b{sub o} was found to be a linear function of the composition. This dependency confirms Vegard's law and indicates the presence of a continuous solid-solution series in the hydrotalcite-pyroaurite system. TGA data show that the temperatures at which interlayer H{sub 2}O molecules and CO{sub 3}{sup 2-} anions are lost, and at which dehydroxylation of the layers occurs, all decrease with increasing mole fraction of iron within the hydroxide layers. Features of the Raman spectra also depend on the iron content. The absence of Raman bands for Fe-rich members (x{sub Fe} > 0.5) is attributed to possible fluorescence phenomena. Based on chemical analysis of both the solids and the reaction solutions after synthesis, preliminary Gibbs free energies of formation have been estimated. Values of {Delta}G{sup o}{sub f}(hydrotalcite) = - 3773.3 {+-} 51.4 kJ/mol and {Delta}G{sup o}{sub f}(pyroaurite) = - 3294.5 {+-} 95.8 kJ/mol were found at 296.15 K. The formal uncertainties of these formations constants are very high. Derivation of more precise values would require carefully designed solubility experiments and improved analytical techniques.

  12. Tablets of functionalized polystyrene beads alone and in combination with solid reagents or catalysts. Preparation and applications in parallel solution and solid phase synthesis.

    PubMed

    Ruhland, Thomas; Holm, Per; Andersen, Kim

    2003-01-01

    Pretreatment of polystyrene beads with a nonpolar organic solvent is the key for the generation of mechanically robust tablets consisting of neat functionalized polystyrene beads, both alone and in combination with solid reagents or catalysts. The novel dosing methodology provides accurately preweighed tablets in virtually any shape and size and with excellent disintegration properties, speeding up parallel solution and solid phase synthesis. The use of tablets is demonstrated in parallel Mitsunobu and acylation reactions.

  13. Bi(x)La(1-x)VO4 solid solutions: tuning of electronic properties via stoichiometry modifications.

    PubMed

    Kwolek, Przemysław; Pilarczyk, Kacper; Tokarski, Tomasz; Lewandowska, Kornelia; Szaciłowski, Konrad

    2014-02-21

    BixLa1-xVO4 solid solutions were obtained in the form of fine powder via a microwave-assisted hydrothermal route. The presence of a solid solution in the studied system was confirmed using X-ray diffraction (XRD) and optical spectroscopy techniques. Pure BiVO4 and LaVO4 were obtained in the monoclinic form, whereas solid solutions in the tetragonal, zircon-type structure. The optical band gap dependence on the composition of the solid solution is parabolic, thus there is a possibility to tune this parameter in a wide concentration range, from 2.4 to 4.0 eV. An absorption coefficient maximum is also concentration-dependent, possibly, due to the structural disorder of the samples. Solid solutions with Bi(3+) concentration between 11.94 and 32.57 at.% exhibit intense, green luminescence. This indicates the presence of Bi-originated electronic states within the band gap. The value of the conduction band edge potential, measured by both electrochemical impedance spectroscopy and work function measurements, is concentration-independent. Moreover, solid solutions exhibit a photoelectrochemical photocurrent switching effect, thus they may be promising materials for molecular electronics and as dioxygen activators.

  14. Atomistic simulation of local structure and mixing properties of mineral solid solutions

    NASA Astrophysics Data System (ADS)

    Urusov, V. S.

    2009-04-01

    At present there are several ways to simulate solid solution structure and properties by using ab initio as well as semi-empirical (atomistic) approaches [1]. The main problem of each approach is a reasonable representation of random distribution of atoms substituting each other over common positions. A procedure in operation here used large supercells and generation of most disordered atomic configurations for some selected compositions of solid solution (1:1, 1:3, 3:1, 4:1, 1:4, etc.). The following binary systems were studied by such a way: NaCl - KCl [2, 3, 4], CaO - MgO, CaO - SrO, SrO - BaO (supercell 444, 512 atoms) [3], TiO2 - SnO2 (444, 384 atoms), Al2O3 - Cr2O3, Al2O3 - Fe2O3, Fe2O3 - Cr2O3 (441, 480 atoms) [5]. The calculation technique was based on the method of semi-empirical potentials using the GULP program [6]. Potential parameters of ionic (halides) or partially covalent (oxides) interatomic interactions were optimized by using of structural, thermodynamic and elastic properties of pure components. Calculated heat capacities and entropies as a function of temperature were in a good agreement with experimental data. Excess mixing properties (enthalpy, volume, bulk modulus, vibrational entropy) were calculated for different compositions of the solid solutions. This allowed to reproduce Gibbs energy as a function of temperature and composition and estimate critical temperature of decomposition and miscibility gap of a solid solution. Statistical analysis of bond lengths frequencies for the nearest and next-nearest neighbors in (Na0.5K0.5)Cl, (Ca0.5Mg0.5)O, (Ti0.5Sn0.5)O2, (Al1.0Cr1.0)O3 solid solutions revealed a detailed picture of the lattice relaxation. These results were compared with earlier predictions made by phenomenological crystal chemical models [7, 8] and available EXAFS data. References 1. V.S.Urusov. J.Solid State Chem. 2000. V.153. 357. 2. Urusov V.S., Petrova T.G., Leonenko E.V., Eremin N.N. Vestn. Mosc. Univ. 2008

  15. Reduced ceria nanofilms from structure prediction.

    PubMed

    Kozlov, Sergey M; Demiroglu, Ilker; Neyman, Konstantin M; Bromley, Stefan T

    2015-03-14

    Experimentally, Ce2O3 films are used to study cerium oxide in its fully or partially reduced state, as present in many applications. We have explored the space of low energy Ce2O3 nanofilms using structure prediction and density functional calculations, yielding more than 30 distinct nanofilm structures. First, our results help to rationalize the roles of thermodynamics and kinetics in the preparation of reduced ceria nanofilms with different bulk crystalline structures (e.g. A-type or bixbyite) depending on the support used. Second, we predict a novel, as yet experimentally unresolved, nanofilm which has a structure that does not correspond to any previously reported bulk A2B3 phase and which has an energetic stability between that of A-type and bixbyite. To assist identification and fabrication of this new Ce2O3 nanofilm we calculate some observable properties and propose supports for its epitaxial growth.

  16. A well-structured metastable ceria surface

    SciTech Connect

    Olbrich, R.; Pieper, H. H.; Oelke, R.; Wilkens, H.; Wollschläger, J.; Reichling, M.; Zoellner, M. H.; Schroeder, T.

    2014-02-24

    By the growth of a 180 nm thick film on Si(111), we produce a metastable ceria surface with a morphology dominated by terraced pyramids with an oriented triangular base. Changes in the nanoscale surface morphology and local surface potential due to annealing at temperatures ranging from 300 K to 1150 K in the ultra-high vacuum are studied with non-contact atomic force microscopy and Kelvin probe force microscopy. As the surface is stable in the temperature range of 300 K to 850 K, it is most interesting for applications requiring regular steps with a height of one O-Ce-O triple layer.

  17. Silicon nitride-aluminum oxide solid solution (SiAION) formation and densification by pressure sintering

    NASA Technical Reports Server (NTRS)

    Yeh, H. C.; Sanders, W. A.; Fiyalko, J. L.

    1975-01-01

    Stirred-ball-mill-blended Si3N4 and Al2O3 powders were pressure sintered in order to investigate the mechanism of solid solution formation and densification in the Si3N4-Al2O3 system. Powder blends with Si3N4:Al2O3 mole ratios of 4:1, 3:2, and 2:3 were pressure sintered at 27.6-MN/sq m pressure at temperatures to 17000 C (3090 F). The compaction behavior of the powder blends during pressure sintering was determined by observing the density of the powder compact as a function of temperature and time starting from room temperature. This information, combined with the results of X-ray diffraction and metallographic analyses regarding solutioning and phase transformation phenomena in the Si3N4-Al2O3 system, was used to describe the densification behavior.

  18. Effective distribution coefficients of a binary ideal solid solution controlled by kink kinetics

    NASA Astrophysics Data System (ADS)

    Matsumoto, Naoko; Kitamura, Masao

    2001-01-01

    Effective distribution coefficients of a binary ideal solid solution growing from dilute surroundings are derived for the steady state using a model in which atoms attach and detach only at kink sites on a (0 0 1) surface of a simple cubic crystal. A system of equations is presented to give the step-edge, terrace, and bulk compositions in terms of attachment and detachment frequencies. The total net flux of atoms from the mother phase to kink sites is also formulated as a function of these compositions and the frequencies. Numerical solutions to the system of equations show that the step-edge, terrace, and bulk compositions are different from one another and that the step-edge, terrace, and bulk distribution coefficients will all approach unity from their respective equilibrium values as the total net flux increases.

  19. NEXAFS Chemical State and Bond Lengths of p-Aminobenzoic Acid in Solution and Solid State

    NASA Astrophysics Data System (ADS)

    Stevens, J. S.; Gainar, A.; Suljoti, E.; Xiao, J.; Golnak, R.; Aziz, E. F.; Schroeder, S. L. M.

    2016-05-01

    Solid-state and solution pH-dependent NEXAFS studies allow direct observation of the electronic state of para-aminobenzoic acid (PABA) as a function of its chemical environment, revealing the chemical state and bonding of the chemical species. Variations in the ionization potential (IP) and 1s→π* resonances unequivocally identify the chemical species (neutral, cationic, or anionic) present and the varying local environment. Shifts in σ* shape resonances relative to the IP in the NEXAFS spectra vary with C-N bond length, and the important effect of minor alterations in bond length is confirmed with nitrogen FEFF calculations, leading to the possibility of bond length determination in solution.

  20. Phase separation in dilute solutions of 3He in solid 4He

    NASA Astrophysics Data System (ADS)

    Huan, C.; Yin, L.; Xia, J. S.; Candela, D.; Cowan, B. P.; Sullivan, N. S.

    2017-03-01

    We report the results of studies of the phase separation of solid solutions of dilute concentrations of 3He in 4He. The temperatures and the kinetics of the phase separation were determined from NMR experiments for 3He concentrations 1.6 ×10-5solution theory as augmented by Edwards and Balibar [Phys. Rev. B 39, 4083 (1989), 10.1103/PhysRevB.39.4083]. The growth of 3He droplets shows a t1 /3 time dependence at long times consistent with Ostwald ripening.

  1. Exact solution of the two-level system and the Einstein solid in the microcanonical formalism

    NASA Astrophysics Data System (ADS)

    Bertoldi, Dalía S.; Bringa, Eduardo M.; Miranda, E. N.

    2011-11-01

    The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In this paper, those two models are solved without any approximation, using the gamma function and its derivatives. Exact values are calculated for the entropy, temperature and specific heat, and the relative error between our exact solution and the approximate one using the Stirling approximation. This error is significant for small systems, with a number of particles N ~ 100, as in studies of atomic clusters or nanoscale structures.

  2. In situ study of the solid-state formation of U(1-x)Am(x)O(2±δ) solid solution.

    PubMed

    Lebreton, Florent; Belin, Renaud C; Prieur, Damien; Delahaye, Thibaud; Blanchart, Philippe

    2012-09-03

    In order to reduce the nuclear waste inventory and radiotoxicity, U(1-x)Am(x)O(2±δ) materials are promising fuels for heterogeneous transmutation. In this context, they are generally fabricated from UO(2+δ) and AmO(2-δ) dioxide powders. In the subsequent solid solution, americium is assumed to be trivalent whereas uranium exhibits a mixed-valence (+IV/+V) state. However, no formation mechanisms were ever evidenced and, more particularly, it was not possible to know whether the reduction of Am(IV) to Am(III) occurs before the solid-solution formation, or only once it is established. In this study, we used high-temperature X-ray diffraction on a UO(2±δ)/AmO(2-δ) (15 mol %) mixture to observe in situ the formation of the U(1-x)Am(x)O(2±δ) solid solution. We show that UO(2+δ) is, at relatively low temperature (<700 K), oxidized to U(4)O(9-δ), which is likely to be caused by oxygen release from the simultaneous AmO(2-δ) reduction to cubic Am(2)O(3±δ). Cubic Am(2)O(3+δ) then transforms to hexagonal Am(2)O(3) at 1300 K. Thus, the initial Am(IV) is fully reduced to Am(III) before the solid solution starts forming at 1740 K. The UO(2) fluorite phase vanishes after 4 h at 1970 K, indicating that the formation of the solid solution is completed, which proves that this solid solution is formed after the complete reduction of Am(IV) to Am(III).

  3. Coordination chemistry study of hydrated and solvated lead(II) ions in solution and solid state.

    PubMed

    Persson, Ingmar; Lyczko, Krzysztof; Lundberg, Daniel; Eriksson, Lars; Płaczek, Anna

    2011-02-07

    The coordination chemistry of lead(II) in the oxygen donor solvents water, dimethylsulfoxide (dmso, Me(2)SO), N,N-dimethylformamide (dmf), N,N-dimethylacetamide (dma), N,N'-dimethylpropyleneurea (dmpu), and 1,1,3,3-tetramethylurea (tmu), as well as in the sulfur donor solvent N,N-dimethylthioformamide (dmtf), has been investigated by extended X-ray absorption fine structure (EXAFS) and/or large angle X-ray scattering (LAXS) in solution, and by single crystal X-ray diffraction and/or EXAFS of solid hydrates and solvates. Lead(II) may either form hemidirected complexes with large bond distance distribution and an apparent gap for excess electron density, or holodirected ones with a symmetric coordination sphere with normal bond distance distribution, depending on the strength of antibonding lead 6s/ligand np molecular orbital interactions and ligand-ligand interactions. The crystallographic data show that the solid lead(II) perchlorate and trifluoromethanesulfonate hydrate structures are hemidirected, while the solid lead(II) solvates of dma and dmpu have regular octahedral configuration with holodirected geometry and mean Pb-O bond distances in the range 2.50-2.52 Å. EXAFS data on the hydrated lead(II) ion in aqueous solution show broad bond distance distribution and a lack of inner-core multiple scattering contributions strongly indicating a hemidirected structure. The Pb-O bond distances found both by EXAFS and LAXS, 2.54(1) Å, point to a six-coordinate hydrated lead(II) ion in hemidirected fashion with an unevenly distributed electron density. The results obtained for the dmso solvated lead(II) ion in solution are ambiguous, but for the most part support a six-coordinate hemidirected complex. The mean Pb-O bond distances determined in dmf and dma solution by LAXS, 2.55(1) and 2.48(1) Å, respectively, indicate that in both solvate complexes lead(II) binds six solvent molecules with the former complex being hemidirected whereas the latter is holodirected. The

  4. A statistical mechanical calculation of the thermodynamic properties of interstitial solid solutions involving second nearest neighbor interactions.

    NASA Technical Reports Server (NTRS)

    Alex, K.; Mclellan, R. B.

    1971-01-01

    A previous calculation of the thermodynamic properties of interstitial solid solutions based on the technique of Kirkwood expansions has been extended to include the effects of second nearest neighbor solute atom mutual interactions. The error inherent in the first order (or quasi-chemical) counting of the degeneracy of the solution crystal is avoided. It is shown that, at high temperatures, even strong second nearest neighbor solute mutual interactions have a negligible effect on the entropy of the solution and a small, temperature-dependent effect on the solute partial enthalpy.

  5. Spectroscopic study of mimetite-vanadinite solid solution series - preliminary results

    NASA Astrophysics Data System (ADS)

    Janicka, Urszula; Bajda, Tomasz; Topolska, Justyna; Manecki, Maciej

    2014-05-01

    Mimetite Pb5(AsO4)3Cl and vanadinite Pb5(VO4)3Cl are minerals from the Pb-apatites family which belong to the apatite supergroup. Most often they crystalize under hypergenic conditions, in oxidation zones of Pb ore deposits, where they form paragenesis with pyromorphite Pb5(PO4)3Cl. These minerals are used in the techniques of soils reclamation. Their crystal structure allows substituting of metal cations as well as of anionic complexes. Natural mimetite often contains admixture of phosphates and/or vanadates. Similarly, vanadinite contains admixtures of phosphates and/or arsenates. Among the lead apatites, properties of the minerals from pyromorphite-mimetite solid solution series are well known, while the knowledge about the mimetite-vanadinite series is incomplete. The aim of this research was synthesis and spectroscopic characterization of mimetite-vanadinite solid solution series. Mimetite, vanadinite and their solid solution were synthesized from aqueous solutions by dropwise mixing of Pb(NO3)2, Na3VO4, Na2HAsO4×7H2O and NaCl at 25 ºC and pH = 3.5. Products of the syntheses were analyzed by X-Ray diffraction (XRD), Infrared absorption spectroscopy (FTIR) and Raman spectroscopy. The precipitates formed in the syntheses were identified by the XRD method as mimetite, vanadinite and their solid solutions. Other crystalline phases were not present in synthetic precipitates within the detection limit of XRD. In the Mid-IR spectra of mimetite-vanadinite solid solutions series, bands characteristic for vibrations of As-O bonds of the AsO4 tetrahedra and vibrations of V-O bonds of the VO4 tetrahedra were observed. The band corresponding to stretching ν3vibrations of AsO4 and VO4 occured in the range 700-900 cm-1. In the Raman spectra, bands which are characteristic for vibrations of As-O bonds of the AsO4 tetrahedra and vibrations of V-O bonds of the VO4 tetrahedra were also observed. The bands attributed to vibrations in the AsO4 tetrahedra appeared at 880-740 cm

  6. Synthesis, characterization, and enthalpy of mixing of the (Fe,Mg)C0 3 solid solution

    NASA Astrophysics Data System (ADS)

    Chai, L.; Navrotsky, A.

    1996-11-01

    Solid solutions along the magnesite-siderite join have been synthesized from mechanical mixtures of iron oxalate and basic magnesium carbonate using hydrothermal synthesis techniques at 500°C and about 2 kilobars. The double capsule method was used to provide the atmosphere necessary to prevent decomposition and oxidation of the Fe 2+-bearing carbonate. The synthetic samples were characterized by x-ray diffraction (XRD) and thermogravimetric analysis (TGA). Unit cell parameters, determined from x-ray diffraction in step scan mode, show a linear relationship with composition. The compositions and homogeneity of the sample were confirmed by electron microprobe analysis. Enthalpy of mixing was measured using a Calvet-type calorimeter at 770°C. A two step calorimetric method was developed and confirmed to be successful in determining the energetics of the Fe 2+-bearing carbonates. The first step involved decomposition of the sample in an oxygen atmosphere, and then the decomposition of the sample in an oxygen atmosphere, and then the decomposition products (a mixture of a spinel phase, MgFe 2O 4, and MgO or hematite) were dissolved in lead borate solvent in air as the second step. The enthalpies of mixing are slightly positive, with a regular solution parameter of 4.44 ± 0.75 kJ/mol. Under the assumption of regular solution, the phase diagram of the FeC0 3sbnd MgCO 3 system has been calculated, and the critical temperature for exsolution is about -6°C. Thus, the (Fe,Mg) CO 3 solid solution is expected to be complete and nearly ideal in all geological environments.

  7. Synthesis and crystallographic study of Pb-Sr hydroxyapatite solid solutions by high temperature mixing method under hydrothermal conditions

    SciTech Connect

    Zhu Kongjun; Yanagisawa, Kazumichi; Shimanouchi, Rie; Onda, Ayumu; Kajiyoshi, Koji; Qiu Jinhao

    2009-06-03

    The solid solutions in the system of Pb and Sr hydroxyapatite, Sr{sub 10-x}Pb{sub x}HAp (x = 0-10), were successfully synthesized by high-temperature mixing method (HTMM) at 160 deg. C for 12 h under hydrothermal conditions. The samples were characterized by X-ray diffraction, chemical analysis and electron microscopic observation, and the site of the metal ions in the solid solutions was analyzed with the Rietveld method. The lattice constants, both a and c, of the solid solutions varied linearly with Pb content. It was found that Pb ions in the solid solutions preferentially occupied the M(2) site in the apatite structure. HTMM gives Sr-Pb HAp solid solutions much better crystallization. However, due to the formation of intermediate compound of Pb{sub 3}O{sub 2}(OH){sub 2} in the Pb(NO{sub 3}){sub 2}.4H{sub 2}O solution before mixing with (NH{sub 4}){sub 2}HPO{sub 4} solution at 160 deg. C, HTMM causes the decrease of crystallization of the samples with high Pb content.

  8. Temperature-dependent vibrational spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in solid state and solution

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Kellner, R.

    The IR spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in the solid state (at 20, 80 and 120°C) as well as in solution (20°C) have been recorded and discussed as to the changes in the zinc coordination sphere that may occur upon heating and dissolution. The decreased number of bands in the high-temperature and in the solution specta as compared with the room temperature solid state spectra has been explained by removal of the intermolecular contacts upon dissolution or thermal averaging in the high temperature solid state.

  9. Optimizing the formation of solid solutions with components of different shapes

    NASA Astrophysics Data System (ADS)

    Escobedo, Fernando A.

    2017-04-01

    A key challenge to engineer ordered solids from the co-assembly of two differently shaped building blocks is to predict the key particle characteristics that lead to maximal mutual ordered-phase compatibility (MaxOC). While both entropy disparity, as captured by the relative size of the components, and energetic inter-species selectivity affect MaxOC, it is the former whose effect is less intuitive and the main focus of this work. Such MaxOC predictive rules are formulated and validated by using Monte Carlo simulation results for hard-core mixtures of octahedra and spheres and of other previously studied mixtures. Specifically, it is proposed that component size ratios should maximize their "substitutional symmetry" and hence minimize the combined free-energy cost associated with mutating a host-particle into a guest-particle in each of the solid phases. For the hard-core mixtures examined, packing entropy stabilizes substitutionally disordered solid solutions but not stoichiometric compounds. Additional molecular simulations were hence used to demonstrate, consistent with recent experimental findings, that such compounds can be formed by strengthening the inter-species compatibility via orientation-dependent attractions.

  10. The origin of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution crystals

    SciTech Connect

    Li, Fei; Zhang, Shujun; Yang, Tiannan; Xu, Zhuo; Zhang, Nan; Liu, Gang; Wang, Jianjun; Wang, Jianli; Cheng, Zhenxiang; Ye, Zuo-Guang; Luo, Jun; Shrout, Thomas R.; Chen, Long-Qing

    2016-12-19

    The discovery of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution single crystals is a breakthrough in ferroelectric materials. A key signature of relaxor-ferroelectric solid solutions is the existence of polar nanoregions, a nanoscale inhomogeneity, that coexist with normal ferroelectric domains. Despite two decades of extensive studies, the contribution of polar nanoregions to the underlying piezoelectric properties of relaxor ferroelectrics has yet to be established. Here we quantitatively characterize the contribution of polar nanoregions to the dielectric/piezoelectric responses of relaxor-ferroelectric crystals using a combination of cryogenic experiments and phase-field simulations. The contribution of polar nanoregions to the room-temperature dielectric and piezoelectric properties is in the range of 50–80%. A mesoscale mechanism is proposed to reveal the origin of the high piezoelectricity in relaxor ferroelectrics, where the polar nanoregions aligned in a ferroelectric matrix can facilitate polarization rotation. This mechanism emphasizes the critical role of local structure on the macroscopic properties of ferroelectric materials.

  11. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    DOE PAGES

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

    2015-10-15

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganesemore » doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

  12. CO oxidation on Ta-Modified SnO2 solid solution catalysts

    NASA Astrophysics Data System (ADS)

    Han, Xue; Xu, Xianglan; Liu, Wenming; Wang, Xiang; Zhang, Rongbin

    2013-06-01

    Co-precipitation method was adopted to prepare Sn-Ta mixed oxide catalysts with different Sn/Ta molar ratios and used for CO oxidation. The catalysts were investigated by N2-Brunauer-Emmett-Teller (N2-BET), X-ray diffraction patterns (XRD), H2-temperature programmed reduction (H2-TPR), Thermal Gravity Analysis - Differential Scanning Calorimetry (TGA-DSC) techniques. It is revealed that a small amount of Ta cations can be doped into SnO2 lattice to form solid solution by co-precipitation method, which resulted in samples having higher surface areas, improved thermal stability and more deficient oxygen species on the surface of SnO2. As a result, those Sn rich Sn-Ta solid solution catalysts with an Sn/Ta molar ratio higher than 4/2 showed significantly enhanced activity as well as good resistance to water deactivation. It is noted here that if tantala disperses onto SnO2 surface instead of doping into its lattice, it will then have negative effect on its activity.

  13. Manipulation of σ{sub y}/κ ratio in single phase FCC solid-solutions

    SciTech Connect

    Lee, J. I.; Oh, H. S.; Park, E. S.

    2016-08-08

    We investigate how to manipulate the ratio between thermal conductivity (κ) and yield strength (σ{sub y}) in face-centered cubic solid-solutions by varying the number of principal elements (NPEs) and temperature. The influence of NPEs on κ and its electronic (κ{sub e}) and lattice (κ{sub l}) contribution is evaluated using the Wiedemann–Franz law. Positive Δκ/ΔT and the highest κ{sub l}/κ{sub e} ratio in high-entropy alloys (HEAs) can be understood by considering severe lattice distortion and compositional complexity. Among the solid-solutions from Ni to quinary alloys, the NiCoFeCrMn HEA exhibits the lowest κ. However, σ{sub y} increases with increasing NPEs and decreasing temperature. Thus, the NiCoFeCrMn HEA exhibits the highest σ{sub y}/κ ratio, higher than those of representative cryogenic alloys, which can be distinctively increased with a decrease in temperature. These results would give us a guideline on how to manipulate properties using HEA design concept in order to develop idealized cryogenic materials.

  14. Mechanical Properties of Mg-Gd and Mg-Y Solid Solutions

    NASA Astrophysics Data System (ADS)

    Kula, Anna; Jia, Xiaohui; Mishra, Raj K.; Niewczas, Marek

    2016-12-01

    The mechanical properties of Mg-Gd and Mg-Y solid solutions have been studied under uniaxial tension and compression between 4 K and 298 K (-269 °C and 25 °C). The results reveal that Mg-Gd alloys exhibit higher strength and ductility under tension and compression attributed to the more effective solid solution strengthening and grain-boundary strengthening effects. Profuse twinning has been observed under compression, resulting in a material texture with strong dominance of basal component parallel to compression axis. Under tension, twining is less active and the texture evolution is controlled mostly by slip. The alloys exhibit pronounced yield stress asymmetry and significantly different work-hardening behavior under tension and compression. Increasing of Gd and/or Y concentration leads to the reduction of the tension-compression asymmetry due to the weakening of the recrystallization texture and more balanced twinning and slip activity during plastic deformation. The results suggest that under compression of Mg-Y alloys slip is more active than twinning in comparison to Mg-Gd alloys.

  15. FTIR assessment of poly(ethylene oxide) irradiated in solid state, melt and aqeuous solution

    NASA Astrophysics Data System (ADS)

    Pucić, Irina; Jurkin, Tanja

    2012-09-01

    FTIR spectroscopy was used to study poly(ethylene oxide), PEO, irradiated in solid and molten aggregate states and as aqueous solutions of various concentrations. The changes in shape and width of -C-O-C- complex absorption intensities at around 1112 cm-1 were the most prominent. On irradiation of solid samples in contact with air shrinking of -C-O-C- complex and increase in its absorption intensities indicated predominant degradation. Crosslinking prevailed on irradiation of molten PEO and of its aqueous solutions in nitrogen atmosphere and manifested itself as widening of -C-O-C- absorption and decrease of corresponding intensities. Partial or complete merging of CH2 wagging vibrations at 1342 cm-1 and 1360 cm-1 that are characteristic of crystalline PEO into a single absorption at around 1350 cm-1 indicated amorphization what was observed for samples that had reduced degree of crystallinity determined by differential scanning calorimetry. DSC could not discriminate between degradation and crosslinking while the changes in width and shape of -C-O-C- complex were independent of the changes in crystallinity. Comparison of FTIR spectra of the same PEO samples obtained as thin film and as KBr pellets revealed that pellet preparation results in a number of spectral artefacts.

  16. High-pressure synthesis, characterization, and equation of state of cubic C-BN solid solutions

    NASA Astrophysics Data System (ADS)

    Knittle, E.; Kaner, R. B.; Jeanloz, R.; Cohen, M. L.

    1995-05-01

    Synthesis of several samples across the cubic Cx(BN)1-x solid solution (x=0.3-0.33,0.5,0.6) at pressures in excess of 30 GPa and temperatures above 1500 K indicates that they are isostructural with diamond and cubic BN (borazon). Measurement of the lattice parameters of C-BN samples quenched to ambient conditions shows that the solid solution between C (diamond) and cubic BN is nonideal, with unit-cell volumes up to 1% larger than predicted based on ideal mixing (Vegard's law). In addition, we have measured the zero-pressure, 300-K vibrational spectra for C0.3(BN)0.7. In the midinfrared absorption spectrum, we observe a reststrahlen band ranging from 1000-1120 cm-1, and the Raman spectrum has a longitudinal optic mode at 1323(+/-2) cm-1. Based on a comparison of the spectrum with that of diamond and cubic BN, we conclude that the bonding in cubic C-BN is partially ionic. In addition to these measurements on quenched samples, we have measured the isothermal bulk modulus of C0.33(BN)0.67 by x-ray diffraction through a diamond cell to over 100 GPa at 300 K. The bulk modulus is 355(+/-19) GPa, which is lower than those of diamond, cubic BN and the value predicted from ideal mixing between the end members, but is consistent with the nonideal expansion observed for the cubic C-BN lattice parameters.

  17. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    DOE PAGES

    Zhang, Yanwen; Stocks, George Malcolm; Jin, Ke; ...

    2015-10-28

    A long-standing objective in materials research is to understand how energy is dissipated in both the electronic and atomic subsystems in irradiated materials, and how related non-equilibrium processes may affect defect dynamics and microstructure evolution. Here we show that alloy complexity in concentrated solid solution alloys having both an increasing number of principal elements and altered concentrations of specific elements can lead to substantial reduction in the electron mean free path and thermal conductivity, which has a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Enhanced radiation resistance with increasing complexity from pure nickel tomore » binary and to more complex quaternary solid solutions is observed under ion irradiation up to an average damage level of 1 displacement per atom. Understanding how materials properties can be tailored by alloy complexity and their influence on defect dynamics may pave the way for new principles for the design of radiation tolerant structural alloys.« less

  18. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    PubMed Central

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

    2015-01-01

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface. PMID:26469151

  19. Manipulation of σy/κ ratio in single phase FCC solid-solutions

    NASA Astrophysics Data System (ADS)

    Lee, J. I.; Oh, H. S.; Park, E. S.

    2016-08-01

    We investigate how to manipulate the ratio between thermal conductivity (κ) and yield strength (σy) in face-centered cubic solid-solutions by varying the number of principal elements (NPEs) and temperature. The influence of NPEs on κ and its electronic (κe) and lattice (κl) contribution is evaluated using the Wiedemann-Franz law. Positive Δκ/ΔT and the highest κl/κe ratio in high-entropy alloys (HEAs) can be understood by considering severe lattice distortion and compositional complexity. Among the solid-solutions from Ni to quinary alloys, the NiCoFeCrMn HEA exhibits the lowest κ. However, σy increases with increasing NPEs and decreasing temperature. Thus, the NiCoFeCrMn HEA exhibits the highest σy/κ ratio, higher than those of representative cryogenic alloys, which can be distinctively increased with a decrease in temperature. These results would give us a guideline on how to manipulate properties using HEA design concept in order to develop idealized cryogenic materials.

  20. Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

    NASA Technical Reports Server (NTRS)

    Dutta, S.

    1977-01-01

    Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.