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Sample records for cuinxzn21-xs2 solid solution

  1. Radionuclide solubility control by solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Brandt, F.; Klinkenberg, M.; Rozov, K.; Bosbach, D. [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy and Climate Research - Nuclear Waste Management and Reactor Safety (IEK-6); Vinograd, V. [Frankfurt Univ. (Germany). Inst. of Geosciences

    2015-07-01

    The migration of radionuclides in the geosphere is to a large extend controlled by sorption processes onto minerals and colloids. On a molecular level, sorption phenomena involve surface complexation, ion exchange as well as solid solution formation. The formation of solid solutions leads to the structural incorporation of radionuclides in a host structure. Such solid solutions are ubiquitous in natural systems - most minerals in nature are atomistic mixtures of elements rather than pure compounds because their formation leads to a thermodynamically more stable situation compared to the formation of pure compounds. However, due to a lack of reliable data for the expected scenario at close-to equilibrium conditions, solid solution systems have so far not been considered in long-term safety assessments for nuclear waste repositories. In recent years, various solid-solution aqueous solution systems have been studied. Here we present state-of-the art results regarding the formation of (Ra,Ba)SO{sub 4} solid solutions. In some scenarios describing a waste repository system for spent nuclear fuel in crystalline rocks {sup 226}Ra dominates the radiological impact to the environment associated with the potential release of radionuclides from the repository in the future. The solubility of Ra in equilibrium with (Ra,Ba)SO{sub 4} is much lower than the one calculated with RaSO{sub 4} as solubility limiting phase. Especially, the available literature data for the interaction parameter W{sub BaRa}, which describes the non-ideality of the solid solution, vary by about one order of magnitude (Zhu, 2004; Curti et al., 2010). The final {sup 226}Ra concentration in this system is extremely sensitive to the amount of barite, the difference in the solubility products of the end-member phases, and the degree of non-ideality of the solid solution phase. Here, we have enhanced the fundamental understanding regarding (1) the thermodynamics of (Ra,Ba)SO{sub 4} solid solutions and (2) the

  2. Synthesis of solid solutions of perovskites

    Energy Technology Data Exchange (ETDEWEB)

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

    1986-03-01

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

  3. Superhard Rhenium/Tungsten Diboride Solid Solutions.

    Science.gov (United States)

    Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

    2016-11-02

    Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

  4. Thermal properties of spinel based solid solutions

    Science.gov (United States)

    O'Hara, Kelley Rae

    Solid solution formation in spinel based systems proved to be a viable approach to decreasing thermal conductivity. Samples with systematically varied additions of MgGa2O4 to MgAl2O 4 were prepared and thermal diffusivity was measured using the laser flash technique. Additionally, heat capacity was measured using differential scanning calorimetry and modeled for the MgAl2O4-MgGa 2O4 system. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. The solid solution continued to decrease the thermal conductivity by 13% up to 1000°C with 5 mol% addition. The decrease in thermal conductivity ultimately resulted in a decrease in heat flux when applied to a theoretical furnace lining, which could lead to energy savings in industrial settings. The MgAl2O4-Al2O3 phase equilibria was investigated to fully understand the system and the thermal properties at elevated temperatures. The solvus line between MgAl2O4 and Al2O3 has been defined at 79.6 wt% Al 2O3 at 1500°C, 83.0 wt% Al2O4 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been identified at temperatures up to 1700°C which could have significant implications for material processing and properties. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present. Thermal properties in the MgAl2O4-Al2O 3 system were investigated in both the single phase solid solution region and the two phase region. The thermal diffusivity decreased through the MgAl 2O4 solid solution region and was at a minimum through the entire metastable (nucleation and growth) region. As Al2O 3 became present as a second phase the thermal diffusivity increased with Al2O3 content. There was an 11.7% increase in thermal diffusivity with a change in overall chemistry of 85.20 wt% Al2O 3 to 87.71 wt% Al2O3, due to the drastic change in

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

    Energy Technology Data Exchange (ETDEWEB)

    Lichtner, Peter C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    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.

  6. Solid Phase versus Solution Phase Synthesis of Heterocyclic Macrocycles

    OpenAIRE

    McAlpine, Shelli R.; Seong Jong Kim

    2013-01-01

    Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A) confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved...

  7. Structural, thermodynamic, and mechanical properties of WCu solid solutions

    Science.gov (United States)

    Liang, C. P.; Wu, C. Y.; Fan, J. L.; Gong, H. R.

    2017-11-01

    Various properties of Wsbnd Cu solid solutions are systematically investigated through a combined use of first-principles calculation, cluster expansion, special quasirandom structures (SQS), and lattice dynamics. It is shown that SQS are effective to unravel the intrinsic nature of solid solutions, and that BCC and FCC W100-xCux solid solutions are energetically more stable when 0 ≤ x ≤ 70 and 70 thermodynamic properties of Wsbnd Cu, and that the coefficients of thermal expansion of W100-xCux solid solutions are much lower than those of corresponding mechanical mixtures. In addition, the G/B values of W100-xCux solid solutions reach a minimum at x = 50, which is fundamentally due to the softening of phonons as well as strong chemical bonding between W and Cu with a mainly metallic feature.

  8. Semiconductor Solid-Solution Nanostructures: Synthesis, Property Tailoring, and Applications.

    Science.gov (United States)

    Liu, Baodan; Li, Jing; Yang, Wenjin; Zhang, Xinglai; Jiang, Xin; Bando, Yoshio

    2017-12-01

    The innovation of band-gap engineering in advanced materials caused by the alloying of different semiconductors into solid-solution nanostructures provides numerous opportunities and advantages in optoelectronic property tailoring. The semiconductor solid-solution nanostructures have multifarious emission wavelength, adjustability of absorption edge, tunable electrical resistivity, and cutting-edge photoredox capability, and these advantages can be rationalized by the assorted synthesis strategies such as, binary, ternary, and quaternary solid-solutions. In addition, the abundance of elements in groups IIB, IIIA, VA, VIA, and VIIA provides sufficient room to tailor-make the semiconductor solid-solution nanostructures with the desired properties. Recent progress of semiconductor solid-solution nanostructures including synthesis strategies, structure and composition design, band-gap engineering related to the optical and electrical properties, and their applications in different fields is comprehensively reviewed. The classification, formation principle, synthesis routes, and the advantage of semiconductor solid-solution nanostructures are systematically reviewed. Moreover, the challenges faced in this area and the future prospects are discussed. By combining the information together, it is strongly anticipated that this Review may shed new light on understanding semiconductor solid-solution nanostructures while expected to have continuous breakthroughs in band-gap engineering and advanced optoelectronic nanodevices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Solid Phase versus Solution Phase Synthesis of Heterocyclic Macrocycles

    Directory of Open Access Journals (Sweden)

    Shelli R. McAlpine

    2013-01-01

    Full Text Available Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved relatively straightforward. Given the ease with which the oxazole Ustat A precursor is formed via our solid phase approach, this route is amenable to rapid analog synthesis.

  10. Solid phase versus solution phase synthesis of heterocyclic macrocycles.

    Science.gov (United States)

    Kim, Seong Jong; McAlpine, Shelli R

    2013-01-16

    Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A) confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved relatively straightforward. Given the ease with which the oxazole Ustat A precursor is formed via our solid phase approach, this route is amenable to rapid analog synthesis.

  11. Modeling supercritical fluid extraction process involving solute-solid interaction

    Energy Technology Data Exchange (ETDEWEB)

    Goto, M.; Roy, B. Kodama, A.; Hirose, T. [Kumamoto Univ., Kumamoto (Japan)

    1998-04-01

    Extraction or leaching of solute from natural solid material is a mass transfer process involving dissolution or release of solutes from a solid matrix. Interaction between the solute and solid matrix often influences the supercritical fluid extraction process. A model accounting for the solute-solid interaction as well as mass transfer is developed. The BET equation is used to incorporate the interaction and the solubility of solutes into the local equilibrium in the model. Experimental data for the supercritical extraction of essential oil and cuticular wax from peppermint leaves are successfully analyzed by the model. The effects of parameters on the extraction behavior are demonstrated to illustrate the concept of the model. 18 refs., 5 figs., 1 tab.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rai, R.N., E-mail: rn_rai@yahoo.co.in [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Kant, Shiva; Reddi, R.S.B. [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Ganesamoorthy, S. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Gupta, P.K. [Laser Materials Development & Devices Division, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India)

    2016-01-15

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

  13. Solute redistribution in dendritic solidification with diffusion in the solid

    Science.gov (United States)

    Ganesan, S.; Poirier, D. R.

    1989-01-01

    An investigation of solute redistribution during dendritic solidification with diffusion in the solid has been performed using numerical techniques. The extent of diffusion is characterized by the instantaneous and average diffusion parameters. These parameters are functions of the diffusion Fourier number, the partition ratio and the fraction solid. Numerical results are presented as an approximate model, which is used to predict the average diffusion parameter and calculate the composition of the interdendritic liquid during solidification.

  14. Heterogeneous Ferroelectric Solid Solutions Phases and Domain States

    CERN Document Server

    Topolov, Vitaly

    2012-01-01

    The book deals with perovskite-type ferroelectric solid solutions for modern materials science and applications, solving problems of complicated heterophase/domain structures near the morphotropic phase boundary and applications to various systems with morphotropic phases. In this book domain state–interface diagrams are presented for the interpretation of heterophase states in perovskite-type ferroelectric solid solutions. It allows to describe the stress relief in the presence of polydomain phases, the behavior of unit-cell parameters of coexisting phases and the effect of external electric fields. The novelty of the book consists in (i) the first systematization of data about heterophase states and their evolution in ferroelectric solid solutions (ii) the general interpretation of heterophase and domain structures at changing temperature, composition or electric field (iii) the complete analysis of interconnection domain structures, unit-cell parameters changes, heterophase structures and stress relief.

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

    Science.gov (United States)

    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.

  16. Design principles for radiation-resistant solid solutions

    Science.gov (United States)

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

    2017-05-01

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

  17. Thermodynamic properties of hematite — ilmenite — geikielite solid solutions

    Science.gov (United States)

    Ghiorso, Mark S.

    1990-11-01

    A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe{2+/ s }Ti{4+/1- s }) A (Fe{2+/1- s }Ti{4+/s}) B O3]-geikielite [(Mg{2+/ t }Ti{4+/1- t }) A (Mg{2+/1- t }Ti{4+/ t }) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0≤s, t≤1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of theRbar 3c - Rbar 3 transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg-Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+-Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (-1488.5 and -822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe-Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility

  18. Synthesis and characterization of solid solutions in ABCO 4 system

    Science.gov (United States)

    Novoselov, A.; Zimina, G.; Komissarova, L.; Pajaczkowska, A.

    2006-01-01

    Formation of continuous solid solutions with a tetragonal structure of K 2NiF 4-type was investigated by direct solid-state synthesis, carbonate precipitations, the freeze-drying method and the Czochralski crystal growth technique. In the systems of SrLaAlO 4-CaLaAlO 4, SrNdAlO 4-CaNdAlO 4, SrPrAlO 4-CaPrAlO 4, SrLaAlO 4-SrLaGaO 4 and SrLaAlO 4-SrLaFeO 4 solid solutions are formed in the whole concentration range (0.0⩽ x⩽1.0) and in the systems of SrLaAlO 4-SrLaMnO 4 and SrLaAlO 4-SrLaCrO 4 in the limited compositional interval of (0.0⩽ x⩽0.20) and (0.0⩽ x⩽0.25), respectively, with composition dependency of lattice constants following Vegard's law.

  19. Nonisothermal nucleation in a solid solution of CuCl in glass: Concentration effect upon heating of the solid solution

    Science.gov (United States)

    Leiman, V. I.; Ashkalunin, A. L.; Derkacheva, O. Yu.; Maksimov, V. M.

    2017-09-01

    The influence of the heating rate of a solid solution of CuCl in glass on the size distribution of the produced CuCl nanoparticles is studied. The distribution curves of CuCl nanocrystals are determined by the method of exciton-thermal analysis. It is established that the concentration of CuCl nanoparticles increases by ten times upon slowing the sample heating process from 2 to 60 min, while the mean radius of particles decreases almost twice. The concentration of CuCl nanoparticles passes through a maximum in the process of heating the sample. The numerical simulation of the nucleation upon slow heating of a solid solution showed that the formation of the concentration maximum of the new phase clusters is determined by a rapid increase in the critical radius owing to an increase in temperature and decrease in the solution supersaturation. As a result, the formation of new phase nuclei ceases at a certain temperature, and a part of the previously formed clusters dissolves.

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

    Science.gov (United States)

    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.

  1. Dynamic Aspects of Solid Solution Cathodes for Electrochemical Power Sources

    DEFF Research Database (Denmark)

    Atlung, Sven; West, Keld; Jacobsen, Torben

    1979-01-01

    Battery systems based on alkali metal anodes and solid solution cathodes,i.e., cathodes based on the insertion of the alkali cation in a "host lattice,"show considerable promise for high energy density storage batteries. Thispaper discusses the interaction between battery requirements, in particu......Battery systems based on alkali metal anodes and solid solution cathodes,i.e., cathodes based on the insertion of the alkali cation in a "host lattice,"show considerable promise for high energy density storage batteries. Thispaper discusses the interaction between battery requirements......, in particularfor vehicle propulsion, and electrochemical and constructional factors. It isargued that the energy obtainable at a given load is limited by saturation ofthe surface layers of cathode particles with cations, and that the time beforesaturation occurs is determined by diffusion of cations and electrons...... into thehost lattice. Expressions are developed for plane, cylindrical, and sphericalparticles, giving the relation between battery load and the amount of cathodematerial utilized before saturation. The particle shape and a single parameterQ is used to describe cathode performance. Q is the ratio between...

  2. Magnetic clusters in ilmenite-hematite solid solutions

    DEFF Research Database (Denmark)

    Frandsen, Cathrine; Burton, B. P.; Rasmussen, Helge Kildahl

    2010-01-01

    We report the use of high-field 57Fe Mössbauer spectroscopy to resolve the magnetic ordering of ilmenite-hematite [xFeTiO3−(1−x)Fe2O3] solid solutions with x>0.5. We find that nanometer-sized hematite clusters exist within an ilmenite-like matrix. Although both phases are antiferromagnetically...... ordered, the hematite clusters show ferrimagnetic behavior due to superexchange coupling with Fe2+ in ilmenite. For ilmenite-rich samples (x=0.95), the clusters are isolated and superparamagnetic. For more hematite-rich samples with x=0.80 and x=0.70, the clusters interact to form a cluster glass....

  3. Luminescence spectra and kinetics of disordered solid solutions

    DEFF Research Database (Denmark)

    Klochikhin, A.; Reznitsky, A.; Permogorov, S.

    1999-01-01

    for the temporal evolution of the luminescence band. It is shown that the changes of band shape with time come from the interplay of population dynamics of extended states and spatially isolated ''radiative" states. Finally, the measurements of the decay of the spectrally integrated luminescence intensity at long......We have studied both theoretically and experimentally the luminescence spectra and kinetics of crystalline, disordered solid solutions after pulsed excitation. First, we present the model calculations of the steady-state luminescence band shape caused by recombination of excitons localized...... only a relatively small group of ''radiative" states forms the steady-state luminescence band. The continuum percolation theory is applied to distinguish the ''radiative'' localized states, which are isolated in space and have no ways for nonradiative transitions along the tail states. It is found...

  4. Preparation and characterization of barium titanate stannate solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Horchidan, Nadejda, E-mail: NHorchidan@stoner.phys.uaic.ro [Department of Physics, ' Al. I. Cuza' University, Bv. Carol 11, Iasi 700506 (Romania); Ianculescu, Adelina C. [Department of Oxide Materials Science and Engineering, Polytechnics University, 1-7 Gh. Polizu, P.O. Box 12-134, 011061 Bucharest (Romania); Curecheriu, Lavinia P.; Tudorache, Florin [Department of Physics, ' Al. I. Cuza' University, Bv. Carol 11, Iasi 700506 (Romania); Musteata, Valentina [Institute of Macromolecular Chemistry ' Petru Poni' , Aleea Grigore Ghica Voda 41A, 700487 Iasi (Romania); Stoleriu, Stefania [Department of Oxide Materials Science and Engineering, Polytechnics University, 1-7 Gh. Polizu, P.O. Box 12-134, 011061 Bucharest (Romania); Dragan, Nicolae; Crisan, Dorel [Institute of Physical Chemistry ' Ilie Murgulescu' , Lab. of Oxide Materials Science, 202 Splaiul Independentei, 060021 Bucharest (Romania); Tascu, Sorin; Mitoseriu, Liliana [Department of Physics, ' Al. I. Cuza' University, Bv. Carol 11, Iasi 700506 (Romania)

    2011-04-07

    Research highlights: > BaSnxTi1-xO3 (x = 0; 0.05; 0.1; 0.15; 0.2) ceramics were prepared by solid state reaction and sintered at 13000C for 4h. > The phase purity, structural parameters and microstructural characteristics were investigated. > The dielectric properties were studied as function of temperature and frequency and empirical parameters {eta} and {delta} were calcutate. > The non-linear dielectric properties (tunability) of the samples were studied at room temperature. > By increasing the Sn addition, the {epsilon}(E) dependence tends to reduce its hysteresis behaviour. - Abstract: BaSn{sub x}Ti{sub 1-x}O{sub 3} (x = 0; 0.05; 0.1; 0.15; 0.2) solid solutions were prepared via conventional solid state reaction and sintered at 1300 {sup o}C for 4 h, resulting in dense single phase ceramics with homogeneous microstructures. Tetragonal symmetry for x {<=} 0.1, cubic for x = 0.2 and a superposition of tetragonal and cubic for x = 0.15 compositions were found by X-ray diffraction analysis. The temperature and frequency dependence of the complex dielectric constant and dc tunability were determined. A transformation from normal ferroelectric to relaxor with diffuse phase transition was observed with increasing the Sn concentration. All the investigated compositions show a relative tunability between 0.55 (for x = 0.2) and 0.74 (for x = 0.1), at a field amplitude of E = 20 kV/cm.

  5. Thermal Expansion of Fluorapatite-Chlorapatite Solid Solutions

    Science.gov (United States)

    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

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

    Science.gov (United States)

    Ngoc, Uyen Nguyen; Schnitzer, Hans

    2009-06-01

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

  7. Solid solutions based on lead-barium metaniobate

    Energy Technology Data Exchange (ETDEWEB)

    Gridnev, S.A.; Barmina, N.V.; Pavlova, N.G.; Parfenova, N.N.; Smirnova, E.P. (Voronezhskij Politekhnicheskij Inst. (USSR); AN SSSR, Moscow. Fiziko-Tekhnicheskij Inst.)

    1982-10-01

    Piezoceramic materials based on solid solutions of (1-x-y-z), PbNb/sub 2/O/sub 6/+xBaNb/sub 2/O/sub 6/+yPb/sub 2/Ti/sub 2/O/sub 6/+zNa/sub 2/Nb/sub 2/O/sub 6/ composition with high Curie temperatures (470-600 deg) are prepared. Polarization conditions are determined and materials with high values of piezomodules d/sub 33/=(40-50)x10/sup -12/ K/N and d/sub 31/=5.3x10/sup -12/ K/N are prepared. High temperature stability (up to 300 deg C) of piezoelectric properties and elastic ductibility is characteristic of the investigated system. Introduction of barium, sodium metaniobates and lead titanate in lead metaniobate ceramics permits to prepare piezomaterials both with high (Qsub(m)=300-350) and with low (Qsub(m)=20) mechanical quality factor.

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

    Science.gov (United States)

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

    2016-12-01

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

  9. (1-xPux)Sb solid solutions. 1. Magnetic configurations

    DEFF Research Database (Denmark)

    Normile, P.S.; Stirling, W.G.; Mannix, D.

    2002-01-01

    , the correlation length is even shorter. The observation of a second-order resonance harmonic is linked to the multi-k nature of the configurations, and its unusual temperature dependence is explained by using the phase diagram established for the x=0.75 sample by neutron diffraction. We conclude with a discussion......Neutron and resonant x-ray magnetic scattering studies have been performed on single crystals of three compositions, x=0.25, 0.50, and 0.75 of the (U1-xPux)Sb solid solution. Neutron diffraction has established the ordering wave vector (k=1 for x=0.25 and 0.50, as in x=0, USb, and k=0.25 for x=0.......75), the average magnetic moment, and the temperature dependence of the magnetic order. For the x=0.75 sample the presence of a third-order harmonic indicates a substantial squaring of the 4+, 4- magnetic configuration. Experiments with a field applied to the sample have shown that the x=0.25 and 0.50 samples...

  10. Local structure in the disordered solid solution of cis- and trans-perinones

    DEFF Research Database (Denmark)

    Teteruk, Jaroslav L.; Glinnemann, Juergen; Heyse, Winfried

    2016-01-01

    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...

  11. Atomistic Simulations of Dislocations in a Model BCC Multicomponent Concentrated Solid Solution Alloy (Postprint)

    Science.gov (United States)

    2016-12-19

    Dislocations ; Atomistic simulations; Concentrated multicomponent solid solution alloy; BCC crystal 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF...This has implications for higher-scale modeling ( dislocation dynamics or crystal plasticity) of HEA alloys, relative to elemental BCC metals, which...AFRL-RX-WP-JA-2017-0302 ATOMISTIC SIMULATIONS OF DISLOCATIONS IN A MODEL BCC MULTICOMPONENT CONCENTRATED SOLID SOLUTION ALLOY

  12. Comparative solution and solid-phase glycosylations toward a disaccharide library

    DEFF Research Database (Denmark)

    Agoston, K.; Kröger, Lars; Agoston, Agnes

    2009-01-01

    A comparative study on solution-phase and solid-phase oligosaccharide synthesis was performed. A 16-member library containing all regioisomers of Glc-Glc, Glc-Gal, Gal-Glc, and Gal-Gal disaccharides was synthesized both in solution and on solid phase. The various reaction conditions for different...

  13. Peptide synthesis: ball-milling, in solution, or on solid support, what is the best strategy?

    OpenAIRE

    Ophélie Maurin; Pascal Verdié; Gilles Subra; Frédéric Lamaty; Jean Martinez; Thomas-Xavier Métro

    2017-01-01

    While presenting particularly interesting advantages, peptide synthesis by ball-milling was never compared to the two traditional strategies, namely peptide syntheses in solution and on solid support (solid-phase peptide synthesis, SPPS). In this study, the challenging VVIA tetrapeptide was synthesized by ball-milling, in solution, and on solid support. The three strategies were then compared in terms of yield, purity, reaction time and environmental impact. The results obtained enabled to dr...

  14. Influence of Ce 0.68 Zr 0.32 O 2 solid solution on depositing ...

    Indian Academy of Sciences (India)

    The results show that the addition of Ce0.68Zr0.32O2 solid solution into slurries can improve -Al2O3-based washcoat adhesion on FeCrAl foils. The more the Ce0.68Zr0.32O2 solid solution added into slurries, the higher was the specific surface area of aged samples. XRD characterization proved that ceria–zirconia solid ...

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Menon, Sumithra Sivadas; Anitha, R.; Baskar, K.; Singh, Shubra, E-mail: shubra6@gmail.com [Crystal Growth Centre, Anna University, Chennai-600025 (India); Gupta, Bhavana [Material Science Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    2016-05-23

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

  17. Solid Solution Effects on the Tensile Behaviour of Concentrated Mg-Zn Alloys

    Science.gov (United States)

    Blake, A. H.; Cáceres, C. H.

    Solute in solution hardens the basal planes but causes solid solution softening on the prismatic (and possibly pyramidal) planes in dilute (slip systems still occurs. Therefore, solid solution effects on the strain hardening rate and ductility of cast polycrystalline Mg-Zn alloys, with Zn contents between 0 and 2.4 at.% have been studied. A constant grain size was obtained in all alloys by adding a small amount of Zr to the melt. The strain-hardening rate is low for dilute concentrations increasing monotonically above 1 at.% Zn. The ductility goes through a maximum at very low concentrations of Zn, decreasing for higher concentrations. This suggests that the solid solution hardening gradually offsets the solid solution softening effects at high concentrations of Zn.

  18. A Local Composition Model for Paraffinic Solid Solutions

    DEFF Research Database (Denmark)

    Coutinho, A.P. João; Knudsen, Kim; Andersen, Simon Ivar

    1996-01-01

    The description of the solid-phase non-ideality remains the main obstacle in modelling the solid-liquid equilibrium of hydrocarbons. A theoretical model, based on the local composition concept, is developed for the orthorhombic phase of n-alkanes and tested against experimental data for binary sy...... systems. It is shown that it can adequately predict the experimental phase behaviour of paraffinic mixtures. This work extends the applicability of local composition models to the solid phase. Copyright (C) 1996 Elsevier Science Ltd....

  19. Nanometric solid solutions of the fluorite and perovskite type crystal structures: Synthesis and properties

    Directory of Open Access Journals (Sweden)

    Snežana Bošković

    2012-09-01

    Full Text Available In this paper a short review of our results on the synthesis of nanosized CeO2, CaMnO3 and BaCeO3 solid solutions are presented. The nanopowders were prepared by two innovative methods: self propagating room temperature synthesis (SPRT and modified glycine/nitrate procedure (MGNP. Different types of solid solutions with rare earth dopants in concentrations ranging from 0–0.25 mol% were synthesized. The reactions forming solid solutions were studied. In addition, the characteristics of prepared nanopowders, phenomena during sintering and the properties of sintered samples are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, T. [Facultad de Quimica UNAM, Ciudad Universitaria, D.F. Mexico (Mexico); Lartigue, J. [Facultad de Quimica UNAM, Ciudad Universitaria, D.F. Mexico (Mexico); Ramos-Bernal, S. [Instituto de Ciencias Nucleares, UNAM, A.P. 70-543 C.P.4510, Ciudad Universitaria, D.F. Mexico (Mexico); Ramos, A. [Instituto de Ciencias Nucleares, UNAM, A.P. 70-543 C.P.4510, Ciudad Universitaria, D.F. Mexico (Mexico); Mosqueira, G.F. [Direccion General de Divulgacion de la Ciencia de la UNAM, A.P. 70-487, C:P, D.F. Mexico 04510 (Mexico); Negron-Mendoza, A. [Instituto de Ciencias Nucleares, UNAM, A.P. 70-543 C.P.4510, Ciudad Universitaria, D.F. Mexico (Mexico)]. E-mail: negron@nuclecu.unam.mx

    2005-12-01

    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 Moessbauer 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.

  1. Design of non-molecular coordination solids from aqueous solution ...

    Indian Academy of Sciences (India)

    We have successfully crystallized four new non-molecular coordination solids utilizing the ... to construe the molecular events preceding crystalliza- ..... uncoordinated carboxylic acid unit and water molecule and oxygen coordinated to copper. leading toa helical chain (figure 5). The terminal car- boxylic acid group of the ...

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

    Science.gov (United States)

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

    2017-05-01

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

  3. The growth and tensile deformation behavior of the silver solid solution phase with zinc

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jiaqi, E-mail: jiaqw10@uci.edu [Department of Electrical Engineering and Computer Science, University of California, Irvine, CA 92697-2660 (United States); Materials and Manufacturing Technology, University of California, Irvine, CA 92697-2660 (United States); Lee, Chin C. [Department of Electrical Engineering and Computer Science, University of California, Irvine, CA 92697-2660 (United States); Materials and Manufacturing Technology, University of California, Irvine, CA 92697-2660 (United States)

    2016-06-21

    The growth of homogeneous silver solid solution phase with zinc are conducted at two different compositions. X-ray diffraction (XRD) and Scanning electron microscope/Energy dispersive X-ray spectroscopy (SEM/EDX) are carried out for phase identification and chemical composition verification. The mechanical properties of silver solid solution phase with zinc are evaluated by tensile test. The engineering and true stress vs. strain curves are presented and analyzed, with those of pure silver in comparison. According to the experimental results, silver solid solution phase with zinc at both compositions show tempered yield strength, high tensile strength and large uniform strain compared to those of pure silver. Fractography further confirmed the superior ductility of silver solid solution phase with zinc at both compositions. Our preliminary but encouraging results may pave the way for the silver based alloys to be applied in industries such as electronic packaging and structure engineering.

  4. Diffusion-Limited Kinetics of the Solution-Solid Phase Transition of Molecular Substances

    National Research Council Canada - National Science Library

    Dimiter N. Petsev; Kai Chen; Olga Gliko; Peter G. Vekilov

    2003-01-01

    For critical tests of whether diffusion-limited kinetics is an option for the solution-solid phase transition of molecular substances or whether they are determined exclusively by a transition state...

  5. Study of reaction sequences for formation of solid solution: 0,48 ...

    African Journals Online (AJOL)

    To study the reaction sequences of formation of solid solution zirconate-lead titanate (PZT) in this work, we took into account the effect of adding oxide dopants on the progress of the reaction, so we added oxides ZnO, Cr2O3, Sb2O3 to our material composition in small quantities so that the solid solution must verify the ...

  6. High pressure x-ray diffraction study of nickel-copper chromites solid solutions

    Science.gov (United States)

    Mikheykin, A. S.; Torgashev, V. I.; Talanov, V. M.; Bush, A. A.; Chernyshov, D.; Yuzyuk, I. Yu; Dmitriev, V. P.

    2014-12-01

    A high-pressure synchrotron radiation diffraction study has been carried out on Ni1-xCuxCr2O4 solid solutions. Observed pressure-controlled phase transitions, along with data previously collected for temperature-induced phase transitions, are analyzed in the framework of the unified phenomenological model that results in mapping of the generic phase diagram for the whole family of Ni1-xCuxCr2O4 solid solutions.

  7. Low temperature preparation of nanocrystalline solid solution of ...

    Indian Academy of Sciences (India)

    SrBa1–Nb2O6 (with = 0.4, 0.5 and 0.6) powders have been prepared by thermolysis of aqueous precursor solutions consisting of triethanolamine (TEA), niobium tartarate and, EDTA complexes of strontium and barium ions. Complete evaporation of the precursor solution by heating at ∼ 200°C, yields in a fluffy, ...

  8. Modelling solid solutions with cluster expansion, special quasirandom structures, and thermodynamic approaches

    Science.gov (United States)

    Saltas, V.; Horlait, D.; Sgourou, E. N.; Vallianatos, F.; Chroneos, A.

    2017-12-01

    Modelling solid solutions is fundamental in understanding the properties of numerous materials which are important for a range of applications in various fields including nanoelectronics and energy materials such as fuel cells, nuclear materials, and batteries, as the systematic understanding throughout the composition range of solid solutions for a range of conditions can be challenging from an experimental viewpoint. The main motivation of this review is to contribute to the discussion in the community of the applicability of methods that constitute the investigation of solid solutions computationally tractable. This is important as computational modelling is required to calculate numerous defect properties and to act synergistically with experiment to understand these materials. This review will examine in detail two examples: silicon germanium alloys and MAX phase solid solutions. Silicon germanium alloys are technologically important in nanoelectronic devices and are also relevant considering the recent advances in ternary and quaternary groups IV and III-V semiconductor alloys. MAX phase solid solutions display a palette of ceramic and metallic properties and it is anticipated that via their tuning they can have applications ranging from nuclear to aerospace industries as well as being precursors for particular MXenes. In the final part, a brief summary assesses the limitations and possibilities of the methodologies discussed, whereas there is discussion on the future directions and examples of solid solution systems that should prove fruitful to consider.

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

    Science.gov (United States)

    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.

  10. Peptide synthesis: ball-milling, in solution, or on solid support, what is the best strategy?

    Directory of Open Access Journals (Sweden)

    Ophélie Maurin

    2017-10-01

    Full Text Available While presenting particularly interesting advantages, peptide synthesis by ball-milling was never compared to the two traditional strategies, namely peptide syntheses in solution and on solid support (solid-phase peptide synthesis, SPPS. In this study, the challenging VVIA tetrapeptide was synthesized by ball-milling, in solution, and on solid support. The three strategies were then compared in terms of yield, purity, reaction time and environmental impact. The results obtained enabled to draw some strengths and weaknesses of each strategy, and to foresee what will have to be implemented to build more efficient and sustainable peptide syntheses in the near future.

  11. Low temperature preparation of nanocrystalline solid solution of ...

    Indian Academy of Sciences (India)

    Unknown

    ASIT B PANDA, AMITA PATHAK and PANCHANAN PRAMANIK*. Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India. Abstract. SrxBa1–xNb2O6 (with x = 0⋅4, 0⋅5 and 0⋅6) powders have been prepared by thermolysis of aqueous precursor solutions consisting of triethanolamine (TEA), ...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    KAUST Repository

    Yuan, Mingjian

    2016-02-29

    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.

  14. Sustainable Solutions for Municipal Solid Waste Management in Thailand

    OpenAIRE

    Thaniya Kaosol

    2009-01-01

    General as well as the MSW management in Thailand is reviewed in this paper. Topics include the MSW generation, sources, composition, and trends. The review, then, moves to sustainable solutions for MSW management, sustainable alternative approaches with an emphasis on an integrated MSW management. Information of waste in Thailand is also given at the beginning of this paper for better understanding of later contents. It is clear that no one single method of MSW disposal can deal with all mat...

  15. Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

    2014-01-01

    We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fulgêncio, F., E-mail: fefulgencio@gmail.com [Departamento de Química, ICEx, Universidade Federal de Minas Gerais – UFMG, C.P. 702, CEP 31270-901 – Belo Horizonte, MG (Brazil); Oliveira, F.C. [Grupo de Pesquisa em Nanociências e Nanomateriais, Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG), Campus Timóteo, Timóteo, MG (Brazil); Windmöller, D.; Araujo, M.H.; Marques-Netto, A.; Machado, J.C. [Departamento de Química, ICEx, Universidade Federal de Minas Gerais – UFMG, C.P. 702, CEP 31270-901 – Belo Horizonte, MG (Brazil); Magalhães, W.F., E-mail: welmag@ufmg.br [Departamento de Química, ICEx, Universidade Federal de Minas Gerais – UFMG, C.P. 702, CEP 31270-901 – Belo Horizonte, MG (Brazil)

    2015-11-05

    Highlights: • Positronium formation in several Ln{sup 3+} complexes, except in Eu{sup 3+} complexes. • Positron annihilation spectroscopies used as a characterization tool of solid solutions and mechanical mixtures. • Measurements performed at different temperatures (80 and 295 K). - Abstract: Measurements using positron annihilation lifetime (PALS) and Doppler broadening annihilation radiation lineshape (DBARLS) spectroscopies were performed in several lanthanide dipivaloylmethanate complexes, Ln(dpm){sub 3} where Ln = Sm{sup 3+}, Gd{sup 3+}, Tb{sup 3+}, Ho{sup 3+}, Er{sup 3+}, Yb{sup 3+} 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 Ln{sub 1−x}Eu{sub x}(dpm){sub 3}. Expressive positronium formation was observed in all Ln(dpm){sub 3} complexes, except in Eu(dpm){sub 3} complex. The results indicate formation of solid solutions in the Sm{sup 3+}, Gd{sup 3+}and Tb{sup 3+} systems, where total inhibition of positronium formation was observed. A Stern–Volmer type equation, I{sub 3}{sup 0}/I{sub 3} = 1 + kx, was used to fit the data, enabling the calculation of the inhibition constants, k. A mechanical mixture behavior, with linear variation of I{sub 3} between the I{sub 3} values of the pure complexes, was observed in systems containing Ho{sup 3+}, Er{sup 3+} and Yb{sup 3+} complexes, where no effective solid solution formation occurred due to differences between the crystalline structures of these complexes and Eu(dpm){sub 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 Sm{sub 1−x}Eu{sub x}(dpm){sub 3} and Gd{sub 1−x}Eu{sub x}(dpm){sub 3} solid solutions. The results indicate that, despite a contraction

  17. The elastic solid solution model for minerals at high pressures and temperatures

    Science.gov (United States)

    Myhill, R.

    2018-02-01

    Non-ideality in mineral solid solutions affects their elastic and thermodynamic properties, their thermobaric stability, and the equilibrium phase relations in multiphase assemblages. At a given composition and state of order, non-ideality in minerals is typically modelled via excesses in Gibbs free energy which are either constant or linear with respect to pressure and temperature. This approach has been extremely successful when modelling near-ideal solutions. However, when the lattice parameters of the solution endmembers differ significantly, extrapolations of thermodynamic properties to high pressures using these models may result in significant errors. In this paper, I investigate the effect of parameterising solution models in terms of the Helmholtz free energy, treating volume (or lattice parameters) rather than pressure as an independent variable. This approach has been previously applied to models of order-disorder, but the implications for the thermodynamics and elasticity of solid solutions have not been fully explored. Solid solution models based on the Helmholtz free energy are intuitive at a microscopic level, as they automatically include the energetic contribution from elastic deformation of the endmember lattices. A chemical contribution must also be included in such models, which arises from atomic exchange within the solution. Derivations are provided for the thermodynamic properties of n-endmember solutions. Examples of the use of the elastic model are presented for the alkali halides, pyroxene, garnet, and bridgmanite solid solutions. Elastic theory provides insights into the microscopic origins of non-ideality in a range of solutions, and can make accurate predictions of excess enthalpies, entropies, and volumes as a function of volume and temperature. In solutions where experimental data are sparse or contradictory, the Helmholtz free energy approach can be used to assess the magnitude of excess properties and their variation as a function

  18. Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

    KAUST Repository

    Xia, Chuan

    2017-01-06

    An effective multifaceted strategy is demonstrated to increase active edge site concentration in NiCoSe solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as-prepared ternary solid solution with extremely high electrochemically active surface area (C = 197 mF cm), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic-like electrical conductivity and lower free energy for atomic hydrogen adsorption in NiCoSe, identified by temperature-dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the NiCoSe solid solutions show a low overpotential of 65 mV at -10 mV cm, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec, and a large exchange current density of 184 μA cm in acidic electrolyte. Further, it is shown that the as-prepared NiCoSe solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.

  19. Zirconium-cerin solid solutions: thermodynamic model and thermal stability at high temperature; Solutions solides de zirconium dans la cerine: modele thermodynamique et stabilite thermique a haute temperature

    Energy Technology Data Exchange (ETDEWEB)

    Janvier, C.

    1998-04-02

    The oxides-gaseous dioxygen equilibria and the textural thermal stability of six zirconium-cerin solutions Ce{sub 1-x}Zr{sub x}O{sub 2} (0solid solutions and the gaseous oxygen by thermal gravimetric analysis at 600 degrees Celsius has shown that these solutions have not a ideal behaviour. A thermodynamic model where the point defects of solutions are included describe them the best. It becomes then possible to know the variations of the concentrations of the point defects in terms of temperature, oxygen pressure and zirconium concentration. A kinetic study (by calcination at 950 degrees Celsius of the solid solutions) of the specific surface area decrease has revealed a minima (0

  20. Cutting solid figures by plane - analytical solution and spreadsheet implementation

    Science.gov (United States)

    Benacka, Jan

    2012-07-01

    In some secondary mathematics curricula, there is a topic called Stereometry that deals with investigating the position and finding the intersection, angle, and distance of lines and planes defined within a prism or pyramid. Coordinate system is not used. The metric tasks are solved using Pythagoras' theorem, trigonometric functions, and sine and cosine rules. The basic problem is to find the section of the figure by a plane that is defined by three points related to the figure. In this article, a formula is derived that gives the positions of the intersection points of such a plane and the figure edges, that is, the vertices of the section polygon. Spreadsheet implementations of the formula for cuboid and right rectangular pyramids are presented. The user can check his/her graphical solution, or proceed if he/she is not able to complete the section.

  1. Solid solution and amorphous phase in Ti–Nb–Ta–Mn systems synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzman, P. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Parra, C. [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Bejar, L. [Instituto de Investigaciones Metalúrgicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia C.P. 58000, Michoacán (Mexico); Medina, A. [Facultad de Ingeniería Mecánica, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, C.P. 58000, Michoacán (Mexico); Guzman, D. [Departamento de Metalurgia, Universidad de Atacama, Av. España 485, Copiapó (Chile)

    2016-06-15

    This work discusses the formation of Ti–30Nb–13Ta–xMn (x: 2, 4 and 6 wt%) solid solution by mechanical alloying using a shaker mill. A solid solution was formed after 15 h of milling and an amorphous phase was formed after 30 h of milling, according to X-ray diffraction results. Disappearance of strongest X-ray diffraction peaks of Nb, Ta and Mn indicated the formation of solid solution, while, X-ray diffraction patterns of powders milled for 30 h showed an amorphous hump with crystalline peaks in the angular range of 35–45° in 2θ. TEM image analysis showed the presence of nanocrystalline intermetallic compounds embedded in an amorphous matrix. Mn{sub 2}Ti, MnTi and NbTi{sub 4} intermetallic compounds were detected and revealed crystallites with size ranging from 3 to 20 nm. The Gibbs free energy for the formation of solid solution and amorphous phase of three ternary systems (Ti–Nb–Ta, Ti–Nb–Mn and Ti–Ta–Mn) was calculated using extended Miedema's model. Experimental and thermodynamic data confirmed that solid solution was first formed in the alloy with 6wt% Mn followed by the formation of an amorphous phase as milling time increases. The presence of Mn promoted the formation of amorphous phase because the atomic radius difference between Mn with Ti, Nb and Ta. - Highlights: • Thermodynamics analysis of extension of solid solution of the Ti–Nb–Ta–Mn system. • Formation of amorphous phase and intermetallic compounds were observed. • Nanocrystalline intermetallic compounds were formed with the sizes between 3 and 20 nm.

  2. Interdiffusion and impurity diffusion in polycrystalline Mg solid solution with Al or Zn

    Energy Technology Data Exchange (ETDEWEB)

    Kammerer, C.C. [University of Central Florida, Advanced Materials Processing and Analysis Center, Department of Materials Science and Engineering, Orlando, FL 32816 (United States); Kulkarni, N.S. [Knoxville, Tennessee 37931 (United States); Warmack, R.J. [Oak Ridge National Laboratory, Measurement Science and Systems Engineering Division, Oak Ridge, TN 37831 (United States); Sohn, Y.H. [University of Central Florida, Advanced Materials Processing and Analysis Center, Department of Materials Science and Engineering, Orlando, FL 32816 (United States)

    2014-12-25

    Highlights: • Interdiffusion coefficients within Mg(Al) and Mg(Zn) solid solutions. • Impurity diffusion of Al and Zn in Mg. • Interdiffusion coefficient in Mg(Zn) was higher than that of Mg(Al). • Zn impurity diffusion coefficient was higher than that of Al in Mg. - Abstract: 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 coefficients 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 coefficients of Al and Zn in pure polycrystalline Mg. For all diffusion couples, electron microprobe analysis was utilized for the measurement of concentration profiles. The interdiffusion coefficient in Mg(Zn) was higher than that of Mg(Al) by an order of magnitude. Additionally, the interdiffusion coefficient increased significantly 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 coefficient in Mg(Al) solid solution were determined to be 186.8 (±0.9) kJ/mol and 7.69 × 10{sup −1} (±1.80 × 10{sup −1}) m{sup 2}/s, respectively, while those determined for Mg(Zn) solid solution were 139.5 (±4.0) kJ/mol and 1.48 × 10{sup −3} (±1.13 × 10{sup −3}) m{sup 2}/s. In Mg, the Zn impurity diffusion coefficient was an order of magnitude higher than the Al impurity diffusion coefficient. 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 × 10{sup −5} (±5.37 × 10{sup −4}) m{sup 2}/s, respectively, while those for diffusion of Zn impurity in Mg were determined to be 118.6 (±6.3) kJ/mol and 2.90 × 10{sup −5} (±4.41 × 10{sup −5

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

    Science.gov (United States)

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

    2017-09-01

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

  4. Phase coexistence in ferroelectric solid solutions: Formation of monoclinic phase with enhanced piezoelectricity

    Directory of Open Access Journals (Sweden)

    Xiaoyan Lu

    2016-10-01

    Full Text Available Phase morphology and corresponding piezoelectricity in ferroelectric solid solutions were studied by using a phenomenological theory with the consideration of phase coexistence. Results have shown that phases with similar energy potentials can coexist, thus induce interfacial stresses which lead to the formation of adaptive monoclinic phases. A new tetragonal-like monoclinic to rhombohedral-like monoclinic phase transition was predicted in a shear stress state. Enhanced piezoelectricity can be achieved by manipulating the stress state close to a critical stress field. Phase coexistence is universal in ferroelectric solid solutions and may provide a way to optimize ultra-fine structures and proper stress states to achieve ultrahigh piezoelectricity.

  5. A solid state and solution NMR study of the tautomerism in hydroxyquinoline carboxylic acids.

    Science.gov (United States)

    Gudat, Dietrich; Nycz, Jacek E; Polanski, Jaroslaw

    2008-01-01

    Some hydroxyquinoline carboxylic acids and their conjugate acids and bases were characterized by 13C and 15N NMR spectroscopy in solution and in the solid state. Differences in 13C and, in particular, 15N chemical shift patterns allow to distinguish between individual tautomers and confirm the presence of zwitterionic species in the solid state. Solution NMR spectra in dimethyl sulfoxide (DMSO) show effects resulting as a consequence of dynamic exchange and suggest the presence of an equilibrium mixture of hydroxyquinoline carboxylic acid and zwitterionic hydroxyquinolinium carboxylate tautomers.

  6. Session 4: Solid solution sulfide photo-catalysts for hydrogen evolution under visible light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tsuji, I.; Kato, H. [Tokyo Univ., Faculty of Science, Dept. of Applied Chemistry (Japan); Kudo, A.; Kobayashi, H. [Kurashiki Univ. of Science and the Arts, (Japan); Kudo, A. [Japan Science and Technology Agency, Core Research for Evolutional Science and Technology (Japan)

    2004-07-01

    In the present study, we tried to make a new visible-light driven photo-catalyst for H{sub 2} evolution by making solid solutions between ZnS photo-catalyst with a wide band gap, and AgInS{sub 2} and CuInS{sub 2} with narrow band gaps. The photophysical and photo-catalytic properties of (MIn){sub x}Zn{sub 2(1-x)}S{sub 2} (M=Cu, Ag) solid solutions were investigated. (authors)

  7. The LiBH4-LiI Solid Solution as an Electrolyte in an All-Solid-State Battery

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Christiansen, Ane Sælland; Viskinde, Rasmus

    2014-01-01

    is compared with a cell with an identical electrode setup but a liquid electrolyte (1 M LiPF6 in EC:DMC). All measurements were carried out at a temperature of 60°C. For the all-solid-state cells, 81% of the theoretical discharge capacity is reached for a discharge rate of 10 μA, but a capacity fade of 1......The charge and discharge performance of an all-solid-state lithium battery with the LiBH4-LiI solid solution as an electrolyte is reported. Lithium titanate (Li4Ti5O12) was used as the positive electrode and lithium metal as the negative electrode. The performance of the all-solid-state cell...... the change in the discharge capacity of the cells and changes in the cell impedance over 200 charge-discharge cycles. This is expectedly due to the possible formation of passivating areas in the cell and/or loss of contact area between the electrolyte and the electrodes....

  8. Study of metal--oxygen solid solutions utilizing solid electrolytic cells

    Energy Technology Data Exchange (ETDEWEB)

    Lauf, Robert John [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-10-01

    A study was made of the thermodynamic and kinetic behavior of oxygen in a number of Group V metals and alloys. Investigations were made with a ThO2Y2O3 electrolyte over the temperature range of 600 to 1150°to 1423°K). The activity of oxygen in three Nb--Ta alloys (nominally 25, 50, and 75 at. % Ta) was found to obey Henry's Law up to the solubility limit in each alloy. The standard entropy and enthalpy of solution of oxygen in the three Nb--Ta alloys were intermediate between those for pure niobium and pure tantalum, and varied almost linearly with Nb : Ta content. The diffusion coefficient of oxygen was measured in niobium and vanadium, and the values were found to be in excellent agreement with literature values obtained by a variety of techniques. The diffusion coefficient of oxygen in each of several dilute substitutional niobium alloys was measured and compared to the diffusion coefficient in pure niobium. The addition of 1 to 5% substitutional solutes resulted in as much as an order-of-magnitude decrease in the oxygen diffusivity. This decrease is believed to be due to trapping of oxygen by substitutional solute atoms. The substitutional-oxygen binding or ''trap'' energies (in eV) for several substitutional solutes in niobium were determined to be: Ta: 0.3 ± 0.1; V: 0.55 ± 0.05; Ti: 0.7 ± 0.1; Zr: 0.7 ± 0.05. The trap energy is rationalized as being the sum of a chemical interaction and an elastic interaction. 27 figures, 9 tables.

  9. Synthesis and Non-isothermal Carbothermic Reduction of FeTiO3-Fe2O3 Solid Solution Systems

    Science.gov (United States)

    Liu, Yiran; Zhang, Jianliang; Xing, Xiangdong; Liu, Zhengjian; Liu, Xingle; Li, Naiyao; Shen, Yansong

    2017-10-01

    To investigate the carbothermic reduction behaviors of xFeTiO3·(1 - x)Fe2O3 solid solutions, the solid solutions with different x values were synthesized and used in the corresponding reactions. With an increase in x, the temperature pertaining to the onset of carbothermic reduction increased, while the rate of reduction of the solid solutions, α, decreased. The lattice parameters calculated from XRD patterns indicated that the solid solution with a higher x led to a larger lattice distortion. The non-isothermal kinetics were calculated, and an average activation energy E value of 3.0 × 102 kJ/mol was obtained.

  10. Contribution of Lattice Distortion to Solid Solution Strengthening in a Series of Refractory High Entropy Alloys

    Science.gov (United States)

    Chen, H.; Kauffmann, A.; Laube, S.; Choi, I.-C.; Schwaiger, R.; Huang, Y.; Lichtenberg, K.; Müller, F.; Gorr, B.; Christ, H.-J.; Heilmaier, M.

    2017-11-01

    We present an experimental approach for revealing the impact of lattice distortion on solid solution strengthening in a series of body-centered-cubic (bcc) Al-containing, refractory high entropy alloys (HEAs) from the Nb-Mo-Cr-Ti-Al system. By systematically varying the Nb and Cr content, a wide range of atomic size difference as a common measure for the lattice distortion was obtained. Single-phase, bcc solid solutions were achieved by arc melting and homogenization as well as verified by means of scanning electron microscopy and X-ray diffraction. The atomic radii of the alloying elements for determination of atomic size difference were recalculated on the basis of the mean atomic radii in and the chemical compositions of the solid solutions. Microhardness (μH) at room temperature correlates well with the deduced atomic size difference. Nevertheless, the mechanisms of microscopic slip lead to pronounced temperature dependence of mechanical strength. In order to account for this particular feature, we present a combined approach, using μH, nanoindentation, and compression tests. The athermal proportion to the yield stress of the investigated equimolar alloys is revealed. These parameters support the universality of this aforementioned correlation. Hence, the pertinence of lattice distortion for solid solution strengthening in bcc HEAs is proven.

  11. Exact Solution of the Two-Level System and the Einstein Solid in the Microcanonical Formalism

    Science.gov (United States)

    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…

  12. Prediction of solid solution formation in a family of diastereomeric salts. A molecular modeling study

    NARCIS (Netherlands)

    Gervais, C.; Grimbergen, R.F.P.; Markovits, I.; Ariaans, G.J.A.; Kaptein, B.; Bruggink, A.; Broxterman, Q.B.

    2004-01-01

    The possibility of solid solution behavior of diastereomeric salts, containing multiple resolving agents of the same family (Dutch Resolution), is predicted by molecular modeling. Super-cells containing different ratios of resolving agents in the diastereomeric salt are constructed and optimized,

  13. Flexible, low-temperature, solution processed ZnO-based perovskite solid state solar cells.

    Science.gov (United States)

    Kumar, Mulmudi Hemant; Yantara, Natalia; Dharani, Sabba; Graetzel, Michael; Mhaisalkar, Subodh; Boix, Pablo P; Mathews, Nripan

    2013-12-07

    A ZnO compact layer formed by electrodeposition and ZnO nanorods grown by chemical bath deposition (CBD) allow the processing of low-temperature, solution based and flexible solid state perovskite CH3NH3PbI3 solar cells. Conversion efficiencies of 8.90% were achieved on rigid substrates while the flexible ones yielded 2.62%.

  14. Vapor-Liquid-Solid Equilibria of Sulfur Dioxide in Aqueous Electrolyte Solutions

    DEFF Research Database (Denmark)

    Pereda, Selva; Thomsen, Kaj; Rasmussen, Peter

    2000-01-01

    The Extended UNIQUAC model for electrolyte systems, combined with the Soave-Redlich-Kwong equation of state is used to describe the complex vapor-liquid-solid equilibria of sulfur dioxide in electrolyte solutions. Model parameters based on 1500 experimental data points are presented. The parameters...

  15. Bridging phases at the morphotropic boundaries of lead oxide solid solutions

    NARCIS (Netherlands)

    Noheda, Beatriz; Cox, DE

    2006-01-01

    Ceramic solid solutions of PbZr1-xTixO3 (PZT) with compositions x similar or equal to 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 less than or similar to 0.5), the

  16. Defect structure of cubic solid solutions of alkaline earth and rare earth fluorides

    NARCIS (Netherlands)

    DenHartog, HW

    1996-01-01

    In this paper we will consider the disorder in some cubic solid solutions consisting of one of the alkaline earth fluorides and one of the rare earth fluorides. This is an attractive group of model materials, because these materials have a rather simple overall cubic structure. We will discuss the

  17. Geochemical and numerical modelling of interactions between solid solutions and an aqueous solution. Extension of a reactive transport computer code called Archimede and application to reservoirs diagenesis; Modelisation geochimique et numerique des interactions entre des solutions solides et une solution aqueuse: extension du logiciel de reaction-transport archimede et application a la diagenese des reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Nourtier-Mazauric, E.

    2003-03-15

    This thesis presents a thermodynamic and kinetic model of interactions between a fluid and ideal solid solutions represented by several end-members. The reaction between a solid solution and the aqueous solution results from the competition between the stoichiometric dissolution of the initial solid solution and the co-precipitation of the least soluble solid solution in the fluid at considered time. This model was implemented in ARCHIMEDE, a computer code of reactive transport in porous media, then applied to various examples. In the case of binary solid solutions, a graphical method allowed to determine the compositions of the precipitating solid solutions, with the aid of the end-member chemical potentials. The obtained program could be used to notably model the diagenesis of clayey or carbonated oil reservoirs, or the ground pollutant dispersion. (author)

  18. Investigation of water and saline solution drops evaporation on a solid substrate

    Directory of Open Access Journals (Sweden)

    Orlova Evgenija G.

    2014-01-01

    Full Text Available Experimental investigation water and saline solution drops evaporation on a solid substrate made of anodized aluminum is presented in the paper. Parameters characterizing drop profile have been obtained (contact angle, contact diameter, height. The specific evaporation rate has been calculated from obtained values. It was found that water and saline solution drops with concentration up to 9.1% evaporate in the pinning mode. However, with increasing the salt concentration in the solution up to 16.7% spreading mode was observed. Two stages of drop evaporation depending on change of the evaporation rate have been separated.

  19. Thermal Analysis of Tantalum Carbide-Hafnium Carbide Solid Solutions from Room Temperature to 1400 °C

    Directory of Open Access Journals (Sweden)

    Cheng Zhang

    2017-07-01

    Full Text Available The thermogravimetric analysis on TaC, HfC, and their solid solutions has been carried out in air up to 1400 °C. Three solid solution compositions have been chosen: 80TaC-20 vol % HfC (T80H20, 50TaC-50 vol % HfC (T50H50, and 20TaC-80 vol % HfC (T20H80, in addition to pure TaC and HfC. Solid solutions exhibit better oxidation resistance than the pure carbides. The onset of oxidation is delayed in solid solutions from 750 °C for pure TaC, to 940 °C for the T50H50 sample. Moreover, T50H50 samples display the highest resistance to oxidation with the retention of the initial carbides. The oxide scale formed on the T50H50 sample displays mechanical integrity to prevent the oxidation of the underlying carbide solid solution. The improved oxidation resistance of the solid solution is attributed to the reaction between Ta2O5 and HfC, which stabilizes the volume changes induced by the formation of Ta2O5 and diminishes the generation of gaseous products. Also, the formation of solid solutions disturbs the atomic arrangement inside the lattice, which delays the reaction between Ta and O. Both of these mechanisms lead to the improved oxidation resistances of TaC-HfC solid solutions.

  20. Solid solution strengthening and diffusion in nickel- and cobalt-based superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Rehman, Hamad ur

    2016-07-01

    Nickel and cobalt-based superalloys with a γ-γ{sup '} microstructure are known for their excellent creep resistance at high temperatures. Their microstructure is engineered using different alloying elements, that partition either to the fcc γ matrix or to the ordered γ{sup '} phase. In the present work the effect of alloying elements on their segregation behaviour in nickel-based superalloys, diffusion in cobalt-based superalloys and the temperature dependent solid solution strengthening in nickel-based alloys is investigated. The effect of dendritic segregation on the local mechanical properties of individual phases in the as-cast, heat treated and creep deformed state of a nickel-based superalloy is investigated. The local chemical composition is characterized using Electron Probe Micro Analysis and then correlated with the mechanical properties of individual phases using nanoindentation. Furthermore, the temperature dependant solid solution hardening contribution of Ta, W and Re towards fcc nickel is studied. The room temperature hardening is determined by a diffusion couple approach using nanoindentation and energy dispersive X-ray analysis for relating hardness to the chemical composition. The high temperature properties are determined using compression strain rate jump tests. The results show that at lower temperatures, the solute size is prevalent and the elements with the largest size difference with nickel, induce the greatest hardening consistent with a classical solid solution strengthening theory. At higher temperatures, the solutes interact with the dislocations such that the slowest diffusing solute poses maximal resistance to dislocation glide and climb. Lastly, the diffusion of different technically relevant solutes in fcc cobalt is investigated using diffusion couples. The results show that the large atoms diffuse faster in cobalt-based superalloys similar to their nickel-based counterparts.

  1. Flexible, Luminescent Metal-Organic Frameworks Showing Synergistic Solid-Solution Effects on Porosity and Sensitivity.

    Science.gov (United States)

    Liu, Si-Yang; Zhou, Dong-Dong; He, Chun-Ting; Liao, Pei-Qin; Cheng, Xiao-Ning; Xu, Yan-Tong; Ye, Jia-Wen; Zhang, Jie-Peng; Chen, Xiao-Ming

    2016-12-23

    Mixing molecular building blocks in the solid solution manner is a valuable strategy to obtain structures and properties in between the isostructural parent metal-organic frameworks (MOFs). We report nonlinear/synergistic solid-solution effects using highly related yet non-isostructural, phosphorescent CuI triazolate frameworks as parent phases. Near the phase boundaries associated with conformational diversity and ligand heterogeneity, the porosity (+150 %) and optical O2 sensitivity (410 times, limit of detection 0.07 ppm) can be drastically improved from the best-performing parent MOFs and even exceeds the records hold by precious-metal complexes (3 ppm) and C70 (0.2 ppm). © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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

  3. Luminescence properties of solid solutions LuxY1-xPO4:Eu3+

    Science.gov (United States)

    Levushkina, V. S.; Spassky, D. A.; Tretyakova, M. S.; Zadneprovski, B. I.; Kamenskikh, I. A.; Vasil'ev, A. N.; Belsky, A.

    2018-01-01

    Solid solutions LuxY1-xPO4 doped with Eu3+ were synthesized by the sol-gel method. Luminescence spectra under UV and X-ray excitation and luminescence excitation spectra in the UV-VUV energy range are presented. Observed variations of the structure of 4f-4f Eu3+ lines with the composition of the solid solution are explained by the fluctuations in the distribution of substitutional cations. The role of electronic structure modification in the fundamental absorption region with changing Y/Lu ratio is discussed and is suggested as the origin of different efficiency of energy transfer to Eu3+ in this region. Temperature dependence of the luminescence yield is related to the competition between emission centers and traps.

  4. Experimental and theoretical investigation of Cr1-xScxN solid solutions for thermoelectrics

    DEFF Research Database (Denmark)

    Kerdsongpanya, Sit; Sun, Bo; Eriksson, Fredrik

    2016-01-01

    The ScN- and CrN-based transition-metal nitrides have recently emerged as a novel and unexpected class of materials for thermoelectrics. These materials constitute well-defined model systems for investigating mixing thermodynamics, phase stability, and band structure aiming for property tailoring....... Here, we demonstrate an approach to tailor their thermoelectric properties by solid solutions. The trends in mixing thermodynamics and densities-of-states (DOS) of rocksalt-Cr1-xScxN solid solutions (0 ≤ x ≤ 1) are investigated by first-principles calculations, and Cr1-xScxN thin films are synthesized...... factors above that expected from the rule-of-mixture. These results corroborate the theoretical predictions and enable tailoring and understanding of structure-transport-property correlations of Cr1-xScxN....

  5. Studying the Super-cooled Solid Solution Breakdown of V-1341 Aluminum Alloy

    Directory of Open Access Journals (Sweden)

    Yu. A. Puchkov

    2017-01-01

    Full Text Available Deformable alloys of the Al-Mg-Si system are widely used in aviation industry, rocket engineering, shipbuilding, as well as on railway and highway transport. These alloys are characterized by high stamping ability, weld-ability, and machinability with a comparatively high strength and corrosion resistance in a heat-strengthened state. A promising alloy of the Al-Mg-Si system with increased structural strength and manufacturability is on par with foreign analogues in properties is the V-1341 alloy [1, 2].The properties of heat-treatable aluminum alloys strongly depend on the cooling rate of the product during quenching [3-12], which determines the structure and level of residual stresses. Decrease in structural strength, tendency to pitting and inter-crystalline corrosion with slow cooling from the quenching temperature is caused by formation of coarse unequiaxed precipitate, precipitates-free zones, and also by decreasing proportion of inclusions of the strengthening phase [3-12].Thus, the relevant task is to study the effect of isothermal quenching modes on the structure of deformable V-1341 aluminum alloy thermally hardened.The paper studies the impact of isothermal time in quenching on the composition and morphology of breakdown products of the V-1341 alloy solid solution. It is shown that at isothermal time under the solid solution breakdown, at first on the dispersoid surface and then in the solid solution are formed and grow large needle-like crystals of the β'-phase which are structural concentrators of stresses. An increasing isothermal time leads to decreasing solid solution super-saturation by doping elements and vacancies. This leads to a decrease in the fraction of the coherent finely dispersed hardening β '' phase, and also to an increase in the width of the precipitates-free zone.

  6. Local atomic structure of solid solutions with overlapping shells by EXAFS: The regularization method

    Energy Technology Data Exchange (ETDEWEB)

    Babanov, Yu.A., E-mail: babanov@imp.uran.ru [M.N. Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation); Ponomarev, D.A.; Ustinov, V.V. [M.N. Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation); Baranov, A.N. [M.V. Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Zubavichus, Ya.V. [Russian Research Centre “Kurchatov Institute”, 123182 Moscow (Russian Federation)

    2016-08-15

    Highlights: • A method for determining bond lengths from combined EXAFS spectra for solid oxide solutions is proposed. • We have demonstrated a high resolution in r-space of close spacing atoms in the Periodical Table. • These results were obtained without any assumptions concerning interatomic distances for multi-component systems. • Coordinates ions for the solid solution with rock salt structure are determined. - Abstract: The regularization method of solving ill-posed problem is used to determine five partial interatomic distances on the basis of combined two EXAFS spectra. Mathematical algorithm and experimental results of the EXAFS analysis for Ni{sub c}Zn{sub 1−c}O (c = 0.0, 0.3, 0.5, 0.7, 1.0) solid solutions with the rock salt (rs) crystal structure are discussed. Samples were synthesized from the binary oxide powders at pressure of 7.7 GPa and temperatures 1450–1650 K. The measurements were performed using synchrotron facilities (Russian Research Centre “Kurchatov Institute”, Moscow). The Ni and Zn K absorption spectra were recorded in transmission mode under room temperature. It is shown, the ideal rock salt lattice is distorted and long-range order exists only in the average (Vegard law). In order to determine coordinates ions for the solid solution with rock salt structure, we used the Pauling model. The simulation is performed for 343,000 cluster of oxide ions. The distribution functions for ions (Ni−O, Ni−Ni, Ni−Zn, Zn−Zn, Zn−O, O−O) depending on the distance are obtained. The width of the Gaussian distribution function is determined by the difference of the radii of the metal ions. The results are consistent with the data both X-ray diffraction and the EXAFS spectroscopy.

  7. Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

    Science.gov (United States)

    Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

    2013-11-01

    Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Al-Fe solid solutions in alloys obtained by melt spinning

    Energy Technology Data Exchange (ETDEWEB)

    Badan, B.; Magrini, M.; Zambon, A. [Univ. di Padova (Italy). Dept. of Mechanical and Management Innovation

    1996-07-01

    The extension of solid solutions is one of the more claimed effects of solidification under high cooling rates. The possibility to increase, by such technology, the extremely small amount (0,006 at% at 500 C) of iron in aluminum was extensively studied and recently received further attention, owing to the interesting technological properties of Al-Fe alloys. However the rapid quenching from the liquid not only affects the amount of iron retained in solid solution, but also the possible formation of other intermetallic phases, and, more generally, the location of iron atoms retained in the metastable solid solution of aluminum. Different situations of iron atoms have been investigated using XRD, TEM and Moessbauer spectroscopy (MS), but from the interpretation of the results some problems to obtain unambiguous conclusions arise. In any case it seems interesting to clarify the actual extension of solubility of iron in aluminum, in rather concentrated alloys, in which the formation of metastable intermetallic compounds cannot be suppressed. The paper reports MS analysis of Al-Fe (0,1--4 at%) alloys, rapidly solidified by melt spinning.

  9. Characterization of powellite-based solid solutions by site-selective time resolved laser fluorescence spectroscopy.

    Science.gov (United States)

    Schmidt, Moritz; Heck, Stephanie; Bosbach, Dirk; Ganschow, Steffen; Walther, Clemens; Stumpf, Thorsten

    2013-06-21

    We present a comprehensive study of the solid solution system Ca2(MoO4)2-NaGd(MoO4)2 on the molecular scale, by means of site-selective time resolved laser fluorescence spectroscopy (TRLFS). Eu(3+) is used as a trace fluorescent probe, homogeneously substituting for Gd(3+) in the solid solution crystal structure. Site-selective TRLFS of a series of polycrystalline samples covering the whole composition range of the solid solution series from 10% substitution of Ca(2+) to the NaGd end-member reveals it to be homogeneous throughout the whole range. The trivalent ions are incorporated into the powellite structure in only one coordination environment, which exhibits a very strong ligand-metal interaction. Polarization-dependent measurements of a single crystal of NaGd(Eu)(MoO4)2 identify the coordination geometry to be of C2v point symmetry. The S4 symmetry of the Ca site within the powellite lattice can be transformed into C2v assuming minor motion in the first coordination sphere.

  10. Structural study of nanocrystalline solid solution of Cu-Mo obtained by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingenieria Metalurgica y de Materiales, Universidad Tecnica Federico Santa Maria, Avenida Espana 1680, Valparaiso (Chile); Instituto de Materiales y Procesos Termomecanicos, Universidad Austral de Chile, General Lagos 2086, Valdivia (Chile); Castro, F. [Centro de Estudios e Investigaciones Tecnicas de Gipuzkoa, Paseo de Manuel Lardizabal, N Degree-Sign 15 20018, San Sebastian (Spain); Martinez, V. [TEKMETALL, Metallurgical Solutions S.L., Paseo neinor, Iribar Kalea 5, F1. B. de Igara 20018, San Sebastian (Spain); Guzman, D. [Departamento de Ingenieria en Metalurgia, Facultad de Ingenieria, Universidad de Atacama y Centro Regional de Investigacion y Desarrollo Sustentable de Atacama (CRIDESAT), Av. Copayapu 485, Copiapo (Chile); Cuevas, F. de las; Lozada, L.; Vielma, N. [Centro de Estudios e Investigaciones Tecnicas de Gipuzkoa, Paseo de Manuel Lardizabal, N Degree-Sign 15 20018, San Sebastian (Spain)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer Extension of solid solution in Cu-Mo system achieved by mechanical alloying. Black-Right-Pointing-Pointer X-ray characterization of Cu-Mo system processed by mechanical alloying. Black-Right-Pointing-Pointer Structural study of nanocrystalline solid solution of Cu-Mo obtained by mechanical alloying. - Abstract: This work studied the structural evolution of Cu-xMo (x = 5 and 8 wt.%) alloys processed by mechanical alloying using x-ray diffraction profiles, scanning electron microscopy, differential scanning calorimetric and microhardness. X-ray diffraction analysis was done using the modified Williamson-Hall and Warren-Averbach methods. These were used to determine structural properties, such as crystallite size, stacking fault probability and energy, dislocation density of metallic powder as a function of the amount of Mo and milling time. The main results obtained for both alloys were higher dislocation density and Vickers microhardness values were measured and crystallites sizes of around 10 nm were measured for both systems at 50 h of milling. Lattice defects increase the free energy and the free energy curves shift upwards, therefore the solubility limits change and Cu-Mo solid solution is formed.

  11. A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent

    Energy Technology Data Exchange (ETDEWEB)

    Waysbort, Daniel [Israel Institute for Biological Research, PO Box 19, Ness-Ziona 74100 (Israel); McGarvey, David J. [R and T Directorate, Edgewood Chemical and Biological Center (ECBC), Aberdeen Proving Ground-Edgewood Area, MD 21010 (United States)], E-mail: david.mcgarvey@us.army.mil; Creasy, William R.; Morrissey, Kevin M.; Hendrickson, David M. [SAIC, P.O. Box 68, Gunpowder Branch, Aberdeen Proving Ground, MD 21010 (United States); Durst, H. Dupont [R and T Directorate, Edgewood Chemical and Biological Center (ECBC), Aberdeen Proving Ground-Edgewood Area, MD 21010 (United States)

    2009-01-30

    A decontamination system for chemical warfare agents was developed and tested that combines a liquid decontamination reagent solution with solid sorbent particles. The components have fewer safety and environmental concerns than traditional chlorine bleach-based products or highly caustic solutions. The liquid solution, based on Decon Green{sup TM}, has hydrogen peroxide and a carbonate buffer as active ingredients. The best solid sorbents were found to be a copolymer of ethylene glycol dimethacrylate and n-lauryl methacrylate (Polytrap 6603 Adsorber); or an allyl methacrylate cross-linked polymer (Poly-Pore E200 Adsorber). These solids are human and environmentally friendly and are commonly used in cosmetics. The decontaminant system was tested for reactivity with pinacolyl methylphosphonofluoridate (Soman, GD), bis(2-chloroethyl)sulfide (Mustard, HD), and S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothioate (VX) by using NMR Spectroscopy. Molybdate ion (MoO{sub 4}{sup -2}) was added to the decontaminant to catalyze the oxidation of HD. The molybdate ion provided a color change from pink to white when the oxidizing capacity of the system was exhausted. The decontaminant was effective for ratios of agent to decontaminant of up to 1:50 for VX (t{sub 1/2} {<=} 4 min), 1:10 for HD (t{sub 1/2} < 2 min with molybdate), and 1:10 for GD (t{sub 1/2} < 2 min). The vapor concentrations of GD above the dry sorbent and the sorbent with decontamination solution were measured to show that the sorbent decreased the vapor concentration of GD. The E200 sorbent had the additional advantage of absorbing aqueous decontamination solution without the addition of an organic co-solvent such as isopropanol, but the rate depended strongly on mixing for HD.

  12. A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent.

    Science.gov (United States)

    Waysbort, Daniel; McGarvey, David J; Creasy, William R; Morrissey, Kevin M; Hendrickson, David M; Durst, H Dupont

    2009-01-30

    A decontamination system for chemical warfare agents was developed and tested that combines a liquid decontamination reagent solution with solid sorbent particles. The components have fewer safety and environmental concerns than traditional chlorine bleach-based products or highly caustic solutions. The liquid solution, based on Decon Greentrade mark, has hydrogen peroxide and a carbonate buffer as active ingredients. The best solid sorbents were found to be a copolymer of ethylene glycol dimethacrylate and n-lauryl methacrylate (Polytrap 6603 Adsorber); or an allyl methacrylate cross-linked polymer (Poly-Pore E200 Adsorber). These solids are human and environmentally friendly and are commonly used in cosmetics. The decontaminant system was tested for reactivity with pinacolyl methylphosphonofluoridate (Soman, GD), bis(2-chloroethyl)sulfide (Mustard, HD), and S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothioate (VX) by using NMR Spectroscopy. Molybdate ion (MoO(4)(-2)) was added to the decontaminant to catalyze the oxidation of HD. The molybdate ion provided a color change from pink to white when the oxidizing capacity of the system was exhausted. The decontaminant was effective for ratios of agent to decontaminant of up to 1:50 for VX (t(1/2) < or = 4 min), 1:10 for HD (t(1/2) < 2 min with molybdate), and 1:10 for GD (t(1/2) < 2 min). The vapor concentrations of GD above the dry sorbent and the sorbent with decontamination solution were measured to show that the sorbent decreased the vapor concentration of GD. The E200 sorbent had the additional advantage of absorbing aqueous decontamination solution without the addition of an organic co-solvent such as isopropanol, but the rate depended strongly on mixing for HD.

  13. Structures in solid state and solution of dimethoxy curcuminoids: regioselective bromination and chlorination

    Science.gov (United States)

    2013-01-01

    Background Several papers described the structure of curcumin and some other derivatives in solid and in solution. In the crystal structure of curcumin, the enol H atom is located symmetrically between both oxygen atoms of the enolone fragment with an O···O distance of 2.455 Å, which is characteristic for symmetrical H-bonds. In the solution, the geometry of the enolone fragment is attributed to the inherent disorder of the local environment, which solvates one of the basic sites better than the other, stabilizing one tautomer over the other. In this paper, how the position of methoxy groups in dimethoxy curcuminoids influence the conformation of molecules and how the halogen atoms change it when they are bonded at α-position in keto-enol part of molecules is described. Results Six isomers of dimethoxy curcuminoids were prepared. Conformations in solid state, which were determined by X-ray single crystallography and 1H MAS and 13C CPMAS NMR measurements, depend on the position of methoxy groups in curcuminoid molecules. In solution, a fast equilibrium between both keto-enol forms exists. A theoretical calculation finding shows that the position of methoxy groups changes the energy of HOMO and LUMO. An efficient protocol for the highly regioselective bromination and chlorination leading to α-halogenated product has been developed. All α-halogenated compounds are present mainly in cis keto-enol form. Conclusions The structures in solid state of dimethoxy curcuminoids depend on the position of methoxy groups. The NMR data of crystalline solid samples of 3,4-diOCH3 derivative, XRD measurements and X-ray structures lead us to the conclusion that polymorphism exists in solids. The same conclusion can be done for 3,5-diOCH3 derivative. In solution, dimethoxy curcuminoids are present in the forms that can be described as the coexistence of two equivalent tautomers being in fast equilibrium. The position of methoxy groups has a small influence on the enolic hydrogen

  14. Effect of carbon on formation of mixed solid solutions during mechanochemical synthesis of Ni-Al-Mo-C mixtures and ordering of solutions during heating

    Science.gov (United States)

    Portnoi, V. K.; Leonov, A. V.; Streletskii, A. N.; Logacheva, A. I.

    2014-03-01

    Solid solutions Ni(Al, Mo, C) are formed via milling the Ni2.8Al1Mo0.2 and Ni3Al0.8Mo0.2 and graphite-containing Ni2.8Al1Mo0.2C(0.25, 0.5) and Ni3Al0.8Mo0.2C(0.25, 0.5) mixtures. In this case, some amount of Mo remains beyond the solid solution. Graphite added to a starting mixture decreases the Mo solubility and favors the amorphization of solid solutions. The complete amorphization was found for the mixture with the 5 at % C and 5 at % Mo, which was added instead of Ni. The heating of mechanically synthesized (MS) powder alloys leads to the ordering of carbon-free and carbon-containing solid solutions with the formation of the L12 and E21 structure, respectively. In the course of the ordering of the Ni(Al, Mo, C) solid solutions, Mo and carbon precipitate in the form of the molybdenum carbide (Mo2C) second phase. The hardness of the MS three-phase Ni-Al-Mo-C solid solutions subjected to hot isostatic pressing is determined by the mass fraction of the formed Mo2C carbide. It is shown that the carbon content in the multicomponent antiperovskite can be estimated by analyzing the ratio of integral intensities of superlattice reflections I (100)/ I (110).

  15. Differences in physical chemistry and dissolution rate of solid particle aerosols from solution pressurised inhalers.

    Science.gov (United States)

    Buttini, Francesca; Miozzi, Michele; Balducci, Anna Giulia; Royall, Paul G; Brambilla, Gaetano; Colombo, Paolo; Bettini, Ruggero; Forbes, Ben

    2014-04-25

    Solution composition alters the dynamics of beclomethasone diproprionate (BDP) particle formation from droplets emitted by pressurised metered dose inhalers (pMDIs). The hypothesis that differences in inhaler solutions result in different solid particle physical chemistry was tested using a suite of complementary calorimetric techniques. The atomisation of BDP-ethanol solutions from commercial HFA-pMDI produced aerodynamically-equivalent solid particle aerosols. However, differences in particle physico-chemistry (morphology and solvate/clathrate formation) were detected by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and supported by hot stage microscopy (HSM). Increasing the ethanol content of the formulation from 8 to 12% (w/w), which retards the evaporation of propellant and slows the increase in droplet surface viscosity, enhanced the likelihood of particles drying with a smooth surface. The dissolution rate of BDP from the 12% (w/w) ethanol formulation-derived particles (63% dissolved over 120 min) was reduced compared to the 8% (w/w) ethanol formulation-derived particles (86% dissolved over 120 min). The addition of 0.01% (w/w) formoterol fumarate or 1.3% (w/w) glycerol to the inhaler solution modified the particles and reduced the BDP dissolution rate further to 34% and 16% dissolved in 120 min, respectively. These data provide evidence that therapeutic aerosols from apparently similar inhaler products, including those with similar aerodynamic performance, may behave non-equivalently after deposition in the lungs. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Fabrication of nanocrystalline alloys Cu–Cr–Mo super satured solid solution by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzmán, D. [Departamento de Ingeniería en Metalurgia, Facultad de Ingeniería, Universidad de Atacama y Centro Regional de Investigación y Desarrollo Sustentable de Atacama (CRIDESAT), Av. Copayapu 485, Copiapó (Chile); Castro, F.; Martínez, V.; Cuevas, F. de las [Centro de Estudios e Investigaciones Técnicas de Gipuzkoa, Paseo de Manuel Lardizábal, N° 15, 20018 San Sebastián (Spain); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Muthiah, T. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile)

    2014-08-01

    This work discusses the extension of solid solubility of Cr and Mo in Cu processed by mechanical alloying. Three alloys processed, Cu–5Cr–5Mo, Cu–10Cr–10Mo and Cu–15Cr–15Mo (weight%) using a SPEX mill. Gibbs free energy of mixing values 10, 15 and 20 kJ mol{sup −1} were calculated for these three alloys respectively by using the Miedema's model. The crystallite size decreases and dislocation density increases when the milling time increases, so Gibbs free energy storage in powders increases by the presence of crystalline defects. The energy produced by crystallite boundaries and strain dislocations were estimated and compared with Gibbs free energy of mixing values. The energy storage values by the presence of crystalline defects were higher than Gibbs free energy of mixing at 120 h for Cu–5Cr–5Mo, 130 h for Cu–10Cr–10Mo and 150 h for Cu–15Cr–15Mo. During milling, crystalline defects are produced that increases the Gibbs free energy storage and thus the Gibbs free energy curves are moved upwards and hence the solubility limit changes. Therefore, the three alloys form solid solutions after these milling time, which are supported with the XRD results. - Highlights: • Extension of solid solution Cr and Mo in Cu achieved by mechanical alloying. • X-ray characterization of Cu–Cr–Mo system processed by mechanical alloying. • Thermodynamics analysis of formation of solid solution of the Cu–Cr–Mo system.

  17. Decay property of regularity-loss type for solutions in elastic solids with voids

    KAUST Repository

    Djouamai, Leila

    2014-01-01

    In this paper, we consider the Cauchy problem for a system of elastic solids with voids. First, we show that a linear porous dissipation leads to decay rates of regularity-loss type of the solution. We show some decay estimates for initial data in Hs(R)∩L1(R). Furthermore, we prove that by restricting the initial data to be in Hs(R)∩L1,γ(R) and γ. ∈. [0, 1], we can derive faster decay estimates of the solution. Second, we show that by adding a viscoelastic damping term, then we gain the regularity of the solution and obtain the optimal decay rate. © 2013 Elsevier Ltd.

  18. B-site substituted solid solutions on the base of sodium-bismuth titanate

    Directory of Open Access Journals (Sweden)

    V. M. Ishchuk

    2016-12-01

    Full Text Available The paper presents results of studies of the formation of phases during the solid-state synthesis in the [(Na0.5Bi0.50.80Ba0.20](Ti1–yByO3 system of solid solutions with B-site substitutions. The substitutions by zirconium, tin and ion complexes (In0.5Nb0.5 and (Fe0.5Nb0.5 have been studied. It has been found that the synthesis is a multi-step process associated with the formation of a number of intermediate phases (depending on the compositions and calcination temperatures. Single-phase solid solutions have been produced at the calcination temperatures in the interval 1000–1100∘C. An increase in the substituting ions concentration leads to a linear increase of the crystal cell size. At the same time, the tolerance factor gets reduced boosting the stability of the antiferroelectric phase as compared to that of the ferroelectric phase.

  19. Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

    Science.gov (United States)

    Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

    2012-10-01

    The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

  20. Dissolution of britholites and monazite / brabantite solid solutions doped with actinides; Etude de la dissolution de britholites et de solutions solides monazite / brabantite dopees avec des actinides

    Energy Technology Data Exchange (ETDEWEB)

    Du Fou De Kerdaniel, E

    2007-12-15

    In the field of the radwaste storage in underground repository, several matrices were considered as promising ceramics for the specific immobilization of actinides. Two of them, britholites and monazite/ brabantite solid solution, have been considered during this work. In order to examine the dissolution mechanisms occurring at the solid liquid interface, several leaching experiments have been conducted on (Ln{sup III}PO{sub 4} ), brabantite (Ca{sup II}An{sup IV}(PO{sub 4}){sub 2}: An = Th, U) and britholites (Ca{sub 9}Nd{sub 0.5}An{sub 0.5}{sup IV} (PO{sub 4}){sub 4.5}(SiO{sub 4}){sub 1.5}F{sub 2}: An = Th, U). Some steady experiments, performed in under saturation conditions for various pH and temperature conditions allowed to evaluate the long term behaviour of such matrices through their chemical durability. On the contrary, the thermodynamic equilibria were examined through the leaching experiments performed near the saturation conditions. By the way, various secondary phases, precipitated onto the surface of altered samples have been identified and characterized. Among them, the (Nd, Ca, Th) - rhabdophane, novelly prepared in over- saturation experiments for a thorium weight loading lower than 11 % appeared to be metastable. Indeed, it turns into TPHPH (Th{sub 2}(PO{sub 4}){sub 2}HPO{sub 4}.H{sub 2}O) and Nd - rhabdophane (NdPO{sub 4}.1/2H{sub 2}O) when increasing leaching time. (author)

  1. Four Thermochromic o-Hydroxy Schiff Bases of α-Aminodiphenylmethane: Solution and Solid State Study

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2017-01-01

    Full Text Available More than a hundred years after the first studies of the photo- and thermochromism of o-hydroxy Schiff bases (imines, it is still an intriguing topic that fascinates several research groups around the world. The reasons for such behavior are still under investigation, and this work is a part of it. We report the solution-based and mechanochemical synthesis of four o-hydroxy imines derived from α-aminodiphenylmethane. The thermochromic properties were studied for the single crystal and polycrystalline samples of the imines. The supramolecular impact on the keto-enol tautomerism in the solid state was studied using SCXRD and NMR, while NMR spectroscopy was used for the solution state. All four imines are thermochromic, although the color changes of the single crystals are not as strong as of the polycrystalline samples. One of the imines shows negative thermochromism, and that one is in keto-amine tautomeric form, both in the solid state as in solution.

  2. Solid state and solution conformation of [Ala7]-phalloidin: a synthetic phallotoxin analogue.

    Science.gov (United States)

    Zanotti, G; Falcigno, L; Saviano, M; D'Auria, G; Bruno, B M; Campanile, T; Paolillo, L

    2001-04-01

    Phallotoxins are toxic compounds produced by poisonous mushroom Amanita phalloides and belong to the class of bicyclic peptides with a transannular thioether bridge. Their intoxication mechanism in the liver involves a specific binding of the toxins to F-actin that, consequently, prevents the depolymerization equilibrium with G-actin. Even though the conformational features of phallotoxins have been worked out in solution, the exact mechanism of interaction with F-actin is still unknown. In this study a toxic phalloidin synthetic derivative, bicyclo(Ala1-D-Thr2-Cys3-cis-4-hydroxy-Pro4-Ala5-2-mercapto-Trp6-Ala7)(S-3-->6) has been synthesized. A substitution at position 7. with an Ala residue replaces the 4,5-dihydroxy-Leu present in the natural phalloidin. This analogue has formed crystals suitable for X-ray analysis, and represents the first case for such a class of compounds. The solid-state structure as well as the solution conformation have been evaluated. NMR techniques have been used to extract interproton distances as restraints in subsequent molecular dynamics calculations. Finally, a direct comparison between structures in solution and in the solid state is presented.

  3. Solution- and solid-phase oligosaccharide synthesis using glucosyl iodides: a comparative study.

    Science.gov (United States)

    Lam, Son N; Gervay-Hague, Jacquelyn

    2002-11-19

    Glycosyl iodide donors have been used in both solid- and solution-phase syntheses yielding alpha-(1 --> 6)-linked glucosyl oligomers in highly efficient protocols. While the solid-phase strategy offers advantages in terms of ease of purification, it requires a total of 7.5 equiv of donor and approximately 12 h to complete the incorporation of one monosaccharide unit. In contrast, solution-phase methods require only 2.5 equiv of donor and 2-3 h reaction time per glycosylation. Moreover, since the reactions are virtually quantitative (> 90%) column chromatography of the material is facile. The overall advantages of solution-phase oligosaccharide synthesis were further illustrated in the convergent synthesis of a hexamer (methoxycarbonylmethyl 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6)-tetrakis-(2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6))-2,3,4-tri-O-benzyl-1-thio-alpha-D-glucopyranoside) that was constructed from dimer donor iodides in a two-plus-two and a two-plus-four fashion. Copyright 2002 Elsevier Science Ltd.

  4. A New Thermodynamic Parameter to Predict Formation of Solid Solution or Intermetallic Phases in High Entropy Alloys (Postprint)

    Science.gov (United States)

    2015-11-02

    AFRL-RX-WP-JA-2016-0345 A NEW THERMODYNAMIC PARAMETER TO PREDICT FORMATION OF SOLID SOLUTION OR INTERMETALLIC PHASES IN HIGH ENTROPY...Interim 22 September 2014 – 21 September 2015 4. TITLE AND SUBTITLE A NEW THERMODYNAMIC PARAMETER TO PREDICT FORMATION OF SOLID SOLUTION OR...simple thermodynamic criterion is proposed to predict the presence or absence of equilibrium intermetallic phases in a high entropy alloy at a given

  5. A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

    Science.gov (United States)

    Wang, Jiali; Wu, Hailong; Cui, Yanhua; Liu, Shengzhou; Tian, Xiaoqing; Cui, Yixiu; Liu, Xiaojiang; Yang, Yin

    2018-02-14

    Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li 2 MnO 3 delivers high capacity over 200 mAh g -1 but suffers from poor structural stability and electronic conductivity. Replacing Mn 4+ ions by relatively larger Sn 4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li 2 MnO 3 material. However, large difference in ionic radii of Mn 4+ and Sn 4+ ions leads to phase separation of Li 2 MnO 3 and Li 2 SnO 3 during high-temperature synthesis. To prepare solid-solution phase of Li 2 MnO 3 -Li 2 SnO 3 , a buffer agent of Ru 4+ , whose ionic radius is in between that of Mn 4+ and Sn 4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li + /e - transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn 4+ ions with larger sizes could partially block the migration of Mn 4+ and Ru 4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

  6. Methods of deoxygenating metals having oxygen dissolved therein in a solid solution

    Science.gov (United States)

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

    2017-06-06

    A method of deoxygenating metal can include forming a mixture of: a metal having oxygen dissolved therein in a solid solution, at least one of metallic magnesium and magnesium hydride, and a magnesium-containing salt. The mixture can be heated at a deoxygenation temperature for a period of time under a hydrogen-containing atmosphere to form a deoxygenated metal. The deoxygenated metal can then be cooled. The deoxygenated metal can optionally be subjected to leaching to remove by-products, followed by washing and drying to produce a final deoxygenated metal.

  7. Synthesis of dental enamel-like hydroxyapatite through solution mediated solid-state conversion.

    Science.gov (United States)

    Zhang, Junling; Jiang, Dongliang; Zhang, Jingxian; Lin, Qingling; Huang, Zhengren

    2010-03-02

    An ordered dental enamel-like structure of hydroxyapatite (HAp) was achieved through a solution mediated solid-state conversion process with organic phosphate surfactant and gelatin as the mediating agent. Transmission electron microscopy (TEM) tests demonstrated uniform sizes in the obtained apatite nanorods which arranged in parallel to each other along the c-axis and formed organized microarchitectural units over 10 microm in size. The sizes of the synthetic hydroxyapatite nanorods were similar to that observed in enamel from human teeth. The formation and regulation of the orientation and size of HAp nanorods might lead to a better understanding of the biomineralization process for the preparation of high performance biomaterials.

  8. Solid solution formation between vanadium(V) and tungsten(V) oxide phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Subrata Chandra; Glaum, Robert [Institut fuer Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universitaet Bonn (Germany); Abdullin, Dinar; Schiemann, Olav [Institut fuer Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universitaet Bonn (Germany); Bac, Nguyen Quang; Lii, Kwang-Hwa [Department of Chemistry, National Central University, Jhongli, Taiwan (China)

    2014-08-15

    The solid solutions (V{sub 1-x}W{sub x})OPO{sub 4} with β-VOPO{sub 4} structure type (0.0 ≤ x ≤ 0.01) and α{sub II}-VOPO{sub 4} structure type (0.04 ≤ x ≤ 0.26) were obtained from mixtures of V{sup V}OPO{sub 4} and W{sup V}OPO{sub 4} by conventional solid state reactions and by solution combustion synthesis. Single crystals of up to 3 mm edge length were obtained by chemical vapor transport (CVT) (800 → 700 C, Cl{sub 2} as a transporting agent). Single crystal structure refinements of crystals at x = 0.10 [a = 6.0503(2) Aa, c = 4.3618(4) Aa, R{sub 1} = 0.021, wR{sub 2} = 0.058, 21 parameters, 344 independent reflections] and x = 0.26 [a = 6.0979(2) Aa, c = 4.2995(1) Aa, R{sub 1} = 0.030, wR{sub 2} = 0.081, 21 parameters, 346 independent reflections] confirm the α{sub II}-VOPO{sub 4} structure type (P4/n, Z = 2) with mixed occupancy V/W for the metal site. Due to the specific redox behavior of W{sup 5+} and V{sup 5+}, solid solutions (V{sub 1-x}W{sub x})OPO{sub 4} should be formulated as (V{sup IV}{sub x}V{sup V}{sub 1-2x}W{sup VI}{sub x})OPO{sub 4}. The valence states of vanadium and tungsten are confirmed by XPS measurements. V{sup 4+} with d{sup 1} configuration was identified by EPR spectroscopy and magnetic measurements. Electronic spectra of the solid solutions show the IVCT(V{sup 4+} → V{sup 5+}) and the LMCT(O{sup 2-} → V{sup 5+}). (V{sub 0.74}W{sub 0.26})OPO{sub 4} powders exhibit semi-conducting behavior (E{sub g} = 0.7 eV). (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Detection of CO2 in solution with a Pt-NiO solid-state sensor.

    Science.gov (United States)

    Yue, Zhao; Niu, Wencheng; Zhang, Wei; Liu, Guohua; Parak, Wolfgang J

    2010-08-01

    A metal insulator semiconductor field effect transistor (MISFET)-type sensor for the detection of CO(2) dissolved in aqueous solution is presented. This all-solid-state device is based on a Pt-NiO thin film as active sensing material on the top of a gate electrode. The fabrication of the sensor is described and its performance is characterized. In particular the transient characteristics and response curves at different biases V(RS) versus the amount of dissolved CO(2) are presented. The sensor shows a linear response to the logarithm of the concentration of dissolved CO(2) at room temperature. Copyright (c) 2010 Elsevier Inc. All rights reserved.

  10. Phosphoramidate-peptide synthesis by solution- and solid-phase Staudinger-phosphite reactions.

    Science.gov (United States)

    Serwa, Remigiusz A; Swiecicki, Jean-Marie; Homann, Denise; Hackenberger, Christian P R

    2010-10-01

    The chemoselective incorporation of phosphoramidate moieties into peptides by a Staudinger-phosphite reaction of azides can be performed in many solvents, including water. In this report, we present two strategies for an efficient synthesis of phosphoramidate-containing peptides, in which the Staudinger-phosphite reaction is performed either on the solid support or in solution with aryl azido-containing peptides. The corresponding Staudinger reactions proceed in high conversion rates and deliver phosphoramidate peptides, in which the modification site is located in the middle of the peptide sequence. © 2010 European Peptide Society and John Wiley & Sons, Ltd.

  11. Solid-phase and solution-phase syntheses of oligomeric guanidines bearing peptide side chains.

    Science.gov (United States)

    Zhang, Zhongsheng; Fan, Erkang

    2005-10-28

    [reaction: see text] Synthetic strategies for preparing N,N'-bridged oligomeric guanidines bearing peptide side chains both on solid support and in solution are presented. Monomers are prepared from common alpha-amino acids and therefore contain conventionally protected peptide side chains. The side chains include alkyl, aromatic, hydroxyl, amino, carboxylic acid, and amide functional groups. Oligomer elongation utilizes acid-sensitive sulfonyl activated thiourea through the formation of carbodiimide intermediate. With proper preparation of monomers, synthesis of oligomer can be performed in two directions (equivalent to N to C terminal or C to N terminal in a peptide sequence) with excellent efficiency.

  12. Thermodynamic study of solid solutions in the SnTe-AgSbTe2 system by means of EMF with solid electrolyte Ag4RbI5

    Science.gov (United States)

    Mashadieva, L. F.; Yusibov, Yu. A.; Kevser, Dzh.; Babanly, M. B.

    2017-09-01

    The results from studying the SnTe-AgSbTe2 system by means of EMF with the solid electrolyte Ag4RbI5 in the temperature range of 300-430 K are presented. The formation of a wide (≥80 mol % of AgSbTe2) region of solid solutions based on SnTe is confirmed. Partial thermodynamic functions Δ G̅, Δ H̅, and Δ S̅ of silver in alloys are calculated from the equations for the EMF temperature dependences. Based on the literature data regarding solid-phase equilibria in the Ag2Te-SnTe-Sb2Te3-Te system, potential-determining reactions are identified that allow us to calculate the standard thermodynamic formation functions and standard entropies of solid solutions (2SnTe) x (AgSbTe2)1- x ( x = 0.2, 0.4, 0.6, 0.8, and 0.9).

  13. Exact solution of the two-level system and the Einstein solid in the microcanonical formalism

    Energy Technology Data Exchange (ETDEWEB)

    Bertoldi, Dalia S; Bringa, Eduardo M; Miranda, E N, E-mail: emiranda@mendoza-conicet.gov.ar [Instituto de Ciencias Basicas, UNCuyo 5500, Mendoza (Argentina)

    2011-11-15

    The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In this paper, those two models are solved without any approximation, using the gamma function and its derivatives. Exact values are calculated for the entropy, temperature and specific heat, and the relative error between our exact solution and the approximate one using the Stirling approximation. This error is significant for small systems, with a number of particles N {approx} 100, as in studies of atomic clusters or nanoscale structures.

  14. Solution and solid-state models of peptide CH...O hydrogen bonds.

    Science.gov (United States)

    Baures, Paul W; Beatty, Alicia M; Dhanasekaran, Muthu; Helfrich, Brian A; Pérez-Segarra, Waleska; Desper, John

    2002-09-25

    Fumaramide derivatives were analyzed in solution by (1)H NMR spectroscopy and in the solid state by X-ray crystallography in order to characterize the formation of CH...O interactions under each condition and to thereby serve as models for these interactions in peptide and protein structure. Solutions of fumaramides at 10 mM in CDCl(3) were titrated with DMSO-d(6), resulting in chemical shifts that moved downfield for the CH groups thought to participate in CH...O=S(CD(3))(2) hydrogen bonds concurrent with NH...O=S(CD(3))(2) hydrogen bonding. In this model, nonparticipating CH groups under the same conditions showed no significant change in chemical shifts between 0.0 and 1.0 M DMSO-d(6) and then moved upfield at higher DMSO-d(6) concentrations. At concentrations above 1.0 M DMSO-d(6), the directed CH...O=S(CD(3))(2) hydrogen bonds provide protection from random DMSO-d(6) contact and prevent the chemical shifts for participating CH groups from moving upfield beyond the original value observed in CDCl(3). X-ray crystal structures identified CH...O=C hydrogen bonds alongside intermolecular NH...O=C hydrogen bonding, a result that supports the solution (1)H NMR spectroscopy results. The solution and solid-state data therefore both provide evidence for the presence of CH...O hydrogen bonds formed concurrent with NH...O hydrogen bonding in these structures. The CH...O=C hydrogen bonds in the X-ray crystal structures are similar to those described for antiparallel beta-sheet structure observed in protein X-ray crystal structures.

  15. Crystalline structure and electrical properties of Dy1-XCaXMnO3 solid solution

    Directory of Open Access Journals (Sweden)

    Durán, P.

    2002-12-01

    Full Text Available Solid solutions corresponding to the Dy1-xCaXMnO3 system, x=0.0 to 0.60 have been studied. The powders were prepared by solid state reaction of the corresponding oxides and carbonates. Sintered bodies were obtained by firing between 1250 and 1450ºC. All the compositions showed single-phased perovskite-type structure with orthorhombic symmetry and Space Group Pbnm. Increase of the CaO content leads to a monotonic decrease of the orthorhombicity factor b/a with the Ca2+ concentration up to x=0.60. All the solid solutions crystallised with the same O’-type orthorhombic perovskite structure such as pure DyMnO3. Electrical measurements have shown semiconducting behaviour for all the solid solutions. The room temperature conductivity increases monotonically with the CaO content. The 60/40 Ca/Dy composition showed a high value of the electrical conductivity and a correlative very low value of the activation energy. Thermally activated small polaron hopping mechanism controls the conductivity of these perovskite ceramics.Se han estudiado soluciones sólidas correspondientes al sistema Dy1-xCaxMnO3, x=0.0 a 0.60. Los polvos cerámicos fueron preparados por reacción en estado sólido de los correspondientes óxidos y carbonatos. Los materiales cerámicos se obtuvieron por sinterización entre 1250º y 1450ºC. Todas las composiciones fueron monofásicas y mostraron una estructura tipo perovskita, con simetría ortorrómbica y Grupo Espacial Pbnm. El aumento del contenido en CaO llevó a una disminución monótona del factor de ortorrombicidad, b/a. Todas las soluciones sólidas cristalizaron con el mismo tipo de estructura perovskita ortorrómbica O’, como la del compuesto puro DyMnO3. Las medidas eléctricas mostraron comportamiento semiconductor en todas las soluciones sólidas. La conductividad a temperatura ambiente aumenta monótonamente con el contenido de CaO. La composición 60/40 mostró un elevado valor de conductividad y un correlativo

  16. Structure and Transport Properties of the BiCuSeO-BiCuSO Solid Solution

    Directory of Open Access Journals (Sweden)

    David Berardan

    2015-03-01

    Full Text Available In this paper, we report on the crystal structure and the electrical and thermal transport properties of the BiCuSe1−xSxO series. From the evolution of the structural parameters with the substitution rate, we can confidently conclude that a complete solid solution exists between the BiCuSeO and BiCuSO end members, without any miscibility gap. However, the decrease of the stability of the materials when increasing the sulfur fraction, with a simultaneous volatilization, makes it difficult to obtain S-rich samples in a single phase. The band gap of the materials linearly increases between 0.8 eV for BiCuSeO and 1.1 eV in BiCuSO, and the covalent character of the Cu-Ch (Ch = chalcogen element, namely S or Se here bond slightly decreases when increasing the sulfur fraction. The thermal conductivity of the end members is nearly the same, but a significant decrease is observed for the samples belonging to the solid solution, which can be explained by point defect scattering due to atomic mass and radii fluctuations between Se and S. When increasing the sulfur fraction, the electrical resistivity of the samples strongly increases, which could be linked to an evolution of the energy of formation of copper vacancies, which act as acceptor dopants in these materials.

  17. Chemically deposited Bi2S3:PbS solid solution thin film as supercapacitive electrode.

    Science.gov (United States)

    Pandit, Bidhan; Sharma, Gagan Kumar; Sankapal, Babasaheb R

    2017-11-01

    Low-cost, easily synthesized, and high energy/power density embedded stable supercapacitive electrodes are the demands for today's renewable and green energy dependent generation. In search of that, Bi2S3:PbS solid solution in thin film form has been synthesized by modest successive ionic layer adsorption and reaction (SILAR) method and characterized by XRD, FESEM, and HRTEM. Formation of solid solution in the form of nanoparticles gilded thin film exposes sufficient electroactive cavities for electroactive ions to incorporate. The composite exhibited excellent specific capacitance of 402.4F/g at current density of 1mA/cm2 with modest charge-discharge cycles. In terms of energy storage, it exhibited maximum specific power of 20.1Wh/kg with accepting specific power of 1.2kW/kg. The combination of two nanoparticles in nanocomposites thin film supplies new tactic for energy storage applications. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Mössbauer spectroscopy investigation of lithium oxide-hematite solid solution

    Science.gov (United States)

    Bushunow, Vasilii; Sorescu, Monica

    2013-03-01

    Lithium oxide-doped hematite xLi2O * (1- x) α-Fe2O3 (x = 0.1-0.7) solid solutions were prepared via ball milling. Samples were taken at 0, 2, 4, 8, and 12 hours ball milling time (BMT). Parameters for the obtained Mössbauer spectra were determined by least-squares fitting using NORMOS-90 software. For all initial Li2O concentrations, partial substitution of Fe3+ in the Li2O lattice and vice versa was seen beginning at two hours BMT. For x = 0.1, 0.3, and 0.5, spectra were fit with one or two sextets and one quadrupole-split doublet. For x = 0.7, all spectra were fit with a single sextet and one quadrupole-split doublet. With increased BMT, the abundance of the doublet increased, irrespective of initial Li2O concentration. For example, the abundance of the doublet increased from 2.3% at 2 h BMT to 11.1% at 12 h BMT for x = 0.1. The increasing abundance of the doublet indicates greater substitution of Li+ by Fe3+ in the Li2O lattice. Increasing the initial concentration of Li2O for constant BMT did not consistently increase the abundance of the doublet. The results of this experiment demonstrate the feasibility of forming solid solutions by purely mechanical methods, e.g. ball milling.

  19. Solid analyte and aqueous solutions sensing based on a flexible terahertz dual-band metamaterial absorber

    Science.gov (United States)

    Yan, Xin; Liang, Lan-Ju; Ding, Xin; Yao, Jian-Quan

    2017-02-01

    A high-sensitivity sensing technique was demonstrated based on a flexible terahertz dual-band metamaterial absorber. The absorber has two perfect absorption peaks, one with a fundamental resonance (f1) of the structure and another with a high-order resonance (f2) originating from the interactions of adjacent unit cells. The quality factor (Q) and figure of merit of f2 are 6 and 14 times larger than that of f1, respectively. For the solid analyte, the changes in resonance frequency are monitored upon variation of analyte thickness and index; a linear relation between the amplitude absorption with the analyte thickness is achieved for f2. The sensitivity (S) is 31.2% refractive index units (RIU-1) for f2 and 13.7% RIU-1 for f1. For the aqueous solutions, the amplitude of absorption decreases linearly with increasing the dielectric constant for the ethanol-water mixture of f1. These results show that the designed absorber cannot only identify a solid analyte but also characterize aqueous solutions through the frequency shift and amplitude absorption. Therefore, the proposed absorber is promising for future applications in high-sensitivity monitoring biomolecular, chemical, ecological water systems, and aqueous biosystems.

  20. Structure and magnetic properties of metastable Co-Cu solid solution nanowire arrays fabricated by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tao; Li, Fashen; Wang, Ying; Song, Lijing [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou Univesity, Lanzhou 730000 (China)

    2006-08-15

    Nanowire arrays of the metastable Co{sub x}Cu{sub 1-x} (0.20{<=}x{<=}0.85) solid solution system which can not be obtained by equilibrium methods, were prepared by electrodeposition in pores of anodic aluminum oxide (AAO) template, and subsequently annealed at different temperatures. The as-deposited samples all show single phase of fcc structure, and lattice parameters decrease with the increase of Co content and fundamentally accord with Vegard's law. The phase transition with heat treatment was investigated by X-ray diffraction and differential thermal analysis (DTA) which further confirmed the formation of solid solution. With Co content increasing, the coercivity along nanowire axis for as-deposited samples increases, but it decreases for the annealed samples at 700 C. This phenomenon was explained considering the interaction of Co particles through Cu in nanowires after phase separation. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. The origin of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution crystals

    Energy Technology Data Exchange (ETDEWEB)

    Li, Fei; Zhang, Shujun; Yang, Tiannan; Xu, Zhuo; Zhang, Nan; Liu, Gang; Wang, Jianjun; Wang, Jianli; Cheng, Zhenxiang; Ye, Zuo-Guang; Luo, Jun; Shrout, Thomas R.; Chen, Long-Qing (Penn); (Xian Jiaotong); (CIW); (Simon); (TRS Techn); (Wollongong)

    2016-12-19

    The discovery of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution single crystals is a breakthrough in ferroelectric materials. A key signature of relaxor-ferroelectric solid solutions is the existence of polar nanoregions, a nanoscale inhomogeneity, that coexist with normal ferroelectric domains. Despite two decades of extensive studies, the contribution of polar nanoregions to the underlying piezoelectric properties of relaxor ferroelectrics has yet to be established. Here we quantitatively characterize the contribution of polar nanoregions to the dielectric/piezoelectric responses of relaxor-ferroelectric crystals using a combination of cryogenic experiments and phase-field simulations. The contribution of polar nanoregions to the room-temperature dielectric and piezoelectric properties is in the range of 50–80%. A mesoscale mechanism is proposed to reveal the origin of the high piezoelectricity in relaxor ferroelectrics, where the polar nanoregions aligned in a ferroelectric matrix can facilitate polarization rotation. This mechanism emphasizes the critical role of local structure on the macroscopic properties of ferroelectric materials.

  2. Investigating conceptual models for physical property couplings in solid solution models of cement

    Energy Technology Data Exchange (ETDEWEB)

    Benbow, Steven; Watson, Claire; Savage, David [Quintesssa Ltd., Henley-on-Thames (United Kingdom)

    2005-11-15

    The long-term behaviour of cementitious engineered barriers is an important process to consider when modelling the migration of radionuclides from a geological repository for nuclear waste. The modelling of cement is complicated by the fact that the cement is dominated by the behaviour of calcium silicate hydrate (CSH) gel which is a complex solid exhibiting incongruent dissolution behaviour. In this report, we have demonstrated the implementation of a solid-solution CSH gel model within a geochemical transport modelling framework using the Raiden computer code to investigate cement/concrete-groundwater interactions. The modelling conducted here shows that it is possible to couple various conceptual models for the evolution of physical properties of concrete with a solid solution model for cement degradation in a fully coupled geochemical transport model to describe the interaction of cement/concrete engineered barriers with groundwater. The results show that changes to the conceptual models and flow rates can give rise to very different evolutions. Most simulations were carried out at a reduced 'experimental' scale rather than full repository scale. The work has shown the possibility to investigate also the changing physical properties of degrading cement. To further develop the model more emphasis is needed on kinetics and the detailed development of a nearly clogged pore space. Modelling of the full repository scale could be another way forward to understand the behaviour of degrading concrete. A general conclusion is that the combined effects of chemical evolution and physical degradation should be analysed in performance assessments of cementitious repositories. Moreover, the project results will be used as one basis in coming reviews of SKB's safety assessments of repositories for spent fuel and low-and intermediate level waste.

  3. Multiferroic phase boundaries and properties of BiFeO3-based solid solutions

    Science.gov (United States)

    Ye, Zuo-Guang

    The presence of morphotropic phase boundary in ferroelectric solid solutions (FE-MPB) is known to be crucial for high piezoelectricity. Similarly, magnetic MPB (M-MPB) is found in a few ferromagnets and is proved to be greatly beneficial to the magnetostricitive response. One naturally asks if in multiferroics that exhibit both ferroelectricity and (ferro-/antiferro-)magnetism, the FE-MPB and M-MPB could exist simultaneously, and if so, what the relation between these two kinds of MPB would be, and how they would affect the properties. In this paper, we report the studies of ferroelectric and magnetic double morphotropic phase boundaries in BiFeO3-based multiferroics. The effects of dysprosium ion on the structure and local polar domains of the BiFeO3-based systems were investigated firstly in the Dy-substituted solid solutions of 0.66Bi1-x DyxFeO3-0.34PbTiO3. It is found that the substitution of Dy affects the structural symmetry and phase component of the multiferroic solid solution, and thereby enhances its ferroelectric order. A (weak) ferromagnetic state is induced at room temperature for the rhombohedral compositions with x >= 0.10. The introduction of Dy into 0.66BiFeO3-0.34PbTiO3 leads to the breaking of its antiferromagnetic order below Néel temperature and thereby the formation of (weak) ferromagnetic ordering at room temperature when the substitution rate exceeds a critical value (x >= 0.10), making the 0.66Bi1-x DyxFeO3-0.34PbTiO3 system one of rare room-temperature ferromagnetic and ferroelectric materials, i.e. a true multifrroic. A comprehensive ferroelectric-magnetic phase diagram is established in terms of temperature and composition, which depicts the coexistence of a FE-MPB and a FM-MPB. These two kinds of MPBs overlap with each other. Such unusual coincidence of both magnetic MPB and ferroelectric MPB, the so-called double MPB, points to new kinds of couplings among the multiple physical quantities so that such effects as magnetoelectricity

  4. The renascence of continuous-flow peptide synthesis - an abridged account of solid and solution-based approaches.

    Science.gov (United States)

    Gordon, Christopher P

    2018-01-03

    Within a decade of Merrifield's seminal description of solid-phase peptide synthesis, the synergies between solid-phase approaches and flow synthesis were noted by a number of groups. However, despite the various advantages flow brings to peptide synthesis, throughout the 1990s and 2000s, interest in the technique was overshadowed by microwave assisted approaches. However, the current expansion of flow technologies has reinvigorated interest in both solid-phase and solution-phase continuous-flow approaches for assembling peptides. This perspective traces the introduction and evolution of continuous-flow solid-phase synthesis from a practical aspect with a particular focus on solid supports, acylation protocols, and racemisation suppression. Practical aspects of solution-phase continuous-flow peptide synthesis are also considered with an evaluation of microreactor systems, coupling protocols, and fragment-based approaches for assembly of extended peptide units.

  5. Generation of WO 3-ZrO 2 catalysts from solid solutions of tungsten in zirconia

    Science.gov (United States)

    Cortés-Jácome, María A.; Angeles-Chavez, Carlos; Bokhimi, Xim; Toledo-Antonio, J. A.

    2006-08-01

    WO 3-ZrO 2 samples were obtained by precipitating zirconium oxynitrate in presence of WO 4dbnd species in solution from ammonium metatungstate at pH=10.0. Samples were characterized by atomic absorption spectroscopy, thermal analysis, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and energy filtered-TEM. The ammonia retained in the dried sample produced a reductive atmosphere to generate W 5+ ions coexisting with W 6+ ions to produce a solid solution of tungsten in the zirconia lattice to stabilize the zirconia tetragonal phase when the sample was annealed at 560 °C. When the sample was annealed at 800 °C, the W atoms near crystallite surface were oxidized to W 6+, producing patches of WO 3 on the zirconia crystallite. The HR-TEM analysis confirmed the existence of the solid solution when the sample was annealed at 560 °C, and two types of crystalline regions were identified: One with nearly spherical morphology, an average diameter of 8 nm and the atomic distribution of tetragonal zirconia. The second one had a non-spherical morphology with well-faceted faces and dimensions larger than 30 nm, and the atom distribution of tetragonal zirconia. When samples were annealed at 800 °C two different zirconia crystallites were formed: Those where only part of the dissolved tungsten atoms segregated to crystallite surface producing patches of nanocrystalline WO 3 on the crystallite surface of tetragonal zirconia stabilized with tungsten. The second type corresponded to monoclinic zirconia crystallites with patches of nanocrystalline WO 3 on their surface. The tungsten segregation gave rise to the WO 3-ZrO 2 catalysts.

  6. Solid phases and solution species of different elements in geologic environments

    Energy Technology Data Exchange (ETDEWEB)

    Rai, D.; Serne, R.J.

    1978-03-01

    An investigation was conducted to predict from thermodynamic data the nature of the solid phases and solution species in various weathering environments of different elements (Am, Sb, Ce, Cs, Co, Cm, Eu, I, Np, Pu, Pm, Ra, Ru, Sr, Tc, T, U, and Zr) that are present in radioactive wastes, to predict the degree of adsorption of different elements by the solid matrices and to compare these predictions with observed results, and to determine the influence of different factors (such as Ph, Eh, complexing ligands) on total pore-water concentration and the nature of solution species of selected elements. Based on the nature of the predominant solution species, qualitative predictions regarding the adsorption and movement of various elements can be made. Soils and sediments mainly show cation exchange capacities (since these materials carry a large net negative charge) and to a limited extent, anion exchange capacities. Thus, most cations migrate through the soil or rock column at speeds slower than the groundwater. Relative to each other, the trivalent cations generally move the slowest, the divalent cations at intermediate velocities and the monovalent cations most rapidly. Tritium is unique in that it readily substitutes for hydrogen in water and migrates, therefore, at the same velocity as water. The simple anions tend to migrate through soils and rocks with little reaction because usually a pH of less than 4 is required to activate a significant soil anion exchange capacity. The migration and retention of inorganic complex species (mononuclear and polynuclear) would also be dependent upon the charge and size of the species. The behavior of organic complexed species of elements is difficult to predict because of the lack of knowledge regarding the exact nature of the organic ligands, a wide variation in amounts and types of organic ligands, and the size and solubility of these organics.

  7. MANAGEMENT OF SOLID WASTE GENERATED BY THE INTEGRATED STEELWORKS ACTIVITY AND SOLUTIONS TO REDUCE THE ENVIRONMENTAL IMPACT

    Directory of Open Access Journals (Sweden)

    Anişoara CIOCAN

    2010-05-01

    Full Text Available The development of steel industry is subject to solve major problems arising from industry-nature relationship, strictly targeted on pollution control and protection of natural resources and energy. In this paper we discussed about the management of solid waste generated by an integrated steelwork located near a major urban area and the adopted solutions for the reduction of environmental impact. There are summarized technical solutions that are currently applied and were proposed some solutions that can be applied in accordance with the environmental legislations. The new solutions are proposed for integrated management of solid wastes in accordance with: the exact quantification (quantitative, qualitative and the generation sources of emissions and solid wastes; controlled storage; minimization of the wastes and its harmfulness; transformation of the wastes into valuable by-products used directly by the company in a subsequent process, or by external down-stream user.

  8. Effect of varying Ga content in ZnO:GaN solid solution synthesized by solution combustion technique for photocatalytic applications

    Science.gov (United States)

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

    2017-05-01

    ZnO:GaN (oxy)nitride solid solution has been established as the most efficient non-oxide photocatalyst for water splitting under visible irradiation with one step photoexcitation and also boasts a band gap tunability from 2.8 eV to 2.5 eV[1]. The solid solution of GaN in ZnO is formed by the intersubstitution of few of Zn/O ions by Ga/N ions, and this results in the introduction of new defect levels above the valence band which narrows the effective band gap enabling activity under visible region of spectra. In this work, we report the synthesis of ZnO:GaN solid solution by a solution combustion technique where metal nitrates and urea are used as precursors. The Zn/Ga ratio was varied from 16 to 1 in the precursors. The as synthesized samples were characterized as phase pure by X-ray diffraction, where the wurtzite structure was retained up to Zn/Ga ratio of 5. The Diffuse reflectance spectroscopy studies revealed that as the Ga content in the solid solution increases there is a reduction in band gap, from 2.9 eV to 2.4 eV. The reduced band gap of the samples facilitates its photocatalytic activity under visible region of the spectra as evaluated by photoelectrochemical measurements.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  10. Research and demonstration results for a new "Double-Solution" technology for municipal solid waste treatment.

    Science.gov (United States)

    Erping, Li; Haoyun, Chen; Yanyang, Shang; Jun, Pan; Qing, Hu

    2017-11-01

    In this paper, the pyrolysis characteristics of six typical components in municipal solid waste (MSW) were investigated through a TG-FTIR combined technique and it was concluded that the main pyrolysis process of the biomass components (including food residues, sawdust and paper) occurred at 150-600°C. The main volatiles were multi-component gas including H2O, CO2, and CO. The main pyrolysis temperatures of three artificial products (PP, PVC and leather) was ranged from 200to 500°C. The wavelength of small molecule gases (CH4, CO2 and CO) and the the chemical bonds (CO and CC) were observed in the infrared spectrum Based on the pyrolysis temperature interval and volatile constituent, a new "double-solution" process of pyrolysis and oxygen-enrichment decomposition MSW was designed. To achieve this process, a double-solution project was built for the direct treatment of MSW (10t/d). The complete setup of equipment and analysis of the byproducts has been reported in this paper to indicate the performance of this process. Energy balance and economic benefits were analysed for the process supporting. It was successfully demonstrated that the double-solution process was the environmentally friendly alternative method for MSW treatment in Chinese rural areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Long-lived non-equilibrium interstitial solid solutions in binary mixtures

    Science.gov (United States)

    Ríos de Anda, Ioatzin; Turci, Francesco; Sear, Richard P.; Royall, C. Patrick

    2017-09-01

    We perform particle resolved experimental studies on the heterogeneous crystallisation process of two component mixtures of hard spheres. The components have a size ratio of 0.39. We compared these with molecular dynamics simulations of homogenous nucleation. We find for both experiments and simulations that the final assemblies are interstitial solid solutions, where the large particles form crystalline close-packed lattices, whereas the small particles occupy random interstitial sites. This interstitial solution resembles that found at equilibrium when the size ratios are 0.3 [L. Filion et al., Phys. Rev. Lett. 107, 168302 (2011)] and 0.4 [L. Filion, Ph.D. thesis, Utrecht University, 2011]. However, unlike these previous studies, for our system simulations showed that the small particles are trapped in the octahedral holes of the ordered structure formed by the large particles, leading to long-lived non-equilibrium structures in the time scales studied and not the equilibrium interstitial solutions found earlier. Interestingly, the percentage of small particles in the crystal formed by the large ones rapidly reaches a maximum of ˜14% for most of the packing fractions tested, unlike previous predictions where the occupancy of the interstitial sites increases with the system concentration. Finally, no further hopping of the small particles was observed.

  12. Long-lived non-equilibrium interstitial solid solutions in binary mixtures.

    Science.gov (United States)

    Ríos de Anda, Ioatzin; Turci, Francesco; Sear, Richard P; Royall, C Patrick

    2017-09-28

    We perform particle resolved experimental studies on the heterogeneous crystallisation process of two component mixtures of hard spheres. The components have a size ratio of 0.39. We compared these with molecular dynamics simulations of homogenous nucleation. We find for both experiments and simulations that the final assemblies are interstitial solid solutions, where the large particles form crystalline close-packed lattices, whereas the small particles occupy random interstitial sites. This interstitial solution resembles that found at equilibrium when the size ratios are 0.3 [L. Filion et al., Phys. Rev. Lett. 107, 168302 (2011)] and 0.4 [L. Filion, Ph.D. thesis, Utrecht University, 2011]. However, unlike these previous studies, for our system simulations showed that the small particles are trapped in the octahedral holes of the ordered structure formed by the large particles, leading to long-lived non-equilibrium structures in the time scales studied and not the equilibrium interstitial solutions found earlier. Interestingly, the percentage of small particles in the crystal formed by the large ones rapidly reaches a maximum of ∼14% for most of the packing fractions tested, unlike previous predictions where the occupancy of the interstitial sites increases with the system concentration. Finally, no further hopping of the small particles was observed.

  13. Efficient production of solid dispersions by spray drying solutions of high solid content using a 3-fluid nozzle

    NARCIS (Netherlands)

    Kauppinen, Ari; Broekhuis, Joep; Grasmeijer, Niels; Tonnis, Wouter; Ketolainen, Jarkko; Frijlink, Henderik W; Hinrichs, Wouter L J

    To evaluate the feasibility of producing solid dispersions with 3-fluid nozzle spray drying to improve the dissolution behavior of lipophilic drugs, 60 experiments were performed based on a Design of Experiment. Solid dispersions with mannitol as a hydrophilic matrix and diazepam as a model drug

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

    Science.gov (United States)

    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

  15. Synthesis, characterization and thermal stability of solid solutions Zr (Y, Fe, MoO2

    Directory of Open Access Journals (Sweden)

    Felipe Legorreta-García

    2015-05-01

    Full Text Available The synthesis of Fe3+, Mo4+ and Y3+ fully stabilized zirconia by the nitrate/urea combustion route and thermal stability in air was investigated. The solid solution obtained was characterized by X ray diffraction (XRD, scanning electron microscopy (SEM and used the BET method for determining specific surface. The ceramic powders obtained were calcined at 1473 K in air atmosphere in order to determine their thermal stability. The scanning electron microscopy (SEM results showed a homogeneous grain surface, measuring several tens of micrometers across. The crystallographic study revealed that by this method it was successfully achieved zirconia doped with Fe3+, Mo4+ and Y3+ ions in the zirconia tetragonal monophase, even after calcinations.

  16. Growth and electronic properties of GaN/ZnO solid solution nanowires

    Science.gov (United States)

    Han, Wei-Qiang; Zhang, Yan; Nam, Chang-Yong; Black, C. T.; Mendez, E. E.

    2010-08-01

    We have grown single-crystal (Ga1-xZnx)(N1-xOx) solid-solution nanowires using nanostructured ZnGa2O4 precursor prepared by a sol-gel method. From electrical transport measurements in individual nanowire field-effect transistors, we have identified the conduction as n-type and obtained a background carrier density (˜1019 cm-3) and an electron mobility (˜1 cm2/V s) that are consistent with chemical disorder and a large number of charge traps, as confirmed by the devices' photocurrent response. From the dependence of the device photoresponse on incident light wavelength, we have determined the energy band gap of (Ga0.88Zn0.12)(N0.88O0.12) to be as much as ˜0.6 eV lower than that of GaN or ZnO.

  17. Free Volumes Associated with Sintering in Gadolinium Doped Ceria Solid Solutions

    Directory of Open Access Journals (Sweden)

    Tomomi Kosaka

    2010-01-01

    Full Text Available Gadolinium-doped ceria (GDC solid solution prepared by the oxalate coprecipitation method is investigated by X-ray diffraction (XRD, complex impedance analysis, and positron lifetime spectroscopy. XRD reveals an expansion of GDC lattice constant by doping gadolinium into a ceria host crystal, in agreement with an oxygen vacancy model. The ionic conductivity of GDC measured at 773 K in air is two orders of magnitude higher than that of undoped ceria. Positron lifetime spectroscopy reveals the presence of vacancy-sized free volumes and nanovoids in interfaces among crystallites. It is found that the vacancy-sized free volumes shrink with increasing sintering temperatures. In the present paper, recent advances in the studies of GDC by XRD, complex impedance measurement, and positron lifetime spectroscopy are reviewed to gain an insight into the sintering mechanism.

  18. Solution and solid state conformational preferences of a family of cyclic disulphide bridged tetrapeptides.

    Science.gov (United States)

    Berger, Nadja; Li, Fee; Mallick, Bert; Brüggemann, J Thomas; Sander, Wolfram; Merten, Christian

    2017-01-01

    A set of cyclic tetrapeptides of the general form cyclo (Boc-Cys-Pro-X-Cys-OMe) with X being L-/D-Ala, L-/D-Val, and L-/D-Trp was synthesized. These peptides serve as model systems for structure elucidation in solution and feature a variety of structural motifs - namely a β-turn with intramolecular hydrogen bonding interactions, cis/trans isomerism, and a disulphide bond. In this work, we performed a comprehensive structural analysis focussing on their β-turn conformational preferences using NMR, VCD, and Raman spectroscopy. Our results provide evidence for a strong influence of a single stereocenter on the structures of the peptides whereas solvent polarity does not significantly affect them. Additionally, the solid state conformational preferences were studied by crystal structure analysis. Overall, a general trend for the conformational preferences of this set of peptides can be concluded from the results of the complementary investigations. © 2016 Wiley Periodicals, Inc.

  19. Transient analytical solution of temperature distribution and fracture limits in pulsed solid-state laser rod

    Directory of Open Access Journals (Sweden)

    Shibib Khalid S.

    2017-01-01

    Full Text Available The exact analytical solution of axis-symmetry transient temperature and Tresca failure stress in pulsed mode solid-state laser rod is derived using integral transform method. The result obtained from this work is compared with previously published data and good agreement is found. The effect of increasing period is studied, and it is found that at constant pulse width as the period is increased, the allowable pumping power is increased too. Furthermore, the effect of changing pulse width with a constant period is studied, and it is found that as the pulse width is increased, the allowable pumping power is decreased. The effect of duty cycle is studied also and it is found that as duty cycle is increased the allowable pumping power is decreased. This work permits proper selection of pulse width, period and duty cycle to avoid laser rod fracture while obtaining maximum output laser power in the designing of laser system.

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

    Science.gov (United States)

    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.

  1. Generalized solutions to linearized equations of thermoelastic solid and viscous thermofluid

    Directory of Open Access Journals (Sweden)

    Anvarbek M. Meirmanov

    2007-03-01

    Full Text Available Within the framework of continuum mechanics, the full description of joint motion of elastic bodies and compressible viscous fluids with taking into account thermal effects is given by the system consisting of the mass, momentum, and energy balance equations, the first and the second laws of thermodynamics, and an additional set of thermomechanical state laws. The present paper is devoted to the investigation of this system. Assuming that variations of the physical characteristics of the thermomechanical system of the fluid and the solid are small about some rest state, we derive the linearized non-stationary dynamical model, prove its well-posedness, establish additional refined global integral bounds for solutions, and further deduce the linearized incompressible models and models incorporating absolutely rigid skeleton, as asymptotic limits.

  2. Synthesis, characterization and thermal stability of solid solutions Zr (Y, Fe, Mo)O {sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Legorreta-Garcia, F.; Esperanza Hernandez-Cruz, L.; Villanueva-Ibanez, M.; Flores-Gonzalez, M. A.

    2015-10-01

    The synthesis of Fe{sup 3}+, Mo{sup 4+} and Y{sup 3+} fully stabilized zirconia by the nitrate/urea combustion route and thermal stability in air was investigated. The solid solution obtained was characterized by X ray diffraction (XRD), scanning electron microscopy (SEM) and used the BET method for determining specific surface. The ceramic powders obtained were calcined at 1473 K in air atmosphere in order to determine their thermal stability. The scanning electron microscopy (SEM) results showed a homogeneous grain surface, measuring several tens of micrometers across. The crystallographic study revealed that by this method it was successfully achieved zirconia doped with Fe{sup 3+}, Mo{sup 4+} and Y{sup 3+} ions in the zirconia tetragonal monophase, even after calcinations. (Author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Hollingsworth, Jennifer A. [Los Alamos National Laboratory; Palaniappan, Kumaranand [Los Alamos National Laboratory; Laocharoensuk, Rawiwan [National Science and Technology Center, Thailand; Smith, Nickolaus A. [Los Alamos National Laboratory; Dickerson, Robert M. [Los Alamos National Laboratory; Casson, Joanna L. [Los Alamos National Laboratory; Baldwin, Jon K. [Los Alamos National Laboratory

    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

  4. Preparation and characterization of Bi4–xPrxTi3O12 solid solutions

    Directory of Open Access Journals (Sweden)

    A. I. Klyndyuk

    2017-12-01

    Full Text Available The Bi4–xPrxTi3O12 (BPT solid solutions (x = 0.05, 0.10, 0.15 with small praseodymium content were prepared by solid-state method. Thermal, electric, and dielectric properties of BPT were studied. It was revealed that BPT titanates crystalize in аn orthorhombic structure and exhibit p-type semiconductivity. Dielectric constant of BPT increased, Curie temperature (TC, electrical conductivity and dielectric losses decreased, but lattice parameters and thermo-EMF coefficient remained practically unchanged with the increase of praseodymium content in layered Bi4–xPrxTi3O12. It was determined that activation energy of direct current (DC electrical conductivity and linear thermal expansion coefficient (LTEC of BPT changes at ferroelectric (FE → paraelectric (PE phase transition. The activation energy and LTEC changed below and above TC from 1.08–1.56 eV to 0.45–0.86 eV and from (9.10–10.80×10–6 K–1 to (13.12-14.61×10–6 K–1, respectively. The AC electrical conductivity studies of BPT illustrated short-range order with ionic translations assisted by small-polaron hopping.

  5. All-Solution-Based Aggregation Control in Solid-State Photon Upconverting Organic Model Composites.

    Science.gov (United States)

    Goudarzi, Hossein; Keivanidis, Panagiotis E

    2017-01-11

    Hitherto, great strides have been made in the development of organic systems that exhibit triplet-triplet annihilation-induced photon-energy upconversion (TTA-UC). Yet, the exact role of intermolecular states in solid-state TTA-UC composites remains elusive. Here we perform a comprehensive spectroscopic study in a series of solution-processable solid-state TTA-UC organic composites with increasing segregated phase content for elucidating the impact of aggregate formation in their TTA-UC properties. Six different states of aggregation are reached in composites of the 9,10-diphenylanthracene (DPA) blue emitter mixed with the (2,3,7,8,12,13,17,18-octaethylporphyrinato)platinum(II) sensitizer (PtOEP) in a fixed nominal ratio (2 wt % PtOEP). Fine-tuning of the PtOEP and DPA phase segregation in these composites is achieved with a low-temperature solution-processing protocol when three different solvents of increasing boiling point are alternatively used and when the binary DPA:PtOEP system is dispersed in the optically inert polystyrene (PS) matrix (PS:DPA:PtOEP). Time-gated (in the nanosecond and microsecond time scales) photoluminescence measurements identify the upper level of PtOEP segregation at which the PtOEP aggregate-based networks favor PtOEP triplet exciton migration toward the PtOEP:DPA interfaces and triplet energy transfer to the DPA triplet manifold. The maximum DPA TTA-UC luminescence intensity is ensured when the bimolecular annihilation constant of PtOEP remains close to γTTA-PtOEP = 1.1 × 10(-13) cm(3) s(-1). Beyond this PtOEP segregation level, the DPA TTA-UC luminescence intensity decreases because of losses caused by the generation of PtOEP delayed fluorescence and DPA phosphorescence in the nanosecond and microsecond time scales, respectively.

  6. High-temperature, Knudsen cell-mass spectroscopic studies on lanthanum oxide/uranium dioxide solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Sunder, S.; McEachern, R.; LeBlanc, J.C

    2001-07-01

    Knudsen cell-mass spectroscopic experiments were carried out with lanthanum oxide/uranium oxide solid solutions (1%, 2% and 5% (metal at.% basis)) to assess the volatilization characteristics of rare earths present in irradiated nuclear fuel. The oxidation state of each sample used was conditioned to the 'uranium dioxide stage' by heating in the Knudsen cell under an atmosphere of 10% C0{sub 2} in CO. The mass spectra were analyzed to obtain the vapour pressures of the lanthanum and uranium species. It was found that the vapour pressure of lanthanum oxide follows Henry's law, i.e., its value is directly proportional to its concentration in the solid phase. Also, the vapour pressure of lanthanum oxide over the solid solution, after correction for its concentration in the solid phase, is similar to that of uranium dioxide. (author)

  7. Smooth and robust solutions for Dirichlet boundary control of fluid-solid conjugate heat transfer problems

    KAUST Repository

    Yan, Yan

    2015-01-01

    We study a new optimization scheme that generates smooth and robust solutions for Dirichlet velocity boundary control (DVBC) of conjugate heat transfer (CHT) processes. The solutions to the DVBC of the incompressible Navier-Stokes equations are typically nonsmooth, due to the regularity degradation of the boundary stress in the adjoint Navier-Stokes equations. This nonsmoothness is inherited by the solutions to the DVBC of CHT processes, since the CHT process couples the Navier-Stokes equations of fluid motion with the convection-diffusion equations of fluid-solid thermal interaction. Our objective in the CHT boundary control problem is to select optimally the fluid inflow profile that minimizes an objective function that involves the sum of the mismatch between the temperature distribution in the fluid system and a prescribed temperature profile and the cost of the control.Our strategy to resolve the nonsmoothness of the boundary control solution is based on two features, namely, the objective function with a regularization term on the gradient of the control profile on both the continuous and the discrete levels, and the optimization scheme with either explicit or implicit smoothing effects, such as the smoothed Steepest Descent and the Limited-memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) methods. Our strategy to achieve the robustness of the solution process is based on combining the smoothed optimization scheme with the numerical continuation technique on the regularization parameters in the objective function. In the section of numerical studies, we present two suites of experiments. In the first one, we demonstrate the feasibility and effectiveness of our numerical schemes in recovering the boundary control profile of the standard case of a Poiseuille flow. In the second one, we illustrate the robustness of our optimization schemes via solving more challenging DVBC problems for both the channel flow and the flow past a square cylinder, which use initial

  8. Crystalline structure and electrical properties of solid solutions YNixMn1-xO3

    Directory of Open Access Journals (Sweden)

    Moure, C.

    1999-12-01

    Full Text Available Solid solutions belonging to the Mn-rich region of the YNiXMn1-XO3 system have been studied. The powders were prepared by solid state reaction between the corresponding oxides. Sintered ceramics were obtained by firing at 1325-1350ºC. The incorporation of 20 atomic % Ni2+ to the Yttrium manganite induces the formation of a perovskite phase, with orthorhombic symmetry. Increase of the Ni amount leads to an increase of the orthorhombicity factor b/a, up to an amount of 50 atomic % Ni2+. Above this Ni amount, a biphasic system has been observed, with the presence of unreacted Y2O3. DC electrical conductivity measurements have shown semiconducting behaviour for all the solid solutions with perovskite-type structure. The room temperature conductivity increases with Ni until ~33 atomic % Ni, and then decreases. The 50/50 Ni/Mn composition has different values of conductivity and activation energy against those corresponding to samples with lower values of that ionic ratio. Small polaron hopping mechanism controls the conductivity in these ceramics. Results are discussed as a function of the Mn3+/Mn4+ ratio for each composition.Se han estudiado las soluciones sólidas correspondientes a la región rica en Mn del sistema YNiXMn1-XO3, entre 0 y 50 atomic % Ni. Los compuestos fueron preparados por reacción en estado sólido de los óxidos correspondientes. Se sinterizaron materiales cerámicos a 1325-1350ºC. Con cantidades de 20 atomic % Ni se produce la formación de una fase con estructura de perovskita, y simetría ortorrómbica. La distorsión ortorrómbica crece con el contenido de Ni. Por encima de 50 atomic % Ni, aparece Y2O3 sin reaccionar. Las soluciones sólidas muestran semiconducción con valores de σ que aumentan con el contenido de Ni hasta ~33 atomic %, para luego decrecer, hasta x=0.5. La composición 50/50 Ni/Mn muestra un comportamiento eléctrico algo diferente. Se discuten los resultados en función de la razón Mn3+/Mn4+ para cada

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

    Science.gov (United States)

    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

  10. Training Course of Experimental Chemistry in the Nuclear Fuel Cycle: Solid State and Solution Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ju hyeong; Park, Kwangheon; Kim, Tae hoon; Park, Hyoung gyu; Kim, Jisu [Kyunghee University, Yongin (Korea, Republic of); Song, Hyuk jin [Dongguk University, Gyeongju (Korea, Republic of); Lee, Chan ki; Kang, Do kyu; Jeong, Hyeon jun [UNIST, Ulsan (Korea, Republic of)

    2016-10-15

    In this experimental study program in Tohoku University, basic experiments were done by the participants. First one is the hydrogen reduction experiment of the mixture of UO{sub 2} and ZrO{sub 2}. Second one is to observe microscopic structure of solid solution of UO{sub 2} and ZrO{sub 2} using SEM/EDX and XRD system, simulated fuel debris. Third one is milking process of {sup 239}Np from {sup 243}Am by solvent extraction using Tri-n-Octylamine (TOA). Last one is solvent extraction in PUREX by the simulated mixed aqueous solution of U, {sup 85}Sr and {sup 239}Np which is represented minor actinide elements included in the spent nuclear fuel. Uranium is separated from aqueous phase to organic phase during solvent extraction procedure using TBP and dodecane. Also, neptunium can be extracted to organic phase as nitric acid concentration change. The extraction behavior of neptunium is different by oxidation state in aqueous phase. The behavior of neptunium is represented as a combined form of these oxidation states in experiment. Therefore, because the oxidation states of neptunium can be controlled by controlling the concentration of nitric acid, the extractability of neptunium can be controlled.

  11. The Diffusion Coefficients Of Cu And Zn In amp913- And amp919- Solid Solutions

    Directory of Open Access Journals (Sweden)

    Adhurim Hoxha

    2015-06-01

    Full Text Available Abstract In this work the multiphase diffusion in the infinite couple Cu-Zn was studied experimentally. The diffusion couples were prepared by platting technique. The samples were annealed in three different temperatures which were taken below the melting temperature of Zn. For each temperature there were used six different annealing times ranging from 1h up to 32h. In the micrographs provided by light microscopy it can be seen the formation of only two of the three intermetalic phases present in the Cu-Zn phase diagram namely amp949- and amp947-phase. WDX EPMA analysis was used to obtain the concentration profiles of the diffusion layers.he diffusion coefficients of Cu and Zn in amp945- and amp951-solid solutions are calculated using the solutions of second Ficks law for independent concentration case. Since the diffusion coefficients depends only on the temperature of annealing and not on the time of it they must be the same for a given temperature. Therefore the diffusion coefficients were averaged for each temperature. Knowing the diffusion coefficients for each temperature enables the calculation of the activation energies and the frequency factors as well.

  12. A solid-state NMR method for solution of zeolite crystal structures.

    Science.gov (United States)

    Brouwer, Darren H; Darton, Richard J; Morris, Russell E; Levitt, Malcolm H

    2005-07-27

    Since zeolites are notoriously difficult to prepare as large single crystals, structure determination usually relies on powder X-ray diffraction (XRD). However, structure solution (i.e., deriving an initial structural model) directly from powder XRD data is often very difficult due to the diffraction phase problem and the high degree of overlap between the individual reflections, particularly for materials with the structural complexity of most zeolites. Here, we report a method for structure determination of zeolite crystal structures that combines powder XRD and nuclear magnetic resonance (NMR) spectroscopy in which the crucial step of structure solution is achieved using solid-state (29)Si double-quantum dipolar recoupling NMR, which probes the distance-dependent dipolar interactions between naturally abundant (29)Si nuclei in the zeolite framework. For two purely siliceous zeolite blind test samples, we demonstrate that the NMR data can be combined with the unit cell parameters and space group to solve structural models that refine successfully against the powder XRD data.

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

    Directory of Open Access Journals (Sweden)

    Hongwei Deng

    2010-11-01

    Full Text Available 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.

  14. Photocatalytic hydrogen production over solid solutions between BiFeO{sub 3} and SrTiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Lingwei; Lv, Meilin [Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, 1239 Siping Road, Shanghai, 200092 (China); Liu, Gang [Shenyang National laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China); Xu, Xiaoxiang, E-mail: xxxu@tongji.edu.cn [Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, 1239 Siping Road, Shanghai, 200092 (China)

    2017-01-01

    Graphical abstract: We have successfully prepared a series of SrTiO{sub 3}-BiFeO{sub 3} solid solutions. These materials own strong visible light absorption and demonstrate appealing photocatalytic activity under both full range and visible light irradiation. - Highlights: • Band gap values can be tuned by adjusting molar ratios between SrTiO{sub 3} and BiFeO{sub 3}. • Photocatalytic activity is greatly improved after constituting solid solutions. • Photocatalytic activity is influenced by surface area and light absorption. • Fe plays an important role for band gap reduction and catalytic activity. - Abstract: Constituting solid solutions has been an appealing means to gain control over various physicochemical properties. In this work, we synthesized a series of SrTiO{sub 3}-BiFeO{sub 3} solid solutions and systematically explored their structural, optical and photocatalytic properties. Our results show that all solid solutions crystallize in a primitive cubic structure and their band gap values can be easily tuned by adjusting molar ratios between SrTiO{sub 3} and BiFeO{sub 3}. Photocatalytic hydrogen production under both full range and visible light irradiation is greatly improved after forming solid solutions. The highest hydrogen production rate obtained is ∼180 μmol/h under full range irradiation (λ ≥ 250 nm) and ∼4.2 μmol/h under visible light irradiation (λ ≥ 400 nm), corresponding to apparent quantum efficiency ∼2.28% and ∼0.10%, respectively. The activity is found to be strongly influenced by surface area and light absorption. Theoretical calculation suggests that Fe contributes to the formation of spin-polarized bands in the middle of original band gap and is responsible for the band gap reduction and visible light photocatalytic activity.

  15. Radiation-induced protein fragmentation and inactivation in liquid and solid aqueous solutions. Role of OH and electrons

    Energy Technology Data Exchange (ETDEWEB)

    Audette-Stuart, Marilyne [Atomic Energy of Canada Limited, CANDU Life Sciences Center, Chalk River Laboratories, Chalk River Ont., K0J 1J0 (Canada); Houee-Levin, Chantal [Laboratoire de Chimie Physique, UMR-8000 CNRS-Universite Paris XI, Centre Universitaire, F-91405 Orsay Cedex (France)]. E-mail: chantal.houee-levin@lcp.u-psud.fr; Potier, Michel [Service de genetique medicale, Hopital Sainte-Justine, Universite de Montreal, Montreal Que., H3 T 1C5 (Canada)

    2005-02-01

    Irradiation of proteins in diluted liquid aqueous solutions produces cleavages and polymerizations of the peptidic chains. In frozen solutions, fragmentation is observed but polymerization products are absent. Loss of activity occurs in both cases. In the solid state, yields of fragmentation do not vary with the quantity of water. The use of scavengers indicates that hydroxyl radical does not contribute significantly to fragmentation and to inactivation in the solid state. Electrons within the water molecules closely associated with the protein are involved in the processes leading to protein fragmentation.

  16. A Review of Solid-Solution Models of High-Entropy Alloys Based on Ab Initio Calculations

    Directory of Open Access Journals (Sweden)

    Fuyang Tian

    2017-11-01

    Full Text Available Similar to the importance of XRD in experiments, ab initio calculations, as a powerful tool, have been applied to predict the new potential materials and investigate the intrinsic properties of materials in theory. As a typical solid-solution material, the large degree of uncertainty of high-entropy alloys (HEAs results in the difficulty of ab initio calculations application to HEAs. The present review focuses on the available ab initio based solid-solution models (virtual lattice approximation, coherent potential approximation, special quasirandom structure, similar local atomic environment, maximum-entropy method, and hybrid Monte Carlo/molecular dynamics and their applications and limits in single phase HEAs.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

    Plummer, L.N.; Busenberg, E.

    1987-01-01

    Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO2-H2O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO3 and SrCO3 in the solid Ca(1−x)SrxCO3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation where A0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A1 is −4.51 ± 0.20 and −3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO3 mole fraction, x, by the relation where R is the gas constant, T is in Kelvins and KA and KS are the aragonite and strontianite equilibrium constants.

  19. Raman and Fourier transform infrared spectroscopic study of pyromorphite-vanadinite solid solutions

    Science.gov (United States)

    Solecka, Urszula; Bajda, Tomasz; Topolska, Justyna; Zelek-Pogudz, Sylwia; Manecki, Maciej

    2018-02-01

    Due to the great range of the application fields for apatites, there is a strong need to complete the data set determining the properties of these minerals. In this study, Raman and Infrared spectra of the phases from pyromorphite Pb5(PO4)3Cl - vanadinite Pb5(VO4)3Cl series were investigated. Totally, 9 samples (2 end-members and 7 solid solutions of the series) were synthesized at 25 °C and pH = 3.5, and analyzed. In the Raman and Infrared spectra of the studied Pb-apatites, the bands typical for the vibrations in the PO4 and the VO4 tetrahedra appeared. The bands attributed to the stretching vibrations (ν1, ν3) occurred in the 1050-910 cm- 1 and 830-720 cm- 1 regions, whereas the bending vibrations (ν2, ν4) were visible at the 580-540 cm- 1, 430-380 cm- 1 and 370-290 cm- 1 range. The position of the bands depended on the P/(P + V) ratio in the analyzed solid, since there are differences in the ionic radii and the atomic mass of P5 + and V5 +, which affect the bong lengths, bond forces and the banding energies of the substituting tetrahedra. The analysis allowed observing gradual shifts of the bands caused by the replacement of phosphorous with vanadium in the studied phases. The positions and the intensities of selected bands are proposed to serve as a semi-quantitative estimation of the chemical composition of the phases from the pyromorphite - vanadinite series.

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

    Science.gov (United States)

    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

  1. Solid state chemical model for the solubility behaviour of CaCO/sub 3/-MgCO/sub 3/ solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Driessens, F.C.M.; Verbeck, R.M.H.

    1981-08-01

    Mg-calcite can contain up to about 6 mol-% MgCO/sub 3/, dolomite between 40 and 51%. Solid solutions of CaCO/sub 3/ and MgCO/sub 3/ are unstable between 20 and 30 mol-% MgCO/sub 3/. The thermodynamic stability of dolomite with respect to calcite and magnesite amounts to about -6.8 kJ mol/sup -1/. It is shown that both the thermodynamical properties and the solubility behaviour of these solids can be explained with a solid-state chemical model based on the theory of subregular solid solutions. Evaluations of the parameters of the model resulted in a critical cluster size of about one unit cell for the dolomite structure. The fact that normal sea water is close to equilibrium with both calcite and dolomite means that the concentrations of Ca/sup 2 +/, Mg/sup 2 +/ and CO/sub 3//sup 2 -/ ions in sea water are restricted by fixed solubility relations.

  2. Optical properties of TixSi1 -xO2 solid solutions

    Science.gov (United States)

    Ondračka, Pavel; Holec, David; Nečas, David; KedroÅová, Eva; Elisabeth, Stéphane; Goullet, Antoine; Zajíčková, Lenka

    2017-05-01

    In this work, we use density functional theory to predict the optical properties of TixSi1 -xO2 solid solutions. The special quasirandom structure method and the simulated annealing procedure were applied to produce models of crystalline and amorphous TixSi1 -xO2 . These were fully structurally optimized by using the vasp package, while their electronic structure and optical properties were subsequently calculated by using the wien2k package employing the TB-mBJ potential. The calculated band gaps for a-TixSi1 -xO2 evaluated by using the Tauc-like fitting approach are 8.53 eV for SiO2, quickly decreasing to 4.0 eV at x =0.19 , 3.52 eV at x =0.34 , and 3.24 eV for TiO2. Experimental samples were prepared by means of plasma-enhanced chemical vapor deposition to support the calculations. Ellipsometry and spectrophotometry yield a compositional trend for the experimental optical band gap comparable with our predictions: a quick decrease from 7.94 eV for pure SiO2 to 3.91 eV at x =0.15 , followed by a much slower decrease over the rest of the composition range ending at 3.26 eV for pure TiO2. A detailed analysis of anatase and rutile-based solid solutions reveals the introduction of silicon-induced oxygen states into the band gap in the TiO2-rich composition region, which results in the predicted reduction of the band gap. However, we show that the optical absorption of those states is negligible. We have obtained good agreement between the calculated and measured imaginary part of the dielectric function ɛi, especially for the TiO2-rich compositions. Finally, we predict an almost-linear refractive index change at 632.8 nm between a-SiO2 (1.36) and a-TiO2 (2.34), which was experimentally confirmed.

  3. Phase Relations in Ternary Systems in the Subsolidus Region: Methods to Formulate Solid Solution Equations and to Find Particular Compositions

    Science.gov (United States)

    Alvarez-Montan~o, Victor E.; Farías, Mario H.; Brown, Francisco; Mun~oz-Palma, Iliana C.; Cubillas, Fernando; Castillon-Barraza, Felipe F.

    2017-01-01

    A good understanding of ternary phase diagrams is required to advance and/or to reproduce experimental research in solid-state and materials chemistry. The aim of this paper is to describe the solutions to problems that appear when studying or determining ternary phase diagrams. A brief description of the principal features shown in phase diagrams…

  4. Reactivity and suitability of t-Boc-protected thiophosphotyrosine intermediate analogs for the solid or solution phase peptide synthesis.

    Science.gov (United States)

    Kim, E K; Choi, H; Lee, E S

    1998-06-01

    N-(tert-Butoxycarbonyl)-O-(dimethylthiophosphono)-L-tyrosine (6) and N-(tert-butoxycarbony)-O-(dicyanoethylthiophosphono)-L-tyros ine (15) were prepared as intermediates for the synthesis of thiophosphotyrosine-containing peptides. The reactivity and suitability of two compounds for the solid phase or solution phase peptide synthesis utilizing t-Boc chemistry were examined.

  5. Structural and vibrational investigations on Ge{sub 34}Sb{sub 66} solid solutions produced by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Rebelo, Q.H.F.; Cotta, E.A. [Departamento de Física, Universidade Federal do Amazonas, 69077-000 Manaus, Amazonas (Brazil); Souza, S.M. de, E-mail: s.michielon@gmail.com [Departamento de Física, Universidade Federal do Amazonas, 69077-000 Manaus, Amazonas (Brazil); Trichês, D.M. [Departamento de Física, Universidade Federal do Amazonas, 69077-000 Manaus, Amazonas (Brazil); Machado, K.D. [Departamento de Física, Centro Politécnico, Universidade Federal do Paraná, 81531-990 Curitiba, Paraná (Brazil); Lima, J.C. de; Grandi, T.A. [Departamento de Física, Centro de Ciências Exatas, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, Santa Catarina (Brazil); Poffo, C.M. [Departamento de Eng. Mecânica, Centro de Ciências Tecnológicas, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, Santa Catarina (Brazil); Manzato, L. [Instituto Federal de Educação, Ciência e Tecnologia do Amazonas, 69075-351 Manaus, Amazonas (Brazil)

    2013-10-25

    Highlights: •A Ge{sub 34}Sb{sub 66} solid solution was prepared by mechanical alloying. •X-ray diffraction results indicate complete dissolution of Ge on the Sb matrix. •Raman measurements indicate the presence of nanocrystalline Ge dispersed in the matrix. -- Abstract: A nanostructured solid solution Ge{sub 34}Sb{sub 66} was produced from Ge and Sb by mechanical alloying and its structural and vibrational properties were investigated by X-ray diffraction (XRD) and micro-Raman spectroscopy. The Rietveld refinement of the XRD measurements allowed the investigation of the evolution of the solid solution with the milling time. The Bragg peaks of the Sb solvent phase showed a strongly reflection-indices-dependent line broadening due to the spatial variation of the Sb/Ge ratio. The asymmetric broadening in the deformed peaks was analyzed considering the Stephens model. Volume fractions of crystalline and interfacial components of the milled powder were estimated from the XRD patterns. Although XRD measurements indicated the formation of a solid solution, Raman measurements revealed the presence of nanocrystalline Ge, and its crystallite size was estimated from the Raman analysis.

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

    Science.gov (United States)

    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…

  7. Formation of a 25 mol% Fe2O3-Al2O3 solid solution prepared by ball milling

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Mørup, Steen; Linderoth, Søren

    1996-01-01

    The phase transformation process of a 25 mol% Fe2O3-Al2O3 powder mixture during high-energy ball milling has been studied by x-ray diffraction and Mossbauer spectroscopy. A metastable solid solution of 25 mol % Fe2O3 in Al2O3 with corundum structure has successfully been prepared after a milling...

  8. STRUCTURAL AND DYNAMIC PROPERTIES OF SOLID-SOLUTIONS OF BAF2 AND GDF3 - AN EPR STUDY

    NARCIS (Netherlands)

    DENHARTOG, HW

    Results of EPR experiments on solid solutions of barium and gadolinium fluoride in the temperature range 300 to 900 K are presented. At room temperature the Gd-ions are located predominantly at trigonal sites. If the temperature is increased, the interstitial fluoride ions are found to dissociate

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

    Science.gov (United States)

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

    2016-01-12

    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.

  10. Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe

    Directory of Open Access Journals (Sweden)

    Jesús-Alejandro Peña-Jiménez

    2016-09-01

    Full Text Available The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN co-doped with the La3+–Mn4+ and Eu3+–Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+–Mn4+ and Eu3+–Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

  11. Solid solutions of gadolinium doped zinc oxide nanorods by combined microwave-ultrasonic irradiation assisted crystallization

    Science.gov (United States)

    Kiani, Armin; Dastafkan, Kamran; Obeydavi, Ali; Rahimi, Mohammad

    2017-12-01

    Nanocrystalline solid solutions consisting of un-doped and gadolinium doped zinc oxide nanorods were fabricated by a modified sol-gel process utilizing combined ultrasonic-microwave irradiations. Polyvinylpyrrolidone, diethylene glycol, and triethylenetetramine respectively as capping, structure directing, and complexing agents were used under ultrasound dynamic aging and microwave heating to obtain crystalline nanorods. Crystalline phase monitoring, lattice parameters and variation, morphology and shape, elemental analysis, functional groups, reducibility, and the oxidation state of emerged species were examined by PXRD, FESEM, TEM, EDX, FTIR, micro Raman, H2-TPR, and EPR techniques. Results have verified that irradiation mechanism of gelation and crystallization reduces the reaction time, augments the crystal quality, and formation of hexagonal close pack structure of Wurtzite morphology. Besides, dissolution of gadolinium within host lattice involves lattice deformation, unit cell distortion, and angular position variation. Structure related shape and growth along with compositional purity were observed through microscopic and spectroscopic surveys. Furthermore, TPR and EPR studies elucidated more detailed behavior upon exposure to the exerted irradiations and subsequent air-annealing including the formed oxidation states and electron trapping centers, presence of gadolinium, zinc, and oxygen disarrays and defects, as well as alteration in the host unit cell via gadolinium addition.

  12. Understanding the defect chemistry of alkali metal strontium silicate solid solutions: insights from experiment and theory

    KAUST Repository

    Bayliss, Ryan D.

    2014-09-24

    © the Partner Organisations 2014. Recent reports of remarkably high oxide ion conduction in a new family of strontium silicates have been challenged. It has recently been demonstrated that, in the nominally potassium substituted strontium germanium silicate material, the dominant charge carrier was not the oxygen ion, and furthermore that the material was not single phase (R. D. Bayliss et. al., Energy Environ. Sci., 2014, DOI: 10.1039/c4ee00734d). In this work we re-investigate the sodium-doped strontium silicate material that was reported to exhibit the highest oxide ion conductivity in the solid solution, nominally Sr0.55Na0.45SiO2.775. The results show lower levels of total conductivity than previously reported and sub-micron elemental mapping demonstrates, in a similar manner to that reported for the Sr0.8K0.2Si0.5Ge0.5O2.9 composition, an inhomogeneous chemical distribution correlating with a multiphase material. It is also shown that the conductivity is not related to protonic mobility. A density functional theory computational approach provides a theoretical justification for these new results, related to the high energetic costs associated with oxygen vacancy formation. This journal is

  13. Inelasticity and precipitation of germanium from a solid solution in Al-Ge binary alloys

    Science.gov (United States)

    Kardashev, B. K.; Korchunov, B. N.; Nikanorov, S. P.; Osipov, V. N.

    2015-08-01

    The influence of precipitation of germanium atoms in a solid solution on the dependence of the inelasticity characteristics on the germanium content in aluminum-germanium alloys prepared by directional crystallization has been studied. It has been shown that the Young's modulus defect, the amplitude-dependent decrement, and the microplastic flow stress at a specified cyclic strain amplitude have extreme values at the eutectic germanium content in the alloy. The eutectic composition of the alloy undergoes a ductilebrittle transition. It has been found that there is a correlation between the dependences of the Young's modulus defect, amplitude-dependent decrement, microplastic flow stress, and specific entropy of the exothermal process of germanium precipitation on the germanium content in the hypoeutectic alloy. The concentration dependences of the inelasticity characteristics and their changes after annealing have been explained by the change in the resistance to the motion of intragrain dislocations due to different structures of the Guinier-Preston zones formed during the precipitation of germanium atoms.

  14. A Unified Physical Model for Creep and Hot Working of Al-Mg Solid Solution Alloys

    Directory of Open Access Journals (Sweden)

    Stefano Spigarelli

    2017-12-01

    Full Text Available The description of the dependence of steady-state creep rate on applied stress and temperature is almost invariably based on the Norton equation or on derived power-law relationships. In hot working, the Norton equation does not work, and is therefore usually replaced with the Garofalo (sinh equation. Both of these equations are phenomenological in nature and can be seldom unambiguously related to microstructural parameters, such as dislocation density, although early efforts in this sense led to the introduction of the “natural power law” with exponent 3. In an attempt to overcome this deficiency, a recent model with sound physical basis has been successfully used to describe the creep response of fcc metals, such as copper. The main advantage of this model is that it does not require any data fitting to predict the strain rate dependence on applied stress and temperature, which is a particularly attractive peculiarity when studying the hot workability of metals. Thus, the model, properly modified to take into account solid solution strengthening effects, has been here applied to the study of the creep and hot-working of simple Al-Mg single phase alloys. The model demonstrated an excellent accuracy in describing both creep and hot working regimes, still maintaining its most important feature, that is, it does not require any fitting of the experimental data.

  15. Slow dynamics and field-induced transitions in a mixed-valence oxide solid solution

    Science.gov (United States)

    Charilaou, M.; Löffler, J. F.; Gehring, A. U.

    2011-06-01

    In this study, the spin-glass-like properties of (x)FeTiO3-(1-x)Fe2O3, with x =0.8 and 0.9, as prominent mixed-valence state solid solution, were investigated by means of ac susceptibility and dc magnetization measurements. Dynamic ac susceptibility indicates freezing at finite temperature Tf, obeying a power law with a dynamic exponent zν≈7, close to that of the 3D Ising spin glass, and relaxation rates in the kHz range. The slow dynamics are explained by the presence of ordered superspins, whose relaxation rate decreases with increasing superspin size. In the frozen state, symmetry breaking is observed at a critical field Hcr which decreases with temperature obeying a power law Hcr2/3∝T, and is followed by a metamagnetic transition with increasing field similar to that of the end-member FeTiO3, obeying a Hcr3/2∝T law. The two transitions converge near the freezing temperature, thus denoting the H-T phase diagram of the system.

  16. Unique Challenges for Modeling Defect Dynamics in Concentrated Solid-Solution Alloys

    Science.gov (United States)

    Zhao, Shijun; Weber, William J.; Zhang, Yanwen

    2017-11-01

    Recently developed concentrated solid solution alloys (CSAs) are shown to have improved performance under irradiation that depends strongly on the number of alloying elements, alloying species, and their concentrations. In contrast to conventional dilute alloys, CSAs are composed of multiple principal elements situated randomly in a simple crystalline lattice. As a result, the intrinsic disorder has a profound influence on energy dissipation pathways and defect evolution when these CSAs are subjected to energetic particle irradiation. Extraordinary irradiation resistance, including suppression of void formation by two orders of magnitude at an elevated temperature, has been achieved with increasing compositional complexity in CSAs. Unfortunately, the loss of translational invariance associated with the intrinsic chemical disorder poses great challenges to theoretical modeling at the electronic and atomic levels. Based on recent computer simulation results for a set of novel Ni-containing, face-centered cubic CSAs, we review theoretical modeling progress in handling disorder in CSAs and underscore the impact of disorder on defect dynamics. We emphasize in particular the unique challenges associated with the description of defect dynamics in CSAs.

  17. The investigation of phenol removal from aqueous solutions by zeolites as solid adsorbents.

    Science.gov (United States)

    Damjanović, Ljiljana; Rakić, Vesna; Rac, Vladislav; Stošić, Dušan; Auroux, Aline

    2010-12-15

    This work reports results on phenol adsorption from aqueous solutions on synthetic BEA (β) and MFI (ZSM-5) zeolites, studied by heat-flow microcalorimetry. For the sake of comparison, the adsorption was performed on activated carbon, a solid customarily used for removal of phenol from water. The obtained values of heats evolved during phenol adsorption indicate the heterogeneity of active sites present on the investigated systems for the adsorption of phenol. In addition, the amounts of adsorbed pollutant were determined and presented in the form of adsorption isotherms, which were interpreted using Langmuir, Freundlich, Dubinin-Astakov and Sips' equations. The latter was found to express high level of agreement with experimental data. The results obtained in this work reveal that the adsorption of phenol on zeolites depends on both Si/Al ratio and on the pore size. Hydrophobic zeolites that possess higher contents of Si show higher affinities for phenol adsorption. Among investigated zeolites, zeolite β possesses the highest capacity for adsorption of phenol. The possibility of regeneration of used adsorbents was investigated by thermal desorption technique. It has been shown that in the case of β zeolite the majority of adsorbed phenol is easily released in the low temperature region. Copyright © 2010 Elsevier B.V. All rights reserved.

  18. Stacking fault energy measurements in solid solution strengthened Ni-Cr-Fe alloys using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Unfried-Silgado, Jimy [Metals Characterization and Processing Laboratory, Brazilian Nanothecnology National Laboratory - CNPEM/ABTLuS, Caixa Postal 6192, CEP 13083-970, Campinas, Sao Paulo (Brazil); Universidade Estadual de Campinas UNICAMP, Faculdade de Engenharia Mecanica FEM, Campinas (Brazil); Universidad Autonoma del Caribe, Grupo IMTEF, Ingenieria Mecanica, Barranquilla (Colombia); Wu, Leonardo [Metals Characterization and Processing Laboratory, Brazilian Nanothecnology National Laboratory - CNPEM/ABTLuS, Caixa Postal 6192, CEP 13083-970, Campinas, Sao Paulo (Brazil); Furlan Ferreira, Fabio [Universidade Federal do ABC, Centro de Ciencias Naturais e Humanas (CCNH), Sao Paulo (Brazil); Mario Garzon, Carlos [Universidad Nacional de Colombia, Departamento de Fisica, Bogota (Colombia); Ramirez, Antonio J, E-mail: antonio.ramirez@lnnano.org.br [Metals Characterization and Processing Laboratory, Brazilian Nanothecnology National Laboratory - CNPEM/ABTLuS, Caixa Postal 6192, CEP 13083-970, Campinas, Sao Paulo (Brazil)

    2012-12-15

    The stacking fault energy (SFE) in a set of experimental Ni-Cr-Fe alloys was determined using line profile analysis on synchrotron X-ray diffraction measurements. The methodology used here is supported by the Warren-Averbach calculations and the relationships among the stacking fault probability ({alpha}) and the mean-square microstrain (<{epsilon}{sup 2}{sub L}>). These parameters were obtained experimentally from cold-worked and annealed specimens extracted from the set of studied Ni-alloys. The obtained results show that the SFE in these alloys is strongly influenced by the kind and quantity of addition elements. Different effects due to the action of carbide-forming elements and the solid solution hardening elements on the SFE are discussed here. The simultaneous addition of Nb, Hf, and, Mo, in the studied Ni-Cr-Fe alloys have generated the stronger decreasing of the SFE. The relationships between SFE and the contributions on electronic structure from each element of additions were established.

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

    Science.gov (United States)

    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…

  20. Solution and Solid Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) Ultraviolet (UV) 229 nm Photochemistry.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Brinzer, Thomas; Asher, Sanford A

    2015-05-01

    We measured the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We also examined the photochemistry of RDX both in solution and solid states. RDX quickly photodegrades with a solution quantum yield of φ ~ 0.35 as measured by high-performance liquid chromatography (HPLC). New spectral features form over time during the photolysis of RDX, indicating photoproduct formation. The photoproduct(s) show stable DUVRR spectra at later irradiation times that allow standoff detection. In the solution-state photolysis, nitrate is a photoproduct that can be used as a signature for detection of RDX even after photolysis. We used high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) and gas chromatography mass spectrometry (GCMS) to determine some of the major solution-state photoproducts. X-ray photoelectron spectroscopy (XPS) was also used to determine photoproducts formed during solid-state RDX photolysis.

  1. Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

    Science.gov (United States)

    Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

    2017-06-22

    Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm-1 ) and dry-air-stable SEs (Li4 SnS4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO2 ) coated by solidified Li4 SnS4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO2 to aqueous solutions are minimized by using predissolved Li4 SnS4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Simple thermodynamic model of the extension of solid solution of Cu-Mo alloys processed by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingenieria Metalurgica y de Materiales, Universidad Tecnica Federico Santa Maria, Avenida Espana 1680, Valparaiso (Chile); Guzman, D. [Departamento de Metalurgia, Facultad de Ingenieria, Universidad de Atacama, Av. Copayapu 485, Copiapo (Chile); Rojas, P.A. [Escuela de Ingenieria Mecanica, Facultad de Ingenieria, Pontificia Universidad Catolica de Valparaiso, Av. Los Carrera 01567, Quilpue (Chile); Ordonez, Stella [Departamento de Ingenieria Metalurgica, Facultad de Ingenieria, Universidad de Santiago de Chile, Av. L. Bernardo O' Higgins 3363, Santiago (Chile); Rios, R. [Instituto de Materiales y Procesos Termomecanicos, Facultad de Ciencias de la Ingenieria, Universidad Austral de Chile, General Lagos 2086, Valdivia (Chile)

    2011-08-15

    Highlights: {yields} Extension of solid solution in Cu-Mo systems achieved by mechanical alloying. {yields} Simple thermodynamic model to explain extension of solid solution of Mo in Cu. {yields} Model gives results that are consistent with the solubility limit extension reported in other works. - Abstract: The objective of this work is proposing a simple thermodynamic model to explain the increase in the solubility limit of the powders of the Cu-Mo systems or other binary systems processed by mechanical alloying. In the regular solution model, the effects of crystalline defects, such as; dislocations and grain boundary produced during milling were introduced. The model gives results that are consistent with the solubility limit extension reported in other works for the Cu-Cr, Cu-Nb and Cu-Fe systems processed by mechanical alloying.

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

    Science.gov (United States)

    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. (c) 2009 European Peptide Society and John Wiley & Sons, Ltd.

  4. Structural, vibrational and photoluminescence properties of Sr{sub (1-x)}Pb{sub x}MoO{sub 4} solid solution synthesized by solid state reaction

    Energy Technology Data Exchange (ETDEWEB)

    Hallaoui, A.; Taoufyq, A. [IM2NP, UMR CNRS 7334, University of Toulon, BP20132, 83957 La Garde (France); LME, Faculty of Sciences, University Ibn Zohr, 80000 Agadir (Morocco); Arab, M. [IM2NP, UMR CNRS 7334, University of Toulon, BP20132, 83957 La Garde (France); Bakiz, B.; Benlhachemi, A.; Bazzi, L. [LME, Faculty of Sciences, University Ibn Zohr, 80000 Agadir (Morocco); Valmalette, J-C.; Villain, S.; Guinneton, F. [IM2NP, UMR CNRS 7334, University of Toulon, BP20132, 83957 La Garde (France); Gavarri, J-R., E-mail: gavarri.jr@univ-tln.fr [IM2NP, UMR CNRS 7334, University of Toulon, BP20132, 83957 La Garde (France)

    2016-07-15

    Highlights: • The solid solution Sr{sub (1-x)}Pb{sub (x)}MoO{sub 4} is characterized by X-ray diffraction. • Raman spectroscopy confirm that the solid solution is disordered. • Photoluminescence experiments are carried out under X-ray excitation. • Emission bands can be decomposed into four components between 2.1 and 2.9 eV. • The intensities of emission bands reach a maximum for 0.1 < x < 0.4. - Abstract: In this paper, strontium lead molybdate Sr{sub 1-x}Pb{sub x}MoO{sub 4} polycrystalline samples with 0 ≤ x ≤ 1 were prepared by solid state preparation method at 1000 °C. These materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and micro-Raman spectroscopy. Their photoluminescence responses were analyzed under X-ray excitation. Rietveld refinements indicate that all the materials present a scheelite-type tetragonal structure. Micro-Raman spectra confirmed the formation of the solid solution with a specific effect due to Sr-O-Mo and Pb-O-Mo links in the scheelite structure. SEM images showed modifications in the shapes and grain sizes as x increased. Broad photoluminescent emission bands were observed in the energy range 2.1–2.9 eV. The emission bands were decomposed into four gaussian components. The intensities of all components presented a strong maximum in the composition range 0.1 < x < 0.4.

  5. Aziridine-2-carboxylic acid-containing peptides: application to solution- and solid-phase convergent site-selective peptide modification.

    Science.gov (United States)

    Galonić, Danica P; Ide, Nathan D; van der Donk, Wilfred A; Gin, David Y

    2005-05-25

    The development of a method for site- and stereoselective peptide modification using aziridine-2-carboxylic acid-containing peptides is described. A solid-phase peptide synthesis methodology that allows for the rapid generation of peptides incorporating the aziridine residue has been developed. The unique electrophilic nature of this nonproteinogenic amino acid allows for site-selective conjugation with various thiol nucleophiles, such as anomeric carbohydrate thiols, farnesyl thiol, and biochemical tags, both in solution and on solid support. This strategy, combined with native chemical ligation, provides convergent and rapid access to complex thioglycoconjugates.

  6. Quantum statistical effects in the mass transport of interstitial solutes in a crystalline solid

    Science.gov (United States)

    Woo, C. H.; Wen, Haohua

    2017-09-01

    The impact of quantum statistics on the many-body dynamics of a crystalline solid at finite temperatures containing an interstitial solute atom (ISA) is investigated. The Mori-Zwanzig theory allows the many-body dynamics of the crystal to be formulated and solved analytically within a pseudo-one-particle approach using the Langevin equation with a quantum fluctuation-dissipation relation (FDR) based on the Debye model. At the same time, the many-body dynamics is also directly solved numerically via the molecular dynamics approach with a Langevin heat bath based on the quantum FDR. Both the analytical and numerical results consistently show that below the Debye temperature of the host lattice, quantum statistics significantly impacts the ISA transport properties, resulting in major departures from both the Arrhenius law of diffusion and the Einstein-Smoluchowski relation between the mobility and diffusivity. Indeed, we found that below one-third of the Debye temperature, effects of vibrations on the quantum mobility and diffusivity are both orders-of-magnitude larger and practically temperature independent. We have shown that both effects have their physical origin in the athermal lattice vibrations derived from the phonon ground state. The foregoing theory is tested in quantum molecular dynamics calculation of mobility and diffusivity of interstitial helium in bcc W. In this case, the Arrhenius law is only valid in a narrow range between ˜300 and ˜700 K. The diffusivity becomes temperature independent on the low-temperature side while increasing linearly with temperature on the high-temperature side.

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

    Science.gov (United States)

    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.

  8. Fast Li ionic conduction in solid solutions of the system Li4GeO4-Li2ZnGeO4-Li3PO4

    NARCIS (Netherlands)

    Kamphorst, J.G.; Hellstrom, E.E.

    A wide range of solid solution formation in the Li4GeO4-Li2ZnGeO4-Li3PO4 system was observed to occur with a structure based on γII-Li3PO4. This includes the fast Li conductor lisicon (Li14Zn(GeO4)4). The ionic conductivities of solid solutions in this systems are reported. Much of the solid

  9. Improving the electrocatalytic properties of Pd-based catalyst for direct alcohol fuel cells: effect of solid solution.

    Science.gov (United States)

    Wen, Cuilian; Wei, Ying; Tang, Dian; Sa, Baisheng; Zhang, Teng; Chen, Changxin

    2017-07-07

    The tolerance of the electrode against the CO species absorbed upon the surface presents the biggest dilemma of the alcohol fuel cells. Here we report for the first time that the inclusion of (Zr, Ce)O2 solid solution as the supporting material can significantly improve the anti-CO-poisoning as well as the activity of Pd/C catalyst for ethylene glycol electro-oxidation in KOH medium. In particular, the physical origin of the improved electrocatalytic properties has been unraveled by first principle calculations. The 3D stereoscopic Pd cluster on the surface of (Zr, Ce)O2 solid solution leads to weaker Pd-C bonding and smaller CO desorption driving force. These results support that the Pd/ZrO2-CeO2/C composite catalyst could be used as a promising effective candidate for direct alcohol fuel cells application.

  10. A Summary of Corrosion Properties of Al-Rich Solid Solution and Secondary Phase Particles in Al Alloys

    Directory of Open Access Journals (Sweden)

    Jichao Li

    2017-03-01

    Full Text Available The heterogeneous structure of Al alloys renders them susceptible to localized corrosion due to the different electrochemical properties existing in the Al-rich solid solution matrix and secondary phase particles. The galvanic interactions between these two phases can result in pit formation either through dissolution of the particles or corrosion of the matrix adjacent to the particles. This detrimentally localized corrosion behavior is closely related to the corrosion properties of the particles and the Al-rich matrix. The comprehensive characterization of this behavior under various and varying conditions is critical to understanding the mechanism of pit formation, selecting appropriate inhibitors, and developing protection strategies. The corrosion properties (corrosion potential, pitting potential and corrosion rate of both secondary phase particles and Al-solid solutions in Al alloys are summarized in this review, aiming to provide a database for corrosion research applicable to the localized corrosion of Al alloys.

  11. Solid Solution Effects on the MgAl2O4-MgGa2O4 System

    Energy Technology Data Exchange (ETDEWEB)

    O' Hara, Kelley [University of Missouri, Rolla; Smith, Jeffrey D [ORNL; Hemrick, James Gordon [ORNL

    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.

  12. Solution- and solid-phase synthesis and anti-HIV activity of maslinic acid derivatives containing amino acids and peptides.

    Science.gov (United States)

    Parra, Andres; Rivas, Francisco; Lopez, Pilar E; Garcia-Granados, Andres; Martinez, Antonio; Albericio, Fernando; Marquez, Nieves; Muñoz, Eduardo

    2009-02-01

    Maslinic acid (1) has been coupled at C-28 with several alpha- and omega-amino acids by using solution- and solid-phase synthetic procedures. Twelve derivatives (2-13) with a single amino acid residue were prepared in solution phase, whereas a dipeptide (14), a tripeptide (15), and a series of conjugate dipeptides (16-24) were synthesized in solid phase. The anti-HIV activity of these compounds was assessed on MT-2 cells infected with viral clones carrying the luciferase gene as a reporter. While in maslinic acid (1) were present both cytotoxic and antiviral activities, only the derivatives 13 and 24 showed anti-HIV-1 activity and therefore represent a novel class of anti-HIV-1 compounds.

  13. Influence of Ce0⋅68Zr0⋅32O2 solid solution on depositing γ ...

    Indian Academy of Sciences (India)

    Unknown

    FeCrAl covered with 1# slurry composing of only γ-Al2O3 is more than that of other three slurries, when thermal shock test and aging treatment were made, viz. Ce0⋅68Zr0⋅32O2 solid solution can improve the bonding between γ-Al2O3-. Figure 1. Morphologies of metallic foils: (a) untreated and. (b) pretreated at 950°C for ...

  14. Induced gyrotropy in NaBi(Mo1-xWxO4)2 solid solutions

    OpenAIRE

    L.Lutsiv-Shumski; Y.Shopa; I.Girnyk

    2000-01-01

    The dependencies of refractive indices and electrogyration parameters on tungsten concentration are obtained for the NaBi(Mo1-xWxO4)2 solid solutions with the sheelite structure. The coefficient of the transverse electrogyration effect is measured and the influence of temperature on the longitudinal electrogyration value is studied. It is shown that the refractive indices and electrogyration coefficients decrease with increasing the tungsten concentration.

  15. Electronic structure and photocatalytic activities of (Bi2-δYδ)Sn2O7 solid solution

    Science.gov (United States)

    Fan, Wenjie; Hu, Jinli; Huang, Jing; Wu, Xin; Lin, Sen; Huang, Caijin; Qiu, Xiaoqing

    2015-12-01

    A series of (Bi2-δYδ)Sn2O7 solid solutions were prepared by a one-step hydrothermal method to investigate the correlation between the electronic structures and photocatalytic activity. All the (Bi2-δYδ)Sn2O7 samples were characterized by X-ray diffraction, transmission electron microscopy, infrared and UV-vis absorption spectroscopy, and the Brunauer-Emmett-Teller technique. The effects of Bi 6s orbitals in (Bi2-δYδ)Sn2O7 solid solutions on the electronic structures and photogradation of colorless 2-naphthol solution were investigated experimentally and theoretically. It is found that the introduction of Y3+ induces the shrinkage of the lattice of (Bi2-δYδ)Sn2O7 solid solutions. Consequently, the contribution of Bi 6s orbitals to electronic structures of (Bi2-δYδ)Sn2O7 solid solutions can be continuously tuned by Y3+ substitution for Bi3+. Density function theory calculations reveal that the Bi 6s and O 2p states dominate the top of valence band of Bi2Sn2O7, while the bottom of conduction band mainly consists of the states of Sn 5s, O 2p and Bi 6p. Once the Bi3+ ions are substituted by Y3+, the intensity of Bi 6s states is weakening at the top of valence band while the bottom of conduction band retains the same feature observed for pure Bi2Sn2O7. Moreover, the band dispersions of valence band and conduction band become narrower after Y3+ introduction into the lattice of (Bi2-δYδ)Sn2O7 solid solutions. As a result, the photocatalytic performance for decomposition of 2-naphthol has been suppressed by the Y3+ substitution, since the electronic structure limits the mobility of the photoinduced charge carriers. Our results suggest that high photocatalytic activity of Bi-containing compounds should originate from the good band dispersions of valence band and conduction band involving the Bi 6s orbitals.

  16. PAC experiments for a short range study of the Zr(10%Pr)O{sub 2} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, J. A.; Caracoche, M. C., E-mail: cristina@fisica.unlp.edu.ar [Universidad Nacional de La Plata, Departamento de Fisica - IFLP, Facultad de Ciencias Exactas (Argentina); Rivas, P. C. [Universidad Nacional de La Plata, IFLP - Facultad de Ciencias Agronomicas y Forestales (Argentina); Rodriguez, A. M. [Universidad Nacional de La Plata, Departamento de Fisica - IFLP, Facultad de Ciencias Exactas (Argentina)

    2006-07-15

    A Zr(10 mol % Pr)O{sub 2} powder obtained by high-energy ball milling has been investigated at nanoscopic scale using primarily the Perturbed Angular Correlations technique. The aim has been to determine the nanoconfigurations around Zr{sup 4+} cations present in the solid solution and their thermal evolution with the intention of providing knowledge on the stability of the system. Results indicate that the milled product is a substitutional cubic solid solution described by two hyperfine interactions: a highly disordered interaction due to oxygen vacancies located very close to Zr{sup 4+} and an ordered interaction probably depicting a charge distribution including Pr{sup 3+} as nearest neighbor to Zr{sup 4+} probes. On cooling from high temperatures, monoclinic zirconia appears mostly at the expense of the oxygen defective cubic form. A gradual cooling indicates that destabilization of the solid solution takes place around 500{sup o}C. Thermal cycling leads to increasing amounts of the monoclinic phase.

  17. Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1- x nanoplate solid solutions

    Science.gov (United States)

    Xu, Huan-Yan; Han, Xu; Tan, Qu; Wu, Ke-Jia; Qi, Shu-Yan

    2017-06-01

    In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1- x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1- x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1- x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1- x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

  18. NUMERICAL AND ANALYTIC SOLUTION OF PRANDTL’S EQUATION FOR SOLID BODIES WITH AGREED CONTACT SURFACES

    Directory of Open Access Journals (Sweden)

    A. Chigarev

    2013-01-01

    Full Text Available The paper considers a method for problem solution pertaining to compression of elastic bodies bounded by cylindrical surfaces whose radii are almost equal. The objective aim does not allow to apply the Hertz theory and reduces to finding approximate solutions of the Prandtl’s equation. The  resulting solution is compared with the solution in the ANSYS system. 

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

    Science.gov (United States)

    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

  20. A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

    Science.gov (United States)

    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.

  1. Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

    Science.gov (United States)

    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

  2. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li(+) /H(+) exchange in aqueous solutions.

    Science.gov (United States)

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren L; Chi, Miaofang

    2015-01-02

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Structural, Electronic, and Optical Properties of BiOX1−xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations

    Science.gov (United States)

    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

  4. Electronic energy migration in solid versus liquid host matrices for concentrated perylenediimide dye solutions.

    Science.gov (United States)

    Colby, Kathryn A; Bardeen, Christopher J

    2011-07-07

    In this paper, we continue our evaluation of Forster-type theories of exciton diffusion in disordered environments. The perylenediimide dye Lumogen Red is used as a donor molecule in two different liquids, CHCl(3) and dimethylformamide, and the energy transfer to the acceptor molecule Rhodamine 700 is measured using time-resolved fluorescence decays. The exciton motion is measured over Lumogen Red concentrations ranging from 1 × 10(-4) to 5 × 10(-2) M, and the results are compared to previous results for exciton diffusion in a solid polymer. Depending on the theoretical approach used to analyze the data, we find that the energy migration in the liquids is a factor of 2-3 faster than in the solid polymer, even after taking molecular translation into account. Measurements for a Lumogen Red concentration of 10 mM in the different host environments yield diffusion constants ranging from 2.2 to 3.1 nm(2)/ns in the liquids, as compared to 1.1-1.2 nm(2)/ns in solid poly(methyl methacrylate) (PMMA). The results in the liquids are in good agreement with theoretical predictions and numerical simulations of previous workers, while the results in solid PMMA are 2-3 times slower. This discrepancy is discussed in the context of the rapid energetic averaging present in the liquid environments but absent in the solid matrix, where unfavorable configurations and low energy trapping sites are frozen in by the static disorder.

  5. Behaviour of Silica and Florisil as Solid Supports in the Removal Process of As(V from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Andreea Gabor

    2015-01-01

    Full Text Available 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.

  6. Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

    Energy Technology Data Exchange (ETDEWEB)

    Hoda, Numan, E-mail: nhoda@akdeniz.edu.tr [Department of Chemistry, Faculty of Sciences, Akdeniz University, 07058 Antalya (Turkey); Budama, Leyla; Çakır, Burçin Acar; Topel, Önder [Department of Chemistry, Faculty of Sciences, Akdeniz University, 07058 Antalya (Turkey); Ozisik, Rahmi [Department of Materials Science and Engineering and Renssleaer Nanotechnology Center, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

    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.

  7. Evaluation of the presence of microorganisms in solid-organ preservation solution

    Directory of Open Access Journals (Sweden)

    André Marcelo Colvara Mattana

    Full Text Available OBJECTIVE: To assess the presence of microorganism contamination in the preservation solution for transplant organs (kidney/pancreas. Method: Between August 2007 and March 2008, 136 samples of preservation solution were studied prior to graft implantation. Variables related to the donor and to the presence of microorganisms in the preservation solution of organs were evaluated, after which the contamination was evaluated in relation to the "recipient culture" variable. Univariate and multivariate statistical analyses were performed. RESULTS: The contamination rate of the preservation solution was 27.9%. Coagulase-negative Staphylococcus was the most frequently isolated microorganism. However, highly virulent agents, such as fungi and enterobacteria, were also isolated. In univariate analysis, the variable "donor antibiotic use" was significantly associated to the contamination of the preservation solution. On the other hand, multivariate analysis found statistical significance in "donor antibiotic use" and "donor's infectious complications" variables. CONCLUSIONS: In this study, 27.9% of the preservation solutions of transplant organs were contaminated. Infectious diseases and non-use of antibiotics by the donor were significantly related to the presence of microorganisms in organ preservation solutions. Contamination in organ preservation solutions was not associated with infection in the recipient.

  8. Comparison of the Solid Solution Properties of Mg-RE (Gd, Dy, Y Alloys with Atomistic Simulation

    Directory of Open Access Journals (Sweden)

    Yurong Wu

    2008-01-01

    Full Text Available Molecular dynamic simulations have been performed to study the solid solution mechanism of Mg100-xREx (RE=Gd,Dy,Y, x=0.5,1,2,3,4  at.%. The obtained results reveal that the additions of Gd, Dy and Y increase the lattice constants of Mg-RE alloys. Also the axis ratio c/a remains unchanged with increase in temperature, restraining the occurrence of nonbasal slip and twinning. Furthermore, it is confirmed that bulk modulus of Mg alloys can be increased remarkably by adding the Gd, Dy, Y, especially Gd, because the solid solubility of Gd in Mg decrease sharply with temperature in comparison with Dy and Y. Consequently, the addition of the RE can enhance the strength of Mg-based alloys, which is in agreement with the experimental results.

  9. Synthetic study on cystinyl peptides using solution and solid phase methodology: human IgG1 hinge region.

    Science.gov (United States)

    Niederhafner, P; Gut, V; Jezek, J; Budesínský, M; Kasicka, V; Wünsch, E; Hlavácek, J

    2010-08-01

    Synthetic study on cystinyl peptides using solution and solid phase methodology was carried out with the central hinge region of immunoglobulin IgG1. In the solid phase synthesis of hexadecapeptide 1c, the time necessary for the formation of disulfide bonds between linear precursors was shortened four times by the action of pure oxygen in buffered solution, in comparison with air oxidation. The product was thus obtained devoid of impurities from side reactions. In the preparation of the shortened bis-cystinyl analogs 2k and 3d of the natural hexadecapeptide 1c, both the classical and polyethylene glycol (PEG6000) solution methods were utilized using a disulfide synthon (Boc-Cys-OPfp)2 to obtain peptide chains in a natural parallel alignment. In the PEG6000 strategy, lysine as a linker on both sides of the polymer was attached to enhance the loading capacity. The leucine residue, instead of proline one, was introduced to the carboxy terminus to facilitate a specific enzymatic cleavage of the peptides from PEG6000 by thermolysine.

  10. Community Solutions for Solid Waste Pollution, Level 6. Teacher Guide. Operation Waste Watch.

    Science.gov (United States)

    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. Solid dispersions in oncology: a solution to solubility-limited oral drug absorption

    NARCIS (Netherlands)

    Sawicki, Emilia

    2017-01-01

    This thesis discusses the formulation method solid dispersion and how it works to resolve solubility-limited absorption of orally dosed anticancer drugs. Dissolution in water is essential for drug absorption because only dissolved drug molecules are absorbed. The problem is that half of the arsenal

  12. Dynamic cyclone for solids removal: innovative sand management solutions for oil and gas production

    Energy Technology Data Exchange (ETDEWEB)

    Furnes, Olav [Inter Scandic a.s (Norway); Arefjord, Anders [CleanUp AS (Norway)

    2004-07-01

    Sand and other solids inevitably occurring in connection with drilling and production operations for exploitation of offshore and onshore petroleum resources represent an increasing challenge for operators and main contractors worldwide. The adherent sand problems can cause severe erosion of conductors, pipelines and critical processing equipment, such as valves, pumps and separator internals, etc. Proliferation of sand could clog up and severely diminish processing capacity in separators, calling for unscheduled shutdowns for separator jetting and equipment cleaning. These and other consequential problems incur considerable costs to the industry, affecting availability and reliability of production as well as undue cost outlays for equipment monitoring, renewal and refurbishment. Such cost impacts could have decisive effects on commercial viability of marginal fields or deep water prospects. Problematic aspects of produced solids could arise at early stages of reservoir drainage, pending geological profile. As sand volumes tend to increase when oil and gas fields mature, viable tail production to recover remaining reserves becomes decisive for operating costs and investment trade-off. The dynamic de-sanding cyclone system described herein is designed to operate without any pressure drop, thus avoiding loss of flow pressure. It consists of an inner and outer cylindrical chamber, allowing for a second separation run for removal of the smaller particles down to 50 micron or less. In additional to tangential flow inlet, an impeller driven by a hydraulic motor adds significantly to centrifugal separation effects, assisting cleaning of solids as part of the process. As the cyclone is designed to perform online de-gassing as well, it can sustain severe slugging during the solids removal operations. Removed solids can be either accumulated in closed, swapping containers or piped as slurry for final disposal. (author)

  13. Enhanced photocatalytic degradation of 2-propanol over macroporous GaN/ZnO solid solution prepared by a novel sol-gel method

    Directory of Open Access Journals (Sweden)

    Lizhong Wang

    2015-10-01

    Full Text Available Macroporous GaN/ZnO solid solution photocatalyst is synthesized through a novel sol-gel method under mild conditions. The performance of as-synthesized solid solution photocatalyst is evaluated for decomposition of gaseous 2-propanol (IPA. It is found that due to enhancement in both the adsorption to gaseous IPA and the absorbance to visible light, the porous GaN/ZnO solid solution exhibits a good photocatalytic performance for IPA decomposition. Moreover, the mechanism for photocatalytic degradation IPA over porous GaN/ZnO solid solution is also investigated in comparison with those for the two end materials ZnO and GaN. The trapping effects with different scavengers prove that both the photoexcited electrons and holes affect the IPA photodegradation process, simultaneously.

  14. Partitioning of organic matter and heavy metals in a sandy soil: Effects of extracting solution, solid to liquid ratio and pH

    NARCIS (Netherlands)

    Fest, P.M.J.; Temminghoff, E.J.M.; Comans, R.N.J.; Riemsdijk, van W.H.

    2008-01-01

    In sandy soils the behavior of heavy metals is largely controlled by soil organic matter (solid and dissolved organic matter; SOC and DOC). Therefore, knowledge of the partitioning of organic matter between the solid phase and soil solution is essential for adequate predictions of the total

  15. Analytical solutions for non-linear conversion of a porous solid particle in a gas–II. Non-isothermal conversion and numerical verification

    NARCIS (Netherlands)

    Brem, Gerrit; Brouwers, J.J.H.

    1990-01-01

    In Part I, analytical solutions were given for the non-linear isothermal heterogeneous conversion of a porous solid particle. Account was taken of a reaction rate of general order with respect to the gas reactant, intrinsic reaction surface area and effective pore diffusion, which change with solid

  16. Luminescent properties of solid solutions in the PbF2-Euf3 system and lead fluoroborate glass ceramics doped with Eu3+ ions

    Science.gov (United States)

    Sevostjanova, T. S.; Khomyakov, A. V.; Mayakova, M. N.; Voronov, V. V.; Petrova, O. B.

    2017-11-01

    Lead fluoroborate glasses doped with Eu3+ are synthesized, studied, and used to produce glassceramics by heat treatment. The structure of glass-ceramics is determined by X-ray diffraction. The optical, mechanical, and luminescent properties of the glass-ceramics are studied. The structure and spectral-luminescent properties of solid solutions in the PbF2-EuF3 system obtained by both solid-phase reaction and coprecipitation from solutions are investigated.

  17. The effect of deformation treatment on the decomposition of supersaturated Ni(Nb,B) and Ni(Mo,B) solid solutions synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Kubalova, L.M., E-mail: kubal@yandex.ru [K.L. Khetagurov North-Ossetian State University, Vatutina Str. 44-46, Vladikavkaz 362025 (Russian Federation); Fadeeva, V.I., E-mail: fadeeva@general.chem.msu.ru [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow 119991 (Russian Federation)

    2014-02-15

    Highlights: • Influence of deformation on decomposition of Ni-based solid solutions was studied. • X-ray diffraction analysis and scanning electron microscopy were used. • Decomposition of Ni(Nb,B), Ni(Mo,B) solid solutions takes place under deformation. • Formation of Ni{sub 21}(Nb,Mo){sub 2}B{sub 6}τ-phases after deformation treatment is observed. • Identity of MA and deformation on the decomposition of solid solutions is shown. -- Abstract: The effect of rotary-shear deformation during powders compacting on the decomposition of supersaturated Ni(Nb,B) and Ni(Mo,B) solid solutions is studied. The metastable fcc solid solutions were synthesized by mechanical alloying (MA) of the mixtures of components of Ni{sub 75}Nb{sub 12}B{sub 13} and Ni{sub 73}Mo{sub 14}B{sub 13} compositions. The powders were compacted on a Bridgman anvil. Col plastic deformation action is realized by using this technique. As a result the initial structure of nonequilibrium supersaturated solid solutions changed. The data of X-ray diffraction analysis and scanning electron microscopy showed a partial decomposition of Ni(Nb,B) and Ni(Mo,B) solid solutions, which leads to the formation of cubic boride τ phases – Ni{sub 21}Nb{sub 2}B{sub 6} with a lattice parameter of a = 1.0572 nm and, correspondingly, Ni{sub 21}Mo{sub 2}B{sub 6} phase with a lattice parameter of a = 1.0498 nm. The τ phase probably forms coherently to the fcc crystal lattice of solid solution because of its lattice parameter is equal to three lattice parameter of nickel. According to the data of local X-ray spectral analysis, the compacted alloys are heterogeneous and are contained boron-reach and also niobium- and molybdenum-rich regions.

  18. Effective scintillation materials based on solid solutions ZnS1–xTex and perspectives of their application

    Directory of Open Access Journals (Sweden)

    Katrunov K. A.

    2011-04-01

    Full Text Available The optimal technological regime of formation ZnS1–xTex solid solution at spacing 0,0≤х≤0,1 has been determined, and has been shown that fritting in hydrogen atmosphere results in more rapid reaction in comparison to argon due to chemical-thermal etching the ZnO layer out. Further annealing in the inert Ar atmosphere leads to the increase of the light output, to the intensive emission band formation and causes afterglow level reduction and the crystalline lattice rearrangement.

  19. Interstitial positions of tin ions in alpha-(FerichSn)(2)O-3 solid solutions prepared by mechanical alloying

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Lin, Rong; Nielsen, Kurt

    1997-01-01

    The microstructure of samples of 91, 85, and 71 mol % alpha-Fe-2-O-3-SnO2. prepared by mechanical alloying, has been studied by x-ray diffraction with Rietveld structure refinements, On the basis of the structure refinements to the whole x-ray diffraction patterns for the four as-milled samples......, it is found that tin ions do not substitute iron ions in the solid solution, although this model is generally assumed in the literature. The Sn4+ ions occupy the empty octahedral holes in the lattice of the alpha-Fe2O3 phase....

  20. αB-Crystallin. A Hybrid Solid-State/Solution-State NMR Investigation Reveals Structural Aspects of the Heterogeneous Oligomer

    Energy Technology Data Exchange (ETDEWEB)

    Jehle, Stefan [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); van Rossum, Barth [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Stout, Joseph R. [Univ. of Washington, Seattle, WA (United States); Noguchi, Satoshi M. [Univ. of Washington, Seattle, WA (United States); Falber, Katja [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Rehbein, Kristina [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Oschkinat, Hartmut [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Klevit, Rachel E. [Univ. of Washington, Seattle, WA (United States); Rajagopal, Ponni [Univ. of Washington, Seattle, WA (United States)

    2008-11-14

    Atomic-level structural information on αB-Crystallin (αB), a prominent member of the small heat-shock protein family, has been a challenge to obtain due its polydisperse oligomeric nature. We show that magic-angle spinning solid-state NMR can be used to obtain high-resolution information on an ~580-kDa human αB assembled from 175-residue 20-kDa subunits. An ~100-residue α-crystallin domain is common to all small heat-shock proteins, and solution-state NMR was performed on two different α- crystallin domain constructs isolated from αB. In vitro, the chaperone-like activities of full-length αB and the isolated α-crystallin domain are identical. Chemical shifts of the backbone and Cβ resonances have been obtained for residues 64–162 (α-crystallin domain plus part of the C-terminus) in αB and the isolated α-crystallin domain by solid-state and solution-state NMR, respectively. Both sets of data strongly predict six β-strands in the α-crystallin domain. A majority of residues in the α-crystallin domain have similar chemical shifts in both solid-state and solution-state, indicating similar structures for the domain in its isolated and oligomeric forms. Sites of intersubunit interaction are identified from chemical shift differences that cluster to specific regions of the α-crystallin domain. Multiple signals are observed for the resonances of M68 in the oligomer, identifying the region containing this residue as existing in heterogeneous environments within αB. Evidence for a novel dimerization motif in the human α-crystallin domain is obtained by a comparison of (i) solid-state and solution-state chemical shift data and (ii) 1H–15N heteronuclear single quantum coherence spectra as a function of pH. The isolated α-crystallin domain undergoes a dimer–monomer transition over the pH range 7.5–6.8. This steep pHdependent switch may be important for αB to function optimally (e.g., to preserve the filament integrity

  1. Laminating solution-processed silver nanowire mesh electrodes onto solid-state dye-sensitized solar cells

    KAUST Repository

    Hardin, Brian E.

    2011-06-01

    Solution processed silver nanowire meshes (Ag NWs) were laminated on top of solid-state dye-sensitized solar cells (ss-DSCs) as a reflective counter electrode. Ag NWs were deposited in <1 min and were less reflective compared to evaporated Ag controls; however, AgNW ss-DSC devices consistently had higher fill factors (0.6 versus 0.69), resulting in comparable power conversion efficiencies (2.7%) compared to thermally evaporated Ag control (2.8%). Laminated Ag NW electrodes enable higher throughput manufacturing and near unity material usage, resulting in a cheaper alternative to thermally evaporated electrodes. © 2011 Elsevier B.V. All rights reserved.

  2. Polyoxometalate clusters integrated into peptide chains and as inorganic amino acids: solution- and solid-phase approaches.

    Science.gov (United States)

    Yvon, Carine; Surman, Andrew J; Hutin, Marie; Alex, Jennifer; Smith, Brian O; Long, De-Liang; Cronin, Leroy

    2014-03-24

    General synthetic methods for the grafting of peptide chains onto polyoxometalate clusters by the use of general activated precursors have been developed. Using a solution-phase approach, pre-synthesized peptides can be grafted to a metal oxide cluster to produce hybrids of unprecedented scale (up to 30 residues). An adapted solid-phase method allows the incorporation of these clusters, which may be regarded as novel hybrid unnatural amino acids, during the peptide synthesis itself. These methods may open the way for the automated synthesis of peptides and perhaps even proteins that contain "inorganic" amino acids. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Sonochemical synthesis of Cd{sub 1−x}Zn{sub x}S solid solutions for application in photocatalytic reforming of glycerol to produce hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Paula A.L., E-mail: paulaaparecida_lopes@hotmail.com [Instituto de Química, Universidade Federal da Bahia, Campus de Ondina, 40170-115 Salvador, BA (Brazil); Mascarenhas, Artur J.S., E-mail: artur@ufba.br [Instituto de Química, Universidade Federal da Bahia, Campus de Ondina, 40170-115 Salvador, BA (Brazil); Instituto Nacional de Ciência e Tecnologia, INCT, de Energia e Ambiente, Universidade Federal da Bahia, 40170-290 Salvador, BA (Brazil); Silva, Luciana A., E-mail: las@ufba.br [Instituto de Química, Universidade Federal da Bahia, Campus de Ondina, 40170-115 Salvador, BA (Brazil); Instituto Nacional de Ciência e Tecnologia, INCT, de Energia e Ambiente, Universidade Federal da Bahia, 40170-290 Salvador, BA (Brazil)

    2015-11-15

    A simple sonochemical method for the preparation of Cd{sub 1−x}Zn{sub x}S solid solutions was successfully applied. The sonochemical method has shown to be fast, with low energy demand and allowed to obtain nano-sized particles. The obtained materials were characterized by XRD, EDX, SEM and DRS UV/vis. The Pt-loaded photocatalysts were evaluated in photoinduced reforming of glycerol under visible light irradiation (λ > 418 nm). Pure CdS and solid solutions obtained by sonochemical method have shown photocatalytic activity with respect to hydrogen gas production. The maximum hydrogen evolution rate achieved was 239 μmol g{sup −1} h{sup −1}, when the solid solution Cd{sub 0.6}Zn{sub 0}.{sub 4}S contaminated with γ-Zn(OH){sub 2} was irradiated with visible light. - Highlights: • Cd{sub 1−x}Zn{sub x}S solid solutions were successfully prepared by a sonochemical method. • The solid solutions are active in photocatalytic reforming of glycerol. • The solid solution Cd{sub 0.6}Zn{sub 0.4}S contaminated with γ-Zn(OH){sub 2} was the more active photocatalyst.

  4. Numerical solution of moving boundary problem for deposition process in solid fuel gas generator

    Science.gov (United States)

    Volokhov, V. M.; Dorofeenko, S. O.; Sharov, M. S.; Toktaliev, P. D.

    2016-11-01

    Moving boundary problem in application to process of depositions formation in gas generator are considered. Gas generator, as a part of fuel preparation system of high-speed vehicle, convert solid fuel into multicomponent multiphase mixture, which further burned down in combustion chamber. Mathematical model of two-phase “gas-solid particles” flow, including Navier-Stokes equations for turbulent flow in gas generator and mass, impulse conservations laws for elementary depositions layer are proposed. Verification of proposed mathematical model for depositions mass in gas generator conditions is done. Further possible improvements of proposed model, based on more detail accounting of particle-wall interaction and wall's surface adhesion properties are analyzed.

  5. Comments on the elastic properties in solid solutions of silver halides

    OpenAIRE

    Skordas, Efthimios S.

    2017-01-01

    Recently first principles microscopic calculations, using the generalized gradient approximation, appeared for the solid mixed system $AgCl{_x}Br_{1-x}$ at various compositions. Here, we suggest a model that can estimate the compressibility of the mixed crystals in terms of the compressibilities of the end members alone. This model makes use of a single parameter, i.e., the compressibility of a defect volume, when considering the volume variation produced by the addition of a "foreign molecul...

  6. Computing phase relations involving ordered solid solutions ab initio: Three thermodynamic approaches to the Fe-Si binary

    Science.gov (United States)

    Asimow, P. D.; Caracas, R.; Wolf, A. S.; Harvey, J. P.

    2016-12-01

    To find inner core compositions (X) consistent with geophysical data, we need phase relations of multicomponent metallic systems at high pressure (P) and temperature (T); the stable phase at a given (P,T,X) determines the physical properties. Given the difficulty of experiments under inner core conditions, reliable computations of such phase relations are needed. Despite advances in computational methods and computing power, challenges include proper treatment of solid solutions with their continuous variation in composition and ordering phenomena. We consider here how to predict phase diagrams from thermodynamic models of partly ordered solid solution phases calibrated with density functional theory to obtain static enthalpy (H) and volume (V), density functional perturbation theory and quasiharmonic approximation for vibrational heat capacity, and three approaches to solution theory to parameterize mixing properties. This approach is applied to B2 and HCP structures in the system Fe-FeSi for comparison to experimental data such as Fischer et al. (2013). We computed H and V of 7 compositions across the Fe-FeSi binary for both B2 and HCP structures, every 20 or 40 GPa from 0 to 400 GPa. We used supercells with up to 24 atoms to explore multiple configurations of the atoms. The H differences among clustered, random, and ordered arrangments of the atoms are neither so small as to imply random mixing nor so large that one configuration will dominate. We computed phonon density of states of at least three compositions for each structure in order to define vibrational heat capacity across each binary using ideal mixing and to test this approximation. We then used three different approaches to solid solution theory to fit the mixing properties: (1) Asymmetric regular solution theory, with (P,T)-dependent Margules parameters to describe the excess H but assuming ideal one-site entropy (S) of mixing; (2) the quasichemical model, accounting for optimized Fe-Si pair

  7. Dislocation glide in Ni-Al solid solutions from the atomic scale up: a molecular dynamics study; Etude du glissement des dislocations dans la solution solide Ni-Al par simulation a l'echelle atomique

    Energy Technology Data Exchange (ETDEWEB)

    Rodary, E

    2003-01-01

    The glide of an edge dislocation in solid solutions is studied by molecular dynamics, at fixed temperature and imposed external stress. We have optimized an EAM potential for Ni(1 a 8% A1): it well reproduces the lattice expansion, local atomic order, stacking fault energy as a function of composition, as well as the elastic properties of the {gamma}' phase with L1{sub 2} structure. On increasing the stress, the dislocation is first immobile, then glides with a velocity proportional to the stress and the velocity saturates on reaching the transverse sound velocity. However, only beyond a static threshold stress, {sigma}{sub s}, does the dislocation glide a distance large enough to allow macroscopic shear; the linear part of the velocity-stress curve extrapolates to zero at a dynamical threshold stress, {sigma}{sub d}, The friction coefficient, and the threshold stresses ({sigma}{sub s} and {sigma}{sub d}), increase with the A1 concentration and decrease with temperature (300 and 500 K). Close to the critical shear stress, {sigma}{sub s}, the dislocation glide is analysed with a 'stop and go' model. The latter yields the flight velocity between obstacles, the mean obstacle density and the distribution of the waiting time on each obstacle as a function of stress, composition and temperature. The obstacle to the glide is proposed to be the strong repulsion between Al atoms brought into nearest neighbour position by the glide process, and not the dislocation-solute interaction. The microscopic parameters so defined are introduced into a micro-mechanical model, which well reproduces the known behaviour of nickel base solid solutions. (author)

  8. Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

    Energy Technology Data Exchange (ETDEWEB)

    Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang; Assary, Rajeev S.; Kowalski, Jeffrey A.; Barton, John L.; Bertke, Jeffery A.; Gray, Danielle L.; Brushett, Fikile R.; Curtiss, Larry A.; Moore, Jeffrey S.

    2016-03-31

    Following the discovery of the redox-active 1,4- bis-BF3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1D and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.

  9. Electrical conductivity in single crystals of GaSe x Te1 - x solid solutions in strong electrical fields

    Science.gov (United States)

    Tagiev, B. G.; Tagiev, O. B.

    2017-06-01

    This paper presents some results of studying the Poole-Frenkel effect with allowance for shielding in layered GaSe and GaTe single crystals and their solid solutions in strong electrical fields of up to 105 V/cm at temperatures of 103-250 K. According to the relationship (σ/σ(0))^{1/2} logσ/σ(0) = E√{ɛ/4π n(0)kT}, there exists a linear dependence between (σ/σ(0))^{1/2} logσ/σ(0) and the electrical field E (σ is the electrical conductivity in strong electrical fields, and σ(0) is the electrical conductivity in the ohmic region). The slopes of these lines have been determined at different temperatures (103-250 K) by estimating the concentration of current carriers n(0) = 3 × 1013-5 × 1015 cm-3 in the ohmic region of the electrical conductivity of solid solutions of layered GaSe x Te1- x single crystals ( x = 1.00, 0.95, 0.90, 0.80, 0.70, 0.30, 0.20, 0.10, 0).

  10. Hydrogen storage and stability properties of Pd-Pt solid-solution nanoparticles revealed via atomic and electronic structure.

    Science.gov (United States)

    Kumara, Loku Singgappulige Rosantha; Sakata, Osami; Kobayashi, Hirokazu; Song, Chulho; Kohara, Shinji; Ina, Toshiaki; Yoshimoto, Toshiki; Yoshioka, Satoru; Matsumura, Syo; Kitagawa, Hiroshi

    2017-11-06

    Bimetallic Pd1-x Pt x solid-solution nanoparticles (NPs) display charging/discharging of hydrogen gas, which has relevance for fuel cell technologies; however, the constituent elements are immiscible in the bulk phase. We examined these material systems using high-energy synchrotron X-ray diffraction, X-ray absorption fine structure and hard X-ray photoelectron spectroscopy techniques. Recent studies have demonstrated the hydrogen storage properties and catalytic activities of Pd-Pt alloys; however, comprehensive details of their structural and electronic functionality at the atomic scale have yet to be reported. Three-dimensional atomic-scale structure results obtained from the pair distribution function (PDF) and reverse Monte Carlo (RMC) methods suggest the formation of a highly disordered structure with a high cavity-volume-fraction for low-Pt content NPs. The NP conduction band features, as extracted from X-ray absorption near-edge spectra at the Pd and Pt L III -edge, suggest that the Pd conduction band is filled by Pt valence electrons. This behaviour is consistent with observations of the hydrogen storage capacity of these NPs. The broadening of the valence band width and the down-shift of the d-band centre away from the Fermi level upon Pt substitution also provided evidence for enhanced stability of the hydride (ΔH) features of the Pd1-x Pt x solid-solution NPs with a Pt content of 8-21 atomic percent.

  11. Nonlinear photoluminescence of graded band-gap Al sub x Ga sub 1 sub - sub x As solid solutions

    CERN Document Server

    Kovalenko, V F; Shutov, S V

    2002-01-01

    The dependence of the photoluminescence (PL) intensity of undoped and doped graded band-gap Al sub x Ga sub 1 sub - sub x As (x <= 0.36) solid solutions on the excitation level J (1 x 10 sup 1 sup 9 <= J <= 1 x 10 sup 2 sup 2 quantum cm sup - sup 2 s) for different values of built-in quasi-electrical field E (85 <= E <= 700 V/cm) has been studied. It is found that the dependence of the near-band-edge PL intensity I in the excitation level J at an accelerating action of the field E has a complex character. The nonlinearity of I(J) dependence is explained by contribution of the two-photon absorption of the radiating recombination in the process of its remission. The optimum range of E values (120 <= E <= 200 V/cm) providing the greatest contribution of the two-photon absorption in the reemission in undoped solid solutions is determined

  12. Accurate solid solution range of BiMnxFe3-xO6 and low temperature magnetism

    Science.gov (United States)

    Jiang, Pengfei; Yue, Mufei; Cong, Rihong; Gao, Wenliang; Yang, Tao

    2017-11-01

    BiMnxFe3-xO6 (x = 1) represents a new type of oxide structure containing Bi3+ and competing magnetic super-exchanges. In literature, multiple magnetic states were realized at low temperatures in BiMnFe2O6, and the hypothetical parent compounds (BiMn3O6, BiFe3O6) were predicted to be different in magnetism. Herein, we performed a careful study on the syntheses of BiMnxFe3-xO6 at ambient pressure, and the solid solution range was determined to be 0.9 ≤ x ≤ 1.3 by Rietveld refinements on high-quality powder X-ray diffraction data. Due to the very similar cationic size of Mn3+ and Fe3+, and possibly the structural rigidity, there was no significant structure change in the whole range of solid solution. The magnetic behavior of BiMnxFe3-xO6 (x = 1.2, 1.22, 1.26, 1.28 and 1.3) was generally similar to BiMnFe2O6, while the relative higher concentration of Mn3+ led to the decreasing of the antiferromagnetic ordering temperature.

  13. Atomistic simulations of nanocrystalline U0.5Th0.5O2 solid solution under uniaxial tension

    Directory of Open Access Journals (Sweden)

    Hongxing Xiao

    2017-12-01

    Full Text Available Molecular dynamics simulations were performed to investigate the uniaxial tensile properties of nanocrystalline U0.5Th0.5O2 solid solution with the Born–Mayer–Huggins potential. The results indicated that the elastic modulus increased linearly with the density relative to a single crystal, but decreased with increasing temperature. The simulated nanocrystalline U0.5Th0.5O2 exhibited a breakdown in the Hall–Petch relation with mean grain size varying from 3.0 nm to 18.0 nm. Moreover, the elastic modulus of U1-yThyO2 solid solutions with different content of thorium at 300 K was also studied and the results accorded well with the experimental data available in the literature. In addition, the fracture mode of nanocrystalline U0.5Th0.5O2 was inclined to be ductile because the fracture behavior was preceded by some moderate amount of plastic deformation, which is different from what has been seen earlier in simulations of pure UO2.

  14. Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

    Energy Technology Data Exchange (ETDEWEB)

    Sumner, S.C.J.

    1986-01-01

    Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemic mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.

  15. Bi(1-x)Ni(x)VO(4-y) Solid Solution with a High Visible-Light Photocatalytic Activity for Degradation Methyl Orange.

    Science.gov (United States)

    Wang Jing; Wei, Yuelin; Huang, Yunfang; Wu, Jihuai; Dong, Qiang; Yin, Shu; Sato, Tsugio

    2015-09-01

    Particulate solid solutions Bi(1-x)Ni(x)VO(4-y) were synthesized by solid-state reaction at high temperature. The samples were characterized by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectrometer (EDS), Brunauer-Emmett-Teller (BET) surface area and Ultraviolet-Visible spectroscopy (UV-Vis). The photocatalytic activity of BiVO4 for photocatalytic degradation of organic contaminants ability in visible light region could be improved by doping of Ni(2+). The high visible light photocatalytic activity of Bi(1-x)Ni(x)VO(4-y) solid solution might be due to the generation of a new band gap and expanding the range of visible light response. It was suggested that the Ni(2+) doping was beneficial to effective charge separation of Bi(1-x)Ni(x)VO(4-y) solid solution, thus improved the photocatalytic activity.

  16. Characterization of Solid Dispersion of Itraconazole Prepared by Solubilization in Concentrated Aqueous Solutions of Weak Organic Acids and Drying.

    Science.gov (United States)

    Parikh, Tapan; Sandhu, Harpreet K; Talele, Tanaji T; Serajuddin, Abu T M

    2016-06-01

    The purpose of this study was to develop an amorphous solid dispersion (SD) of an extremely water-insoluble and very weakly basic drug, itraconazole (ITZ), by interaction with weak organic acids and then drying that would enhance dissolution rate of drug and physical stability of formulation. Aqueous solubility of ITZ in concentrated solutions of weak organic acids, such as glutaric, tartaric, malic and citric acid, was determined. Solutions with high drug solubility were dried using vacuum oven and the resulting SDs having 2 to 20% drug load were characterized by differential scanning calorimetry (DSC), powder X-ray diffractometry (PXRD) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The dissolution of SDs was initially studied in 250 mL of 0.1 N HCl (pH 1.1), and any undissolved solids were collected and analyzed by PXRD. The pH of the dissolution medium was then changed from 1.1 to 5.5, particle size of precipitates were measured, and drug concentrations in solution were determined by filtration through membrane filters of varying pore sizes. The aqueous solubility of ITZ was greatly enhanced in presence of weak acids. While the solubility of ITZ in water was ~4 ng/ mL, it increased to 25-40 mg per g of solution at 25°C and 200 mg per g of solution at 65°C at a high acid concentration leading to extremely high solubilization. PXRD of SDs indicated that ITZ was present in the amorphous form, wherein the acid formed a partially crystalline matrix. ATR-FTIR results showed possible weak interactions, such as hydrogen bonding, between drug and acid but there was no salt formation. SDs formed highly supersaturated solutions at pH 1.1 and had superior dissolution rate as compared to amorphous drug and physical mixtures of drug and acids. Following the change in pH from 1.1 to 5.5, ITZ precipitated as mostly nanoparticles, providing high surface area for relatively rapid redissolution. A method of highly solubilizing an

  17. Chemical preparation of crystalline, nonmolecular solids, including solution-liquid-solid (SLS) growth of semiconductor fibers and varied routes to nanocrystalline molybdenum disilicide

    Science.gov (United States)

    Trentler, Timothy John

    New methods for the preparation of crystalline, nonmolecular solids under milder conditions and/or with control of crystallite size or morphology were developed in two separate projects. In one project, polycrystalline 13-15 semiconductor fibers (dimensions 10-100 nm x 50-1000 nm) were grown by solution-based chemical methods. Crystal precursor species of the general formula (Rsb{x}InEHsb{x}rbracksb{n}, where E is a pnictide and R is an alkyl group, were prepared by the phosphinolysis or arsinolysis of alkylindanes in aromatic solvents. Thermal decomposition of these precursors in solution, which was catalyzed by various protic reagents (MeOH, PhSH, Etsb2NH, or PhCOsb2H), resulted in crystalline InE when In metal was present in the form of submicron droplets dispersed in the solvent. Crystallization was determined to occur (at the lowest temperatures reported for 13-15 semiconductors, halides by NaK alloy in an ultrasonically agitated hydrocarbon solvent followed by thermal processing (900sp°C) under vacuum to eliminate byproduct salts. MoSisb2 crystallites averaging 20-50 nm were obtained. Solvent degradation during this process resulted in the incorporation of substantial carbonaceous impurity (believed to be SiC) in these products. To eliminate the carbon, similar solventless reductions (without ultrasound) were conducted in molten magnesium, but average particle sizes have not been refined into the nanometer regime (currently 100-200 nm). The second method was the reaction of MoClsb3 and Si in the solid state. These reactants underwent an ignition at approximately 500sp°C that resulted in the evolution of SiClsb4 and the formation of MoSisb2 crystallites. Crystallite size was dependent on reaction scale and was only nanocrystalline for very small scales. Addition of an inert salt to the reaction mixture, however, moderated the exothermic process and allowed for the preparation of nanocrystalline product (˜50 nm). Some of the nanocrystalline MoSisb2 powders

  18. From solid solution to cluster formation of Fe and Cr in α-Zr

    Energy Technology Data Exchange (ETDEWEB)

    Burr, P.A., E-mail: burr.patrick@gmail.com [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London, SW7 2AZ (United Kingdom); Institute of Materials Engineering, Australian Nuclear Science & Technology Organisation, Menai, New South Wales 2234 (Australia); Wenman, M.R. [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London, SW7 2AZ (United Kingdom); Gault, B.; Moody, M.P. [Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH (United Kingdom); Ivermark, M. [High Temperature Materials, Sandvik Materials Technology, 734 27 Hallstahammar (Sweden); University of Manchester, School of Materials, M13 9PL (United Kingdom); Rushton, M.J.D. [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London, SW7 2AZ (United Kingdom); Preuss, M. [University of Manchester, School of Materials, M13 9PL (United Kingdom); Edwards, L. [Institute of Materials Engineering, Australian Nuclear Science & Technology Organisation, Menai, New South Wales 2234 (Australia); Grimes, R.W. [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London, SW7 2AZ (United Kingdom)

    2015-12-15

    To understand the mechanisms by which the re-solution of Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, the solubility and clustering of Fe and Cr in model binary Zr alloys was investigated using a combination of experimental and modelling techniques — atom probe tomography (APT), x-ray diffraction (XRD), thermoelectric power (TEP) and density functional theory (DFT). Cr occupies both interstitial and substitutional sites in the α-Zr lattice; Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of Fe and Cr content in the α-Zr matrix deviates from Vegard's law and is strongly anisotropic for Fe additions, expanding the c-axis while contracting the a-axis. Matrix content of solutes cannot be reliably estimated from lattice parameter measurements, instead a combination of TEP and APT was employed. Defect clusters form at higher solution concentrations, which induce a smaller lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased apparent solubility of defect clusters; the implications for irradiation induced microstructure changes in Zr alloys are discussed.

  19. General traveling wave solutions of the strain wave equation in microstructured solids via the new approach of generalized (G′/G-expansion method

    Directory of Open Access Journals (Sweden)

    Md. Nur Alam

    2014-03-01

    Full Text Available The new approach of generalized (G′/G-expansion method is significant, powerful and straightforward mathematical tool for finding exact traveling wave solutions of nonlinear evolution equations (NLEEs arise in the field of engineering, applied mathematics and physics. Dispersive effects due to microstructure of materials combined with nonlinearities give rise to solitary waves. In this article, the new approach of generalized (G′/G-expansion method has been applied to construct general traveling wave solutions of the strain wave equation in microstructured solids. Abundant exact traveling wave solutions including solitons, kink, periodic and rational solutions have been found. These solutions might play important role in engineering fields.

  20. Structural analysis and magnetic properties of solid solutions of Co–Cr system obtained by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Betancourt-Cantera, J.A. [Área Académica de Ciencias de la Tierra y Materiales, UAEH Carr., Pachuca-Tulancingo Km. 4.5, Pachuca, Hidalgo 42184 (Mexico); Sánchez-De Jesús, F., E-mail: fsanchez@uaeh.edu.mx [Área Académica de Ciencias de la Tierra y Materiales, UAEH Carr., Pachuca-Tulancingo Km. 4.5, Pachuca, Hidalgo 42184 (Mexico); Bolarín-Miró, A.M. [Área Académica de Ciencias de la Tierra y Materiales, UAEH Carr., Pachuca-Tulancingo Km. 4.5, Pachuca, Hidalgo 42184 (Mexico); Betancourt, I.; Torres-Villaseñor, G. [Departamento de Materiales Metálicos y Cerámicos, Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, México D.F. 04510 (Mexico)

    2014-03-15

    In this paper, a systematic study on the structural and magnetic properties of Co{sub 100−x}Cr{sub x} alloys (0solid solutions based on Co-hcp, Co-fcc and Cr-bcc structures were obtained. The saturation polarization indicated a maximum value of 1.17 T (144 Am{sup 2}/kg) for the Co{sub 90}Cr{sub 10}, which decreases with the increasing of the Cr content up to x=80, as a consequence of the dilution effect of the magnetic moment which is caused by the Cr content and by the competition between ferromagnetic and antiferromagnetic exchange interactions. The coercivity increases up to 34 kA/m (435 Oe) for Co{sub 40}Cr{sub 60}. For Cr rich compositions, it is observed an important decrease reaching 21 kA/m (272 Oe) for Co{sub 10}Cr{sub 90,} it is related to the grain size and the structural change. Besides, the magnetic anisotropy constant was determined for each composition. Magnetic thermogravimetric analysis allowed to obtain Curie temperatures corresponding to the formation of hcp-Co(Cr) and fcc-Co(Cr) solid solutions. - Highlights: • Mechanical alloying (MA) induces the formation of solid solutions of Co–Cr system in non-equilibrium. • We report the crystal structure and the magnetic behavior of Co–Cr alloys produced by MA. • MA improves the magnetic properties of Co–Cr system.

  1. Structure induced Yb valence changes in the solid solution Yb(x)Ca(1-x)C2.

    Science.gov (United States)

    Link, Pascal; Glatzel, Pieter; Kvashnina, Kristina; Trots, Dmytro M; Smith, Ronald I; Ruschewitz, Uwe

    2013-06-17

    The solid solution Yb(x)Ca(1-x)C2 (0 ≤ x ≤ 1) was synthesized by reaction of the elements at 1323 K. The crystal structures within this solid solution, as elucidated from synchrotron powder diffraction data, depend on x and exhibit some interesting features that point to a structure dependent valence state of Yb. Compounds with x ≥ 0.75 crystallize in the tetragonal CaC2 type structure (I4/mmm, Z = 2) and obey Vegard's law; for x ≤ 0.75 the monoclinic ThC2 type structure (C2/c, Z = 4) is found, which coexists with the monoclinic CaC2-III type structure (C2/m, Z = 4) for x ≤ 0.25. The monoclinic modifications show a strong deviation from Vegard's law. Their unit cell volumes are remarkably larger than expected for a typical Vegard system. HERFD-XANES spectroscopic investigations reveal that different Yb valence states are responsible for the observed volume anomalies. While all tetragonal compounds contain mixed-valent Yb with ∼75% Yb(3+) (similar to pure YbC2), all monoclinic modifications contain exclusively Yb(2+). Therefore, Yb(x)Ca(1-x)C2 is a very rare example of a Yb containing compound showing a strong structure dependence of the Yb valence state. Moreover, temperature dependent synchrotron powder diffraction, neutron TOF powder diffraction, and HERFD-XANES spectroscopy experiments reveal significant Yb valence changes in some compounds of the Yb(x)Ca(1-x)C2 series that are induced by temperature dependent phase transitions. Transitions from the tetragonal CaC2 type structure to the monoclinic ThC2 or the cubic CaC2-IV type structure (Fm3m, Z = 4) are accompanied by drastic changes of the mean Yb valence from ∼2.70 to 2.0 in compounds with x = 0.75 and x = 0.91. Finally, the determination of lattice strain arising inside the modifications with ordered dumbbells (ThC2 and CaC2 type structures) by DSC measurements corroborated our results concerning the close relationship between crystal structure and Yb valence in the solid solution Yb(x)Ca(1-x

  2. Decay property of regularity-loss type of solutions in elastic solids with voids

    KAUST Repository

    Said-Houari, Belkacem

    2013-12-01

    In this article, we consider two porous systems of nonclassical thermoelasticity in the whole real line. We discuss the long-time behaviour of the solutions in the presence of a strong damping acting, together with the heat effect, on the elastic equation and establish several decay results. Those decay results are shown to be very slow and of regularity-loss type. Some improvements of the decay rates have also been given, provided that the initial data belong to some weighted spaces. © 2013 Copyright Taylor and Francis Group, LLC.

  3. Miscibility Studies of Hydroxypropyl Cellulose/Poly(Ethylene Glycol in Dilute Solutions and Solid State

    Directory of Open Access Journals (Sweden)

    K. Sudharsan Reddy

    2012-01-01

    Full Text Available The miscibility of Hydroxypropyl cellulose (HPC/poly(ethylene glycol (PEG blends over an extended range of concentrations in water. The viscosity, ultrasonic velocity, and refractive index of the above blend solutions have been measured at 30°C. The interaction parameters such as and μ proposed by Chee and α proposed by Sun have been obtained using the viscosity data to probe the miscibility of the polymer blends. The values indicated that the blends were miscible when HPC content is more than 40% in the blend. The obtained results have been confirmed by the ultrasonic velocity and refractive index studies. The films of the blends were prepared by solution casting method using water as a solvent. The prepared films have been characterized by analytical techniques such as FTIR, DSC, X-RD, and SEM to probe the miscibility of HPC/PEG blends. The compatibility in the above compositions may be due to the formation of H-bonding between hydroxyl groups of HPC and etheric oxygen atom of PEG molecules.

  4. Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state

    Science.gov (United States)

    El-Kemary, Maged; Sobhy, Saffaa; El-Daly, Samy; Abdel-Shafi, Ayman

    2011-09-01

    We report on steady-state UV-visible absorption and emission characteristics of Paracetamol, drug used as antipyretic agent, in water and within cyclodextrins (CDs): β-CD, 2-hydroxypropyl- β-CD (HP- β-CD) and 2,6-dimethyl- β-CD (Me- β-CD). The results reveal that Paracetamol forms a 1:1 inclusion complex with CD. Upon encapsulation, the emission intensity enhances, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the Me- β-CD shows the largest effect for the drug. The observed binding constant showing the following trend: Me- β-CD > HP- β-CD > β-CD. The less complexing effectiveness of HP- β-CD is due to the steric effect of the hydroxypropyl-substituents, which can hamper the inclusion of the guest molecules. The solid state inclusion complex was prepared by co-precipitation method and its characterization was investigated by Fourier transform infrared spectroscopy, 1H NMR and X-ray diffractometry. These approaches indicated that Paracetamol was able to form an inclusion complex with CDs, and the inclusion compounds exhibited different spectroscopic features and properties from Paracetamol.

  5. On the solid, liquid and solution structural organization of imidazolium ionic liquids

    Directory of Open Access Journals (Sweden)

    Dupont Jairton

    2004-01-01

    Full Text Available 1,3-dialkyl imidazolium salts are one of the most popular and investigated classes of room temperature ionic liquids. Although in various cases the physical-chemical properties and/or the outcome of the processes in these liquids significantly differ from those performed in "classical" dipolar organic solvents, they are still regarded as merely homogeneous solvents. In this brief overview it is developed the concept that pure 1,3-dialkylimidazolium ionic liquids are better described as hydrogen-bonded polymeric supramolecules of the type {[(DAIx(Xx-n] n+ [(DAIx-n(Xx] n-}n where DAI is the 1,3-dialkylimidazolium cation and X the anion. This structural pattern is a general trend for the solid phase and is maintained to a great extent in the liquid phase and even in the gas phase. The introduction of other molecules and macromolecules occurs with a disruption of the hydrogen bond network and in some cases can generate nano-structures with polar and non-polar regions where inclusion-type compounds can be formed.

  6. Hopping conduction via highly localized impurity states of indium in PbTe and its solid solutions. Review

    CERN Document Server

    Ravich, Y I

    2002-01-01

    Results of experimental investigation of the transport phenomena in PbTe and Pb sub 1 sub - sub x Sn sub x Te solid solutions with high contents of In impurity (up to 20 at %) at temperatures up to 400 K have been considered. An analysis of the experimental data has been made on the base of an idea of hopping conductivity via highly localized impurity states creates by indium atoms. The temperature dependences of transport coefficients unusual for the IV-VI-type semiconductors, the change of sing of the thermoelectromotive force at negative Hall coefficient, the positive Nernst-Ettingshausen coefficient are explained. The activation energy of the hoping conductivity, characterizing discrepancy between impurity energy levels the effective wave function radius and the density of localized states as the energy function are found experimentally

  7. Simulation of ceramic materials relevant for nuclear waste management: Case of La1-xEuxPO4 solid solution

    Science.gov (United States)

    Kowalski, Piotr M.; Ji, Yaqi; Li, Yan; Arinicheva, Yulia; Beridze, George; Neumeier, Stefan; Bukaemskiy, Andrey; Bosbach, Dirk

    2017-02-01

    Using powerful computational resources and state-of-the-art methods of computational chemistry we contribute to the research on novel nuclear waste forms by providing atomic scale description of processes that govern the structural incorporation and the interactions of radionuclides in host materials. Here we present various results of combined computational and experimental studies on La1-xEuxPO4 monazite-type solid solution. We discuss the performance of DFT + U method with the Hubbard U parameter value derived ab initio, and the derivation of various structural, thermodynamic and radiation-damage related properties. We show a correlation between the cation displacement probabilities and the solubility data, indicating that the binding of cations is the driving factor behind both processes. The combined atomistic modeling and experimental studies result in a superior characterization of the investigated material.

  8. Infrared Optical Properties of β-Spodumene Solid Solution Glass-Ceramic for Fiber-Optic Devices

    Science.gov (United States)

    Sakamoto, Akihiko; Yamamoto, Shigeru

    2006-09-01

    The IR optical properties of an opaque β-spodumene solid solution (s.s.) glass-ceramic for fiber-optic devices were studied in relation to its refractive indices in both crystalline and glass phases. We investigated the refractive indices of both phases on the basis of IR transmittance change due to the structural relaxation of the glass phase. The refractive indices of this β-spodumene s.s. glass-ceramic at a wavelength of 1550 nm in the crystalline and glass phases were first determined to be 1.530 and 1.495, respectively. It was found from the refractive index data that the optical scattering intensity of this glass-ceramic approximately follows the Rayleigh-Gans model. We also demonstrated that the inner diameter of an opaque glass-ceramic capillary used in optical fiber connectors can be optically measured with a sub-micrometer accuracy using an IR laser.

  9. Multidrug, Anti-HIV Amorphous Solid Dispersions: Nature and Mechanisms of Impacts of Drugs on Each Other's Solution Concentrations.

    Science.gov (United States)

    Arca, Hale Çiğdem; Mosquera-Giraldo, Laura I; Dahal, Durga; Taylor, Lynne S; Edgar, Kevin J

    2017-09-25

    Drug therapy has been instrumental in prolonging the lives of patients infected by human immunodeficiency virus (HIV). In order to combat development of resistance, therapies involving three or more drugs in combination are recommended by the World Health Organization (WHO) to suppress HIV and prevent development of acquired immune deficiency syndrome (AIDS). It is desirable for multidrug combinations to be coformulated into single dosage forms where possible, to promote patient convenience and adherence to dosage regimens, for which amorphous solid dispersion (ASD) is particularly well-suited. We investigated multidrug ASDs of three model anti-HIV drugs, ritonavir (Rit), etravirine (Etra), and efavirenz (Efa), in cellulosic polymer matrices. We hypothesized that the presence of multiple drugs would reduce crystallization tendency, thereby providing stable, supersaturating formulations for bioavailability enhancement. We explored new ASD polymers including cellulose acetate suberate (DSSub 0.9, CASub) and cellulose acetate adipate propionate (DSAd 0.9, CAAdP), and control commercial cellulosic polymers including 6-carboxycellulose acetate butyrate (CCAB) and carboxymethyl cellulose acetate butyrate (CMCAB). We succeeded in preparing three-drug ASDs containing very high drug loadings (45% drug total; 15% of each drug); each polymer tested was effective at stabilizing the amorphous drugs in the solid phase, as demonstrated by XRD, SEM, and DSC studies. In pH 6.8 dissolution studies ASDs released each anti-HIV drug over 8 h, affording supersaturated solutions of each drug, but unexpectedly failing in some cases to reach maximum possible supersaturation. In a second set of dissolution studies (pH 6.8), the cause of the observed solution concentration limitations was investigated by studying release from single- and two-drug ASDs. Concentrations of Rit, Etra, and Efa achieved from three-drug ASDs were higher than those achieved from crystalline drugs. Surprisingly

  10. Oligo(p-phenylenevinylene)-peptide conjugates: synthesis and self-assembly in solution and at the solid-liquid interface.

    Science.gov (United States)

    Matmour, Rachid; De Cat, Inge; George, Subi J; Adriaens, Wencke; Leclère, Philippe; Bomans, Paul H H; Sommerdijk, Nico A J M; Gielen, Jeroen C; Christianen, Peter C M; Heldens, Jeroen T; van Hest, Jan C M; Löwik, Dennis W P M; De Feyter, Steven; Meijer, E W; Schenning, Albertus P H J

    2008-11-05

    Two oligo(p-phenylenevinylene)-peptide hybrid amphiphiles have been synthesized using solid- and liquid-phase strategies. The amphiliphiles are composed of a pi-conjugated oligo(p-phenylenevinylene) trimer (OPV) which is coupled at either a glycinyl-alanyl-glycinyl-alanyl-glycine (GAGAG) silk-inspired beta-sheet or a glycinyl-alanyl-asparagyl-prolyl-asparagy-alanyl-alanyl-glycine (GANPNAAG) beta-turn forming oligopeptide sequence. The solid-phase strategy enables one to use longer peptides if strong acidic conditions are avoided, whereas the solution-phase coupling gives better yields. The study of the two-dimensional (2D) self-assembly of OPV-GAGAG by scanning tunneling microscopy (STM) at the submolecular level demonstrated the formation of bilayers in which the molecules are lying antiparallel in a beta-sheet conformation. In the case of OPV-GANPNAAG self-assembled monolayers could not be observed. Absorption, fluorescence, and circular dichroism studies showed that OPV-GAGAG and OPV-GANPNAAG are aggregated in a variety of organic solvents. In water cryogenic temperature transmission electron microscopy (cryo-TEM), atomic force microscopy (AFM), light scattering, and optical studies reveal that self-assembled nanofibers are formed in which the helical organization of the OPV segments is dictated by the peptide sequence.

  11. Structural Behaviour of Solid Solutions in the NdAlO3-SrTiO3 System

    Science.gov (United States)

    Ohon, Natalia; Stepchuk, Roman; Blazhivskyi, Kostiantyn; Vasylechko, Leonid

    2017-02-01

    Single-phase mixed aluminates-titanates Nd1- x Sr x Al1- x Ti x O3 ( x = 0.3 ÷ 0.9) were prepared from stoichiometric amounts of constituent oxides Nd2O3, Al2O3, TiO2 and strontium carbonate SrCO3 by solid-state reaction technique in air at 1773 K. Crystal structure parameters of Nd1- x Sr x Al1- x Ti x O3 were refined by full-profile Rietveld refinement in space groups R overline{3} c ( x = 0.3, 0.5, 0.7 and 0.8) and Pm overline{3} m ( x = 0.9). Comparison of the obtained structural parameters with the literature data for the end members of the system NdAlO3 and SrTiO3 revealed formation of two kinds of solid solutions Nd1-xSrxAl1-xTixO3 with the cubic and rhombohedral perovskite structure. Morphotropic rhombohedral-to-cubic phase transition in Nd1-xSrxAl1-xTixO3 series occurs at x = 0.84. Based on the results obtained as well as the literature data for the parent compounds, the tentative phase diagram of the NdAlO3-SrTiO3 pseudo-binary system have been constructed.

  12. Machine learning assisted first-principles calculation of multicomponent solid solutions: estimation of interface energy in Ni-based superalloys

    Science.gov (United States)

    Chandran, Mahesh; Lee, S. C.; Shim, Jae-Hyeok

    2018-02-01

    A disordered configuration of atoms in a multicomponent solid solution presents a computational challenge for first-principles calculations using density functional theory (DFT). The challenge is in identifying the few probable (low energy) configurations from a large configurational space before DFT calculation can be performed. The search for these probable configurations is possible if the configurational energy E({\\boldsymbol{σ }}) can be calculated accurately and rapidly (with a negligibly small computational cost). In this paper, we demonstrate such a possibility by constructing a machine learning (ML) model for E({\\boldsymbol{σ }}) trained with DFT-calculated energies. The feature vector for the ML model is formed by concatenating histograms of pair and triplet (only equilateral triangle) correlation functions, {g}(2)(r) and {g}(3)(r,r,r), respectively. These functions are a quantitative ‘fingerprint’ of the spatial arrangement of atoms, familiar in the field of amorphous materials and liquids. The ML model is used to generate an accurate distribution P(E({\\boldsymbol{σ }})) by rapidly spanning a large number of configurations. The P(E) contains full configurational information of the solid solution and can be selectively sampled to choose a few configurations for targeted DFT calculations. This new framework is employed to estimate (100) interface energy ({σ }{{IE}}) between γ and γ \\prime at 700 °C in Alloy 617, a Ni-based superalloy, with composition reduced to five components. The estimated {σ }{{IE}} ≈ 25.95 mJ m‑2 is in good agreement with the value inferred by the precipitation model fit to experimental data. The proposed new ML-based ab initio framework can be applied to calculate the parameters and properties of alloys with any number of components, thus widening the reach of first-principles calculation to realistic compositions of industrially relevant materials and alloys.

  13. Structural and Microstructural Correlations of Physical Properties in Natural Almandine-Pyrope Solid Solution: Al70Py29

    Science.gov (United States)

    Sibi, N.; Subodh, G.

    2017-09-01

    Garnets are naturally occurring minerals with the general formula X3Y2Z3O12 having various applications. In the present study, the structural and physical properties of a garnet mineral obtained from Indian Rare Earth Ltd., Manavalakurichi, Tamil Nadu, India were comprehensively investigated. The compositional analysis using electron probe micro analysis (EPMA) revealed that the mineral belongs to almandine-pyrope solid solution (Al70Py29) with the chemical formula (Fe1.72Mg0.8Mn0.01Ca0.02) (Fe0.04Al2.36) Si2.93O12. Rietveld refinement of the x-ray diffraction pattern confirms that the space group is Ia{ - }\\overline{3} d with refined cubic lattice parameter a = 11.550(4) Å. The refined occupancy values of multiple cations in the dodecahedral and octahedral sites are in agreement with the EPMA data. Fourier transform infrared and FT Raman spectra show bands corresponding to almandine-pyrope solid solution. Peak splitting of IR and Raman bands confirms presence of multiple cations in the dodecahedral site. Thermogravimetric/differential thermal analysis shows that the mineral is stable up to 600°C in spite of the presence of Fe2+ ions. Low temperature magnetic susceptibility data is in agreement with the amount of Fe2+ ions present in the mineral. The dielectric constant of the mineral varied from 6 to 16.5 when sintered at temperatures ranging from 600°C to 1250°C.

  14. Evolution of magnetic properties in the normal spinel solid solution Mg(1-x)Cu(x)Cr2O4.

    Science.gov (United States)

    Kemei, Moureen C; Moffitt, Stephanie L; Shoemaker, Daniel P; Seshadri, Ram

    2012-02-01

    We examine the evolution of magnetic properties in the normal spinel oxides Mg(1-x)Cu(x)Cr2O4 using magnetization and heat capacity measurements. The end-member compounds of the solid solution series have been studied in some detail because of their very interesting magnetic behavior. MgCr2O4 is a highly frustrated system that undergoes a first-order structural transition at its antiferromagnetic ordering temperature. CuCr2O4 is tetragonal at room temperature as a result of Jahn-Teller active tetrahedral Cu2+ and undergoes a magnetic transition at 135 K. Substitution of magnetic cations for diamagnetic Mg2+ on the tetrahedral A site in the compositional series Mg(1-x)Cu(x)Cr2O4 dramatically affects magnetic behavior. In the composition range 0 ≤ x ≤ ≈0.3, the compounds are antiferromagnetic. A sharp peak observed at 12.5 K in the heat capacity of MgCr2O4 corresponding to a magnetically driven first-order structural transition is suppressed even for small x. Uncompensated magnetism--with open magnetization loops--develops for samples in the x range ≈0.43 ≤ x ≤ 1. Multiple magnetic ordering temperatures and large coercive fields emerge in the intermediate composition range 0.43 ≤ x ≤ 0.47. The Néel temperature increases with increasing x across the series while the value of the Curie-Weiss Θ(CW) decreases. A magnetic temperature-composition phase diagram of the solid solution series is presented.

  15. Evolution of magnetic properties in the normal spinel solid solution Mg1-xCuxCr2O4

    Science.gov (United States)

    Kemei, Moureen C.; Moffitt, Stephanie L.; Shoemaker, Daniel P.; Seshadri, Ram

    2012-02-01

    We examine the evolution of magnetic properties in the normal spinel oxides Mg1-xCuxCr2O4 using magnetization and heat capacity measurements. The end-member compounds of the solid solution series have been studied in some detail because of their very interesting magnetic behavior. MgCr2O4 is a highly frustrated system that undergoes a first-order structural transition at its antiferromagnetic ordering temperature. CuCr2O4 is tetragonal at room temperature as a result of Jahn-Teller active tetrahedral Cu2+ and undergoes a magnetic transition at 135 K. Substitution of magnetic cations for diamagnetic Mg2+ on the tetrahedral A site in the compositional series Mg1-xCuxCr2O4 dramatically affects magnetic behavior. In the composition range 0 ≤ x ≤≈ 0.3, the compounds are antiferromagnetic. A sharp peak observed at 12.5 K in the heat capacity of MgCr2O4 corresponding to a magnetically driven first-order structural transition is suppressed even for small x. Uncompensated magnetism—with open magnetization loops—develops for samples in the x range ≈0.43 ≤ x ≤ 1. Multiple magnetic ordering temperatures and large coercive fields emerge in the intermediate composition range 0.43 ≤ x ≤ 0.47. The Néel temperature increases with increasing x across the series while the value of the Curie-Weiss ΘCW decreases. A magnetic temperature-composition phase diagram of the solid solution series is presented.

  16. Ligand effects on ESR and optical properties of gold atoms in gamma irradiated organic solid solutions at 77 K.

    Science.gov (United States)

    Hase, Yoko Miyatake; Ito, Yoshitaka; Tajima, Yusuke

    2005-10-13

    Ligand effects on ESR and optical properties of Au0 atoms produced at 77 K in gamma irradiated solid solutions of AuCl/MTHF and AuCl/EtOH with and without HCl were investigated. Four groups of ESR lines were observed at 73 K more clearly around the magnetic fields at about 250, 280, 340, and 400 mT for both gamma irradiated MTHF and EtOH solid solutions with HCl than those without HCl. The values of a and g(J) calculated by Breit-Rabi analysis showed a remarkable dependence on the solvent polarity. It was confirmed that the signals were the hyperfine quartet corresponding to the transitions between the Zeeman levels of Au0 atoms with nuclear spin of 3/2 in the ground state, 2S(1/2). It was also confirmed that Au0 atoms produced after gamma irradiation were located in the nuclear environment of isotropic interaction with surrounding ligand molecules. Delocalization of the unpaired spin density of Au0 onto ligands is found to be as large as one in the case of Cu0 atoms. Our previous hypothesis of the occurrence of configuration mixing of d valence orbital into the wave function of the atom in its 2S(1/2) was strongly supported. The dependence of the ESR, optical absorption, and the steady-state emission and excitation characteristics on solvent polarity was cleared in this study. We observed two kinds of emissions i.e., a band at 385 nm and a set of emission bands at 456, 482, 484, and 520 nm. These correspond to two bands out of the six kinds of emissions observed previously. The bands were attributed to exciplex (Au0 x Ln...Au+)* and the excited Au0 atoms trapped in a large cavity, respectively. The negative counterion of Au+ of the gold compound plays an important role for the formation of the exciplexes.

  17. Use of complementary neutron techniques in studying the effect of a solid/liquid interface on bulk solution structures

    Energy Technology Data Exchange (ETDEWEB)

    Butler, P.D.; Hamilton, W.A.; Magid, L.J. [and others

    1996-12-31

    By appropriate combination of neutron scattering techniques, it is possible to obtain structural information at various distances from a solid/liquid interface and thus probe in some detail how the surface structures evolve into bulk structures. We have used neutron reflectometry (NR) with a newly developed shear cell, near surface small angle neutron scattering (NSSANS) again in combination with the new shear cell, and regular small angle neutron scattering (SANS) with a standard Couette shear cell to probe the structures formed in our aqueous surfactant systems and how they react to a flow field, particularly in the near surface region of a solid/liquid interface. We present data for a 20mM aqueous solutions of 70% cetyltrimethylammonium 3,5-dichlorobenzoate (abbreviated CTA3,5ClBz) and 30% CTAB. This system forms a very viscoelastic solution containing long threadlike micelles. NR only probes to a depth of about 0.5 {mu}m from the surface in these systems and clearly indicates that adsorbed onto the surface is, surfactant layer which is insensitive to shear. The depth probed by the NSSANS is on the order of 20-30 {mu}m and is determined by the transmission of the sample, the angle of incidence, and the wavelength. In this region, the rods align under shear into a remarkably well ordered hexagonal crystal. The SANS from the Couette cell averages over the entire sample, so that the signal is dominated by scattering from the bulk. While the near surface hexagonal structure is clearly visible, these data are not consistent with the crystal structure persisting throughout the bulk, leading to the postulate that the bulk structure is a two dimensional (2D) liquid where the rods align with the flow, but do not order in the other two dimensions.

  18. Structural and magnetic characterization of the complete delafossite solid solution (CuAlO₂)₁-x(CuCrO₂)x.

    Science.gov (United States)

    Barton, Phillip T; Seshadri, Ram; Knöller, Andrea; Rosseinsky, Matthew J

    2012-01-11

    We have prepared the complete delafossite solid solution series between diamagnetic CuAlO(2) and the t(2g)(3)frustrated antiferromagnet CuCrO(2). The evolution with composition x in CuAl(1-x)Cr(x)O(2) of the crystal structure and magnetic properties has been studied and is reported here. The room-temperature unit cell parameters follow the Végard law and increase with x as expected. The μ(eff) is equal to the Cr(3+) spin-only S = 3/2 value throughout the entire solid solution. Θ(CW) is negative, indicating that the dominant interactions are antiferromagnetic, and its magnitude increases with Cr substitution. For dilute Cr compositions, the nearest-neighbor exchange coupling constant J(BB) was estimated by mean-field theory to be 3.0 meV. Despite the sizable Θ(CW), long-range antiferromagnetic order does not develop until x is almost 1, and is preceded by glassy behavior. The data presented here, and those on dilute Al substitution from Okuda et al, suggest that the reduction in magnetic frustration due to the presence of non-magnetic Al does not have as dominant an effect on magnetism as chemical disorder and dilution of the magnetic exchange. For all samples, the 5 K isothermal magnetization does not saturate in fields up to 5 T and minimal hysteresis is observed. The presence of antiferromagnetic interactions is clearly evident in the sub-Brillouin behavior with a reduced magnetization per Cr atom. An inspection of the scaled Curie plot reveals that significant short-range antiferromagnetic interactions occur in CuCrO(2) above its Néel temperature, consistent with its magnetic frustration. Uncompensated short-range behavior is present in the Al-substituted samples and is likely a result of chemical disorder.

  19. Solid nanoarchitecture--Cu(II) solution: dynamics of the chemical communication.

    Science.gov (United States)

    Millesi, Salvatrice; Maccarrone, Giuseppe; Gulino, Antonino

    2015-03-07

    Molecular monolayers and similar nanoarchitectures represent a promising future of the nanotechnology. Many of these systems behave as stimuli responsive materials since they undergo readable changes upon external stimuli. Therefore, chemical communication between these systems and the surrounding environment is a field extremely important. In the present study we explored by optical read-out the chemical communication between a porphyrin monolayer covalently bound to a quartz substrate (hardware) and copper(II) ions (stimulus). Different physical states can be safely distinguished since the intensity of the Soret band (output) associated with a calculated distribution diagram provided the degree of porphyrin complexation and, therefore, of the state of the optically active system as a result of a solution mediated interfacial communication.

  20. Syntheses and high temperature phase transformation of alunite-natroalunite solid solution series. Myobanseki-natlium myobanseki koyotai no gosei to koon sohenka

    Energy Technology Data Exchange (ETDEWEB)

    Kawano, M. (Kagoshima University, Kagoshima (Japan). Faculty of Agriculture); Shimoda, S. (University of Tsukuba, Tsukuba (Japan). Institute of Geoscience); Tomita, K. (Kgoshima University, Kgoshima (Japan). Faculty of Science)

    1991-05-01

    This paper explains the syntheses of the alunite-natroalunite solid solution series and its mineralogical properties, precipitation condition and high temperature phase transformations by heat treatment. The alunite-natroalunite solid solution series were synthesized and deposited by precipitation from mixed solutions of potassium sulfate, sodium sulfate and aluminuim sulfate for reaction of two days at boiling temperature under atmospheric pressure. The K ions in the initial solution were preferentially taken into the structure during crystallization of the alunite, and amounts of products suddenly decreased with decreasing K mol percent of the solution. Structural changes of alunites were observed by the thermal treatment. At 530 degrees C, formation of KAL (SO {sub 2}){sub 2} from alunite and Al {sub 2} (SO {sub 4}){sub 3} from natroalunite occurred simultaneously with the removal of OH ions. 22 refs., 13 figs., 7 tabs.

  1. Characterization of nanostructured alpha-Fe2O3-SnO2 solid solutions prepared by high energy ball milling

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Lin, R.; Mørup, Steen

    1998-01-01

    Solid solutions of SnO2 in alpha-Fe2O3 with SnO2 contents up to 20+-4 mol% have been prepared by mechanical alloying of alpha-Fe2O3 and SnO2 powder blends. X-ray diffraction and Mossbauer spectroscopy investigations show that the mechanical milling results in alloying on an atomic scale...... and that true solid solution formation occurs. We suggest that the high defect concentration and the chemical enthalpy of Fe3+ -O2- -Sn4+ interfaces between nanostructured alpha-Fe2O3 and SnO2 regions may serve as a driving force for the formation of a solid solution in the immiscible ceramic system....

  2. Structural and Optical Investigations of Heterostructures Based on AlxGa1-xAsyP1-y:Si Solid Solutions Obtained by MOCVD

    Directory of Open Access Journals (Sweden)

    P. V. Seredin

    2014-01-01

    Full Text Available We investigated MOCVD epitaxial heterostructures based on AlxGa1−xAs ternary solid solutions, obtained in the range of compositions x~0.20–0.50 and doped with high concentrations of phosphorus and silicon atoms. Using the methods of high-resolution X-ray diffraction, scanning electron microscopy, X-ray microanalysis, Raman spectroscopy, and photoluminescence spectroscopy we have shown that grown epitaxial films represent five-component (AlxGa1−xAs1−yPy1−zSiz solid solutions. The implementation of silicon in solid solution with a concentration of ~ 0.01 at.% leads to the formation of the structure with deep levels, DX centers, the occurrence of which fundamentally affects the energy characteristics of received materials.

  3. Calcium-magnesium carbonate solid solutions from Holocene conglomerate cements and travertines in the Coast Range of California

    Science.gov (United States)

    Barnes, I.; O'Neil, J.R.

    1971-01-01

    Two calcium-magnesium carbonate solid solutions form Holocene travertines and conglomerate cements in fresh water stream channels of the Coast Range of California. Calcite does not yield the {015} diffraction maximum. The {006} diffraction maximum is lacking over most of the range of composition of calcite. Calcite has compositions from CaCO3 to Ca0.5Mg0.5CO3. Dolomite yields both the {006} and {015} diffraction maxima over its entire composition range, Ca0.6Mg0.4CO3 to Ca0.5Mg0.5CO3. The Ca-Mg carbonates form in isotopic equilibrium and thermodynamic disequilibrium from dispersion of Ca2+-rich water into CO32--rich water within the alluvium. The stable isotope data suggest that all the Mg-rich carbonates are primary precipitates and not a result of Mg-substitution in precursor CaCO3. There is a correlation between ??C13 and Mg content of the carbonates which predicts a 5%. fractionation of C13 between dolomite and calcite at sedimentary temperatures. C14 is incorporated in Ca-Mg carbonates forming from C13-poor meteoric waters and C13-rich waters from Cretaceous sediments. C14 ages of the Ca-Mg carbonates are apparent, and cannot be corrected to absolute values. Solution rates of calcite decrease with increasing MgCO3 content; dolomite dissolves slower than any calcite. ?? 1971.

  4. An analysis of the high-temperature phase structure of multiferroic solid solutions of the PFW–PT

    Directory of Open Access Journals (Sweden)

    Aleksandr A. Naberezhnov

    2016-10-01

    Full Text Available The temperature evolution of multiferroic solid solutions of the PFW–PT system, namely a (1–xPb(Fe2/3W1/3O3–(xPbTiO3 crystal structure where x = 0, 0.2, 0.3, has been studied by neutron powder diffraction in the region of the morphotropic phase boundary. The coexistence of cubic and tetragonal phases in the solutions with x = 0.2, 0.3 was found below T = 259 and 285K, respectively. As a result of the data treatment, the atom coordinates, the occupation factors and the temperature dependences of cell parameters were determined in the cubic perovskite phase. The refinement of the crystal structure in terms of ideal perovskite exhibited anomalously large Debye–Waller factors for the lead cations, indicating the appearance of random static displacements of these cations from the ideal perovskite (000 position. Using the split-ion model we estimated the value of Pb static shifts (∼0.1Å from their high-symmetry positions along the [110] direction. It was shown that these shifts decrease with increasing the PbTiO3 concentration.

  5. Effects of the Solid Solution Heat Treatment on the Corrosion Resistance Property of SSC13 Cast Alloy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kuk-Jin [Hi-Sten Co., Ltd., Gimhae (Korea, Republic of); Lim, Su Gun [Gyeongsang National University, Jinju (Korea, Republic of); Pak, S. J. [Gachon BioNano Research Institute, Gachon University, Sungnam (Korea, Republic of)

    2015-04-15

    Recently, Stainless steels have been increasingly selected as the fitting or the valve materials of water pipes as the human health issue is getting higher and higher. Therefore, the connectors attached at pipes to deliver water are exposed to more severe environments than the pipes because crevice or galvanic corrosion is apt to occur at the fittings or the valves. Effects of the solid solution annealing, cooling rate after this heat treatment, and passivation on the corrosion properties of the shell mold casted SSC13 (STS304 alloy equivalent) were studied. The heating and quenching treatment more or less reduced hardness but effectively improved corrosion resistance. It was explained by the reduction of delta ferrite contents. Independent of heat treatment, the chemical passivation treatment also lowered corrosion rate but the improvement of corrosion resistance depended on temperature and time for passivation treatment indicating that the optimum conditions for passivation treatment were the bath temperature of 34 .deg. C and operating time of 10 minutes. Therefore it is suggested that the corrosion resistance of SSC13 can be effectively improved with the heat treatment, where SSC13 is heated for 10 minutes at 1120 °C and quenched and passivation treatment, where SSC13 is passivated for at least 10 seconds at 34 °C nitric acid solution.

  6. Evaluation of Solid-Solution Hardening in Several Binary Alloy Systems Using Diffusion Couples Combined with Nanoindentation

    Science.gov (United States)

    Kadambi, Sourabh B.; Divya, V. D.; Ramamurty, U.

    2017-10-01

    Analysis of solid-solution hardening (SSH) in alloys requires the synthesis of large composition libraries and the measurement of strength or hardness from these compositions. Conventional methods of synthesis and testing, however, are not efficient and high-throughput approaches have been developed in the past. In the present study, we use a high-throughput combinatorial approach to examine SSH at large concentrations in binary alloys of Fe-Ni, Fe-Co, Pt-Ni, Pt-Co, Ni-Co, Ni-Mo, and Co-Mo. The diffusion couple (DC) method is used to generate concentration ( c) gradients and the nanoindentation (NI) technique to measure the hardness ( H) along these gradients. The obtained H -c profiles are analyzed within the framework of the Labusch model of SSH, and the c^{2/3} dependence of H predicted by the model is found to be generally applicable. The SSH behavior obtained using the combinatorial method is found to be largely consistent with that observed in the literature using conventional and DC-NI methods. This study evaluates SSH in Fe-, Ni-, Co-, and Pt-based binary alloys and confirms the applicability of the DC-NI approach for rapidly screening various solute elements for their SSH ability.

  7. Mechanistic insight into the dramatic improvement of probucol dissolution in neutral solutions by solid dispersion in Eudragit E PO with saccharin.

    Science.gov (United States)

    Higashi, Kenjirou; Seo, Atsunori; Egami, Kiichi; Otsuka, Naoya; Limwikrant, Waree; Yamamoto, Keiji; Moribe, Kunikazu

    2016-05-01

    Solid dispersion using Eudragit E PO (EPO) improves the dissolution of poorly water-soluble drugs in acidic solutions; however, the dissolution extremely decreases in neutral solutions. In this report, ternary solid dispersions containing probucol (PBC), EPO, and saccharin (SAC) were prepared to enable high drug dissolution at neutral pH. Cryogenic-grinding was used to obtain ternary solid dispersions. Dissolution tests at neutral pH values were conducted to confirm the usefulness of the cryogenic-ground mixture (cryo-GM). The molecular state of each component and intermolecular interactions in the ternary cryo-GM were evaluated using powder X-ray diffraction (PXRD) and (13) C solid-state NMR including spin-lattice relaxation time evaluation. PBC dispersed in ternary cryo-GM had an improved dissolution in neutral solutions. PBC and SAC were in amorphous states in EPO polymer matrices. The weak hydrophobic interaction between PBC and EPO and the ionic bond or hydrogen bond between EPO and SAC were demonstrated. These two molecular interactions improved the dissolution of PBC in neutral solutions. Preparation of ternary solid dispersion is a potential method of improving drug solubility and absorption. © 2015 Royal Pharmaceutical Society.

  8. (Mg,Co)O Solid-Solution Precursors for the Large-Scale Synthesis of Carbon Nanotubes by Catalytic Chemical Vapor Deposition

    OpenAIRE

    Bacsa, Revathi; Laurent, Christophe; Peigney, Alain; Vaugien, Thibaud; Flahaut, Emmanuel; Bacsa, Wolfgang; Rousset, Abel

    2002-01-01

    Single- and double-walled carbon nanotubes were produced in high yield using the selective reduction of solid solutions of Mg1–xCoxO in a methane and hydrogen atmosphere at 1000°C. The solid solutions were prepared using combustion synthesis with urea as the fuel. The BET surface areas ranged from 10 to 65 m2/g depending on the fuel content. A single crystalline phase was obtained only for fuel-rich compositions. Increased fuel content increased the surface area by a factor of 6. However, ver...

  9. Partitioning of platinum-group elements (PGE) and chalcogens (Se, Te, As, Sb, Bi) between monosulfide-solid solution (MSS), intermediate solid solution (ISS) and sulfide liquid at controlled fO2-fS2 conditions

    Science.gov (United States)

    Liu, Yanan; Brenan, James

    2015-06-01

    In order to better understand the behavior of highly siderophile elements (HSEs: Os, Ir, Ru, Rh, Pt, Pd, Au, Re), Ag, Pb and chalcogens (As, Se, Sb, Te and Bi) during the solidification of sulfide magmas, we have conducted a series of experiments to measure partition coefficients (D values) between monosulfide solid solution (MSS) and sulfide melt, as well as MSS and intermediate solid solution (ISS), at 0.1 MPa and 860-926 °C, log fS2 -3.0 to -2.2 (similar to the Pt-PtS buffer), with fO2 controlled at the fayalite-magnetite-quartz (FMQ) buffer. The IPGEs (Os, Ir, Ru), Rh and Re are found to be compatible in MSS relative to sulfide melt with D values ranging from ∼20 to ∼5, and DRe/DOs of ∼0.5. Pd, Pt, Au, Ag, Pb, as well as the chalcogens, are incompatible in MSS, with D values ranging from ∼0.1 to ∼1 × 10-3. For the same metal/sulfur ratio, D values for the IPGEs, Rh and Re are systematically larger than most past studies, correlating with higher oxygen content in the sulfide liquid, reflecting the significant effect of oxygen on increasing the activity coefficients for these elements in the melt phase. MSS/ISS partitioning experiments reveal that Ru, Os, Ir, Rh and Re are partitioned into MSS by a factor of >50, whereas Pd, Pt, Ag, Au and the chalcogens partition from weakly (Se, As) to strongly (Ag, Au) into ISS. Uniformly low MSS- and ISS- melt partition coefficients for the chalcogens, Pt, Pd, Ag and Au will lead to enrichment in the residual sulfide liquid, but D values are generally too large to reach early saturation in Pt-Pd-chalcogen-rich accessory minerals, based on current solubility estimates. Instead, these phases likely precipitate at the last dregs of crystallization. Modeled evolution curves for the PGEs and chalcogens are in reasonably good agreement with whole-rock sulfide compositions for the McCreedy East deposit (Sudbury, Ontario), consistent with an origin by crystallization of MSS, then MSS + ISS from sulfide magma.

  10. Synthesis and properties of barium titanate solid solution thin films deposited on copper substrates

    Science.gov (United States)

    Ihlefeld, Jon Fredrick

    Barium titanate thin films were deposited via chemical solution deposition using a hybrid-chelate chemistry directly on copper foil substrates. A process was developed to crystallize and densify the ferroelectric films at 900°C by using a reductive atmosphere containing nitrogen, hydrogen, water vapor, and oxygen impurities such that film constituents were oxidized to form barium titanate and the foil substrate remained metallic. The crystallized films are polycrystalline with equiaxed morphology and average grain diameters in excess of 100 mn. The dielectric properties exhibit permittivities in excess of 1800 at room temperature and zero bias with tunabilites of greater than 90% and high field loss tangents of less than 1%. The phase transition temperature and temperature coefficient of capacitance modified by partially substituting zirconium, hafnium, and tin for titanium. The resulting films were single phase and the phase transition shifts were consistent with bulk materials. A reduction in permittivity was observed for increasing substituent level and was attributed to a reduction in grain size for both barium titanate zirconate and barium titanate hafnate. Processing conditions were chosen to stabilize Sn2+ during the firing process in an attempt to flux the system and increase grain size. The barium titanate stannate films had less reduction in grain size per substituent level than either zirconium or hafnium, however a similar reduction in permittivity was observed. The diminished dielectric response was explained by a defect reaction involving divalent tin and oxygen vacancies that quenched the extrinsic domain response to the dielectric constant. Barium borate fluxes were used to improve densification and crystallinity. Barium borate additions between 0 and 3% uniformly increased grain size and density, while levels greater than 3% resulted in anomalous grain growth. Films with exaggerated grains show tetragonal peak splitting in the X-ray diffraction

  11. Evidence on unusual way of cocaine smuggling: cocaine-polymethyl methacrylate (PMMA) solid solution--study of clandestine laboratory samples.

    Science.gov (United States)

    Gostic, T; Klemenc, S

    2007-07-04

    An abandoned clandestine laboratory was seized in Slovenia. All confiscated exhibits were analysed in a forensic laboratory, where the following analytical methods were applied: capillary gas chromatography coupled with mass spectrometry (GC-MS) combined also by solid-phase micro extraction (SPME) and pyrolysis (Py) technique, Fourier transform infrared spectrometry (FTIR) and scanning electron microscopy with energy dispersive X-ray detector (SEM-EDX). The most interesting analytical findings can be summarised as follows: at the crime scene some plastic pieces, which contained cocaine dissolved (as solid solution) in polymethyl methacrylate-plexiglass (PMMA), were found. The highest cocaine concentration measured in the plastic sample was about 15% by weight. Two larger lumps of material (12 and 3 kg) were composed mainly of PMMA and CaCO3 and contained only 0.4 and 0.5% of cocaine, respectively. As for the low cocaine concentration, we assume that those two lumps of material represent discarded waste product--residue after the isolation of cocaine from plastic. Higher quantities of pure solvents (41 l) and solvent mixtures (87 l) were seized. We identified three types of pure solvents (acetone, gasoline and benzine) and two different types of solvent mixtures (benzine/acetone and gasoline/acetone). The total seized volume (87 l) of solvent mixtures holds approximately 395 g of solid residue formed mainly of PMMA and cocaine. Obviously solvent mixtures were used for isolation of cocaine from the plastic. Small quantities of relatively pure cocaine base were identified on different objects. There were two cotton sheets, most probably used for filtration. One sheet had traces of cocaine base (76% purity) on the surface, while cocaine in hydrochloride form (96%) was identified on the other sheet. GC-MS analyses of micro traces isolated from analytical balances showed the presence of cocaine and some common adulterants: phenacetine, lidocaine and procaine. A cocaine

  12. Synthesis of (Cr,V){sub 2}(C,N) solid solution powders by thermal processing precursors

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Anrui [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Liu, Ying [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Key Laboratory of Advanced Special Material & Technology, Ministry of Education, Chengdu, 610065 (China); Ma, Shiqing; Qiu, Yuchong; Rong, Pengcheng; Ye, Jinwen [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China)

    2017-06-01

    The single-phase (Cr,V){sub 2}(C,N) solid solution powders were fabricated via carbothermal reduction-nitridation (CRN) processing technique. The effects of heat treatment temperature, nitrogen pressure and carbon proportion were experimentally studied in detail by X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and thermal analysis. The chemical transformations of vanadium and chromium compounds were as follows: precursors → V{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} → Cr{sub 3}C{sub 2}, Cr{sub 2}O{sub 3}, (Cr,V){sub 2}(C,N) → (Cr,V){sub 2}(C,N). When the heat-treated temperature was below 1200 °C, chromium oxides didn’t completely react. However, higher temperature ∼1300 °C could not only lead to the segregation of some nitrides and carbon black, but also to the occurrence of fiber-bridged particles. The system nitrogen pressure over 0.03 MPa would cause a subtle transformation of (Cr,V){sub 2}(C,N) to VCrN{sub 2}. When the carbon proportion was below 15 wt%, the oxides could not be completely reduced, while when the carbon proportion was above 15.5 wt%, some undesired carbides, like Cr{sub 23}C{sub 6} and Cr{sub 3}C{sub 2}, would form. Ultimately, the homogeneously distributed pure-phase (Cr,V){sub 2}(C,N) spherical particles with the average size of ∼1.5 μm were obtained at the optimal conditions of the treatment of precursors at 1200 °C for 1 h with the nitrogen pressure of 0.03 MPa and carbon content of 15.5 wt%. The chemical composition of the solid solution with the optimal process could be drawn as (Cr{sub 0.85}V{sub 0.15}){sub 2}(C{sub 0.57}N{sub 0.43}). Thermal processing precursors method shows the advantages of lower synthesis temperature, shorter period and finer particles when comparing with the conventional preparations. - Highlights: • Single phase of (Cr,V){sub 2}(C,N) powders were synthesized for the first time. • Precursors were used to prepared the powders by carbothermal

  13. Structural determination of new solid solutions [Y2-x Mx ][Sn2-x Mx ]O7-3x/2 (M = Mg or Zn by Rietveld method

    Directory of Open Access Journals (Sweden)

    Mohamed Douma

    2010-12-01

    Full Text Available New [Y2-x Mx][Sn2-x Mx]O7-3x/2 (0 ≤x≤ 0.30 for M = Mg and 0 ≤x≤ 0.36 for M = Zn solid solutions with the pyrochlore structure were synthesized via high-temperature solid-state reaction method. Powder X-ray diffraction (PXRD patterns and Fourier transform infrared (FT-IR spectra showed that these materials are new non-stoichiometric solid solutions with the pyrochlore type structure. The structural parameters for the solids obtained were successfully determined by Rietveld refinement based on the analysis of the PXRD diagrams. Lattice parameter (a of these solid solutions decreases when x increases in both series. All samples obtained have the pyrochlore structure Fd-3m, no. 227 (origin at center -3m with M2+ (M = Mg2+ or Zn2+ cations in Y3+ and Sn4+ sites, thus creating vacancies in the anionic sublattice.

  14. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with (pyrazol-1-yl)acetic acid.

    Science.gov (United States)

    Chen, Xiao-Yan; Goff, George S; Scott, Brian L; Janicke, Michael T; Runde, Wolfgang

    2013-03-18

    As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

  15. Modifying Optical Properties of ZnO Films by Forming Zn[subscript 1-x] Co[subscript x]O Solid Solutions via Spray Pyrolysis

    Science.gov (United States)

    Bentley, Anne K.; Weaver, Gabriela C.; Russell, Cianan B.; Fornes, William L.; Choi, Kyoung-Shin; Shih, Susan M.

    2007-01-01

    A simple and cost-effective experiment for the development and characterization of semiconductors using Uv-vis spectroscopy is described. The study shows that the optical properties of ZnO films can be easily modified by forming Zn[subscript 1-x] Co[subscript x]O solid solutions via spray pyrolysis.

  16. Modeling of the solid-solution partitioning of heavy metals and arsenic in embanked flood plain soils of the rivers Rhine and Meuse

    NARCIS (Netherlands)

    Schröder, T.J.; Hiemstra, T.; Vink, J.P.M.

    2005-01-01

    The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected

  17. Immobilization of ZnS–AgInS2 Solid Solution Nanoparticles on ZnO Rod Array Electrodes and Their Photoresponse with Visible Light Irradiation

    National Research Council Canada - National Science Library

    Sasamura, Tetsuya; Okazaki, Ken-ichi; Tsunoda, Ryuta; Kudo, Akihiko; Kuwabata, Susumu; Torimoto, Tsukasa

    2010-01-01

    ZnS–AgInS2 solid solution (ZAIS) nanoparticles having elements of low toxicity were immobilized on thin ZnO rod array films, and the resulting film worked as an n-type semiconductor electrode for which the photoresponse varied...

  18. Conductivity and thermopower studies of bis-tetramethyltetraselenafulvalenium hexafluorophosphide, bis-tetramethyltetrathiafulvalenium hexafluorophosphide, and their solid solutions, (TMTSF1-xTMTTFx)2PF6

    DEFF Research Database (Denmark)

    Mortensen, Kell; Engler, E. M.

    1984-01-01

    The conductivity σ and the thermoelectric power S have been studied experimentally on the organic conductors bis-tetramethyltetraselenafulvalenium hexafluorophosphide [(TMTSF)2PF6] and bis-tetramethyltetrathiafulvalenium hexafluorophosphide [(TMTTF)2PF6] and their solid solutions: (TMTSF1-xTMTTFx)2...

  19. Pebble fabrication of super advanced tritium breeders using a solid solution of Li2+xTiO3+y with Li2ZrO3

    Directory of Open Access Journals (Sweden)

    Tsuyoshi Hoshino

    2016-12-01

    Full Text Available Lithium titanate with excess lithium (Li2+xTiO3+y is one of the most promising candidates among advanced tritium breeders for demonstration power plant reactors because of its good tritium release characteristics. However, the tritium breeding ratio (TBR of Li2+xTiO3+y is smaller than that of e.g., Li2O or Li8TiO6 because of its lower Li density. Therefore, new Li-containing ceramic composites with both high stability and high Li density have been developed. Thus, this study focused on the development of a solid solution with a new characteristic. The solid-solution pebbles of Li2+xTiO3+y with Li2ZrO3 (Li2+x(Ti,ZrO3+y, designated as LTZO, were fabricated by an emulsion method. The X-ray diffraction patterns of sintered LTZO pebbles are approximately the same as those of Li2+xTiO3+y pebbles, and no peaks attributable to Li2ZrO3 are observed. These results demonstrate that LTZO pebbles are not a two-phase material but rather a solid solution. Furthermore, LTZO pebbles were easily sintered under air. Thus, the LTZO solid solution is a candidate breeder material for super advanced (SA tritium breeders.

  20. Isotopically exchangeable phosphate in freshwater sediments: Effects of u.v.-irradiation, formaldehyde, solid/solution ratio, and pH on its experimental determination

    NARCIS (Netherlands)

    Vaas, L.H.; Comans, R.N.J.; Reith, J.M.M.; Weijden, C.H. van der; Das, H.A.

    The influence of bioactivities, solid/solution ratio and the pH on the isotopic exchangeability of phosphate in a freshwater sediment was investigated. From the comparison of the results obtained for the same sample in the presence or absence of formaldehyde, it is concluded that microorganisms

  1. Hydrophobically assisted switching phase synthesis: the flexible combination of solid-phase and solution-phase reactions employed for oligosaccharide preparation.

    Science.gov (United States)

    Bauer, Jörg; Rademann, Jörg

    2005-05-25

    Hydrophobically assisted switching phase (HASP) synthesis is a concept that allows the choice between the advantages of solid-supported chemistry and those of solution-phase synthesis. Starting from the examination of adsorption and desorption properties of hydrophobic molecules to and from reversed-phase silica, we designed a dilipid as a quantitative and fully reversible HASP anchor, permitting final product release. The utility of this new tool in synthetic organic chemistry was demonstrated on oligosaccharide preparation. The synthesis of a pentarhamnoside was accomplished by repetitive glycosylation reactions. Glycosylations were conducted preferably in solution, whereas all protecting group manipulations were performed on solid support. Without the need for chromatographic purification of intermediates, the HASP system furnished the final product after 12 linear steps with average yields of 94% per step at a scale of 0.1 mmol, thus overcoming several of the limitations encountered in the solid-phase synthesis of complex carbohydrates.

  2. Effect of Heat Treatment on the Lithium Ion Conduction of the LiBH4–LiI Solid Solution

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Mýrdal, Jón Steinar Garðarsson; Blanchard, Didier

    2013-01-01

    The LiBH4–LiI solid solution is a good Li+ conductor and a promising crystalline electrolyte for all-solid-state lithium based batteries. The focus of the present work is on the effect of heat treatment on the Li+ conduction. Solid solutions with a LiI content of 6.25–50% were synthesized by high......, resulting in conductivities exceeding 0.1 mS/cm at 30 °C and 10 mS/cm at 140 °C. It was found that the formation of defect-rich microstructures during ball milling increased the specific conductivities of these compounds significantly. The phase transition temperatures between the orthorhombic and hexagonal...

  3. Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300{sup o}C

    Energy Technology Data Exchange (ETDEWEB)

    Lemire, R.J.; Tosello, N.B.; Halliday, J.D

    1999-12-01

    The major contributions of the isotopes {sup 122}Sb and {sup 124}Sb to activity transport in a CANDU reactor primary heat transport system (HTS), have been associated with oxygen ingress during reactor shutdown. As part of a program to minimize the release and redeposition of these isotopes, the solubilities of antimony(III) and (V) oxides and salts have been measured in basic solutions at temperatures from 25 to 300{sup o}C. The results provide information on the charge and the stability as a function of temperature of antimony solution species and, hence, a guide to the trends in the temperature dependence of the solubilities of antimony solids. In solutions in which oxidation of antimony(III) to antimony(V) is minimized, the solubility of Sb{sub 2}O{sub 3} increases by about two orders of magnitude between 25 and 200{sup o}C, and then levels out or decreases slightly. At 250{sup o}C, in oxidizing solutions, Sb{sub 2}O{sub 5}{center_dot}xH{sub 2}O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na{sub 2{alpha}}[H(H{sub 2}O)]{sub 2-2{alpha}}Sb{sub 2}O{sub 6}, which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200{sup o}C and decreases at temperatures above 250{sup o}C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO{sub 3}{sup -} or Sb(OH){sub 6}{sup -}), even though the compositions of antimony-containing solids in basic oxidizing solutions are strongly dependent on the cations and their aqueous phase concentrations. All solids used in the present experiments would be expected to generate total solution antimony concentrations {>=} 0.00005 mol{center_dot}dm{sup -3} in any neutral or basic aqueous solutions (assuming no added sodium salts). Therefore, under HTS conditions, precipitation of any antimony oxides or mixed oxides is unlikely. It cannot be

  4. Magnetic properties of HoCoC2, HoNiC2 and their solid solutions

    Science.gov (United States)

    Michor, H.; Steiner, S.; Schumer, A.; Hembara, M.; Levytskyy, V.; Babizhetskyy, V.; Kotur, B.

    2017-11-01

    Magnetic properties of single crystalline HoCoC2 and the evolution of magnetic and structural features in a series of polycrystalline solid solutions HoCo1-xNixC2 (0 ⩽ x ⩽ 1) are investigated by means of X-ray diffraction, magnetization, magnetic susceptibility and specific heat measurements. The crystal structures of all investigated samples refers to the CeNiC2-type structure (space group Amm 2 and Pearson symbol oS8). Non-isoelectronic substitution of Co by Ni causes a non-linear increase of the unit cell volume and especially a non-monotonous variation of the a and c lattice parameters as well as a pronounced reduction of the C-C bond length of carbon dimers. Temperature dependent magnetization and specific heat measurements reveal a crossover from a ferromagnetic for HoCoC2 with TC = 10.6 (1) K to an antiferromagnetic ground state for HoNiC2 with TN = 2.78 (6) K and a non-monotonous variation of the magnetic ordering temperature with a minimum at intermediate compositions. Crystalline electric field effects of HoCoC2 and HoNiC2 are analysed using combined thermodynamic and magnetic susceptibility data. The electrical resistivity of HoNiC2 displays a distinct anomaly near room temperature which indicates the formation of a charge density wave (CDW) state as earlier reported for several other rare earth nickel dicarbides.

  5. Vibrational and electronic spectroscopy of the retro-carotenoid rhodoxanthin in avian plumage, solid-state films, and solution.

    Science.gov (United States)

    Berg, Christopher J; LaFountain, Amy M; Prum, Richard O; Frank, Harry A; Tauber, Michael J

    2013-11-15

    Rhodoxanthin is one of few retro-carotenoids in nature. These chromophores are defined by a pattern of single and double bond alternation that is reversed relative to most carotenoids. Rhodoxanthin is found in the plumage of several families of birds, including fruit doves (Ptilinopus, Columbidae) and the red cotingas (Phoenicircus, Cotingidae). The coloration associated with the rhodoxanthin-containing plumage of these fruit dove and cotinga species ranges from brilliant red to magenta or purple. In the present study, rhodoxanthin is characterized in situ by UV-Vis reflectance and resonance Raman spectroscopy to gain insights into the mechanisms of color-tuning. The spectra are compared with those of the isolated pigment in solution and in thin solid films. Key vibrational signatures are identified for three isomers of rhodoxanthin, primarily in the fingerprint region. Electronic structure (DFT) calculations are employed to describe the normal modes of vibration, and determine characteristic modes of retro-carotenoids. These results are discussed in the context of various mechanisms that change the electronic absorption, including structural distortion of the chromophore or enhanced delocalization of π-electrons in the ground-state. From the spectroscopic evidence, we suggest that the shift in absorption is likely a consequence of perturbations that primarily affect the excited state of the chromophore. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Kinetics of the fcc → hcp Phase Transformation in Cu-Ge Solid Solutions Upon Isothermal Aging

    Science.gov (United States)

    Polatidis, E.; Zotov, N.; Bischoff, E.; Mittemeijer, E. J.

    2017-11-01

    The kinetics of the ζ-phase formation from a supersaturated α-Cu(Ge) solid solution ( i.e., transformation from the fcc crystal structure to the hcp crystal structure) containing 10.8 at. pct Ge [at isothermal temperatures of 573 K, 613 K, and 653 K (300 °C, 340 °C, and 380 °C)] were studied by X-ray diffraction (XRD) for phase fraction determination. Both in situ and ex situ annealing experiments were performed. The transformation kinetics were modeled on the basis of a versatile modular model. The transformation kinetics complied with a site-saturation nucleation mode and strongly anisotropic interface-controlled growth mode in association with a corresponding impingement mode: diffusion of Ge (towards the stacking faults, SFs) does not control the transformation rate. Transmission electron microscopy (TEM) investigations showed that segregation of Ge at the stacking faults (SFs) takes place (relatively fast) prior to the structural transformation (fcc → hcp).

  7. First-principles investigation of competing magnetic interactions in (Mn ,Fe )Ru2Sn Heusler solid solutions

    Science.gov (United States)

    Decolvenaere, Elizabeth; Gordon, Michael; Seshadri, Ram; Van der Ven, Anton

    2017-10-01

    Many Heusler compounds possess magnetic properties well suited for applications as spintronic materials. The pseudobinary Mn0.5Fe0.5Ru2Sn , formed as a solid solution of two full Heuslers, has recently been shown to exhibit exchange hardening suggestive of two magnetic phases, despite existing as a single chemical phase. We have performed a first-principles study of the chemical and magnetic degrees of freedom in the Mn1 -xFexRu2Sn pseudobinary to determine the origin of the unique magnetic behavior responsible for exchange hardening within a single phase. We find a transition from antiferromagnetic (AFM) to ferromagnetic (FM) behavior upon replacement of Mn with Fe, consistent with experimental results. The lowest energy orderings in Mn1 -xFexRu2Sn consist of chemically and magnetically uniform (111) planes, with Fe-rich regions preferring FM ordering and Mn-rich regions preferring AFM ordering, independent of the overall composition. Analysis of the electronic structure suggests that the magnetic behavior of this alloy arises from a competition between AFM-favoring Sn-mediated superexchange and FM-favoring RKKY exchange mediated by spin-polarized conduction electrons. Changes in valency upon replacement of Mn with Fe shifts the balance from superexchange-dominated interactions to RKKY-dominated interactions.

  8. Magnetic Solid Phase Extraction and Removal of Five Cationic Dyes from Aqueous Solution Using Magnetite Nanoparticle Loaded Platanusorientalis Waste Leaves

    Directory of Open Access Journals (Sweden)

    Elaheh Madrakian

    2016-12-01

    Full Text Available This paper reports on synthesis of a magnetic adsorbent for wastewater treatment purposes. In this regard, platanus orientalis waste leaves were chosen as a cheap material for preparing the magnetic adsorbent by loading magnetite nanoparticles on it. The synthesized adsorbent was characterized using scanning electron microscope and X-ray diffractometer. Then, it was used for magnetic solid phase extraction and removal of five cationic dyes including methyl violet (MV, methylene blue (MB, malachite green (MG, crystal violet (CV, and neutral red (NR from aqueous solution as a model application. Different important factors affecting the adsorption process were optimized, and the results showed that under the optimized conditions (pH 10 for CV, MV, MB, and MG; pH 6 for NR; adsorbent dosage, 20 mg; agitation time, 25 min efficient removal of the investigated dyes (adsorption capacities between of 89-133 mg g-1 is achievable using the synthesized adsorbent. Furthermore, the reusability experiments showed that the adsorbent could be reused at least ten cycles without any significant loss in its sorption behavior.

  9. Characterization and magnetic properties of nanoparticles based on FePt solid solution with an oxide shell

    Energy Technology Data Exchange (ETDEWEB)

    Shpetnyi, I.; Kovalenko, A.S. [Sumy State University, Rimsky-Korsakov Street 2, 40007 Sumy (Ukraine); Klimenkov, M. [Institute for Applied Materials, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Protsenko, I.Yu. [Sumy State University, Rimsky-Korsakov Street 2, 40007 Sumy (Ukraine); Chernov, S.V. [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany); Nepijko, S.A., E-mail: nepijko@uni-mainz.de [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany); Elmers, H.J.; Schönhense, G. [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany)

    2015-01-01

    We present the results of magnetic properties investigations of ferromagnetic nanoparticles which ensembled with ferromagnetic shell. The aim of this work is to study the connection of structure–phase composition and thermal treatment with the magnetic properties, partially, with the coercive force and the exchange bias field in a two-dimension spin system of core–shell type. It is found that the exchange bias field increases with the growth of the oxide shell thickness. This is realized by annealing in a dosed oxygen flow. The decrease of the coercive force with the increase of annealing temperature is connected with the concentration effect (the concentration of ferromagnetic particles decreases). - Highlights: • We investigated particles that have core–shell structure, where core material is a solid solution Fe{sub x}Pt{sub 1−x} and shell consists of γ-Fe{sub 2}O{sub 3} with spinel structure. • It is defined that exchange bias field increases with the increase of oxide shell thickness. • Coercive force after annealing decreases due to decrease of ferromagnetic particles concentration. • Analysis of exchange bias field and coercive force measurements for FePt systems of different effective thicknesses of components showed the possibility to control magnetic hardness of the studied system.

  10. Diminished oligomerization in the synthesis of new anti-angiogenic cyclic peptide using solution instead of solid-phase cyclization.

    Science.gov (United States)

    Rubio, Sandra; Clarhaut, Jonathan; Péraudeau, Elodie; Vincenzi, Marian; Soum, Claire; Rossi, Filomena; Guillon, Jean; Papot, Sébastien; Ronga, Luisa

    2016-05-01

    The design and synthesis of novel peptides that inhibit angiogenesis is an important area for anti-angiogenic drug development. Cyclic and small peptides present several advantages for therapeutic application, including stability, solubility, increased bio-availability and lack of immune response in the host cell. We describe here the synthesis and biological evaluations of a new cyclic peptide analog of CBO-P11: cyclo(RIKPHE), designated herein as CBO-P23M, a hexamer peptide encompassing residues 82 to 86 of VEGF which are involved in the interaction with VEGF receptor-2. CBO-P23M was prepared using in solution cyclization, therefore reducing the peptide cyclodimerization occurred during solid-phase cyclization. The cyclic dimer of CBO-P23M, which was obtained as the main side product during synthesis of the corresponding monomer, was also isolated and investigated. Both peptides markedly reduce VEGF-A-induced phosphorylation of VEGFR-2 and Erk1/2. Moreover, they exhibit anti-angiogenic activity in an in vitro morphogenesis study. Therefore CBO-P23M and CBO-P23M dimer appear as attractive candidates for the development of novel angiogenesis inhibitors for the treatment of cancer and other angiogenesis-related diseases. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 368-375, 2016. © 2016 Wiley Periodicals, Inc.

  11. Role of bond strength on the lattice thermal expansion and oxide ion conductivity in quaternary pyrochlore solid solutions.

    Science.gov (United States)

    Radhakrishnan, A N; Prabhakar Rao, P; Mahesh, S K; Thampi, D S Vaisakhan; Koshy, Peter

    2012-02-20

    Quaternary pyrochlore-type solid solutions, CaGdZrNb(1-x)Ta(x)O(7) (x = 0, 0.2, 0.4, 0.6, 0.8, 1), were prepared by a high-temperature ceramic route. The pyrochlore phases of the compounds were confirmed by powder X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. The crystallographic parameters of the pyrochlore compounds were accurately determined by Rietveld analysis of the powder XRD data. The isovalent substitution of Ta in place of Nb at the B site can reveal the effect of chemical bonding on lattice thermal expansion and oxide ion conductivity because both Nb and Ta have the same ionic radius (0.64 Å). Lattice thermal expansion coefficients of the samples were calculated from high-temperature XRD measurements, and it was found that the thermal expansion coefficient decreases with substitution of Ta. Oxide ion conductivity measured by a two-probe method also shows the same trend with substitution of Ta, and this can be attributed to the high bond strength of the Ta-O bond compared to that of the Nb-O bond. Microstructural characterization using scanning electron microscopy proves that the size of the grains has a small effect on the oxide ion conductivity. Our studies established the role of chemical bonding in deciding the conductivity of pyrochlore oxides and confirmed that the 48f-48f mechanism of oxide ion conduction is dominant in pyrochlore oxides.

  12. Calibration of laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for the quantitative analysis of solid samples

    Energy Technology Data Exchange (ETDEWEB)

    Leach, James [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    Inductively coupled plasma mass spectrometry (ICP-MS) has become the method of choice for elemental and isotopic analysis. Several factors contribute to its success. Modern instruments are capable of routine analysis at part per trillion levels with relative detection limits in part per quadrillion levels. Sensitivities in these instruments can be as high as 200 million counts per second per part per million with linear dynamic ranges up to eight orders of magnitude. With standards for only a few elements, rapid semiquantitative analysis of over 70 elements in an individual sample can be performed. Less than 20 years after its inception ICP-MS has shown to be applicable to several areas of science. These include geochemistry, the nuclear industry, environmental chemistry, clinical chemistry, the semiconductor industry, and forensic chemistry. In this introduction, the general attributes of ICP-MS will be discussed in terms of instrumentation and sample introduction. The advantages and disadvantages of current systems are presented. A detailed description of one method of sample introduction, laser ablation, is given. The paper also gives conclusions and suggestions for future work. Chapter 2, Quantitative analysis of solids by laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for calibration, has been removed for separate processing.

  13. A space-charge treatment of the increased concentration of reactive species at the surface of a ceria solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Zurhelle, Alexander F.; Souza, Roger A. de [Institute of Physical Chemistry, RWTH Aachen University (Germany); Tong, Xiaorui; Mebane, David S. [Department of Mechanical and Aerospace Engineering, West Virginia University, Morgantown, WV (United States); Klein, Andreas [Institute of Materials Science, TU Darmstadt (Germany)

    2017-11-13

    A space-charge theory applicable to concentrated solid solutions (Poisson-Cahn theory) was applied to describe quantitatively as a function of temperature and oxygen partial pressure published data obtained by in situ X-ray photoelectron spectroscopy (XPS) for the concentration of Ce{sup 3+} (the reactive species) at the surface of the oxide catalyst Ce{sub 0.8}Sm{sub 0.2}O{sub 1.9}. In contrast to previous theoretical treatments, these calculations clearly indicate that the surface is positively charged and compensated by an attendant negative space-charge zone. The high space-charge potential that develops at the surface (>0.8 V) is demonstrated to be hardly detectable by XPS measurements because of the short extent of the space-charge layer. This approach emphasizes the need to take into account defect interactions and to allow deviations from local charge neutrality when considering the surfaces of oxide catalysts. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Probing organometallic reactions by time-resolved infrared spectroscopy in solution and in the solid state using quantum cascade lasers.

    Science.gov (United States)

    Calladine, James A; Horvath, Raphael; Davies, Andrew J; Wriglesworth, Alisdair; Sun, Xue-Zhong; George, Michael W

    2015-05-01

    The photochemistry and photophysics of metal carbonyl compounds (W(CO)6, Cp*Rh(CO)2 (Cp* = η(5)-C5Me5), and fac-[Re(CO)3(4,4'-bpy)2Br] [bpy = bipyridine]) have been examined on the nanosecond timescale using a time-resolved infrared spectrometer with an external cavity quantum cascade laser (QCL) as the infrared source. We show the photochemistry of W(CO)6 in alkane solution is easily monitored, and very sensitive measurements are possible with this approach, meaning it can monitor small transients with absorbance changes less than 10(-6) ΔOD. The C-H activation of Cp*Rh(CO)(C6H12) to form Cp*Rh(CO)(C6H11)H occurs within the first few tens of nanoseconds following photolysis, and we demonstrate that kinetics obtained following deconvolution are in excellent agreement with those measured using an ultrafast laser-based spectrometer. We also show that the high flux and tunability of QCLs makes them suited for solid-state and time-resolved measurements.

  15. Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich, Wilhelm-Johnen-Strasse, 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen (Germany); Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich, Wilhelm-Johnen-Strasse, 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen (Germany); Blanca-Romero, Ariadna [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich, Wilhelm-Johnen-Strasse, 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen (Germany); Vinograd, Victor [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich, Wilhelm-Johnen-Strasse, 52425 Jülich (Germany); Institute of Geoscience, Goethe Universität Frankfurt am Main, Altenhöferallee 1, 60438 Frankfurt (Germany); Bosbach, Dirk [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich, Wilhelm-Johnen-Strasse, 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen (Germany)

    2014-12-15

    We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computed for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.

  16. Analytical solutions for the temperature field in a 2D incompressible inviscid flow through a channel with walls of solid fuel

    Directory of Open Access Journals (Sweden)

    Sorin BERBENTE

    2011-12-01

    Full Text Available A gas (oxidizer flows between two parallel walls of solid fuel. A combustion is initiated: the solid fuel is vaporized and a diffusive flame occurs. The hot combustion products are submitted both to thermal diffusion and convection. Analytical solutions can be obtained both for the velocity and temperature distributions by considering an equivalent mean temperature where the density and the thermal conductivity are evaluated. The main effects of heat transfer are due to heat convection at the flame. Because the detailed mechanism of the diffusion flame is not introduced the reference chemical reaction is the combustion of premixed fuel with oxidizer in excess. In exchange the analytical solution is used to define an ideal quasi-uniform combustion that could be realized by an n adequate control. The given analytical closed solutions prove themselves flexible enough to adjust the main data of some existing experiments and to suggest new approaches to the problem.

  17. From solid to liquid: Assessing the release of carbon from soil into solution in response to forest management

    Science.gov (United States)

    James, J. N.; Gross, C. D.; Butman, D. E.; Harrison, R. B.

    2016-12-01

    Dissolved organic matter (DOM) is a crucial conduit for internal cycling of carbon within soils as well as for the transfer of organic matter out of soil and into aquatic systems. Little is known about how the quantity, quality, lability and chemical characteristics of DOM changes in response to human management of forest soils. To examine the processes that release soil organic matter (SOM) into solution, we gathered samples from adjacent native and industrially managed Eucalyptus grandis plantation forests across Sao Paulo State, Brazil and from adjacent old-growth and Douglas-fir (Pseudotsuga menzisii) plantation forests in the coastal Pacific Northwest. Samples from each soil horizon were taken from soil profiles excavated to at least 1.5 m at each site. Water extractable organic matter (WEOM) was extracted twice from each sample using 0.5 M K2SO4 and Milli-Q water to quantify both dissolved and exchange phase organic matter. These extracts were measured for total organic carbon (TOC), 13C and 14C, and chemical characteristics were assessed by fluorescence spectroscopy (EEMs and SUVA254). At the same time, solid phase characteristics of the soil samples were quantified, including bulk density, pH, total carbon and nitrogen, microbial biomass, and 13C and 14C. Characterization of bulk SOM was undertaken by Fourier Transform Infrared Spectroscopy (FTIR) by subtracting mineral matrix spectra of each sample from the bulk spectra. Organic matter lability was assessed by incubations using difference in TOC for WEOM extracts and repeated measurement of CO2 efflux for bulk SOM. All together, these analyses permit a unique snapshot of the natural separation of organic matter from solid into liquid phase through the entire soil profile. Initial results reveal that small but measureable quantities of WEOM may be released from deep B and C horizons in soil, and that this material is labile to microbial decomposition. By identifying differences in SOM and DOM cycling due to

  18. Indications of the formation of an oversaturated solid solution during hydrogenation of Mg-Ni based nanocomposite produced by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Guzman, D. [Departamento de Ingenieria en Metalurgia, Facultad de Ingenieria, Universidad de Atacama y Centro Regional de Investigacion y Desarrollo Sustentable de Atacama, CRIDESAT, Av. Copayapu 485, Copiapo (Chile); Ordonez, S. [Departamento de Ingenieria Metalurgica, Facultad de Ingenieria, Universidad de Santiago de Chile, Av. Lib. Bernardo O' Higgins 3363, Santiago (Chile); Fernandez, J.F.; Sanchez, C. [Departamento de Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco 28049, Madrid (Spain); Serafini, D. [Departamento de Fisica, Facultad de Ciencias, Universidad de Santiago de Chile and Center for Interdisciplinary Research in Materials, CIMAT, Av. Lib. Bernardo O' Higgins 3363, Santiago (Chile); Rojas, P.A. [Escuela de Ingenieria Mecanica, Facultad de Ingenieria, Av. Los Carrera 01567, Quilpue, Pontificia Universidad Catolica de Valparaiso, PUCV (Chile); Aguilar, C. [Instituto de Materiales y Procesos Termomecanicos, Facultad de Ciencias de la Ingenieria, Universidad Austral de Chile, Av. General Lagos 2086, Valdivia (Chile)

    2009-07-15

    An oversaturated solid solution of H in a nanocomposite material formed mainly by nanocrystalline Mg{sub 2}Ni, some residual nanocrystalline Ni and an Mg rich amorphous phase has been found for the first time. The nanocomposite was produced by mechanical alloying starting from Mg and Ni elemental powders, using a SPEX 8000D mill. The hydriding characterization of the nanocomposite was carried out by solid-gas reaction method in a Sievert's type apparatus. The maximum hydrogen content reached in a period of 21 Ks without prior activation was 2.00 wt.% H under hydrogen pressure of 2 MPa at 363 K. The X-ray diffraction analysis showed the presence of an oversaturated solid solution between nanocrystalline Mg{sub 2}Ni and H without any sign of Mg{sub 2}NiH{sub 4} hydride formation. The dehydriding behaviour was studied by differential scanning calorimetry and thermogravimetry. The results showed the existence of two desorption peaks, the first one associated with the transformation of the oversaturated solid solution into Mg{sub 2}NiH{sub 4}, and the second one with the Mg{sub 2}NiH{sub 4} desorption. (author)

  19. SOLUTIONING

    Directory of Open Access Journals (Sweden)

    Maria de Hoyos Guajardo, Ph.D. Candidate, M.Sc., B.Eng.

    2004-11-01

    Full Text Available The theory that is presented below aims to conceptualise how a group of undergraduate students tackle non-routine mathematical problems during a problem-solving course. The aim of the course is to allow students to experience mathematics as a creative process and to reflect on their own experience. During the course, students are required to produce a written ‘rubric’ of their work, i.e., to document their thoughts as they occur as well as their emotionsduring the process. These ‘rubrics’ were used as the main source of data.Students’ problem-solving processes can be explained as a three-stage process that has been called ‘solutioning’. This process is presented in the six sections below. The first three refer to a common area of concern that can be called‘generating knowledge’. In this way, generating knowledge also includes issues related to ‘key ideas’ and ‘gaining understanding’. The third and the fourth sections refer to ‘generating’ and ‘validating a solution’, respectively. Finally, once solutions are generated and validated, students usually try to improve them further before presenting them as final results. Thus, the last section deals with‘improving a solution’. Although not all students go through all of the stages, it may be said that ‘solutioning’ considers students’ main concerns as they tackle non-routine mathematical problems.

  20. Facile Synthesis of ZnxCd1-xS Solid Solution Microspheres through Ultrasonic Spray Pyrolysis for Improved Photocatalytic Activity

    Directory of Open Access Journals (Sweden)

    Jianhui Huang

    2017-01-01

    Full Text Available Nanocrystal ZnxCd1-xS solid solutions were successfully prepared using a facile and reproducible method of ultrasonic spray pyrolysis with Cd(Ac2·2H2O, ZnCl2, and thiourea as precursors. Scanning electron microscopy and transmission electron microscopy images show that the prepared particles possess microspherical morphology. The band gaps of the solid solutions can be tuned by changing the constituent stoichiometries of Cd and Zn. The X-ray diffraction peaks gradually shift to small angle, and the absorption edge shifts to long wavelength with increasing Cd molar fraction in the solid solution. The sample prepared at the Cd/Zn ratio of 1 : 1 displays the optimal activity by using the photocatalytic degradation of methyl orange in the aqueous solution as model reactions under visible light irradiation. This study provides an effective route to prepare spherical ternary photocatalysts with mesoporous structure for further investigations and practical applications.

  1. Localization and reactivity of a hydrophobic solute in lecithin and caseinate stabilized solid lipid nanoparticles and nanoemulsions.

    Science.gov (United States)

    Yucel, Umut; Elias, Ryan J; Coupland, John N

    2013-03-15

    The distribution and reactivity of the lipophilic spin probe 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-1-oxyl nitroxide (PTMIO) in tetradecane (C14)- and eicosane (C20)-in-water emulsions and solid lipid nanoparticles (SLN) respectively, were investigated by electron paramagnetic resonance (EPR) spectroscopy. The lipid phase (10 wt% C14 or C20) was emulsified into either caseinate solutions (1 wt%) or lecithin+bile salt dispersions (2.4 wt%+0.6 wt%) at 70-75 °C. In C14 emulsions stabilized with lecithin+bile salt, three populations of PTMIO were observed: a population in the lipid phase (~60%, a(N)~13.9 G), an aqueous phase population (~20%, a(N)~15.4 G) with high mobility, and an immobilized surface layer population (~20%, a(N)~14.2 G) with low mobility. However, in C14 emulsions stabilized by caseinate, only two distinct populations of PTMIO were seen: a lipid phase population (~70%, a(N)~13.8 G) and an aqueous phase population (~30%, a(N)~15.5 G) with high mobility. In C20 SLN stabilized with either lecithin+bile salt or caseinate, PTMIO was excluded from the lipid phase. In lecithin+bile salt-stabilized C20 SLN, the majority of the probe (~77%) was in the interfacial layer. For both surfactant systems the rate of PTMIO reduction by aqueous iron/ascorbate was greater for C20 SLN than C14 emulsions. Lecithin affects the properties of emulsions and SLN as delivery systems by providing a distinct environment for small molecules. Copyright © 2013 Elsevier Inc. All rights reserved.

  2. From composites to solid solutions: modeling of ionic conductivity in the CaF2-BaF2 system.

    Science.gov (United States)

    Zahn, Dirk; Heitjans, Paul; Maier, Joachim

    2012-05-14

    By using calcium fluorite and barium fluorite as test materials, we demonstrated that homovalent "dopants" can greatly affect ionic conductivity through locally changing the defect density. Whilst this doping is a state-of-the-art effect in the case of dopants that replace native ions of different charge (heterovalent dopants), it is a rather surprising effect at a first glance for substitutional dopants of the same charge; here, the phenomenon is not electrostatic, but elastic in nature. As a consequence of size mismatch, the smaller Ca atoms in the BaF(2) lattice favored the formation of interstitial sites that were located close to the Ca atoms, whilst doping larger Ba species into the CaF(2) phase favored vacancy formation. In terms of conductivity, and in agreement with the different mobilities, the first doping effect was favorable, whilst the other decreased conductivity. The concentration effects were formalized by a heterogeneous Frenkel reaction that was distinguished from the mean Frenkel reaction by additional (elastic) trapping that became more pronounced the lower the temperature. It was very revealing to relate this phenomenon to CaF(2)-BaF(2) multilayers and composites. In very general terms, these effects in the solid solutions were understood as being the atomistic limit of the interfacial charge-transfer that occurred at the hetero-interface of the crystallites or films, and reflected the transition from heterogeneous doping (higher-dimensional doping) to homogeneous doping (zero-dimensional doping). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Solubility and hydrolysis of Np(V) in dilute to concentrated alkaline NaCl solutions. Formation of Na-Np(V)-OH solid phases at 22 C

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, Vladimir G. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; Fellhauer, David; Gaona, Xavier; Dardenne, Kathy; Rothe, Joerg; Altmaier, Marcus [Karlsruhe Institute of Technology (Germany). Inst. for Nuclear Waste Disposal; Kalmykov, Stepan N. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; NRC Kurchatov Institute, Moscow (Russian Federation)

    2017-03-01

    The solubility of Np(V) was investigated at T=22±2 C in alkaline NaCl solutions of different ionic strength (0.1-5.0 M). The solid phases controlling the solubility at different -log{sub 10} m{sub H{sup +}}(pH{sub m}) and NaCl concentration were characterized by XRD, quantitative chemical analysis, SEM-EDS and XAFS (both XANES and EXAFS). Aqueous phases in equilibrium with Np(V) solids were investigated for selected samples within 8.9≤pH{sub m}≤10.3 by UV-vis/NIR absorption spectroscopy. In 0.1 M NaCl, the experimental solubility of the initial greenish NpO{sub 2}OH(am) solid phase is in good agreement with previous results obtained in NaClO{sub 4} solutions, and is consistent with model calculations for fresh NpO{sub 2}OH(am) using the thermodynamic data selection in NEA-TDB. Below pH{sub m}∝11.5 and for all NaCl concentrations studied, Np concentration in equilibrium with the solid phase remained constant during the timeframe of this study (∝2 years). This observation is in contrast to the aging of the initial NpO{sub 2}OH(am) into a more crystalline modification with the same stoichiometry, NpO{sub 2}OH(am, aged), as reported in previous studies for concentrated NaClO{sub 4} and NaCl. Instead, the greenish NpO{sub 2}OH(am) transforms into a white solid phase in those systems with [NaCl]≥1.0 M and pH{sub m}≥11.5, and into two different pinkish phases above pH{sub m}∝13.2. The solid phase transformation is accompanied by a drop in Np solubility of 0.5-2 log{sub 10}-units (depending upon NaCl concentration). XANES analyses of green, white and pink phases confirm the predominance of Np(V) in all cases. Quantitative chemical analysis shows the incorporation of Na{sup +} in the original NpO{sub 2}OH(am) material, with Na:Np ≤ 0.3 for the greenish solids and 0.8 ≤ Na:Np ≤ 1.6 for the white and pinkish phases. XRD data confirms the amorphous character of the greenish phase, whereas white and pink solids show well-defined but discrepant XRD patterns

  4. Hydrogen Production from Water by Photolysis, Sonolysis and Sonophotolysis with Solid Solutions of Rare Earth, Gallium and Indium Oxides as Heterogeneous Catalysts

    Directory of Open Access Journals (Sweden)

    Marta Penconi

    2015-07-01

    Full Text Available In this work, we present the hydrogen production by photolysis, sonolysis and sonophotolysis of water in the presence of newly synthesized solid solutions of rare earth, gallium and indium oxides playing as catalysts. From the experiments of photolysis, we found that the best photocatalyst is the solid solution Y0.8Ga0.2InO3 doped by sulphur atoms. In experiments of sonolysis, we optimized the rate of hydrogen production by changing the amount of water, adding ethanol and tuning the power of our piezoelectric transducer. Finally, we performed sonolysis and sonophotolysis experiments in the presence of S:Y0.8Ga0.2InO3 finding a promising synergistic effect of UV-visible electromagnetic waves and 38 kHz ultrasound waves in producing H2.

  5. Synthesis of solid solutions of Dy xBi 2-xO 3 with x=0, 1 and 2: Structural, optical and ac impedance analysis

    Science.gov (United States)

    Iyyapushpam, S.; Chithra lekha, P.; Pathinettam Padiyan, D.

    2010-01-01

    Dysprosium hydroxide, bismuth hydroxide and mixed dysprosium bismuth hydroxide are prepared in the form of a gel by means of chemical precipitation technique. A simple gel to crystalline conversion technique has been followed by means of refluxing process. The synthesized hydroxides are characterized by thermogravimetry and differential thermal analysis. The formed hydroxides are converted into its oxides by calcining at a temperature of 700 °C for 2 h and solid solutions of Dy xBi 2-xO 3 with x=0, 1 and 2 are formed. The hydroxides and oxides of these solid solutions are investigated by means of XRD and found to be polycrystalline in nature. The Nyquist plot shows a single relaxation process. The enhanced conductivity is observed in dysprosium-based oxides and hydroxides. The optical band gap energy is in agreement with the ac conductivity values.

  6. Structure, elastic stiffness, and hardness of Os 1- xRu xB 2 solid solution transition-metal diborides

    KAUST Repository

    Kanoun, Mohammed

    2012-05-31

    On the basis of recent experiments, the solid solution transition-metal diborides were proposed to be new ultra-incompressible hard materials. We investigate using density functional theory based methods the structural and mechanical properties, electronic structure, and hardness of Os 1-xRu xB 2 solid solutions. A difference in chemical bonding occurs between OsB 2 and RuB 2 diborides, leading to significantly different elastic properties: a large bulk, shear moduli, and hardness for Os-rich diborides and relatively small bulk, shear moduli, and hardness for Ru-rich diborides. The electronic structure and bonding characterization are also analyzed as a function of Ru-dopant concentration in the OsB 2 lattice. © 2012 American Chemical Society.

  7. Adsorption and nanowear properties of bovine submaxillary mucin films on solid surfaces: Influence of solution pH and substrate hydrophobicity

    DEFF Research Database (Denmark)

    Sotres, Javier; Madsen, Jan Busk; Arnebrant, Thomas

    2014-01-01

    The adsorption and mechanical stability of bovine submaxillary mucins (BSM) films at solid-liquid interfaces were studied with respect to both substrate hydrophobicity and solution pH. Dynamic light scattering revealed a single peak distribution in neutral aqueous solution (pH 7.4) and a small...... fraction with enhanced aggregation was observed in acidic solution (pH 3.8). Both substrate hydrophobicity and solution pH were found to affect the spontaneous adsorption of BSM onto solid surfaces; BSM adsorbed more onto hydrophobic surfaces than hydrophilic ones, and adsorbed more at pH 3.8 than at pH 7.......4. Thus, the highest "dry" adsorbed mass was observed for hydrophobic surfaces in pH 3.8 solution. However, a highest "wet" adsorbed mass, i.e. which includes the solvent coupled to the film, was observed for hydrophobic surfaces at pH 7.4. The mechanical stability of the films was studied...

  8. Aromatic hydrazones derived from nicotinic acid hydrazide as fluorimetric pH sensing molecules: Structural analysis by computational and spectroscopic methods in solid phase and in solution

    Science.gov (United States)

    Benković, T.; Kenđel, A.; Parlov-Vuković, J.; Kontrec, D.; Chiş, V.; Miljanić, S.; Galić, N.

    2018-02-01

    Structural analyses of aroylhydrazones were performed by computational and spectroscopic methods (solid state NMR, 1 and 2D NMR spectroscopy, FT-IR (ATR) spectroscopy, Raman spectroscopy, UV-Vis spectrometry and spectrofluorimetry) in solid state and in solution. The studied compounds were N‧-(2,3-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (1), N‧-(2,5-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N‧-(3-chloro-2-hydroxy-phenylmethylidene)-3-pyridinecarbohydrazide (3), and N‧-(2-hydroxy-4-methoxyphenyl-methylidene)-3-pyridinecarbohydrazide (4). Both in solid state and in solution, all compounds were in ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd), stabilized by intramolecular H-bond between hydroxyl proton and nitrogen atom of the Cdbnd N group. In solid state, the Cdbnd O group of 1-4 were involved in additional intermolecular H-bond between closely packed molecules. Among hydrazones studied, the chloro- and methoxy-derivatives have shown pH dependent and reversible fluorescence emission connected to deprotonation/protonation of salicylidene part of the molecules. All findings acquired by experimental methods (NMR, IR, Raman, and UV-Vis spectra) were in excellent agreement with those obtained by computational methods.

  9. Modeling of the evolution of a dislocation structure and development of microplastic deformation in single crystals of fcc substitutional solid solutions

    Science.gov (United States)

    Kulagina, V. V.; Dudarev, E. F.; Rudchenko, V. V.

    1980-07-01

    An analysis is made of evolution of a dislocation structure during the initial stage of plastic deformation and the stress-strain diagrams are derived theoretically for single crystals of fcc substitutional solid solutions. The example of Cu-Al alloys is used to confirm the theoretically predicted relationship between the stress and strain, and also between the flow stress and the resistance to the motion of a single dislocation.

  10. Formation of solid solutions of gallium in Fe–Cr and Fe–Co alloys: Mössbauer studies and first-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Serikov, V.V. [Institute of Metal Physics UB RAS, S. Kovalevskaya str. 18, 620990 Ekaterinburg (Russian Federation); Kleinerman, N.M., E-mail: kleinerman@imp.uran.ru [Institute of Metal Physics UB RAS, S. Kovalevskaya str. 18, 620990 Ekaterinburg (Russian Federation); Vershinin, A.V.; Mushnikov, N.V.; Protasov, A.V.; Stashkova, L.A. [Institute of Metal Physics UB RAS, S. Kovalevskaya str. 18, 620990 Ekaterinburg (Russian Federation); Gorbatov, O.I. [Institute of Metal Physics UB RAS, S. Kovalevskaya str. 18, 620990 Ekaterinburg (Russian Federation); Department of Materials Science and Engineering, KTH Royal Institute of Technology, SE - 100 44 Stockholm (Sweden); Ruban, A.V. [Department of Materials Science and Engineering, KTH Royal Institute of Technology, SE - 100 44 Stockholm (Sweden); Gornostyrev, Yu.N. [Institute of Metal Physics UB RAS, S. Kovalevskaya str. 18, 620990 Ekaterinburg (Russian Federation)

    2014-11-25

    Highlights: • Structure features of the formation of quasibinary solid solutions Fe–Co–Ga and Fe–Cr–Ga are found. • The first-principles calculation of mixing and solubility energies for Ga in an Fe–X alloy are given. • Ga handicaps the processes of phase separation in the Fe–Cr system and ordering in the Fe–Co system. • Preference of Ga entering in the neighborhood of a second element can help study multielement alloys. - Abstract: Investigation of Ga influence on the structure of Fe–Cr and Fe–Co alloys was performed with the use of Mössbauer spectroscopy and X-ray diffraction methods. The experimental results are compared with results of first-principles calculations of the mixing and solubility energies for Ga in an Fe–X (X = Co, Cr) alloy both in ferromagnetic and paramagnetic states. It is shown that Ga mainly goes into the solid solutions of the base alloys. In the alloys of the Fe–Cr system, doping with Ga handicaps the decomposition of solid solutions, observed in the binary alloys, and increases its stability. In the alloys with Co, Ga also favors the uniformity of solid solutions. The results of the first-principles calculations testify in favor of a preferable dissolution of Ga in the FeCo regions of a multicomponent structure rather than FeCr regions, both types of regions being in the ferromagnetic state at the temperature of annealing. The analysis of Mössbauer experiments gives some grounds to conclude that if, owing to liquation, clusterization, or initial stages of phase separation, there exist regions enriched in iron, some amount of Ga atoms prefer to enter the nearest surroundings of iron atoms, thus forming binary Fe–Ga regions (or phases)

  11. Electronic structures of anatase (TiO2)1-x(TaON)x solid solutions: a first-principles study.

    Science.gov (United States)

    Dang, Wenqiang; Chen, Hungru; Umezawa, Naoto; Zhang, Junying

    2015-07-21

    Sensitizing wide band gap photo-functional materials under visible-light irradiation is an important task for efficient solar energy conversion. Although nitrogen doping into anatase TiO2 has been extensively studied for this purpose, it is hard to increase the nitrogen content in anatase TiO2 because of the aliovalent nitrogen substituted for oxygen, leading to the formation of secondary phases or defects that hamper the migration of photoexcited charge carriers. In this paper, electronic structures of (TiO2)1-x(TaON)x (0 ≤ x ≤ 1) solid solutions, in which the stoichiometry is satisfied with the co-substitution of Ti for Ta along with O for N, are investigated within the anatase crystal structure using first-principles calculations. Our computational results show that the solid solutions have substantially narrower band gaps than TiO2, without introducing any localized energy states in the forbidden gap. In addition, in comparison with the pristine TiO2, the solid solution has a direct band gap when the content of TaON exceeds 0.25, which is advantageous to light absorption. The valence band maximum (VBM) of the solid solutions, which is mainly composed of N 2p states hybridized with O 2p, Ti 3d or Ta 5d orbitals, is higher in energy than that of pristine anatase TiO2 consisting of non-bonding O 2p states. On the other hand, incorporating TaON into TiO2 causes the formation of d-d bonding states through π interactions and substantially lowers the conduction band minimum (CBM) because of the shortened distance between some metal atoms. As a result, the anatase (TiO2)1-x(TaON)x is expected to become a promising visible-light absorber. In addition, some atomic configurations are found to possess exceptionally narrow band gaps.

  12. Structure and Membrane Interactions of the Antibiotic Peptide Dermadistinctin K by Multidimensional Solution and Oriented 15N and 31P Solid-State NMR Spectroscopy

    OpenAIRE

    Verly, Rodrigo M.; Moraes, Cléria Mendonça; Resende, Jarbas M.; Aisenbrey, Christopher; Bemquerer, Marcelo Porto; Piló-Veloso, Dorila; Valente, Ana Paula; Almeida, Fábio C.L.; Bechinger, Burkhard

    2009-01-01

    DD K, a peptide first isolated from the skin secretion of the Phyllomedusa distincta frog, has been prepared by solid-phase chemical peptide synthesis and its conformation was studied in trifluoroethanol/water as well as in the presence of sodium dodecyl sulfate and dodecylphosphocholine micelles or small unilamellar vesicles. Multidimensional solution NMR spectroscopy indicates an α-helical conformation in membrane environments starting at residue 7 and extending to the C-terminal carboxyami...

  13. Room-temperature synthesis of Zn(0.80)Cd(0.20)S solid solution with a high visible-light photocatalytic activity for hydrogen evolution.

    Science.gov (United States)

    Wang, Dong-Hong; Wang, Lei; Xu, An-Wu

    2012-03-21

    Visible light photocatalytic H(2) production from water splitting is of great significance for its potential applications in converting solar energy into chemical energy. In this study, a series of Zn(1-x)Cd(x)S solid solutions with a nanoporous structure were successfully synthesized via a facile template-free method at room temperature. The obtained solid solutions were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and N(2) adsorption-desorption analysis. The solid solutions show efficient photocatalytic activity for H(2) evolution from aqueous solutions containing sacrificial reagents S(2-) and SO(3)(2-) under visible-light irradiation without a Pt cocatalyst, and loading of the Pt cocatalyst further improves the visible-light photocatalytic activity. The optimal photocatalyst with x = 0.20 prepared at pH = 7.3 displays the highest activity for H(2) evolution. The bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S nanoparticles exhibit a high H(2) evolution rate of 193 μmol h(-1) and 458 μmol h(-1) under visible-light irradiation (λ ≥ 420 nm), respectively. In addition, the bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S catalysts show a high H(2) evolution rate of 252 and 640 μmol h(-1) under simulated solar light irradiation, respectively. Moreover, the Zn(0.80)Cd(0.20)S catalyst displays a high photocatalytic stability for H(2) evolution under long-term light irradiation. The incorporation of Cd in the solid solution leads to the visible light absorption, and the high content of Zn in the solid solution results in a relatively negative conduction band, a modulated band gap and a rather wide valence bandwidth, which are responsible for the excellent photocatalytic performance of H(2) production and for the high photostability

  14. Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels: The case for a solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Perry, Nicola H. [Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208 (United States); Mason, Thomas O., E-mail: t-mason@northwestern.edu [Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208 (United States); Ma Chengcheng; Navrotsky, Alexandra [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States); Shi Yezhou; Bettinger, Joanna S.; Toney, Michael F. [SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (United States); Paudel, Tula R.; Lany, Stephan [National Renewable Energy Laboratory, Golden, CO 80401 (United States); Zunger, Alex [University of Colorado, Boulder, CO 80309 (United States)

    2012-06-15

    In prior first-principles theoretical work we predicted a complete solid solution in the Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co{sub 3}O{sub 4} and Co{sub 2}ZnO{sub 4} have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co{sup 3+} spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature. - Graphical abstract: The first-principles theoretical prediction of a complete solid solution in Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels has been confirmed experimentally by calorimetric, structural, and electrical measurements. The large mixing enthalpy observed exceeds the predicted value and cannot be accounted for by strain or cation distribution contributions alone, since such effects are small in this system; instead, changes in the spin state of Co{sup 3+} are proposed to account for the mixing thermodynamics. Highlights: Black-Right-Pointing-Pointer Experiments confirm theory prediction of a solid solution in Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels. Black-Right-Pointing-Pointer Thermodynamics of mixing studied by calorimetric, electrical, structural methods. Black-Right-Pointing-Pointer Cation distributions found to be mostly normal for various compositions. Black

  15. Drastic lowering of the order-disorder phase transition temperatures in Zr1-xMxW2O8-y(M=Sc,Y,In) solid solutions

    Science.gov (United States)

    Yamamura, Yasuhisa; Nakajima, Noriyuki; Tsuji, Toshihide; Kojima, Ayumi; Kuroiwa, Yoshihiro; Sawada, Akikatsu; Aoyagi, Shinobu; Kasatani, Hirofumi

    2004-09-01

    ZrW2O8 undergoes an order-disorder phase transition associated with the orientational disordering of the WO4 tetrahedra at 440K . We have showed previously that the phase transition temperatures of Zr1-xMxW2O8-y(M=Sc,Y,In) solid solutions are decreased by a maximum of 80K with only 4% trivalent Sc content. In order to understand the drastic composition dependence on the transition temperature, precise x-ray diffraction experiments on the solid solutions were performed by using a synchrotron radiation. The results provided the evidence of the strong correlation between the phase transition temperature and the number of WO4 units with the ordered orientation. A model was proposed to interpret the drastic composition dependence on the transition temperature, by considering the existence of a local region including the WO4 pairs with the orientational disorder in Zr1-xMxW2O8-y(M=Sc,Y,In) . The local region has the crystal structure of the high-temperature phase in a nonequilibrium state, and spreads out around the substituted trivalent cations. The size of the local region was estimated to be a few unit cells. The local regions play just like nonmagnetic impurities in a site-diluted magnetic system, leading to drastic lowering of the phase transition temperatures in Zr1-xMxW2O8-y solid solutions.

  16. A Study on Microstructural Change and Properties of Mg-1.4 wt%Ca-xwt%Zn Alloys by Two-Step Solid Solution and Aging Treatment

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Seong Mo; Kim, Hye Sung [Pusan National University, Busan (Korea, Republic of); Jeong, Ha-Guk [Korea Institute of Industrial Technology, Incheon (Korea, Republic of); Kim, Teak-Soo [Korea Institute of Industrial Technology, Incheon (Korea, Republic of)

    2015-09-15

    Optimum heat treatment conditions to improve the hardness and corrosion resistance of ternary Mg-Ca-Zn alloys have been studied, based on the theoretical models and DSC (Differential scanning calorimetry) experimental data. Two-step heating process at 420 ℃ and 480 ℃ has been applied and we have found that the low melting point phase, Ca{sub 2}Mg{sub 6}Zn{sub 3} can effectively be dissolved into α-Mg matrix without premature melting. Due to preceding treatment at lower temperature followed by the second stage solid solution heat treatment at 480 ℃, Mg-1.4 wt%Ca-xwt%Zn alloys (x=0, 1.5 and 4.0) exhibit improved corrosion resistance than that from the single step solid solution treated alloy at 480 ℃. However, aging treatment of the alloy at 200 ℃ has led to the homogeneous precipitation of Ca{sub 2}Mg{sub 6}Zn{sub 3} and Mg{sub 2}Ca phases in the matrix as well as at the grain boundary. This microstructural change results in the deterioration of corrosion resistance mainly originated from galvanic corrosion between the matrix and the precipitates. The hardness of Mg-1.4%Cax%Zn alloy, on the other hand, significantly increases with Zn addition by applying two-step solid solution and aging heat treatment.

  17. Unexpected formation of scheelite-structured Ca1-xCdxWO4 (0 ≤ x ≤ 1) continuous solid solutions with tunable photoluminescent and electronic properties.

    Science.gov (United States)

    Wang, Yunjian; Wu, Changjiang; Geng, Lei; Chen, Shifu

    2017-08-30

    Design of a solid solution with tunable functionality is an attractive strategy toward realizing novel devices with multi-functionalities. In this work, a series of Ca1-xCdxWO4 solid solutions in the entire range 0 ≤ x ≤ 1 with tetragonal scheelite structure have been successfully prepared for the first time. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectroscopies indicated that all the nanocrystals have a tetragonal scheelite structure without wolframite phase. Structural refinement data revealed that the lattice volume decreased with the replacement of Ca2+ by Cd2+ ions. UV-Vis diffuse reflectance spectra indicated that optical band gap reduced with the replacement of Ca2+ by Cd2+ ions. Scanning electron microscopic (SEM) images showed that morphologies of the nanocrystals changed with the chemical compositions. The structure evolution of the solid solutions was further investigated by high-resolution transmission electron microscopy (HRTEM). Moreover, the influence of chemical compositions on the photoluminescent and electric performance has been performed and discussed. The reported synthetic approach and findings reported here are important to understand the structure and structure-property relation of scheelite-structured tungstate and molybdate compounds, which has potential applications in the design of other kinds of novel functional materials.

  18. High-frequency and -field EPR spectroscopy of tris(2,4-pentanedionato)manganese(III): investigation of solid-state versus solution Jahn-Teller effects.

    Science.gov (United States)

    Krzystek, J; Yeagle, Gregory J; Park, Ju-Hyun; Britt, R David; Meisel, Mark W; Brunel, Louis-Claude; Telser, Joshua

    2003-07-28

    High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy of a classical coordination complex, Mn(acac)(3) (Hacac = 2,4-pentanedione), has been performed on both solid powder and frozen solution (in CH(2)Cl(2)/toluene, 3:2 v/v) samples. Parallel mode detection X-band EPR spectra exhibiting resolved (55)Mn hyperfine coupling were additionally obtained for frozen solutions. Magnetic susceptibility and field-dependent magnetization measurements were also made on powder samples. Analysis of the entire EPR data set for the frozen solution allowed extraction of the relevant spin Hamiltonian parameters: D = -4.52(2); |E| = 0.25(2) cm(-1); g(iso) = 1.99(1). The somewhat lower quality solid-state HFEPR data and the magnetic measurements confirmed these parameters. These parameters are compared to those for other complexes of Mn(III) and to previous studies on Mn(acac)(3) using X-ray crystallography, solution electronic absorption spectroscopy, and powder magnetic susceptibility. Crystal structures have been reported for Mn(acac)(3) and show tetragonal distortion, as expected for this Jahn-Teller ion (Mn(3+), 3d(4)). However, in one case, the molecule exhibits axial compression and, in another, axial elongation. The current HFEPR studies clearly show the negative sign of D, which corresponds to an axial (tetragonal) elongation in frozen solution. The correspondence among solution and solid-state HFEPR data, solid-state magnetic measurements, and an HFEPR study by others on a related complex indicates that the form of Mn(acac)(3) studied here exhibits axial elongation in all cases. Such tetragonal elongation has been found for Mn(3+) and Cr(2+) complexes with homoleptic pseudooctahedral geometry as well as for Mn(3+) in square pyramidal geometry. This taken together with the results obtained here for Mn(acac)(3) in frozen solution indicates that axial elongation could be considered the "natural" form of Jahn-Teller distortion for octahedral high-spin 3d(4

  19. Small-angle neutron scattering study of protein crowding in liquid and solid phases: lysozyme in aqueous solution, frozen solution, and carbohydrate powders.

    Science.gov (United States)

    Curtis, Joseph E; Nanda, Hirsh; Khodadadi, Sheila; Cicerone, Marcus; Lee, Hyo Jin; McAuley, Arnold; Krueger, Susan

    2012-08-16

    The structure, interactions, and interprotein configurations of the protein lysozyme were studied in a variety of phases. These properties have been studied under a variety of solution conditions before, during, and after freezing and after freeze-drying in the presence of glucose and trehalose. Contrast variation experiments have also been performed to determine which features of the scattering in the frozen solutions are from the protein and which are from the ice structure. Data from lysozyme at concentrations ranging from 1 to 100 mg/mL in solution and water ice with NaCl concentrations ranging from 0 to 0.4 mol/L are fit to model small-angle neutron scattering (SANS) intensity functions consisting of an ellipsoidal form factor and either a screened-Coulomb or hard-sphere structure factor. Parameters such as protein volume fraction and long dimension are followed as a function of temperature and salt concentration. The SANS results are compared to real space models of concentrated lysozyme solutions at the same volume fractions obtained from Monte Carlo simulations. A cartoon representation of the frozen lysozyme solution in 0 mol/L NaCl is presented based on the SANS and Monte Carlo results, along with those obtained from other complementary methods.

  20. Triclinic-monoclinic-orthorhombic (T-M-O) structural transitions in phase diagram of FeVO4-CrVO4 solid solutions

    Science.gov (United States)

    Bera, Ganesh; Reddy, V. R.; Rambabu, P.; Mal, P.; Das, Pradip; Mohapatra, N.; Padmaja, G.; Turpu, G. R.

    2017-09-01

    Phase diagram of FeVO4-CrVO4 solid solutions pertinent with structural and magnetic phases is presented with unambiguous experimental evidences. Solid solutions Fe1-xCrxVO4 (0 ≤ x ≤ 1.0) were synthesized through the standard solid state route and studied by X-ray diffraction, scanning electron microscopy, energy dispersive spectra of X-rays, Raman spectroscopy, d.c. magnetization, and 57Fe Mössbauer spectroscopic studies. FeVO4 and CrVO4 were found to be in triclinic (P-1 space group) and orthorhombic structures (Cmcm space group), respectively. Cr incorporation into the FeVO4 lattice leads to the emergence of a new monoclinic phase dissimilar to the both end members of the solid solutions. In Fe1-xCrxVO4 up to x = 0.10, no discernible changes in the triclinic structure were found. A new structural monoclinic phase (C2/m space group) emerges within the triclinic phase at x = 0.125, and with the increase in Cr content, it gets stabilized with clear single phase signatures in the range of x = 0.175-0.25 as evidenced by the Rietveld analysis of the structures. Beyond x = 0.33, orthorhombic phase similar to CrVO4 (Cmcm space group) emerges and coexists with a monoclinic structure up to x = 0.85, which finally tends to stabilize in the range of x = 0.90-1.00. The Raman spectroscopic studies also confirm the structural transition. FeVO4 Raman spectra show the modes related to three nonequivalent V ions in the triclinic structure, where up to 42 Raman modes are observed in the present study. With the stabilization of structures having higher symmetry, the number of Raman modes decreases and the modes related to symmetry inequivalent sites collate into singular modes from the doublet structure. A systematic crossover from two magnetic transitions in FeVO4, at 21.5 K and 15.4 K to single magnetic transition in CrVO4, at 71 K (antiferromagnetic transition), is observed in magnetization studies. The intermediate solid solution with x = 0.15 shows two magnetic transitions

  1. Photocatalytic H2 production from spinels ZnGa2-xCrxO4 (0≤x≤2) solid solutions

    Science.gov (United States)

    Xu, Xiaoxiang; Xie, Yinghao; Ni, Shuang; Azad, Abul K.; Cao, Tongcheng

    2015-10-01

    Solid solutions of ZnGa2-xCrxO4 (0≤x≤2) were successfully prepared by solid state reactions. Introducing Cr into ZnGa2O4 crystal structure significantly improves its light absorption and greatly enhances its photocatalytic activity. An optimized Cr content (x=1.5 for ZnGa0.5Cr1.5O4) was found for the solid solutions with the highest photocatalytic hydrogen production rate (~775 μmol/h). Compositional analysis suggests there is a strong enrichment of Cr at the surface of sample ZnGa0.5Cr1.5O4 compared with other samples. Theoretical calculations suggest their electronic structures involve spin-polarized conduction band (CB) and valence band (VB) that are mainly composed of Cr 3d orbitals. The highest photocatalytic activity observed in ZnGa0.5Cr1.5O4 is probably due to the higher Cr content at the surface that favors the Cr 3d orbital overlapping.

  2. Photocatalytic degradation of H2S aqueous media using sulfide nanostructured solid-solution solar-energy-materials to produce hydrogen fuel.

    Science.gov (United States)

    Lashgari, Mohsen; Ghanimati, Majid

    2017-11-06

    H2S is a corrosive, flammable and noxious gas, which can be neutralized by dissolving in alkaline media and employed as H2-source by utilizing inside semiconductor-assisted/photochemical reactors. Herein, through a facile hydrothermal route, a ternary nanostructured solid-solution of iron, zinc and sulfur was synthesized in the absence and presence of Ag-dopant, and applied as efficient photocatalyst of hydrogen fuel production from H2S media. The effect of pH on the photocatalyst performance was scrutinized and the maximum activity was attained at pH=11, where HS(-) concentration is high. BET, diffuse reflectance and photoluminescence studies indicated that the ternary solid-solution photocatalyst, in comparison to its solid-solvent (ZnS), has a greater surface area, stronger photon absorption and less charge recombination, which justify its superiority. Moreover, the effect of silver-dopant on the photocatalyst performance was examined. The investigations revealed that although silver could boost the absorption of photons and increase the surface area, it could not appreciably enhance the photocatalyst performance due to its weak influence on retarding the charge-recombination process. Finally, the phenomenon was discussed in detail from mechanistic viewpoint. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Synthesis and electrical properties of the pyrochlore-type Gd2-yLayZr2O7 solid solution

    Directory of Open Access Journals (Sweden)

    León, C.

    2008-06-01

    Full Text Available Different compositions in the pyrochlore-type Gd2-yLayZr2O7 solid solution (0 ≤ y ≤ 1 were prepared at room-temperature by mechanically milling stoichiometric mixtures of the corresponding oxides. Irrespective of their lanthanum content, as-prepared powder samples consist of single-phase anion deficient fluorite materials, although long-range ordering of cations and anion vacancies characteristic of pyrochlores was observed in all cases after firing the samples at 1500°C. Interestingly, activation energy for oxygen migration in the series decreases as La-content increases, from 1.13 eV for Gd2Zr2O7 to 0.81 eV for GdLaZr2O7, whereas ionic conductivity was found to be almost La-content independent, at least for y ≤ 0.8 at T = 500°C and y ≤ 0.4 at T = 800°C. These results are explained in terms of weaker ion-ion interactions in better ordered structures (i.e., as La-content increases and highlight the importance of structural ordering/disordering in determining the dynamics of mobile oxygen ions.Partiendo de mezclas estequiométricas de los óxidos correspondientes, se prepararon por molienda mecánica y a temperatura ambiente diferentes composiciones en la solución sólida Gd2-yLayZr2O7 (0 ≤ y ≤ 1 con estructura de tipo pirocloro y conductora de iones oxígeno. Independientemente del contenido de lantano, los polvos extraídos del molino presentaron difractogramas similares al de una fluorita no estequiométrica aunque en todos los casos, el tratamiento térmico a 1500°C indujo la aparición del ordenamiento de largo alcance de cationes y vacancias aniónicas característico de pirocloros. La energía de activación para el proceso de migración de iones oxígeno en la serie disminuye a medida que se incrementa el contenido de lantano, desde 1.13 eV de Gd2Zr2O7 hasta 0.81 eV de GdLaZr2O7, mientras que la conductividad resultó ser prácticamente independiente del mismo hasta y ≤ 0.8 para T = 500°C e y ≤ 0.4 para T = 800

  4. A study of low-energy ion induced radiolysis of thiol-containing amino acid cysteine in the solid and aqueous solution states

    Science.gov (United States)

    Ke, Zhigang; Huang, Qing; Dang, Bingrong; Lu, Yilin; Yuan, Hang; Zhang, Shuqing; Yu, Zengliang

    2010-09-01

    The radiolysis of cysteine under plasma discharge and irradiation of low-energy ion beam was investigated. The damage of cysteine in aqueous solution under discharge was assessed via the acid ninhydrin reagent and the yield of cystine produced from the reaction was analyzed by FTIR. In addition, the generation of hydrogen sulfide was also identified. The destruction of solid cysteine under low-energy ion beam irradiation was estimated via monitoring IR bands of different functional groups (-SH, -NH 3, -COO -) of cysteine, and the production of cystine from ion-irradiated solid cysteine after dissolution in water was also verified. These results may help us to understand the inactivation of sulphydryl enzymes under direct and indirect interaction with the low-energy ion irradiation.

  5. A study of low-energy ion induced radiolysis of thiol-containing amino acid cysteine in the solid and aqueous solution states

    Energy Technology Data Exchange (ETDEWEB)

    Ke Zhigang [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Huang Qing, E-mail: huangq@ipp.ac.c [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Dang Bingrong [Institute of Modern Physics, Chinese Academy of Sciences, 509 Nanchang Road, Lanzhou 730000 (China); Lu Yilin [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Department of Physics, Anhui University, Hefei 230031 (China); Yuan Hang; Zhang Shuqing; Yu Zengliang [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China)

    2010-09-15

    The radiolysis of cysteine under plasma discharge and irradiation of low-energy ion beam was investigated. The damage of cysteine in aqueous solution under discharge was assessed via the acid ninhydrin reagent and the yield of cystine produced from the reaction was analyzed by FTIR. In addition, the generation of hydrogen sulfide was also identified. The destruction of solid cysteine under low-energy ion beam irradiation was estimated via monitoring IR bands of different functional groups (-SH, -NH{sub 3}, -COO{sup -}) of cysteine, and the production of cystine from ion-irradiated solid cysteine after dissolution in water was also verified. These results may help us to understand the inactivation of sulphydryl enzymes under direct and indirect interaction with the low-energy ion irradiation.

  6. Site-selective radiolabeling of peptides by (18)F-fluorobenzoylation with [(18F)]SFB in solution and on solid phase: a comparative study.

    Science.gov (United States)

    Kuchar, Manuela; Pretze, Marc; Kniess, Torsten; Steinbach, Jörg; Pietzsch, Jens; Löser, Reik

    2012-10-01

    Peptides labeled with short-lived positron-emitting radionuclides are of outstanding interest as probes for molecular imaging by positron emission tomography (PET). Herein, the site-selective incorporation of fluorine-18 into lysine-containing peptides using the prosthetic labeling agent N-succinimidyl 4-[(18)F]fluorobenzoate ([(18)F]SFB) is described. The reaction of [(18)F]SFB with four biologically relevant resin-bound peptides was studied and optimized. For comparison, each peptide was 18F-fluorobenzoylated in solution under different conditions and the product distribution was analyzed confirming the advantages of the solid-phase approach. The method's feasibility for selective radiolabeling either at the N-terminus or at the lysine side chain was demonstrated. Labeling on solid phase with [(18)F]SFB resulted in crude (18)F-fluorobenzoylpeptides whose radiochemical purities were typically greater than 90% and that could be prepared in synthesis times from 65 to 76 min.

  7. Synthesis and thermostructural studies of a CuFe(1-x)Cr(x)O(2) delafossite solid solution with 0

    Science.gov (United States)

    Lalanne, M; Barnabé, A; Mathieu, F; Tailhades, Ph

    2009-07-06

    In this work, different CuFe(1-x)Cr(x)O(2) compositions with 0 solid-state reaction. These oxides crystallize with the delafossite structure. The phase stability and thermal behavior of the complete CuFe(1-x)Cr(x)O(2) solid solution was studied by thermogravimetric analysis and high-temperature X-ray diffraction experiments under an air atmosphere up to 1000 degrees C. For x = 0, CuFeO(2) is oxidized into the spinel (CuFe(2)O(4)) and copper monoxide (CuO) phases, whereas for x = 1, CuCrO(2) is thermally stable. For all of the intermediate compositions (0 < x < 1), complex oxidation, reduction, and phase transitions between delafossite and spinel have been observed. chromium tends to stabilize the stoichiometric delafossite phase, while iron favors the delafossite-to-spinel phase transition.

  8. Structural disorder and transformation in crystal growth: direct observation of ring-opening isomerization in a metal–organic solid solution

    Directory of Open Access Journals (Sweden)

    Ji-Jun Jiang

    2014-09-01

    Full Text Available A rare example is reported in which discrete Ag2L2 ring and (AgL∞ chain motifs [L = N,N′-bis(3-imidazol-1-yl-propyl-pyromellitic diimide] co-crystallize in the same crystal lattice with varying ratios and degrees of disorder. Crystal structures obtained from representative crystals reveal compatible packing arrangements of the cyclic and polymeric isomers within the crystal lattice, which enables them to co-exist within a crystalline solid solution. A feasible pathway for transformation between the isomers is suggested via facile rotation of the coordinating imidazolyl groups. This chemical system could provide a chance for direct observation of ring-opening isomerization at the crystal surface. Mass spectrometry and 1H NMR titration show a dynamic equilibrium between cyclic and oligomeric species in solution, and a potential crystallization process is suggested involving alignment of precursors directed by aromatic stacking interactions between pyromellitic diimide units, followed by ring-opening isomerization at the interface between the solid and the solution. Both cyclic and oligomeric species can act as precursors, with interconversion between them being facile due to a low energy barrier for rotation of the imidazole rings. Thermogravimetric analysis and variable-temperature powder X-ray diffraction indicate a transition to a different crystalline phase around 120°C, which is associated with loss of solvent from the crystal lattice.

  9. Solid-state structure, dynamical properties in solution and computational studies of a new sodium hemispherand complex

    NARCIS (Netherlands)

    van Veggel, F.C.J.M.; van Duynhoven, J.P.M.; van Duynhoven, John P.M.; Harkema, Sybolt; Oude Wolbers, M.P.; Reinhoudt, David

    1996-01-01

    The solid-state structure of 1·NaClO4 has been determined by X-ray diffraction and shows the Na+ complexed in an approximate hexagonal bipyrimidal fashion. The six ether oxygens form the ground plane, the inner carbonyl group and one of the two outer carbonyl groups occupy the apical positions. The

  10. La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO{sub 2} reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Valderrama, Gustavo [Laboratorio de Catalisis, Petroleo y Petroquimica, Unidad de Estudios Basicos, Universidad de Oriente - Nucleo Bolivar, La Sabanita - Calle San Simon, Estado Bolivar 8001 (Venezuela); Kiennemann, Alain [Laboratoire des Materiaux et Procedes pour la Catalyse, UMR 7515, ECPM, Universite Louis Pasteur, 25 rue Becquerel, 67087 Strasbourg Cedex 2 (France); Goldwasser, Mireya R. [Centro de Catalisis, Petroleo y Petroquimica, Facultad de Ciencias - Universidad Central de Venezuela. Paseo los Ilustres, Los Chaguaramos, Caracas 1040 (Venezuela)

    2010-04-02

    La{sub 1-x}Sr{sub x}Ni{sub 0.4}Co{sub 0.6}O{sub 3} and La{sub 0.8}Sr{sub 0.2}Ni{sub 1-y}Co{sub y}O{sub 3} solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO{sub 2} to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH{sub 4}/CO{sub 2} = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La{sub 0.9}Sr{sub 0.1}CoO{sub 3} and/or La{sub 0.9}Sr{sub 0.1}NiO{sub 3} as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni{sup 0}, Co{sup 0} with particle sizes in the range of nanometers over the SrO and La{sub 2}O{sub 3} phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction. (author)

  11. Solid solution studies of layered honeycomb-ordered phases O₃–Na₃M₂SbO₆ (M=Cu, Mg, Ni, Zn)

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Whitney; Berthelot, Romain; Sleight, A.W. [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2013-05-01

    Complete solid solutions with the composition Na₃M2–xxSbO₆ where M, M´=Cu, Mg, Ni, Zn have been synthesized by conventional solid state techniques and were investigated using X-ray diffraction, magnetic susceptibility and optical measurements. All compositions crystallize in a monoclinic unit cell and exhibit a layered structure with a honeycomb cationic ordering within the slabs. These compounds also exhibit Curie–Weiss behavior at high temperature and the magnetic moment values verify the presence of Cu²⁺ and/or Ni²⁺. The antiferromagnetic order of Na₃Ni₂SbO₆ is suppressed upon substitution of Ni²⁺ with Mg²⁺ or Zn²⁺. The spin gap observed in Na₃Cu₂SbO₆ is also suppressed by substitution of Cu²⁺ with Mg²⁺ or Zn²⁺. The Na₃Ni2–xCuxSbO₆ compositions follow an expected transition from an antiferromagnetic ordering to the spin gap of the copper end member. The estimated band gaps for these compounds have been determined from diffuse reflectance measurements. - Graphical abstract: Complete solid solutions with the composition Na₃M2–xxSbO₆ where M, M´=Cu, Mg, Ni, Zn have been synthesized using conventional solid state techniques and were investigated using X-ray diffraction, magnetism and optical measurements. Based on an ionic radii point of view the lattice parameter shifting in the composition containing copper are opposite of what would be expected. The Cu²⁺ is Jahn–Teller active which distorts the C2/m cell, increasing the β angle between the a and c parameters and explains this shifting pattern. Highlights: • The solid solutions O₃–Na₃M2–xxSbO₆(M, M´=Cu, Mg, Ni, Zn) were synthesized. • These compounds crystallize in the C2/m space group. • The Jahn–Teller active Cu²⁺ causes distortion of the monoclinic cell. • The Cu²⁺ spin gap magnetic properties are diluted upon 25% substitution

  12. Leachable diphenylguanidine from rubber closures used in pre-filled syringes: A case study to understand solid and solution interactions with oxytocin.

    Science.gov (United States)

    Zidan, Ahmed S; Aqueel, Sabir M; Alayoubi, Alaadin; Mohammad, Adil; Zhang, Jinhui; Rahman, Ziyaur; Faustino, Patrick; Lostritto, Richard T; Ashraf, Muhammad

    2017-10-30

    Leachables derived from multi-component drug-device syringe systems can result in changes to the quality of drug products. Diphenylguanidine (DPG), a leachable released from styrene butadiene rubber syringe plungers, interacts with Oxytocin to form protein-adducts. This study investigated the mechanism and kinetics of this interaction in both solid and solution states through in-vitro tests and spectroscopic methods For solid state interaction, the protein-adducts with DPG were characterized using SEM, XRD, DSC, FTIR, 13 C ss NMR, and dissolution analysis. For solution state interaction, LC-HRMS was used to assess stability of Oxytocin solutions in presence of various concentrations of DPG at 25°C and 40°C for 4 weeks. Moreover, molecular docking analysis was used to identify possible molecular configurations of the interaction.Results were consistent with the formation of a new solid state with distorted surface morphology for oxytocin-DPG adducts, in which the oxytocin carbonyl group(s) and the secondary amine groups of DPG interact. This interaction was also confirmed by molecular docking analysis through hydrogen bonding (2.31Å) and Van der Waal attraction (3.14Å). Moreover, LC-HRMS analysis revealed an increase in Oxytocin stability and suppression of Oxytocin dimerization by DPG. A potential reduction in the rate of Oxytocin dissolution from the formed adducts was indicative of its strong association with DPG. Hence, the leaching potential of DPG from rubber closures and plungers should be monitored and controlled to maintain the quality and stability of the pharmaceutical product. Published by Elsevier B.V.

  13. Solid-phase extraction on C18 silica as a purification strategy in the solution synthesis of a 1-thio-beta-D-galactopyranoside library.

    Science.gov (United States)

    Nilsson, U J; Fournier, E J; Hindsgaul, O

    1998-09-01

    A novel strategy for the purification of carbohydrate-based chemical libraries synthesized in solution was developed. Purification of reaction products was accomplished by means of solid-phase extraction enabled by protecting the 2-, 3-, 4-, and 6-hydroxyl groups of a galactose derivative as their hydrophobic O-laurates. The presence of multiple O-laurates allowed adsorption of reaction products onto C18 silica while reagents and by-products were washed away with MeOH. Products were quantitatively eluted with pentane. Purification of products using solid-phase extraction offers the combined advantages of solution synthesis (normal solution reactivity and ease of reaction monitoring) with those of solid-phase synthesis (facile product isolation permitting the use of large excesses of reagents). To demonstrate the utility of the hydrophobic recovery-procedure, tetra-O-lauroyl-beta-D-galactopyranose-1-thiol was subjected to high-yielding reactions with a panel of Michael-acceptors and an alpha-chloro ketone. The resulting ketone adducts were then either reduced to the alcohols or reductively aminated with a selection of amino acids to give 30 different 1-thio-beta-D-galactosides as mixtures of four diastereomers after removal of protecting groups. At each step, the product was separated from the reagents and their by-products by simple adsorption onto C18 silica, washing with MeOH and elution of product with pentane. After completion of the combinatorial chemistry sequence, the O-laurates were cleaved by methanolysis and the product methyl laurate in turn removed from the desired water-soluble products by C18 adsorption. Individual library members were thus conveniently produced on 10-30 mg scales at purity levels of > 90%. One of the 1-thio-beta-D-galactosides thus produced was found to be a competitive inhibitor of the beta-galactosidase from E. coli with Ki value of 1.7 microM.

  14. Changes in the Spectral Features of Zinc Phthalocyanine Induced by Nitrogen Dioxide Gas in Solution and in Solid Polymer Nanofiber Media.

    Science.gov (United States)

    Zugle, Ruphino; Tetteh, Samuel

    2017-03-01

    The changes in the spectral features of zinc phthalocyanine in the visible domain as a result of its interaction with nitrogen dioxide gas were assessed in this work. This was done both in solution and when the phthalocyanine was incorporated into a solid polystyrene polymer nanofiber matrix. The spectral changes were found to be spontaneous and marked in both cases suggesting a rapid response criterion for the detection of the gas. In particular, the functionalised nano-fabric material could serve as a practical fire alarm system as it rapidly detects the nitrogen dioxide gas generated during burning.

  15. Enhanced detection of explosives by turn-on resonance Raman upon host-guest complexation in solution and the solid state

    DEFF Research Database (Denmark)

    Witlicki, Edward H.; Bähring, Steffen; Johnsen, Carsten

    2017-01-01

    complexation occur via a mechanism of resonance between the 785 nm laser line and the strongly absorbing charge-transfer chromophore arising from the complex between electron-donating TTF-C[4]P and electron-accepting nitroaromatic explosives. The addition of chloride forms the Cl-·TTF-C[4]P complex resetting......The recognition of nitroaromatic explosives by a tetrakis-tetrathiafulvalene-calix[4]pyrrole receptor (TTF-C[4]P) yields a "turn on" and fingerprinting response in the resonance Raman scattering observed in solution and the solid state. Intensity changes in nitro vibrations with analyte...

  16. Synthesis of the metastable α-Al1.8Fe0.2O3 solid solution from precursors prepared by combustion

    OpenAIRE

    Cordier, Anne; Peigney, Alain; De Grave, Eddy; Flahaut, Emmanuel; Laurent, Christophe

    2006-01-01

    The aim of the paper is to synthesise α-Al1.8Fe0.2O3 solid solutions from precursors prepared by the nitrate/fuel combustion synthesis route, using either citric acid or urea, or a mixture of both as the fuel, and different fuel/nitrates ratios. In a first part, global reactions are proposed for each synthesis, which are useful to explain the differences in powder volume, morphology, crystallisation state and specific surface area reported in the second part of the study. In a third part, the...

  17. Long-time Luminescence Kinetics of Localized excitons and conduction Band Edges Smearing in ZnSe(1-c)Tec Solid Solutions

    DEFF Research Database (Denmark)

    Klochikhin, O.; Ogloblin, S. G.; Permogorov, S.

    2000-01-01

    It is shown that the integrated luminescence intensity of localized excitons in solid solutions ZnSe(1 - c)Tec has a component slowly decaying with time. After the excitation above the mobility threshold, the long-time intensity decreases exponentially, with a fractional exponent changing from a ...... a value corresponding to the critical index of anomalous diffusion to the index of normal diffusion as the temperature increases from 5 to 80 K. This change allows estimation of the energy scale for the fluctuation tail of the conduction band. (C) 2000 MAIK "Nauka / Interperiodica"....

  18. Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

    Energy Technology Data Exchange (ETDEWEB)

    Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

    2016-12-23

    The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Tetragonal-cubic phase boundary in nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions synthesized by gel-combustion

    Energy Technology Data Exchange (ETDEWEB)

    Fabregas, Ismael O. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Craievich, Aldo F.; Fantini, Marcia C.A. [Instituto de Fisica, Universidade de Sao Paulo, Travessa R da Rua do Matao, No. 187, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Millen, Ricardo P.; Temperini, Marcia L.A. [Instituto de Quimica, Universidade de Sao Paulo, Avenida Prof. Lineu Prestes 748, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Lamas, Diego G., E-mail: dlamas@uncoma.edu.ar [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Laboratorio de Caracterizacion de Materiales, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen Capital, Prov. de Neuquen (Argentina)

    2011-04-21

    Research highlights: > Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders, that exhibit the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms (t' and t'') and the cubic phase. > Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. > The crystallographic features of ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. > Compositional t'/t'' and t''/cubic phase boundaries are located at (9 {+-} 1) and (10.5 {+-} 0.5) mol% Y{sub 2}O{sub 3}, respectively. > For the whole series of nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions, the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid

  20. Synthesis and characterization of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gatimu, Alvin J.; Berthelot, Romain; Muir, Sean; Sleight, Arthur W. [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2012-06-15

    The effects of Ti, Fe and Co substitutions for Ir on the structure and on the physical properties of Sr{sub 2}IrO{sub 4} are investigated. A complete solid solution Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} is obtained while both Fe and Co doping are relatively limited. In each case however, the c-axis cell parameter and the initial IrO{sub 6} octahedra tilting decreases with substitution. Doping with Ti, Fe and Co results in a decrease of the magnetic susceptibility and in an increase in the paramagnetic effective moment for Co and Fe doped samples and a suppression of the weak ferromagnetic ordering observed for Sr{sub 2}IrO{sub 4}. - Graphical abstract: Solid solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) have been synthesized and characterized by powder X-ray diffraction, magnetism and electrical measurements. Changes in the a parameter and decreases in both the c-axis cell parameters and the initial IrO{sub 6} octahedra tilting are found to be correlated. Highlights: Black-Right-Pointing-Pointer Solid Solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) are synthesized. Black-Right-Pointing-Pointer The Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} solid solution is complete while those of Fe and Co are relatively limited. Black-Right-Pointing-Pointer The change in a cell parameter with substitution is much less than that of the c parameter. Black-Right-Pointing-Pointer Decreased tilting and the smaller size of the M cation contrastingly affect the a parameter. Black-Right-Pointing-Pointer Doping results in a suppression of the weak ferromagnetic ordering in Sr{sub 2}IrO{sub 4}.

  1. Strong work-hardening behavior induced by the solid solution strengthening of dendrites in TiZr-based bulk metallic glass matrix composites

    Energy Technology Data Exchange (ETDEWEB)

    Ma, D.Q. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Jiao, W.T. [College of Education, Hebei Normal University of Science and Technology, Qinhuangdao 066004 (China); Zhang, Y.F. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Hebei Vocational and Technical College of Building Materials, Qinhuangdao 066004 (China); Wang, B.A.; Li, J.; Zhang, X.Y. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Ma, M.Z., E-mail: mz550509@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Liu, R.P. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China)

    2015-03-05

    Highlights: • Hardness of dendrite of TiZr-based BMGMCs increases. • Strong work-hardening behavior is obtained after solid solution strengthening. • Lattice distortions of dendrite suffering from rapid cooling are detected. - Abstract: A series of TiZr-based bulk metallic glass matrix composites (BMGMCs) with distinguished mechanical properties are successfully fabricated by adding different volume fractions of Ta (Ti{sub 38.8}Zr{sub 28.8}Cu{sub 6.2}Be{sub 16.2}Nb{sub 10} as the basic composition, denoted as Ta{sub 0.0}–Ta{sub 8.0}). Along with the growth of precipitated phase, typical dendritic morphology is fully developed in the TiZr-based BMGMCs of Ta{sub 8.0}. Energy-dispersive spectrometry analysis of the dendrites and glass matrix indicates that the metallic elements of Nb and Ta should preferentially form solid solution into dendrites. The chaotic structure of high-temperature precipitate phase is trapped down by the rapid cooling of the copper-mould. The detected lattice distortions in the dendrites are attributed to the strong solid solution strengthening of the metallic elements of Ti, Zr, Nb, and Ta. These lattice distortions increase the resistance of the dislocation motion and pin the dislocations, thus the strength and hardness of dendrite increase. Dendrites create a strong barrier for the shear band propagation and generate multiple shear bands after solid solution strengthening, thereby providing the TiZr-based BMGMCs with greatly improved capacity to sustain plastic deformation and resistance to brittle fracture. Thus, the TiZr-based BMGMCs possess distinguished work-hardening capability. Among these TiZr-based BMGMCs, the sample Ta{sub 0.5} possesses the largest plastic strain (ε{sub p}) at 20.3% and ultimate strength (σ{sub max}) of 2613 MPa during compressive loading. In addition, the sample of Ta{sub 0.5} exhibits work-hardening up to an ultrahigh tensile strength of 1680 MPa during the tensile process, and then progressively

  2. Adsorption of Polyacrylamide (PAA) from Solution on Solid Surfaces (Adsorbsiya Polyakrilamida (PAA) 12 Rastvorov na Tverdoi Poverkhosti),

    Science.gov (United States)

    and under filtration conditions. Both ammoniacal and calciferous polyacrylamide solutions were investigated. In the absence of dissolved inorganic...salts, calciferous polyacrylamide is less highly absorbed when its degree of hydrolysis is increased. Presumably this is true of ammoniacal

  3. Role of the chemical substitution on the luminescence properties of solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} (0 ≤ x ≤1)

    Energy Technology Data Exchange (ETDEWEB)

    Taoufyq, A. [Institut Matériaux Microélectronique et Nanosciences de Provence, Aix Marseille Université, CNRS, Université de Toulon, IM2NP UMR 7334, 83957 La Garde (France); Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir (Morocco); CEA, DEN, Département d' Etudes des Réacteurs, Service de Physique Expérimentale, Laboratoire Dosimétrie Capteurs Instrumentation, 13108 Saint-Paul-lez-Durance (France); Mauroy, V.; Guinneton, F. [Institut Matériaux Microélectronique et Nanosciences de Provence, Aix Marseille Université, CNRS, Université de Toulon, IM2NP UMR 7334, 83957 La Garde (France); Bakiz, B. [Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir (Morocco); Villain, S. [Institut Matériaux Microélectronique et Nanosciences de Provence, Aix Marseille Université, CNRS, Université de Toulon, IM2NP UMR 7334, 83957 La Garde (France); and others

    2015-10-15

    Highlights: • Luminescence can be modified by chemical substitution in solid solutions Ca{sub 1−x}Cd{sub x}WO{sub 4}. • The various emission spectra (charge transfer) were obtained under X-ray excitation. • Scheelite or wolframite solid solutions presented two types of emission spectra. • A luminescence component depended on cadmium substitution in each solid solution. • A component was only characteristic of oxyanion symmetry in each solid solution. - Abstract: We have investigated the chemical substitution effects on the luminescence properties under X-ray excitation of the solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} with 0 ≤ x ≤ 1. Two types of wide spectral bands, associated with scheelite-type or wolframite-type solid solutions, have been observed at room temperature. We decomposed each spectral band into several spectral components characterized by energies and intensities varying with composition x. One Gaussian component was characterized by an energy decreasing regularly with the composition x, while the other Gaussian component was only related to the tetrahedral or octahedral configurations of tungstate groups WO{sub 4}{sup 2−} or WO{sub 6}{sup 6−}. The luminescence intensities exhibited minimum values in the composition range x < 0.5 corresponding to scheelite-type structures, then, they regularly increased for cadmium compositions x > 0.5 corresponding to wolframite-type structures.

  4. Solution- and Solid-Phase Macrocyclization of Peptides by the Ugi-Smiles Multicomponent Reaction: Synthesis of N-Aryl-Bridged Cyclic Lipopeptides.

    Science.gov (United States)

    Morejón, Micjel C; Laub, Annegret; Westermann, Bernhard; Rivera, Daniel G; Wessjohann, Ludger A

    2016-08-19

    A new multicomponent methodology for the solution- and solid-phase macrocyclization of peptides is described. The approach comprises the utilization of the Ugi-Smiles reaction for the cyclization of 3-nitrotyrosine-containing peptides either by the N-terminus or the lysine side-chain amino groups. Both the on-resin and solution cyclizations took place with good to excellent efficiency in the presence of an aldehyde and a lipidic isocyanide, while the use of paraformaldehyde required an aminocatalysis-mediated imine formation prior to the on-resin Ugi-Smiles ring closure. The introduction of a turn motif in the peptide sequence facilitated the cyclization step, shortened the reaction time, and delivered crude products with >90% purity. This powerful method provided a variety of structurally novel N-aryl-bridged cyclic lipopeptides occurring as single atropisomers.

  5. Cluster formation of endohedral metallofullerenes with Y, Gd, and Ho in a solution and on a solid surface

    Science.gov (United States)

    Kareev, I. E.; Bubnov, V. P.; Alidzhanov, E. K.; Pashkevich, S. N.; Lantukh, Yu. D.; Letuta, S. N.; Razdobreev, D. A.

    2016-09-01

    The formation of endohedral metallofullerene clusters with Y, Gd, and Ho in an N, N-dimethylformamide solution and on a mica substrate surface has been investigated using static and dynamic light scattering and atomic force microscopy, respectively. It has been found that the size distribution of the clusters depends on the concentration of endohedral metallofullerenes and on the exposure time of the solution. It has been shown that the clusters are resistant to high temperatures and ultrasound effects. The concentration of endohedral metallofullerenes at which only single clusters are formed in the solutions has been determined. It has been established that an increase in the concentration of endohedral metallofullerenes leads to the agglomeration of single clusters. The fractal dimension has been estimated, and the zeta potential of endohedral metallofullerene clusters has been measured.

  6. Structure and membrane interactions of the antibiotic peptide dermadistinctin K by multidimensional solution and oriented 15N and 31P solid-state NMR spectroscopy.

    Science.gov (United States)

    Verly, Rodrigo M; de Moraes, Cléria Mendonça; Resende, Jarbas M; Aisenbrey, Christopher; Bemquerer, Marcelo Porto; Piló-Veloso, Dorila; Valente, Ana Paula; Almeida, Fábio C L; Bechinger, Burkhard

    2009-03-18

    DD K, a peptide first isolated from the skin secretion of the Phyllomedusa distincta frog, has been prepared by solid-phase chemical peptide synthesis and its conformation was studied in trifluoroethanol/water as well as in the presence of sodium dodecyl sulfate and dodecylphosphocholine micelles or small unilamellar vesicles. Multidimensional solution NMR spectroscopy indicates an alpha-helical conformation in membrane environments starting at residue 7 and extending to the C-terminal carboxyamide. Furthermore, DD K has been labeled with (15)N at a single alanine position that is located within the helical core region of the sequence. When reconstituted into oriented phosphatidylcholine membranes the resulting (15)N solid-state NMR spectrum shows a well-defined helix alignment parallel to the membrane surface in excellent agreement with the amphipathic character of DD K. Proton-decoupled (31)P solid-state NMR spectroscopy indicates that the peptide creates a high level of disorder at the level of the phospholipid headgroup suggesting that DD K partitions into the bilayer where it severely disrupts membrane packing.

  7. Attractive forces between hydrophobic solid surfaces measured by AFM on the first approach in salt solutions and in the presence of dissolved gases.

    Science.gov (United States)

    Azadi, Mehdi; Nguyen, Anh V; Yakubov, Gleb E

    2015-02-17

    Interfacial gas enrichment of dissolved gases (IGE) has been shown to cover hydrophobic solid surfaces in water. The atomic force microscopy (AFM) data has recently been supported by molecular dynamics simulation. It was demonstrated that IGE is responsible for the unexpected stability and large contact angle of gaseous nanobubbles at the hydrophobic solid-water interface. Here we provide further evidence of the significant effect of IGE on an attractive force between hydrophobic solid surfaces in water. The force in the presence of dissolved gas, i.e., in aerated and nonaerated NaCl solutions (up to 4 M), was measured by the AFM colloidal probe technique. The effect of nanobubble bridging on the attractive force was minimized or eliminated by measuring forces on the first approach of the AFM probe toward the flat hydrophobic surface and by using high salt concentrations to reduce gas solubility. Our results confirm the presence of three types of forces, two of which are long-range attractive forces of capillary bridging origin as caused by either surface nanobubbles or gap-induced cavitation. The third type is a short-range attractive force observed in the absence of interfacial nanobubbles that is attributed to the IGE in the form of a dense gas layer (DGL) at hydrophobic surfaces. Such a force was found to increase with increasing gas saturation and to decrease with decreasing gas solubility.

  8. Oxalate coprecipitation synthesis and transport properties of polycrystalline Sr{sub 1-x}La{sub x}PbO{sub 3-{delta}} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Drozd, Vadim A.; Gabovich, Alexander M.; Pekala, Marek; Nedilko, Sergey A.; Gierlowski, Piotr

    2004-03-24

    Solid solutions Sr{sub 1-x}La{sub x}PbO{sub 3-{delta}} with x=0, 0.05, 0.1, 0.15, 0.2 and 0.25 were synthesized by oxalate precursor coprecipitation methods. The solid solutions obtained were analyzed by the XRD technique and iodometric titration. Resistivity {rho} and thermoelectric power S were measured for temperatures 20 K

  9. Relative Stability of FE and AFE States in (Na0,5Bi0,5) TiO3-based Solid Solutions

    Science.gov (United States)

    Sobolev, V. L.; Ishchuk, V. M.; Gusakova, L. G.; Kisel, N. G.; Kuzenko, D. V.; Spiridonov, N. A.

    2015-03-01

    Changes of the relative stability of antiferroelectric (AFE) and ferroelectric (FE) phases in the [(Na0.5Bi0.5)0.80 Ba0.20](Ti1-yBy) O3 system of solid solutions with the B-site ion substitutions have been studied. Ions of zirconium and tin along some ions complexes such as (InNb), (FeNb) and several others were used for substitutions. The increase in the substituent ion content leads to nearly linear variation of the crystal cell size along with changes of the relative stability of the AFE and FE phases according to the tolerance factor variation. Substituent ions with ionic radii larger than the ionic radius of original ion evoke a decrease of the FE-AFE phase transition temperature. The substituent ions with smaller ionic radii have the opposite effect. Our results demonstrate that the size of the substituent ion causes a predominant influence on the relative stability of the FE and AFE states in (Na0.5Bi0.5) TiO3-based solid solutions. Our studies also indicate the way to raise the FE-AFE phase transition temperature.

  10. Use of a screening method to determine excipients which optimize the extent and stability of supersaturated drug solutions and application of this system to solid formulation design.

    Science.gov (United States)

    Vandecruys, Roger; Peeters, Jef; Verreck, Geert; Brewster, Marcus E

    2007-09-05

    Assessing the effect of excipients on the ability to attain and maintain supersaturation of drug-based solution may provide useful information for the design of solid formulations. Judicious selection of materials that affect either the extent or stability of supersaturating drug delivery systems may be enabling for poorly soluble drug candidates or other difficult-to-formulate compounds. The technique suggested herein is aimed at providing a screening protocol to allow preliminary assessment of these factors based on small to moderate amounts of drug substance. A series of excipients were selected that may, by various mechanisms, affect supersaturation including pharmaceutical polymers such as HMPC and PVP, surfactants such as Polysorbate 20, Cremophor RH40 and TPGS and hydrophilic cyclodextrins such as HPbetaCD. Using a co-solvent based method and 25 drug candidates, the data suggested, on the whole, that the surfactants and the selected cyclodextrin seemed to best augment the extent of supersaturation but had variable benefits as stabilizers, while the pharmaceutical polymers had useful effect on supersaturation stability but were less helpful in increasing the extent of supersaturation. Using these data, a group of simple solid dosage forms were prepared and tested in the dog for one of the drug candidates. Excipients that gave the best extent and stability for the formed supersaturated solution in the screening assay also gave the highest oral bioavailability in the dog.

  11. The effect of Mn substitution on the structure and magnetic properties of Se(Cu{sub 1-x}Mn{sub x})O{sub 3} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Escamilla, R [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, 04510 Mexico DF (Mexico); Duran, A [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, 04510 Mexico DF (Mexico); Rosales, M I [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, 04510 Mexico DF (Mexico); Moran, E [Laboratorio Complutense de Altas Presiones and Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense, 28040-Madrid (Spain); Alario-Franco, M A [Laboratorio Complutense de Altas Presiones and Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense, 28040-Madrid (Spain)

    2003-04-02

    The effects of Mn substitution on the structure and magnetic properties of the SeMO{sub 3} (M = Cu{sub 1-x}Mn{sub x}) solid solution have been studied. Rietveld refinements of the x-ray diffraction patterns of these samples indicate that the manganese ions occupy copper sites. This replacement induces significant changes in the M-O bond lengths that give rise to abrupt decreases of the [M-O{sub 6}] octahedral distortion. In contrast, the M-O(1)-M and M-O(2)-M bond angles remain essentially constant. The magnetic behaviour of this solid solution was studied in the temperature range of 2 K < T < 300 K. The temperature dependence of the inverse magnetic susceptibility is well described by the Curie-Weiss law at high temperatures, in the composition range studied. We found that the substitution of Mn for Cu induces a sharp drop in the saturation moment of SeCuO{sub 3}. At about 10% of Mn there is a change from positive to negative Weiss constant {theta}{sub W} that is mainly due to the [M-O{sub 6}] octahedral distortion introduced by the substitution of the larger Mn ions in the structure. The M- H isotherms show a weak ferromagnetism at about 52 K in SeMnO{sub 3}.

  12. Combined major and trace element LA-ICP-MS analysis of compositional variations in simple solid solutions through cross correlation with an EPMA-characterized working standard.

    Science.gov (United States)

    Zellmer, Georg F; Dulski, Peter; Iizuka, Yoshiyuki

    2012-08-01

    Determining correlated major and trace element zoning profiles is an important goal in modern microanalysis and is critical to some geospeedometric applications. We show that a precise determination of relative variations in major element compositions of simple solid solutions is possible by LA-ICPMS, and that low accuracy (analytical bias) can be corrected for through cross correlation with electron problem microanalyzer (EPMA)-characterized working standards. Further, the relative uncertainties on binary or quasibinary solid solution endmember proportions are always lower than the relative uncertainties on the ratio of the principle substituting elements by at least a factor of 2. In calcic plagioclase, for example, the relative uncertainty on X(An) is a factor of (1-X(An)) smaller than the relative uncertainty on Ca/Na. Using a well-characterized, concentrically zoned bytownite crystal as an example, we compare reproducibilities of FE-EPMA and W-EPMA analyses with 2 μm beam diameter and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with 16 μm beam diameter. While the accuracy of LA-ICP-MS analyses is low (analytical bias), the precision of LA-ICP-MS analyses is slightly higher than that of FE-EPMA data and comparable to that of the W-EPMA data. EPMA-corrected LA-ICP-MS data can thus be used to characterize major oxide compositional variations and potential covariations with trace elements within individual crystals.

  13. Synthesis of coffinite, USiO4, and structural investigations of UxTh(1-x)SiO4 solid solutions.

    Science.gov (United States)

    Labs, Sabrina; Hennig, Christoph; Weiss, Stephan; Curtius, Hilde; Zänker, Harald; Bosbach, Dirk

    2014-01-01

    The miscibility behavior of the USiO4-ThSiO4 system was investigated. The end members and 10 solid solutions UxTh(1-x)SiO4 with x = 0.12-0.92 were successfully synthesized, without formation of other secondary uranium or thorium phases. Lattice parameters of the solid solutions evidently follow Vegard's Law. Investigation of the local structure with EXAFS reveals small differences between the U and Th environment attributed to different atomic radii of the metal atoms but no implications for a miscibility gap. The data provided confirm complete miscibility for the system USiO4-ThSiO4. The structure of the end members was studied in detail with XRD and discussed with special regard to the oxygen positions and the often neglected Si-O bond length. USiO4 could be obtained without UO2 impurities and the lattice parameters derived from Rietveld refinement as c = 6.2606(3) Å and a = 6.9841(3) Å. The Si-O distance in USiO4 appears to be 1.64 Å, which is more reasonable than earlier reported values.

  14. In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

    Science.gov (United States)

    Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

    2015-04-14

    Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

  15. Microstructural features of the La{sub 1−x}Ca{sub x}FeO{sub 3−δ} solid solutions prepared via Pechini route

    Energy Technology Data Exchange (ETDEWEB)

    Gerasimov, E.Yu., E-mail: gerasimov@catalysis.ru [Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Acad. Lavrentieva 5, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090 (Russian Federation); Isupova, L.A. [Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Acad. Lavrentieva 5, Novosibirsk 630090 (Russian Federation); Tsybulya, S.V. [Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Acad. Lavrentieva 5, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090 (Russian Federation)

    2015-10-15

    Highlights: • La{sub 1−x}Ca{sub x}FeO {sub (3−δ)} (0 ≤ x ≤ 0.7) perovskite were prepared by Pechini method. • Planar defects in direction (1 0 1) were observed in the perovskite surface. • α-Fe{sub 2}O{sub 3} particles (1–10 nm) on the surface of perovskite were revealed. • Amount of α-Fe{sub 2}O{sub 3} particles on the perovskite surface grew with rising x values. - Abstract: Solid solutions with La{sub 1−x}Ca{sub x}FeO{sub 3−δ} (0 ≤ x ≤ 0.7) perovskite-like structure prepared via Pechini route have been investigated by using high resolution transmission electron microscopy and X-ray diffraction. Extended planar defects lying in (1 0 1) crystallographic planes and α-Fe{sub 2}O{sub 3} nanoparticles on the surface of perovskite microcrystals are characteristic of the samples under investigation. It was found that testing of the samples in catalytic deep CH{sub 4} oxidation process results in partial destruction of solid solutions with formation of planar defects in the bulk and α-Fe{sub 2}O{sub 3} particles on the surface.

  16. SOLID SOLUTION EFFECTS ON THE THERMAL PROPERTIES IN THE MgAl2O4-MgGa2O4

    Energy Technology Data Exchange (ETDEWEB)

    O' Hara, Kelley [University of Missouri, Rolla; Smith, Jeffrey D [ORNL; Sander, Todd P. [Missouri University of Science and Technology; Hemrick, James Gordon [ORNL

    2013-01-01

    Solid solution eects on thermal conductivity within the MgO-Al2O3-Ga2O3 system were studied. Samples with systematically varied additions of MgGa2O4 to MgAl2O4 were prepared and the laser ash technique was used to determine thermal diusivity at temperatures between 200C and 1300C. Heat capacity as a function of temperature from room temperature to 800C was also determined using dierential scanning calorimetry. Solid solution in the MgAl2O4-MgGa2O4 system decreases the thermal conductivity up to 1000C. At 200C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. At 1000C the thermal conductivity decreased 13% with a 5 mol% addition. Steady state calculations showed a 12.5% decrease in heat ux with 5 mol% MgGa2O4 considered across a 12 inch thickness.

  17. Ab initio Assessment of Bi1-xRExCuOS (RE=La, Gd, Y, Lu) Solid Solution as Semiconductor for Photochemical Water Splitting

    KAUST Repository

    Lardhi, Sheikha F.

    2017-04-12

    The investigation of BiCuOCh (Ch = S, Se and Te) semiconductors family for thermoelectric or photovoltaic materials is an increasing topic of research. These materials can also be considered for photochemical water splitting if one representative having a bandgap, Eg, around 2 eV can be developed. With this aim, we simulated the solid solution Bi1-xRExCuOS (RE = Y, La, Gd and Lu) from pure BiCuOS (Eg~1.1 eV) to pure RECuOS compositions (Eg~2.9 eV) by DFT calculations based on the HSE06 range-separated hybrid functional with inclusion of spin-orbit coupling. Starting from the thermodynamic stability of the solid solution, a large variety of properties were computed for each system including bandgap, dielectric constants, effective masses and exciton binding energies. We discussed the variation of these properties based on the relative organization of Bi and RE atoms in their common sublattice to offer a physical understanding of the influence of the RE doping of BiCuOS. Some compositions were found to give appropriate properties for water splitting application. Furthermore, we found that at low RE fractions the transport properties of BiCuOS are improved that can find applications beyond water splitting.

  18. The impact of local structure variation on thermal quenching of luminescence in Ca3MoxW1-xO6:Eu3+ solid solution phosphors

    Science.gov (United States)

    Wang, Chunhao; Ye, Shi; Li, Ye; Zhang, Qinyuan

    2017-03-01

    Near-ultraviolet (NUV, 365-410 nm) excitable white light emitting diodes require intense absorption in the NUV region for the tri-color phosphors (red, green, and blue). Optional red phosphor Ca3MoO6:Eu3+ meets the requirement of NUV absorption but suffers from severe quenching, while Ca3WO6:Eu3+ has good resistance to thermal quenching but could not absorb NUV light efficiently. It is requisite to investigate the candidate Ca3MoxW1-xO6:Eu3+ to balance the both effects. Results indicate that thermal quenching turns to be worse with an increase in Mo contents in the solid solutions with inevitable distortions or defects, especially when exciting the charge transfer band of WO6 and MoO6 groups. Temperature-dependent Raman spectroscopy is utilized to reveal the impact of structural variation in the quenching process since the variations influence the energy transfer between WO6/MoO6 groups and Eu3+ ions or among Eu3+ ions. Results show that the tilting or distortion of the Ca/W/MoO6 octahedral framework and weakened Eu3+-O bonds have large impacts on thermal quenching performance of Eu3+ luminescence in the solid solutions. The research would benefit the design of novel red phosphors.

  19. Hierarchical architectures of ZnS–In{sub 2}S{sub 3} solid solution onto TiO{sub 2} nanofibers with high visible-light photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Chengbin, E-mail: chem_cbliu@hnu.edu.cn [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063 (China); Meng, Deshui; Li, Yue; Wang, Longlu [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Liu, Yutang, E-mail: liuyutang@126.com [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Luo, Shenglian [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063 (China)

    2015-03-05

    Graphical abstract: A unique hierarchical architecture of ZnS–In{sub 2}S{sub 3} solid solution onto TiO{sub 2} nanofibers was fabricated. The hierarchical heterostructures exhibit high visible light photocatalytic activity and outstanding recycling performance. - Highlights: • Novel hierarchical heterostructure of TiO{sub 2}@ZnS–In{sub 2}S{sub 3} solid solution. • Efficient inhibition of ZnS–In{sub 2}S{sub 3} solid solution aggregation. • High visible light photocatalytic activity. • Highly stable recycling performance. - Abstract: A unique hierarchical architecture of ZnS–In{sub 2}S{sub 3} solid solution nanostructures onto TiO{sub 2} nanofibers (TiO{sub 2}@ZnS–In{sub 2}S{sub 3}) has been successfully fabricated by simple hydrothermal method. The ZnS–In{sub 2}S{sub 3} solid solution nanostructures exhibit a diversity of morphologies: nanosheet, nanorod and nanoparticle. The porous TiO{sub 2} nanofiber templates effectively inhibit the aggregation growth of ZnS–In{sub 2}S{sub 3} solid solution. The formation of ZnS–In{sub 2}S{sub 3} solid solution is proved by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and the intimate contact between TiO{sub 2} nanofibers and ZnS–In{sub 2}S{sub 3} solid solution favors fast transfer of photogenerated electrons. The trinary TiO{sub 2}@ZnS–In{sub 2}S{sub 3} heterostructures exhibit high adsorption capacity and visible light photocatalytic activity for the degradation of rhodamine B dye (RhB), remarkably superior to pure TiO{sub 2} nanofibers or binary structures (ZnS/TiO{sub 2} nanofibers, In{sub 2}S{sub 3}/TiO{sub 2} nanofibers and ZnS–In{sub 2}S{sub 3} solid solution). Under visible light irradiation the RhB photocatalytic degradation rate over TiO{sub 2}@ZnS–In{sub 2}S{sub 3} heterostructures is about 16.7, 12.5, 6.3, 5.9, and 2.2 times that over pure TiO{sub 2} nanofibers, ZnS nanoparticles, In{sub 2}S{sub 3}/TiO{sub 2} nanofibers, ZnS/TiO{sub 2} nanofibers, and Zn

  20. Determination of lead in solution by solid phase extraction, elution, and spectrophotometric detection using 4-(2-pyridylazo)-resorcinol

    OpenAIRE

    Rahman, Ismail M. M.; Furusho, Yoshiaki; Begum, Zinnat A.; Sato, Rika; Okumura, Hiroshi; Honda, Hiroko; Hasegawa, Hiroshi

    2013-01-01

    Lead (+2) was selectively adsorbed on a solid phase extraction (SPE) gel (molecular recognition technology, MRT), quantitatively extracted, and spectrophotometrically determined as the Pb(II)-PAR (4-(2-pyridylazo)- resorcinol) complex. The linear range was 0.01 to 0.75 mg L-1 and the detection limit was 6.4 μg L-1. The MRT-SPE allows selective Pb(II) extraction from complex ion-rich matrices, which is difficult with other techniques. Interference from common matrix ions such as Fe2+, Ni2+, Cu...

  1. NaCu(Ta1-yNby)4O11 solid solution: A tunable band gap spanning the visible-light wavelengths

    Science.gov (United States)

    Palasyuk, Olena; Maggard, Paul A.

    2012-07-01

    The new solid-solution NaCu(Ta1-yNby)4O11 (0≤y≤0.7) was synthesized by solid-state methods in the form of bulk powders that ranged from light-yellow to brown colored and were characterized by powder X-ray diffraction techniques (Space group R-3c (#167); Z=6; a=6.214(1)-6.218(1) Å and c=36.86(1)-36.94(1) Å). Full-profile Rietveld refinements confirmed a site-differentiated ordering of the Cu(I) and Na cations, i.e., occupying the 12c (linear environment) and 18d (seven-coordinate environment) crystallographic sites respectively. Conversely, a statistical mixture of Ta(V) and Nb(V) cations occurred over the 6b (octahedral environment) or the 18e (pentagonal-bipyramidal environment) crystallographic sites, without any preferential segregation. The UV-Vis diffuse reflectance spectra showed a significant red-shift of the optical bandgap size (indirect) from ˜2.70 eV to ˜1.80 eV across the solid solution with increasing Nb(V) content. Electronic-structure calculations using the tight-binding linear-muffin-tin-orbital approach showed that the reduction in bandgap size arises from the introduction of the lower-energy Nb 4d0 orbitals into the conduction band and consequently a lower energy of the conduction band edge. The lowest-energy bandgap transitions were found to be derived from electronic transitions between the filled Cu(I) and the empty Nb(V) d-orbitals, with a small amount of mixing with the O 2p orbitals. The resulting conduction and valence band energies are found to approximately bracket the redox potentials for water reduction and oxidation, and meeting the thermodynamic requirements for photocatalytic water-splitting reactions.

  2. 2D all-solid state fabric supercapacitor fabricated via an all solution process for use in smart textiles

    Science.gov (United States)

    Jang, Yunseok; Jo, Jeongdai; Woo, Kyoohee; Lee, Seung-Hyun; Kwon, Sin; Kim, Kwang-Young; Kang, Dongwoo

    2017-05-01

    We propose a method to fabricate a supercapacitor for smart textiles using silver (Ag) nanoparticle (NP) ink, simple spray patterning systems, and intense pulsed light (IPL) sintering systems. The Ag NP current collectors provided as high conductivity as the metal current collectors. The spray patterning technique is useful for fabricating supercapacitors because it is simple, fast, and cheap. IPL systems reduced the sintering temperature of Ag NPs and prevented thermal damage to the textiles during the Ag NP sintering process. The two-dimensional (2D) all-solid state fabric supercapacitor with an interdigitated configuration, developed here, exhibited a specific capacitance of 25.7 F/g and an energy density of 1.5 Wh/kg at a power density of 64.3 W/kg. These results support the utility of our proposed method in the development of energy textiles.

  3. 2-Amino-4-methylpyrimidine: A simple supramolecular scaffold for carboxylic acid complexes both in solid and solution states

    Energy Technology Data Exchange (ETDEWEB)

    Kumar Mahapatra, Ajit, E-mail: mahapatra574@gmail.co [Department of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711103 (India); Sahoo, Prithidipa; Goswami, Shyamaprosad [Department of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711103 (India); Fun, Hoong-Kun [X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia)

    2011-01-15

    Studies concentrating on hydrogen bonding interactions between 2-amino-4-methylpyrimidine (AMPY) with selected dicarboxylic acids have been investigated in the solid state. Two pyrimidinium-dicarboxylate organic salts with stoichiometry 1:1 [AMPY: maleic acid] and 2:1 [AMPY:D(+)-malic acid] have been prepared and characterized by X-ray crystallographic analysis. Maleic and D(+)-malic acids were found to exhibit unique supramolecular polymeric structures with AMPY involving proton transfer to the specific ring nitrogen of AMPY. As an extension, AMPY has been used to build a receptor structure 1. Receptor 1 shows binding of dicarboxylic acids in CH{sub 3}CN and represents a marginal selectivity with D(+)-malic acid. Binding interactions were investigated by UV-vis and fluorescence studies.

  4. X-ray and neutron scattering on disordered nanosize clusters: a case study of lead-zirconate-titanate solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Frantti, Johannes; Fujioka, Yukari [Finnish Research and Engineering, Helsinki (Finland)

    2015-04-01

    Defects and frequently used defect models of solids are reviewed. Signatures for identifying the disorder from x-ray and neutron scattering data are given. To give illustrative examples how technologically important defects contribute to x-ray and neutron scattering numerical method able to treat non-periodical solids possessing several simultaneous defect types is given for simulating scattering in nanosize disordered clusters. The approach takes particle size, shape, and defects into account and isolates element specific signals. As a case study a statistical approximation model for lead-zirconate titanate [Pb(Zr{sub x}Ti{sub 1-x})O{sub 3}, PZT] is introduced. PZT is a material possessing several defect types, including substitutional, displacement and surface defects. Spatial composition variation is taken into account by introducing a model in which the edge lengths of each cell depend on the distribution of Zr and Ti ions in the cluster. Spatially varying edge lengths and angles is referred to as microstrain. The model is applied to compute the scattering from ellipsoid shaped PZT clusters and to simulate the structural changes as a function of average composition. Two-phase co-existence range, the so called morphotropic phase boundary composition is given correctly. The composition at which the rhombohedral and tetragonal cells are equally abundant was x ∼ 0.51. Selected x-ray and neutron Bragg reflection intensities and line shapes were simulated. Examples of the effect of size and shape of the scattering clusters on diffraction patterns are given and the particle dimensions, computed through Scherrer equation, are compared with the exact cluster dimensions. Scattering from two types of 180 domains in spherical particles, one type assigned to Ti-rich PZT and the second to the MPB and Zr-rich PZT, is computed. We show how the method can be used for modelling polarization reversal. (copyright 2015 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Taxonomy of Means and Ends in Aquaculture Production—Part 2: The Technical Solutions of Controlling Solids, Dissolved Gasses and pH

    Directory of Open Access Journals (Sweden)

    Bjorgvin Vilbergsson

    2016-09-01

    Full Text Available In engineering design, knowing the relationship between the means (technique and the end (desired function or outcome is essential. The means in Aquaculture are technical solutions like airlifts that are used to achive desired functionality (an end like controlling dissolved gasses. In previous work, the authors identified possible functions by viewing aquaculture production systems as transformation processes in which inputs are transformed by treatment techniques (means and produce outputs (ends. The current work creates an overview of technical solutions of treatment functions for both design and research purposes. A comprehensive literature review of all areas of technical solutions is identified and categorized into a visual taxonomy of the treatment functions for controlling solids, controlling dissolved gasses and controlling pH alkalinity and hardness. This article is the second in a sequence of four and partly presents the treatments functions in the taxonomy. The other articles in this series present complementary aspects of this research: Part 1, A transformational view on aquaculture and functions divided into input, treatment and output functions; Part 2, The current taxonomy paper; Part 3, The second part of the taxonomy; and Part 4, Mapping of the means (techniques for multiple treatment functions.

  6. Fabrication of Nb{sub 3}Al superconducting wires by utilizing the mechanically alloyed Nb(Al){sub ss} supersaturated solid-solution with low-temperature annealing

    Energy Technology Data Exchange (ETDEWEB)

    Pan, X.F. [National Engineering Laboratory for Superconducting Material, Western Superconducting Technologies (WST) Co., Ltd., Xi’an 710018 (China); Superconducting Materials Center, Northwest Institute for Nonferrous Metal Research, Xi’an 710016 (China); Yan, G., E-mail: gyan@c-nin.com [National Engineering Laboratory for Superconducting Material, Western Superconducting Technologies (WST) Co., Ltd., Xi’an 710018 (China); Superconducting Materials Center, Northwest Institute for Nonferrous Metal Research, Xi’an 710016 (China); Qi, M. [Superconducting Materials Center, Northwest Institute for Nonferrous Metal Research, Xi’an 710016 (China); Cui, L.J. [National Engineering Laboratory for Superconducting Material, Western Superconducting Technologies (WST) Co., Ltd., Xi’an 710018 (China); Chen, Y.L.; Zhao, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains (Ministry of Education of China), Superconductivity and New Energy R and D Center, Southwest Jiaotong University, Chengdu 610031 (China); Li, C.S. [Superconducting Materials Center, Northwest Institute for Nonferrous Metal Research, Xi’an 710016 (China); Liu, X.H. [National Engineering Laboratory for Superconducting Material, Western Superconducting Technologies (WST) Co., Ltd., Xi’an 710018 (China); Feng, Y.; Zhang, P.X. [National Engineering Laboratory for Superconducting Material, Western Superconducting Technologies (WST) Co., Ltd., Xi’an 710018 (China); Key Laboratory of Magnetic Levitation Technologies and Maglev Trains (Ministry of Education of China), Superconductivity and New Energy R and D Center, Southwest Jiaotong University, Chengdu 610031 (China); Liu, H.J. [Institute of Plasma Physics, Chinese Academy of Sciences (CAS), Hefei 230031 (China); and others

    2014-07-15

    Highlights: • This paper reported superconducting properties of the powder-in-tube Nb{sub 3}Al wires. • The Nb{sub 3}Al wires were made by using Nb(Al){sub ss} supersaturated solid solution powders. • The Cu-matrix Nb{sub 3}Al superconducting wires have been successfully fabricated. • The transport J{sub c} of Nb{sub 3}Al wires at 4.2 K, 10 T is up to 12,700 A/cm{sup 2}. - Abstract: High-performance Nb{sub 3}Al superconducting wire is a promising candidate to the application of high-field magnets. However, due to the production problem of km-grade wires that are free from low magnetic field instability, the Nb{sub 3}Al wires made by rapid heating, quenching and transformation (RHQT) are still not available to the large-scale engineering application. In this paper, we reported the properties of the in situ powder-in-tube (PIT) Nb{sub 3}Al superconducting wires, which were made by using the mechanically alloyed Nb(Al){sub ss} supersaturated solid solution, as well as the low temperature heat-treatment at 800 °C for 10 h. The results show that Nb{sub 3}Al superconductors in this method possess very fine grains and well superconducting properties, though a little of Nb{sub 2}Al and Nb impurities still keep being existence at present work. At the Nb{sub 3}Al with a nominal 26 at.% Al content, the onset T{sub c} reaches 15.8 K. Furthermore, a series of Nb{sub 3}Al wires and tapes with various sizes have been fabricated; for the 1.0 mm-diameter wire, the J{sub c} at 4.2 K, 10 T and 14 T have achieved 12,700 and 6900 A/cm{sup 2}, respectively. This work suggests it is possible to develop high-performance Cu-matrix Nb{sub 3}Al superconducting wires by directly using the Nb(Al){sub ss} supersaturated solid-solution without the complex RHQT heat-treatment process.

  7. A note on the different crystalline features of the EuMnO3-based solid solutions as a function of the modifying cation nature

    Directory of Open Access Journals (Sweden)

    Peña, O.

    2010-12-01

    Full Text Available The structural properties of solid solutions based on EuMnO3, in which Eu has been substituted by divalent Ca2+ and Mn by the divalent cation Ni2+ or the variable valence cation Co2+-Co3+ have been studied by X-ray diffraction (XRD and X-ray absorption spectroscopy (XAS. These substitutions lead to changes in the lattice parameters and the symmetry of the orthorhombic, O’ perovskite-type of the pristine compound EuMnO3. The structural changes depend on several factors. Solid solutions Eu(Mn,NiO3 and Eu(Mn,CoO3 change from the O’-type to O-type orthorhombic perovskite symmetry when the content of the Mn3+ cation decreases due to the progressive substitution by Ni and Co. This change occurs for a percentage of the Ni2+ cation of 20 at%, whereas for the Co cation, only 10 at% are needed for such a transition. (Eu,CaMnO3 solid solutions showed a different behaviour. Even at an amount as high as 50 at% Ca2+ there is no transition from O’ to O-type orthorhombic perovskite symmetry. The tolerance factor, t, increases monotonically for both Eu(Mn,NiO3 and (Eu,CaMnO3, while for Eu(Mn,CoO3 it first decreases and then increases. The increase is lower for Ni-based and Co-based samples than for the Ca-based ones.Las propiedades estructurales de las soluciones sólidas basadas en EuMnO3, en donde Eu ha sido sustituido por Ca2+, y Mn por Ni2+ o por un catión de valencia variable tal como Co, (II ó III han sido estudiadas por Difracción de Rayos X, (DRX. Estas sustituciones llevan a cambios en los parámetros de red y en la simetría de la perovskita tipo O’ propia del compuesto EuMnO3. Los cambios estructurales dependen de la cantidad y del tipo de catión sustituyente. Ni y Co inducen un cambio desde la estructura tipo O’ a la O para 20 at% Ni y 10 at% Co respectivamente. Por su parte, la incorporación de Ca en lugares A induce este cambio para x(Ca > 50 at%. El factor de tolerancia de la estructura perovskita también muestra un comportamiento

  8. Adsorption of Reactive Blue 171 from Aqueous Solution using Low Cost Activated Carbon Prepared from Agricultural Solid Waste: Albizia amara

    Directory of Open Access Journals (Sweden)

    K. Anitha

    2015-07-01

    Full Text Available The adsorption of Reactive Blue 171 (Reactive Dye from aqueous solution using activated carbon prepared from Albizia amara pod shell waste as an adsorbent have been carried out. The experimental adsorption data fitted reasonably well to Langmuir and Freundlich adsorption isotherms. Kinetic parameters as a function of Initial dye concentration have been calculated and the kinetic data were substituted in Pseudo First Order, Elovich and Pseudo Second order equations. A probable explanation is offered to account for the results of kinetic study. The thermodynamic parameter enthalpy change (∆H suggests the exothermic nature of absorption of Reactive Blue 171 onto activated Albizia amara pod shell waste carbon.

  9. Adsorption characteristics of graphene oxide as a solid adsorbent for aniline removal from aqueous solutions: Kinetics, thermodynamics and mechanism studies

    Directory of Open Access Journals (Sweden)

    Ali Fakhri

    2017-01-01

    Full Text Available The aim of this study is to investigate the possibility of graphene oxide (GO as an alternative adsorbent for aniline removal from aqueous solution. Adsorption properties of GO for aniline removal were regularly investigated, including pH effect, adsorbent dose, temperature, contact time and initial concentration. The adsorption amount of aniline decreased with increasing pH. The experimental data were evaluated by Langmuir, Freundlich, Temkin and Harkins–Jura models in order to describe the equilibrium isotherms. Equilibrium data fitted well to the Langmuir model. The kinetic parameters achieved at different concentrations were analyzed using a pseudo first-order, pseudo second-order kinetic equation and intra-particle diffusion model. The experimental data fitted very well the pseudo second-order kinetic model. Thermodynamic parameters (free energy change, enthalpy change, and entropy change announced that the removal of aniline from GO was endothermic and spontaneous. The study showed that GO could be used as an efficient adsorbent material for the adsorption of aniline from aqueous solution.

  10. In-Depth Comparison of Lysine-Based Antibody-Drug Conjugates Prepared on Solid Support Versus in Solution

    Directory of Open Access Journals (Sweden)

    Keith J. Arlotta

    2018-01-01

    Full Text Available Antibody drug conjugates are a rapidly growing form of targeted chemotherapeutics. As companies and researchers move to develop new antibody–drug conjugate (ADC candidates, high-throughput methods will become increasingly common. Here we use advanced characterization techniques to assess two trastuzumab-DM1 (T-DM1 ADCs; one produced using Protein A immobilization and the other produced in solution. Following determination of payload site and distribution with liquid chromatography-mass spectrometry (LC/MS, thermal stability, heat-induced aggregation, tertiary structure, and binding affinity were characterized using differential scanning calorimetry (DSC, dynamic light scattering (DLS, Raman spectroscopy, and isothermal titration calorimetry (ITC, respectively. Small differences in the thermal stability of the CH2 domain of the antibody as well as aggregation onset temperatures were observed from DSC and DLS, respectively. However, no significant differences in secondary and tertiary structure were observed with Raman spectroscopy, or binding affinity as measured by ITC. Lysine-based ADC conjugation produces an innately heterogeneous population that can generate significant variability in the results of sensitive characterization techniques. Characterization of these ADCs indicated nominal differences in thermal stability but not in tertiary structure or binding affinity. Our results lead us to conclude that lysine-based ADCs synthesized following Protein A immobilization, common in small-scale conjugations, are highly similar to equivalent ADCs produced in larger scale, solution-based methods.

  11. Effect of nitrogen on the preparation (powder synthesis - sintering) and on the dielectric properties of 'MgAlON' spinel solid solutions; Role de l'azote sur l'elaboration (synthese de poudre-frittage) et les proprietes dielectriques de solutions solides spinelles de type 'MgAlON'

    Energy Technology Data Exchange (ETDEWEB)

    Morey, O

    2000-02-10

    The aim of this work is to show the effect of nitrogen on the synthesis, the sintering and the dielectric behaviour of 'MgAlON' spinel solid solutions. 'MgAlON' solid solutions (1.1 {<=} N {<=} 4.2 %) have been prepared by solid state reactions between Al{sub 2}O{sub 3}, MgO and AlN at high temperature (1450 degrees Celsius) under nitrogen atmosphere and characterized by granulometric analysis, Brunauer-Emmet-Teller (BET) surface area analysis, X-ray diffraction, scanning electron microscopy, Al{sup 27} NMR, FTIR spectroscopy and thermoluminescence. Point defects have been revealed. They are in particular due to the nitrogen amount incorporated into the structure. The O/N substitution in the anionic lattice induces a delay to the densification when the nitrogen composition increases. The dielectric properties of these materials have been studied by two methods. The first one has a macroscopic character and is destructive. It allows to know the breakdown voltage and to calculate the dielectric rigidity of the material. The second one ('SEMM': 'Scanning Electron Microscopy Mirror') has a microscopic character and is nondestructive. Its principle is based on the charge injection with an electric beam. It gives the yield of charge trapping of the material. The good behaviour of these materials to the charge injection has been correlated to the oxygen vacancies in increasing amount with the nitrogen composition. (O.M.)

  12. EPR properties of some new cadmium and rare-earth molybdates, molybdato-tungstates and their solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, S.M., E-mail: skaczmarek@zut.edu.pl [Faculty of Mechanical Engineering and Mechatronics, Institute of Physics, West Pomeranian University of Technology, Al. Piastow 17, 70-310 Szczecin (Poland); Leniec, G.; Fuks, H. [Faculty of Mechanical Engineering and Mechatronics, Institute of Physics, West Pomeranian University of Technology, Al. Piastow 17, 70-310 Szczecin (Poland); Tomaszewicz, E.; Dabrowska, G. [Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, Al. Piastow 42, 71-065 Szczecin (Poland); Skibinski, T. [Faculty of Mechanical Engineering and Mechatronics, Institute of Physics, West Pomeranian University of Technology, Al. Piastow 17, 70-310 Szczecin (Poland)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Some new molybdato-tungstates of rare earths were synthesized and investigated. Black-Right-Pointing-Pointer EPR and XRD of the obtained phases revealed scheelite-like structures. Black-Right-Pointing-Pointer Rare-earths ions enter at axial symmetry sites convenient for phosphors or lasers. - Abstract: A reactivity in the solid state between CdMoO{sub 4} and RE{sub 2}(MoO{sub 4}){sub 3} or RE{sub 2}(WO{sub 4}){sub 3}, where RE = Nd, Sm, Dy, was investigated using X-ray diffraction and electron paramagnetic resonance techniques. Obtained phases have shown scheelite-like structure, congruent melting and axial or close to axial symmetry of RE{sup 3+} ions. The main type of magnetic interactions in samples under studies is proved to be ferromagnetic one. Besides RE{sup 3+} ions, isolated and paired centers o molybdenum (5+) were found in the electron paramagnetic resonance spectra.

  13. Temperature induced phase transformations and microstructural changes in nanostructured FeCu solid solutions using in situ neutron powder thermo-diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Blanco, D. [Unidad de Magnetometria, SCT' s, Universidad de Oviedo, Julian Claveria, 8, 33006 Oviedo (Spain); Departamento de Fisica, Universidad de Oviedo, Calvo Sotelo s/n, Oviedo 33007 (Spain); Gorria, P., E-mail: pgorria@uniovi.e [Departamento de Fisica, Universidad de Oviedo, Calvo Sotelo s/n, Oviedo 33007 (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, Calvo Sotelo s/n, Oviedo 33007 (Spain); Smith, R.I. [ISIS facility, RAL, Chilton, Didcot, Oxon OX11 0QX (United Kingdom)

    2009-08-26

    In situ neutron powder thermo-diffraction experiments in the temperature range from 300 K to 1170 K have been carried out in nanostructured and metastable Fe{sub 15}Cu{sub 85} and Fe{sub 85}Cu{sub 15} solid solutions, which were synthesized by means of a mechanical alloying technique. We report on the microstructural changes and the phase transformations that take place during controlled heating and cooling processes. The average crystalline grain size is similar for both samples in the as-milled state (approx16-20 nm) while the induced strain is 2.5 times higher in the Fe-rich powders, reaching 1%. Moreover, the alpha-gamma transformation for Fe{sub 15}Cu{sub 85} starts at temperatures lower (approx900 K) than that expected for pure Fe (1183 K) due likely to the existence of local inhomogeneities in the composition of the ball milled material.

  14. Simulation of ceramic materials relevant for nuclear waste management: Case of La{sub 1−x}Eu{sub x}PO{sub 4} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de; Ji, Yaqi; Li, Yan; Arinicheva, Yulia; Beridze, George; Neumeier, Stefan; Bukaemskiy, Andrey; Bosbach, Dirk

    2017-02-15

    Using powerful computational resources and state-of-the-art methods of computational chemistry we contribute to the research on novel nuclear waste forms by providing atomic scale description of processes that govern the structural incorporation and the interactions of radionuclides in host materials. Here we present various results of combined computational and experimental studies on La{sub 1−x}Eu{sub x}PO{sub 4} monazite-type solid solution. We discuss the performance of DFT + U method with the Hubbard U parameter value derived ab initio, and the derivation of various structural, thermodynamic and radiation-damage related properties. We show a correlation between the cation displacement probabilities and the solubility data, indicating that the binding of cations is the driving factor behind both processes. The combined atomistic modeling and experimental studies result in a superior characterization of the investigated material.

  15. Preparation of solid-solution type Fe-Co nanoalloys by synchronous deposition of Fe and Co using dual arc plasma guns.

    Science.gov (United States)

    Sadakiyo, Masaaki; Heima, Minako; Yamamoto, Tomokazu; Matsumura, Syo; Matsuura, Masashi; Sugimoto, Satoshi; Kato, Kenichi; Takata, Masaki; Yamauchi, Miho

    2015-09-28

    We succeeded in the efficient preparation of well-dispersed Fe-Co nanoalloys (NAs) using the arc plasma deposition method. Synchronous shots of dual arc plasma guns were applied to a carbon support to prepare the solid-solution type Fe-Co NAs having an approximately 1 : 1 atomic ratio. The alloy structures with and without a reductive thermal treatment under a hydrogen atmosphere were examined using X-ray powder diffraction, scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray analysis, high resolution STEM, and magnetic measurements, suggesting that highly crystalline spherical particles of ordered B2-type Fe-Co NAs form by the thermal treatment of the deposited grains.

  16. Structure of 1,5-benzodiazepinones in the solid state and in solution: Effect of the fluorination in the six-membered ring

    Directory of Open Access Journals (Sweden)

    Marta Pérez-Torralba

    2013-10-01

    Full Text Available Two novel tetrafluorinated 1,5-benzodiazepinones were synthesized and their X-ray structures determined. 6,7,8,9-Tetrafluoro-4-methyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one crystallizes in the monoclinic P21/c space group and 6,7,8,9-tetrafluoro-1,4-dimethyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one in the triclinic P−1 space group. Density functional theory studies at the B3LYP/6-311++G(d,p level were carried out on these compounds and on four non-fluorinated derivatives, allowing to calculate geometries, tautomeric energies and ring-inversion barriers, that were compared with the experimental results obtained by static and dynamic NMR in solution and in solid state.

  17. Scanning proximal microscopy study of the thin layers of silicon carbide-aluminum nitride solid solution manufactured by fast sublimation epitaxy

    Directory of Open Access Journals (Sweden)

    Tománek P.

    2013-05-01

    Full Text Available The objective of the study is a growth of SiC/(SiC1−x(AlNx structures by fast sublimation epitaxy of the polycrystalline source of (SiC1−x(AlNx and their characterisation by proximal scanning electron microscopy and atomic force microscopy. For that purpose optimal conditions of sublimation process have been defined. Manufactured structures could be used as substrates for wide-band-gap semiconductor devices on the basis of nitrides, including gallium nitride, aluminum nitride and their alloys, as well as for the production of transistors with high mobility of electrons and also for creation of blue and ultraviolet light emitters (light-emitted diodes and laser diodes. The result of analysis shows that increasing of the growth temperature up to 2300 K allows carry out sublimation epitaxy of thin layers of aluminum nitride and its solid solution.

  18. The high-temperature heat capacity of the (Th,U)O2 and (U,Pu)O2 solid solutions

    Science.gov (United States)

    Vălu, S. O.; Beneš, O.; Manara, D.; Konings, R. J. M.; Cooper, M. W. D.; Grimes, R. W.; Guéneau, C.

    2017-02-01

    The enthalpy increment data for the (Th,U)O2 and (U,Pu)O2 solid solutions are reviewed and complemented with new experimental data (400-1773 K) and many-body potential model simulations. The results of the review show that from room temperature up to about 2000 K the enthalpy data are in agreement with the additivity rule (Neumann-Kopp) in the whole composition range. Above 2000 K the effect of Oxygen Frenkel Pair (OFP) formation leads to an excess enthalpy (heat capacity) that is modeled using the enthalpy and entropy of OFP formation from the end-members. A good agreement with existing experimental work is observed, and a reasonable agreement with the results of the many-body potential model, which indicate the presence of the diffuse Bredig (superionic) transition that is not found in the experimental enthalpy increment data.

  19. The key role of the composition and structural features in fluoride ion conductivity in tysonite Ce1-xSrxF3-x solid solutions.

    Science.gov (United States)

    Dieudonné, Belto; Chable, Johann; Body, Monique; Legein, Christophe; Durand, Etienne; Mauvy, Fabrice; Fourcade, Sébastien; Leblanc, Marc; Maisonneuve, Vincent; Demourgues, Alain

    2017-03-14

    Pure tysonite-type Ce1-xSrxF3-x solid solutions for 0 ≤ x conductivity found for Ce0.975Sr0.025F2.975 (3 × 10-4 S cm-1 at RT, Ea = 0.31 eV) is correlated to the largest dispersion of F2-(Ce,Sr) and F3-(Ce,Sr) distances which induces the maximum sheet buckling. Such a relationship between composition, structural features and fluoride ion conductivity is extended to other tysonite-type fluorides. The key role of the difference between AE2+ and RE3+ ionic radii and of the thickness of the slab buckling is established and could allow designing new ionic conductors.

  20. Structural, morphology and optical properties of Zn(1-x)CdxO solid solution grown on c-plane sapphire substrate

    Science.gov (United States)

    Fouzri, A.; Boukadhaba, M. A.; Oumezzine, M.; Bchetnia, A.; Sallet, V.

    2012-06-01

    Zn(1-x)CdxO solid solutions with a composition ranging from pure ZnO up to x=0.046 have been grown on cplane sapphire substrates by using metal organic chemical vapor deposition (MO-CVD). The lattice deformation, morphology and optical properties of these films were examined in detail using high resolution X-ray diffraction, atomic force microscopy (AFM) and photoluminescence (PL) as Cd incorporation. Our study reveals significant microstructure modification of Zn(1-x)CdxO from x≥0.7% but single phase of wurtzite structure is maintained for all films. The Pl spectra and the band gap of the Zn(1-x)CdxO film show red shift to visible light range which is interpreted in terms of band gap modulation due to Cd incorporation. Increase of Cd content leads to the emission broadening with growing lower energy peak (at 10K) and degraded crystallinity.

  1. Structural, morphology and optical properties of Zn(1-xCdxO solid solution grown on c-plane sapphire substrate

    Directory of Open Access Journals (Sweden)

    Bchetnia A.

    2012-06-01

    Full Text Available Zn(1-xCdxO solid solutions with a composition ranging from pure ZnO up to x=0.046 have been grown on cplane sapphire substrates by using metal organic chemical vapor deposition (MO-CVD. The lattice deformation, morphology and optical properties of these films were examined in detail using high resolution X-ray diffraction, atomic force microscopy (AFM and photoluminescence (PL as Cd incorporation. Our study reveals significant microstructure modification of Zn(1-xCdxO from x≥0.7% but single phase of wurtzite structure is maintained for all films. The Pl spectra and the band gap of the Zn(1-xCdxO film show red shift to visible light range which is interpreted in terms of band gap modulation due to Cd incorporation. Increase of Cd content leads to the emission broadening with growing lower energy peak (at 10K and degraded crystallinity.

  2. Binding of CO and NH3 at a five-coordinate Ru(II) centre in the solid state and in solution.

    Science.gov (United States)

    Ma, Erin S F; Mudalige, Dona C; James, Brian R

    2013-10-07

    The known five-coordinate, square-pyramidal, green trans-RuCl2(P-N)(PR3) complexes (P-N = o-diphenylphosphino-N,N'-dimethylaniline; R = Ph (1a), p-tolyl), in the solid state at ambient conditions, or in CDCl3 solution at low temperatures, coordinate CO (at 1 atm) to form beige-coloured trans-monocarbonyl derivatives. In the solution reactions at room temperature, the PR3 ligand dissociates and the yellow dicarbonyl complex RuCl2(CO)2(P-N) is formed as a mixture of trans,cis- and cis,cis-isomers. With use of (13)CO, the carbonyls complexes are characterized by variable temperature NMR and IR data, and (for the monocarbonyls) elemental analyses. Similarly, 1a and the dibromo analogue (1b) in the solid state bind NH3 to form the beige trans-monoammine species RuX2(P-N)(PPh3)(NH3), trans-4a (X = Cl) and trans-4b (X = Br), with cis P-atoms. The solution NH3 reactions, however, generate a species, speculatively thought to be the unusual, tight ion-pair, bisammine species [RuX(P-N)(PPh3)(NH3)2···X], 5a (X = Cl) and 5b (X = Br), in which a halide is considered strongly H-bonded to the cis-ammine ligands, although an alternative RuX(P-N)(PPh3)(NH3)2 formulation with a monodentate P-N ligand cannot be ruled out; dissolution in CDCl3 of isolated 5a and 5b, which are characterized by NMR, elemental analysis, and conductivity data, results in a partial, reversible loss of NH3 to form some cis- and trans-4a or -4b, respectively. Treatment of 5a with one mole equivalent of NH4PF6 in acetone solution removes the H-bonded chloride to give [RuCl(P-N)(PPh3)(NH3)2]PF6 (6), and this is converted by thermal loss of NH3 to generate the extremely air-sensitive, five-coordinate, ionic species [RuCl(P-N)(PPh3)(NH3)]PF6 (7). NMR evidence is presented for formation of the tris(ammine) species [Ru(P-N)(PPh3)(NH3)3](PF6)2 (8) via treatment of trans-RuCl2(P-N)(PPh3) with an atmosphere of NH3 in the presence of 2 mole equivalents of NH4PF6.

  3. Reactions of nitrogen oxides with heme models. Spectral and kinetic study of nitric oxide reactions with solid and solute Fe(III)(TPP)(NO3).

    Science.gov (United States)

    Kurtikyan, Tigran S; Gulyan, Gurgen M; Martirosyan, Garik G; Lim, Mark D; Ford, Peter C

    2005-05-04

    The reaction(s) of nitric oxide (nitrogen monoxide) gas with sublimed layers containing the nitrato iron(III) complex Fe(III)(TPP)(eta(2)-O(2)NO) (1, TPP = meso-tetraphenyl porphyrinate(2)(-)) leads to formation of several iron porphyrin species that are ligated by various nitrogen oxides. The eventual products of these low-temperature solid-state reactions are the nitrosyl complex Fe(TPP)(NO), the nitro-nitrosyl complex Fe(TPP)(NO(2))(NO), and 1 itself, and the relative final quantities of these were functions of the NO partial pressure. It is particularly notable that isotope labeling experiments show that the nitrato product is not simply unreacted 1 but is the result of a series of transformations taking place in the layered material. Thus, the nitrato complex formed from solid Fe(TPP)(eta(2)-O(2)NO) maintained under a (15)NO atmosphere was found to be the labeled analogue Fe(TPP)(eta(2)-O(2)(15)NO). The reactivities of the layered solids are compared to the behaviors of the same species in ambient temperature solutions. To interpret the reactions of the labeled nitrogen oxides, the potential exchange reactions between N(2)O(3) and (15)NO were examined, and complete isotope scrambling was observed between these species under the reaction conditions (T = 140 K). Overall it was concluded from isotope labeling experiments that the sequence of reactions is initiated by reaction of 1 with NO to give the nitrato nitrosyl complex Fe(TPP)(eta(1)-ONO(2))(NO) (2) as an intermediate. This is followed by a reaction in the presence of excess NO that is equivalent to the loss of the nitrate radical NO(3)(*)( )()to give Fe(TPP)(NO) as another transient species. A plausible pathway involving NO attack on the coordinated nitrate of 2 resulting in the release of N(2)O(4) concerted with electron transfer to the metal center is proposed.

  4. Microanalytical techniques applied to phase identification and measurement of solute redistribution at the solid/liquid interface of frozen Fe-4.3Ni doublets

    CERN Document Server

    Faryna, M; Okane, T

    2002-01-01

    A Fe-4.3M alloy has been solidified directionally by using the Bridgman system. The solidification conditions were chosen to obtain an oriented cellular structure of delta-ferrite. These are: a positive temperature gradient of about 60 K/cm and a growth rate of 6.6 mu m/s. A change in these conditions can lead either to the formation of austenite or to the competitive growth of delta-ferrite/gamma-austenite. The solid/liquid interface of delta-ferrite cells has been frozen and double instability has been revealed at the tip of the cells. The instability is described as the first harmonic wave of fundamental undulation, which appeared at the formerly planar solid/liquid interface. This means that a doublet structure is formed only with the imposed specific conditions of solidification. The Ni-solute redistribution after back-diffusion has been measured across the delta-ferrite doublet. Results of energy dispersive x-ray (EDX) measurements on the distribution of Ni and Fe correspond well to the theoretical pred...

  5. Removal of Cs{sup +}, Sr{sup 2+}, and Co{sup 2+} ions from the mixture of organics and suspended solids aqueous solutions by zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Xiang Hong; Fang, Fang; Lu, Chun Hai [College of Nuclear Technology and Automation Engineering, Chengdu University of Technology, Chengdu (China); Zheng, Lei [Southwest University of Science and Technology, Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education, Mianyang (China)

    2017-04-15

    Serving as an excellent adsorbent and inorganic ion exchanger in the water purification field, zeolite 4A has in this work presented a strong capability for purifying radioactive waste, such as Sr{sup 2+}, Cs{sup +}, and Co{sup 2+} in water. During the processes of decontamination and decommissioning of suspended solids and organics in low-level radioactive wastewater, the purification performance of zeolite 4A has been studied. Under ambient temperature and neutral condition, zeolite 4A absorbed simulated radionuclides such as Sr{sup 2+}, Cs{sup +}, and Co{sup 2+} with an absorption rate of almost 90%. Additionally, in alkaline condition, the adsorption percentage even approached 98.7%. After conducting research on suspended solids and organics of zeolite 4A for the treatment of radionuclides, it was found that the suspended clay was conducive to absorption, whereas the absorption of organics in solution was determined by the species of radionuclides and organics. Therefore, zeolite 4A has considerable potential in the treatment of radioactive wastewater.

  6. Perovskite solid solutions La0.75Bi0.25Fe1-xCrxO3: Preparation, structural, and magnetic properties

    Science.gov (United States)

    Ivanov, S. A.; Beran, P.; Bazuev, G.; Tellgren, R.; Sarkar, T.; Nordblad, P.; Mathieu, R.

    2017-10-01

    Solid solutions of La0.75Bi0.25Fe1-xCrxO3 (x = 0.1, 0.25, 0.5, and 0.75) prepared by conventional solid state reaction have been studied by means of X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic measurements. The NPD and XRPD patterns indicate orthorhombic structure (space group Pnma) for all compositions in the whole temperature range investigated (4-900 K). The lattice parameters of La0.75Bi0.25Fe1-xCrxO3 were found to decrease with the Cr content. It was established that the Fe3+ and Cr3+ cations are randomly positioned at the B-site of the perovskite structure. All samples order antiferromagnetically below transition temperatures that decrease with increasing Cr content, from around 700 K for x = 0.1 to about 300 K for x = 0.75. The antiferromagnetic arrangement of the Fe3+/Cr3+ magnetic moments in the B-site is of G-type along the x-axis (Gx mode) with propagation vector k = (0,0,0) for all concentrations of Cr. Effects of the composition on several structural distortion parameters were investigated and an anomalous variation of the octahedral deformation with Cr content was found. Whilst the overall octahedral deformation varies irregularly with increasing Cr content, the octahedral tilting was found to decrease monotoneously.

  7. Detailed investigation on structural, dielectric, magnetic and magnetodielectric properties of BiFeO3-BaSrTiO3 solid solutions

    Science.gov (United States)

    Pal, Jaswinder; Kumar, Sunil; Singh, Lakhwant; Singh, Mandeep; Singh, Anupinder

    2017-11-01

    Polycrystalline (1 - x) BiFeO3-xBa0.8Sr0.2TiO3 (0.1 ≤ x ≤ 0.9) ceramics have been synthesized by using the solid-state-reaction method. The structural, dielectric, ferroelectric, magnetic and electrical properties of the resulting solid solutions have been investigated. XRD analysis reveals that the composition-driven rhombohedral to cubic phase transition occurs at x ≈ 0.4. Experimental results reveal that BST substitution leads to the suppression of the spiral spin structure, resulting in the appearance of net magnetization. The electrical conductivity has been found to increase with increase in frequency of applied electric field. The dielectric constant (ε‧) and the dielectric loss (ε″) have been found to decrease with increase in frequency of applied electric field and shows non-Debye relaxation behavior. The samples have been found to exhibit magnetoelectric coupling (up to x = 0.2). An enhancement in ferroelectric properties with increasing BST content (up to x = 0.3) has been observed.

  8. Optical spectroscopy and magnetic behaviour of Sm3+ and Eu3+ cations in Li6Eu1-xSmx(BO3)3 solid solution

    Science.gov (United States)

    Belhoucif, Rekia; Velázquez, Matias; Plantevin, Olivier; Aschehoug, Patrick; Goldner, Philippe; Christian, George

    2017-11-01

    A new borate solid solution series of powders, Li6Eu1-xSmx(BO3)3 (LSEBx, x = 0.35, 0.5, 0.6, 1), were synthesized by solid-state reaction, characterized and their luminescent properties were investigated. The absorption spectra indicate that absorption takes place mainly from the Sm3+6H5/2 ground state, with a strong band at 405 nm. The photoluminescence spectra reveal that the Eu3+ red emission intensity strongly depends on the Sm3+ content x. Judd-Ofelt theory was applied to experimental data for the quantitative determination of phenomenological parameters Ωi (i = 2, 4, 6) Judd Ofelt parameters, radiative transition rates and emission quantum efficiency. Owing to the energy transfer from Sm3+ to Eu3+ the intense red light detected at 613 nm at room temperature under UV or blue light excitation, was improved by ∼35% as compared with Sm3+-free samples. This energy transfer was confirmed by faster decay times of Sm3+ as energy donors. Moreover, the energy transfer between Sm3+ and Eu3+ is unidirectional and irreversible, implying that the energy transfer wastage between Sm3+ and Eu3+ is very low. Magnetic susceptibility (χ) measurements of LSEBx were carried out in the temperature range 2-320 K and are used to compare calculated and experimental energy levels.

  9. Removal of Cs+, Sr2+, and Co2+ Ions from the Mixture of Organics and Suspended Solids Aqueous Solutions by Zeolites

    Directory of Open Access Journals (Sweden)

    Xiang-Hong Fang

    2017-04-01

    Full Text Available Serving as an excellent adsorbent and inorganic ion exchanger in the water purification field, zeolite 4A has in this work presented a strong capability for purifying radioactive waste, such as Sr2+, Cs+, and Co2+ in water. During the processes of decontamination and decommissioning of suspended solids and organics in low-level radioactive wastewater, the purification performance of zeolite 4A has been studied. Under ambient temperature and neutral condition, zeolite 4A absorbed simulated radionuclides such as Sr2+, Cs+, and Co2+ with an absorption rate of almost 90%. Additionally, in alkaline condition, the adsorption percentage even approached 98.7%. After conducting research on suspended solids and organics of zeolite 4A for the treatment of radionuclides, it was found that the suspended clay was conducive to absorption, whereas the absorption of organics in solution was determined by the species of radionuclides and organics. Therefore, zeolite 4A has considerable potential in the treatment of radioactive wastewater.

  10. Research Update: Prediction of high figure of merit plateau in SnS and solid solution of (Pb,SnS

    Directory of Open Access Journals (Sweden)

    Shiqiang Hao

    2016-10-01

    Full Text Available Direct conversion between thermal and electrical energy can be achieved by thermoelectric materials, which provide a viable route for power generation and solid state refrigeration. Here, we use a combination of energetic, electronic, and vibrational first-principles based results to predict the figure of merit performance in hole doped single crystals of SnS and (Pb,SnS. We find high ZT values for both materials, specifically for (Pb,SnS along the b-axis. Both SnS and (Pb,SnS have excellent power factors when doped, due to a combination of increased electrical conductivity (due to doping and a significantly enhanced Seebeck coefficient obtained by a doping-induced multiband effect. Anharmonic phonon calculations combined with a Debye-Calloway model show that the lattice thermal conductivity of both compounds is low, due to intrinsic anharmonicity, and is lowered further by the random, solid solution nature of the cation sublattice of (Pb,SnS. (Pb,SnS exhibits a high ZT plateau ranging from 1.3 at 300 K to 1.9 at 800 K. The overall ZT of the hole doped (Pb,SnS crystals is predicted to outperform most of the current state-of-the-art thermoelectric sulfide materials.

  11. Synthesis of {beta}-phase Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xianli [Key Laboratory of Bionic Engineering, College of Biology and Agriculture Engineering, Jilin University, Nanling Campus, Changchun 130025 (China); Jilin Weather Modification Office, Changchun 130062 (China); Zhang, Jinghong [Key Laboratory of Automobile Materials, College of Materials Science and Engineering, Jilin University, Nanling Campus, Changchun 130025 (China); Jilin Weather Modification Office, Changchun 130062 (China); Zhang, Guilan, E-mail: lxl5211@126.com [Key Laboratory of Bionic Engineering, College of Biology and Agriculture Engineering, Jilin University, Nanling Campus, Changchun 130025 (China); Jiang, Zhonghao [Key Laboratory of Automobile Materials, College of Materials Science and Engineering, Jilin University, Nanling Campus, Changchun 130025 (China); Jin, Dezhen [Jilin Weather Modification Office, Changchun 130062 (China)

    2011-06-15

    Research highlights: {yields} Wet-chemical-chelating reaction processing has been used to synthesized A series of single {beta}-phase nano-Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions powders. {yields} Citric acid as complexing agent takes part in the process of chemical reaction and the chemical reactions can be described in this paper. {yields} The lattice parameters have been ascertained by the results of XRD. {yields} Crystalline sizes, which decrease with copper iodide concentration increasing, have been demonstrated by XRD and TEM. -- Abstract: A series of single {beta}-phase nano-Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions powders were synthesized by wet-chemical-chelating reaction processing and citric acid used as complexing agent. The Ag{sub 1-x}Cu{sub x}I powders were determined by X-ray diffraction and transmission electron microscopy. It was demonstrated that the crystalline size and lattice parameter of the Ag{sub 1-x}Cu{sub x}I powders decrease with an increase in the amount of CuI substitution. The copper in the lattice of the Ag{sub 1-x}Cu{sub x}I can effectively prevent the crystalline growth of the Ag{sub 1-x}Cu{sub x}I powders and citrate used in the Ag{sub 1-x}Cu{sub x}I powders synthesized process can accelerate single {beta}-phase crystalline structure formation.

  12. Precipitation in solid solution and structural transformations in single crystals of high rhenium ruthenium-containing nickel superalloys at high-temperature creep

    Energy Technology Data Exchange (ETDEWEB)

    Alekseev, A.A.; Petrushin, N.V.; Zaitsev, D.V.; Treninkov, I.A.; Filonova, E.V. [All-Russian Scientific Research Institute of Aviation Materials (VIAM), Moscow (Russian Federation)

    2010-07-01

    The phase composition and structure of single crystals of two superalloys (alloy 1 and alloy 2) were investigated in this work. For alloy 1 (Re - 9 wt%) the kinetics of precipitation in solid solution at heat treatment (HT) was investigated. TEM and X-Ray examinations have revealed that during HT rhombic phase (R-phase) precipitation (Immm class (BCR)) occurs. The TTT diagram is plotted, it contains the time-temperature area of the existence of R-phase particles. The element content of R-phase is identified (at. %): Re- 51.5; Co- 23.5; Cr- 14.8; Mo- 4.2; W- 3.3; Ta- 2.7. For alloy 2 (Re - 6.5 wt %, Ru - 4 wt %) structural transformations at high-temperature creep are investigated. By dark-field TEM methods it is established, that in alloy 2 the additional phase with a rhombic lattice is formed during creep. Particles of this phase precipitate in {gamma}-phase and their quantity increases during high-temperature creep. It is revealed that during creep 3-D dislocation network is formed in {gamma}-phase. At the third stage of creep the process of inversion structure formation is observed in the alloy, i.e. {gamma}'-phase becomes a matrix. Thus during modeling creep the volume fraction of {gamma}'-phase in the samples increases from 30% (at creep duration of 200 hrs) up to 55% (at 500 hrs). The processes of structure formation in Re and Ru-containing nickel superalloys are strongly affected by decomposition of solid solution during high-temperature creep that includes precipitation of additional TCP-phases. (orig.)

  13. Solid state and solution characterization of a new dinuclear nickel (II) complex: The search for synthetic models for urease

    Science.gov (United States)

    Horn, Adolfo; Fim, Luciana; Bortoluzzi, Adailton J.; Szpoganicz, Bruno; Silva, Marlon de S.; Novak, Miguel A.; Neto, Mario Benassi; Eberlin, Lívia Schiavinato; Catharino, Rodrigo Ramos; Eberlin, Marcos Nogueira; Fernandes, Christiane

    2006-09-01

    The X-ray molecular structure and, magnetic, and spectroscopic properties, as well as the analysis of the structural behavior in solution of a novel nickel (II) complex [Ni 2(HBPClNOL) 2(OAc)](ClO 4) 1 are reported. Complex 1 was prepared by the reaction between the ligand H 2BPClNOL ( N-(2-hydroxybenzyl)- N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)]propylamine), [Ni(H 2O) 6](ClO 4) 2 and sodium acetate. Magnetic measurements indicate the presence of a weak antiferromagnetic coupling between the Ni(II) ions in 1, resulting in J = -4.23 cm -1. Mass spectrometric characterization of the complex 1 was also performed via ESI-MS and ESI-MS/MS experiments and reveals that there are at least three different cations in solution, one mononuclear [Ni(H 2BPClNOL)(OAc)] + and two dinuclear [Ni 2(HBPClNOL) 2(OAc)] + and [Ni 2(HBPClNOL) 2(ClO 4)] + cations, as well as likely a fourth one [Ni(HBPClNOL)] +. Potentiometric titration experiments confirm that under acid conditions, the dinuclear unit is broken. However, under neutral/basic pH values the dinuclear unit is stable and shows the presence of two water molecules coordinated to the nickel ions, resulting in the cation [Ni 2(HBPClNOL) 2(H 2O) 2] 2+. This cation shows two protonation/deprotonation equilibriums with p Ka values of 9.68 and at 10.29, which are related to the aquo/hydroxo equilibrium associated with the water molecules coordinated to the metal ions.

  14. Characterization investigations during mechanical alloying and sintering of Ni-W solid solution alloys dispersed with WC and Y{sub 2}O{sub 3} particles

    Energy Technology Data Exchange (ETDEWEB)

    Genc, Aziz, E-mail: agenc@itu.edu.t [Particulate Materials Laboratories, Department of Metallurgical and Materials Engineering, Istanbul Technical University, Maslak, 34469 Istanbul (Turkey); Luetfi Ovecoglu, M. [Particulate Materials Laboratories, Department of Metallurgical and Materials Engineering, Istanbul Technical University, Maslak, 34469 Istanbul (Turkey)

    2010-10-15

    Research highlights: {yields} Characterization investigations on the Ni-W solid solution alloys fabricated via mechanical alloying and the evolution of the properties of the powders with increasing MA durations. {yields} Reinforcement of the selected Ni-W powders with WC and Y{sub 2}O{sub 3} particles and further MA together for 12 h. {yields} There is no reported literature on the development and characterization of Ni-W solid solution alloys matrix composites fabricated via MA. {yields} Sintering of the developed composites and the characterization investigations of the sintered samples. {yields} Identification of new 'pomegranate-like' structures in the bulk of the samples. - Abstract: Blended elemental Ni-30 wt.% W powders were mechanically alloyed (MA'd) for 1 h, 3 h, 6 h, 12 h, 24 h, 36 h and 48 h in a Spex mixer/mill at room temperature in order to investigate the effects of MA duration on the solubility of W in Ni and the grain size, hardness and particle size. Microstructural and phase characterizations of the MA'd powders were carried out using X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). On the basis of achieved saturation on the solid solubility, hardness and particle size, the Ni-30 wt.% W powders MA'd for 48 h were chosen as the matrix which was reinforced with different amounts of WC and/or with 1 wt.% Y{sub 2}O{sub 3} particles. The reinforced powders were further MA'd for 12 h. The MA'd powders were sintered at 1300 {sup o}C for 1 h under Ar and H{sub 2} gas flowing conditions. Microstructural characterizations of the sintered samples were conducted via XRD and SEM. Sintered densities were measured by using the Archimedes' method. Vickers microhardness tests were performed on both MA'd powders and the sintered samples. Sliding wear experiments were done in order to investigate wear behaviors of the sintered samples.

  15. Crystal phase transition in LixNa1-xGdF4 solid solution nanocrystals - Tuning of optical properties

    KAUST Repository

    Bański, Mateusz

    2014-01-01

    The influence of precursor composition on the crystallization of LixNa1-xGdF4 is investigated and discussed. Nanocrystals are prepared from the thermal decomposition of trifluoroacetates in the presence of trioctylphosphine oxide to provide control over particle size. A crystal phase transition from hexagonal to cubic and to tetragonal is observed by increasing lithium trifluoroacetate (Li-TFA) in the solution. Controlling the composition of LixNa1-xGdF4 nanocrystals results in modified crystal field symmetry and emission properties from doped europium (Eu3+) ions. We report that for lithium (Li+) substitution <15%, the hexagonal crystal field is preferred, while the Eu3+ emission is already tuned, whereas at higher Li+ substitution, a phase change takes place and the number of crystalline matrix defects increases which is reflected in the optical properties of Eu3+. From Eu3+ emission properties, the optimum Li+ content is determined to be ∼6.2% in the prepared LixNa1-xGdF4 nanocrystals.

  16. Crystalline structure of the manganites solid solution RE(Me,MnO3, (RE=Gd,Er; Me=Ni,Co

    Directory of Open Access Journals (Sweden)

    Peña, O.

    2009-08-01

    Full Text Available The structural properties of the manganites solid solution RE(Me,MnO3, RE=Er,Gd, have been studied by X-ray diffraction and electric measurements. Powders were prepared by solid state reaction between the component oxides. Incorporation of Ni2+ or Co2+ on the lattice in the Mn sites leads to changes in the parameters and symmetry of the perovskite or hexagonal compounds GdMnO3 and ErMnO3 respectively. The phase transitions depend on the amount of substituted Jahn-Teller Mn3+ cations, and, therefore, of the cooperative Jahn-Teller interaction weakness. Solid solutions based on GdMnO3 perovskite compound change from O’-type to O-type orthorhombic perovskite symmetry when the Mn3+ cation amount decreases, because of the progressive substitution for Ni, Co. This transition occurs for lower amount of Ni2+ than for Co2+ cation. The Er-based solid solutions showed a different behaviour. For Ni2+ and Co2+ incorporation there are changes from hexagonal ErMnO3-type lattice to perovskite-type symmetry, for 20 at% and 30 at% respectively of substituting cations. The resultant perovskites crystallised directly in the O-type orthorhombic perovskite structure. The steric influence seems to play a secondary role, such as it can be deduced of the small variation of the Goldschmidt tolerance factor, t, for perovskite structure.

    Las propiedades estructurales de las soluciones sólidas RE(Me,MnO3, RE=Gd,Er, Me=Ni,Co, han sido estudiadas por difracción de rayos X, (DRX y medidas eléctricas. Las fases se sintetizaron por reacción en estado sólido entre los óxidos componentes. La incorporación de los cationes Ni2+ y Co2+,3+ en la red en lugar de Mn lleva a cambios en los parámetros de red y en la simetría de la perovskita, GdMnO3 o del compuesto hexagonal Er

  17. Tsdc and Neutron-Scattering Measurements on Ba1-Xlaxf2+X and Ba1-Xuxf2+2x Solid-Solutions

    DEFF Research Database (Denmark)

    Ouwerkerk, M; Veldkamp, F. F.; Andersen, Niels Hessel

    1985-01-01

    A study was made of the dynamical behaviour of bound interstitial fluoride ions in disordered Ba1−xLaxF2+x and Ba1−xUxF2+2x solid solutions with Thermally Stimulated Depolarisation Current measurements and neutron scattering measurements, and a combination of both techniques. From 10 K to 400 K...... the TSDC spectra showed four reorientation peaks to be present in Ba1−xLaxF2+x, and six in Ba1−xUxF2+2x, along with the relaxation of the macroscopic space charge. The position of a space charge peak shifted to lower temperatures with increasing solute content. The dipolar realaxations were concentration...... invariant. In Ba1−xLaxF2+x neutral associates, L-shaped- and (222)- clusters occur. The present study reveals (212)-clusters to be present in Ba1−xUxF2+2x. The relations between ion dynamics and defect structures are discussed....

  18. Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2Reduction: A Case of ZnXCa1-XIn2S4.

    Science.gov (United States)

    Zeng, Chao; Huang, Hongwei; Zhang, Tierui; Dong, Fan; Zhang, Yihe; Hu, Yingmo

    2017-08-23

    Photocatalytic CO 2 reduction into solar fuels illustrates huge charm for simultaneously settling energy and environmental issues. The photoreduction ability of a semiconductor is closely correlated to its conduction band (CB) position. A homogeneous-phase solid-solution with the same crystal system always has a monotonously changed CB position, and the high CB level has to be sacrificed to achieve a benign photoabsorption. Herein, we report the fabrication of heterogeneous-phase solid-solution Zn X Ca 1-X In 2 S 4 between trigonal ZnIn 2 S 4 and cubic CaIn 2 S 4 . The Zn X Ca 1-X In 2 S 4 solid solutions with orderly tuned photoresponsive range from 540 to 640 nm present a more negative CB level and highly enhanced charge-separation efficiency. Profiting from these merits, all of these Zn X Ca 1-X In 2 S 4 solid solutions exhibit remarkably strengthened photocatalytic CO 2 reduction performance under visible light (λ > 420 nm) irradiation. Zn 0.4 Ca 0.6 In 2 S 4 , bearing the most negative CB position and highest charge-separation efficiency, casts the optimal photocatalytic CH 4 and CO evolution rates, which reach 16.7 and 6.8 times higher than that of ZnIn 2 S 4 and 7.2 and 3.9 times higher than that of CaIn 2 S 4 , respectively. To verify the crucial role of the heterogeneous-phase solid solution in promoting the band structure and photocatalytic performance, another heterogeneous-phase solid-solution Zn X Cd 1-X In 2 S 4 has been synthesized. It also displays an upshifted CB level and promoted charge separation. This work may provide a new perspective into the development of an efficient visible-light driven photocatalyst for CO 2 reduction and other photoreduction reactions.

  19. Synthesis, sintering and dissolution of thorium and uranium (IV) mixed oxide solid solutions: influence of the method of precursor preparation; Synthese, frittage et caracterisation de solutions solides d'oxydes mixtes de thorium et d'uranium (IV): influence de la methode de preparation du precurseur

    Energy Technology Data Exchange (ETDEWEB)

    Hingant, N

    2008-12-15

    Mixed actinide dioxides are currently considered as potential fuels for the third and fourth generations of nuclear reactors. In this context, thorium-uranium (IV) dioxide solid solutions were studied as model compounds to underline the influence of the method of preparation on their physico-chemical properties. Two methods of synthesis, both based on the initial precipitation of oxalate precursors have been developed. The first consisted in the direct precipitation ('open' system) while the second involved hydrothermal conditions ('closed' system). The second method led to a significant improvement in the crystallization of the samples especially in the field of the increase of the grain size. In these conditions, the formation of a complete solid solution Th{sub 1-x}U{sub x}(C{sub 2}O{sub 4}){sub 2}.2H{sub 2}O was prepared between both end-members. Its crystal structure was also resolved. Whatever the initial method considered, these compounds led to the final dioxides after heating above 400 C. The various steps associated to this transformation, involving the dehydration of precursors then the decomposition of oxalate groups have been clarified. Moreover, the use of wet chemistry methods allowed to reduce the sintering temperature of the final thorium-uranium (IV) dioxide solid solutions. Whatever the method of preparation considered, dense samples (95% to 97% of the calculated value) were obtained after only 3 hours of heating at 1500 C. Additionally, the use of hydrothermal conditions significantly increased the grain size, leading to the reduction of the occurrence of the grain boundaries and of the global residual porosity. The significant improvement in the homogeneity of cations distribution in the samples was also highlighted. Finally, the chemical durability of thorium-uranium (IV) dioxide solid solutions was evaluated through the development of leaching tests in nitric acid. The optimized homogeneity especially in terms of the

  20. Structure and Charge Density Properties of (1 - x)(Na1- y K y NbO3)- xBaTiO3 Lead-Free Ceramic Solid Solution

    Science.gov (United States)

    Sasikumar, S.; Saravanan, R.

    2017-07-01

    (1 - x)(Na1- y K y )NbO3- xBaTiO3 (abbreviated as NKN-BT, x = 0.1, 0.2; y = 0.01, 0.05) ceramics were synthesized by the solid-state reaction method. Powder x-ray diffraction analysis in combination with the profile refinement method was employed for quantitative phase analysis and structural refinement. The x-ray diffraction study shows that phase transition occurs from tetragonal to distorted cubic with the compositions between x = 0.1 and x = 0.2. The spatial arrangements of the electron distribution and bonding nature of the samples have been analyzed through the maximum entropy method. The optical band gap energy of the prepared solid solutions has been determined using UV-visible spectrophotometry. The optical band gap energy of the solid solutions decreases with the increase in BaTiO3 content. The elemental composition of these ceramics has been studied using energy dispersive x-ray analysis and the microstructure has been examined by scanning electron microscopy. The piezoelectric coefficient ( d 33 ) measurement of the ceramics shows the enhancement of piezoelectric properties in the tetragonal phase. The maximum value of the piezoelectric coefficient ( d 33 ) obtained for the solid solution is 120 pC/N. With increasing BaTiO3 content in the solid solutions, the ferroelectric behavior weakens.

  1. Solid-solution partitioning and thionation of diphenylarsinic acid in a flooded soil under the impact of sulfate and iron reduction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Meng [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tu, Chen [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Hu, Xuefeng; Zhang, Haibo [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Lijuan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Wei, Jing [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Li, Yuan [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Luo, Yongming, E-mail: ymluo@yic.ac.cn [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Christie, Peter [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)

    2016-11-01

    Diphenylarsinic acid (DPAA) is a major organic arsenic (As) compound derived from abandoned chemical weapons. The solid-solution partitioning and transformation of DPAA in flooded soils are poorly understood but are of great concern. The identification of the mechanisms responsible for the mobilization and transformation of DPAA may help to develop effective remediation strategies. Here, soil and Fe mineral incubation experiments were carried out to elucidate the partitioning and transformation of DPAA in anoxic (without addition of sulfate or sodium lactate) and sulfide (with the addition of sulfate and sodium lactate) soil and to examine the impact of sulfate and Fe(III) reduction on these processes. Results show that DPAA was more effectively mobilized and thionated in sulfide soil than in anoxic soil. At the initial incubation stages (0–4 weeks), 6.7–74.5% of the total DPAA in sulfide soil was mobilized likely by sorption competition with sodium lactate. At later incubation stage (4–8 weeks), DPAA was almost completely released into the solution likely due to the near-complete Fe(III) reduction. Scanning transmission X-ray microscopy (STXM) results provide further direct evidence of elevated DPAA release coupled with Fe(III) reduction in sulfide environments. The total DPAA fraction decreased significantly to 24.5% after two weeks and reached 3.4% after eight weeks in sulfide soil, whereas no obvious elimination of DPAA occurred in anoxic soil at the initial two weeks and the total DPAA fraction decreased to 10.9% after eight weeks. This can be explained in part by the enhanced mobilization of DPAA and sulfate reduction in sulfide soil compared with anoxic soil. These results suggest that under flooded soil conditions, Fe(III) and sulfate reduction significantly promote DPAA mobilization and thionation, respectively, and we suggest that it is essential to consider both sulfate and Fe(III) reduction to further our understanding of the environmental fate of

  2. From Ag{sub 2}Sb{sub 2}O{sub 6} to Cd{sub 2}Sb{sub 2}O{sub 7}: Investigations on an anion-deficient to ideal pyrochlore solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Laurita, Geneva [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Vielma, Jason [Department of Physics, Oregon State University, Corvallis, OR 97331 (United States); Winter, Florian [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, D-48149 Münster (Germany); Berthelot, Romain [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); CNRS, Univ. Bordeaux, ICMCB, UPR9048, F-33600 Pessac (France); Largeteau, Alain [CNRS, Univ. Bordeaux, ICMCB, UPR9048, F-33600 Pessac (France); Pöttgen, Rainer [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, D-48149 Münster (Germany); Schneider, G. [Department of Physics, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2014-02-15

    A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized through the standard solid state ceramic method. Each composition has been characterized by various different techniques, including powder X-ray diffraction, optical spectroscopy, electron paramagnetic resonance and {sup 121}Sb Mössbauer spectroscopy. Computational methods based on density functional theory complement this investigation. Photocatalytic activity has been studied, and transport properties have been measured on pellets densified by spark plasma sintering. The analysis of the data collected from these various techniques enables a comprehensive characterization of the complete solid solution and revealed an anomalous behavior in the Cd-rich end of the solid solution, which has been proposed to arise from a possible radical O{sup −} species in small concentrations. - Graphical abstract: A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized and investigated through various techniques including X-ray diffraction, electron paramagnetic spectroscopy, and {sup 121}Sb-Mössbauer spectroscopy. Optical and electrical measurements have been performed, and computational methods have been applied to determine the density of states. Photocatalytic activity was monitored by the degradation of Methylene Blue, and upon cadmium substitution, the degradation amount decreased, which is attributed primarily to the changing optical and electrical properties of the solid solution. Display Omitted - Highlights: • A complete solid solution between Ag{sub 2}Sb{sub 2}O{sub 6} and Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized. • XRD reveals a relatively constant lattice parameter as the series progresses. • Optical and electrical properties have been measured for the solid solution.

  3. Equilibrium, kinetics and thermodynamics studies of chitosan-based solid phase nanoparticles as sorbent for lead (II) cations from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shaker, Medhat A., E-mail: drmashaker@yahoo.com [Current address: Chemistry Department, Faculty of Science, University of Jeddah, Jeddah (Saudi Arabia); Permanent address: Chemistry Department, Faculty of Science, Damanhour University, Damanhour (Egypt)

    2015-07-15

    Ternary nanoparticles of chitosan, non-viable biomass (Pseudomonas sp.) and gelatin, CPG were synthesized by chemical crosslinking method and applied as a novel and cost-effective solid phase to adsorb Pb(II) cations from aqueous solution. Characterization of the fabricated CPG nanoparticles and their complexation behavior were extensively interrogated by dynamic light scattering (DLS), FTIR, TGA, XRD and SEM techniques. The extent of adsorption was found to be a function of medium pH, contact time, initial Pb(II) concentration and temperature. The Langmuir, Freundlich, Dubinin–Radushkevich and Redlich–Peterson models were used to illustrate the isotherms of the adsorption system. The adsorption of Pb(II) cations onto CPG best-fits the Langmuir isotherm model which predicts two stoichiometric temperature-independent adsorption sites, A and B with variable capacities, 35.4 and 91.1 mg g{sup −1}, respectively and removal capacity above 90%. Thermodynamic studies revealed that the adsorption process was physical, spontaneous, and endothermic. The adsorption rate is influenced by temperature and the adsorption kinetic is well confirmed with pseudo-second-order equation compared with three other investigated kinetic models. Present study indicated potential applications of CPG nanoparticles as excellent natural and promising solid phase for Pb(II) extraction in wastewater treatment. - Graphical abstract: Display Omitted - Highlights: • Kinetics and thermodynamics of Pb{sup 2+} biosorption onto CPG nanoparticles are studied. • Adsorption kinetic data are best modeled using second-order rate equations. • The Pb{sup 2}adsorption onto CPG was physical diffusion controlled reaction. • The experimental equilibrium results well fit the Langmuir model. • The thermodynamics show endothermic, favorable and spontaneous adsorption processes.

  4. The Solid Solutions (Per2[PtxAu(1−x(mnt2]; Alloying Para- and Diamagnetic Anions in Two-Chain Compounds

    Directory of Open Access Journals (Sweden)

    Manuel Matos

    2017-06-01

    Full Text Available The α-(Per2[M(mnt2] compounds with M = Pt and Au are isostructural two-chain solids that in addition to partially oxidized conducting perylene chains also contain anionic chains that can be either paramagnetic in the case of M = Pt or diamagnetic for M = Au. The electrical transport and magnetic properties of the solid solutions (Per2[Ptx-Au(1−x(mnt2] were investigated. The incorporation of paramagnetic [Pt(mnt2] impurities in the diamagnetic chains, and the effect of breaking the paramagnetic chains with diamagnetic centers for the low and high Pt range of concentrations were respectively probed. In the low Pt concentration range, there is a fast decrease of the metal-to-insulator transition from 12.4 K in the pure Au compound to 9.7 K for x = 0.1 comparable to the 8.1 K in the pure Pt compound. In the range x = 0.50−0.95, only β-phase crystals could be obtained. The spin-Peierls transition of the pure Pt compound, simultaneous with metal-to-insulator (Peierls transition is still present for 2% of diamagnetic impurities (x = 0.98 with transition temperature barely affected. Single crystal X-ray diffraction data obtained a high-quality structural refinement of the α-phase of the Au and Pt compounds. The β-phase structure was found to be composed of ordered layers with segregated donors and anion stacks, which alternate with disordered layers. The semiconducting properties of the β-phase are due to the disorder localization effects.

  5. Synthesis, structure and magnetic ordering of the mullite-type Bi2Fe(4-x)CrxO9 solid solutions with a frustrated pentagonal Cairo lattice.

    Science.gov (United States)

    Rozova, M G; Grigoriev, V V; Bobrikov, I A; Filimonov, D S; Zakharov, K V; Volkova, O S; Vasiliev, A N; Antipov, E V; Tsirlin, A A; Abakumov, A M

    2016-01-21

    Highly homogeneous mullite-type solid solutions Bi2Fe(4-x)CrxO9 (x = 0.5, 1, 1.2) were synthesized using a soft chemistry technique followed by a solid-state reaction in Ar. The crystal structure of Bi2Fe3CrO9 was investigated using X-ray and neutron powder diffraction, transmission electron microscopy and (57)Fe Mössbauer spectroscopy (S.G. Pbam, a = 7.95579(9) Å, b = 8.39145(9) Å, c = 5.98242(7) Å, RF(X-ray) = 0.022, RF(neutron) = 0.057). The ab planes in the structure are tessellated with distorted pentagonal loops built up by three tetrahedrally coordinated Fe sites and two octahedrally coordinated Fe/Cr sites, linked together in the ab plane by corner-sharing forming a pentagonal Cairo lattice. Magnetic susceptibility measurements and powder neutron diffraction show that the compounds order antiferromagnetically (AFM) with the Néel temperatures decreasing upon increasing the Cr content from TN ∼ 250 K for x = 0 to TN ∼ 155 K for x = 1.2. The magnetic structure of Bi2Fe3CrO9 at T = 30 K is characterized by a propagation vector k = (1/2,1/2,1/2). The tetrahedrally coordinated Fe cations form singlet pairs within dimers of corner-sharing tetrahedra, but spins on the neighboring dimers are nearly orthogonal. The octahedrally coordinated (Fe,Cr) cations form antiferromagnetic up-up-down-down chains along c, while the spin arrangement in the ab plane is nearly orthogonal between nearest neighbors and collinear between second neighbors. The resulting magnetic structure is remarkably different from the one in pure Bi2Fe4O9 and features several types of spin correlations even on crystallographically equivalent exchange that may be caused by the simultaneous presence of Fe and Cr on the octahedral site.

  6. Thermally driven metastable solid-solution Li0.5FePO4 in nanosized particles and its phase separation behaviors

    Science.gov (United States)

    Yoo, Sunyoung; Kang, Byoungwoo

    2013-10-01

    Nanosized LiFePO4 particles easily show a fast electrochemical response that can be achieved via a non-equilibrium pathway. To understand this intriguing phase transition behavior in nanosized LiFePO4 particles, the metastable solid-solution phase was prepared by thermal treatment with a chemically delithiated nanosized Li0.5FePO4 sample. Thermal treatment makes all the nanosized particles transform easily to the metastable solid-solution phase because of the large thermal energy while an electrochemical reaction does not. The phase separation behavior of the metastable solid-solution sample (Li0.5FePO4) was investigated under various kinetic conditions to understand critical factors affecting the phase separation behavior of nanosized LiFePO4 particles. The main findings in this study are as follows. The first finding is that the depressed phase separation behavior of the metastable phase may originate from the nanoparticle effect, in which the formation of a second phase inside a nanosized particle is not energetically favored because of the large interfacial energy. Therefore, phase separation in nanosized particles occurs between particles rather than inside a particle. If there was no over-potential, such as in the relaxed pellet experiment or in the relaxed electrode experiment in the electrolyte, the metastable phase was quite stable showing no phase separation behavior even though efficient pathways for lithium ions and electrons were well developed. The second finding is that the phase separation behavior of the metastable phase actually depends on the over-potential. Under open circuit voltage (OCV) conditions, the metastable phase started to exhibit a slight structural change during a long relaxation time, about ten days. The slow change of the metastable phase may be due to the low driving force, less than 10 mV, which comes from the energetic difference between the two-phase state and the metastable phase. This indicates that the phase separation

  7. Structures, electron density and characterization of novel photocatalysts, (BaTaO2N)1-x(SrWO2N)x solid solutions.

    Science.gov (United States)

    Hibino, Keisuke; Yashima, Masatomo; Oshima, Takayoshi; Fujii, Kotaro; Maeda, Kazuhiko

    2017-10-18

    Tungsten-modified barium tantalum oxynitride is a new visible-light photocatalyst for water oxidation. In the present work, novel barium tantalum strontium tungsten oxynitride solid solutions, (BaTaO2N)1-x(SrWO2N)x, with a cubic Pm3[combining macron]m perovskite-type structure (x = 0.01 and 0.02) have been prepared by heating oxide precursors under an ammonia flow. These (BaTaO2N)1-x(SrWO2N)x catalysts exhibited photocatalytic water oxidation activity under visible light irradiation. The crystal structure, electron-density distribution, and optical properties of (BaTaO2N)1-x(SrWO2N)x (x = 0, 0.01, and 0.02) have been studied using synchrotron X-ray powder diffraction, Rietveld analysis, the maximum-entropy method (MEM), and UV-Vis reflectance measurements. The lattice parameters of (BaTaO2N)1-x(SrWO2N)x decreased linearly with increasing SrWO2N content x. The minimum electron density (MED) at the (Ta,W)-(O,N) bond, determined by the MEM analysis of (BaTaO2N)1-x(SrWO2N)x, increased with x, as supported by DFT-based calculations. These results indicate the formation of (BaTaO2N)1-x(SrWO2N)x solid solutions and enhanced covalent bonding due to the stronger W-N bond. The MED of the (Ta,W)-(O,N) bond was higher than that of (Ba,Sr)-(O,N), indicating that the (Ta,W)-(O,N) bond is more covalent. The presence of nitrogen in (BaTaO2N)1-x(SrWO2N)x was confirmed by the occupancy factor refined using neutron diffraction data and by the weight gain observed by thermogravimetric analysis in air. UV-Vis reflectance spectra and DFT calculations indicated that (BaTaO2N)1-x(SrWO2N)x contains W(5+) cations with a [Xe] 4f(14) 5d(1) electron configuration and exhibits a more n-type semiconducting character compared with BaTaO2N, which could improve the photocatalytic water oxidation activity under visible-light irradiation.

  8. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: zhuyuanrong07@mails.ucas.ac.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: mengwei@craes.org.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2016-02-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  9. Facile synthesis and photocatalytic properties of ZnO core/ZnS-CdS solid solution shell nanorods grown vertically on reductive graphene oxide.

    Science.gov (United States)

    Xu, Jimeng; Sang, Huanxin; Wang, Xitao; Wang, Kang

    2015-05-28

    In the present study, ZnS-CdS solid solution sensitized ZnO nanorods were anchored on graphene sheets by combining a hydrothermal process and ion exchange technique, and the significant influence of CdS content in the shell on photo absorption and photocatalytic performance were investigated. Electron microscopic images reveal that the as-prepared nanocomposites display a sandwich-like 3D structure, consisting of ZnO nanorods with a ZnxCd1-xS or CdS shell grown vertically on both sides of the graphene sheets. UV/Vis DRS shows that the solid solution sensitized nanocomposites have enhanced visible light absorption and also exhibited a red-shift of the band-edge as compared to RGO/ZnO and RGO/ZnO@ZnS. Fluorescence emission spectra indicate that the deposition of CdS on the shell with an appropriate CdS/ZnS ratio and the incorporation of graphene causes improved charge separation. The photocatalytic experiments demonstrate that the RGO/ZnO@ZnxCd1-xS nanocomposites possess much higher photocatalytic activity for H2 evolution than the RGO/ZnO nanorods and RGO/ZnO@ZnS core/shell nanorods. Under the irradiation of a 300 W Xe lamp, the highest photocatalytic hydrogen production rate of 1865 μmol h(-1) g(-1) is observed over the RGO/ZnO@Zn0.6Zn0.4S sample, which is about 2.1 and 1.4 times more active than RGO/ZnO and RGO/ZnO@ZnS, respectively. Under the irradiation of visible light (>420 nm), the RGO/ZnO and RGO/ZnO@ZnS nanorods are barely active, whereas RGO/ZnO@Zn0.6Zn0.4S displays a hydrogen production rate of 160 μmol h(-1) g(-1). The highly improved performance of the composites can be ascribed to the increased light absorption and efficient charge separation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Caisso, Marie [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Institut Européen des Membranes, UMR 5635 CNRS-ENSCM-UM2, CC047, Université Montpellier 2, F-34095 Montpellier Cedex 5 (France); Lebreton, Florent; Horlait, Denis [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Picart, Sébastien [CEA, DEN, DRCP/SERA/LCAR, F-30207 Bagnols-sur-Cèze Cedex (France); Martin, Philippe M.; Bès, René [CEA, DEN, DEC/SESC/LLCC, F-13108 Saint-Paul-Lez-Durance Cedex (France); Renard, Catherine; Roussel, Pascal [Unité de Catalyse et Chimie du Solide, UMR 8012 CNRS, Ecole Nationale Supérieure de Chimie de Lille BP 90108, 59652 Villeneuve d’Ascq Cedex (France); Neuville, Daniel R. [Institut de Physique du Globe de Paris-CNRS, Géochimie and Cosmochimie, 1 rue Jussieu, 75005 Paris (France); Dardenne, Kathy; Rothe, Jörg [Karlsruhe Institute of Technology, Institute for Nuclear Waste Disposal (KIT-INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Delahaye, Thibaud, E-mail: thibaud.delahaye@cea.fr [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Ayral, André [Institut Européen des Membranes, UMR 5635 CNRS-ENSCM-UM2, CC047, Université Montpellier 2, F-34095 Montpellier Cedex 5 (France)

    2014-10-15

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

  11. A simple template-free synthesis of nanoporous ZnS-In2S3-Ag2S solid solutions for highly efficient photocatalytic H2 evolution under visible light.

    Science.gov (United States)

    Li, Yingxuan; Chen, Gang; Zhou, Chao; Sun, Jingxue

    2009-04-21

    Nanoporous ZnS-In(2)S(3)-Ag(2)S solid solutions synthesized by a facile template-free method showed relatively high activities for photocatalytic H(2) evolution under visible-light irradiation (lambda >400 nm) even in the absence of co-catalysts.

  12. On the ‘centre of gravity’ method for measuring the composition of magnetite/maghemite mixtures, or the stoichiometry of magnetite-maghemite solid solutions, via 57Fe Mössbauer spectroscopy

    DEFF Research Database (Denmark)

    Fock, Jeppe; Bogart, Lara K.; González-Alonso, David

    2017-01-01

    spectrum, and is correlated to the sample’s composition or stoichiometry. We present data on high-purity magnetite and maghemite powders, and mixtures thereof, as well as comparison literature data from nanoparticulate mixtures and solid solutions, to show that a linear correlation exists between δ̅RT...

  13. Synthesis and photocatalytic oxidation of different organic dyes by using Mn 2O 3/TiO 2 solid solution and visible light

    Science.gov (United States)

    Ghorai, Tanmay K.; Pramanik, Susmita; Pramanik, Panchanan

    2009-08-01

    Mn 2O 3/TiO 2 solid solution was prepared from two different oxides, manganese oxide (from KMnO 4 and ethanol) and TiO 2, these samples were characterized by BET, XRD, EDAX, SEM, FT-IR, ESR, XPS and UV-vis absorption spectroscopy. Photocatalytic activities of Mn 2O 3/TiO 2 powder was investigated by photooxidation of different dyes like Rhodamine B, thymol blue, methyl orange and Bromocresol green under visible light (300-W Xe lamp; λ > 420 nm). The results show that the alloy of TiO 2 with 1 mol% of Mn 2O 3 (MNT1) exhibit photocatalytic activity 3-5 times higher than that of P25 TiO 2 for oxidation of various dyes (RB, TB, MO and BG). The average particle size and crystallite size of MNT1 were found to be 100 nm and 12 nm measured from SEM and XRD, respectively. The EPR spectra of the Mn 2O 3/TiO 2 samples is a sharp five-line Mn(III) component centered on geff = 1 .99.

  14. Study on microstructure evolution of deformed Mg-Gd-Y-Nd-Zr heat-resistant magnesium alloys after solid solution and ageing

    Directory of Open Access Journals (Sweden)

    Jianmin Yu

    2016-01-01

    Full Text Available The microstructure evolution of Mg-Gd-Y-Nd-Zr heat-resistant magnesium alloy after deformation and T5 or T6 treatment were studied. In thermoplastic deformation, dynamic recrystallization and dynamic precipitation has been taken place at the same time. The dynamic precipitation reduces the recrystallization nucleation driving force in the grain; it will prevent to occur dynamic recrystallization partially. Solid solution temperature was 530oC and hold 4h. Age hardening treatments were performed at 225oC and hold 16h. The alloy showed the comprehensive properties are obviously improved from T6 to T5 heat treatment. After T5 heat treatment the tensile strength of alloy increased to 359.3 MPa, increased by around 48.5%; Elongation is increasing from 5.17% to 6.5%. After peak ageing treatment, the main precipitation is β' phase, the precipitation phase have obvious pinning effect to grain boundary of the alloy, it will prevent the grain growth ageing for a long-time. At the same time, strengthening role of precipitate phase make its strength increased significantly.

  15. Heterophase states and domain effects in solid solutions of (1 - x)BiFeO3 - xPbTiO3

    Science.gov (United States)

    Topolov, V. Yu.

    2012-05-01

    Examples of heterophase states in multiferroic solid solutions of (1 - x)BiFeO3 - xPbTiO3 with the perovskite-type structure are studied taking into account the features of elastic matching of polydomain (twinned) ferroelectric phases near the morphotropic phase boundary and in a wide temperature range. Conditions for the complete stress relief are examined in the heterophase states P4mm-P4mm and P4mm-Cc to interpret variations of the phase content [S. Bhattacharjee et al., Phys. Rev. B 84, 104116 (2011)] [S. Bhattacharjee and D. Pandey, J. Appl. Phys. 110, 084105 (2011)] in (1-x)BiFeO3-xPbTiO3. The key role of some 90° domain types of the low-temperature ferroelectric P4mm phase in the stress relief at the phase coexistence is emphasized. An agreement between the evaluated and experimental data on the volume fraction of the low-temperature P4mm phase in heterophase samples is observed.

  16. Hydrated and Solvated Tin(II) Ions in Solution and the Solid State, and a Coordination Chemistry Overview of the d10s2Metal Ions.

    Science.gov (United States)

    Persson, Ingmar; D'Angelo, Paola; Lundberg, Daniel

    2016-12-19

    The coordination chemistry of d 10 s 2 metal ions is strongly affected by an (at least partially) occupied d 10 s 2 metal ion-ligand atom antibonding orbital, which may cause a void in the coordination sphere due to repulsion between the electrons in the antibonding orbital on the metal ion and those on the ligands. The character of the formed d 10 s 2 metal ion-ligand atom bond plays an important role in the electron density in the antibonding orbital and thereby also in the coordination chemistry. The hydrated tin(II) ion, [Sn(H 2 O) 3 ] 2+ , and the trihydroxidostannate ion, [Sn(OH) 3 ] - , have very different mean Sn-O bond lengths (2.21 and 2.08 Å, respectively) and O-Sn-O angles (ca. 78 and 90°, respectively) both in the solid state and in solution. On increasing the covalency of the tin(II)-ligand bonds, the repulsion decreases and higher coordination numbers are obtained, as seen in the dimethylsulfoxide- and N,N-dimethylthioformamide-solvated tin(II) ions, both of which are five-coordinate with square-pyramidal structures. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Calculation of thermodynamic functions of saturated solid solution of AgIn2Te3I compound in the Ag–In–Te–I system

    Directory of Open Access Journals (Sweden)

    Moroz Mykola

    2017-01-01

    Full Text Available Triangulation of Ag–In–Te–I system in the vicinity of AgIn2Te3I compound was investigated by X-ray diffraction and differential thermal analysis methods. The spatial position of the phase region AgIn2Te3I–InTe–Ag2Te–AgI regarding the figurative point of silver was used in order to write the equation of virtual potential-forming reaction. Potential-forming reaction was performed in electrochemical cell (ECC of the type (– C | Ag | Ag3GeS3I(Br glass | D | C (+ where C are inert (graphite electrodes; Ag and D are the electrodes of the ECC; D represents the alloy of four-phase region; Ag3GeS3I glass is a membrane with purely ionic Ag+ conductivity. Linear dependence of the EMF of cell on temperature in the range of 440−480 К was used to calculate the standard thermodynamic functions of saturated solid solution of AgIn2Te3I compound in Ag–In–Te–I system.

  18. Calculation of thermodynamic functions of saturated solid solution of AgIn2Te3I compound in the Ag-In-Te-I system

    Science.gov (United States)

    Moroz, Mykola; Prokhorenko, Sergiy; Prokhorenko, Myroslava; Reshetnyak, Oleksandr

    2017-01-01

    Triangulation of Ag-In-Te-I system in the vicinity of AgIn2Te3I compound was investigated by X-ray diffraction and differential thermal analysis methods. The spatial position of the phase region AgIn2Te3I-InTe-Ag2Te-AgI regarding the figurative point of silver was used in order to write the equation of virtual potential-forming reaction. Potential-forming reaction was performed in electrochemical cell (ECC) of the type (-) C | Ag | Ag3GeS3I(Br) glass | D | C (+) where C are inert (graphite) electrodes; Ag and D are the electrodes of the ECC; D represents the alloy of four-phase region; Ag3GeS3I glass is a membrane with purely ionic Ag+ conductivity). Linear dependence of the EMF of cell on temperature in the range of 440-480 K was used to calculate the standard thermodynamic functions of saturated solid solution of AgIn2Te3I compound in Ag-In-Te-I system.

  19. The solid solution Sr3Ti2-xFexO7-δ (x ≤ 0.5: characterization of Fe (III – Fe (IV mixed valences

    Directory of Open Access Journals (Sweden)

    I. Zvereva

    2016-03-01

    Full Text Available The results of a magneto chemical and Mössbauer characterization are reported for the solid solution Sr3Ti2-xFexO7-δ (x ≤ 0.5, the intergrowth of a double perovskite block and one rock-salt layer type. The charge compensation mechanism induced by the introduction of iron atoms in the matrix of Sr3Ti2O7 is sensitive to the conditions of synthesis, namely an oxidation process triggers the formation of mixed Fe(III-Fe(IV valences. The crystallographic characterization - variation of the cell parameters and structure calculations – brings evidence for the respective occurrence of mixed valences and oxygen vacancies which form in the middle plane of the double perovskite block. Ferromagnetic exchange interactions which are absent in the Fe(III containing compositions, appear and progressively strengthen depending on the oxidizing treatment. They are ascribed to the presence of an increasing amount of Fe(IV species. Remarkably, a mixed valence state of iron forms during annealing in air with an increasing contribution of the Fe(IV species for the larger iron contents, as deduced from Mössbauer data.

  20. Mechanochemical synthesis, structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1-xMbxF2 (M: Ca, Sr, Ba)

    Science.gov (United States)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2016-10-01

    The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides Ma1-xMbxF2 (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca1-xSrxF2 and Ba1-xSrxF2 samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and 19F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of 19F chemical shifts with the superposition model along with probability calculations for the intensity of the individual 19F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F- ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.

  1. Order-disorder transition and electrical conductivity of the brownmillerite solid-solutions system Ba sub 2 (In, M) sub 2 O sub 5 (M=Ga, Al)

    CERN Document Server

    Yamamura, H; Kakinuma, K; Mori, T; Haneda, H

    1999-01-01

    The brownmillerite solid-solution systems Ba sub 2 (In sub 1 sub - sub x M sub x) sub 2 O sub 5 (M=Ga, Al) were investigated by means of high-temperature X-ray diffraction (XRD), dilatometry, and electrical-conductivity measurements. XRD showed that the Ba sub 2 (In sub 1 sub - sub x Ga sub x) sub 2 O sub 5 system had orthorhombic symmetry in the composition range 0.0<=x<=0.2 and cubic symmetry in the range 0.3<=x. The Al system also changed to cubic symmetry from orthorhombic symmetry in the range 0.2<=x. While the orthorhombic phase showed an order-disorder transition in the electrical conductivity measurements, the transition temperature decreased with increasing the M content. The order-disorder transition temperature and the crystal-structure transition temperature were very different. Such a transition was not observed in the cubic phases, and their electrical conductivity were fairly low compared to those of the disordered cubic phase after the transition due to the heating process. These p...

  2. An artificial photosynthesis anode electrode composed of a nanoparticulate photocatalyst film in a visible light responsive GaN-ZnO solid solution system

    Science.gov (United States)

    Imanaka, Yoshihiko; Anazawa, Toshihisa; Manabe, Toshio; Amada, Hideyuki; Ido, Sachio; Kumasaka, Fumiaki; Awaji, Naoki; Sánchez-Santolino, Gabriel; Ishikawa, Ryo; Ikuhara, Yuichi

    2016-10-01

    The artificial photosynthesis technology known as the Honda-Fujishima effect, which produces oxygen and hydrogen or organic energy from sunlight, water, and carbon dioxide, is an effective energy and environmental technology. The key component for the higher efficiency of this reaction system is the anode electrode, generally composed of a photocatalyst formed on a glass substrate from electrically conductive fluorine-doped tin oxide (FTO). To obtain a highly efficient electrode, a dense film composed of a nanoparticulate visible light responsive photocatalyst that usually has a complicated multi-element composition needs to be deposited and adhered onto the FTO. In this study, we discovered a method for controlling the electronic structure of a film by controlling the aerosol-type nanoparticle deposition (NPD) condition and thereby forming films of materials with a band gap smaller than that of the prepared raw material powder, and we succeeded in extracting a higher current from the anode electrode. As a result, we confirmed that a current approximately 100 times larger than those produced by conventional processes could be obtained using the same material. This effect can be expected not only from the materials discussed (GaN-ZnO) in this paper but also from any photocatalyst, particularly materials of solid solution compositions.

  3. A comparative structure and morphology study of Zn (1- x ) Cd x O solid solution grown on ZnO and different sapphire orientations

    Science.gov (United States)

    Fouzri, A.; Sallet, V.; Oumezzine, M.

    2011-09-01

    Zn (1- x) Cd xO solid solutions with a constant Cadmium flow 10 cc have been grown on ZnO, c-, a- and r-plane sapphire substrates using metal organic chemical vapor deposition (MO-CVD). The optical transmission spectra and energy band-gap equation established by Mikano et al. were used to estimate cadmium mole fraction of alloy. Lattice parameters and morphology of these films were examined using high resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM) as Cd incorporation and employed substrate. By comparison, we observe significant differences between Cd incorporation and morphologies depending on nature and substrate orientation but the hexagonal wurtzite structure is maintained. Higher Cd incorporation (11.2 at%) is obtained on Zn (1- x) Cd xO grown on r-plane sapphire, which is confirmed by the greatest energy shift (340 meV) to lower energy measured by room temperature photoluminescence. However, the lattice parameter c remains unchanged while parameter a is identical for films deposited on ZnO and r-plane sapphire substrates and for those deposited on c- and a-plane sapphire substrates.

  4. Influence of Zn substitution for Mg on microwave dielectric properties of spinel-structured (Mg1-xZnx)Ga2O4 solid solutions

    Science.gov (United States)

    Kan, Akinori; Takahashi, Susumu; Moriyama, Tohru; Ogawa, Hirotaka

    2014-09-01

    The microwave dielectric properties and crystal structure of spinel-structured (1 - x)MgGa2O4-xZnGa2O4 ceramics were characterized in this study. From the linear variation in the lattice parameters, the formation of solid solution was obtained over the whole composition range. On the basis of the refined atomic coordinates, the variations in the volume of tetrahedron and octahedron were estimated and the expansion of the MO4 (M = Mg, Zn, and Ga) tetrahedron was recognized. The covalency of the cation-oxygen bond in the 8a site decreased with increasing composition x, suggesting the preferential Zn substitution for Mg in 8a site. The ɛr values of Zn-substituted ceramics were higher than that of MgGa2O4 ceramic. The Q · f values higher than 1.8 × 105 GHz were obtained when the ceramics were sintered at temperatures higher than 1475 °C.

  5. First principles studies on the impact of point defects on the phase stability of (AlxCr1−x2O3 solid solutions

    Directory of Open Access Journals (Sweden)

    C. M. Koller

    2016-02-01

    Full Text Available Density Functional Theory applying the generalised gradient approximation is used to study the phase stability of (AlxCr1−x2O3 solid solutions in the context of physical vapour deposition (PVD. Our results show that the energy of formation for the hexagonal α phase is lower than for the metastable cubic γ and B1-like phases–independent of the Al content x. Even though this suggests higher stability of the α phase, its synthesis by physical vapour deposition is difficult for temperatures below 800 °C. Aluminium oxide and Al-rich oxides typically exhibit a multi-phased, cubic-dominated structure. Using a model system of (Al0.69Cr0.312O3 which experimentally yields larger fractions of the desired hexagonal α phase, we show that point defects strongly influence the energetic relationships. Since defects and in particular point defects, are unavoidably present in PVD coatings, they are important factors and can strongly influence the stability regions. We explicitly show that defects with low formation energies (e.g. metal Frenkel pairs are strongly preferred in the cubic phases, hence a reasonable factor contributing to the observed thermodynamically anomalous phase composition.

  6. Room-temperature ferromagnetism of 2H-SiC-α-Al2O3 solid solution nanowires and the physical origin.

    Science.gov (United States)

    Sun, Yong; Lu, Cheng; Cui, Hao; Wang, Jing; Ma, Yanming; Wang, Chengxin

    2015-03-21

    In this work we report the first synthesis of 2H-SiC-α-Al2O3 solid solution (SS) nanowires with 2H-SiC as the host phase. The one dimensional (1D) fake binary-system exhibits interesting room-temperature ferromagnetism and spin-glass-like (SGL) behavior. This novel diluted magnetic semiconductor (DMS) was designed on the basis of SiC which is the most promising fundamental semiconductor used in next-generation electronics as the substitute for Si. A systematic investigation of the magnetic properties reveals the origin of the material's room-temperature ferromagnetism and spin-glass behavior. Spin-polarized density functional theory (DFT) calculations reveal that the net moment originates from a strong coupling between atoms around local Si vacancies produced by the SS defect reaction. Unlike random defects derived magnetic behavior, the SS resulted magnetism is significant to be utilized in functional devices since it belongs to a stable crystal structure that is possible to be prepared rationally in a controlled manner.

  7. Charged defects and ferroelectricity in (1-x)PbZrO3-x(Na1/2Bi1/2)TiO3 solid solution

    Science.gov (United States)

    Lee, Jung-Kun; Youn, Hyuk-Jun; Hong, Kug Sun; Park, Seung-Eek

    1999-01-01

    The crystal structure, dielectric/ferroelectric properties, and domain configuration of (1-x) PbZrO3-x(Na1/2Bi1/2)TiO3 solid solution with 0.14⩽x⩽0.4 were investigated using x-ray powder diffraction, D-E hysteresis, ɛr(T) measurements, and transmission electron microscopy. A sluggish transition from normal ferroelectric to relaxor state was observed as a function of composition. With an increasing amount of (Na1/2Bi1/2)TiO3, this transition was accompanied by changes in crystal structure (rhombohedral to pseudocubic), domain size and morphology (normal micron-size domain to polar nanodomain), and thermal phase transition behavior (normal ferroelectric transition to diffuse transition behavior with polarization relaxation). For intermediate compositions (i.e., x=0.25) between normal ferroelectric (x=0.16) and relaxor (x=0.4), a spontaneous relaxor-to-normal ferroelectric transition occurred at 80 °C in the ɛr(T) curve. It is suggested that this transition originates from the introduction of charged defects such as NaPb' and BiPb•, resulting in the disturbance of long-range interactions among polar ordered BO6-octahedra and short-range structural order of charged defects (i.e., NaPb'-BiPb•).

  8. Polyvinylimidazole/sol-gel composite as a novel solid-phase microextraction coating for the determination of halogenated benzenes from aqueous solutions.

    Science.gov (United States)

    Farjaminezhad, Manoochehr; Saber Tehrani, Mohammad; Aberoomand Azar, Parviz; Hussain, Syed Waqif; Bohlooli, Shahab

    2014-06-01

    A polyvinylimidazole/sol-gel composite is proposed as a novel solid-phase microextraction fiber to extract five halobenzenes from the headspace of aqueous solutions in combination with gas chromatography with mass spectrometry. The prepared fiber was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The obtained results showed that porous polyvinylimidazole/sol-gel composite was chemically deposited on fused silica fiber. The effect of important extraction parameters including extraction temperature, extraction time, and salt content were investigated. The optimum conditions were as follows: extraction temperature 25°C, extraction time 20 min, and salt concentration 30 w/v%. Detection limits and relative standard deviations of the developed method for halogenated benzenes were below 0.1 pg/mL and 15%, respectively. Repeatability of the proposed method, explained by relative standard deviation, varied between 5.48 and 9.15% (n = 5). The limits of detection (S/N = 3) ranged between 0.01 and 0.10 ng/L using gas chromatography with mass spectrometry with selected ion monitoring mode. For real sample analysis, three types of water samples with different matrices (ground, surface, and tap water) were studied. The optimized procedure was applied to extraction and method validation of halogenated benzenes in spiked water samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A neutron diffraction study of crystal and low-temperature magnetic structures within the (Na,Li)FeGe2O6 pyroxene-type solid solution series

    Science.gov (United States)

    Redhammer, Günther J.; Senyshyn, Anatoliy; Lebernegg, Stefan; Tippelt, Gerold; Dachs, Edgar; Roth, Georg

    2017-10-01

    Solid solution compounds along the Li1- x Na x FeGe2O6 clinopyroxene series have been prepared by solid state ceramic sintering and investigated by bulk magnetic and calorimetric methods; the Na-rich samples with x(Na) > 0.7 were also investigated by low-temperature neutron diffraction experiments in a temperature range of 4-20 K. For samples with x(Na) > 0.76 the crystal structure adopts the C2/ c symmetry at all measuring temperatures, while the samples display P21/ c symmetry for smaller Na contents. Magnetic ordering is observed for all samples below 20 K with a slight decrease of T N with increasing Na content. The magnetic spin structures change distinctly as a function of chemical composition: up to x(Na) = 0.72 the magnetic structure can be described by a commensurate arrangement of magnetic spins with propagation vector k = (½, 0 0), an antiferromagnetic (AFM) coupling within the Fe3+O6 octahedra zig-zag chains and an alternating AFM and ferromagnetic (FM) interaction between the chains, depending on the nature of the tetrahedral GeO4 chains. The magnetic structure can be described in magnetic space group P a21/ c. Close to the structural phase transition for sample with x(Na) = 0.75, magnetic ordering is observed below 15 K; however, it becomes incommensurately modulated with k = (0.344, 0, 0.063). At 4 K, the magnetic spin structure best can be described by a cycloidal arrangement within the M1 chains, the spins are within the a- c plane. Around 12 K the cycloidal structure transforms to a spin density wave (SDW) structure. For the C2/ c structures, a coexistence of a simple collinear and an incommensurately modulated structure is observed down to lowest temperatures. For 0.78 ≤ x(Na) ≤ 0.82, a collinear magnetic structure with k = (0 1 0), space group P C21/ c and an AFM spin structure within the M1 chains and an FM one between the spins is dominating, while the incommensurately modulated structure becomes dominating the collinear one in the

  10. From solid to liquid: assessing the release of organic matter into soil solution in response to land-use conversion in Brazilian Oxisols

    Science.gov (United States)

    James, Jason; Gross, Cole; Dwivedi, Pranjal; Bernardi, Rodolpho; Guerrini, Irae; Harrison, Rob; Butman, David

    2017-04-01

    Recent advances in freshwater research indicate that roughly double the quantity of carbon is exported from soils to streams and rivers than was previously estimated, and that the age of carbon exported from major rivers globally increases with greater human disturbance in the watershed. This implies that human land-use can release old, previously mineral-associated C into solution with subsequent export to groundwater and ultimately freshwater systems where terrestrial organic matter is either mineralized to CO2, stored in aquatic sediments, or exported to the ocean. Consequently, it is important to understand the mechanisms that cause the release of SOM that is mineral-bound into solution in response to human disturbance and land-use change. Research methods have been established to examine both the fast turnover, dissolved pool of soil organic matter (SOM), as well as the slow turnover, mineral-associated pool. However, to better characterize the response of the total SOM pool to disturbance, it is necessary to understand the interactions between these functional pools by examining them both simultaneously. This study seeks to examine the interaction between dissolved organic matter (DOM) and bulk SOM throughout the soil profile in response to conversion of Brazilian Cerrado (savannah forest) to Eucalyptus plantation forest on the same soil type. The water-extractable organic matter was obtained from soil samples down to 150 cm, characterized using fluorescence and NMR spectroscopy, and carbon-dated. Simultaneously, bulk mineral soil samples were analyzed for microbial biomass, carbon content and age, and characterized using Fourier Transform Infrared Spectroscopy. SOM spectra were obtained by washing subsamples with sodium hypochlorite and subtracting the subsequent mineral matrix spectra from bulk soil spectra. Preliminary results show that microbial biomass decreases much more quickly with depth than DOM, suggesting that C released into solution from deeper

  11. Oxygen isotope analysis of carbonates in the calcite-dolomite-magnesite solid-solution by high-temperature pyrolysis: initial results.

    Science.gov (United States)

    Crowley, Stephen F; Spero, Howard J; Winter, David A; Sloane, Hilary J; Croudace, Ian W

    2008-06-01

    Accurate and efficient measurement of the oxygen isotope composition of carbonates (delta(C) (18)O) based on the mass spectrometric analysis of CO(2) produced by reacting carbonate samples with H(3)PO(4) is compromised by: (1) uncertainties associated with fractionation factors (alpha(CO)(2)C) used to correct measured oxygen isotope values of CO(2)(delta(CO(2)(18)O) to delta(C) (18)O; and (2) the slow reaction rates of many carbonates of geological and environmental interest with H(3)PO(4). In contrast, determination of delta(C) (18)O from analysis of CO produced by high-temperature (>1400 degrees C) pyrolytic reduction, using an elemental analyser coupled to continuous-flow isotope-ratio mass spectrometry (TC/EA CF-IRMS), offers a potentially efficient alternative that measures the isotopic composition of total carbonate oxygen and should, therefore, theoretically be free of fractionation effects. The utility of the TC/EA CF-IRMS technique was tested by analysis of carbonates in the calcite-dolomite-magnesite solid-solution and comparing the results with delta(C) (18)O measured by conventional thermal decomposition/fluorination (TDF) on the same materials. Initial results show that CO yields are dependent on both the chemical composition of the carbonate and the specific pyrolysis conditions. Low gas yields (+0.2 per thousand) deviations in delta(C(TC/EA) (18)O compared with delta(C(TDF) (18)O. At a pyrolysis temperature of 1420 degrees C the difference between delta(C) (18)O measured by TC/EA CF-IRMS and TDF (Delta(C(TC/EA,TDF) (18)O) was found to be negatively correlated with gas yield (r = -0.785) and this suggests that delta(C) (18)O values (with an estimated combined standard uncertainty of +/-0.38 per thousand) could be derived by applying a yield-dependent correction. Increasing the pyrolysis temperature to 1500 degrees C also resulted in a statistically significant correlation with gas yield (r = -0.601), indicating that delta(C) (18)O values (with an

  12. Theoretical solid state physics

    CERN Document Server

    Haug, Albert

    2013-01-01

    Theoretical Solid State Physics, Volume 1 focuses on the study of solid state physics. The volume first takes a look at the basic concepts and structures of solid state physics, including potential energies of solids, concept and classification of solids, and crystal structure. The book then explains single-electron approximation wherein the methods for calculating energy bands; electron in the field of crystal atoms; laws of motion of the electrons in solids; and electron statistics are discussed. The text describes general forms of solutions and relationships, including collective electron i

  13. Impact of Mg2+ ion incorporation on the phase development of ZrO2-type solid solutions and their application in the catalytic oxidation of carbon monoxide

    Science.gov (United States)

    Nemec, Vinko; Kaper, Helena; Pétaud, Guillaume; Ivanda, Mile; Štefanić, Goran

    2017-07-01

    The precursors of ZrO2-MgO system covering the whole concentration range were prepared by co-precipitation of the corresponding nitrate salts. The obtained precursors were calcined in air at different temperatures up to 1000 °C and analyzed at room temperature using X-ray powder diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESM) and energy dispersive X-ray spectrometry (EDS). Maximum solubility of Mg2+ ions (∼32 mol%) was obtained in the amorphous precursor. After crystallization at 600 °C the solid solubility of Mg2+ ions decreases to ∼26 mol% of which ∼22 mol% was incorporated inside ZrO2-type lattice while the remaining part of Mg2+ ions was adsorbed on the surface of the particles. Further thermal treatment decreases solubility of Mg2+ ions to 18 mol% (800 °C) and finally to 9 mol% (1000 °C). On the other side of the concentration range, the solubility of Zr4+ ions in MgO lattice was 10 mol%) polymorphs. A precise determination of unit-cell parameters shows that the increase in the Mg2+ content causes a decrease in the parameter c of tetragonal ZrO2 lattice, which in a solid solution with a Mg2+ content ≥10 mol% becomes very close to the lattice parameter a (approaching cubic lattice). The results of FE-SEM analysis show that the addition of Mg2+ ions promotes sintering of samples. The influence of thermal treatment on the crystallization of the amorphous precursors to ZrO2-type lattice was examined by differential thermal analysis and thermogravimetric measurement. The obtained results show that the crystallization temperature increases with increasing Mg content, from 445 °C (0 mol% MgO) to 625 °C (∼50 mol% MgO). The ZrO2 doped with 3 mol% MgO was used as catalyst support for platinum nanoparticles and compared to commercially available 3% yttria-doped stabilized zirconia (3YSZ). The catalysts were used for catalytic CO oxidation and show slightly better performance of the ZrO2-MgO system, which

  14. Neutron powder diffraction investigation of magnetic structure and spin reorientation transition of HoFe{sub 1-x}Cr{sub x}O{sub 3} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xinzhi [Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413 (China); Hao, Lijie, E-mail: haolijie@ciae.ac.cn [Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413 (China); Liu, Yuntao; Ma, Xiaobai; Meng, Siqin; Li, Yuqing; Gao, Jianbo; Guo, Hao; Han, Wenze; Sun, Kai; Wu, Meimei [Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413 (China); Chen, Xiping; Xie, Lei [Institute of Nuclear Physics and Chemistry, CAEP, Mianyang 621900 (China); Klose, Frank [Australian Nuclear Science and Technology Organization, Lucas Heights, New South Wales 2234 (Australia); Department of Physics and Materials Science, The City University of Hong Kong, Hong Kong (China); Chen, Dongfeng, E-mail: dongfeng@ciae.ac.cn [Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413 (China)

    2016-11-01

    Orthoferrite solid solution HoFe{sub 1−x}Cr{sub x}O{sub 3} (x=0, 0.2,…,1.0) was synthesized via solid state reaction methods. The crystal structure, magnetism and spin reorientation properties of this system were investigated by X-ray diffraction, neutron powder diffraction and magnetic measurements. For compositions of x≤0.6, the system exhibits similar magnetic properties to HoFeO{sub 3}. With increasing Cr-doping, the system adopts a Γ{sub 4}(G{sub x}A{sub y}F{sub z}) magnetic configuration with a decreased Neel temperature from 640 K to 360 K. A Γ{sub 42} spin reorientation of Fe(Cr){sup 3+} was also observed in this system with an increase in transition temperature from 56 K to about 200 K due to competition between the Fe(Cr)–Fe(Cr) and Ho–Fe(Cr) interactions. For the x≥0.8, the system behaves more like HoCrO{sub 3} which adopts a Γ{sub 2}(F{sub x}C{sub y}G{sub z}) configuration with no spin reorientation below the Neel temperature T{sub N}. Throughout the whole substitution range, we found that the saturated moment of Fe(Cr) was less than the ideal value for a free ion, which implies the existence of spin fluctuation in this system. A systematic magnetic structure variation with Cr-substitution is revealed by Rietveld refinement. A phase diagram combining the results of the magnetic measurements and neutron powder diffraction results was obtained. - Highlights: • With Cr-substitution in the HoFe{sub 1−x}Cr{sub x}O{sub 3} system, A Γ{sub 42} spin reorientation of Fe(Cr){sup 3+} was observed with an increase in transition temperature from 56 K to about 200 K for x=0−0.6. • The saturated moment of Fe(Cr) position was found to be systematically less than the ideal value of free ion, and thus implies the presence of spin quantum fluctuation. • A composition–temperature phase diagram throughout x=0–1 for HoFe{sub 1−x}Cr{sub x}O{sub 3} system was established.

  15. Partition coefficients for Ni, Cu, Pd, Pt, Rh, and Ir between monosulfide solid solution and sulfide liquid and the formation of compositionally zoned Ni-Cu sulfide bodies by fractional crystallization of sulfide liquid

    DEFF Research Database (Denmark)

    Barnes, S.J.; Makovicky, E.; Makovicky, M.

    1996-01-01

    to be concentrated in the Fe-rich ore. The origin of this zonation could be due to crystal fractionation of Fe-rich monosulfide solid solution from a sulfide liquid. The crystal fractionation would produce an Fe-rich cumulate enriched in Os, Ir, Ru, and Rh and a fractionated liquid enriched in Cu, Pt, Pd, and Au...... (Alexo, Abitibi Greenstone Belt) and a zoned tholeiite-related ore (Oktyabr'sky, Noril'sk region, Siberia). In both cases, the experimental partition coefficients numerically model the composition zones of the actual ores. This supports the model of fractional crystallization of a monosulfide solid...

  16. Solution solide d'apatites de plomb, d'argent et de sodium : synthèse, caractérisation structurale et propriétés électriques

    Science.gov (United States)

    Mehnaoui, M.; Ternane, R.; Madani, A.; Trabelsi-Ayadi, M.

    2004-12-01

    A continuous solid solution of Pb8Na2-xAgx(PO4)6 (0≤ x ≤2) crystallizing in the anionic-deficient apatite structure was obtained by solid-state reaction. The samples were characterized by using X-ray diffraction, infrared absorption spectroscopy, Raman scattering spectroscopy, 31P MAS-NMR and chemical analysis. The electrical conductivity versus x measured in a wide range of temperature increases with silver content. For each composition, conductivity values obey the Arrhenius law. Correlations between electrical and structural properties are established.

  17. Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

    Science.gov (United States)

    Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

    2017-05-02

    Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO2 oxide material are reported. Heterometallic compounds LiFeL3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac)3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac)3 (1) and LiFe(ptac)3 (2) that consist of discrete heterocyclic tetranuclear molecules Li2Fe2L6. The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L]+ peaks (M = Li2Fe2L6). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac)3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1H and 7Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure α-modification of layered oxide Li

  18. Magnetic, dielectric and microwave properties of the BaFe12-xGaxO19 (x ≤ 1.2) solid solutions at room temperature

    Science.gov (United States)

    Trukhanov, S. V.; Trukhanov, A. V.; Kostishyn, V. G.; Panina, L. V.; Trukhanov, An. V.; Turchenko, V. A.; Tishkevich, D. I.; Trukhanova, E. L.; Oleynik, V. V.; Yakovenko, O. S.; Matzui, L. Yu.; Vinnik, D. A.

    2017-11-01

    The BaFe12-xGaxO19 (x = 0.1-1.2) solid solutions of the barium hexagonal ferrite of M-type were synthesized and attested by the powder X-ray diffraction method at 300 K. The unit cell parameters were refined. With increase of substitution level the parameters of unit cell monotonically decrease. These samples were investigated by the vibration magnetometry method. With increase of substitution level the magnetic parameters monotonically decrease. The concentration dependence of the TC Curie temperature as well as the MS spontaneous specific magnetization and the HC coercive force at 300 K is constructed. The microwave properties of the considered samples in the external magnetic bias field were also investigated at 300 K. It is shown that with increase of Ga3+ concentration from x = 0.1 to x = 0.6 the frequency value of the natural ferromagnetic resonance decreases in the beginning, and at further increase in concentration up to x = 1.2 it increases again. With increase in Ga3+ concentration the line width of the natural ferromagnetic resonance increases that indicates the increase of frequency range where there is an intensive absorption of electromagnetic radiation. At the same time the peak amplitude of the resonant curve changes slightly. The frequency shift of the natural ferromagnetic resonance in the external magnetic bias field takes place more intensively for the samples with small Ga3+ concentration. It is shown the prospects of use of the Ga-substituted barium hexagonal ferrite as the material effectively absorbing the high-frequency electromagnetic radiation.

  19. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state (13)C NMR and solution (31)P NMR spectroscopy.

    Science.gov (United States)

    Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P

    2016-02-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state (13)C NMR and solution (31)P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Many-body effects in the mobility and diffusivity of interstitial solute in a crystalline solid: The case of helium in BCC tungsten

    Science.gov (United States)

    Wen, Haohua; Semenov, A. A.; Woo, C. H.

    2017-09-01

    The many-body dynamics of a crystalline solid containing an interstitial solute atom (ISA) is usually interpreted within the one-particle approximation as a random walker hopping among trapping centers at periodic lattice sites. The corresponding mobility and diffusivity can be formulated based on the transition-state theory in the form of the Arrhenius law. Possible issues arising from the many-body nature of the dynamics may need to be understood and resolved both scientifically and technologically. Noting the congruence between the dynamics of the many-body and stochastic systems within the Mori-Zwanzig theory, we analyzed the dynamics of a model particle subjected to a saw-tooth potential in a noisy medium. The ISA mobility is found to be governed by two sources of dissipative friction: that which is produced by the scattering of lattice waves by the moving ISA (phonon wind), and that which is derived from the energy dissipation associated with overcoming the migration barrier screened by lattice waves (i.e., phonon screened). The many-body effect in both cases increases with temperature, so that the first component of the friction is important at high temperatures and the second component is important at low temperatures. A formulation built on this mechanistic structure of the dissipative friction requires the mobility and diffusivity to be expressed not only in terms of the migration enthalpy and entropy, but also of the phonon drag coefficient. As a test, the complex temperature dependence of the mobility and diffusivity of interstitial helium in BCC W obtained from molecular-dynamics simulation is very well reproduced.

  1. Quenching effects on piezoelectric properties and depolarization temperatures of (Bi0.5Na0.5)TiO3-based solid solution systems

    Science.gov (United States)

    Miura, Tatsuki; Nagata, Hajime; Takenaka, Tadashi

    2017-10-01

    Lead-free ferroelectric and piezoelectric ceramics, (Bi0.5Na0.5(1- x )Li0.5 x )TiO3 and (1 - y)(Bi0.5Na0.48Li0.02)TiO3-yBaTiO3 (abbreviated as BNLT100x and BNLBT4-100y, respectively), were fabricated by a quenching procedure after sintering, and then their electrical properties were investigated with the aim of increasing their depolarization temperature T d. From the measurements by a resonance-antiresonance method, the electromechanical coupling factors k 33 of BNLT100x and BNLBT4-100y were exactly the same after the quenching treatment as compared with the nonquenched one. The T d of all BNLT100x quenched from 1100 °C reached around 240 °C, and they are almost 60 °C higher for x = 0, 0.02, 0.04, and almost 80 °C higher for x = 0.08 than those of nonquenched ceramics. We also found, from the measurement on BNLBT4-100y quenched from 1100 °C, that the T d values were enhanced to higher temperature by the quenching treatment, even in the case of rhombohedral side (100y 6), and MPB composition (100y = 6). Moreover, we confirmed that the rhombohedrality 90-α and the tetragonality c/a values were enhanced by the quenching treatment. This result revealed that, even in the tetragonal symmetry, the lattice distortion (tetragonality) could also be stabilized by the quenching treatment in BNT-based solid solution ceramics.

  2. Engineering study for a demonstration program to consider high and low technology solutions for solid waste disposal and energy conservation in Laporte County, Indiana

    Energy Technology Data Exchange (ETDEWEB)

    1979-09-01

    The purpose of this study was to determine the feasibility of providing a solid waste resource recovery system for LaPorte County, Indiana. This was accomplished by determining the quantities and composition of the solid waste in the County, projecting these quantities, analyzing the potential markets for the recovered materials and energy, and making an economic analysis of the possible resource recovery systems available and suitable for the quantities of solid waste available.

  3. Photocatalytical water decomposition on visible light-driven solid-solution compounds K{sub 4}Ce{sub 2}Ta{sub 10-x}Nb{sub x}O{sub 30} (x = 0-10)

    Energy Technology Data Exchange (ETDEWEB)

    Tian Mengkui, E-mail: tianmk@hotmail.com [School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou (China); Shangguan Wenfeng, E-mail: shanguan@sjtu.edu.cn [Centre for Combustion and Environmental Protection, Shanghai Jiao Tong University, Shanghai 200030 (China)

    2012-01-05

    Highlights: Black-Right-Pointing-Pointer Visible light driven solid-solution compounds K{sub 4}Ce{sub 2}Ta{sub 10-x}Nb{sub x}O{sub 30} (x = 0-10) were synthesized by solid state reaction. Black-Right-Pointing-Pointer These solid-solution compounds demonstrated water decomposition activities under visible light irradiation. Black-Right-Pointing-Pointer Their electronic structures were studied based on the first principle calculation. Black-Right-Pointing-Pointer The proposed band structure has good agreement with their absorption properties and photocatalytic activities. - Abstract: A series of single phase solid-solution K{sub 4}Ce{sub 2}Ta{sub 10-x}Nb{sub x}O{sub 30} (x = 0-10) photocatalysts were synthesized by conventional high temperature solid state reaction. Their UV-vis diffuse reflectance spectra showed their absorbance edges shifted to long wavelength zone consistently with the increase of the amount of Nb for substituting Ta in these compounds, and the onsets of absorbance edges ranging from about 540 nm to 690 nm, corresponding to bandgap energy of 1.8-2.3 eV. These series of photocatalysts possess appropriate band gap (ca. 1.8-2.3 eV) and chemical level to use solar energy to decompose water into H{sub 2}, and the photocatalytical activities under visible light ({lambda} > 420 nm) demonstrated that the activities decreased correspondingly with the increase of the amount of Nb in these compounds, which is regarded as the result of the differences of their band structures. Furthermore, the photocatalytical activities and the photophysical properties of these visible light-driven photocatalysts K{sub 4}Ce{sub 2}Ta{sub 10-x}Nb{sub x}O{sub 30} (x = 0-10) were bridged by the first principle calculation based on Density Functional Theory with General Gradient Approximation and Plane-wave Pseudopotential methods.

  4. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  5. Tuning of Photoluminescence by Cation Nanosegregation in the (CaMg) x (NaSc) 1–x Si 2 O 6 Solid Solution

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Zhiguo; Liu, Guokui; Wen, Jianguo; Mei, Zhigang; Balasubramanian, Mahalingam; Molokeev, Maxim S.; Peng, Licong; Gu, Lin; Miller, Dean J.; Liu, Quanlin; Poeppelmeier, Kenneth R.

    2016-02-03

    Controlled photoluminescence tuning is important for the optimization and modification of phosphor materials. Herein we report an isostructural solid solution of (CaMg)x(NaSc)1-xSi2O6 (0 < x < 1) in which cation nanosegregation leads to the presence of two dilute Eu2+ centers. The distinct nanodomains of isostructural (CaMg)Si2O6 and (NaSc)Si2O6 contain a proportional number of Eu2+ ions with unique, independent spectroscopic signatures. Density functional theory calculations provided a theoretical understanding of the nanosegregation and indicated that the homogeneous solid solution is energetically unstable. It is shown that nanosegregation allows predictive control of color rendering and therefore provides a new method of phosphor development.

  6. Influence of baking on the photoluminescence spectra of In{sub 1-x} Ga{sub x} As{sub y} P{sub 1-y} solid solutions grown on Inp substrates

    Energy Technology Data Exchange (ETDEWEB)

    Mishurnyi, V.A.; Gorbatchev, A.Y.; Anda, F. De; Nieto N, J. [Instituto de Investigacion en Comunicacion Optica, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi (Mexico)

    2004-07-01

    The influence of thermal treatments on the photoluminescence spectra of In{sub 1-x} Ga{sub x} As{sub y} P{sub 1-y} epitaxial layers of various compositions grown by LPE on In P substrates has been studied. To prevent the epitaxial layers from degradation, due to phosphor evaporation during the baking, their surface was covered by spin-on SiO{sub 2} layers. The photoluminescence spectra did not change for solid solutions whose compositions were near In P and InGaAs. For compositions in the middle of the lattice-matched region, the variations were very noticeable because the appearance of additional peaks in the luminescence spectra. This could be related to the decomposition of those solid solutions whose compositions lie inside a theoretically predicted miscibility gap. (Author)

  7. Evidence of the participation of electronic excited states in the mechanism of positronium formation in substitutional Tb1-xEux(dpm)(3) solid solutions studied by optical and positron annihilation spectroscopies

    OpenAIRE

    Fulgencio, F.; Oliveira, F.C. [UNESP; Windmoeller, D.; Brito, Hermi Felinto de; Malta, O. L.; Sa, G. F. de; Magalhaes, W.F.; Machado, J. C.

    2012-01-01

    Positronium formation in the bimary molecular solid solutions Tb1-xEux (dpm)(3) (dpm = dipivaloylmethanate) has been investigated. A strong linear correlation between the D-5(4) Tb(III) energy level excited state lifetime and the positronium formation probability has been observed. This correlation indicates that the ligand-to-metal charge transfer LMCT states act in both luminescence quenching and positronium formation inhibition, as previously proposed. A kinetic mechanism is proposed to ex...

  8. Crystal structure of (Bi0.94Sb1.06)S3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series

    DEFF Research Database (Denmark)

    Poleti, Dejan; Karanović, Ljiljana; Balic Zunic, Tonci

    2012-01-01

    The intermediate member of the (Bi,Sb)(2)S-3 solid-solution series was prepared by dry synthesis at low temperature (200 degrees C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S-3, which is very close to the formula (Bi0.94Sb1.06...

  9. Synthesis, magnetic and dielectric characterization of nanocrystalline solid solutions of In{sub 2−x}Ni{sub x}O{sub 3} (x = 0.05, 0.10 and 0.15)

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, Tokeer, E-mail: tahmad3@jmi.ac.in [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Khatoon, Sarvari [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Coolahan, Kelsey [Department of Physics and Astronomy, Rowan University, 201 Mullica Hill Road, Glassboro, NJ 08028 (United States)

    2013-09-01

    Graphical abstract: Monophasic and crystalline In{sub 2−x}Ni{sub x}O{sub 3} nanoparticles of size 8–15 nm have been synthesized solvothermally and showed red shift in energy band gap which decreases on increasing Ni{sup 2+} concentration in In{sub 2}O{sub 3} host lattice. - Highlights: • Monophasic Ni-doped In{sub 2}O{sub 3} nanoparticles by solvothermal method for first time. • Plausible reaction mechanism using thermogravimetric analysis. • High surface area with small particle size obtained. • Solid solutions exhibit paramagnetism with very weak antiferromagnetic interactions. - Abstract: In{sub 2−x}Ni{sub x}O{sub 3} (x = 0.05, 0.10 and 0.15) nanoparticles were successfully synthesized by solvothermal method by the thermal decomposition of oxalate precursor at 450 °C for the first time. X-ray diffraction studies showed the formation of highly crystalline and monophasic cubic structure of In{sub 2}O{sub 3} which is attributed to the formation of solid solution. These nanoparticles show good optical transmittance in the visible region. Optical measurements showed an energy band gap which decreases with increasing Ni concentration. The grain size decreases from 15 nm to 8 nm and surface area increases from 90 to 254 m{sup 2} g{sup −1} on increasing the Ni concentration. High dielectric constant and dielectric loss has been obtained which indicates the conducting nature of these solid solutions. Magnetic measurements showed that the samples are strong paramagnetic in nature with very weak antiferromagnetic interactions. No evidence of ferromagnetism is observed for these solid solutions at room temperature.

  10. Dimensional t-factor variation and increase of stability of the ferroelectric state in (Na0.5Bi0.5)TiO3-based solid solutions

    Science.gov (United States)

    Ishchuk, V. M.; Kuzenko, D. V.; Sobolev, V. L.

    The influence of the B-site ion substitutions in (1‑x)(Bi1/2Na1/2)TiO3-xBaTiO3 system of solid solutions on the relative stability of the antiferroelectric (AFE) and ferroelectric (FE) phases has been studied. The ions of zirconium, tin, and (In0.5Nb0.5), (Fe0.5Nb0.5), (Al0.5V0.5) ion complexes have been used as substituting elements. An increase in the concentration of the substituting ion results in a near linear variation in the size of the crystal lattice cell. Along with the cell size variation, a change in the relative stability of the AFE and FE phases takes place according to the changes of the tolerance factor of the solid solution. An increase in the tolerance factor leads to the increase in the temperature of the FE-AFE phase transition, and vice versa. Obtained results indicate the way for raising the temperature of the FE-AFE phase transition in (Bi1/2Na1/2)TiO3-based solid solutions.

  11. Magnetic and electrical properties of (FeIn{sub 2}S{sub 4}){sub 1−x}(CuIn{sub 5}S{sub 8}){sub x} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Trukhanov, S.V., E-mail: truhanov@ifttp.bas-net.by [Scientific Practical Materials Research Centre of NASB, 220072 Minsk (Belarus); Bodnar, I.V.; Zhafar, M.A., E-mail: chemzav@bsuir.by [Belarussian State University of Informatics and Radioelectronics, 220013 Minsk (Belarus)

    2015-04-01

    In this study, single crystals of FeIn{sub 2}S{sub 4} and CuIn{sub 5}S{sub 8} compounds, and (FeIn{sub 2}S{sub 4}){sub 1−x}(CuIn{sub 5}S{sub 8}){sub x} solid solutions were grown using the Bridgman method. The magnetic and electrical properties of the samples obtained were investigated at temperatures of 5–300 K and in a magnetic field range of 0–14 T. It was established that all of the solid solutions were paramagnets down to low temperatures of ~10 K. It was shown that the ground state of the magnetic phase of the samples was a spin glass state, where the freezing temperature increased monotonically with the increase in the concentration of Fe{sup 2+} cations. All of the samples exhibited semiconductor characteristics in terms of electrical resistivity. The concentration-dependent critical magnetic temperatures, magnetic moment, and activation energy were plotted, which are probably explained by the magnetic state formation of the (FeIn{sub 2}S{sub 4}){sub 1−x}(CuIn{sub 5}S{sub 8}){sub x} solid solution single crystals based on the empirical Goodenough–Kanamori rules.

  12. X-ray excited photoluminescence near the giant resonance in solid-solution Gd(1-x)Tb(x)OCl nanocrystals and their retention upon solvothermal topotactic transformation to Gd(1-x)Tb(x)F3.

    Science.gov (United States)

    Waetzig, Gregory R; Horrocks, Gregory A; Jude, Joshua W; Zuin, Lucia; Banerjee, Sarbajit

    2016-01-14

    Design rules for X-ray phosphors are much less established as compared to their optically stimulated counterparts owing to the absence of a detailed understanding of sensitization mechanisms, activation pathways and recombination channels upon high-energy excitation. Here, we demonstrate a pronounced modulation of the X-ray excited photoluminescence of Tb(3+) centers upon excitation in proximity to the giant resonance of the host Gd(3+) ions in solid-solution Gd1-xTbxOCl nanocrystals prepared by a non-hydrolytic cross-coupling method. The strong suppression of X-ray excited optical luminescence at the giant resonance suggests a change in mechanism from multiple exciton generation to single thermal exciton formation and Auger decay processes. The solid-solution Gd1-xTbxOCl nanocrystals are further topotactically transformed with retention of a nine-coordinated cation environment to solid-solution Gd1-xTbxF3 nanocrystals upon solvothermal treatment with XeF2. The metastable hexagonal phase of GdF3 can be stabilized at room temperature through this topotactic approach and is transformed subsequently to the orthorhombic phase. The fluoride nanocrystals indicate an analogous but blue-shifted modulation of the X-ray excited optical luminescence of the Tb(3+) centers upon X-ray excitation near the giant resonance of the host Gd(3+) ions.

  13. Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu); Synthese, caracterisation et etudes cinetique et thermodynamique de la dissolution de ThO{sub 2} et des solutions solides Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu)

    Energy Technology Data Exchange (ETDEWEB)

    Heisbourg, G

    2003-12-01

    The aim of this work was to understand the mechanisms of dissolution of ThO{sub 2} and of thorium mixed oxides such as Th{sub 1-x}U{sub x}O{sub 2} and Th{sub 1-x}Pu{sub x}O{sub 2} in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th{sub 1-x}U{sub x}O{sub 2} (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th{sub 1-x}Pu{sub x}O{sub 2} (x= 0.13; 0.32 and 0.66). They have been characterized by XRD, SEM, TEM, XPS, XAS, PIXE and EPMA. The sintering conditions of these materials have been studied and optimized in order to obtain sintered samples with a measured density very near the theoretical densities. A kinetic study of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}U{sub x}O{sub 2} has been carried out in several aqueous media (HNO{sub 3}, HCl, H{sub 2}SO{sub 4}) in terms of several parameters: protons concentration, temperature, pH, ionic strength, nature of the electrolyte solution and uranium molar ratio for the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO{sub 2}. The leaching tests carried out in natural waters of compositions near those of the deep geologic sites considered for the storage of nuclear wastes have shown that the dissolution of the solids was bound to the complexing effect of the constitutional ions of the water considered. The leaching tests carried out on sintered samples of the same composition have led to the same normalized dissolution velocities. The thermodynamic aspect of the dissolution of the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in nitric medium has been studied at last. (O.M.)

  14. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state.

    Science.gov (United States)

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar

    2012-09-17

    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen-donor solvents water, dimethyl sulfoxide (DMSO), and N,N'-dimethylpropyleneurea (DMPU) has been studied in solution by extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS) and in the solid state by single-crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and DMSO-solvated oxovanadium(IV) ions, vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O═V-O(perp) bond angle is ca. 98°. In the DMPU-solvated oxovanadium(IV) ion, the space-demanding properties of the DMPU molecule leave no solvent molecule in the trans position to the oxo group, which reduces the coordination number to 5. The O═V-O bond angle is consequently much larger, 107°, and the mean V═O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and DMSO-solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in the cis position with a mean V═O bond distance of 1.6 Å and a O═V═O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen-donor ligands.

  15. Synthesis, composition, and structure of sillenite-type solid solutions in the Bi2O3-SiO2-MnO2 system.

    Science.gov (United States)

    Mel'nikova, Tatyana I; Kuz'micheva, Galina M; Rybakov, Victor B; Bolotina, Nadezhda B; Dubovsky, Alexander B

    2011-03-07

    Individual compounds and solid solutions are obtained under hydrothermal conditions in the Bi(2)O(3)-SiO(2)-MnO(2) system in the form of faceted crystals and epitaxial films on the Bi(24)Si(2)O(40) substrate. The crystals have the shape of a cube (for the molar ratio of the starting components Na(2)SiO(3)·9H(2)O:Mn(NO(3))(2)·6H(2)O > 1), a tetrahedron (for Na(2)SiO(3)·9H(2)O:Mn(NO(3))(2)·6H(2)O < 1), or a tetrahedron-cube combination (for Na(2)SiO(3)·9H(2)O:Mn(NO(3))(2)·6H(2)O = 1). Crystal-chemical analysis based on the data of single-crystal and powder X-ray diffraction, IR spectra, and the results of calculation of the local balance by the bond-valence method reveals formation of the Bi(24)(Si(4+),Mn(4+))(2)O(40) phases, which probably include Mn(5+) ions (epitaxial films), as well as the Bi(24)(Si(4+),Bi(3+),Mn(4+))(2)O(40) and Bi(24)(Si(4+),Mn(4+))(2)O(40) phases in the (1 - x)Bi(3+)(24)Si(4+)(2)O(40) - x(Bi(3+)(24)Mn(4+)(2)O(40)) system and the Bi(24)(Bi(3+),Mn(4+))(2)O(40) phase in the (1 - x)Bi(3+)(24)Bi(3+)(2)(O(39)ⁱ(1)) - x(Bi(3+)(24)Mn(4+)(2)O(40)) system. Precision X-ray diffraction studies of single crystals of the Bi(24)(Bi,Si,Mn)(2)O(40) general composition show that these sillenites crystallize in space group P23 and not I23 as the Bi(24)Si(2)O(40) phase. The dissymmetrization of sillenite phases is observed for the first time. It is explained by a kinetic (growth) phase transition of the order-disorder type due to population of a crystallographic site by atoms with different crystal-chemical properties and quasi-equilibrium conditions of crystal growth in the course of a hydrothermal synthesis below 400 °C at unequal molar amounts of the starting components in the batch. © 2011 American Chemical Society

  16. GEMAS: prediction of solid-solution phase partitioning coefficients (Kd) for oxoanions and boric acid in soils using mid-infrared diffuse reflectance spectroscopy.

    Science.gov (United States)

    Janik, Leslie J; Forrester, Sean T; Soriano-Disla, José M; Kirby, Jason K; McLaughlin, Michael J; Reimann, Clemens

    2015-02-01

    The authors' aim was to develop rapid and inexpensive regression models for the prediction of partitioning coefficients (Kd), defined as the ratio of the total or surface-bound metal/metalloid concentration of the solid phase to the total concentration in the solution phase. Values of Kd were measured for boric acid (B[OH]3(0)) and selected added soluble oxoanions: molybdate (MoO4(2-)), antimonate (Sb[OH](6-)), selenate (SeO4(2-)), tellurate (TeO4(2-)) and vanadate (VO4(3-)). Models were developed using approximately 500 spectrally representative soils of the Geochemical Mapping of Agricultural Soils of Europe (GEMAS) program. These calibration soils represented the major properties of the entire 4813 soils of the GEMAS project. Multiple linear regression (MLR) from soil properties, partial least-squares regression (PLSR) using mid-infrared diffuse reflectance Fourier-transformed (DRIFT) spectra, and models using DRIFT spectra plus analytical pH values (DRIFT + pH), were compared with predicted log K(d + 1) values. Apart from selenate (R(2)  = 0.43), the DRIFT + pH calibrations resulted in marginally better models to predict log K(d + 1) values (R(2)  = 0.62-0.79), compared with those from PSLR-DRIFT (R(2)  = 0.61-0.72) and MLR (R(2)  = 0.54-0.79). The DRIFT + pH calibrations were applied to the prediction of log K(d + 1) values in the remaining 4313 soils. An example map of predicted log K(d + 1) values for added soluble MoO4(2-) in soils across Europe is presented. The DRIFT + pH PLSR models provided a rapid and inexpensive tool to assess the risk of mobility and potential availability of boric acid and selected oxoanions in European soils. For these models to be used in the prediction of log K(d + 1) values in soils globally, additional research will be needed to determine if soil variability is accounted on the calibration. © 2014 SETAC.

  17. Non-monotonic compositional dependence of isothermal bulk modulus of the (Mg1–xMnxCr2O4 spinel solid solutions, and its origin and implication

    Directory of Open Access Journals (Sweden)

    Xi Liu

    2016-12-01

    Full Text Available The compressibility of the spinel solid solutions, (Mg1−xMnxCr2O4 with x = 0.00 (0, 0.20 (0, 0.44 (2, 0.61 (2, 0.77 (2 and 1.00 (0, has been investigated by using a diamond-anvil cell coupled with synchrotron X-ray radiation up to ∼10 GPa (ambient T. The second-order Birch–Murnaghan equation of state was used to fit the PV data, yielding the following values for the isothermal bulk moduli (KT, 198.2 (36, 187.8 (87, 176.1 (32, 168.7 (52, 192.9 (61 and 199.2 (61 GPa, for the spinel solid solutions with x = 0.00 (0, 0.20 (0, 0.44 (2, 0.61 (2, 0.77 (2 and 1.00 (0, respectively (KT′ fixed as 4. The KT value of the MgCr2O4 spinel is in good agreement with existing experimental determinations and theoretical calculations. The correlation between the KT and x is not monotonic, with the KT values similar at both ends of the binary MgCr2O4MnCr2O4, but decreasing towards the middle. This non-monotonic correlation can be described by two equations, KT = −49.2 (11x + 198.0 (4 (x ≤ ∼0.6 and KT = 92 (41x + 115 (30 (x ≥ ∼0.6, and can be explained by the evolution of the average bond lengths of the tetrahedra and octahedra of the spinel solid solutions. Additionally, the relationship between the thermal expansion coefficient and composition is correspondingly reinterpreted, the continuous deformation of the oxygen array is demonstrated, and the evolution of the component polyhedra is discussed for this series of spinel solid solutions. Our results suggest that the correlation between the KT and composition of a solid solution series may be complicated, and great care should be paid while estimating the KT of some intermediate compositions from the KT of the end-members.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fabián, Martin, E-mail: fabianm@saske.sk [Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, 04001 Košice (Slovakia); Antić, Bratislav [“Vinča” Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade (Serbia); Girman, Vladimír [Institute of Physics, P. J. Šafárik University, Park Angelinum 9, 04154 Košice (Slovakia); Vučinić-Vasić, Milica [Faculty of Technical Sciences, University of Novi Sad, Trg D. Obradovića 6, 21000 Novi Sad (Serbia); Kremenović, Aleksandar [Laboratory of Crystallography, Faculty of Mining and Geology, University of Belgrade, Djusina 7, 11001 Belgrade (Serbia); Suzuki, Shigeru [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, 980-8577 Sendai (Japan); Hahn, Horst [Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Šepelák, Vladimír [Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, 04001 Košice (Slovakia)

    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.

  19. Synthesis, second-harmonic generation (SHG), and photoluminescence (PL) properties of noncentrosymmetric bismuth selenite solid solutions, Bi2-xLnxSeO5 (Ln = La and Eu; x = 0-0.3)

    Science.gov (United States)

    Qi, Hai-Xin; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

    2018-02-01

    A series of La3+ or Eu3+-doped noncentrosymmetric (NCS) bismuth selenite solid solutions, Bi2-xLnxSeO5 (x = 0.1, 0.2, and 0.3), have been successfully synthesized via standard solid-state reactions under vacuum with Bi2O3, La2O3 (or Eu2O3), and SeO2 as starting materials. Crystal structures and phase purities of the resultant materials were thoroughly characterized by powder X-ray diffraction using the Rietveld method. The results clearly show that the reported materials crystallize in the orthorhombic space group, Abm2 (No. 39), and exhibit pseudo-three-dimensional frameworks consisting of BiO3, BiO5, and SeO3 polyhedra that share edges and corners. Detailed diffraction studies indicate that the cell volume of Bi2-xLnxSeO5 decreases with an increasing amount of Ln3+ on the Bi3+ sites. However, no ordering between Ln3+ and Bi3+ was observed in the Bi2-xLnxSeO5 solid solutions. Powder second-harmonic generation (SHG) measurements, using 1064 nm radiation, reveal that SHG efficiencies of Bi2-xLnxSeO5 solid solutions continuously decrease as more Ln3+ cations are added to the sites of polarizable Bi3+ cations. Photoluminescence (PL) measurements on Bi2-xEuxSeO5 exhibit three specific emission peaks at 592, 613, and 702 nm (5D0 → 7F1, 2, 4) owing to the 4f-4f intrashell transitions of Eu3+ ions.

  20. Lithium-ion conductivity in the novel La{sub 1/3-x}Li{sub 3x}NbO{sub 3} solid solution with perovskite-related structure

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Martin, S.; Moran, E.; Alario-Franco, M.A. [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Rojo, J.M. [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid (Spain); Tsukamoto, H. [Japan Storage Battery Co., LTD, Nishionosho, Kisshoin, Minami-ku., Kyoto (Japan)

    1998-12-02

    The stoichiometric range, crystal chemistry, ionic conductivity and electrochemical window of the La{sub 1/3-x}Li{sub 3x}NbO{sub 3} solid solution with a perovskite-related structure have been studied. The range of existence of the solid solution appears to be 0{<=}x{<=}0.06. These niobates have a basic diagonal unit cell a{approx}{radical}2a{sub p} b{radical}2a{sub p} c{approx}2a{sub p}. Ionic conductivity of the materials and its dependence with the composition and temperature have been examined. We have found that the highest conductivity value is 4.3x1O{sup -5} S cm{sup -1} at 300K for x=0.04. The electrochemical window of the compounds has been investigated by potentiostatic discharge and charge. Electrochemical experiments show that the use of the materials as solid electrolytes in secondary batteries is limited down to 1.75 V using Li metal as anode

  1. Crystal structure and Mössbauer effect in multiferroic 0.5BiFeO3-0.5Pb(Fe0.5Ta0.5O3 solid solution

    Directory of Open Access Journals (Sweden)

    Stoch Agata

    2017-06-01

    Full Text Available Multiferroic 0.5BiFeO3-0.5Pb(Fe0.5Ta0.5O3 solid solution is a material that exhibits ferroelectric and antiferromagnetic orderings in ambient temperature. The solid solution was obtained as a result of a conventional reaction in a solid state. The obtained material is a dense, fine-grained sinter whose surface was observed by scanning electron microscopy (SEM and stoichiometry was confirmed by energy dispersive X-ray spectroscopic (EDS analysis. According to the X-ray powder diffraction (XRD measurements, the main phase is R3c space group with admixture of Pm-3m regular phase. Small contribution of pyrochlore-like phase was also observed. Mössbauer spectroscopy suggested random distribution of Fe3+/Ta5+ cations in the B sites of ABO3 compound. Reduction of the magnetic hyperfine field with an increase in the substitution of Ta5+ in Fe3+ neighbourhood was also observed.

  2. Giant magnetic coercivity in YNi{sub 4}B-type SmNi{sub 3}TB (T=Mn–Cu) solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Jinlei; Yan, Chang [Research Center for Solid State Physics and Materials, School of Mathematics and Physics, Suzhou University of Science and Technology, Suzhou 215009 (China); Yapaskurt, V.O. [Department of Petrology, Geological Faculty Moscow State University, Leninskie Gory, Moscow 119992 (Russian Federation); Morozkin, A.V., E-mail: morozkin@tech.chem.msu.ru [Department of Chemistry, Moscow State University, Leninskie Gory, House 1, Building 3, GSP-2, Moscow 119992 (Russian Federation)

    2016-12-01

    The effects of transition metal substitution for Ni on the magnetic properties of the YNi{sub 4}B-type SmNi{sub 4}B via SmNi{sub 3}TB (T=Mn, Fe, Co, Cu) solid solutions have been investigated. SmNi{sub 4}B, SmNi{sub 3}MnB, SmNi{sub 3}FeB, SmNi{sub 3}CoB and SmNi{sub 3}CuB show ferromagnetic ordering at 40 K, 210 K, 322 K, 90 K and 57 K and field sensitive metamagnetic-like transitions at 15 K, 100 K, 185 K, 55 K and 15 K in a magnetic field of 10 kOe, respectively. The magnetocaloric effects of SmNi{sub 3}TB (T=Mn–Cu) were calculated in terms of isothermal magnetic entropy change (ΔS{sub m}). The magnetic entropy ΔS{sub m} reaches value of –0.94 J/kg K at 40 K for SmNi{sub 4}B, –1.5 J/kg K at 205 K for SmNi{sub 3}MnB, –0.54 J/kg K at 320 K for SmNi{sub 3}FeB, –0.49 J/kg K at 90 K for SmNi{sub 3}CoB and –0.54 J/kg K at 60 K for SmNi{sub 3}CuB in field change of 0–50 kOe around the Curie temperature. They show positive ΔS{sub m} of +0.71 J/kg K at ~10 K for SmNi{sub 4}B, +1.69 J/kg K at 30 K for SmNi{sub 3}MnB, +0.89 J/kg K at 110 K for SmNi{sub 3}FeB, +1.08 J/kg K at 25 K for SmNi{sub 3}CoB and +1.12 J/kg K at 10 K for SmNi{sub 3}CuB in field change of 0–50 kOe around the low temperature metamagnetic-like transition. Below the field induced transition temperature (change of magnetic structure), SmNi{sub 3}TB (T=Mn–Cu) exhibits giant magnetic coercivity of 74 kOe at 5 K for SmNi{sub 4}B, 69 kOe at 20 K (90 kOe at 10 K) for SmNi{sub 3}MnB, 77 kOe at 60 K for SmNi{sub 3}FeB, 88 kOe at 20 K for SmNi{sub 3}CoB and 52 kOe at 5 K for SmNi{sub 3}CuB. - Highlights: • YNi{sub 4}B-type SmNi{sub 3}{Mn, Fe, Co, Ni, Cu}B exhibit the Curie points at 39–322 K. • SmNi{sub 3}{Mn, Fe, Co, Ni, Cu}B show field induced transition at 15–185 K. • SmNi{sub 3}MnB shows huge magnetic hysteresis with coercive field of 69 kOe at 20 K. • SmNi{sub 3}FeB shows huge magnetic hysteresis with coercive field of 77 kOe at 60 K. • SmNi{sub 3}CoB shows giant coercive

  3. Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)

    2016-10-15

    Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

  4. Magnetic behavior of solid solutions REMe0.50Mn0.50O3 (RE = Y, La, Pr, Nd, Eu, Gd, Er ; Me = Ni,Co

    Directory of Open Access Journals (Sweden)

    Tartaj, J.

    2008-06-01

    Full Text Available Partial substitution of Mn by a divalent metal in rare-earth manganites REMexMn1 xO3 results in the simultaneous presence of Mn3+ and Mn4+. The RE sublattice has its own properties and can interact with the local field imposed by the ferromagnetic Mn network. Its orientation differs depending on the RE nature, adopting a parallel direction with respect to the local field, or it may align in opposite direction, resulting in uncompensated antiferromagnetic structure. For divalent elements (e.g., Ni2+, the solid solution is limited to RENi2+0.5Mn4+0.5O3 ; at this frontier composition, the ferromagnetic superexchange Ni2+-O-Mn4+ interactions are optimized. For Me = Co, this limit can be extended, meaning that part of cobalt takes a 3+ state ; in this case, presence of Co3+ modifies the magnetic coupling, leading to qualitatively different behaviours during the ZFC/FC cycles. In this work, we have chosen the specific composition REMe0.50Mn0.50O3 for which the strongest magnetic interactions are expected, emphasizing the results obtained for Me = Ni and Co and comparing various rare-earth elements (RE = Y, La, Pr, Nd, Eu, Gd and Er. As expected from the general behaviour of the series (RE,CaMnO3, we find that in the RE(Mn,MeO3, the larger the RE ionic radius, the highest the transition temperature, reaching 235 K in LaCo0.50Mn0.50O3 compared to 68 K in ErCo0.50Mn0.50O3.La sustitución parcial de Mn por un catión divalente en manganitas de tierras raras TRMexMn1 xO3 induce la presencia simultánea de Mn3+ y Mn4+. La subred TR tiene sus propiedades intrínsecas y puede interactuar con el campo local impuesto por la red ferromagnética del Mn. Su orientación difiere dependiendo de la naturaleza de la TR, adoptando una dirección paralela con respecto al campo local, o puede alinearse en sentido opuesto, produciendo una estructura antiferromagnética no compensada. Para cationes divalentes (Ni2+, la solución sólida está limitada a TRNi2+0.5Mn4+0.5O3

  5. Experimental determination of the high temperature heat capacity of a natural xenotime-(Y) solid solution and synthetic DyPO{sub 4} and ErPO{sub 4} endmembers

    Energy Technology Data Exchange (ETDEWEB)

    Gysi, Alexander P., E-mail: agysi@mines.edu [Department of Geology and Geological Engineering, Colorado School of Mines, 1516 Illinois Street, Golden, CO 80401 (United States); Harlov, Daniel [Geoforschungszentrum Potsdam (GFZ), Telegrafenberg, D-14473 Potsdam (Germany); Filho, Deusavan Costa [Department of Geology and Geological Engineering, Colorado School of Mines, 1516 Illinois Street, Golden, CO 80401 (United States); Williams-Jones, Anthony E. [Department of Earth and Planetary Sciences, McGill University, 3450 University St., Montreal, QC H3A 2A7 (Canada)

    2016-03-20

    Highlights: • A new DSC calibration method for minerals of geological interest is described. • The heat capacity of DyPO{sub 4}, ErPO{sub 4} and xenotime-(Y) were reliably determined using DSC. • The excess heat capacity of xenotime-(Y) indicates a non-ideal solution with other HREE. - Abstract: The heat capacity of natural xenotime-(Y) and synthetic DyPO{sub 4} and ErPO{sub 4} crystals was determined by differential scanning calorimetry (DSC) at temperatures of 298.15 K to 868.15 K and a pressure of 0.1 MPa. The aim of the study was to develop a method to accurately measure the isobaric heat capacity (C{sub P}) of rare earth element (REE) phosphates, compare the results to data from adiabatic calorimetric experiments, and evaluate the deviation from ideality of the C{sub P} of the natural xenotime-(Y) solid solution. The measured C{sub P} data (in J mol{sup −1} K{sup −1}) can be described by the relationships: 185.5 − 751.9T{sup −0.5} − 3.261e + 06 T{sup −2} for DyPO{sub 4}; 207.2 − 1661T{sup −0.5} − 5.289e + 05 T{sup −2} for ErPO{sub 4}; and 208 − 1241T{sup −0.5} − 2.493e + 06 T{sup −2} for xenotime-(Y); where T is the temperature in K. The heat capacity data for natural xenotime-(Y) were used to determine the excess function for the solid solution, which yields an excess heat capacity ranging between 7.9 and 10.7%, well within the range of the DSC method used in this study. The experiments indicate that xenotime-(Y) forms a non-ideal solid solution. Future DSC studies will provide important data for developing a solid solution model for the incorporation of REE in xenotime-(Y).

  6. An All-Solid-State pH Sensor Employing Fluorine-Terminated Polycrystalline Boron-Doped Diamond as a pH-Insensitive Solution-Gate Field-Effect Transistor.

    Science.gov (United States)

    Shintani, Yukihiro; Kobayashi, Mikinori; Kawarada, Hiroshi

    2017-05-05

    A fluorine-terminated polycrystalline boron-doped diamond surface is successfully employed as a pH-insensitive SGFET (solution-gate field-effect transistor) for an all-solid-state pH sensor. The fluorinated polycrystalline boron-doped diamond (BDD) channel possesses a pH-insensitivity of less than 3mV/pH compared with a pH-sensitive oxygenated channel. With differential FET (field-effect transistor) sensing, a sensitivity of 27 mv/pH was obtained in the pH range of 2-10; therefore, it demonstrated excellent performance for an all-solid-state pH sensor with a pH-sensitive oxygen-terminated polycrystalline BDD SGFET and a platinum quasi-reference electrode, respectively.

  7. Perovskite solid solutions La0.75Bi0.25Fe1-xCrxO3: Preparation, structural, and magnetic properties

    Czech Academy of Sciences Publication Activity Database

    Ivanov, S. A.; Beran, Přemysl; Bazuev, G. V.; Tellgren, R.; Sarkar, T.; Nordblad, P.; Mathieu, R.

    2017-01-01

    Roč. 254, OCT (2017), s. 166-177 ISSN 0022-4596 R&D Projects: GA MŠk LM2015056 Institutional support: RVO:61389005 Keywords : ceramics * electronic materials * neutron scattering * X-ray diffraction * crystal structure * magnetic properties Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.299, year: 2016

  8. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

    Czech Academy of Sciences Publication Activity Database

    Popr, M.; Filippov, Sergey K.; Matushkin, Nikolai; Dian, J.; Jindřich, J.

    2015-01-01

    Roč. 11, February (2015), s. 192-199 ISSN 1860-5397 R&D Projects: GA ČR GAP108/12/0640 Institutional support: RVO:61389013 Keywords : cyclodextrin s * inclusion properties * solid surface Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.697, year: 2015

  9. Magnetoelectric and electric measurements of the (1-x)BiFeO{sub 3}–(x)Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Bochenek, D., E-mail: dariusz.bochenek@us.edu.pl [University of Silesia, Faculty of Computer Science and Material Science, Institute of Technology and Mechatronics, 12, Żytnia St., 41–200, Sosnowiec (Poland); Niemiec, P. [University of Silesia, Faculty of Computer Science and Material Science, Institute of Technology and Mechatronics, 12, Żytnia St., 41–200, Sosnowiec (Poland); Guzdek, P. [Institute of Electron Technology Cracow Division, 39, Zabłocie St., Cracow, 30-701 (Poland); Wzorek, M. [Institute of Electron Technology, Al. Lotników 32/46, 02-668, Warsaw (Poland)

    2017-07-01

    In the paper ferro–electro–magnetic (1-x)BiFeO{sub 3}-(x)Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} (BF-PFN) solid solutions were obtained (containing the percentage BF/PFN: 60/40 and 70/30). Individual components of the solid solution were prepared by follows methods: synthesizing a powder BF was performed by calcining the simple oxides (Bi{sub 2}O{sub 3}, Fe{sub 2}O{sub 3}), and synthesizing a powder PFN was carried out by calcining a mixture of complex oxides (FeNbO{sub 4}, PbO). Compaction of synthesized and mixed BiFeO{sub 3}, PbFe{sub 1/2}Nb{sub 1/2}O{sub 3} powders was carried out by free sintering methods. X–ray, microstructure, dielectric, magnetic and magnetoelectric studies, DC electrical conductivity and electrical hysteresis loop were carried out. Magnetoelectric effect measurements performed at room temperature showed coupling between electric and magnetic subsystem of the BF–PFN solid solutions. - Highlights: • BF-PFN samples have a densely packed microstructure, with well crystallized grains. • Bi atoms possibly migrate from BF toward PFN component during sintering. • BF-PFN have a diffuse character of the ferroelectric–paraelectric phase transition. • Magnetoelectric coefficient (α{sub ME}) for BF-PFN is higher, than for pure BF. • The α{sub ME} for BF-PFN is about three times higher than for 0.75BiFeO{sub 3}–0.25BaTiO{sub 3}.

  10. The effect of solid solution treatment on the hardness and microstructure of 0.6%wt C-10.8%wt Mn-1.44%wt Cr austenitic manganese steel

    Science.gov (United States)

    Nurjaman, F.; Bahfie, F.; Astuti, W.; Shofi, A.

    2017-04-01

    Austenitic manganese steel is steel alloy that has high manganese content (10-14%wt Mn). The characteristics of austenitic manganese steel are good in toughness, ductility, and wear resistance. Effect of solid solution treatment on the hardness and microstructure of austenitic manganese steel was studied in this experiment. The solid solution treatment process of austenitic manganese steel, 0.6%wt C-10.8%wt Mn-1.44%wt Cr, was conducted by heating the material at varied temperatures (950°C, 1000°C, 1050°C) for an hour and then quenching it in two different quenching media, i.e. oil and water. Further, the samples were tempered at three different temperatures (300°C, 400°C, and 500°C) for 2 hours. The treated materials were analyzed by Rockwell Hardness Tester to obtain the information of materials hardness and by an optical microscope and XRD to investigate the microstructure phase of the treated materials. Heating the austenitic manganese steel at 950°C for an hour followed by water quenching dissolved all carbide in as-cast condition and resulted the fully austenitic on its microstructure. Carbide precipitation occurred due to the prolongation of soaking time in solid solution treatment and tempering process. The optimum hardness of sample was 53.3 HRC, which was resulted by heating this material until 1000°C for an hour, followed by water quenching and tempering at 400°C for 2 hours.

  11. Local polar structure and multiferroic properties of (1−x)Bi{sub 0.9}Dy{sub 0.1}FeO{sub 3}−xPbTiO{sub 3} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Jian [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education and International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an 710049 (China); Department of Chemistry and 4D LABS, Simon Fraser University, Burnaby, British Columbia, V5A 1S6 (Canada); Wu, Hua [Department of Applied Physics, Donghua University, Ren Min Road 2999, Songjiang District, 201620 Shanghai (China); Department of Chemistry and 4D LABS, Simon Fraser University, Burnaby, British Columbia, V5A 1S6 (Canada); Ren, Wei, E-mail: zye@sfu.ca, E-mail: wren@mail.xjtu.edu.cn [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education and International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an 710049 (China); Ye, Zuo-Guang, E-mail: zye@sfu.ca, E-mail: wren@mail.xjtu.edu.cn [Department of Chemistry and 4D LABS, Simon Fraser University, Burnaby, British Columbia, V5A 1S6 (Canada); Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education and International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an 710049 (China)

    2014-08-14

    The multiferroic (1–x)[0.9BiFeO{sub 3}–0.1DyFeO{sub 3}]–xPbTiO{sub 3} (BDF–xPT) solid solution with compositions around the morphotropic phase boundary (x = 0.25, 0.28, 0.31, 0.34, and 0.37) has been synthesized in the form of ceramics. The phase symmetry, microstructure, ferroelectricity, piezoresponse, and ferromagnetic properties have been characterized by various techniques. It is found that, with increasing content of lead titanate from x = 0.25 to x = 0.37, the grain size increases and the ferroelectric property is improved. The ferroelectric performance is further enhanced by the introduction of an excess amount (2%) of TiO{sub 2} or by sintering in oxygen atmosphere, which reduces the leakage. The local polar structure is imaged by piezoresponse force microscopy. Both the out-of-plane and in-plane images reveal distinct ferroelectric domain structures, with the amplitude and the average domain size decreasing with the increase of lead titanate amount. Compared with the (1–x)BiFeO{sub 3}–xPbTiO{sub 3} binary solid solution of about the same concentration of PT, the magnetic properties are enhanced in BDF–xPT due to the presence of dysprosium, as demonstrated by the ferromagnetic hysteresis loops displayed at room temperature and at 10 K, but the remnant magnetization decreases with increasing PT content. The simultaneous presence of ferroelectricity and ferromagnetism entitles the BDF–xPT solid solution a room-temperature multiferroic material.

  12. BiOCl{sub x}Br{sub y}I{sub z} (x + y + z = 1) solid solutions with controllable band gap and highly enhanced visible light photocatalytic performances

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xiuguo; Zhang, Yangyang; Li, Chunmei; Zhang, Zhifeng; Peng, Zheng; Si, Huayan; Zhang, Jianmin [School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Li, Yanting, E-mail: yantingcn@stdu.edu.cn [School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Hebei Provincial Key Laboratory of Traffic Engineering materials, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China)

    2015-07-25

    Highlights: • BiOCl{sub x}Br{sub y}I{sub z} solid solutions were prepared by hydrolysis method. • Band gap of the solid solutions can be controllable by adjusting the molar ratio of halogen ions. • The samples show higher visible light photocatalytic activity than pure BiOX. • Orbital diversification of VB is beneficial to separating the holes and electrons effectively. • The mechanisms are discussed by active species trapping and band theory. - Abstract: A series of BiOCl{sub x}Br{sub y}I{sub z} solid solutions with controllable band gap and highly enhanced visible light photocatalytic performances were synthesized by a simple hydrolysis method. The samples were characterized by X-ray powder diffraction, UV–vis diffuse reflectance spectra, scanning electron microscope, high-resolution transmission electron microscopy and Brunauer–Emmett–Teller analysis. By adjusting the molar ratio of halogen ions, the band gap of BiOCl{sub x}Br{sub y}I{sub z} could be controllable to the suitable value for a photocatalytic reaction. Especially, BiOCl{sub x}Br{sub y}I{sub z} with a 1:1:2 molar ratio of Cl, Br to I showed the highest visible light photocatalytic activity for the degradation of methyl orange than individual BiOX systems. The degradation efficiency could reach over 90% within 60 min. The possible mechanism of photogenerated carrier transfer and higher photocatalytic activity was analyzed by active species trapping and energy band theory.

  13. Heat capacity and neutron diffraction studies on the frustrated magnetic Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Pedro, I. de, E-mail: depedrovm@unican.es [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, 48080 Bilbao (Spain); Rojo, J.M. [Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, 48080 Bilbao (Spain); Rodriguez Fernandez, J.; Sanchez Marcos, J. [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Fernandez-Diaz, M.T. [Institut Laue-Langevin, BP 156X, F-38042 Grenoble Cedex (France); Rojo, T. [Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, 48080 Bilbao (Spain)

    2012-04-15

    The Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution exhibits a complex magnetic behaviour due to the bond-frustration in its magnetic structure. Heat capacity measurements of the (x=0.1-0.5) phases show a three-dimensional magnetic ordering ({lambda} anomaly) that shifts to lower temperatures and becomes broader as the AsO{sub 4}{sup 3-} content increases. For x=0.75, no significant feature was observed whereas for higher arsenate ion content, x=0.9 and 1, a small maximum was detected. The magnetic structures of solid solution are consistent with the existence of predominant antiferromagnetic superexchange interactions through the |OH| and |XO{sub 4}| (X=P and As) groups between the Co{sup +2} ions. The substitution of PO{sub 4}{sup 3-} by AsO{sub 4}{sup 3-} anions by more than 90% substantially modifies the magnetic exchange pathways in the solid solution, leading to an incommensurate antiferromagnetic structure in Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [x=0.9 and 1] phases. -