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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. PMID:27494765

  2. General and facile synthesis of ceria-based solid solution nanocrystals and their catalytic properties

    SciTech Connect

    Zhou Huanping; Si Rui; Song Weiguo; Yan Chunhua

    2009-09-15

    Uniform Ce{sub 1-x}Zr{sub x}O{sub 2} (x=0.2-0.8) nanocrystals with ultra-small size were synthesized through a thermolysis process, facilitated by the initial formation of precursor (hydrated (Ce,Zr)-hydroxides) at low temperature. TEM, XRD, EDAX, and Raman spectra were employed to study the formation of the solid solutions with various Ce/Zr ratios. Ultraviolet-visible (UV-vis) spectra showed that the ratios of Ce{sup 3+} to Ce{sup 4+} in both surface and bulk for the as-prepared Ce{sub 1-x}Zr{sub x}O{sub 2} nanocrystals increased with the zirconium content x. The well-distributed Zr and Ce in the hydrated (Ce,Zr)-hydroxides before their thermolysis became the crucial factor for the structural homogeneity of the products. In addition, this strategy was extended to the synthesis of Ce{sub 1-x}Gd{sub x}O{sub 1-x/2}, Ce{sub 1-x}Sm{sub x}O{sub 1-x/2}, and Ce{sub 1-x}Sn{sub x}O{sub 2} solid solutions. Catalytic measurements indicated that the ceria-based catalysts were active for CO oxidation at temperatures beyond 250 deg. C and the sequence of catalytic activity was Ce{sub 0.5}Zr{sub 0.5}O{sub 2}>Ce{sub 0.8}Zr{sub 0.2}O{sub 2}>Ce{sub 0.2}Zr{sub 0.8}O{sub 2}>Ce{sub 0.5}Sm{sub 0.5}O{sub 1.75}. - Abstract: Uniform ultra-small nanostructured Ce{sub 1-x}Zr{sub x}O{sub 2}, Ce{sub 1-x}Gd{sub x}O{sub 1-x/2}, Ce{sub 1-x}Sm{sub x}O{sub 1-x/2}, and Ce{sub 1-x}Sn{sub x}O{sub 2} solid solutions with homogeneous textures were synthesized through a thermolysis process, facilitated by the initial formation of precursors (hydrated (Ce,M)-hydroxides). Display Omitted

  3. Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity

    PubMed Central

    2012-01-01

    A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g−1 exhibited a considerably high OSC of 427 μmol-O g−1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC. PMID:23025588

  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. PMID:21371821

  5. Electrochemically Deposited Ceria Structures for Advanced Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Brown, Evan C.

    As the pursuit towards emissions reduction intensifies with growing interest and nascent technologies, solid oxide fuel cells (SOFCs) remain an illustrious candidate for achieving our goals. Despite myriad advantages, SOFCs are still too costly for widespread deployment, even as unprecedented materials developments have recently emerged. This suggests that, in addition to informed materials selection, the necessary power output--and, thereby, cost-savings--gains must come from the fuel cell architecture. The work presented in this manuscript primarily investigates cathodic electrochemical deposition (CELD) as a scalable micro-/nanoscale fabrication tool for engineering ceria-based components in a SOFC assembly. Also, polymer sphere lithography was utilized to deposit fully connected, yet fully porous anti-dot metal films on yttira-stabilized zirconia (YSZ) with specific and knowable geometries, useful for mechanistic studies. Particular attention was given to anode structures, for which anti-dot metal films on YSZ served as composite substrates for subsequent CELD of doped ceria. By tuning the applied potential, a wide range of microstructures from high surface area coatings to planar, thin films was possible. In addition, definitive deposition was shown to occur on the electronically insulating YSZ surfaces, producing quality YSZ|ceria interfaces. These CELD ceria deposits exhibited promising electrochemical activity, as probed by A.C. Impedance Spectroscopy. In an effort to extend its usefulness as a SOFC fabrication tool, the CELD of ceria directly onto common SOFC cathode materials without a metallic phase was developed, as well as templated deposition schemes producing ceria nanowires and inverse opals.

  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. PMID:27388961

  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. A single step solution combustion approach for preparing gadolinia doped ceria solid oxide fuel cell electrolyte material suitable for wet powder and plasma spraying processes

    NASA Astrophysics Data System (ADS)

    Shri Prakash, B.; William Grips, V. K.; Aruna, S. T.

    2012-09-01

    The present study explores the versatility of solution combustion method for preparing powders of varying characteristics suitable for intermediate temperature solid oxide fuel cell (IT-SOFC) fabrication. The promising electrolyte material for IT-SOFC, Gd0.2Ce0.8O2-δ (GDC), is considered for the present investigation. GDC powders consisting of sub-micron sized particles (<250 nm) and micron sized (>20 μm) particles are produced by varying the fuel used in the combustion reaction. Highly sinteractive nano-GDC powders prepared using oxalyl dihydrazide as a fuel results in dense pellets with high conductivity (3 × 10-4 Scm-1 at 400 °C). This powder also results in a stable suspension suitable for wet powder spraying and electrophoretic deposition. Powders with larger particle size (>20 μm) prepared by solution combustion method using mixture of fuels, exhibits necessary flowability for atmospheric plasma spraying (APS). GDC coatings fabricated by APS using flowable powders are dense with superior adhesion between the splats. Good adhesion between the splats in the APS coatings is attributed to the higher level of melting of the combustion synthesized particles in the plasma flame owing to their low specific mass.

  9. 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

  10. 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.

  11. 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

  12. Synthesis and atomic level in situ redox characterization in ceria and ceria zirconia

    NASA Astrophysics Data System (ADS)

    Wang, Ruigang

    2007-12-01

    Nanocrystalline ceria-based oxides are widely used in automotive three-way catalytic converters to reduce the emissions of carbon monoxide, nitrogen oxides, and unburned hydrocarbons. The primary function of ceria-based oxides in the catalytic process is to adjust the local oxygen partial pressure and maintain an air-to-fuel ratio near the stoichiometric value (˜14.5) required for the optimal catalyst performance for carbon monoxide, hydrocarbon oxidation, and nitrogen oxides reduction. In this dissertation, a study of the relationship between the nanoscale structure, chemistry, and the redox behavior on high surface area ceria and ceria zirconia is presented. Precipitation and spray freezing methods were used to synthesize nanocrystalline ceria and ceria zirconia solid solution powders respectively. The effect of thermal treatments in oxidizing and reducing atmospheres on the reducibility of the materials has been systematically investigated. X-ray diffraction and thermogravimetric analysis were used to characterize the average structure and reducibility. In situ environmental transmission electron microscope was exploited to visualize the dynamic changes during redox processes at the atomic level. This resulted in the identification of the nanoscale structure and chemistry for the most active nanoparticles in these oxides. The correlation between ex situ macroscopic redox properties and in situ redox behavior of individual nanoparticles is demonstrated. The addition of zirconia to ceria clearly enhances the reducibility and thermal stability of ceria. A fundamental difference between ceria and ceria zirconia during in situ redox processes is related to oxygen vacancy ordering. Ceria showed oxygen vacancy ordering during reduction, whereas ceria zirconia did not. It is suggested that the absence of oxygen vacancy ordering might be a fundamental factor for improved redox properties of ceria zirconia compared with pure ceria. The 50% ceria-50% zirconia solid

  13. 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

  14. 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.

  15. Continuum modeling of size effects on the composition and stresses in nanoparticles of ionic solids with application to ceria

    NASA Astrophysics Data System (ADS)

    Haftbaradaran, Hamed; Mossaiby, Farshid

    2016-03-01

    Owing to its broad potential applications, nanostructured ceria has been subject of intense investigation in the past few decades. Experiments have demonstrated that various material properties of the nanostructured ionic solids including ceria vary with the feature size. Here, we present a theoretical study of the size effects on the composition, defect concentrations and stresses in free-standing nanoparticles of nonstoichiometric ionic solids. To this end, a continuum model is developed which accounts for the highly nonlinear coupling between mechanical, chemical and electrical driving forces, and their effects on the thermodynamic equilibrium of the defect species. It is demonstrated that the model, once applied to the case of ceria, predicts size-dependent defect concentrations and surface stresses. It is further shown that the theoretical predictions of the size effects on the composition and lattice parameter are in good agreement with the experimental observations.

  16. 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.

  17. 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

  18. 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.

  19. Reduced-temperature firing of solid oxide fuel cells with zirconia/ceria bi-layer electrolytes

    NASA Astrophysics Data System (ADS)

    Gao, Zhan; Kennouche, David; Barnett, Scott A.

    2014-08-01

    Solid oxide fuel cells (SOFCs) with bi-layer Zirconia/Ceria electrolytes have been studied extensively because of their great potential for producing high power density at reduced operating temperature, important for reducing cost and thereby allowing broader SOFC commercialization. The bi-layer electrolytes are designed to take advantage of the high oxygen ion conductivity of Ceria, the low electronic conductivity of Zirconia, and the low reactivity of Ceria with high-performance cathodes. However, zirconia/ceria processing has proven problematic due to interdiffusion during high temperature co-firing, or ceria layer porosity after two-step firing. Here we first show a new method for bi-layer co-firing at a reduced temperature of 1250 °C, ∼150 °C lower than the usual sintering temperature, achieved using Fe2O3 as a sintering aid. This novel process enables high power density SOFCs by producing: (1) low-resistance Y0.16Zr0.92O2-δ (YSZ)/Gd0.1Ce0.9O1.95 (GDC) electrolytes that also yield high open-circuit voltage, (2) dense GDC layers that prevent reactions between highly-active La0.6Sr0.4Fe0.8Co0.2O3 (LSFC) cathode materials and YSZ, and (3) Ni-YSZ anodes with high electrochemical activity due to fine-scale microstructure with high TPB densities.

  20. Thickness effects of yttria-doped ceria interlayers on solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Fan, Zeng; An, Jihwan; Iancu, Andrei; Prinz, Fritz B.

    2012-11-01

    Determining the optimal thickness range of the interlayed yttria-doped ceria (YDC) films promises to further enhance the performance of solid oxide fuel cells (SOFCs) at low operating temperatures. The YDC interlayers are fabricated by the atomic layer deposition (ALD) method with one super cycle of the YDC deposition consisting of 6 ceria deposition cycles and one yttria deposition cycle. YDC films of various numbers of ALD super cycles, ranging from 2 to 35, are interlayered into bulk fuel cells with a 200 um thick yttria-stabilized zirconia (YSZ) electrolyte. Measurements and analysis of the linear sweep voltammetry of these fuel cells reveal that the performance of the given cells is maximized at 10 super cycles. Auger elemental mapping and X-ray photoelectron spectroscopy (XPS) techniques are employed to determine the film completeness, and they verify 10 super cycles of YDC to be the critical thickness point. This optimal YDC interlayer condition (6Ce1Y × 10 super cycles) is applied to the case of micro fuel cells as well, and the average performance enhancement factor is 1.4 at operating temperatures of 400 and 450 °C. A power density of 1.04 W cm-2 at 500 °C is also achieved with the optimal YDC recipe.

  1. Mechanistic studies of water electrolysis and hydrogen electro-oxidation on high temperature ceria-based solid oxide electrochemical cells.

    PubMed

    Zhang, Chunjuan; Yu, Yi; Grass, Michael E; Dejoie, Catherine; Ding, Wuchen; Gaskell, Karen; Jabeen, Naila; Hong, Young Pyo; Shavorskiy, Andrey; Bluhm, Hendrik; Li, Wei-Xue; Jackson, Gregory S; Hussain, Zahid; Liu, Zhi; Eichhorn, Bryan W

    2013-08-01

    Through the use of ambient pressure X-ray photoelectron spectroscopy (APXPS) and a single-sided solid oxide electrochemical cell (SOC), we have studied the mechanism of electrocatalytic splitting of water (H2O + 2e(-) → H2 + O(2-)) and electro-oxidation of hydrogen (H2 + O(2-) → H2O + 2e(-)) at ∼700 °C in 0.5 Torr of H2/H2O on ceria (CeO2-x) electrodes. The experiments reveal a transient build-up of surface intermediates (OH(-) and Ce(3+)) and show the separation of charge at the gas-solid interface exclusively in the electrochemically active region of the SOC. During water electrolysis on ceria, the increase in surface potentials of the adsorbed OH(-) and incorporated O(2-) differ by 0.25 eV in the active regions. For hydrogen electro-oxidation on ceria, the surface concentrations of OH(-) and O(2-) shift significantly from their equilibrium values. These data suggest that the same charge transfer step (H2O + Ce(3+) <-> Ce(4+) + OH(-) + H(•)) is rate limiting in both the forward (water electrolysis) and reverse (H2 electro-oxidation) reactions. This separation of potentials reflects an induced surface dipole layer on the ceria surface and represents the effective electrochemical double layer at a gas-solid interface. The in situ XPS data and DFT calculations show that the chemical origin of the OH(-)/O(2-) potential separation resides in the reduced polarization of the Ce-OH bond due to the increase of Ce(3+) on the electrode surface. These results provide a graphical illustration of the electrochemically driven surface charge transfer processes under relevant and nonultrahigh vacuum conditions. PMID:23822749

  2. 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

    2015-11-01

    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. PMID:26307555

  3. 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.

  4. 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

  5. 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.

  6. 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

    2016-05-01

    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. PMID:27078722

  7. 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.

  8. 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.

  9. 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.

  10. 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. PMID:25936125

  11. 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.

  12. 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. PMID:21494706

  13. A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

    NASA Astrophysics Data System (ADS)

    Cuglietta, Mark; Kuhn, Joel; Kesler, Olivera

    2013-06-01

    Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co3O4, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm2 in humidified hydrogen and methane, respectively, at 800 °C.

  14. Electrochemical synthesis and properties of ceria films grown on stainless steel

    NASA Astrophysics Data System (ADS)

    Živković, Lj. S.; Lair, V.; Lupan, O.; Ringuedé, A.

    2011-12-01

    Electrochemical synthesis of ceria films was performed on a stainless steel substrate in view of Solid Oxide Fuel Cells (SOFC) applications. Films were obtained from aqueous nitrate solutions via cathodic deposition method at room temperature. A constant potential value of -0.8 V/(SCE) was applied to reduce the molecular oxygen as hydroxide precursor, leading to a formation of adherent, homogeneous and covering films in 20 min deposition time. Structure, morphology and composition of as-grown coatings were studied by X-ray diffraction, Raman and energy-dispersive X-ray spectroscopy, as well as scanning electron microscopy. Cubic fluorite-type nanostructured ceria of leaf-like particles was synthesized. Thermal annealing (600°C, 1 h) was found to enhance ceria crystallinity.

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

    PubMed

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

    2016-01-01

    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 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. PMID:27571083

  16. 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.

  17. 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. PMID:27009532

  18. 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. PMID:23919513

  19. Cathodes for ceria-based fuel cells

    SciTech Connect

    Doshi, R.; Krumpelt, M.; Ricvhards, V.L.

    1997-08-01

    Work is underway to develop a solid oxide fuel cell that has a ceria-based electrolyte and operates at lower temperatures (500-600{degrees}C) than conventional zirconia-based cells. At present the performance of this ceria-based solid oxide fuel cell is limited by the polarization of conventional cathode materials. The performance of alternative cathodes was measured by impedance spectroscopy and dc polarization. The performance was found to improve by using a thin dense interface layer and by using two-phase cathodes with an electrolyte and an electronic phase. The cathode performance was also found to increase with increasing ionic conductivity for single phase cathodes.

  20. Oxygen vacancy formation in CeO2 and Ce(1-x)Zr(x)O2 solid solutions: electron localization, electrostatic potential and structural relaxation.

    PubMed

    Wang, Hai-Feng; Li, Hui-Ying; Gong, Xue-Qing; Guo, Yang-Long; Lu, Guan-Zhong; Hu, P

    2012-12-28

    Ceria (CeO(2)) and ceria-based composite materials, especially Ce(1-x)Zr(x)O(2) solid solutions, possess a wide range of applications in many important catalytic processes, such as three-way catalysts, owing to their excellent oxygen storage capacity (OSC) through the oxygen vacancy formation and refilling. Much of this activity has focused on the understanding of the electronic and structural properties of defective CeO(2) with and without doping, and comprehending the determining factor for oxygen vacancy formation and the rule to tune the formation energy by doping has constituted a central issue in material chemistry related to ceria. However, the calculation on electronic structures and the corresponding relaxation patterns in defective CeO(2-x) oxides remains at present a challenge in the DFT framework. A pragmatic approach based on density functional theory with the inclusion of on-site Coulomb correction, i.e. the so-called DFT + U technique, has been extensively applied in the majority of recent theoretical investigations. Firstly, we review briefly the latest electronic structure calculations of defective CeO(2)(111), focusing on the phenomenon of multiple configurations of the localized 4f electrons, as well as the discussions of its formation mechanism and the catalytic role in activating the O(2) molecule. Secondly, aiming at shedding light on the doping effect on tuning the oxygen vacancy formation in ceria-based solid solutions, we summarize the recent theoretical results of Ce(1-x)Zr(x)O(2) solid solutions in terms of the effect of dopant concentrations and crystal phases. A general model on O vacancy formation is also discussed; it consists of electrostatic and structural relaxation terms, and the vital role of the later is emphasized. Particularly, we discuss the crucial role of the localized structural relaxation patterns in determining the superb oxygen storage capacity in kappa-phase Ce(1-x)Zr(1-x)O(2). Thirdly, we briefly discuss some

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Hydrothermal preparation and electrochemical properties of Gd 3+ and Bi 3+, Sm 3+, La 3+, and Nd 3+ codoped ceria-based electrolytes for intermediate temperature-solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Dikmen, Sibel; Aslanbay, Hasan; Dikmen, Erdal; Şahin, Osman

    The structure, the thermal expansion coefficient, electrical conductivities of Ce 0.8Gd 0.2- xM xO 2- δ (for M: Bi, x = 0-0.1, and for M: Sm, La, and Nd, x = 0.02) solid solutions, prepared for the first time hydrothermally, are investigated. The uniformly small particle size (28-59 nm) of the materials allows sintering of the samples into highly dense ceramic pellets at 1300-1400 °C. The maximum conductivity, σ 700 °C around 4.46 × 10 -2 S cm -1 with E a = 0.52 eV, is found at x = 0.1 for Bi-co-doping. Among various metal-co-dopings, for x = 0.02, the maximum conductivity, σ 700 °C around 2.88 × 10 -2 S cm -1 with E a = 0.67 eV, is found for Sm-co-doping. The electrolytic domain boundary (EDB) of Ce 0.8Gd 0.1Bi 0.1O 2- δ is found to be 1.2 × 10 -19 atm, which is relatively lower than that of the singly doped samples. The thermal expansion coefficients, determined from high-temperature X-ray data are 11.6 × 10 -6 K -1 for the CeO 2, 12.1 × 10 -6 K -1 for Ce 0.8Gd 0.2O 2- δ, and increase with co-doping to 14.2 × 10 -6 K -1 for Ce 0.8Gd 0.18Bi 0.02O 2- δ. The maximum power densities for the single cell based on the codoped samples are higher than that of the singly doped sample. These results suggest that co-doping can further improve the electrical performance of ceria-based electrolytes.

  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. Absorption spectra of cold dilute solid solutions

    SciTech Connect

    Holland, R.F.; Maier, W.B. II; Freund, S.; Beattie, W.H.

    1983-06-01

    Infrared absorption spectra have been obtained for some compounds trapped in crystalline solids by freezing liquid Xe, Kr, Ar, or CH/sub 4/ solutions. The optical quality of the solid solutions is good, and they have been cooled to approx.80 K in 1.35 cm sample thicknesses to study the absorption in fundamental vibrational bands of the solutes. In the cases discussed, the bands are narrow, with observed full widths at half-maximum absorbance 0.05--0.30 cm/sup -1/ greater than the instrumental resolution (0.18--0.29 cm/sup -1/). The spectra appear to be free of ''multiple site'' and solute aggregate absorptions. Spectra displaying isotropic splitting in bands of natural BCl/sub 3/, SeF/sub 6/, OsO/sub 4/, TiCl/sub 4/, and MoF/sub 6/ are presented, and band frequencies are compared with some results obtained in evaporative matrices, in the gas phase, and in liquid solutions. For this comparison we have obtained some spectra of SeF/sub 6/ and BCl/sub 3/ gas.

  9. Oxygen transport in ceria: a first-principles study

    NASA Astrophysics Data System (ADS)

    Sergei, Simak

    2012-02-01

    Ceria (CeO2) is an important material for environmentally benign applications, ranging from solid-oxide fuel cells (SOFC) to oxygen storage [1-2]. The key characteristic needed to be improved is the mobility of oxygen ions. Optimization of ionic transport in ceria has been the topic of many studies. In particular, it has been discovered how the ionic conductivity in ceria might be improved by choosing the proper kind and concentration of dopants [3]. In this presentation we will approach the problem from a different direction by adjusting structural parameters of ceria via the change of external conditions. A systematic first-principles study of the energy landscape and kinetics of reduced ceria as a function of external parameters reveals a physically transparent way to improve oxygen transport in ceria. [4pt] [1] N. Skorodumova, S. Simak, B. Lundqvist, I. Abrikosov, and B. Johansson, Physical Review Letters 89, 14 (2002). [0pt] [2] A. Trovarelli, in Catalysis by Ceria and related materials (Imperial College Press, London, 2002). [0pt] [3] D. A. Andersson, S. I. Simak, N. V. Skorodumova, I. A.Abrikosov, and B. Johansson, Proceedings of the National Academy of Sciences of the United States of America 103, 3518 (2006).

  10. 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.

  11. 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.

  12. Pair correlations in crystalline solid solutions

    SciTech Connect

    Ice, G.E.; Sparks, C.J.; Shaffer, L.; Zschack, P.

    1994-06-01

    Recent measurements of pair correlations in metallic solid solutions challenge simple models of atomic size in alloy structure. These measurements take advantage of intense and tunable synchrotron X radiation to control the x-ray scattering contrast between atoms in a solid solution. For binary alloys with elements nearby in the periodic table it is possible to tune the x-ray energy near the K edge so that the scattering contrast varies from near zero to {plus_minus}5 electron units. Even larger contrast variation is possible near L edges or with complementary x-ray and neutron diffraction data sets. With adjusted scattering contrast it is possible to measure short-range-order (SRO), even in alloys with elements nearby in the periodic table. It is also possible to detect chemically-specific static displacements of {plus_minus}0.001 {angstrom} or less and with fewer assumptions than with previous experimental methods. We compare the measured chemically-specific static displacements in Fe{sub 22.5}Ni{sub 77.5} and Cr{sub 47}Fe{sub 53} with previous models and with the results of other experiments.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. Theoretical Study of Sulphur Interaction with Ceria

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    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 (CeO2) 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, H2S 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 CeO2, 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.

  20. Concepts for future solid state lighting solutions

    NASA Astrophysics Data System (ADS)

    von Malm, N.; Wirth, R.; Illek, S.; Steegmüller, U.

    2010-08-01

    In this contribution the relevant technological aspects of LED-based lamps for solid state lighting are discussed. In addition to general energy efficiency considerations improvements in LED chip technology and white light generation are presented.

  1. Magnetic behavior of solid Ar-O2 solutions

    DOE PAGESBeta

    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 amore » 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.« less

  2. Electrospinning of Ceria and Nickel Oxide Nanofibers

    NASA Astrophysics Data System (ADS)

    Yerasi, Jyothi Swaroop Reddy

    Electrospinning uses an electrical charge to draw very fine fibers from a liquid. It has very high potential for industrial processing. Electrospinning is cost effective, repeatable and it can produce long, continuous nanofibers. Polymers such as polyalcohol, polyamides, and PLLA can be easily electrospun. The increase in demand for clean energy combined with the research work in progress and the potential advantages of electrospun electrodes over conventionally fabricated SOFCs makes electrospinning a strong candidate. In this thesis, ceramic nanofibers (ceria and nickel oxide) that can potentially be used in SOFCs are fabricated. A three-phase approach is implemented in the fabrication of ceria and nickel oxide nanofibers. The first phase involves the preparation of the composite ceramic-polymer solution to be electrospun. The second phase gives the processing conditions such as voltage applied, feed rate, and gauge of syringe tip used for successfully electrospinning composite ceramic-polymer fibers. The final stage demonstrates the temperature cycles used to burn out the polymer and calcine the ceramic particles in the ceramic-polymer nanofibers leaving behind ceria and nickel oxide nanofibers. Techniques such as scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray Diffraction (XRD) were used to measure the average diameter of the fibers formed and to understand the chemical composition and crystallanity of the nanofibers after calcination. This thesis also discusses the advantages and possibility of fabricating side-by-side nanofibers and oriented nanofiber mats.

  3. 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.

  4. Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors.

    PubMed

    Khalil, Kamal M S

    2007-03-01

    Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite. PMID:17182052

  5. Solid solutions based on bismuth and antimony tellurides andbismuth selenides

    SciTech Connect

    Abrikosov, N.K.; Stasova, M.M.

    1986-05-01

    The phase diagrams of the systems Bi-Te, Bi-Se, and Sb-Te serve as a basis for constructing multiphase diagrams of ternary semiconductor systems. This paper studies layered structures with large unit-cell parameters in the regions of the solid solutions to explain the ordering processes in the solid solutions of semiconductor and intermetallic systems. The laws governing the formation and structral features of bismuth and antimony chalcogenides are studied to obtain thermoelectric materials and identification of minerals.

  6. 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.

  7. 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. PMID:25189707

  8. 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.

  9. Thermal conductivity of halide solid solutions: measurement and prediction.

    PubMed

    Gheribi, Aïmen E; Poncsák, Sándor; St-Pierre, Rémi; Kiss, László I; Chartrand, Patrice

    2014-09-14

    The composition dependence of the lattice thermal conductivity in NaCl-KCl solid solutions has been measured as a function of composition and temperature. Samples with systematically varied compositions were prepared and the laser flash technique was used to determine the thermal diffusivity from 373 K to 823 K. A theoretical model, based on the Debye approximation of phonon density of state (which contains no adjustable parameters) was used to predict the thermal conductivity of both stoichiometric compounds and fully disordered solid solutions. The predictions obtained with the model agree very well with our measurement. A general method for predicting the thermal conductivity of different halide systems is discussed. PMID:25217938

  10. Synthesis and Characterization of Pure and Doped Ceria Films by Sol-gel and Sputtering

    SciTech Connect

    Koch, Kurt T.; Saraf, Laxmikant V.

    2004-12-01

    Synthesis and Characterization of Pure and Doped Ceria Films by Sol-gel and Sputtering. KURT T. KOCH (University of Missouri, Rolla, MO, 65409) LAXMIKANT SARAF (Environmental and Molecular Science Laboratory (Part of Pacific Northwest National Laboratory), Richland, Washington 99352). Pure and doped Ceria are known for their ability to gain or lose Oxygen, which is of interest to the Solid Oxide Fuel Cell (SOFC) and catalyst community. Current efforts are focused in SOFCs to reduce the operating temperature of the cell while maintaining ionic conduction. Ceria is known for its high ionic conductivity in the intermediate temperature region. (600-800 C) We have prepared pure and doped Ceria films by Sol-gel and magnetron sputtering methods. These films were characterized by X-ray diffraction (XRD), nuclear reaction analysis (NRA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Oxygen conduction measurements. We have observed greater volume diffusion in nanocrystalline Ceria compared to bulk polycrystalline films as a result of low density. Near surface diffusion properties with increasing temperature indicate a decrease in the volume diffusion as a result of grain growth. However, a linear increase in O2 content at {approx}600nm depth was observed and can be correlated to the redistribution of O2 in the samples. Surface roughness of <111> and <200> oriented Ceria films on Al2O3 and YSZ was observed to be 0.13nm and 0.397nm, respectively. In the case of Ceria grown on YSZ, structural properties from XRD results showed a highly oriented structure with cube on cube growth. XRD results from Ceria grown on Al2O3 showed an oriented state near the surface. structure whose degree of orientation appeared to be partially dependent on substrate temperature. Preliminary XPS results indicate reduction in Ceria from the Ce4+ to Ce3+ state near the surface.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Solid-liquid phase boundaries of lens protein solutions.

    PubMed Central

    Berland, C R; Thurston, G M; Kondo, M; Broide, M L; Pande, J; Ogun, O; Benedek, G B

    1992-01-01

    We report measurement of the solid-liquid phase boundary, or liquidus line, for aqueous solutions of three pure calf gamma-crystallin proteins: gamma II, gamma IIIa, and gamma IIIb. We also studied the liquidus line for solutions of native gamma IV-crystallin calf lens protein, which consists of 85% gamma IVa/15% gamma IVb. In all four proteins the liquidus phase boundaries lie higher in temperature than the previously determined liquid-liquid coexistence curves. Thus, over the range of concentration and temperature for which liquid-liquid phase separation occurs, the coexistence of a protein crystal phase with a protein liquid solution phase is thermodynamically stable relative to the metastable separated liquid phases. The location of the liquidus lines clearly divides these four crystallin proteins into two groups: those in which liquidus lines flatten at temperatures greater than 70 degrees C: gamma IIIa and gamma IV, and those in which liquidus lines flatten at temperatures less than 50 degrees C: gamma II and gamma IIIb. We have analyzed the form of the liquidus lines by using specific choices for the structures of the Gibbs free energy in solution and solid phases. By applying the thermodynamic conditions for equilibrium between the two phases to the resulting chemical potentials, we can estimate the temperature-dependent free energy change upon binding of protein and water into the solid phase. PMID:1741375

  16. 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.

  17. Solid Solution Model for Interstellar Dust Grains and Their Organics

    NASA Astrophysics Data System (ADS)

    Freund, Minoru M.; Freund, Friedemann T.

    2006-03-01

    We present a dust grain model based on the fundamental principle of solid solutions. The model is applicable to the mineral (silicate) component of the dust in the interstellar medium (ISM). We show that nanometer-sized mineral grains, which condense in the gas-rich outflow of late-stage stars or expanding gas shells of supernova explosions, do not consist of just high melting point oxides or silicates. Instead they form solid solutions with gas-phase components H2O, CO, and CO2 that are omnipresent in environments where the grains condense. Through a series of thermodynamically well-understood solid-state processes, these solid solutions become ``parents'' of organic matter that precipitates inside the grains. Thus, the mineral dust grains and their organics become part of the same thermodynamically defined solid phase and, hence, physically inseparable. This model can account for many astronomical observations, which no prior model can adequately address, specifically: (1) Organics in the diffuse ISM are identified by a 3.4 μm IR band, characteristic of aliphatic hydrocarbons composed of CH2 and of CH3 groups. (2) The methylene-to-methyl ratio is nearly constant, implying a CH2:CH3 ratio of ~5:2. (3) The intensity ratio between the 9.7 and the 3.4 μm band is nearly constant, implying a silicate-to-organics ratio of ~10:1. (4) In dense clouds the complex 3.4 μm band is replaced by a weak, featureless 3.47 μm band. (5) Whereas silicate grains identified by their 9.7 μm band tend to align in magnetic fields, grains with a strong 3.4 μm organic signature do not tend to align.

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

    DOE PAGESBeta

    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 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. 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. PMID:25986594

  20. Synthesis and Characterization of Pure and Doped Ceria Films by Sol-Gel and Sputtering

    SciTech Connect

    Koch, K.T.; Saraf, L.

    2004-01-01

    Pure and doped Ceria are known for their ability to gain or lose Oxygen, which is of interest to the Solid Oxide Fuel Cell (SOFC) and catalyst community. Current efforts are focused in SOFCs to reduce the operating temperature of the cell while maintaining ionic conduction. Ceria is known for its high ionic conductivity in the intermediate temperature region. (600-800° C) We have prepared pure and doped Ceria films by Sol-gel and magnetron sputtering methods. Enhanced grain-boundary contribution in the conductivity can be studied in the Sol-gel process due to excellent control over the synthesis conditions, which enabled us to control the average grain size. Sputtered films were grown and investigated as a prelude to possible multi-layered CeO2 structures in the near future. These films were characterized by X-ray diffraction (XRD), nuclear reaction analysis (NRA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Oxygen conduction measurements. We have observed greater volume diffusion in nanocrystalline Ceria compared to bulk polycrystalline films as a result of low density. Near surface diffusion properties with increasing temperature indicate a decrease in the volume diffusion as a result of grain growth. However, a linear increase in O2 content at ~600nm depth was observed and can be correlated to the redistribution of O2 in the samples. Surface roughness of <111> and <200> oriented Ceria films on Al2O3 and YSZ was observed to be 0.13nm and 0.397nm, respectively. In the case of Ceria grown on YSZ, structural properties from XRD results showed a highly oriented structure with cube on cube growth. XRD results from Ceria grown on Al2O3 showed an oriented structure whose degree of orientation appeared to be partially dependent on substrate temperature. Preliminary XPS results indicate reduction in Ceria from the Ce4+ to Ce3+ state near the surface.

  1. 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.

  2. 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.

  3. 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.

  4. 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. PMID:17107929

  5. 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.

  6. Synthesis and characterization of ceria nanomaterials

    NASA Astrophysics Data System (ADS)

    Cheong Ng, Nitzia

    Cerium dioxide or ceria, CeO2, has been widely used in industry as catalyst for automotive exhaust controls, chemical mechanical polishing (CMP) slurries, and high temperature fuel cells because of its unique metal oxide properties. This well-known rare metal oxide has high thermal stability, electrical conductivity and chemical diffusivity. Proper synthesis method requires knowledge of reaction temperature, concentration, and time effects on the synthesis. In this work, ceria nanomaterials were prepared via the hydrothermal method using a Teflon autoclave. Cerium nitrate solution was used as the source and three different precursors: NaOH, H2O 2, and NH4OH were used as the oxidizing agents. CeO 2 nanoplates, nanocubes and nanorods were produced and studied using transmission electron microscopy (TEM), BET specific surface area, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Through characterization, CeO2 nanomaterials showed the presence of mixed valence states (Ce3+ and Ce4+) through XPS spectra. Deconvolution was performed to investigate the ratio of Ce 3+/Ce4+ concentration in the synthesized CeO2 nanostructures. Nanocubes showed a higher Ce3+ concentration. CeO2 nanomaterials were found to be mesoporous. Nanoplates synthesized with H2O2, and NH4OH were found with surface areas of 95.11 m2/g and 62.07 m2/g, respectively. Nanorods and nanocubes showed surface areas of 16.77 m2/g and 16.55 m2/g, respectively. The prepared ceria nanoplates, nanocubes and nanorods had crystallite size in the range of 5--25 nm and pore size range of 7--15 nm. XRD spectra confirmed that the peaks were indexed to the cubic phase of CeO2 with fluorite structure and with an average lattice parameter, 5.407 A. Higher Ce3+ concentration and exposed surface of crystalline planes suggest that nanorods are better catalyst for CO oxidation and oxygen storage capacity (OSC).

  7. 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.

  8. Vibrational spectroscopic study of hydroxylpyromorphite-hydroxylmimetite solid solutions

    NASA Astrophysics Data System (ADS)

    Kwaśniak-Kominek, Monika; Matusik, Jakub; Bajda, Tomasz; Manecki, Maciej

    2013-04-01

    Hydroxylpyromorphite Pb5(PO4)3OH and hydroxylmimetite Pb5(AsO4)3OH minerals belong to the apatite supergroup. Their structure allows isomorphous substitutions in both cationic and anionic positions. They are isostructural with pyromorphite Pb5(PO4)3Cl and mimetite Pb5(AsO4)3OH which are the end products of in situ phosphate induced remediation of soils polluted with heavy metals e.g. lead. The research objective was to synthesize and characterize the members of above mentioned solid solution. The minerals were synthesized at room temperature and analyzed by X-Ray diffraction and Infrared spectroscopy (FTIR-DRIFT). The product syntheses was crystalline phase without any impurities within the detection limit of XRD. Shifts of certain diffraction peaks were observed in solid solution series due to replacement PO4 after AsO4. The bands v3 and v4 attributed to vibrations in the PO4 and AsO4 tetrahedra appear at 1050-790 and 580-534 cm-1. Due to difference in atomic mass of P and As as well as bonding strength of P-O and As-O the skeletal bands shift to lower wavenumbers with the increase of AsO4 substitution. The correlation between the position of vibrational modes and the chemical composition is observed. The OH stretching mode in the FTIR spectra appears in the range of 3765-3552 cm-1 as a sharp band for the end members of the solid solution. For the intermediate minerals the OH band becomes complex. The analysis of deconvoluted OH bands indicated several vibrational modes which suggested a significant change of OH group local environment induced by substitutions. The study was supported by the AGH University of Science and Technology (Krakow, Poland) as the research project No. 307 473 638.

  9. 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)

  10. 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).

  11. 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.

  12. 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. PMID:25317965

  13. 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

  14. Synthesis and characterization of cadmium-calcium hydroxyapatite solid solutions

    NASA Astrophysics Data System (ADS)

    Zhao, Xin; Zhu, Yi-nian; Dai, Liu-qin

    2014-06-01

    A series of cadmium-calcium hydroxyapatite solid solutions was prepared by an aqueous precipitation method. By various means, the characterizations confirmed the formation of continuous solid solutions over all ranges of Cd/(Cd+Ca) atomic ratio. In the results, both lattice parameters a and c display slight deviations from Vegard's rule when the Cd/(Cd+Ca) atomic ratio is greater than 0.6. The particles change from smaller acicular to larger hexagonal columnar crystals as the Cd/(Cd+Ca) atomic ratio increases from 0-0.60 to 0.60-1.00. The area of the phosphate peak for symmetric P-O stretching decreases with the increase in Cd/(Cd+Ca) atomic ratio, and the peak disappears when the Cd/(Cd+Ca) atomic ratio is greater than 0.6; the two phosphate peaks of P-O stretching gradually merge together for the Cd/(Cd+Ca) atomic ratio near 0.60. These variations can be explained by a slight tendency of larger Cd ions to occupy M(2) sites and smaller Ca ions to prefer M(1) sites in the structure.

  15. 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.

  16. 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.

  17. A novel composite cathode Er0.4Bi1.6O3-Pr0.5Ba0.5MnO3-δ for ceria-bismuth bilayer electrolyte high performance low temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Hou, Jie; Bi, Lei; Qian, Jing; Gong, Zheng; Zhu, Zhiwen; Liu, Wei

    2016-01-01

    A novel composite cathode consisting of A-site disordered Pr0.5Ba0.5MnO3-δ (PBM) and Er0.4Bi1.6O3 (ESB) is developed for solid oxide fuel cells (SOFCs) with ceria-bismuth bilayer electrolyte. Based on Sm0.075Nd0.075Ce0.85O2-δ|ESB (SNDC|ESB) bilayer structured film, the single cell NiO-SNDC|SNDC|ESB|ESB-PBM achieves an encouraging performance with the maximum power density (MPD) of 994 mW cm-2 and an interfacial polarization resistance (Rp) of 0.027 Ω cm2 at 650 °C. Although a possible reaction between ESB and PBM has been identified in the cathode, the ascendant electrochemical performance including the very high fuel cell performance and Rp obtained here can demonstrate that the novel cobalt-free composite cathode ESB-PBM is a preferable alternative for ceria-bismuth bilayer electrolyte high performance low temperature SOFCs (HPLT-SOFCs) and the interfacial reaction in the cathode seems not to be detrimental to the electrochemical performance.

  18. 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.

  19. 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.

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

    SciTech Connect

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

    1990-02-01

    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)SO{sub 4} and (Sr, Ca)CO{sub 3orth.} 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)CO{sub 3orth.} 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, recrystallization experiments in the highly soluble KCl-KBr-H{sub 2}O system demonstrate equilibrium. The phase diagram reveals an alyotropic maximum located at {chi}{sub KBr} = 0.676 and at a total solubility product, {Sigma}II = (K{sup +})((Cl{sup {minus}}) + (Br{sup {minus}})) = 15.35.

  1. 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

  2. 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. PMID:18562111

  3. 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).

  4. carbonate solid solution at high pressures up to 55 GPa

    NASA Astrophysics Data System (ADS)

    Spivak, Anna; Solopova, Natalia; Cerantola, Valerio; Bykova, Elena; Zakharchenko, Egor; Dubrovinsky, Leonid; Litvin, Yuriy

    2014-09-01

    Magnesite, siderite and ferromagnesites Mg1- x Fe x CO3 ( x = 0.05, 0.09, 0.2, 0.4) were characterized using in situ Raman spectroscopy at high pressures up to 55 GPa. For the Mg-Fe-carbonates, the Raman peak positions of six modes (T, L, ν4, ν1, ν3 and 2ν2) in the dependence of iron content in the carbonates at ambient conditions are presented. High-pressure Raman spectroscopy shows that siderite undergoes a spin transition at ~40 GPa. The examination of the solid solutions with compositions Mg0.6Fe0.4CO3, Mg0.8Fe0.2CO3, Mg0.91Fe0.09CO3 and Mg0.95Fe0.05CO3 indicates that with increase in the amount of the Fe spin transition pressure increases up to ~45 GPa.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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

  13. Optical properties of Sm-doped ceria nanostructured films grown by electrodeposition at low temperature

    NASA Astrophysics Data System (ADS)

    Ursaki, V. V.; Lair, V.; Żivković, L.; Cassir, M.; Ringuedé, A.; Lupan, O.

    2012-09-01

    Nanostructured undoped and samarium doped ceria thin nanocolumnar films are electrodeposited onto (FTO) glass substrates at low-temperature (30 °C) with a subsequent thermal annealing at 600 °C for 1 h. Films are obtained from mixed Sm3+/Ce3+ aqueous nitrate solutions, applying a -0.8 V/(SCE) potential for 1 h. Cubic fluorite type ceria nanostructured films of high crystal quality are synthesized as confirmed by X-ray diffraction and Raman spectroscopy. SEM analysis demonstrates that doping with Sm improves the quality of the film with respect to crack formation. The incorporation and activation of the Sm3+ ions in the ceria host as well as the Stark splitting of the manifolds responsible for emission in the red-orange spectral range are investigated by means of photoluminescence spectroscopy.

  14. 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.

  15. Solid solution cermet: (Ti,Nb)(CN)-Ni cermet.

    PubMed

    Kwon, Hanjung; Jung, Sun-A

    2014-11-01

    Solid solution powders without W, (Ti,Nb)(CN) powders with a B1 structure (NaCl like), were synthesized by high energy milling and carbothermal reduction in nitrogen. The range of molar ratios of Ti/Nb for forming complete (Ti,Nb)(CN) phase was broader than that of Ti/W for the (Ti,W)(CN) phase because carbide or carbonitride of Nb had a B1 crystal structure identical to Ti(CN) while WC had a hexagonal crystal structure. The results revealed that the hardness of (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,W)(CN)-Ni cermets. The lower density of the (Ti,Nb)(CN) powder contributed to the higher hardness compared to (Ti,W)(CN) because the volumetric ratio of (Ti,Nb)(CN) in the (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,Nb)(CN) in the (Ti,W)(CN)-Ni cermets at the same weight ratio of Ni. Additionally, it was assumed that intrinsic the properties of (Ti,Nb)(CN) could also be the cause for the high hardness of the (Ti,Nb)(CN)-Ni cermets. PMID:25958611

  16. 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.

  17. 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

  18. 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.

  19. Synthesis and characterisation of chromium lutetium gallium garnet solid solution

    SciTech Connect

    Galindo, R.; Badenes, J.A. . E-mail: jbadenes@qio.uji.es; Llusar, M.; Tena, M.A.; Monros, G.

    2007-03-22

    The chromium lutetium gallium garnet system has been studied. Samples with 2xCaOxCr{sub 2}O{sub 3}(3 - 2x)Lu{sub 2}O{sub 3}5Ga{sub 2}O{sub 3} (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3,) and xCr{sub 2}O{sub 3}(3 - x)Lu{sub 2}O{sub 3}5Ga{sub 2}O{sub 3} (x = 0, 0.05, 0.075 and 0.3) compositions have been prepared in Ca,Cr:LGG and Cr:LGG systems, respectively. Samples were prepared by ceramic method, fired at 1250 deg. C/6 h and characterised by XRD, lattice parameters, UV-vis-NIR spectroscopy, CIE L * a * b * measurements and SEM/EDX. Results indicate that Ca,Cr:LGG and Cr:LGG solid solutions are obtained. In Cr:LGG system only Cr(III) is stabilised in octahedral positions substituting for Lu(III) and Ga(III). Both Cr(III) and Cr(IV) are present in Ca,Cr:LGG. The calcium is a charge compensator to stabilise Cr(IV) and this is the predominant oxidation state up to x = 0.075 composition. From this composition, Cr(III) becomes more stabilised in garnet lattice. Cr(IV) occupies generally tetrahedral and dodecahedral sites substituting for Ga(III) and Lu(III), while Cr(III) is in octahedral site substituting for Ga(III)

  20. 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.

  1. 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

  2. General solution technique for transient thermoelasticity of transversely isotropic solids in Cartesian coordinates

    NASA Astrophysics Data System (ADS)

    Noda, N.; Ashida, F.; Okumura, I. A.

    1992-07-01

    In the present paper we propose a new general solution technique for transient thermoelastic problems of transversely isotropic solids in Cartesian coordinates. The solution technique consists of five fundamental solutions. By considering the relations among the material constants of transverse isotropy, the solution technique is classified into five groups. One among those corresponds to Goodier's thermoelastic potential function as well as the generalized Boussinesq solutions and the Michell function. For an application of the solution technique, an inverse problem of transient thermoelasticity in a transversely isotropic semi-infinite solid is analyzed.

  3. 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.

  4. Solid-liquid interfacial energy of neopentylglycol solid solution in equilibrium with neopentylglycol-(D) camphor eutectic liquid

    NASA Astrophysics Data System (ADS)

    Bayram, Ü.; Aksöz, S.; Maraşlı, N.

    2012-01-01

    The grain boundary groove shapes for equilibrated solid neopentylglycol (NPG) solution (NPG-3 mol% D-camphor) in equilibrium with the NPG-DC eutectic liquid (NPG-36.1 mol% D-camphor) have been directly observed using a horizontal linear temperature gradient apparatus. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient ( Г), solid-liquid interfacial energy ( σSL) of NPG solid solution have been determined to be (7.5±0.7)×10 -8 K m and (8.1±1.2)×10 -3 J m -2, respectively. The Gibbs-Thomson coefficient versus TmΩ1/3, where Ω is the volume per atom was also plotted by linear regression for some organic transparent materials and the average value of coefficient ( τ) for nonmetallic materials was obtained to be 0.32 from graph of the Gibbs-Thomson coefficient versus TmΩ1/3. The grain boundary energy of solid NPG solution phase has been determined to be (14.6±2.3)×10 -3 J m -2 from the observed grain boundary groove shapes. The ratio of thermal conductivity of equilibrated eutectic liquid to thermal conductivity of solid NPG solution was also measured to be 0.80.

  5. 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.

  6. 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.

  7. 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

  8. 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)

  9. Local structure of the halite-sylvine solid solution according to the computer simulation data

    SciTech Connect

    Urusov, V. S. Leonenko, E. V.

    2008-09-15

    The structural, elastic, and thermodynamic properties of halite NaCl and sylvine KCl and the miscibility properties of the NaCl-KCl solid solution found by computer simulation are in good agreement with the experimental data. Analysis of the relaxation of the solid solution structure suggests that both anion and cation sublattices are distorted; however, the anion sublattice is distorted much more strongly. Calculations of the local bond valence at all types of ions in the solid solution show opposite deviations from the balance at cations, whereas the general balance is retained. The values of the electrostatic potential in the ion positions reflect weakening of bonding in the solid solution with respect to its pure components. In addition, with an increase in the average interatomic distance in the first coordination sphere around cations, the modulus of the electrostatic potential at cations decreases.

  10. 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…

  11. Positron annihilation studies in binary solid solutions and mechanical mixtures of lanthanide dipivaloylmethanate complexes

    NASA Astrophysics Data System (ADS)

    Fulgêncio, F.; Oliveira, F. C.; Windmöller, D.; Araujo, M. H.; Marques-Netto, A.; Machado, J. C.; Magalhães, W. F.

    2015-11-01

    Measurements using positron annihilation lifetime (PALS) and Doppler broadening annihilation radiation lineshape (DBARLS) spectroscopies were performed in several lanthanide dipivaloylmethanate complexes, Ln(dpm)3 where Ln = Sm3+, Gd3+, Tb3+, Ho3+, Er3+, Yb3+ and dpm = 2,2,6,6-tetramethyl-3,5-pentanedionate, and also on their binary solid solutions and mechanical mixtures, biphasic systems, of the general formula Ln1-xEux(dpm)3. Expressive positronium formation was observed in all Ln(dpm)3 complexes, except in Eu(dpm)3 complex. The results indicate formation of solid solutions in the Sm3+, Gd3+and Tb3+ systems, where total inhibition of positronium formation was observed. A Stern-Volmer type equation, I30/I3 = 1 + kx, was used to fit the data, enabling the calculation of the inhibition constants, k. A mechanical mixture behavior, with linear variation of I3 between the I3 values of the pure complexes, was observed in systems containing Ho3+, Er3+ and Yb3+ complexes, where no effective solid solution formation occurred due to differences between the crystalline structures of these complexes and Eu(dpm)3. No positronium quenching reactions were observed in the solid solutions. DBARLS results confirmed those of PALS, evidencing that the positron annihilation spectroscopies are useful techniques to characterize the formation of solid solutions. PALS measurements at 80 K were performed in the Sm1-xEux(dpm)3 and Gd1-xEux(dpm)3 solid solutions. The results indicate that, despite a contraction in the crystalline structures, the solid solution structure remains intact at low temperatures. The temperature dependence of the inhibition constant do not seem to be understood from the positronium formation spur model and might be related to intra and intermolecular energy and charge transfer processes in the solid solutions, which is currently being studied.

  12. Magnetic properties of Sm1-xYxSe solid solutions

    NASA Astrophysics Data System (ADS)

    Beeken, R. B.; Bissell, P. R.

    1991-05-01

    Sm1-xYxSe solid solutions prepared as sintered pellets exhibit a miscibility gap in the composition range from x = 0.50 to x = 0.80. Lattice parameter and magnetic susceptibility determinations on alloys within the remaining composition regions indicate that the samarium cations remain essentially divalent throughout this series of solid solutions. An enhancement of the SmSe Van Vleck paramagnetism with increasing yttrium substitution is attributed to the conduction electrons introduced by chemical alloying.

  13. 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.

  14. 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. PMID:27191014

  15. Subdiffusion kinetics of nanoprecipitate growth and destruction in solid solutions

    NASA Astrophysics Data System (ADS)

    Sibatov, R. T.; Svetukhin, V. V.

    2015-06-01

    Based on fractional differential generalizations of the Ham and Aaron-Kotler precipitation models, we study the kinetics of subdiffusion-limited growth and dissolution of new-phase precipitates. We obtain the time dependence of the number of impurities and dimensions of new-phase precipitates. The solutions agree with the Monte Carlo simulation results.

  16. Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

    NASA Astrophysics Data System (ADS)

    Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

    2015-10-01

    We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

  17. 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.

  18. 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. PMID:26368067

  19. 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.

  20. 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.

  1. 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.

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

    PubMed

    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 Pt(2+) 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 Pt(2+) and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts. PMID:26908356

  3. 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

  4. Crystal-Phase Control by Solution-Solid-Solid Growth of II-VI Quantum Wires.

    PubMed

    Wang, Fudong; Buhro, William E

    2016-02-10

    A simple and potentially general means of eliminating the planar defects and phase alternations that typically accompany the growth of semiconductor nanowires by catalyzed methods is reported. Nearly phase-pure, defect-free wurtzite II-VI semiconductor quantum wires are grown from solid rather than liquid catalyst nanoparticles. The solid-catalyst nanoparticles are morphologically stable during growth, which minimizes the spontaneous fluctuations in nucleation barriers between zinc blende and wurtzite phases that are responsible for the defect formation and phase alternations. Growth of single-phase (in our cases the wurtzite phase) nanowires is thus favored. PMID:26731426

  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. 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.

  7. Existence of Solutions for a Mathematical Model Related to Solid-Solid Phase Transitions in Shape Memory Alloys

    NASA Astrophysics Data System (ADS)

    Bonetti, Elena; Colli, Pierluigi; Fabrizio, Mauro; Gilardi, Gianni

    2016-01-01

    We consider a strongly nonlinear PDE system describing solid-solid phase transitions in shape memory alloys. The system accounts for the evolution of an order parameter χ (related to different symmetries of the crystal lattice in the phase configurations), of the stress (and the displacement u), and of the absolute temperature ϑ. The resulting equations present several technical difficulties to be tackled; in particular, we emphasize the presence of nonlinear coupling terms, higher order dissipative contributions, possibly multivalued operators. As for the evolution of temperature, a highly nonlinear parabolic equation has to be solved for a right hand side that is controlled only in L 1. We prove the existence of a solution for a regularized version by use of a time discretization technique. Then, we perform suitable a priori estimates which allow us pass to the limit and find a weak global-in-time solution to the system.

  8. Mechanical properties of mesoporous ceria nanoarchitectures.

    PubMed

    Sayle, Thi X T; Inkson, Beverley J; Möbus, Günter; Parker, Stephen C; Seal, Sudipta; Sayle, Dean C

    2014-12-01

    Architectural constructs are engineered to impart desirable mechanical properties facilitating bridges spanning a thousand meters and buildings nearly 1 km in height. However, do the same 'engineering-rules' translate to the nanoscale, where the architectural features are less than 0.0001 mm in size? Here, we calculate the mechanical properties of a porous ceramic functional material, ceria, as a function of its nanoarchitecture using molecular dynamics simulation and predict its yield strength to be almost two orders of magnitude higher than the parent bulk material. In particular, we generate models of nanoporous ceria with either a hexagonal or cubic array of one-dimensional pores and simulate their responses to mechanical load. We find that the mechanical properties are critically dependent upon the orientation between the crystal structure (symmetry, direction) and the pore structure (symmetry, direction). PMID:25322448

  9. 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.

  10. 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. PMID:26691211

  11. On the Effect of Atoms in Solid Solution on Grain Growth Kinetics

    NASA Astrophysics Data System (ADS)

    Hersent, Emmanuel; Marthinsen, Knut; Nes, Erik

    2014-10-01

    The discrepancy between the classical grain growth law in high purity metals (grain size ) and experimental measurements has long been a subject of debate. It is generally believed that a time growth exponent less than 1/2 is due to small amounts of impurity atoms in solid solution even in high purity metals. The present authors have recently developed a new approach to solute drag based on solute pinning of grain boundaries, which turns out to be mathematically simpler than the classic theory for solute drag. This new approach has been combined with a simple parametric law for the growth of the mean grain size to simulate the growth kinetics in dilute solid solution metals. Experimental grain growth curves in the cases of aluminum, iron, and lead containing small amounts of impurities have been well accounted for.

  12. Iron salts in solid state and in frozen solutions as dosimeters for low irradiation temperatures.

    PubMed

    Martínez, T; Lartigue, J; Ramos-Bernal, S; Ramos, A; Mosqueira, G F; Negrón-Mendoza, A

    2005-01-01

    The aim of this work is to study the irradiation of iron salts in solid state (heptahydrated ferrous sulfate) and in frozen acid solutions. The study is focused on finding their possible use as dosimeters for low temperature irradiations and high doses. The analysis of the samples was made by UV-visible and Mössbauer spectroscopies. The output signal was linear from 0 to 10 MGy for the solid samples, and 0-600 Gy for the frozen solutions. The obtained data is reproducible and easy to handle. For these reasons, heptahydrate iron sulfate is a suitable dosimeter for low temperature and high irradiation doses, in solid state, and in frozen solution. PMID:15985374

  13. 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.

  14. Distribution of solute at solid-liquid interface during solidification of melt

    NASA Astrophysics Data System (ADS)

    Fukui, Keisuke; Maeda, Kouji

    1998-11-01

    A model for predicting a distribution coefficient (ki) of solute at the solid-liquid (S-L) interface, when the solid layer is growing, is proposed. The interfacial distribution coefficient is expressed as a function of two gradients of the liquid concentration and equilibrium concentration at the S-L interface. The model is applied to the solidification of a simple eutectic binary liquid of lauric acid and myristic acid in an enclosed rectangular box in which a vertical wall is cooled. The impurity-concentration profile in solid is predicted from the direct numerical computations.

  15. 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.

  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. Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

    NASA Astrophysics Data System (ADS)

    Jivani, A. R.; Jani, A. R.

    2011-12-01

    Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

  18. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    PubMed

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency. PMID:26344143

  19. 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.

  20. Analytical solution of the heat equation in a longitudinally pumped cubic solid-state laser

    SciTech Connect

    Sabaeian, Mohammad; Nadgaran, Hamid; Mousave, Laleh

    2008-05-01

    Knowledge about the temperature distribution inside solid-state laser crystals is essential for calculation of thermal phase shift, thermal lensing, thermally induced birefringence, and heat-induced crystal bending. Solutions for the temperature distribution for the case of steady-state heat loading have appeared in the literature only for simple cylindrical crystal shapes and are usually based on numerical techniques. For the first time, to our knowledge, a full analytical solution of the heat equation for an anisotropic cubic cross-section solid-state crystal is presented. The crystal is assumed to be longitudinally pumped by a Gaussian pump profile. The pump power attenuation along the crystal and the real cooling mechanisms, such as convection, are considered in detail. A comparison between our analytical solutions and its numerical counterparts shows excellent agreement when just a few terms are employed in the series solutions.

  1. Copper-ceria interaction: A combined photoemission and DFT study

    NASA Astrophysics Data System (ADS)

    Szabová, Lucie; Skála, Tomáš; Matolínová, Iva; Fabris, Stefano; Farnesi Camellone, Matteo; Matolín, Vladimír

    2013-02-01

    Stoichiometric and partially reduced ceria films were deposited on preoxidized Ru(0 0 0 1) crystal by Ce evaporation in oxygen atmosphere of different pressures at 700 K. Copper-ceria interaction was investigated by deposition of metalic copper on both types of substrate. The samples were characterized by low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) of core states and resonant photoelectron spectroscopy (RPES) of the valence bands. Copper adsorption on stoichiometric ceria caused reduction of CeO2, while on the oxygen-defficient ceria it partially reoxidized the substrate. This is in agreement with DFT+U calculations of copper adsorption on stoichiometric and defective ceria surfaces.

  2. Special quasirandom structures for gadolinia-doped ceria and related materials.

    PubMed

    Wang, H; Chroneos, A; Jiang, C; Schwingenschlögl, U

    2012-09-01

    Gadolinia doped ceria in its doped or strained form is considered to be an electrolyte for solid oxide fuel cell applications. The simulation of the defect processes in these materials is complicated by the random distribution of the constituent atoms. We propose the use of the special quasirandom structure (SQS) approach as a computationally efficient way to describe the random nature of the local cation environment and the distribution of the oxygen vacancies. We have generated two 96-atom SQS cells describing 9% and 12% gadolinia doped ceria. These SQS cells are transferable and can be used to model related materials such as yttria stabilized zirconia. To demonstrate the applicability of the method we use density functional theory to investigate the influence of the local environment around a Y dopant in Y-codoped gadolinia doped ceria. It is energetically favourable if Y is not close to Gd or an oxygen vacancy. Moreover, Y-O bonds are found to be weaker than Gd-O bonds so that the conductivity of O ions is improved. PMID:22828722

  3. Characterization of Sm-Doped Ceria Ceramics Synthesized by Two Different Methods

    NASA Astrophysics Data System (ADS)

    Arabaci, Aliye; Serin, Özgün

    2015-07-01

    Ceria-based materials have attracted much attention as electrolyte materials for low and intermediate temperature solid oxide fuel cells (SOFCs). In this study, we examined the effect of synthesis method on the microstructure and the ionic conductivity of ceria-based electrolytes. Sm0.2Ce0.8O1.9 (SDC) electrolytes for SOFCs were prepared using the Pechini and cellulose templating (CT) methods. Microstructures of the calcined and sintered samples were characterized by XRD and SEM techniques. The XRD results indicate that a single-phase fluorite structure formed at the relatively low calcination temperature of 500 °C. The relative densities of the sintered pellets were higher than 90%, which was proved by the SEM images. Calcined powders were characterized by FTIR technique. The electrical properties of the samarium-doped ceria electrolytes were analyzed by electrochemical impedance spectroscopy. The total ionic conductivities are 3.02 × 10-2 and 3.42 × 10-2 S/cm at 750 °C for the SDC electrolytes prepared by the Pechini method and the CT method, respectively.

  4. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    DOE PAGESBeta

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; et al

    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

  5. Numerical solution of a coupled pair of elliptic equations from solid state electronics

    NASA Technical Reports Server (NTRS)

    Phillips, T. N.

    1983-01-01

    Iterative methods are considered for the solution of a coupled pair of second order elliptic partial differential equations which arise in the field of solid state electronics. A finite difference scheme is used which retains the conservative form of the differential equations. Numerical solutions are obtained in two ways, by multigrid and dynamic alternating direction implicit methods. Numerical results are presented which show the multigrid method to be an efficient way of solving this problem.

  6. 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

  7. 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.

  8. 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…

  9. Thermal transport properties of halide solid solutions: Experiments vs equilibrium molecular dynamics.

    PubMed

    Gheribi, Aïmen E; Salanne, Mathieu; Chartrand, Patrice

    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. PMID:25833567

  10. Damage accumulation in ion-irradiated Ni-based concentrated solid-solution alloys

    DOE PAGESBeta

    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.

  11. 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…

  12. 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.

  13. Dynamic nuclear polarization methods in solids and solutions to explore membrane proteins and membrane systems.

    PubMed

    Cheng, Chi-Yuan; Han, Songi

    2013-01-01

    Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments. PMID:23331309

  14. Dynamic Nuclear Polarization Methods in Solids and Solutions to Explore Membrane Proteins and Membrane Systems

    NASA Astrophysics Data System (ADS)

    Cheng, Chi-Yuan; Han, Songi

    2013-04-01

    Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments.

  15. Electronic Properties of 1,2;8,9-Dibenzopentacene in Solutions, Solid Matrices, and Thin Films

    NASA Astrophysics Data System (ADS)

    Tovstopyat, A.; Zojer, E.; Leising, G.

    2016-03-01

    The optical properties of 1,2;8,9-dibenzopentacene molecules in different environments, namely solutions, solid solutions, and thin films, focusing on the shift of the electronic levels as a function of the dielectric properties of the surrounding media are investigated. In all cases, we find that the optical gap of 1,2;8,9-dibenzopentacene is somewhat larger than that of pentacene (by ~0.21 eV in solution) in spite of the larger extent of the π-electron system in the former molecule. This a priori unexpected finding is rationalized on the basis of quantum-mechanical simulations.

  16. On the solute coupling at the moving solid/liquid interface during equiaxed solidification

    NASA Astrophysics Data System (ADS)

    Yao, X.

    2006-08-01

    Integral mass conservation was widely accepted for the solute coupling to solve solute redistribution during equiaxed solidification so far. The present study revealed that the integral form was invalid for moving boundary problems as it could not represent the mass balance at the moving interface. Accordingly, differential mass conservation at the solid/liquid interface was used to solve solute diffusion for spherical geometry. The model was applied for hydrogen diffusion in solidification to validate that the hydrogen enrichment was significant and depended on the growth rate.

  17. 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.

  18. Synthesis and characterization of Sr(Al,Cr) 12O 19 solid solution

    NASA Astrophysics Data System (ADS)

    Sandiumenge, Felip; Galí, Salvador

    1989-09-01

    Magnetoplumbite-type crystalline powders with SrAl 12- xCr xO 19 composition were synthesized in the range 0 ≤ x ≤ 4.4 by two different solid state reactions in air. The limited substitution of Al by trivalent Cr is accompanied by the appearance of a sesquioxide Al 2- yCr yO 3 solid solution and a new cubic phase with composition 3Al 2O 3 · SrCrO 4. These results are compared with those obtained in the synthesis of Sr(Fe,Cr) 12O 19 and Sr(Al,Fe) 12O 19 solid solutions. Finally, the cation distribution of Al and Cr in the system Sr(Al,Cr) 12O 19(Al,Cr) 2O 3 was obtained from X-ray diffraction profile analysis. The cationic distribution suggests that the solid solution range depends more on the crystal chemistry of the substitution than on the starting compounds used in the synthesis.

  19. 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

  20. 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...

  1. Probing adsorption sites for CO on ceria.

    PubMed

    Mudiyanselage, Kumudu; Kim, Hyun You; Senanayake, Sanjaya D; Baber, Ashleigh E; Liu, Ping; Stacchiola, Dario

    2013-10-14

    Ceria based catalysts show remarkable activity for CO conversion reactions such as CO oxidation and the water-gas shift reaction. The identification of adsorption sites on the catalyst surfaces is essential to understand the reaction mechanisms of these reactions, but the complexity of heterogeneous powder catalysts and the propensity of ceria to easily change oxidation states in the presence of small concentrations of either oxidizing or reducing agents make the process difficult. In this study, the adsorption of CO on CuOx/Cu(111) and CeOx/Cu(111) systems has been studied using infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. IR peaks for the adsorbed CO on O/Cu(111) with only chemisorbed oxygen, well-ordered Cu2O/Cu(111) and disordered copper oxide [CuOx/Cu(111)] were observed at 2070-2072, 2097-2098 and 2101-2111 cm(-1), respectively. On CeOx/Cu(111) systems CO chemisorbs at 90 K only on Cu sites under ultra-high vacuum (UHV) conditions, whereas at elevated CO pressures and low temperatures adsorption of CO on Ce(3+) is observed, with a corresponding IR peak at 2162 cm(-1). These experimental results are further supported by DFT calculations, and help to unequivocally distinguish the presence of Ce(3+) cations on catalyst samples by using CO as a probe molecule. PMID:23942870

  2. Kr and Xe irradiations in lanthanum (La) doped ceria: Study at the high dose regime

    NASA Astrophysics Data System (ADS)

    Yun, Di; Oaks, Aaron J.; Chen, Wei-ying; Kirk, Marquis A.; Rest, Jeffrey; Insopov, Zinetula Z.; Yacout, Abdellatif M.; Stubbins, James F.

    2011-11-01

    In order to understand cavity and bubble formation and growth in oxide nuclear fuel materials, ion beam irradiation experiments were conducted with two common fission gas species: Kr and Xe. Ceria (CeO 2) was selected as a surrogate material for uranium dioxide (UO 2) due to its many similar properties to UO 2. Ion beam energies were chosen such that both cavities and gas bubbles structures were induced by ion irradiations. The ion irradiation experiments were carried out at 600 °C, at which temperature, cavity/gas bubble structures are believed to be immobile in this material. Lanthanum (La) was chosen as a dopant in CeO 2 to investigate the effect of impurities. The presence of La in the CeO 2 lattice also introduces a predictable initial concentration of oxygen vacancies, similar to the introduction of oxygen vacancies by the existence of Pu 3+ in MOX fuel [1]. The influence of two La concentrations, 5% and 25%, were examined. The study focused on the high dose regime where cavity/gas bubble structures were clearly identifiable with their sizes and number densities readily measurable. Cavity/gas bubble coarsening by coalescence was identified with TEM (Transmission Electron Microscopy) characterizations of as-irradiated La doped CeO 2 specimens. The results revealed that lanthanum trapping has significant influence on the cavity/bubble growth in the material lattice by comparing the cavity/gas bubble size distributions between 5% La doped ceria and 25% La doped ceria. Lattice and kinetic Monte Carlo calculations described in a previous work have provided insights to the interpretations of the experimental results [2]. Solid state Xe precipitates were observed in low energy Xe implantation in 5% La doped ceria to a very high fluence of 1 × 10 17 ions/cm 2 at 600 °C. The solid state Xe precipitate structures are represented by faceted morphology. Very similar observations of solid state/near solid state Xe bubbles were made by Nogita et al. in the outer region

  3. 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. PMID

  4. 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.

  5. Synthesis and properties of samaria-doped ceria electrolyte for IT-SOFCs by EDTA-citrate complexing method

    NASA Astrophysics Data System (ADS)

    Wu, Wen-Chang; Huang, Jui-Ting; Chiba, Atsushi

    An ultra-fine samaria-doped ceria (Ce 0.8Sm 0.2O 1.9, SDC) electrolyte prepared by a non-ion selective EDTA-citric complexing method is developed herein for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The rigid agglomerates due to organic compounds that exist in the SDC precursors during the EDTA-citrate complexing synthesis process inhibit crystalline growth and grain growth, leading to the generation of ultra-fine grain following the sintering procedure. Calcination is necessary above 500 °C for all precursors. The average grain size of the pellets after sintering at 1400 °C for 2 h is submicron in scale (from 200 nm to 600 nm) with various pH values, and the pellets are smaller than those obtained from other synthesis processes. Dense pellets with pH values of 10 (relative density of 99%) are obtained with precursor powder calcination at 900 °C for 3 h. Electrical conductivity is dependent on the calcination temperature and pH value of the solution, and the maximum electrical conductivity is 0.01 S cm -1 at 700 °C with a pH value of 10.

  6. 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.

  7. 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.

  8. Synthesis and Optical Properties of GaN/ZnO Solid Solution Nanocrystals

    SciTech Connect

    Han, W.; Liu, Z; Yu, H

    2010-01-01

    We devised a synthesis route to prepare narrow band gap GaN/ZnO solid solution nanocrystals via nitriding a homogeneous Ga-Zn-O nanoprecursor. The nanocrystals were characterized by several following methods: x-ray diffractometer, transmission electron microscopy, ultraviolet-visible diffuse reflection, and Raman spectroscopy. Here, we can control the composition of nanocrystals by the nitridation temperature. From 550 to 850 C, the corresponding crystalline size varies from 6.1 to 27 nm. It has been demonstrated that the sample prepared at 650 C had the narrowest band gap of 2.21 eV. Microstructural investigations show that the (101) surface is the predominantly exposed one for the GaN/ZnO solid solution nanocrystals. We also discuss the influence of chemical disorder based on the Raman spectra acquired.

  9. p-t-x diagram of Pb(TiZr)O/sub 3/ solid solutions

    SciTech Connect

    Polandov, I.N.; Alekhina, N.S.; Gulish, O.K.; Isaev, G.P.; Malyutin, B.I.

    1986-07-01

    This paper attempts to generalize work the authors performed at high pressures on the phase equilibria in the PbTiO/sub 3/-PbZrO/sub 3/ system for Ti contents up to 50 at.%, i.e., the most interesting compositions from the practical standpoint. It is established that the rhombohedral ferroelectric phase, localized near the Curie point, not only expands its region of temperature stability, but also shifts its region of temperature stability to higher pressures with rise of solid solution Ti content. The authors construct for the first time the complete p-t-x diagram of Pb(Ti, Zr)O/sub 3/ solid solutions with Ti contents up to 50 at.%.

  10. Criterion for the formation of solid solutions based on silicon carbide

    SciTech Connect

    Safaraliev, G.K.; Sukhanek, G.K.; Tairov, Yu.M.; Tsvetkov, V.F.

    1987-04-01

    Criteria for the formation of solid solutions based on silicon carbide were determined based on correlations obtained between the maximum solubility of impurities in SiC and their electronegativity and also between the semiempirical orbital radii r/sub sigma/ and r/sub ..pi../ of the elements. It was established experimentally that the solid solutions (SiC)/sub 1-x/(AlN)/sub x/ with a wide range of concentrations (0.04 less than or equal to x less than or equal to 0.95) form in the system SiC-AlN at temperatures T greater than or equal to 1800/sup 0/K. For 0.2 less than or equal to x less than or equal to 0.95 they crystallize in the polytypal modification 2H.

  11. Accelerated exploration of multi-principal element alloys with solid solution phases.

    PubMed

    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

  12. 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.

  13. High-temperature decomposition of solid solutions of beta-tantalum with copper in films

    NASA Astrophysics Data System (ADS)

    Tuleushev, Yu. Zh.; Volodin, V. N.; Zhakanbaev, E. A.

    2014-05-01

    Using high-temperature X-ray diffractometry and electron microprobe analysis decomposition of alloys of beta-tantalum with copper produced by codeposition of sputtered ultradisperse particles of tantalum and copper has been established. At a temperature of 900°C, the precipitation of copper from the solid solution into an individual phase starts, and its diffusion onto the film surface with the formation of globular particles and simultaneous transition of the matrix β-modification into α-tantalum. The suggested mechanism of decomposition of solid solutions includes the following stages: the precipitation of copper into an individual phase, its diffusion onto the surface because of lattice pressure and the concentration gradient inside and outside the tantalum matrix, the coalescence of nanosized formations into drops at the coating surface, and the subsequent evaporation of copper from them in a vacuum.

  14. Regression relations for estimating the mechanical properties of steels subjected to solid-solution hardening

    NASA Astrophysics Data System (ADS)

    Protopopov, E. A.; Val'ter, A. I.; Protopopov, A. A.; Malenko, P. I.

    2015-07-01

    An approach is proposed to obtain regression relations to estimate the mechanical properties of steels subjected to solid-solution hardening. The applicability of the developed approach is shown for hot-rolled sheet austenitic iron-nickel and nickel alloys after quenching, toughened low-alloy structural steels with a sorbite structure in the case of full hardenabilty, sheet corrosion-resistant ferritic steels after softening heat treatment, and corrosion-resistant austenitic steels after austenitization. The derived regression relations serve as the basis for correcting the chemical composition of a metal melt to ensure the required level of the mechanical properties of ready products by controlling the degree of solid-solution hardening.

  15. 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

  16. 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

  17. Designing room-temperature multiferroic materials in a single-phase solid-solution film

    NASA Astrophysics Data System (ADS)

    Mao, H. J.; Song, C.; Cui, B.; Peng, J. J.; Li, F.; Xiao, L. R.; Pan, F.

    2016-09-01

    The search for multiferroic materials with simultaneous ferroelectric and ferromagnetic properties in a single phase at room temperature continues to be fuelled from the perspective of developing multifunctional devices. Here we design a single-phase multiferroic La0.67Sr0.33MnO3-BaTiO3 film, which possesses epitaxial single-crystal and solid-solution structure, high magnetic Curie temperature (~640 K) as well as switchable ferroelectric polarization. Moreover, a notable strain-mediated magnetoelectric coupling at room temperature in the way of modulating the magnetism with an external applied voltage is also observed. The synthetic solid-solution multiferroic film may open an extraordinary avenue for exploring a series of room-temperature multiferroic materials.

  18. Hydrolysis of lanthanide dicarbides: Rates of reaction of cubic and tetragonal solid solutions with water

    SciTech Connect

    McColm, I.J. )

    1993-05-01

    Two series of solid solutions, Ho[sub 1[minus]x]La[sub x]C[sub 2] and Nd[sub 1[minus]x]LaC[sub 2], have been made and their X-ray unit cell parameters measured. The Ho[sub 1[minus]x]La[sub x]C[sub 2] series contains two tetragonal phases and a cubic solid solution series which has enabled the reaction rate constants for the water hydrolysis reaction of a cubic dicarbide phase to be determined for the first time. By comparing the linear rate constants and the activation energies across the two series the nature of bonding in general and the structure of the cubic phase are elucidated. A comparison with microhardness data is made and the change in M-C[sub 2] bonding as a function of composition is considered. 10 refs., 9 figs., 3 tabs.

  19. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    NASA Astrophysics Data System (ADS)

    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.

    2015-10-01

    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.

  20. 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

    2015-01-01

    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

  1. 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.

  2. 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. PMID:26695560

  3. 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)

  4. On the effect of concentrated solid solutions on properties of clusters in a model binary alloy

    NASA Astrophysics Data System (ADS)

    Lepinoux, J.; Sigli, C.

    2016-04-01

    In a series of papers aimed at better understanding precipitation in binary alloys, it was shown that Cluster Dynamics (CD) is a valuable tool to bridge the gap between microscopic and macroscopic scales, provided that cluster-free energies are carefully derived from Monte Carlo calculations. Indeed, in such conditions, CD predictions compare well with Atomistic Kinetic MC simulations. Nevertheless, in a recent work, the authors pointed out some limitations of this approach at high solute concentration. The present work aims at revisiting the notion of cluster-free energy in the context of concentrated solid solutions at thermal equilibrium.

  5. Numerical solution of a coupled pair of elliptic equations from solid state electronics

    NASA Technical Reports Server (NTRS)

    Phillips, T. N.

    1984-01-01

    Iterative methods are considered for the solution of a coupled pair of second order elliptic partial differential equations which arise in the field of solid state electronics. A finite difference scheme is used which retains the conservative form of the differential equations. Numerical solutions are obtained in two ways, by multigrid and dynamic alternating direction implicit methods. Numerical results are presented which show the multigrid method to be an efficient way of solving this problem. Previously announced in STAR as N83-30109

  6. 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.

  7. 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. PMID:25886029

  8. 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. PMID:27192540

  9. 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

  10. Nanocrystalline ceria powders through citrate-nitrate combustion.

    PubMed

    Purohit, R D; Saha, S; Tyagi, A K

    2006-01-01

    Nanocrystalline ceria powders have been synthesized by combustion technique using citric acid as a fuel and nitrate as an oxidizer. The auto-ignition of the gels containing cerium nitrate and citric acid resulted in ceria powders. A theory based on adiabatic flame temperature for different citric acid-to-cerium nitrate molar ratios has been proposed to explain the nature of combustion reaction and its correlation with the powder characteristics. Specific surface area and primary particle size of the ceria powder obtained through fuel-deficient precursor was found to be approximately = 127 m2/g and 2.5-10 nm, respectively. The combustion synthesized ceria powder when cold pressed and sintered in air at 1250 degrees C for 1 hour resulted in approximately = 96% of its theoretical density with sub-micron grains. PMID:16573097

  11. High-Performance Hydrogen Evolution from MoS2(1-x) P(x) Solid Solution.

    PubMed

    Ye, Ruquan; del Angel-Vicente, Paz; Liu, Yuanyue; Arellano-Jimenez, M Josefina; Peng, Zhiwei; Wang, Tuo; Li, Yilun; Yakobson, Boris I; Wei, Su-Huai; Yacaman, Miguel Jose; Tour, James M

    2016-02-17

    A MoS2(1-x) P(x) solid solution (x = 0 to 1) is formed by thermally annealing mixtures of MoS2 and red phosphorus. The effective and stable electrocatalyst for hydrogen evolution in acidic solution holds promise for replacing scarce and expensive platinum that is used in present catalyst systems. The high performance originates from the increased surface area and roughness of the solid solution. PMID:26644209

  12. Thermodynamic modelling of miscibility in (InAs) x (GaAs)1-x solid solutions

    NASA Astrophysics Data System (ADS)

    Adhikari, Jhumpa

    2013-05-01

    Current methods used to model the solution thermodynamics of III-V compound semiconductors involve the use of the valence force field as the molecular model and the regular solution model (with the temperature independent interaction parameter and underlying assumption of random mixing) as the engineering model. In this study, excess free energy models (with three or less adjustable parameters) are investigated to predict the solid-solid miscibility of (InAs) x (GaAs)1- x . The models investigated include the Porter/one-constant Margules (OCM) model, the two-constant Margules (TCM) model and the non-random two liquid (NRTL) model. These models are fit to excess free energy values derived from free energy change of mixing (variation with composition) data available from molecular simulations at different temperatures. The parameters in all the models have been found to be temperature dependent. The coexistence compositions are best predicted by the NRTL model, indicating the need to consider non-random mixing effects present in these solid solutions. The TCM model predicts better equilibrium composition data as compared to the OCM model.

  13. 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.

  14. 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 . PMID:27479937

  15. 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. PMID:27240774

  16. Existence of a solid solution from brucite to {beta}-Co(OH){sub 2}

    SciTech Connect

    Giovannelli, F.; Delorme, F.; Autret-Lambert, C.; Seron, A.; Jean-Prost, V.

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer A solid solution exist between Mg(OH){sub 2} and {beta}-Co(OH){sub 2}. Black-Right-Pointing-Pointer Synthesis has been performed through an easy and fast coprecipitation route. Black-Right-Pointing-Pointer No long range-ordering of the cations occurs. -- Abstract: This study shows that between brucite (Mg(OH){sub 2}) and {beta}-Co(OH){sub 2}, all the compositions are possible. The solid solution Mg{sub 1-x}Co{sub x}(OH){sub 2} has been synthesized by an easy and fast coprecipitation route and characterized by XRD and TEM. Single phase powders have been obtained. The particles exhibit platelets morphology with a size close to one hundred nanometers. XRD analysis shows an evolution of the cell parameters when x increases and demonstrates that no ordering of the cations occurs. However, extra reflections on TEM electron diffraction patterns seem to indicate that local ordering can exist. The compounds issued from this solid solution could be good candidates as precursors in order to obtain Mg-Co mixed oxide with all possible cationic ratios.

  17. 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.

  18. Crystal chemical properties of synthetic lazulite-scorzalite solid-solution series

    NASA Astrophysics Data System (ADS)

    Schmid-Beurmann, P.; Knitter, St.; Cemič, L.

    Members of the lazulite-scorzalite (MgAl2- (PO4)2(OH)2-FeAl2(PO4)2(OH)2) solid-solution series were synthesized in compositional steps of 12.5mol% at T=485°C and P=0.3GPa under hydrothermal conditions and controlled oxygen fugacities of the Ni/NiO-buffer. X-ray powder diffraction and 57Fe-Mössbauer studies show that under these conditions a complete solid-solution series is formed which is characterized by the substitution of Mg2+ and Fe2+ on the octahedral Me2+ site. The 57Fe-Mössbauer spectra which reveal the presence of both ferrous and ferric iron and the compositional data were interpreted in terms of a defect model with a distribution of the ferric ions over both the Me2+ and the Al3+ positions and vacancies on the Me2+ site. The 57Fe-Mössbauer parameters of the synthetic compounds correspond to those of natural lazulites except for the total absorption ratio of the ferric iron A(Fe3+)/(A(Fe3+)+A(Fe2+)), which is significantly higher in natural lazulites of the same composition. The total absorption ratio of the ferric iron increases from 4% in pure scorzalite to 15% in a Mg-rich solid-solution with xFe=12(1)%

  19. Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes

    SciTech Connect

    Brown, Christopher F.; Geiszler, Keith N.; Vickerman, Tanya S.

    2005-11-01

    129I is a contaminant of interest in the vadose zone and groundwater at numerous federal and privately-owned facilities. Several techniques have been utilized to extract iodine from solid matrices; however, all of them rely on two fundamental approaches: liquid extraction or chemical/heat facilitated volatilization. While these methods are typically chosen for their ease of implementation, they do not totally dissolve the solid. Because some of the iodine partitions onto the soil, extraction methods that do not result in total sample dissolution could underestimate the total iodine content of solid samples. We defined a method that produces complete solid dissolution and conducted laboratory tests to assess its efficacy to completely extract iodine from solid matrices. Testing consisted of potassium nitrate/potassium hydroxide fusion of the sample, followed by sample dissolution in a mixture of sulfuric acid and sodium bisulfite. Direct analysis of the dissolved sample was performed via inductively coupled plasma mass spectrometry (Perkin Elmer Elan DRC II) using a tertiary amine (Spectrasol CFA-C) carrier solution. The fusion extraction method resulted in complete sample dissolution of all solid matrices tested: sediment, glass samples containing low-levels of iodine, as well as tank waste material collected from the Hanford Site. Quantitative analysis of iodine (127I and 129I) showed better than ? 10% accuracy for certified reference standards, with the linear operating range extending more than three orders of magnitude (0.005 to 5 ug/L). Extraction and analysis of four replicates of standard reference material (San Joaquin Soil) from the National Institute of Standards and Technology, Gaithersburg, MD, resulted in an average recovery of 98% with a relative percent deviation of 6%. This simple and cost-effective technique can be applied to solid samples of varying matrices with little or no adaptation.

  20. 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.

  1. 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.

  2. Investigations on the predictability of the formation of glassy solid solutions of drugs in sugar alcohols.

    PubMed

    Langer, M; Höltje, M; Urbanetz, N A; Brandt, B; Höltje, H-D; Lippold, B C

    2003-02-18

    A prerequisite for the formation of glassy solid solutions prepared by the melting method is the miscibility of the respective drug and the carrier in the molten state. As could be shown experimentally, all investigated drug/sugar alcohol combinations miscible in the molten state form to some extent glassy solid solutions, dependent on their tendency to recrystallize during preparation. Therefore, the present study focuses on the evaluation of factors that govern the miscibility of molten drugs and sugar alcohols as carriers. In this context, solubility parameters are discussed as a means of predicting miscibility in comparison to a new approach, using calculated interaction parameters derived from molecular dynamics (MD) studies. There is evidence that a Coulomb interaction term C(SR), comprising short-range electrostatic interactions and hydrogen bonding energy is essential for the miscibility of drug and carrier in the molten state. To relate C(SR) to the molecular volume, a non-dimensional parameter P(i) is defined. For this parameter, a limiting value for miscibility exists. Contrary, calculated solubility parameter differences between drug and sugar alcohol in the range of 8-15 MPa(1/2) are not suitable for a prediction of miscibility or immiscibility, since the mixtures deviate from regular solution behavior. In irregular mixtures of drugs and sugar alcohols, an excess entropy and the formation of hydrogen bonds between unlike molecules favor miscibility, that cannot be predicted by regular solution theory. PMID:12550792

  3. 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.

  4. 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. PMID:24491530

  5. 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.

  6. A structural study of the intermolecular interactions of tyramine in the solid state and in solution

    NASA Astrophysics Data System (ADS)

    Quevedo, Rodolfo; Nuñez-Dallos, Nelson; Wurst, Klaus; Duarte-Ruiz, Álvaro

    2012-12-01

    The nature of the interactions between tyramine units was investigated in the solid state and in solution. Crystals of tyramine in its free base form were analyzed by Fourier transform infrared (FT-IR) spectroscopy and single-crystal X-ray diffraction (XRD). The crystal structure shows a linear molecular organization held together by "head-to-tail" intermolecular hydrogen bonds between the amino groups and the phenolic hydroxyl groups. These chains are arranged in double layers that can geometrically favor the formation of templates in solution, which may facilitate macrocyclization reactions to form azacyclophane-type compounds. Computational calculations using the PM6-DH+ method and electrospray ionization mass spectrometry (ESI-HRMS) reveal that the formation of a hydrogen-bonded tyramine dimer is favored in solution.

  7. 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.

  8. Effect of Sr and Ca solid-solution behaviour on superconductive properties as determined by microstructure analysis

    NASA Astrophysics Data System (ADS)

    Hong, Zhanglian; Wang, Minquan; Xiong, Guohong; Fan, Xianping

    1997-02-01

    The effects of the Sr and Ca composition and site-selection in a solid solution of a Bi-system superconductor on the superconductive properties were studied. Results showed that the Sr and Ca solid-solution behaviour had a remarkable effect on the superconductive properties. Further analysis indicated that this effect originated from varied hole concentration which was determined by the content of Sr atoms substituting for Bi atoms within the BiO layers. This substitution was influenced by the Sr and Ca solid-solution behaviour. This result offers a new mechanism for clarifying why the bivalent Sr and Ca cations affect the superconductive properties.

  9. Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

    DOE PAGESBeta

    An, Zhinan; Jia, Haoling; Wu, Yueying; Rack, Philip D.; Patchen, Allan D.; Liu, Yuzi; Ren, Yang; Li, Nan; Liaw, Peter K.

    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.

  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

    2007-01-01

    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. PMID:18181526

  12. Thermodynamics of aluminosilicate garnet solid solution: new experimental data, an optimized model, and thermometric applications

    NASA Astrophysics Data System (ADS)

    Ganguly, J.; Cheng, Weiji; Tirone, Massimiliano

    1996-12-01

    We have experimentally determined the displacement of the equilibrium Grossular + 2 Kyanite + Quartz ⇆ 3 Anorthite (GASP) as a function of garnet composition in the systems Mg-Ca-Mn, Fe-Mg-Ca and Fe-Mg-Ca-Mn at 1000°C. The results were treated along with selected experimental and observational data available in the literature as well as binary parameters from other workers to obtain a set of mutually compatible binary mixing parameters of the quaternary (Fe,Mg,Ca,Mn)- aluminosilicate garnet solid solution. Attempts to determine equilibrium garnet composition in the GASP equilibrium in the Ca-Mg binary were unsuccessful due to the formation of pyroxene. Calculations of binary and ternary miscibility gaps show that the P,T,X combination required for unmixing of garnet solid solution is not realized by natural samples. The solution model was applied to account for compositional effects on Fe-Mg exchange between garnet and ortho- or clino-pyroxene. Applications of the revised thermometric formulations to selected natural assemblages yield P-T conditions which are much less sensitive to compositional effects compared to the other available formulations, and are consistent with independent constraints.

  13. Solution and Solid State Nuclear Magnetic Resonance Spectroscopic Characterization of Efavirenz.

    PubMed

    Sousa, Eduardo Gomes Rodrigues de; Carvalho, Erika Martins de; San Gil, Rosane Aguiar da Silva; Santos, Tereza Cristina Dos; Borré, Leandro Bandeira; Santos-Filho, Osvaldo Andrade; Ellena, Javier

    2016-09-01

    Samples of efavirenz (EFZ) were evaluated to investigate the influence of the micronization process on EFZ stability. A combination of X-ray diffraction, thermal analysis, FTIR, observations of isotropic chemical shifts of (1)H in distinct solvents, their temperature dependence and spin-lattice relaxation time constants (T1), solution (1D and 2D) (13)C nuclear magnetic resonance (NMR), and solid-state (13)C NMR (CPMAS NMR) provides valuable structural information and structural elucidation of micronized EFZ and heptane-recrystallized polymorphs (EFZ/HEPT). This study revealed that the micronization process did not affect the EFZ crystalline structure. It was observed that the structure of EFZ/HEPT is in the same form as that obtained from ethyl acetate/hexane, as shown in the literature. A comparison of the solid-state NMR spectra revealed discrepancies regarding the assignments of some carbons published in the literature that have been resolved. PMID:26886313

  14. Elastic properties and electronic structures of Y atom solid solute supercell γ-Fe

    NASA Astrophysics Data System (ADS)

    Yang, Jian; Hou, Xiaoru; Xing, Xiaolei; Yun, Xiao; Yang, Yulin; Ren, Xuejun; Yang, Qingxiang

    2014-11-01

    Elastic properties and electronic structures of a Y atom solid solute supercell γ-Fe structure, which includes either a Y atom octahedral interstitial solid solute (Y-OISS), a Y atom tetrahedral interstitial solid solute (Y-TISS), a Y atom vertex substitutional solid solute (Y-VSSS) and a Y atom face-centered substitutional solid solute (Y-FSSS) have been calculated using a first-principles density functional theory plane-wave ultrasoft pseudopotential method, i.e. the Generalized Gradient Approximation (GGA) Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. The results indicate that, the Y-VSSS and Y-FSSS supercell γ-Fe are stable, while the Y-OISS and Y-TISS supercell γ-Fe are both unstable, especially Y-TISS. The bulk moduli of the Y-OISS, Y-TISS, Y-VSSS and Y-FSSS supercell γ-Fe are 234.72, 200.32, 262.45 and 262.56 GPa, and the shear moduli are 74.23, 52.02, 156.78 and 156.76 GPa, which shows that the directional bonding in Y-SSS supercell γ-Fe is stronger than that in Y-ISS and that the Y-ISS supercell γ-Fe is much stiff than the Y-SSS. The ratios between the shear modulus and bulk modulus of Y-OISS, Y-TISS, Y-VSSS and Y-FSSS supercell γ-Fe are 0.32, 0.26, 0.60 and 0.60, respectively, which implies that the Y-SSS supercell γ-Fe is essentially brittle and that the Y-ISS is slightly ductile. Poisson's ratio of them are 0.47, 0.38, 0.25 and 0.35, which shows that compared with Y-ISS supercell γ-Fe, the Y-SSS supercell γ-Fe has good plasticity in the investigated binary alloys. The universal elastic anisotropy indexes of the Y-OISS, Y-TISS, Y-VSSS and Y-FSSS supercell γ-Fe are 1.765, 1.205, 0.965 and 0.95, the result indicates that the anisotropy decreases in the following sequence: Y-OISS supercell γ-Fe > Y-TISS > Y-FSSS > Y-VSSS. The amounts of transferred charges (per supercell) from Fe atom to Y atom is in the order of Y-VSSS supercell γ-Fe = Y-FSSS > Y-TISS > Y-OISS, respectively, which indicates that their ionicity is Y

  15. 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. PMID:26185165

  16. 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.

  17. 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.

  18. 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.

  19. Thermodynamic properties of CexTh1-xO2 solid solution from first-principles calculations

    SciTech Connect

    Xiao, Haiyan Y.; Zhang, Yanwen; Weber, William J.

    2012-11-02

    A systematic study based on first-principles calculations along with a quasi-harmonic approximation has been conducted to calculate the thermodynamic properties of the CexTh1xO2 solid solution. The predicted density, thermal expansion coefficients, heat capacity and thermal conductivity for the CexTh1xO2 solid solution all agree well with the available experimental data. The thermal expansion coefficient for ThO2 increases with CeO2 substitution, and complete substitution shows the highest expansion coefficient. On the other hand, the mixed CexTh1xO2 (0 < x < 1) solid solution generally exhibits lower heat capacity and thermal conductivity than the ThO2 and CeO2 end members. Our calculations indicate a strong effect of Ce concentration on the thermodynamic properties of the CexTh1xO2 solid solution.

  20. 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.

  1. Structural and Electronic Properties of a Wide-Gap Quaternary Solid Solution: \\(Zn, Mg\\) \\(S, Se\\)

    NASA Astrophysics Data System (ADS)

    Saitta, A. M.; de Gironcoli, S.; Baroni, S.

    1998-06-01

    The structural properties of the (Zn, Mg) (S, Se) solid solutions are determined by a combination of the computational alchemy and the cluster expansion methods with Monte Carlo simulations. We determine the phase diagram of the alloy and show that the homogeneous phase is characterized by a large amount of short-range order occurring among first-nearest neighbors. Electronic-structure calculations performed using the special quasirandom structure approach indicate that the energy gap of the alloy is rather sensitive to this short-range order.

  2. Phase Diagram of Pb(Zr,Ti)O{sub 3} Solid Solutions from First Principles

    SciTech Connect

    Kornev, Igor A.; Bellaiche, L.; Janolin, P.-E.; Dkhil, B.; Suard, E.

    2006-10-13

    A first-principles-derived scheme that incorporates ferroelectric and antiferrodistortive degrees of freedom is developed to study finite-temperature properties of Pb(Zr{sub 1-x}Ti{sub x})O{sub 3} solid solution near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground state for some Ti compositions (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.

  3. Phase Diagram of Pb(Zr,Ti)O3 Solid Solutions from First Principles

    NASA Astrophysics Data System (ADS)

    Kornev, Igor A.; Bellaiche, L.; Janolin, P.-E.; Dkhil, B.; Suard, E.

    2006-10-01

    A first-principles-derived scheme that incorporates ferroelectric and antiferrodistortive degrees of freedom is developed to study finite-temperature properties of Pb(Zr1-xTix)O3 solid solution near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.

  4. Electron-microscope study of lanthanum-doped lead zirconate-titanate solid solutions

    SciTech Connect

    Ishchuk, V.M.; Presnyakova, O.V.

    1985-12-01

    This paper examines the structure of specimens of lanthanumdoped lead zirconate-titanate solid solutions in the hysteresis region of the phase diagram, using transmission electron microscopy. The electron-microscopic images of PLZT ceramic of composition display an unusual diffraction contrast. An analysis of the images obtained for different orientations of the cleavages of specimens of composition indicate that the second-phase inclusions are cylindrical in the main. The authors hypothesize that the inclusions are a ferroelectric phase in an antiferroelectric matrix.

  5. 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.

  6. Predicting hardness of covalent/ionic solid solution from first-principles theory

    NASA Astrophysics Data System (ADS)

    Hu, Q. M.; Kádas, K.; Hogmark, S.; Yang, R.; Johansson, B.; Vitos, L.

    2007-09-01

    We introduce a hardness formula for the multicomponent covalent and ionic solid solutions. This expression is tested on nitride spinel materials A3N4 (A=C,Si,Ge) and applied to titanium nitrogen carbide (TiN1-xCx with 0⩽x ⩽1), off-stoichiometric transition-metal nitride (TiN1-x and VN1-x with x ⩽0.25), and B-doped semiconductors (C1-xBx, Si1-xBx, and Ge1-xBx with x ⩽0.1). In all cases, the theoretical hardness is in good agreement with experiments.

  7. Hydration and proton transport in solid solutions based on Ba2CaWO6

    NASA Astrophysics Data System (ADS)

    Animitsa, I. E.; Kochetova, N. A.; Denisova, T. A.; Zhuravlev, N. A.; Baklanova, I. V.

    2009-02-01

    Hydrated alkaline-earth metal tungstates Ba4Ca2 + x W2 - x O12 - 2 x with perovskite structure were studied by the thermogravimetry, 1H NMR, IR, and Raman spectroscopy methods. Electrical conductivity and transfer numbers were measured with varying T, p_{O_2 } and p_{H_2 O} . The solid solutions are capable of reversibly intercalating water and can exhibit high-temperature proton transport. The localization of protons on oxygen results in the appearance of energetically nonequivalent OH groups; a small fraction of protons are present in the form of H2O and H3O+.

  8. Direct observation of charge mediated lattice distortions in complex oxide solid solutions

    SciTech Connect

    Sang, Xiahan; Grimley, Everett D.; Niu, Changning; Irving, Douglas L.; LeBeau, James M.

    2015-02-09

    Using aberration corrected scanning transmission electron microscopy combined with advanced imaging methods, we directly observe atom column specific, picometer-scale displacements induced by local chemistry in a complex oxide solid solution. Displacements predicted from density functional theory were found to correlate with the observed experimental trends. Further analysis of bonding and charge distribution was used to clarify the mechanisms responsible for the detected structural behavior. By extending the experimental electron microscopy measurements to previously inaccessible length scales, we identified correlated atomic displacements linked to bond differences within the complex oxide structure.

  9. Formation of non-equilibrium Fe-Au solid solutions in nanoclusters

    NASA Astrophysics Data System (ADS)

    Mukherjee, P.; Zhou, Lin; Kramer, M. J.; Shield, J. E.

    2013-06-01

    Fe-Au nanoclusters ranging in composition from ˜33 to 79 at. % Fe were prepared by inert gas condensation. Resulting phases were single crystalline solid solutions for all compositions with significant defects present. The as-deposited clusters formed in a bcc structure for Fe content >65 at. % and in a fcc structure for Fe < 65 at. %. Lattice parameters were expanded beyond rule-of-mixture estimates. The lattice expansion is explained by an analytical self-interstitial model. All clusters were ferromagnetic, although the fcc structures showed low magnetization. The low magnetizations are thought to arise from antiferromagnetic cores with uncompensated ferromagnetic surface spins.

  10. Formation of 3He droplets in dilute 3He-4He solid solutions

    NASA Astrophysics Data System (ADS)

    Huan, Chao; Candela, Don; Kim, Sung; Yin, Liang; Xia, Jiang-Sheng; Sullivan, Neil

    2015-03-01

    We review the different stages of the formation of 3He droplets in dilute solid 3He-4He solutions. The studies are interesting because the phase separation in isotopic helium mixtures is a first-order transition with a conserved order parameter. The rate of growth of the droplets as observed in NMR studies is compared with the rates expected for homogeneous nucleation followed by a period of coarsening known as Ostwald ripening. Work suported by the National Science Foundation - DMR-1303599 and DMR- 1157490 (National High Magnetic Field Laboratory).

  11. 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. PMID:25859922

  12. Synthetic supercontainers exhibit distinct solution versus solid state guest-binding behavior.

    PubMed

    Dai, Feng-Rong; Sambasivam, Uma; Hammerstrom, Alex J; Wang, Zhenqiang

    2014-05-21

    The phase-dependent host-guest binding behavior of a new family of synthetic supercontainers has been probed in homogeneous solution and at liquid-liquid, solid-liquid, and solid-gas interfaces. The synthetic hosts, namely, type II metal-organic supercontainers (MOSCs), are constructed from the assembly of divalent metal ions, 1,4-benzenedicarboxylate (BDC) linker, and sulfonylcalix[4]arene-based container precursors. One member of the MOSCs, MOSC-II-tBu-Ni, which is derived from Ni(II), BDC, and p-tert-butylsulfonylcalix[4]arene (TBSC), crystallizes in the space group R3 and adopts pseudo face-centered cubic (fcc) packing, whereas other MOSCs, including TBSC analogue MOSC-II-tBu-Co, p-tert-pentylsulfonylcalix[4]arene (TPSC) analogues MOSC-II-tPen-Ni/Co, and p-tert-octylsulfonylcalix[4]arene (TOSC) analogues MOSC-II-tOc-Ni/Mg/Co, all crystallize in the space group I4/m and assume a pseudo body-centered cubic (bcc) packing mode. This solid-state structural diversity is nevertheless not reflected in their solution host-guest chemistry, as evidenced by the similar binding properties of MOSC-II-tBu-Ni and MOSC-II-tBu-Co in solution. Both MOSCs show comparable binding constants and adsorb ca. 7 equiv of methylene blue (MB) and ca. 30 equiv of aspirin in chloroform. In contrast, the guest-binding behavior of the MOSCs in solid state reveals much more variations. At the solid-liquid interface, MOSC-II-tBu-Co adsorb ca. 5 equiv of MB from an aqueous solution at a substantially faster rate than MOSC-II-tBu-Ni does. However, at the solid-gas interface, MOSC-II-tBu-Ni has higher gas uptake than MOSC-II-tBu-Co, contradicting their overall porosity inferred from the crystal structures. This discrepancy is attributed to the partial collapse of the solid-state packing of the MOSCs upon solvent evacuation. It is postulated that the degree of porosity collapse correlates with the molecular size of the MOSCs, i.e., the larger the MOSCs, the more severe they suffer from the loss of

  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. PMID:24402204

  14. Mechanisms of reduced solute diffusivity at nanoconfined solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Mahadevan, T.; Kojic, M.; Ferrari, M.; Ziemys, A.

    2013-06-01

    We report results from molecular simulations that reveal the causes of reduced diffusivity at solid-liquid interfaces in the presence of nanoscale confinement. The diffusion of a 2 M glucose solution was simulated inside a 10 nm silica channel together with the calculated thermodynamic properties of diffusion. A strong energy-entropy compensation mechanism was found at the interface with a free energy minimum of -0.6 kcal/mol. Using the Eyring equation the average jump length was reduced by 15% at interface. The complete loss of solute diffusivity at silica surface was explained by the substantial loss of the probability of productive displacements. The results suggested that glucose molecule diffusivity close to the surface might be related to a stiffer cage of the hydration shell, which affects the probability of cage breaking. These results help in understanding of diffusion mechanisms at interface and predicting mass transport in nanoconfinement for engineering and biomedical applications.

  15. 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.

  16. Human Thrombin Detection Through a Sandwich Aptamer Microarray: Interaction Analysis in Solution and in Solid Phase

    PubMed Central

    Sosic, Alice; Meneghello, Anna; Cretaio, Erica; Gatto, Barbara

    2011-01-01

    We have developed an aptamer-based microarray for human thrombin detection exploiting two non-overlapping DNA thrombin aptamers recognizing different exosites of the target protein. The 15-mer aptamer (TBA1) binds the fibrinogen-binding site, whereas the 29-mer aptamer (TBA2) binds the heparin binding domain. Extensive analysis on the complex formation between human thrombin and modified aptamers was performed by Electrophoresis Mobility Shift Assay (EMSA), in order to verify in solution whether the chemical modifications introduced would affect aptamers/protein recognition. The validated system was then applied to the aptamer microarray, using the solid phase system devised by the solution studies. Finally, the best procedure for Sandwich Aptamer Microarray (SAM) and the specificity of the sandwich formation for the developed aptasensor for human thrombin were optimized. PMID:22163703

  17. Predominance of the triketo tautomer in acyldipivaloylmethanes in solution and the solid state

    NASA Astrophysics Data System (ADS)

    Stilinović, Vladimir; Portada, Tomislav; Kaitner, Branko

    2014-04-01

    A series of five acyldipivaloylmethanes was prepared and studied with respect to keto-enol tautomerism. In the solid state all the compounds exist as triketo tautomers with the triketo group of approximate C3 symmetry. MNR and IR spectroscopy were employed to study the compounds in a variety of solvents. No diketoenol tautomers were detected in any of the solutions. However, a slow deuteration was noticed in the CD3OD solution of acetyldipivaloylmethane which indicates presence of a minute amount of the enol form of this compound. The predominance of the triketo tautomer in all the compounds was explained by the destabilisation of the enol due to steric repulsions of the bulky tert-butyl substituents.

  18. 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.

  19. 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

  20. 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

    2012-09-01

    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). PMID:22908900

  1. Surface interactions between fayalite slags and synthetic spinels and solid solutions

    NASA Astrophysics Data System (ADS)

    Donald, J. R.; Toguri, J. M.; Doyle, C.

    1998-04-01

    To obtain a better understanding of the complex corrosion mechanisms occurring at the interface, the surface and interfacial properties between fayalite-type slags and homogeneous, synthetic spinels and solid solutions of these spinels were investigated. These oxides represent the conventional refractory components. The sessile drop technique incorporating high-temperature X-ray radiography was employed for this purpose. The experimental temperature was 1200 °C and the oxygen potential was 10-9 atm controlled by CO/CO2 gas mixture. The contact angles between the solid substrates and molten silica-rich fayalite slag ranged from 0 deg for MgFe2O4 to 23 deg for MgAl2O4. When iron-rich slags were employed, the contact angles ranged from 15 deg for MgCr2O4 to 22 deg for MgAl2O4. The interfacial reactions between the slags and the various spinel materials and the dissolution of the solids into the slags are discussed.

  2. The role of atomic ordering on phonon transport in substitutional solid solutions

    NASA Astrophysics Data System (ADS)

    Duda, John Charles

    The past several decades have seen sudden and rapid advances in micro- and nanotechnology. Consequently, a wide array of novel electronic, optical, and magnetic devices have been developed, all sharing one common feature: characteristic lengths scales on the order of a few to hundreds of nanometers. In almost all cases, it is the high density of interfaces that provides the material properties allowing for the purposeful and unique operation for which these devices were designed. However, these material boundaries have a marked impact on the thermal properties of the device as well. While thermal conductivity is often a critical property in modern device design, it frequently remains an afterthought. In many cases, the electrical or optical operating principles of a given device require a specific set of materials be used. As a result, the thermal performance of such a device can only be controlled through packaging techniques. Ultimately, it would be advantageous if the thermal transport properties of a given material system could be independently tuned while keeping the constituent components of the system fixed, a concept that has implications for both current- and next-generation applications. Many random substitutional solid solutions (alloys) will display a tendency to chemically order given the appropriate kinetic and thermodynamic conditions. Such order-disorder transitions result in crystallographic reconfigurations, where the atomic basis, symmetry, and periodicity of the alloy change dramatically. The objective of this work is to demonstrate that through exploitation of chemically-ordered solid-solutions, new strategies to gain control over the thermal conductivities of solid-state material systems are possible. Both non-equilibrium molecular dynamics (NEMD) simulations and harmonic lattice dynamics (LD) calculations will be implemented to achieve this goal. The results of these simulations will show that through the exploitation of chemical ordering

  3. Magneto-optical spectroscopic studies of solid and solution-phase tetra-phenyl porphyrin

    NASA Astrophysics Data System (ADS)

    Wahlen-Strothman, Jacob; Pan, Zhen Wen; Lamarche, Cody; Manning, Lane; Rawat, Naveen; Tokumoto, Takahisa; McGill, Stephen; Furis, Madalina; Chu, Kelvin

    2012-02-01

    Tetraphenylporphyrin (TPP) is a heterocyclic model system for porphyrins found in heme proteins, cytochromes and photosynthetic cofactors. TPP can accommodate a metal ion in the center; D-shell ion porphyrin complexes with a crystalline solid phase are of interest for magnetic studies because of the possibility of macroscopic long-range magnetic order of the ion spins. We have investigated the 5K magnetic properties of poly-crystalline thin films of TPP complexed with Zn, Mn and Cu and deposited through a room temperature capillary pen technique that produces grain size in the 100 micron to 1mm range. Our novel setup measures the UV/VIS, linear dichroism and MCD simultaneously and incorporates a photoelastic modulator and a microscopy superconducting magnet for high-field (5T) measurements. In addition, we present 25T data on samples from the new split magnet at NHMFL. We present solution and crystalline data on metal-complexed TPP; data are analyzed in terms of A and B-type MCD using a perimeter model. We find good agreement with previous solution data, and novel crystalline phase spectra that are correlated to the long range ordering of the solid state.

  4. Electrophysical properties of solid solutions of silver in PbTe

    SciTech Connect

    Sharov, M. K.

    2012-05-15

    The thermopower coefficient {alpha}{sub 0} and the electrical conductivity {sigma} of Pb{sub 1-x}Ag{sub x}Te solid solutions, where x = (0-0.007), are measured at T = 300 K. The hole concentration p is calculated. All samples are of the p type. With increasing silver content, {alpha}{sub 0} decreases, while p and {sigma} increase. For undoped crystals, {alpha}{sub 0} = 251.0 {mu}V/K, p = 1.1 Multiplication-Sign 10{sup 18} cm{sup -3}, and {sigma} = 165 {Omega}{sup -1} cm{sup -1}. At the silver-solubility limit for x = 0.007, {alpha}{sub 0} = 193.8 {mu}V/K, p = 2.3 Multiplication-Sign 10{sup 18} cm{sup -3}, and {sigma} = 216 {Omega}{sup -1} cm{sup -1}. The hole concentration in all samples is much lower than the concentration of introduced silver atoms. The hole gas in Pb{sub 1-x}Ag{sub x}Te solid solutions is weakly degenerate in the entire silver-concentration range.

  5. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    DOE PAGESBeta

    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.; et al

    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

  6. Mechanical Properties of Mg-Gd and Mg-Y Solid Solutions

    NASA Astrophysics Data System (ADS)

    Kula, Anna; Jia, Xiaohui; Mishra, Raj K.; Niewczas, Marek

    2015-12-01

    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.

  7. 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.

  8. 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.

  9. Pressureless sintered beta-prime-Si3N4 solid solution - Fabrication, microstructure, and strength

    NASA Technical Reports Server (NTRS)

    Dutta, S.

    1977-01-01

    Pressureless sintering of beta-prime-Si3N4 solid solution was studied as a function of temperature using Si3N4, A1N, and Al2O3 as basic constituents. 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 M Pa were achieved at moderate temperature (1000 C), but decreased to 228 M Pa 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.

  10. Mechanistic study of carvacrol processing and stabilization as glassy solid solution and microcapsule.

    PubMed

    Tackenberg, Markus W; Geisthövel, Carola; Marmann, Andreas; Schuchmann, Heike P; Kleinebudde, Peter; Thommes, Markus

    2015-01-30

    Essential oils and other liquid active pharmaceutical ingredients (APIs) are frequently microencapsulated to improve shelf life, handling, and for tailoring release. A glassy solid solution (GSS), a single-phase system, where the excipient is plasticized by the API, could be an alternative formulation system. Thus this study focuses on the investigation of two formulation strategies using carvacrol as a model compound, namely a microcapsule (MC) and a glassy solid solution (GSS). Applying the solubility parameter approach, polyvinylpyrrolidone (PVP) was chosen as a suitable matrix material for a GSS system, whereas maltodextrin and sucrose served as excipients for a microcapsule (MC) system. Differential scanning calorimetry (DSC) measurements of the excipients' glass transition temperatures and the melting point of carvacrol verified plasticizing properties of carvacrol on PVP. Batch mixing processes, as preliminary experiments for future extrusion processes, were performed to prepare GSSs and MCs with various amounts of carvacrol, followed by crushing and sieving. Maximally 4.5% carvacrol was encapsulated in the carbohydrate material, whereas up to 16.3% were stabilized as GSS, which is an outstanding amount. However, grinding of the samples led to a loss of up to 30% of carvacrol. PMID:25498156

  11. Transformation of photophysical properties from solution to solid state in alkoxy-cyano-diphenylacetylene molecules.

    PubMed

    Karunakaran, Venugopal; Prabhu, Deepak D; Das, Suresh; Varughese, Sunil

    2015-07-28

    Detailed photophysical properties of cyano and mono (MA)/bis alkoxy (DA) substituted diphenylacetylene moieties with different alkyl chain lengths (methyl (1), octyl (8) and dodecyl (12)) were investigated in solution and the solid state in an effort to determine the effect of self-aggregation on these properties. The solvated molecules showed a minimal bathochromic shift with an increase of solvent polarity in their absorption spectra, whereas a significant shift was observed in the emission spectra. This could be attributed to the relatively low change in dipole moment between ground and Franck-Condon excited states and luminescence arising from the intramolecular charge transfer state with a dipole moment significantly higher than that of the ground state. In solid state the emission quantum yields of these materials were significantly higher than in solution. For DA1, polymorphic materials with distinct photophysical properties were obtained. The DA1 materials obtained by fast precipitation (DA1) showed broad fluorescence with peaks at 398, 467 and 535 nm upon excitation at different wavelengths. Detailed analysis of absorption, emission and excitation spectra and lifetime experiments indicated that these peaks could be attributed to the monomer, J- and H-type aggregates respectively. Whereas the crystals obtained by slow crystallization (DA1C) showed only one emission peak at around 396 nm attributed to the monomer. This is supported by the single crystal X-ray structure which consists of a monomer molecule having minimal interaction with nearest neighbour molecules. PMID:26118371

  12. 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

  13. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    DOE PAGESBeta

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

    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

  14. Controlling the Electronic Structures of Perovskite Oxynitrides and their Solid Solutions for Photocatalysis.

    PubMed

    Umezawa, Naoto; Janotti, Anderson

    2016-05-10

    Band-gap engineering of oxide materials is of great interest for optoelectronics, photovoltaics, and photocatalysis applications. In this study, electronic structures of perovskite oxynitrides, LaTiO2 N and SrNbO2 N, and solid solutions, (SrTiO3 )1-x (LaTiO2 N)x and (SrTiO3 )1-x (SrNbO2 N)x , are investigated using hybrid density functional calculations. Band gaps of LaTiO2 N and SrNbO2 N are much smaller than that of SrTiO3 owing to the formation of a N 2p band, which is higher in energy than the O 2p band. The valence- and conduction-band offsets of SrTiO3 /LaTiO2 N and SrTiO3 /SrNbO2 N are computed, and the adequacy for H2 evolution is analyzed by comparing the positions of the band edges with respect to the standard hydrogen electrode (SHE). The band gap of (SrTiO3 )1-x (LaTiO2 N)x and (SrTiO3 )1-x (SrNbO2 N)x solid solutions are also discussed. PMID:27072042

  15. Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

    USGS Publications Warehouse

    Plummer, L.N.; Busenberg, E.; Glynn, P.D.; Blum, A.E.

    1992-01-01

    Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25

  16. Secrets of solid state and aqueous solution structures of [Ni(tmdta)](2-).

    PubMed

    Meier, Roland; Platas-Iglesias, Carlos; Heinemann, Frank W; Linti, Gerald; Schulte, Jürgen; Srivastava, Sunil K

    2014-07-01

    The molecular structures of Li2[Ni(tmdta)]·5H2O (1a, tmdta = trimethylenediaminetetraacetate), {C(NH2)3}2[Ni(tmdta)]·6H2O (1b), and {Ni(H2O)6}[Ni(tmdta)]·2H2O (2a) have been determined. The central trimethylenediamine chelate ring shows half-chair (hc) geometries in 1a and 1b, while a twist-boat (tb) conformation is encountered in 2a. The coexistence of tb and hc forms in the solid state prompted us to elucidate the existence of a tb ⇌ hc equilibrium in aqueous solution. Evaluation of the data from solid state vibrational spectra (Raman and IR) for the hc and tb forms showed excellent agreement with simulated spectra obtained with DFT computations (TPSSh/TZVP). This outstanding matching between theory and experiment enabled us to build composite spectra with varying hc:tb ratios. Comparison of these results with Raman and IR spectra recorded for [Ni(tmdta)](2-) in aqueous solution revealed that simulated Raman and IR spectra with a hc:tb ratio = 2:3 match the solution spectra in an accurate way. This equilibrium ratio enabled us to compute (13)C NMR sifts for the paramagnetic solution spectrum of [Ni(tmdta)](2-) based on the relative contributions by hc and tb fractions. This leads to computed shifts that agree closely with the experimental ones. Also, the kinetics of the skeleton dynamics could be estimated quantitatively by temperature-dependent (13)C NMR spectroscopic measurements. An interesting effect encountered for the very first time here concerns a drastic intensity difference of the 10Dq band ((3)A2g → (3)T2g(F) transition) in solid state electronic spectra of tb vs hc isomers, where the intensity of this band in the case of the hc form is much lower than that of the tb conformer and thus more similar to the case of the usual Ni(II) chromophore in octahedral environment. The equilibrium constants for complex formation and protonation of Ni(II)-tmdta at low pH have been estimated by pH-dependent UV-vis titration experiments. Correlation of these

  17. Temperature Dependence of the Mechanical Properties of Equiatomic Solid Solution Alloys with FCC Crystal Structures

    SciTech Connect

    Wu, Zhenggang; Bei, Hongbin; Pharr, George M.; George, Easo P.

    2014-10-03

    We found that compared to decades-old theories of strengthening in dilute solid solutions, the mechanical behavior of concentrated solid solutions is relatively poorly understood. A special subset of these materials includes alloys in which the constituent elements are present in equal atomic proportions, including the high-entropy alloys of recent interest. A unique characteristic of equiatomic alloys is the absence of “solvent” and “solute” atoms, resulting in a breakdown of the textbook picture of dislocations moving through a solvent lattice and encountering discrete solute obstacles. Likewise, to clarify the mechanical behavior of this interesting new class of materials, we investigate here a family of equiatomic binary, ternary and quaternary alloys based on the elements Fe, Ni, Co, Cr and Mn that were previously shown to be single-phase face-centered cubic (fcc) solid solutions. The alloys were arc-melted, drop-cast, homogenized, cold-rolled and recrystallized to produce equiaxed microstructures with comparable grain sizes. Tensile tests were performed at an engineering strain rate of 10-3 s-1 at temperatures in the range 77–673 K. Unalloyed fcc Ni was processed similarly and tested for comparison. The flow stresses depend to varying degrees on temperature, with some (e.g. NiCoCr, NiCoCrMn and FeNiCoCr) exhibiting yield and ultimate strengths that increase strongly with decreasing temperature, while others (e.g. NiCo and Ni) exhibit very weak temperature dependencies. Moreover, to better understand this behavior, the temperature dependencies of the yield strength and strain hardening were analyzed separately. Lattice friction appears to be the predominant component of the temperature-dependent yield stress, possibly because the Peierls barrier height decreases with increasing temperature due to a thermally induced increase of dislocation width. In the early stages of plastic flow (5–13% strain, depending on material), the

  18. Effect of solid solutions and second phases on the thermal conductivity of zirconium diboride ceramics

    NASA Astrophysics Data System (ADS)

    Harrington, Gregory John Kenneth

    The research presented in this dissertation is focused on the thermal conductivity (k) of ZrB2 ceramics. The goal was to develop a better understanding of how various solid solutions and second phases affect the thermal and electrical transport in ZrB2, with a focus on the effect of C, W, and ZrC. The first study showed C additions improved densification and it was proposed that the reduction of boria was the impetus for this result. Boron carbide was formed by the reaction of excess C with reduced B and its formation was mitigated by the addition of ZrH2. This allowed the ZrB2-C binary system to be evaluated for study two. Study two showed the k of ZrB2 is reduced by C in solid solution and as a second phase due to the decrease in the electron contribution to thermal conductivity. Conductivities of 99 (25°C) and 76 W/m*K (2000°C) were obtained for the most pure ZrB2 (0.026 wt% C in solution and 0.2 vol% zirconia) produced in this study, which are the highest reported values for ZrB2 processed using commercial powders since 1980. The third study evaluated the electrical resistivity of ZrB2 up to 1860°C using the van der Pauw technique. Separate linear regimes were observed below and above 950°C, whereas, previous studies assumed a linear relation. Finally the effect of ZrC on the (Zr,W)B2 solid solution was evaluated in study four. The formation of (Zr,W)C initially increased k, but further ZrC additions decreased k. In the end, this research provides both: (1) usable information for the design of future ultra-high temperature ceramic systems; and (2) fundamental research that lays the groundwork for future studies aimed at understanding thermal transport in diboride based materials.

  19. Temperature Dependence of the Mechanical Properties of Equiatomic Solid Solution Alloys with FCC Crystal Structures

    DOE PAGESBeta

    Wu, Zhenggang; Bei, Hongbin; Pharr, George M.; George, Easo P.

    2014-10-03

    We found that compared to decades-old theories of strengthening in dilute solid solutions, the mechanical behavior of concentrated solid solutions is relatively poorly understood. A special subset of these materials includes alloys in which the constituent elements are present in equal atomic proportions, including the high-entropy alloys of recent interest. A unique characteristic of equiatomic alloys is the absence of “solvent” and “solute” atoms, resulting in a breakdown of the textbook picture of dislocations moving through a solvent lattice and encountering discrete solute obstacles. Likewise, to clarify the mechanical behavior of this interesting new class of materials, we investigate heremore » a family of equiatomic binary, ternary and quaternary alloys based on the elements Fe, Ni, Co, Cr and Mn that were previously shown to be single-phase face-centered cubic (fcc) solid solutions. The alloys were arc-melted, drop-cast, homogenized, cold-rolled and recrystallized to produce equiaxed microstructures with comparable grain sizes. Tensile tests were performed at an engineering strain rate of 10-3 s-1 at temperatures in the range 77–673 K. Unalloyed fcc Ni was processed similarly and tested for comparison. The flow stresses depend to varying degrees on temperature, with some (e.g. NiCoCr, NiCoCrMn and FeNiCoCr) exhibiting yield and ultimate strengths that increase strongly with decreasing temperature, while others (e.g. NiCo and Ni) exhibit very weak temperature dependencies. Moreover, to better understand this behavior, the temperature dependencies of the yield strength and strain hardening were analyzed separately. Lattice friction appears to be the predominant component of the temperature-dependent yield stress, possibly because the Peierls barrier height decreases with increasing temperature due to a thermally induced increase of dislocation width. In the early stages of plastic flow (5–13% strain, depending on material), the temperature

  20. Oxygen vacancy ordering within anion-deficient Ceria

    SciTech Connect

    Hull, S.; Norberg, S.T.; Ahmed, I.; Eriksson, S.G.; Marrocchelli, D.; Madden, P.A.

    2009-10-15

    The structural properties of anion deficient ceria, CeO{sub 2-{delta}}, have been studied as a function of oxygen partial pressure, p(O{sub 2}), over the range 0>=log{sub 10p}(O{sub 2})>=-18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O{sub 2}) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, delta, and the isotropic thermal vibration parameters, u{sub Ce} and u{sub O}, starting at log{sub 10p}(O{sub 2}){approx}-11. The increases are continuous, but show a distinct kink at log{sub 10p}(O{sub 2}){approx}-14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O{sup 2-} vacancies preferentially align as pairs in the <111> cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO{sub 2}-Ce{sub 2}O{sub 3} system at ambient temperature and, in particular, to the nature of the long-range ordering of O{sup 2-} vacancies within the crystal structure of Ce{sub 7}O{sub 12}. - Graphical abstract: Partial radial distribution function for oxygen vacancies within CeO{sub 1.710} at 1273 K (solid line) showing the increased tendency for local ordering in <111> directions compared to a random distribution (dashed line).

  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, Dean A.

    2004-03-15

    ABSTRACT -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, co-precipitates of U(IV) and Np(IV) [(UxNp1-x )O2(am), with values for x of 0.95, 0.85, 0.50, 0.15, and 0.05] were prepared, characterized, and used to determine their solubility as a function of K2CO3 concentrations ranging from 1.0 m to 5.0 m in the presence of 0.01 m Na2S2O4 and 0.01 m KOH, and as a function of KHCO3 concentrations ranging from 0.1 m to 0.8 m in the presence of 0.01 m Na2S2O4. The solubility data show that the equilibrium in these systems is reached in <7 days, the solubility-controlling solids are amorphous, and that we were successful in maintaining U and Np in the tetravalent state. A scanning electron microscope equipped with energy dispersive spectrometry and x-ray absorption spectroscopic analyses of the solids indicated the equilibrated co-precipitates to be solid solutions. A close agreement between the thermodynamic predictions, assuming an ideal solid solution, and the experimental solubilities shows that U(IV) and Np(IV) form an ideal solid solution and that non-ideal solid solution behavior for this system can be ruled out.

  2. Ceria co-doping: synergistic or average effect?

    PubMed

    Burbano, Mario; Nadin, Sian; Marrocchelli, Dario; Salanne, Mathieu; Watson, Graeme W

    2014-05-14

    Ceria (CeO2) co-doping has been suggested as a means to achieve ionic conductivities that are significantly higher than those in singly doped systems. Rekindled interest in this topic over the last decade has given rise to claims of much improved performance. The present study makes use of computer simulations to investigate the bulk ionic conductivity of rare earth (RE) doped ceria, where RE = Sc, Gd, Sm, Nd and La. The results from the singly doped systems are compared to those from ceria co-doped with Nd/Sm and Sc/La. The pattern that emerges from the conductivity data is consistent with the dominance of local lattice strains from individual defects, rather than the synergistic co-doping effect reported recently, and as a result, no enhancement in the conductivity of co-doped samples is observed. PMID:24658460

  3. Dopant-mediated oxygen vacancy tuning in ceria nanoparticles.

    PubMed

    Babu, Suresh; Thanneeru, Ranjith; Inerbaev, Talgat; Day, Richard; Masunov, Artëm E; Schulte, Alfons; Seal, Sudipta

    2009-02-25

    Ceria nanoparticles with 20 and 40 at.% RE (RE = Y, Sm, Gd, and Yb) dopants were synthesized through a microemulsion method. Independently of the dopant nature and concentration, nearly monodispersed nanoparticles of size 3-5 nm were observed in high resolution transmission electron microscopic analysis. The ceria lattice either expands or contracts depending on the dopant cation ionic radii, as indicated by x-ray diffraction studies. X-ray photoelectron and Raman spectroscopic studies were used to quantify the cerium oxidation state and oxygen vacancy concentration. The results show the tunability of the oxygen vacancy and Ce(3+) concentrations based on the dopant properties. First principles simulations using the free energy density functional theory method support the observed experimental trends. The reported results establish a relationship between the oxygen vacancies and oxidation states in doped ceria required for tailoring properties in catalytic and biomedical applications. PMID:19417474

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

    SciTech Connect

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

    2014-03-17

    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 (Gd{sub Ce}{sup ′}−V{sub o}{sup ••}){sup *} and (2Gd{sub Ce}{sup ′}−V{sub o}{sup ••}){sup x} generated due to association of oxygen vacancies and reduced cerium or dopant cations site (Gd{sup 3+}), 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.

  5. Fast vacancy-mediated oxygen ion incorporation across the ceria-gas electrochemical interface

    NASA Astrophysics Data System (ADS)

    Feng, Zhuoluo A.; El Gabaly, Farid; Ye, Xiaofei; Shen, Zhi-Xun; Chueh, William C.

    2014-07-01

    Electrochemical incorporation reactions are ubiquitous in energy storage and conversion devices based on mixed ionic and electronic conductors, such as lithium-ion batteries, solid-oxide fuel cells and water-splitting membranes. The two-way traffic of ions and electrons across the electrochemical interface, coupled with the bulk transport of mass and charge, has been challenging to understand. Here we report an investigation of the oxygen-ion incorporation pathway in CeO2-δ (ceria), one of the most recognized oxygen-deficient compounds, during hydrogen oxidation and water splitting. We probe the response of surface oxygen vacancies, electrons and adsorbates to the electrochemical polarization at the ceria-gas interface. We show that surface oxygen-ion transfer, mediated by oxygen vacancies, is fast. Furthermore, we infer that the electron transfer between cerium cations and hydroxyl ions is the rate-determining step. Our in operando observations reveal the precise roles of surface oxygen vacancy and electron defects in determining the rate of surface incorporation reactions.

  6. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

  7. Effect of Ceria on the Sulfation and Desulfation Characteristics of a Model Lean NOx Trap Catalyst

    SciTech Connect

    Ji, Yaying; Toops, Todd J; Crocker, Mark

    2009-01-01

    The effect of ceria addition on the sulfation and desulfation characteristics of a model Ba-based lean NO{sub x} trap (LNT) catalyst was studied. According to DRIFTS and NO{sub x} storage capacity measurements, ceria is able to store sulfur during catalyst exposure to SO{sub 2}, thereby helping to limit sulfation of the main (Ba) NO{sub x} storage phase and maintain NO{sub x} storage capacity. Temperature programmed desulfation experiments revealed that desulfation of a model ceria-containing catalyst occurred in two stages, corresponding to sulfur elimination from the ceria phase at {approx}450 C, followed by sulfur loss from the Ba phase at {approx}650 C. Significantly, the ceria-containing catalyst displayed relatively lower sulfur evolution from the Ba phase than its non-ceria analog, confirming that the presence of ceria lessened the degree of sulfur accumulation on the Ba phase.

  8. Iron site occupancies in magnetite-ulvospinel solid solution: A new approach using XMCD

    SciTech Connect

    Pearce, C. I.; Henderson, C. M. B.; Telling, N. D.; Pattrick, R. A.D.; Vaughan, D. J.; Charnock, J. M.; Arenholz, E.; Tuna, F.; Coker, V.S.; Laan, G. van der

    2009-06-22

    Ordering of Fe{sup 3+} and Fe{sup 2+} between octahedral (Oh) and tetrahedral (Td) sites in synthetic members of the magnetite (Fe{sub 3}O{sub 4}) - ulvoespinel (Fe{sub 2}TiO{sub 4}) solid-solution series was determined using Fe L{sub 2,3}-edge X-ray magnetic circular dichroism (XMCD) coupled with electron microprobe and chemical analysis, Ti L-edge spectroscopy, Fe K-edge EXAFS and XANES, Fe{sub 57} Moessbauer spectroscopy, and unit cell parameters. Microprobe analysis, cell edges and chemical FeO determinations showed that the bulk compositions of the samples were stoichiometric magnetite-ulvoespinel solid-solutions. Surface sensitive XMCD showed that the surfaces of these oxide minerals were more sensitive to redox conditions and some samples required re-equilibration with suitable solid-solid buffers. Detailed site-occupancy analysis of these samples gave XMCD-Fe{sup 2+}/Fe{sup 3+} ratios very close to stoichiometric values. L{sub 2,3}-edge spectroscopy showed that Ti{sup 4+} was restricted to Oh sites. XMCD results showed that significant Fe{sup 2+} only entered Td when the Ti content was > 0.40 apfu while Fe{sup 2+} in Oh increased from 1 a.p.f.u in magnetite to a maximum of {approx}1.4 apfu in USP45. As the Ti content increased from this point, the steady increase in Fe{sup 2+} in Td sites was clearly observable in the XMCD spectra, concurrent with a slow decrease in Fe{sup 2+} in Oh sites. Calculated magnetic moments showed a steady decrease from magnetite (4.06 {mu}{sub B}) to USP45 (1.5 {mu}{sub B}) and then a slower decrease towards the value for ulvoespinel (0 {mu}{sub B}). Two of the synthesized samples were also partially maghemitized by re-equilibrating with an oxidizing Ni-NiO buffer and XMCD showed that Fe{sup 2+} oxidation only occurred at Oh sites, with concomitant vacancy formation restricted to this site. This study shows the advantage of using XMCD as a direct measurement of Fe oxidation state in these complex magnetic spinels. These results

  9. Computer simulation of the motion of a straight dislocation line in concentrated solid solutions. II. [in fcc alloys

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

    An investigation was undertaken to determine if the size and modulus interaction of a solute atom with a screw dislocation and the modulus interaction with an edge dislocation contributed to strengthening, in addition to the size interaction with an edge dislocation. The results indicate that the size interaction between solute atom and an edge dislocation accounts for most of the solid solution strengthening in f.c.c. alloys. The contribution to the yield stress from the modulus interaction with an edge dislocation is less than 15%. The interaction between a solute atom and a screw dislocation is much less than that between a solute atom and an edge dislocation.

  10. Structural Modification of Nanocrystalline Ceria using Ion Beams

    SciTech Connect

    Zhang, Yanwen; Edmondson, Philip D; Varga, Tamas; Moll, Sandra; Namavar, Fereydoon; Weber, William J

    2011-01-01

    Exceptional size-dependent electronic-ionic conductivity of nanostructured ceria can significantly alter materials properties in chemical, physical, electronic and optical applications. Using energetic ions, we have demonstrated effective modification of interface volume and grain size in nanocrystalline ceria from a few nm up to ~ 25 nm, which is the critical region for controlling size-dependent material property. The unique self-healing response of radiation damage at grain boundaries is applied to control the grain size at nanoscale as a function of ion dose and irradiation temperature. Structural modification by energetic ions is proposed to achieve disirable electronic-ionic conductivity.

  11. Solid-state stability study of meropenem – solutions based on spectrophotometric analysis

    PubMed Central

    2013-01-01

    Background B-Lactam antibiotics are still the most common group of chemotherapeutic drugs that are used in the treatment of bacterial infections. However, due to their chemical instability the potential to apply them as oral pharmacotherapeutics is often limited and so it is vital to employ suitable non-destructive analytical methods. Hence, in order to analyze such labile drugs as β-lactam analogs, the application of rapid and reliable analytical techniques which do not require transferring to solutions or using organic solvents, following the current green approach to pharmaceutical analysis, is necessary. The main objective of the present research was to develop analytical methods for the evaluation of changes in meropenem in the solid state during a stability study. Results The UV, FT-IR and Raman spectra of meropenem were recorded during a solid-state stability study. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities were calculated according to the density-functional theory (DFT/B3LYP method) with a 6-31G(d,p) basis set. As the differences between the observed and scaled wavenumber values were small, a detailed interpretation of the FT-IR and Raman spectra was possible for non-degraded and degraded samples of meropenem. The problem of the overlapping spectra of meropenem and ring-containing degradation products was solved by measuring changes in the values of the first-derivative amplitudes of the zero-order spectra of aqueous solutions of meropenem. Also, molecular electrostatic potential (MEP), front molecular orbitals (FMOs) and the gap potential between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were determined. Conclusions Based on the findings of this work, it appears possible to use time-saving and reliable spectrophotometric analytical methods, supported by quantum-chemical calculations, for solid-state stability investigations of

  12. Comparative Pulmonary Toxicity of Two Ceria Nanoparticles with the Same Primary Size

    PubMed Central

    Peng, Lu; He, Xiao; Zhang, Peng; Zhang, Jing; Li, Yuanyuan; Zhang, Junzhe; Ma, Yuhui; Ding, Yayun; Wu, Zhenqiang; Chai, Zhifang; Zhang, Zhiyong

    2014-01-01

    Ceria nanoparticles (nano-ceria) have recently gained a wide range of applications, which might pose unwanted risks to both the environment and human health. The greatest potential for the environmental discharge of nano-ceria appears to be in their use as a diesel fuel additive. The present study was designed to explore the pulmonary toxicity of nano-ceria in mice after a single exposure via intratracheal instillation. Two types of nano-ceria with the same distribution of a primary size (3–5 nm), but different redox activity, were used: Ceria-p, synthesized by a precipitation route, and Ceria-h, synthesized by a hydrothermal route. Both Ceria-p and Ceria-h induced oxidative stress, inflammatory responses and cytotoxicity in mice, but their toxicological profiles were quite different. The mean size of Ceria-p agglomerates was much smaller compared to Ceria-h, thereby causing a more potent acute inflammation, due to their higher number concentration of agglomerates and higher deposition rate in the deep lung. Ceria-h had a higher reactivity to catalyzing the generation of reactive oxygen species (ROS), and caused two waves of lung injury: bronchoalveolar lavage (BAL) inflammation and cytotoxicity in the early stage and redox-activity-evoked lipid peroxidation and pro-inflammation in the latter stage. Therefore, the size distribution of ceria-containing agglomerates in the exhaust, as well as their surface chemistry are essential characteristics to assess the potential risks of using nano-ceria as a fuel additive. PMID:24727375

  13. Zirconium complexes with lactic acid in the solution and solid states

    NASA Astrophysics Data System (ADS)

    Demkowicz, Paul Andrew

    Lactic acid complexes of zirconium are used in a great number of industrial applications. Among these is their use as crosslinking agents for hydraulic fracturing fluids used in secondary oil recovery operations. Because of a poor understanding of zirconium lactate complex chemistry and crosslinking reactions, however, the design of superior fluid systems is often not guided by sound chemical principles and leads to empirical guesswork. Zirconium lactate solutions were characterized using Fourier transform infrared (FT-IR) spectroscopy, 1H, 13C, and 17O nuclear magnetic resonance (NMR) spectroscopy, and potentiometry. The results indicate that lactic acid is coordinated bidentate to zirconium via the alcohol and carboxylate groups. The average number of lactate ligands per zirconium ion is approximately 2 and is demonstrated to be relatively constant from pH 4--9. The lability of the lactate complexes increases as the pH is decreased. The NMR data reveal that there are both large and small complex molecules present in solution, with the size of the complex depending on the extent of zirconium hydrolysis. Large complexes consist of lactic acid coordinated to polynuclear zirconium hydroxy ions. The molecular size of these complexes is sufficient to hinder their tumbling in solution and cause broadening of the measured NMR signals. Small complexes involve lactic acid coordinated to hydroxylated species containing fewer zirconium ions, such that the rotational motion in solution is sufficiently rapid to result in narrow NMR signals. Zirconium lactate complexes were precipitated from solution and analyzed in the solid state using FT-IR spectroscopy, 13C magic angle spinning (MAS) NMR spectroscopy, elemental analysis, thermal gravitational analysis, and x-ray diffraction. Two distinct types of crystalline compounds were synthesized with four lactate ligands per zirconium ion. The coordination of lactic acid to zirconium is different in the two compounds, with one showing

  14. Phase diagram of PZT solid solutions near the morphotropic phase boundary from first principles

    NASA Astrophysics Data System (ADS)

    Kornev, I.; Bellaiche, L.; Janolin, P.-E.; Dkhil, B.; Suard, E.

    2007-03-01

    A first-principles-derived scheme, that incorporates ferroelectric and antiferrodistortive degrees of freedom, is developed to study finite-temperature properties of Pb(Zr1-xTix)O3 solid solutions near its morphotropic phase boundary [1]. The use of this numerical technique (i) resolves controversies about the monoclinic ground-state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points, that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions. [1] Igor A. Kornev, L. Bellaiche, P.-E. Janolin, B. Dkhil, and E. Suard, Phys. Rev. Lett. 97, 157601 (2006) This work is supported by ONR grants N00014-04-1-0413, N00014-01-1-0600 and N00014-01-1-0365, by NSF grant DMR- 0404335, and by DOE grant DE-FG02-05ER46188.

  15. Solution-based carbohydrate synthesis of individual solid, hollow, and porous carbon nanospheres using spray pyrolysis.

    PubMed

    Wang, Chengwei; Wang, Yuan; Graser, Jake; Zhao, Ran; Gao, Fei; O'Connell, Michael J

    2013-12-23

    A facile and scalable solution-based, spray pyrolysis synthesis technique was used to synthesize individual carbon nanospheres with specific surface area (SSA) up to 1106 m(2)/g using a novel metal-salt catalyzed reaction. The carbon nanosphere diameters were tunable from 10 nm to several micrometers by varying the precursor concentrations. Solid, hollow, and porous carbon nanospheres were achieved by simply varying the ratio of catalyst and carbon source without using any templates. These hollow carbon nanospheres showed adsorption of to 300 mg of dye per gram of carbon, which is more than 15 times higher than that observed for conventional carbon black particles. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed, with no capacitance loss after 20,000 cycles. PMID:24274705

  16. Compression behavior of quaternary and higher order solid-solution L1(2) trialuminides

    NASA Technical Reports Server (NTRS)

    Kumar, K. S.; Brown, S. A.

    1992-01-01

    Results from preliminary studies undertaken to evaluate the existence of single-phase L1(2) solid solutions between pairs of ternary L1(2) trialuminides are presented. Two-kilogram ingots of selected quaternary compositions were cast, homogenized and forged into pancakes; compression specimens were machined from the forgings and tested as a function of temperature. The results are compared against existing data for the ternary alloys. The ternary L1(2) trialuminides Al66Ti25Mn9, Al67Ti25Cr8, and Al22Ti8Fe3 were found to exhibit continuous solubility in one another. The quaternary Cr-Mn composition does not indicate any strength advantage over its ternary counterparts. The continuous replacement of Mn with Fe enhances the strength of the quaternary compound over the ternary Al66Ti25 Mn9.

  17. Theoretical study on phase coexistence in ferroelectric solid solutions near the tricritical point

    SciTech Connect

    Lu, Xiaoyan E-mail: dzk@psu.edu; Li, Hui; Zheng, Limei; Cao, Wenwu

    2015-04-07

    Phase coexistence in ferroelectric solid solutions near the tricritical point has been theoretically analyzed by using the Landau-Devonshire theory. Results revealed that different phases having similar potential wells could coexist in a narrow composition range near the tricritical point in the classical Pb(Zr{sub 1−x}Ti{sub x})O{sub 3} system. The potential barrier between potential wells increases with the decrease of temperature. Coexisting phases or different domains of the same phase can produce adaptive strains to maintain atomic coherency at the interfaces or domain walls. Such compatibility strains have influence on the energy potential as well as the stability of relative phases, leading to the appearance of energetically unfavorable monoclinic phases. Those competing and coexisting phases also construct an easy phase transition path with small energy barrier in between, so that very small stimuli can produce large response in compositions near the morphotropic phase boundary, especially near the tricritical point.

  18. Analysis of electrostatic stability and ordering in quaternary perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Caetano, Clovis; Butler, Keith T.; Walsh, Aron

    2016-04-01

    There are three distinct classes of perovskite structured metal oxides, defined by the charge states of the cations: AIBVO3,AIIBIVO3 , and AIIIBIIIO3 . We investigated the stability of cubic quaternary solid solutions A B O3-A'B'O3 using a model of point-charge lattices. The mixing enthalpies were calculated and compared for the three possible types of combinations of the compounds, both for the random alloys and the ground-state-ordered configurations. The mixing enthalpy of the (I,V)O3-(III,III)O3 alloy is always larger than the other alloys. We found that, different from homovalent alloys, for these heterovalent alloys a lattice constant mismatch between the constituent compounds could contribute to stabilize the alloy. At low temperatures, the alloys present a tendency to spontaneous ordering, forming superlattices consisting of alternated layers of AB O 3 and A'B'O3 along the [110 ] direction.

  19. Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

    DOEpatents

    Anderson, I.E.; Lograsso, B.K.; Ellis, T.W.

    1994-11-29

    A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material. 9 figures.

  20. Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state.

    PubMed

    Silver, Mark A; Cary, Samantha K; Johnson, Jason A; Baumbach, Ryan E; Arico, Alexandra A; Luckey, Morgan; Urban, Matthew; Wang, Jamie C; Polinski, Matthew J; Chemey, Alexander; Liu, Guokui; Chen, Kuan-Wen; Van Cleve, Shelley M; Marsh, Matthew L; Eaton, Teresa M; van de Burgt, Lambertus J; Gray, Ashley L; Hobart, David E; Hanson, Kenneth; Maron, Laurent; Gendron, Frédéric; Autschbach, Jochen; Speldrich, Manfred; Kögerler, Paul; Yang, Ping; Braley, Jenifer; Albrecht-Schmitt, Thomas E

    2016-08-26

    Berkelium is positioned at a crucial location in the actinide series between the inherently stable half-filled 5f(7) configuration of curium and the abrupt transition in chemical behavior created by the onset of a metastable divalent state that starts at californium. However, the mere 320-day half-life of berkelium's only available isotope, (249)Bk, has hindered in-depth studies of the element's coordination chemistry. Herein, we report the synthesis and detailed solid-state and solution-phase characterization of a berkelium coordination complex, Bk(III)tris(dipicolinate), as well as a chemically distinct Bk(III) borate material for comparison. We demonstrate that berkelium's complexation is analogous to that of californium. However, from a range of spectroscopic techniques and quantum mechanical calculations, it is clear that spin-orbit coupling contributes significantly to berkelium's multiconfigurational ground state. PMID:27563098

  1. Magnetic properties of Ho1- x Lu x B12 solid solutions

    NASA Astrophysics Data System (ADS)

    Gabáni, S.; Gaz̆o, E.; Pristás̆, G.; Takác̆ová, I.; Flachbart, K.; Shitsevalova, N.; Siemensmeyer, K.; Sluchanko, N.

    2013-05-01

    Magnetic properties of the geometrically frustrated antiferromagnet HoB12 (with T N = 7.4 K) modified by substitution of magnetic Ho atoms through non-magnetic Lu ones are presented and discussed. In this case, in Ho1- x Lu x B12 solid solutions, both chemical pressure resulting from different Lu3+ and Ho3+ radii and magnetic dilution take place with increasing Lu content ( x) that change properties of the system. The received results show strong indication for the existence of a quantum critical point near x = 0.9, which separates the region of magnetic order (starting with HoB12 for x = 0) and the nonmagnetic region (ending with superconducting LuB12 for x = 1).

  2. Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

    SciTech Connect

    Anderson, Iver E.; Lograsso, Barbara K.; Ellis, Timothy W.

    1994-01-01

    A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material.

  3. Properties of solid solutions based on LaMnO{sub 3}

    SciTech Connect

    Naumovich, E.N.; Kharton, V.V.; Vecher, A.A.; Nikolaev, A.V.; Bugoffa, A.A.A.

    1995-12-31

    The purpose of the present work was to investigate the cathode and sintering agent materials for application to SOFC. Recently, the authors have focused their researchers on the development of low cost technologies of SOFC fabrication. In the present work, the authors used the easily available technique of electrode layers preparation by baking of pastes containing cathode materials and sintering agents. The data on crystal structure, electrical conductivity, thermal expansion and oxygen semipermeability of the perovskite-like solid solutions La{sub x}Sr{sub y}MnO{sub 3} (x = 0.3--0.6; y = 0.3--0.5), La{sub 1{minus}x}Pb{sub x}MnO{sub 3} (x = 0--0.5) and La{sub 0.6}Sr{sub 0.4}Mn{sub 1{minus}x}Ni{sub x}O{sub 3} (x = 0--0.5) are presented.

  4. Variable valence of praseodymium in rare-earth oxide solid solutions

    SciTech Connect

    Kravchinskaya, M.V.; Merezhinskii, K.Y.; Tikhonov, P.A.

    1986-06-01

    Solid solutions of elevated praseodymium oxide content have interesting electrical properties, making them the basis for the manufacture of high-temperature electrically conducting materials. Establishment of the composition-structure-valence state relationships enables control of the material properties. The authors performed investigations using a thermogravimetric apparatus with an electronic microbalance of type EM-5-3M, and using x-ray phase analysis of powders (DRON-1 diffractometer, CuK /SUB alpha/ -radiation). The authors also studied the kinetics of praseodymium oxidation with a thermogravimetric apparatus under isothermal conditions. Evaluation of the results with the equation of Kolmogorov, Erofeev, and Avraam indicates that the process is limited by the chemical oxidation of praseodymium and not by diffusion.

  5. Solid solution barium-strontium chlorides with tunable ammonia desorption properties and superior storage capacity

    NASA Astrophysics Data System (ADS)

    Bialy, Agata; Jensen, Peter B.; Blanchard, Didier; Vegge, Tejs; Quaade, Ulrich J.

    2015-01-01

    Metal halide ammines are very attractive materials for ammonia absorption and storage-applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35-50% barium and 65-50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia.

  6. Strength, thermal defects, and solid solution hardening in nickel-containing B2 iron aluminides

    SciTech Connect

    Schneibel, J.H.; Munroe, P.R.; Pike, L.M.

    1996-12-31

    Nickel-containing ternary iron aluminides with an aluminum concentration of 45 at.% were investigated with respect to room temperature strength, equilibrium vacancy concentration, and the kinetics of vacancy removal. As compared to binary iron aluminides with the same Al concentration, nickel additions reduce the thermal equilibrium vacancy concentration at 1,273 K, whereas they increase this concentration at 973 K. Furthermore, at low temperatures such as 673 K, nickel additions increase dramatically the time needed to reach vacancy equilibrium. During prolonged annealing at 673 K, the density of <001> dislocations in Fe-45Al-3Ni (at.%) increased by an order of magnitude. This suggests that dislocations act as sinks for vacancies. At the same time, the number density of small (20--50 nm) voids decreased, indicating that they were not stable in the absence of substantial vacancy supersaturations. The findings show also that the solid solution strengthening of iron aluminides due to Ni is much weaker than previously thought.

  7. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    NASA Astrophysics Data System (ADS)

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-07-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica.

  8. Temperature dependence of the activity of Al in dilute Ni(Al) solid solutions

    SciTech Connect

    Jiang Yong; Smith, J. R.; Evans, A. G.

    2006-12-01

    Activities of dilute Al solid solutions in Ni are determined from a first-principles approach. Both thermal lattice vibration and electronic contributions to free energies are considered and compared. Vibrational contributions tend to dominate the temperature dependencies of the free energies, though electron thermal effects are significant. Calculations show opposing temperature trends for the formation enthalpies and entropies, leading to a partial cancellation of their role in the overall energetics. Nevertheless, their remaining temperature effects are strong. Over the temperature range, 400 K

  9. Surface properties of semiconductor analogs of CdBVI and their solid substitution solutions

    NASA Astrophysics Data System (ADS)

    Kirovskaya, I. A.; Nor, P. E.; Bukashkina, T. L.; Mironova, E. V.

    2016-03-01

    The physicochemical (acidic-basic, adsorption, and electrophysical) surface properties of binary semiconductor analogs of CdBVI (CdTe, CdSe, and CdS), and (CdTe) x (CdSe)1- x , and (CdTe) x (CdS)1- x solid substitution solutions were studied using modern methods and equipment. The nature of the active centers and the mechanisms of acidic-basic, adsorption (involving CO), and electronic interactions, interrelated tendencies in variation of the surface properties under study, and their correlations with the known bulk physicochemical properties were elucidated; the property-composition diagrams were constructed, which were used to reveal the most active adsorbents suggested for use as materials for CO (carbon monoxide) microimpurity sensors.

  10. SOLIEX: A Novel Solid-Liquid Method of Radionuclides Extraction from Radioactive Waste Solutions - 13486

    SciTech Connect

    Shilova, E.; Viel, P.; Huc, V.

    2013-07-01

    This paper describes recent developments in new solid-liquid extraction method, called SOLIEX, to remove cesium from alkaline solutions. SOLIEX relies on the use of a reversible complexing system comprising a carbon felt bearing molecular traps (calixarenes). This complexing system exhibits a high selectivity for Cs, and is thus expected to be helpful for the treatment of highly diluted cesium wastes even with a high concentration of competing alkali metal cations. As additional advantage, this complexing system can be adapted by molecular engineering to capture other radionuclides, such as Sr, Eu, Am. Finally, this complexing system can be easily and efficiently regenerated by using a cost effective stripping procedure, which limits further generation of waste to meet 'zero liquid' discharge requirements for nuclear facilities. (authors)

  11. Covalent binding of biological samples to solid supports for scanning probe microscopy in buffer solution.

    PubMed Central

    Karrasch, S; Dolder, M; Schabert, F; Ramsden, J; Engel, A

    1993-01-01

    Scanning force microscopy allows imaging of biological molecules in their native state in buffer solution. To this end samples have to be fixed to a flat solid support so that they cannot be displaced by the scanning tip. Here we describe a method to achieve the covalent binding of biological samples to glass surfaces. Coverslips were chemically modified with the photoactivatable cross-linker N-5-azido-2-nitrobenzoyloxysuccinimide. Samples are squeezed between derivatized coverslips and then cross-linked to the glass surface by irradiation with ultraviolet light. Such samples can be imaged repeatedly by the scanning force microscope without loss of image quality, whereas identical but not immobilized samples are pushed away by the stylus. Images FIGURE 4 FIGURE 5 FIGURE 6 FIGURE 7 FIGURE 8 PMID:8312482

  12. Development of anion-conducting ionomer binder solutions for electrodes of solid alkaline fuel cells.

    PubMed

    Shin, Mun-Sik; Kang, Moon-Sung; Park, Jin-Soo

    2014-10-01

    For solid alkaline fuel cell applications, membrane-electrode assemblies (MEAs) should be prepared. Thus, in this study, anion-conducting ionomer binder was prepared for electrodes of MEAs. Specifically, we synthesized water soluble anionic binder solutions based on quaternized chitosan derivatives (QCDs) and cross-linked QCDs and prepared a novel electrode. The electrochemical and physicochemical properties of ionomer binder and electrode were investigated by FT-IR, NMR and ionic conductivity. The ionic conductivity of these cross-linked QCDs was 9.7 x 10(-3) S cm(-1) in deionized water at room temperature. The membrane electrode assemblies (MEAs) were prepared by a spray method and were investigated in terms of cyclic voltammetry, impedance and fuel cell performance. The MEA with the 35 wt% QCD ionomer showed the highest performance and confirmed the successful formation of ionomer binder at the electrode of the MEA by the on-site crosslinking reaction. PMID:25942868

  13. Analysis of lasers as a solution to efficiency droop in solid-state lighting

    DOE PAGESBeta

    Chow, Weng W.; Crawford, Mary H.

    2015-10-06

    This letter analyzes the proposal to mitigate the efficiency droop in solid-state light emitters by replacing InGaN light-emitting diodes (LEDs) with lasers. The argument in favor of this approach is that carrier-population clamping after the onset of lasing limits carrier loss to that at threshold, while stimulated emission continues to grow with injection current. A fully quantized (carriers and light) theory that is applicable to LEDs and lasers (above and below threshold) is used to obtain a quantitative evaluation. The results confirm the potential advantage of higher laser output power and efficiency above lasing threshold, while also indicating disadvantages includingmore » low efficiency prior to lasing onset, sensitivity of lasing threshold to temperature, and the effects of catastrophic laser failure. As a result, a solution to some of these concerns is suggested that takes advantage of recent developments in nanolasers.« less

  14. Analysis of lasers as a solution to efficiency droop in solid-state lighting

    SciTech Connect

    Chow, Weng W.; Crawford, Mary H.

    2015-10-06

    This letter analyzes the proposal to mitigate the efficiency droop in solid-state light emitters by replacing InGaN light-emitting diodes (LEDs) with lasers. The argument in favor of this approach is that carrier-population clamping after the onset of lasing limits carrier loss to that at threshold, while stimulated emission continues to grow with injection current. A fully quantized (carriers and light) theory that is applicable to LEDs and lasers (above and below threshold) is used to obtain a quantitative evaluation. The results confirm the potential advantage of higher laser output power and efficiency above lasing threshold, while also indicating disadvantages including low efficiency prior to lasing onset, sensitivity of lasing threshold to temperature, and the effects of catastrophic laser failure. As a result, a solution to some of these concerns is suggested that takes advantage of recent developments in nanolasers.

  15. Localized surface plasmon resonances after selective oxidization of AuCu solid solution nanocrystalline films

    NASA Astrophysics Data System (ADS)

    Sousanis, A.; Grammatikopoulos, S.; Delimitis, A.; Dracopoulos, V.; Poulopoulos, P.

    2015-07-01

    AuxCu100-x, 4 ≤ x ≤ 12 at.%, solid solution nanocrystalline films with thickness between 1.5 and 100 nm were grown on Si(100) and Corning glass substrates at room temperature by radio frequency magnetron sputtering. After post annealing at 430 °C in a furnace with air, phase separation occurred between CuO and Au. The Au nanoparticles showed intense localized surface plasmon resonances with an amplitude increasing with Au concentration. We show the evolution of these resonances with the annealing time and correlate the structure to optical properties. The controllable tuning of position and intensity of plasmon resonances render this system a good candidate for applications.

  16. Solution- and solid-state NMR studies of GPCRs and their ligands.

    PubMed

    Tapaneeyakorn, Satita; Goddard, Alan D; Oates, Joanne; Willis, Christine L; Watts, Anthony

    2011-06-01

    G protein-coupled receptors (GPCRs) represent one of the major targets of new drugs on the market given their roles as key membrane receptors in many cellular signalling pathways. Structure-based drug design has potential to be the most reliable method for novel drug discovery. Unfortunately, GPCR-ligand crystallisation for X-ray diffraction studies is very difficult to achieve. However, solution- and solid-state NMR approaches have been developed and have provided new insights, particularly focussing on the study of protein-ligand interactions which are vital for drug discovery. This review provides an introduction for new investigators of GPCRs/ligand interactions using NMR spectroscopy. The guidelines for choosing a system for efficient isotope labelling of GPCRs and their ligands for NMR studies will be presented, along with an overview of the different sample environments suitable for generation of high resolution structural information from NMR spectra. PMID:20951674

  17. Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

    NASA Astrophysics Data System (ADS)

    Menendez-Mora, Christian L.

    High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus

  18. Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

    USGS Publications Warehouse

    Busenberg, Eurybiades; Plummer, L. Niel

    1989-01-01

    The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and

  19. Flow-Solution-Liquid-Solid Growth of Semiconductor Nanowires: A Novel Approach for Controlled Synthesis

    SciTech Connect

    Hollingsworth, Jennifer A.; Palaniappan, Kumaranand; Laocharoensuk, Rawiwan; Smith, Nickolaus A.; Dickerson, Robert M.; Casson, Joanna L.; Baldwin, Jon K.

    2012-06-07

    Semiconductor nanowires (SC-NWs) have potential applications in diverse technologies from nanoelectronics and photonics to energy harvesting and storage due to their quantum-confined opto-electronic properties coupled with their highly anisotropic shape. Here, we explore new approaches to an important solution-based growth method known as solution-liquid-solid (SLS) growth. In SLS, molecular precursors are reacted in the presence of low-melting metal nanoparticles that serve as molten fluxes to catalyze the growth of the SC-NWs. The mechanism of growth is assumed to be similar to that of vapor-liquid-solid (VLS) growth, with the clear distinctions of being conducted in solution in the presence of coordinating ligands and at relatively lower temperatures (<300 C). The resultant SC-NWs are soluble in common organic solvents and solution processable, offering advantages such as simplified processing, scale-up, ultra-small diameters for quantum-confinement effects, and flexible choice of materials from group III-V to groups II-VI, IV-VI, as well as truly ternary I-III-VI semiconductors as we recently demonstrates. Despite these advantages of SLS growth, VLS offers several clear opportunities not allowed by conventional SLS. Namely, VLS allows sequential addition of precursors for facile synthesis of complex axial heterostructures. In addition, growth proceeds relatively slowly compared to SLS, allowing clear assessments of growth kinetics. In order to retain the materials and processing flexibility afforded by SLS, but add the elements of controlled growth afforded by VLS, we transformed SLS into a flow based method by adapting it to synthesis in a microfluidic system. By this new method - so-called 'flow-SLS' (FSLS) - we have now demonstrated unprecedented fabrication of multi-segmented SC-NWs, e.g., 8-segmented CdSe/ZnSe defined by either compositionally abrupt or alloyed interfaces as a function of growth conditions. In addition, we have studied growth rates as a

  20. Investigating the effect of compression on solute transport through degrading municipal solid waste

    SciTech Connect

    Woodman, N.D. Rees-White, T.C.; Stringfellow, A.M.; Beaven, R.P.; Hudson, A.P.

    2014-11-15

    Highlights: • The influence of compression on MSW flushing was evaluated using 13 tracer tests. • Compression has little effect on solute diffusion times in MSW. • Lithium tracer was conservative in non-degrading waste but not in degrading waste. • Bromide tracer was conservative, but deuterium was not. - Abstract: The effect of applied compression on the nature of liquid flow and hence the movement of contaminants within municipal solid waste was examined by means of thirteen tracer tests conducted on five separate waste samples. The conservative nature of bromide, lithium and deuterium tracers was evaluated and linked to the presence of degradation in the sample. Lithium and deuterium tracers were non-conservative in the presence of degradation, whereas the bromide remained effectively conservative under all conditions. Solute diffusion times into and out of less mobile blocks of waste were compared for each test under the assumption of dominantly dual-porosity flow. Despite the fact that hydraulic conductivity changed strongly with applied stress, the block diffusion times were found to be much less sensitive to compression. A simple conceptual model, whereby flow is dominated by sub-parallel low permeability obstructions which define predominantly horizontally aligned less mobile zones, is able to explain this result. Compression tends to narrow the gap between the obstructions, but not significantly alter the horizontal length scale. Irrespective of knowledge of the true flow pattern, these results show that simple models of solute flushing from landfill which do not include depth dependent changes in solute transport parameters are justified.

  1. Reactive transport in a partially molten system with binary solid solution

    NASA Astrophysics Data System (ADS)

    Jordan, Jacob S.; Hesse, Marc A.

    2015-12-01

    Melt extraction from the Earth's mantle through high-porosity channels is required to explain the composition of the oceanic crust. Feedbacks from reactive melt transport are thought to localize melt into a network of high-porosity channels. Recent studies invoke lithological heterogeneities in the Earth's mantle to seed the localization of partial melts. Therefore, it is necessary to understand the reaction fronts that form as melt flows across the lithological interface between the heterogeneity and the ambient mantle. Here we present a chromatographic analysis of reactive melt transport across lithological boundaries, using the theory of hyperbolic conservation laws. This is an extension of linear trace element chromatography to the coupling of major elements and energy transport. Our analysis allows the prediction of the nonlinear feedbacks that arise in reactive melt transport due to changes in porosity. This study considers the special case of a partially molten porous medium with binary solid solution. As melt traverses a lithological contact, binary solid solution leads to the formation of a reacted zone between an advancing reaction front and the initial contact. The analysis also shows that the behavior of a fertile heterogeneity depends on its absolute concentration, in addition to compositional differences between itself and the refractory background. We present a regime diagram that predicts if melt emanating from a fertile heterogeneity localizes into high-porosity channels or develops a zero porosity shell. The theoretical framework presented here provides a useful tool for understanding nonlinear feedbacks in reactive melt transport, because it can be extended to more complex and realistic phase behaviors.

  2. Detection of nitroaromatics in the solid, solution, and vapor phases using silicon quantum dot sensors.

    PubMed

    Nguyen, An; Gonzalez, Christina M; Sinelnikov, Regina; Newman, W; Sun, Sarah; Lockwood, Ross; Veinot, Jonathan G C; Meldrum, Al

    2016-03-11

    Silicon quantum dots (Si-QDs) represent a well-known QD fluorophore that can emit throughout the visible spectrum depending on the interface structure and surface functional group. Detection of nitroaromatic compounds by monitoring the luminescence response of the sensor material (typically fluorescent polymers) currently forms the basis of new explosives sensing technologies. Freestanding silicon QDs may represent a benign alternative with a high degree of chemical and physical versatility. Here, we investigate dodecyl and amine-terminated Si-QD luminescence response to the presence of nitrobenzene and dinitrotoluene (DNT) in various solid, solution, and vapor forms. For dinitrotoluene vapor the 3σ detection limit was 6 ppb for monomer-terminated QDs. For nitroaromatics dissolved in toluene the detection limit was on the order of 400 nM, corresponding to ∼100 pg of material distributed over ∼1 cm(2) on the sensor surface. Solid traces of nitroaromatics were also easily detectable via a simple 'touch test'. The samples showed minimal interference effects from common contaminants such as water, ethanol, and acetonitrile. The sensor can be as simple and inexpensive as a small circle of filter paper dipped into a QD solution, with a single vial of QDs able to make hundreds of these sensors. Additionally, a trial fiber-optic sensor device was tested by applying the QDs to one end of a 2 × 2 fiber coupler and exposing them to controlled DNT vapor. Finally, the quenching mechanism was explored via luminescence dynamics measurements and is different for blue (amine) and red (dodecyl) fluorescent silicon QDs. PMID:26863492

  3. Detection of nitroaromatics in the solid, solution, and vapor phases using silicon quantum dot sensors

    NASA Astrophysics Data System (ADS)

    Nguyen, An; Gonzalez, Christina M.; Sinelnikov, Regina; Newman, W.; Sun, Sarah; Lockwood, Ross; Veinot, Jonathan G. C.; Meldrum, Al

    2016-03-01

    Silicon quantum dots (Si-QDs) represent a well-known QD fluorophore that can emit throughout the visible spectrum depending on the interface structure and surface functional group. Detection of nitroaromatic compounds by monitoring the luminescence response of the sensor material (typically fluorescent polymers) currently forms the basis of new explosives sensing technologies. Freestanding silicon QDs may represent a benign alternative with a high degree of chemical and physical versatility. Here, we investigate dodecyl and amine-terminated Si-QD luminescence response to the presence of nitrobenzene and dinitrotoluene (DNT) in various solid, solution, and vapor forms. For dinitrotoluene vapor the 3σ detection limit was 6 ppb for monomer-terminated QDs. For nitroaromatics dissolved in toluene the detection limit was on the order of 400 nM, corresponding to ∼100 pg of material distributed over ∼1 cm2 on the sensor surface. Solid traces of nitroaromatics were also easily detectable via a simple ‘touch test’. The samples showed minimal interference effects from common contaminants such as water, ethanol, and acetonitrile. The sensor can be as simple and inexpensive as a small circle of filter paper dipped into a QD solution, with a single vial of QDs able to make hundreds of these sensors. Additionally, a trial fiber-optic sensor device was tested by applying the QDs to one end of a 2 × 2 fiber coupler and exposing them to controlled DNT vapor. Finally, the quenching mechanism was explored via luminescence dynamics measurements and is different for blue (amine) and red (dodecyl) fluorescent silicon QDs.

  4. Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

    SciTech Connect

    Bialy, Agata; Blanchard, Didier; Vegge, Tejs; Quaade, Ulrich J.

    2015-01-15

    Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia. - Graphical abstract: Thermal desorption curves of ammonia from Ba{sub x}Sr{sub (1−x)}Cl{sub 2} mixtures with x equal to 0.125, 0.25 and 0.5 and atomic structure of Sr(NH{sub 3}){sub 8}Cl{sub 2}. - Highlights: • Solid solutions of strontium and barium chloride were synthesized by spray drying. • Adjusting molar ratios led to different crystallographic phases and compositions. • Different molar ratios led to different ammonia ab-/desorption properties. • 35–50 mol% BaCl{sub 2} in SrCl{sub 2} yields higher ammonia density than any other metal halide. • DFT calculations can be used to predict properties of the mixtures.

  5. Insights into Analogue Perovskite Solid Solutions from High-Resolution Neutron Powder Diffraction

    NASA Astrophysics Data System (ADS)

    Redfern, S. A.; Chaddock, E. H.; Becerro, A. I.

    2002-12-01

    Neutron powder diffraction provides a powerful tool for the study of phase transitions as a function of pressure, temperature, or chemical composition. The structural information obtainable from powders using diffractometers such as HRPD (ISIS, UK) or D2B (ILL, France) rivals, and in some respects exceeds what may be possible using conventional crystallographic techniques reliant on single crystals. We have used both instruments to explore the subtle phase transitions observed in the (CaxSr1-x)TiO3 and (SrxBa1-x)SnO3 solid solutions. We have also used low resolution high flux instruments to explore the thermal dependence of the superlattice behavior below the cubic to tetragonal phase transition in (CaxSr1-x)TiO3. In each case a sequence of phase transitions from Pm-3m through I4/mcm to Pbnm is seen as a function of composition, and is driven by the change in average radius of the B-cation. This sequence of transitions is the same as expected for a magnesium silicate perovskite structure on increasing temperature. It is now recognised that lower mantle perovskite is likely aluminous, with solid solution towards either a stoichiometric or oxygen-defect end-member. The analogue systems we have characterised have been doped with trivalent cations on the B site to explore the effect of such substitution on the sequence of phase transitions. High-temperature neutron diffraction shows that oxygen defects stabilize the higher symmetry structures, lowering Tc for the transition to cubic. New developments in high-T high-P neutron diffraction techniques will allow the extension of these ambient pressure studies to the investigation of the influence of pressure as a variable, and hence the extension of such analogue studies to the whole range of variables experienced in the lower mantle. These will be briefly outlined.

  6. Nanocrystalline Ce1- x La x O2- δ Solid Solutions Synthesized by Hydrolyzing and Oxidizing

    NASA Astrophysics Data System (ADS)

    Hou, Xueling; Xue, Yun; Han, Ning; Lu, Qianqian; Wang, Xiaochen; Phan, Manh-Huong; Zhong, Yunbo

    2016-05-01

    We undertook a novel batch production approach for the synthesis of CeO2 nanopowders doped with rare earth elements. Solid solution nanopowders of Ce1- x La x O2- δ ( x = 0.15) were successfully synthesized in a large-scale and low-cost production by hydrolyzing and oxidizing Ce-La-C alloys at room temperature and subsequent calcining of their powders at different temperatures (873-1073 K) for 1 h. The Ce-La-C alloys were prepared in a vacuum induction melting furnace. The final products were characterized by x-ray diffraction, transmission electron microscopy, Brunner-Emmet-Teller (BET) surface area analyzer, and Raman spectroscopy. The calculated lattice parameters of the cubic fluorite-type phase of CeO2 tended to increase when La3+ was incorporated into CeO2. The F 2g band shift and the absence of a peak corresponding to La2O3 in the Raman spectra consistently confirmed the incorporation of the La3+ ion into CeO2, and the formation of Ce1- x La x O2- δ solid solutions as manifested by increased oxygen vacancy defects. High-quality Ce1- x La x O2- δ nanopowders of ~10-15 nm diameter with a high BET surface area of ~77 m2 g-1 were obtained. The average crystallite size of Ce1- x La x O2- δ was found to be smaller than that of CeO2 for the same calcination temperature of 1073 K, demonstrating that the introduction of La3+ into CeO2 can stabilize the host lattice and refine the grain size at high temperatures.

  7. Iron-ceria Aerogels Doped with Palladium as Water-gas Shift Catalysts for the Production of Hydrogen

    SciTech Connect

    Bali, S.; Huggins, F; Ernst, R; Pugmire, R; Huffman, G; Eyring, E

    2010-01-01

    Mixed 4.5% iron oxide-95.5% cerium oxide aerogels doped with 1% and 2% palladium (Pd) by weight have been synthesized, and their activities for the catalysis of water-gas shift (WGS) reaction have been determined. The aerogels were synthesized using propylene oxide as the proton scavenger for the initiation of hydrolysis and polycondensation of a homogeneous alcoholic solution of cerium(III) chloride heptahydrate and iron(III) chloride hexahydrate precursor. Palladium was doped onto some of these materials by gas-phase incorporation (GPI) using ({eta}{sup 3}-allyl)({eta}{sup 5}-cyclopentadienyl)palladium as the volatile Pd precursor. Water-gas shift catalytic activities were evaluated in a six-channel fixed-bed reactor at atmospheric pressure and reaction temperatures ranging from 150 to 350 C. Both 1% and 2% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels showed WGS activities that increased significantly from 150 to 350 C. The activities of 1% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels were also compared with that of the 1% Pd-doped ceria aerogel without iron. The WGS activity of 1% Pd on 4.5% iron oxide-95.5% cerium oxide aerogels is substantially higher (5 times) than the activity of 1% Pd-doped ceria aerogel without iron. The gas-phase incorporation results in a better Pd dispersion. Ceria aerogel provides a nonrigid structure wherein iron is not significantly incorporated inside the matrix, thereby resulting in better contact between the Fe and Pd and thus enhancing the WGS activity. Further, neither Fe nor Pd is reduced during the ceria-aerogel-catalyzed WGS reaction. This behavior contrasts with that noted for other Fe-based WGS catalysts, in which the original ferric oxide is typically reduced to a nonstoichiometric magnetite form.

  8. Photosensitizer-Loaded Branched Polyethylenimine-PEGylated Ceria Nanoparticles for Imaging-Guided Synchronous Photochemotherapy.

    PubMed

    Yang, Zhang-You; Li, Hong; Zeng, Yi-Ping; Hao, Yu-Hui; Liu, Cong; Liu, Jing; Wang, Wei-Dong; Li, Rong

    2015-11-01

    A multifunctional theranostic platform based on photosensitizer (chlorin e6, Ce6)-loaded branched polyethylenimine-PEGylated ceria nanoparticles (PPCNPs-Ce6) was created for the development of effective cancer treatments involving the use of imaging-guided synchronous photochemotherapy. PPCNPs-Ce6 with high Ce6 photosensitizer loading (Ce6: cerium ∼40 wt %) significantly enhanced the delivery of Ce6 into cells and its accumulation in lysosomes, remarkably improving photodynamic therapeutic (PDT) efficacy levels compared to those in the administration of free Ce6 at ultralow drug doses (∼200 nM). Interestingly, PPCNPs-Ce6 efficiently induced HeLa cell death even at low concentrations (∼10 μM) without the use of laser irradiation and exhibit chemocytotoxicity. Inductively coupled plasma mass spectrometry (ICP-MS) and biology transmission electron microscopy (Bio-TEM) analyses demonstrated that ceria nanoparticles enter cells abundantly and accumulate in lysosomes or large vesicles. We then evaluated the effects of the different materials on lysosomal integrity and function, which revealed that PPCNPs-Ce6 catastrophically impaired lysosomal function compared to results with PPCNPs and Ce6. Studies of apoptosis revealed greater induction of apoptosis by PPCNPs-Ce6 treatment. This multifunctional nanocarrier also exhibited a high degree of solubility and stability in aqueous solutions, suggesting its applicability for extensive biomedical application. PMID:26485120

  9. Insight into microstructural development by XBroad program: Case of in-situ formation of the Al-Zn solid solution

    NASA Astrophysics Data System (ADS)

    Skoko, Željko; Popović, Jasminka; Dekanić, Krešimir

    2015-05-01

    Formation of the Al-15 at% Zn solid solution was followed by in-situ high-temperature X-ray powder diffraction (XRPD) measurements. It was found that the temperature of 200 °C marked an onset of the dissolution of Zn atoms in Al matrix, while the solid solution was formed at 300 °C. Change in the shape of Zn precipitates during the solid solution formation was analyzed by the XBroad program. The program provides adequate information about changes in size and/or transformation of shapes during different crystallization/dissolution processes without any prior information on structural features of the system under study. It was demonstrated that the XBroad program is an excellent tool for the quick and effective microstructural analysis easily used by material science community regardless of their background in the field of crystallography.

  10. Mechanical properties of (Bi,Sb)2Te3 solid solutions obtained by directional crystallization and spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Lavrent'ev, M. G.; Osvenskii, V. B.; Pivovarov, G. I.; Sorokin, A. I.; Bulat, L. P.; Bublik, V. T.; Tabachkova, N. Yu.

    2016-01-01

    We have studied the temperature dependence of the mechanical strength at uniaxial compression for solid solutions based on bismuth and antimony chalcogenides, which were prepared by three methods: (i) vertical zone melting (VZM), (ii) hot extrusion, and (iii) spark plasma sintering (SPS). In the samples of solid solutions obtained by VZM and extrusion, a brittle-ductile transition was observed in a wised temperature interval of 200-350°C. In nanostructured SPS samples, transition from brittle to plastic fracture was observed within 170-200°C. The room-temperature strength of nanostructured samples was eight to nine times as large as that of VZM samples, and the stress-strain curves of these materials were significantly different. At a temperature of about 300°C, the strength of nanostructured solid solutions decreases to nearly zero.

  11. Understanding the solution phase chemistry and solid state thermodynamic behavior of pharmaceutical cocrystals

    NASA Astrophysics Data System (ADS)

    Maheshwari, Chinmay

    Cocrystals have drawn a lot of research interest in the last decade due to their potential to favorably alter the physicochemical and biopharmaceutical properties of active pharmaceutical ingredients. This dissertation focuses on the thermodynamic stability and solubility of pharmaceutical cocrystals. Specifically, the objectives are to; (i) investigate the influence of coformer properties such as solubility and ionization characteristics on cocrystal solubility and stability as a function of pH, (ii) to measure the thermodynamic solubility of metastable cocrystals, and study the solubility differences measured by kinetic and equilibrium methods, (iii) investigate the role of surfactants on the solubility and synthesis of cocrystals, (iv) investigate the solid state phase transformation of reactants to cocrystals and the factors that influence the reaction kinetics and, (v) provide models that enable the prediction of cocrystal formation by calculating the free energy of formation for a solid to solid transformation of reactants to cocrystals. Cocrystal solubilities were measured directly when cocrystals were thermodynamically stable, while solubilities were calculated from eutectic concentration measurements when cocrystals were of higher solubility than its components. Cocrystal solubility was highly dependent on coformer solubilities for gabapentin-lactam and lamotrigine cocrystals. It was found that melting point is not a good indicator of cocrystal solubility as solute-solvent interactions quantified by the activity coefficient play a huge role in the observed solubility. Similar to salts, cocrystals also exhibit pHmax, however the salts and cocrystals have different dependencies on the parameters that govern the value of pHmax. It is also shown that cocrystals could provide solubility advantage over salts as lamotrigine-nicotinamide cocrystal hydrate has about 6 fold higher solubility relative to lamotrigine-saccharin salt. In the case of mixtures of solid

  12. Magneto-optical spectroscopic studies of solid and solution-phase tetra-phenyl porphyrin

    NASA Astrophysics Data System (ADS)

    Wahlen-Strothman, Jacob; Pan, Zhen Wen; Manning, Lane; Furis, Madalina; Chu, Kelvin

    2011-03-01

    Tetraphenylporphyrin (TPP) is a synthetic heterocyclic compound that serves as a model system for heme proteins and cytochromes. TPP can accomodate a metal ion in the center; D-shell ion porphyrin complexes with a crystalline solid phase are of interest for magnetic studies because of the possibility of macroscopic long range magnetic order of the ion spins. We have investigated the 5K magnetic properties of poly-crystalline thin films of the heme protoporphyrin IX analogue tetra-phenyl porphyrin, complexed with Zn and Mn, deposited through a capillary pen technique that produces 100um to 1 mm sized grains. Our novel experimental setup measures the UV/VIS, linear dichroism and magnetic circular dichorism simultaneously, incorporates a photoelastic modulator and a microscopy superconducting magnet for high-field (5T) measurements. We present solution and crystalline data on metal-complexed TPP; data are analyzed in terms of A and B-type MCD using a perimeter model. We find good agreement with previous solution data, and novel crystalline phase spectra that are correlated to the long range ordering. This work supported by NSF DMR-0821268, DUE-0942562 and EPS-0701410.

  13. Fabrication and Performance of All-Solid-State Chloride Sensors in Synthetic Concrete Pore Solutions

    PubMed Central

    Gao, Xiaojian; Zhang, Jian; Yang, Yingzi; Deng, Hongwei

    2010-01-01

    One type of all-solid-state chloride sensor was fabricated using a MnO2 electrode and a Ag/AgCl electrode. The potentiometric response of the sensor to chloride in synthetic concrete pore solutions was systematically studied, and the polarization performance was also evaluated. The results show a good linear relationship between the potential reading of the sensor and the logarithm of chloride activity (concentration ranges from 0.05 to 5.0 M), and the potential value remains stable with increasing immersion time. The existence of K+, Ca2+, Na+ and SO42− ions have little influence on the potentiometric response of the sensor to chloride, but the pH has a significant influence on the potential value of the sensor at low chloride concentration. The potential reading of the sensor increases linearly with the solution temperature over the range from 5 to 45 °C. Meanwhile, an excellent polarization behavior is proven by galvanostatic and potentiodynamic tests. All of the results reveal that the developed sensor has a great potential for monitoring chloride ions in concrete environments. PMID:22163467

  14. Fabrication and performance of all-solid-state chloride sensors in synthetic concrete pore solutions.

    PubMed

    Gao, Xiaojian; Zhang, Jian; Yang, Yingzi; Deng, Hongwei

    2010-01-01

    One type of all-solid-state chloride sensor was fabricated using a MnO(2) electrode and a Ag/AgCl electrode. The potentiometric response of the sensor to chloride in synthetic concrete pore solutions was systematically studied, and the polarization performance was also evaluated. The results show a good linear relationship between the potential reading of the sensor and the logarithm of chloride activity (concentration ranges from 0.05 to 5.0 M), and the potential value remains stable with increasing immersion time. The existence of K(+), Ca(2+), Na(+) and SO(4) (2-) ions have little influence on the potentiometric response of the sensor to chloride, but the pH has a significant influence on the potential value of the sensor at low chloride concentration. The potential reading of the sensor increases linearly with the solution temperature over the range from 5 to 45 °C. Meanwhile, an excellent polarization behavior is proven by galvanostatic and potentiodynamic tests. All of the results reveal that the developed sensor has a great potential for monitoring chloride ions in concrete environments. PMID:22163467

  15. Fatigue crack growth behavior of a solid solution-strengthened nickel-base superalloy (Incoloy 825)

    NASA Astrophysics Data System (ADS)

    Bartosiewicz, L.; Krause, A. R.; Spis, A.; Raghavan, J.; Putatunda, S. K.

    1992-02-01

    Fatigue crack growth behavior of a solid solution-strengthened nickel-base superalloy (Incoloy 825)* was investigated. The investigation also examined the influence of heat treatment on resultant microstructures and the near-threshold fatigue crack growth behavior. In addition, the influence of load ratios (R), material strength, and grain size on fatigue threshold was studied. Compact tension specimens prepared from Incoloy 825 with transverse-longitudinal (TL) orientation in the as-received, as well as two different heat treated conditions, were used. The heat treatment studies revealed a peak hardness condition after solution treatment at 1200 °C for 1/2 hr, followed by aging at 600 °C for 434 hr. Among all the heat treated conditions, the fatigue threshold was the highest and the near-threshold crack growth rate was lowest in this peak aged condition. Fatigue threshold values were observed to decrease with an increase in load ratio, whereas an increased grain diameter resulted in a higher fatigue threshold. An earlier mathematical model was found applicable to characterize the relationship between load ratio and fatigue threshold. Preferential etching of grain boundary suggests formation of a thin film of carbide precipitation along the grain boundary region in the aged specimens. This carbide precipitation facilitated intergranular crack growth in these samples, resulting in higher roughness-induced crack closure. The highest fatigue threshold in the peak aged condition can be attributed to this large roughness-induced crack closure process.

  16. Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution-solid interface.

    PubMed

    Fang, Yuan; Ghijsens, Elke; Ivasenko, Oleksandr; Cao, Hai; Noguchi, Aya; Mali, Kunal S; Tahara, Kazukuni; Tobe, Yoshito; De Feyter, Steven

    2016-07-01

    A dominant theme within the research on two-dimensional chirality is the sergeant-soldiers principle, wherein a small fraction of chiral molecules (sergeants) is used to skew the handedness of achiral molecules (soldiers) to generate a homochiral surface. Here, we have combined the sergeant-soldiers principle with temperature-dependent molecular self-assembly to unravel a peculiar chiral amplification mechanism at the solution-solid interface in which, depending on the concentration of a sergeant-soldiers solution, the majority handedness of the system can either be amplified or entirely reversed after an annealing step, furnishing a homochiral surface. Two discrete pathways that affect different stages of two-dimensional crystal growth are invoked for rationalizing this phenomenon and we present a set of experiments where the access to each pathway can be precisely controlled. These results demonstrate that a detailed understanding of subtle intermolecular and interfacial interactions can be used to induce drastic changes in the handedness of a supramolecular network. PMID:27325099

  17. Paper bioassay based on ceria nanoparticles as colorimetric probes.

    PubMed

    Ornatska, Maryna; Sharpe, Erica; Andreescu, Daniel; Andreescu, Silvana

    2011-06-01

    We report the first use of redox nanoparticles of cerium oxide as colorimetric probes in bioanalysis. The method is based on changes in the physicochemical properties of ceria nanoparticles, used here as chromogenic indicators, in response to the analyte. We show that these particles can be fully integrated in a paper-based bioassay. To construct the sensor, ceria nanoparticles and glucose oxidase were coimmobilized onto filter paper using a silanization procedure. In the presence of glucose, the enzymatically generated hydrogen peroxide induces a visual color change of the ceria nanoparticles immobilized onto the bioactive sensing paper, from white-yellowish to dark orange, in a concentration-dependent manner. A detection limit of 0.5 mM glucose with a linear range up to 100 mM and a reproducibility of 4.3% for n = 11 ceria paper strips were obtained. The assay is fully reversible and can be reused for at least 10 consecutive measurement cycles, without significant loss of activity. Another unique feature is that it does not require external reagents, as all the sensing components are fixed onto the paper platform. The bioassay can be stored for at least 79 days at room temperature while maintaining the same analytical performance. An example of analytical application was demonstrated for the detection of glucose in human serum. The results demonstrate the potential of this type of nanoparticles as novel components in the development of robust colorimetric bioassays. PMID:21524141

  18. Phase stability of ScN-based solid solutions for thermoelectric applications from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Kerdsongpanya, Sit; Alling, Björn; Eklund, Per

    2013-08-01

    We have used first-principles calculations to investigate the trends in mixing thermodynamics of ScN-based solid solutions in the cubic B1 structure. 13 different Sc1-xMxN (M = Y, La, Ti, Zr, Hf, V, Nb, Ta, Gd, Lu, Al, Ga, In) and three different ScN1-xAx (A = P, As, Sb) solid solutions are investigated and their trends for forming disordered or ordered solid solutions or to phase separate are revealed. The results are used to discuss suitable candidate materials for different strategies to reduce the high thermal conductivity in ScN-based systems, a material having otherwise promising thermoelectric properties for medium and high temperature applications. Our results indicate that at a temperature of T = 800 °C, Sc1-xYxN; Sc1-xLaxN; Sc1-xGdxN, Sc1-xGaxN, and Sc1-xInxN; and ScN1-xPx, ScN1-xAsx, and ScN1-xSbx solid solutions have phase separation tendency, and thus, can be used for forming nano-inclusion or superlattices, as they are not intermixing at high temperature. On the other hand, Sc1-xTixN, Sc1-xZrxN, Sc1-xHfxN, and Sc1-xLuxN favor disordered solid solutions at T = 800 °C. Thus, the Sc1-xLuxN system is suggested for a solid solution strategy for phonon scattering as Lu has the same valence as Sc and much larger atomic mass.

  19. Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

    NASA Astrophysics Data System (ADS)

    González-López, Jorge; Ruiz-Hernández, Sergio E.; Fernández-González, Ángeles; Jiménez, Amalia; de Leeuw, Nora H.; Grau-Crespo, Ricardo

    2014-10-01

    The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilisation of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural occurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the observed range of compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x = 0.027, and above x = 0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

  20. Solid solution trends that impact electrical design of submicron layers in dielectric capacitors

    NASA Astrophysics Data System (ADS)

    Levi, Roni D.

    It is predictable that future thin layer multilayer dielectrics and thin films embedded capacitors will require higher field and higher reliability performance. This thesis explores the fundamental factors that would limit the high field and reliability performance in thin layer dielectrics based on BaTiO3. Those factors have different origins: On one side, the nature of the metal-dielectric interface was shown to affect the high field dielectric properties of capacitive structures. In addition to that, the intrinsic bulk properties of BaTiO3 based solid solutions affect the high field properties of thin dielectric layers depending on composition and annealing conditions. Both effects were investigated in this study. The temperature dependence of the electrical leakage current density of chemical solution deposited BaTiO3 films on high purity Ni foils was investigated as function of the underlying Ni microstructure. The electrical properties were then characterized on capacitors with and without the presence of Ni grain boundaries. When a Ni grain boundary from the substrate was present in the capacitor used during the electrical measurements, the loss tangent of the capacitor rose rapidly for dc biases exceeding ˜25kV/cm. The critical bias increases to ˜100kV/cm when no substrate grain boundaries are included in the capacitor. In addition, the capacitance-voltage curves are much more symmetric when grain boundaries are absent. This disparity in the electrical behavior was analyzed in terms of the mechanisms of charge conduction across the Ni-dielectric interface. While a reverse biased Schottky emission mechanism dominates the current in areas free of Ni grain boundaries, the Schottky barrier at the cathode is less effective when Ni grain boundaries are present due to local enhancement of the electric field. This, leads to a larger leakage current dominated by the forward biased Schottky barrier at the anode. In addition to the interface influence, the

  1. Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution.

    PubMed

    Kitamura, Fumi; Sawaguchi, Kana; Mori, Asami; Takagi, Shoji; Suzuki, Takayoshi; Kobayashi, Atsushi; Kato, Masako; Nakajima, Kiyohiko

    2015-09-01

    We prepared hydrazone-palladium(II) complexes of [PdCl2(HL(n))] and [PdCl(L(n))] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HL(n) {N'-(pyridin-2-ylmethylene)picolinohydrazide (HL(1)), N'-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL(2)), and N'-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL(3))}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HL(n))] (1, n = 1; 2, n = 2) and in [PdCl2(HL(3))] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(L(n))] (4, n = 1; 5, n = 2) and in [PdCl(L(n))] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. (1)H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. PMID:26305775

  2. Synthesis and solubility of Pb-Ca and P-As hydroxylapatite solid solutions

    NASA Astrophysics Data System (ADS)

    Puzio, Bartosz; Młynarska, Maria; Motyka, Joanna; Oknińska, Joanna; Mandelt, Agnieszka; Chlebowska, Patrycja; Kwaśniak-Kominek, Monika; Manecki, Maciej

    2016-04-01

    The objective of the study are three solid solution series: - HPY hydroxylpyromorphite Pb5(PO4)3OH - HAP hydroxylapatite Ca5(PO4)3OH - HAP hydroxylapatite Ca5(PO4)3OH - JBM johnbaumite Ca5(AsO4)3OH - JBM johnbaumite Ca5(AsO4)3OH - HMI hydroxylmimetite Pb5(AsO4)3OH The phases were synthesized from aqueous solutions at high pH (over 8) at ambient temperature by dropwise mixing of chemical reagents: Pb(NO3)2, Ca(NO3)2.4H2O, (NH4)H2PO4, and Na2AsHO4.7H2O. The products of all syntheses are crystalline, monomineral fine powders (crystal size less than 1 μm). Their chemical composition is close to theoretical. Systematic shift of XRD peaks and FTIR or Raman bands is observed within the solid solution series. Dissolution experiments were run at 5oC, 25oC, 45oC, and 65oC. An aliquot of 0.5g of each phase was dissolved in 250 mL of 0.05M NH4NO3 (pH between 3 and 5) for about 3 months. In all cases dissolution resulted in increase of pH by about 1. The systems were considered in equilibrium when three consecutive samplings (ca. two weeks apart) resulted in similar concentrations (within 3 standard deviations). The dissolution of all phases in question is incongruent. The amount of precipitating secondary phases was too small for identification. The results of HPY - HAP dissolution experiments are inconclusive due to strongly incongruent dissolution. This is partially in contrary to recent report by Zhu et al. (2015). Systematic increase of solubility is observed in HAP - JBM series. Also, the solubility of these phases increases with the increase of temperature. This is more pronounced for HAP than for JBM. Systematic increase of solubility is also observed in HMI - JBM series. This work is partially funded by AGH research grant no 11.11.140.319 and partially by Polish NCN grant No 2014/01/M/ST10/00355. Zhu,Y., Zhu, Z., Zhao, X., Liang, Y., Huang, Y., 2015. Characterization, dissolution, and solubility of lead hydroxypyromorphite Pb5(PO4)3OH at 25-45oC. Journal of Chemistry

  3. Solution and Solid-State Studies of DNA-Programmable Nanoparticle Single Crystals

    NASA Astrophysics Data System (ADS)

    Auyeung, Evelyn

    This thesis lays the foundation for three main areas that have significantly advanced the field of DNA-programmable nanoparticle assembly: (1) the synthesis of nanoparticle superlattices with novel lattice symmetries (2) post-assembly characterization and applications of superlattices that have been transferred from solution to the solid state and (3) the realization of a slow-cooling strategy for synthesizing faceted nanoparticle single crystals. Together, these advances mark a turning point in the evolution of DNA-programmable assembly from a simple proof-of-concept demonstrated in 1996 to a powerful materials development strategy that has inspired many ongoing investigations in fields including catalysis, plasmonics, and electronics. Chapter 1 begins with an overview of controlled crystallization and its importance across fields including chemistry and materials science. This followed by a description of DNA-programmable assembly and a discussion on its advantages as an assembly strategy. Chapter 2 describes a powerful strategy for synthesizing nanoparticle superlattices using a coreless nanoparticle consisting purely of spherically-oriented oligonucleotides. This "three dimensional spacer approach" allows for the synthesis of nanoparticle superlattices with exotic structures, including one with no mineral equivalent. While DNA is a versatile ligand for nanoparticle assembly, the resulting superlattices are only stable in solution. Chapter 3 addresses these limitations and presents a method for transitioning these materials from solution to the solid state through silica encapsulation. This encapsulation process has transformed the ability to interrogate these materials using electron microscopy, and it has enabled all the studies in subsequent chapters of this thesis. In Chapter 4, a slow-cooling crystallization technique is described that allows for the synthesis of single crystalline microcrystals with well-defined facets from DNA-nanoparticle building blocks

  4. The study of magnetic phase diagram of Fe1-xZnxCr2S4 solid solutions

    NASA Astrophysics Data System (ADS)

    Aminov, T. G.; Kirdyankin, D. I.; Shabunina, G. G.; Novotortsev, V. M.

    2013-08-01

    A magnetic phase diagram of Fe1-хZnхCr2S4 solid solutions was studied. The temperature and concentration ranges of existence of magnetoactive phases based on ferrimagnet FeCr2S4 (0≤х≤0.63), antiferromagnet ZnCr2S4 (0.73≤х≤1), and a spin glass (0.63≤х≤0.73) were determined. The concentration dependences of the saturation magnetic moments and Curie temperatures of the solid solutions synthesized were investigated experimentally and theoretically.

  5. Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

    DOEpatents

    Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

    1994-01-01

    A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

  6. A facile and rapid room-temperature route to hierarchical bismuth oxyhalide solid solutions with composition-dependent photocatalytic activity.

    PubMed

    Zhang, Juan; Han, Qiaofeng; Zhu, Junwu; Wang, Xin

    2016-09-01

    The unique nanosheet-based flower-like BiOCl1-xBrx (x=0-1) hierarchical solid solutions have been prepared by the reaction of Bi2O3 and KCl/KBr in mixed solution of glacial acetic acid (HAc) and H2O in dozens of minutes under ambient conditions. During the preparation process, the intermediate bismuth oxide acetate (CH3COOBiO) plays a key role in the formation of BiOCl1-xBrx solid solutions in such a short time. The as-prepared hierarchical BiOCl1-xBrx solid solutions possess high specific surface areas and modified band structures, which exhibit enhanced photocatalytic activity for Rhodamine B (RhB) degradation in comparison with pure BiOCl and BiOBr under visible light irradiation, with the activity reaching the maximum at x=0.5. The photodegradation efficiency of the BiOCl0.5Br0.5 solid solution is twice and 12times higher than P25 TiO2 under UV and visible light irradiation, respectively. PMID:27236841

  7. Enhancing oxide ion incorporation kinetics by nanoscale Yttria-doped ceria interlayers.

    PubMed

    Fan, Zeng; Prinz, Fritz B

    2011-06-01

    Interlayering 17.5 nm of Yttria-doped ceria (YDC) thin films between bulk yttria-stabilized-zirconia electrolyte and a porous Pt cathode enhanced the performance of low-temperature solid oxide fuel cells. The added YDC interlayer (14.11% doped Y(2)O(3)) was fabricated by atomic layer deposition and reduced the cathode/electrolyte interfacial resistances while increasing the exchange current density j(0) by a factor of 4 at operating temperatures between 300-500 °C. Tafel plots and the fitted impedance data suggest that the charge transfer coefficient α of interlayered SOFCs was 1.25 times higher, and the electrode/interfacial activation energy was reduced from 0.85 to 0.76 eV. PMID:21563786

  8. Influence of the pH on the dissolution of TPD and associated solid solutions

    NASA Astrophysics Data System (ADS)

    Robisson, A. C.; Dacheux, N.; Aupiais, J.

    2002-12-01

    The dissolution of thorium phosphate diphosphate (TPD) doped or not with trivalent actinides and that of associated solid solutions with tetravalent plutonium was studied from a kinetic point of view as a function of the acidity or the basicity of the leachate. From the evolution of the normalized mass losses, the dissolution rates were determined. For all the solids considered, the values were found between 1.2×10 -5 and 4.4×10 -9 g m -2 d -1 which confirms the very good durability of TPD to aqueous corrosion. The expression of the dissolution rate was given in acidic and in basic media (10 -1-10 -4 M HNO 3 or HClO 4 and 10 -1-10 -4 M NaOH). The partial orders related to the proton and hydroxide ion concentrations were found to be equal to n=0.31-0.40 and to m=0.37, respectively. The associated dissolution rate constant at pH=0 and pH=14 were found to k 298 K,0.1 M'=1.2×10 -5 to 2.4×10 -5 g m -2 d -1 and to k 298 K,0.1 M″, (7.8±1.9)×10 -5 g m -2 d -1, respectively. In these conditions, the dissolution rate value extrapolated in neutral medium was evaluated to 2.4×10 -7 to 3.6×10 -7 g m -2 d -1 at room temperature and to 5.0×10 -6 to 7.5×10 -6 g m -2 d -1 at 90 °C which remains very low by comparison to the other ceramics studied for the same applications.

  9. Pressure-volume equation of state for pyrope-almandine solid solutions

    NASA Astrophysics Data System (ADS)

    Nestola, Fabrizio; Milani, Sula; Angel, Ross J.; Pasqual, Daria; Geiger, Charles A.

    2013-04-01

    Garnet is a key phase of Earth's upper mantle and one of the most abundant solid inclusions in diamonds. The pyrope component (Mg3Al2Si3O12, Py) of garnet found in diamonds of peridotitic and eclogitic origin can be as high as about 79 and 43%, respectively and the almandine component (Fe3Al2Si3O12, Al) is about 11 and 33%, respectively. Thus such garnets are largely Py-Al-rich solid solutions (Stachel and Harris, 2008). To determine the depth of formation of diamond-inclusion pairs, precise and accurate thermoelastic parameters for both the diamond and the solid inclusion phase are necessary (e.g. Izraeli et al., 1999; Howell et al., 2010; Nestola et al., 2011; Howell et al., 2012). We are presently investigating the pressure-volume equation of state for a series of synthetic garnets along the binary pyrope-almandine by X-ray single-crystal diffraction using a diamond anvil cell up to a maximum of 8 GPa pressure. We have completed measurements on two crystals of composition Fe3Al2Si3O12 and Fe1.20Mg1.80Al2Si3O12. The equation of state coefficients obtained by fitting a third-order Birch-Murnaghan to the pressure-volume data show that an increase in the pyrope component in garnet causes a slight decrease of the isothermal bulk modulus, KT0, by about 3%, whereas the first pressure derivative term does not vary. Applying our results to obtain the pressure of formation of a natural diamond-garnet pair, and assuming a garnet composition close to Fe1.20Mg1.80Al2Si3O12, we obtain a pressure of encapsulation (or formation if garnet and diamond are syngenetic) of garnet in diamond between 6.5 and 7.0 GPa. References Howell, D., Wood, I.G., Dobson, D.P., Jones, A.P., Nasdala, L., Harris, J.W. (2010) Contrib. Mineral. Petrol., 160, 705-717. Howell, D., Wood, I.G., Nestola, F., Nimis, P., Nasdala, L. (2012) Eur. J. Mineral., ,. Izraeli, E.S., Harris, J.W., Navon, O. (1999) Earth Planet Sci. Lett., 173, 351-360. Nestola, F., Nimis, P., Ziberna, L., Longo, M., Marzoli, A

  10. Comparative analysis of zaleplon complexation with cyclodextrins and hydrophilic polymers in solution and in solid state.

    PubMed

    Jablan, Jasna; Szalontai, Gábor; Jug, Mario

    2012-12-01

    The aim of this work was to investigate the potential synergistic effect of water-soluble polymers (hypromellose, HPMC and polyvinylpyrrolidone, PVP) on zaleplon (ZAL) complexation with parent β-cyclodextrin (βCD) and its randomly methylated derivative (RAMEB) in solution and in solid state. The addition of HPMC to the complexation medium improved ZAL complexation and solubilization with RAMEB (K(ZAL/RAMEB)=156±5M(-1) and K(ZAL/RAMEB/HPMC)=189±8M(-1); p<0.01), while such effect was not observed for βCD (K(ZAL/βCD)=112±2M(-1) and K(ZAL/βCD/HPMC)=119±8M(-1); p>0.05). Although PVP increased the ZAL aqueous solubility from 0.22 to 0.27mg/mL, it did not show any synergistic effects on ZAL solubilization with the cyclodextrins tested. Binary and ternary systems of ZAL with βCD, RAMEB and HPMC were prepared by spray-drying. Differential scanning calorimetry, X-ray powder diffraction and scanning electron microscopy demonstrated a partial ZAL amorphization in spray-dried binary and ternary systems with βCD, while the drug was completely amorphous in all samples with RAMEB. Furthermore, inclusion complex formation in all systems prepared was confirmed by solid-state NMR spectroscopy. The in vitro dissolution rate followed the rank order ZAL/RAMEB/HPMC>ZAL/RAMEB=ZAL/βCD/HPMC>ZAL/βCD≫ZAL, clearly demonstrating the superior performance of RAMEB on ZAL complexation in the solid state and its synergistic effect with HPMC on drug solubility. Surprisingly, when loaded into tablets made with insoluble microcrystalline cellulose, RAMEB complexes had no positive effect on drug dissolution, because HPMC and RAMEB acted as a binders inside the tablets, prolonging their disintegration. Oppositely, the formulation with mannitol, a soluble excipient, containing a ternary RAMEB system, released the complete drug-dose in only 5min, clearly demonstrating its suitability for the development of immediate-release oral formulation of ZAL. PMID:22898722

  11. Thermodynamic Destabilization of Ti-O Solid Solution by H2 and Deoxygenation of Ti Using Mg.

    PubMed

    Zhang, Ying; Fang, Zhigang Zak; Sun, Pei; Zhang, Tuoyang; Xia, Yang; Zhou, Chengshang; Huang, Zhe

    2016-06-01

    Reactive metals including Ti, Zr, Hf, and V, among others, have a strong chemical affinity to oxygen, which makes them difficult to produce and costly to use. It is especially challenging to produce pure or metal alloy powders of these elements when extremely low oxygen content is required, because they have high solubility for oxygen, and the solid solution of these metals with oxygen is often more stable thermodynamically than their oxides. We report a novel thermochemical approach to destabilize Ti(O) solid solutions using hydrogen, thus enabling deoxygenation of Ti powder using Mg, which has not been possible before because of the thermodynamic stability of Ti(O) solid solutions relative to MgO. The work on Ti serves as an example for other reactive metals. Both analytical modeling and experimental results show that hydrogen can indeed increase the oxygen potential of Ti-O solid solution alloys; in other words, the stability of Ti-O solid solutions is effectively decreased, thus increasing the thermodynamic driving force for Mg to react with oxygen in Ti. Because hydrogen can be easily removed from Ti by a simple heat treatment, it is used only as a temporary alloying element to destabilize the Ti-O systems. The thermodynamic approach described here is a breakthrough and is applicable to a range of different materials. This work is expected to provide an enabling solution to overcome one of the key scientific and technological hurdles to the additive manufacturing of metals, which is emerging rapidly as the future of the manufacturing industry. PMID:27196140

  12. Fluoride solid electrolytes: investigation of the tysonite-type solid solutions La1-xBaxF3-x (x < 0.15).

    PubMed

    Chable, Johann; Dieudonné, Belto; Body, Monique; Legein, Christophe; Crosnier-Lopez, Marie-Pierre; Galven, Cyrille; Mauvy, Fabrice; Durand, Etienne; Fourcade, Sébastien; Sheptyakov, Denis; Leblanc, Marc; Maisonneuve, Vincent; Demourgues, Alain

    2015-12-01

    Pure tysonite La1-xBaxF3-x solid solutions for x < 0.15 were prepared by solid state synthesis in a platinum tube under an azote atmosphere with subsequent quenching for 0.07 ≤x < 0.15. The solid solutions were studied by X-ray, electron and neutron diffractions and by (19)F NMR and impedance spectroscopy. The evolution of the cell parameters obeying Vegard's rule was determined for 0 < x≤ 0.15 and atomic position parameters were accurately refined for x = 0.03, 0.07 and 0.10. The chemical pressure induced by large Ba(2+) cations leads to an increase of the unit cell parameters. Fluorine environment and mobilities are discussed on the basis of the results of neutron diffraction and (19)F solid state NMR. The F1 subnetwork is lacunar; fluorine exchange occurs according to the order: F1-F1 and F1-F2,3. 2D EXSY NMR spectra of La0.97Ba0.03F2.97 reveal, for the first time, a chemical exchange between F2 and F3 sites that requires two successive jumps. The ionic conductivity was evaluated from sintered pellets and different shaping methods were compared. The only structural features which could explain the conductivity maximum are a crossover together with a smaller dispersion of F1-F1,2,3 distances at x = 0.05-0.07. PMID:26246328

  13. Ceria loaded nanoreactors: a nontoxic superantioxidant system with high stability and efficacy

    NASA Astrophysics Data System (ADS)

    Spulber, M.; Baumann, P.; Liu, J.; Palivan, C. G.

    2015-01-01

    Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of CeNP, it is necessary to find new solutions, which simultaneously reduce their inherent toxicity while preserving their unique catalytic regenerative qualities. Here we introduce a straightforward strategy based on CeNP encapsulation in polymer vesicles which reduces their toxicity, but preserves their superantioxidant character. We have engineered antioxidant nanoreactors, which serve the dual purpose of: (i) separation of CeNP, which inhibits aggregate formation, and (ii) protection of CeNP from hydrogen peroxide, thus eliminating the Fenton-like reaction which induces cytotoxicity. Nanoreactors containing CeNP possess a higher scavenging activity than free CeNP for both hydroxyl and superoxide radicals, as indicated by spin trapping EPR. Due to the regenerative redox chemistry of ceria, the nanoreactors are active for long periods of time, without requiring additional reducing agents. Upon uptake by cells, the nanoreactors show almost no toxicity compared with the free CeNP after a long term exposure, thus proving their high efficacy as ROS scavengers. Our strategy of engineering CeNP-containing nanoreactors represents a versatile, simple and economical solution to reduce CeNP toxicity, while preserving their functionality; thus nanoreactors are the ideal candidates for fighting oxidative stress in a large variety of medical situations.Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of Ce

  14. Non-Prestonian behavior of rectangular shaped ceria slurry in shallow trench isolation chemical mechanical planarization.

    PubMed

    Kim, Ye-Hwan; Jung, Yeon-Gil; Yoon, Gwang Seob; Moon, Jinok; Watanabe, Akira; Naito, Makio; Paik, Ungyu

    2012-03-01

    Rectangular ceria particles were synthesized using the flash creation method. The influence of the morphology of ceria particles and the surfactant concentration on the removal rate was systematically investigated. These ceria slurries with polymeric surfactant molecules as the passivation agents of Si3N4 film, shows an exceptional non-Prestonian behaviors. The non-Prestonian behavior can be attributed to the increase in the contact area of the ceria particles with the SiO2 film, which is dominated by the morphology of the ceria particles. Force measurements using an atomic force microscope (AFM) at different concentrations of polymeric surfactant molecules was used to identify the interactions between the polymeric molecules and the oxide film and analyze the non-Prestonian behavior of ceria slurry having rectangular abrasives. PMID:22755127

  15. Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

    NASA Astrophysics Data System (ADS)

    Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

    2016-02-01

    Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

  16. Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

    USGS Publications Warehouse

    Plummer, L.N.; Busenberg, E.

    1987-01-01

    Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

  17. Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation.

    PubMed

    Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

    2016-01-01

    Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge. PMID:26755070

  18. Characterizing the Solid-Solution Coefficient and Plant Uptake Factor of As, Cd and Pb in California Croplands

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In risk assessment models, the solid-solution partition coefficient (Kd), and plant uptake factor (PUF), are often employed to model the fate and transport of trace elements in soils. The trustworthiness of risk assessments depends on the reliability of the parameters used. In this study, we exami...

  19. Community Solutions to Solid Waste Pollution. Operation Waste Watch: The New Three Rs for Elementary School. Grade 6. [Second Edition.

    ERIC Educational Resources Information Center

    Virginia State Dept. of Waste Management, Richmond. Div. of Litter & Recycling.

    This publication, the last in a series of seven for elementary schools, is an environmental education curriculum guide with a focus on waste management issues. It contains a unit of exercises selected for sixth grade students focusing on community solutions to solid waste pollution. Waste management activities included in this unit seek to…

  20. Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

    2016-01-01

    Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

  1. The formation of supersaturated solid solutions in Fe–Cu alloys deformed by high-pressure torsion

    PubMed Central

    Bachmaier, A.; Kerber, M.; Setman, D.; Pippan, R.

    2012-01-01

    Fully dense bulk nanocomposites have been obtained by a novel two-step severe plastic deformation process in the immiscible Fe–Cu system. Elemental micrometer-sized Cu and Fe powders were first mixed in different compositions and subsequently high-pressure-torsion-consolidated and deformed in a two-step deformation process. Scanning electron microscopy, X-ray diffraction and atom probe investigations were performed to study the evolving far-from-equilibrium nanostructures which were observed at all compositions. For lower and higher Cu contents complete solid solutions of Cu in Fe and Fe in Cu, respectively, are obtained. In the near 50% regime a solid solution face-centred cubic and solid solution body-centred cubic nanograined composite has been formed. After an annealing treatment, these solid solutions decompose and form two-phase nanostructured Fe–Cu composites with a high hardness and an enhanced thermal stability. The grain size of the composites retained nanocrystalline up to high annealing temperatures. PMID:22368454

  2. Structural and optical properties of PVP-capped nanocrystalline ZnxCd1-xS solid solutions

    NASA Astrophysics Data System (ADS)

    Askari, Mina; Soltani, Nayereh; Saion, Elias; Yunus, W. Mahmood Mat; Maryam Erfani, H.; Dorostkar, Mahdi

    2015-05-01

    Nanocrystalline ZnxCd1-xS solid solutions were prepared in a microwave-assisted hydrothermal process with gradient distribution of components (x = 0.1, 0.3, 0.5, 0.7, and 0.9). The growth of the cubic-structured quantum dots was observed for all component stoichiometries with the crystallite size between 4.5 and 5.7 nm. The obvious peak shifts have been found in the XRD patterns and the lattice parameters showed linear variation with x increasing. The evolution of the optical properties of obtained solid solutions including absorption and photoemission was also monitored in detail. The solid solutions show a considerable shift in the nanoparticle optical absorption edge from 482 to 343 nm with the increasing of Zn fraction. The band gaps of the solid solutions were estimated to be between 2.94 and 3.40 eV and the position of conduction band was shifted toward more negative potential with x increasing. The photoluminescence spectra showed a broad blue-green emission spreading up to 600 nm with emergence of three dominant peaks belong to sulfur, zinc, and cadmium vacancies.

  3. Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

    PubMed Central

    Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

    2016-01-01

    Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge. PMID:26755070

  4. Ceria loaded nanoreactors: a nontoxic superantioxidant system with high stability and efficacy.

    PubMed

    Spulber, M; Baumann, P; Liu, J; Palivan, C G

    2015-01-28

    Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of CeNP, it is necessary to find new solutions, which simultaneously reduce their inherent toxicity while preserving their unique catalytic regenerative qualities. Here we introduce a straightforward strategy based on CeNP encapsulation in polymer vesicles which reduces their toxicity, but preserves their superantioxidant character. We have engineered antioxidant nanoreactors, which serve the dual purpose of: (i) separation of CeNP, which inhibits aggregate formation, and (ii) protection of CeNP from hydrogen peroxide, thus eliminating the Fenton-like reaction which induces cytotoxicity. Nanoreactors containing CeNP possess a higher scavenging activity than free CeNP for both hydroxyl and superoxide radicals, as indicated by spin trapping EPR. Due to the regenerative redox chemistry of ceria, the nanoreactors are active for long periods of time, without requiring additional reducing agents. Upon uptake by cells, the nanoreactors show almost no toxicity compared with the free CeNP after a long term exposure, thus proving their high efficacy as ROS scavengers. Our strategy of engineering CeNP-containing nanoreactors represents a versatile, simple and economical solution to reduce CeNP toxicity, while preserving their functionality; thus nanoreactors are the ideal candidates for fighting oxidative stress in a large variety of medical situations. PMID:25501999

  5. Perovskite solid solutions with multiferroic morphotropic phase boundaries and property enhancement

    NASA Astrophysics Data System (ADS)

    Algueró, M.; Amorín, H.; Fernández-Posada, C. M.; Peña, O.; Ramos, P.; Vila, E.; Castro, A.

    2016-05-01

    Recently, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of phases in the BiFeO3-BiCoO3 perovskite binary system, associated with the existence of a discontinuous morphotropic phase boundary (MPB) between multiferroic polymorphs of rhombohedral and tetragonal symmetries. This might be a general property of multiferroic phase instabilities, and a novel promising approach for room temperature magnetoelectricity. We review here our current investigations on the identification and study of additional material systems, alternative to BiFeO3-BiCoO3 that has only been obtained by high pressure synthesis. Three systems, whose phase diagrams were, in principle, liable to show multiferroic MPBs have been addressed: the BiMnO3-PbTiO3 and BiFeO3-PbTiO3 binary systems, and the BiFeO3-BiMnO3-PbTiO3 ternary one. A comprehensive study of multiferroism across different solid solutions was carried out based on electrical and magnetic characterizations, complemented with mechanical and electromechanical measurements. An in-depth structural analysis was also accomplished when necessary.

  6. Dynamic effects in the production of diamond from solid-solution carbon

    SciTech Connect

    Sobolev, V.V.; Didyk, R.P.; Merezhko, Y.I.; Skidanenko, A.I.; Slobodskoi, V.Y.

    1984-03-01

    The authors examine the scope for diamond to grow at atmospheric pressure in iron alloys. For the purpose of this investigation, diamond nuclei were produced in a cast-iron specimen by a dynamic pressure of 80-90GPa. The mass proportion of diamond polycrystals of maximum size 40-50 ..mu..m did not exceed 1%. The largest diamond content occurred in the fraction 0.1-5 ..mu..m and constituted about 80%. The studies show that: the presence of diamond inclusions in a metal matrix substantially influences the structural transformations during isothermal heating and slow cooling; the solid-solution carbon, the carbon compounds, and the graphite inclusions can serve as sources of carbon in the growth of diamond crystals in the metastable region; and dynamic pressures generate numerous defects in cast-iron specimens, which are sources of vacancies, which facilitate the diffusion of the carbon to the growing diamond crystals and the removal of iron from them.

  7. Adsorption of phenol and reactive dye from aqueous solution on activated carbons derived from solid wastes.

    PubMed

    Nakagawa, Kyuya; Namba, Akio; Mukai, Shin R; Tamon, Hajime; Ariyadejwanich, Pisit; Tanthapanichakoon, Wiwut

    2004-04-01

    Activated carbons were produced from several solid wastes, namely, waste PET, waste tires, refuse derived fuel and wastes generated during lactic acid fermentation from garbage. Activated carbons having various pore size distributions were obtained by the conventional steam-activation method and via the pre-treatment method (i.e., mixture of raw materials with a metal salt, carbonization and acid treatment prior to steam-activation) that was proposed by the authors. The liquid-phase adsorption characteristics of organic compounds from aqueous solution on the activated carbons were determined to confirm the applicability of these carbons, where phenol and a reactive dye, Black5, were employed as representative adsorbates. The hydrophobic surface of the carbons prepared was also confirmed by water vapor adsorption. The characteristics of a typical commercial activated carbon were also measured and compared. It was found that the activated carbons with plentiful mesopores prepared from PET and waste tires had quite high adsorption capacity for large molecules. Therefore they are useful for wastewater treatment, especially, for removal of bulky adsorbates. PMID:15026233

  8. Carbon enters silica forming a cristobalite-type CO2-SiO2 solid solution.

    PubMed

    Santoro, Mario; Gorelli, Federico A; Bini, Roberto; Salamat, Ashkan; Garbarino, Gaston; Levelut, Claire; Cambon, Olivier; Haines, Julien

    2014-01-01

    Extreme conditions permit unique materials to be synthesized and can significantly update our view of the periodic table. In the case of group IV elements, carbon was always considered to be distinct with respect to its heavier homologues in forming oxides. Here we report the synthesis of a crystalline CO2-SiO2 solid solution by reacting carbon dioxide and silica in a laser-heated diamond anvil cell (P = 16-22 GPa, T>4,000 K), showing that carbon enters silica. Remarkably, this material is recovered to ambient conditions. X-ray diffraction shows that the crystal adopts a densely packed α-cristobalite structure (P4(1)2(1)2) with carbon and silicon in fourfold coordination to oxygen at pressures where silica normally adopts a sixfold coordinated rutile-type stishovite structure. An average formula of C0.6(1)Si0.4(1)O2 is consistent with X-ray diffraction and Raman spectroscopy results. These findings may modify our view on oxide chemistry, which is of great interest for materials science, as well as Earth and planetary sciences. PMID:24781844

  9. First-Principles Design of Hydrogen Dissociation Catalysts Based on Isoelectronic Metal Solid Solutions.

    PubMed

    Seo, Dong-Hwa; Shin, Hyeyoung; Kang, Kisuk; Kim, Hyungjun; Han, Sang Soo

    2014-06-01

    We report an innovative route for designing novel functional alloys based on first-principles calculations, which is an isoelectronic solid solution (ISS) of two metal elements to create new characteristics that are not native to the constituent elements. Neither Rh nor Ag exhibits hydrogen storage properties, whereas the Rh50Ag50 ISS exhibits properties similar to Pd; furthermore, Au cannot dissociate H2, and Ir has a higher energy barrier for the H2 dissociation reaction than Pt, whereas the Ir50Au50 ISS can dissociate H2 in a similar way to Pt. In the periodic table, Pd is located between Rh and Ag, and Pt is located between Ir and Au, leading to similar atomic and electronic structures between the pure metals (Pd and Pt) and the ISS alloys (Rh50Ag50 and Ir50Au50). From a practical perspective, the Ir-Au ISS would be more cost-effective to use than pure Pt, and could exhibit catalytic activity equivalent to Pt. Therefore, the Ir50Au50 ISS alloy can be a potential catalyst candidate for the replacement of Pt. PMID:26273859

  10. Carbon enters silica forming a cristobalite-type CO2-SiO2 solid solution

    NASA Astrophysics Data System (ADS)

    Santoro, Mario; Gorelli, Federico A.; Bini, Roberto; Salamat, Ashkan; Garbarino, Gaston; Levelut, Claire; Cambon, Olivier; Haines, Julien

    2014-04-01

    Extreme conditions permit unique materials to be synthesized and can significantly update our view of the periodic table. In the case of group IV elements, carbon was always considered to be distinct with respect to its heavier homologues in forming oxides. Here we report the synthesis of a crystalline CO2-SiO2 solid solution by reacting carbon dioxide and silica in a laser-heated diamond anvil cell (P=16-22 GPa, T>4,000 K), showing that carbon enters silica. Remarkably, this material is recovered to ambient conditions. X-ray diffraction shows that the crystal adopts a densely packed α-cristobalite structure (P41212) with carbon and silicon in fourfold coordination to oxygen at pressures where silica normally adopts a sixfold coordinated rutile-type stishovite structure. An average formula of C0.6(1)Si0.4(1)O2 is consistent with X-ray diffraction and Raman spectroscopy results. These findings may modify our view on oxide chemistry, which is of great interest for materials science, as well as Earth and planetary sciences.

  11. Synthesis and sintering of a monazite brabantite solid solution ceramic for nuclear waste storage

    NASA Astrophysics Data System (ADS)

    Montel, Jean-Marc; Glorieux, Benoit; Seydoux-Guillaume, Anne-Magali; Wirth, Richard

    2006-12-01

    Various geological arguments suggest that monazite can be an interesting waste-form for actinides such as Np, Pu, Cm and Am. We set up a simple procedure for making dense pellets of monazite brabantite solid solution ceramics with composition Ca0.092Th0.092Ce0.089La0.727PO4. It consists of co-milling CaCO3, ThO2, CeO2, La2O3, and NH4H2PO4, 1250 °C calcination, milling, cold-pressing, and sintering at 1450 °C for 4 h. X-ray investigations showed that the reaction scheme from oxides to monazite is complex and involves various P+La-based intermediate compounds. The final density of the the product is around 95% of the theoretical density. The texture is homogeneous with a typical grain of size 5 20 μm. This process is designed to be adapted to hot cells and telemanipulators.

  12. Solid / solution interaction: The effect of carbonate alkalinity on adsorbed thorium

    NASA Astrophysics Data System (ADS)

    LaFlamme, Brian D.; Murray, James W.

    1987-02-01

    Elevated activities of dissolved Th have been found in Soap Lake, an alkaline lake in Eastern Washington. Dissolved 232Th ranges from less than 0.001 to 4.9 dpm/L compared to about 1.3 × 10 -5 dpm/ L in sea water. The enhanced activity in the lake coincides with an increase in carbonate alkalinity. Experiments were conducted to evaluate the effect of pH, ionic strength and carbonate alkalinity on Th adsorption on goethite. Thorium (10 -13 M total) in the presence of 5.22 mg/L α-FeOOH and 0.1 M NaNO 3 has an adsorption edge from pH 2-5. At pH 9.0 ± 0.6 the percent Th absorbed on the solid began to decrease from 100% at 100 meq/L carbonate alkalinity and exhibited no adsorption above 300 meq/L. The experimental data were modeled to obtain the intrinsic adsorption equilibrium constants for Th hydrolysis species. These adsorption constants were incorporated in the model to interpret the observed effect of carbonate alkalinity on Th adsorption. There are two main effects of the alkalinity. To a significant degree the decrease in Th adsorption is due to competition of HCO -3 and CO 2-3 ions for surface sites. Dissolved Th carbonate complexes also contribute to the increase of Th in solution.

  13. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    PubMed Central

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-01-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01–1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica. PMID:27416784

  14. Unexpected structural softening of interstitial boron solid solution WB{sub 3+x}

    SciTech Connect

    Wu, Hao; Sun, Hong E-mail: chen@physics.unlv.edu; Chen, Changfeng E-mail: chen@physics.unlv.edu

    2014-11-24

    Using first-principles calculations, we reveal an unexpected structural softening in a recently proposed WB{sub 3+x} structural model that tries to explain the X-ray diffraction, high resolution TEM, pressure dependence of the normalized lattice c/a ratio, and hardness experimental results of the synthesized tungsten boride compounds with a nominal composition WB{sub 4}. We show that the interstitial boron in WB{sub 3+x}, which was proposed to strengthen the covalent bonding network, unexpectedly weakens the atomic bonding, resulting in a large reduction of its indentation strength to well below that of WB{sub 3}. This is in direct contradiction to the experimental results showing that synthesized WB{sub 4} is harder than WB{sub 3}. The unusual structural softening is attributed to the unique three-center covalent bonding formed by the interstitial boron atoms that can easily deform under indentation. Our results show that the proposed interstitial boron solid solution WB{sub 3+x} structure is incompatible with experimental results, which calls for further investigations to determine the crystal structure of the synthesized WB{sub 4}.

  15. Vibrational spectroscopy of synthetic analogues of ankoleite, chernikovite and intermediate solid solution

    NASA Astrophysics Data System (ADS)

    Clavier, N.; Crétaz, F.; Szenknect, S.; Mesbah, A.; Poinssot, C.; Descostes, M.; Dacheux, N.

    2016-03-01

    Ankoleite (K(UO2)PO4·nH2O), chernikovite (H3O(UO2)PO4·nH2O) and intermediate solid solutions are frequently encountered in the uranium ores that result from the alteration of uranium primary minerals. This paper reports a thorough FTIR and Raman study related to synthetic analogues for these minerals. First, the vibration bands associated to the UO22 + uranyl ion were used to calculate the U = O bond length which appeared in good agreement with the data coming from PXRD. Then, the examination of the phosphate vibration modes in both sets of spectra confirmed the general formulation of the samples and ruled out the presence of hydrogenphosphate groups. Finally, the presence of H2O as well as protonated H3O+ and/or H5O2+ species was also pointed out, and could be used to clearly differentiate the various phases prepared. Vibrational spectroscopy then appeared as an efficient method for the investigation of such analogues of natural samples. It should be particularly relevant when identifying these phases in mineral ores or assemblies.

  16. Evolution of Quantum Critical Behavior In A Concentrated Ternary Solid Solution: NiCoCrx

    NASA Astrophysics Data System (ADS)

    Sales, Brian; Jin, Ke; Bei, Hongbin; Stocks, Malcolm; Samolyuk, German; May, Andrew; McGuire, Michael

    The face centered cubic (fcc) alloy NiCoCrx with x near 1 is found to be close to the Cr concentration where the ferromagnetic transition temperature, Tc goes to 0. Near this composition these alloys exhibit a resistivity linear in temperature to 2 K, a perfectly linear magnetoresistance, and an excess -TlnT contribution to the low temperature heat capacity. As the Cr concentration is decreased from 1, the Curie temperature and the saturation magnetization, M0, both increase exponentially with x. For x = 0.5, Tc ~ 217 K, but M0 is only 0.26 Bohr magnetons/atom, indicating highly itinerant ferromagnets for 0.5 solid solution fcc alloys are ideal model systems to study the effects of chemical disorder on emergent properties near a quantum critical point. Research supported by the DOE Office of Science, Materials Science and Engineering Division, and the Energy Dissipation to Defect Evolution EFRC.

  17. Transport properties of Ho1- x Lu x B12 solid solutions

    NASA Astrophysics Data System (ADS)

    Gabáni, S.; Bat'ko, I.; Bat'ková, M.; Flachbart, K.; Gaz̆o, E.; Pristás̆, G.; Takác̆ová, I.; Bogach, A. V.; Sluchanko, N. E.; Shitsevalova, N. Yu.

    2013-05-01

    Our studies of Ho1- x Lu x B12 solid solutions have shown that the temperature of antiferromagnetic (AF) order in geometrically frustrated system of HoB12 ( T N = 7.4 K) is linearly suppressed to zero temperature, i.e. T N → 0, as lutetium concentration increases to x→ x c ≈ 0.9. In this contribution, we present original results of electrical resistivity measurements on Ho1- x Lu x B12 single crystalline samples with x = 0, 0.2, 0.5, 0.7, 0.9, 1 in the temperature range 0.06-300 K and in magnetic fields ( B) up to 8 T. Complex B vs T N phase diagrams were received from precise temperature ρ( T) and field ρ( B) dependences of resistivity with several AF phases for x ≤ 0.5 pointing to a possibility of quantum critical point at x c ≈ 0.9. The scattering of conduction electrons in the AF phase and in the paramagnetic phase as well as Hall effect results are analyzed and discussed for various concentrations x, when magnetic dilution increases with the increasing content of nonmagnetic Lu ions in the Ho1- x Lu x B12 system.

  18. Quantitative Computer Tomography for Determining Composition of Microgravity and Ground Based Solid Solutions

    NASA Technical Reports Server (NTRS)

    Gillies, D. C.; Engel, H. P.

    1999-01-01

    Advances in x-ray Computer Tomography (CT) have been led by the medical profession, and by evaluation of industrial products, particularly castings. Porosity can readily be determined as a function of the density of a material, and CT is thus an industrially important NDE tool. Providing high purity, 100% dense standards of pure elements and compounds can be fabricated, the composition of solid solution alloys can be determined by measuring the CT number, which is a function of the absorption of the sample. Average densities across slices 1 mm thick can generally be determined to better than 1 percent. With present technology this spatial sensitivity is less than ideal, but important benefits can nevertheless be obtained by using CT, particularly single crystals, prior to making any destructive assault upon the sample. The sample can in fact be examined prior to removal from the mold within which it has been grown and, in the cases of microgravity flight samples, before removal from the cartridge assembly. This greatly assists the researcher in the characterization of the products, particularly as a guide to cutting and sampling. Examples of work with germanium-silicon alloys and mercury cadmium telluride taken with a radioactive cobalt source will be demonstrated.

  19. Advances in adsorption of surfactants and their mixtures at solid/solution interfaces.

    PubMed

    Zhang, Rui; Somasundaran, P

    2006-11-16

    Surfactants and their mixtures can drastically change the interfacial properties and hence are used in many industrial processes such as dispersion/flocculation, flotation, emulsification, corrosion inhibition, cosmetics, drug delivery, chemical mechanical polishing, enhanced oil recovery, and nanolithography. A review of studies on adsorption of single surfactant as well as mixtures of various types (anionic-cationic, anionic-nonionic, cationic-nonionic, cationic-zwitterionic and nonionic-nonionic) is presented here along with mechanisms involved. Results obtained using techniques such as zeta potential, flotation, AFM, specular neutron reflectivity, small angle neutron scattering, fluorescence, ESR, Raman spectroscopy, ellipsometry, HPLC and ATR-IR are reviewed along with those from traditional techniques to elucidate the mechanisms of adsorption and particularly to understand synergistic/antagonistic interactions at solution/liquid interfaces and nanostructures of surface aggregates. In addition, adsorption of several mixed surfactant systems is considered due to their industrial relevance. Finally an attempt is made to derive structure-property relationships to provide a solid foundation for the design and use of surfactant formulations for industrial applications. PMID:17052678

  20. Carbonation of municipal solid waste incineration electrostatic precipitator fly ashes in solution.

    PubMed

    De Boom, Aurore; Aubert, Jean-Emmanuel; Degrez, Marc

    2014-05-01

    Carbonation was applied to a Pb- and Zn-contaminated fraction of municipal solid waste incineration electrofilter fly ashes in order to reduce heavy metal leaching. Carbonation tests were performed in solution, by Na2CO3 addition or CO2 bubbling, and were compared with washing (with water only). The injection of CO2 during the washing did not modify the mineralogy, but the addition of Na2CO3 induced the reaction with anhydrite, forming calcite. Microprobe analyses showed that Pb and Zn contamination was rather diffuse and that the various treatments had no effect on Pb and Zn speciation in the residues. The leaching tests indicated that carbonation using Na2CO3 was successful because it gave a residue that could be considered as non-hazardous material. With CO2 bubbling, Pb and Zn leaching was strongly decreased compared with material washed with water alone, but the amount of chromium extracted became higher than the non-hazardous waste limits for landfilling. PMID:24718362

  1. Iridium-Tin oxide solid-solution nanocatalysts with enhanced activity and stability for oxygen evolution

    NASA Astrophysics Data System (ADS)

    Li, Guangfu; Yu, Hongmei; Yang, Donglei; Chi, Jun; Wang, Xunying; Sun, Shucheng; Shao, Zhigang; Yi, Baolian

    2016-09-01

    Addressing major challenges from the material cost, efficiency and stability, it is highly desirable to develop high-performance catalysts for oxygen evolution reaction (OER). Herein we explore a facile surfactant-assisted approach for fabricating Irsbnd Sn (Ir/Sn = 0.6/0.4, by mol.) nano-oxide catalysts with good morphology control. Direct proofs from XRD and X-ray photoelectron spectra indicate hydrophilic triblock polymer (TBP, like Pluronic® F108) surfactant can boost the formation of stable solid-solution structure. With the TBP hydrophilic and block-length increase, the fabricated Irsbnd Sn oxides undergoing the rod-to-sphere transition obtain the relatively lower crystallization, decreased crystallite size, Ir-enriched surface and incremental available active sites, all of which can bolster the OER activity and stability. Meanwhile, it is observed that the coupled Ir oxidative etching takes a crucial role in determining the material structure and performance. Compared with commercial Ir black, half-cell tests confirm F108-assistant catalysts with over 40 wt% Ir loading reduction show 2-fold activity enhancement as well as significant stability improvement. The lowest cell voltage using 0.88 mg cm-2 Ir loading is only 1.621 V at 1000 mA cm-2 and 80 °C with a concomitant energy efficiency of 75.8% which is beyond the DOE 2017 efficiency target of 74%.

  2. Thermal conductivity of near-stoichiometric (U, Er)O 2 solid solutions

    NASA Astrophysics Data System (ADS)

    Kim, Si-Hyung; Kim, Yeon-Gu; Kim, Han-Soo; Na, Sang-Ho; Lee, Young-Woo; Suhr, Dong-Soo

    2005-06-01

    Thermal diffusivities of UO 2 and UO 2 doped with 1, 3, 5, 7 and 10 mol % ErO 1.5 were measured in the range of 298-1673 K by a laser flash method and their thermal conductivities were calculated from the thermal diffusivity, the measured sample density and published specific heat capacity data. The temperature dependence of the thermal conductivity up to 1673 K in UO 2 and UO 2-doped with ErO 1.5 was found to be modeled well using the phonon conduction equation, K = ( A + BT) -1. The thermal conductivities of the UO 2 and (U, Er)O 2 solid solutions gradually decreased with the temperature. The thermal conductivity of the doped UO 2 decreased relative to UO 2 with an increase of ErO 1.5 content at low temperatures, while it was independent of the ErO 1.5 content at higher temperatures. The variation of parameters A and B as a function of ErO 1.5 content is found experimentally and it is found that the dependence of the thermal conductivity of (U, Er)O 2 on temperature up to 1673 K and on the ErO 1.5 content can be expressed as K={K}/{1+K(kAy+kByT)}.

  3. Optical Absorption and Electron Paramagnetic Resonance studies of two different solid solutions of Pyralspite Garnet

    NASA Astrophysics Data System (ADS)

    Watanabe, S.; Espinoza, S. R. Q.; Chubaci, J. F. D.; Cano, N. F.; Cornejo, D. R.

    2015-04-01

    Two different solid solutions of pyralspite garnet have been investigated as to their optical absorption and EPR properties. The absorption band around 9850 cm-1 is due to Fe2+. After heating above 950 °C we found this band diminishes considerably; which was interpreted as Fe2+ loosing an electron to become Fe3+. The EPR spectrum of sample consisted of a straight line with angular coefficient of about 176°. After 600°C/1hr annealing, the spectrum starts deviating from a straight line. A strong typical EPR signal is observed around g = 2.0 after annealing at 850°C. We assume that with high temperature annealing a large number of Fe2+ are converted to Fe3+ as the optical absorption has shown. These results were also confirmed by chemical reaction. The susceptibility vs. magnetic field measurement has shown that the samples annealed at temperatures below 850°C present normal paramagnetic behavior, however, annealed above 900 °C, they show hysteresis, namely ferromagnetic behavior.

  4. Absorption and spectra of optical parameters in amorphous solid solutions of the Se-S system

    SciTech Connect

    Djalilov, N. Z.; Damirov, G. M.

    2011-04-15

    A study of the optical properties of the Se-S system has revealed a correlation between the dependences of optical absorption coefficient {alpha}, effective concentration of charged defects N{sub t}, and characteristic energy E{sub 0} corresponding to the Urbach optical absorption in the spectral region where the Urbach rule works for the Se-S system on the S concentration. These optical properties are controlled by charged defects. It is shown that concentrations of intrinsic charged defects can be changed by variation in composition of the Se-S system. Reflectance spectra of amorphous solid solutions of the Se-S system are studied within the energy range 1-6 eV. Using the Kramers-Kronig method, spectral dependences of optical constants and derivative optical and dielectric functions are calculated. Variation in the spectra of optical parameters with composition of the Se-S system are explained within a cluster model in which the density of electron states is a function of atomic configurations in clusters, i.e., of the character of a short-range order.

  5. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface.

    PubMed

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-01-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica. PMID:27416784

  6. Bridging Phases at the Morphotropic Boundaries of Lead Oxide Solid Solutions

    SciTech Connect

    Noheda,B.; Cox, D.

    2006-01-01

    Ceramic solid solutions of PbZr(1-x)TixO3 (PZT) with compositions of about x= 0.50 are well-known for their extraordinarily large piezoelectric responses. The latter are highly anisotropic, and it was recently shown that, for the rhombohedral compositions (x< 0.5), the piezoelectric coefficients were largest away from the polar direction, contrary to common belief. Shortly afterwards a low-symmetry monoclinic phase was observed by synchrotron x-ray diffraction at around x=0.50. Similar behavior and features are also present in a number of related lead-based strongly-piezoelectric single crystals, such as PMN-PT, PZN-PT, and PSN-PT, with piezoelectric coefficients of about 2500 pm/V, the highest values recorded to date. Recent experimental and theoretical work has greatly improved our understanding of these technologically-important systems, but there are still some open questions. In this review we try to summarize the most recent progress in the field.

  7. Vibrational spectroscopy of synthetic analogues of ankoleite, chernikovite and intermediate solid solution.

    PubMed

    Clavier, N; Crétaz, F; Szenknect, S; Mesbah, A; Poinssot, C; Descostes, M; Dacheux, N

    2016-03-01

    Ankoleite (K(UO2)PO4·nH2O), chernikovite (H3O(UO2)PO4·nH2O) and intermediate solid solutions are frequently encountered in the uranium ores that result from the alteration of uranium primary minerals. This paper reports a thorough FTIR and Raman study related to synthetic analogues for these minerals. First, the vibration bands associated to the UO2(2 +) uranyl ion were used to calculate the U = O bond length which appeared in good agreement with the data coming from PXRD. Then, the examination of the phosphate vibration modes in both sets of spectra confirmed the general formulation of the samples and ruled out the presence of hydrogenphosphate groups. Finally, the presence of H2O as well as protonated H3O(+) and/or H5O2(+) species was also pointed out, and could be used to clearly differentiate the various phases prepared. Vibrational spectroscopy then appeared as an efficient method for the investigation of such analogues of natural samples. It should be particularly relevant when identifying these phases in mineral ores or assemblies. PMID:26688205

  8. Synthesis of ZnxCd1-xS Solid Solution by Stratified Method

    SciTech Connect

    Arai, Takeo; Nakazato, Makoto; Shinoda, Kozo; Jeyadevan, Balachandran; Tohji, Kazuyuki

    2006-05-15

    In this study, we focused our attention on photocatalytic decomposition of hydrogen sulfide as the resource of hydrogen using solar energy and prepared ZnxCd1-xS solid solution as photocatalyst. Samples were prepared by 'stratified' method using Zn and Cd hydroxides as precursors and 'coprecipitation' method under various Zn/ Cd ratios to study the influence of Cd concentration on the properties such as crystal structure, light absorption and reactivity. The continuous change in the crystal lattice constant and UV-VIS reflection spectra from ZnS to CdS was observed in the ZnxCd1-xS samples prepared by both 'coprecipitation' and 'stratified' methods with increasing concentration of Cd. In the case of coprecipitation method, the reactivity was improved with the increase of Cd. But, in the case of stratified method, the particles prepared at Zn:Cd=2:1 showed higher reactivity than the samples prepared at higher ratios of Cd and the samples prepared by coprecipitation method with similar Zn/Cd ratios. The samples prepared by stratified method at higher ratio of Zn/Cd turned black from yellow in color when exposed to light irradiation. This was believed due to the metal deposited by photocatalytic reduction of precursors. This metal deposition influences the photoreactivity of ZnxCd1-xS particles and is optimum for Zn0.67Cd0.33S.

  9. High-Field Dynamic Nuclear Polarization for Solid and Solution Biological NMR

    PubMed Central

    Barnes, A.B.; Paëpe, G. De; van der Wel, P.C.A.; Hu, K.-N.; Joo, C.-G.; Bajaj, V.S.; Mak-Jurkauskas, M.L.; Sirigiri, J.R.; Herzfeld, J.; Temkin, R.J.; Griffin, R.G.

    2008-01-01

    Dynamic nuclear polarization (DNP) results in a substantial nuclear polarization enhancement through a transfer of the magnetization from electrons to nuclei. Recent years have seen considerable progress in the development of DNP experiments directed towards enhancing sensitivity in biological nuclear magnetic resonance (NMR). This review covers the applications, hardware, polarizing agents, and theoretical descriptions that were developed at the Francis Bitter Magnet Laboratory at Massachusetts Institute of Technology for high-field DNP experiments. In frozen dielectrics, the enhanced nuclear polarization developed in the vicinity of the polarizing agent can be efficiently dispersed to the bulk of the sample via 1H spin diffusion. This strategy has been proven effective in polarizing biologically interesting systems, such as nanocrystalline peptides and membrane proteins, without leading to paramagnetic broadening of the NMR signals. Gyrotrons have been used as a source of high-power (5–10 W) microwaves up to 460 GHz as required for the DNP experiments. Other hardware has also been developed allowing in situ microwave irradiation integrated with cryogenic magic-angle-spinning solid-state NMR. Advances in the quantum mechanical treatment are successful in describing the mechanism by which new biradical polarizing agents yield larger enhancements at higher magnetic fields. Finally, pulsed methods and solution experiments should play a prominent role in the future of DNP. PMID:19194532

  10. First-principles study of the solid solution of hydrogen in lanthanum

    SciTech Connect

    Schoellhammer, Gunther; Herzig, Peter; Wolf, Walter; Vajda, Peter; Yvon, Klaus

    2011-09-01

    Results from first-principles investigations of the energetical, structural, electronic, and vibrational properties of model structures probing the metal-rich region of the lanthanum-hydrogen system, i.e., the region of the solid solution of hydrogen in lanthanum, are presented. We have studied the site preference and the ordering tendency of hydrogen atoms interstitially bonded in close-packed lanthanum. Spatially separated hydrogen atoms have turned out to exhibit an energetical preference for the occupation of octahedral interstitial sites at low temperature. Indications for a reversal of the site preference in favor of the occupation of tetrahedral interstitial sites at elevated temperature have been found. Linear arrangements consisting of pairs of octahedrally and/or tetrahedrally coordinated hydrogen atoms collinearly bonded to a central lanthanum atom have turned out to be energetically favorable structure elements. Further stabilization is achieved if such hydrogen pairs are in turn linked together so that extended chains of La-H bonds are formed. Pair formation and chain linking counteract the energetical preference for octahedral coordination observed for separated hydrogen atoms.

  11. Planet Patrol. An Environmental Unit on Solid Waste Solutions for Grades 4-6.

    ERIC Educational Resources Information Center

    Procter and Gamble Educational Services, Cincinnati, OH.

    This classroom unit was developed for use in grades 4-6 to help teach the concept of solid waste management. The teacher's guide provides an overview of the issue of solid waste disposal, a description of government, industry, and consumer roles in resolving the solid waste issue, and four lessons involving sanitary landfills, the reduction of…

  12. Relationships between the solution and solid-state properties of solution-cast low-k silica thin films.

    PubMed

    Chiang, Chao-Ching; Su, Chien-You; Yang, An-Chih; Wang, Ting-Yu; Lee, Wen-Ya; Hua, Chi-Chung; Kang, Dun-Yen

    2016-07-27

    This paper reports on the fabrication of low-k (amorphous) silica thin films cast from solutions without and with two different types of surfactants (TWEEN® 80 and Triton™ X-100) to elucidate the relationships between the structural/morphological features of the casting solutions and the physical properties of the resulting thin films. Cryogenic transmission microscopy (cryo-TEM), static/dynamic light scattering (SLS/DLS), and small-angle X-ray scattering (SAXS) revealed contrasting colloidal dispersion states and phase behavior among the three casting solutions. Casting solution with the Triton™ X-100 surfactant produced stable (>90 days) nanoparticles with good dispersion in solution (mean particle size ∼10 nm) as well as good mesopore volume (characterized by nitrogen physisorption) in powder and thin films of high mechanical strength (characterized by the nanoindentation test). The longer main chain and bulkier side units of the TWEEN® 80 surfactant led to stable micelle-nanoparticle coexisting dispersion, which resulted in the highest mesopore volume in powder and thin films with the lowest dielectric constant (∼3) among the samples in this study. The casting solution without the surfactant failed to produce a stabilized solution or thin films of acceptable uniformity. These findings demonstrate the possibility of fine-tuning low-k silica film properties by controlling the colloidal state of casting solutions. PMID:27401818

  13. Solid reaction products and aluminate solutions that form during the operation of an air-aluminum chemical power supply

    NASA Astrophysics Data System (ADS)

    Okorokova, N. S.; Sevruk, S. D.; Suvorova, E. V.; Farmakovskaya, A. A.

    2015-12-01

    A solution to the set of problems concerning the solid reaction products and the aluminate solutions that form during the operation of an aluminum-closed power supply system for self-contained objects is proposed. The system is based on a resource-saving technology using an aluminum energy carrier in an air-aluminum chemical power supply and related energy installations. The boundaries of the metastable and labile state regions of aluminate solutions and the real degrees of supersaturation that can be attained when aluminum is dissolved in an electrolyte during the operation of an air-aluminum chemical power supply are determined.

  14. Synthesis, Solution and Solid State Structure of Titanium-Maltol Complex

    PubMed Central

    Lamboy, José L.; Pasquale, Antonio; Rheingold, Arnold. L.; Meléndez, Enrique

    2007-01-01

    The reaction of Cp2TiCl2 with two equivalents of maltol (3-hydroxy-2-methyl-4-pyrone) in water, at room temperature and pH of 5.4, leads to a complete replacement of Cp and chloride ligands affording, Ti(maltolato)2(OH)2. The complex has been characterized by IR, NMR and ESI-MS spectroscopic and cyclic voltammetry methods. In DMSO-d6 solution, the complex shows two isomers in a ratio of 4:1, in which one OH signal can be identified per isomer. This suggests that in solution the complex is monomeric, most likely a chiral cis-Ti(maltolato)2(OH)2 and trans-Ti(maltolato)2(OH)2. The monomeric nature of the complex (in water/methanol 1:1) was verified by ESI-MS spectroscopy, showing a parent peak at 329 m/z. Electrochemical behavior of Ti(maltolato)2(OH)2 using cyclic voltammetry experiments showed the complex undergoes irreversible reduction in aprotic solvents. In D2O solution, at pH of 8.4, the 1H NMR spectrum of the complex shows a mixture of monomer and tetramer Ti(IV)-maltol complexes in a ratio of 1:1. The crystallization of Ti(maltolato)2(OH)2 at pH of 8.4 leads to the formation of [Ti4(maltolato)8(μ-O4)]•18H2O. A single crystal of [Ti4(maltolato)8(μ-O4)]•18H2O was analyzed by X-ray diffraction methods. The complex crystallizes in a monoclinic space group P2(1)/c with a = 12.617(4) Å, b = 24.058(8) Å, c = 22.686(7) Å, β= 97.678(4)° and V = 6824(4) Å3 for Z = 4. Solid state structure determination of the Ti-maltol complex showed to be tetrameric, containing two bridging oxides (in cis position) and two bidentate maltol ligands per titanium in a pseudo-octahedral coordination geometry. PMID:18425211

  15. MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

    USGS Publications Warehouse

    Glynn, P.D.

    1991-01-01

    The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

  16. Correlated analysis of chemical variations with spectroscopic features of the K-Na jarosite solid solutions relevant to Mars

    NASA Astrophysics Data System (ADS)

    Ling, Zongcheng; Cao, Fengke; Ni, Yuheng; Wu, Zhongchen; Zhang, Jiang; Li, Bo

    2016-06-01

    Detailed chemical, structural and spectroscopic properties of jarosite solid solution minerals are key information for their potential discoveries by future remote sensing and in-situ detections on Mars. We successfully synthesized seven homogeneous K-Na jarosite solid solutions under hydrothermal conditions at 140 °C, whose phase identifications and chemical compositions are confirmed by X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). The chemical ratios of K/(K+Na) in jarosite solid solutions lead to systematic shifts of their characteristic Raman peaks ν1 (SO4)2- (from 1006 to 1011.3 cm-1), ν3 (SO4)2- (from 1100.6 to 1111.2 cm-1), ν2 (SO4)2- (from 434.2 to 444.8 cm-1) with the increase of Na content. While the OH stretching mode decreases with even larger peak position variations (e.g., ∼3410 cm-1 peak shifts from 3410.5 to 3385.7 cm-1) as the K-Na jarosite solid solutions are enriched in Na content. Raman spectroscopic measurements of the seven K-Na jarosite solid solutions enabled us to build a calibration that uses Raman peak positions to estimate K-Na variation in jarosite, which is the key step for their possible applications in the future Raman applications on Mars' missions (e.g., ExoMars and Mars 2020 missions). The band assignments and compositional related variations of their XRD, near-infrared (NIR) and mid-infrared (MIR) spectra also provide informative clues for identifying the jarosite minerals and inferring their composition during martian in-situ and remote sensing measurements.

  17. Disinfection effects of undoped and silver-doped ceria powders of nanometer crystallite size.

    PubMed

    Tsai, Dah-Shyang; Yang, Tzu-Sen; Huang, Yu-Sheng; Peng, Pei-Wen; Ou, Keng-Liang

    2016-01-01

    Being endowed with an ability of capturing and releasing oxygen, the ceria surface conventionally assumes the role of catalyzing redox reactions in chemistry. This catalytic effect also makes possible its cytotoxicity toward microorganisms at room temperature. To study this cytotoxicity, we synthesized the doped and undoped ceria particles of 8-9 nm in size using an inexpensive precipitation method and evaluated their disinfecting aptitudes with the turbidimetric and plate count methods. Among the samples being analyzed, the silver-doped ceria exhibits the highest sterilization ability, yet the undoped ceria is the most intriguing. The disinfection effect of undoped ceria is moderate in magnitude, demanding a physical contact between the ceria surface and bacteria cell wall, or the redox catalysis that can damage the cell wall and result in the cell killing. Evidently, this effect is short-range and depends strongly on dispersion of the nanoparticles. In contrast, the disinfection effects of silver-doped ceria reach out several millimeters since it releases silver ions to poison the surrounding microorganisms. Additionally, the aliovalent silver substitution creates more ceria defects. The synergetic combination, silver poisoning and heterogeneous redox catalysis, lifts and extends the disinfecting capability of silver-doped ceria to a superior level. PMID:27330294

  18. Disinfection effects of undoped and silver-doped ceria powders of nanometer crystallite size

    PubMed Central

    Tsai, Dah-Shyang; Yang, Tzu-Sen; Huang, Yu-Sheng; Peng, Pei-Wen; Ou, Keng-Liang

    2016-01-01

    Being endowed with an ability of capturing and releasing oxygen, the ceria surface conventionally assumes the role of catalyzing redox reactions in chemistry. This catalytic effect also makes possible its cytotoxicity toward microorganisms at room temperature. To study this cytotoxicity, we synthesized the doped and undoped ceria particles of 8–9 nm in size using an inexpensive precipitation method and evaluated their disinfecting aptitudes with the turbidimetric and plate count methods. Among the samples being analyzed, the silver-doped ceria exhibits the highest sterilization ability, yet the undoped ceria is the most intriguing. The disinfection effect of undoped ceria is moderate in magnitude, demanding a physical contact between the ceria surface and bacteria cell wall, or the redox catalysis that can damage the cell wall and result in the cell killing. Evidently, this effect is short-range and depends strongly on dispersion of the nanoparticles. In contrast, the disinfection effects of silver-doped ceria reach out several millimeters since it releases silver ions to poison the surrounding microorganisms. Additionally, the aliovalent silver substitution creates more ceria defects. The synergetic combination, silver poisoning and heterogeneous redox catalysis, lifts and extends the disinfecting capability of silver-doped ceria to a superior level. PMID:27330294

  19. Phase-field modeling of two-dimensional solute precipitation/dissolution: Solid fingers and diffusion-limited precipitation

    SciTech Connect

    Xu, Zhijie; Meakin, Paul

    2011-01-28

    Two-dimensional dendritic growth due to solute precipitation was simulated using a phase-field model reported earlier [Z. Xu and P. Meakin, J. Chem. Phys. 129, 014705 (2008)]. It was shown that diffusion-limited precipitation due to the chemical reaction at the solid-liquid interface posses similarities with diffusion-limited aggregation (DLA). The diffusion-limited precipitation is attained by setting the chemical reaction rate much larger compared to the solute diffusion to eliminate the effect of the interface growth kinetics. The phase-field simulation results were in reasonable agreement with the analytical solutions. The fractal solid fingers can be formed in the diffusion-limited precipitation and have a fractal dimension measured , close to 1.64, the fractal dimensionality of large square lattice diffusion-limited aggregation (DLA) clusters.

  20. Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain.

    PubMed

    Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios

    2009-12-01

    The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis. PMID:19824037

  1. Phase-field modeling of two-dimensional solute precipitation∕dissolution: solid fingers and diffusion-limited precipitation.

    PubMed

    Xu, Zhijie; Meakin, Paul

    2011-01-28

    Two-dimensional dendritic growth due to solute precipitation was simulated using a phase-field model reported earlier [Z. Xu and P. Meakin, J. Chem. Phys. 129, 014705 (2008)]. It was shown that diffusion-limited precipitation due to the chemical reaction at the solid-liquid interface has similarities with diffusion-limited aggregation (DLA). The diffusion-limited precipitation is attained by setting the chemical reaction rate much larger compared to the solute diffusion to eliminate the effect of the interface growth kinetics. The phase-field simulation results were in reasonable agreement with the analytical solutions. The fractal solid fingers can be formed in the diffusion-limited precipitation and have a fractal dimension measured d(f)=1.68, close to 1.64, the fractal dimensionality of large square lattice DLA clusters. PMID:21280717

  2. Phase-field modeling of two-dimensional solute precipitation/dissolution: Solid fingers and diffusion-limited precipitation

    NASA Astrophysics Data System (ADS)

    Xu, Zhijie; Meakin, Paul

    2011-01-01

    Two-dimensional dendritic growth due to solute precipitation was simulated using a phase-field model reported earlier [Z. Xu and P. Meakin, J. Chem. Phys. 129, 014705 (2008)]. It was shown that diffusion-limited precipitation due to the chemical reaction at the solid-liquid interface has similarities with diffusion-limited aggregation (DLA). The diffusion-limited precipitation is attained by setting the chemical reaction rate much larger compared to the solute diffusion to eliminate the effect of the interface growth kinetics. The phase-field simulation results were in reasonable agreement with the analytical solutions. The fractal solid fingers can be formed in the diffusion-limited precipitation and have a fractal dimension measured d_f = 1.68, close to 1.64, the fractal dimensionality of large square lattice DLA clusters.

  3. Calculation of the standard heat capacity at constant pressure for cobalt ferrite-zinc ferrite solid solutions

    SciTech Connect

    Chachanidze, G.D.; Pavlenishvili, T.A.; Machaladze, T.E.; Khutsishvili, D.I.

    1994-08-01

    Magnetic, electrical, and other properties of Co{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} solid solutions are widely studied because of their high coercive force and Curie temperature ({Tc}), which makes these compounds applicable in modern electronic devices. However, the information published on their thermodynamic properties is limited. This paper focuses on calculation of the standard heat capacity C{sub p}{sup 0} (298 K) for cobalt zinc ferrites using correlation analysis of the relationship between C{sub p}{sup 0} (298 K) and the saturation magnetic moment {mu}{sub o}. The authors studied the solid solutions Co{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (x = 0.2, 0.4, 0.5, 0.6, and 0.8), whose magnetic and thermal parameters, crucial in our calculations, are known to be strongly dependent on the preparation conditions. An equation was derived for calculation of the standard heat capacity at constant pressure from the saturation magnetic moment of Co{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} solid solutions. The equation allows a satisfactory estimation of the standard heat capacity at 298 Kelvin for any cobalt ferrite-zinc ferrite solid, providing the saturation magnetic moment is available.

  4. Synthesis and structure of Ce1-xEuxPO4 solid solutions for minor actinides immobilization

    NASA Astrophysics Data System (ADS)

    Wang, Xiaohuan; Teng, Yuancheng; Huang, Yi; Wu, Lang; Zeng, Pan

    2014-08-01

    Ce1-xEuxPO4 (x = 0-1) solid solutions were synthesized by the solid state reaction process using europium (Eu) as the surrogate for trivalent minor actinide americium (Am). The effects of calcination temperature, holding time and Eu content on the crystalline phase, microstructure and morphology of Ce1-xEuxPO4 (x = 0-1) were investigated. The monazite-type EuPO4 and CePO4 coexisted after being calcined at 1000 °C for 4 h, suggesting the CePO4 and EuPO4 phases would form initially separately. Pure and single-phase monazite-type Ce1-xEuxPO4 (x = 0-1) powders were obtained at 1300 °C for 4 h. The results of the XRD patterns Rietveld refinement and μ-Raman analysis confirmed the formation of a Ce1-xEuxPO4 (x = 0-1) continuous solid solution. The grain size of Ce0.5Eu0.5PO4 increased obviously as the holding time extended. The Ce, Eu, P and O elements were almost distributed homogeneously in the Ce0.5Eu0.5PO4 solid solution.

  5. Electrochemical reactivity and proton transport mechanisms in nanostructured ceria.

    PubMed

    Ding, J; Strelcov, E; Kalinin, S V; Bassiri-Gharb, N

    2016-08-26

    Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria. PMID:27407076

  6. Electrochemical reactivity and proton transport mechanisms in nanostructured ceria

    NASA Astrophysics Data System (ADS)

    Ding, J.; Strelcov, E.; Kalinin, S. V.; Bassiri-Gharb, N.

    2016-08-01

    Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria.

  7. Ab initio analysis of the defect structure of ceria

    NASA Astrophysics Data System (ADS)

    Zacherle, T.; Schriever, A.; De Souza, R. A.; Martin, M.

    2013-04-01

    We calculated the formation energies of all simple point defects in cubic fluorite structured CeO2 using density functional theory within the GGA+U approximation. All possible defect charge states were considered, and also polarons CeCe' and associates of polarons with oxygen vacancies: (VO··-CeCe')· and (CeCe'-VO··-CeCe')×. From the individual defect energies, we extracted Schottky, Frenkel, and anti-Frenkel energies: we find that anti-Frenkel disorder has the lowest energy in ceria. Energies for the reduction and the hydration of ceria are also computed, and the results are in good agreement with experiment. Finally, point-defect concentrations and conductivities are predicted for undoped and donor-doped systems as a function of oxygen partial pressure and temperature. The characteristic slopes found in experiment are reproduced.

  8. Structural modification of nanocrystalline ceria by ion beams

    SciTech Connect

    Zhang, Yanwen; Edmondson, Philip D.; Varga, Tamas; Moll, Sandra; Namavar, Fereydoon; Lan, Chune; Weber, William J.

    2011-01-01

    Exceptional size-dependent electronic–ionic conductivity of nanostructured ceria can significantly alter materials properties in chemical, physical, electronic and optical applications. Using energetic ions, we have demonstrated effective modification of interface volume and grain size in nanocrystalline ceria from a few nm up to ~25 nm, which is the critical region for controlling size-dependent material property. The grain size increases and follows an exponential law as a function of ion fluence that increases with temperature, while the cubic phase is stable under the irradiation. The unique self-healing response of radiation damage at grain boundaries is utilized to control the grain size at the nanoscale. Structural modification by energetic ions is proposed to achieve desirable electronic–ionic conductivity.

  9. Sintering and mechanical properties of gadolinium-doped ceria ceramics

    NASA Astrophysics Data System (ADS)

    Yasuda, K.; Uemura, K.; Shiota, T.

    2012-01-01

    Gadolinium-doped ceria (GDC) ceramics were made by sintering at various temperatures from 1000°C to 1400°C in air. The true density and apparent density were measured to calculate the relative density of GDC ceramics. The change in relative density revealed that densification of GDC ceramics increased up to 1200°C, and thereafter turned downward. It was suggested that pores were formed at 1300°C and 1400°C due to non-stoichiometry of ceria. JIS-type specimens were cut from the sintered body and tested by 4-point bending. Young's modulus and bending strength decreased with increasing the sintering temperature from 1200°C to 1400°C, corresponding to the change in the relative density.

  10. Kinetic Growth of Ultralong Metastable Zincblende MnSe Nanowires Catalyzed by a Fast Ionic Conductor via a Solution-Solid-Solid Mechanism.

    PubMed

    Zhang, Li; Yang, Qing

    2016-07-13

    The metastable semiconductor phase allows for the exploration of unusual properties and functionalities of abnormal structures, although it is often difficult to prevent thermodynamic transformations to lower energy structures from higher, unfavored energy states. Here, we show for the first time the preparation of high-quality ultralong metastable zincblende (ZB)-MnSe nanowires with a four-coordinate structure via solution-solid-solid (SSS) growth in a mild solution-phase synthetic environment (120-220 °C) in the presence of a trace amount of Ag(I). The metastable ZB-MnSe nanowires are stabilized kinetically due to the catalysis of early formed body-centered cubic (bcc) fast-ionic (superionic) Ag2Se nanocrystals from the Ag(I) source, and the ZB-MnSe nanowires grow epitaxially along the ⟨110⟩ axis rather than the ⟨111⟩ axis, as commonly observed for typical four-coordinate Grimm-Sommerfeld bonding solids. Our method provides a new route for the growth of metastable nanostructures. PMID:27254244

  11. Characterization of interactions between soil solid phase and soil solution in the initial ecosystem development phase

    NASA Astrophysics Data System (ADS)

    Zimmermann, Claudia; Schaaf, Wolfgang

    2010-05-01

    In the initial phase of soil formation interactions between solid and liquid phases and processes like mineral weathering, formation of reactive surfaces and accumulation of organic matter play a decisive role in developing soil properties. As part of the Transregional Collaborative Research Centre (SFB/TRR 38) 'Patterns and processes of initial ecosystem development' in an artificial catchment, these interactions are studied at the catchment 'Chicken Creek' (Gerwin et al. 2009). To link the interactions between soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale, microcosm experiments under controlled laboratory conditions were carried out. Main objectives were to determine the transformation processes of C and N from litter decomposition within the gaseous, liquid and solid phase, the interaction with mineral surfaces and its role for the establishment of biogeochemical cycles. The microcosm experiments were established in a climate chamber at constant 10 ° C. In total 48 soil columns (diameter: 14.4 cm; height: 30 cm) were filled with two different quaternary substrates (sand and loamy sand) representing the textural variation within the catchment at a bulk density of 1.4-1.5 g*cm-3. The columns were automatically irrigated four times a day with 6.6 ml each (corresponding to 600 mm*yr-1). The gaseous phase in the headspace of the microcosms was analysed continuously for CO2 and N2O contents. C and N transformation processes were studied using 13C and 15N labelled litter of two different plant species occurring at the catchment (Lotus corniculatus, Calamagrostis epigejos) that was incorporated into the microcosm surface. All treatments including a control ran with four replicates over a period of 40 weeks. Two additional microcosms act as pure litter controls where substrate was replaced by glass pearls. Litter and substrate were analysed before and after the experiment. Percolate was continuously collected and

  12. Crystal Violet Lactone Salicylaldehyde Hydrazone Zn(II) Complex: a Reversible Photochromic Material both in Solution and in Solid Matrix

    PubMed Central

    Li, Kai; Li, Yuanyuan; Tao, Jing; Liu, Lu; Wang, Lili; Hou, Hongwei; Tong, Aijun

    2015-01-01

    Crystal violet lactone (CVL) is a classic halochromic dye which has been widely used as chromogenic reagent in thermochromic and piezochromic systems. In this work, a very first example of CVL-based reversible photochromic compound was developed, which showed distinct color change upon UV-visible light irradiation both in solution and in solid matrix. Moreover, metal complex of CVL salicylaldehyde hydrozone was facilely synthesized, exhibiting reversible photochromic properties with good fatigue resistance. It was served as promising solid material for photo-patterning. PMID:26412101

  13. Crystal Violet Lactone Salicylaldehyde Hydrazone Zn(II) Complex: a Reversible Photochromic Material both in Solution and in Solid Matrix.

    PubMed

    Li, Kai; Li, Yuanyuan; Tao, Jing; Liu, Lu; Wang, Lili; Hou, Hongwei; Tong, Aijun

    2015-01-01

    Crystal violet lactone (CVL) is a classic halochromic dye which has been widely used as chromogenic reagent in thermochromic and piezochromic systems. In this work, a very first example of CVL-based reversible photochromic compound was developed, which showed distinct color change upon UV-visible light irradiation both in solution and in solid matrix. Moreover, metal complex of CVL salicylaldehyde hydrozone was facilely synthesized, exhibiting reversible photochromic properties with good fatigue resistance. It was served as promising solid material for photo-patterning. PMID:26412101

  14. Crystal Violet Lactone Salicylaldehyde Hydrazone Zn(II) Complex: a Reversible Photochromic Material both in Solution and in Solid Matrix

    NASA Astrophysics Data System (ADS)

    Li, Kai; Li, Yuanyuan; Tao, Jing; Liu, Lu; Wang, Lili; Hou, Hongwei; Tong, Aijun

    2015-09-01

    Crystal violet lactone (CVL) is a classic halochromic dye which has been widely used as chromogenic reagent in thermochromic and piezochromic systems. In this work, a very first example of CVL-based reversible photochromic compound was developed, which showed distinct color change upon UV-visible light irradiation both in solution and in solid matrix. Moreover, metal complex of CVL salicylaldehyde hydrozone was facilely synthesized, exhibiting reversible photochromic properties with good fatigue resistance. It was served as promising solid material for photo-patterning.

  15. Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573–1773 K temperature range† †Electronic supplementary information (ESI) available: XRD patterns and SEM images. See DOI: 10.1039/c4cp04916k Click here for additional data file.

    PubMed Central

    Takacs, M.; Steinfeld, A.

    2015-01-01

    This work encompasses the thermodynamic characterization and critical evaluation of Zr4+ 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% Zr4+ 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 p O2. 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 Zr4+ 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 Zr4+ 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. PMID:25714616

  16. Magnetism of the solid solution GdGa1 - xGex (abstract)

    NASA Astrophysics Data System (ADS)

    Leithe-Jasper, A.; Hiebl, K.

    1996-04-01

    Ternary metal excess rare-earth gallides and germanides have been extensively investigated concerning their interesting physical properties with respect to magnetic and electronic correlations, such as magnetic ordering, intermediate valency, Kondo or heavy fermion behavior. A solid solution of the binary phases GdGa and GdGe was found investigating the phase equilibria in the pseudobinary system Gd-Ga-Ge at T=800 °C. Samples with the composition GdGa1-xGex (x=0, 0.1, 0.15, 0.25, 0.5) were prepared by arc melting the elements under inert atmosphere and subsequent annealing (350 h) in evacuated silica capsules. The crystal structure and unit-cell dimensions were determined by x-ray powder analyses (Guinier technique, Cu Kα1 radiation). Powder patterns were indexed on the basis of a C-centered orthorhombic unit cell. No deviations of the structure type α-ITI (CrB) have been encountered. A monotonic decrease of the unit-cell volume versus Ge concentration is observed. However, a significant decrease of the b and c parameters is thereby compensated by an increase of the a parameter. Magnetic measurements were performed by SQUID and ac techniques over a temperature range T=5-300 K and in external fields up to 6 T. All samples exhibit ferromagnetic order with slightly decreasing Tc as well as values of magnetization (at T=5 K and H=0.1 T) with increasing concentration x. However, metamagnetic transitions are revealed for all samples with x≳0. The results are discussed within the concept of indirect exchange interaction (RKKY-type interaction).

  17. Effect of Heat-Treatment and Composition on Structure and Luminescence Properties of Spinel-Type Solid Solution Nanocrystals.

    PubMed

    Sakoda, Kazuki; Hirano, Masanori

    2015-08-01

    The compositional dependence of the structure and properties of spinel-type solid solutions, Zn(A,Ga)2O4 was investigated by comparison with samples hydrothermally prepared and those after heat treatment at 1000 °C in air. Nanocrystalline spinel-type solid solutions in the whole composition range in the ZnAl2O4-ZnGa2O4 system were directly formed from the aqueous precursor solutions of ZnSO4, Al(NO3)3 and Ga(NO3)3 under hydrothermal conditions at 180 °C for 5 h in the presence of tetramethylammonium hydroxide. The incorporation of aluminum into the lattice, Zn(AlxGa1-x)2O4, resulted in lower crystallinity of the spinel. The relationship between the lattice parameter of as-prepared samples and the Al atomic ratio in the spinel composition was slightly apart from the ideal linear relationship that was obtained in the samples after heat treatment at 1000 °C. The optical band gap of both as-prepared solid solutions and those heat treated linearly increased from 4.1~4.2 to 5.25 eV by the incorporation of aluminum ion into the lattice, Zn(AlxGa1-x)2O4. Two main broad-band emission spectra centered at around 360 and 430 nm in the range of 300-600 nm were observed in the spinel solid solutions under excitation at 270 nm, thought their broad-band emission spectra and their peak wavelengths subtly changed depending on the composition and heat treatment. PMID:26369200

  18. Kinetics of CO2 Reduction over Nonstoichiometric Ceria

    PubMed Central

    2015-01-01

    The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

  19. Soot Combustion over Nanostructured Ceria with Different Morphologies.

    PubMed

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-01-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions. PMID:27353143

  20. Soot Combustion over Nanostructured Ceria with Different Morphologies

    NASA Astrophysics Data System (ADS)

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-06-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions.

  1. Soot Combustion over Nanostructured Ceria with Different Morphologies

    PubMed Central

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-01-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions. PMID:27353143

  2. Formation of III–V ternary solid solutions on GaAs and GaSb plates via solid-phase substitution reactions

    SciTech Connect

    Vasil’ev, V. I.; Gagis, G. S. Kuchinskii, V. I.; Danil’chenko, V. G.

    2015-07-15

    Processes are considered in which ultrathin layers of III–V ternary solid solutions are formed via the delivery of Group-V element vapors to GaAs and GaSb semiconductor plates, with solid-phase substitution reactions occurring in the surface layers of these plates. This method can form defect-free GaAs{sup 1–x}P{sup x}, GaAs{sup x}Sb{sup 1–x}, and GaP{sup x}Sb{sup 1–x} layers with thicknesses of 10–20 nm and a content x of the embedded components of up to 0.04.

  3. Characterization of ceria-based SOFCs

    SciTech Connect

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

    1996-12-31

    Solid Oxide Fuel Cells (SOFCs) operating at low temperatures (500-700 C) offer many advantages over conventional zirconia-based fuel cells operating at higher temperatures. Cathode performance is being improved by using better materials and/or microstructures. Fabrication of thin dense electrolytes is also necessary to achieve high cell performances.

  4. Structural Changes Associated with Transthyretin Misfolding and Amyloid Formation Revealed by Solution and Solid-State NMR.

    PubMed

    Lim, Kwang Hun; Dasari, Anvesh K R; Hung, Ivan; Gan, Zhehong; Kelly, Jeffery W; Wemmer, David E

    2016-04-01

    Elucidation of structural changes involved in protein misfolding and amyloid formation is crucial for unraveling the molecular basis of amyloid formation. Here we report structural analyses of the amyloidogenic intermediate and amyloid aggregates of transthyretin using solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. Our solution NMR results show that one of the two main β-sheet structures (CBEF β-sheet) is maintained in the aggregation-competent intermediate, while the other DAGH β-sheet is more flexible on millisecond time scales. Magic-angle-spinning solid-state NMR revealed that AB loop regions interacting with strand A in the DAGH β-sheet undergo conformational changes, leading to the destabilized DAGH β-sheet. PMID:26998642

  5. Supersaturated Al(Ti) solid solutions with partial L1{sub 2} ordering prepared by mechanical alloying

    SciTech Connect

    Fan, G.J.; Quan, M.X.; Hu, Z.Q.

    1995-08-01

    The authors report phase formation during mechanical alloying of Al rich Ti-Al powder blends. Their experimental results further support the idea that the synthesis of Al rich supersaturated solid solutions in the Al-Ti system occurs in the following two steps. First, the ordered L1{sub 2}-Al{sub 3}Ti intermetallic compound is formed at Al/Ti interfaces. Second, the ordered L1{sup 2}-Al{sub 3}Ti compound was partially disordered by mechanical deformation. Meanwhile, Ti or Al atoms dissolve into the partially disordered phase and a supersaturated solid solution is finally obtained. However, the disordering is not complete and the resulting alloys may exhibit partial L1{sub 2} ordering.

  6. YbCu2Si2-LaCu2Si2 Solid Solutions with Enhanced Thermoelectric Power Factors

    NASA Astrophysics Data System (ADS)

    Lehr, Gloria J.; Morelli, Donald T.; Jin, Hyungyu; Heremans, Joseph P.

    2015-06-01

    Cryogenic Peltier coolers are ideal for cooling infrared sensors on satellites. To make these thermoelectric devices a realistic option for this application, the efficiency of thermoelectric materials at cryogenic temperatures must be substantially enhanced. Intermediate valence Yb-based compounds have large peaks in the Seebeck coefficient at low temperatures; to optimize these materials this must be understood. We created solid solutions between the intermediate valence compound YbCu2Si2 and an isostructural compound LaCu2Si2 to manipulate the temperature at which the Seebeck coefficient peaks and to maximize zT by reduction of lattice thermal conductivity. An enormous power factor of 110 μW/cm K2 at 100 K and a maximum zT of 0.14 at 125 K were achieved for one of these solid solutions.

  7. Mechanical alloying synthesis of K{sub 2}Bi{sub 8}Se{sub 13}-type solid solutions.

    SciTech Connect

    Toumpas, N.; Kyratsi, T.; Hatzikraniotis, E.; Tsiappos, A.; Pavlidou, E.; Paraskevopoulos, K. M.; Chung, D. Y.; Kanatzidis, M. G.; Materials Science Division; Univ. of Cyprus; Aristotle Univ. Thessaloniki; Northwestern Univ.

    2008-01-01

    Solid solutions of K{sub 2}Bi{sub 8-x}Sb{sub x}Se{sub 13} are an interesting series of materials for thermoelectric investigations due to their very low thermal conductivity and highly anisotropic electrical properties. In this work, we aimed to synthesize solid solutions of O-K{sub 2}Bi{sub 8-x}Sb{sub x}Se{sub 13} type materials using powder techniques. The synthesis was based on mechanical alloying as well as sintering procedures. The products were studied in terms of structural features, composition and purity with powder x-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Preliminary results on thermoelectric properties as well as IR reflectivity measurements are presented.

  8. Solid Solution Effects on the MgAl2O4-MgGa2O4 System

    SciTech Connect

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

    2009-01-01

    Phase relations between two spinel compounds (MgAl2O4 and MgGa2O4) were studied. Stoichiometric MgAl2O4 was formed in the laboratory through a coprecipitation method. Complete solid solution formation int eh MgAl2O4-MgGa2O4 systems was confirmed through X-ray diffraction analysis. Solid solution between MgAl2O4-MgGa2O4 decreases thermal conductivity at all temperatures up to 900oC. At 200oC with 10 mol% additoin of MgGa2O4 thermal conductivity decreases approximately 25%, and at 900oC there was still an 8% decrease. Additionally, preliminary studies show that porosity between 5% and 10% does not have an appreciable effect on the thermal conductivity in this study.

  9. Solid solution decomposition and growth of precipitates in Be-Fe alloys from Mössbauer investigations

    NASA Astrophysics Data System (ADS)

    Filippov, V. P.; Gladkov, V. P.; Martynenko, S. S.; Petrov, V. I.

    2014-04-01

    Mössbauer spectra of fine-grained hot-pressed beryllium and coarse-grained beryllium samples containing different amounts of impurities were obtained after homogenization and after annealing for different durations. Mössbauer spectra of solid solution of iron in beryllium and decomposed during isothermal annealing two different iron containing phases were fitted by a convolution equation of three Lorentz lines. The models of solid solution decomposition and growth of secondary particle precipitates were investigated. The average distance between dislocations and the average grain size were obtained from the application of the models. The dependencies between the decomposition mechanism, the average grain size, the impurity concentrations and the type of the secondary particles precipitates were revealed. The possibility of a coherent analysis of the decomposition process by means of a kinetic law classification and secondary particle precipitates growth processes based on diffusion models has been shown.

  10. Spectral and electroluminescent properties of coordination compounds of terbium (III) with ibuprofen (in solid form, chloroform solutions, and polyvinylcarbazole films)

    NASA Astrophysics Data System (ADS)

    Samsonova, L. G.; Kopylova, T. N.; Degtyarenko, K. M.; Ponarin, N. V.; Meshkova, S. B.; Zheltvai, I. I.

    2015-08-01

    Spectral properties of terbium (III) complexes with composition of TbL3DL, where L is an anion of d,l-2-(4-isobutylphenyl)propanoic acid (ibuprofen) and DL is 2,2'-dipyridyl (Dipy), 1,10-phenanthroline (Phen), or triphenylphosphine oxide (TPPO), have been studied in a solid form, chloroform solutions, and polyvinylcarbazole (PVC) films. It has been demonstrated that, in PVC films, occupation of the emitting level of terbium (III) involves the participation of polymer. The emission decay lifetimes of terbium in the chloroform solutions and PVC films have been measured. The possibility of the appearance of electroluminescence of complexes in PVC films has been studied.

  11. Some properties of solid solutions of the TlInSe/sub 2/-TlNdSe/sub 2/

    SciTech Connect

    Godzhaev, E.M.; Rzaeva, K.M.

    1987-05-01

    Solid solutions of the title system are investigated. Schematic diffractograms of the alloys TlIn/sub 1-x/-Nd/sub x/Se/sub 2/ are represented. Tables show the results of indexing the x-ray diffractograms of alloys of the title system. Current-voltage characteristics of the alloys are investigated under static conditions and the variation in the band-gap width was calculated as a function of the composition of the title solution from temperature dependences of the electrical conductivity and Hall effect.

  12. The role of strain and structure on oxygen ion conduction in nanoscale zirconia and ceria thin films

    NASA Astrophysics Data System (ADS)

    Jiang, Jun

    Solid oxide fuel cells (SOFCs), an all solid-state energy conversion device, are promising for their high efficiency and materials stability. The solid oxide electrolytes are a key component that must provide high ionic conductivity, which is especially challenging for intermediate temperature SOFCs operating between 500 °C - 700 °C. Doped zirconia and ceria are the most common solid electrolyte materials. Recent reports have suggested that nanoscale ytrria stabilized zirconia (YSZ) thin films may provide better performance in this regard. However, the mechanism behind the increased conductivity of nanoscale thin films is still unclear and the reported experimental results are controversial. In the thesis presented here, the effects of mechanical strain and microstructure on the ionic conductivity have been investigated in ultrathin zirconia- and ceria-based thin films. Reactive RF co-sputtering with metal targets was used to prepare zirconia and ceria based thin films for high purity, modulated composition and thickness. The films were as thin as 10-20 atomic layers thick. X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy were the main tools to investigate the composition, crystal orientation and microstructure of these sputtered thin films. Microscale interdigitated Pt electrodes were prepared through a lift-off process using photolithography. The electrochemical properties of these sputtered doped zirconia and ceria thin films were investigated using impedance spectroscopy. YSZ thin films deposited on MgO (111) and, especially, MgO (100) showed highly variable crystal orientations, while MgO (110) offered much more stable growth. Regardless of whether the growth was epitaxial or highly disordered polycrystalline, 50 nm thick YSZ thin films on MgO (100), (110), and (111) substrates exhibited similar conductivity with YSZ single crystal. While decreasing the thickness further to 12 nm, the conductivities of YSZ thin films

  13. Thermophysical characteristics of Pb0.679Cd0.321F2 solid-solution crystals

    NASA Astrophysics Data System (ADS)

    Popov, P. A.; Matovnikov, A. V.; Moiseev, N. V.; Buchinskaya, I. I.; Karimov, D. N.; Sorokin, N. I.; Sulyanova, E. A.; Sobolev, B. P.; Krutov, M. A.

    2015-01-01

    The thermal conductivity (at temperatures of 50-300 K) and specific heat (at 58-307 K) of Pb0.679Cd0.321F2 solid solution crystals with a fluorite structure, as well as the specific heat of crystals of fluorite modification β-PbF2 (in a temperature range of 79-311 K), have been experimentally investigated for the first time. The temperature dependences of the phonon mean free path in these crystals are determined.

  14. Dependence of the hybridization parameter on nitrogen molar fraction in nitrogen-containing GaPN solid solutions

    NASA Astrophysics Data System (ADS)

    Nikitina, E. V.; Sobolev, M. S.; Pirogov, E. V.; Egorov, A. Yu.

    2013-12-01

    Heterostructures with GaP1 - x N x layers synthesized by molecular beam epitaxy on GaP(001) substrates have been studied by photoluminescence and X-ray diffraction measurement. The results are compared to parameters calculated using the band anticrossing (BAC) model. Results of this comparative study lead to the conclusion that the hybridization parameter of GaP1 - x N x depends on the molar fraction of nitrogen in the solid solution.

  15. Thermodynamic mixing properties of the UO2-HfO2 solid solution: Density functional theory and Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Yuan, Ke; Ewing, Rodney C.; Becker, Udo

    2015-03-01

    HfO2 is a neutron absorber and has been mechanically mixed with UO2 in nuclear fuel in order to control the core power distribution. During nuclear fission, the temperature at the center of the fuel pellet can reach above 1300 K, where hafnium may substitute uranium and form the binary solid solution of UO2-HfO2. UO2 adopts the cubic fluorite structure, but HfO2 can occur in monoclinic, tetragonal, and cubic structures. The distribution of Hf and U ions in the UO2-HfO2 binary and its atomic structure influence the thermal conductivity and melting point of the fuel. However, experimental data on the UO2-HfO2 binary are limited. Therefore, the enthalpies of mixing of the UO2-HfO2 binary with three different structures were calculated in this study using density functional theory and subsequent Monte Carlo simulations. The free energy of mixing was obtained from thermodynamic integration of the enthalpy of mixing over temperature. From the ΔG of mixing, a phase diagram of the binary was obtained. The calculated UO2-HfO2 binary forms extensive solid solution across the entire compositional range, but there are a variety of possible exsolution phenomena associated with the different HfO2 polymorphs. As the structure of the HfO2 end member adopts lower symmetry and becomes less similar to cubic UO2, the miscibility gap of the phase diagram expands, accompanied by an increase in cell volume by 7-10% as the structure transforms from cubic to monoclinic. Close to the UO2 end member, which is relevant to the nuclear fuel, the isometric uranium-rich solid solutions exsolve as the fuel cools, and there is a tendency to form the monoclinic hafnium-rich phase in the matrix of the isometric, uranium-rich solid solution phase.

  16. Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions

    SciTech Connect

    Tyrsted, Christoffer; Ørnsbjerg; #8197; Jensen, Kirsten Marie; Bøjesen, Espen Drath; Lock, Nina; Christensen, Mogens; Billinge, Simon J.L.; Brummerstedt; #8197; Iversen, Bo

    2012-10-23

    The formation and evolution of ceria nanoparticles during hydrothermal synthesis was investigated by in-situ total scattering and powder diffraction. The nucleation of pristine crystalline ceria nanoparticles originated from previously unknown cerium dimer complexes. The nanoparticle growth was highly accelerated under supercritical conditions.

  17. Rationalization of interactions in precious metal/ceria catalysts using the d-band center model.

    PubMed

    Acerbi, N; Tsang, S C Edman; Jones, G; Golunski, S; Collier, P

    2013-07-22

    A correlation between ceria reducibility and the precious-metal d-band center is reported for ceria-supported precious-metal catalysts. The results could provide the missing link to fully explain the occurrence of strong metal-support interaction (SMSI) and hydrogen spillover in catalysts that consist of dispersed metals in contact with reducible metal oxides. PMID:23780919

  18. Reversibility of hydrogen chemisorption on a ceria-supported rhodium catalyst

    SciTech Connect

    Bernal, S.; Calvino, J.J.; Cifredo, G.A.; Izquierdo, J.M. Rodriguez ); Perrichon, V.; Laachir, A. )

    1992-09-01

    Cerium dioxide is an important component of the so-called three-way catalysts. This work reports on some new aspects of the chemistry of hydrogen-ceria systems. It is shown that, at room temperature, in the presence of highly dispersed rhodium, ceria chemisorbs large amounts of hydrogen. As deduced from magnetic measurements carried out in situ, this spillover process leads to the reduction of ceria to an extent of 21% of the total amount of cerium ions present in the sample, which is roughly equivalent to the complete surface reduction of the oxide. It is found that over a highly hydroxylated sample the reduction of ceria induced by the spillover process is partly reversible even at 295 K. If the sample is pumped off at 773 K, the initial oxidation state of ceria is almost completely recovered. Both the rate and extent of hydrogen chemisorption on ceria were found to be sensitive to the specific pretreatment applied to the catalyst. Over bare ceria, hydrogen chemisorption at 298 K was negligible, temperatures as high as 473 K being necessary to activate the process. In contrast to the rhodium-containing catalyst, over pure ceria the desorption of hydrogen leads to a much larger extent to water formation, thus revealing a deeper irreversible reduction of the oxide.

  19. Eco-friendly Synthesis of Ceria Foam via Carboxymethylcellulose Gelation: Application for the Epoxidation of Chalcone

    EPA Science Inventory

    A simple and innovative process is described for the eco-friendly preparation of ceria foams via the carboxymethylcellulose gelation by Ce4+ cations; heat treatment of the ensuing xerogels produces ceria foams. The influence of the concentration of cerium and of the calcination t...

  20. Formation and Characteristics of Anatase-Type Titania Solid Solution Nanoparticles Doped with Nb5+ M (M = Ga3+, Al3+, Sc3+)

    NASA Astrophysics Data System (ADS)

    Hirano, Masanori; Ito, Takaharu

    2011-10-01

    Anatase-type titania solid solutions co-doped with Nb5+ and cation M (M = Ga3+, Al3+, Sc3+) with composition Ti1-2XNbXMXO2 were directly formed as nanoparticles from precursor solutions of TiOSO4, NbCl5, and metal salts (Ga(SO4)3, Al(NO3)3, and Sc(NO3)3) under mild hydrothermal conditions at 180 °C for 5 h using the hydrolysis of urea. The effect of co-doped cation M on the formation and properties of anatase-type titania solid solutions was investigated. The region of anatse-type solid solution depended on the co-doped cation M. The composition range of anatase-type titania solid solution in the case of M = Sc3+ was much wider than that in the case of M = Ga3+ and Al3+. The increase in the amount of co-doped cation M = Ga3+, Al3+ enhanced the crystallite growth of anatase solid solutions under the hydrothermal conditions. The solid solutions co-doped with M = Al3+ showed the most improved photocatalytic activity in the three cations. The anatase-to-rutile phase transformation of solid solutions was promoted at lower temperature via the presence of co-doped cation M = Ga3+.

  1. The reaction of ceria coatings on mica with H{sub 2}S An in-situ X-ray diffraction study

    SciTech Connect

    Bertaux, S.; Reynders, P.; Schweda, E

    2004-05-05

    Thin layers of ceria were deposited on the surface of mica platelets in solution. The reaction of such particles with hydrogen sulfide yields a red colored special effect pigment. The ceria layer reacts with H{sub 2}S to produce a variety of sulfide and oxysulfide phases. The reaction path discovered in situ by time and temperature resolved X-ray diffraction is CeO{sub 2}{yields}CeS{sub 2}{yields}C-Ce{sub 2}S{sub 3}{yields}Ce{sub 10}S{sub 14}O. The reaction itself is extremely variable depending on gas flow, heating rates and decomposition atmospheres. Effects on the thin film are recorded by scanning electron microscopy (SEM) and revealed a destruction of the layer once red Ce{sub 10}S{sub 14}O was formed. The product layer then reveals the typical nonwetting behaviour of a liquid on a surface.

  2. Novel ceria-zirconia-yttria mesostructures: Synthesis, characterization, diffusional studies & the effects of morphology on their properties

    NASA Astrophysics Data System (ADS)

    Cordova Morales, Alma Iris

    Ceria-zirconia-yttria (CZY) mixed oxides are used as catalyst supports for three-way catalysts for automotive exhaust emission control and in solid oxide fuel cells. By improving the morphology of CZY mesopores it is possible to reduce the sintering of supported noble metals and enhance overall catalyst lifetime and performance. However, limited studies have been published on the synthetic control of the morphology of CZY materials and the effects that CZY pore geometry has on catalyst operation. To create optimized CZY catalyst supports, novel mesoporous CZY oxides were synthesized via classical sol-gel and evaporation induced self-assembly (EISA) methods, obtaining mesostructures that exhibited excellent physical and diffusional properties. This dissertation provides a detailed analysis of the factors and mechanisms that promote the creation of ordered mesoporous CZY structures via classical sol-gel and EISA approaches. Classical sol-gel methods are reaction-limited syntheses in which, for the case of CZY materials, the formation of polyoxides occurs rapidly as a result of the availability of water and hydrolyzing agents in the initial solution, yielding disordered oxide mesostructures. Alternatively, EISA is a diffusion-limited process, where the rate of oxide forming reactions is limited by the slow diffusion of water into the initial ethanolic-metal salts solution. The slow loss of ethanol by evaporation enables the condensation-polymerization of metal oxy-hydroxide species to coincide with the ordering of these oligomers around the self-organized polymer template. Thus, for the templated synthesis of mesoporous CZY materials, it is the rate of metal oxide condensation that determines the nature of the resulting oxide structure. The choice of templating technique used during CZY synthesis heavily influenced post-calcination morphologies and pore sizes, but to-date no relationships between pore morphology and catalyst performance for CZY materials was presented

  3. Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

    PubMed Central

    Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; Di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

    2015-01-01

    Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1–0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J–V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. PMID:26577287

  4. A study of room-temperature LixMn1.5Ni0.5O4 solid solutions

    DOE PAGESBeta

    Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying

    2015-01-26

    Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4 (Phase I), Li0.5Mn1.5Ni0.5O4 (Phase II) and Mn1.5Ni0.5O4 (Phase III). A phase diagram capturing the structuralmore » changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.« less

  5. Controlling the oxygen potential to improve the densification and the solid solution formation of uranium-plutonium mixed oxides

    NASA Astrophysics Data System (ADS)

    Berzati, Ségolène; Vaudez, Stéphane; Belin, Renaud C.; Léchelle, Jacques; Marc, Yves; Richaud, Jean-Christophe; Heintz, Jean-Marc

    2014-04-01

    Diffusion mechanisms occurring during the sintering of oxide ceramics are affected by the oxygen content of the atmosphere, as it imposes the nature and the concentration of structural defects in the material. Thus, the oxygen partial pressure, p(O2), of the sintering gas has to be precisely controlled, otherwise a large dispersion in various parameters, critical for the manufacturing of ceramics such as nuclear oxides fuels, is likely to occur. In the present work, the densification behaviour and the solid solution formation of a mixed uranium-plutonium oxide (MOX) were investigated. The initial mixture, composed of 70% UO2 + 30% PuO2, was studied at p(O2) ranging from 10-15 to 10-4 atm up to 1873 K both with dilatometry and in situ high temperature X-ray diffraction. This study has shown that the initial oxides UO2+x and PuO2-x first densify during heating and then the solid solution formation starts at about 200 K higher. The densification and the formation of the solid solution both occur at a lower temperature when p(O2) increases. Based on this result, it is possible to better define the sintering atmosphere, eventually leading to optimized parameters such as density, oxygen stoichiometry and cations homogenization of nuclear ceramics and of a wide range of industrial ceramic materials.

  6. A study of room-temperature LixMn1.5Ni0.5O4 solid solutions

    PubMed Central

    Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying

    2015-01-01

    Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4 (Phase I), Li0.5Mn1.5Ni0.5O4 (Phase II) and Mn1.5Ni0.5O4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. The work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance. PMID:25619504

  7. Study of Kinetic Coefficients of (GeTe)1-x - (Ga2Te3)x Solid Solutions

    NASA Astrophysics Data System (ADS)

    Akperov, M. H.; Atalay, T.; Aþkin, H.; Erer, A. M.

    1998-04-01

    In this study, such kinetic cparametres as thermoelectro motor force (thermo e.m.f), electrical coductivity, heat conductivity, Hall and Nernst-Ettingshausen coeficients are investigated, as a function of chemical composition of (GeTe)1-x-(Ga2Te3)x and temperature, by physicochemical methods and x-rays analysis. The kinetic parameters (GeTe)1-x-(Ga2Te3)x solid solutions are investigated between x=0 and 0,015 and between 77 and 900 K. Adding of Ga2Te3 to GeTe reduces the phase transition temperature of b-GeTe to a-GeTe. It is observed that in the region of solid solution the rhombohedral modification of GeTe are protected. Doping of GeTe with Ga2Te3 does not affect the kinetic parameters of GeTe. Anomalies in the rhombohedral phase of solid solutions are related with splitting of cubic phase extremums due to deformation of the rhombohedral lattice. Decreasing of Hall coefficient while increasing thermo e.m.f near phase transition point, in the cubic phase were explained with changing of Hall factor A.

  8. Microwave dielectric properties of Na(x)Nd((2-x)/3)TiO(3) solid solutions.

    PubMed

    Kagomiya, Isao; Yamada, Yuko; Kakimoto, Ken-ichi; Ohsato, Hitoshi

    2008-12-01

    Na(x)Nd((2-x)/3)TiO(3) solid solutions possess tetragonal or orthorhombic perovskite structure, where the A-sites are characterized by 2 kinds of cations (Na(+), Nd(3+)) and vacancies. We have measured microwave dielectric properties of Na(x)Nd((2-x)/3)TiO(3) solid solutions (x = 0.05 to 0.5) to investigate an effect of the compositional ordering in the A-sites of the perovskite structure. According to powder x-ray diffraction, the A-site is disordered in the composition range of x = 0.29 to 0.5. A compositional ordering (Na(+), vacancy / Nd(3+)) in A-sites appeared when x = 0.05 to 0.2. The quality factor (Q x f), where Q is the inverse of dielectric loss and f is frequency, was found to be slightly improved with decreasing Na content in the range of x = 0.05 to 0.2, suggesting that the Q x f of the Na(x)Nd((2-x)/3)TiO(3) solid solutions depends on the compositional ordering in A-sites. PMID:19126483

  9. Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

    2015-11-01

    Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1-0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J-V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms.

  10. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

    SciTech Connect

    Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; Bennett, Joseph W.; Grinberg, Ilya; Rappe, Andrew M.

    2011-12-15

    Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn1/3Nb2/3)O₃ and Pb(Mg1/3Nb2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.

  11. Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

    NASA Astrophysics Data System (ADS)

    Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

    2013-03-01

    A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

  12. Structural and photo luminescent properties of uncapped nanocrystalline Cd 1- xZn xS solid solutions

    NASA Astrophysics Data System (ADS)

    Arora, Sonia; Manoharan, S. Sundar

    2008-10-01

    Uncapped nanocrystalline Cd 1- xZn xS (0.0 ⩽ x ⩾ 0.5) solid solution prepared by microwave assisted combustion route shows hexagonal to cubic phase transformation for even low doping of zinc up to 5 at.% as evident from the X-ray diffraction patterns and the selected area electron diffraction patterns. The solid solutions show a considerable shift in the optical absorption edge from ˜2.43 eV (CdS) to ˜2.73 eV for the equi-atomic composition (Cd 0.5Zn 0.5S). The blue emission in CdS shows effect of quantum confinement. The photo luminescence spectra of Zn lean compositions (up to 5 at.%) show emergence of a peak at λ ˜ 530 nm along with the blue emission features of CdS. However, solid solutions with higher zinc content (up to 50 at.%), show a systematic increase in the intensity of peak at 530 nm with a blue shift up to 30 at.% of zinc doping. Beyond 30%, a broad blue-green emission with full width at half maxima of ˜100 nm for Cd 0.5Zn 0.5S is observed.

  13. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

    DOE PAGESBeta

    Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; Bennett, Joseph W.; Grinberg, Ilya; Rappe, Andrew M.

    2011-12-15

    Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn1/3Nb2/3)O₃ and Pb(Mg1/3Nb2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impactmore » on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

  14. 2,6-Diketopiperazines from amino acids, from solution-phase to solid-phase organic synthesis.

    PubMed

    Perrotta, E; Altamura, M; Barani, T; Bindi, S; Giannotti, D; Harmat, N J; Nannicini, R; Maggi, C A

    2001-01-01

    A method to prepare 1,3-disubstituted 2,6-diketopiperazines (2,6-DKP) as useful heterocyclic library scaffolds in the search of new leads for drug discovery is described. The method can be used in solution-phase and solid-phase conditions. In the key step of the synthesis, the imido portion of the new molecule is formed in solution through intramolecular cyclization, under basic conditions, of a secondary amide nitrogen on a benzyl ester. A Wang resin carboxylic ester is used as the acylating agent under solid-phase conditions, allowing the cyclization to take place with simultaneous cleavage of the product from the resin ("cyclocleavage"). The synthetic method worked well with several couples of amino acids, independently from their configuration, and was used for the parallel synthesis of a series of fully characterized compounds. The use of iterative conditions in the solid phase (repeated addition of fresh solvent and potassium carbonate to the resin after filtering out the product-containing solution) allowed us to keep diastereoisomer content below the detection limit by HPLC and (1)H NMR (200 MHz). PMID:11549363

  15. Solid-solution partitioning of plutonium in surface waters at the Atomic Weapons Establishment Aldermaston (UK).

    PubMed

    McCubbin, David; Leonard, Kinson S; Greenwood, Richard C; Taylor, Benjamin R

    2004-10-01

    The Atomic Weapons Establishment (AWE) at Aldermaston (Berkshire, UK) has provided and maintained the warheads for the UK's nuclear deterrent for more than 50 years. Whilst the site is radiologically safe, in a few locations the soil contains specific activities of plutonium (Pu) above background arising from a legacy of historic operations. Run-off water (a mixture of rainwater and groundwater) from part of the site is routed into a water management system, and after analysis and radiological assessment, released into local streams. Water and sediment samples have been collected from a number of closely spaced locations within this system to assess the solid-solution partitioning of Pu. Survey work was complemented by batch type desorption experiments to assess redissolution from 'contaminated' sediment into 'uncontaminated' water. The survey data indicate that specific activities of both dissolved and particle bound 239 + 240Pu varied by roughly two orders of magnitude, ranging from approximately 0.7 microBq kg(-1) up to approximately 44 microBq kg(-1), and approximately 1.2 Bq kg(-1) up to approximately 400 Bq kg(-1), respectively, consistent with water originating from different parts of the site. Apparent Kd values varied by an order of magnitude (from 0.7-16 x 10(6)) with an average value of 4 x 10(6). Results from the desorption experiments indicated the extent of redissolution was very small and the derived Kd's corroborated values obtained from the survey work. Kd's given here are compared with other literature values, and are the greatest reported to date. Results are also provided describing the variation in water quality parameters in shallow groundwater samples. Alkalinity values ranged from 120 to 388 mg l(-1) CaCO3 with an average value of 195 mg l(-1) CaCO3. Corresponding values for pH were 6.6-8.3 with an average of 7.5. Over half of the samples were estimated to be supersaturated with respect to calcite. It is suggested that the state of calcite

  16. The effects of solid solution on the stability of the 10 Å phase

    NASA Astrophysics Data System (ADS)

    Howe, H.; Pawley, A. R.; Droop, G.

    2014-12-01

    Subduction of hydrous phases enables the transport of water into the typically anhydrous mantle. Dehydration of these phases has a dramatic expression at the Earth's surface in the form of earthquakes and arc volcanism. Within a subduction zone, talc (Mg3Si4O10(OH)2) is found within the hydrothermally altered oceanic crust and pelagic sediments of the subducting slab, as well as the metasomatised mantle wedge. The 10 Å phase (Mg3Si4O10(OH)2.H2O) forms from the breakdown of talc at low temperatures and pressures above 5 GPa, and is thought to be stable to depths up to 200 km1. Previous work has focused on the stability of Mg end-members of talc and the 10 Å phase. However, natural samples of talc show deviation from end member composition, most significantly in the substitution of iron for magnesium. It is likely that the stability of iron-bearing talc and its high pressure equivalent, the 10 Å phase, will differ from that of Mg end-member compositions, as demonstrated by previous studies examining the effect of solid solution in phyllosilicates such as antigorite. High pressure experiments using the multi-anvil press at the University of Manchester have bracketed the reaction talc + H2O = 10 Å phase for Mg end-member compositions. Samples of iron-bearing talc and the 10 Å phase have been synthesised at pressures of 2 GPa and 6.2 GPa, respectively. By performing phase equilibrium experiments on iron-bearing talc and 10 Å phase it is possible to quantify the effect of composition on the position of the reaction talc + H2O = 10 Å phase, as well the thermal breakdown of the 10 Å phase to enstatite and coesite. Univarient breakdown reactions assume that the 10 Å dehydrates at one discrete depth, where the thermal stability has been exceeded. The results are expected to show that instead, fluid release from 10 Å phase dehydration is more likely to occur over a range of depths during subduction, dependant on the bulk composition and the thermal regime of the

  17. Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

    NASA Astrophysics Data System (ADS)

    Purohit, Parag

    Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification. Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used. It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone

  18. Distribution and bioavailability of ceria nanoparticles in an aquatic ecosystem model.

    PubMed

    Zhang, Peng; He, Xiao; Ma, Yuhui; Lu, Kai; Zhao, Yuliang; Zhang, Zhiyong

    2012-10-01

    Along with the increasing utilization of engineered nanoparticles, there is a growing concern for the potential environmental and health effects of exposure to these newly designed materials. Understanding the behavior of nanoparticles in the environment is a basic need. The present study aims to investigate the distribution and fate of ceria nanoparticles in an aquatic system model which consists of sediments, water, hornworts, fish and snails, using a radiotracer technique. Concentrations of ceria in the samples at regular time intervals were measured. Ceria nanoparticles were readily removed from the water column and partitioned between different organisms. Both snail and fish have fast absorption and clearance abilities. Hornwort has the highest bioaccumulation factors. At the end of the experiment, sediments accumulated most of the nanoparticles with a recovery of 75.7 ± 27.3% of total ceria nanoparticles, suggesting that sediments are major sinks of ceria nanoparticles. PMID:22694776

  19. Effect of Ceria on the Storage and Regeneration Behavior of a Model Lean NOx Trap Catalyst

    SciTech Connect

    Ji, Yaying; Toops, Todd J; Crocker, Dr. Mark

    2007-01-01

    In this study the effect of ceria addition on the performance of a model Ba-based lean NO{sub x} trap (LNT) catalyst was examined. The presence of ceria improved NO{sub x} storage capacity in the temperature range 200-400 C under both continuous lean and lean-rich cycling conditions. Temperature-programmed experiments showed that NO{sub x} stored in the ceria-containing catalyst was thermally less stable and more reactive to reduction with both H{sub 2} and CO as reductants, albeit at the expense of additional reductant consumed by reduction of the ceria. These findings demonstrate that the incorporation of ceria in LNTs not only improves NO{sub x} storage efficiency but also positively impacts LNT regeneration behavior.

  20. Reply to Dr. Stoesselfs Comment on "Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems"

    NASA Astrophysics Data System (ADS)

    Glynn, Pierre D.; Reardon, Eric J.; Plummer, L. Niel; Busenberg, Eurybiades

    1992-06-01

    In reply to the Critical Comment of R. K. Stoessell (this issue), limiting activity coefficients of bromide in halite ( γNaBr) have been calculated by least-squares fitting of SIMONS et al.'s (1952) bromide distribution coefficient data for the Na(Cl,Br)-NaOH-H 2O system at 35°C. Regular and subregular solidsolution model fits give γNaBr = 7.4 and γNaBr = 8.8, respectively. The Br contents of halite at equilibrium with seawater at initial halite saturation, calculated from the regular and subregular fits, are 17 ppm and 14 ppm, respectively. A survey of literature data for trace bromide in halite shows a wide spread in distribution coefficients, with lower values ( DBr≈ 0.01) reported by BLOCH and SCHNERB (1953), PUCHELT et al. (1972), and LUTZ (1975), and higher values ( DBr- ≈ 0.03) reported by BRAITSCH and HERRMANN (1963), KüHN (1968), HERRMANN (1972), HERRMANN (1980), MCCAFFREY et al. (1987), VALIASHKO et al. (1976), VALIASHKO and LAVROVA (1976), and Fontes (pers. commun., 1990). The measurement of stoichiometric saturation states for halite (or sylvite) with trace bromide mole-fractions is not practical, given the insensitivity of the measured solubilities on the bromide mole-fractions. Distribution coefficient measurements, with proof of thermodynamic equilibrium, need to be obtained instead, to conclusively determine the thermodynamic-mixing properties of both Na(Cl,Br) and K(Cl,Br) solidsolution series at very low mole-fractions of bromide. The applicability of the stoichiometric saturation concept to the interpretation of precipitation processes is questionable, primarily because the concept requires solid-solutions to behave as one-component solids with fixed composition. Lippmann diagrams are useful in depicting stoichiometric saturation, endmember saturation, and thermodynamic equilibrium states in binary-solid-solution aqueous-solution systems. Lippmann diagrams can contribute a better understanding of these systems, regardless of the

  1. Manganese and Ceria Sorbents for High Temperature Sulfur Removal from Biomass-Derived Syngas -- The Impact of Steam on Capacity and Sorption Mode

    SciTech Connect

    Cheah, S.; Parent, Y. O.; Jablonski, W. S.; Vinzant, T.; Olstad, J. L.

    2012-07-01

    Syngas derived from biomass and coal gasification for fuel synthesis or electricity generation contains sulfur species that are detrimental to downstream catalysts or turbine operation. Sulfur removal in high temperature, high steam conditions has been known to be challenging, but experimental reports on methods to tackle the problem are not often reported. We have developed sorbents that can remove hydrogen sulfide from syngas at high temperature (700 C), both in dry and high steam conditions. The syngas composition chosen for our experiments is derived from statistical analysis of the gasification products of wood under a large variety of conditions. The two sorbents, Cu-ceria and manganese-based, were tested in a variety of conditions. In syngas containing steam, the capacity of the sorbents is much lower, and the impact of the sorbent in lowering H{sub 2}S levels is only evident in low space velocities. Spectroscopic characterization and thermodynamic consideration of the experimental results suggest that in syngas containing 45% steam, the removal of H{sub 2}S is primarily via surface chemisorptions. For the Cu-ceria sorbent, analysis of the amount of H{sub 2}S retained by the sorbent in dry syngas suggests both copper and ceria play a role in H{sub 2}S removal. For the manganese-based sorbent, in dry conditions, there is a solid state transformation of the sorbent, primarily into the sulfide form.

  2. A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

    USGS Publications Warehouse

    Davis, J.A.; Fuller, C.C.; Cook, A.D.

    1987-01-01

    The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

  3. Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry.

    PubMed

    Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik

    2015-11-01

    Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD. PMID:26457879

  4. Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules

    PubMed Central

    Nims, Robert J.; Maas, Steve; Weiss, Jeffrey A.

    2014-01-01

    Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio (www.febio.org). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the

  5. Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

    PubMed

    Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

    2014-10-01

    Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the

  6. Phase transition in multiferroic YMnO3 and its solid solution YMn(0.93)Fe(0.07)O3

    NASA Astrophysics Data System (ADS)

    Salazar-Kuri, U.; Mendoza, M. E.; Siqueiros, J. M.

    2012-09-01

    Ceramics of YMnO3 and its Fe substituted YMn(0.93)Fe(0.07)O3 solid solution were synthesized by solid state reaction of the oxides at 1200 °C. Hexagonal phase was identified in both cases by X-ray powder diffraction. Rietveld refinement of cell parameters showed an increase of the parameter values for the solid solution. Dielectric permittivity measurements versus temperature showed a phase transition at 655 °C for yttrium manganite, however, for the solid solution no phase transition was detected on heating up to 700 °C. Dielectric loss measurements showed higher slope changes and better defined local maxima for the solid solution than for the pure phase.

  7. Processing of solid solution, mixed uranium/refractory metal carbides for advanced space nuclear power and propulsion systems

    NASA Astrophysics Data System (ADS)

    Knight, Travis Warren

    Nuclear thermal propulsion (NTP) and space nuclear power are two enabling technologies for the manned exploration of space and the development of research outposts in space and on other planets such as Mars. Advanced carbide nuclear fuels have been proposed for application in space nuclear power and propulsion systems. This study examined the processing technologies and optimal parameters necessary to fabricate samples of single phase, solid solution, mixed uranium/refractory metal carbides. In particular, the pseudo-ternary carbide, UC-ZrC-NbC, system was examined with uranium metal mole fractions of 5% and 10% and corresponding uranium densities of 0.8 to 1.8 gU/cc. Efforts were directed to those methods that could produce simple geometry fuel elements or wafers such as those used to fabricate a Square Lattice Honeycomb (SLHC) fuel element and reactor core. Methods of cold uniaxial pressing, sintering by induction heating, and hot pressing by self-resistance heating were investigated. Solid solution, high density (low porosity) samples greater than 95% TD were processed by cold pressing at 150 MPa and sintering above 2600 K for times longer than 90 min. Some impurity oxide phases were noted in some samples attributed to residual gases in the furnace during processing. Also, some samples noted secondary phases of carbon and UC2 due to some hyperstoichiometric powder mixtures having carbon-to-metal ratios greater than one. In all, 33 mixed carbide samples were processed and analyzed with half bearing uranium as ternary carbides of UC-ZrC-NbC. Scanning electron microscopy, x-ray diffraction, and density measurements were used to characterize samples. Samples were processed from powders of the refractory mono-carbides and UC/UC 2 or from powders of uranium hydride (UH3), graphite, and refractory metal carbides to produce hypostoichiometric mixed carbides. Samples processed from the constituent carbide powders and sintered at temperatures above the melting point of UC

  8. Lung deposition and extrapulmonary translocation of nano-ceria after intratracheal instillation

    NASA Astrophysics Data System (ADS)

    He, Xiao; Zhang, Haifeng; Ma, Yuhui; Bai, Wei; Zhang, Zhiyong; Lu, Kai; Ding, Yayun; Zhao, Yuliang; Chai, Zhifang

    2010-07-01

    The broad potential applications of manufactured nanomaterials call for urgent assessment of their environmental and biological safety. However, most of the previous work focused on the cell level performance; little was known about the consequences of nanomaterial exposure at the whole-body and organ levels. In the present paper, the radiotracer technique was employed to study the pulmonary deposition and the translocation to secondary target organs after ceria nanoparticles (nano-ceria) were intratracheally instilled into Wistar rats. It was found that 63.9 ± 8.2% of the instilled nano-ceria remained in the lung by 28 d postexposure and the elimination half-life was 103 d. At the end of the test period, only 1/8-1/3 of the daily elimination of nano-ceria from the lung was cleared via the gastrointestinal tract, suggesting that phagocytosis by alveolar macrophages (AMs) with subsequent removal towards the larynx was no longer the predominant route for the elimination of nano-ceria from the lung. The whole-body redistribution of nano-ceria demonstrated that the deposited nano-ceria could penetrate through the alveolar wall into the systemic circulation and accumulate in the extrapulmonary organs. In vitro study suggested that nano-ceria would agglomerate and form sediments in the bronchoalveolar aqueous surrounding while binding to protein would be conducive to the redispersion of nano-ceria. The decrease in the size of agglomerates might enhance the penetration of nano-ceria into the systemic circulation. Our findings suggested that the effect of nanomaterial exposure, even at low concentration, should be assessed because of the potential lung and systemic cumulative toxicity of the nanomaterials.

  9. Spectroscopic Investigation of Surface-Dependent Acid–Base Property of Ceria Nanoshapes

    SciTech Connect

    Wu, Zili; Mann, Amanda K. P.; Li, Meijun; Overbury, Steven H.

    2015-03-12

    In addition to their well-known redox character, the acid-base property is another interesting aspect of ceria-based catalysts. Thus, the effect of surface structure on the acid-base property of ceria was studied in detail by utilizing ceria nanocrystals with different morphologies (cubes, octahedra and rods) that exhibit crystallographically well-defined surface facets. The nature, type, strength and amount of acid and base sites on these ceria nanoshapes were investigated via in situ IR spectroscopy combined with various probe molecules. Pyridine adsorption shows the presence of Lewis acid sites (Ce cations) on the ceria nanoshapes. These Lewis acid sites are relatively weak and similar in strength among the three nanoshapes according to the probing by both pyridine and acetonitrile. Both Br nsted (hydroxyl group) and Lewis (surface lattice oxygen) base sites are present on the ceria nanoshapes as probed by CO2 adsorption. CO2 and chloroform adsorption indicate that the strength and amount of the Lewis base sites are shape dependent: rods > cubes > octahedra. Moreover, the weak and strong surface dependence of the acid and base sites, respectively, are a result of interplay between the surface structure dependent coordination unsaturation status of the Ce cations and O anions and the amount of defect sites on the three ceria nanoshapes. Furthermore, it was found that the nature of the acid-base sites of ceria can be impacted by impurities, such as Na and P residues that result from their use as structure-directing reagent in the hydrothermal synthesis of the ceria nanocrystals. Finally, our observation calls for precaution in interpreting the catalytic behavior of nanoshaped ceria where trace impurities may be present.

  10. Spectroscopic Investigation of Surface-Dependent Acid–Base Property of Ceria Nanoshapes

    DOE PAGESBeta

    Wu, Zili; Mann, Amanda K. P.; Li, Meijun; Overbury, Steven H.

    2015-03-12

    In addition to their well-known redox character, the acid-base property is another interesting aspect of ceria-based catalysts. Thus, the effect of surface structure on the acid-base property of ceria was studied in detail by utilizing ceria nanocrystals with different morphologies (cubes, octahedra and rods) that exhibit crystallographically well-defined surface facets. The nature, type, strength and amount of acid and base sites on these ceria nanoshapes were investigated via in situ IR spectroscopy combined with various probe molecules. Pyridine adsorption shows the presence of Lewis acid sites (Ce cations) on the ceria nanoshapes. These Lewis acid sites are relatively weak andmore » similar in strength among the three nanoshapes according to the probing by both pyridine and acetonitrile. Both Br nsted (hydroxyl group) and Lewis (surface lattice oxygen) base sites are present on the ceria nanoshapes as probed by CO2 adsorption. CO2 and chloroform adsorption indicate that the strength and amount of the Lewis base sites are shape dependent: rods > cubes > octahedra. Moreover, the weak and strong surface dependence of the acid and base sites, respectively, are a result of interplay between the surface structure dependent coordination unsaturation status of the Ce cations and O anions and the amount of defect sites on the three ceria nanoshapes. Furthermore, it was found that the nature of the acid-base sites of ceria can be impacted by impurities, such as Na and P residues that result from their use as structure-directing reagent in the hydrothermal synthesis of the ceria nanocrystals. Finally, our observation calls for precaution in interpreting the catalytic behavior of nanoshaped ceria where trace impurities may be present.« less

  11. Spectroscopic Investigation of Surface Dependent Acid-base Property of Ceria Nanoshapes

    DOE PAGESBeta

    Wu, Zili; Mann, Amanda K; Li, Meijun; Overbury, Steven

    2015-01-01

    In addition to their well-known redox character, the acid-base property is another interesting aspect of ceria-based catalysts. Herein, the effect of surface structure on the acid-base property of ceria was studied in detail by utilizing ceria nanocrystals with different morphologies (cubes, octahedra and rods) that exhibit crystallographically well-defined surface facets. The nature, type, strength and amount of acid and base sites on these ceria nanoshapes were investigated via in situ IR spectroscopy combined with various probe molecules. Pyridine adsorption shows the presence of Lewis acid sites (Ce cations) on the ceria nanoshapes. These Lewis acid sites are relatively weak andmore » similar in strength among the three nanoshapes according to the probing by both pyridine and acetonitrile. Both Br nsted (hydroxyl group) and Lewis (surface lattice oxygen) base sites are present on the ceria nanoshapes as probed by CO2 adsorption. CO2 and chloroform adsorption indicate that the strength and amount of the Lewis base sites are shape dependent: rods > cubes > octahedra. The weak and strong surface dependence of the acid and base sites, respectively, are a result of interplay between the surface structure dependent coordination unsaturation status of the Ce cations and O anions and the amount of defect sites on the three ceria nanoshapes. Furthermore, it was found that the nature of the acid-base sites of ceria can be impacted by impurities, such as Na and P residues that result from their use as structure-directing reagent in the hydrothermal synthesis of the ceria nanocrystals. This observation calls for precaution in interpreting the catalytic behavior of nanoshaped ceria where trace impurities may be present.« less

  12. Magnetothermoelectrical and adhesive properties of commutation contacts of thermoelements on the basis of extruded samples of Bi85Sb15 solid solution

    NASA Astrophysics Data System (ADS)

    Tagiyev, M. M.

    2003-09-01

    A study of electrical and adhesive properties of transient contacts for extruded samples of Bi85Sb15 solid solutions have been conducted with alloys: 25Bi + 50Pb + 12.5Cd + 12.5Sn with Tm = 343 K (Wood"s alloy) and 57Bi + 45Sn with Tm =412 K in temperature range ~77-300 K and magnetic field intensity (H) up to ~74x104 A/m. It is shown that resistance of transient contacts (rk) of the extruded of Bi85Sb15 solid solution with the specified contact alloys at ~77K is determined by the resistance of the structure the solid solution Bi85Sb15-solid solution Bi85Sb15, heavily doped by Pb and Sn atoms, diffused from contact alloy into near-contact area of the Bi85Sb15 solid solution. It is established, that by doping extruded samples of Bi85Sb15 solid solution with Pb atoms it is possible to achieve reduction of a transient contact resistance rk in Bi85Sb15 solid solution - contact alloy interface.

  13. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li(+) /H(+) exchange in aqueous solutions.

    PubMed

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren L; Chi, Miaofang

    2015-01-01

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7 La3 Zr2 O12 garnet as a Li-stable solid electrolyte. The material underwent a Li(+) /H(+) exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6 %. When treated with a 2 M LiOH solution, the Li(+) /H(+) exchange was reversed without any structural change. These observations suggest that cubic Li7 La3 Zr2 O12 is a promising candidate for the separator in aqueous lithium batteries. PMID:25331968

  14. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    DOE PAGESBeta

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchangedmore » even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.« less

  15. Determining mineral weathering rates based on solid and solute weathering gradients and velocities: Application to biotite weathering in saprolites

    USGS Publications Warehouse

    White, A.F.

    2002-01-01

    Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area. Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6 x 10-17 mol m-2 s-1 for biotite. Faster weathering rates of 1.8 to 3.6 ?? 10-16 mol m-2 s-1 are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering. ?? 2002 Elsevier Science B.V. All rights reserved.

  16. Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

    PubMed

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  17. Structural, Electronic, and Optical Properties of BiOX1−xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations

    PubMed Central

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1−xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1−xBrx, BiOBr1−xIx, and BiOCl1−xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1−xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1−xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1−xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1−xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical–chemical properties with different halogen compositions indicates that the parameters of BiOX1−xYx solid solutions are determined by the differences of the physical–chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1−xYx solid solutions from Vegard’s law observed in experiments can be explained. Moreover, the composition ratio of BiOX1−xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  18. Phase-field modeling of two-dimensional solute precipitation/dissolution: Solid fingers and diffusion-limited precipitation

    SciTech Connect

    Zhijie Xu; Paul Meakin

    2011-01-01

    Two-dimensional dendritic growth due to solute precipitation was simulated using a phase-field model reported earlier [Z. Xu and P. Meakin, J. Chem. Phys. 129, 014705 (2008)]. It was shown that diffusion-limited precipitation due to the chemical reaction at the solid–liquid interface has similarities with diffusion-limited aggregation (DLA). The diffusion-limited precipitation is attained by setting the chemical reaction rate much larger compared to the solute diffusion to eliminate the effect of the interface growth kinetics. The phase-field simulation results were in reasonable agreement with the analytical solutions. The fractal solid fingers can be formed in the diffusion-limited precipitation and have a fractal dimension measured df = 1.68, close to 1.64, the fractal dimensionality of large square lattice DLA clusters.

  19. Selenium distribution in the epitaxial layers of PbTe/sub 1-z/Se/sub z/ solid solutions

    SciTech Connect

    Yakimchuk, D.Yu.; Tsveibak, I.Ya.; Sokolov, I.A.; Krapukhin, V.V.

    1987-03-01

    The authors have studied the Se distribution over the thickness of epitaxial layers of PbTe/sub 1-z/Se/sub z/ solid solutions that were obtained on PbTe (100) substrates by the method of forced cooling of solutions in melts in lead in the range 540-490/sup 0/C. The Se concentration has been found to have a considerable gradient. Theoretical analysis has shown that the Se distribution coefficient exceeds the values that are known from the literature and the molar fraction of PbSe in the liquid phase at the onset of the growth of the epitaxial layer is lower than the initial value; this indicates that the substrate dissolves when it comes into contact with the solution in a melt.

  20. Poloxamer-based curcumin solid dispersions for ex tempore preparation of supersaturated solutions intended for antimicrobial photodynamic therapy.

    PubMed

    Vukićević, Milica; Hegge, Anne Bee; Vulić, Predrag; Tønnesen, Hanne Hjorth

    2014-06-19

    Abstract Phototoxic effect of curcumin supersaturated solutions toward pathogenic bacteria has already been demonstrated. However, to be useful in the clinical practice, a supersaturated solution needs to be physically and chemically stabile over the relevant time period. Poloxamer-based solid dispersions (SD) intended for ex tempore preparation of a supersaturated solution were designed to simultaneously facilitate dissolution and inhibit precipitation of curcumin in vitro. Due to the transformation of the crystalline compound to an amorphous form, as shown by X-ray powder diffraction, the desired concentration of curcumin could easily be achieved upon hydration of SDs. The efficiency of selected poloxamers (Pluronic® F-127, F-68 and P-123) as the precipitation inhibitors (PIs) and influence of an additional PI (polyethylene glycol 400, hydroxypropyl methylcellulose, and hyaluronic acid) on the physical stability of the solutions were examined by UV-Vis spectrophotometry. HPLC-PDA was employed to evaluate hydrolytic and photolytic stability of curcumin in the SD solutions. At sub-micellar concentrations, Pluronics® F-127 and P-123, but not F-68, delayed curcumin precipitation in aqueous media and protected the compound from hydrolytic degradation up to 24 h. Complete inactivation of Enterococcus faecalis was achieved after exposure to solutions of selected SDs at curcumin concentration ≥1 µM and the light dose of 9.4 J/cm(2). PMID:24946137

  1. Minimal cross-sensitivity to humidity during ethanol detection by SnO2-TiO2 solid solutions.

    PubMed

    Tricoli, Antonio; Righettoni, Marco; Pratsinis, Sotiris E

    2009-08-01

    A nanocomposite material is presented that optimally combines the excellent gas sensitivity of SnO2 and the selectivity of TiO2. Nanostructured, rutile titanium-tin oxide solid solutions up to 81.5% Ti, as determined by x-ray diffraction, are made by scalable spray combustion (flame spray pyrolysis) of organometallic precursor solutions, directly deposited and in situ annealed onto sensing electrodes in one step. Above that content, segregation of anatase TiO2 takes place. It was discovered that at low titanium contents (less than 5 Ti%), these materials exhibit higher sensitivity to ethanol vapor than pure SnO2 and, in particular, limited cross-sensitivity to relative humidity, a long standing challenge for metal oxide gas sensors. These solid solutions are aggregated nanoparticles with an enhanced presence of Ti on their surface as indicated by Raman and IR-spectroscopy. The presence of such low Ti-content in the SnO2 lattice drastically reduces the band gap of these solid solutions, as determined by UV-vis absorption, almost to that of pure TiO2. Furthermore, titania reduces the number of rooted and terminal OH species (that are correlated to the cross-sensitivity of tin oxide to water) on the particle surface as determined by IR-spectroscopy. The present material represents a new class of sensors where detection of gases and organic vapors can be accomplished without pre-treatment of the gas mixture, avoiding other semiconducting components that require more heating power and that add bulkiness to a sensing device. This is attractive in developing miniaturized sensors especially for microelectronics and medical diagnostics. PMID:19597246

  2. Physicochemical characterization of 2-hydroxybenzophenone with β-cyclodextrin in solution and solid state.

    PubMed

    Sancho, Matias I; Russo, Marcos G; Moreno, M Sergio; Gasull, Estela; Blanco, Sonia E; Narda, Griselda E

    2015-05-01

    The characterization of the inclusion complex between 2-hydroxybenzophenone (2OHBP) and β-cyclodextrin (βCD) in the solid state was performed using Fourier transform infrared spectroscopy (FTIR), powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The apparent formation constant of the complex was determined by phase solubility diagrams and liquid chromatography (HPLC) at different temperatures. The formation of the inclusion complex induced slight shifts in the FTIR spectrum while by PXRD a new crystalline phase was observed. TEM studies revealed that the complex forms aggregates of nanometric size. The inclusion complex showed a higher solubility in the tested dissolution media than free 2OHBP. Moreover, the freeze-dried solid complex exhibits a higher thermal stability than the solid free drug. The thermodynamic analysis allowed us to conclude that the encapsulation process is endothermic in water and exothermic in methanol-water. PMID:25893377

  3. Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

    SciTech Connect

    Hoda, Numan; Budama, Leyla; Çakır, Burçin Acar; Topel, Önder; Ozisik, Rahmi

    2013-09-01

    Graphical abstract: TEM image of Pt nanoparticles produced by reducing by NaBH{sub 4} within PB-b-PEO micelles in aqueous media (scale bar 1 nm). - Highlights: • Pt nanoparticles were synthesized within amphiphilic diblock copolymer micelles. • The effects of reducing agents and precursor dose on Pt np size were investigated. • The effect on fabrication of Pt np by reducing in aqueous and solid phases was compared. • The size of nanoparticles was about 1.4 nm for all doses and reducing agents types. - Abstract: Fabrication of Pt nanoparticles using an amphiphilic copolymer template in aqueous solution was achieved via polybutadiene-block-polyethyleneoxide copolymer micelles, which acted as nanoreactors. In addition, Pt nanoparticles were synthesized using hydrogen gas as the reducing agent in solid state for the first time to compare against solution synthesis. The influences of loaded precursor salt amount to micelles and the type of reducing agent on the size of nanoparticles were investigated through transmission electron microscopy. It was found that increasing the ratio of precursor salt to copolymer and using different type of reducing agent, even in solid phase reduction, did not affect the nanoparticle size. The average size of Pt nanoparticles was estimated to be 1.4 ± 0.1 nm. The reason for getting same sized nanoparticles was discussed in the light of nucleation, growth process, stabilization and diffusion of nanoparticles within micelles.

  4. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives - their stability, complexation ability in solution or when deposited on solid anionic surface.

    PubMed

    Popr, Martin; Filippov, Sergey K; Matushkin, Nikolai; Dian, Juraj; Jindřich, Jindřich

    2015-01-01

    The thermal stability of the monosubstituted cationic cyclodextrin (CD) derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively), was studied via (1)H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxyphenol and p-nitroaniline) were determined by isothermal titration calorimetry (ITC) and compared to the native β-CD. Permanently charged cationic CD derivatives were successfully deposited on the anionic solid surface of polymeric Nafion(®) 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV-vis spectroscopy. The obtained results are promising for future industrial applications of the monosubstituted β-CD derivatives, because the preparation of cationic CD derivatives is applicable in large scale, without the need of chromatographic purification. Their ionic deposition on a solid surface is simple, yet robust and a straightforward process as well. PMID:25815069

  5. Behaviour of Silica and Florisil as Solid Supports in the Removal Process of As(V) from Aqueous Solutions

    PubMed Central

    Gabor, Andreea; Davidescu, Corneliu Mircea; Negrea, Adina; Ciopec, Mihaela; Lupa, Lavinia

    2015-01-01

    In this study two solid supports, silica and florisil, were impregnated with crown ether (dibenzo-18-crown-6) and Fe(III) ions and their efficiency was compared in the adsorption process of As(V) from aqueous solutions. The solid supports were impregnated with crown ether due to their ability to build complexes with positives ions. Fe(III) was used because of As(V) affinity for it. The impregnated solid supports were characterized by energy dispersive X-ray analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and the specific surface area. The influence of the solid : liquid ratio on the adsorption process, kinetic studies for the pseudo-first-order and pseudo-second-order, and activation energy were studied. Thermodynamic studies as well as equilibrium studies were carried out. The obtained results showed that, from the two considered materials, impregnated silica presents a higher efficiency with a good selectivity, able to remove As(V) from aqueous solutions containing trace concentrations. PMID:25821633

  6. Pyramidal growth of ceria nanostructures by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Bârcă, E. S.; Filipescu, M.; Luculescu, C.; Birjega, R.; Ion, V.; Dumitru, M.; Nistor, L. C.; Stanciu, G.; Abrudeanu, M.; Munteanu, C.; Dinescu, M.

    2016-02-01

    We report in this paper on the deposition and characterization of CeO2 nanostructured thin films with hierarchical morphology. Micro-sized ceria powder (CeO2, 99.9% purity) was pressed to obtain a ceramic target. An ArF laser working at 193 nm irradiated the target in controlled oxygen gas flow at constant pressure (0.1 mbar). Silicon wafers used as substrates for thin films were heated at different temperatures, up to 773 K. The influence of substrate temperature on the structure and surface morphology of ceria thin films was studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and scanning electron microscopy (SEM). The refractive indices and information about roughness and thickness were revealed by spectroellipsometry. Crystalline cubic ceria thin films exhibiting a hierarchical structure that combines columnar and dendritic growth were obtained at temperatures above 473 K. For the samples obtained at 773 K, columns ending in pyramidal formations with sharp edges and sizes of hundreds of nanometers were observed, indicating a high crystallinity of the layer. XRD analysis reveals a consistent increase of the X-ray coherence length/crystallite size along the [111] direction with increasing temperature. Using a semi-empirical formula, Raman crystallites sizes were calculated and it was found that size increases with the temperature increasing. The spectroellipsometry investigations evidenced the increasing of refractive index with the substrate temperature increase. High surface roughness and pyramidal structures were noticed from the atomic force microscopy images for layers deposited at substrate temperature above 473 K.

  7. Iterative synthesis of Leishmania phosphoglycans by solution, solid-phase, and polycondensation approaches without involving any glycosylation.

    PubMed

    Ruhela, Dipali; Vishwakarma, Ram A

    2003-05-30

    A general strategy (solution, solid-phase, and polycondensation) for the synthesis of antigenic phosphoglycans (PG) of the protozoan parasite Leishmania is presented. Phosphoglycans constitute the variable structural and functional domain of major cell-surface lipophosphoglycan (LPG) and secreted proteophosphoglycan (PPG), the molecules involved in infectivity and survival of the Leishmania parasite inside human macrophages. We have shown that the chemically labile, anomerically phosphodiester-linked phosphoglycan repeats can be assembled in an iterative and efficient manner from a single key intermediate, without involving any glycosylation steps. Furthermore, the phosphoglycan chain can be extended toward either the nonreducing (6'-OH) or the reducing (1-OH) end. We also describe a new and efficient solid-phase methodology to construct phosphoglycans based on design and application of a novel cis-allylphosphoryl solid-phase linker that enabled the selective cleavage of the first anomeric-phosphodiester linkage without affecting any of the other internal anomeric-phosphodiester groups of the growing PG chain on the solid support. The strategy to construct larger phosphoglycans in a one-pot synthesis by polycondensation of a single key intermediate is also described, enabling CD spectrometric measurements to show the helical nature of phosphoglycans. Our versatile synthetic approach provides easy access to Leishmania phosphoglycans and the opportunity to address key immunological, biochemical, and biophysical questions pertaining to the phosphoglycan family (LPG and PPG) unique to the parasite. PMID:12762750

  8. Variable temperature electrochemical strain microscopy of Sm-doped ceria

    SciTech Connect

    Jesse, Stephen; Morozovska, A. N.; Kalinin, Sergei V; Eliseev, E. A.; Yang, Nan; Doria, Sandra; Tebano, Antonello

    2013-01-01

    Variable temperature electrochemical strain microscopy has been used to study the electrochemical activity of Sm-doped ceria as a function of temperature and bias. The electrochemical strain microscopy hysteresis loops have been collected across the surface at different temperatures and the relative activity at different temperatures has been compared. The relaxation behavior of the signal at different temperatures has been also evaluated to relate kinetic process during bias induced electrochemical reactions with temperature and two different kinetic regimes have been identified. The strongly non-monotonic dependence of relaxation behavior on temperature is interpreted as evidence for water-mediated mechanisms.

  9. Metal Structural Environment in ZnxNi1-xO Macroscale and Nanoscale Solid Solutions

    SciTech Connect

    Peck, Matthea A.; Langell, Marjorie A.

    2014-08-21

    The metal structural environments in macroscale and nanoscale ZnxNi1–xO solid solutions were examined using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). XRD demonstrates that solid solutions form for both macroscale (bulk) and nanoscale crystallites, and that the lattice parameter increases linearly as the amount of zinc increases, an indication of a homogeneous solid solution. XAS for both the bulk material and the nanoparticles reveals that the zinc atoms are incorporated into the rocksalt lattice and do not form zinc oxide clusters. The X-ray absorption near edge spectroscopy (XANES) of the Zn k-edge region in the solid solution is similar to the Ni k-edge region of NiO, and not the Zn k-edge region of ZnO. XPS confirms that solid solutions are formed; Auger parameters for zinc are consistent with a different geometry than the tetrahedral coordination of wurtzite ZnO. Nanoscaled solid solutions show evidence of a lattice contraction relative to macroscale solutions of the same concentration. While the contraction persists across the entire concentration range, the nanoparticle lattice parameter approaches the bulk ZnxNi1–xO value as the concentration of zinc increases to predict ZnO rocksalt lattice parameters that are in agreement with observed ZnO data.

  10. Community Solutions for Solid Waste Pollution, Level 6. Teacher Guide. Operation Waste Watch.

    ERIC Educational Resources Information Center

    Virginia State Dept. of Waste Management, Richmond. Div. of Litter & Recycling.

    Operation Waste Watch is a series of seven sequential learning units which addresses the subject of litter control and solid waste management. Each unit may be used in a variety of ways, depending on the needs and schedules of individual schools, and may be incorporated into various social studies, science, language arts, health, mathematics, and…

  11. K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides

    PubMed Central

    D’Angelo, Paola; Migliorati, Valentina; Spezia, Riccardo; De Panfilis, Simone; Persson, Ingmar; Zitolo, Andrea

    2014-01-01

    The potentiality of high energy XANES (X-ray absorption near edge structure) as a structural tool for lanthanoid-containing systems has been explored. The K-edge XANES spectra of La3+, Gd3+, and Lu3+ ions both in DMSO solution and solid octakis(DMSO) lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signal if a deconvolution procedure is carried out. We found that in solid octakis(DMSO) lanthanoid(III) iodides the Ln3+ ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln3+ ions retain a regular eight-coordination structure and the coordination number does not change along the series. At variance with water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln3+ ions in DMSO solution. PMID:23657739

  12. Chemical effects induced by gamma-irradiation in solid and in aqueous methanol solutions of 4-iodophenol

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Wassil, A. I.; Al-Resayes, S. I.; Al-Otaibi, A. M.

    2005-05-01

    The present work is a study on radiolyses of 4-iodophenol in aqueous methanol solutions. The radiolysis products are separated and identified using spectrophotometric and chromatographic techniques. The radiolytic products (I-2, I- and IO3-) formed in aerated solutions at room temperature were identified and the yields are investigated as a function of absorbed gamma-ray dose. The formation of I-2 is mainly dependent on the acidity of solution and produced via the pathway of secondary free radical reactions. Aromatic products of lower and higher molecular weight than the corresponding investigated compound were analysed and separated by HPLC. The results have been discussed in view of mechanisms based on free radicals and ion-molecule interactions. The chemical effects induced by gamma-irradiation in solid 4-iodophenol have also been investigated and the degradation products were identified in solid state by NMR, GC/MS experiments and HPLC after dissolution in aqueous methanol. The results were evaluated and compared with radiolysis data.

  13. Slow exchange model of nonrigid rotational motion in RNA for combined solid-state and solution NMR studies.

    PubMed

    Emani, Prashant S; Olsen, Gregory L; Echodu, Dorothy C; Varani, Gabriele; Drobny, Gary P

    2010-12-01

    Functional RNA molecules are conformationally dynamic and sample a multitude of dynamic modes over a wide range of frequencies. Thus, a comprehensive description of RNA dynamics requires the inclusion of a broad range of motions across multiple dynamic rates which must be derived from multiple spectroscopies. Here we describe a slow conformational exchange theoretical approach to combining the description of local motions in RNA that occur in the nanosecond to microsecond window and are detected by solid-state NMR with nonrigid rotational motion of the HIV-1 transactivation response element (TAR) RNA in solution as observed by solution NMR. This theoretical model unifies the experimental results generated by solution and solid-state NMR and provides a comprehensive view of the dynamics of HIV-1 TAR RNA, a well-known paradigm of an RNA where function requires extensive conformational rearrangements. This methodology provides a quantitative atomic level view of the amplitudes and rates of the local and collective displacements of the TAR RNA molecule and provides directly motional parameters for the conformational capture hypothesis of this classical RNA-ligand interaction. PMID:21067190

  14. K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Spezia, Riccardo; De Panfilis, Simone; Persson, Ingmar; Zitolo, Andrea

    2013-06-14

    The potential of high energy XANES (X-ray absorption near edge structure) as a tool for the structural analysis of lanthanoid-containing systems has been explored. The K-edge XANES spectra of La(3+), Gd(3+), and Lu(3+) ions both in DMSO solution and solid octakis(DMSO)lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range of 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of the XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signals if a deconvolution procedure is carried out. We found that in solid octakis(DMSO)lanthanoid(III) iodides the Ln(3+) ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln(3+) ions retain a regular eight-coordination structure and the coordination number does not change along the series. In contrast to when in water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln(3+) ions in DMSO solution. PMID:23657739

  15. Processing by both classical and mechanosynthesis routes and characterization of a new solid solution of tungsten-bronze structure ceramics

    SciTech Connect

    Khachane, M.; Moure, A. . E-mail: amoure@icmm.csic.es; Elaatmani, M.; Zegzouti, A.; Daoud, M.; Castro, A.

    2006-10-12

    A new family of ferroelectric compounds with Ba{sub 2-x}Na{sub 1+x}Li {sub x}Nb{sub 5}O{sub 15} composition (0 {<=} x {<=} 1) and tetragonal tungsten-bronze structure is processed for the first time. This new family of materials derived from Ba{sub 2}NaNb{sub 5}O{sub 15} compound was processed by classical solid-state reaction and by mechanosynthesis. The powders prepared by these two routes were characterized by X-ray diffraction (at room and high temperature), differential thermal analysis, thermogravimetry and scanning electron microscopy. The results confirm the formation of the solid solution in the whole range of composition. The influence of Li addition on the dielectric permittivity and losses and on the ferro-paraelectric transition temperature is also studied.

  16. Zr and Sn substituted (Na0.5Bi0.5)TiO3 -based solid solutions

    NASA Astrophysics Data System (ADS)

    Ishchuk, V. M.; Gusakova, L. G.; Kisel, N. G.; Kuzenko, D. V.; Spiridonov, N. A.; Sobolev, V. L.

    2016-02-01

    The paper attempts to investigate the phase formation of a Zr- and Sn-substituted [(Na0.5Bi0.5)0.80Ba0.20](Ti1-yBy)O3 system during its solid state synthesis. The synthesis was found to be a multi-step process associated with the formation of a number of intermediate phases which however depended on the compositions and sintering temperatures. Single phase solid solutions were obtained when the sintering temperature was increased to 1000 °C-1100 °C. Increase in the concentration of substituting ions, on the one hand, tends to linearly increase the crystal cell size whereas the tolerance factor, on the other hand, gets reduced bolstering the stability of anti-ferroelectric phase as compared to that of ferroelectric phase’.

  17. Phenylazoindole dyes 3: Determination of azo-hydrazone tautomers of new phenylazoindole dyes in solution and solid state

    NASA Astrophysics Data System (ADS)

    Babür, Banu; Seferoğlu, Nurgül; Aktan, Ebru; Hökelek, Tuncer; Şahin, Ertan; Seferoğlu, Zeynel

    2015-02-01

    A new two series of phenylazo indole dyes was synthesized and the structures of the dyes were confirmed by UV-vis, FT-IR, HRMS and 1H/13C NMR spectroscopic techniques. Five of these dyes (I, I‧, II‧, III and III‧) were also characterized in solid state by using single crystal X-ray diffraction studies besides other spectroscopic techniques. The geometries of the azo and hydrazone tautomeric forms of the dyes were optimized by using Density Functional Theory (DFT). In addition, the effects of the donor and acceptor groups on the azo and hydrazone forms of the dyes were evaluated experimentally and theoretically. The results indicate that the phenylazoindole dyes derived from 2-phenyl indole as coupling component exist as azo form in solution, gas phase and solid state.

  18. Influence of chemical substitution on the photoluminescence of Sr(1-x)PbxWO4 solid solution

    NASA Astrophysics Data System (ADS)

    Hallaoui, A.; Taoufyq, A.; Arab, M.; Bakiz, B.; Benlhachemi, A.; Bazzi, L.; Villain, S.; Valmalette, J.-C.; Guinneton, F.; Gavarri, J.-R.

    2015-07-01

    The solid solution Sr1-xPbxWO4 based on luminescent tungstates SrWO4 and PbWO4 has been synthesized by solid-state reaction for all compositions 0≤x≤1. Using Rietveld method, the structural data of all polycrystalline samples have been refined and crystal cell parameters exhibited a linear behavior as a function of x. All substituted structures are of scheelite type. Scanning electron microscopy showed that a high level of crystallization characterized the samples, with modifications in sizes and shapes depending on composition x. Infrared and Raman spectroscopy have been performed to characterize the evolution of vibrational modes with substitution rate. Finally, a systematic study of luminescence under X-ray excitation has been performed: in the composition range x=0.2 to 0.4, intensities of emission exhibited increased values. The luminescence profiles have been interpreted in terms of four Gaussian components, two of them depending on substitution rate.

  19. Influence of the process parameters on the spray pyrolysis technique, on the synthesis of gadolinium doped-ceria thin film

    SciTech Connect

    Halmenschlager, C.M.; Neagu, R.; Rose, L.; Malfatti, C.F.

    2013-02-15

    Graphical abstract: Gas-tight CGO made by spray pyrolysis suitable to be used as SOFC electrolyte. Display Omitted Highlights: ► Dense and crystalline CGO films deposited by spray pyrolysis on various substrates. ► Solvent did not have a strong influence on the film microstructure, defect concentration or thickness. ► The substrate did not have a strong influence on the film microstructure, defect concentration or thickness. ► Films with at least 2.5 μm of thickness presented high impermeability. ► The films obtained are suitable to use as a SOFC electrolyte. -- Abstract: This work presents the results of a process of optimization applied to gadolinia-doped ceria (Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9−x}, or CGO) thin films, deposited by spray pyrolysis (SP). Spray pyrolysis is a high thermal deposition method that combines material deposition and heat treatment. This combination is advantageous since the post-deposition heat treatment step is not necessary. However, stresses are solidified in the coating during the deposition, which may lead to the initiation of a crack in the coating. The aim of this work was to achieve thin, dense, and continuous CGO coatings, which may be used as gas separation membranes and as a solid state electrochemical interfaces. Dense, flat, low-defect substrates such as silica slides, silicon mono crystal wafers, and porous substrates were used as substrates in this work. Cerium ammonium nitrate and gadolinium acetylacetonate were dissolved in ethanol and butyl carbitol to form a precursor solution that was sprayed on the heated substrates. Process parameters such as solvent composition, deposition rate and different heating regimes were analyzed. The microstructure was analyzed by secondary electron microscopy (SEM) and was found that thin, dense, and defect-free films could be produced on dense and porous substrates. The results obtained show that it is possible to obtain a CGO dense film deposited by spray pyrolysis. X

  20. Thermodynamics of the Magnetite-Ulvöspinel (Fe3O4-Fe2TiO4) Solid Solution

    SciTech Connect

    Lilova, Kristina I.; Pearce, Carolyn I.; Gorski, Christopher A.; Rosso, Kevin M.; Navrotsky, Alexandra

    2012-09-17

    The thermodynamics of mixing and its dependence on cation distribution in the Fe3O4– 14 Fe2TiO4 (magnetite-ulvöspinel) spinel solid solution were studied using high temperature oxide melt solution calorimetry and a range of structural and spectroscopic probes. The enthalpies of formation of ilmenite and ulvöspinel from the oxides and from the elements were obtained using oxidative drop solution calorimetry at 973 K in molten sodium molybdate. The enthalpy of mixing, determined from the fit to the measured enthalpies of drop solution calorimetry, is endothermic and represented by a quadratic formalism, ΔHmix = (22.60 ± 8.46)x(1–x) kJ/mol, where x is the mole fraction of ulvöspinel. The entropies of mixing are more complex than those for a regular solution and have been calculated based on average measured and theoretical cation distributions. Calculated free energies of mixing show evidence for a solvus at low temperature in good agreement with that observed experimentally.