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Sample records for solid solutions ln2-xdyxw3o12

  1. Formation of high oxide ion conductive phases in the sintered oxides of the system Bi2O3-Ln2O3 (Ln = La-Yb)

    International Nuclear Information System (INIS)

    Iwahara, H.; Esaka, T.; Sato, T.; Takahashi, T.

    1981-01-01

    The electrical conduction in various phases of the system Bi 2 O 3 -Ln 2 O 3 (Ln = La, Nd, Sm, Dy, Er, or Yb) was investigated by measuring ac conductivity and the emf of the oxygen gas concentration cell. High-oxide-ion conduction was observed in the rhombohedral and face-centered cubic (fcc) phase in these systems. The fcc phase could be stabilized over a wide range of temperature by adding a certain amount of Ln 2 O 3 . In these cases, the larger the atomic number of Ln, the lower the content of Ln 2 O 3 required to form the fcc solid solution, except in the case of Yb 2 O 3 . The oxide ion conductivity of this phase decreased with increasing content of Ln 2 O 3 . Maximum conductivity was obtained at the lower limit of the fcc solid solution formation range in each system, which was more than one order of magnitude higher than those of conventional stabilized zirconias. Lattice parameters of the fcc phase were calculated from the x-ray diffraction patterns. The relationship between the oxide ion conductivity and the lattice parameter was also discussed

  2. Investigations of the physical and chemical properties of solid solutions Pb/Mnsub(1/2), Nbsub(1/2)/O3 - PbTiO3 - PbZrO3

    International Nuclear Information System (INIS)

    Szadkowska, A.; Majewska-Pilchowska, K.

    1981-01-01

    The preparation of the PMTZ materials on the basis of solid solutions Pb/Mnsub(1/2)/O 3 - PbTiO 3 - PbZrO 3 has been described. The X-ray analysis of the examined materials has been made, and porosity and grain size have been determined. Dielectric constant and mechanical quality factor as a function of PbZrO 3 content have been determined. The obtained results indicate that solid solutions Pb/Mnsub(1/2), Nbsub(1/2)/O 3 - PbTiO 3 - PbZrO 3 are useful piezoelectric materials. (author)

  3. Studies on the Ln/sub 2/O/sub 3/ (Ln: rare-earth elements)-SrO-V/sub 2/O/sub 3/ system, 2. Some physical properties for Ln sub(1-x)Sr sub(x)VO sub(3-0. 1x) and SrO. Ln sub(1-x)Sr sub(x)VO sub(3-0. 1x) (Ln: Nd or Eu)

    Energy Technology Data Exchange (ETDEWEB)

    Shin-ike, T [Osaka Dental Coll., Hirakata (Japan); Adachi, G; Shiokawa, J

    1981-01-01

    Electrical and magnetic properties of the perovskite type solid solutions, Ln sub(1-x)Sr sub(x)VO sub(3-0.1x) (Ln: Nd or Eu), and the K/sub 2/NiF/sub 4/ type solid solutions, SrO.Ln sub(1-x)Sr sub(x)VO sub(3-0.1x) (Ln: Nd or Eu), were studied in the temperature range 77 - 300 K. The electrical conductivity increased with x for the perovskite type solid solutions and the reverse behavior was observed for the K/sub 2/NiF/sub 4/ type compounds. All the solid solutions examined exhibited a metal-insulator transition at some values of x. Both Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) and Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) were antiferromagnets having a weak ferromagnetism at a low value of x at a low temperature. The K/sub 2/NiF/sub 4/ type solid solutions revealed a weak ferromagnetism at a high value of x at a low temperature.

  4. Shell model for BaTiO3-Bi(Zn1/2Ti1/2)O3 perovskite solid solutions

    Science.gov (United States)

    Vielma, J.; Jackson, D.; Roundy, D.; Schneider, G.

    2010-03-01

    Even though the composition of BaTiO3-Bi(Zn1/2Ti1/2)O3 perovskite solid solutions is similar to other ferroelectric compounds, the dielectric response is unusual. Results of permittivity measurements as a function of temperature show a diffuse phase transition indicative of a weakly coupled relaxor behavior.footnotetextC. C. Huang and D. P. Cann, J. Appl. Phys. 104, 024117 (2008) To investigate the weakly coupled relaxor behavior in these materials at intermediate length scales we are developing a newly calibrated shell model based on first-principles supercell calculations of both the solid solution and its compositional endpoints. Initial results for its phase diagram will presented.

  5. The effect of lanthanides on color properties of the (Bi2O30.7(Ln2O30.3 compounds

    Directory of Open Access Journals (Sweden)

    Šulcová P.

    2008-01-01

    Full Text Available (Bi2O30.7(Ln2O30,3 solid solutions were synthesized as new inorganic yellow and orange pigments and their color properties have been investigated as possible ecological materials. The pigments were prepared by the solid state reaction of mixed oxides (Bi2O30.7(Ln2O30.3 of various rare earth cations (Ln = Eu, Gd, Tm, Yb and Lu. All the synthesized pigment samples were found to have color coordinates, low a* and high b* and exhibit the color from pale light yellow to orange. Reflectance spectra of the samples show high reflectance percentage in the 600 - 700 nm range. Characterization of the (Bi2O30.7(Ln2O30,3 solid solutions suggests that they have a potential to be alternative yellow colorants for paints, inks, plastics, and ceramics.

  6. Theoretical prediction of morphotropic compositions in Na1/2Bi1/2TiO3-based solid solutions from transition pressures

    Science.gov (United States)

    Gröting, Melanie; Albe, Karsten

    2014-02-01

    In this article we present a method based on ab initio calculations to predict compositions at morphotropic phase boundaries in lead-free perovskite solid solutions. This method utilizes the concept of flat free energy surfaces and involves the monitoring of pressure-induced phase transitions as a function of composition. As model systems, solid solutions of Na1/2Bi1/2TiO3 with the alkali substituted Li1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 and the alkaline earth substituted CaTiO3 and BaTiO3 are chosen. The morphotropic compositions are identified by determining the composition at which the phase transition pressure equals zero. In addition, we discuss the different effects of hydrostatic pressure (compression and tension) and chemical substitution on the antiphase tilts about the [111] axis (a-a-a-) present in pure Na1/2Bi1/2TiO3 and how they develop in the two solid solutions Na1/2Bi1/2TiO3-CaTiO3 and Na1/2Bi1/2TiO3-BaTiO3. Finally, we discuss the advantages and shortcomings of this simple computational approach.

  7. Systems Ln-Fe-O ( Ln=Eu, Gd): thermodynamic properties of ternary oxides using solid-state electrochemical cells

    Science.gov (United States)

    Parida, S. C.; Rakshit, S. K.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-05-01

    The standard molar Gibbs energies of formation of LnFeO 3(s) and Ln3Fe 5O 12(s) where Ln=Eu and Gd have been determined using solid-state electrochemical technique employing different solid electrolytes. The reversible e.m.f.s of the following solid-state electrochemical cells have been measured in the temperature range from 1050 to 1255 K. Cell (I): (-)Pt / { LnFeO 3(s)+ Ln2O 3(s)+Fe(s)} // YDT/CSZ // {Fe(s)+Fe 0.95O(s)} / Pt(+); Cell (II): (-)Pt/{Fe(s)+Fe 0.95O(s)}//CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+); Cell (III): (-)Pt/{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}//YSZ//{Ni(s)+NiO(s)}/Pt(+); and Cell(IV):(-)Pt/{Fe(s)+Fe 0.95O(s)}//YDT/CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+). The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the e.m.f. data. The standard Gibbs energies of formation of solid EuFeO 3, Eu 3Fe 5O 12, GdFeO 3 and Gd 3Fe 5O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by Δ fG°m(EuFeO 3, s) /kJ mol -1 (± 3.2)=-1265.5+0.2687( T/K) (1050 ⩽ T/K ⩽ 1570), Δ fG°m(Eu 3Fe 5O 12, s)/kJ mol -1 (± 3.5)=-4626.2+1.0474( T/K) (1050 ⩽ T/K ⩽ 1255), Δ fG°m(GdFeO 3, s) /kJ mol -1 (± 3.2)=-1342.5+0.2539( T/K) (1050 ⩽ T/K ⩽ 1570), and Δ fG°m(Gd 3Fe 5O 12, s)/kJ·mol -1 (± 3.5)=-4856.0+1.0021( T/K) (1050 ⩽ T/K ⩽ 1255). The uncertainty estimates for Δ fG°m include the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagrams for the systems Eu-Fe-O and Gd-Fe-O and chemical potential diagrams for the system Gd-Fe-O were computed at 1250 K.

  8. 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.

  9. Phase equilibria in the MgMoO4-Ln2(MoO4)3 (Ln=La,Gd) systems

    International Nuclear Information System (INIS)

    Fedorov, N.F.; Ipatov, V.V.; Kvyatkovskij, O.V.

    1980-01-01

    Phase equilibria in the MgMoO 4 -Ln 2 (MoO 4 ) 3 systems (Ln=La, Gd) have been studied by static and dynamic methods of the physico-chemical analysis, using differential thermal, visual-polythermal, crystal-optical, X-ray phase, and infrared spectroscopic methods, and their phase diagrams have been constructed. Phase equilibria in the systems studied are characterized by limited solubility of components in the liquid state, formation of solid solutions on the base of α- and β-forms of Gd 2 (MoO 4 ) 3 . Eutectics in the MgMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=La, Gd) systems corresponds to the composition of 71 mode % La 2 (MoO 4 ) 3 -29 mole % MgMoO 4 , tsub(melt)--935+-5 deg C and 57 mole % Gd 2 (MoO 4 ) 3 -43 mole % MgMoO 4 , tsub(melt)=1020+-5 deg C. The region of glass formation has been established [ru

  10. Magnetic properties of Aurivillius lanthanide-bismuth (LnFeO3nBi4Ti3O12 (n = 1,2 layered titanates

    Directory of Open Access Journals (Sweden)

    Tartaj, J.

    2008-06-01

    Full Text Available Bismuth titanates of Aurivillius layer-structure (BiFeO3nBi4Ti3O12, are of great technological interest because of their applications as non-volatile ferroelectric memories and high-temperature piezoelectric materials. The synthesis and crystallographic characterization of a new family of compounds (LnFeO3nBi4Ti3O12 was recently reported, in which the layers consist of LnFeO3 perovskites with a lanthanide Ln3+ substituting diamagnetic Bi3+. We report herein the magnetic properties of bulk samples, with Ln = Nd, Eu, Gd and Tb, and n = 1 and 2. Single-layer materials are paramagnetic, similar to non-substituted bismuth titanate Bi5FeTi3O15, and show crystal field effects due to the crystallographic environment of Eu3+ and Tb3+. Several anomalies are detected in the magnetization M(T of double-layer (LnFeO32Bi4Ti3O12 compounds, related to the strong magnetism of Tb and Gd, since they weakly appear for Nd and they are absent in the VanVleck Eu3+ ion and in the parent Bi6Fe2Ti3O18 compound.Los titanatos de hierro y bismuto con estructura laminar tipo Aurivillius, (BiFeO3nBi4Ti3O12, tienen un gran interés tecnológico debido a sus aplicaciones como memorias ferroeléctricas no volátiles y como piezoeléctrico cerámico de alta temperatura. La síntesis y la caracterización cristalina de una nueva familia de compuestos (LnFeO3nBi4Ti3O12 han sido recientemente reportadas, en la que el catión diamagnético Bi3+ ha sido sustituido por los paramagnéticos Ln3+ en los bloques de perovskita. Se estudian las propiedades magnéticas de muestras cerámicas en volumen con Ln = Nd, Eu, Gd y Tb, y n = 1 y 2. Los materiales con n=1 son paramagnéticos y similares al no sustituido Bi5FeTi3O15, y muestran efectos de campo cristalino debido al entorno cristalino de Eu3+ y Tb3+. Se han detectado algunas anomalías en la magnetización M(T de los compuestos n=2 (LnFeO32Bi4Ti3O12 que están relacionadas con el fuerte magnetismo de Tb y Gd, que aparecen d

  11. Thermal expansion of Cr2xFe2-2xMo3O12, Al2xFe2-2xMo3O12 and Al2xCr2-2xMo3O12 solid solutions

    International Nuclear Information System (INIS)

    Ari, M.; Jardim, P.M.; Marinkovic, B.A.; Rizzo, F.; Ferreira, F.F.

    2008-01-01

    The transition temperature from monoclinic to orthorhombic and the thermal expansion of the orthorhombic phase were investigated for three systems of the family A 2 M 3 O 12 : Cr 2x Fe 2-2x Mo 3 O 12 , Al 2x Fe 2-2x Mo 3 O 12 and Al 2x Cr 2-2x Mo 3 O 12 . It was possible to obtain a single-phase solid solution in all studied samples (x=0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1). A linear relationship between the transition temperature and the fraction of A 3+ cations (x) was observed for each system. In all orthorhombic solid solutions studied here the observed thermal expansion was anisotropic. These anisotropic thermal expansion properties of crystallographic axes a, b and c result in a low positive or near-zero overall linear coefficient of thermal expansion (α l =α V /3). The relationship between the size of A 3+ cations in A 2 M 3 O 12 and the coefficient of thermal expansion is discussed. Near-zero thermal expansion of Cr 2 Mo 3 O 12 is explained by the behavior of Cr-O and Mo-O bond distances, Cr-Mo non-bond distances and Cr-O-Mo bond angles with increasing temperature, estimated by Rietveld analysis of synchrotron X-ray powder diffraction data. - Graphical abstract: In this figure, all published overall linear coefficients of thermal expansion for orthorhombic A 2 M 3 O 12 family obtained through diffraction methods as a function of A 3+ cation radii size, together with dilatometric results, are plotted. Our results indicate that Cr 2 Mo 3 O 12 does not exactly follow the established relationship

  12. Structural and electrical properties of (1-x)(Na1/2Bi1/2)TiO3-xPb(Mg1/3Nb2/3)O3 solid solution

    International Nuclear Information System (INIS)

    Lee, J.-K.; Yi, J.Y.; Hong, K.S.

    2004-01-01

    Structural, dielectric and piezoelectric properties of (1-x)(Na 1/2 Bi 1/2 )TiO 3 -xPb(Mg 1/3 Nb 2/3 )O 3 (NBT-xPMN) solid solution have been investigated. An addition of PMN into NBT transformed the structure of sintered samples from rhombohedral to pseudocubic phase where x is larger than 0.1. In calcined powders, however, the intermediate structure were observed between rhombohedral and cubic phases near x=0.1. The formation of solid solution between NBT and PMN modified the dielectric and piezoelectric properties of NBT to be suitable for high temperature dielectric and piezoelectric material. With increasing the content of PMN, the temperature-stability of ε r (T) increased and the high temperature dielectric loss decreased. In addition, the piezoelectric property of NBT-xPMN was enhanced, for the decrease of coercive field and conductivity promoted the domain reversal under the high electric field of the poling process

  13. 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}.

  14. Phase relations and crystal structures in the systems (Bi,Ln)2WO6 and (Bi,Ln)2MoO6 (Ln=lanthanide)

    International Nuclear Information System (INIS)

    Berdonosov, Peter S.; Charkin, Dmitri O.; Knight, Kevin S.; Johnston, Karen E.; Goff, Richard J.; Dolgikh, Valeriy A.; Lightfoot, Philip

    2006-01-01

    Several outstanding aspects of phase behaviour in the systems (Bi,Ln) 2 WO 6 and (Bi,Ln) 2 MoO 6 (Ln=lanthanide) have been clarified. Detailed crystal structures, from Rietveld refinement of powder neutron diffraction data, are provided for Bi 1.8 La 0.2 WO 6 (L-Bi 2 WO 6 type) and BiLaWO 6 , BiNdWO 6 , Bi 0.7 Yb 1.3 WO 6 and Bi 0.7 Yb 1.3 WO 6 (all H-Bi 2 WO 6 type). Phase evolution within the solid solution Bi 2- x La x MoO 6 has been re-examined, and a crossover from γ(H)-Bi 2 MoO 6 type to γ-R 2 MoO 6 type is observed at x∼1.2. A preliminary X-ray Rietveld refinement of the line phase BiNdMoO 6 has confirmed the α-R 2 MoO 6 type structure, with a possible partial ordering of Bi/Nd over the three crystallographically distinct R sites. - Graphical abstract: A summary of phase relations in the lanthanide-doped bismuth tungstate and bismuth molybdate systems is presented, together with some additional structural data on several of these phases

  15. Formation enthalpies of LaLn'O{sub 3} (Ln'=Ho, Er, Tm and Yb) interlanthanide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Jianqi [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States); College of Physical Science and Technology, Sichuan University, Chengdu 610064 (China); Key Laboratory of Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Key Laboratory of High Energy Density Physics of Ministry of Education, Sichuan University, Chengdu 610064 (China); Guo, Xiaofeng [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States); Mielewczyk-Gryn, Aleksandra [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States); Faculty of Applied Physics and Mathematics, Department of Solid State Physics, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk (Poland); Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States)

    2015-07-15

    High-temperature oxide melt solution calorimetry using 3Na{sub 2}O·MoO{sub 3} at 802 °C was performed for interlanthanide perovskites LaLn'O{sub 3} (Ln'=Ho, Er, Tm and Yb) and lanthanide oxides (La{sub 2}O{sub 3}, Ho{sub 2}O{sub 3}, Er{sub 2}O{sub 3}, Tm{sub 2}O{sub 3} and Yb{sub 2}O{sub 3}). The enthalpies of formation of these interlanthanide perovskites from binary lanthanide oxides at room temperature (25 °C) were determined to be −8.3±3.4 kJ/mol for LaHoO{sub 3}, −9.9±3.0 kJ/mol for LaErO{sub 3}, −10.8±2.7 kJ/mol for LaTmO{sub 3} and −12.3±2.9 kJ/mol for LaYbO{sub 3}. There is a roughly linear relationships between these enthalpy values and the tolerance factor for these and for other LaM{sup 3+}O{sub 3} (M=In, Sc, Ga, Al, Fe and Cr) perovskites, confirming that the distortion of the perovskites as results from ionic radius difference of A-site and B-site cations, is the main factor determining the stability of these compounds. - Graphical abstract: A linear relationship between the enthalpy of formation and the tolerance factor for interlanthanide LaLn'O{sub 3} (Ln'=Ho, Er, Tm, and Yb) and other LaM{sup 3+}O{sub 3} (M=In, Sc, Ga, Al, Fe and Cr) perovskites. - Highlights: • Interlanthanide perovskites were synthesized by solid state reactions. • Their enthalpies of formation were measured by oxide melt solution calorimetry. • ΔH{sub f,ox} shows a linear relationship with tolerance factor.

  16. Synthesis and properties of γ-Ga2O3-Al2O3 solid solutions

    Science.gov (United States)

    Afonasenko, T. N.; Leont'eva, N. N.; Talzi, V. P.; Smirnova, N. S.; Savel'eva, G. G.; Shilova, A. V.; Tsyrul'nikov, P. G.

    2017-10-01

    The textural and structural properties of mixed oxides Ga2O3-Al2O3, obtained via impregnating γ-Al2O3 with a solution of Ga(NO3)3 and subsequent heat treatment, are studied. According to the results from X-ray powder diffraction, gallium ions are incorporated into the structure of aluminum oxide to form a solid solution of spinel-type γ-Ga2O3-Al2O3 up to a Ga2O3 content of 50 wt % of the total weight of the sample, accompanied by a reduction in the specific surface area, volume, and average pore diameter. It is concluded that when the Ga2O3 content exceeds 50 wt %, the β-Ga2O3 phase is observed along with γ-Ga2O3-Al2O3 solid solution. 71Ga and 27Al NMR spectroscopy shows that gallium replaces aluminum atoms from the tetrahedral position to the octahedral coordination in the structure of γ-Ga2O3-Al2O3.

  17. Investigation of phase relationships in subsolidus region of Ln2O3-MoO3-B2O3 systems

    International Nuclear Information System (INIS)

    Lysanova, C.V.; Dzhurinskij, B.F.; Komova, M.G.; Tananaev, I.V.

    1983-01-01

    Phase formation in subsolidus region of Ln 2 O 3 -MoO 3 B 2 O 3 systems (Ln-La, Nd) is studied. Three compounds with mixed oxyanions-boratomolybdates of LnMoBO 6 composition (Ln-La, Ce, Pr, Nd), Ln 2 MoB 2 O 9 (Ln-La, Ce, Pr, Nd, Sm, EU, Gde Tb) Ln 6 Mo 3 B 4 0 24 (Ln-Pr, Nd) are revealed and described

  18. Crystallization of rare earth germanates in the K2O-Ln2O3-GeO2-H2O at 280 deg C

    International Nuclear Information System (INIS)

    Panasenko, E.B.; Begunova, R.G.; Sklokina, N.F.

    1980-01-01

    Crystallization of rare earth germanates in potassium hydroxide solutions is studied at 280 deg C. Stability limits for different crystalline phases are established. Diorthogermanates Ln 2 O 3 x2GeO 3 (three structural modifications) are formed with all lanthanides except lanthanum. Germanates-apatites 7Ln 2 O 3 x9GeO 2 are characteristic for ''large'' lanthanides La-Nd. Alkali germanate of the composition 0.5 K 2 OxLn 2 O 3 xGeO 2 xnH 2 O is realized with the elements of the end of rare earth series, i.e., Tm-Lu. Some properties of the germanates synthesized are considered [ru

  19. Solid solutions in the system Nd2(SeO4)3 - Sm2(SeO4)3 - H2O

    International Nuclear Information System (INIS)

    Serebrennikov, V.V.; Tsybukova, T.N.; Velikov, A.A.

    1984-01-01

    Using the method of isothermal solubility at 25 deg C the system Nd 2 (SeO 4 ) 3 -Sm 2 (SeO 4 ) 3 -H 2 O has been studied. Roentgenographic recording of solid ''residues'' is realized. For solid solutions energies of interchange and formation heats are calculated. Formation heats of solid solutions on the basis of samarium selenates are also found experimentally

  20. New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO32H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

    Science.gov (United States)

    Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

    2013-02-18

    We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

  1. Studies on the Ln/sub 2/O/sub 3/ (Ln: rare-earth elements)-SrO-V/sub 2/O/sub 3/ system, 1. Phase diagrams at 1400/sup 0/C

    Energy Technology Data Exchange (ETDEWEB)

    Shin-ike, T [Osaka Dental Coll., Hirakata (Japan); Adachi, G; Shiokawa, J

    1980-11-01

    Rare-earth oxides Ln/sub 2/O/sub 3/ (Ln : Nd, Eu or Er), strontium oxide SrO and vanadium oxide V/sub 2/O/sub 3/ were mixed in a given molecular ratio, heated at 1400/sup 0/C in vacuum. The products were examined by an x-ray diffraction method to study the phase relations of the ternary systems. On heating, part of the trivalent vanadium was oxidized to the tetravalent state by atmospheric oxygen. In this experimental condition, the following ternary-phase solid solutions were identified: perovskite type Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3. cubic, x < 0.3: orthorhombic) and Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4: cubic, x < 0.4: orthorhombic), K/sub 2/NiF/sub 4/ type SrO.Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3) and SrO.Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4) and Eu/sub 3/Ti/sub 2/O/sub 7/ type SrO.2Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3) and SrO.2Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4). For the Er/sub 2/O/sub 3/-SrO-V/sub 2/O/sub 3/ system, only a mixture of Er/sub 2/O/sub 3/, SrVO sub(2.9), ErVO/sub 3/, SrO and V/sub 2/O/sub 3/ was obtained.

  2. Polymorphism of Bi1-xLnxO1.5 phases (04Ln2O9 (x=0.33; Ln=La, Pr, Nd)

    International Nuclear Information System (INIS)

    Drache, Michel; Huve, Marielle; Roussel, Pascal; Conflant, Pierre

    2003-01-01

    The Bi 1-x Ln x O 1.5 solid solutions (Ln=La, Pr, Nd), of the β 2 /β 1 /ε (Bi-Sr-O) structural type, have been investigated in their Ln-rich domains. For Ln=La, Pr, and Nd, the upper limits are 0.35, 0.35 and 0.33, respectively. The Bi 4 Ln 2 O 9 ε phase (x=0.33) appears to be the single definite compound. For Bi 4 La 2 O 9 , Bi 4 Pr 2 O 9 and Bi 4 Nd 2 O 9 , the ε-type cells are respectively: a=9.484(4) A, b=3.982(2) A, c=7.030(3) A, β=104.75(3) deg.; a=9.470(5) A, b=3.945(2) A, c=6.968(4) A, β=104.73(3) deg. and a=9.439(3) A, b=3.944(2) A, c=6.923(2) A, β=105.03(3) deg. . Upon heating, each monoclinic (ε) compound transforms successively into rhombohedral phases (β 2 /β 1 ) and finally into a cubic fluorite-type phase. For La- and Pr-based compounds, all transitions are reversible; for Nd, depending on the thermal treatment, the reversibility of ε→β 2 can be incomplete. These transformations are characterized using X-ray thermodiffractometry, differential thermal analysis, dilatometry and impedance spectroscopy versus temperature. Examination of Bi 4 (Ln, Ln') 2 O 9 samples allows to correlate the evolution of the thermal behavior and of the unit cell parameters, to the lanthanide size. A partial plot of the (Bi 2 O 3 ) 1-x -(La 2 O 3 ) x phase diagram (0≤x≤0.40) is proposed

  3. Luminescence of Ce3+ ions in Y3Al5O12 - Y3Ga5O12 solid solution

    International Nuclear Information System (INIS)

    Zorenko, Yu.V.; Nazar, I.V.; Limarenko, L.N.; Pashkovskij, M.V.

    1996-01-01

    Regularities of changes in spectral and energetic characteristics of the Ce 3+ ions radiation in the Y 3 Al 5-x Ga x O 12 solid solutions, related to change in the matrix crystal field force and dissipation of the luminescence excitation energy because of transfers between the valency zone ceiling and the Ce 3+ excited ion basis state are obtained. 9 refs., 3 figs., 1 tab

  4. Electric Properties of Pb(Sb1/2Nb1/2)O3 PbTiO3 PbZrO3 Ceramics

    Science.gov (United States)

    Kawamura, Yasushi; Ohuchi, Hiromu

    1994-09-01

    Solid-solution ceramics of ternary system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 were prepared by the solid-state reaction of powder materials. Ceramic, electric, dielectric and piezoelectric properties and crystal structures of the system were studied. Sintering of the system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 is much easier than that of each end composition, and well-sintered high-density ceramics were obtained for the compositions near the morphotropic transformation. Piezoelectric ceramics with high relative dielectric constants, high radial coupling coefficient and low resonant resistance were obtained for the composition near the morphotropic transformation. The composition Pb(Sb1/2Nb1/2)0.075Ti0.45Zr0.475O3 showed the highest dielectric constant (ɛr=1690), and the composition Pb(Sb1/2Nb1/2)0.05Ti0.45Zr0.5O3 showed the highest radial coupling coefficient (kp=64%).

  5. Residual tensile stresses and piezoelectric properties in BiFeO3-Bi(Zn1/2Ti1/2O3-PbTiO3 ternary solid solution perovskite ceramics

    Directory of Open Access Journals (Sweden)

    Weilin Zheng

    2016-08-01

    Full Text Available For low dielectric loss perovskite-structured (1-x-yBiFeO3-xBi(Zn1/2Ti1/2O3-yPbTiO3 (BF-BZT-PT (x = 0.04-0.15 and y = 0.15-0.26 ceramics in rhombohedral/tetragonal coexistent phase, structural phase transitions were studied using differential thermal analyzer combined with temperature-dependent dielectric measurement. Two lattice structural phase transitions are disclosed in various BF-BZT-PT perovskites, which is different from its membership of BiFeO3 exhibiting just one lattice structural phase transition at Curie temperature TC= 830oC. Consequently, residual internal tensile stresses were revealed experimentally through XRD measurements on ceramic pellets and counterpart powders, which are reasonably attributed to special structural phase transition sequence of BF-BZT-PT solid solution perovskites. Low piezoresponse was observed and argued extrinsically resulting from residual tensile stresses pinning ferroelectric polarization switching. Post-annealing and subsequent quenching was found effective for eliminating residual internal stresses in those BZT-less ceramics, and good piezoelectric property of d33 ≥ 28 pC/N obtained for 0.70BF-0.08BZT-0.22PT and 0.05 wt% MnO2-doped 0.70BF-0.04BZT-0.26PT ceramics with TC ≥ 640oC, while it seemed no effective for those BZT-rich BF-BZT-PT ceramics with x = 0.14 and 0.15 studied here.

  6. Insertion of water into rare earth oxocuprates (Ln)Ba 2Cu 3O 7-δ

    Science.gov (United States)

    Günther, Wulf; Schöllhorn, Robert

    1996-02-01

    The solid state reaction of LnBa 2Cu 3O 7-δ bulk material with water vapour corresponds to a quantitative topotactic reaction of the solid with H 2O to a maximum stoichiometry of LnBa 2Cu 3O 7-δ(H 2O) 1. The reaction proceeds in a temperature window which depends upon the oxygen content (δ) of the starting phase and is correlated with a structural transition via intermediate states. Although the integral copper oxidation state is not affected by the water intercalation, electronic and transport properties are strongly influenced. The insertion of water into these defect perovskites has to be described as a topotactic acid/base process.

  7. Hierarchical architectures of ZnS–In2S3 solid solution onto TiO2 nanofibers with high visible-light photocatalytic activity

    International Nuclear Information System (INIS)

    Liu, Chengbin; Meng, Deshui; Li, Yue; Wang, Longlu; Liu, Yutang; Luo, Shenglian

    2015-01-01

    Graphical abstract: A unique hierarchical architecture of ZnS–In 2 S 3 solid solution onto TiO 2 nanofibers was fabricated. The hierarchical heterostructures exhibit high visible light photocatalytic activity and outstanding recycling performance. - Highlights: • Novel hierarchical heterostructure of TiO 2 @ZnS–In 2 S 3 solid solution. • Efficient inhibition of ZnS–In 2 S 3 solid solution aggregation. • High visible light photocatalytic activity. • Highly stable recycling performance. - Abstract: A unique hierarchical architecture of ZnS–In 2 S 3 solid solution nanostructures onto TiO 2 nanofibers (TiO 2 @ZnS–In 2 S 3 ) has been successfully fabricated by simple hydrothermal method. The ZnS–In 2 S 3 solid solution nanostructures exhibit a diversity of morphologies: nanosheet, nanorod and nanoparticle. The porous TiO 2 nanofiber templates effectively inhibit the aggregation growth of ZnS–In 2 S 3 solid solution. The formation of ZnS–In 2 S 3 solid solution is proved by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and the intimate contact between TiO 2 nanofibers and ZnS–In 2 S 3 solid solution favors fast transfer of photogenerated electrons. The trinary TiO 2 @ZnS–In 2 S 3 heterostructures exhibit high adsorption capacity and visible light photocatalytic activity for the degradation of rhodamine B dye (RhB), remarkably superior to pure TiO 2 nanofibers or binary structures (ZnS/TiO 2 nanofibers, In 2 S 3 /TiO 2 nanofibers and ZnS–In 2 S 3 solid solution). Under visible light irradiation the RhB photocatalytic degradation rate over TiO 2 @ZnS–In 2 S 3 heterostructures is about 16.7, 12.5, 6.3, 5.9, and 2.2 times that over pure TiO 2 nanofibers, ZnS nanoparticles, In 2 S 3 /TiO 2 nanofibers, ZnS/TiO 2 nanofibers, and ZnS-In 2 S 3 solid solution, respectively. Furthermore, the TiO 2 @ZnS–In 2 S 3 heterostructures show highly stable recycling performance

  8. Investigation of BaMoO4-Ln2(MoO4)3 systems (Ln = Nd, Sm, Yb)

    International Nuclear Information System (INIS)

    Vakulyuk, V.V.; Evdokimov, A.A.; Khomchenko, G.P.

    1982-01-01

    Using the methods of X-ray phase and differential-thermal analyses phase ratios in the systems BaMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=Nd, Sm, Yb); BaNd 2 (MoO 4 ) 4 -MaGd 2 (MoO 4 ) are studied. Unit cell parameters and the character of melting of the compounds BaLn 2 (MoO 4 ) 4 are specified. Effect of growth conditions on laminated nature of BaGd 2 (MoO 4 ) 4 monocrystals is studied

  9. Structuring effects of [Ln6O(OH)8(NO3)6(H2O)12]2+ entities

    International Nuclear Information System (INIS)

    Guillou, O.; Daiguebonne, C.; Calvez, G.; Le Dret, F.; Car, P.-E.

    2008-01-01

    In order to obtain highly porous lanthanide-based coordination polymers we are currently investigating reactions between [Ln 6 O(OH) 8 (NO 3 ) 6 (H 2 O) 12 ] 2+ di-cationic hexanuclear entities and sodium salts of benzene-poly-carboxylic acids. Two new coordination polymers obtained during this study are reported here. In both cases, the hexanuclear entity has been destroyed during the reaction. However the resulting compounds are original thanks to a structuring effect of the poly-metallic complex. The first compound of chemical formula [Y 2 (C 8 H 4 O 4 ) 3 (DMF)(H 2 O)],2DMF crystallizes in the monoclinic system, space group P121/n (n o 14) with a = 16.0975(3) A, b = 14.4605(3) A, c = 17.7197(4) A, β = 92.8504(9) o and Z = 4. The second compound of chemical formula Y 2 (NO 3 ) 2 (C 10 H 2 O 8 )(DMF) 4 crystallizes in the triclinic system, space group P-1 (n o 2) with a = 7.5312(3) A, b = 9.0288(3) A, c = 13.1144(6) A, α = 92.6008(14) o , β = 94.9180(14) o , γ = 112.1824(16) o and Z = 2. Both crystal structures are 2D. Both crystal structures are described and the original structural features are highlighted and related to a potential structuring effect of the hexanuclear precursor

  10. Bi3+ sensitized Y2WO6:Ln3+ (Ln=Dy, Eu, and Sm) phosphors for solar spectral conversion.

    Science.gov (United States)

    Huang, M N; Ma, Y Y; Xiao, F; Zhang, Q Y

    2014-01-01

    The phosphors of Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) were synthesized by solid-state reaction in this study. The crystal structure, photoluminescence properties and energy transfer mechanism were investigated. By introducing Bi3+ ions, the excitation band of the phosphors was broadened to be 250-380 nm, which could be absorbed by the dye-sensitized solar cells (DSSCs). The overlap between excitation of W-O groups/Bi3+ and the emission of Ln3+ (Dy, Eu, and Sm) indicated that the probability of energy transfer from W-O groups and Bi3+ to Ln3+. The energy transfer efficiency from Bi3+ to Ln3+ (Ln=Dy, Eu and Sm) are calculated to be 16%, 20% and 58%. This work suggested that Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) might be a promising ultraviolet-absorbing luminescent converter to enhance the photoelectrical conversion efficiency of dye-sensitized solar cells (DSSCs). Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Phase relations in Ca(Sr)MoO4-Ln2(NoO4)3 systems (Ln = Pr-Lu)

    International Nuclear Information System (INIS)

    Vakalyuk, V.V.; Evdokimov, A.A.; Berezina, T.A.

    1982-01-01

    Using the methods of X-ray phase and differential thermal analyses phase ratios in the systems Ca(Sr)MoO 4 -Ln 2 (MoO 4 ) 3 at Ln=Pr-Lu are studied and phase diagrams of the systems CaMoO 4 -Ln 2 (MoO 4 ) 3 , for Ln=Nd, Gd, Yb and SrMoO 4 -Sm 2 (MoO 4 ) 3 are built. It is shown that phase ratios in the systems are similar for the following groups of rare earths: Pr-Sm, Eu-Tb, Ho-Lu. In the first group of systems ordered phase over all subsolidus region are formed, in the second one - ordered phases with scheelite-like structure and wide regions of homogeneity on the basis of Ca(Sr)MoO 4 are formed above the temperature of polymorphous transformation of rare earth molybdates, for the third group of systems intermediate compounds are not detected

  12. Structure of trihydrated rare-earth acid diphosphates LnHP2O3H2O (Ln=La, Er)

    International Nuclear Information System (INIS)

    Ben Moussa, S.; Ventemillas, S.; Cabeza, A.; Gutierrez-Puebla, E.; Sanz, J.

    2004-01-01

    In trihydrated lanthanum acid-diphosphates LnHP 2 O 7 ·3H 2 O, prepared from acid LnCl 3 and Na 4 P 2 O 7 solutions (pH=1), two crystal forms were obtained. Layered structures of two representative members of this family have been determined by single-crystal X-ray diffraction (XRD) technique. In the case of orthorhombic LaHP 2 O 7 ·3H 2 O (type I), lanthanum cations are ninefold coordinated and diphosphate groups adopt a staggered (alternated) configuration. In the case of triclinic ErHP 2 O 7 ·3H 2 O (type II), erbium cations are eightfold coordinated and diphosphate groups adopt an eclipsed configuration. In agreement with Infrared (IR) spectroscopic data, a bended configuration for diphosphate groups has been deduced. In both structures, one-dimensional chains of edge-sharing rare-earth polyhedra are linked together by diphosphate groups to form the phosphate layers. In both diphosphates, PO 4 and HPO 4 environments have been identified by 31 P MAS-NMR technique. In the two compounds, OH groups of HPO 4 tetrahedra point out of diphosphate planes interacting with adjacent layers. In La-diphosphate, the interaction between HPO 4 groups and water molecules of adjacent layers is favored; however, in Er-diphosphate, the interaction between phosphate acid groups of contiguous layers is produced. Based on structural information deduced, differences detected in IR and NMR spectra of two disphosphates are discussed

  13. Behaviour of LaAlO 3 +LnTiTaO 6 (Ln= Ce, Pr or Nd)

    Indian Academy of Sciences (India)

    The 0.1LaAlO3+0.9LnTiTaO6 (Ln= Ce, Pr or Nd) ceramics are prepared through solid state ceramic route. The structure of the materials is studied using X-ray diffraction analysis. The microstructure is analysed using scanning electron microscopy. The dielectric properties in the radio as well as in the microwave frequencies ...

  14. Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors: Morphology-tunable and luminescence properties

    Science.gov (United States)

    Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

    2018-02-01

    4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu3 + and Tb3 +. Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu3 +-doped, Tb3 +-doped and Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu3 + shows a red emission (615 nm); the Tb3 + shows a green emission (545 nm); for the Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors, a combination of blue (5d-4f of Eu2 +), green (5D4-7F5 of Tb3 +) and red (5D0-7F2 of Eu3 +) emissions emerges to achieve white emission. In addition, the energy transfer among Eu3 +, Eu2 + and Tb3 + ions was also discussed.

  15. Synthesis, structural and semiconducting properties of Ba(Cu1/3 Sb2/3)O3-PbTiO3 solid solutions

    Science.gov (United States)

    Singh, Chandra Bhal; Kumar, Dinesh; Prashant, Verma, Narendra Kumar; Singh, Akhilesh Kumar

    2018-05-01

    We report the synthesis and properties of a new solid solution 0.05Ba(Cu1/3Sb2/3)O3-0.95PbTiO3 (BCS-PT) which shows the semiconducting properties. In this study, we have designed new perovskite-type (ABO3) solid solution of BCS-PT that have tunable optical band gap. BCS-PT compounds were prepared by conventional solid-state reaction method and their structural, micro-structural and optical properties were analyzed. The calcination temperature for BCS-PT solid solutions has been optimized to obtain a phase pure system. The Reitveld analysis of X-ray data show that all samples crystallize in tetragonal crystal structure with space group P4mm. X-ray investigation revealed that increase in calcination temperature led to increase of lattice parameter `a' while `c' parameter value lowered. The band gap of PbTiO3 is reduced from 3.2 eV to 2.8 eV with BCS doping and with increasing calcination temperature it further reduces to 2.56 eV. The reduced band gap indicated that the compounds are semiconducting and can be used for photovoltaic device applications.

  16. Effects of chlorides on the hydration of 12CaO{center_dot}7Al2O3 solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Sango, H.; Miyakawa, T.; Yasue, T.; Arai, Y. [Nihon Univ., Tokyo (Japan). Faculty of Science and Engineering

    1995-01-01

    The purpose of this paper was to compare the hydration rate of C12A7ss and to study the effects of chlorides on the hydration products and the hydration rate of C12A7ss. In this paper, `C12A7ss` is a general term for C11A7{center_dot}Ca(OH)2, 11CaO{center_dot}7Al2O3{center_dot}CaF2 and 11CaO{center_dot}7Al2O3{center_dot}CaCl2. The hydration process and the hydration rate of 12CaO{center_dot}7Al2O3 solution (C12A7ss) with and without various chlorides (CaCl2, MgCl2, NaCl, NH4Cl and AlCl3) has been determined at 25{degree}C. Various C12A7ss were prepared in burning method. When C12A7ss with various chlorides are hydrated, 3CaO{center_dot} Al2O3{center_dot}CaCl2{center_dot}10H2O(Friedel`s salt) is formed as the primary hydrate. The hydration rate of C12A7ss is decreased by the coexistence of CaCl2, MgCl2, NaCl or NH4Cl except AlCl3. As a result, the setting time of C12A7ss is extended and the unhydrate exists for a long time comparatively. 14 refs., 7 figs., 1 tab.

  17. Red emitting phosphors of Eu3+ doped Na2Ln2Ti3O10 (Ln = Gd, Y) for white light emitting diodes

    International Nuclear Information System (INIS)

    Zhang, Niumiao; Guo, Chongfeng; Yin, Luqiao; Zhang, Jianhua; Wu, Mingmei

    2015-01-01

    Highlights: • Layered red phosphors Na 2 Ln 2 Ti 3 O 10 (Ln = Gd, Y):Eu 3+ were prepared. • The synthesis parameters of phosphors were optimized. • PL and thermal stability of the samples were investigated. • LED devices were also fabricated including the present red phosphor. - Abstract: A series of Eu 3+ doped Na 2 Ln 2 Ti 3 O 10 (Ln = Gd, Y) red-emitting phosphors for application in ultraviolet based light emitting diodes (LEDs) were successfully synthesized by a modified sol–gel method. Their structure and luminescent properties were characterized by powder X-ray diffraction (XRD), photoluminescence excitation (PLE) and emission (PL) spectra and absorption spectra, according to these results the optimal compositions and synthesis parameters were determined. In addition, the thermal stabilities of the phosphors were investigated according to the temperature-dependent PL spectra. The red and white-LEDs (W-LEDs) comprising the Na 2 Ln 2 Ti 3 O 10 :Eu 3+ (Ln = Gd, Y) red emitting phosphors were fabricated with a near-ultraviolet (n-UV) chip. In comparison with Na 2 Y 1.4 Eu 0.6 Ti 3 O 10 , the Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 phosphor offers higher brightness, quantum efficiency, and excellent thermal stability. W-LEDs comprising Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 showed bright white emission with a color rendering index (Ra) of 82, a color temperature of 2151 K, and Commission Internationale de I’Eclairage (CIE) color coordinates of (0.34, 0.37). The phosphor Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 is more suitable candidate for application in LEDs

  18. Synthesis and characterization of K2Ln2/3Ta2O7·nH2O (Ln= La, Pr, Nd), layered tantalates photo catalysts for water splitting

    International Nuclear Information System (INIS)

    Valencia S, H.; Tavizon, G.; Pfeiffer, H.; Acosta, D.; Negron M, A.

    2015-01-01

    Three compounds of the K 2 Ln 2/3 Ta 2 O 7 (Ln = La, Nd, Pr) cation-deficient Ruddlesden-Popper series were prepared by the Pechini (polymeric complex) method. The crystal structures of the hydrated form of these compounds were determined by Rietveld analysis of the X-ray power diffraction data and High Resolution Transmission Electron Microscopy (HRTEM). The samples were also analyzed to determine specific area (Bet), degree of hydration (Thermogravimetric analysis), and photo catalytic activity for hydrogen evolution from water and aqueous methanol solution. (Author)

  19. A method for the estimation of the enthalpy of formation of mixed oxides in Al2O3-Ln2O3 systems

    International Nuclear Information System (INIS)

    Vonka, P.; Leitner, J.

    2009-01-01

    A new method is proposed for the estimation of the enthalpy of formation (Δ ox H) of various Al 2 O 3 -Ln 2 O 3 mixed oxides from the constituent binary oxides. Our method is based on Pauling's concept of electronegativity and, in particular, on the relation between the enthalpy of formation of a binary oxide and the difference between the electronegativities of the oxide-forming element and oxygen. This relation is extended to mixed oxides with a simple formula given for the calculation of Δ ox H. The parameters of this equation were fitted using published experimental values of Δ ox H derived from high-temperature oxide melt solution calorimetry. Using our proposed method, we obtained a standard deviation (σ) of 4.87 kJ mol -1 for this data set. Taking into account regularities within the lanthanide series, we then estimated the Δ ox H values for Al 2 O 3 -Ln 2 O 3 mixed oxides. The values estimated using our method were compared with those obtained by Aronson's and Zhuang's empirical methods, both of which give significantly poorer results. - Graphical abstract: Enthalpy of formation of Ln-Al-O oxides from the constituent binary ones.

  20. Development of electrolyte-supported intermediate-temperature single-chamber solid oxide fuel cells using Ln{sub 0.7}Sr{sub 0.3}Fe{sub 0.8}Co{sub 0.2}O{sub 3-{delta}} (Ln = Pr, La, Gd) cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz de Larramendi, I.; Ruiz de Larramendi, J.I.; Rojo, T. [Departamento de Quimica Inorganica, Universidad del Pais Vasco, Apdo.644, 48080 Bilbao (Spain); Lamas, D.G.; Cabezas, M.D.; Walsoee de Reca, N.E. [CINSO, CONICET-CITEFA, J.B. de La Salle 4397 (B1603ALO) Villa Martelli, Pcia. de Buenos Aires (Argentina)

    2009-09-05

    Iron-cobalt-based perovskite oxides with general formula Ln{sub 0.7}Sr{sub 0.3}Fe{sub 0.8}Co{sub 0.2}O{sub 3-{delta}} (where Ln = La, Pr and Gd) have been investigated for their application as intermediate-temperature cathodes in solid oxide fuel cells (SOFCs). Powdered samples of these materials were synthesized by a novel gel combustion process and then characterized by X-ray powder diffraction (XPD) and scanning electron microscopy (SEM). XPD patterns were satisfactorily indexed with an orthorhombic GdFeO{sub 3}-type structure and, for all samples, a mean particle size of less than 1 {mu}m was estimated from the SEM data. Experimental single-chamber SOFCs using with these materials as cathodes and NiO-SDC (samaria-doped ceria) and SDC as anode and electrolyte, respectively, were evaluated at 600 C in a methane/oxygen mixtures. Peak power densities of 65.4, 48.7 and 46.2 mW cm{sup -2} were obtained for Ag vertical stroke Ln{sub 0.7}Sr{sub 0.3}Fe{sub 0.8}Co{sub 0.2}O{sub 3-{delta}} vertical stroke SDC vertical stroke NiO-SDC vertical stroke Pt cells with Ln = Pr, La and Gd, respectively. The relatively high power density obtained for the Pr compound shows that it could be an interesting material for cathode of single-chamber SOFCs. (author)

  1. 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.

  2. Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

    Science.gov (United States)

    Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

    2013-06-17

    Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)22.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}22CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

  3. Nanostructured LnBaCo2O6− (Ln = Sm, Gd with layered structure for intermediate temperature solid oxide fuel cell cathodes

    Directory of Open Access Journals (Sweden)

    Augusto E. Mejía Gómez

    2017-04-01

    Full Text Available In this work, we present the combination of two characteristics that are beneficial for solid oxide fuel cell (SOFC cathodic performance in one material. We developed and evaluated for the first time nanostructured layered perovskites of formulae LnBaCo2O6-d with Ln = Sm and Gd (SBCO and GBCO, respectively as SOFC cathodes, finding promising electrochemical properties in the intermediate temperature range. We obtained those nanostructures by using porous templates to confine the chemical reagents in regions of 200-800 nm. The performance of nanostructured SBCO and GBCO cathodes was analyzed by electrochemical impedance spectroscopy technique under different operating conditions using Gd2O3-doped CeO2 as electrolyte. We found that SBCO cathodes displayed lower area-specific resistance than GBCO ones, because bulk diffusion of oxide ions is enhanced in the former. We also found that cathodes synthesized using smaller template pores exhibited better performance.

  4. Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

    International Nuclear Information System (INIS)

    Fabregas, Ismael O.; Craievich, Aldo F.; Fantini, Marcia C.A.; Millen, Ricardo P.; Temperini, Marcia L.A.; Lamas, Diego G.

    2011-01-01

    Research highlights: → Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO 2 -Y 2 O 3 nanopowders, that exhibit the presence at room temperature of three different phases depending on Y 2 O 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 2 -Y 2 O 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 2 O 3 , respectively. → For the whole series of nanocrystalline ZrO 2 -Y 2 O 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 2 -Y 2 O 3 solid solutions, the presence at room temperature of three different phases depending on Y 2 O 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 2 -Y 2 O 3 solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro

  5. Phase formation in the Li2MoO4-Rb2MoO4-Ln2(MoO4)3 systems and the properties of LiRbLn2(MoO4)4

    International Nuclear Information System (INIS)

    Basovich, O.M.; Khajkina, E.G.; Vasil'ev, E.V.; Frolov, A.M.

    1995-01-01

    Phase equilibria within subsolidus range of ternary salt systems Li 2 MoO 4 -Rb 2 MoO 4 -Ln 2 (MoO 4 ) 4 (Ln - Nd, Er) are analyzed. Formation of ternary molybdate LiRbNd 2 (MoO 4 ) 4 is proved along LiNd(MoO 4 ) 2 -RbNd(MoO 4 )-2 cross-section. Phase diagram of this cross-section is plotted. Similar compounds are synthesized for Ln = La-Eu. The parameters of their monoclinic elementary cells are determined. Luminescent properties of LiRbLa 2 (MoO 4 ) 4 -Nd 3+ are studied. 17 refs., 4 figs., 2 tabs

  6. Solid-soluted content of cerium in solid solution of sphene

    International Nuclear Information System (INIS)

    Zhao Wei; Teng Yuancheng; Li Yuxiang; Ren Xuetan; Huang Junjun

    2010-01-01

    The sphene solid solution was synthesized by solid-state method,with calcium carbonate, silica, titanium dioxide, cerium oxalate and alumina as raw materials. The solid-soluted content of cerium in sphene was researched by means of X-ray diffraction (XRD), backscattering scanning electron microscopy (BSE), energy dispersive spectroscopy (EDS) and so on. The influence of A l3+ ion introduction to sphene on the solid-soluted content of cerium in sphene solid solution was studied. The results indicate that when introducing Al 3+ to sphene as electrovalence compensation, Ce 4+ could be well solidified to Ca 1-x Ce x Ti 1-2x A l2x SiO 5 , and the solid-soluted content is approximately 12.61%. With no electrovalence compensation, Ce 4+ could be solidified to Ca 1-2x Ce x TiSiO 5 , and the solid-soluted content is approximately 10.98%. The appropriate synthesis temperature of sphene solid solution is 1 260 degree C.(authors)

  7. AgLnSb/sub 2/O/sub 7/ compounds with weberite structure

    Energy Technology Data Exchange (ETDEWEB)

    Lopatin, S S; Aver' yanova, L N; Belyaev, I N; Zvyagintsev, B I; Dyatlov, Eh V [Rostovskij-na-Donu Gosudarstvennyj Univ. (USSR)

    1982-11-01

    The interaction between AgSbO/sub 3/ and LnSbO/sub 4/ in the solid phase at 1100-1150 deg C has been investigated. AgLnSb/sub 2/O/sub 7/ compounds with weberite crystal structure are formed in Ln=La, Pr, Nd, Sm cases but in Ln=Eu, Cd, Dy, Er cases the formation of termary oxides of the indicated composition has not been observed. Inasmuch as compounds of the general formula A/sub 2/B/sub 2/O/sub 7/ with average cation radii Rsub(B) >0.60 A and 1.65 <= Rsub(A)/Rsub(B) <= 2.20 can crystallize in weberite, pyrochlore and laminated perovskite-like structurer, conditions of the existence of the above mentioned structures depending on A and B dimensions and electronegativity are discussed.

  8. Hydrothermal synthesis and photoluminescent properties of hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower-like clusters

    Science.gov (United States)

    Amurisana, Bao.; Zhiqiang, Song.; Haschaolu, O.; Yi, Chen; Tegus, O.

    2018-02-01

    3D hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower clusters were successfully prepared on glass slide substrate by a simple, economical hydrothermal process with the assistance of disodium ethylenediaminetetraacetic acid (Na2H2L, where L4- = (CH2COO)2N(CH2)2N(CH2COO)24-). In this process, Na2H2L was used as both a chelating agent and a structure-director. The hierarchical flower clusters have an average diameter of 7-12 μm and are composed of well-aligned microrods. The influence of the molar ratio of Na2H2L/Gd3+ and reaction time on the morphology was systematically studied. A possible crystal growth and formation mechanism of hierarchical flower clusters is proposed based on the evolution of morphology as a function of reaction time. The self-assembled GdPO4·H2O:Ln3+ superstructures exhibit strong orange-red (Eu3+, 5D0 → 7F1), green (Tb3+, 5D4 → 7F5) and near ultraviolet emissions (Ce3+, 5d → 7F5/2) under ultraviolet excitation, respectively. This study may provide a new channel for building hierarchically superstructued oxide micro/nanomaterials with optical and new properties.

  9. Synthesis and characterization of charge-substituted garnets YCaLnGa5O12 (Ln = Ce,Pr,Tb)

    International Nuclear Information System (INIS)

    Gramsch, S.A.

    1993-01-01

    A low temperature method is described for the preparation of the new garnet compounds YCaLnGa 5 O l2 (Ln=Ce, Pr, Th). In this set of compounds (Ca 2+ + Ln 4+ ) replaces 2 Y 3+ in the parent gallium based garnet Y 3 Ga 5 O l2 in order to stabilize as effectively as possible the Ln 4+ species in the eight-coordinate ''A'' site of the garnet structure. Characterization of the oxides by x-ray powder diffraction and thermogravimetric analysis is discussed with regard to the structural relationship of the substituted compound to the parent material. The tetravalent ions Pr 4+ and Tb 4+ exhibit increased thermal stability in reducing conditions as compared to the Ln 4+ states in the fluorite (LnO 2 ) and perovskite (BaLnO 3 ) type structures. This result is discussed with reference to the complex crystal chemistry of these systems

  10. Multiferroic properties in NdFeO3-PbTiO3 solid solutions

    Science.gov (United States)

    Kumar, Sunil; Pal, Jaswinder; Kaur, Shubhpreet; Agrawal, P.; Singh, Mandeep; Singh, Anupinder

    2018-05-01

    The x(NdFeO3) - 1-x(PbTiO3) where x = 0.2 solid solution was prepared using solid state reaction route. The X-ray diffraction (XRD) data reveals the single phase formation. The microstructure shows grain growth with lesser porosity. The energy dispersive analysis confirms the presence of elements in stochiometric proportion. The polarization vs. Electric field loop estabilished a ferroelectric type behavior but lossy in nature. This lossy nature may be due to the presence of large leakage current in solid solution. The Magnetization vs. Magnetic field plot exhibits a unsaturated hysteriss loop indicates that the sample is not purely ferromagnetic.

  11. Thermodynamic characteristics of systems with solid solutions composed of crystal hydrates of lanthanide and yttrium chlorides, at 250C. III. Systems of Roozeboom's type IV, with restricted solid solutions

    International Nuclear Information System (INIS)

    Sokolova, N.P.

    1983-01-01

    The values of the activity, the activity coefficients, the free energy of mixing and the excess free energy of mixing have been calculated for CeCl 3 -LnCl 3 -H 2 O systems (where Ln identical with Sm, Gd, Dy, Ho, Er, Y) containing solid solutions of types IV and IVa. It is shown that the stability of the solid solutions decreases with increasing difference between the radii of the cations of cerium and the second lanthanide, which enter into the composition of the components of the solid solutions. The factors determining the composition of a liquid solution corresponding to the eutonic point are specified

  12. Synthesis and characterization of K{sub 2}Ln{sub 2/3}Ta{sub 2}O{sub 7}·nH{sub 2}O (Ln= La, Pr, Nd), layered tantalates photo catalysts for water splitting

    Energy Technology Data Exchange (ETDEWEB)

    Valencia S, H.; Tavizon, G. [UNAM, Instituto de Quimica, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Pfeiffer, H. [UNAM, Instituto de Investigaciones en Materiales, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Acosta, D. [UNAM, Instituto de Fisica, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Negron M, A., E-mail: hvalencia@utp.edu.co [UNAM, Instituto de Ciencias Nucleares, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico)

    2015-07-01

    Three compounds of the K{sub 2}Ln{sub 2/3}Ta{sub 2}O{sub 7} (Ln = La, Nd, Pr) cation-deficient Ruddlesden-Popper series were prepared by the Pechini (polymeric complex) method. The crystal structures of the hydrated form of these compounds were determined by Rietveld analysis of the X-ray power diffraction data and High Resolution Transmission Electron Microscopy (HRTEM). The samples were also analyzed to determine specific area (Bet), degree of hydration (Thermogravimetric analysis), and photo catalytic activity for hydrogen evolution from water and aqueous methanol solution. (Author)

  13. Syntheses, crystal structures and solid-state properties of the lanthanoid-containing nanoclusters [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-}

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Rakesh; Saini, Mukesh Kumar; Hussain, Firasat [Department of Chemistry, University of Delhi (India)

    2014-12-15

    A series of lanthanoid-substituted polyoxometalates have been synthesized by a self-assembly process in potassium chloride solution by the reaction of dilacunary [P{sub 2}W{sub 19}O{sub 69}(H{sub 2}O)]{sup 14-} with mid- and late-lanthanoid Ln(NO{sub 3}){sub 3}.nH{sub 2}O salts leading to the formation of the tetrameric tungstophosphates [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-} [Ln = Y{sup 3+} (1), Sm{sup 3+} (2), Eu{sup 3+} (3), Gd{sup 3+} (4), Tb{sup 3+} (5), Dy{sup 3+} (6), Ho{sup 3+} (7), Er{sup 3+} (8), Tm{sup 3+} (9), Yb{sup 3+} (10)]. The polyanions were isolated as potassium or mixed-alkali salts. Most of the compounds were characterized by single-crystal X-ray diffraction and various analytical techniques, such as FTIR, UV/Vis, {sup 31}P NMR and photoluminescence spectroscopy, magnetism, as well as thermogravimetric analysis. The FTIR spectra suggest that all the compounds are isomorphous. The crystal structures of these complexes consist of four A-[α-PW{sub 10}O{sub 36}]{sup 7-} units, each incorporating two Ln{sup III} ions to create four Keggin-like anions that further assemble with three additional tungstate units to form a tetramer species with C{sub 2} symmetry. The photoluminescent properties of 3a and 6a were investigated following photoexcitation at room temperature. The magnetic properties of 3a, 4a, 5a and 6a were investigated at room temperature, the complexes exhibiting paramagnetic behaviour. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

    International Nuclear Information System (INIS)

    Lilova, Kristina I.; Navrotsky, Alexandra; Melot, Brent C.; Seshadri, Ram

    2010-01-01

    CoAl 2 O 4 , CoGa 2 O 4 , and their solid solution Co(Ga z Al 1-z ) 2 O 4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO.B 2 O 3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing. - Graphical abstract: Measured enthalpies of mixing of CoAl 2 O 4 -CoGa 2 O 4 solid solutions are close to zero but entropies of mixing reflect the complex cation distribution, so the system is not an ideal solution.

  15. Determination of standard Gibbs free energy of formation for Ca2P2O7 and Ca(PO3)2 from solid-state EMF measurements using yttria stabilised zirconia as solid electrolyte

    International Nuclear Information System (INIS)

    Sandstroem, Malin Hannah; Bostroem, Dan; Rosen, Erik

    2006-01-01

    The equilibrium reactions: 3Ca 2 P 2 O 7 (s)+6Ni(s)-bar 2Ca 3 (PO 4 ) 2 (s)+2Ni 3 P(s)+52O 2 (g) and 2Ca(PO 3 ) 2 (s)+6Ni(s)-bar Ca 2 P 2 O 7 (s)+2Ni 3 P(s)+52O 2 (g) were studied in the temperature range 890K to 1140K. The oxygen equilibrium pressures were determined using galvanic cells incorporating yttria stabilized zirconia as solid electrolyte. From the measured data and using the literature values of standard Gibbs free energy of formation for Ca 3 (PO 4 ) 2 and Ni 3 P, the following relationship of the standard Gibbs free energy of formation for Ca 2 P 2 O 7 and Ca(PO 3 ) 2 were calculated:Δ f G o (Ca 2 P 2 O 7 )+/-11/(kJ.mol -1 )=-3475.9+1.5441(T/K)-0.1051(T/K).ln(T/K)andΔ f G o (Ca(PO 3 ) 2 )+/-12/(kJ.mol -1 )=-3334.8+6.1561(T/K)-0.6950(T/K).ln(T/K)

  16. Direct formation of new, phase-stable, and photoactive anatase-type Ti1-2XNbXScXO2 solid solution nanoparticles by hydrothermal method

    International Nuclear Information System (INIS)

    Hirano, Masanori; Ito, Takaharu

    2008-01-01

    A new anatase phase of photoactive Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was directly formed as nanoparticles from precursor solutions of TiOSO 4 , NbCl 5 , and Sc(NO 3 ) 3 under mild hydrothermal conditions at 180 deg. C for 5 h using the hydrolysis of urea. With the increase of the content of niobium and scandium from X = 0 to 0.2, the lattice parameters a 0 and c 0 , the crystallite size, and the optical band gap of anatase gradually increased. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The anatase-type Ti 1-2X Nb X Sc X O 2 (X = 0.05) showed approximately two times and three times as high photocatalytic activity as those of the hydrothermal anatase-type pure TiO 2 and commercially available reference pure TiO 2 (ST-01), respectively. The anatase phase of Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) existed stably up to 900 deg. C during heat treatment in air. New rutile-type Ti 1-2X Nb X Sc X O 2 solid solutions are formed through the phase transformation. The starting temperature of anatase-to-rutile phase transformation for Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was delayed but its completing temperature was accelerated

  17. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

    Science.gov (United States)

    De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

    2014-03-28

    New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

  18. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce, Nd

    International Nuclear Information System (INIS)

    De Almeida, Lucie; Grandjean, Stephane; Abraham, Francis; Rivenet, Murielle; Patisson, Fabrice

    2014-01-01

    New hydrazinium lanthanide oxalates N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce (Ce-H_yO_x) and Nd (Nd- H_yO_x), were synthesized by hydrothermal reaction at 150 C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2_1/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Angstroms, β = 116.638(4) degrees, V = 2021.4(7) Angstroems"3, Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO_9 and NdO_8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm"-"1 confirms the coordination of N_2H_5"+ to the metal. These polyhedra are connected through μ"2 and μ"3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-H_yO_x) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO_2 and Ce_0_._5Nd_0_._5O_1_._7_5 are formed at low temperature from Ce-H_yO_x and CeNd-H_yO_x, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxy-mono-cyanamides Ln_2O_2CN_2 are formed. (authors)

  19. Monodisperse and core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln=Eu, Tb, Dy, Sm, Er, Ho, and Tm) spherical particles: A facile synthesis and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zhenhe, E-mail: xuzh056@163.com [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China); Feng, Bin [China National Aviation Fuel Group Corporation, Planning and Development Department, Beijing 100088 (China); Bian, Shasha; Liu, Tao; Wang, Mingli; Gao, Yu; Sun, Di; Gao, Xin [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China); Sun, Yaguang, E-mail: yaguangsun@yahoo.com.cn [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China)

    2012-12-15

    The core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles were realized by coating the Lu{sub 2}O{sub 3}:Ln{sup 3+} phosphors onto the surface of non-aggregated, monodisperse and spherical SiO{sub 2} particles by the Pechini sol-gel method. The as-synthesized products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray (EDX) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photolumiminescence (PL), and low-voltage cathodoluminescence (CL). The results indicate that the 800 Degree-Sign C annealed sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores, in spherical shape with a narrow size distribution. The as-obtained particles show strong light emission with different colors corresponding to different Ln{sup 3+} ions under ultraviolet-visible light excitation and low-voltage electron beams excitation, which have potential applications in fluorescent lamps and field emission displays. - Graphical Abstract: Representative SEM and TEM images of the core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Eu{sup 3+} particles; CIE chromaticity diagram showing the emission colors for SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+}; Multicolor emissions of SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles. Highlights: Black-Right-Pointing-Pointer The core-shell particles were realized by coating the phosphors onto the surface of SiO{sub 2} particles. Black-Right-Pointing-Pointer The sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores. Black-Right-Pointing-Pointer The particles show different light emission colors corresponding to Ln{sup 3+} ions. Black-Right-Pointing-Pointer They have potential applications in fluorescent lamps and field emission displays.

  20. Systematic evaluation of Co-free LnBaFe2O5+δ (Ln = Lanthanides or Y) oxides towards the application as cathodes for intermediate-temperature solid oxide fuel cells

    International Nuclear Information System (INIS)

    Chen Dengjie; Wang Fucun; Shi Huangang; Ran Ran; Shao Zongping

    2012-01-01

    Co-free oxides with a nominal composition of LnBaFe 2 O 5+δ , where Ln = La, Pr, Nd, Sm, Gd, and Y, were synthesized and phase structure, oxygen content, electronic conductivity, oxygen desorption, thermal expansion, microstructure and electrochemical performance were systematically investigated. Among the series of materials tested, LaBaFe 2 O 5+δ oxide showed the largest electronic conductivity and YBaFe 2 O 5+δ oxide had the smallest thermal expansion coefficient (TEC) of 14.6 × 10 −6 K −1 within a temperature range of 200–900 °C. All LnBaFe 2 O 5+δ oxides typically possess the TEC values smaller than 20 × 10 −6 K −1 . The oxygen content, electronic conductivity and TEC values are highly dependent on the cation size of the Ln 3+ dopant. The lowest electrode polarization resistance in air under open circuit voltage condition was obtained for SmBaFe 2 O 5+δ electrode and was approximately 0.043, 0.084, 0.196, 0.506 and 1.348 Ω cm 2 at 800, 750, 700, 650 and 600 °C, respectively. The SmBaFe 2 O 5+δ oxide also demonstrated the best performance after a cathodic polarization. A cell with a SmBaFe 2 O 5+δ cathode delivered peak power densities of 1026, 748, 462, 276 and 148 mW cm −2 at 800, 750, 700, 650 and 600 °C, respectively. The results suggest that certain LnBaFe 2 O 5+δ oxides have sufficient electrochemical performance to be promising candidates for cathodes in intermediate-temperature solid oxide fuel cells.

  1. Thermochemistry of rare earth doped uranium oxides Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} (Ln = La, Y, Nd)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lei; Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu

    2015-10-15

    Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10–50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO{sub 1.5}, UO{sub 2} and UO{sub 3} in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3} for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U{sup 5+}, U{sup 6+}, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements. - Highlights: • We synthesize, characterize Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} solid solutions (Ln = La, Y, Nd). • Formation enthalpies become more exothermic with increasing rare earth content. • Oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3}. • Direct calorimetric measurements are in good agreement with free energy data.

  2. 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

  3. A new continuous two-step molecular precursor route to rare-earth oxysulfides Ln2O2S

    International Nuclear Information System (INIS)

    De Crom, N.; Devillers, M.

    2012-01-01

    A continuous two-step molecular precursor pathway is designed for the preparation of rare-earth oxysulfides Ln 2 O 2 S (Ln=Y, La, Pr, Nd, Sm–Lu). This new route involves a first oxidation step leading to the rare-earth oxysulfate Ln 2 O 2 SO 4 which is subsequently reduced to the rare-earth oxysulfide Ln 2 O 2 S by switching to a H 2 –Ar atmosphere. The whole process occurs at a temperature significantly lower than usual solid state synthesis (T≤650 °C) and avoids the use of dangerous sulfur-based gases, providing a convenient route to the synthesis of the entire series of Ln 2 O 2 S. The molecular precursors consist in heteroleptic dithiocarbamate complexes [Ln(Et 2 dtc) 3 (phen)] and [Ln(Et 2 dtc) 3 (bipy)] (Et 2 dtc=N,N-diethyldithiocarbamate; phen=1,10-phenanthroline; bipy=2,2′-bipyridine) and were synthesized by a new high yield and high purity synthesis route. The nature of the molecular precursor determines the minimum synthesis temperature and influences therefore the purity of the final Ln 2 O 2 S crystalline phase. - Graphical abstract: A continuous two-step molecular precursor pathway was designed for the preparation of rare-earth oxysulfides Ln 2 O 2 S (Ln=Y, La, Pr, Nd, Sm–Lu), starting from heteroleptic dithiocarbamate complexes. The influence of the nature of the molecular precursor on the minimum synthesis temperature and on the purity of the final Ln 2 O 2 S crystalline phase is discussed. Highlights: ► A new high yield and high purity synthesis route of rare earth dithiocarbamates is described. ► These compounds are used as precursors in a continuous process leading to rare-earth oxysulfides. ► The oxysulfides are obtained under much more moderate conditions than previously described.

  4. Tricolor emission Ca3Si2O7:Ln (Ln=Ce, Tb, Eu) phosphors for near-UV white light-emitting-diode

    International Nuclear Information System (INIS)

    Mao, Zhi-yong; Zhu, Ying-chun; Gan, Lin; Zeng, Yi; Xu, Fang-fang; Wang, Yang; Tian, Hua; Li, Jian; Wang, Da-jian

    2013-01-01

    Tricolor emission in a same Ca 3 Si 2 O 7 host with independent Ln (Ln=Ce 3+ , Eu 2+ , Tb 3+ ) dopants is demonstrated to construct a near-UV white light emitting diode (LED). The luminescence properties and thermal quenching properties, as well as the applications in near-UV white LED are investigated. These phosphors show typical blue, red, and green, three-basal-color, luminescence in the CIE chromaticity diagram for Ce 3+ , Eu 2+ and Tb 3+ dopants, respectively. Thermal quenching properties show that the luminescence thermal stability strongly depends on the different dopant types; better thermal quenching property of Ce 3+ and Tb 3+ is recorded in comparison with that of Eu 2+ . The white LED prototype fabricated with near-UV chip and as-prepared tricolor phosphors exhibits acceptable CIE chromaticity coordinates (0.32, 0.30) with a CCT of 6000 K and a CRI of 87, indicating the potential application of Ca 3 Si 2 O 7 :Ln phosphors in near-UV white LED. - Highlights: ► Tricolor Ca 3 Si 2 O 7 : Ln phosphors were demonstrated to construct near-UV white LED. ► Eu 2+ doped Ca 3 Si 2 O 7 red-emitting phosphor was confirmed by this work once again. ► Thermal quenching properties for Ca 3 Si 2 O 7 :Ln phosphors were reported for the first time. ► Performances of fabricated white LED indicated the potential application of phosphors.

  5. XPS study of the Ln 5p,4f-electronic states of lanthanides in Ln2O3

    International Nuclear Information System (INIS)

    Teterin, Yu.A.; Teterin, A.Yu.; Utkin, I.O.; Ryzhkov, M.V.

    2004-01-01

    The present work analyses the fine structure of the low binding energy (E b , 0-50 eV) X-ray photoelectron spectra XPS of lanthanide (La through Lu excepted for Pm) oxides, and compares it with the non-relativistic X α -discrete variation calculation results for the clusters reflecting the close environment of lanthanides in oxides. The obtained results show that the Ln 4f n -electrons of lanthanides in oxides by their spectral parameters have much in common with the M 3d-electrons in oxides of the 3d-transition metals. According to these data, the Ln 4f shell of lanthanides is rather outer and can participate in the formation of molecular orbitals in compounds. The XPS data at least do not contradict the theoretical suggestion about the significant participation of the Ln 4f-electrons in formation of the molecular orbitals in the studied materials. The spectra in the Ln 5p-O 2s binding energy region of the studied lanthanide oxides were found to exhibit the complicated structure instead of separated peaks due to the electrons of the Ln 5p 3/2,5/2 and O 2s atomic shells. Taking into account the energy differences between the inner (Ln 3d) and outer (Ln 5p) electronic shells for some metallic lanthanides and their oxides, the Ln 5p atomic shells were shown to participate in the formation of the inner valence molecular orbitals (IVMO). That agrees qualitatively with the calculation results

  6. 2-D and 3-D phosphotungstate-based TM-Ln heterometallic derivatives constructed from dimeric [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} fragments and copper-organic complex linkers

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Sensen [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Zhao, Junwei, E-mail: zhaojunwei@henu.edu.cn [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Chen, Lijuan [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Basic Experiment Teaching Center, Henan University, Kaifeng, Henan 475004 (China); Li, Yuye; Zhang, Jingli; Li, Yanzhou [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Niu, Jingyang, E-mail: jyniu@henu.edu.cn [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

    2012-12-15

    Three organic-inorganic hybrid TM-Ln heterometallic phosphotungstates [Cu(dap){sub 2}(H{sub 2}O)][Cu(dap){sub 2}]{sub 3.5}[La({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (1) [Cu(dap){sub 2}(H{sub 2}O)]{sub 0.5}[Cu(dap){sub 2}]{sub 4}[Nd({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}4H{sub 2}O (2) and [Cu(dap){sub 2}(H{sub 2}O)]{sub 2}[Cu(dap){sub 2}]{sub 3.5}[Eu({alpha}-PW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (3) (dap=1,2-diaminopropane) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common features are that 1-3 all consist of asymmetric sandwich-type subunits [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} and [Cu(dap){sub 2}]{sup 2+} bridges. Both 1 and 2 display the 2-D (4,4)-topological sheets whereas 3 exhibits the 3-D 5-connected (4{sup 6}{center_dot}6{sup 4}) topological framework. The magnetic properties of 2 and 3 and the luminescence performance of 3 have been measured. - Graphical Abstract: Three TM-Ln heterometallic phosphotungstates 1-3 have been synthesized and characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, X-ray diffraction, thermogravimetric analyses magnetic susceptibility and luminescent properties. Highlights: Black-Right-Pointing-Pointer Cu{sup II}-Ln{sup III} heterometallic polyoxometalates. Black-Right-Pointing-Pointer 2-D and 3-D organic-inorganic hybrid phosphotungstates. Black-Right-Pointing-Pointer 2-D and 3-D structures consisting of Cu{sup II}-Ln{sup III} heterometals.

  7. 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.

  8. Red emitting phosphors of Eu{sup 3+} doped Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y) for white light emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Niumiao [National Key Laboratory of Photoelectric Technology and Functional Materials Culture Base in Shaanxi Province, National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Institute of Photonics & Photon-Technology, Northwest University, Xi’an 710069 (China); Guo, Chongfeng, E-mail: guocf@nwu.edu.cn [National Key Laboratory of Photoelectric Technology and Functional Materials Culture Base in Shaanxi Province, National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Institute of Photonics & Photon-Technology, Northwest University, Xi’an 710069 (China); Yin, Luqiao; Zhang, Jianhua [Key Laboratory of Advanced Display and System Applications (Shanghai University), Ministry of Education, Shanghai 200072 (China); Wu, Mingmei, E-mail: ceswmm@mail.sysu.edu.cn [School of Chemistry and Chemical Engineering, Sun Yat-Sen University, No. 135, Xingang Xi Road, Guangzhou 510275 (China)

    2015-06-25

    Highlights: • Layered red phosphors Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y):Eu{sup 3+} were prepared. • The synthesis parameters of phosphors were optimized. • PL and thermal stability of the samples were investigated. • LED devices were also fabricated including the present red phosphor. - Abstract: A series of Eu{sup 3+} doped Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y) red-emitting phosphors for application in ultraviolet based light emitting diodes (LEDs) were successfully synthesized by a modified sol–gel method. Their structure and luminescent properties were characterized by powder X-ray diffraction (XRD), photoluminescence excitation (PLE) and emission (PL) spectra and absorption spectra, according to these results the optimal compositions and synthesis parameters were determined. In addition, the thermal stabilities of the phosphors were investigated according to the temperature-dependent PL spectra. The red and white-LEDs (W-LEDs) comprising the Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10}:Eu{sup 3+} (Ln = Gd, Y) red emitting phosphors were fabricated with a near-ultraviolet (n-UV) chip. In comparison with Na{sub 2}Y{sub 1.4}Eu{sub 0.6}Ti{sub 3}O{sub 10}, the Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} phosphor offers higher brightness, quantum efficiency, and excellent thermal stability. W-LEDs comprising Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} showed bright white emission with a color rendering index (Ra) of 82, a color temperature of 2151 K, and Commission Internationale de I’Eclairage (CIE) color coordinates of (0.34, 0.37). The phosphor Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} is more suitable candidate for application in LEDs.

  9. Host-sensitized luminescence properties in CaNb2O6:Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) phosphors with abundant colors.

    Science.gov (United States)

    Li, Kai; Liu, Xiaoming; Zhang, Yang; Li, Xuejiao; Lian, Hongzhou; Lin, Jun

    2015-01-05

    A series of Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f-f transitions of Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) samples. They show both host emission and respective emission lines derived from the characteristic f-f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) demonstrate the energy transfer from the hosts to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+). The energy transfer mechanisms in CNO:Eu(3+)/Tb(3+)/Dy(3+) phosphors have been determined to be a resonant type via dipole-dipole mechanisms. For CNO:Sm(3+), the metal-metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu(3+)/Tb(3+)/Dy(3+) samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy(3+). The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.

  10. Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

    Science.gov (United States)

    Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

    2008-02-04

    New heterospin complexes have been obtained by combining the binuclear complexes [{Cu(H(2)O)L(1)}Ln(O(2)NO)(3)] or [{CuL(2)}Ln(O(2)NO)(3)] (L(1) = N,N'-propylene-di(3-methoxysalicylideneiminato); L(2) = N,N'-ethylene-di(3-methoxysalicylideneiminato); Ln = Gd(3+), Sm(3+), Tb(3+)), with the mononuclear [CuL(1)(2)] and the nickel dithiolene complexes [Ni(mnt)(2)](q)- (q = 1, 2; mnt = maleonitriledithiolate), as follows: (1)infinity[{CuL(1)}(2)Ln(O(2)NO){Ni(mnt)(2)}].Solv.CH(3)CN (Ln = Gd(3+), Solv = CH(3)OH (1), Ln = Sm(3+), Solv = CH(3)CN (2)) and [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)][Ni(mnt)(2)] (3) with [Ni(mnt)2]2-, [{(CH(3)CN)CuL(1)}(2)Ln(H(2)O)][Ni(mnt)(2)]3.2CH(3)CN (Ln = Gd(3+) (4), Sm(3+) (5), Tb(3+) (6)), and [{(CH(3)OH)CuL(2)}{CuL(2)}Gd(O(2)NO){Ni(mnt)(2)}][Ni(mnt)(2)].CH(2)Cl(2) (7) with [Ni(mnt))(2]*-. Trinuclear, almost linear, [CuLnCu] motifs are found in all the compounds. In the isostructural 1 and 2, two trans cyano groups from a [Ni(mnt)2]2- unit bridge two trimetallic nodes through axial coordination to the Cu centers, thus leading to the establishment of infinite chains. 3 is an ionic compound, containing discrete [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)](2+) cations and [Ni(mnt)(2)](2-) anions. Within the series 4-6, layers of discrete [CuLnCu](3+) motifs alternate with stacks of interacting [Ni(mnt)(2)](*-) radical anions, for which two overlap modes, providing two different types of stacks, can be disclosed. The strength of the intermolecular interactions between the open-shell species is estimated through extended Hückel calculations. In compound 7, [Ni(mnt)(2)](*-) radical anions coordinate group one of the Cu centers of a trinuclear [Cu(2)Gd] motif through a CN, while discrete [Ni(mnt)(2)](*-) units are also present, overlapping in between, but also with the coordinated ones. Furthermore, the [Cu(2)Gd] moieties dimerize each other upon linkage by two nitrato groups, both acting as chelate toward the gadolinium ion from one unit and monodentate toward a

  11. Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen)2(L)3(HL)]·H2O [Ln = La, Ce; Phen = Phenanthroline; HL = Salicylic Acid

    International Nuclear Information System (INIS)

    Iravani, Effat; Nami, Navabeh; Nabizadeh, Fatemeh; Bayani, Elham; Neumueller, Bernhard

    2013-01-01

    The reaction of LnCl 3 ·7H 2 O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 .deg. C in H 2 O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen) 2 (L) 3 (HL)]·H 2 O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln 3+ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln 3+ ). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln 2 O 3

  12. Synthesis, structure, and polymorphism of A{sub 3}LnSi{sub 2}O{sub 7} (A=Na, K; Ln=Sm, Ho, Yb)

    Energy Technology Data Exchange (ETDEWEB)

    Latshaw, Allison M.; Yeon, Jeongho; Smith, Mark D.; Loye, Hans-Conrad zur, E-mail: zurloye@mailbox.sc.edu

    2016-03-15

    Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family, K{sub 3}SmSi{sub 2}O{sub 7}, Na{sub 3}HoSi{sub 2}O{sub 7}, and two polymorphs of Na{sub 3}YbSi{sub 2}O{sub 7}, are reported. K{sub 3}SmSi{sub 2}O{sub 7} crystallizes in the hexagonal space group P6{sub 3}/mcm, Na{sub 3}HoSi{sub 2}O{sub 7} and Na{sub 3}YbSi{sub 2}O{sub 7} crystallize in the hexagonal space group P6{sub 3}/m, and Na{sub 3}YbSi{sub 2}O{sub 7} crystallizes in the trigonal space group P31c. The Na{sub 3}YbSi{sub 2}O{sub 7} composition that crystallizes in P31c is a new structure type. The magnetic properties for the Ho and Yb analogs are reported. - Graphical abstract: The different structure types and polymorphs of the A{sub 3}LnSi{sub 2}O{sub 7} family reported. - Highlights: • Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family are presented. • Na{sub 3}YbSi{sub 2}O{sub 7} is reported as two polymorphs, one is a new structure type. • Crystals synthesized out of molten fluoride fluxes.

  13. Hierarchical domain structure of lead-free piezoelectric (Na{sub 1/2} Bi{sub 1/2})TiO{sub 3}-(K{sub 1/2} Bi{sub 1/2})TiO{sub 3} single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Chengtao, E-mail: lchentao@vt.edu; Wang, Yaojin; Ge, Wenwei; Li, Jiefang; Viehland, Dwight [Materials Science and Engineering, Virginia Tech, Blacksburg, Virginia 24061 (United States); Delaire, Olivier [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Li, Xiaobin; Luo, Haosu [Shanghai Institute of Ceramics, Chinese Academy of Sciences, 215 Chengbei Road, Jiading, Shanghai 201800 (China)

    2016-05-07

    We report a unique hierarchical domain structure in single crystals of (Na{sub 1/2}Bi{sub 1/2})TiO{sub 3}-xat. %(K{sub 1/2}Bi{sub 1/2})TiO{sub 3} for x = 5 and 8 by transmission electron microscopy (TEM). A high density of polar nano-domains with a lamellar morphology was found, which were self-assembled into a quadrant-like configuration, which then assembled into conventional ferroelectric macro-domains. Studies by high resolution TEM revealed that the polar lamellar regions contained a coexistence of in-phase and anti-phase oxygen octahedral tilt regions of a few nanometers in size. Domain frustration over multiple length scales may play an important role in the stabilization of the hierarchy, and in reducing the piezoelectric response of this Pb-free piezoelectric solid solution.

  14. Comparative investigation of the solution species [U(CO3)5]6- and the crystal structure of Na6[U(CO3)5].12H2O.

    Science.gov (United States)

    Hennig, Christoph; Ikeda-Ohno, Atsushi; Emmerling, Fanziska; Kraus, Werner; Bernhard, Gert

    2010-04-21

    The limiting U(IV) carbonate species in aqueous solution was investigated by comparing its structure parameters with those of the complex preserved in a crystal structure. The solution species prevails in aqueous solution of 0.05 M U(IV) and 1 M NaHCO(3) at pH 8.3. Single crystals of Na(6)[U(CO(3))(5)].12H(2)O were obtained directly from this mother solution. The U(IV) carbonate complex in the crystal structure was identified as a monomeric [U(CO(3))(5)](6-) anionic complex. The interatomic distances around the U(IV) coordination polyhedron show average distances of U-O = 2.461(8) A, U-C = 2.912(4) A and U-O(dist) = 4.164(6) A. U L(3)-edge EXAFS spectra were collected from the solid Na(6)[U(CO(3))(5)].12H(2)O and the corresponding solution. The first shell of the Fourier transforms (FTs) revealed, in both samples, a coordination of ten oxygen atoms at an average U-O distance of 2.45 +/- 0.02 A, the second shell originates from five carbon atoms with a U-C distance of 2.91 +/- 0.02 A, and the third shell was fit with single and multiple scattering paths of the distal oxygen at 4.17 +/- 0.02 A. These data indicate the identity of the [U(CO(3))(5)](6-) complex in solid and solution state. The high negative charge of the [U(CO(3))(5)](6-) anion is compensated by Na(+) cations. In solid state the Na(+) cations form a bridging network between the [U(CO(3))(5)](6-) units, while in liquid state the Na(+) cations seem to be located close to the anionic complex. The average metal-oxygen distances of the coordination polyhedron show a linear correlation to the radius contraction of the neighbouring actinide(IV) ions and indicate the equivalence of the [An(CO(3))(5)](6-) coordination within the series of thorium, uranium, neptunium and plutonium.

  15. Presence of a monoclinic (Pm) phase in the morphotropic phase boundary region of multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution: A Rietveld study

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Rishikesh, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in; Singh, Akhilesh Kumar, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in [School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India)

    2014-07-28

    We present here the results of structural studies on multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution using Rietveld analysis on powder x-ray diffraction data in the composition range 0.35 ≤ x ≤ 0.55. The stability region of various crystallographic phases at room temperature for (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} is determined precisely. Structural transformation from pseudo-cubic (x ≤ 0.40) to tetragonal (x ≥ 0.50) phase is observed via phase coexistence region demarcating the morphotropic phase boundary. The morphotropic phase boundary region consists of coexisting tetragonal and monoclinic structures with space group P4mm and Pm, respectively, stable in composition range 0.41 ≤ x ≤ 0.49 as confirmed by Rietveld analysis. The results of Rietveld analysis completely rule out the coexistence of rhombohedral and tetragonal phases in the morphotropic phase boundary region reported by earlier workers. A comparison between the bond lengths for “B-site cations-oxygen anions” obtained after Rietveld refinement, with the bond length calculated using Shannon-Prewitt ionic radii, reveals the ionic nature of B-O (Ni/Ti-O) bonds for the cubic phase and partial covalent character for the other crystallographic phases.

  16. Near-infrared photoluminescence in La0.98AlO3: 0.02Ln3+(Ln = Nd/Yb) for sensitization of c-Si solar cells

    Science.gov (United States)

    Sawala, N. S.; Koparkar, K. A.; Bajaj, N. S.; Omanwar, S. K.

    2016-05-01

    The host matrix LaAlO3 was synthesized by conventional solid state reaction method in which the Nd3+ ions and Yb3+ ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd3+ ion doped LaAlO3 converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb3+ ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La0.98AlO3: 0.02Ln3+(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

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

    Science.gov (United States)

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

    2015-10-01

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

  18. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    Science.gov (United States)

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

  19. Solid solutions on the base of CuCr2Se4 and CUsUb(1/2)Insub(1/2)Crsub(2)Sesub(4)

    International Nuclear Information System (INIS)

    Smirnov, S.G.; Rozantsev, A.V.; Kesler, Ya.A.; Gordeev, I.V.; Tret'yakov, Yu.D.

    1983-01-01

    The CuCr 2 Se 4 interaction with Cusub(1/2)Insub(1/2)Crsub(2)Sesub(4) for determining the fields of solid solutions existence and studying their crystallochemical properties is investigated. Solid solutions of the (1-x)Cusub(1/2)Insub(1/2)Crsub(2)Sesub(4)xxCuCrsub(2)Sesub(4) are prepared, two limited regions of solid solutions of spinel type at 0 <= x <= 0.2 and 0.8 <= x <= 1 are determined. X-ray radiography investigation of synthesized solid solutions is carried out. It has been found that at 0 <= x <= 0.2 solid solutions are crystallized in the ordered spinel structure F anti 43m

  20. 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.

  1. Crystal structure and magnetic properties of the solid-solution phase Ca3Co2-v Sc v O6

    International Nuclear Information System (INIS)

    Hervoches, Charles H.; Fredenborg, Vivian Miksch; Kjekshus, Arne; Fjellvag, Helmer; Hauback, Bjorn C.

    2007-01-01

    The two crystallographically non-equivalent Co atoms of the quasi-one-dimensional crystal structure of Ca 3 Co 2 O 6 form chains with alternating, face-sharing polyhedra of Co2O 6 trigonal prisms and Co1O 6 octahedra. This compound forms a substitutional solid-solution phase with Sc, in which the Sc atoms enter the Co2 sublattice exclusively. The homogeneity range of Ca 3 Co 2- v Sc v O 6 (more specifically Ca 3 Co1Co2 1- v Sc v O 6 ) extends up to v∼0.55. The crystal structure belongs to space group R3-barc with lattice parameters (in hexagonal setting): 9.0846(3)≤a≤9.1300(2) A and 10.3885(4)≤c≤10.4677(4) A. The magnetic moment decreases rapidly with increasing amount of the non-magnetic Sc solute in the lattice. - Graphical abstract: The quasi-one-dimensional Ca 3 Co 2 O 6 phase forms a substitutional solid-solution system with Sc, in which the Sc atoms enter the Co2 sublattice exclusively. The homogeneity range of Ca 3 Co 2- v Sc v O 6 extends up to v∼0.55. The magnetic moment decreases rapidly with increasing amount of the non-magnetic Sc solute in the lattice

  2. Low-Temperature Transformations of Protonic Forms of Layered Complex Oxides HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd)

    International Nuclear Information System (INIS)

    Abdulaeva, L.D.; Silyukov, O.I.; Zvereva, I.A.; Petrov, Yu.V.

    2013-01-01

    In the present work protonic forms of layered Ruddlesden-Popper oxides HLnTiO 4 and H 2 Ln 2 Ti 3 O 10 (Ln = La, Nd) were used as the starting point for soft chemistry synthesis of two series of perovskite-like compounds by acid leaching and exfoliation, promoted by vanadyl sulfate. The last route leads to the nano structured VO 2+ containing samples. Characterization by SEM, powder XRD, and TGA has been performed for the determination of the structure and composition of synthesized oxides

  3. Phase transition of the orthorhombic fluorite-related compounds Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, Eu)

    Energy Technology Data Exchange (ETDEWEB)

    Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.j [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro; Nishimine, Hiroaki; Wakeshima, Makoto [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Sato, Mineo [Department of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181 (Japan)

    2009-12-04

    Rare earth iridium oxides Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) were prepared and their structures were determined by X-ray diffraction measurements. At room temperature, Pr{sub 3}IrO{sub 7} crystallized in an orthorhombic superstructure of cubic fluorite with space group Cmcm. The differential thermal analysis (DTA) and specific heat measurements for Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) showed a phase transition at 262, 342, 420, and 485 K, respectively. At low temperatures, Ln{sub 3}IrO{sub 7} crystallized in a monoclinic structure with the space group P2{sub 1}/n. The transition temperatures increased with decreasing the ionic radius of rare earths, which indicates that the transition is stress-induced and occurs with the lattice contraction on cooling. These results for Ln{sub 3}IrO{sub 7} were compared with the phase transitions observed for Ln{sub 3}MoO{sub 7}, Ln{sub 3}RuO{sub 7}, Ln{sub 3}ReO{sub 7}, and Ln{sub 3}OsO{sub 7}.

  4. Stress relaxation of La1/2Sr1/2MnO3 and La2/3Ca1/3MnO3 at solid oxide fuel cell interfaces

    International Nuclear Information System (INIS)

    Lussier, A.; Dvorak, J.; Stadler, S.; Holroyd, J.; Liberati, M.; Arenholz, E.; Ogale, S.B.; Wu, T.; Venkatesan, T.; Idzerda, Y.U.

    2008-01-01

    Interfacial stress is thought to have significant effects on electrical and oxygen transport properties in thin films of importance in solid oxide fuel cell applications. We investigate how in-plane biaxial stress modifies the electronic structure of La 2/3 Ca 1/3 MnO 3 and La 1/2 Sr 1/2 MnO 3 thin films prepared by pulsed laser deposition on three different substrates to vary the in-plane stress from tensile to compressive. The electronic structure was probed by X-ray absorption spectroscopy of the Mn L 2,3 -edge to characterize the interfacial disruption in this region in an element-specific, site-specific manner. The compressive or tensile interfacial strain modifies the relative concentrations of La and Sr in the interfacial region in order to achieve a better lattice match to the contact material. This atomic migration generates an interfacial region dominated by a compound with a single valency for the transition metal ion, resulting in a severe barrier to oxygen and electron transport through this region

  5. Physicochemical investigation of Bi2MoO6 solid-phase interaction with Sm2MoO6

    International Nuclear Information System (INIS)

    Khajkina, E.G.; Kovba, L.M.; Bazarova, Zh.G.; Khal'baeva, K.M.; Khakhinov, V.V.; Mokhosoev, M.V.

    1986-01-01

    Bi 2 MoO 6 -Sm 2 MoO 6 interaction in the temperature range of 700-1000 deg C is studied using X-ray phase analysis and vibrational spectroscopy. Formation of monoclinic solid solutions based on γ'-Bi 2 MoO 6 and B 2-x Sm x MoO 6 varied composition phase with α-Ln 2 MoO 6 structure which homogeneity region extent at 1000 deg C constitutes ∼ 50 mol % (0.7≤x≤1.7) is stated. Crystallographic characteristics of the synthesized phases are determined

  6. Preparation, structural, dielectric and magnetic properties of LaFeO3–PbTiO3 solid solutions

    International Nuclear Information System (INIS)

    Ivanov, S.A.; Tellgren, R.; Porcher, F.; Ericsson, T.; Mosunov, A.; Beran, P.; Korchagina, S.K.; Kumar, P. Anil; Mathieu, R.; Nordblad, P.

    2012-01-01

    Highlights: ► Solid-solutions of (1−x)LaFeO 3 –(x)PbTiO 3 were synthesized by solid-state reaction. ► XRPD and NPD evidence orthorhombic (x 0.8) crystal structures. ► LaFeO 3 -rich compositions order antiferromagnetically (x 3 -rich compositions exhibit ferroelectric order (x larger than 0.8). ► Magnetic and dielectric (relaxor) ordering coexist near room-temperature around x = 0.4. -- Abstract: Solid solutions of (1−x)LaFeO 3 –(x)PbTiO 3 (0 3+ cations in the B-site with propagation vector k = (0,0,0). Based on the obtained experimental data, a combined structural and magnetic phase diagram has been constructed. The factors governing the structural, dielectric and magnetic properties of (1−x)LaFeO 3 –(x)PbTiO 3 solid solutions are discussed, as well as their possible multiferroicity.

  7. In pursuit of the rhabdophane crystal structure: from the hydrated monoclinic LnPO{sub 4}.0.667H{sub 2}O to the hexagonal LnPO{sub 4} (Ln = Nd, Sm, Gd, Eu and Dy)

    Energy Technology Data Exchange (ETDEWEB)

    Mesbah, Adel, E-mail: adel.mesbah@cea.fr [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Clavier, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Elkaim, Erik [Synchrotron SOLEIL, L' Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Szenknect, Stéphanie; Dacheux, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France)

    2017-05-15

    The dehydration process of the hydrated rhabdophane LnPO{sub 4}.0.667H{sub 2}O (Ln = La to Dy) was thoroughly studied over the combination of in situ high resolution synchrotron powder diffraction and TGA experiments. In the case of SmPO{sub 4}.0.667H{sub 2}O (monoclinic, C2), a first dehydration step was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2) with Z =12 and a =17.6264(1) Å, b =6.9704(1) Å, c =12.1141(1) Å, β=133.74(1) °, V =1075.33(1) Å{sup 3}. In agreement with the TGA and dilatometry experiments, all the water molecules were evacuated above 220 °C yielding to the anhydrous form, which crystallizes in the hexagonal P3{sub 1}21 space group with a =7.0389(1) Å, c =6.3702(1) Å and V =273.34(1) Å{sup 3}. This study was extended to selected LnPO{sub 4}.0.667H{sub 2}O samples (Ln= Nd, Gd, Eu, Dy) and the obtained results confirmed the existence of two dehydration steps before the stabilization of the anhydrous form, with the transitory formation of LnPO{sub 4}.0.5H{sub 2}O. - Graphical abstract: The dehydration process of the rhabdophane SmPO{sub 4}.0.667H{sub 2}O was studied over combination of in situ high resolution synchrotron powder diffraction and TGA techniques, a first dehydration was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2). Then above 220 °C, the anhydrous form of the rhabdophane SmPO{sub 4} was stabilized and crystallizes in the hexagonal P3{sub 1}21 space group. - Highlights: • In situ synchrotron powder diffraction was carried out during the dehydration of the rhabdopahe LnPO{sub 4}.0.667H{sub 2}O. • The heat of the rhabdophane LnPO{sub 4}.0.667H{sub 2}O leads to LnPO{sub 4}.0.5H{sub 2}O then to anhydrous rhabdophane LnPO{sub 4}. • LnPO{sub 4}.0.5H{sub 2}O (monoclinic, C2) and LnPO{sub 4} (Hexagonal, P3{sub 1}21) were solved over the use of direct methods.

  8. Composition dependent room temperature structure, electric and magnetic properties in magnetoelectric Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3}−Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3} solid-solutions

    Energy Technology Data Exchange (ETDEWEB)

    Matteppanavar, Shidaling [Department of Physics, Jnanabharathi Campus, Bangalore University, Bangalore, 560056 (India); Rayaprol, Sudhindra [UGC-DAE-Consortium for Scientific Research, Mumbai Centre, B A R C Campus, Mumbai, 400085 (India); Angadi, Basavaraj, E-mail: brangadi@gmail.com [Department of Physics, Jnanabharathi Campus, Bangalore University, Bangalore, 560056 (India); Sahoo, Balaram [Materials Research Centre, Indian Institute of Science, Bangalore, 560012 (India)

    2016-08-25

    We report on the studies of room temperature (RT) crystal structure, electric and magnetic properties of (1−x) Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} – x Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3} (PFN{sub 1−x} – PFW{sub x}) (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) solid solutions through the measurements of X-ray diffraction, FTIR, scanning electron microscopy (SEM), Neutron diffraction, Raman, Magnetic, Mössbauer and ferroelectric measurements. FTIR spectra showed two main perovskite related transmission bands. The SEM analysis shows an average grain size of 2 μm for all the solid solutions. Rietveld refinement was performed on RT X-ray diffraction (XRD) and neutron diffraction (ND), which reveals, the monoclinic phase for x = 0.0 with space group Cm and Cubic phase for x = 1.0 with space group Pm-3m. In other words, increasing x, the samples exhibit a gradual phase transition from monoclinic to cubic. In addition, the Raman spectroscopy corroborates the change in structural symmetry from monoclinic (Cm) to cubic (Pm-3m) on varying x. The coexistence of both monoclinic and cubic symmetries was observed between x = 0.2–0.8. Magnetic measurements shows that, the magnetic phase transition from paramagnetic to antiferromagnetic (AFM) was observed at or above RT for x = 0.6 and above. The magnetic structure was refined using the propagation vector k = (½, ½, ½) and structure was found to be G-type antiferromagnetic. Magnetic properties (M-H loops) shows, a weak ferromagnetic behaviour with antiferromagnetic ordering at RT. At RT, x = 0.0–0.6 the samples exhibits disordered paramagnetic property but weakly coupled with antiferromagnetic domains. But, x = 0.8 and 1.0 samples show antiferromagnetic and they are weakly coupled with paramagnetic domains. The temperature dependent magnetization (M(T)) confirms, the augmentation of Néel temperature (T{sub N}) from 155 K to 350 K on increasing x. Mössbauer spectroscopy confirms superparamagnetic nature with the presence of

  9. Observation of Vacancies, Faults, and Superstructures in Ln5Mo2O12 (Ln = La, Y, and Lu) Compounds with Direct Mo-Mo Bonding.

    Science.gov (United States)

    Colabello, Diane M; Sobalvarro, Elizabeth M; Sheckelton, John P; Neuefeind, Joerg C; McQueen, Tyrel M; Khalifah, Peter G

    2017-11-06

    Among oxide compounds with direct metal-metal bonding, the Y 5 Mo 2 O 12 (A 5 B 2 O 12 ) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2 O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal-metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal-metal bonding have integer oxidation states resulting from the lifting of orbital degeneracy typically induced by the metal-metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5 Mo 2 O 12 (Ln = La-Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2 O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1-2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5 Mo 2 O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. This represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one

  10. Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen){sub 2}(L){sub 3}(HL)]·H{sub 2}O [Ln = La, Ce; Phen = Phenanthroline; HL = Salicylic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Iravani, Effat [UNiv. of Applied Science and Technology, Tehran (Iran, Islamic Republic of); Nami, Navabeh; Nabizadeh, Fatemeh; Bayani, Elham [Islamic Azad Univ., Mazandaran (Iran, Islamic Republic of); Neumueller, Bernhard [Philipps-Universitat Marburg, Marburg (Germany)

    2013-11-15

    The reaction of LnCl{sub 3}·7H{sub 2}O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 .deg. C in H{sub 2}O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen){sub 2}(L){sub 3}(HL)]·H{sub 2}O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln{sup 3+} ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln{sup 3+}). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln{sub 2}O{sub 3}.

  11. Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln = Nd, Gd, Er) at high pressure.

    Science.gov (United States)

    Turner, Katlyn M; Tracy, Cameron L; Mao, Wendy L; Ewing, Rodney C

    2017-11-09

    Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln=Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare it to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant property that influences their compression response. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the O> bond in stannate pyrochlore is more covalent than the O> bonds in titanates, zirconate, and hafnates. In stannates, the pyrochlore cation and anion sublattices begin to disorder at 0.3 GPa. The extent of sublattice disorder vs. pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to a cotunnite-like structure (Pnma) at ~28 GPa; similar transitions have been observed in titanate, zirconate, and hafnate pyrochlore at varying pressures with cation radius ratio. The extent of the phase transition vs. pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multiscale defect-fluorite + weberite structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlore treated to similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B0, of stannates varies linearly and inversely with cation radius ratio. The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates, and suggest that the size of the Ln3+ cation is a primary determining factor of B0. Additionally, when normalized to rA/rB, the bulk moduli of stannates are comparable to those of zirconates and hafnates, which vary from titanates. Our results suggest that the cation radius ratio strongly influences the bulk moduli of stannates as well as

  12. First-Principles Modeling of ThO2 Solid Solutions with Oxides of Trivalent Cations

    Science.gov (United States)

    Alexandrov, Vitaly; Asta, Mark; Gronbech-Jensen, Niels

    2010-03-01

    Solid solutions formed by doping ThO2 with oxides of trivalent cations, such as Y2O3 and La2O3, are suitable for solid electrolyte applications, similar to doped zirconia and ceria. ThO2 has also been gaining much attention as an alternative to UO2 in nuclear energy applications, the aforementioned trivalent cations being important fission products. In both cases the mixing energetics and short-range ordering/clustering are key to understanding structural and transport properties. Using first-principles atomistic calculations, we address intra- and intersublattice interactions for both cation and anion sublattices in ThO2-based fluorite-type solid solutions and compare the results with similar modeling studies for related trivalent-doped zirconia systems.

  13. Synthesis, characterization and thermal expansion studies on ThO2-SmO1.5 solid solutions

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Antony, M.P.

    2008-01-01

    Full text: A highly homogeneous Th 1-x Sm x O 2 ; 0 ≤ x ≤ 0.8 solid solutions were synthesized by co-precipitation technique and the co-precipitated samples were sintered at 1473 K. Compositions of the solid solutions were characterized by standard wet-chemical analysis. X-ray diffraction measurements were performed in the sintered pellets for structural analysis, lattice parameter calculation and determination of solid solubility of SmO 1.5 in ThO 2 matrix. Bulk and theoretical densities of solid solutions were also determined. A fluorite structure was observed for ThO 2 -SmO 1.5 solid solutions with 0-55.2 mol % SmO 1.5 . Their thermal expansion coefficients were measured using high temperature X-ray diffraction technique. The mean linear thermal expansivity, αm for ThO 2 -SmO 1.5 solid solutions containing 17.9, 41.7 and 52.0 mole percent of SmO 1.5 were determined in the temperature range 298 to 2000 K for the first time. The mean linear thermal expansion coefficients for ThO 2 -SmO 1.5 solid solutions are 10.47x10 -6 K -1 , 11.16x10 -6 K -1 and 11.45x10 -6 K -1 , respectively. The percentage linear thermal expansion in this temperature range, for ThO 2 -SmO 1.5 solid solutions containing 17.9, 41.7 and 52.0 mol % SmO 1.5 are 1.82,1.94 and 1.99 respectively. It is suggested that the solid solutions are stable up to 2000 K. It is also suggested that the effect and nature of the dopant are the important parameters influenced in the thermal expansion of the ThO 2

  14. Structural, magnetic and electronic properties of rare earth ternary oxides Li Ln(II) 2 Ln(III)O4

    International Nuclear Information System (INIS)

    Malki, M.

    1987-06-01

    Properties of a new class of rare earth ternary oxides Li Ln(II) 2 Ln(III)O 4 where Ln(II) is a divalent metal (Sr, Eu) and Ln(III) a trivalent rare earth (Eu, Gd, Dy, Er and Y). These orthorhombic compounds (type Li Eu 3 O 4 ) allow the study of many magnetic phenomena and their evolution in function of the nature of Ln(II) and Ln(III): diamagnetic ions Sr 2+ , Y 3+ ; isotrope magnetic ions: Eu 2+ , Gd 3+ and anisotrope magnetic ions Dy 3+ , Er 3+ . Magnetic and electric properties are obtained by classical techniques and from hyperfine interaction by Moessbauer spectroscopy. The possibility to use several Moessbauer resonance (nuclei Eu 151, Gd 155, Dy 161 and Er 166) completes informations obtained by the macroscopic study [fr

  15. Host-Sensitized and Tunable Luminescence of GdNbO4:Ln3+ (Ln3+ = Eu3+/Tb3+/Tm3+) Nanocrystalline Phosphors with Abundant Color.

    Science.gov (United States)

    Liu, Xiaoming; Chen, Chen; Li, Shuailong; Dai, Yuhua; Guo, Huiqin; Tang, Xinghua; Xie, Yu; Yan, Liushui

    2016-10-17

    Up to now, GdNbO 4 has always been regarded as an essentially inert material in the visible region with excitation of UV light and electron beams. Nevertheless, here we demonstrate a new recreating blue emission of GdNbO 4 nanocrystalline phosphors with a quantum efficiency of 41.6% and host sensitized luminescence in GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) nanocrystalline phosphors with abundant color in response to UV light and electron beams. The GdNbO 4 and GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) nanocrystalline phosphors were synthesized by a Pechini-type sol-gel process. With excitation of UV light and low-voltage electron beams, the obtained GdNbO 4 nanocrystalline phosphor presents a strong blue luminescence from 280 to 650 nm centered around 440 nm, and the GdNbO 4 :Ln 3+ nanocrystalline phosphors show both host emission and respective emission lines derived from the characterize f-f transitions of the doping Eu 3+ , Tb 3+ , and Tm 3+ ions. The luminescence color of GdNbO 4 :Ln 3+ nanocrystalline phosphors can be tuned from blue to green, red, blue-green, orange, pinkish, white, etc. by varying the doping species, concentration, and relative ratio of the codoping rare earth ions in GdNbO 4 host lattice. A single-phase white-light-emission has been realized in Eu 3+ /Tb 3+ /Tm 3+ triply doped GdNbO 4 nanocrystalline phosphors. The luminescence properties and mechanisms of GdNbO 4 and GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) are updated.

  16. XRD and DSC study of the formation and the melting of a new zeolite like borosilicate CsBSi5O12 and (Cs,Rb)BSi5O12 solid solutions

    International Nuclear Information System (INIS)

    Bubnova, R.S.; Ugolkov, V.L.; Krzhizhanovskaya, M.G.; Filatov, S.K.; Paufler, P.

    2007-01-01

    Polycrystalline CsBSi 5 O 12 was prepared from a stoichiometric mixture by solid-state reaction above 1000 C. The solid solutions Cs 1-x Rb x BSi 5 O 12 were obtained at 1000 C during a long heat treatment of polycrystalline Cs 1-x Rb x BSi 2 O 6 boropollucites (x Rb = 0, 0.05, 0.2, 0.4). A new borosilicate compound and its solid solutions were studied using X-ray powder diffraction (XRD), annealing, differential scanning calorimetry (DSC), and thermogravimetry (TG). For Cs,Rb-boropollucites the new phase formation is accompanied by significant mass losses detected by DSC and TG. The following mechanism of phase transformations is assumed: (Cs,Rb)BSi 2 O 6 → (Cs,Rb)BSi 5 O 12 + (Cs,Rb)BO 2 ↑. The zeolite phase forms as a result of the boropollucite decomposition over 1000 C. Zeolite decomposes also on further heating and the SiO 2 reflections are observed in the XRD pattern only. Thus above 1000 C both boropollucite and zeolite phases are unstable presumably due to the ability of the alkali cations to leave the structure. Using XRD the unit cell parameters of CsBSi 5 O 12 have been determined in the orthorhombic crystal system: a = 16.242(4) A, b = 13.360(4) A, c = 4.874(1) A. The compound is isostructural with the zeolite compound CsAlSi 5 O 12 . In the crystal structure of Cs 1-x Rb x BSi 5 O 12 solid solutions the changes of cell parameters are insignificant under the substitution of Cs by Rb atoms that indicates a very limited substitution range. (orig.)

  17. Synthesis, structures, and luminescent properties of sodium rare-earth metal(III) chloride oxotellurates(IV), Na{sub 2}Ln{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4} (Ln = Sm, Eu, Gd, Tb, Dy, and Ho)

    Energy Technology Data Exchange (ETDEWEB)

    Charkin, Dmitri O.; Dorofeev, Sergey G.; Berdonosov, Peter S.; Dolgikh, Valery A. [Department of Chemistry, Lomonosov Moscow State University (Russian Federation); Zitzer, Sabine; Greiner, Stefan; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart (Germany); Olenev, Andrei V. [Department of Chemistry, Lomonosov Moscow State University (Russian Federation); Sine Theta Ltd., Moscow (Russian Federation)

    2017-11-17

    Six sodium rare-earth metal(III) chloride oxotellurates(IV), Na{sub 2}Ln{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4}, isostructural to Na{sub 2}Y{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4}, were synthesized by flux techniques and characterized by single-crystal XRD. The compounds crystallize in the monoclinic space group C2/c with lattice constants a = 23.967(1), b = 5.6342(3), c = 16.952(1) Aa, β = 134.456(5) for Ln = Sm, a = 23.932(2), b = 5.6044(5), c = 17.134(1) Aa, β = 135.151(6) for Ln = Eu, a = 23.928(1), b = 5.5928(1), c = 17.1133(8) Aa, β = 135.366(3) for Ln = Gd, a = 23.907(1), b = 5.569(3), c = 16.745(1) Aa, β = 134.205(3) for Ln = Tb, a = 23.870(1), b = 5.547(3), c = 16.665(1) Aa, β = 134.102(3) for Ln = Dy, and a = 23.814(1), b = 5.526(3), c = 16.626(1) Aa, β = 134.016(3) for Ln = Ho and Z = 4. Their crystal structure can be considered as a framework built of intergrowing Ln-O and Na-(O,Cl) slabs with channel walls decorated by tellurium atoms of [TeO{sub 3}]{sup 2-} groups. The luminescent properties of the new compounds due to the Ln{sup 3+} cations are described and discussed. We also discuss the crystal chemistry of various alkali-metal rare-earth metal(III) halide oxochalcogenates(IV). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn2O5+δ (Ln=Gd, Pr)

    Science.gov (United States)

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana; Jacobson, Allan J.

    2016-07-01

    The A-site ordered double-perovskite oxides, LnBaMn2O5+δ (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn2O5+δ. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn2O5+δ. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln3+ ions larger than Y3+. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn2O5 and fully-oxidized LnBaMn2O6 during changes of the oxygen partial pressure between air and 1.99% H2/Ar. In addition, the oxygen non-stoichiometries of GdBaMn2O5+δ and PrBaMn2O5+δ were determined as a function of pO2 at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching 6. The stabilities of the LnBaMn2O5+δ phases extend over a wide range of oxygen partial pressures (∼10-25≤pO2 (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln3+ cation the lower pO2 for phase conversion. At some temperatures and pO2 conditions, the LnBaMn2O5+δ compounds are unstable with respect to decomposition to BaMnO3-δ and LnMnO3. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions.

  19. Electromechanical properties of Na0.5Bi0.5TiO3-SrTiO3-PbTiO3 solid solutions

    Science.gov (United States)

    Svirskas, Šarūnas; Dunce, Marija; Birks, Eriks; Sternberg, Andris; Banys, Jūras

    2018-03-01

    Thorough studies of electric field-induced strain are presented in 0.4Na1/2Bi1/2TiO3-(0.6-x)SrTiO3-xPbTiO3 (NBT-ST-PT) ternary solid solutions. The increase of concentration of lead x induces crossover from relaxor to ferroelectric. Strain in a relaxor state can be described by electrostrictive behavior. The electrostrictive coefficients correspond to other well-known relaxor ferroelectrics. The concentration region with a stable ferroelectric phase revealed that the polarization dependence of strain does not exhibit nonlinearity, although they are inherent to the electric field dependence of strain. In this case, electric field dependence of strain is described in terms of the Rayleigh law and the role of domain wall contribution is extracted. Finally, the character of strain at the electric field-induced phase transition between the nonpolar and the ferroelectric states is studied. The data shows that in the vicinity of the electric field induced phase transition the strain vs. electric field displays electrostrictive character.

  20. Investigation of the system ThO2-NpO2-P2O5. Solid solutions of thorium-neptunium (IV) phosphate-diphosphate

    International Nuclear Information System (INIS)

    Dacheux, N.; Thomas, A.C.; Brandel, V.; Genet, M.

    1998-01-01

    Considering that phosphate matrices could be potential candidates for the immobilization of actinides or for the final disposal of the excess plutonium from dismantled nuclear weapons, the chemistry of thorium phosphates has been re-examined. In the ThO 2 -P 2 O 5 system, the thorium phosphate-diphosphate Th 4 (PO 4 ) 4 P 2 O 7 (TPD) can be synthesized by wet and dry chemical processes. The substitution of thorium by other tetravalent actinides like uranium or plutonium can be obtained for 0 4-x Np x (PO 4 ) 4 P 2 O 7 (TNPD) with 0 4+ by Np 4+ in the TPD structure is evaluated to 2.08 (which corresponds to about 52 mol% of thorium replaced by neptunium (IV)). The field of existence of solid solutions Th 4-x U -x Np -x Pu U x U Np x Np Pu x Pu (PO 4 )4P 2 O 7 has been calculated. These solid solutions should be synthesized for 5x U +7x Np +9x Pu ≤15. In the NpO 2 -P 2 O 5 system, the unit cell parameters of Np 2 O(PO 4 ) 2 were refined by analogy with U 2 O(PO 4 ) 2 which crystallographic data have been published recently. For Np 2 O(PO 4 ) 2 the unit cell is orthorhombic with the following cell parameters: a=7.033(2)A, b=9.024(3)A, c=12.587(6)A and V=799(1)A 3 . The unit cell parameter obtained for α-NpP 2 O 7 (a=8.586(1)A) is in good agreement with those already reported in literature. (orig.)

  1. FTIR spectra of the solid solutions (Na0.88K0.12)VO3, (Na0.5K0.5)VO3, and Na(V0.66P0.34)O3

    Science.gov (United States)

    de Waal, D.; Heyns, A. M.

    1992-03-01

    It is known that three different solid solutions, (Na0.88K0.12)VO3, (Na0.5K0.5)VO3 and Na(V0.66P0.34)O3, form in the (Na,K)(V,P)O3 system. These compounds all have monoclinic crystal structures similar to the pure alkali metal metavanadates containing small cations, e.g. Li+ and Na+ (Space group C2/c). Metavanadates with large cations like K+, Rb+, C+s and NH+4 form orthorhombic crystals, space group Pbcm. All those are structurally related to the silicate pyroxenes. Na(V0.66P0.34)O3 and (Na0.88K0.12)VO3 have the same modified diopside structure as (alpha) - NaVO3 while (Na0.5K0.5)VO3 adopts the true diopside structure. The infrared spectra of the three solid solutions are reported here in comparison with those of (alpha) -NaVO3 and KVO3. The results are also correlated with those obtained in two independent high pressure Raman studies of NH4VO3 and RbVO3 as the introduction of a larger cation like K+ should increase the pressure in the structure.

  2. Structural anomalies, spin transitions and charge disproportionation in LnCoO.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Henry, P.; André, G.

    2008-01-01

    Roč. 103, č. 7 (2008), 07B703/1-07B703/3 ISSN 0021-8979 R&D Projects: GA ČR GA202/06/0051 Institutional research plan: CEZ:AV0Z10100521 Keywords : LnCoO 3 * neutron diffraction * thermal expansion * spin-state transition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.201, year: 2008

  3. The solubility and site preference of Fe3+ in Li7-3xFexLa3Zr2O12 garnets

    Science.gov (United States)

    Rettenwander, D.; Geiger, C. A.; Tribus, M.; Tropper, P.; Wagner, R.; Tippelt, G.; Lottermoser, W.; Amthauer, G.

    2015-10-01

    A series of Fe3+-bearing Li7La3Zr2O12 (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and 57Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe3+ pfu could be incorporated in Li7-3xFexLa3Zr2O12 garnet solid solutions. At Fe3+ concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe3+ contents lower than 0.52 Fe3+ pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a0, for all solid-solution garnets is similar with a value of a0≈12.98 Å regardless of the amount of Fe3+. 57Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe3+ contents greater than 0.16 Fe3+ pfu. The composition of different phase pure Li7-3xFexLa3Zr2O12 garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li6.89Fe0.03La3.05Zr2.01O12, Li6.66Fe0.06La3.06Zr2.01O12, Li6.54Fe0.12La3.01Zr1.98O12, and Li6.19Fe0.19La3.02Zr2.04O12. The 57Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe3+ occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe3+ in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe3+ has a distorted 4-fold coordination.

  4. Tunable emission in Ln3+ (Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor synthesized by combustion method

    Science.gov (United States)

    Kolte, M. M.; Pawade, V. B.; Bhattacharya, A. B.; Dhoble, S. J.

    2018-05-01

    Ln3+ (Ln = Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor has been synthesized by Combustion method (CS) at 550° C successfully. Ln3+ (Ln = Ce3+, Dy3+, Tb3+) ions when doped in KNa3Al4Si4O16 host lattice, it shows blue and green emission band under the near Ultraviolet (NUV) excitation wavelength. The Photoluminescence excitation (PLE) and emission spectra are observed due to f-f and d-f transition of rare earth ions. Also, an effective energy transfer (ET) study from Ce3+ → Dy3+ and Ce3+ → Tb3+ ions has been studied and confirmed on the basis of Dexter-Foster theory. Further synthesized phosphor is well characterized by XRD, SEM, TEM and decay time measurement. However, the analysis of crystallite size, lattice strain has been studied by using theoretical as well as experimental techniques. Hence, the observed tunable emission in Ln3+ doped KNa3Al4Si4O16 phosphor may be applicable for solid state lighting technology.

  5. Monodisperse and hollow structured Y{sub 2}O{sub 3}:Ln{sup 3+} (Ln = Eu, Dy, Er, Tm) nanospheres: A facile synthesis and multicolor-tunable luminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ruiqing; Zi, Wenwen; Li, Linlin; Liu, Lu; Zhang, Junjun [College of Chemistry, Jilin University, Changchun 130026 (China); Zou, Lianchun, E-mail: zoulianchun@126.com [Teaching Center of Basic Courses, Jilin University, Changchun 130062 (China); Gan, Shucai, E-mail: gansc@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130026 (China)

    2014-12-25

    Highlights: • We reported a simple route to synthesize the Y{sub 2}O{sub 3} HNSs. • A possible formation mechanism of the Y{sub 2}O{sub 3} HNSs was proposed. • The Ln-doped Y{sub 2}O{sub 3} HNSs exhibit characteristic emission with different colors. • White-light-emitting phosphor Y{sub 2}O{sub 3}:Tm{sup 3+}, Dy{sup 3+} was also successfully synthesized. - Abstract: A novel, fast and simple method was developed to synthesize the undoped and lanthanide-doped yttrium oxide hollow nanospheres (Y{sub 2}O{sub 3}⋅HNSs) with multicolored downconversion emission under mild conditions by employing poly (acrylic acid sodium salt) microspheres (PAAS MSs) as active templates followed by a subsequent calcination process. The structure, morphology, formation process, and fluorescent properties are well investigated using various techniques. The results show that the samples can be well indexed to the pure cubic phase of Y{sub 2}O{sub 3}. The possible formation mechanism of the PAAS MSs, PAA-Y precursor, and Y{sub 2}O{sub 3} HNSs are proposed and discussed in detail. Upon ultraviolet excitation, the obtained Y{sub 2}O{sub 3}:Ln{sup 3+} (Ln = Eu, Dy, Er, Tm) HNSs exhibit strong red, yellow–green, blue, yellow emission, respectively. Moreover, a novel single-phased and near-UV-pumped white-light-emitting phosphor Y{sub 2}O{sub 3}:Tm{sup 3+}, Dy{sup 3+} was also successfully fabricated through optimizing the molar ratio among Tm{sup 3+} and Dy{sup 3+} in the Y{sub 2}O{sub 3} host. This material may find potential applications in field-emission display devices and white ultraviolet light-emitting diodes (UV LEDs). Furthermore, this synthesis route may be of great significance in the preparation of other hollow spherical materials.

  6. A new promising phosphor, Na3La2(BO3)3:Ln (Ln=Eu, Tb)

    International Nuclear Information System (INIS)

    Li Zhihua; Zeng Jinghui; Zhang Guochun; Li Yadong

    2005-01-01

    We present an efficient way to search a host for ultraviolet (UV) phosphor from UV nonlinear optical (NLO) materials. With the guidance, Na 3 La 2 (BO 3 ) 3 (NLBO), as a promising NLO material with a broad transparency range and high damage threshold, was adopted as a host material for the first time. The lanthanide ions (Tb 3+ and Eu 3+ )-doped NLBO phosphors have been synthesized by solid-state reaction. Luminescent properties of the Ln-doped (Ln=Tb 3+ , Eu 3+ ) sodium lanthanum borate were investigated under UV ray excitation. The emission spectrum was employed to probe the local environments of Eu 3+ ions in NLBO crystal. For red phosphor, NLBO:Eu, the measured dominating emission peak was at 613 nm, which is attributed to 5 D - 7 F 2 transition of Eu 3+ . The luminescence indicates that the local symmetry of Eu 3+ in NLBO crystal lattice has no inversion center. Optimum Eu 3+ concentration of NLBO:Eu 3+ under UV excitation with 395 nm wavelength is about 30 mol%. The green phosphor, NLBO:Tb, showed bright green emission at 543 with 252 nm excited light. The measured concentration quenching curve demonstrated that the maximum concentration of Tb 3+ in NLBO was about 20%. The luminescence mechanism of Ln-doped NLBO (Tb 3+ and Eu 3+ ) was analyzed. The relative high quenching concentration was also discussed

  7. Synthesis, microstructure and mechanical properties of (Ti1−x,Nbx)2AlC/Al2O3 solid solution composites

    International Nuclear Information System (INIS)

    Zhu, Jianfeng; Han, Na; Wang, Anning

    2012-01-01

    (Ti,Nb) 2 AlC/Al 2 O 3 in-situ solid solution composites were successfully synthesized from the elemental powder mixtures of Nb 2 O 5 , Ti, Al and carbon black using hot-press-aided reaction synthesis. The reaction path was investigated by differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), and a possible reaction mechanism was proposed to explain the formation of (Ti,Nb) 2 AlC/Al 2 O 3 composites in which the thermite reaction between Al and Nb 2 O 5 formed Al 2 O 3 and Nb, and the latter together with TiAl and TiC reacted to form (Ti,Nb) 2 AlC. The synthesized composites show plate-like grains packed in a laminated structure typical of Ti 2 AlC, and the fine Al 2 O 3 particles formed in-situ tend to disperse on the matrix grain boundaries. Compared with the monolithic Ti 2 AlC synthesized using an identical process, the Vickers hardness, maximum compressive stress, flexural strength and fracture toughness of (Ti 0.96 ,Nb 0.04 ) 2 AlC/5 wt% Al 2 O 3 were enhanced by 33.8%, 12.1%, 118.4% and 111.8%, respectively. The mechanisms by which Al 2 O 3 increases the strength and toughness of the material were also discussed.

  8. Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

    Science.gov (United States)

    Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

    2013-11-04

    Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

  9. Effect of Ca substitution on the electrochemical properties of the Ruddlesden-Popper oxides Sr3.2-xCaxLn0.8Fe1.5Co1.5O10-δ

    Science.gov (United States)

    Padmasree, K. P.; Lai, Ke-Yu; Kaveevivitchai, Watchareeya; Manthiram, Arumugam

    2018-01-01

    The Ruddlesden-Popper (R-P) oxides Sr3.2-xCaxLn0.8Fe1.5Co1.5O10-δ with x = 0 and 0.4 and Ln = La, Pr, and Nd, have been synthesized and the effect of Ca on their electrochemical properties as cathodes in solid oxide fuel cells (SOFC) has been investigated. The substitution of Ca for Sr in Sr3.2-xCaxLn0.8Fe1.5Co1.5O10-δ decreases the amount of oxygen loss on heating and the thermal expansion coefficient (TEC). The phase instability of these materials at high temperature is a significant issue that restricts their application as SOFC cathodes, and the substitution of Ca effectively stabilizes the Sr3.2-xCaxLn0.8Fe1.5Co1.5O10-δ phase at 800 °C. Among the different lanthanides with and without Ca in Sr3.2-xCaxLn0.8Fe1.5Co1.5O10-δ, the Ln = Nd samples exhibit an enhancement in cathode performance in SOFC compared to Ln = La and Pr samples, which may be attributed to the higher concentration of oxygen vacancies in the Ln = Nd samples. Comparing the various compositions studied, the Sr2.8Ca0.4Nd0.8Fe1.5Co1.5O10-δ cathode material exhibits superior performance in SOFC with good phase stability.

  10. Study of LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) double perovskites as new cathode material for IT-SOFC

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, E; Mueller, M; Mogni, L; Caneiro, A, E-mail: mogni@cab.cnea.gov.a [Centro Atomico Bariloche-CNEA, Instituto Balseiro. Av. Bustillo 9500, S. C. de Bariloche 8400 (Argentina)

    2009-05-01

    Oxides with double perovskites structures of general composition LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) were synthesized by solid state reaction with the purpose to evaluate new materials to be used as cathodes in intermediate temperature solid oxide fuel cell (IT-SOFC). A preliminary study about electrochemical properties was performed by impedance spectroscopy between 500 and 800 deg. C under atmosphere of pure O{sub 2}. Symmetrical cells were obtained by spray deposition of LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) at both sides of a dense ceramic electrolyte. The impedance spectroscopy measurements as a function of temperatures show a hysteresis loop which could be associated to a tetragonal/orthorhombic phase transition. The existence of this transition was corroborated by high temperature X-Ray diffraction and Differential Scanning Calorimetry measurements.

  11. Synthesis of Multicolor Core/Shell NaLuF4:Yb3+/Ln3+@CaF2 Upconversion Nanocrystals

    Directory of Open Access Journals (Sweden)

    Hui Li

    2017-02-01

    Full Text Available The ability to synthesize high-quality hierarchical core/shell nanocrystals from an efficient host lattice is important to realize efficacious photon upconversion for applications ranging from bioimaging to solar cells. Here, we describe a strategy to fabricate multicolor core @ shell α-NaLuF4:Yb3+/Ln3+@CaF2 (Ln = Er, Ho, Tm upconversion nanocrystals (UCNCs based on the newly established host lattice of sodium lutetium fluoride (NaLuF4. We exploited the liquid-solid-solution method to synthesize the NaLuF4 core of pure cubic phase and the thermal decomposition approach to expitaxially grow the calcium fluoride (CaF2 shell onto the core UCNCs, yielding cubic core/shell nanocrystals with a size of 15.6 ± 1.2 nm (the core ~9 ± 0.9 nm, the shell ~3.3 ± 0.3 nm. We showed that those core/shell UCNCs could emit activator-defined multicolor emissions up to about 772 times more efficient than the core nanocrystals due to effective suppression of surface-related quenching effects. Our results provide a new paradigm on heterogeneous core/shell structure for enhanced multicolor upconversion photoluminescence from colloidal nanocrystals.

  12. Near-infrared photoluminescence in La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{sup 3+}(Ln = Nd/Yb) for sensitization of c-Si solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sawala, N. S., E-mail: nssawala@gmail.com; Koparkar, K. A.; Omanwar, S. K. [Department of Physics, SantGadge Baba Amravati University, Amravati - MH, 444602 (India); Bajaj, N. S. [Department of Physics, Toshniwal Art, Commerce and Science College, Sengoan, Hingoli - MH (India)

    2016-05-06

    The host matrix LaAlO{sub 3} was synthesized by conventional solid state reaction method in which the Nd{sup 3+} ions and Yb{sup 3+} ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd{sup 3+} ion doped LaAlO{sub 3} converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb{sup 3+} ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{sup 3+}(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

  13. Kinetics and thermodynamics of the dissolution of Th1-xMxO2 solid solutions (M = U, Pu)

    International Nuclear Information System (INIS)

    Hubert, S.; Heisbourg, G.; Dacheux, N.; Moisy, Ph.; Purans, J.

    2004-01-01

    Kinetics of the dissolution of Th 1-x M x O 2 (M = U, Pu) solid solutions was investigated as a function of several chemical parameters such as pH, substitution ratio, temperature, ionic strength, and electrolyte. Several compositions of Th 1-x U x O 2 and Th 1-x Pu x O 2 were synthesized and characterized before and after leaching by using several methods such as XRD, EXAFS, BET, PIXE, SEM, and XPS. Leaching tests were performed in nitric, hydrochloric or sulfuric media and groundwater. The normalized dissolution rates were evaluated for Th 1-x U x O 2 , and Th 0.88 Pu 0.12 O 2 leading to the determination of the partial order related to the proton concentration, n, and to the corresponding normalized dissolution rate constant at pH = 0, k'T. While for Th enriched solids, the solid solutions Th 1-x U x O 2 have the same dissolution behaviour than ThO 2 with a partial order n ∼ 0.3, in the case of uranium enriched solids, Th 1-x U x O 2 has the same dissolution behaviour than UO 2 with a partial order of n = 1, indicating that uranium oxidation rate becomes the limiting step of the dissolution process. The stoichiometry of the release of both actinides (U or Pu, Th) was verified until the precipitation of thorium occurred in the leachate for pH > 2, while uranium was released in the solution as an uranyl form. For uranium enriched solid solutions, thermodynamic equilibrium was reached after 100 days, and solubility constant of secondary phase was determined. In the case of Th 1-x Pu x O 2 , the dissolution behaviour is similar to that of ThO 2 , but only kinetic aspect of the dissolution can be studied. From the analysis of XPS and EXAFS data on leached and un-leached Th 1-x U x O 2 samples, the dissolution mechanism of solid solutions was explained and will be discussed. The role of the electrolytes on the dissolution of the solid solutions is discussed. Kinetics parameters of dissolution are also given in groundwater and in neutral media

  14. Structural, electrical and multiferroic characteristics of thermo-mechanically fabricated BiFeO3-(BaSr)TiO3 solid solutions

    Science.gov (United States)

    Behera, C.; Choudhary, R. N. P.; Das, Piyush R.

    2018-05-01

    A solid solution consisting of two perovskite compounds (BiFeO3 and (BaSr)TiO3) of chemical composition (Bi1/2Ba1/4Sr1/4)(Fe1/2Ti1/2)O3 has been fabricated in the low dimensional regime by thermo-mechanical (ball milling and heating) approach. The effect of particle size on the structural, micro-structural, relative permittivity, switching (ferroelectric and magnetic) and conduction phenomena of the material has been studied using various experimental techniques such as x-rays diffraction, transmission and scanning electron microscopy, ferroelectric and magnetic hysteresis, dynamic magneto-electric coupling measurement and impedance spectroscopy techniques. All the above extracted properties are found to be particle size dependent. The first order magneto-electric coupling constant is found to be 2.56, 6.6 and 8.7 mV cm‑1.Oe for 30, 60 and 90 h milled calcined (hmc) sample respectively. As the above micro/nano-material with different particle size, has a high relative dielectric constant and low tangent loss, it can be used for some multifunctional devices including capacity energy storage device in nano-electronics.

  15. Influence of lead oxide addition on LnTiTaO 6 (Ln = Ce, Pr and Nd)

    Indian Academy of Sciences (India)

    The effect of PbO addition on the structural, processing and microwave dielectric properties of LnTiTaO6 (Ln = Ce, Pr and Nd) ceramics are reported. Conventional solid state ceramic route was used for the preparation of samples. Phase pure LnTiTaO6 (Ln = Ce, Pr and Nd) ceramics are prepared at a calcination ...

  16. Solid-solid interactions in Co3O4-MoO3/MgO system

    International Nuclear Information System (INIS)

    Radwan, Nagi R.E.; Ghozza, Ahmed M.; El-Shobaky, Gamil A.

    2003-01-01

    Cobalt/magnesium mixed oxide solids and cobalt-molybdenum/magnesium mixed oxide solids were prepared by thermal decomposition of basic magnesium carbonate pretreated with different proportions of cobalt nitrate and then with calculated amounts of ammonium molybdate. The proportions of cobalt expressed as Co 3 O 4 were 0.1, 0.2 and 0.3 mol while the concentrations of molybdenum expressed as mol% MoO 3 were 2.5 and 5.0. The prepared mixed solid specimens were calcined in air at 400-1000 deg. C. The solid-solid interactions in Co 3 O 4 -MoO 3 were investigated using DTA, TG and X-ray powder diffraction (XRD) techniques. The results obtained revealed that MgO dissolved cobalt oxide in its lattice forming CoO-MgO solid solution. The amount of cobalt dissolved increases by increasing the temperature in the range 800-1000 deg. C. This finding was confirmed by X-ray diffractograms in which all the diffraction lines of cobalt oxide disappeared at 1000 deg. C. MoO 3 present interacted readily with MgO and cobalt oxide by heat treatment at temperature starting from 400 deg. C producing MgMoO 4 and CoMoO 4 which remained stable by heating at 1000 deg. C. The impregnation of basic magnesium carbonate with cobalt nitrate much enhanced its thermal decomposition yielding MgO, which decomposed completely at 395.5 deg. C instead of 525 deg. C. The formation of magnesium cobaltite (MgCo 2 O 4 ) has been ruled out via XRD investigation at relatively high diffraction angles

  17. Synthesis of anatase nanoparticles with extremely wide solid solution range and ScTiNbO6 with α-PbO2 structure

    International Nuclear Information System (INIS)

    Hirano, Masanori; Ito, Takaharu

    2009-01-01

    Anatase-type nanoparticles Sc X Ti 1-2X Nb X O 2 with wide solid solution range (X=0-0.35) were hydrothermally formed at 180 deg. C for 5 h. The lattice parameters a 0 and c 0 , and the optical band gap of anatase gradually and linearly increased with the increase of the content of niobium and scandium from X=0 to 0.35. Their photocatalytic activity and adsorptivity by the measurement of the concentration of methylene blue (MB) that remained in the solution in the dark or under UV-light irradiation were evaluated. The anatase phase existed stably up to 900 deg. C for the samples with X=0.25-0.30 and 750 deg. C for that with X=0.35 during heat treatment in air. The phase with α-PbO 2 structure and the rutile phases coexisted in the samples with X=0.25-0.30 after heated at temperatures above 900-950 deg. C. The α-PbO 2 structure having composition ScTiNbO 6 with possibly some cation order similar to that seen in wolframite existed as almost completely single phase after heat treatment at temperatures 900-1500 deg. C through phase transformation from anatase-type ScTiNbO 6 . - Graphical abstract: Anatase-type Sc X Ti 1-2X Nb X O 2 solid solutions with wide solid solution range (X=0-0.35) were hydrothermally formed as nanoparticles from the precursor solutions of Sc(NO 3 ) 3 , TiOSO 4 , NbCl 5 at 180 deg. C for 5 h using the hydrolysis of urea. Anatase-type ScTiNbO 6 was synthesized under hydrothermal condition. ScTiNbO 6 having α-PbO 2 structure with possibly some cation order similar to that seen in wolframite was formed through phase transformation above 900 deg. C.

  18. Enhanced visible light-responsive photocatalytic activity of LnFeO3 (Ln = La, Sm) nanoparticles by synergistic catalysis

    International Nuclear Information System (INIS)

    Li, Li; Wang, Xiong; Zhang, Yange

    2014-01-01

    Highlights: • LnFeO 3 (Ln = La, Sm) nanoparticles were prepared by a facile sol–gel method. • The samples exhibit superior visible-light-responsive photocatalytic activity. • Synergistic effect will enhance the photodegradation of RhB under visible light. - Abstract: LnFeO 3 (Ln = La, Sm) nanoparticles were prepared by a facile sol–gel method with assistance of glycol at different calcination temperatures. The as-synthesized LnFeO 3 was characterized by X-ray diffraction, transmission electron microscopy, differential scanning calorimeter and thermogravimetric analysis, and UV–vis absorption spectroscopy. The photocatalytic behaviors of LnFeO 3 nanoparticles were evaluated by photodegradation of rhodamine B under visible light irradiation. The results indicate that the visible light-responsive photocatalytic activity of LnFeO 3 nanoparticles was enhanced remarkably by the synergistic effect between the semiconductor photocatalysis and Fenton-like reaction. And a possible catalytic mechanism was also proposed based on the experimental results

  19. High-temperature x-ray diffraction study of HfTiO4-HfO2 solid solutions

    International Nuclear Information System (INIS)

    Carpenter, D.A.

    1975-01-01

    High-temperature x-ray diffraction techniques were used to determine the axial thermal expansion curves of HfTiO 4 -HfO 2 solid solutions as a function of composition. Data show increasing anisotropy with increasing HfO 2 content. An orthorhombic-to-monoclinic phase transformation was detected near room temperature for compositions near the high HfO 2 end of the orthorhombic phase field and for compositions within the two-phase region (HfTiO 4 solid solution plus HfO 2 solid solution). An orthorhombic-to-cubic phase transformation is indicated by data from oxygen-deficient materials at greater than 1873 0 K. (U.S.)

  20. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

    International Nuclear Information System (INIS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-01-01

    Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln 3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. Highlights: ► Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. ► Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). ► These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

  1. Thermal decomposition of heavy rare-earth butanoates, Ln(C3H7CO2)3 (Ln = Er, Tm, Yb and Lu) in argon

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Yue, Zhao; Tang, Xiao

    2016-01-01

    was observed in all four compounds, but its course depends on the rare-earth element. Decomposition to sesquioxides proceeds via the formation of dioxymonocarbonates (Ln2O2CO3) and release of 4-heptanone (C3H7COC3H7) as well as carbon dioxide (CO2) without evidence for an intermediate oxobutanoate stage...... of Ln2O2CO3 and Ln2O3. The stability of this intermediate state seems to decrease with the mass of the rare-earth elements. Complete conversion to Ln2O3 is reached at about 1100 °C. The overall thermal decomposition behaviour of the title compounds is different from previous reports for other rare....... During the decomposition of Ln2O2CO3 into the respective sesquioxides (Ln2O3), an intermediate plateau extending from approximately 550 to 850 °C appears in the TG traces. The overall composition during this stage corresponds approximately to Ln2O2.8(CO3)0.2, but the state is more probably a mixture...

  2. Structure refinement, far infrared spectroscopy, and dielectric characterization of (1-x)La(Mg1/2Ti1/2)O3-xLa2/3TiO3 solid solutions

    Science.gov (United States)

    Salak, Andrei N.; Khalyavin, Dmitry D.; Ferreira, Victor M.; Ribeiro, José L.; Vieira, Luís G.

    2006-05-01

    Dielectric properties of (1-x)La(Mg1/2Ti1/2)O3-xLa2/3TiO3 [(1-x)LMT-xLT] ceramics (0infrared (FIR) frequency ranges. The crystal structure sequence in (1-x)LMT-xLT reported by different authors has been analyzed and revised. FIR spectroscopy was used to characterize the lattice contribution to the dielectric response at microwave frequencies. The complex dielectric function was evaluated from the reflectivity data and extrapolated down to a gigahertz range. Compositional variations of the fundamental microwave dielectric parameters estimated by different methods are compared and discussed. The dependence of the quality factor on the composition in LMT-LT is interpreted in terms of the reduction of spatial phonon correlations originated from the increasing amount of La vacancies. This approach could account for the compositional behavior of the dielectric loss commonly observed in a number of microwave mixed systems.

  3. A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr)

    Energy Technology Data Exchange (ETDEWEB)

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana; Jacobson, Allan J., E-mail: ajjacob@uh.edu

    2016-07-15

    The A-site ordered double-perovskite oxides, LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn{sub 2}O{sub 5+δ}. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn{sub 2}O{sub 5+δ}. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln{sup 3+} ions larger than Y{sup 3+}. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn{sub 2}O{sub 5} and fully-oxidized LnBaMn{sub 2}O{sub 6} during changes of the oxygen partial pressure between air and 1.99% H{sub 2}/Ar. In addition, the oxygen non-stoichiometries of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} were determined as a function of pO{sub 2} at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching ~6. The stabilities of the LnBaMn{sub 2}O{sub 5+δ} phases extend over a wide range of oxygen partial pressures (∼10{sup −25}≤pO{sub 2} (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln{sup 3+} cation the lower pO{sub 2} for phase conversion. At some temperatures and pO{sub 2} conditions, the LnBaMn{sub 2}O{sub 5+δ} compounds are unstable with respect to decomposition to BaMnO{sub 3−δ} and LnMnO{sub 3}. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions. - Graphical abstract: Structure of Ln

  4. Magnetic interactions in rhenium-containing rare earth double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths)

    Energy Technology Data Exchange (ETDEWEB)

    Nishiyama, Atsuhide; Doi, Yoshihiro; Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp

    2017-04-15

    The perovskite-type compounds containing both rare earth and rhenium Sr{sub 2}LnReO{sub 6} (Ln=Y, Tb-Lu) have been prepared. Powder X-ray diffraction measurements and Rietveld analysis show that Ln{sup 3+} and Re{sup 5+} ions are structurally ordered at the B site of the perovskite SrBO{sub 3}. Magnetic anomalies are found in their magnetic susceptibility and specific heat measurements at 2.6–20 K for Ln=Y, Tb, Dy, Yb, Lu compounds. They are due to magnetic interactions between Re{sup 5+} ions. The results of the magnetic hysteresis and remnant magnetization measurements for Sr{sub 2}YReO{sub 6} and Sr{sub 2}LuReO{sub 6} indicate that the antiferromagnetic interactions between Re{sup 5+} ions below transition temperatures have a weak ferromagnetic component. The analysis of the magnetic specific heat data for Sr{sub 2}YbReO{sub 6} shows that both the Yb{sup 3+} and Re{sup 5+} ions magnetically order at 20 K. For the case of Sr{sub 2}DyReO{sub 6}, magnetic ordering of the Re{sup 5+} moments occurs at 93 K, and with decreasing temperature, the moments of Dy{sup 3+} ferromagnetically order at 5 K from the measurements of magnetic susceptibility and specific heat. - Graphical abstract: Crystal structure of double perovskite Sr{sub 2}LnReO{sub 6}. Red and black lines show cubic and monoclinic unit cells, respectively. - Highlights: • Double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths) were prepared. • They show an antiferromagnetic transition at 2.6–20 K. • In Sr{sub 2}DyReO{sub 6}, Dy and Re moments magnetically order at 5 and 93 K, respectively.

  5. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li7La3Zr2O12 Pellets

    International Nuclear Information System (INIS)

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi

    2016-01-01

    All-solid-state lithium-ion batteries using Li + -ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZAl), which is a Al-doped Li 7 La 3 Zr 2 O 12 (LLZ) with Li + -ion conductivity of ~10 –4 S ⋅cm −1 at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO 2 /LLZAl/lithium-metal configuration. It is expected that the LiCoO 2 –LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li 3 BO 3 , which is a mechanically soft solid electrolyte with a low melting point at around 700

  6. X-ray photoelectron spectroscopic study of direct reforming catalysts Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln = La, Nd, and Sm) for high temperature-operating solid oxide fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Keunsoo [Department of Engine Research, Korea Institute of Machinery and Materials, 156 Gajeongbuk-Ro, Daejeon 305-343 (Korea, Republic of); Jeong, Jihoon [Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Azad, Abul K. [Faculty of Integrated Technologies, University Brunei Darussalam, Jalan Tunku Link, Gadong BE1410 (Brunei Darussalam); Jin, Sang Beom [Department of Advanced Materials Science and Engineering, Hanbat National University, 125, Dongseo-Daero, Yusung-Gu, Daejeon 305-719 (Korea, Republic of); Kim, Jung Hyun, E-mail: jhkim2011@hanbat.ac.kr [Department of Advanced Materials Science and Engineering, Hanbat National University, 125, Dongseo-Daero, Yusung-Gu, Daejeon 305-719 (Korea, Republic of)

    2016-03-01

    Graphical abstract: Measured Ti 2p peaks and deconvolution peaks of Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} under oxidizing condition (left) and NSTM under reducing condition (right). - Highlights: • Chemical states of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) were analyzed. • Charge compensation occurred with the reduction of Mn and Ti. • The Nd substitution effect allowed some Ti to convert into a metallic behavioral component. • NSTM and SSTM had a large amount of lattice oxygen; however, LSTM retained a large quantity of adsorbed oxygen. - Abstract: Chemical states of lanthanide doped perovskite for direct reforming anode catalysts, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln = La, Nd, and Sm) have been studied by X-ray Photoelectron Spectroscopy (XPS) in order to determine the effects of various lanthanide substitution in complex perovskites for high temperature-operating solid oxide fuel cells (HT-SOFC). The charge state of lanthanide ions remained at 3+ and the binding energies of the lanthanide ions in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} were located in a relatively lower range compared to those of conventional lanthanide oxides. Mn and Ti were regarded as charge compensation components in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}; Mn was more influential than Ti. In the cases of substituting Nd and Sm into Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}, some portion of Ti showed metallic behavior; the specific Mn satellite peak indicating an electro-catalytic effect had occurred. Three types of oxygen species comprised of lattice oxygen, carbonate species, and adsorbed oxygen species were observed in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} from the O 1s spectra; a high portion of lattice oxygen was observed in both Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O

  7. 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.

  8. Growth and characterization of Pb(Lu{sub 1/2}Nb{sub 1/2})O{sub 3}-Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} ternary piezo-/ferroelectric crystals

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ying [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117 (China); He, Chao [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Yang, Xiaoming [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117 (China); Li, Xiuzhi; Wang, Zujian [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Huang, Zhigao; Lai, Fachun [College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117 (China); Long, Xifa, E-mail: lxf@fjirsm.ac.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2016-08-05

    Piezo-/ferroelectric crystals of Pb(Lu{sub 1/2}Nb{sub 1/2})O{sub 3}-Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} ternary solid solution system with high Curie temperature, in the vicinity of morphotropic phase boundary (MPB) region, are grown by the top-seeded solution growth (TSSG) method for the first time. The compositions and structures of the crystals are analyzed, all the structures are found to have pure perovskite structure using X-ray diffraction analysis. Di-/piezo-/ferroelectric properties of the crystals are also characterized systematically. The Curie temperature T{sub c} and coercive field E{sub c}, increase gradually with increasing PbTiO{sub 3} content. In particular, the crystal with composition 0.34PLN-0.31PMN-0.35PT possesses excellent electric properties including the Curie temperature, the rhombohedral–tetragonal phase transition temperature, the piezoelectric coefficient, the remnant polarization and the coercive field, which are T{sub c} = 228 °C, T{sub RT} = 156 °C, d{sub 33} = 2092 pC N{sup −1}, Pr = 35.5 μC cm{sup −2} and E{sub c} = 8.1 kV cm{sup −1}, respectively, making it a promising material for transducers or detectors in a wide temperature range. - Highlights: • PLN-PMN-PT Piezo-/ferroelectric crystals are grown by TSSG method. • The Curie temperature and coercive field increase gradually with increasing PT. • The crystal of 0.34PLN-0.31PMN-0.35PT possesses excellent electric properties.

  9. Narrow spectral emission CaMoO{sub 4}: Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+} phosphor crystals for white light emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Khanna, A. [Smart Lighting Engineering Research Center, 110, 8th Street, Troy, New York, 12180 (United States); Electrical, Computer and Systems Engineering Department, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, New York, 12180 (United States); Dutta, P.S., E-mail: duttap@rpi.edu [Smart Lighting Engineering Research Center, 110, 8th Street, Troy, New York, 12180 (United States); Electrical, Computer and Systems Engineering Department, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, New York, 12180 (United States)

    2013-02-15

    Alkaline earth metal molybdates are promising candidates as a host material for high efficiency narrow spectral emission phosphors. These phosphors could potentially be used for the fabrication of phosphor-converted light emitting diodes (pc-LEDs). Phosphor crystals of calcium molybdate doped with rare earth dopant Ln{sup 3+}(Ln=Eu, Dy, Tb) grown using flux growth method have been shown to exhibit higher excitation efficiency than the powders synthesized by solid-state reaction process. Molybdenum (VI) oxide has been found to be a suitable flux for growing large size optically transparent high quality crystals at a temperature around 1100 Degree-Sign C. Using the excitation wavelengths of 465 nm, 454 nm and 489 nm for CaMoO{sub 4}: Eu{sup 3+}, CaMoO{sub 4}: Dy{sup 3+} and CaMoO{sub 4}: Tb{sup 3+}, respectively, intense emission lines at wavelengths of 615 nm, 575 nm and 550 nm were observed. The optimized doping concentrations of 12%, 2% and 5% for Eu{sup 3+}, Dy{sup 3+} and Tb{sup 3+}, respectively, provided the highest luminescence intensity. - Graphical Abstract: CaMoO{sub 4}: Eu{sup 3+} phosphor crystals grown using a molybdenum (VI) oxide flux exhibited around 1.5 times the emission intensity of powders obtained from solid-state reaction at the same synthesis temperature. These crystals were found to efficiently emit 615 nm red light when excited by near UV light up to a wavelength of 395 nm. Highlights: Black-Right-Pointing-Pointer CaMoO{sub 4}: Ln{sup 3+} (Ln=Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+}) phosphor crystals were successfully grown using high temperature flux (solutions) containing molybdenum (VI) oxide or lithium chloride. Black-Right-Pointing-Pointer Narrow spectral emission at 615 nm, 575 nm and 550 nm, respectively, was observed from CaMoO{sub 4}: Ln{sup 3+} (Ln=Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+}) phosphor crystals. Black-Right-Pointing-Pointer The optimized doping concentrations of Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+} in CaMoO{sub 4} for highest

  10. Nitrate conversion and supercritical fluid extraction of UO2-CeO2 solid solution prepared by an electrolytic reduction-coprecipitation method

    International Nuclear Information System (INIS)

    Zhu, L.Y.; Duan, W.H.; Wen, M.F.; Xu, J.M.; Zhu, Y.J.

    2014-01-01

    A low-waste technology for the reprocessing of spent nuclear fuel (SNF) has been developed recently, which involves the conversion of actinide and lanthanide oxides with liquid N 2 O 4 into their nitrates followed by supercritical fluid extraction of the nitrates. The possibility of the reprocessing of SNF from high-temperature gas-cooled reactors (HTGRs) with nitrate conversion and supercritical fluid extraction is a current area of research in China. Here, a UO 2 -CeO 2 solid solution was prepared as a surrogate for a UO 2 -PuO 2 solid solution, and the recovery of U and Ce from the UO 2 -CeO 2 solid solution with liquid N 2 O 4 and supercritical CO 2 containing tri-n-butyl phosphate (TBP) was investigated. The UO 2 -CeO 2 solid solution prepared by electrolytic reduction-coprecipitation method had square plate microstructures. The solid solution after heat treatment was completely converted into nitrates with liquid N 2 O 4 . The XRD pattern of the nitrates was similar to that of UO 2 (NO 3 ) 2 . 3H 2 O. After 120 min of online extraction at 25 MPa and 50 , 99.98% of the U and 98.74% of the Ce were recovered from the nitrates with supercritical CO 2 containing TBP. The results suggest a promising potential technology for the reprocessing of SNF from HTGRs. (orig.)

  11. Estimation of tau1 for the host Kramers' Ln3+ ions (Ln = Nd, Sm and Yb) from the EPR linewidths of Gd3+ impurity ions in Ln2(SO4)3.8H2O

    International Nuclear Information System (INIS)

    Malhotra, V.M.; Buckmaster, H.A.

    1981-01-01

    It is shown that the EPR linewidth data published by Misra and Mikolajczak for Gd 3+ impurity ions in Ln 2 (SO 4 ) 3 .8H 2 O (Ln = Nd, Sm and Yb) single crystals at 77 and 300 K can be used to estimate the effective spin-lattice relaxation time of Kramers' host ions. The various relaxation mechanisms which are operative in the lanthanides are reviewed and discussed. The estimated relaxation times are shown to be a sensitive function of the host ion energy level splittings and the temperature. The estimated effective spin-lattice relaxation times in these hosts are in reasonable agreement with those expected from a resonance Orbach process

  12. Vibrational spectra of mixed oxides of Ln2MgTiO6 composition

    International Nuclear Information System (INIS)

    Porotnikov, N.V.; German, M.; Kovba, L.M.

    1984-01-01

    In the range 33-4000 cm -1 IR and Raman spectra of complex oxides of the composition Ln 2 MgTiO 6 (Ln=La-Yb and Y) have been studied. Using the Magnesium isotope-substituted compositions Lasub(2)sup(24,26)MgTiOsub(6), Smsub(2)sup(24,26)MgTiOsub(6) and Ybsub(2)sup(24,26)MgTiOsub(6), it has been shoWn that in Ln 2 MgTiO 6 titanium and magnesium ions are located in sites With octahedral coordination, of rare earth ions highly-coordinated polyhedrons with coordination number 10-12 are characteristic

  13. Multielectronic conduction in La1-xSrxGa1/2Mn1/2O3-δ as solid oxide fuel cell cathode

    Science.gov (United States)

    Iguchi, E.; Hashimoto, Y.; Kurumada, M.; Munakata, F.

    2003-08-01

    Four-probe dc conductivities, capacitances, and thermopower have been measured in the temperature range of 80-1123 K for La1-xSrxGa1/2Mn1/2O3-δ, which is a desirable cathode material for lanthanum-gallate electrolytes of solid oxide fuel cells. The dc conductivities in the specimens (0.1⩽x⩽0.3) are insensitive to x but the thermopower is very sensitive to x, although the x=0 specimen exhibits a somewhat different conduction behavior. At T500 K, the band conduction dominates the electronic transports. The ionic conduction due to O2- migration seems difficult to contribute directly to the dc conduction even at high temperature.

  14. Magnetic upconverting fluorescent NaGdF4:Ln3+ and iron-oxide@NaGdF4:Ln3+ nanoparticles

    Science.gov (United States)

    Shrivastava, Navadeep; Rocha, Uéslen; Muraca, Diego; Jacinto, Carlos; Moreno, Sergio; Vargas, J. M.; Sharma, S. K.

    2018-05-01

    Microwave assisted solvothermal method has been employed to synthesize multifunctional upconverting β-NaGdF4:Ln3+ and magnetic-upconverting Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (Ln = Yb and Er) nanoparticles. The powder x-ray diffraction data confirms the hexagonal structure of NaGdF4:Ln3+ and high resolution transmission electron microscopy shows the formation of rod shaped NaGdF4:Ln3+ (˜ 20 nm) and ovoid shaped Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (˜ 15 nm) nanoparticles. The magnetic hysteresis at 300 K for β-NaGdF4:Ln3+ demonstrates paramagnetic features, whereas iron-oxide@β-NaGdF4:Ln3+ exhibits superparamagnetic behavior along with a linear component at large applied field due to paramagnetic NaGdF4 matrix. Both nanoparticle samples provide an excellent green emitting [(2H11/2, 4S3/2)→4I15/2 (˜ 540 nm)] upconversion luminescence emission under excitation at 980 nm. The energy migration between Yb and Er in NaGdF4 matrix has been explored from 300-800 nm. Intensity variation of blue, green and red lines and the observed luminescence quenching due to the presence of Fe3O4/γ-Fe2O3 in the composite has been proposed. These kinds of materials contain magnetic and luminescence characteristics into single nanoparticle open new possibility for bioimaging applications.

  15. Synthesis and properties of compounds (Ln(NO/sub 3/)/sub 2/(OP(N(CH/sub 3/)/sub 2/)/sub 3/)/sub 4/)B(C/sub 6/H/sub 5/)/sub 4/ (Ln=Y,La, Ce-Lu)

    Energy Technology Data Exchange (ETDEWEB)

    Skopenko, V V; Zub, Yu L; Matishinets, I M [Kievskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1984-01-01

    From acetone solutions with the yield 75-80% compounds of the composition (Ln(NO/sub 3/)/sub 2/(OP(Nx(CN/sub 3/)/sub 2/)/sub 3/))B(C/sub 6/H/sub 5/)/sub 4/ (Ln=Y, La, Ce-Lu) have been separated. Comparing diffractograms the existence of two isostructural series with morphotropic transition at the Nd/Sm boundary has been established. Using the data of conductometry and IR spectroscopy it has been shown that the cation coordination number of the central atom is eight: four O atoms from two bidentate-cyclic nitrate groups and four O atoms from four monodentate phosphineoxide ligands. Measurement of electric conductivity of the substances separated in nitromethane has shown that the value lambdasub(M) varies inconsiderably from the value 48 Ohm/sup -1/xcm/sup 2/xmol/sup -1/.

  16. Structures, magnetic, and thermal properties of Ln3MoO7 (Ln=La, Pr, Nd, Sm, and Eu)

    International Nuclear Information System (INIS)

    Nishimine, Hiroaki; Wakeshima, Makoto; Hinatsu, Yukio

    2005-01-01

    Ternary lanthanide-molybdenum oxides Ln 3 MoO 7 (Ln=La, Pr, Nd, Sm, Eu) have been prepared. Their structures were determined by X-ray diffraction measurements. They crystallize in a superstructure of cubic fluorite and the space group is P2 1 2 1 2 1 . The Mo ion is octahedrally coordinated by six oxygens and the slightly distorted octahedra share corners forming a zig-zag chain parallel to the b-axis. These compounds have been characterized by magnetic susceptibility and specific heat measurements. The La 3 MoO 7 shows complex magnetic behavior at 150 and 380K. Below these temperatures, there is a large difference in the temperature-dependence of the magnetic susceptibility measured under zero-field-cooled condition and under field-cooled condition. The Nd 3 MoO 7 show a clear antiferromagnetic transition at 2.5K. From the susceptibility measurements, both Pr 3 MoO 7 and Sm 3 MoO 7 show the existence of magnetic anomaly at 8.0 and 2.5K, respectively. The results of the specific heat measurements also show anomalies at the corresponding magnetic transition temperatures. The differential scanning calorimetry measurements indicate that two phase-transitions occur for any Ln 3 MoO 7 compound in the temperature range between 370 and 710K

  17. Study of valence of cerium and praseodymium ions in Pr1-xCexO2 solid solutions

    International Nuclear Information System (INIS)

    Gartsman, K.G.; Kartenko, N.F.; Melekh, B.T.

    1990-01-01

    Effect of preparation conditions of Pr 1-x Ce x O 2 solid solutions on Ce and Pr ion valence within Pr 1-x Ce x O 2 system is studied. The data obtained enable to conclude that praseodymium may depending on annealing conditions change its state from Pr 3+ to Pr 4+ , while Ce 4+ is stable in Pr 1-x Ce x O 2 solid solutions

  18. Crystallographic and infrared spectroscopic study of bond distances in Ln[Fe(CN)6].4H2O (Ln=lanthanide)

    International Nuclear Information System (INIS)

    Zhou Xianju; Wong, W.-T.; Faucher, Michele D.; Tanner, Peter A.

    2008-01-01

    Along with crystallographic data of Ln[Fe(CN) 6 ].4H 2 O (Ln=lanthanide), the infrared spectra are reassigned to examine bond length trends across the series of Ln. The changes in mean Ln-O, Ln-N, C≡N and Fe-C distances are discussed and the bond natures of Ln-N and Ln-O are studied by bond length linear or quadratic fitting and comparisons with relevant ionic radii. The two different C≡N bond distances have been simulated by the covalo-electrostatic model. - Graphical abstract: Crystallographic and FTIR data for Ln[Fe(CN) 6 ].4H 2 O enable the changes in Ln-O, Ln-N, C≡N and Fe-C distances to be determined and modeled across the lanthanide series

  19. Reduction of the Curie temperature in the multiferroic Bi5Fe1+xTi3−xO15 solid solution

    International Nuclear Information System (INIS)

    Salazar-Kuri, U; Mendoza, M E; Silva, R; Siqueiros, J M; Gervacio-Arciniega, J J

    2014-01-01

    In this work, the phase diagram of the system Bi 4 Ti 3 O 12 -BiFeO 3 in the region of the solid solution Bi 5 Fe 1+x Ti 3−x O 15 was refined. The limit of solubility was determined to be at x = 0.1. The Curie temperature (T C ) of the ferroelectric phase transition was determined by dielectric permittivity measurements at 100 kHz for the phase Bi 5 FeTi 3 O 15 as well as for the solid solution. A decrease in T C from 750 °C to 742 °C (solid solution at x = 0.1) was found. These results can be explained in terms of the perturbation of the oxygen octahedral perovskite layers resulting from the substitution of Ti 4+ by Fe 3+ ions. (paper)

  20. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln==Sm, Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln==Tb, Dy, Ho)

    International Nuclear Information System (INIS)

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

    2013-01-01

    Solvothermal reactions of Ln 2 O 3 , As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien) 2 (1κ 2 -AsS 4 )] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln 2 O 3 oxides were converted to [Ln(dien) 2 ] 3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS 4 unit. In 1−3, the AsS 4 units interconnect the [Ln(dien) 2 ] 3+ cations via Ln−S bonds as tridentate μ-1κ,2κ 2 -AsS 4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n (Ln1). In 4−6, the AsS 4 units coordinate with the Ln 3+ ion of [Ln(dien) 2 ] 3+ as 1κ 2 -AsS 4 chelating ligands to form neutral coordination compounds [Ln(dien) 2 (1κ 2 -AsS 4 )] (Ln2). The Ln 3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln 3+ ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n and [Ln(dien) 2 (1κ 2 -AsS 4 )] were prepared by solvothermal methods and the soft Lewis basic AsS 4 3– ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS 4 ligand coordinate Ln 3+ ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors with optical band gaps in the range 2.18−3.21 eV

  1. Characterization investigations during mechanical alloying and sintering of Ni-W solid solution alloys dispersed with WC and Y2O3 particles

    International Nuclear Information System (INIS)

    Genc, Aziz; Luetfi Ovecoglu, M.

    2010-01-01

    Research highlights: → 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. → Reinforcement of the selected Ni-W powders with WC and Y 2 O 3 particles and further MA together for 12 h. → There is no reported literature on the development and characterization of Ni-W solid solution alloys matrix composites fabricated via MA. → Sintering of the developed composites and the characterization investigations of the sintered samples. → 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 2 O 3 particles. The reinforced powders were further MA'd for 12 h. The MA'd powders were sintered at 1300 o C for 1 h under Ar and H 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.

  2. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb)

    Energy Technology Data Exchange (ETDEWEB)

    Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan)

    2013-02-15

    Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln{sup 3+} sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. Highlights: Black-Right-Pointing-Pointer Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. Black-Right-Pointing-Pointer Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). Black-Right-Pointing-Pointer These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

  3. Study on structural and optical properties of α-(AlxCr1-x)2O3 (0 ≤ x ≤ 1) solid solutions

    Science.gov (United States)

    Jangir, Ravindra; Kumar, Dharmendra; Srihari, Velaga; Ganguli, Tapas

    2018-04-01

    We report on structural and optical properties for ternary α-(AlxCr1-x)2O3 (0 ≤ x ≤ 1) solid solutions synthesized by using solid sate reaction method. Single R-3c phase was obtained for the Aluminum composition of 0 ≤ x ≤ 1. Due to difference in the ionic radia of Al3+ and Cr3+, in plane lattice parameter showed deviation from the vegard's law. Optical absorption spectra for the solid solutions showed a blue shift of ˜ 0.5 eV in the optical gap. It has also been observed that Cr 3d level shifted towards the O 2p level in the valance band which indicates the enhancement of hybridization in the d and p levels, which is related to the delocalization of hole states, responsible for p-type conduction in wide band gap semiconductors. The results suggests that ternary α-(AlxCr1-x)2O3 (0 ≤ x ≤ 1) can be useful in the field of UV transparent electronics and UV photodetectors.

  4. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

    Science.gov (United States)

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-02-01

    Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

  5. Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions. Chemical composition range and flux crystal growth

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov, V.A. [N.I. Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, 603950 (Russian Federation); Marychev, M.O., E-mail: marychev@yandex.ru [N.I. Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, 603950 (Russian Federation); Andreev, P.V.; Lykov, V.A.; Faddeev, M.A. [N.I. Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, 603950 (Russian Federation); Koseva, I. [Bulgarian Academy of Science, Institute of General and Inorganic Chemistry, BU-1113 Sofia (Bulgaria); Nikolov, V. [N.I. Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, 603950 (Russian Federation)

    2015-11-01

    A series of Ca{sub 2−x}Li{sub 2x}GeO{sub 4} specimens with 0 < 2x < 2, were synthesized by the classical solid state method. X-ray analysis revealed that for 0 < 2x < 0.6 only Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions of Ca{sub 2}GeO{sub 4} structure crystallized. The cell parameters of these solid solutions linearly decreased upon increasing the lithium concentration, which means that the solutions are in accordance with the Vegard's law. For 2x > 0.6 the specimens contained two phases: (i) Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions with maximum lithium concentration approximately equal to that for 2x = 0.6 and minimum values of the cell parameters and (ii) Li{sub 2}CaGeO{sub 4} phase. Li{sub 2}O·MoO{sub 3}–Ca{sub 2}GeO{sub 4} high-temperature solutions were used to grow Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions and Li{sub 2}CaGeO{sub 4} single crystals by the high temperature solution (flux) method. Li{sub 2}CaGeO{sub 4} crystals were grown in the concentration range 8–26 wt. % Ca{sub 2}GeO{sub 4} in the temperature range 830–980 °C. Crystals with chemical compositions of the Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions with different Li concentrations were grown in the concentration range 26–40 wt. % Ca{sub 2}GeO{sub 4} in the temperature range 980–1090 °C. - Highlights: • Ca{sub 2−x}Li{sub 2x}GeO{sub 4} solid solutions are established for the first time. • The Li concentration range into the solutions is between 0 and 0.6. • The solid solutions are in accordance to Vegard's law. • Suitable solutions are found out for Ca{sub 2−x}Li{sub 2x}GeO{sub 4} and Li{sub 2}CaGeO{sub 4} crystal growth.

  6. Sr2+ and Cs+ ion exchange properties of KLn(PO3)4: Ln = Ce and Eu

    International Nuclear Information System (INIS)

    Samatha, B.; Achary, S.N.; Tyagi, A.K.; Ramkumar, Jayshree; Chandramouleeswaran, S.

    2014-01-01

    With the aim to study the potential of layered phosphates as ion exchangers two stoichiometric compositions as KLn(PO 3 ) 4 with Ln = Ce and Eu were prepared by solid state reaction and characterized by powder X-ray diffraction method. The Cs + and Sr 2+ exchange properties of both materials were investigated using standard solutions of Sr 2 + or Cs + in low acidic aqueous medium

  7. The role of Ln

    NARCIS (Netherlands)

    Katayama, Y.; Kayumi, T.; Ueda, J.; Dorenbos, P.; Viana, B; Tanabe, S

    2017-01-01

    In this paper, Mn2+ and Ln3+ (Ln = Eu, Yb) co-doped MgGeO3 phosphors were prepared using a solid state reaction technique, and their optical properties were investigated. Mn2+-doped samples exhibit persistent luminescence in the red region, peaking at 677 nm, because of the 4T1 → 6A1 transition of

  8. LN2 Dewar 42 Delivery Overfill Inlet Solution

    Energy Technology Data Exchange (ETDEWEB)

    Wu, J.; Mulholland, G.T.; /Fermilab

    1991-02-26

    Pressure vessels must be protected against overpressure scenarios. A scenario of particular concern is that from a high pressure LN2 pump, now standard on LN2 delivery trailers. A safety mechanism must be in place to prevent the overfilling, and subsequent overpressure from occurring because these pumps have a higher mass flow output than reasonably sized relief valves provide. The original solution to the problem was to close a valve on the fill line when a certain liquid level in the dewar is reached. The valve remains closed until the level drops below that threshold. The trigger level was about 13,000 gallons for the 20,000 gallon capacity dewar. The solution was in place from 1989 until present, 2004.

  9. Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

    Energy Technology Data Exchange (ETDEWEB)

    Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

    2015-03-15

    Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7} in the reaction of hydrogen evolution from aqueous isopropanol solution. - Graphical abstract: Layered HLnTiO{sub 4} (Ln=La, Nd) compounds form partially hydrated Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O compounds during thermal dehydration, further heating results to the formation to defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7}, pyrochlor-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation to layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. Structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7}. - Highlights: • We studied dehydration and further thermolysis of HLnTiO{sub 4} (Ln=La, Nd) compounds. • XRD, STA and solid state IR studies were carried out. • A new series of metastable Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O compounds was obtained. • We examined the photocatalytic activity of all obtained compounds. The hydrogen evolution rate increased in the course of the structure changes during thermolysis.

  10. High temperature X-ray diffraction studies on HfO2-Gd2O3 system

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Antony, M.P.; Ananthasivan, K.; Joseph, M.

    2016-01-01

    High temperature X-ray diffraction (HTXRD) technique is an important experimental tool for measuring thermal expansion of materials of interest. A series of solid solutions containing GdO 1.5 in HfO 2 ,Hf 1-y Gd y )O 2 (y = 0.15, 0.2, 0.3, 0.41 and 0.505) were prepared by solid state method. Structural characterization and computation of lattice parameter was carried out by using room temperature X-ray diffraction measurements. The room temperature lattice parameter estimated for (Hf 1-y Gd y )O 2 (y=0.15, 0.2, 0.3, 0.41 and 0.505) are 0.51714 nm, 0.51929 nm, 0.52359nm, 0.52789nm and 0.53241 nm, respectively. Thermal expansion coefficients and percentage linear thermal expansion of the HfO 2 -Gd 2 O 3 solid solutions containing 20 and 41 mol% GdO 1.5 were determined using HTXRD in the temperature range 298 to 1673K. The mean linear thermal expansion coefficients of the solid solutions containing 20 and 41 mol. %Gd are 11.65 x 10 -6 K -1 and 12.07 x 10 -6 K -1 , respectively. (author)

  11. Synthesis, surface modification/decoration of luminescent–magnetic core/shell nanomaterials, based on the lanthanide doped fluorides (Fe3O4/SiO2/NH2/PAA/LnF3)

    International Nuclear Information System (INIS)

    Runowski, Marcin; Lis, Stefan

    2016-01-01

    The synthesized magnetite nanoparticles (10–15 nm) were successfully coated with amine modified silica nanoshell, which led to the formation of core/shell type nanostructures (30–50 nm). The as-prepared nanoparticles were surface modified with polyacrylic acid (PAA) via electrostatic interactions of –NH 2 and –COOH groups. Afterwards, the surface PAA molecules acted as complexing agents of the introduced lanthanide (Ln 3+ ) ions. Subsequently, the as-prepared nanostructures were surface decorated with luminescent LnF 3 nanoparticles, forming Eu 3+ or Tb 3+ doped Fe 3 O 4 /SiO 2 /NH 2 /PAA/LnF 3 nanomaterials (50–100 nm). The obtained luminescent–magnetic products exhibited simultaneously bright red or green emission under UV lamp irradiation (λ ex =254 nm), and a response for the applied magnetic field (strong magnet attracts the colloidal particles, dispersed in aqueous medium). After the synthesis, properties of the nanomaterials were investigated by powder X-ray diffraction (XRD) technique, transmission electron microscopy (TEM), infrared spectroscopy (IR) and spectrofluorometry (analysis of excitation/emission spectra and luminescence decay curves). Such advanced nanomaterials can be potentially used in multimodal imaging, targeted therapies and as multifunctional contrast agents, novel luminescent–magnetic tracers, protection of documents, etc. - Highlights: • Luminescent–magnetic nanomaterials Fe 3 O 4 /SiO 2 /NH 2 /PAA/LnF 3 were synthesized. • Core/shell nanostructures were obtained by surface modification of nanoparticles. • Luminescent lanthanide fluoride nanoparticles doped with Eu 3+ and Tb 3+ ions. • Multifunctional core/shell nanostructures exhibited red or green emission. • Nanomaterials formed stable aqueous colloids.

  12. Nd(BrO3)3-Yb(BrO3)3-H2O and Nd2(SeO4)3-Yb2(SeO4)3-H2O systems at 25 deg C

    International Nuclear Information System (INIS)

    Serebrennikov, V.V.; Batyreva, V.A.; Tsybukova, T.N.

    1981-01-01

    Using the methods of isothermal solubility the Nd(BrO 3 ) 3 - Yb(BrO 3 ) 3 -H 2 O and Nd 2 (SeO 4 ) 3 -Yb 2 (SeO 4 ) 3 -H 2 O systems are studied at 25 deg C. The compositions of the solid phases are determined by the method of ''residues''. The formation of two series of solid solutions in both systems is established. Besides, there is a crystallization region of Nd 2 (SeO 4 ) 3 in the system of selenates. The solubility diagrams of the systems are presented [ru

  13. Magnetoelectric effect in (BiFeO3x–(BaTiO31-x solid solutions

    Directory of Open Access Journals (Sweden)

    Kowal Karol

    2015-03-01

    Full Text Available The aim of the present work was to study magnetoelectric effect (ME in (BiFeO3x-(BaTiO31-x solid solutions in terms of technological conditions applied in the samples fabrication process. The rapidly growing interest in these materials is caused by their multiferroic behaviour, i.e. coexistence of both electric and magnetic ordering. It creates possibility for many innovative applications, e.g. in steering the magnetic memory by electric field and vice versa. The investigated samples of various chemical compositions (i.e. x = 0.7, 0.8 and 0.9 were prepared by the solid-state sintering method under three sets of technological conditions differing in the applied temperature and soaking time. Measurements of the magnetoelectric voltage coefficient αME were performed using a dynamic lock-in technique. The highest value of αME was observed for 0.7BiFeO3-0.3BaTiO3 solid solution sintered at the highest temperature (T = 1153 K after initial electrical poling despite that the soaking time was reduced 10 times in this case.

  14. The influence of excess K2O on the electrical properties of (K,Na)1/2Bi1/2TiO3 ceramics

    Science.gov (United States)

    Li, Linhao; Li, Ming; Sinclair, Derek C.

    2018-04-01

    The solid solution (KxNa0.50-x)Bi0.50TiO3 (KNBT) between Na1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 (KBT) has been extensively researched as a candidate lead-free piezoelectric material because of its relatively high Curie temperature and good piezoelectric properties, especially near the morphotropic phase boundary (MPB) at x ˜ 0.10 (20 mol. % KBT). Here, we show that low levels of excess K2O in the starting compositions, i.e., (Ky+0.03Na0.50-y)Bi0.50TiO3.015 (y-series), can significantly change the conduction mechanism and electrical properties compared to a nominally stoichiometric KNBT series (KxNa0.50-x)Bi0.50TiO3 (x-series). Impedance spectroscopy measurements reveal significantly higher bulk conductivity (σb) values for y ≥ 0.10 samples [activation energy (Ea) ≤ 0.95 eV] compared to the corresponding x-series samples which possess bandgap type electronic conduction (Ea ˜ 1.26-1.85 eV). The largest difference in electrical properties occurs close to the MPB composition (20 mol. % KBT) where y = 0.10 ceramics possess σb (at 300 °C) that is 4 orders of magnitude higher than that of x = 0.10 and the oxide-ion transport number in the former is ˜0.70-0.75 compared to processing. This demonstrates the electrical properties of KNBT to be sensitive to low levels of A-site nonstoichiometry and indicates that excess K2O in KNBT starting compositions to compensate for volatilisation can lead to undesirable high dielectric loss and leakage currents at elevated temperatures.

  15. Study of the solid-solid surface adsorption of Eu2O3 on various Al2O3 supports

    International Nuclear Information System (INIS)

    Liu Rongchuan; Yu Zhi; Zhou Yuan; Yoshitake Yamazaki

    1997-12-01

    Solid-solid surface interactions of Eu 2 O 3 on various oxide substrates are investigated with X-ray and Moessbauer experiments. The results indicate that the interaction of Eu 2 O 3 on the complex support differs from that having simple support. An incorporation model is used to explain how Eu 2 O 3 disperses onto the surface of γ-alumina or η-alumina

  16. Lanthanide doped BaTiO{sub 3}−SrTiO{sub 3} solid-solution phosphors: Structure, optical spectroscopy and upconverted temperature sensing behavior

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Daqin, E-mail: dqchen@hdu.edu.cn; Xu, Wei; Zhou, Yang; Chen, Yan, E-mail: chenyan@hdu.edu.cn

    2016-08-15

    Lanthanide doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} (x = 0–1) solid-solution phosphors were successfully prepared by a conventional solid-state reaction. Using Eu{sup 3+} dopants as the structural probe, the variation of {sup 5}D{sub 0} → {sup 7}F{sub 2}/{sup 5}D{sub 0} → {sup 7}F{sub 1} emission intensity ratio with increase of Eu{sup 3+} content and the excitation-wavelength-dependent luminescence in the Ba{sub 1-x}Sr{sub x}TiO{sub 3} sample were demonstrated to be originated from the different emission behaviors of Eu{sup 3+} in Ba{sup 2+}/Sr{sup 2+} site and Ti{sup 4+} site. Furthermore, upconversion luminescence for the Yb{sup 3+}/Er{sup 3+} co-doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} samples were investigated, and it was found that the emission intensity of Yb{sup 3+}/Er{sup 3+}: Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} phosphor was about 5 and 2 times as high as those of Yb{sup 3+}/Er{sup 3+}: BaTiO{sub 3} and Yb{sup 3+}/Er{sup 3+}: SrTiO{sub 3} ones. Using the investigated Yb{sup 3+}/Er{sup 3+}: Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} solid-solution as the optical thermometric medium, the temperature sensitivity was determined to be 0.76% K{sup −1} at the temperature of 610 K based on the temperature-dependent fluorescence intensity ratio of the thermally coupled {sup 2}H{sub 11/2} and {sup 4}S{sub 3/2} emitting-states of Er{sup 3+}. - Highlights: • Lanthanide doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} (x = 0–1) solid-solutions were fabricated. • Excitation-wavelength-dependent Eu{sup 3+} emissions were recorded. • Enhanced Er{sup 3+} luminescence was realized by partial substitution of Ba{sup 2+} by Sr{sup 2+}. • T-sensitive emissions of two Er{sup 3+} thermally coupled states were observed. • The upconversion phosphor exhibited a high sensitivity of 0.76% K{sup −1}.

  17. Energy transfer and tunable luminescence of Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} phosphors for white LED applications

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Zhang; Wanjun, Tang, E-mail: tangmailbox@126.com

    2016-01-15

    Highlights: • Iso-structural garnet-type Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} solid solution were synthesized. • Efficient energy transfer from [VO{sub 4}]{sup 3−} to Eu{sup 3+} ions in this phosphor is observed obviously. • Tuning the Y/Eu ratio generates the varied hues from yellowish-green to reddish-orange. • This kind of phosphor can be potentially used in UV pumped LEDs. - Abstract: A series of solid-solution phosphors Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} were prepared using solution combustion reaction. X-ray diffraction studies verified the formation of single phase Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} with garnet structure. Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} phosphors show not only a broad emission band with a maximum at 510 nm due to the [VO{sub 4}]{sup 3−} group but also several sharp emission lines due to the Eu{sup 3+} ions. The energy transfer from [VO{sub 4}]{sup 3−} to Eu{sup 3+} was discussed on the base of the spectral analysis. The color-tunable emissions of the Na{sub 2}(Y,Eu)Mg{sub 2}V{sub 3}O{sub 12} phosphor as a function of Y/Eu ratio are realized by continuously generating the varied hues from yellowish-green to reddish-orange. This indicates that the obtained phosphor may have potential applications in the field of UV-based white LEDs.

  18. Preparation and X-ray diffraction characterization of Th1-xBixO2-0.5x (where x= 0 to 0.5) solid solutions

    International Nuclear Information System (INIS)

    Kanrar, Buddhadev; Misra, N.L.

    2015-01-01

    Solid solutions of ThO 2 and Bi 2 O 3 were prepared by solid state reactions of these oxides. X-ray diffraction studies indicated that Bi +3 up to 50 at% can be dissolved in ThO 2 lattice. Rietveld refinement of the XRD patterns indicated single phase solid solutions up to 50 atom% of Bi +3 in ThO 2 lattice. The cell parameters of the solid solutions were found to decrease with increasing amount of Bi +3 in the lattice. (author)

  19. The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets

    International Nuclear Information System (INIS)

    Rettenwander, D.; Geiger, C.A.; Tribus, M.; Tropper, P.; Wagner, R.; Tippelt, G.; Lottermoser, W.; Amthauer, G.

    2015-01-01

    A series of Fe 3+ -bearing Li 7 La 3 Zr 2 O 12 (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and 57 Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe 3+ pfu could be incorporated in Li 7−3x Fe x La 3 Zr 2 O 12 garnet solid solutions. At Fe 3+ concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe 3+ contents lower than 0.52 Fe 3+ pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a 0 , for all solid-solution garnets is similar with a value of a 0 ≈12.98 Å regardless of the amount of Fe 3+ . 57 Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO 3 in syntheses with Fe 3+ contents greater than 0.16 Fe 3+ pfu. The composition of different phase pure Li 7−3x Fe x La 3 Zr 2 O 12 garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li 6.89 Fe 0.03 La 3.05 Zr 2.01 O 12 , Li 6.66 Fe 0.06 La 3.06 Zr 2.01 O 12 , Li 6.54 Fe 0.12 La 3.01 Zr 1.98 O 12 , and Li 6.19 Fe 0.19 La 3.02 Zr 2.04 O 12 . The 57 Fe Mössbauer spectrum of cubic Li 6.54 Fe 0.12 La 3.01 Zr 1.98 O 12 garnet indicates that most Fe 3+ occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe 3+ in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li 6.54 Fe 0.12 La 3.01 Zr 1.98 O 12 this Fe 3+ has a distorted 4-fold coordination. - Graphical abstract: Cubic nominally Li 7 La 3 Zr 2 O

  20. Study of the sintering process and the formation of a (Th, U) O2 solid solution

    International Nuclear Information System (INIS)

    Tomasi, Roberto

    1979-01-01

    The effect of some variables in the (Th, U) O 2 sintering process and solid solution formation was studied. ThO 2 , U 3 O 8 and UO 2 powder were prepared. The ThO 2 powders were obtained by calcination of thorium at 500 and 750 deg C; the U 3 O 8 powders were derived from the calcination of ADU at 660 and 750 deg C; the UO 2 powder were prepared from ADU and from ATCU. The different characteristics of these materials were determined by measurements of surface area, by scanning electron microscopy, tap density tests, X-ray diffractometry and by measurements of the O/U ratios. The oxide mixtures were chosen in order to produce a final composition with 10 w/o of UO 2 . A mixture of thorium oxalate and ADU was also prepared by calcining these salts in air at 700 deg C, in order to obtain certain amount of solid solution prior to sintering. The sintering operations were developed in an argon atmosphere at temperatures between 1400 and 1700 deg C, during interval varying from 1 to 4 hours. The effect of the mixture characteristics on the sintering process and solid solution formation were studied considering the results of densification, microstructure development and X-ray diffractometry. The ThO 2 powder characteristics have a main effect on the mixtures compactability and sinterability, the higher calcining temperatures increasing the green density, but decreasing the final density of the sintered pellets. In the sintering of mixtures containing U 3 O 3 , this oxide is reduced to UO 2 and it is possible to obtain pellets with density and microstructures similar to those produced from mixtures containing UO 2 . But if oxygen in excess is present during sintering, the process is affected, occurring exaggerated grain growth. The densification results were related to the Coble's kinetics equation for second stage of sintering, valid for bulk diffusion, grain boundary acting as vacancy sinks. The sintering activation energy is independent from the powder starting

  1. Development and characterization of nickel catalysts supported in CeO2-ZrO2-Al2O3, CeO2-La2O3-Al2O3 e ZrO2-La2O3-Al2O3 matrixes evaluated for methane reforming reactions

    International Nuclear Information System (INIS)

    Abreu, Amanda Jordão de

    2012-01-01

    Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al 2 O 3 . However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al 2 O 3 supported on solid solutions formed by ZrO 2 -CeO 2 , La 2 O 3 and CeO 2 -ZrO 2 -La 2 O 3 were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al 2 O 3 catalysts and the best catalysts are Ni/CeO 2 -La 2 O 3 -Al 2 O 3 . (author)

  2. Structural properties of CaTi{sub 1-x}(Nb{sub 2/3}Li{sub 2/3}){sub x}O{sub 3-d}elta (CNLTO) and CaTi{sub 1-x}(Nb{sub 1/2}Ln{sub 1/2}){sub x}O{sub 3} (Ln=Fe (CNFTO), Bi (CNBTO)), modified dielectric ceramics for microwave applications

    Energy Technology Data Exchange (ETDEWEB)

    Costa, R.C.S. [Laboratorio de Telecomunicacoes e Ciencia e Engenharia dos Materiais (LOCEM), Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, CEP 60455-760, Fortaleza, Ceara (Brazil); Departamento de Engenharia de Teleinformatica, CP 6007, Universidade Federal do Ceara, CEP 60455-760, Fortaleza, Ceara (Brazil); Bruno Costa, A.D.S. [Departamento de Engenharia de Teleinformatica, CP 6007, Universidade Federal do Ceara, CEP 60455-760, Fortaleza, Ceara (Brazil); Freire, F.N.A.; Santos, M.R.P.; Almeida, J.S.; Sohn, R.S.T.M. [Laboratorio de Telecomunicacoes e Ciencia e Engenharia dos Materiais (LOCEM), Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, CEP 60455-760, Fortaleza, Ceara (Brazil); Sasaki, J.M. [Laboratorio de Raios-X, Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, CEP 60455-760, Fortaleza, Ceara (Brazil); Sombra, A.S.B., E-mail: sombra@fisica.ufc.b [Laboratorio de Telecomunicacoes e Ciencia e Engenharia dos Materiais (LOCEM), Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, CEP 60455-760, Fortaleza, Ceara (Brazil)

    2009-05-01

    This paper presents an investigation of the structural characteristics of Nb{sub 1/2}Bi{sub 1/2} (CNBTO), Nb{sub 1/2}Fe{sub 1/2} (CNFTO) and Nb{sub 2/3}Li{sub 1/3} (CNLTO) substitution into the B-site of calcium titanate ceramics. The modified CaTiO{sub 3} (CTO) ceramics were prepared by the conventional solid-state method. The compounds were investigated, by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDXS). The X-ray analysis shows that all samples have an orthorhombic structure. The refinement analysis of all samples were also performed and discussed in this paper. For all studied samples, a Raman mode at 805 cm{sup -1} was detected and its intensity increases as the substitution increases. The dielectric permittivity and loss at microwave frequencies (MW) were investigated. The CNLTO phase, present the highest dielectric constant (k=35.8) at 3.9 GHz with loss (tg alpha=7x10{sup -3}). The lowest value of k=25.7 (f=4.8 GHz) and tg alpha=3x10{sup -3}, was obtained for the CNFTO phase. These measurements confirm the possible use of such material for microwave devices like dielectric resonator antennas.

  3. 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.......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...

  4. Synthesis and electronic properties of LnRhAsO and LnIrAsO compositions

    International Nuclear Information System (INIS)

    Muir, Sean; Sleight, A.W.; Subramanian, M.A.

    2011-01-01

    The synthesis and characterization of the new compositions LnRhAsO (Ln=Ce, Nd) and LnIrAsO (Ln=La, Ce, Nd) are reported. These compounds crystallize in the ZrCuSiAs type structure, isostructural to iron pnictide LnFeAsO materials. Upon substitution of Rh for Fe, both a and c lattice parameters increase relative to 3d transition metal compounds; however, when Ir is substituted for Rh the a-parameter decreases slightly while the c-parameter expands. The decrease in a lattice parameter corresponds to a short metal-metal distance in Ir compounds. CeRhAsO and CeIrAsO compositions show abrupt decreases in resistivity at 7 and 10 K, respectively, coinciding with a small shift in magnetization at the transition temperature. - Graphical abstract: LnIrAsO (Ln=La, Ce, Nd) and LnRhAsO (Ln=Ce, Rh) have been synthesized. These new transition metal oxypnictide compositions are isostructural to LaFeAsO. The 5d Ir compositions demonstrate a shorter metal-metal interaction than the 4d Rh compositions. Highlights: → LnIrAsO (Ln=La, Ce, Nd) and LnRhAsO (Ln=Ce, Nd) have been synthesized. → Ir compositions show a decreased a-parameter and increased c-parameter relative to Rh compositions. → All LnIrAsO and LnRhAsO compositions are metallic while CeIrAsO and CeRhAsO show a sudden drop in resistivity at 10 and 7 K, respectively.

  5. Syntheses, crystal structures and photoluminescence properties of two rare-earth molybdates CsLn(MoO{sub 4}){sub 2} (Ln=Eu, Tb)

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dan; Ma, Fa-Xue; Liu, Bao-Zhong; Fan, Yun-Chang; Han, Xue-Feng; Zhang, Lei; Nie, Cong-Kui [Henan Polytechnic Univ. (China). College of Chemistry and Chemical Engineering

    2018-04-01

    Single crystals of two cesium rare-earth molybdates CsLn(MoO{sub 4}){sub 2} (Ln=Eu, Tb) have been prepared using the high temperature molten salt (flux) method. Single-crystal X-ray diffraction analyses reveal that they crystallize in the orthorhombic space group Pccm (No. 49) and features a 2D layer structure that is composed of [Ln(MoO{sub 4}){sub 2}]{sub ∞} and [Cs]{sub ∞} layers. Under near-UV light excitation, emission spectrum of CsEu(MoO{sub 4}){sub 2} consists of several sharp lines due to the characteristic electronic transitions of Eu{sup 3+} ions, whereas CsTb(MoO{sub 4}){sub 2} exhibits characteristic green emission of Tb{sup 3+} ions.

  6. Surface and catalytic properties of MoO3/Al2O3 system doped with Co3O4

    International Nuclear Information System (INIS)

    Zahran, A.A.; Shaheen, W.M.; El-Shobaky, G.A.

    2005-01-01

    Thermal solid-solid interactions in cobalt treated MoO 3 /Al 2 O 3 system were investigated using X-ray powder diffraction. The solids were prepared by wet impregnation method using Al(OH) 3 , ammonium molybdate and cobalt nitrate solutions, drying at 100 deg. C then calcination at 300, 500, 750 and 1000 deg. C. The amount of MoO 3 , was fixed at 16.67 mol% and those of cobalt oxide were varied between 2.04 and 14.29 mol% Co 3 O 4 . Surface and catalytic properties of various solid samples precalcined at 300 and 500 deg. C were studied using nitrogen adsorption at -196 deg. C, conversion of isopropanol at 200-500 deg. C and decomposition of H 2 O 2 at 30-50 deg. C. The results obtained revealed that pure mixed solids precalcined at 300 deg. C consisted of AlOOH and MoO 3 phases. Cobalt oxide-doped samples calcined at the same temperature consisted also of AlOOH, MoO 3 and CoMoO 4 compounds. The rise in calcination temperature to 500 deg. C resulted in complete conversion of AlOOH into very poorly crystalline γ-Al 2 O 3 . The further increase in precalcination temperature to 750 deg. C led to the formation of Al 2 (MoO 4 ) 3 , κ-Al 2 O 3 besides CoMoO 4 and un-reacted portion of Co 3 O 4 in the samples rich in cobalt oxide. Pure MoO 3 /Al 2 O 3 preheated at 1000 deg. C composed of MoO 3 -αAl 2 O 3 solid solution (acquired grey colour). The doped samples consisted of the same solid solution together with CoMoO 4 and CoAl 2 O 4 compounds. The increase in calcination temperature of pure and variously doped solids from 300 to 500 deg. C increased their specific surface areas and total pore volume which suffered a drastic decrease upon heating at 750 deg. C. Doping the investigated system with small amounts of cobalt oxide (2.04 and 4 mol%) followed by heating at 300 and 500 deg. C increased its catalytic activity in H 2 O 2 decomposition. This increase, measured at 300 deg. C, attained 25.4- and 12.9-fold for the solids precalcined at 300 and 500 deg. C, respectively

  7. Electronic structure and photocatalytic activities of (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Wenjie; Hu, Jinli; Huang, Jing; Wu, Xin; Lin, Sen, E-mail: slin@fzu.edu.cn; Huang, Caijin; Qiu, Xiaoqing, E-mail: qiuxq@fzu.edu.cn

    2015-12-01

    Highlights: • (Bi{sub 2−δ}Y{sub δ})Sn2O7 solid solutions were synthesized by one-step hydrothermal method. • The contribution of Bi 6s orbitals to electronic structures can be continuously tuned. • The high photocatalytic activity should originate from the good band dispersions. - Abstract: A series of (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} solid solutions were prepared by a one-step hydrothermal method to investigate the correlation between the electronic structures and photocatalytic activity. All the (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} 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 (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} 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 Y{sup 3+} induces the shrinkage of the lattice of (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} solid solutions. Consequently, the contribution of Bi 6s orbitals to electronic structures of (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} solid solutions can be continuously tuned by Y{sup 3+} substitution for Bi{sup 3+}. Density function theory calculations reveal that the Bi 6s and O 2p states dominate the top of valence band of Bi{sub 2}Sn{sub 2}O{sub 7}, while the bottom of conduction band mainly consists of the states of Sn 5s, O 2p and Bi 6p. Once the Bi{sup 3+} ions are substituted by Y{sup 3+}, 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 Bi{sub 2}Sn{sub 2}O{sub 7}. Moreover, the band dispersions of valence band and conduction band become narrower after Y{sup 3+} introduction into the lattice of (Bi{sub 2−δ}Y{sub δ})Sn{sub 2}O{sub 7} solid solutions. As a result, the

  8. Synthesis and crystal structure of the solid solution Co3(SeO3)3-x(PO3OH)x(H2O) involving crystallographic split positions of Se4+ and P5+.

    Science.gov (United States)

    Zimmermann, Iwan; Johnsson, Mats

    2013-10-21

    Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) μB per Co atom was observed.

  9. Nitrate conversion and supercritical fluid extraction of UO{sub 2}-CeO{sub 2} solid solution prepared by an electrolytic reduction-coprecipitation method

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, L.Y. [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology; China Institute of Atomic Energy, Beijing (China); Duan, W.H.; Wen, M.F.; Xu, J.M.; Zhu, Y.J. [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology

    2014-04-01

    A low-waste technology for the reprocessing of spent nuclear fuel (SNF) has been developed recently, which involves the conversion of actinide and lanthanide oxides with liquid N{sub 2}O{sub 4} into their nitrates followed by supercritical fluid extraction of the nitrates. The possibility of the reprocessing of SNF from high-temperature gas-cooled reactors (HTGRs) with nitrate conversion and supercritical fluid extraction is a current area of research in China. Here, a UO{sub 2}-CeO{sub 2} solid solution was prepared as a surrogate for a UO{sub 2}-PuO{sub 2} solid solution, and the recovery of U and Ce from the UO{sub 2}-CeO{sub 2} solid solution with liquid N{sub 2}O{sub 4} and supercritical CO{sub 2} containing tri-n-butyl phosphate (TBP) was investigated. The UO{sub 2}-CeO{sub 2} solid solution prepared by electrolytic reduction-coprecipitation method had square plate microstructures. The solid solution after heat treatment was completely converted into nitrates with liquid N{sub 2}O{sub 4}. The XRD pattern of the nitrates was similar to that of UO{sub 2}(NO{sub 3}){sub 2} . 3H{sub 2}O. After 120 min of online extraction at 25 MPa and 50 , 99.98% of the U and 98.74% of the Ce were recovered from the nitrates with supercritical CO{sub 2} containing TBP. The results suggest a promising potential technology for the reprocessing of SNF from HTGRs. (orig.)

  10. Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

    Science.gov (United States)

    Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

    2018-03-01

    A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

  11. Luminescent and scintillation properties of the Pr"3"+ doped single crystalline films of Lu_3Al_5_−_xGa_xO_1_2 garnet

    International Nuclear Information System (INIS)

    Gorbenko, V.; Zorenko, Yu; Zorenko, T.; Voznyak, T.; Paprocki, K.; Fabisiak, K.; Fedorov, A.; Bilski, P.; Twardak, A.; Zhusupkalieva, G.

    2016-01-01

    The Pr"3"+ d–f luminescence was investigated in the single crystalline films (SCF) of Lu_3Al_5_−_xGa_xO_1_2:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B_2O_3 flux. The shape of CL spectra and decay kinetics of Pr"3"+ ions in Lu_3Al_5_−_xGa_xO_1_2 SCFs strongly depend on the total gallium concentration x and distribution of Ga"3"+ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu_3Al_5_−_xGa_xO_1_2:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 22.5 range. - Highlights: • Single crystalline films of Lu_3Al_5_−_x Ga_xO_1_2:Pr garnet at x = 1–3 were grown by the LPE method. • Pr"3"+ emission spectra, light yield and decay time of films show strong dependence on Ga content. • The maximal light yield of Lu_3Al_5_−_x Ga_xO_1_2:Pr film is observed at Ga content x = 2.0–2.5.

  12. A solid solution series of atacamite type Ni{sub 2x}Mg{sub 22x}Cl(OH){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Bette, Sebastian [TU Bergakademie Freiberg, Institute of Inorganic Chemistry, Leipziger Strasse 29, Freiberg 09596 (Germany); Dinnebier, Robert E. [Max Planck Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart 70569 (Germany); Röder, Christian [TU Bergakademie Freiberg, Institute of Theoretical Physics, Leipziger Strasse 23, Freiberg 09596 (Germany); Freyer, Daniela, E-mail: daniela.freyer@chemie.tu-freiberg.de [TU Bergakademie Freiberg, Institute of Inorganic Chemistry, Leipziger Strasse 29, Freiberg 09596 (Germany)

    2015-08-15

    For the first time a complete solid solution series Ni{sub 2x}Mg{sub 22x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these two metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 22x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 22x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 22x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes

  13. Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions

    International Nuclear Information System (INIS)

    Hinatsu, Y.; Fujino, T.

    1988-01-01

    Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions with fluorite structure were measured from 4.2 K to room temperature. An antiferromagnetic transition was observed for all the solid solutions examined in this study (y ≤ 0.33). The Neel temperature of the oxygen-hypostoichiometric solid solutions (x 2 solid solutions, but different from that of (U,Th)O 2 solid solutions. The effective magnetic moment decreased with increasing calcium concentration, which indicates the oxidation of uranium in the solid solutions. From the analysis of the magnetic susceptibility data, it was found that the oxidation state of uranium was either tetravalent or pentavalent. The Neel temperature of the hyperstoichiometric solid solutions (x > 0) did not change appreciably with calcium concentrations. From the comparison of the magnetic susceptibility data of the hypostoichiometric solid solutions with those of the hyperstoichiometric solid solutions, the effect of oxygen vacancies is more significant than that of interstitial oxygens on the decrease of magnetic interactions between uranium ions

  14. Cr6+-containing phases in the system CaO-Al2O3-CrO42--H2O at 23 °C

    Science.gov (United States)

    Pöllmann, Herbert; Auer, Stephan

    2012-01-01

    Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO·Al2O3·CaCrO4·nH2O and C31/2Ca(OH)2·1/2CaCrO12H2O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l.

  15. Bi2(Sr, Ln)2CuOz (Ln = Nd, Sm) phases: stability, crystal growth and superconducting properties

    International Nuclear Information System (INIS)

    Faqir, H.; Kikuchi, M.; Syono, Y.; Mansori, M.; Satre, P.; Sebaoun, A.; Vacquier, G.

    2000-01-01

    Bi 2 (Sr,Ln) 2 CuO z (Ln = Nd, Sm) single crystals were successfully grown by a self-flux method from stoichiometric and (Bi, Cu)-rich melts. Thermal analysis and thermogravimetry were used to determine stability and the melting sequence of Bi 2 (Sr,Ln) 2 CuO z phases in air. As-grown crystals of the ideal Bi 2 (Sr,Ln) 2 CuO z phase, of dimensions 1x0.5x0.03 mm 3 , exhibit superconducting behaviour with critical temperature T c = 21 K for the Bi 1.9 Sr 1.6 Nd 0.6 CuO z crystal and Tc = 14 K for the Bi 1.8 Sr 1.6 Sm 0.6 CuO z crystal. The compositions of these crystals were homogeneous and close to the stoichiometric composition. We report on the growth of Bi 2 Sr 2-x Sm x CuO z single crystals of large dimensions 9x3x0.03 mm 3 using Bi 2 Sr 1.5 Sm 0.5 CuO z as precursor and Bi 2 CuO 4 as flux. (author)

  16. Solid-state synthesis of Li_4Ti_5O_1_2 whiskers from TiO_2-B

    International Nuclear Information System (INIS)

    Yao, Wenjun; Zhuang, Wei; Ji, Xiaoyan; Chen, Jingjing; Lu, Xiaohua; Wang, Changsong

    2016-01-01

    Highlights: • The Li_4Ti_5O_1_2 whiskers were synthesized from TiO_2-B whiskers via a solid state reaction. • The TiO_2-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li_4Ti_5O_1_2 whiskers. - Abstract: In this work, Li_4Ti_5O_1_2 (LTO) was synthesized from the precursors of TiO_2-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO_2-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO_2-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

  17. On the structure of rare earth periodates of LnIO5x4H2O (Ln=Pr-Lu, Y)

    International Nuclear Information System (INIS)

    Shamraj, N.B.; Varfolomeev, M.B.; Saf'yanov, Yu.N.; Kuz'min, Eh.A.; Ilyukhin, V.V.; AN SSSR, Moscow. Inst. Kristallografii)

    1977-01-01

    The crystal structure of three representatives of an isotypic series of monoclinic periodates of rare earth elements in the series from Pr to Lu and Y was deciphered. The monoclinic cell for all LnIO 5 x4H 2 O contains Z=4 formula units. The architectural motif consists in layers of octahedra of IO 4 (OH) 2 and polyhedra of LnO 5 (H 2 O 3 ) parallel to the (100) plane. Adhesion between the layers is achieved through H-bonds

  18. 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.

  19. Photoluminescence properties of La{sub 2x}Ga{sub 2y}In{sub 2z}O{sub 3} solid solutions used as photocatalysts for water splitting and promising panchromatic emitters

    Energy Technology Data Exchange (ETDEWEB)

    Penconi, Marta; Cesaretti, Alessio [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); Ortica, Fausto [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); CEMIN, Via Elce di Sotto 8, 06123 Perugia (Italy); CIRIAF, Via G. Duranti 67, 06125 Perugia (Italy); Istituto Nazionale di Fisica Nucleare (INFN), Sezione di Perugia, Via Pascoli, 06123 Perugia (Italy); Elisei, Fausto [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); CEMIN, Via Elce di Sotto 8, 06123 Perugia (Italy); CIRIAF, Via G. Duranti 67, 06125 Perugia (Italy); Gentili, Pier Luigi, E-mail: pierluigi.gentili@unipg.it [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); CIRIAF, Via G. Duranti 67, 06125 Perugia (Italy)

    2016-09-15

    The steady-state and time-resolved photoluminescence of nine ternary solid solutions, whose general formula is La{sub 2x}Ga{sub 2y}In{sub 2z}O{sub 3}, used as heterogeneous photocatalysts for the production of hydrogen by water splitting, has been investigated in order to characterize the properties of their electronic excited states. The comparison with the parent binary oxides (LaGaO{sub 3}, LaInO{sub 3} and GaInO{sub 3}) proved to be essential for understanding the composition of the solids in terms of phases and allowed the different emissions to be assigned to specific crystal structures and band gap transitions. Upholding what was previously deduced by means of the X-ray powder diffraction and micro-Raman techniques, the structural properties of the La{sub 2x}Ga{sub 2y}In{sub 2z}O{sub 3} samples were corroborated. By doing so, the employment of photoluminescence as a distinctive feature to strengthen the structural information gathered by other techniques is demonstrated. Moreover, the luminescence lifetimes of the photo-generated electron–hole pairs were measured and analyzed in view of the photocatalytic activity of the samples, with their efficiency being directly proportional to the excited state lifetime. Finally, the metal oxides solid solutions have been found able to emit over the entire visible region up to near-IR. Therefore, they might be appealing panchromatic emitters for display and lightning technologies. - Highlights: • The photoluminescence is useful to gain insight on structural composition of solid solutions. • Determination of electronic lifetimes by both Least-Squares and Maximum Entropy method. • Direct electronic transitions last less than indirect phonon-assisted transitions. • La{sub 2x}Ga{sub 2y}In{sub 2z}O{sub 3} are promising panchromatic emitters. • La{sub 2x}Ga{sub 2y}In{sub 2z}O{sub 3} have lifetimes ranging from tens of μs up to tens of ms.

  20. Calorimetric measurements on plutonium rich (U,Pu)O2 solid solutions

    International Nuclear Information System (INIS)

    Kandan, R.; Babu, R.; Nagarajan, K.; Vasudeva Rao, P.R.

    2008-01-01

    Enthalpy increments of U (1-y) Pu y O 2 solid solutions with y = 0.45, 0.55 and 0.65 were measured using a high-temperature differential calorimeter by employing the method of inverse drop calorimetry in the temperature range 956-1803 K. From the fit equations for the enthalpy increments, other thermodynamic functions such as heat capacity, entropy and Gibbs energy function have been computed in the temperature range 298-1800 K. The results are presented and compared with the data available in the literature. The results indicate that the enthalpies of U (1-y) Pu y O 2 solid solutions with y = 0.45, 0.55 and 0.65 obey the Neumann-Kopp's molar additivity rule

  1. Structural, magnetic, and dielectric properties of solid solutions between BiMnO{sub 3} and YMnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Belik, Alexei A., E-mail: Alexei.BELIK@nims.go.jp

    2017-02-15

    Bi{sub 1−x}Y{sub x}MnO{sub 3} (0.1≤x≤0.9) solid solutions were prepared by the high-pressure high-temperature method at 6 GPa and 1573 K. They crystallize in the GdFeO{sub 3}-type perovskite structure with the Pnma symmetry. Crystal structures of Bi{sub 0.9}Y{sub 0.1}MnO{sub 3} and Bi{sub 0.5}Y{sub 0.5}MnO{sub 3} are studied by synchrotron X-ray powder diffraction at room temperature. Only one Néel temperature, T{sub N}, is found in samples with 0.1≤x≤0.9 in comparison with two Néel temperatures observed in YMnO{sub 3} (T{sub N}=29 and 39 K). Samples with 0.5≤x≤0.9 have almost constant T{sub N}=44 K, while T{sub N} starts to increase linearly for other compositions: T{sub N}=46 K for x=0.3, T{sub N}=58 K for x=0.2, and T{sub N}=68 K for x=0.1. Field-induced transitions from canted-antiferromagnetic states to antiferromagnetic states are detected at about 30 kOe for x=0.2 and 70 kOe for x=0.1. Dielectric constant increases below T{sub N} in samples with 0.5≤x≤1, while it decreases below T{sub N} in samples with 0.1≤x≤0.3. Our data suggest that a magnetic structure changes near x=0.4. By extrapolation, we could estimate lattice parameters (a=5.9221 Å, b=7.5738 Å, and c=5.4157 Å) and T{sub N}=79 K for a hypothetical Pnma modification of BiMnO{sub 3}. - Graphical abstract: Bi{sub 1−x}Y{sub x}MnO{sub 3} solid solutions were prepared in the whole compositional range by the high-pressure method. Magnetic and dielectric data suggest that a magnetic structure changes near x=0.4. No ferroelectric properties were found. - Highlights: • Orthorhombic Bi{sub 1−x}Y{sub x}MnO{sub 3} solid solutions are prepared by the high-pressure method. • Structural, magnetic, and dielectric properties are studied. • One Néel temperature is found in all the samples. • T{sub N}=44 K for x=0.5–0.9, 46 K for x=0.3, 58 K for x=0.2, and 68 K for x=0.1. • No ferroelectricity is observed.

  2. Structures and solid solution mechanisms of pyrochlore phases in the systems Bi2O3-ZnO-(Nb, Ta)2O5

    International Nuclear Information System (INIS)

    Tan, K.B.; Khaw, C.C.; Lee, C.K.; Zainal, Z.; Miles, G.C.

    2010-01-01

    Research highlights: → Combined XRD and ND Rietveld structural refinement of pyrochlores. → Structures and solid solution mechanisms of Bi-pyrochlores. → Bi and Zn displaced off-centre to different 96g A-site positions. → Summary of composition-structure-property of Bi-pyrochlores. - Abstract: The crystal structures of two pyrochlore phases have been determined by Rietveld refinement of combined X-ray and neutron powder diffraction data. These are stoichiometric, Bi 1.5 ZnTa 1.5 O 7 and non-stoichiometric Bi 1.56 Zn 0.92 Nb 1.44 O 6.86 . In both structures, Zn is distributed over A- and B-sites; Bi and Zn are displaced off-centre, to different 96g A-site positions; of the three sets of oxygen positions, O(1) are full, O(2) contain vacancies and O(3) contain a small number of oxygen, again in both cases. Comparisons between these structures, those of related Sb analogues and literature reports are made.

  3. Li{sub 35}Ln{sub 9}Si{sub 30}N{sub 59}O{sub 2}F with Ln = Ce, Pr - highly condensed nitridosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Lupart, Saskia; Durach, Dajana; Schnick, Wolfgang [Department Chemie, Lehrstuhl fuer Anorganische Festkoerperchemie, Ludwig-Maximilians-Universitaet Muenchen (Germany)

    2011-10-15

    The isotypic nitridosilicates Li{sub 35}Ln{sub 9}Si{sub 30}N{sub 59}O{sub 2}F (Ln = Ce, Pr) were synthesized by reaction of LnF{sub 3} and LiN{sub 3} with Si(NH){sub 2} in liquid lithium flux in weld shut tantalum ampoules. The crystal structures of the isotypic compounds were solved and refined on the basis of single-crystal X-ray diffraction (P anti 3c1 (no. 165), Z = 2; Li{sub 35}Ce{sub 9}Si{sub 30}N{sub 59}O{sub 2}F:, a = 1479.9(2), c = 1538.3(3) pm, R{sub 1} = 0.0526, 1671 data, 175 parameters; Li{sub 35}Pr{sub 9}Si{sub 30}N{sub 59}O{sub 2}F: a = 1477.3(2), c = 1533.9(3) pm, R{sub 1} = 0.0441, 1331 data, 175 parameters). The silicate substructure represents a 3D network of all side corner sharing SiN{sub 4} tetrahedra. At one discrete and not condensed mixed anion position an atomic ratio O:F = 2:1 is assumed in order to achieve charge neutrality. With an atomic ratio Si:N = 30:59, the degree of condensation of the silicate substructure is slightly above κ = 1/2. Accordingly, there are triply crosslinking N{sup [3]} atoms in the silicate substructure. The obtained structures prove that by employing the lithium flux technique not only nitridosilicates with a low degree of condensation can be obtained by using rather mild reaction conditions at low temperatures. Lattice energy calculations (MAPLE) and EDX measurements confirmed the electrostatic bonding interactions and the chemical composition. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Ln28Ti2O7 (Ln = La, Nd, Sm, Gd): a novel series of defective Ruddlesden–Popper phases formed by topotactic dehydration of HLnTiO4

    OpenAIRE

    Thangadurai, V; Subbanna, GN; Gopalakrishnan, J

    1998-01-01

    Topotactic dehydration of HLnTiO4 (Ln = La, Nd, Sm or Gd) around 480–500 °C yields a new series of metastable layered perovskite oxides, Ln28Ti2O7, that possess a defective Sr3Ti2O7 structure, where the cubooctahedral sites within the double-perovskite layers are most likely vacant.

  5. 3d-4f {Co(II)3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts.

    Science.gov (United States)

    Evangelisti, Fabio; Moré, René; Hodel, Florian; Luber, Sandra; Patzke, Greta Ricarda

    2015-09-02

    Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [Co(II)3Ln(hmp)4(OAc)5H2O] ({Co(II)3Ln(OR)4}; Ln = Ho-Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {Co(II)3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln(3+) centers as redox-inactive Ca(2+) analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s(-1)). Furthermore, they open up the important family of 3d-4f complexes for photocatalytic applications. The stability of the {Co(II)3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln(3+) centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born-Oppenheimer molecular dynamics studies.

  6. Investigation into isomolar series of Al(NO3)3, Na3VO4 solution mixture and composition of solid phases

    International Nuclear Information System (INIS)

    Chernysh, L.F.; Nakhodnova, A.P.; Makarova, R.A.

    1979-01-01

    Conducted is investigation of properties of isomolar series of aluminium nitrate and sodiUm vanadate solutions at pH of the latter 12.5; 10.0; 7.0 and the temperature of 25 deg C using the methods of pH-metry, conductometry, ''seeming'' volume of precipitations, residual concentration of aluminium and vanadium. It is shown, that the composition property diagram of the system investigated does not reflect the true composition of solid-phase products of the reaction, which depends on the component ratio in solution. Bottom phases of isomolar series are mainly heterogeneous. At the excess of sodium vanadate solution and its high pH values conditions for the basic salt formation are created. At pH of the Na 3 VO 4 solution of 12.5 and 10.0 and Al(NO 3 ) 3 : Na 3 VO 4 ratios 4:6 and 3:7 respectively obtained are the basic aluminium vanadates of the (AlOH) 3 (VO 4 ) 2 x 7.5H 2 O and (AlOH) 2 V 2 O 7 x5H 2 O composition, some of their physicochemical properties being investigated

  7. The orthorhombic fluorite related compounds Ln/sub 3/RuO/sub 7/, Ln=Nd, Sm and Eu

    International Nuclear Information System (INIS)

    Van Berkel, F.P.F.; Ijdo, D.J.W.

    1986-01-01

    Fluorite-related Ru(V) compound with composition Ln/sub 3/RuO/sub 7/ have been found. These compounds with space group Cmcm adopt a superstructure of the cubic fluorite structure with a/sub orth/=2a/sub c/, b/sub orth/=c/sub orth/=a/sub c/√2. These compounds have the same structure as La/sub 3/NbO/sub 7/

  8. Modeling 4f–4f intensity parameters as a function of structural distortions in Ln(2,2′-bipyridine-1,1′-dioxide){sub 4}(ClO{sub 4}){sub 3} complexes (Ln=Pr{sup 3+}, Nd{sup 3+})

    Energy Technology Data Exchange (ETDEWEB)

    Carneiro, A.N. [Departamento de Química Fundamental, Universidade Federal de Pernambuco-CCEN, Cidade Universitária, Recife-PE 50670-901 (Brazil); Huskowska, E.; Gawryszewska, P. [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, Wroclaw (Poland); Legendziewicz, J., E-mail: janina.legendziewicz@chem.uni.wroc.pl [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, Wroclaw (Poland); Malta, O.L. [Departamento de Química Fundamental, Universidade Federal de Pernambuco-CCEN, Cidade Universitária, Recife-PE 50670-901 (Brazil)

    2016-01-15

    This work reports on the influence of structural distortions on 4f–4f intensity parameters. These distortions in the first coordination sphere were applied to two complexes with similar structures, Ln(bpyO{sub 2}){sub 4}(ClO{sub 4}){sub 3} (Ln=Pr{sup 3+}, Nd{sup 3+} ions and bpyO{sub 2}=2,2′-bipyridine-1,1′-dioxide). The 4f–4f intensity theory and the PM3/Sparkle model were used. It is concluded that larger distortions are predicted in the case of the Pr complex, and that this point might contribute to the rationalization of the much higher values of the Ω{sub λ} intensity parameters in the Pr complex than in the Nd one. - Highlights: • The influence of structural distortions on 4f–4f intensity parameters was demonstrated for Nd and Pr complexes with 2,2′-bipyridine-1,1′-dioxide.

  9. Thermodynamics of Bi2O3-SiO2 system

    Directory of Open Access Journals (Sweden)

    Onderka B.

    2017-01-01

    Full Text Available Thermodynamic properties of the liquid Bi2O3-SiO2 solutions were determined from the results of the electrochemical measurements by use of the solid oxide galvanic cells with YSZ (Yttria-Stabilized-Zirconia electrolyte. Activities of Bi2O3 in the solutions were determined for 0.2, 0.3, 0.4, and 0.5 SiO2 mole fractions in the temperature range 1073-1293 K from measured electromotive force (e.m.f of the solid electrolyte galvanic cell: Bi, Bi2O3-SiO2 | YSZ | air (pO2 = 0.213 bar Additionally, heat capacity data obtained for two solid phases 6Bi2O3•SiO2 and 2Bi2O33SiO2 were included into optimization of thermodynamic properties of the system. Optimization procedure was supported by differential thermal analysis (DTA data obtained in this work as well as those accepted from the literature. Using the data obtained in this work, and the information about phase equilibria found in the literature, binary system Bi2O3-SiO2 was assessed with the ThermoCalc software.

  10. Prism inside. Spectroscopic and magnetic properties of the lanthanide(III) chloride oxidotungstates(VI) Ln{sub 3}Cl{sub 3}[WO{sub 6}] (Ln = La - Nd, Sm - Tb)

    Energy Technology Data Exchange (ETDEWEB)

    Dorn, Katharina V.; Blaschkowski, Bjoern; Hartenbach, Ingo [Institute for Inorganic Chemistry, University of Stuttgart (Germany); Foerg, Katharina; Netzsch, Philip; Hoeppe, Henning A. [Institute for Physics, University of Augsburg (Germany)

    2017-11-17

    The lanthanide(III) chloride oxidotungstates(VI) with the formula Ln{sub 3}Cl{sub 3}[WO{sub 6}] for Ln = La - Nd, Sm - Tb were synthesized by solid-state reactions utilizing the respective lanthanide trichloride, lanthanide sesquioxide (where available), and tungsten trioxide together with lithium chloride as flux. The title compounds crystallize hexagonally in space group P6{sub 3}/m (no. 176, a = 941-909, c = 543-525 pm, Z = 2). The structures comprise crystallographically unique Ln{sup 3+} cations surrounded by six O{sup 2-} and four Cl{sup -} anions (C.N. = 10) forming distorted tetracapped trigonal prisms as well as rather uncommon trigonal prismatic [WO{sub 6}]{sup 6-} units, whose edges are coordinated by nine Ln{sup 3+} cations. Thus, a {sup 3}{sub ∞}{([WO_6]Ln"e_9_/_3)"3"+} framework (e = edge-sharing) is created, which contains tube-shaped channels along [001] lined with chloride anions. To elucidate the spectroscopic and magnetic properties of the obtained pure phase samples, single-crystal Raman (for Ln = La - Nd, Sm-Tb), diffuse reflectance (for Ln = La, Pr, Nd, Gd), and luminescence spectroscopy (for bulk Ln{sub 3}Cl{sub 3}[WO{sub 6}] (Ln = La, Eu, Gd, Tb) and Eu{sup 3+}- or Tb{sup 3+}-doped derivatives of La{sub 3}Cl{sub 3}[WO{sub 6}] and Gd{sub 3}Cl{sub 3}[WO{sub 6}], respectively) were performed and their temperature-dependent magnetic moments (for Ln = Pr, Nd, Gd) were determined. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Ternary phosphates in Ca3(PO4)2-Na3Ln(PO4)2 (Ln-Nd, Eu, Er) systems

    International Nuclear Information System (INIS)

    Lazoryak, B.I.; Ivanov, L.N.; Strunenkova, T.V.; Golubev, V.N.; Viting, B.N.

    1990-01-01

    Ternary phosphates, formed in Ca 3 (PO 4 ) 2 -Na 3 Ln(PO 4 ) 2 (Ln-Nd, Eu, Er) systems were investigated by the methods of X-ray phase, luminescent analyses and IR spectroscopy. 5 regions of homogeneity were found. Two of them (I and II) were distinguished for all systems. Samples in the region of up to 14.285 mol.% Na 3 Ln(PO 4 ) 2 crystallize on the basis of β-Ca 3 (PO 4 ) 2 structure, and in other homogeneity regions - on the basis of β-K 2 SO 4 structure

  12. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} Pellets

    Energy Technology Data Exchange (ETDEWEB)

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi, E-mail: kanamura@tmu.ac.jp [Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo (Japan)

    2016-08-30

    All-solid-state lithium-ion batteries using Li{sup +}-ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li{sub 6.25}Al{sub 0.25}La{sub 3}Zr{sub 2}O{sub 12} (LLZAl), which is a Al-doped Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZ) with Li{sup +}-ion conductivity of ~10{sup –4} S ⋅cm{sup −1} at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO{sub 2}/LLZAl/lithium-metal configuration. It is expected that the LiCoO{sub 2}–LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li{sub 3}BO{sub 3}, which is a

  13. phase formation and thermal stability of fcc (fluorite) Ce1-xTbxO2-d solid solutions

    NARCIS (Netherlands)

    de Vries, Karel Jan; de Vries, K.J.; Meng, G.Y.

    1998-01-01

    Ce1−xTbxO2−δ solid solutions (x = 0.3, 0.4, and 0.5) were synthesized by a coprecipitation method, using ammonia. The formation process of the solid solutions was studied as a function of temperature up to 1200°C by X-ray diffraction, thermogravimetric analysis, and differential scanning

  14. Comparative magnetic studies of (Sm, Nd) trichloroacetates and their heteronuclear CuLn2(CCl3COO)8.6H2O systems: structure and spectroscopy of a new type of Eu trichloroacetate

    International Nuclear Information System (INIS)

    Wojciechowski, W.; Legendziewicz, J.; Puchalska, M.; Ciunik, Z.

    2004-01-01

    Two series of compounds: heteronuclear CuLn 2 (CCl 3 COO) 8 .6H 2 O (Ln = Nd and Sm) and their simple analogues Ln(CCl 3 COO) 3 .2H 2 O (Ln = Eu, Nd, Sm) were synthesized. New Eu(III) trichloroacetate; Eu(CCl 3 COO) 3 .3H 2 O.CH 3 OH was obtained, its molecular structure was determined by X-ray diffraction and compared with the data of respective systems reported earlier. Magnetization was measured and the susceptibility was derived in the limit of low field. Magnetic susceptibilities were calculated and discussed for series of homo- and hetero-nuclear chloroacetates.Untypical hysteresis was found (two loops) in samarium trichloroacetate. This phenomenon is most probably the effect of flops of spins in magnetic fields of 30,000Oe and very weak (if any) interaction intermediated by weak hydrogen bonding between the chains. A similar magnetic behavior was observed in neodymium carboxylate where the magnetic ordering was observed as a result of Nd-Nd interaction at low temperature (1.6K). For this system, the magnetic moment depends on magnitude of the magnetic field and ferromagnetic ordering appears at low temperatures. The strongest interactions of coupled ions and antiferromagnetic ordering with T N =6.5K were found in CuSm 2 (CCl 3 COO) 8 .6H 2 O single crystals.Heisenberg model was applied in the calculations for three interacting ions located linearly. The following relation was derived: χ M =Ng 2 μ β 2 kT(12)+(12)exp(J 2 /kT)+5exp(J 2 /kT)-exp(1,5J 1 /kT)2+2exp(J 2 /kT)+4exp(J 2 /kT)-exp(1,5J 1 /kT) and applied in calculations of the exchange integrals. Mechanism of the exchange interaction was discussed on the basis of the obtained results.

  15. Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO2 and of solid solutions Th1-xMxO2 (M = U, Pu)

    International Nuclear Information System (INIS)

    Heisbourg, G.

    2003-12-01

    The aim of this work was to understand the mechanisms of dissolution of ThO 2 and of thorium mixed oxides such as Th 1-x U x O 2 and Th 1-x Pu x O 2 in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th 1-x U x O 2 (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th 1-x Pu x O 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 2 and of solid solutions Th 1-x U x O 2 has been carried out in several aqueous media (HNO 3 , HCl, H 2 SO 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 1-x U x O 2 in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO 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 1-x U x O 2 in nitric medium has been studied at last. (O.M.)

  16. Color tunable emission in Ce3+ and Tb3+ co-doped Ba2Ln(BO3)2Cl (Ln=Gd and Y) phosphors for white light-emitting diodes.

    Science.gov (United States)

    Zhang, Niumiao; Guo, Chongfeng; Jing, Heng; Jeong, Jung Hyun

    2013-12-01

    Ce(3+) and Tb(3+) co-doped Ba2Ln(BO3)2Cl (Ln=Y and Gd) green emitting phosphors were prepared by solid state reaction in reductive atmosphere. The emission and excitation spectra as well as luminescence decays were investigated, showing the occurrence of efficient energy transfer from Ce(3+) to Tb(3+) in this system. The phosphors exhibit both a blue emission from Ce(3+) and a green emission from Tb(3+) under near ultraviolet light excitation with 325-375 nm wavelength. Emission colors of phosphors could be tuned from deep blue through cyan to green by adjusting the Tb(3+) concentrations. The energy transfer efficiency and emission intensity of Ba2Y(BO3)2Cl:Ce(3+), Tb(3+) precede those of Ba2Gd(BO3)2Cl:Ce(3+), Tb(3+), and the sample Ba2Y(BO3)2Cl:0.03Ce(3+), 0.10Tb(3+) is the best candidate for n-UV LEDs. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Dielectric relaxation in epitaxial films of paraelectric-magnetic SrTiO.sub.3./sub.-SrMnO.sub.3./sub. solid solution

    Czech Academy of Sciences Publication Activity Database

    Savinov, Maxim; Bovtun, Viktor; Tereshina-Chitrova, Evgenia; Stupakov, Alexandr; Dejneka, Alexandr; Tyunina, Marina

    2018-01-01

    Roč. 112, č. 5 (2018), s. 1-4, č. článku 052901. ISSN 0003-6951 R&D Projects: GA ČR GA15-15123S Institutional support: RVO:68378271 Keywords : dielectric relaxation * epitaxial films * paraelectric-magnetic * SrTiO 3 -SrMnO 3 solid solution Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics , supercond.) Impact factor: 3.411, year: 2016

  18. Solubility of NaNd(CO3)2.6H2O(c) in concentrated Na2CO3 and NaHCO3 solutions

    International Nuclear Information System (INIS)

    Rao, L.; Rai, D.; Felmy, A.R.; Fulton, R.W.; Novak, C.F.

    1996-01-01

    NaNd(CO 3 ) 2 x 6 H 2 O(c) was identified to be the final equilibrium solid phase in suspensions containing concentrated sodium carbonate (0.1 to 2.0 M) and sodium bicarbonate (0.1 to 1.0 M), with either NaNd(CO 3 ) 2 x 6 H 2 O(c) or Nd 2 (CO 3 ) 3 x xH 2 O(s) as initial solids. A thermodynamic model, based on Pitzer's specific into-interaction approach, was developed to interpret the solubility of NaNd(CO 3 ) 2 x 6 H 2 O(c) as functions of sodium carbonate and sodium bicarbonate concentrations. In this model, the solubility data of NaNd(CO 3 ) 2 x 6 H 2 O(c) were explained by assuming the formation of NdCO 3 + , Nd(CO 3 ) 2 - and Nd(CO 3 ) 3 3- species and invoking the specific ion interactions between Na + and Nd(CO 3 ) 3 3- . Ion interaction parameters for Na + -Nd(CO 3 ) 3 3- were developed to fit the solubility data. Based on the model calculations, Nd(CO 3 ) 3 3- was the predominant aqueous neodymium species in 0.1 to 2 M sodium carbonate and 0.1 to 1 M sodium bicarbonate solutions. The logarithm of the NaNd(CO 3 ) 2 x 6 H 2 O solubility product (NaNd(CO 3 ) 2 x 6 H 2 O(c)=Na + +Nd 3+ +2 CO 3 2- +6 H 2 O) was calculated to be -21.39. This model also provided satisfactory interpretation of the solubility data of the analogous Am(III) system in less concentrated carbonate and bicarbonate solutions. (orig.)

  19. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian, E-mail: jiadingxian@suda.edu.cn

    2013-10-15

    Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in the neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors

  20. Magnetism of cyano-bridged hetero-one-dimensional Ln3+-M3+ complexes (Ln3+ = Sm, Gd, Yb; M3+ = FeLS, Co).

    Science.gov (United States)

    Figuerola, Albert; Diaz, Carmen; Ribas, Joan; Tangoulis, Vassilis; Sangregorio, Claudio; Gatteschi, Dante; Maestro, Miguel; Mahía, José

    2003-08-25

    The reaction of Ln(NO(3))(3).aq with K(3)[Fe(CN)(6)] or K(3)[Co(CN)(6)] and 2,2'-bipyridine in water led to five one-dimensional complexes: trans-[M(CN)(4)(mu-CN)(2)Ln(H(2)O)(4) (bpy)](n)().XnH(2)O.1.5nbpy (M = Fe(3+) or Co(3+); Ln = Sm(3+), Gd(3+), or Yb(3+); X = 4 or 5). The structures for [Fe(3)(+)-Sm(3+)] (1), [Fe(3)(+)-Gd(3+)] (2), [Fe(3)(+)-Yb(3+)] (3), [Co(3)(+)-Gd(3+)] (4), and [Co(3)(+)-Yb(3+)] (5) have been solved; they crystallize in the triclinic space P1 and are isomorphous. The [Fe(3+)-Sm(3+)] complex is a ferrimagnet, its magnetic studies suggesting the onset of weak ferromagnetic 3-D ordering at 3.5 K. The [Fe(3+)-Gd(3+)] interaction is weakly antiferromagnetic. The isotropic nature of Gd(3+) allowed us to evaluate the exchange interaction (J = 0.77 cm(-)(1)).

  1. The influence of thermal treatment on the phase development in HfO2-Al2O3 and ZrO2-Al2O3 systems

    International Nuclear Information System (INIS)

    Stefanic, G.; Music, S.; Trojko, R.

    2005-01-01

    Amorphous precursors of HfO 2 -AlO 1.5 and ZrO 2 -AlO 1.5 systems covering the whole concentration range were co-precipitated from aqueous solutions of the corresponding salts. The thermal behaviour of the amorphous precursors was examined by differential thermal analysis, X-ray powder diffraction (XRD), laser Raman spectroscopy and scanning electron microscopy. The crystallization temperature of both systems increased with increase in the AlO 1.5 content, from 530 to 940 deg. C in the HfO 2 -AlO 1.5 system, and from 405 to 915 deg. C in the ZrO 2 -AlO 1.5 system. The results of phase analysis indicate an extended capability for the incorporation of Al 3+ ions in the metastable HfO 2 - and ZrO 2 -type solid solutions obtained after crystallization of amorphous co-gels. Precise determination of lattice parameters, performed using whole-powder-pattern decomposition method, showed that the axial ratio c f /a f in the ZrO 2 - and HfO 2 -type solid solutions with 10 mol% or more of Al 3+ approach 1. The tetragonal symmetry of these samples, as determined by laser Raman spectroscopy, was attributed to the displacement of the oxygen sublattice from the ideal fluorite positions. It was found that the lattice parameters of the ZrO 2 -type solid solutions decreased with increasing Al 3+ content up to ∼10 mol%, whereas above 10 mol%, further increase of the Al 3+ content has very small influence on the unit-cell volume of both HfO 2 - and ZrO 2 -type solid solutions. The reason for such behaviour was discussed. The solubility of Hf 4+ and Zr 4+ ions in the aluminium oxides lattice appeared to be negligible

  2. β-Y(BO{sub 2}){sub 3}. A new member of the β-Ln(BO{sub 2}){sub 3} (Ln = Nd, Sm, Gd-Lu) structure family

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Martin K.; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

    2017-07-01

    β-Y(BO{sub 2}){sub 3} was synthesized in a Walker-type multianvil module at 5.9 GPa/1000 C. The crystal structure has been elucidated through single-crystal X-ray diffraction. β-Y(BO{sub 2}){sub 3} crystallizes in the orthorhombic space group Pnma (no. 62) with the lattice parameters a = 15.886(2), b = 7.3860(6), and c = 12.2119(9) Aa. Its crystal structure will be discussed in the context of the isotypic lanthanide borates β-Ln(BO{sub 2}){sub 3} (Ln = Nd, Sm, Gd-Lu).

  3. Thermodynamic modeling of La2O3-SrO-Mn2O3-Cr2O3 for solid oxide fuel cell applications

    DEFF Research Database (Denmark)

    Povoden-Karadeniz, E.; Chen, Ming; Ivas, Toni

    2012-01-01

    The thermodynamic La–Sr–Mn–Cr–O oxide database is obtained as an extension of thermodynamic descriptions of oxide subsystems using the calculation of phase diagrams approach. Concepts of the thermodynamic modeling of solid oxide phases are discussed. Gibbs energy functions of SrCrO4, Sr2.67Cr2O8......, Sr2CrO4, and SrCr2O4 are presented, and thermodynamic model parameters of La–Sr–Mn–Chromite perovskite are given. Experimental solid solubilities and nonstoichiometries in La1xSrxCrO3d and LaMn1xCrxO3d are reproduced by the model. The presented oxide database can be used for applied computational...... thermodynamics of traditional lanthanum manganite cathode with Cr-impurities. It represents the fundament for extensions to higher orders, aiming on thermodynamic calculations in noble symmetric solid oxide fuel cells...

  4. Phase relations and linear thermal expansion of cubic solid solutions in the Th1-xMxO2-x/2 (M=Eu, Gd, Dy) systems

    International Nuclear Information System (INIS)

    Mathews, M.D.; Ambekar, B.R.; Tyagi, A.K.

    2005-01-01

    Cell parameters and linear thermal expansion studies of the Th-M oxide systems with general compositions Th 1-x M x O 2-x/2 (M=Eu 3+ , Gd 3+ and Dy 3+ , 0.0= 1.5 in the ThO 2 lattice. The upper solid solubility limits of EuO 1.5 , GdO 1.5 and DyO 1.5 in the ThO 2 lattice under conditions of slow cooling from 1673K are represented as Th 0.50 Eu 0.50 O 1.75 , Th 0.60 Gd 0.40 O 1.80 and Th 0.85 Dy 0.15 O 1.925 , respectively. The linear thermal expansion (293-1123K) of MO 1.5 and their single-phase solid solutions with thoria were investigated by dilatometery. The average linear thermal expansion coefficients (α-bar ) of the compounds decrease on going from EuO 1.5 to DyO 1.5 . The values of α-bar for EuO 1.5 , GdO 1.5 and DyO 1.5 containing solid solutions showed a downward trend as a function of the dopant concentration. The linear thermal expansion (293-1473K) of the solid solutions investigated by high-temperature XRD also showed a similar trend

  5. Ion-irradiation resistance of the orthorhombic Ln_2TiO_5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) series

    International Nuclear Information System (INIS)

    Aughterson, Robert D.; Lumpkin, Gregory R.; Ionescu, Mihail; Reyes, Massey de los; Gault, Baptiste; Whittle, Karl R.; Smith, Katherine L.; Cairney, Julie M.

    2015-01-01

    The response of Ln_2TiO_5 (where Ln is a lanthanide) compounds exposed to high-energy ions was used to test their suitability for nuclear-based applications, under two different but complementary conditions. Eight samples with nominal stoichiometry Ln_2TiO_5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy), of orthorhombic (Pnma) structure were irradiated, at various temperatures, with 1 MeV Kr"2"+ ions in-situ within a transmission electron microscope. In each case, the fluence was increased until a phase transition from crystalline to amorphous was observed, termed critical dose D_c. At certain elevated temperatures, the crystallinity was maintained irrespective of fluence. The critical temperature for maintaining crystallinity, T_c, varied non-uniformly across the series. The T_c was consistently high for La, Pr, Nd and Sm_2TiO_5 before sequential improvement from Eu to Dy_2TiO_5 with T_c's dropping from 974 K to 712 K. In addition, bulk Dy_2TiO_5 was irradiated with 12 MeV Au"+ ions at 300 K, 723 K and 823 K and monitored via grazing-incidence X-ray diffraction (GIXRD). At 300 K, only amorphisation is observed, with no transition to other structures, whilst at higher temperatures, specimens retained their original structure. The improved radiation tolerance of compounds containing smaller lanthanides has previously been attributed to their ability to form radiation-induced phase transitions. No such transitions were observed here. - Highlights: • First ion-irradiation studies on a number of novel compounds including Pr_2TiO_5, Eu_2TiO_5 and Tb_2TiO_5. • Systematic in-situ ion-irradiation study of almost complete Ln_2TiO_5 series (Ln = lanthanides) with orthorhombic crystal structure type. • The first grazing incidence study of bulk irradiated Dy_2TiO_5 looking for irradiation induced phase transition.

  6. Synthesis and characterization of γ-Bi2O3 based solid electrolyte ...

    Indian Academy of Sciences (India)

    The temperature dependence of the electrical properties of -Bi2O3 solid solution was measured by four-point probe d.c. conductivity method. In the investigated system, the highest value of conductivity was observed for σ T = 0.016 ohm-1 cm-1 at 650 °C on 4 mole% Nb2O5 addition. The electrical conductivity curves of ...

  7. Li{sub 3}Gd{sub 3}Te{sub 2}O{sub 12}:Eu{sup 3+}- an intense red phosphor for solid state lighting applications

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Hansnath [Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036 (India); Asiri Naidu, S. [Department of Chemistry, Rajiv Gandhi University of Knowledge Technologies, Nuzvid, Andhra Pradesh 521202 (India); Varadaraju, U.V., E-mail: varada@iitm.ac.in [Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036 (India)

    2017-02-15

    Li{sub 3}Gd{sub 33x}Eu{sub 3x}Te{sub 2}O{sub 12} (x=0.05−1.0) phases with garnet structure were synthesized by high temperature solid state reaction and the photoluminescence properties were investigated. The appearance of bands due to intra 4 f transitions of Gd{sup 3+} in the excitation spectra recorded by monitoring the 612 nm emission line of the activator indicates Gd{sup 3+}→Eu{sup 3+} energy transfer in this host lattice. Under 395 nm excitation, the electric dipole transition is predominant in the emission spectrum of Eu{sup 3+} and is in agreement with the C{sub 2} point group (noncentrosymmetric) of the EuO{sub 8} polyhedron. The critical concentration of the Eu{sup 3+} activator in this series was found to be 0.6 (x=0.2) above which, concentration quenching occurs. The emission intensity of the phosphor composition, Li{sub 3}Gd{sub 2.4}Eu{sub 0.6}Te{sub 2}O{sub 12} is ~4 times that of the commercial sample of Y{sub 2}O{sub 3}:Eu{sup 3+} phosphor. - Highlights: • New Eu{sup 3+} doped garnet. • Intense electric dipole emission. • Gd{sup 3+}→Eu{sup 3+} energy transfer.

  8. Unlimited mutual solubility in the system LaTiO/sub 3/-YTiO/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Bazuev, G V; Shvejkin, G P [AN SSSR, Sverdlovsk. Inst. Khimii

    1982-08-01

    Formation of unlimited series of solid solutions of substitution Lasub(1-x)Ysub(x)TiOsub(3) (1) with the structure of rhombic perovskite (sp. gr. Pbnm) is established using X-ray diffraction. With the increase of yttrium content in 1 a distortion of perovskite structure is intensified with the decrease of parameters a and c, increase of parameter b and decrease of unit cell volume V take place. Anomalies on the cirves, expressing the dependences b=f(x) and V=f(rsub(Lnsub(3+))sup(3)) in the limits 1 are connected with considerable distortion of oxygen octahedrons TiO/sub 6/ of LnTiO/sub 3/, where Ln-Sm, Gd and Y.

  9. Corrections to O(α7(lnα)mc2) fine-structure splittings and O(α6(lnα)mc2) energy levels in helium

    International Nuclear Information System (INIS)

    Zhang, T.

    1996-01-01

    Fully relativistic formulas for the energy-level shifts arising from no-pair exchange diagrams of two transverse photons plus an arbitrary number of Coulomb photons are derived in closed form within the external potential Bethe-Salpeter formalism. O(α 7 (lnα)mc 2 ) corrections to the fine-structure splittings of helium are obtained and expressed in terms of expectation values of nonrelativistic operators. O(α 7 mc 2 ) operators from exchange diagrams are found in nonrelativistic approximation. O(α 6 m 2 c 2 /M) nucleus-electron operators contributing to the fine-structure splittings are derived. Nonrelativistic operators of O(α 6 mc 2 ) corrections to the triplet levels of helium are presented. Nonrelativistic operators of O(α 6 (lnα)mc 2 ) corrections to the helium singlet levels and to positronium S levels are derived. O(α 6 m 2 c 2 /M) hydrogen and O(α 6 mc 2 ) positronium P levels, and O(α 6 (lnα)mc 2 ) corrections of first order to positronium S levels, are calculated using the derived operators for helium, in agreement with those obtained previously by others, except for one term in corrections to positronium P levels. In addition, the O(α 6 mc 2 ) Dirac energies for hydrogenic non-S levels are exactly reproduced in a perturbative calculation. copyright 1996 The American Physical Society

  10. First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

    Science.gov (United States)

    Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

    2008-03-17

    In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

  11. Coexistence of room temperature ferroelectricity and ferrimagnetism in multiferroic BiFeO3-Bi0.5Na0.5TiO3 solid solution

    International Nuclear Information System (INIS)

    Tian, Z.M.; Wang, C.H.; Yuan, S.L.; Wu, M.S.; Ma, Z.Z.; Duan, H.N.; Chen, L.

    2011-01-01

    Highlights: → In this study, the coexistence of ferroelectrics and ferrimagnetism have been observed at room temperature for the (1 - x)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 (x = 0.37) solid solutions. → X-ray diffraction and Raman spectroscopy measurements show a single-phase perovskite structure with no impurities identified. → A magnetic transition from paramagnetic (PM) to ferrimagnetic (Ferri) ordering is observed for the solution with Curie temperature T C ∼ 330 K. - Abstract: The structure, ferroelectric and magnetic properties of (1 - x)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 (x = 0.37) solid solution fabricated by a sol-gel method have been investigated. X-ray diffraction and Raman spectroscopy measurements show a single-phase perovskite structure with no impurities identified. Compared with pure BiFeO 3 , the coexistence of ferroelectricity and ferrimagnetism have been observed at room temperature for the solution with remnant polarization P r = 1.41 μC/cm 2 and remnant magnetization M r = 0.054 emu/g. Importantly, a magnetic transition from ferrimagnetic (FM) ordering to paramagnetic (PM) state is observed, with Curie temperature T C ∼ 330 K, being explained in terms of the suppression of cycloid spin configuration by the structural distortion.

  12. 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

  13. Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures

    Energy Technology Data Exchange (ETDEWEB)

    Nayyar, Iffat H.; Chamberlin, Sara E.; Kaspar, Tiffany C.; Govind, Niranjan; Chambers, Scott A.; Sushko, Petr

    2017-01-01

    The electronic and optical properties of a-(Fe1xVx)2O3 at low (x = 0.04) and high (x = 0.5) doping levels are investigated using a combination of periodic and embedded cluster approaches, and time dependent density functional theory. At low V concentrations the onset of the optical absorption is B0.5 eV (i.e., nearly 1.6 eV lower than that in pure a-Fe2O3) and corresponds to the electron transitions from V 3d to Fe 3d* orbitals. At high V concentrations, optical absorption energies and intensities are sensitive to specific arrangements of Fe and V atoms and their spin configuration that determine Fe–V hybridization. The onset of the lowest inter-vanadium absorption band in the case of Fe2O3/V2O3 hetero-structures is as low as B0.3 eV and the corresponding peak is at B0.7 eV. In contrast, in the case of solid solutions this peak has lower intensity and is shifted to higher energy (B1.2 eV). Analysis of the orbital character of electronic excitation suggests that Fe2O3/V2O3 hetero-structures absorb light much more effectively than random alloys, thus promoting efficient photo-induced carrier generation. These predictions can be tested in a-(Fe1xVx)2O3 thin films synthesized with well-controlled spatial distribution of Fe and V species.

  14. 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.)

  15. Optical and crystal chemistry studies of Na3Ln(PO4)2-K3Ln(PO4)2 (Ln=Eu, Gd)

    International Nuclear Information System (INIS)

    Mesnaoui, M.; Maazaz, M.

    1987-01-01

    In these systems, large single phase domains are separated by two phase regions. The structural evolution as a function of composition is analysed both by X-ray diffraction and by using Eu 3+ and Gd 3+ as luminescent local structural probes. Due to layer type structure of the K 3 Ln(PO 4 ) 2 phases an exchange reaction resulting in total substitution of sodium for potassium can be carried out with formation of metastable Na 3 Ln(PO 4 ) 2 phases, the structure of which is close to those of the potassium compounds. 10 refs.; 18 figs [fr

  16. Synthesis, crystal structure, optical and thermal properties of lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho).

    Science.gov (United States)

    Förg, Katharina; Höppe, Henning A

    2015-11-28

    Lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho) were synthesised as colourless (Ln = Tb, Dy) and light pink (Ln = Ho) crystalline powders by reaction of Tb4O7/Dy2O3/Ho2O3 with H3PO3 at 380 °C. All compounds crystallise isotypically (P2(1)/c (no. 14), Z = 4, a(Tb) = 1368.24(4) pm, b(Tb) = 710.42(2) pm, c(Tb) = 965.79(3) pm, β(Tb) = 101.200(1)°, 3112 data, 160 parameters, wR2 = 0.062, a(Ho) = 1363.34(5) pm, b(Ho) = 709.24(3) pm, c(Ho) = 959.07(4) pm, β(Ho) = 101.055(1)°, 1607 data, 158 parameters, wR2 = 0.058). The crystal structure comprises two different infinite helical chains of corner-sharing phosphate tetrahedra. In-between these chains the lanthanide ions are located, coordinated by seven oxygen atoms belonging to four different polyphosphate chains. Vibrational, UV/Vis and fluorescence spectra of Ln[H(PO3)4] (Ln = Tb, Dy, Ho) as well as Dy[H(PO3)4]:Ln (Ln = Ce, Eu) and the magnetic and thermal behaviour of Tb[H(PO3)4] are reported.

  17. The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb…Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb…Yb) and Sc(PO3)3

    Science.gov (United States)

    Höppe, Hennig A.

    2009-07-01

    The incommensurately modulated room-temperature phases β-Ln(PO3)3(Ln=Y,Tb…Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO3)3(Ln=Y,Dy…Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO3)3, P21/c, Z=12,a=14.1422(6), b=20.0793(9),c=10.1018(4) A˚, β=127.532(3)∘). α-Tb(PO3)3 is isotypic with Gd(PO3)3(α-Tb(PO3)3, I2/a,Z=16,a=25.875(6), b=13.460(3), c=10.044(2) A˚, β=119.13(3)∘). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO3)3 is isotypic with that of Lu(PO3)3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed.

  18. Subsolidus phase relations of Bi2O3-Nd2O3-CuO

    International Nuclear Information System (INIS)

    Sun Yezhou

    1997-01-01

    The subsolidus phase relations of the Bi 2 O 3 -Nd 2 O 3 -CuO ternary system and its binary systems along with crystallographic parameters of the compounds were investigated by X-ray powder diffraction and differential thermal analysis. The room temperature section of the phase diagram of the Bi 2 O 3 -Nd 2 O 3 -CuO system can be divided into two diphase regions and six triphase regions. No ternary compound was found. There exist two solid solutions (α, β) and a compound Bi 0.55 Nd 0.45 O 1.5 in the (Bi 2 O 2 ) 1-x (Nd 2 O 3 ) x system. Both solid solution α (0.05≤x≤0.30) and β (0.53≤x≤0.73) belong to the rhombohedral system (R3m). The lattice parameters represented by a hexagonal cell are a=3.9832(4), c=27.536(5) A for Bi 0.8 Nd 0.2 O 1.5 (α phase) and a=3.8826(3), c=9.727(1) A for Bi 0.4 Nd 0.8 O 1.5 (β phase). The Bi 0.55 Nd 0.45 O 1.5 compound crystallizes in a face-centered cubic (f.c.c.) lattice with a=5.5480(2) A. (orig.)

  19. The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb...Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb...Yb) and Sc(PO3)3

    International Nuclear Information System (INIS)

    Hoeppe, Hennig A.

    2009-01-01

    The incommensurately modulated room-temperature phases β-Ln(PO 3 ) 3 (Ln=Y,Tb...Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO 3 ) 3 (Ln=Y,Dy...Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO 3 ) 3 ,P2 1 /c,Z=12,a=14.1422(6),b=20.0793(9),c=10.1018(4)A, β=127.532(3) 0 ). α-Tb(PO 3 ) 3 is isotypic with Gd(PO 3 ) 3 (α-Tb(PO 3 ) 3 ,I2/a,Z=16,a=25.875(6),b=13.460(3),c=10.044(2)A, β=119.13(3) 0 ). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO 3 ) 3 is isotypic with that of Lu(PO 3 ) 3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO 4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed. - Abstract: Basic structure from which all crystal structures of the late lanthanoids' polyphosphates at room temperature and below can be derived.

  20. Magnetism of cyano-bridged Ln3+-M3+ complexes. Part II: one-dimensional complexes (Ln3+ = Eu, Tb, Dy, Ho, Er, Tm; M3+ = Fe or Co) with bpy as blocking ligand.

    Science.gov (United States)

    Figuerola, Albert; Ribas, Joan; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

    2005-10-03

    The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to 13 one-dimensional complexes: trans-[M(CN)4(mu-CN)2Ln(H2O)4(bpy)]n.4nH2O.1.5nbpy (Ln = Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Lu3+; M = Fe3+, Co3+). The structures for [EuFe]n (1), [TbFe]n (2), [DyFe]n (3), [HoFe]n (4), [ErFe]n (5), [TmFe]n (6), [LuFe]n (7), [EuCo]n (8), [TbCo]n (9), [DyCo]n (10), [HoCo]n (11), [ErCo]n (12), and [TmCo]n (13) have been solved: they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular architecture created by the interplay of coordinative, hydrogen bonding, and pi-pi interactions. A stereochemical study of the eight-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. The Ln3+-Fe3+ interaction is antiferromagnetic in [DyFe]n and [TbFe]n. For [EuFe]n, [HoFe]n, [ErFe]n, and [TmFe]n, there is no sign of any significant interaction. The magnetic behavior of [DyFe]n suggests the onset of weak long-range ferromagnetic ordering at 2.5 K.

  1. Synthesis, surface modification/decoration of luminescent–magnetic core/shell nanomaterials, based on the lanthanide doped fluorides (Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Runowski, Marcin; Lis, Stefan, E-mail: blis@amu.edu.pl

    2016-02-15

    The synthesized magnetite nanoparticles (10–15 nm) were successfully coated with amine modified silica nanoshell, which led to the formation of core/shell type nanostructures (30–50 nm). The as-prepared nanoparticles were surface modified with polyacrylic acid (PAA) via electrostatic interactions of –NH{sub 2} and –COOH groups. Afterwards, the surface PAA molecules acted as complexing agents of the introduced lanthanide (Ln{sup 3+}) ions. Subsequently, the as-prepared nanostructures were surface decorated with luminescent LnF{sub 3} nanoparticles, forming Eu{sup 3+} or Tb{sup 3+} doped Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3} nanomaterials (50–100 nm). The obtained luminescent–magnetic products exhibited simultaneously bright red or green emission under UV lamp irradiation (λ{sub ex}=254 nm), and a response for the applied magnetic field (strong magnet attracts the colloidal particles, dispersed in aqueous medium). After the synthesis, properties of the nanomaterials were investigated by powder X-ray diffraction (XRD) technique, transmission electron microscopy (TEM), infrared spectroscopy (IR) and spectrofluorometry (analysis of excitation/emission spectra and luminescence decay curves). Such advanced nanomaterials can be potentially used in multimodal imaging, targeted therapies and as multifunctional contrast agents, novel luminescent–magnetic tracers, protection of documents, etc. - Highlights: • Luminescent–magnetic nanomaterials Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3} were synthesized. • Core/shell nanostructures were obtained by surface modification of nanoparticles. • Luminescent lanthanide fluoride nanoparticles doped with Eu{sup 3+} and Tb{sup 3+} ions. • Multifunctional core/shell nanostructures exhibited red or green emission. • Nanomaterials formed stable aqueous colloids.

  2. Development and characterization of nickel catalysts supported in CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} matrixes evaluated for methane reforming reactions; Desenvolvimento e caracterização de catalisadores de níquel suportados em matrizes CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} avaliados para as reações de reforma do metano

    Energy Technology Data Exchange (ETDEWEB)

    Abreu, Amanda Jordão de

    2012-07-01

    Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al{sub 2}O{sub 3}. However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al{sub 2}O{sub 3} supported on solid solutions formed by ZrO{sub 2}-CeO{sub 2}, La{sub 2}O{sub 3} and CeO{sub 2}-ZrO{sub 2}-La{sub 2}O{sub 3} were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al{sub 2}O{sub 3} catalysts and the best catalysts are Ni/CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3}. (author)

  3. Determination of the constants of the solubility product of Ln(OH)3 and the effect of the chloride ions on the lanthanum hydrolysis, praseodymium and lutetium in aqueous solutions of ion force 2 Molar

    International Nuclear Information System (INIS)

    Lopez G, H.D.

    2005-01-01

    The behavior of lanthanum (III), praseodymium (III), and lutetium (III) was studied in 2 M NaClO 4 (aq) and 2 M NaCl (aq) at 303 K and free -CO 2 conditions. Solubility diagrams (p Ln(aq)-pC H ) were obtained by means of a radiochemical method. The pC H borderlines of saturation and unsaturation zones of the solutions and solubility product constants for Ln(OH) 3 were determined from these diagrams. The fitting of the solubility equation to the experimental values of p Ln(aq)-pC H diagrams allowed the calculation of the first hydrolysis and solubility product constants. Independently, the stability constants for the first species of hydrolysis were determined by means of pH titrations, the data were treated with the program SUPERQUAD and fitted to the mean ligand number equation. The stability constants for the species LnCl 2+ were as well calculated in 2M ionic strength and 303 K from the hydrolysis constant values obtained in both perchlorate and chloride media. The values obtained for La, Pr and Lu were: logK ps : 21.11 ± 0.09, 19.81 ± 0.11 and 18.10 ± 0.13 in 2M NaClO 4 ; logK ps : 22.22 ± 0.09, 21.45 ± 0.14 and 18.52 ± 0.29 in 2M NaCl; log β 1 : - 8.64 ± 0.02, - 8.37 ± 0.01 and - 7.95 ± 0.11 in 2M NaClO 4 ; log β 1 / : - 9.02 ± 0.11, - 8.75 ± 0.01 and - 8.12 ± 0.03 in 2M NaCl and the values for log β 1,Cl were - 0.0255, - 0.155 and - 0.758, respectively. (Author)

  4. Optical and scintillation characteristics of Gd.sub.2./sub.YAl.sub.2./sub.Ga.sub.3./sub.O.sub.12./sub.:Ce and Lu.sub.2./sub.YAl.sub.2./sub.Ga.sub.3./sub.O.sub.12./sub.:Ce single crystals

    Czech Academy of Sciences Publication Activity Database

    Chewpraditkul, W.; Sakthong, O.; Pattanaboonmee, N.; Chewpraditkul, We.; Szczesniak, T.; Swiderski, L.; Moszynski, M.; Kamada, K.; Yoshikawa, A.; Nikl, Martin

    2017-01-01

    Roč. 468, Jun (2017), 395–398 ISSN 0022-0248 R&D Projects: GA ČR GA16-15569S Institutional support: RVO:68378271 Keywords : Ce-doping * Czochralski method * Gd 2 YAl 2 Ga 3 O 12 :Ce * Lu 2 YAl 2 Ga 3 O 12 :Ce * luminescence * scintillator materials Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.751, year: 2016

  5. Interplay of structural chemistry and magnetism in perovskites; A study of CaLn2Ni2WO9; Ln=La, Pr, Nd

    Science.gov (United States)

    Chin, Chun-Mann; Paria Sena, Robert; Hunter, Emily C.; Hadermann, Joke; Battle, Peter D.

    2017-07-01

    Polycrystalline samples of CaLn2Ni2WO9 (Ln=La, Pr, Nd) have been synthesized and characterised by a combination of X-ray and neutron diffraction, electron microscopy and magnetometry. Each composition adopts a perovskite-like structure with a 5.50, b 5.56, c 7.78 Å, β 90.1° in space group P21/n. Of the two crystallographically distinct six-coordinate sites, one is occupied entirely (Ln=Pr) or predominantly (Ln=La, Nd) by Ni2+ and the other by Ni2+ and W6+ in a ratio of approximately 1:2. None of the compounds shows long-range magnetic order at 5 K. The magnetometry data show that the magnetic moments of the Ni2+ cations form a spin glass below 30 K in each case. The Pr3+ moments in CaPr2Ni2WO9 also freeze but the Nd3+ moments in CaNd2Ni2WO9 do not. This behaviour is contrasted with that observed in other (A,A')B2B'O9 perovskites.

  6. Correlation of the Na2SiO3 to NaOH Ratios and Solid to Liquid Ratios to the Kedah’s Soil Strength

    Directory of Open Access Journals (Sweden)

    Nur Hamzah Hazamaah

    2016-01-01

    Full Text Available Geopolymer was used for the soil stabilization of Kedah’s soil at different ratios of solid to liquid and Na2SiO3 to NaOH in order to achieve the desired compressive strength. The geopolymerization process which produces an aluminosilicate gel was occurred due to the mixing of Kedah’s soil and fly ash with Na2SiO3 and NaOH. Soil stabilization by geopolymer was synthesized by the activation of fly ash and Kedah’s soil with Na2SiO3 and NaOH at different ratios of solid to liquid (1.5, 2.0, 2.5 and 3.0 and Na2SiO3 to NaOH (0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 at a specific constant concentration of NaOH solution of 6M. The compressive strength up to 5.12 MPa was obtained at 3.0 of solid to liquid ratio and 2.5 of Na2SiO3 to NaOH ratio in 7 days curing at room temperature.

  7. Hydrothermal synthesis, structure, and optical properties of two nanosized Ln{sub 26} rate at CO{sub 3} (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu; Huang, Lian; Miao, Hao; Wan, Hong Xiang; Mei, Hua; Liu, Ying [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University (China); Xu, Yan [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University (China); State Key Laboratory of Coordination Chemistry, Nanjing Tech University (China)

    2015-02-16

    Two Ln{sub 26} rate at CO{sub 3} (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs) formulated as [Dy{sub 26}Cu{sub 3}(Nic){sub 24}(CH{sub 3}COO){sub 8}(CO{sub 3}){sub 11}(OH){sub 26}(H{sub 2}O){sub 14}]Cl . 3 H{sub 2}O (1; HNic=nicotinic acid) and [Tb{sub 26}NaAg{sub 3}(Nic){sub 27}(CH{sub 3}COO){sub 6}(CO{sub 3}){sub 11}(OH){sub 26}Cl(H{sub 2}O){sub 15}] . 7.5 H{sub 2}O (2) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X-ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Aa, b=33.346(11) Aa, c=24.424(8) Aa, β=93.993(5) , V=29065(16) Aa{sup 3}, whereas 2 crystallizes in the triclinic space group P anti 1 with a=20.4929(19) Aa, b=24.671(2) Aa, c=29.727(3) Aa, α=81.9990(10) , β=88.0830(10) , γ=89.9940(10) , V=14875(2) Aa{sup 3}. Structural analysis indicates the framework of 1 is a 3D perovskite-like structure constructed out of CO{sub 3} rate at Dy{sub 26} building units and Cu{sup +} centers by means of nicotinic acid ligand bridging. In 2, however, nanosized CO{sub 3} rate at Tb{sub 26} units and [Ag{sub 3}Cl]{sup 2+} centers are connected by Nic{sup -} bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d-4f cluster-based MOF is quite rare as most of the reported analogous compounds are 3d-4f ones. Additionally, the solid-state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic{sup -} to Tb{sup 3+} ions, which we called the ''antenna effect''. Compound 2 shows a good two-photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM{sup -1} (1 GM = 10{sup -50} cm{sup 4} s photon{sup -1}), which indicates that compound 2 might be a good choice for third-order nonlinear optical materials. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. 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.

  9. Structural and magnetic properties of a mechanochemically activated Ti-Fe2O3 solid mixture

    International Nuclear Information System (INIS)

    Cristobal, A.A.; Ramos, C.P.; Bercoff, P.G.; Conconi, S.; Aglietti, E.F.; Botta, P.M.; Lopez, J.M. Porto

    2010-01-01

    The mechanochemical effects on the reactivity and properties of a titanium/hematite powder mixture with molar ratio of 1/2 are investigated. Crystalline-phase structure, composition, hyperfine and magnetic behaviors were analyzed as a function of activation time by means of X-ray diffraction, scanning electron microscopy, Moessbauer spectroscopy and vibrating sample magnetometry. The results showed that at relatively short activation times metallic Ti reduces part of the ferric ions, yielding a complex product formed mainly by a mix of two solid solutions Fe 3-x Ti x O 4 (titanomagnetites), both with very different x values (0 < x < 1). Also metallic iron and superparamagnetic hematite particles were detected by Moessbauer spectroscopy. As the mechanical treatment extends the composition of the reactive mixture changes, prevailing in the end the solid solution with higher x value. In contrast, when these activated samples are thermally treated the fraction of the solid solution which is richer in Ti diminishes. This fact produces a significant variation of the saturation magnetization of the obtained material.

  10. First-principles study of (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions

    Science.gov (United States)

    Amoroso, Danila; Cano, Andrés; Ghosez, Philippe

    2018-05-01

    (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions are the building blocks of lead-free piezoelectric materials that attract a renewed interest. We investigate the properties of these systems by means of first-principles calculations, with a focus on the lattice dynamics and the competition between different ferroelectric phases. We first analyze the four parent compounds in order to compare their properties and their different tendency towards ferroelectricity. The core of our study is systematic characterization of the binary systems (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 within both the virtual crystal approximation and direct supercell calculations. In the case of Ca doping, we find a gradual transformation from B -site to A -site ferroelectricity due to steric effects that largely determines the behavior of the system. In the case of Zr doping, in contrast, the behavior is eventually dominated by cooperative Zr-Ti motions and the local electrostatics. In addition, our comparative study reveals that the specific microscopic physics of these solids sets severe limits to the applicability of the virtual crystal approximation for these systems.

  11. Probing structural homogeneity of La{sub 1-x}Gd{sub x}PO{sub 4} monazite-type solid solutions by combined spectroscopic and computational studies

    Energy Technology Data Exchange (ETDEWEB)

    Huittinen, N., E-mail: n.huittinen@hzdr.de [Helmholtz-Zentrum Dresden - Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden (Germany); Arinicheva, Y. [Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Nuclear Waste Management and Reactor Safety (IEK-6), 52425 Jülich (Germany); Kowalski, P.M.; Vinograd, V.L. [Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Nuclear Waste Management and Reactor Safety (IEK-6), 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstraße 2, 52062 Aachen (Germany); Neumeier, S. [Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Nuclear Waste Management and Reactor Safety (IEK-6), 52425 Jülich (Germany); Bosbach, D. [Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Nuclear Waste Management and Reactor Safety (IEK-6), 52425 Jülich (Germany); JARA High-Performance Computing, Schinkelstraße 2, 52062 Aachen (Germany)

    2017-04-01

    Here we study the homogeneity of Eu{sup 3+}-doped La{sub 1-x}Gd{sub x}PO{sub 4} (x = 0, 0.11, 0.33, 0.55, 0.75, 0.92, 1) monazite-type solid solutions by a combination of Raman and time-resolved laser fluorescence spectroscopies (TRLFS) with complementary quasi-random structure-based atomistic modeling studies. For the intermediate La{sub 0.45}Gd{sub 0.55}PO{sub 4} composition we detected a significant broadening of the Raman bands corresponding to the lattice vibrations of the LnO{sub 9} polyhedron, indicating much stronger distortion of the lanthanide cation site than the PO{sub 4} tetrahedron. A distortion of the crystal lattice around the dopant site was also confirmed in our TRLFS measurements of Eu{sup 3+} doped samples, where both the half width (FWHM) of the excitation peaks and the {sup 7}F{sub 2}/{sup 7}F{sub 1} ratio derived from the emission spectra increase for intermediate solid-solution compositions. The observed variation in FWHM correlates well with the simulated distribution of Eu···O bond distances within the investigated monazites. The combined results imply that homogenous Eu{sup 3+}-doped La{sub 1-x}Gd{sub x}PO{sub 4} monazite-type solid solutions are formed over the entire composition range, which is of importance in the context of using these ceramics for immobilization of radionuclides. - Highlights: •Homogenous Eu{sup 3+}-doped La{sub 1-x}Gd{sub x}PO{sub 4} monazite-type solid solutions have been synthesized. •Solid solution formation is accompanied by slight distortion of the LnO{sub 9} polyhedron. •Raman and laser spectroscopic trends are observed within the monazite series. •Results are explained with atomistic simulations of Eu-O bond distance distribution.

  12. Mechanical alloying of an immiscible α-Fe2O3-SnO2 ceramic

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Lin, Rong; Mørup, Steen

    1997-01-01

    in the immiscible ceramic oxide system. X-ray diffraction and Mossbauer spectroscopy investigations show that mechanical milling of alpha-Fe2O3 and SnO2 involves 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....

  13. Simultaneous achievement of high dielectric constant and low temperature dependence of capacitance in (111-oriented BaTiO3-Bi(Mg0.5Ti0.5O3-BiFeO3 solid solution thin films

    Directory of Open Access Journals (Sweden)

    Junichi Kimura

    2016-01-01

    Full Text Available The temperature dependence of the capacitance of (111c-oriented (0.90–xBaTiO3-0.10Bi(Mg0.5Ti0.5O3-xBiFeO3 solid solution films is investigated. These films are prepared on (111cSrRuO3/(111Pt/TiO2/SiO2/(100Si substrates by the chemical solution deposition technique. All the films have perovskite structures and the crystal symmetry at room temperature varies with increasing x ratio, from pseudocubic when x = 0–0.30 to rhombohedral when x = 0.50–0.90. The pseudocubic phase shows a high relative dielectric constant (εr (ranging between 400 and 560 at room temperature and an operating frequency of 100 kHz and a low temperature dependence of capacitance up to 400°C, while maintaining a dielectric loss (tan δ value of less than 0.2 at 100 kHz. In contrast, εr for the rhombohedral phase increases monotonically with increasing temperature up to 250°C, and increasingly high tan δ values are recorded at higher temperatures. These results indicate that pseudocubic (0.90–xBaTiO3-0.10Bi(Mg0.5Ti0.5O3-xBiFeO3 solid solution films with (111 orientation are suitable candidates for high-temperature capacitor applications.

  14. Preparation and electrical properties of (1 - x)Sr(Fe1/2Nb1/2)O3-xPbTiO3 ferroelectric ceramics

    International Nuclear Information System (INIS)

    Fang Bijun; Cheng Zhenquan; Sun Renbing; Ding Chenlu

    2009-01-01

    (1 - x)Sr(Fe 1/2 Nb 1/2 )O 3 -xPbTiO 3 (SFN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via the wolframite precursor route. X-ray diffraction (XRD) measurement confirmed that the synthesized SFN-PT ceramics are of pure perovskite structure. With the increase of the concentration of PbTiO 3 (PT), crystal structure of the sintered SFN-PT ceramics changes from rhombohedral phase to tetragonal phase. Dielectric response of the SFN-PT ceramics changes from diffused and broad dielectric peaks to relatively sharp ones accompanied by the increase of the temperature of dielectric maximum (T m ). Small content of MnO 2 or Li 2 CO 3 doping can greatly decrease the dielectric loss of the SFN-PT ceramics, furthermore, the abnormal increase of dielectric constant and loss tangent in the paraelectric phase is suppressed accordingly. Typical P-E hysteresis loops are observed in the SFN-PT ceramics, however, the saturate polarization (P s ) is small. MnO 2 or Li 2 CO 3 doping can greatly decrease the coercive field (E c ) of the SFN-PT ceramics accompanied by large increase of P s . Piezoelectric constant d 33 of the SFN-PT ceramics is small except for SFN30-PT70 ceramics, which reaches 22pC/N

  15. Microstructural features of the La1−xCaxFeO3−δ solid solutions prepared via Pechini route

    International Nuclear Information System (INIS)

    Gerasimov, E.Yu.; Isupova, L.A.; Tsybulya, S.V.

    2015-01-01

    Highlights: • La 1−x Ca x FeO (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 2 O 3 particles (1–10 nm) on the surface of perovskite were revealed. • Amount of α-Fe 2 O 3 particles on the perovskite surface grew with rising x values. - Abstract: Solid solutions with La 1−x Ca x FeO 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 2 O 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 4 oxidation process results in partial destruction of solid solutions with formation of planar defects in the bulk and α-Fe 2 O 3 particles on the surface

  16. Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solutions

    Science.gov (United States)

    Schliesser, Jacob M.; Huang, Baiyu; Sahu, Sulata K.; Asplund, Megan; Navrotsky, Alexandra; Woodfield, Brian F.

    2018-03-01

    We have measured the heat capacities of several well-characterized bulk and nanophase Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solution samples from which magnetic properties of transitions and third-law entropies have been determined. The magnetic transitions show several features common to effects of particle and magnetic domain sizes. From the standard molar entropies, excess entropies of mixing have been generated for these solid solutions and compared with configurational entropies determined previously by assuming appropriate cation and valence distributions. The vibrational and magnetic excess entropies for bulk materials are comparable in magnitude to the respective configurational entropies indicating that excess entropies of mixing must be included when analyzing entropies of mixing. The excess entropies for nanophase materials are even larger than the configurational entropies. Changes in valence, cation distribution, bonding and microstructure between the mixing ions are the likely sources of the positive excess entropies of mixing.

  17. Phase diagrams for the M2MoO4–Ln2(MoO43–Hf(MoO42 systems, where M = Li–Cs, Tl and Ln = La–Lu

    Directory of Open Access Journals (Sweden)

    Zh. G. Bazarova

    2017-12-01

    Full Text Available In this paper, the results of systematic studies of complex molybdate systems M2MoO4–Ln2(MoO43–Hf(MoO42 (M = Li–Cs, Tl; Ln = La–Lu are presented. Subsolidus phase diagrams of ternary systems were constructed and new triple molybdates were obtained. The optimum synthesis conditions for poly- and monocrystalline form were determined. According to single-crystal data, the structure of one of the representatives of triple molybdates was determined.

  18. The phase diagram and magnetic properties of Co and Ti co-doped (1−x)BiFeO_3–xLaFeO_3 solid solutions

    International Nuclear Information System (INIS)

    Wu, Jiangtao; Xu, Jun; Li, Nan; Jiang, Yaqi; Xie, Zhaoxiong

    2015-01-01

    Single phase Co and Ti co-doped Bi_1_−_xFeO_3−La_xFeO_3 (x = 0–1) solid solutions were prepared by the sol–gel method. Room temperature x-ray powder diffraction (XRD) patterns showed that the structures of as-prepared Bi_1_−_xLa_xFe_0_._9_0Co_0_._0_5Ti_0_._0_5O_3 solid solutions transformed from rhombohedral R3c to tetragonal P4mm and then to orthorhombic Pnma, with increasing La concentration from 0 to 1. In situ high-temperature XRD (HTXRD) analysis further revealed that rhombohedral structure R3c (x ≤ 0.16) and tetragonal structure P4mm (0.17 ≤ x ≤ 0.40) changed to orthorhombic Pnma along with increasing temperature, and the phase transition temperature decreased with the increase of La doping concentration. However, the orthorhombic structure Pnma (x ≥ 0.41) kept stable even when the temperature reached 850 °C. The phase diagram of as-prepared binary solid solutions of Bi_1_−_xLa_xFe_0_._9_0Co_0_._0_5Ti_0_._0_5O_3(x = 0–1) was drawn on the basis of XRD and HTXRD analysis. Magnetic measurement revealed that the magnetic properties are greatly enhanced with the increase of La content. - Highlights: • Single phase Co and Ti co-doped (1−x)BiFeO_3–xLaFeO_3 (x = 0–1) solid solutions were synthesized. • The phase transitions were investigated by tuning composition and temperature. • Phase diagram was constructed according to the results of XRD for the first time. • The magnetization of solid solution can be enhanced when increasing La content.

  19. Quenching of I(2P1/2) by O3 and O(3P).

    Science.gov (United States)

    Azyazov, Valeriy N; Antonov, Ivan O; Heaven, Michael C

    2007-04-26

    Oxygen-iodine lasers that utilize electrical or microwave discharges to produce singlet oxygen are currently being developed. The discharge generators differ from conventional chemical singlet oxygen generators in that they produce significant amounts of atomic oxygen. Post-discharge chemistry includes channels that lead to the formation of ozone. Consequently, removal of I(2P1/2) by O atoms and O3 may impact the efficiency of discharge driven iodine lasers. In the present study, we have measured the rate constants for quenching of I(2P1/2) by O(3P) atoms and O3 using pulsed laser photolysis techniques. The rate constant for quenching by O3, (1.8 +/- 0.4) x 10(-12) cm3 s-1, was found to be a factor of 5 smaller than the literature value. The rate constant for quenching by O(3P) was (1.2 +/- 0.2) x 10(-11) cm3 s-1.

  20. Effects of composition modulation on the luminescence properties of Eu(3+) doped Li1-xAgxLu(MoO4)2 solid-solution phosphors.

    Science.gov (United States)

    Cheng, Fangrui; Xia, Zhiguo; Molokeev, Maxim S; Jing, Xiping

    2015-11-07

    Double molybdate scheelite-type solid-solution phosphors Li1-xAgxLu1-y(MoO4)2:yEu(3+) were synthesized by the solid state reaction method, and their crystal structures and luminescence properties were investigated in detail. The composition modulation and structural evolution of this series of samples were studied and the selected AgEu(MoO4)2, AgLu(MoO4)2, LiLu(MoO4)2 and LiEu(MoO4)2 phases were analyzed based on the Rietveld refinement. Depending on the variation of the Li/Ag ratio in Li1-xAgxLu1-y(MoO4)2:yEu(3+) phosphors, the difference in the luminescence properties of Li1-xAgxLu1-y(MoO4)2:yEu(3+) phosphors was ascribed to two factors, one reason could be assigned to the coupling effect and the nonradiative transition between the energy levels of LixAg1-xLu(MoO4)2 matrices and the activator Eu(3+), another could be due to the near ultraviolet energy absorption and transmission efficiency between the charge-transfer (CT) band of O(2-)-Mo(6+) and the 4f → 4f emissive transitions of Eu(3+). The ultraviolet-visible diffuse reflection spectra (UV-vis DRS) and Raman spectra analysis were also used to verify the above mechanism.

  1. Hydrogen storage in TiCr1.2(FeV)x BCC solid solutions

    International Nuclear Information System (INIS)

    Santos, Sydney F.; Huot, Jacques

    2009-01-01

    The Ti-V-based BCC solid solutions have been considered attractive candidates for hydrogen storage due to their relatively large hydrogen absorbing capacities near room temperature. In spite of this, improvements of some issues should be achieved to allow the technological applications of these alloys. Higher reversible hydrogen storage capacity, decreasing the hysteresis of PCI curves, and decrease in the cost of the raw materials are needed. In the case of vanadium-rich BCC solid solutions, which usually have large hydrogen storage capacities, the search for raw materials with lower cost is mandatory since pure vanadium is quite expensive. Recently, the substitutions of vanadium in these alloys have been tried and some interesting results were achieved by replacing vanadium by commercial ferrovanadium (FeV) alloy. In the present work, this approach was also adopted and TiCr 1.2 (FeV) x alloy series was investigated. The XRD patterns showed the co-existence of a BCC solid solution and a C14 Laves phase in these alloys. SEM analysis showed the alloys consisted of dendritic microstructure and C14 colonies. The amount of C14 phase increases when the amount of (FeV) decreases in these alloys. Concerning the hydrogen storage, the best results were obtained for the TiCr 1.2 (FeV) 0.4 alloy, which achieved 2.79 mass% of hydrogen storage capacity and 1.36 mass% of reversible hydrogen storage capacity

  2. Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

    Science.gov (United States)

    Anovitz, Lawrence M.; Essene, E.J.; Metz, G.W.; Bohlen, S.R.; Westrum, E.F.; Hemingway, B.S.

    1993-01-01

    The heat capacity of a synthetic almandine, Fe3Al2Si3O12, was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp298 = 342.80 ?? 1.4 J/mol ?? K and S298o = 342.60 J/mol ?? K. Mo??ssbauer characterizations show the almandine to contain less than 2 ?? 1% of the total iron as Fe3+. X-ray diffraction studies of this synthetic almandine yield a = 11.521 ?? 0.001 A?? and V298o = 115.11 +- 0.01 cm3/mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with TN = 7.5 K. Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ??Gf,298o = -4938.3 kJ/mol and ??Hf,298o= -5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P for almandine and is metastably located at ca. 570??C at P = 1 bar, with a dP dT of +17 bars/??C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In {norm of matrix}O2-T space, almandine oxidizes near QFM by the reactions almandine + O2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz. With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks. ?? 1993.

  3. Syntheses, crystal structures, and properties of the isotypic pair [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O and [In(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Van, Nguyen-Duc; Kleeberg, Fabian M.; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

    2015-11-15

    Single crystals of [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O and [In(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O were obtained by reactions of aqueous solutions of the acid (H{sub 3}O){sub 2}[B{sub 12}H{sub 12}] with chromium(III) hydroxide and indium metal shot, respectively. The title compounds crystallize isotypically in the trigonal system with space group R anti 3c (a = 1157.62(3), c = 6730.48(9) pm for the chromium, a = 1171.71(3), c = 6740.04(9) pm for the indium compound, Z = 6). The arrangement of the quasi-icosahedral [B{sub 12}H{sub 12}]{sup 2-} dianions can be considered as stacking of two times nine layers with the sequence..ABCCABBCA.. and the metal trications arrange in a cubic closest packed..abc.. stacking sequence. The metal trications are octahedrally coordinated by six water molecules of hydration, while another fifteen H{sub 2}O molecules fill up the structures as zeolitic crystal water or second-sphere hydrating species. Between these free and the metal-bonded water molecules, bridging hydrogen bonds are found. Furthermore, there is also evidence of hydrogen bonding between the anionic [B{sub 12}H{sub 12}]{sup 2-} clusters and the free zeolitic water molecules according to B-H{sup δ-}..{sup δ+}H-O interactions. Vibrational spectroscopy studies prove the presence of these hydrogen bonds and also show slight distortions of the dodecahydro-closo-dodecaborate anions from their ideal icosahedral symmetry (I{sub h}). Thermal decomposition studies for the example of [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O gave no hints for just a simple multi-stepwise dehydration process. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    DEFF Research Database (Denmark)

    Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina

    2016-01-01

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical bar...

  5. Influence of lead oxide addition on LnTiTaO6 (Ln = Ce, Pr and Nd) microwave ceramics

    International Nuclear Information System (INIS)

    Padma Kumar, H.; Thomas, J.K.; John, Annamma; Solomon, Sam

    2011-01-01

    The effect of PbO addition on the structural, processing and microwave dielectric properties of LnTiTaO 6 (Ln = Ce, Pr and Nd) ceramics are reported. Conventional solid state ceramic route was used for the preparation of samples. Phase pure LnTiTaO 6 (Ln = Ce, Pr and Nd) ceramics are prepared at a calcination temperature of 1300 deg C. The samples are sintered at optimized temperatures. Addition of PbO reduces the sintering temperature. The crystal structure of the materials was analysed using X-ray diffraction techniques and the surface morphology of the sintered samples was analysed using scanning electron microscopy. The dielectric constant at microwave frequency range decreases for higher PbO addition for all the samples but the quality factor improves on small PbO addition. The thermal stability of resonant frequency was also improved with PbO addition on all the systems. A number of samples with improved microwave dielectric properties were obtained on all the systems suitable for practical applications. (author)

  6. Synthesis and characterization of CeO2-TiO2-Pr6O11 solid solutions for environmentally benign nontoxic red pigments

    International Nuclear Information System (INIS)

    George, Giable; Rao, Padala Prabhakar; Reddy, Mundlapudi Lakshmipathi

    2006-01-01

    New inorganic pigments Ce 1-(x+y) Ti x Pr y O 2 (x ranges from 0.05 to 0.195 and y ranges from 0.005 to 0.15) based on CeO 2 -TiO 2 -Pr 6 O 11 solid solutions have been synthesized by solid-state route with a goal of preparing environmentally secure red colorants. Characterizations using XRD, UV-vis spectroscopy and CIE 1976 color coordinates assessment reveals the formation of pigments displaying colors ranging from brick red to dark brown. The coloring mechanism is based on the introduction of additional electronic level of energy in the cerianite forbidden band from the unpaired 4f electron of lanthanide ion. (author)

  7. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H2O and D2O solutions

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I.

    1983-01-01

    The exchange reaction between central ions in the NdD - Ln' 3+ systems, where Ln' 3+ is a substituting cation (Eu 3+ and Ho 3+ , D 4 =cyclohexanediaminetetraacetate) is studied and the electrophilic suhstitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solVed in heavy water containing 99.9% D 2 O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized

  8. Investigation into isomolar series of Al(NO/sub 3/)/sub 3/, Na/sub 3/VO/sub 4/ solution mixture and composition of solid phases

    Energy Technology Data Exchange (ETDEWEB)

    Chernysh, L F; Nakhodnova, A P; Makarova, R A [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1979-11-01

    Conducted is investigation of properties of isomolar series of aluminium nitrate and sodium vanadate solutions at pH of the latter 12.5; 10.0; 7.0 and the temperature of 25 deg C using the methods of pH-metry, conductometry, ''seeming'' volume of precipitations, residual concentration of aluminium and vanadium. It is shown, that the composition property diagram of the system investigated does not reflect the true composition of solid-phase products of the reaction, which depends on the component ratio in solution. Bottom phases of isomolar series are mainly heterogeneous. At the excess of sodium vanadate solution and its high pH values conditions for the basic salt formation are created. At pH of the Na/sub 3/VO/sub 4/ solution of 12.5 and 10.0 and Al(NO/sub 3/)/sub 3/: Na/sub 3/VO/sub 4/ ratios 4:6 and 3:7 respectively obtained are the basic aluminium vanadates of the (AlOH)/sub 3/(VO/sub 4/)/sub 2/x 7.5H/sub 2/O and (AlOH)/sub 2/V/sub 2/O/sub 7/x5H/sub 2/O composition, some of their physicochemical properties being investigated.

  9. Valence states of cobalt and crystal structure peculiarities of solid solution YBa2Cu3-xCoxO6+σ

    International Nuclear Information System (INIS)

    Voronin, V.I.; Goshchinskij, B.N.; Mitberg, Eh.B.; Leonidov, I.A.; Kozhevnikov, V.L.

    2000-01-01

    Crystal structure of solid solution YBa 2 Cu 3-x Co x O 6+σ , where x = 0.2, 0.4, 0.6 and 0.8, is studied by the method of powder neutron diffraction. Charge states of the cation are calculated using the interatomic distances obtained. It is shown that cobalt in Cu1 position has valency 3 + and octahedral coordination at x = 0.2 and 0.4. Increase in doping degree involves both transition of a portion of cobalt ions in the positions mentioned to the state with valence 4 + and tetrahedral coordination and partial substitution of copper in Cu2 position [ru

  10. 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.

  11. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  12. Some regularities in aging of solid oxide electrolytes ZrO2+Y2O3

    International Nuclear Information System (INIS)

    Vlasov, A.N.

    1983-01-01

    A study was made on the temperature effect on the rate and depth of aging of solid oxide electrolytes ZrO 2 +Y 2 O 3 and ZrO 2 +Ho 2 O 3 , stabilized by 10-15 mol.% R 2 O 3 following isothermal hold-up during 2000-3000 h in the 725-1550 deg C range in oxidizing medium. It was shown that solid electrolyte aging proceeds only at temperatures below a certain boundary value. The depth of complete aging at that increases with the R 2 O 3 concentration and a temperature decrease. The aging rate depends substantially on both temperature and concentration of a stabilizing addition. A decrease in the electric conductivity with time is accompanied by an increase in the conductivity activation energy

  13. Phase Equilibrium in the System Ln-Mn-O II. Ln=Nd at 1100 C

    International Nuclear Information System (INIS)

    Kitayama, Kenzo; Kanzaki, Tadao

    2001-01-01

    Phase equilibrium is established in a Nd-Mn-O system at 1100 C by changing the oxygen partial pressure from 0 to 12.00 in -log(Po(sub 2)/atm); a phase diagram at 1100 C is presented for a Nd(sub 2)O(sub 3)-MnO-MnO(sub 2) system. Under the experimental conditions, Nd(sub 2)O(sub 3), MnO, Mn(sub 3)O(sub 4), and NdMnO(sub 3) phases are present at 1100 C, but Nd(sub 2)MnO(sub 4), Mn(sub 2)O(sub 3), and MnO(sub 2) are not stable in the system. Wide ranges of nonstoichiometry were found in the NdMnO(sub 3) phase, which coexisted with Nd(sub 2)O(sub 3). X ranges from -0.006 at log Po(sub 2)=-10.85 to 0.104 at log Po(sub 2)=0 in the form of NdMnO(sub 3+X). The nonstoichiometry is represented by the equation No/N(sub NdMnO(sub 3))=4.34x10(sup -5)(log Po(sub 2))(sup 3)+1.99x10(sup -3)(log Po(sub 2))(sup 2)+2.65x10(sup -2)(log Po(sub 2))+0.104; the activities of the components in the solid solution are also calculated with this equation. NdMnO(sub 3) has a composition range to the Nd(sub 2)O(sub 3)-rich or Nd(sub 2)O(sub 3)-poor side of LaMnO(sub 3). Lattice constants of NdMnO(sub 3) made in different oxygen partial pressures were determined

  14. The effect of Mn substitution on the structure and magnetic properties of Se(Cu1-xMnx)O3 solid solution

    International Nuclear Information System (INIS)

    Escamilla, R; Duran, A; Rosales, M I; Moran, E; Alario-Franco, M A

    2003-01-01

    The effects of Mn substitution on the structure and magnetic properties of the SeMO 3 (M = Cu 1-x Mn 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 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 3 . At about 10% of Mn there is a change from positive to negative Weiss constant θ W that is mainly due to the [M-O 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 3

  15. Some crystal chemistry of (Ln,Ce)2CuO4-δ superconductors

    International Nuclear Information System (INIS)

    Goodman, P.; Keating, A.; Myhra, S.; White, T.J.

    1989-01-01

    Compounds of the form (Ln, Sr, Ce) 2 CuO 4-δ (Ln = rare earth element) crystallise as the Nd 2 CuO 4 structure type, K 2 NiF 4 structure type or perfectly and imperfectly ordered intergrowths of these parent structures. These structurally similar phases exhibit superconductivity in which the charge carriers are holes (in Sr-doped material) or electrons (in Ce doped material). In this study, X-ray Photoelectron Spectroscopy (XPS) and High Resolution Electron Microscopy (HREM) were used to investigate the charge balancing mechanisms operating in each superconducting regime and the structural changes accompanying compositional variation. It was found that under slightly reducing conditions charge coupled cation substitutions predominate, whilst at low pO 2 ( -5 atm) perfectly ordered oxygen superlattices form. The structural and electronic changes which accompany deoxygenation were observed in situ during XPS and HREM observations. 29 refs., 8 figs., 3 tabs

  16. Thermal expansion studies on HfO2-Gd2O3 system

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Antony, M.P.; Nagarajan, K.

    2014-01-01

    A series of solid solutions containing GdO 1.5 in HfO 2 , (Hf 1-y Gd y ) O 2 (y = 0.15, 0.2, 0.3, 0.41 and 0.505) were prepared by solid state method. Structural characterization and computation of lattice parameter was carried out using room temperature X-ray diffraction measurements

  17. Crystal structure of fluorite-related Ln3SbO7 (Ln=La–Dy) ceramics studied by synchrotron X-ray diffraction and Raman scattering

    International Nuclear Information System (INIS)

    Siqueira, K.P.F.; Borges, R.M.; Granado, E.; Malard, L.M.; Paula, A.M. de; Moreira, R.L.; Bittar, E.M.; Dias, A.

    2013-01-01

    Ln 3 SbO 7 (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) ceramics were synthesized by solid-state reaction in optimized conditions of temperature and time to yield single-phase ceramics. The crystal structures of the obtained ceramics were investigated by synchrotron X-ray diffraction, second harmonic generation (SHG) and Raman scattering. All samples exhibited fluorite-type orthorhombic structures with different oxygen arrangements as a function of the ionic radius of the lanthanide metal. For ceramics with the largest ionic radii (La–Nd), the ceramics crystallized into the Cmcm space group, while the ceramics with intermediate and smallest ionic radii (Sm–Dy) exhibited a different crystal structure belonging to the same space group, described under the Ccmm setting. The results from SHG and Raman scattering confirmed these settings and ruled out any possibility for the non-centrosymmetric C222 1 space group describing the structure of the small ionic radii ceramics, solving a recent controversy in the literature. Besides, the Raman modes for all samples are reported for the first time, showing characteristic features for each group of samples. - Graphical abstract: Raman spectrum for La 3 SbO 7 ceramics showing their 22 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. - Highlights: • Ln 3 SbO 7 ceramics belonging to the space groups Cmcm and Ccmm are synthesized. • SXRD, SHG and Raman scattering confirmed the orthorhombic structures. • Ccmm instead of C222 1 is the correct one based on SHG and Raman data

  18. Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300oC

    International Nuclear Information System (INIS)

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

    1999-12-01

    The major contributions of the isotopes 122 Sb and 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 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 2 O 3 increases by about two orders of magnitude between 25 and 200 o C, and then levels out or decreases slightly. At 250 o C, in oxidizing solutions, Sb 2 O 5 ·xH 2 O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na 2α [H(H 2 O)] 2-2α Sb 2 O 6 , which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200 o C and decreases at temperatures above 250 o C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO 3 - or Sb(OH) 6 - ), 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·dm -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 ruled out that hydrated Sb 2 O 5 (especially the pyrochlore form) might be less soluble in near-neutral, low

  19. Synthesis, structural and microwave dielectric properties of Al2W3-xMoxO12 (x = 0-3) ceramics

    International Nuclear Information System (INIS)

    Surjith, A.; James, Nijesh K.; Ratheesh, R.

    2011-01-01

    Highlights: → Solid state synthesis of phase pure Al 2 W 3-x Mo x O 12 (x = 0-3) compositions. → Sintering studies of Al 2 W 3-x Mo x O 12 (x = 0-3) ceramics. → Structural and microstructural evaluation using powder X-ray diffraction and SEM studies. → Microwave dielectric property evaluation of Al 2 W 3-x Mo x O 12 (x = 0-3) ceramics through Hakki and Coleman post resonator and cavity perturbation techniques. → Structure-property correlation through Laser Raman studies. - Abstract: Low dielectric ceramics in the Al 2 W 3-x Mo x O 12 (x = 0-3) system have been prepared through solid state ceramic route. The phase purity of the ceramic compositions has been studied using powder X-ray diffraction (XRD) studies. The microstructure of the sintered ceramics was evaluated by Scanning Electron Microscopy (SEM). The crystal structure of the ceramic compositions as a result of Mo substitution has been studied using Laser Raman spectroscopy. The microwave dielectric properties of the ceramics were studied by Hakki and Coleman post resonator and cavity perturbation techniques. Al 2 Mo x W 3-x O 12 (x = 0-3) ceramics exhibited low dielectric constant and relatively high unloaded quality factor. The temperature coefficient of resonant frequency of the compositions is found to be in the range -41 to -72 ppm/deg. C.

  20. Electron magnetic resonance of diluted solid solutions of Gd{sup 3+} in SrTiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Biasi, R.S. de, E-mail: rsbiasi@ime.eb.br [Secao de Engenharia Mecanica e de Materiais, Instituto Militar de Engenharia, 22290-270 Rio de Janeiro, RJ (Brazil); Grillo, M.L.N., E-mail: mluciag@uerj.br [Instituto de Fisica, Universidade do Estado do Rio de Janeiro, 20550-013 Rio de Janeiro, RJ (Brazil)

    2011-10-17

    Highlights: {yields} EMR is an effective method to study the range of the exchange interaction in solid solutions. {yields} The range of the exchange interaction between Gd{sup 3+} ions in SrTiO{sub 3} is about 0.96 nm. {yields} The linewidth increases faster with Gd concentration in SrTiO{sub 3} than in other host lattices, such as CeO{sub 2}, SrO, CaO and ZrSiO{sub 4}. - Abstract: Electron magnetic resonance (EMR) spectra of gadolinium-doped strontium titanate (SrTiO{sub 3}) have been studied at room temperature for gadolinium concentrations between 0.20 and 1.20 mol%. The results suggest that the Gd{sup 3+} ions occupy substitutional sites, replacing the Sr{sup 2+} ion, that the electron magnetic resonance linewidth increases with increasing gadolinium concentration and that the range of the exchange interaction between Gd{sup 3+} ions is about 0.96 nm, of the same order as that of the same ion in other host lattices, such as ceria (CeO{sub 2}), quicklime (CaO), strontia (SrO) and zircon (ZrSiO{sub 4}). The fact that the electron magnetic resonance linewidth of the Gd{sup 3+} ion increases, regularly and predictably, with Gd concentration, shows that the Gd{sup 3+} ion can be used as a probe to study, rapidly and non-destructively, the crystallinity and degradation of SrTiO{sub 3}.

  1. Yttrium aluminum garnet (YAG) obtained by rare-earth mixed oxide (RE2O3)

    International Nuclear Information System (INIS)

    Castro, D.F.; Daguano, J.K.M.F.; Rodrigues Junior, D.; Suzuki, P.A.; Silva, O.M.M.

    2010-01-01

    In this work, the substitution of commercial Y 2 O 3 by a rare earth mixed oxide, RE 2 O 3 , to form Yttrium aluminum Garnet-Y 3 Al 5 O 12 , was investigated. Al 2 O 3 :Y 2 O 3 and Al 2 O 3 :RE 2 O 3 powder-mixtures, in a molar ratio of 60:40, were milled and subsequently cold uniaxially-pressed. Compacts were sintered at 1000, 1400 or 1600 deg C, for 120 minutes. RE 2 O 3 oxide was characterized by high-resolution synchrotron X-ray diffraction (HRXRD) and compared to Y 2 O 3 . X-ray diffraction pattern of the RE 2 O 3 indicates a true solid solution formation. Rietveld refinement of the sintered YAG and (RE)AG reveled a similar crystal structure to the YAGs obtained by the use of Al 2 O 3 -Y 2 O 3 or Al 2 O 3 -RE 2 O 3 respectively. Microstructural analysis of both, YAG or (RE)AG, revealed similar grain sizes of about 2.5 μm besides mechanical properties, with hardness of 400HV and fracture toughness of 3.8MPa.m1/2. It could be, thus, demonstrated that pure Y 2 O 3 can be substituted by the rare-earth solid solution, RE 2 O 3 , in the formation YAGs, presenting similar microstructural and mechanical properties. (author)

  2. Syntheses, structures and properties of three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers based on 2,2'-dipyridyl-5,5'-dicarboxylate ligands.

    Science.gov (United States)

    Zhao, Junwei; Cheng, Yamin; Shang, Sensen; Zhang, Fang; Chen, Li; Chen, Lijuan

    2013-12-01

    Three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers [Ln(III)Cu2(I)(Hbpdc)4] · Cl · xH2O [Ln(III) = La(III), x = 8 (1); Ln(III) = Pr(III), x=9 (2); Ln(III) = Eu(III), x = 8 (3)] (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1-3 display the two-dimensional sheet structure constructed from [Cu(I)(Hbpdc)2](-) fragments through Ln(3+) connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the Eu(III) ions, Hbpdc(-) ligands and Cu(I) cations make contributions to its luminescent properties simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Effects of the co-addition of LiSbO3-LiTaO3 on the densification of (Na1/2K1/2)NbO3 lead free ceramics by atmosphere sintering

    International Nuclear Information System (INIS)

    Jiang Na; Fang Bijun; Wu Jian; Du Qingbo

    2011-01-01

    Research highlights: → This manuscript shows a synthesis method that can easily obtain excellent lead-free samples, which is valuable for industrial production. → Pure phase perovskite 0.94(Na 1/2 K 1/2 )NbO 3 -0.03LiSbO 3 -0.03LiTaO 3 (0.94NKN-0.03LS-0.03LT) lead-free piezoelectric ceramics with high relative density, being 94.73%, and excellent integral electrical properties, piezoelectric constant d 33 being 228 pC/N, were prepared by atmosphere sintering method. Which can be attributed to the co-doping of LiSbO 3 -LiTaO 3 . - Abstract: Pure phase perovskite 0.94(Na 1/2 K 1/2 )NbO 3 -0.03LiSbO 3 -0.03LiTaO 3 (0.94NKN-0.03LS-0.03LT) lead-free piezoelectric ceramics were prepared by the conventional solid-state reaction method. Due to the co-addition of LiSbO 3 -LiTaO 3 , the 0.94NKN-0.03LS-0.03LT ceramics prepared by atmosphere sintering at 1040 deg. C exhibit high relative density, being 94.73%, and rather homogenous microstructure. X-ray diffraction (XRD) measurement confirmed that the sintered ceramics exhibit pure tetragonal perovskite structure. The 0.94NKN-0.03LS-0.03LT ceramics exhibit excellent integral electrical properties, in which the value of piezoelectric constant d 33 is 228 pC/N, the electromechanical coupling factors K p and K t are 0.220 and 0.230, respectively, the mechanical quality factor Q m is 32.19, and the remnant polarization P r is 23.06 μC/cm 2 . Such excellent electrical properties are considered as correlating with the high relative density of the synthesized ceramics induced by the co-doping of LiSbO 3 -LiTaO 3 .

  4. Luminescence of Eu:Y3Al5O12, Eu:Lu3Al5O12, and Eu:GdAlO3 Nanocrystals Synthesized by Solution Combustion

    Science.gov (United States)

    Vilejshikova, E. V.; Khort, A. A.; Podbolotov, K. B.; Loiko, P. A.; Shimanski, V. I.; Shashkov, S. N.; Yumashev, K. V.

    2017-11-01

    Nanocrystals of rare-earth garnets Y3Al5O12 and Lu3Al5O12 and perovskite GdAlO3 highly doped (10-20 at%) with Eu3+ are synthesized by the solution combustion technique and subsequent annealing in air at 800 and 1300oC. Their structure, morphology, and phase composition are studied. These materials exhibit intense red luminescence under UV excitation. Eu:GdAlO3 luminescence has CIE 1931 color coordinates (0.632, 0.368); dominant wavelength, 599.6 nm; and color purity, >99%. Judd-Ofelt parameters, luminescence branching ratios, and lifetimes of the Eu3+ 5D0 state are determined. The luminescence quantum yield for Eu:GdAlO3 (10 at%) reaches 74% with a lifetime of 1.4 ms for the 5D0 state. The synthesized materials are promising for red ceramic phosphors.

  5. Chemical solution deposition of CaCu3Ti4O12 thin film

    Indian Academy of Sciences (India)

    Administrator

    CaCu3Ti4O12; thin film; chemical solution deposition; dielectric properties. 1. Introduction. The CaCu3Ti4O12. (CCTO) compound has recently attracted considerable ... and Kelvin probe force microscopy (Chung et al 2004). Intrinsic .... SEM images of CCTO thin films as a function of sintering temperature. silicon based ...

  6. Determination of the constants of the solubility product of Ln(OH){sub 3} and the effect of the chloride ions on the lanthanum hydrolysis, praseodymium and lutetium in aqueous solutions of ion force 2 Molar; Determinacion de las constantes del producto de solubilidad de Ln(OH){sub 3} y el efecto de los iones cloruro sobre la hidrolisis de lantano, praseodimio y lutecio en soluciones acuosas de fuerza ionica 2 Molar

    Energy Technology Data Exchange (ETDEWEB)

    Lopez G, H.D

    2005-07-01

    The behavior of lanthanum (III), praseodymium (III), and lutetium (III) was studied in 2 M NaClO{sub 4} (aq) and 2 M NaCl (aq) at 303 K and free -CO{sub 2} conditions. Solubility diagrams (p Ln(aq)-pC{sub H}) were obtained by means of a radiochemical method. The pC{sub H} borderlines of saturation and unsaturation zones of the solutions and solubility product constants for Ln(OH){sub 3} were determined from these diagrams. The fitting of the solubility equation to the experimental values of p Ln(aq)-pC{sub H} diagrams allowed the calculation of the first hydrolysis and solubility product constants. Independently, the stability constants for the first species of hydrolysis were determined by means of pH titrations, the data were treated with the program SUPERQUAD and fitted to the mean ligand number equation. The stability constants for the species LnCl{sup 2+} were as well calculated in 2M ionic strength and 303 K from the hydrolysis constant values obtained in both perchlorate and chloride media. The values obtained for La, Pr and Lu were: logK{sub ps}: 21.11 {+-} 0.09, 19.81 {+-} 0.11 and 18.10 {+-} 0.13 in 2M NaClO{sub 4}; logK{sub ps}: 22.22 {+-} 0.09, 21.45 {+-} 0.14 and 18.52 {+-} 0.29 in 2M NaCl; log {beta}{sub 1}: - 8.64 {+-} 0.02, - 8.37 {+-} 0.01 and - 7.95 {+-} 0.11 in 2M NaClO{sub 4}; log {beta}{sub 1}{sup /} : - 9.02 {+-} 0.11, - 8.75 {+-} 0.01 and - 8.12 {+-} 0.03 in 2M NaCl and the values for log {beta}{sub 1,Cl} were - 0.0255, - 0.155 and - 0.758, respectively. (Author)

  7. Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters.

    Science.gov (United States)

    Akhtar, Muhammad Nadeem; Lan, Yanhua; AlDamen, Murad A; Zheng, Yan-Zhen; Anson, Christopher E; Powell, Annie K

    2018-03-06

    Three isostructural lanthanide series with a core of MnMnLn 2 are reported. These three families have the formulae of [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (piv) 6 (NO 3 ) 2 ] {no crystallization solvent, Ln = La, Ce, Pr, Nd, Eu (1-4, 6); solv = 3MeCN, Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y (5, 7-13)}, where H 2 edte = N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and piv = pivalate; [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (benz) 6 (NO 3 ) 2 ], where benz = benzoate, or [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (benz) 6 (NO 3 ) 22MeCN {Ln = Gd, Tb, Dy (14-16); and [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (piv) 8 ].solv {solv = 4MeCN, Ln = La (17); solv = 2MeCN·tol·H 2 O, Ln = Pr, Nd, Sm, Tb (18-20, 22); solv = 2MeCN·H 2 O, Ln = Gd (21). These compounds crystallize in two different systems, namely, monoclinic in the space groups P2 1 /n for 1-4, 6, and 14-16 and C2/c for 5, 7-13, 18-20, and 22 and triclinic in the space group P1[combining macron] for 17 and 21. The crystal structures of these compounds display a face-fused dicubane structure connected by different types of bridged oxygen atoms. Solid-state dc magnetic susceptibility characterization was carried out for 1-22, and fitting showed that Mn III Mn III is antiferromagnetically (AF) coupled and Mn II Mn III , Mn II Ln and Mn III Ln are weakly ferromagnetically coupled. In addition, ac measurements were carried out and showed that only 7, 15, and 22 for Tb, 8 and 16 for Dy, and 20 for Sm exhibited slow magnetization relaxation. In the case of 15, it was possible to determine the energy barrier of the slow-relaxation behavior by fitting peak temperatures to the Arrhenius law, which gave a value of U eff = 21.2 K and a pre-exponential factor of τ 0 = 4.0 × 10 -9 s.

  8. Systematics in the electron transport and magnetic properties of LnBO3 perovskites

    International Nuclear Information System (INIS)

    Ganguly, P.; Rao, C.N.R.

    1980-01-01

    Systematics in the electrical and magnetic properties of transition metal perovskites LnBO 3 (Ln = rare-earth ion, B = 3d transition metal) with the variation of Ln and B ions are reviewed. The electrical resistivity and activation energy of LnBO 3 compounds increase with the decreasing size of the Ln 3+ ion for a given B ion. The low-spin to high-spin transition temperature of Co 3+ ion in LnCoO 3 similarly increase with the decrease in size of Ln 3+ while the magnetic ordering temperatures in LnVO 3 , LnFeO 3 , LnCrO 3 and LnSrCo 2 O 6 decrease with decreasing size of the rare-earth ion. These results may be understood in terms of the increasing acidity of the rare earth ion with decreasing size and the competition between the Ln 3+ and the B 3+ ions for covalency with the oxygen ions. The effect of this competition on the metal oxygen covalency and crystal field parameter is discussed in relation to the results obtained and Goodenough's phase diagram. The possibility of d-f exchange interaction in Lasub(1-x)Lnsub(x)NiOsub(3) is also discussed in the light of ESR results. (auth.)

  9. Dissolution of britholites and monazite / brabantite solid solutions doped with actinides

    International Nuclear Information System (INIS)

    Du Fou De Kerdaniel, E.

    2007-12-01

    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 III PO 4 ), brabantite (Ca II An IV (PO 4 ) 2 : An = Th, U) and britholites (Ca 9 Nd 0.5 An 0.5 IV (PO 4 ) 4.5 (SiO 4 ) 1.5 F 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 2 (PO 4 ) 2 HPO 4 .H 2 O) and Nd - rhabdophane (NdPO 4 .1/2H 2 O) when increasing leaching time. (author)

  10. Raman spectra of the solid-solution between Rb sub 2 La sub 2 Ti sub 3 O sub 1 sub 0 and RbCa sub 2 Nb sub 3 O sub 1 sub 0

    CERN Document Server

    Kim, H J; Yun, H S

    2001-01-01

    A site preference of niobium atom in Rb sub 2 sub - sub x La sub 2 Ti sub 3 sub - sub x Nb sub x O sub 1 sub 0 (0.0<=x<=1.0) and RbLa sub 2 sub - sub x Ca sub x Ti sub 2 sub - sub x Nb sub 1 sub + sub x O sub 1 sub 0 (0.0<=x<= 2.0), which are the solid-solutions between Rb sub 2 La sub 2 Ti sub 3 O sub 1 sub 0 are RbCa sub 2 Nb sub 3 O sub 1 sub 0 , has been investigated by Raman spectroscopy. The Raman spectra of Rb sub 2 sub - sub x La sub 2 Ti sub 3 sub - sub x Nb sub x O sub 1 sub 0 (0.0<=x<=1.0) gave an evidence that niobium atoms substituted for titanium atoms preferably occupy the highly distorted outer octahedral sites rather than the central ones in triple-octahedral perovskite layers. In contrast, the Raman spectra of RbLa sub 2 sub - sub x Ca sub x Ti sub 2 sub - sub x Nb sub 1 sub + sub x O sub 1 sub 0 (0.0<=x<= 2.0) showed no clear information for the cationic arrangement in perovskite slabs. This difference indicated that a site preference of niobium atoms is observed onl...

  11. Behaviour of Fe4O5-Mg2Fe2O5 solid solutions and their relation to coexisting Mg-Fe silicates and oxide phases

    Science.gov (United States)

    Uenver-Thiele, Laura; Woodland, Alan B.; Miyajima, Nobuyoshi; Ballaran, Tiziana Boffa; Frost, Daniel J.

    2018-03-01

    Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5-Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg-Fe silicates. Multi-anvil experiments were performed at 11-20 GPa and 1100-1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential "water-storing" mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = - 1981.5 kJ mol- 1. Solid solution is complete across the Fe4O5-Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg-Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.

  12. Low-temperature sol-gel synthesis of NaZr2P3O12

    International Nuclear Information System (INIS)

    Agrawal, D.K.; Adair, J.H.

    1990-01-01

    The NZP family of new low-expansion materials has attracted wide interest for its potential in advanced technological applications. NaZr 2 P 3 O 12 , which is the parent composition of this family, has been synthesized by the solution sol-gel method using special precursor solutions, which led to its formation (although poorly crystalline) at temperatures as low as 120 degrees C. The lowest temperature of formation of a single phase of NaZr 2 P 3 O 12 with a high degree of crystallinity was found to be 600 degrees C

  13. Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, K.T., E-mail: katob@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Prusty, Debadutta [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Kale, G.M. [Institute for Materials Research, University of Leeds, Leeds, LS2 9JT (United Kingdom)

    2012-02-05

    Highlights: Black-Right-Pointing-Pointer Refinement of phase diagram for the system Mg-Rh-O and thermodynamic data for spinel compounds MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} is presented. Black-Right-Pointing-Pointer A solid-state electrochemical cell is used for thermodynamic measurement. Black-Right-Pointing-Pointer An advanced design of the solid-state electrochemical cell incorporating buffer electrodes is deployed to minimize polarization of working electrode. Black-Right-Pointing-Pointer Regular solution model for the spinel solid solution MgRh{sub 2}O{sub 4} - Mg{sub 2}RhO{sub 4} based on ideal mixing of cations on the octahedral site is proposed. Black-Right-Pointing-Pointer Factors responsible for stabilization of tetravalent rhodium in spinel compounds are identified. - Abstract: Pure stoichiometric MgRh{sub 2}O{sub 4} could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh{sub 2}O{sub 3} in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh{sub 2}O{sub 3}. The spinel phase can be considered as a solid solution of Mg{sub 2}RhO{sub 4} in MgRh{sub 2}O{sub 4}. The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg{sub 1+x}Rh{sub 2-x}O{sub 4} was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured

  14. A feasibility study of the preparation of (U,Gd)3O8 solid solutions by thermal decomposition of co-precipitated carbonate mixtures

    International Nuclear Information System (INIS)

    Ravindran, P.V.; Rajagopalan, K.V.; Mathur, K.P.

    1998-01-01

    Co-precipitation from equimolar nitrate solutions of uranium (VI) and gadolinium has been used to obtain a mixture of (NH 4 ) 4 UO 2 (CO 3 ) 3 and Gd 2 (CO 3 ) 3 .3H 2 O at a pre-determined composition. Simultaneous measurements by TG, DTA and evolved gas analysis (EGA) showed that a calcination temperature of 700 C was necessary to decompose the carbonate completely to oxides. X-ray diffraction data indicated that a solid solution of Gd 2 O 3 in U 3 O 8 cannot be obtained by heating the carbonate mixtures up to 800 C in inert atmospheres. (orig.)

  15. Structural and magnetic properties of a mechanochemically activated Ti-Fe{sub 2}O{sub 3} solid mixture

    Energy Technology Data Exchange (ETDEWEB)

    Cristobal, A.A. [Instituto de Investigaciones en Ciencia y Tecnologia de Materiales (INTEMA), CONICET-UNMdP, J.B. Justo 4302 - B7608FDQ, Mar del Plata (Argentina); Ramos, C.P. [Centro Atomico Constituyentes (CAC), CNEA, Av. Gral. Paz 1499 (1650), San Martin (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Bercoff, P.G. [Facultad de Matematica, Astronomia y Fisica (FaMAF), Universidad Nacional de Cordoba, Medina Allende s/n, Ciudad Universitaria, (5000) Cordoba (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Conconi, S.; Aglietti, E.F. [Centro de Tecnologia de Recursos Minerales y Ceramica (CETMIC), CONICET - CIC, Camino, P. Centenario y 506 - B1897ZCA, M.B. Gonnet (Argentina); Botta, P.M., E-mail: pbotta@fi.mdp.edu.ar [Instituto de Investigaciones en Ciencia y Tecnologia de Materiales (INTEMA), CONICET-UNMdP, J.B. Justo 4302 - B7608FDQ, Mar del Plata (Argentina); Lopez, J.M. Porto [Instituto de Investigaciones en Ciencia y Tecnologia de Materiales (INTEMA), CONICET-UNMdP, J.B. Justo 4302 - B7608FDQ, Mar del Plata (Argentina)

    2010-12-15

    The mechanochemical effects on the reactivity and properties of a titanium/hematite powder mixture with molar ratio of 1/2 are investigated. Crystalline-phase structure, composition, hyperfine and magnetic behaviors were analyzed as a function of activation time by means of X-ray diffraction, scanning electron microscopy, Moessbauer spectroscopy and vibrating sample magnetometry. The results showed that at relatively short activation times metallic Ti reduces part of the ferric ions, yielding a complex product formed mainly by a mix of two solid solutions Fe{sub 3-x}Ti{sub x}O{sub 4} (titanomagnetites), both with very different x values (0 < x < 1). Also metallic iron and superparamagnetic hematite particles were detected by Moessbauer spectroscopy. As the mechanical treatment extends the composition of the reactive mixture changes, prevailing in the end the solid solution with higher x value. In contrast, when these activated samples are thermally treated the fraction of the solid solution which is richer in Ti diminishes. This fact produces a significant variation of the saturation magnetization of the obtained material.

  16. Bulk solid state rechargeable lithium ion battery fabrication with Al-doped Li7La3Zr2O12 electrolyte and Cu0.1V2O5 cathode

    International Nuclear Information System (INIS)

    Jin, Ying; McGinn, Paul J.

    2013-01-01

    A simple, low-temperature route was developed to process bulk solid-state Li-ion batteries employing Al-doped Li 7 La 3 Zr 2 O 12 solid electrolyte (thickness: ∼ 0.5 mm; 25 °C conductivity: ∼ 2 × 10 −4 S cm −1 ). A composite Cu 0.1 V 2 O 5 –based slurry was directly painted on Li 7 La 3 Zr 2 O 12 and dried at 120 °C to prepare the cathode film. The opposite side of the electrolyte was subsequently exposed to molten Li to form the anode. The discharge capacity of the solid state battery was 53 mAh g −1 (calculated based on the weight of active cathode material) at room temperature with 5 μA cm −2 discharging current. Severe capacity decay occurred after the initial discharging. A comparable liquid electrolyte battery was tested at room temperature for comparison and had a much slower decay rate. However, when the operating temperature of the solid state battery was increased to 50 °C, the cell performance significantly improved. At 50 °C, the battery exhibited 176 mAh g −1 initial discharging capacity at 5 μA cm −2 current density and 93 mAh g −1 initial capacity under a 10 μA cm −2 discharging current density. After 20 cycles, the capacity decayed to 68.6 mAh g −1 when cycled at a 10 μA cm −2 current density. Impedance spectroscopy was used to investigate the interface resistance of the battery at different temperatures. The results indicated that both the cathode and anode interface resistance were dramatically reduced at 50 °C. The decrease in interface resistances at elevated temperature is proposed as the main reason for the observed battery performance enhancement

  17. Structures and solid solution mechanisms of pyrochlore phases in the systems Bi{sub 2}O{sub 3}-ZnO-(Nb, Ta){sub 2}O{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Tan, K.B., E-mail: tankb@science.upm.edu.m [Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Khaw, C.C. [Department of Engineering, Universiti Tunku Abdul Rahman, 53300 Setapak, Kuala Lumpur (Malaysia); Lee, C.K. [Academic Science Malaysia, 902-4 Jalan Tun Ismail, 50480 Kuala Lumpur (Malaysia); Zainal, Z. [Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Miles, G.C. [Department of Engineering Materials, The University of Sheffield, Mappin Street, Sheffield, S1 3JD (United Kingdom)

    2010-10-22

    Research highlights: {yields} Combined XRD and ND Rietveld structural refinement of pyrochlores. {yields} Structures and solid solution mechanisms of Bi-pyrochlores. {yields} Bi and Zn displaced off-centre to different 96g A-site positions. {yields} Summary of composition-structure-property of Bi-pyrochlores. - Abstract: The crystal structures of two pyrochlore phases have been determined by Rietveld refinement of combined X-ray and neutron powder diffraction data. These are stoichiometric, Bi{sub 1.5} ZnTa{sub 1.5}O{sub 7} and non-stoichiometric Bi{sub 1.56}Zn{sub 0.92}Nb{sub 1.44}O{sub 6.86}. In both structures, Zn is distributed over A- and B-sites; Bi and Zn are displaced off-centre, to different 96g A-site positions; of the three sets of oxygen positions, O(1) are full, O(2) contain vacancies and O(3) contain a small number of oxygen, again in both cases. Comparisons between these structures, those of related Sb analogues and literature reports are made.

  18. Optical and magnetic properties of solid solutions of In{sub 2-x}Mn{sub x}O{sub 3} (0.05, 0.10 and 0.15) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Khatoon, Sarvari [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Coolahan, Kelsey; Lofland, Samuel E. [Department of Physics and Astronomy, Rowan University, 201 Mullica Hill Road, Glassboro, NJ 08028 (United States); Ahmad, Tokeer, E-mail: tahmad3@jmi.ac.in [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India)

    2012-12-25

    Highlights: Black-Right-Pointing-Pointer Monophasic Mn-doped In{sub 2}O{sub 3} nanoparticles by solvothermal method for first time. Black-Right-Pointing-Pointer Plausible reaction mechanism and kinetics study using thermogravimetric analysis. Black-Right-Pointing-Pointer Highest surface area obtained so far as compared to the literature report. Black-Right-Pointing-Pointer Particle size decreases with increasing Mn concentration. Black-Right-Pointing-Pointer High degree of optical transparency ({approx}95%) is observed. - Abstract: Mn-doped indium oxide (In{sub 2-x}Mn{sub x}O{sub 3}) nanoparticles (7-12 nm) with x = 0.05, 0.10 and 0.15 have been synthesized by solvothermal method using oxalate precursor route for the first time. Powder X-ray diffraction studies showed the formation of monophasic cubic structure of In{sub 2-x}Mn{sub x}O{sub 3} solid solutions. X-ray diffraction and UV-visible reflectance studies revealed that Mn{sup 2+} ions are doped into the In{sub 2}O{sub 3} lattice. Reflectance measurements showed red shift in an energy band gap which decreases with an increase in the Mn concentration. Maximum surface area of 768 m{sup 2} g{sup -1} is obtained for In{sub 1.85}Mn{sub 0.15}O{sub 3} nanoparticles. Magnetization measurement revealed that all the samples are paramagnetic in nature with very weak antiferromagnetic interactions.

  19. The solubility and site preference of Fe{sup 3+} in Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnets

    Energy Technology Data Exchange (ETDEWEB)

    Rettenwander, D., E-mail: daniel.rettenwander@sbg.ac.at [Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg (Austria); Geiger, C.A. [Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg (Austria); Tribus, M.; Tropper, P. [Institute of Mineralogy and Petrography, Faculty of Geo- and Atmospheric Sciences, University of Innsbruck, Innrain 52, 6020 Innsbruck (Austria); Wagner, R.; Tippelt, G.; Lottermoser, W.; Amthauer, G. [Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg (Austria)

    2015-10-15

    A series of Fe{sup 3+}-bearing Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and {sup 57}Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe{sup 3+} pfu could be incorporated in Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnet solid solutions. At Fe{sup 3+} concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe{sup 3+} contents lower than 0.52 Fe{sup 3+} pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a{sub 0}, for all solid-solution garnets is similar with a value of a{sub 0}≈12.98 Å regardless of the amount of Fe{sup 3+}. {sup 57}Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO{sub 3} in syntheses with Fe{sup 3+} contents greater than 0.16 Fe{sup 3+} pfu. The composition of different phase pure Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li{sub 6.89}Fe{sub 0.03}La{sub 3.05}Zr{sub 2.01}O{sub 12}, Li{sub 6.66}Fe{sub 0.06}La{sub 3.06}Zr{sub 2.01}O{sub 12}, Li{sub 6.54}Fe{sub 0.12}La{sub 3.01}Zr{sub 1.98}O{sub 12}, and Li{sub 6.19}Fe{sub 0.19}La{sub 3.02}Zr{sub 2.04}O{sub 12}. The {sup 57}Fe Mössbauer spectrum of cubic Li{sub 6.54}Fe{sub 0.12}La{sub 3.01}Zr{sub 1.98}O{sub 12} garnet indicates that most Fe{sup 3+} occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe{sup 3+} in smaller

  20. Hydrothermal synthesis, thermal, structural, spectroscopic and magnetic studies of the Mn5-x Co x (HPO4)2(PO4)2(H2O)4 (x=1.25, 2, 2.5 and 3) finite solid solution

    International Nuclear Information System (INIS)

    Larrea, Edurne S.; Mesa, Jose L.; Pizarro, Jose L.; Arriortua, Maria I.; Rojo, Teofilo

    2007-01-01

    The Mn 5- x Co x (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 (x=1.25, 2, 2.5, 3) finite solid solution has been synthesized by mild hydrothermal conditions under autogeneous pressure. The phases crystallize in the C2/c space group with Z=4, belonging to the monoclinic system. The unit-cell parameters obtained from single crystal X-ray diffraction are: a=17.525(1), b=9.0535(6), c=9.4517(7) A, β=96.633(5) o being R1=0.0436, wR2=0.0454 for Mn75Co25; a=17.444(2), b=9.0093(9), c=9.400(1) A, β=96.76(1) o being R1=0.0381, wR2=0.0490 for Mn60Co40; a=17.433(2), b=8.9989(9), c=9.405(1) A, β=96.662(9) o being R1=0.0438, wR2=0.0515 for Mn50Co50 and a=17.4257(9), b=8.9869(5), c=9.3935(5) A, β=96.685(4) o being R1=0.0296, wR2=0.0460 for Mn40Co60. The structure consists of a three dimensional network formed by octahedral pentameric entities (Mn,Co) 5 O 16 (H 2 O) 6 sharing vertices with the (PO 4 ) 3- and (HPO 4 ) 2- tetrahedra. The limit of thermal stability of these compounds is, approximately, 165 deg. C, near to this mean temperature the phases loose their water content in two successive steps. IR spectra show the characteristic bands of the water molecules and the phosphate and hydrogen-phosphate oxoanions. The diffuse reflectance spectra are consistent with the presence of MO 6 octahedra environments in slightly distorted octahedral geometry, except for the M(3)O 6 octahedron which presents a remarkable distortion and so a higher Dq parameter. The mean value for the Dq and B-Racah parameter for the M(1),(2)O 6 octahedra is 685 and 850 cm -1 , respectively. These parameters for the most distorted M(3)O 6 polyhedron are 825 and 880 cm -1 , respectively. The four phases exhibit antiferromagnetic couplings as the major magnetic interactions. However, a small spin canting phenomenon is observed at low temperatures for the two phases with major content in the anisotropic-Co(II) cation. - Graphical abstract: Crystal structure of the finite solid solution Mn 5-x Co x (HPO 4 ) 2 (PO 4 ) 2 (H

  1. Low temperature phase transition of the stoichiometric Ln2NiO4 oxides

    International Nuclear Information System (INIS)

    Fernandez, F.; Saez-Puche, R.; Botto, I.L.; Baran, E.J.

    1991-01-01

    In this paper we will present a comparative study of the structural phase transition in Ln 2 NiO 4 oxides, by means of neutron diffraction and infrared(IR) spectroscopy. In the Ln 2 NiO 4 oxides (Ln=La, Pr and Nd), there is a low temperature structural phase transition from the orthorhombic symmetry to a tetragonal phase, of first order character. The IR spectra show, at low temperature, a splitting of the bands related with the stretching Ni-O, strongly correlated with the phase transformation. From the neutron data, the phase transition can be visualized as a sudden tilt of the nickel octahedra

  2. Discovery of novel solid solution Ca3Si3-x O3+x N4-2x : Eu2+ phosphors: structural evolution and photoluminescence tuning.

    Science.gov (United States)

    Wang, Baochen; Liu, Yan-Gai; Huang, Zhaohui; Fang, Minghao; Wu, Xiaowen

    2017-12-22

    Discovery of novel phosphors is one of the main issues for improving the color rendering index (CRI) and correlated color temperature (CCT) of white light-emitting diodes (w-LEDs). This study mainly presents a systematic research on the synthesis, crystal structure variation and photoluminescence tuning of novel (oxy)nitride solid solution Ca 3 Si 3-x O 3+x N 4-2x : Eu 2+ phosphors. XRD refinements show that lattice distortion occurs when x value diverges the optimum one (x = 1). The lattice distortion causes a widening of emission spectrum and an increase of Stokes shift (ΔSS), which leads to a bigger thermal quenching. With decrease of x value, the emission spectrum shows an obvious red-shift from 505.2 to 540.8 nm, which is attributed to the crystal field splitting. The enhanced crystal field splitting also broadens the excitation spectrum, making it possible to serve as the phosphor for near ultraviolet (n-UV) LEDs. A 3-phosphor-conversion w-LED lamp was fabricated with the as-prepared phosphor, which exhibits high CRI (Ra = 85.29) and suitable CCT (4903.35 K). All these results indicate that the Ca 3 Si 3-x O 3+x N 4-2x : Eu 2+ phosphor can serve as the green phosphor for n-UV w-LEDs, with a tunable spectrum by controlling the crystal structure and morphology.

  3. Ionic conductivity of LISICON solid solutions, Li 2+2 xZn 1- xGeO 4

    Science.gov (United States)

    Bruce, P. G.; West, A. R.

    1982-10-01

    The conductivity of LISICON γII-type solid solutions of general formula Li 2+2 xZn 1- xGeO 4 (-0.36 class of Li + ion conductors, was measured over the temperature range ˜25 to 300°C. Conductivities appear to be very composition dependent near the stoichiometric composition x = 0, but less so in the range 0.15 ≲ x ≲ 0.87. It is shown that interstitial Li + ions rather than cation vacancies give rise to high conductivities. The solid electrolyte properties and possible applications of the solid solutions are evaluated. The LISICON composition, x = 0.75, decomposes readily above ˜300°C by precipitation of Li 4GeO 4, thereby limiting its possible usefulness, but compositions in the range x = 0.45 to 0.55 appear to be stable at all temperatures. However, irreversible decreases in conductivity (aging effects) occur on annealing, even at room temperature. The conductivity data of quenched samples give linear Arrhenius plots, but with anomalously high prefactors, over the range ˜25 to 130°C; at higher temperatures reversible changes of slope to lower activation energies occur. A variety of minor polymorphic transitions occur on annealing γII solid solutions below ˜300°C and their relationship to the conductivity was also determined.

  4. 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

  5. Fe2O3-Cr2O3 system revised

    Czech Academy of Sciences Publication Activity Database

    Grygar, Tomáš; Bezdička, Petr; Dědeček, Jiří; Petrovský, Eduard; Schneeweiss, Oldřich

    2003-01-01

    Roč. 47, č. 1 (2003), s. 32-39 ISSN 0862-5468 R&D Projects: GA ČR GA205/00/1349; GA MŠk LN00A028; GA ČR GV202/98/K002; GA MŠk ME 209 Institutional research plan: CEZ:AV0Z3012916; CEZ:AV0Z4032918 Keywords : solid solutions * Vegard law * iron oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 0.449, year: 2003

  6. Solution Synthesis, Structure, and CO2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe3 )2 ]3 }.

    Science.gov (United States)

    Woen, David H; Chen, Guo P; Ziller, Joseph W; Boyle, Timothy J; Furche, Filipp; Evans, William J

    2017-02-13

    The first crystallographically characterizable complex of Sc 2+ , [Sc(NR 2 ) 3 ] - (R=SiMe 3 ), has been obtained by LnA 3 /M reactions (Ln=rare earth metal; A=anionic ligand; M=alkali metal) involving reduction of Sc(NR 2 ) 3 with K in the presence of 2.2.2-cryptand (crypt) and 18-crown-6 (18-c-6) and with Cs in the presence of crypt. Dark maroon [K(crypt)] + , [K(18-c-6)] + , and [Cs(crypt)] + salts of the [Sc(NR 2 ) 3 ] - anion are formed, respectively. The formation of this oxidation state of Sc is also indicated by the eight-line EPR spectra arising from the I=7/2 45 Sc nucleus. The Sc(NR 2 ) 3 reduction differs from Ln(NR 2 ) 3 reactions (Ln=Y and lanthanides) in that it occurs under N 2 without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR 2 ) 3 ] reacts with CO 2 to produce an oxalate complex, {K 2 (18-c-6) 3 }{[(R 2 N) 3 Sc] 2 (μ-C 2 O 4 -κ 1 O:κ 1 O'')}, and a CO 2 - radical anion complex, [(R 2 N) 3 Sc(μ-OCO-κ 1 O:κ 1 O')K(18-c-6)] n . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Luminescence and scintillation response of YGd.sub.2./sub.Al.sub.2./sub.Ga.sub.3./sub.O.sub.12./sub.:Ce and LuGd.sub.2./sub.Al.sub.2./sub.Ga.sub.3./sub.O.sub.12./sub.:Ce scintillators

    Czech Academy of Sciences Publication Activity Database

    Chewpraditkul, Wa.; Pattanaboonmee, N.; Chewpraditkul, W.; Kamada, K.; Yoshikawa, A.; Nikl, Martin

    2016-01-01

    Roč. 90, Jul (2016), s. 153-156 ISSN 1350-4487. [International Conference on Luminescent Detectors and Transformers of Ionizing Radiation (LUMDETR). Tartu (Estonsko), 20.09.2015-25.09.2015] R&D Projects: GA ČR GAP204/12/0805 Institutional support: RVO:68378271 Keywords : YGd 2 Al 2 Ga 3 O 12 :Ce * LuGd 2 Al 2 Ga 3 O 12 :Ce * light yield * luminescence * scintillation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.442, year: 2016

  8. Re-dispersion and film formation of GdVO4 :  Ln3+ (Ln3+ = Dy3+, Eu3+, Sm3+, Tm3+) nanoparticles: particle size and luminescence studies.

    Science.gov (United States)

    Shanta Singh, N; Ningthoujam, R S; Phaomei, Ganngam; Singh, S Dorendrajit; Vinu, A; Vatsa, R K

    2012-04-21

    GdVO(4) : Ln(3+) (Ln(3+) = Dy(3+), Eu(3+), Sm(3+), Tm(3+)) nanoparticles are prepared by a simple chemical route at 140 °C. The crystallite size can be tuned by varying the pH of the reaction medium. Interestingly, the crystallite size is found to increase significantly when pH increases from 6 to 12. This is related to slower nucleation of the GdVO(4) formation with increase of VO(4)(3-) present in solution. The luminescence study shows an efficient energy transfer from vanadate absorption of GdVO(4) to Ln(3+) and thereby enhanced emissions are obtained. A possible reaction mechanism at different pH values is suggested in this study. As-prepared samples are well dispersed in ethanol, methanol and water, and can be incorporated into polymer films. Luminescence and its decay lifetime studies confirm the decrease in non-radiative transition probability with the increase of heat treatment temperature. Re-dispersed particles will be useful in potential applications of life science and the film will be useful in display devices.

  9. Síntesis hidrotermal de monocristales LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho y Er

    Directory of Open Access Journals (Sweden)

    Señarís Rodríguez, M. A.

    2008-08-01

    Full Text Available Ten single crystals of the series LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er were synthesized by hydrothermal synthesis in a single step and without subsequent thermal treatments from aqueous solutions of metals salts at 240 ºC. The obtained single crystals have a size of various micrometers and their morphology changes throughout the serie: they are polygonal in the case of the compounds with Ln= Pr, Nd, Sm, Eu and Gd and needle-like in the case of the compounds with Ln= Y, Tb, Dy, Ho and Er. After the analysis of the obtained products employing different conditions of synthesis we attributed the different morphology to a greater growth rate along the c axis when the smaller ions (Y, Tb, Dy, Ho y Er are involved, due to their better adaptation to the compound’s crystal structure.Se han conseguido preparar monocristales de 10 óxidos mixtos de la serie LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho y Er mediante síntesis hidrotermal optimizada, en un único paso y sin tratamientos térmicos posteriores partiendo de las correspondientes sales metálicas en disolución acuosa a 240 ºC. Los monocristales obtenidos son relativamente grandes, de varias micras y su morfología varía a lo largo de la serie: es poligonal en el caso de los compuestos de los lantánidos del inicio de la serie (Ln= Pr, Nd, Sm, Eu y Gd y acicular en el caso de los compuestos de Y y de los lantánidos del final de la serie (Ln= Tb, Dy, Ho y Er. Tras el análisis de los productos obtenidos empleando distintas condiciones de síntesis atribuimos la diferente morfología a una mayor velocidad de crecimiento cristalino a lo largo del eje c cuando intervienen los iones más pequeños (Y, Tb, Dy, Ho y Er debido a la mejor adaptación de éstos últimos a la estructura cristalina del compuesto.

  10. High-temperature superconductivity in solid solutions based on mixed yttrium and barium cuprate

    International Nuclear Information System (INIS)

    Bazuev, G.V.; Kirsanov, N.A.; Makarova, O.V.; Zubkov, V.G.; Shveikin, G.P.

    1990-01-01

    The discovery of high-temperature superconductivity (T c = 30-40 K) in mixed lanthanum and alkaline earth cuprates La 2-x M x CuO 4 , where M = Ba and Ca (1-3) stimulated an extensive search for new superconducting phases based on mixed oxides of these elements. The superconducting transition temperature T c in LnBa 2 Cu 3 O 7-z phases is practically independent of the REE and lies between 90-96 K. The crystal structure of superconducting YBa 2 Cu 3 O 7-z is similar to perovskite, has orthorhombic symmetry (4,5), and is related to the lanthanum barium cuprite tetragonal defect structure La 3 Ba 3 Cu 6 O 14.1 (8). A study of possible solid solutions (SS) based on YBa 2 Cu 3 O 7-z through iso- or heterovalent substitution for Y 3+ and Ba 2+ and of their electrical properties seems warranted. In the present work, the authors report the synthesis, x-ray diffraction study, and specific electric resistivity of SS Y 1-x M x (Ba 1-y M y ') 2 Cu 3 O 7-z , where M = La, Lu, Sc, In, K, Zr, and Ce and M' = Ca, Sr, Mg, K, and La

  11. Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

    International Nuclear Information System (INIS)

    Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

    2012-01-01

    A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

  12. Separating NaCl and AlCl3·6H2O Crystals from Acidic Solution Assisted by the Non-Equilibrium Phase Diagram of AlCl3-NaCl-H2O(-HCl Salt-Water System at 353.15 K

    Directory of Open Access Journals (Sweden)

    Huaigang Cheng

    2017-08-01

    Full Text Available Extracting AlCl3·6H2O from acid leaching solution through crystallization is one of the key processes to extracting aluminum from fly ash, coal gangue and other industrial solid wastes. However, the obtained products usually have low purity and a key problem is the lack of accurate data for phase equilibrium. This paper presented the non-equilibrium phase diagrams of AlCl3-NaCl-H2O (HCl salt-water systems under continuous heating and evaporation conditions, which were the main components of the acid leaching solution obtained through a sodium-assisted activation hydrochloric acid leaching process. The ternary system was of a simple eutonic type under different acidities. There were three crystalline regions; the crystalline regions of AlCl3·6H2O, NaCl and the mixture AlCl3·6H2O/NaCl, respectively. The phase diagram was used to optimize the crystallization process of AlCl3·6H2O and NaCl. A process was designed to evaporate and remove NaCl at the first stage of the evaporation process, and then continue to evaporate and crystallize AlCl3·6H2O after solid-liquid separation. The purities of the final salt products were 99.12% for NaCl and up to 97.35% for AlCl3·6H2O, respectively.

  13. Eu3+/Tb3+-doped La2O2CO3/La2O3 nano/microcrystals with multiform morphologies: facile synthesis, growth mechanism, and luminescence properties.

    Science.gov (United States)

    Li, Guogang; Peng, Chong; Zhang, Cuimiao; Xu, Zhenhe; Shang, Mengmeng; Yang, Dongmei; Kang, Xiaojiao; Wang, Wenxin; Li, Chunxia; Cheng, Ziyong; Lin, Jun

    2010-11-15

    LaCO(3)OH nano/microcrystals with a variety of morphologies/sizes including nanoflakes, microflowers, nano/microrhombuses, two-double microhexagrams sandwichlike microspindles, and peach-nucleus-shaped microcrystals have been synthesized via a facile homogeneous precipitation route under mild conditions. A series of controlled experiments indicate that the pH values in the initial reaction systems, carbon sources, and simple ions (NH(4)(+) and Na(+)) were responsible for the shape determination of the LaCO(3)OH products. A possible formation mechanism for these products with diverse architectures has been presented. After annealing at suitable temperatures, LaCO(3)OH was easily converted to La(2)O(2)CO(3) and La(2)O(3) with the initial morphologies. A systematic study on the photoluminescence and cathodoluminescence properties of Eu(3+)- or Tb(3+)-doped La(2)O(2)CO(3)/La(2)O(3) samples has been performed in detail. The excitation and site-selective emission spectra were recorded to investigate the microstructure, site symmetry, and difference in the (5)D(0) → (7)F(2) transition of Eu(3+) ions in La(2)O(2)CO(3) and La(2)O(3) host lattices. In addition, the dependence of the luminescent intensity on the morphology for the as-prepared La(2)O(2)CO(3)/La(2)O(3):Ln(3+) (Ln = Eu, Tb) samples has been investigated. The ability of generating diverse morphologies and multiemitting colors for different rare-earth activator ion (Ln = Eu, Tb) doped La(2)O(2)CO(3)/La(2)O(3) nano/microstructures provides a great opportunity for the systematic evaluation of morphology-dependent luminescence properties, as well as the full exploration of their application in many types of color display fields.

  14. 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

  15. 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 ErMnO

  16. Propane-1,2-diammonium bis(pyridine-2,6-dicarboxylato-κ3O,N,O′nickelate(II tetrahydrate

    Directory of Open Access Journals (Sweden)

    Mohammad Ghadermazi

    2008-07-01

    Full Text Available The reaction of nickel(II nitrate hexahydrate, propane-1,2-diamine and pyridine-2,6-dicarboxylic acid in a 1:2:2 molar ratio in aqueous solution resulted in the formation of the title compound, (C3H12N2[Ni(C7H3NO42]·4H2O or (p-1,2-daH2[Ni(pydc2]·4H2O (where p-1,2-da is propane-1,2-diamine and pydcH2 is pyridine-2,6-dicarboxylic acid. The geometry of the resulting NiN2O4 coordination can be described as distorted octahedral. Considerable C=O...π stacking interactions are observed between the carboxylate C=O groups and the pyridine rings of the (pydc2− fragments, with O...π distances of 3.1563 (12 and 3.2523 (12 Å and C=O...π angles of 95.14 (8 and 94.64 (8°. In the crystal structure, a wide range of non-covalent interactions, consisting of hydrogen bonding [O—H...O, N—H...O and C—H...O, with D...A distances ranging from 2.712 (2 to 3.484 (2 Å], ion pairing, π–π [centroid-to-centroid distance = 3.4825 (8 Å] and C=O...π stacking, connect the various components to form a supramolecular structure.

  17. Light emissions from LiNbO sub 3 /SiO sub 2 /Si structures

    CERN Document Server

    Wu, X L; Tang, N; Deng, S S; Bao, X M

    2003-01-01

    LiNbO sub 3 (LN) films with a high degree of (006) texture were deposited on Si-based dense SiO sub 2 layers by pulsed laser deposition. After annealing, the LN/SiO sub 2 /Si structures were revealed to have ultraviolet-, green-, and red-emitting properties related to self-trapped excitons and E' defect pairs in the SiO sub 2 surface, which are induced by the photorefractive effect of the LN films. The emission wavelength can be tuned by introducing different dopants into the LN films. Waveguiding properties of the structures were demonstrated. The results obtained indicate that the LN/SiO sub 2 /Si structures could be expected to have important applications in modern optoelectronic integration. (letter to the editor)

  18. Improving the SMM and luminescence properties of lanthanide complexes with LnO9 cores in the presence of ZnII: an emissive Zn2Dy single ion magnet.

    Science.gov (United States)

    Fondo, Matilde; Corredoira-Vázquez, Julio; Herrera-Lanzós, Antía; García-Deibe, Ana M; Sanmartín-Matalobos, Jesús; Herrera, Juan Manuel; Colacio, Enrique; Nuñez, Cristina

    2017-12-12

    Mononuclear complexes of stoichiometry [Ln(H 3 L)(H 2 O)(NO 3 )](NO 3 ) 2 (Ln = Tb, 1; Dy, 2, Er, 3), which crystallise with different solvates, and the heterotrinuclear compound [Zn 2 Dy(L)(NO 3 ) 3 (OH)] (4) can be obtained with the same H 3 L compartmental ligand. The single X-ray crystal structure of the mononuclear complexes shows a LnO 9 core with a muffin-like disposition while the geometry of the DyO 9 core in 4 seems to be closer to spherical capped square antiprism. The analysis of the magnetic properties of all the complexes demonstrates that the mononuclear lanthanide compounds do not show slow relaxation of the magnetization, even when the samples are diluted with a diamagnetic matrix and subjected to a dc applied field of 1000 Oe. Nevertheless, the heterotrinuclear dysprosium complex 4·3H 2 O is a field-induced single ion magnet, with an estimated U eff barrier of 59 K. The luminescence characterisation of all the metal complexes in methanol solution at 298 K also shows a notable increase in the fluorescence emission of the heterotrinuclear complex with respect to the mononuclear ones, in such a way that 4 can be defined as a fluorescent single ion magnet.

  19. Characterization of Bi2/3Cu3Ti4O12 ceramics synthesized by semi-wet route

    Directory of Open Access Journals (Sweden)

    Pooja Gautam

    2016-12-01

    Full Text Available Bi2/3Cu3Ti4O12 (BCTO ceramic was synthesized by the semi-wet route using metal nitrate solutions and solid TiO2 powder in a stoichiometric ratio. Fourier transform infrared (FTIR study of BCTO precursor powder and calcined ceramic showed the presence of alcoholic functional groups and the stretching band of Ti-O and Cu-O respectively. X-ray diffraction (XRD, scanning electron microscope (SEM and energy dispersive x-ray spectroscopy (EDX were employed to characterize the structure, surface morphology and purity of the sintered BCTO ceramic respectively. X-ray diffraction study confirmed the single phase formation of BCTO ceramic at 1073 K. The average dimension of grains calculated by SEM and AFM was found to be in the range of 0.73±0.2 µm with clear grain boundaries. Magnetic property was investigated over a wide temperature range 2–300 K at a magnetic field of 7 tesla. The Curie temperature was calculated by zero field cooled (MZFC and field cooled (MFC magnetization at 100 Oe applied field which was found to be 125 K. The sintered BCTO ceramic shows high dielectric constant (ε'=2.9×104 at 323 K and 100 Hz.

  20. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H/sub 2/O and D/sub 2/O solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1983-10-01

    The exchange reaction between central ions in the NdD/sup -/Ln'/sup 3 +/ systems, where Ln'/sup 3 +/ is a substituting cation (Eu/sup 3 +/ and Ho/sup 3 +/, D/sup 4/=cyclohexanediaminetetraacetate) is studied and the electrophilic substitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solved in heavy water containing 99.9% D/sub 2/O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized.

  1. Análise de linfonodos no câncer colorretal: o impacto do uso de uma solução clareadora de gorduras Lymph node analysis in colorectal cancer: the impact of the use of fat clearance solution

    Directory of Open Access Journals (Sweden)

    Rair Geraldo Richard Xavier

    2008-12-01

    Full Text Available INTRODUÇÃO: O acometimento de linfonodos (LN é o principal fator prognóstico em carcinomas colorretais (CCR e recomendam-se técnicas especiais para melhorar a análise dos LN. O objetivo deste trabalho foi avaliar o impacto do uso de uma solução clareadora de gorduras na dissecção de LN em CCR. Material e método: Analisaram-se prospectivamente 74 adenocarcinomas (35 homens, média de 62,9 anos, a maioria pT3. Após o exame de rotina e dissecção de LN pelo método convencional (MC, a gordura foi imersa por 36 h (três trocas em uma solução (SC composta por álcool (65%, éter (20%, ácido acético (5% e formol (10% e realizou-se nova dissecção. Mediu-se o diâmetro dos LN e determinou-se o número de LN positivos (LN+ e negativos BACKGROUND: Lymph node (LN involvement is the most important prognostic factor in colorectal carcinomas and special methods are recommended to improve LN analysis. The objective of this study was to evaluate the impact of the use of a fat bleaching solution in LN dissection in colorectal carcinomas. METHOD: 74 adenocarcinomas (35 men - average age: 62.9 were prospectively analysed, most of them were pT3. After routine exam and LN dissection through conventional method, the fat was soaked in a solution containing alcohol (65%, ether (20%, acetic acid (5% and formalin (10% for 36 hours (three changes. A new dissection was performed subsequently. LN diameters were measured and the number of positive (LN+ and negative LN with < 4 mm was determined. Some LN+ obtained after the bleaching procedure were immunolabelled by AE1/AE3. RESULTS:3,167 LN (42.8/case were dissected: 1,814 (24.5/case by CM and 1,355 (18.3/case after the bleaching procedure. 196 LN+ were detected: 170 (86.7% detected by CM and 26 (13.2% after the bleaching procedure. 1,068 (59% of the LN conventionally dissected were < 4mm (range 0.4-23 mm and 1,261 (93% of the LN dissected after the bleaching procedure were < 4 mm (range 0.2-11 mm. 39

  2. Catalytic Oligomerization of Terminal Alkynes by Lanthanide Carbyls (η5-C5Me5)2LnCH(SiMe3)2 (Ln = Y, La, Ce)

    NARCIS (Netherlands)

    Heeres, H.J.; Teuben, J.H.

    1991-01-01

    Lanthanide and group 3 carbyls Cp*2LnCH(SiMe3)2 (1, Ln = Y; 2, Ln = La; 3, Ln = Ce) are active catalyst precursors for the oligomerization of terminal alkynes HC≡CR (R = alkyl, aryl, SiMe3). The regioselectivity and the extent of oligomerization depend strongly on the lanthanide applied as well as

  3. Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand.

    Science.gov (United States)

    Figuerola, Albert; Ribas, Joan; Llunell, Miquel; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

    2005-10-03

    The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.

  4. An anti CuO{sub 2}-type metal hydride square net structure in Ln{sub 2}M{sub 2}As{sub 2}H{sub x} (Ln = La or Sm, M = Ti, V, Cr, or Mn)

    Energy Technology Data Exchange (ETDEWEB)

    Mizoguchi, Hiroshi; Park, SangWon; Hosono, Hideo [Tokyo Institute of Technology, Yokohama (Japan). Materials Research Center for Element Strategy; Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya [High-Energy Accelerator Research Organization (KEK), Tsukuba (Japan). Inst. of Materials Structure Science

    2015-03-02

    Using a high pressure technique and the strong donating nature of H{sup -}, a new series of tetragonal La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type layered mixed-anion arsenides, Ln{sub 2}M{sub 2}As{sub 2}H{sub x}, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x∼3). In these compounds, an unusual M{sub 2}H square net, which has anti CuO{sub 2} square net structures accompanying two As{sup 3-} ions, is sandwiched by (LaH){sub 2} fluorite layers. Notably, strong metal-metal bonding with a distance of 2.80 Aa was confirmed in La{sub 2}Ti{sub 2}As{sub 2}H{sub 2.3}, which has metallic properties. In fact, these compounds are situated near the boundary between salt-like ionic hydrides and transition-metal hydrides with metallic characters.

  5. Synthesis and characterization of Sr2Ir1−xMxO4 (M=Ti, Fe, Co) solid solutions

    International Nuclear Information System (INIS)

    Gatimu, Alvin J.; Berthelot, Romain; Muir, Sean; Sleight, Arthur W.; Subramanian, M.A.

    2012-01-01

    The effects of Ti, Fe and Co substitutions for Ir on the structure and on the physical properties of Sr 2 IrO 4 are investigated. A complete solid solution Sr 2 Ir 1−x Ti x O 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 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 2 IrO 4 . - Graphical abstract: Solid solutions of Sr 2 Ir 1−x M x O 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 6 octahedra tilting are found to be correlated. Highlights: ► Solid Solutions of Sr 2 Ir 1−x M x O 4 (M=Ti, Fe, Co) are synthesized. ► The Sr 2 Ir 1−x Ti x O 4 solid solution is complete while those of Fe and Co are relatively limited. ► The change in a cell parameter with substitution is much less than that of the c parameter. ► Decreased tilting and the smaller size of the M cation contrastingly affect the a parameter. ► Doping results in a suppression of the weak ferromagnetic ordering in Sr 2 IrO 4 .

  6. Solid-state synthesis of Li{sub 4}Ti{sub 5}O{sub 12} whiskers from TiO{sub 2}-B

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Wenjun [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Zhuang, Wei [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); College of Biotechnology and Pharmaceutical Engineering, National Engineering Technique Research Center for Biotechnology, Nanjing Tech University, No. 30, Puzhu South Road, Nanjing 211816 (China); Ji, Xiaoyan [Division of Energy Science/Energy Engineering, Luleå University of Technology, Luleå 97187 Sweden (Sweden); Chen, Jingjing; Lu, Xiaohua [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Wang, Changsong, E-mail: wcs@njtech.edu.cn [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China)

    2016-03-15

    Highlights: • The Li{sub 4}Ti{sub 5}O{sub 12} whiskers were synthesized from TiO{sub 2}-B whiskers via a solid state reaction. • The TiO{sub 2}-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li{sub 4}Ti{sub 5}O{sub 12} whiskers. - Abstract: In this work, Li{sub 4}Ti{sub 5}O{sub 12} (LTO) was synthesized from the precursors of TiO{sub 2}-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO{sub 2}-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO{sub 2}-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

  7. Role of alkali carbonate and salt in topochemical synthesis of K1/2Na1/2NbO3 and NaNbO3 templates

    Science.gov (United States)

    Lee, Jae-Seok; Jeon, Jae-Ho; Choi, Si-Young

    2013-11-01

    Since the properties of lead-free piezoelectric materials have thus far failed to meet those of lead-based materials, either chemical doping or morphological texturing should be employed to improve the piezoelectric properties of lead-free piezoelectric ceramics. The goal of this study was to synthesize plate-like K1/2Na1/2NbO3 and NaNbO3 particles, which are the most favorable templates for morphological texturing of K1/2Na1/2NbO3 ceramics. To achieve this goal, Bi2.5Na3.5Nb5O18 precursors in a plate-like shape were first synthesized and subsequently converted into K1/2Na1/2NbO3 or NaNbO3 particles that retain the morphology of Bi2.5Na3.5Nb5O18. In this study, we found that sodium or potassium carbonate does not play a major role in converting the Bi2.5Na3.5Nb5O18 precursor to K1/2Na1/2NbO3 or NaNbO3, on the contrary to previous reports; however, the salt contributes to the conversion reaction. All synthesis processes have been performed via a molten salt method, and scanning electron microscopy, scanning probe microscopy, and inductively coupled plasma mass spectroscopy were used to characterize the synthesized K1/2Na1/2NbO3 or NaNbO3 templates.

  8. Relaxor behavior in lead-free Ba(Ti1−xScx/2Nbx/2O3 ceramics

    Directory of Open Access Journals (Sweden)

    N. Bensemma

    2014-06-01

    Full Text Available Solid solutions of (1−xBaTiO3-xBaSc1/2Nb1/2O3 (BT-BSN with x = 0.025, 0.05, 0.075, 0.1 and 0.125 were prepared by a high temperature solid-state reaction technique. The effects of the Ba(Sc1/2Nb1/2O3 addition on the phase composition, dielectric properties, as well as polarization-electric field (P-E loops of the BT-BSN solid solution were investigated. The room-temperature X-ray diffraction analyses of all the ceramics revealed a perovskite phase after sintering at 1350 °C with a composition-dependent symmetry. Temperature and frequency dependence of the dielectric permittivity and losses have been explored: ceramics of compositions x ≤ 0.075 showed normal ferroelectric behavior, while ceramics with x ≥ 0.1 were of relaxor type. The degree of diffuseness and the relaxor effect increase while the transition temperature (TC or Tm decreases when both scandium and niobium are introduced in the BaTiO3 lattice. Ceramics of composition x = 0.125 exhibited interesting relaxor characteristics at 10 kHz: ΔTm = 20 K, ɛr = 12,000, and Tm = 140 K. In addition, modeled using Vogel–Fülcher relation, this same composition showed the fitting parameters: Ea = 0.0503 eV, f0 = 1.129 × 1014 Hz and TVF = 166.85 K.

  9. Dense garnet-like Li5La3Nb2O12 solid electrolyte prepared by self-consolidation method

    Science.gov (United States)

    Zhao, Pengcheng; Xiang, Yu; Xu, Yan; Wen, Yuehua; Zhang, Wenfeng; Zhu, Xiayu; Li, Meng; Zhang, Sontong; Ming, Hai; Jin, Zhaoqing; Cao, Gaoping

    2018-06-01

    Li5La3Nb2O12 (LLNO) is a typical garnet-like solid electrolyte with solitary cubic structure. However, its ionic conductivity is relatively low due to the low relative density when prepared by cold isostatic pressing method, which usually involves high-pressure machines, poor productivity, tedious pressing operations, and low density. In this paper, self-consolidation method is developed to sinter dense LLNO electrolyte. Although not any pressing operations are employed in the entire process, the relative density of LLNO is promoted up to 95%, which is much higher than the reported values of 45-80%. SEM images reveal that the sample is built by huge particles in size of 80 μm indicating that there are few boundaries in the sample. Moreover, a rich content of Li-Al-O compounds is detected out in the boundary areas, which may act as sintering aids for the sample to consolidate automatically. According to the highest density, the bulk ionic conductivity of LLNO sample reaches up to 1.61 × 10-4 S cm-1 at 30 °C, which is in the same order of magnitude as the value of cubic Li7La3Zr2O12 electrolyte. This work verifies the self-consolidation mechanism for the sintering of ceramic electrolytes and could significantly facilitate the development of LLNO membrane technology.

  10. Local structure of Th1-xMO2 solid solutions (M = U, Pu)

    International Nuclear Information System (INIS)

    Hubert, S.; Heisbourg, G.; Moisy, Ph.; Dacheux, N.; Purans, J.E.

    2004-01-01

    X-ray absorption spectroscopy of Th 1-x U x O 2 and Th 1-x Pu x O 2 solid solutions was carried out on the Th, U L 3 -edges, and Pu L 3 edge to study the local structure environment of actinide mixed oxides. Various compositions of Th 1-x M x O 2 solid solutions have been prepared through the coprecipitation of the mixed oxalates from chloride or nitrate solutions: x = 0.11, 0.24, 0.37, 0.53, 0.67, 0.81, 0.91 and 1 for Th 1-x U x O 2 , and x = 0.13, 0.32, 0.66 and 1 for Th 1-x Pu x O 2 . They were characterized using X- ray diffraction. XRD analysis allowed to confirm that the variation of the lattice parameters varies linearly with the composition between the end members, suggesting that the atomic volume was conserved regardless of the details of the local distortions of the lattice, following the Vegard's law. Extending X-ray absorption fine structure (EXAFS) provides a direct characterization of the local distortions present in solid solutions. We found that opposite to the lattice parameter obtained by XRD, the interatomic distances given by EXAFS do not follow completely to neither the Vegard's law nor the virtual crystal approximation (VCA). However, the average lattice parameter obtained from EXAFS data for the first and the second shells agrees well with the one calculated from XRD data. (authors)

  11. Crystal structure of (Al,V)4(P4O12)3, archetype of double cubic ring tetraphosphate

    International Nuclear Information System (INIS)

    Yakubovich, O. V.; Biralo, G. V.; Dimitrova, O. V.

    2012-01-01

    The crystal structure of the (Al,V) 4 (P 4 O 12 ) 3 solid solution, obtained in the single-crystal form by hydrothermal synthesis in the Al(OH) 3 -VO 2 -NaCl-H 3 PO 4 -H 2 O system, has been solved by X-ray diffraction analysis (Xcalibur-S-CCD diffractometer, R = 0.0257): a = 13.7477(2) Å, sp. gr. I 4 bar 3d, Z = 4, and ρ calcd = 2.736 g/cm 3 . It is shown that the crystal structure of the parent cubic Al 4 (P 4 O 12 ) 3 modification can formally be considered an archetype for the formation of double isosymmetric tetraphosphates on its basis.

  12. Phase equilibria in the CdMoO4-Gd2(MoO4)3 system

    International Nuclear Information System (INIS)

    Tunik, T.A.; Fedorov, N.F.; Razumovskij, S.N.

    1980-01-01

    The constitutional diagram of the CdMoO 4 -Cd 2 (MoO 4 ) 3 system has been plotted using statistical and dynamic methods as well as a complex of instrumental analysis procedures. Three major phases have been found to occur in the systems, viz.: CdMoO 4 based solid solutions that crystallize in the range from 0 to 25 mol.percent of Cd 2 (MoO 4 ) 3 and pass in transit the two-phase narrow region becoming then solid solutions having a distorted scheelite structure and existing in concentrations from 40 to 65 mol.% of Cd 2 (MoO 4 ) 3 . The entire range, in which the Cd 2 (MoO 4 ) 3 solid solutions can exist, amounts to less than 5 mol.%. Certain crystallochemical constants of the phases that occur in the system have been determined [ru

  13. Ordered oxygen deficient '112'perovskites, LnBaCo2 O5⋅ 50 ...

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 32; Issue 3. Ordered oxygen deficient '112' perovskites, LnBaCo2O5.50+: complex magnetism and transport properties. B Raveau Md Motin Seikh V Pralong V Caignaert. Volume 32 Issue 3 June 2009 pp 305-312 ...

  14. An anti CuO{sub 2}-type metal hydride square net structure in Ln{sub 2}M{sub 2}As{sub 2}H{sub x} (Ln = La or Sm, M = Ti, V, Cr, or Mn)

    Energy Technology Data Exchange (ETDEWEB)

    Mizoguchi, Hiroshi; Park, SangWon; Hosono, Hideo [Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya [Institute of Materials Structure Science, High-Energy Accelerator Research Organization (KEK), Tsukuba 305-0801 (Japan)

    2015-03-02

    Using a high pressure technique and the strong donating nature of H{sup -}, a new series of tetragonal La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type layered mixed-anion arsenides, Ln{sub 2}M{sub 2}As{sub 2}H{sub x}, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x∼3). In these compounds, an unusual M{sub 2}H square net, which has anti CuO{sub 2} square net structures accompanying two As{sup 3-} ions, is sandwiched by (LaH){sub 2} fluorite layers. Notably, strong metal-metal bonding with a distance of 2.80 Aa was confirmed in La{sub 2}Ti{sub 2}As{sub 2}H{sub 2.3}, which has metallic properties. In fact, these compounds are situated near the boundary between salt-like ionic hydrides and transition-metal hydrides with metallic characters. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Thermodynamic mixing properties of the UO{sub 2}–HfO{sub 2} solid solution: Density functional theory and Monte Carlo simulations

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Ke, E-mail: keyuan@umich.edu [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Becker, Udo [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States)

    2015-03-15

    HfO{sub 2} is a neutron absorber and has been mechanically mixed with UO{sub 2} in nuclear fuel in order to control the core power distribution. During nuclear fission, the temperature at the center of the fuel pellet can reach above 1300 K, where hafnium may substitute uranium and form the binary solid solution of UO{sub 2}–HfO{sub 2}. UO{sub 2} adopts the cubic fluorite structure, but HfO{sub 2} can occur in monoclinic, tetragonal, and cubic structures. The distribution of Hf and U ions in the UO{sub 2}–HfO{sub 2} binary and its atomic structure influence the thermal conductivity and melting point of the fuel. However, experimental data on the UO{sub 2}–HfO{sub 2} binary are limited. Therefore, the enthalpies of mixing of the UO{sub 2}–HfO{sub 2} binary with three different structures were calculated in this study using density functional theory and subsequent Monte Carlo simulations. The free energy of mixing was obtained from thermodynamic integration of the enthalpy of mixing over temperature. From the ΔG of mixing, a phase diagram of the binary was obtained. The calculated UO{sub 2}–HfO{sub 2} binary forms extensive solid solution across the entire compositional range, but there are a variety of possible exsolution phenomena associated with the different HfO{sub 2} polymorphs. As the structure of the HfO{sub 2} end member adopts lower symmetry and becomes less similar to cubic UO{sub 2}, the miscibility gap of the phase diagram expands, accompanied by an increase in cell volume by 7–10% as the structure transforms from cubic to monoclinic. Close to the UO{sub 2} end member, which is relevant to the nuclear fuel, the isometric uranium-rich solid solutions exsolve as the fuel cools, and there is a tendency to form the monoclinic hafnium-rich phase in the matrix of the isometric, uranium-rich solid solution phase.

  16. BaO-Nd2O3-CuOx subsolidus equilibria under carbonate-free conditions at pO2=100 Pa and at pO2=21 kPa

    International Nuclear Information System (INIS)

    Wong-Ng, W.; Cook, L.P.; Suh, J.; Coutts, R.; Stalick, J.K.; Levin, I.; Huang, Q.

    2003-01-01

    Subsolidus phase equilibria of the BaO-Nd 2 O 3 -CuO x system at pO 2 =100 Pa (0.1% O 2 volume fraction, 810 deg. C) and at pO 2 =21 kPa (21% O 2 volume fraction, 930 deg. C) have been investigated by applying controlled-atmosphere methods to minimize the presence of carbonate and CO 2 and H 2 O contamination. Under carbonate-free conditions, the BaO-Nd 2 O 3 -CuO x phase diagrams at pO 2 =100 Pa and at pO 2 =21 kPa are similar to one another except for differences in the extent of the solid solutions. Apart from the limiting binary phases, the ternary system consists of three solid solutions and one stoichiometric ternary compound. The first solid solution is the high T c series, Ba 2-x Nd 1+x Cu 3 O 6+z (0.3≥x≥0 at pO 2 =100 Pa; 0.95≥x≥ 0 at pO 2 =21 kPa). At pO 2 =21 kPa, a compositionally dependent phase change was detected, from tetragonal (0.7>x≥0) to orthorhombic (0.95≥x≥0.7). The second solid solution series, the 'brown-phase' Ba 1+x Nd 2-x CuO z , has a narrow homogeneity region (0.10>x≥0 at pO 2 =100 Pa; 0.15>x≥0 at pO 2 =21 kPa). In the high BaO part of the phase diagram, a third solid solution (Ba 2-x Nd x )CuO 3+z (x=0 to ∼ 0.3 at pO 2 =100 Pa; x=0-0.45 at pO 2 =21 kPa) was confirmed, as well as a nominally stoichiometric phase, Ba 4 Nd 2 Cu 2 O z . The latter phase is an insulator, with a structure comprised of unusual CuO 5 linear chains. A significant difference in tie line distribution involving the Ba 2-x Nd 1+x Cu 3 O 6+z superconductor was found under carbonate-free conditions relative to literature studies completed in air. Instead of the BaCuO 2+x -Ba 2+x Nd 4-x Cu 2 O z tie line normally encountered in air, a Ba 2-x Nd 1+x Cu 3 O 6+z -(Ba,Nd) 2 CuO 3+x tie line was established. This tie line substantially expands the field of stability of the Ba 2-x Nd 1+x Cu 3 O 6+z superconductor phase into the BaO-rich region of the phase diagram. Implications for the processing of materials based on the Ba 2-x Nd 1+x Cu 3 O 6+z

  17. Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

    Science.gov (United States)

    Ravella, Uday K; Liu, Jingjing; Corbel, Gwenaël; Skinner, Stephen J; Lacorre, Philippe

    2016-08-23

    Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 μm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Thermoelectric properties of Bi2Te3 base solid solutions in the Bi2Te3-InS system

    International Nuclear Information System (INIS)

    Safarov, M.G.; Rustamov, P.G.; Alidzhanov, M.A.

    1979-01-01

    The rich Bi 2 Te 3 part ot the Bi 2 Te 3 -InS constitutional diagram has been studied with a view to produce new Bi 2 Te 3 -based solid solutions and to establish the maximum solubility of InS in Bi 2 Te 3 . The methods of differential-thermal, X-ray phase and microstructural analysis have been used. The alloys microhardness, density and thermal electric properties have been measured. A large region of Bi 2 Te 3 -based restricted solid solutions has been detected; it reaches 14.0 mol.% InS at room temperature. Studied have been the thermoelectromotive forces, electric and thermal conductivity of the alloys, containing up to 5 mol.% InS in the 300-700 K temperature range

  19. Neutron investigation of Ru-doped Nd1/2Ca1/2MnO3. Comparison with Cr-doped Nd1/2Ca1/2MnO3

    International Nuclear Information System (INIS)

    Moritomo, Yutaka; Nonobe, Toshihiko; Machida, Akihiko; Ohoyama, Kenji

    2002-01-01

    Lattice and magnetic properties are investigated for 3% Ru- and Cr-doped Nd 1/2 Ca 1/2 MnO 3 . The parent Nd 1/2 Ca 1/2 MnO 3 is a charge-ordered insulator (T CO =250K). With decreasing temperature below ≅210K, these compounds are separated into two perovskite phases, that is, the long-c and short-c phases. The long-c region shows a ferromagnetic transition at T C ≅210K for the Ru-doped compound and ≅130K for the Cr-doped compound, while the short-c region shows antiferromagnetic transition at T N ≅150K for Ru and ≅110K for Cr. We discuss the origin of the enhanced T C for the Ru-doped compound in terms of the effective one-electron bandwidth W of the e g -band. (author)

  20. Ferroelectric properties of sandwich structured (Bi, La)4T3O12/Pb(Zr, Ti)O3/ (Bi, La)4Ti3O12 thin films on Pt/Ti/SiO2/Si substrates

    International Nuclear Information System (INIS)

    Bao Dinghua; Wakiya, Naoki; Shinozaki, Kazuo; Mizutani, Nobuyasu

    2002-01-01

    Sandwich structured (Bi, La) 4 Ti 3 O 12 /Pb(Zr, Ti)O 3 /(Bi, La) 4 Ti 3 O 12 thin films were fabricated on Pt/Ti/SiO 2 /Si substrates, with the intention of simultaneously utilizing the advantages of both (Bi, La) 4 Ti 3 O 12 (BLT) and Pb(Zr, Ti)O 3 (PZT) thin films such as non-fatigue behaviours of BLT and good ferroelectric properties of PZT. Both BLT and PZT layers were prepared by a chemical solution deposition technique. The experiments demonstrated that the sandwich structure showed fatigue-free characteristics at least up to 10 10 switching bipolar pulse cycles under 8 V and excellent retention properties. The sandwich structured thin films also exhibited well-defined hysteresis loops with a remanent polarization (2P r ) of 8.8 μC cm -2 and a coercive field (E c ) of 47 kV cm -1 . The room-temperature dielectric constant and dissipation factor were 210 and 0.031, respectively, at a frequency of 100 kHz. These results suggest that this sandwich structure is a promising material combination for ferroelectric memory applications. (author)

  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. Modelling of the solid state electrochromic system WO/sub 3//HSbO/sub 3/ x 2H/sub 2/O/Ni(OH)/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Lagzdons, J L; Bajars, G E; Lusis, A R [AN Litovskoj SSR, Vilnyus. Inst. Fiziki Poluprovodnikov

    1984-08-16

    The problem of compatibility of electrochromic materials (ECM) with the solid electrolyte and the selection of solid electrolytes has been studied by means of modelling. The model electrochromic system (ECS) containing cathodically coloring ECM (WO/sub 3/), anodically coloring ECM (Ni(OH)/sub 2/), and a solid proton electrolyte (HSbO/sub 3/ x 2H/sub 2/O), as well as ECS containing H/sub x/WO/sub 3/ as counterelectrode has been investigated by the aid of cyclic voltammograms. Results show the compatibility of both the cathodic (WO/sub 3/) and anodic (Ni(OH)/sub 2/) ECM with solid proton electrolyte. Effective electrochromic devices can be worked out on their basis.

  3. Kramers non-magnetic superconductivity in LnNiAsO superconductors.

    Science.gov (United States)

    Li, Yuke; Luo, Yongkang; Li, Lin; Chen, Bin; Xu, Xiaofeng; Dai, Jianhui; Yang, Xiaojun; Zhang, Li; Cao, Guanghan; Xu, Zhu-an

    2014-10-22

    We investigated a series of nickel-based oxyarsenides LnNiAsO (Ln=La, Ce, Pr, Nd, Sm) compounds. CeNiAsO undergoes two successive anti-ferromagnetic transitions at TN1=9.3 K and TN2=7.3 K; SmNiAsO becomes an anti-ferromagnet below TN≃3.5 K; NdNiAsO keeps paramagnetic down to 2 K but orders anti-ferromagnetically below TN≃1.3 K. Superconductivity was observed only in Kramers non-magnetic LaNiAsO and PrNiAsO with Tc=2.7 K and 0.93 K, respectively. The superconductivity of PrNiAsO is further studied by upper critical field and specific heat measurements, which reveal that PrNiAsO is a weakly coupled Kramers non-magnetic superconductor. Our work confirms that the nickel-based oxyarsenide superconductors are substantially different in mechanism to iron-based ones, and are likely to be described by the conventional superconductivity theory.

  4. Synthesis and structural characteristics of the spinel-type solid solutions in the Mn-V-Fe-O system

    International Nuclear Information System (INIS)

    Ponomaryov, V.I.; Dubrovina, I.N.; Zakharov, R.G.

    1976-01-01

    The part of the spinel region bounded by the compounds Mn 3 O 4 , Mn 2 VO 4 , Fe 2 VO 4 , and Fe 3 O 4 in the four-component system Mn-V-Fe-O was studied. The compounds were synthesized by ceramic technology. Samples were heated in a CO 2 atmosphere free of oxygen at 1100 0 C for 25-50 hr. It was found that the average composition of the spinel compound in the system had the formula Mnsub(1.00)Fesub(1.33)Vsub(0.67)O 4 . X-ray and neutron radiogrphic analyses were made. Crystallo-chemical formulas of the solid solutions considered are tabulated. The magnetic moments of saturation, calculated by the Neel model, are shown, and their experimental values are presented. The crystallo-chemical formulas of the spinel solid solutions in the Mn-V-Fe-O system are of interest in interpreting the concentration dependence of the physico-chemical properties of solid solutions of oxides based on metals with varying valence

  5. Preparation and electrical properties of (1 - x)Sr(Fe{sub 1/2}Nb{sub 1/2})O{sub 3}-xPbTiO{sub 3} ferroelectric ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Fang Bijun [School of Materials Science and Engineering, Jiangsu Polytechnic University, Changzhou, Jiangsu 213164 (China)], E-mail: fangbj@em.jpu.edu.cn; Cheng Zhenquan; Sun Renbing; Ding Chenlu [School of Materials Science and Engineering, Jiangsu Polytechnic University, Changzhou, Jiangsu 213164 (China)

    2009-03-05

    (1 - x)Sr(Fe{sub 1/2}Nb{sub 1/2})O{sub 3}-xPbTiO{sub 3} (SFN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via the wolframite precursor route. X-ray diffraction (XRD) measurement confirmed that the synthesized SFN-PT ceramics are of pure perovskite structure. With the increase of the concentration of PbTiO{sub 3} (PT), crystal structure of the sintered SFN-PT ceramics changes from rhombohedral phase to tetragonal phase. Dielectric response of the SFN-PT ceramics changes from diffused and broad dielectric peaks to relatively sharp ones accompanied by the increase of the temperature of dielectric maximum (T{sub m}). Small content of MnO{sub 2} or Li{sub 2}CO{sub 3} doping can greatly decrease the dielectric loss of the SFN-PT ceramics, furthermore, the abnormal increase of dielectric constant and loss tangent in the paraelectric phase is suppressed accordingly. Typical P-E hysteresis loops are observed in the SFN-PT ceramics, however, the saturate polarization (P{sub s}) is small. MnO{sub 2} or Li{sub 2}CO{sub 3} doping can greatly decrease the coercive field (E{sub c}) of the SFN-PT ceramics accompanied by large increase of P{sub s}. Piezoelectric constant d{sub 33} of the SFN-PT ceramics is small except for SFN30-PT70 ceramics, which reaches 22pC/N.

  6. Room-temperature picosecond high-order stimulated Raman scattering in laser garnet crystal hosts Gd3Ga5O12, Gd3Sc2Ga3O12, and Ca3(Nb,Ga)2Ga3O12

    International Nuclear Information System (INIS)

    Kaminskii, Alexandr A; Eichler, H J; Findeisen, J; Ueda, Ken-ichi; Fernandez, J; Balda, R

    1998-01-01

    High-order Stokes and anti-Stokes generation in the visible and near-infrared in cubic laser crystal hosts Gd 3 Ga 5 O 12 , Gd 3 Sc 2 Ga 3 O 12 , and Ca 3 (Nb,Ga) 2 Ga 3 O 12 was observed for the first time. All scattering-laser components were identified and attributed to the SRS-active vibration modes of these garnet crystals. (letters to the editor)

  7. Dimensional t-factor variation and increase of stability of the ferroelectric state in (Na0.5Bi0.5TiO3-based solid solutions

    Directory of Open Access Journals (Sweden)

    V. M. Ishchuk

    2017-10-01

    Full Text Available The influence of the B-site ion substitutions in (1−x(Bi1∕2Na1∕2TiO3–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∕2TiO3-based solid solutions.

  8. Solid State Formation Mechanism of Li4Ti5O12 from an Anatase TiO2 Source

    DEFF Research Database (Denmark)

    Shen, Yanbin; Søndergaard, Martin; Christensen, Mogens

    2014-01-01

    Solid state synthesis of Li4Ti5O12 anode material for Li ion batteries typically results in products containing rutile TiO2 and Li2TiO3 impurities, and subsequent high calcination temperatures lead to particle growth that reduces capacity and rate ability. Here, the formation and growth of Li4Ti5O......12 particles by a solid-state reaction using anatase TiO2 with various crystallite sizes and Li2CO3 is investigated by in situ high temperature powder X-ray diffraction (HT-PXRD) and thermal gravimetry-differential thermal analysis (TG-DTA). The combined data provide insight into the origin...... crystallite sizes (∼50 nm, ∼30 nm, ∼20 nm, and amorphous) were explored, and decreasing crystallite sizes causes a reduced initial reaction temperature. Using anatase with a crystallite size of ∼20 nm resulted in phase pure Li4Ti5O12 at the lowest temperature (800 °C). PXRD and TG-DTA results also revealed...

  9. K2Ln2As2Se9 (Ln = Sm, Gd): the first quaternary rare-earth selenoarsenate compounds with a 3D framework containing chairlike As2Se4 units.

    Science.gov (United States)

    Wu, Yuandong; Bensch, Wolfgang

    2009-04-06

    The new compounds K(2)Ln(2)As(2)Se(9) (Ln = Sm, Gd) were obtained by applying the reactive flux method. The structure consists of a three-dimensional (3D) [Ln(2)As(2)Se(9)](2-) framework with K(+) ion-filling tunnels running along the b axis. The two unique Ln(3+) cations are coordinated by two Se(2)(2-) dumbbells, two AsSe(3)(3-) pyramids, and one chairlike As(2)Se(4)(2-) unit in a bicapped trigonal-prismatic geometry. The Ln(3+)-centered trigonal prisms share triangular faces with neighboring prisms, forming one-dimensional chains along the b axis. These chains are linked to each other to form layers by sharing Se(2-) anions on the capped sites of the trigonal prisms. The As(2)Se(4) units connect these layers to form the 3D framework.

  10. Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion

    Directory of Open Access Journals (Sweden)

    Zhiping Zhang

    2017-11-01

    Full Text Available Zr2WP2O12/ZrO2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr2WP2O12/ZrO2 composites with different mass ratio. Relative densities of all the resulting Zr2WP2O12/ZrO2 samples were also tested by Archimedes' methods. The obtained Zr2WP2O12/ZrO2 composites were comprised of orthorhombic Zr2WP2O12 and monoclinic ZrO2. As the increase of the Zr2WP2O12, the relative densities of Zr2WP2O12/ZrO2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr2WP2O12/ZrO2 composites can be tailored from 4.1 × 10−6 K−1 to −3.3 × 10−6 K−1 by changing the content of Zr2WP2O12. The 2:1 Zr2WP2O12/ZrO2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of −0.09 × 10−6 K−1. These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

  11. Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

    Science.gov (United States)

    Zhang, Zhiping; Sun, Weikang; Liu, Hongfei; Xie, Guanhua; Chen, Xiaobing; Zeng, Xianghua

    2017-01-01

    Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

  12. Microstructure optimization for high-performance PrBa0.5Sr0.5Co1.5Fe0.5O5+δ-La2NiO4+δ core-shell cathode of solid oxide fuel cells

    Science.gov (United States)

    Li, Jin; Qiu, Peng; Xia, Meng; Jia, Lichao; Chi, Bo; Pu, Jian; Li, Jian

    2018-03-01

    Four PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF)-La2NiO4+δ (LN) core-shell cathodes, designated as PL-0, PL-1, PL-3 and PL-5, are prepared by infiltrating LN solution into PBSCF scaffold, and they are investigated in terms of the effect of LN thickness on their electrochemical performance. PL-3 with a continuous LN coating of a moderate average thickness (∼9 nm) demonstrates the lowest initial polarization resistance (0.51 Ω cm2) and highest power density (0.71 W cm-2) among all the cathodes. Polarized at 400 mA cm-2 and 700 °C for up to 40 h, the polarization resistance of all the prepared cathodes increases to approach a stable level after early stage decrease due to current activation, and PL-3 exhibits a slower average rate of performance degradation (25%). The electrochemical performance improvement is mainly attributed to that LN has a relatively high oxygen surface exchange coefficient and continuous LN coating depresses Sr segregation at PBSCF/LN interface.

  13. Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

    Science.gov (United States)

    Zhang, Lei; Navrotsky, Alexandra

    2015-10-01

    Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

  14. High-pressure synthesis and magnetic behavior of A-site columnar-ordered double perovskites, LnMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} (Ln = Sm, Gd)

    Energy Technology Data Exchange (ETDEWEB)

    Shimura, Gen; Niwa, Ken; Shirako, Yuichi; Hasegawa, Masashi [Department of Crystalline Materials Science, Nagoya University, 464-8601, Nagoya (Japan)

    2017-01-26

    A-site columnar-ordered double perovskites, LnMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} (Ln = Sm, Gd), were successfully synthesized under high pressure and high temperature (6 GPa, 1375 K). From the synchrotron powder X-ray diffraction patterns, all of the diffraction peaks can be indexed by the P4{sub 2}/nmc space group with lattice parameters a, c ∼ 2a{sub p} (a{sub p}: primitive cubic perovskite lattice) and no ordering of the B-site cations. Rietveld analysis of the synchrotron powder X-ray diffraction patterns and Curie-Weiss fitting of their magnetizations reveal that the ionic formulae of these perovskites are Ln{sup 3+}Mn{sup 2+}(Ga{sup 3+}{sub 0.5}Ti{sup 4+}{sub 0.5}){sub 2}O{sup 2-}{sub 6}. SmMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} shows canted-antiferromagnetic behavior, whereas GdMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} exhibits two different magnetic states at low temperature depending on the applied magnetic field and shows an unusual magnetization curve. These magnetic behaviors originate by decreasing the antiferromagnetic interaction by substituting Ga{sup 3+}(d{sup 10}) for Ti{sup 4+}(d{sup 0}) and by decreasing the ferromagnetic interaction between columnar-ordered Ln{sup 3+} and Mn{sup 2+}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Photocatalytic performance of nano-photocatalyst from TiO{sub 2} and Fe{sub 2}O{sub 3} by mechanochemical synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Ghorai, Tanmay K., E-mail: tanmay_ghorai@yahoo.co.in [Department of Chemistry, West Bengal State University, Barasat, North 24 Pgs, Kolkata 700126 (India); Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302 (India); Chakraborty, Mukut [Department of Chemistry, West Bengal State University, Barasat, North 24 Pgs, Kolkata 700126 (India); Pramanik, Panchanan [Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302 (India)

    2011-08-11

    Graphical abstract: Nano-particles of homogeneous solution between TiO{sub 2} and Fe{sub 2}O{sub 3} (up to 5 mol%) have been prepared by mechanochemical milling. The results show that the alloy of TiO{sub 2} with 5 mol% of Fe{sub 2}O{sub 3} (YFT1) exhibit photocatalytic activity 3-5 times higher than that of P25 TiO{sub 2} for oxidation of various dyes (RB, MO, TB and BG) under visible light irradiation. The average particle size and crystallite size of YFT1 were found to be 30 {+-} 5 nm and 12 nm measured from TEM and XRD. Optical adsorption edge is found to be 2.26 eV. Tentative schematic diagram of reaction mechanism of YFT/RFT photocatalysts under visible light irradiation. Highlights: > Synthesis of nano-sized homogeneous solid solution between Fe{sub 2}O{sub 3} and TiO{sub 2} with high photocatalytic activity for oxidative degradation of different dyes was successfully obtained through mechanochemical synthesis. XRD data shows the formation of solid solution having anatase structure with no free Fe{sub 2}O{sub 3} up to 5 mol% of Fe{sub 2}O{sub 3}. Fe{sub 2}O{sub 3}/TiO{sub 2} catalyst have crystallite size about 12-13 nm measured from XRD and particle size about 30 {+-} 5 nm measured from TEM. FT-IR of all Fe{sub 2}O{sub 3}/TiO{sub 2} prepared catalysts is similar to pure TiO{sub 2}. The maximum solubility of Fe{sub 2}O{sub 3} in TiO{sub 2} is 5 mol% of Fe{sub 2}O{sub 3} irrespective of source and this composition has highest photocatalytic activity that is 3-5 times higher than P25 TiO{sub 2} for the oxidation of different dyes. We also observed that the rate of degradation of Rhodamine B is faster among all the four dyes under prepared catalyst and visible light. - Abstract: Nano-particles of homogeneous solid solution between TiO{sub 2} and Fe{sub 2}O{sub 3} (up to 10 mol%) have been prepared by mechanochemical milling of TiO{sub 2} and yellow Fe{sub 2}O{sub 3}/red Fe{sub 2}O{sub 3}/precipitated Fe (OH){sub 3} using a planetary ball mill. Such novel solid

  16. Synthesis and characterization of type solid solution in the binary ...

    Indian Academy of Sciences (India)

    We have investigated Bi2O3–Eu2O3 binary system by doping with Eu2O3 in the composition range from 1 to 10 mole% via solid state reactions and succeeded to stabilize -Bi2O3 ... Our experimental observations strongly suggested that oxygen deficiency type non-stoichiometry is present in doped type solid solutions.

  17. Low-temperature magnetic susceptibility of the solid solutions (ErxY1-x)3Al5O12

    International Nuclear Information System (INIS)

    Bagdasarov, Kh.S.; Dodokin, A.P.; Sorokin, A.A.

    1988-01-01

    Measurements of magnetic susceptibility of erbium-yttrium alumogarnets in the 0.04-4.2 K temperature range are carried out. (Er x I 1-x ) 3 Al 5 O 12 monocrystals were grown by the method of vertical directed crystallization. The specimens were produced as 5 cm high cylinders 0.63 cm in diameter; the axis of the cylinders coincided with the (100) direction of the crystals. Magnetic susceptibility was measured by the Harsthorn bridge method at the frequency of 33 Hz. The analysis of measurement results shows that susceptibility of the investigated crystals at T >or approx. 2T N is well described by the Curie-Weiss law. Existence of threshold concentration of the magnetic component testifies to an essential role of exchange interactions in establishment of the magnetic order in Er 3 Al 5 O 12

  18. Effect of alkali-earth ions on local structure of the LaAlO3-La0.67A0.33MnO3 (A = Ca, Sr, Ba) diluted solid solutions: 27Al NMR studies

    International Nuclear Information System (INIS)

    Charnaya, E.V.; Cheng Tien; Lee, M.K.; Sun, S.Y.; Chejina, N.V.

    2007-01-01

    27 Al Magic Angle Spinning (MAS) NMR studies are carried out for diluted alkali-earth metal doped lanthanum manganite solid solutions in the lanthanum aluminate (1-y)LaAlO 3 -yLa 0.67 A 0.33 MnO 3 (A = Ca, Sr, Ba) with y = 0, 2, 3, and 5 mol %. The spectra depend on the dopant species and show higher substitutional ordering for the Ba containing mixed crystals. Magnetically shifted lines are observed in all solid solutions and attributed to Al in the octahedral oxygen environment near manganese trivalent ions. Nonlinear dependences of their intensity are referred to the manganese-rich cluster formation. An additional MAS NMR line corresponding to aluminium at sites different from the octahedral site in pure LaAlO 3 is observed only in solutions doped with Ba. 3Q MAS NMR revealed that the broadening of this line is governed mainly by quadrupole coupling and allowed calculating the isotropic chemical shift [ru

  19. Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln2Sr(Ba)Fe2O7 (Ln = La, Nd, Eu)

    International Nuclear Information System (INIS)

    Gurusinghe, Nicola N.M.; Figuera, Juand de la; Marco, José F.; Thomas, Michael F.; Berry, Frank J.; Greaves, Colin

    2013-01-01

    Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A 2 B 2 O 7 of composition Ln 2 Sr(Ba)Fe 2 O 7 (Ln = La, Nd, Eu) have been prepared. La 2 SrFe 2 O 7 and La 2 BaFe 2 O 7 crystallise in the tetragonal space group I4/mmm. The structures of Eu 2 SrFe 2 O 7 and Nd 2 SrFe 2 O 7 are best described in space group P4 2 /mnm. Substitution on the A site with smaller lanthanide- and larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La 2 SrFe 2 O 7 the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La 2 BaFe 2 O 7 the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd 2 SrFe 2 O 7 the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of 57 Fe Mössbauer spectra recorded from La 2 SrFe 2 O 7 between 290 and 600 K indicate a magnetic ordering temperature of T N ≥ 535 K

  20. Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, Er) at high pressure

    Science.gov (United States)

    Turner, Katlyn M.; Tracy, Cameron L.; Mao, Wendy L.; Ewing, Rodney C.

    2017-12-01

    Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn-O〉 bond in stannate pyrochlore is more covalent than the 〈B-O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18-40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite  +  weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B 0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B 0. Additionally, when normalized to r A

  1. Synthesis and photoluminescence properties of GdBO3:Ln3+ (Ln = Eu, Tb) nanofibers by electrospinning

    International Nuclear Information System (INIS)

    Shen, Hongzhi; Feng, Shuo; Wang, Ying; Gu, Yipeng; Zhou, Jing; Yang, Hang; Feng, Guanlin; Li, Liang; Wang, Wenquan; Liu, Xiaoyang; Xu, Dapeng

    2013-01-01

    Highlights: ► GdBO 3 :Ln 3+ nanofibers were synthesized successfully by electrospinning. ► The samples have the average diameter of 150 nm and the flexible morphology. ► The GdBO 3 : Eu 3+ nanofibers have the stronger orange emission. ► The luminescence properties are different from the reported bulk material. ► We describe the energy transform process of GdBO 3 :Ln 3+ system. - Abstract: GdBO 3 :Ln 3+ (Ln = Eu, Tb) nanofibers were synthesized using electrospinning combined with heat treatment. The synthesized nanofibers were characterized by X-ray diffraction, Raman spectroscopy, field emission-scanning electron microscopy, thermogravimetric and differential thermal analyses, and photoluminescence. The experimental results show that the flexible synthesized nanofibers have an average diameter of approximately 150 nm. The nanofibers consist of crystalline grains with diameters of about 40 nm and have a vaterite-type structure of GdBO 3 . The GdBO 3 :Eu 3+ nanofibers exhibit strong orange and weak red emissions with a low ratio of red to orange emission intensities, which is different from those of the reported bulk materials and nanoparticles. The luminescence properties of the synthesized GdBO 3 :Tb 3+ nanofibers are essentially consistent with those of the synthesized GdBO 3 :Tb 3+ powders by solid-state reaction.

  2. Controllable synthesis of Ln3+ (Ln = Tb, Eu) doped zinc phosphate nano-/micro-structured materials: phase, morphology and luminescence properties

    Science.gov (United States)

    Yue, Dan; Lu, Wei; Li, Chunyang; Zhang, Xinlei; Liu, Chunxia; Wang, Zhenling

    2014-01-01

    Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These investigations indicate that different phosphate sources MnH(3-n)PO4 (M = NH4+ or Na+, n = 1, 2, 3) can lead to the altering of morphology from nanosheet to microflower, but have no significant effect on the phase structure of the samples. The microlump, nanosheet, and microflower (constructed by the primary microlumps or nanosheets) of orthorhombic ZPT:Ln3+ could be selectively prepared by adjusting the pH value from 3.5 to 7.0. A mixture of orthorhombic ZPT:Ln3+ and monoclinic AZP:Ln3+ with a microflower morphology was obtained when the pH value was adjusted to 8.0. Monoclinic AZP:Ln3+ microplate, microcube and nanoparticle morphologies were obtained at pH values of 8.5, 9.0 and 11.0 respectively. The phase transformation and growth mechanism of the diverse morphologies were proposed, and ZPT:Ln3+ (Ln3+ = Eu or Tb) samples exhibit red or green emission under the excitation of UV light.Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These

  3. Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

    Science.gov (United States)

    Shirage, Parasharam M; Kihou, Kunihiro; Lee, Chul-Ho; Takeshita, Nao; Eisaki, Hiroshi; Iyo, Akira

    2012-09-19

    The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

  4. Li_2ZrO_3-coated Li_4Ti_5O_1_2 with nanoscale interface for high performance lithium-ion batteries

    International Nuclear Information System (INIS)

    Zhang, Han; Liu, Yang; Wang, Ting; Yang, Yang; Shi, Shaojun; Yang, Gang

    2016-01-01

    Graphical abstract: - Highlights: • Zr doped and Li_2ZrO_3 coated Li_4Ti_5O_1_2 are prepared by a solid-state method. • Zr-doping and LZO coating are positive in improving lithium diffusion ability. • Li_2ZrO_3 coated Li_4Ti_5O_1_2 deliver 168.1 mAh g"−"1 higher than 150.2 mAh g"−"1 of Li_4Ti_5O_1_2. • Li_2ZrO_3 coated Li_4Ti_5O_1_2 remains 162 mAh g"−"1 after 100 cycles. • The lowest D_L_i"+ is 5.97 × 10"−"1"7 and 1.85 × 10"−"1"5 cm"2 s"−"1 of Li_4Ti_5O_1_2 before and after coating. - Abstract: Zr doped sample of Li_4Ti_4_._9_9Zr_0_._0_1O_1_2 (LZTO) and Li_2ZrO_3 (LZO) coated Li_4Ti_5O_1_2 (LTO) are prepared by a solid-state method. The lattice structure of LTO is remained after doping element of Zr and coating layer of LZO. The crystal structure and electrochemical performance of the material are investigated by X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and charge-discharge tests, respectively. Zr-doping and LZO coating play the positive role in improving the diffusion ability of lithium cations. LZTO and LZO-LTO show much improved specific capacity and rate capability compared with pristine sample of LTO. LZO-LTO has the smallest voltage differential (ΔV) of the redox peaks because the coating of Li_2ZrO_3 is helpful for the diffusion ability of lithium ions during charge/discharge processes. LZTO and LZO-LTO as electrode deliver the initial capacities of 164.8, 168.1 mAh g"−"1, respectively, which are much higher than 150.2 mAh g"−"1 of intrinsic sample of LTO. Even at the current density of 2 A g"−"1, LTZO and LZO-LTO offer capacity of 96 and 106 mAh g"−"1, which are much higher than 33 mAh g"−"1 of LTO. The improved electrochemical performance is attributed to the improved diffusion ability of lithium. During the whole discharge process, the lowest value of LTO is 5.97 × 10"−"1"7 cm"2 s"−"1 that is

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

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 29; Issue 1. Influence of Ce0.68Zr0.32O2 solid solution on depositing -alumina washcoat on FeCrAl foils. Mei-Qing Shen Li-Wei Jia Wen-Long Zhou Jun Wang Ying Huang. Composites Volume 29 Issue 1 February 2006 pp 73-76 ...

  6. Microstructures and mechanical properties of Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Lei [Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang, Liaoning 110819 (China); Key Laboratory for Advanced Ceramics and Application of Shenyang, Shenyang University of Chemical Technology, Shenyang, Liaoning 110142 (China); Ma, Weimin, E-mail: maleisy2003@163.com [Key Laboratory for Advanced Ceramics and Application of Shenyang, Shenyang University of Chemical Technology, Shenyang, Liaoning 110142 (China); Sun, Xudong, E-mail: xdsun@mail.neu.edu.cn [Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang, Liaoning 110819 (China); Ji, Lianyong; Liu, Jianan; Hang, Kai [Key Laboratory for Advanced Ceramics and Application of Shenyang, Shenyang University of Chemical Technology, Shenyang, Liaoning 110142 (China)

    2015-09-25

    Highlights: • Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) composites were prepared using vacuum sintering. • The phase composition and microstructure are studied. • Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) materials show superior mechanical properties. • The solid solution strengthening and stress-induced phase transformation toughening mechanism are proposed. • Two kinds of mechanisms explain the improvement of mechanical properties. - Abstract: Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) composite ceramics were prepared by vacuum sintering using Gd{sub 2}Zr{sub 2}O{sub 7} and ZrO{sub 2}(3Y) nanoparticles. The ceramics were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), the three-point-bending technique and single-edge-notched-beam tests. The effect of various proportions of ZrO{sub 2}(3Y) on the phase composition, microstructure, bending strength and fracture toughness of the final Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) composite ceramics was also analyzed. The change from m-ZrO{sub 2} to t-ZrO{sub 2} phase contents, before and after fracture, was measured using XRD quantitative phase analysis. The results confirm that, with the increasing content of ZrO{sub 2}(3Y), a phase transition from solid solution to saturated precipitation occurs and the bending strength and fracture toughness of the samples increase gradually. When the content of ZrO{sub 2}(3Y) reached 95 vol.%, the Gd{sub 2}Zr{sub 2}O{sub 7}/ZrO{sub 2}(3Y) composite ceramics had a bending strength of 547 MPa and a fracture toughness of 5.5 MPa m{sup 1/2}, indicating that stress-induced phase transformation toughening was an efficient way to increase the mechanical properties of the Gd{sub 2}Zr{sub 2}O{sub 7} ceramics.

  7. Solution synthesis, structure, and CO{sub 2} reduction reactivity of a Scandium(II) complex, {Sc[N(SiMe_3)_2]_3}{sup -}

    Energy Technology Data Exchange (ETDEWEB)

    Woen, David H.; Chen, Guo P.; Ziller, Joseph W.; Furche, Filipp; Evans, William J. [Department of Chemistry, University of California, Irvine, CA (United States); Boyle, Timothy J. [Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, NM (United States)

    2017-02-13

    The first crystallographically characterizable complex of Sc{sup 2+}, [Sc(NR{sub 2}){sub 3}]{sup -} (R=SiMe{sub 3}), has been obtained by LnA{sub 3}/M reactions (Ln=rare earth metal; A=anionic ligand; M=alkali metal) involving reduction of Sc(NR{sub 2}){sub 3} with K in the presence of 2.2.2-cryptand (crypt) and 18-crown-6 (18-c-6) and with Cs in the presence of crypt. Dark maroon [K(crypt)]{sup +}, [K(18-c-6)]{sup +}, and [Cs(crypt)]{sup +} salts of the [Sc(NR{sub 2}){sub 3}]{sup -} anion are formed, respectively. The formation of this oxidation state of Sc is also indicated by the eight-line EPR spectra arising from the I=7/2 {sup 45}Sc nucleus. The Sc(NR{sub 2}){sub 3} reduction differs from Ln(NR{sub 2}){sub 3} reactions (Ln=Y and lanthanides) in that it occurs under N{sub 2} without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR{sub 2}){sub 3}] reacts with CO{sub 2} to produce an oxalate complex, {K_2(18-c-6)_3}{[(R_2N)_3Sc]_2(μ-C_2O_4-κ"1O:κ"1O'')}, and a CO{sub 2}{sup -} radical anion complex, [(R{sub 2}N){sub 3}Sc(μ-OCO-κ{sup 1}O:κ{sup 1}O')K(18-c-6)]{sub n}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Pseudo-solid-solution CuCo2O4/C nanofibers as excellent anodes for lithium ion batteries

    International Nuclear Information System (INIS)

    Zhang, Hang; Tang, Zhiyong; Zhang, Kang; Wang, Lei; Shi, Huimin; Zhang, Guanhua; Duan, Huigao

    2017-01-01

    Ternary transition metal oxides have received intense research interest as electrode materials for lithium ion batteries, due to their high specific capacity originating from the synergic effects of multiple metal active sites. Reducing the size of metal oxides nanoparticles and dispersing these nanoparticles in carbon matrix are considering effective strategies to improve the electrochemical performance of transition metal oxides. Ternary CuCo 2 O 4 nanoclusters ultra-uniformly dispersed in carbon nanofiber matrix forming a pseudo-solid-solution structure are successfully synthesized by a facile electrospinning method followed by an appropriate annealing process. As the anodic electrode for lithium ion batteries, the pseudo-solid-solution CuCo 2 O 4 /C electrode exhibits a high reversible specific capacity, improved rate capacity and excellent cycling stability. A discharge capacity of 865 mAh g −1 is obtained at the current density of 200 mA g −1 after 400 cycles. Surprisingly, the electrode still retains about 610 mAh g −1 after 800 cycles even at the current density of 600 mA g −1 . The superior lithium storage performance of the pseudo-solid-solution CuCo 2 O 4 /C composites is mainly attributed to the unique amorphous structure. The ultrafine CuCo 2 O 4 nanoclusters uniformly dispersed in carbon matrix can buffer the volume change and improve the conductivity of the metal oxide based electrode, guaranteeing the structure stability and fast electron transfer.

  9. The effect of Bi2 O3 on the electrical properties of Zr O2: 3 wt% Mg O ceramic solid electrolytes

    International Nuclear Information System (INIS)

    Cosentino, I.C.

    1991-01-01

    Zr O 2 : 3 wt% Mg O ceramic solid electrolytes have been prepared to study the effect of Bi 2 O 3 addition on densification and electrical conductivity. Microstructural characterization have been done by X-ray diffractometry, scanning electron microscopy and electron microprobe analyses. Electrical conductivity measurements have been done by two probe dc technique in the 400 0 C - 700 0 C temperature range. The results show that 5 wt% Bi 2 O 3 addition improves densification: 93% TD and 98% TD specimens are obtained from zirconia stabilized by powder mixture and by coprecipitation of oxides, respectively. Moreover, electrical conductivity values are found to be two orders of magnitude higher for Zr O 2 : 3 wt% Mg O with 5% Bi 2 O 3 . (author)

  10. The structural, electronic, magnetic, and mechanical properties of perovskite oxides PbM1/2Nb1/2O3 (M = Fe, Co and Ni)

    Science.gov (United States)

    Erkisi, A.; Surucu, G.; Deligoz, E.

    2018-03-01

    In this study, the structural, electronic, magnetic, and mechanical properties of perovskite oxides PbM1/2Nb1/2O3 (M = Fe, Co and Ni) are investigated. The systems are treated in ferromagnetic order. The calculations are carried out in the framework of density functional theory (DFT) within the plane-wave pseudopotential method. The exchange-correlation potential is approximated by generalized-gradient spin approach (GGA). The intra-atomic Coulomb repulsion is also taken into account in calculations (GGA + U). We have considered two generalized-gradient spin approximation functionals, which are Perdew-Burke-Ernzerhof (PBE) and PBE for solids (PBEsol) for structural parameter calculations when it included Hubbard potential. Although the spin-polarized electronic band structures of PbCo1/2Nb1/2O3 and PbNi1/2Nb1/2O3 systems exhibit metallic property in ferromagnetic phase, a bandgap is observed in spin-down states of PbFe1/2Nb1/2O3 resulting in half-metallic behavior. The main reason for this behavior is attributed to the hybridization between d-states of transition metal atoms and p-states of oxygen atoms. The stability mechanically and the calculated mechanical properties by using elastic constants show that these compounds are mechanically stable in tetragonal phase and have anisotropic character mechanically.

  11. Effect of surface treatment of thermoelectric materials on the properties of thermoelements made from solid solutions of Bi2Te3-Bi2Se3 and Bi2Te3-Sb2Te3 systems

    International Nuclear Information System (INIS)

    Alieva, T.D.; Abdinov, D.Sh.; Salaev, Eh.Yu.

    1981-01-01

    Effect of surface treatment technology of samples of solid solutions of Ei 2 Te 3 -Bi 2 Se 3 and Bi 2 Te 3 -Sb 2 Te 3 systems on their thermoelectric efficiency is studied. Branches of thermoelements have been produced with the help of electroerosion or mechanical cutting of monocrystal ingots of semiconducting solid Bi 2 Te 3 -base solutions. It is shown that in case of the treatment of side surfaces of branches of thermoelements produced of monocrystals of Bi 2 Te 3 base solid solutions their thermoelectrical efficiency grows considerably. Maximum growth of efficiency (approximately 20%) is observed during mechanical grinding of branches surfaces with diamond paste with the following chemical or electrochemical etching [ru

  12. Structure and some magnetic properties of (BiFeO3x-(BaTiO31−x solid solutions prepared by solid-state sintering

    Directory of Open Access Journals (Sweden)

    Kowal Karol

    2015-03-01

    Full Text Available This paper presents the results of the study on structure and magnetic properties of the perovskite-type (BiFeO3x-(BaTiO31−x solid solutions. The samples differing in the chemical composition (x = 0.9, 0.8, and 0.7 were produced according to the conventional solid-state sintering method from the mixture of powders. Moreover, three different variants of the fabrication process differing in the temperatures and soaking time were applied. The results of X-ray diffraction (XRD, Mössbauer spectroscopy (MS, and vibrating sample magnetometry (VSM were collected and compared for the set of the investigated materials. The structural transformation from rhombohedral to cubic symmetry was observed for the samples with x = 0.7. With increasing of BaTiO3 concentration Mössbauer spectra become broadened reflecting various configurations of atoms around 57Fe probes. Moreover, gradual decreasing of the average hyperfine magnetic field and macroscopic magnetization were observed with x decreasing.

  13. Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li7La3Zr2O12 Solid Electrolytes.

    Science.gov (United States)

    Rettenwander, Daniel; Redhammer, Günther; Preishuber-Pflügl, Florian; Cheng, Lei; Miara, Lincoln; Wagner, Reinhard; Welzl, Andreas; Suard, Emmanuelle; Doeff, Marca M; Wilkening, Martin; Fleig, Jürgen; Amthauer, Georg

    2016-04-12

    Several "Beyond Li-Ion Battery" concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li 7 La 3 Zr 2 O 12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet ( Ia 3̅ d , No. 230) to "non-garnet" ( I 4̅3 d , No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10 -4 S cm -1 to 1.2 × 10 -3 S cm -1 , which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm 2 , the lowest reported value for LLZO so far. These results illustrate that understanding the structure-properties relationships in this class of materials

  14. Origin of giant dielectric permittivity and weak ferromagnetic behavior in (1−xLaFeO3−xBaTiO3 (0.0 ≤ x ≤ 0.25 solid solutions

    Directory of Open Access Journals (Sweden)

    T. Sreenivasu

    2016-12-01

    Full Text Available The solid solutions of (1−x LaFeO3–xBaTiO3 (0.0≤x≤0.25 have been synthesized successfully by the conventional solid-state reaction method. Room temperature (RT X-ray diffraction studies reveal the stabilization of orthorhombic phase with Pbnm space group. Complete solubility in the perovskite series was demonstrated up to x=0.25. The dielectric permittivity shows colossal dielectric constant (CDC at RT. The doping of BaTiO3 in LaFeO3 exhibit pronounced CDC up to a composition x=0.15, further it starts to decrease. The frequency-dependent dielectric loss exhibits polaronic conduction, which can attribute to presence of multiple valence of iron. The relaxation frequency and polaronic conduction mechanism was shifted towards RT as function of x. Moreover, large magnetic moment with weak ferromagnetic behavior is observed in doped LaFeO3 solid solution, which might be the destruction of spin cycloid structure due to insertion of Ti in Fe–O–Fe network of LaFeO3.

  15. Synthesis and characterizations of two anhydrous metal borophosphates: MIII2BP3O12 (M=Fe, In)

    International Nuclear Information System (INIS)

    Zhang Weilong; Lin Chensheng; Geng Lei; Li Yeyu; Zhang Hao; He Zhangzhen; Cheng Wendan

    2010-01-01

    Two members of M III 2 BP 3 O 12 borophosphates, namely Fe 2 BP 3 O 12 and In 2 BP 3 O 12 , were synthesized by the solid-state method and characterized by the X-ray single crystal diffraction, the powder diffraction and the electron microscopy. They both crystallize in the hexagonal system, space group P6(3)/m (no. 176) and feature 3D architectures, build up of the M 2 O 9 units and B(PO 4 ) 3 groups via sharing the corners; however, they are not isomorphic for the different crystallographically distinct atomic positions. Optical property measurements of both compounds and magnetic susceptibility measurements of Fe 2 BP 3 O 12 also have been performed. Moreover, in order to gain further insights into the relationship between physical properties and band structure of the M III 2 BP 3 O 12 borophosphates, theoretical calculations based on density functional theory (DFT) were performed using the total-energy code CASTEP. - Graphical abstract: Two anhydrous metal borophosphates of M III 2 BP 3 O 12 (M=Fe, In) have been prepared and characterized. They both crystallize in the hexagonal system, space group P6(3)/m (no. 176) and feature 3D architectures build up of the M 2 O 9 units and B(PO 4 ) 3 groups via sharing the corners, but they are not isomorphic for the different crystallographically distinct atomic positions.

  16. Studies on solid solutions based on layered honeycomb-ordered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn)

    Energy Technology Data Exchange (ETDEWEB)

    Berthelot, Romain; Schmidt, Whitney; 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)

    2012-12-15

    Three complete solid solutions between the layered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) have been prepared by conventional solid state method and investigated through X-ray diffraction, magnetism and optical measurements. All compositions are characterized by a M{sup 2+}/X{sup 6+} honeycomb ordering within the slabs and crystallize in a hexagonal unit cell. However, a structural transition based on a different stacking is observed as nickel (space group P6{sub 3}/mcm) is substituted by zinc or cobalt (space group P6{sub 3}22). All compositions exhibit a paramagnetic Curie-Weiss behavior at high temperatures; and the magnetic moment values confirm the presence of Ni{sup 2+} and/or Co{sup 2+} cations. The low-temperature antiferromagnetic order of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. The color of the obtained compositions varies from pink, to light green and white when M=Co, Ni, Zn, respectively. - Graphical abstract: The comparison between the structure of Na{sub 2}Ni{sub 2}TeO{sub 6} (left) and Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Zn) (right) evidences the stacking difference with distinct atom sequences along the hexagonal c-axis. Highlights: Black-Right-Pointing-Pointer Solid solutions between lamellar phases Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) are investigated. Black-Right-Pointing-Pointer A M{sup 2+}/X{sup 6+} honeycomb ordering characterized all the compositions. Black-Right-Pointing-Pointer A structural transition is shown when Ni is replaced by Co or Zn. Black-Right-Pointing-Pointer The low-temperature AFM ordering of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. Black-Right-Pointing-Pointer Color changes from pink to light green and white when M=Co, Ni, Zn, respectively.

  17. Solid state reactions of MoO3 and Na2MoO4 with (U.85,Ce.15)O2x

    International Nuclear Information System (INIS)

    Dahale, N.D.; Keskar, Meera; Singh Mudher, K.D.; Chawla, K.L.

    1999-01-01

    (U .85 ,Ce .15 )MoO 6-x was prepared by the solid state reactions of (U .85 ,Ce .15 )O 2±x with MoO 3 in air at 600 deg C. Solid state reactions of Na 2 MoO 4 with (U .85 ,Ce .15 )MoO 6.x up to 550 deg C in air led to the formation of Na 2 (U .85 ,Ce .15 )Mo 2 O 10-x and Na 2 (U .85 , Ce .15 ) 2 Mo 3 O 16-x . These compounds were characterised by x-ray and thermal methods. The x-ray powder data of (U .85 , Ce .15 ) MoO 6-x were indexed on monoclinic system whereas, data of Na 2 (U .85 ,Ce .15 ) Mo 2 O 10-x and Na 2 (U .85 ,Ce .15 ) 2 Mo 3 O 16-x were indexed on orthorhombic and monoclinic system respectively. (author)

  18. Raman, dielectric and variable range hopping nature of Gd2O3-doped K0.5N0.5NbO3 piezoelectric ceramics

    Directory of Open Access Journals (Sweden)

    Mahesh Peddigari

    2015-10-01

    Full Text Available (K0.5Na0.5NbO3 (KNN + x wt% Gd2O3 (x = 0 -1.5 ceramics have been prepared by conventional solid state reaction method. The effect of Gd2O3 on the structural, microstructural and dielectric properties of KNN ceramics were studied systematically. The effect of Gd2O3 on phase transformation from orthorhombic to psuedocubic structure is explained interms of changes in the internal vibration modes of NbO6 octahedra. The Raman intensity of the stretching mode v1 enhanced and shifted toward higher wavenumber with Gd2O3 concentration, which is attributed to the increase in polarizability and change in the O-Nb-O bond angles. Microstructural analysis revealed that the grain size of the KNN ceramics decreases from 2.26 ± 1.07 μm to 0.35 ± 0.13 μm and becomes homogenous with an increase in Gd2O3 concentration. The frequency dependent dielectric spectra are analyzed by using Havriliak-Negami function. The fitted symmetry parameter and relaxation time (τ are found to be 0.914 and 8.78 × 10−10 ± 5.5 × 10−11 s, respectively for the sample doped with x = 1.0. The addition of Gd2O3 to the KNN shifted the polymorphic phase transition orthorhombic to tetragonal transition temperature (TO-T from 199oC to 85oC with enhanced dielectric permittivity (ε′ = 1139 at 1 MHz. The sample with x = 1.0, shown a high dielectric permittivity (ε′ = 879 and low dielectric loss (<5% in the broad temperature range (-140oC – 150oC with the Curie temperature 307 oC can have the potential for high temperature piezoelectric and tunable RF circuit applications. The temperature dependent AC-conductivity follows the variable range hopping conduction mechanism by obtaining the slope -0.25 from the ln[ln(ρac] versus ln(T graph in the temperature range of 133 K-308 K. The effect of Gd2O3 on the Mott’s parameters such as density of states (N(EF, hopping length (RH, and hopping energy (WH have been discussed.

  19. Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

    Science.gov (United States)

    Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

    2015-01-01

    For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

  20. Leaching behavior of gamma-emitting fission products and Np from neutron-irradiated UO_2-ZrO_2 solid solutions in non-filtered surface seawater

    International Nuclear Information System (INIS)

    Sasaki, Takayuki; Takeno, Yuu; Kobayashi, Taishi; Kirishima, Akira; Sato, Nobuaki

    2016-01-01

    The gamma ray radionuclides Cs-137, Ba-140, I-131, Ce-141, Ru-103, Zr-95, and Np-239 were produced by neutron irradiation of UO_2-ZrO_2 solid solutions that were synthesized as simulated fuel debris under reducing and oxidizing conditions. The leaching ratio of radionuclides was investigated under atmospheric conditions at 25°C for non-filtered natural surface seawater, as well as deionized water after filtration with a membrane of 0.45-μm pore size or that of nominal molecular weight limit of 3 kDa. The uranium molar concentration was affected by the oxidation state in the solid solution samples. The congruent dissolution of Cs, I, and Ba with the hexavalent uranium of U_3O_8 was facilitated in the seawater samples, whereas a lower leaching ratio of nuclides was observed in the deionized water samples. Neptunium-239, originally produced from uranium-238 in U_3O_8, showed behavior that was similar to that of Cs, I, and Ba. However, the dissolution of Np (as a parent nuclide of Pu-239) in the debris of UO_2 and UO_2-ZrO_2 was suppressed in the same manner as Zr(IV) and Ce(IV). The concentration exhibited no filtration dependence after 15 d, which shows that most of the leached nuclides can exist in their ionic form in seawater. (author)

  1. Layered P2-Na 2/3 Co 1/2 Ti 1/2 O 2 as a high-performance cathode material for sodium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Sabi, Noha; Doubaji, Siham; Hashimoto, Kazuki; Komaba, Shinichi; Amine, Khalil; Solhy, Abderrahim; Manoun, Bouchaib; Bilal, Essaid; Saadoune, Ismael

    2017-02-01

    Layered oxides are regarded as promising cathode materials for sodium-ion batteries. We present Na2/3Co1/2Ti1/2O2 as a potential new cathode material for sodium-ion batteries. The crystal features and morphology of the pristine powder were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The cathode material is evaluated in galvanostatic charge-discharge and galvanostatic intermittent titration tests, as well as ex-situ X-ray diffraction analysis. Synthesized by a high-temperature solid state reaction, Na2/3Co1/2Ti1/2O2 crystallizes in P2-type structure with P6(3)/mmc space group. The material presents reversible electrochemical behavior and delivers a specific discharge capacity of 100 mAh g(-1) when tested in Na half cells between 2.0 and 4.2 V (vs. Na+/Na), with capacity retention of 98% after 50 cycles. Furthermore, the electrochemical cycling of this titanium-containing material evidenced a reduction of the potential jumps recorded in the NaxCoO2 parent phase, revealing a positive impact of Ti substitution for Co. The ex-situ XRD measurements confirmed the reversibility and stability of the material. No structural changes were observed in the XRD patterns, and the P2-type structure was stable during the charge/discharge process between 2.0 and 4.2 V vs. Na+/Na. These outcomes will contribute to the progress of developing low cost electrode materials for sodium-ion batteries. (C) 2017 Elsevier B.V. All rights reserved.

  2. Solution growth of Tb doped Gd_2O_3 film

    International Nuclear Information System (INIS)

    Ghosh, M.; Pitale, S.; Desai, D.G.; Patra, G.D.; Sen, S.; Gadkari, S.C.

    2016-01-01

    Nanomaterials of Gd_2O_3 have proven applications in medical imaging and cancer therapy due to the presence of element Gd. Also Gd_2O_3 films have been grown by vapor phase method as well as self assembly in solution and studied as a high-k dielectric and efficient luminescence material. Here, we report a method to obtain Tb doped Gd_2O_3 film by solution growth method followed by suitable heat treatment. Uniform films of Tb doped Gadolinium hydroxycarbonate have been deposited on fused quartz substrates kept inside a solution containing gadolinium nitrate, terbium nitrate and Urea maintained at 90°C. Gadolinium hydroxy-carbonate films are then treated at 800°C for 2 hour to obtain Tb doped cubic Gd_2O_3 as confirmed by X-ray diffraction measurement. The photoluminescence spectra display characteristic Tb emission at 544 nm when excited at 285 nm. The lifetime of Tb emission is found to be of the order of few microseconds. (author)

  3. The Osmium(VIII) Oxofluoro Cations OsO(2)F(3)(+) and F(cis-OsO(2)F(3))(2)(+): Syntheses, Characterization by (19)F NMR Spectroscopy and Raman Spectroscopy, X-ray Crystal Structure of F(cis-OsO(2)F(3))(2)(+)Sb(2)F(11)(-), and Density Functional Theory Calculations of OsO(2)F(3)(+), ReO(2)F(3), and F(cis-OsO(2)F(3))(2)(+).

    Science.gov (United States)

    Casteel, William J.; Dixon, David A.; Mercier, Hélène P. A.; Schrobilgen, Gary J.

    1996-07-17

    Osmium dioxide tetrafluoride, cis-OsO(2)F(4), reacts with the strong fluoride ion acceptors AsF(5) and SbF(5) in anhydrous HF and SbF(5) solutions to form orange salts. Raman spectra are consistent with the formation of the fluorine-bridged diosmium cation F(cis-OsO(2)F(3))(2)(+), as the AsF(6)(-) and Sb(2)F(11)(-) salts, respectively. The (19)F NMR spectra of the salts in HF solution are exchange-averaged singlets occurring at higher frequency than those of the fluorine environments of cis-OsO(2)F(4). The F(cis-OsO(2)F(3))(2)(+)Sb(2)F(11)(-) salt crystallizes in the orthorhombic space group Imma. At -107 degrees C, a = 12.838(3) Å, b = 10.667(2) Å, c = 11.323(2) Å, V = 1550.7(8) Å(3), and Z = 4. Refinement converged with R = 0.0469 [R(w) = 0.0500]. The crystal structure consists of discrete fluorine-bridged F(cis-OsO(2)F(3))(2)(+) and Sb(2)F(11)(-) ions in which the fluorine bridge of the F(cis-OsO(2)F(3))(2)(+) cation is trans to an oxygen atom (Os-O 1.676 Å) of each OsO(2)F(3) group. The angle at the bridge is 155.2(8) degrees with a bridging Os---F(b) distance of 2.086(3) Å. Two terminal fluorine atoms (Os-F 1.821 Å) are cis to the two oxygen atoms (Os-O 1.750 Å), and two terminal fluorine atoms of the OsO(2)F(3) group are trans to one another (1.813 Å). The OsO(2)F(3)(+) cation was characterized by (19)F NMR and by Raman spectroscopy in neat SbF(5) solution but was not isolable in the solid state. The NMR and Raman spectroscopic findings are consistent with a trigonal bipyramidal cation in which the oxygen atoms and a fluorine atom occupy the equatorial plane and two fluorine atoms are in axial positions. Density functional theory calculations show that the crystallographic structure of F(cis-OsO(2)F(3))(2)(+) is the energy-minimized structure and the energy-minimized structures of the OsO(2)F(3)(+) cation and ReO(2)F(3) are trigonal bipyramidal having C(2)(v)() point symmetry. Attempts to prepare the OsOF(5)(+) cation by oxidative fluorination of cis-OsO

  4. Microwave dielectric properties of CaCu{sub 3}Ti{sub 4}O{sub 12}-Al{sub 2}O{sub 3} composite

    Energy Technology Data Exchange (ETDEWEB)

    Rahman, Mohd Fariz Ab; Abu, Mohamad Johari; Zaman, Rosyaini Afindi; Ahmad, Zainal Arifin [School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Karim, Saniah Ab; Mohamed, Julie Juliewatty, E-mail: juliewatty.m@umk.edu.my [Advance Materials Research Cluster, Faculty of Earth Sciences, Universiti Malaysia Kelantan, Jeli Campus, 17600 Jeli, Kelantan (Malaysia); Ain, Mohd Fadzil [School of Electrical and Electronic Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

    2016-07-19

    (1-x)CaCu{sub 3}Ti{sub 4}O{sub 12} + (x)Al{sub 2}O{sub 3} composite (0 ≤ x ≤0.25) was prepared via conventional solid-state reaction method. The fabrication of sample was started with synthesizing stoichiometric CCTO from CaCO{sub 3}, CuO and TiO{sub 2} powders, then wet-mixed in deionized water for 24 h. The process was continued with calcined CCTO powder at 900 °C for 12 h before sintered at 1040 °C for 10 h. Next, the calcined CCTO powder with different amount of Al{sub 2}O{sub 3} were mixed for 24 h, then palletized and sintered at 1040 °C for 10. X-ray diffraction analysis on the sintered samples showed that CCTO powder was in a single phase, meanwhile the trace of secondary peaks which belong to CaAl{sub 2}O{sub 4} and Corundum (Al{sub 2}O{sub 3}) could be observed in the other samples Scanning electron microscopy analysis showed that the grain size of the sample is firstly increased with addition of Al{sub 2}O{sub 3} (x = 0.01), then become smaller with the x > 0.01. Microwave dielectric properties showed that the addition of Al{sub 2}O{sub 3} (x = 0.01) was remarkably reduced the dielectric loss while slightly increased the dielectric permittivity. However, further addition of Al{sub 2}O{sub 3} was reduced both dielectric loss and permittivity at least for an order of magnitude.

  5. Assembly of cerium(III)-stabilized polyoxotungstate nanoclusters with SeO{sub 3}{sup 2-}/TeO{sub 3}{sup 2-} templates. From single polyoxoanions to inorganic hollow spheres in dilute solution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Chao; Wang, Xin-Long; Shao, Kui-Zhan; Su, Zhong-Min; Wang, En-Bo [Institute of Functional Materials Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun (China); Li, Hao-Long [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University. Changchun (China)

    2013-08-12

    A versatile one-pot strategy was employed to synthesize three cerium(III)-stabilized polyoxotungstates nanoclusters by combining cerium linkers and SeO{sub 3}{sup 2-}/TeO{sub 3}{sup 2-} heteroanion templates: K{sub 32}Na{sub 16}[{(XO_3)W_1_0O_3_4}{sub 8}{Ce_8(H_2O)_2_0}(WO{sub 2}){sub 4}-(W{sub 4}O{sub 12})].n H{sub 2}O [X=Se, n=81 (1); X=Te, n=114 (2)] and K{sub 12}Na{sub 22}[{(SeO_3)W_1_0O_3_4}{sub 8}{Ce_8(H_2O)_2_0}(WO{sub 2}){sub 4}-{(W_4O_6)Ce_4(H_2O)_1_4(SeO_3)_4(NO_3)_2}] . 79 H{sub 2}O (3), which are the first lanthanide-containing polyoxotungstates with selenium or tellurium heteroatoms. The three clusters were characterized by single-crystal X-ray structure analysis, IR spectroscopy, thermogravimetric/differential thermal analysis, UV/Vis spectroscopy, ESI-MS, and X-ray photoelectron spectroscopy. Their electrochemical, photoluminescence, and magnetic properties were investigated. Their behavior in solution was studied by transmission electron microscopy, which showed that their single polyoxoanions assemble into intact, uniform-sized, purely inorganic hollow spheres in dilute water/acetone solution. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Interfacial reactions of Ba 2YCu 3O 6+z with coated conductor buffer layer, LaMnO 3

    Science.gov (United States)

    Liu, G.; Wong-Ng, W.; Kaduk, J. A.; Cook, L. P.

    2010-03-01

    Chemical interactions between the Ba 2YCu 3O 6+x superconductor and the LaMnO 3 buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba 2YCu 3O 6+x-LaMnO 3 system. The Ba 2YCu 3O 6+x-LaMnO 3 join within the BaO-(Y 2O 3-La 2O 3)-MnO 2-CuO x multi-component system is non-binary. At 810 °C ( pO2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba 2-x(La 1+x-yY y)Cu 3O 6+z, Ba(Y 2-xLa x)CuO 5, (La 1-xY x)MnO 3, (La,Y)Mn 2O 5. The crystal chemistry and crystallography of Ba(Y 2-xLa x)CuO 5 and (La 1-xY x)Mn 2O 5 were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y 2-xLa x)CuO 5 are Ba(Y 1.8La 0.2)CuO 5 and Ba(Y 0.1La 1.9)CuO 5, respectively. The structure of Ba(Y 1.8La 0.2)CuO 5 is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å 3, and D x = 6.29 g cm -3. YMn 2O 5 and LaMn 2O 5 do not form solid solution at 810 °C ( pO2 = 100 Pa) or at 950 °C (in air). The structure of YMn 2O 5 was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å 3. A reference X-ray pattern was prepared for YMn 2O 5.

  7. Host composition dependent tunable multicolor emission in the single-phase Ba2(Ln(1-z)Tb(z))(BO3)2Cl:Eu phosphors.

    Science.gov (United States)

    Xia, Zhiguo; Zhuang, Jiaqing; Meijerink, Andries; Jing, Xiping

    2013-05-14

    A new strategy based on the host composition design has been adopted to obtain efficient color-tunable emission from Ba2Ln(0.97-z)Tb(z)(BO3)2Cl:0.03Eu (Ln = Y, Gd and Lu, z = 0-0.97) phosphors. This study reveals that the single-phase Ba2Ln(1-z)Tb(z)(BO3)2Cl compounds can be applied to use allowed Eu(2+) absorption transitions to sensitize Eu(3+) emission via the energy transfer Eu(2+) → (Tb(3+))n → Eu(3+). The powder X-ray diffraction (XRD) and Rietveld refinement analysis shows single-phase Ba2Ln(1-z)Tb(z)(BO3)2Cl. As-prepared Ba2Ln(0.97-z)Tb(z)(BO3)2Cl:0.03Eu phosphors show intense green, yellow, orange and red emission under 377 nm near ultraviolet (n-UV) excitation due to a variation in the relative intensities of the Eu(2+), Tb(3+) and Eu(3+) emission depending on the Tb content (z) in the host composition, allowing color tuning. The variation in emission color is explained by energy transfer and has been investigated by photoluminescence and lifetime measurements and is further characterized by the Commission Internationale de l'éclairage (CIE) chromaticity indexes. The quantum efficiencies of the phosphors are high, up to 74%, and show good thermal stabilities up to 150 °C. This investigation demonstrates the possibility to sensitize Eu(3+) line emission by Eu(2+)via energy migration over Tb(3+) resulting in efficient color tunable phosphors which are promising for use in solid-state white light-emitting diodes (w-LEDs).

  8. Atomic-Scale Structure of Al2O3-ZrO2 Mixed Oxides Prepared by Laser Ablation

    International Nuclear Information System (INIS)

    Yang Xiuchun; Dubiel, M.; Hofmeister, H.; Riehemann, W.

    2007-01-01

    By means of x-ray diffractometry (XRD) and X-ray absorption fine structure spectroscopy, the phase composition and atomic structure of laser evaporated ZrO2 and ZrO2-Al2O3 nanopowders have been studied. The results indicate that pure ZrO2 exists in the form of tetragonal structure, Al2O3 doped ZrO2 nanoparticles, however, have cubic structure. Compared to bulk tetragonal ZrO2, pure tetragonal ZrO2 nanoparticles have a shorter Zr-O- and Zr-Zr shell, indicating that the lattice contracts with decreasing particle size. For Al2O3 doped ZrO2 solid solution, the distances of first Zr-O and Zr-Zr (Al) coordination decrease with increasing solid solubility. The disorder degree of the ZrO2 lattice increases with increasing solid solubility. The coevaporated ZrO2-Al2O3 is quickly solidified into amorphous phase when it is ablated in a higher pressure. The amorphous phase contains Zr-O-Zr (Al) clusters and has shorter Zr-O distance and tower Zr-O coordination number

  9. 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.

  10. Synthesis of nano-scale fast ion conducting cubic Li7La3Zr2O12.

    Science.gov (United States)

    Sakamoto, Jeff; Rangasamy, Ezhiylmurugan; Kim, Hyunjoung; Kim, Yunsung; Wolfenstine, Jeff

    2013-10-25

    A solution-based process was investigated for synthesizing cubic Li7La3Zr2O12 (LLZO), which is known to exhibit the unprecedented combination of fast ionic conductivity, and stability in air and against Li. Sol-gel chemistry was developed to prepare solid metal-oxide networks consisting of 10 nm cross-links that formed the cubic LLZO phase at 600 ° C. Sol-gel LLZO powders were sintered into 96% dense pellets using an induction hot press that applied pressure while heating. After sintering, the average LLZO grain size was 260 nm, which is 13 times smaller compared to LLZO prepared using a solid-state technique. The total ionic conductivity was 0.4 mS cm(-1) at 298 K, which is the same as solid-state synthesized LLZO. Interestingly, despite the same room temperature conductivity, the sol-gel LLZO total activation energy is 0.41 eV, which 1.6 times higher than that observed in solid-state LLZO (0.26 eV). We believe the nano-scale grain boundaries give rise to unique transport phenomena that are more sensitive to temperature when compared to the conventional solid-state LLZO.

  11. Predictable self-assembled [2×2] Ln(III)4 square grids (Ln = Dy,Tb)-SMM behaviour in a new lanthanide cluster motif.

    Science.gov (United States)

    Anwar, Muhammad Usman; Thompson, Laurence Kenneth; Dawe, Louise Nicole; Habib, Fatemah; Murugesu, Muralee

    2012-05-14

    The ditopic carbohydrazone ligand (L1) produces the square, self-assembled [2×2] grids [Dy(4)(L1)(4)(OH)(4)]Cl(2) (1) and [Ln(4)(L1)(4)(μ(4)-O)(μ(2)-1,1-N(3))(4)] (Ln = Dy (2), Tb (3)), with 2 exhibiting SMM behaviour. Two relaxation processes occur with U(eff) = 51 K, 91 K in the absence of an external field, and one with U(eff) = 270 K in the presence of a 1600 Oe optimum field. This journal is © The Royal Society of Chemistry 2012

  12. In situ formation of CA6 platelets in Al2O3 and Al2O3/ZrO2 matrices

    OpenAIRE

    Belmonte , M.; SÁnchez-Herencia , A.; Moreno , R.; Miranzo , P.; Moya , J.; Tomsia , A.

    1993-01-01

    Al2O3 and Al2O3/ZrO2 compacts containing CaO as a dopant have been sintered under different conditions and atmospheres: air, high vacuum (> 10-6torr). SEM observations have been made on the polished surfaces of sintered and also of annealed samples. Only after the annealing treatment in air at temperatures ranging from 1400° to 1 500°C, a massive formation of CA6 platelets was detected in samples sintered in low oxygen partial pressure atmospheres.ln order to clarify the mechanism of formatio...

  13. Hydrothermal-precipitation preparation of CdS@(Er3+:Y3Al5O12/ZrO2) coated composite and sonocatalytic degradation of caffeine.

    Science.gov (United States)

    Huang, Yingying; Wang, Guowei; Zhang, Hongbo; Li, Guanshu; Fang, Dawei; Wang, Jun; Song, Youtao

    2017-07-01

    Here, we reported a novel method to dispose caffeine by means of ultrasound irradiation combinated with CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) coated composite as sonocatalyst. The CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) was synthesized via hydrothermal-precipitation method and then characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and UV-vis diffuse reflectance spectra (DRS). After that, the sonocatalytic degradation of caffeine in aqueous solution was conducted adopting CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) and CdS@ZrO 2 coated composites as sonocatalysts. In addition, some influencing factors such as CdS and ZrO 2 molar proportion, caffeine concentration, ultrasonic irradiation time, sonocatalyst dosage and addition of several inorganic oxidants on sonocatalytic degradation of caffeine were investigated by using UV-vis spectra and gas chromatograph. The experimental results showed that the presence of Er 3+ :Y 3 Al 5 O 12 could effectively improve the sonocatalytic degradation activity of CdS@ZrO 2 . To a certain extent some inorganic oxidants can also enhance sonocatalytic degradation of caffeine in the presence of CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ). The best sonocatalytic degradation ratio (94.00%) of caffeine could be obtained when the conditions of 5.00mg/L caffeine, 1.00g/L prepared CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ), 10.00mmol/LK 2 S 2 O 8 , 180min ultrasonic irradiation (40kHz frequency and 50W output power), 100mL total volume and 25-28°C temperature were adopted. It seems that the method of sonocatalytic degradation caused by CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) displayspotentialadvantages in disposing caffeine. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Solid-State Synthesis and Structure of the Enigmatic Ammonium Octaborate: (NH4)2[B7O9(OH)5]·3/4B(OH)3·5/4H2O.

    Science.gov (United States)

    Neiner, Doinita; Sevryugina, Yulia V; Schubert, David M

    2016-09-06

    The compound known since the 19th century as ammonium octaborate was structurally characterized revealing the ammonium salt of the ribbon isomer of the heptaborate anion, [B7O9(OH)5](2-), with boric acid and water molecules. Of composition (NH4)2B7.75O12.63·4.88H2O, it approximates the classical ammonium octaborate composition (NH4)2B8O13·6H2O and has the structural formula {(NH4)2[B7O9(OH)5]}4·3B(OH)3·5H2O. It spontaneously forms at room temperature in solid-state mixtures of ammonium tetraborate and ammonium pentaborate. It crystallizes in the monoclinic space group P21/c with a = 11.4137(2) Å, b = 11.8877(2) Å, c = 23.4459(3) Å, β = 90.092(1)°, V = 3181.19(8) Å(3), and Z = 2 and contains well-ordered ammonium cations and [B7O9(OH)5](2-) anions and disordered B(OH)3 and H2O molecules linked by extensive H bonding. Expeditious solid-state formation of the heptaborate anion under ambient conditions has important implications for development of practical syntheses of industrially useful borates.

  15. A novel broadband emission phosphor Ca2KMg2V3O12 for white light emitting diodes

    International Nuclear Information System (INIS)

    Li, Junfu; Qiu, Kehui; Li, Junfeng; Li, Wei; Yang, Qian; Li, Junhan

    2010-01-01

    A novel broadband emission phosphor Ca 2 KMg 2 V 3 O 12 was first synthesized by solution combustion method. The X-ray diffraction showed that Ca 2 KMg 2 V 3 O 12 phase can be obtained at 600-900 o C through combustion route. The crystal structure of this material was refined by Rietveld method using powder X-ray diffraction. It crystallizes in cubic system and belongs to space group Ia3d with z = 8, a = 0.12500 nm. The excitation band of Ca 2 KMg 2 V 3 O 12 peaks at 320 nm in a region between 260 nm and 425 nm, and the emission spectrum exhibits an intense band centered at about 528 nm covering from 400 nm to 800 nm. The colour coordinates of samples prepared at different ignition temperatures are in a range of x = 0.323-0.339, y = 0.430-0.447.

  16. Controllable growth and photocatalytic activity of Cu{sub 2}O solid microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Hong; Zhang, Junying, E-mail: zjy@buaa.edu.cn; Wang, Mei

    2013-09-01

    Graphical abstract: - Highlights: • 3 μm uniform Cu{sub 2}O solid microspheres with abundant nanopores are achieved. • NH{sub 2}OH·HCl and SDS are main factors that manipulate morphologies of Cu{sub 2}O particles. • Surface features of microspheres influenced the photocatalytic activity of Cu{sub 2}O. • Microspheres are transforming to polyhedrons with extended holding time. - Abstract: A series of Cu{sub 2}O solid microspheres with different surface features were prepared and their photocatalytic activities were studied. The experiment conditions were investigated and the formation mechanism was explored systematically. It was found that varying the amounts of NH{sub 2}OH·HCl reductant in alkaline solutions changed the reaction process and thus altered the surface features of Cu{sub 2}O microspheres. Sodium dodecyl sulfate (SDS) surfactant, introduced as a morphology directing agent, caused the nuclei aggregation and growth process of Cu{sub 2}O solid microspheres by precisely realizing the opposite charges’ directional attraction. This SDS-mediated method can be readily extended to synthesizing solid microspheres of other metal oxides. Meanwhile, it was found that Cu{sub 2}O solid microspheres with abundant nanopores on the surface showed much higher efficient catalytic activity for decoloring methyl orange (MO) aqueous solution than with other surface features under visible light irradiation. Furthermore, we found that prolonging the holding time made Cu{sub 2}O microspheres transform to polyhedrons.

  17. Determination of 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in soy sauce by headspace derivatization solid-phase microextraction combined with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Lee, Maw-Rong; Chiu, Tzu-Chun; Dou, Jianpeng

    2007-05-22

    This study proposes a method for identifying 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in aqueous matrices by using headspace on-fiber derivatization following solid-phase microextraction combined with gas chromatography-mass spectrometry. The optimized SPME experimental procedures for extracting 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in aqueous solutions involved a 85 microm polyacrylate-coated fiber at pH 6, a sodium chloride concentration of 0.36 g mL(-1), extraction at 50 degrees C for 15 min and desorption of analytes at 260 degrees C for 3 min. Headspace derivatization was conducted in a laboratory-made design with N-methyl-N-(trimethylsilyl)-trifluoroacetamide vapor following solid-phase microextraction by using 3 microL N-methyl-N-(trimethylsilyl)-trifluoroacetamide at an oil bath temperature of 230 degrees C for 40 s. This method had good repeatability (R.S.D.s or = 0.9972) for ultrapure water and soy sauce samples that were spiked with two analytes. Detection limits were obtained at the ng mL(-1). The result demonstrated that headspace on-fiber derivatization following solid-phase microextraction was a simple, fast and accurate technique for identifying trace 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in soy sauce.

  18. Crystal structures of the solid solutions Na3Zn0.912Cd0.088B5O10 and Na3Zn0.845Mg0.155B5O10

    Directory of Open Access Journals (Sweden)

    Xue-An Chen

    2017-11-01

    Full Text Available Two new pentaborates, trisodium zinc cadmium pentaborate, Na3Zn0.912Cd0.088B5O10, and trisodium zinc magnesium pentaborate, Na3Zn0.845Mg0.155B5O10, have been synthesized by high-temperature solution reactions at 1023 K. Their crystal structures were determined by single-crystal X-ray diffraction. Both solid solutions crystallize in the orthorhombic form of the parent compound Na3ZnB5O10 (space group type Pbca, Z = 8 and contain the double ring [B5O10]5− anion composed of one BO4 tetrahedron and four BO3 triangles as the basic structural motif. The anions are bridged by tetrahedrally coordinated and occupationally disordered M2+ (M = Zn/Cd, Zn/Mg cations via common O atoms to form [MB5O10]n3n− layers. The intralayer intersecting channels and the interlayer voids are occupied by Na+ cations to balance the charge.

  19. Note: High-power piezoelectric transformer fabricated with ternary relaxor ferroelectric Pb(Mg(1/3)Nb(2/3))O3-Pb(In(1/2)Nb(1/2))O3-PbTiO3 single crystal.

    Science.gov (United States)

    Wang, Qing; Ma, Chuanguo; Wang, Feifei; Liu, Bao; Chen, Jianwei; Luo, Haosu; Wang, Tao; Shi, Wangzhou

    2016-03-01

    A plate-shaped piezoelectric transformer was designed and fabricated using ternary relaxor ferroelectric single crystal Pb(Mg(1/3)Nb(2/3))O3-Pb(In(1/2)Nb(1/2))O3-PbTiO3. Both the input and output sections utilized the transverse-extensional vibration mode. The frequency and load dependences of the electrical properties for the proposed transformer were systematically studied. Results indicated that under a matching load resistance of 14.9 kΩ, a maximum output power of 2.56 W was obtained with the temperature rise less than 5 °C. The corresponding power density reached up to 50 W/cm(3). This ternary single-crystal transformer had potential applications in compact-size converters requiring high power density.

  20. Possibility of adjusting the photoluminescence spectrum of Ca scheelites to the emission spectrum of incandescent lamps: [ nCaWO4-(1- n)CaMoO4]: Eu3+ solid solutions

    Science.gov (United States)

    Bakovets, V. V.; Zolotova, E. S.; Antonova, O. V.; Korol'kov, I. V.; Yushina, I. V.

    2016-12-01

    The specific features of the photoluminescence of [ nCaWO4-(1- n)CaMoO4]:Eu3+ solid solutions with the scheelite structure are examined using X-ray phase analysis and photoluminescence, Raman scattering, and diffuse reflectance spectroscopy. The studied features are associated with a change in the long- and short-range orders of the crystal lattice upon variations in the composition of solutions in the range n = 0-1.0 (with a pitch of 0.2) at a concentration of red photoluminescence activator Eu3+ of 2 mol %. The mechanism of the modification of photoluminescence of solid solutions upon variations in their composition has been discussed. Anomalies in the variations in parameters of the crystal lattice, its short-range order, and luminescence spectra have been observed in the transition from pure compounds CaMoO4:Eu3+ and CaWO4:Eu3+ to solutions; the concentration of Eu3+ ions in the centrosymmetric localization increases (decreases) in the transition from the molybdate (tungstate). It has been demonstrated that the spectral radiant emittance of solid solution [0.4CaWO4-0.6CaMoO4]:Eu3+ (2 mol %) is the closest to that of an incandescent lamp.

  1. Infrared reflectivity of the solid solutions LaNi1-xFexO3 (0.00≤x≤1.00)

    International Nuclear Information System (INIS)

    Massa, N.E.; Falcon, H.; Salva, H.; Carbonio, R.E.

    1997-01-01

    We report temperature-dependent far- and midinfrared reflectivity spectra of LaNi (1-x) Fe x O 3 solid solutions that span the passage from LaFeO 3 , a room-temperature antiferromagnetic insulator, to LaNiO 3 , a known metal oxide. Light Ni doping creates defects that induce extra bands assigned to electronic transitions within the insulating gap. An incipient Drude term emerges in the reflectivity spectrum of LaNi 0.39 Fe 0.61 O 3 together with subbands that contribute to the electronic background. At these concentrations the dielectric response shows a picture in which the spectral weigh switches over toward far-infrared frequencies while phonon features develop strong antiresonances near longitudinal-optical modes. Further increment of carriers produces phonon screening and the development of a reflectivity tail that extends beyond 1 eV. We assign extra-non-Drude terms in the 700 endash 4000cm -1 frequency region to transitions due to intrinsic defects. While the increment in reflectivity at far-infrared frequencies is evident for Fe concentrations well above the insulator-metal transition (x∼0.30), the spectral features of a metal oxide, with phonons mostly screened, are found for x=0.23. These metallic spectra show an absorption dip at ∼650cm -1 that is traced to the perovskite symmetric stretching longitudinal mode. Electron-phonon interactions are thus present in solid solutions even when the numbers of effective carriers are those of a metal. This characterization is also supported by the observation of weak reflectivity dips in LaNiO 3 that have a direct correspondence to longitudinal-optical mode frequencies of the insulating phases of our series. We infer that strong electron-phonon interactions play a role in the conductivity of those solid solutions and are likely related to polaron formation and carrier phonon-assisted hopping motion. (Abstract Truncated)

  2. The system HoCl3-YCl3-H2O (25 deg C)

    International Nuclear Information System (INIS)

    Sorokina, A.A.; Yudina, N.G.

    1981-01-01

    By solubility method the system HoCl 3 -YCl 3 -H 2 O at 25 deg C has been studied. It is shown that in this system the continuous serie of solid solutions is formed. The liquid solutions of this system have been investigated by the isopiestic method. The values of activity coefficients, activity, free energy formation and excess free energy of solid solutions are calculated [ru

  3. High-pressure investigations of lanthanoid oxoarsenates. I. Single crystals of scheelite-type Ln[AsO{sub 4}] phases with Ln = La-Nd from monazite-type precursors

    Energy Technology Data Exchange (ETDEWEB)

    Metzger, Sebastian J.; Ledderboge, Florian; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie; Heymann, Gunter; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

    2016-08-01

    Transparent single crystals of the scheelite-type Ln[AsO{sub 4}] phases with Ln = La-Nd are obtained by the pressure-induced monazite-to-scheelite type phase transition in a Walker-type module under high-pressure and high-temperature conditions of 11 GPa at 1100-1300 C. Coinciding with this transition, there is an increase in density and a reduction in molar volume of about 4.5 % for the scheelite-type phases (tetragonal, I4{sub 1}/a) for La[AsO{sub 4}] (a = 516.92(4), c = 1186.1(9) pm), Ce[AsO{sub 4}] (a = 514.60(1), c = 1175.44(2) pm), Pr[AsO{sub 4}] (a = 512.63(4), c = 1168.25(9) pm), and Nd[AsO{sub 4}] (a = 510.46(4), c = 1160.32(11) pm) as compared to the well-known monazite-type phases (monoclinic, P2{sub 1}/n). Surprisingly enough, the scheelite-type oxoarsenates(V) exhibit a lower coordination number for the Ln{sup 3+} cations (CN = 8 versus CN = 8 + 1), whereas the isolated tetrahedral [AsO{sub 4}]{sup 3-} anions (d(As-O) = 168.9-169.3 pm for the scheelites as compared to d(As-O) = 167.1-169.9 pm for the monazites) remain almost unchanged. So the densification must occur because of the loss of two edge-connections of the involved [LnO{sub 8+1}]{sup 15-} polyhedra with the [AsO{sub 4}]{sup 3-} tetrahedra in the monazite- resulting in exclusively vertex connected [LnO{sub 8}]{sup 13-} and [AsO{sub 4}]{sup 3-} units in the scheelite-type structure.

  4. Precipitation of Nd-Ca carbonate solid solution at 25 degrees C

    International Nuclear Information System (INIS)

    Carroll, S.A.

    1993-01-01

    The formation of a Nd-Ca carbonate solid solution was studied by monitoring the reactions of calcite with aqueous Nd, orthorhombic NdOHCO 3 (s) with aqueous Ca, and calcite with hexagonal Nd-carbonate solid phase as a function of time at 25 degrees C and controlled pCO 2 (g). All experiments reached steady state after 200 h of reaction. The dominant mechanism controlling the formation of the solid solution was precipitation of a Nd-Ca carbonate phase from the bulk solution as individual crystals or at the orthorhombic NdOHCO 3 (s)-solution interface. The lack of Nd adsorption or solid solution at the calcite-solution interface suggests that the solid solution was orthorhombic and may be modeled as a mixture of orthorhombic NdOHCO 3 (s) and aragonite. Orthorhombic NdOHCO 3 (s) was determined to be the stable Nd-carbonate phase in the Nd-CO 2 -H 2 O system at pCO 2 (g) 0.1 atmospheres at 25 degrees C. The equilibrium constant corrected to zero ionic strength for orthorhombic NdOHCO 3 (s) solubility is 10 10.41(±0.29) for the following: NdOHCO 3 (s) + 3H + = Nd 3+ + CO 2 (g) + H 2 O. Results are discussed in relation to radioactive waste disposal by burial, and specifically in relation to americium chemistry

  5. CO gas sensing properties of In_4Sn_3O_1_2 and TeO_2 composite nanoparticle sensors

    International Nuclear Information System (INIS)

    Mirzaei, Ali; Park, Sunghoon; Sun, Gun-Joo; Kheel, Hyejoon; Lee, Chongmu

    2016-01-01

    Highlights: • In4Sn3O12–TeO2 composite nanoparticles were synthesized via a facile hydrothermal route. • The response of the In4Sn3O12–TeO2 composite sensor to CO was stronger than the pristine In4Sn3O12 sensor. • The response of the In4Sn3O12–TeO2 composite sensor to CO was faster than the pristine In4Sn3O12 sensor. • The improved sensing performance of the In4Sn3O12–TeO2 nanocomposite sensor is discussed in detail. • The In4Sn3O12-based nanoparticle sensors showed selectivity to CO over NH3, HCHO and H2. - Abstract: A simple hydrothermal route was used to synthesize In_4Sn_3O_1_2 nanoparticles and In_4Sn_3O_1_2–TeO_2 composite nanoparticles, with In(C_2H_3O_2)_3, SnCl_4, and TeCl_4 as the starting materials. The structure and morphology of the synthesized nanoparticles were examined by X-ray diffraction and scanning electron microscopy (SEM), respectively. The gas-sensing properties of the pure and composite nanoparticles toward CO gas were examined at different concentrations (5–100 ppm) of CO gas at different temperatures (100–300 °C). SEM observation revealed that the composite nanoparticles had a uniform shape and size. The sensor based on the In_4Sn_3O_1_2–TeO_2 composite nanoparticles showed stronger response to CO than its pure In_4Sn_3O_1_2 counterpart. The response of the In_4Sn_3O_1_2–TeO_2 composite-nanoparticle sensor to 100 ppm of CO at 200 °C was 10.21, whereas the maximum response of the In_4Sn_3O_1_2 nanoparticle sensor was 2.78 under the same conditions. Furthermore, the response time of the composite sensor was 19.73 s under these conditions, which is less than one-third of that of the In_4Sn_3O_1_2 sensor. The improved sensing performance of the In_4Sn_3O_1_2–TeO_2 nanocomposite sensor is attributed to the enhanced modulation of the potential barrier height at the In_4Sn_3O_1_2–TeO_2 interface, the stronger oxygen adsorption of p-type TeO_2, and the formation of preferential adsorption sites.

  6. Crystallochemical features of solid solutions based on Ga/sub 2/3/Cr/sub 2/S/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Titov, V.V.; Kesler, Ya.A.; Gordeev, I.V.; Stupnikov, V.A.

    1988-04-01

    Ga/sub 2/3/Cr/sub 2/S/sub 4/ shows a rare type of phase transition where increases in temperature and pressure produce the disordered modification. A source of disordering can be isomorphous substitution in the tetrahedral sublattice. The authors therefore made and examined solid solutions of Ga/sub (2/3-2x/3)/M/sub x/(Cr/sub 2/)S/sub 4/ type, where M = Fe, Co, Ni, Cu. Specimens containing Fe and show a quasi-continuous solid-solution series, where the Fe system obeys Vegard's rule. Specimens containing nickel show a narrow ordering range. The most interesting results have been obtained for specimens containing copper. Cu/sub x/Ga/sub 2/3(1-x)/Cr/sub 2/S/sub 4/ specimens show a transition from a structure ordered on the tetrahedral positions, symmetry F/anti/43m, to the normal-spinel structure, Fd3m.

  7. Crystal structure and phase transition studies in perovskite-type oxides using powder-diffraction techniques and symmetry-mode analysis : SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) and ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm)

    OpenAIRE

    Iturbe Zabalo, Edurne

    2013-01-01

    La tesis se ha centrado en la síntesis y caracterización estructural de materiales tipo perovskita: SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) y ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm). El estudio de las estructuras de los materiales se ha realizado mediante el análisis de los patrones de difracción en polvo de rayos-X, sincrotrón y/o neutrones. En el refinamiento por el método de Rietveld de las estructuras se han sustituido las coordenadas atómicas (el método más común), por coordenadas colect...

  8. Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses for ∼1.2 μm laser applications

    Science.gov (United States)

    Wang, Shunbin; Li, Chengzhi; Yao, Chuanfei; Jia, Shijie; Jia, Zhixu; Qin, Guanshi; Qin, Weiping

    2017-02-01

    Intense ∼1.2 μm fluorescence is observed in Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses under 915 nm laser diode excitation. The 1.2 μm emission can be ascribed to the transition 5I6→5I8 of Ho3+. With the introducing of BaF2, the content of OH in the glasses drops markedly, and the 1.2 μm emission intensity increases gradually as increasing the concentration percentage of BaF2. Furthermore, microstructured fibers based on the TeO2-BaF2-Y2O3 glasses are fabricated by using a rod-in-tube method, and a relative positive gain of ∼9.42 dB at 1175.3 nm is obtained in a 5 cm long fiber.

  9. Thermoelectric properties of Bi2Te3-Bi2Se3 solid solutions prepared by attrition milling and hot pressing

    International Nuclear Information System (INIS)

    Lee, Go-Eun; Kim, Il-Ho; Choi, Soon-Mok; Lim, Young-Soo; Seo, Won-Seon; Park, Jae-Soung; Yang, Seung-Ho

    2014-01-01

    Bi 2 Te 3-y Se y (y = 0.15 - 0.6) solid solutions were prepared by attrition milling and hot pressing. The lattice constants decreased with increasing Se content, indicating that the Se atoms were successfully substituted into the Te sites. All specimens exhibited n-type conduction, and their electrical resistivities increased slightly with increasing temperature. With increasing Se content, the Seebeck coefficients increased while the thermal conductivity decreased due to the increase in phonon scattering. The maximum figure of merit obtained was 0.63 at 440 K for the undoped Bi 2 Te 2.4 Se 0.6 solid solution.

  10. Facile in-situ reduction: Crystal growth and magnetic studies of reduced vanadium (III/IV) silicates CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y)

    Science.gov (United States)

    Abeysinghe, Dileka; Smith, Mark D.; Morrison, Gregory; Yeon, Jeongho; zur Loye, Hans-Conrad

    2018-04-01

    A series of lanthanide containing mixed-valent vanadium (III/IV) silicates of the type CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y) was synthesized as high quality single crystals from a molten chloride eutectic flux, BaCl2/NaCl. Utilizing Ca metal as the reducing agent, an in-situ reduction of V5+ to V3+/4+ as well as of Ce4+ to Ce3+ was achieved. The structures of 14 reported isostructural compounds were determined by single crystal X-ray diffraction. They crystallize in the tilasite (CaMgAsO4F) structure type in the monoclinic space group C2/c. The extended structure contains 1D chains of VO6 octahedra that are connected to each other via SiO4 groups and (Ca/Ln)O7 polyhedra. The magnetic susceptibility and the field dependent magnetization data were measured for CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm, Gd-Lu, Y), and support the existence of antiferromagnetic behavior at low temperatures.

  11. Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

    Science.gov (United States)

    Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

    2005-08-31

    A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

  12. Relaxation electron excitations in Al2O3, Y3Al5O12 and YAlO3

    International Nuclear Information System (INIS)

    Kuznetsov, A.I.; Namozov, B.R.; Myurk, V.V.

    1985-01-01

    Excitation spectra of short-wave Al 2 O 3 , YAlO 3 and Y 3 Al 5 O 12 crystal luminescence, cathodoluminescence (including time resolution) and lay-temperature thermoluminescence are investigated. Analysis of experimental data permits to distingnish among these objects pairs of bands of supposedly characteristic luminescences: 7.5 and 3.8 eV (Al 2 O 3 ), 5.9 and 4.2 eV (YAlO 3 ), and 4.9 and 4.2 eV (Y 3 Al 5 O 12 ), where recombination luminescence is characteristic for long-wave ones, at that time exciton-like luminescence - for short-wave ones. A hypothesis about strong difference between states of an autolocalized exciton and ''autolocalized hole + electron'' (responsible for short-wave and long-wave bands of characteristic luminescence) is expressed; the difference is based on their genetic origin from different regions of a valent zone (in particular, long-wave bands - from the subzone of heavy holes of a valent zone ceiling, originating from nonbinding 2p-orbitals of oxygen)

  13. Chemical solution deposition of CaCu 3 Ti 4 O 12 thin film

    Indian Academy of Sciences (India)

    CaCu3Ti4O12 (CCTO) thin film was successfully deposited on boron doped silica substrate by chemical solution deposition and rapid thermal processing. The phase and microstructure of the deposited films were studied as a function of sintering temperature, employing X-ray diffractometry and scanning electron ...

  14. Thermal expansion studies on uranium-neodymium mixed oxide solid solutions

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Venkata Krishnan, R.; Antony, M.P.; Nagarajan, K.

    2012-01-01

    Uranium-Neodymium mixed oxides solid solutions (U 1-y Nd y ) O 2 (y=0.2-0.95) were prepared by combustion synthesis using citric acid as fuel. Structural characterization and computation of lattice parameter was carried out from room temperature X-ray diffraction measurements. Single-phase fluorite structure was observed up to y=0.80. For solid solutions with y>0.80 additional Nd 2 O 3 lines were visible

  15. Liquid-Solid-Solution Assembly of CoFe2O4/Graphene Nanocomposite as a High-Performance Lithium-Ion Battery Anode

    International Nuclear Information System (INIS)

    Zhu, Yanfang; Lv, Xingbin; Zhang, Lili; Guo, Xiaodong; Liu, Daijun; Chen, Jianjun; Ji, Junyi

    2016-01-01

    Graphical abstract: CoFe 2 O 4 /rGO composites are fabricated via a liquid-solid-solution assemble strategy with a well controlled CoFe 2 O 4 size, the composite exhibits a high rate performance for lithium ion batteries anode. - Highlights: • Crumpled CoFe 2 O 4 @graphene composite with uniform CoFe 2 O 4 nanoparticles intimately anchored on graphene sheets was fabricated. • The novel fabrication strategy: liquid-solid-solution strategy where the CoFe 2 O 4 are nucleation and controlled growth at the oil/water interface. • High reversible specific capacity of 1102 mAh g −1 after 100 cycles and high rate capability of 410 mAh g −1 within 230 s charging. - Abstract: CoFe 2 O 4 /graphene composites were fabricated via a novel one-pot liquid-solid-solution (LSS) hydrothermal process. Through ions electrostatic adsorption onto graphene sheets and oil microemulsion encapsulation, CoFe 2 O 4 nanoparticles can be uniformly anchored on crumpled graphene sheets without aggregation, and the size distribution of CoFe 2 O 4 particles can be controlled by the microemulsion shell in the range of 50–100 nm. With the synergistic effect between CoFe 2 O 4 and graphene, the CoFe 2 O 4 /graphene hybrid exhibits a high reversible specific capacity of 1102 mAh g −1 at 0.2 A g −1 after 100 cycles, and a good cycling stability as well. Moreover, the composite has good rate capability. The specific capacity can reach a high value of 410 mAh g −1 even under a high current density of 6.4 A g −1 (corresponds to a charge time of ∼230 s), indicating its promising application as an anode material for lithium ion batteries.

  16. Removal of diethyl phthalate from water solution by adsorption, photo-oxidation, ozonation and advanced oxidation process (UV/H2O2, O3/H2O2 and O3/activated carbon)

    International Nuclear Information System (INIS)

    Medellin-Castillo, Nahum A.; Ocampo-Pérez, Raúl; Leyva-Ramos, Roberto; Sanchez-Polo, Manuel; Rivera-Utrilla, José; Méndez-Díaz, José D.

    2013-01-01

    The objective of this work was to compare the effectiveness of conventional technologies (adsorption on activated carbon, AC, and ozonation) and technologies based on advanced oxidation processes, AOPs, (UV/H 2 O 2 , O 3 /AC, O 3 /H 2 O 2 ) to remove phthalates from aqueous solution (ultrapure water, surface water and wastewater). Diethyl phthalate (DEP) was chosen as a model pollutant because of its high water solubility (1080 mg/L at 293 K) and toxicity. The activated carbons showed a high adsorption capacity to adsorb DEP in aqueous solution (up to 858 mg/g), besides the adsorption mechanism of DEP on activated carbon is governed by dispersive interactions between π electrons of its aromatic ring with π electrons of the carbon graphene planes. The photodegration process showed that the pH solution does not significantly affect the degradation kinetics of DEP and the first-order kinetic model satisfactorily fitted the experimental data. It was observed that the rate of decomposition of DEP with the O 3 /H 2 O 2 and O 3 /AC systems is faster than that with only O 3 . The technologies based on AOPs (UV/H 2 O 2 , O 3 /H 2 O 2 , O 3 /AC) significantly improve the degradation of DEP compared to conventional technologies (O 3 , UV). AC adsorption, UV/H 2 O 2 , O 3 /H 2 O 2 , and O 3 /AC showed a high yield to remove DEP; however, the disadvantage of AC adsorption is its much longer time to reach maximum removal. The best system to treat water (ultrapure and natural) polluted with DEP is the O 3 /AC one since it achieved the highest DEP degradation and TOC removal, as well as the lower water toxicity. -- Highlights: ► Activated carbons showed a high adsorption capacity (up to 858 mg/g) to remove DEP. ► The pH solution did not significantly affect the photodegradation kinetics of DEP. ► The O 3 /H 2 O 2 and O 3 /AC systems were more efficient than O 3 to degrade DEP. ► The generation of HO • from O 3 was enhanced by ACs, mainly by those of basic nature. ► O

  17. Isotope effects in aqueous systems. Excess thermodynamic properties of 1,3-dimethylurea solutions in H2O and D2O

    International Nuclear Information System (INIS)

    Jakli, G.; Hook, W.A. Van

    1997-01-01

    The osmotic coefficients of 1,3-dimethylurea-h 2 (DMUh 2 )/H 2 O and 1,3-dimethylurea-d 2 (DMUd 2 )/D 2 O solutions (1, 2, 4, 12, and 20 m aq , 15 < t/degree C < 80) were obtained from differential vapor pressure measurements. Excess partial molar free energies, enthalpies, and entropies for the solvent and their isotope effects were calculated from the temperature derivatives of the osmotic coefficients. New partial molar volume data are reported at 25 C at low and intermediate concentrations. The thermodynamic properties of solution are compared with those of urea and discussed using the cage model of hydrophobic hydration. The results support the mixed (polar-apolar) character of this compound and show that its structural effect on water changes with temperature and concentration

  18. Solubility of NpO2 in Na2CO3 solutions

    International Nuclear Information System (INIS)

    Joe, Kih Soo; Yang, Han Beom; Lee, Eil Hee; Kim, Kwang Wook

    2010-03-01

    Solubilities of NpO 2 were measured in 0.1 M Na 2 CO 3 (pH 11.25) and 0.1 M Na 2 CO 3 -0.5M H 2 O 2 (pH 11.25), respectively, for two weeks. Three detection methods such as gas proportional counting (GPC), liquid scintillation counting (LSC) and ICP-MS were used for the measurement of dissolved NpO 2 in the solutions and the results by different methods were compared with each other. The solubility of NpO 2 increased as the contact time increased and those after 2 weeks showed 4.4 x 10 -9 M in 0.10 M Na 2 CO 3 (pH 11.25) and 2.4 x 10 -8 M in 0.10 M Na 2 CO 3 -0.5M H 2 O 2 (pH 11.25), respectively

  19. Phase equilibria and crystal chemistry of the CaO-½Gd2O3-CoOz system at 885 °C in air

    Science.gov (United States)

    Wong-Ng, W.; Laws, W.; Lapidus, S. H.; Ribaud, L.; Kaduk, J. A.

    2017-10-01

    The CaO-½Gd2O3-CoOz system prepared at 885 °C in air consists of two thermoelectric calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3-xGdx)Co4O9-z (0 ≤ x ≤ 0.42) which has a misfit layered structure, and the 1D Ca3Co2O6 compound which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound. In the peripheral binary systems, Gd was not present in the Ca site of CaO, while a small solid solution region was identified for (Gd1-xCax)O(3-z)/2 (0 ≤ x ≤ 0.075). A solid solution region of distorted perovskite, (Gd1-xCax)CoO3-z (0 ≤ x ≤ 0.24, space group Pnma) was established. The structure of a member of the solid solution, (Gd0.92Ca0.08)CoO3-z, was determined using high resolution synchrotron radiation. A ternary oxide compound CaGdCoO4-z which has an orthorhombic structure (Bmab) was found to be stable at this temperature. Five solid solution tie-line regions and six three-phase regions were determined in the CaO-½Gd2O3-CoOz system. A comparison of the phase diagrams of the CaO-½R2O3-CoOz (R = La, Sm and Gd) systems is provided.

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

    Science.gov (United States)

    Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

    1990-01-01

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

  1. Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

    Science.gov (United States)

    Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

    2014-02-03

    There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)32CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)22CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)33CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)32CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

  2. Novel composition above the limit of Bi:Zr solid solution; synthesis and physical properties of Bi1.33Zr0.67O3

    International Nuclear Information System (INIS)

    Meatza, Iratxe de; Chapman, Jon P.; Mauvy, Fabrice; Larramendi, Jose I. Ruiz de; Arriortua, Maria I.; Rojo, Teofilo

    2004-01-01

    This paper presents an increase to x = 0.67 of the zirconium content in the conductive Bi 2-x Zr x O 3solid solution. Complete incorporation of Zr in the β III -Bi 2 O 3 structure, confirmed by X-ray powder diffraction, has produced a phase with a lower volume and superior conductivity than those predicted by an earlier study. The observed β III -δ Bi 2-x Zr x O 3+δ phase transition around 730 deg. C has been characterised for the first time and shows a segregation of a mixture of predominantly γ-Bi 2 O 3 and approximately 30% of the ZrO 2 , before total reincorporation of the Zr in the high temperature δ-phase

  3. Decanuclear Ln10 Wheels and Vertex-Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties.

    Science.gov (United States)

    Das, Sourav; Dey, Atanu; Kundu, Subrata; Biswas, Sourav; Narayanan, Ramakirushnan Suriya; Titos-Padilla, Silvia; Lorusso, Giulia; Evangelisti, Marco; Colacio, Enrique; Chandrasekhar, Vadapalli

    2015-11-16

    The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The Effects of the Addition of Silica Mol Fraction (x = 1.5; 2; 2.5) as a Solid Electrolyte on Ion Conductivity of NASICON (Na1-xZr2SixP3-xO12) Using Solid-State Method

    Science.gov (United States)

    Pratiwi, V. M.; Purwaningsih, H.; Widyastuti; Fajarin, R.; Setyawan, H.

    2017-05-01

    Energy is a very important in modern life and need innovations to develop it. One innovation is the application of energyfor storage devices, such as batteries, capacitors, fuel cells, etc. For 30 years, the application of the NASICON (Na1+xZr2SixP3-xO12) into the NASICON gas sensor material was successfully prepared by using solid-state method. The raw materials such as SiO2, Na2CO3, ZrO2, and NaH2PO4 with a little methanol were mixed in Ballmill equipment. The silica powder was made by the extraction of bagasse ash by using sol-gel method. The x-ray diffraction patternshowedthat the result of silica extraction was amorphous and the NASICON structure wassynthesizedto bemonoclinic. The scanning electron microscopy results indicated that silica had non-uniform surface morphology and the NASICON had good surface morphology only on the form of Na3Zr2Si2PO12. The ionic conductivty of NASICON wasshown on LCR Nyquist plot of the three compositions. The highest NASICON conductivity was found inthe composition of x = 2.0, i.e. 1.142x10-8 S/m.

  5. Functional engineering of perovskite nanosheets. Impact of lead substitution on exfoliation in the solid solution RbCa{sub 2-x}Pb{sub x}Nb{sub 3}O{sub 10}

    Energy Technology Data Exchange (ETDEWEB)

    Ziegler, Christian; Lotsch, Bettina V. [Max Planck Institute for Solid State Research, Stuttgart (Germany); Department of Chemistry, University of Munich (LMU), Munich (Germany); Nanosystems Initiative Munich (NIM) and Center for Nanoscience (CeNS), Munich (Germany); Dennenwaldt, Teresa [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany); Ecole Polytechnique Federale de Lausanne (Switzerland); Weber, Daniel; Duppel, Viola; Kamella, Claudia; Tuffy, Brian; Moudrakovski, Igor [Max Planck Institute for Solid State Research, Stuttgart (Germany); Podjaski, Filip [Max Planck Institute for Solid State Research, Stuttgart (Germany); Ecole Polytechnique Federale de Lausanne (Switzerland); Scheu, Christina [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany)

    2017-11-17

    Tuning the chemical composition and structure for targeted functionality in two-dimensional (2D) nanosheets has become a major objective in the rapidly growing area of 2D materials. In the context of photocatalysis, both miniaturization and extending the light absorption of UV active photocatalysts are major assets. Here, we investigate the solid solution between two photocatalytic systems known from literature to evolve H{sub 2} from water/methanol under UV - RbCa{sub 2}Nb{sub 3}O{sub 10} (E{sub g} = 3.7 eV) - and visible light irradiation - RbPb{sub 2}Nb{sub 3}O{sub 10} (E{sub g} = 3.0 eV) - by synthesizing hypothetical RbCa{sub 2-x}Pb{sub x}Nb{sub 3}O{sub 10}. While the calcium niobate can easily be exfoliated into individual nanosheets via cation-proton exchange and subsequent treatment with tetra-n-butylammonium hydroxide (TBAOH), the lead niobate barely yields nanosheets. Spectroscopic and microscopic analysis suggest that this is caused by volatilization of Pb during synthesis, leading to a local 3D linkage of RbPb{sub 2}Nb{sub 3}O{sub 10} perovskite units with Pb deficient units. On the one hand, this linkage progressively prevents exfoliation along with an increasing Pb content. On the other hand, introducing Pb into the perovskite blocks successively leads to bandgap narrowing, thus gradually enhancing the light harvesting capability of the solid solution. Finding a compromise between this narrowing of the bandgap and the possibility of exfoliation, visible light sensitized nanosheets can be engineered in good yield for an initial molar ratio of Ca:Pb ≥ 1:1. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Effect of trivalent transition metal ion substitution in Dy2O3 system

    International Nuclear Information System (INIS)

    Dhilip, M.; Saravana Kumar, K.; Anbarasu, V.

    2015-01-01

    One of the very promising approaches to create novel materials is to combine different physical properties in one material to achieve rich functionality. Magnetoelectric multiferroics are attracting attention for fundamental physics due to their unique coupling behaviour between ferroelectricity, ferromagnetism and ferroelasticity and also because of their promising applications for devices in spintronics, information storage, sensing and actuation. The existence of spontaneous magnetization in the perovskite like phase (layer of perovskite) has encouraged exploring the possibility of fabrication of a multiferroic material for multifunctional devices using the concept of magnetoelectric effect. The rare earth orthoferrites (LnFeO 3 where, Ln = La, Sm, Gd, Dy, Er and Yb) are a class of materials having potential for various applications. These compounds and metal ion substituted ferrites crystallising in perovskite structure show promise as catalysts gas separators, cathodes in solid oxide fuel cells, sensor materials, magneto-optic materials and as spin valves. In this present work, Fe substituted in Dysprosium Oxide compounds were prepared by standard solid state reaction at a temperature of 1300℃. The structural analysis of the prepared samples was characterized with powder X-Ray Diffraction technique and the lattice parameters were calculated with PodwerX indexing software. The structural analysis reveals that the substitution of Fe in Dy 2 O 3 system leads to change of crystalline structure from Cubic to Tetragonal. Further, decreasing trend of volume of the unit cell confirms the occupation of smaller ionic radii element Fe in the Dy site of Dy 2 O 3 system. Hence the possibilities of incorporation of trivalent transition metal ion in to the host Dy 2 O 3 site were analyzed. (author)

  7. Synthesis and electrochemistry of cubic rocksalt Li-Ni-Ti-O compounds in the phase diagram of LiNiO{sub 2}-LiTiO{sub 2}-Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lianqi; Noguchi, Hideyuki; Li, Decheng; Muta, Takahisa; Wang, Xiaoqing; Yoshio, Masaki [Department of Applied Chemistry, Saga University, Saga 840-8052 (Japan); Taniguchi, Izumi [Department of Chemical Engineering, Tokyo Institute of Technology, 12-1, Ookayama-2, Meguro-ku, Tokyo 152-8552 (Japan)

    2008-10-15

    On the basis of extreme similarity between the triangle phase diagrams of LiNiO{sub 2}-LiTiO{sub 2}-Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2} and LiNiO{sub 2}-LiMnO{sub 2}-Li[Li{sub 1/3}Mn{sub 2/3}]O{sub 2}, new Li-Ni-Ti-O series with a nominal composition of Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} (0 {<=} z {<=} 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li-Ni-Ti-O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi{sub 1/2}Ti{sub 1/2}O{sub 2} and Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2} (high temperature form). Charge-discharge tests showed that Li-Ni-Ti-O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g{sup -1} for 0.2 {<=} z {<=} 0.27) at room temperature in the voltage range of 4.5-2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g{sup -1} for 0 {<=} z {<=} 0.27), cycleability and rate capability at an elevated temperature of 50 C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li{sup +}. A preliminary electrochemical comparison between Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} (0 {<=} z {<=} 0.5) and Li{sub 6/5}Ni{sub 2/5}Ti{sub 2/5}O{sub 2} indicated that charge-discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} while +3 in Li{sub 6/5}Ni{sub 2/5}Ti{sub 2/5}O{sub 2}. Reduction of Ti{sup 4+} at a plateau of around 2.3 V could be clearly detected in Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} with 0.27 {<=} z {<=} 0.5 at 50 C after a deep charge associated with charge compensation from oxygen ion during initial cycle

  8. Efficient NIR (near-infrared) luminescent ZnLn-grafted (Ln=Nd, Yb or Er) PNBE (Poly(norbornene))

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Lin; Feng, Hei-Ni; Fu, Guo-Rui; Li, Bao-Ning [School of Chemical Engineering, Shaanxi Key Laboratory of Degradable Medical Material, Northwest University, Xi’an 710069, Shaanxi (China); Lü, Xing-Qiang, E-mail: lvxq@nwu.edu.cn [School of Chemical Engineering, Shaanxi Key Laboratory of Degradable Medical Material, Northwest University, Xi’an 710069, Shaanxi (China); Wong, Wai-Kwok [Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong (China); Jones, Richard A. [Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165 (United States)

    2017-06-15

    Through the ring-opening metathesis polymerization (ROMP) of norbornene (NBE) with each of allyl-containing complex monomers [Zn(L){sub 2}(µ{sub 1}-OAc)Ln(µ{sub 2}-OAc){sub 2}] (Ln=La, 1; Nd, 2; Yb, 3; Er, 4 or Gd, 5; HL=4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol), a series of ZnLn-grafted polymers Poly([Zn(L){sub 2}(µ{sub 1}-OAc)Ln(µ{sub 2}-OAc){sub 2}]-co-NBE) with desired physical properties were obtained, respectively. Within near-infrared (NIR) luminescent polymers, Poly(3-co-NBE) endows an attractive quantum yield of 1.47% in solid state, and exhibits an effective prevention of high-concentration self-quenching. - Graphical abstract: Through grafting of [Zn(L){sub 2}(µ{sub 1}-OAc)Ln(µ{sub 2}-OAc){sub 2}] (Ln=Nd, 2; Yb, 3 or Er, 4) into PNBE with desired physical properties including NIR luminescence, Poly(3-co-NBE) exhibits an attractive quantum yield of 1.47% and an effective emitters' clustering prevention.

  9. Thermodynamic properties of solid solutions in the system Ag2S–Ag2Se

    International Nuclear Information System (INIS)

    Pal’yanova, G.A.; Chudnenko, K.V.; Zhuravkova, T.V.

    2014-01-01

    We have summarized experimental data on the phase diagram of the system Ag 2 S–Ag 2 Se. Standard thermodynamic functions of four solid solutions in this system have been calculated using the model of regular and subregular solutions: a restricted fcc solid solution γ-Ag 2 S-Ag 2 S 1−x Se x (x 2 S–Ag 2 Se, monoclinic solid solution (α) from Ag 2 S to Ag 2 S 0.4 Se 0.6 , and orthorhombic solid solution (α) from Ag 2 S 0.3 Se 0.7 to the Ag 2 Se. G mix and S mix have been evaluated using the subregular model for asymmetric solution for the region Ag 2 S 0.4 Se 0.6 –Ag 2 S 0.3 Se 0.7 . The thermodynamic data can be used for modeling in complex natural systems and in matters of semiconductor materials

  10. Tailoring the piezoelectric and relaxor properties of (Bi1/2 Na1/2) TiO3- BaTiO3 via zirconium doping

    DEFF Research Database (Denmark)

    Glaum, Julia; Simons, Hugh; Acosta, Matias

    2013-01-01

    This article details the influence of zirconium doping on the piezoelectric properties and relaxor characteristics of 94(Bi1/2Na1/2)TiO3-6Ba(ZrxTi1-x)O3 (BNT-6BZT) bulk ceramics. Neutron diffraction measurements of BNT-6BZT doped with 0%-15% Zr revealed an electric-field-induced transition...

  11. Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

    Science.gov (United States)

    Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

    2012-02-20

    Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

  12. Fracture toughness of neutron irradiated solid and powder HIP 316L(N). ITER Task 214, NET deliverable GB6 ECN-5

    International Nuclear Information System (INIS)

    Rensman, J.; Van den Broek, F.P.; Jong, M.; Van Osch, E.V.

    1998-04-01

    The fracture toughness properties of unirradiated and neutron irradiated type 316L(N) stainless steel plate (European Reference Heat ERHII), conventional 316L(N) solid HIP joints (heat PM-130), and 316L(N)-1G powder HIP material have been measured. Compact tension specimens with a thickness of 12 and 5 mm were irradiated in the High Flux Reactor (HFR) in Petten, The Netherlands, simulating the fusion reactor's first wall conditions by a combination of high displacement damage with proportional amounts of helium. The solid HIP (or HIP-bonded) CT-specimens were irradiated in two separate experiments: SIWAS-6 with 1.3 to 2.3 dpa (1.7 dpa av.) at 353 K, and CHARIOT-3 with 2.7 to 3.1 dpa (2.9 dpa av.) at 600 K. The plate material and powder HIP CT-specimens were irradiated in one experiment only, SIWAS-6. The helium content is up to 20 appm for the 2.9 dpa (av.) dose level. Testing temperatures of 353K and 573K have been used for the fracture toughness experiments. The report contains the experimental conditions and summarises the results, which are given in terms of J-resistance curve fits. The main conclusions are that all three materials have very high toughness in the unirradiated state with little difference between them; the solid HIP has the highest toughness, the powder HIP lowest. The toughness of all three materials is reduced significantly by irradiation, the reduction is the least for the plate material and the highest for the powder HIP material. However, many, but not all, of the solid HIP CT specimens showed debonding of the joint during testing. The machined notch of the CT specimens was not exactly on the joint interface, which could lead to unjustified interpretation of the measured values as being the toughness of the joint, the toughness of the joint being probably much lower. The reduction by irradiation of the fracture toughness of the powder HIP material is clearly larger than for plate material, which is confirmed by the observed early initiation

  13. Effect of Cu2+ ion incorporation on the phase development of ZrO2-type solid solutions during the thermal treatments

    International Nuclear Information System (INIS)

    Stefanic, Goran; Music, Svetozar; Ivanda, Mile

    2010-01-01

    The amorphous precursors of the ZrO 2 -CuO system at the ZrO 2 -rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. Thermal behavior of the amorphous precursors was monitored using X-ray powder diffraction, Raman spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectrometry, differential scanning calorimetry and thermogravimetric analysis. The crystallization temperature of the amorphous precursors rose with an increase in the CuO content for ∼180 o C. Maximum solubility of Cu 2+ ions in the ZrO 2 lattice (∼23 mol%) occurs in the metastable products obtained upon crystallization of the amorphous precursors. The results of Raman spectroscopy indicate that the incorporation of Cu 2+ ions stabilize the tetragonal ZrO 2 polymorph. A precise determination of lattice parameters, using both Rietveld and Le Bail refinements of the powder diffraction patterns, showed that the axial ratio c/a in the ZrO 2 -type solid solutions with a Cu 2+ content ≥20 mol% approach 1 (formation of t''-form of tetragonal phase). The terminal solid solubility limit of Cu 2+ ions in the ZrO 2 lattice rapidly drops with an increase in treatment temperature (up to 1000 o C) that is followed by the formation of and increase in phases structurally closely related to tenorite and monoclinic ZrO 2 . Low thermal stability of the t-ZrO 2 -type phase was attributed to the reduction of the sintering temperature in the presence of CuO and a significant difference in size and shape of zirconia and tenorite particles, which prevent surface interactions.

  14. High dielectric constant observed in (1 − x)Ba(Zr0.07Ti0.93)O3–xBa(Fe0.5Nb0.5)O3 binary solid-solution

    International Nuclear Information System (INIS)

    Kruea-In, Chatchai; Eitssayeam, Sukum; Pengpat, Kamonpan; Rujijanagul, Gobwute

    2012-01-01

    Binary solid-solutions of the (1 − x)Ba(Zr 0.07 Ti 0.93 )O 3 –xBa(Fe 0.5 Nb 0.5 O 3 ) system, with 0.1 ≤ x ≤ 0.9,were fabricated via a solid-state processing technique. X-ray diffraction analysis revealed that all samples exhibited a single perovskite phase. The BaFe 0.5 Nb 0.5 O 3 also promoted densification and grain growth of the system. Dielectric measurements showed that all samples displayed a relaxor like behavior. The x = 0.1 sample presented a dielectric-frequency and temperature with low loss tangent ( 0.2 samples, the dielectric data showed a broad dielectric constant–temperature curve with a giant dielectric characteristic. In addition, a high dielectric constant > 50,000 (at 10 kHz and temperature > 150 °C) was observed for the x = 0.9 sample.

  15. Synthesis, Characterization and Sonocatalytic Activity of Co/N/Er3+ : Y3Al5O12 /TiO2 Film for the Degradation of Organic Dyes

    Directory of Open Access Journals (Sweden)

    Wang L.

    2015-07-01

    Full Text Available The sonocatalytic degradation of organic dyes (C.I. 50040, C.I. Reactive Red 1, C.I. Acid Orange 7 catalysed by Co/N/Er3+ : Y3Al5O12/TiO2 films was studied. For the preparation of Co/N/Er3+ : Y3Al5O12/TiO2 films, the sol-gel coating process was used. The phase composition, morphology, precursor at different temperatures and emitting light properties of the calcined powders were analysed by X-ray diffraction (XRD, absorption spectra and upconversion emission spectra. The X-ray diffraction of powder samples of Co/N/Er3+ : Y3Al5O12/TiO2 took on anatase mine peaks and upconversion luminous agent, respectively. Analysis of absorption spectra of amorphous Co/N/Er3+ : Y3Al5O12/TiO2 showed that doping N stretching vibration peak of water or hydroxyl adsorption, Co2+ ion had very strong absorption in 1.0–1.7 μm wavelength range, the transition luminescence of Er3+ ions was just on Co2+ ions absorption band. The emission spectrum indicated that Co/N/Er3+ : Y3Al5O12/TiO2 could launch green 500–560 nm and red 650–700 nm, 525, 550 and 660 nm peaks corresponding to 2H11/2, 4S3/2 → 4I15/2 and 4H9/2 → 4I15/2 transition of Er3+. Doping Co and N enhanced the upconversion luminescence and absorption effect. Sonocatalytic degradation effect of organic dyes loading Co/N/Er3+ : Y3Al5O12/TiO2 was better when ultrasonic intensity was equal to 15 W cm–2. The degradation ratios of aqueous solutions of these three kinds of organic dyes by ultrasonic irradiation were obviously lower than by ultrasonic irradiation together with Co/N/Er3+ : Y3Al5O12/TiO2 films in the same conditions. Degradation kinetics of organic dyes by ultrasonic irradiation and by ultrasonic irradiation cooperating with Co/N/Er3+ : Y3Al5O12/TiO2 films followed the first-order reaction.

  16. Synthesis and the crystal and molecular structures of 4-(piperidyl-1)-2-phenylpyrido[2,3-a]anthraquinone-7,12 Mono- and dibromohydrates (HL)Br . 3H2O and (H2L)Br2 . 3H2O

    International Nuclear Information System (INIS)

    Kovalchukova, O. V.; Stash, A. I.; Belsky, V. K.; Strashnova, S. B.; Zaitsev, B. E.; Ryabov, M. A.

    2009-01-01

    4-(Piperidyl-1)-2-phenylpyrido[2,3-a]anthraquinone-7,12 monobromohydrate (HL)Br . 3H 2 O (I) and 4-(piperidyl-1)-2-phenylpyrido[2,3-a]anthraquinone-7,12 dibromohydrate (H 2 L)Br 2 . 3H 2 O (II) are isolated in the crystalline state. The crystal structures of compounds I and II are determined using X-ray diffraction. It is established that the protonation of 4-(piperidyl-1)-2-phenylpyrido[2,3-a]anthraquinone-7,12 proceeds primarily through the pyridine atom at pH 2-3. The attachment of the second proton occurs through the piperidine nitrogen atom at pH ∼ 1.

  17. Beam-Mode Piezoelectric Properties of Ternary Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals for Medical Linear Array Applications

    Science.gov (United States)

    Wang, Wei; Wang, Sheng; Zhang, Yaoyao; Zhao, Xiangyong; Luo, Haosu

    2011-11-01

    In this work, the dielectric and beam-mode piezoelectric properties of ternary 0.35Pb(In1/2Nb1/2)O3-0.35Pb(Mg1/3Nb2/3)O3-0.30PbTiO3 (PIMNT35/35/30) piezoelectric single crystals were investigated. The Curie temperature ( T C) and rhombohedral-to-tetragonal phase-transition temperature ( T rt) are 187°C and 127°C, about 30°C higher than those of PMNT crystals. The beam-mode coupling coefficient k {33/ w } was found to be 90.3%. Furthermore, 3.5-MHz linear arrays based on PIMNT35/35/30 crystals and Pb(Zr1- x Ti x )O3 ceramic (PZT-5H) were simulated using PiezoCAD software. The results indicate that the sensitivity and -6 dB bandwidth of a PIMNT35/35/30 transducer would be approximately 4 dB and 20% higher, respectively, compared with a traditional PZT transducer.

  18. Solid-phase reduction of silico-12-molybdic acid H4SiMo12O40 by some organic oxygen containing compounds

    International Nuclear Information System (INIS)

    Chuvaev, V.F.; Pinchuk, I.N.; Spitsyn, V.I.

    1982-01-01

    A study is made on reduction reactions of anhydrous silico-12-molybdic acid by vapors of organic oxygen-containing compounds at 170 deg C: alcohols, simple carbonyl compounds. Methods of thermal analysis, electron paramagnetic resonance, paramagnetic resonance were used to established that depending on the nature of organic reagent and temperature, H 6 SiMo 2 5 Mo 10 6 O 40 two-electron or H 8 SiMo 4 5 Mo 8 6 O 40 four-electron flues form. It is shown that the increase of heterogeneous reduction temperature can lead to formation of anhydrous phases of SiMo 12 O 38 -(n/2), able to attach water reversibly with formation of corresponding blue. Characteristics of blues, prepared during solid-phase reduction of silico-12-molybdic acid and mixed valent forms with corresponding reduction degree, separated from water solutions, were compared

  19. Order-disorder reactions in the ferroelectric perovskites Pb(Sc/sub 1/2/Nb/sub 1/2/)O/sub 3/ and Pb(Sc/sub 1/2/Ta/sub 1/2/)O/sub 3/. 2. Relation between ordering and properties

    Energy Technology Data Exchange (ETDEWEB)

    Stenger, C G.F.; Burggraaf, A J [Technische Hogeschool Twente, Enschede (Netherlands)

    1980-10-16

    The ordering of the trivalent and pentavalent cations in the pervoskites Pb(Sc/sub 1/2/Nb/sub 1/2/)O/sub 3/ and Pb(Sc/sub 1/2/Ta/sub 1/2/)O/sub 3/ can be varied by suitable heat treatments. The degree as well as the kind of order strongly affects the character of the FE ..-->.. PE phase transition. A spatially homogeneous disorder leads to a diffuse phase transition whereas a hybrid crystal with a nonhomogeneous disorder shows a sequence of two FE ..-->.. PE transitions.

  20. Luminescent properties of Y3Al5−xGaxO12:Ce crystals

    International Nuclear Information System (INIS)

    Zorenko, Yu.; Zorenko, T.; Malinowski, P.; Sidletskiy, O.; Neicheva, S.

    2014-01-01

    Absorption, luminescent and scintillation properties of Ce 3+ doped Y 3 Al 5−x Ga x O 12 crystals with Ga content in the x=1–5 range were investigated in this work and compared with the properties of YAG:Ce crystals. Apart from the traditional spectral methods (absorption, cathodoluminescence and light yield measurements), the intrinsic and Ce 3+ related luminescence of Y 3 Al 5−x Ga x O 12 :Ce solid-solution were also investigated using the luminescent spectroscopy under excitation by synchrotron radiation in the 3.7–25 eV range. We show that the optical properties Y 3 Al 5−x Ga x O 12 :Ce garnets monotonically change with increasing the Ga content in the x=0–3 range due to preferable localization of Ga ions in the tetrahedral position of the garnet lattice. At the highest Ga concentration (x>3) the deviation of the optical properties of Y 3 Al 5−x Ga x O 12 :Ce garnets is observed from the respective properties of these crystals with Ga content in the x=0–3 range due to occupation by Ga ions of the octahedral position in the garnet host. - Highlights: • Different dependence of optical properties of Y 3 Al 5−x Ga x O 12 :Ce crystals on Ga content in x=0–3 and 3–5 ranges. • Elimination of the luminescence of Y Al antisite defects in Y 3 Al 5−x Ga x O 12 :Ce crystals at x>2. • Significant improvement of the scintillation properties of Y 3 Al 5−x Ga x O 12 :Ce crystals at x=2 and 3 in comparison with YAG:Ce

  1. Piezoelectric and ferroelectric properties of lead-free (1-x)(Na{sub 1−y}K{sub y})(Nb{sub 1−z}Sb{sub z})O{sub 3}-xBaTiO{sub 3} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Sasikumar, S., E-mail: sasikuhan@gmail.com [Research Centre and Post Graduate Department of Physics, The Madura College, Madurai 625 011, Tamil Nadu (India); Saravanan, R. [Research Centre and Post Graduate Department of Physics, The Madura College, Madurai 625 011, Tamil Nadu (India); Aravinth, K. [SSN Research Center, SSN College of Engineering, Kalavakkam 603 110, Tamil Nadu (India)

    2017-05-01

    The solid solutions of lead-free (1-x)(Na{sub 1-y}K{sub y})(Nb{sub 1-z}Sb{sub z})O{sub 3}-xBaTiO{sub 3} (with x=0.1, 0.2; y=0.03, 0.05; z=0.05, 0.1) (abbreviated as (1-x)NKNS-xBT) ceramics have been synthesized using conventional solid-state reaction method. The results of X-ray diffraction analysis show that all the grown specimens of NKNS display typical perovskite structure. With BaTiO{sub 3} (BT) addition, a structural phase transition from tetragonal to cubic structure has been observed. The structural parameters of (1-x)NKNS-xBT powders were determined by profile refinements based on the analysis of X-ray powder diffraction. The charge density distributions of the prepared samples have been investigated by observed structure factors to understand the chemical bonding nature of (1-x)NKNS-xBT powders. The optical absorption of the ceramics has been investigated using UV–visible spectrophotometer. Scanning electron microscopic (SEM) measurements were performed to study the surface morphology of the prepared solid solutions. The elemental compositions of the (1-x)NKNS-xBT samples were analyzed by energy-dispersive X-ray (EDS) spectrometer. The dielectric constant versus temperature plots of the solid solutions exhibit ferroelectric to paraelectric phase transition, which is dependent on the BaTiO{sub 3} content. The ferroelectric nature of the samples has been determined through polarization and electric field hysteresis measurements.

  2. Rare earth ruthenium gallides with the ideal composition Ln_2Ru_3Ga_5 (Ln = La-Nd, Sm) crystallizing with U_2Mn_3Si_5 (Sc_2Fe_3Si_5) type structure

    International Nuclear Information System (INIS)

    Jeitschko, Wolfgang; Schlueter, Martin

    2010-01-01

    The rare earth ruthenium gallides Ln_2Ru_3Ga_5 (Ln = La, Ce, Pr, Nd, Sm) were prepared by arc-melting of cold-pressed pellets of the elemental components. They crystallize with a tetragonal structure (P4/mnc, Z = 4) first reported for U_2Mn_3Si_5. The crystal structures of the cerium and samarium compounds were refined from single-crystal X-ray data, resulting in significant deviations from the ideal compositions: Ce_2Ru_2_._3_1_(_1_)Ga_5_._6_9_(_1_), a = 1135.10(8) pm, c = 580.58(6) pm, R_F = 0.022 for 742 structure factors; Sm_2Ru_2_._7_3_(_2_)Ga_5_._2_7_(_2_), a = 1132.95(9) pm, c = 562.71(6) pm, R_F = 0.026 for 566 structure factors and 32 variable parameters each. The deviations from the ideal compositions 2:3:5 are discussed. A mixed Ru/Ga occupancy occurs only for one atomic site. The displacement parameters are relatively large for atoms with mixed occupancy within their coordination shell and small for atoms with no neighboring sites of mixed occupancy. Chemical bonding is analyzed on the basis of interatomic distances. Ln-Ga bonding is stronger than Ln-Ru bonding. Ru-Ga bonding is strong and Ru-Ru bonding is weak. The Ga-Ga interactions are of similar strength as in elemental gallium. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  3. Pressure induced Amorphization of Ln1/3(Nb,Ta)O3

    International Nuclear Information System (INIS)

    Melchior, A.; Noked, O.; Sterer, E.; Shuker, R.

    2014-01-01

    The research focuses on the phenomenon of pressure induced amorphization (PIA) in Ln1/3MO3, Ln - La,Pr,Nd and M-Nb,Ta. In most pressure induced phase transitions the material changes from a crystalline phase to another crystalline phase. However, if this transition is kinetically hindered, the increased free energy due to the applied pressure will result in a structural collapse to an amorphous intermediate phase. This phenomenon is known as pressure induced amorphization

  4. Solid-state reaction mechanism and microwave dielectric properties of CaTiO3–LaAlO3 ceramics

    International Nuclear Information System (INIS)

    Jiang, Juan; Fang, Danhua; Lu, Chao; Dou, Zhanming; Wang, Gan; Zhang, Fan; Zhang, Tianjin

    2015-01-01

    Highlights: • CaTiO 3 –LaAlO 3 perovskite ceramics were prepared by four sintering reaction routes. • The solid-state reaction mechanism was investigated by XRD and TG/DSC techniques. • Sintering routes had more influence on the parameters of Q × f and τ f than on ε r . - Abstract: 0.675CaTiO 3 –0.325LaAlO 3 perovskite ceramics were prepared by a conventional sintering process through four reaction routes. The solid-state reaction mechanisms were investigated by X-ray diffraction and thermogravimetric/differential scanning calorimetric analysis techniques. The results show that interactions occurred between mixtures of CaCO 3 and TiO 2 as well as La 2 O 3 and Al 2 O 3 , and they can influence the sintering behavior of the mixtures. Prior to the formation of solid solutions, the perovskite phases CaTiO 3 and LaAlO 3 were formed regardless of the combination of oxide powders used as reagents. From the powder mixtures which were calcined at 1200 °C, a Ca-rich Ca 9 Al 6 O 18 phase was present at 1400 °C if free La 2 O 3 and Al 2 O 3 used in the reaction mixtures. Ca-rich phases were also formed at higher temperature (1450 °C) if LaAlO 3 was present. The densities of the ceramics obtained by the four routes were different at specific sintering temperatures, and the highest density was obtained for the reaction route two. Results indicated that the preparation pathways had more influence on Q × f and temperature coefficient of the resonant frequency (τ f ) than on the dielectric constants (ε r ), and Q × f decreased and τ f increased rapidly when the secondary phase presented. Route four is considered as an optimal pathway for the preparation of 0.675CaTiO 3 –0.325LaAlO 3 ceramics.

  5. The effects of additives on the microstructure and sinterability of molybdenum oxide - study of related solid solutions

    International Nuclear Information System (INIS)

    Kassem, M.

    2006-01-01

    This study focuses on the phase transformation induced during mixing a fixed quantity of MoO 3 with various concentration of V 2 O 5 , Bn 2 O 5 , Al 2 O 3 and pure aluminium. These concentrations are 2, 3, 4, 5, 10, 20, 40 and 50%. Employing several physical techniques such as x-ray powder diffraction, FTIR and DTA, different solid solution were identified. Also the compressibility and sintering of these solid solutions have been studied via the variation of the density of pellets prepared from these solid solutions (Author)

  6. 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}.

  7. High energy storage efficiency with fatigue resistance and thermal stability in lead-free Na{sub 0.5}K{sub 0.5}NbO{sub 3}/BiMnO{sub 3} solid-solution films

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yizhu; Zhou, Yunpeng; Lu, Qingshan; Zhao, Shifeng [Inner Mongolia Key Lab of Nanoscience and Nanotechnology and School of Physical Science and Technology, Inner Mongolia University, Hohhot (China)

    2018-02-15

    The ferroelectric, leakage, dielectric, and energy storage properties of lead-free Na{sub 0.5}K{sub 0.5}NbO{sub 3}/BiMnO{sub 3} (KNN/BMO) solid-solution films are investigated. The strong ferroelectric relaxation behaviors of slim ferroelectricity with small remanent polarization and coercive field induce a high energy-storage density and efficiency at room temperature. The energy density reaches 14.8 J cm{sup -3}, even the efficiency is up to 79.79% under the applied electric field of 985.66 kV cm{sup -1}. Moreover, the energy storage performances of KNN/BMO solid-solution films exhibit good thermal stability over a wide temperature range and high ferroelectric fatigue endurance after switching 10{sup 6} bipole electrical cycles. KNN/BMO solid-solution films can replace lead-based films and other outstanding lead-free systems in the energy storage performance. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Specific non-bonding contacts in the crystal structure of [Mo33-S)(μ-S2)3(S2CNEt2)3]Cl0.53Br0.47 solid solution

    International Nuclear Information System (INIS)

    Virovets, A.V.; Volkov, O.V.

    2000-01-01

    Solid solution [Mo 3 S 7 (dtc) 3 ]Cl 0.53 Br 0.47 (dtc diethyl-dithiocarbamate) featuring the following parameters of monoclinic all: a = 14.541(2), b = 12.407(2), c = 18.117(2) A, β = 90.032(9) deg, sp.gr. P2 1 /n, Z = 4, d cal = 2.107 g/cm 3 , was studied by the method of X-ray diffraction analysis. Formation of ionic pairs with axial contact 3S ax ...Br, its length 3.028-3.105 A, in the compound structure was ascertained. For compounds [Mo 3 S 7 (dtc) 3 ] Hal (Hal = Cl, Br, I) a regular growth in S...Hal distances in the series Cl-Br-I was pointed out, meanwhile the distances remained shorted than the van-der-Waals sums of sulfur and halogen radii [ru

  9. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    Science.gov (United States)

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

  10. Photoluminescence properties of lanthanide-organic frameworks (LnOFs) with thiophene-2,5-dicarboxylate and acetate

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jing; Wei, Qing; Xie, Gang; Chen, Sanping [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); Zhang, Sheng [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); College of Chemistry and Chemical Engineering, Baoji Univ. of Arts and Science, Baoji, Shaanxi (China)

    2017-07-17

    S-heterocyclic dicarboxylic acid, thiophene-2,5-dicarboxylic acid (H{sub 2}TDC), was employed to construct a series of lanthanide-organic frameworks (LnOFs) with coligand acetate, formulated as [Ln(TDC)(OAc)(H{sub 2}O)]{sub n} [Ln = Eu (1), Tb (2), Gd (3), Dy (4), Sm (5)] under hydrothermal conditions. Structure analysis reveals that 1-5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC{sup 2-} and OAc{sup -} display (κ{sup 1}-κ{sup 1})-(κ{sup 1}-κ{sup 1})-μ{sub 4} and (κ{sup 2}-κ{sup 1})-μ{sub 2} coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 C. As for 1, 2, 4, and 5, the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with {sup 5}D{sub 4} lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H{sub 2}TDC ligand and the {sup 5}D{sub 4} state energy level of Tb{sup 3+}. The energy transfer mechanisms in compounds 1 and 2 were also discussed. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu)

    Energy Technology Data Exchange (ETDEWEB)

    Gurusinghe, Nicola N.M. [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Figuera, Juand de la; Marco, José F. [Instituto de Quimica-Fisica “Rocasolano”, CSIC, Serrano 119, 28006 Madrid (Spain); Thomas, Michael F. [Department of Physics, University of Liverpool, Liverpool. L69 3BX (United Kingdom); Berry, Frank J., E-mail: f.j.berry.1@bham.ac.uk [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Greaves, Colin [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2013-09-01

    Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A{sub 2}B{sub 2}O{sub 7} of composition Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu) have been prepared. La{sub 2}SrFe{sub 2}O{sub 7} and La{sub 2}BaFe{sub 2}O{sub 7} crystallise in the tetragonal space group I4/mmm. The structures of Eu{sub 2}SrFe{sub 2}O{sub 7} and Nd{sub 2}SrFe{sub 2}O{sub 7} are best described in space group P4{sub 2}/mnm. Substitution on the A site with smaller lanthanide- and larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La{sub 2}BaFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of {sup 57}Fe Mössbauer spectra recorded from La{sub 2}SrFe{sub 2}O{sub 7} between 290 and 600 K indicate a magnetic ordering temperature of T{sub N} ≥ 535 K.

  12. Selective Hydrogenolysis of Glycerol and Crude Glycerol (a By-Product or Waste Stream from the Biodiesel Industry to 1,2-Propanediol over B2O3 Promoted Cu/Al2O3 Catalysts

    Directory of Open Access Journals (Sweden)

    Malaya R. Nanda

    2017-06-01

    Full Text Available The performance of boron oxide (B2O3-promoted Cu/Al2O3 catalyst in the selective hydrogenolysis of glycerol and crude glycerol (a by-product or waste stream from the biodiesel industry to produce 1,2-propanediol (1,2-PDO was investigated. The catalysts were characterized using N2-adsorption-desorption isotherm, Inductively coupled plasma atomic emission spectroscopy (ICP-AES, X-ray diffraction (XRD, ammonia temperature programmed desorption (NH3-TPD, thermogravimetric analysis (TGA, temperature programmed reduction (TPR, and transmission electron microscopy (TEM. Incorporation of B2O3 to Cu/Al2O3 was found to enhance the catalytic activity. At the optimum condition (250 °C, 6 MPa H2 pressure, 0.1 h−1 WHSV (weight hourly space velocity, and 5Cu-B/Al2O3 catalyst, 10 wt% aqueous solution of glycerol was converted into 1,2-PDO at 98 ± 2% glycerol conversion and 98 ± 2% selectivity. The effects of temperature, pressure, boron addition amount, and liquid hourly space velocity were studied. Different grades of glycerol (pharmaceutical, technical, or crude glycerol were used in the process to investigate the stability and resistance to deactivation of the selected 5Cu-B/Al2O3 catalyst.

  13. Growing large columnar grains of CH3NH3PbI3 using the solid-state reaction method enhanced by less-crystallized nanoporous PbI2 films

    Science.gov (United States)

    Zheng, Huifeng; Wang, Weiqi; Liu, Yangqiao; Sun, Jing

    2017-03-01

    Compact, pinhole-free and PbI2-free perovskite films, are desirable for high-performance perovskite solar cells (PSCs), especially if large columnar grains are obtained in which the adverse effects of grain boundaries will be minimized. However, the conventional solid-state reaction methods, originated from the two-step method, failed to grow columnar grains of CH3NH3PbI3 in a facile way. Here, we demonstrate a strategy for growing large columnar grains of CH3NH3PbI3, by less-crystallized nanoporous PbI2 (ln-PbI2) film enhanced solid-state reaction method. We demonstrated columnar grains were obtainable only when ln-PbI2 films were applied. Therefore, the replacement of compact PbI2 by ln-PbI2 in the solid-sate reaction, leads to higher power conversion efficiency, better reproducibility, better stability and less hysteresis. Furthermore, by systematically investigating the effects of annealing temperature and duration, we found that an annealing temperature ≥120 °C was also critical for growing columnar grains. With the optimal process, a champion efficiency of 16.4% was obtained and the average efficiency reached 14.2%. Finally, the mechanism of growing columnar grains was investigated, in which a VPb″ -assisted hooping model was proposed. This work reveals the origins of grain growth in the solid-state reaction method, which will contribute to preparing high quality perovskite films with much larger columnar grains.

  14. The electrical properties and relaxation behavior of AgNb{sub 1/2}Ta{sub 1/2}O{sub 3} ceramic

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, K.Ganga, E-mail: kotagirigangaprasad@gmail.com; Niranjan, Manish K.; Asthana, Saket

    2017-02-01

    Polycrystalline AgNb{sub 1/2}Ta{sub 1/2}O{sub 3} powder was prepared by solid state reaction method. Preliminary x-ray diffractogram analysis of some aspects of crystal structure showed that a single phase compound formed exhibiting a monoclinic system. Impedance spectroscopy showed the presence of both bulk and grain boundary effects in the material. The relaxation behavior was studied by fitting electric modulus with Bergman function confirms us the existence of non-Debye type of relaxation the material. The ac conductivity spectrum obeyed Funke's double power law and fitting in results, the hopping parameters n{sub 1},n{sub 2} were indicating the existence of small and large range polaron hopping in the material. The band gap of the material 3.02 eV measured by using UV visible spectroscopy.

  15. 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...

  16. Structural characterization of M(IV)1-xLn(III)xO2-x/2 (M = Ce, Th) mixed-oxides prepared from oxalate precursors. Multi-parametric study of dissolution and microstructural evolution

    International Nuclear Information System (INIS)

    Horlait, D.

    2011-01-01

    In the framework of Gen IV program development, several physico-chemical properties of some foreseen fuels, including the chemical durability, have to be evaluated. In this aim, a study was undertaken on M(IV) 1-x Ln(III) x O 2 (M=Ce,Th) model compounds prepared from oxalate precursors. The fluorite-type structure of CeO 2 and ThO 2 remains stable up to x ≅ 0.4, the substitution of M(IV) by Ln(III) occurring simultaneously to the formation of oxygen vacancies. For higher x values, a cubic superstructure is formed as a result of oxygen vacancies ordering. The normalized dissolution rates of such solids were found to be strongly enhanced by the Ln(III) fraction. On the contrary, the nature of the M(IV) and Ln(III) elements did not modify significantly the normalized dissolution rates. The effect of temperature and acid concentration suggested the existence of surface-controlling dissolution reactions. Simultaneously, the microstructural evolution of both powdered and sintered samples revealed some important changes in the reactive surface during dissolution tests. ESEM images allowed observing the existence of preferential dissolution sites located at grains boundaries and around crystalline defects, leading to the formation of corrosion pits. In addition, the formation of gelatinous phases, acting as diffusion barriers (thus slowing down the dissolution process) was also evidenced. (author) [fr

  17. Synthesis and luminescent spectroscopy of lanthanide complexes with dimethylpyridine-2,6-dicarboxylate (dmpc)

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M.; Hijazi, Ahmed K. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Al-Rawashdeh, Nathir A. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Department of Chemistry, United Arab Emirates University, Al Ain 15551 (United Arab Emirates); Al-Hassan, Khader A.; Al-Haj, Yaser A. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan); Ebqa' ai, Mohammad A. [Al-Qunfudah Center For Scientific Research, Umm Al-Qura University, College in Al-Qunfudah, Makkah (Saudi Arabia); Altalafha, Ammar Y. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan)

    2015-05-15

    A series of lanthanide complexes with the general formulae [Ln(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) and [La(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} were prepared by direct reaction between hydrated lanthanide(III) nitrate and dimethylpyridine-2,6-dicarboxylate (dmpc) in a 1:1 M ratio in ethylacetate–chloroform mixture. The luminescence properties of the dmpc and its Ln(III) complexes were investigated in solid state and in methanol, DMF and DMSO solutions. The Tb–dmpc, Eu–dmpc, Sm–dmpc and Dy–dmpc complexes exhibit characteristic luminescence of Tb(III), Eu(III), Sm(III) and Dy(III) ions indicating energy transfer from the dmpc to the Ln(III) ions. Scavenging activities of the dmpc and its Ln(III) complexes on DPPH{sup •} free radical were investigated in DMSO solution at a different concentrations ranges. - Highlights: • Nine new lanthanide complexes with dmpc ligand are prepared and characterized. • Ln–dmpc {Ln=Eu, Tb, Sm, Dy} complexes exhibit characteristic emissions of Ln ions. • The solvent effect on the luminescence intensity is investigated. • The antioxidant activity of the dmpc is enhanced upon complexation with lanthanide.

  18. KMoWP3O12, a tunnel structure of the KMo2O12-type

    International Nuclear Information System (INIS)

    Benmoussa, A.; Leclaire, A.; Grandin, A.; Raveau, B.

    1989-01-01

    Potassium molybdotungstotriphosphate(V), KMoWP 3 O 12 , M r =603.80, orthorhombic, Pbcm, a=8.8180(6), b=9.1574(8), c=12.3836(8) A, V=1000.0(2) A 3 , Z=4, D x =4.01 Mg m -3 , λ(Mo Kα)=0.71073 A, μ=13.9 mm -1 , T=294 K, F(000)=276, R=0.035 and wR=0.042 for 2291 observed reflections. The framework is built up from MoO 6 octahedra and PO 4 tetrahedra which delimit tunnels running along b, where the K ions are located. The structure leads to the formula KMoWO(PO 4 )(P 2 O 7 ). (orig.)

  19. Investigation on structural, Mössbauer and ferroelectric properties of (1−x)PbFe{sub 0.5}Nb{sub 0.5}O{sub 3}–(x)BiFeO{sub 3} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Dadami, Sunanda T.; Matteppanavar, Shidaling; Shivaraja, I. [Department of Physics, JB Campus, Bangalore University, Bangalore 560056 (India); Rayaprol, Sudhindra [UGC-DAE-Consortium for Scientific Research, Mumbai Centre, BARC Campus, Mumbai 400085 (India); Angadi, Basavaraj, E-mail: brangadi@gmail.com [Department of Physics, JB Campus, Bangalore University, Bangalore 560056 (India); Sahoo, Balaram [Materials Research Centre, Indian Institute of Science, Bangalore 560012 (India)

    2016-11-15

    In this study, (1−x)PbFe{sub 0.5}Nb{sub 0.5}O{sub 3}(PFN)–(x)BiFeO{sub 3}(BFO) multiferroic solid solutions with x=0.0, 0.1, 0.2, 0.3 and 0.4 were synthesized through single step solid state reaction method and characterized thoroughly through X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red (FTIR), Raman, Mössbauer spectroscopy and ferroelectric studies. The room temperature (RT) XRD studies confirmed the formation of single phase with negligible amount of secondary phases (x=0.2 and 0.4). The zoomed XRD patterns of (1−x)PFN–(x)BFO solid solutions showed the clear structural phase transition from monoclinic (Cm) to rhombohedral (R3c) at x=0.4. The Raman spectra of the (1−x)PFN–(x)BFO solid solutions showed the composition dependent phase transition from monoclinic (Cm) to rhombohedral (R3c). With increasing x in PFN, the modes related monoclinic symmetry changes to those of rhombohedral symmetry. The RT Mössbauer spectroscopy results evidenced the existence of composition dependent phase transition from paramagnetic to weak antiferromagnetic ordering and weak antiferromagnetic to antiferromagnetic ordering. The Mössbauer spectroscopy showed paramagnetic behavior with a doublet for x=0.0, 0.1 and 0.2 are shows the weak antiferromagnetic with paramagnetic ordering. For x=0.3 and 0.4 shows the sextet pattern and it is a clear evidence of antiferromagnetism. The ferroelectric (P–E) loops at RT indicate the presence of small polarization, as the x concentration increases in PFN, the remnant polarization and coercive field were decreased, which may due to the increase in the conductivity and leaky behavior of the samples. - Highlights: • Structural, Mössbauer, ferroelectric studies on (1−x)PFN–xBiFeO{sub 3} multiferroics. • Composition dependent changes in crystallographic and magnetic structure. • System exhibits phase transition from monoclinic to rhombohedral with x. • Supporting results from Raman

  20. Room-temperature ferromagnetism in Fe-based perovskite solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials

    Science.gov (United States)

    Hung, Nguyen The; Bac, Luong Huu; Trung, Nguyen Ngoc; Hoang, Nguyen The; Van Vinh, Pham; Dung, Dang Duc

    2018-04-01

    The integration of ferromagnetism in lead-free ferroelectric materials is important to fabricate smart materials for electronic devices. In this work, (1 - x)Bi0.5Na0.5TiO3 + xMgFeO3-δ materials (x = 0-9 mol%) were prepared through sol-gel method. X-ray diffraction characterization indicated that MgFeO3-δ materials existed as a well solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials. The rhombohedral structure of Bi0.5Na0.5TiO3 materials was distorted due to the random distribution of Mg and Fe cations into the host lattice. The reduced optical band gap and the induced room-temperature ferromagnetism were due to the spin splitting of transition metal substitution at the B-site of perovskite Bi0.5Na0.5TiO3 and the modification by A-site co-substitution. This work elucidates the role of secondary phase as solid solution in Bi0.5Na0.5TiO3 material for development of lead-free multiferroelectric materials.

  1. A new-type inorganic [KNbO{sub 3}]{sub 0.9}[BaCo{sub 1/2}Nb{sub 1/2}O{sub 3-δ}]{sub 0.1} perovskite oxide as sensitizer for photovoltaic cell

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Limin [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); University of Chinese Academy of Sciences, Beijing (China); Jia, Junhong; Yi, Gewen [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China)

    2017-02-15

    An electrode with [KNbO{sub 3}]{sub 0.9}[BaCo{sub 1/2}Nb{sub 1/2}O{sub 3-δ}]{sub 0.1} (KBCNO) perovskite oxide as sensitizer and well-aligned TiO{sub 2} nanorod arrays is prepared via conventional standard solid-state synthesis method, followed by pulsed laser deposition technique for the first time. Enhanced absorption in visible light region is observed for KBCNO rate at TiO{sub 2} NRs photoelectrode, which is mainly because the inserted Co 3d electronic states can hybridize with O 2p states in the gap of KBCNO, reducing the band gap to 1.90 eV. Additionally, the oxygen vacancies existing in KBCNO can not only serve as photoinduced charge traps and adsorption sites but also prevent recombination of photoinduced electron-hole, giving rise to enhanced separation of photogenerated electron-hole pair and leading to an improved performance in solar energy conversion. The KBCNO rate at TiO{sub 2} NRs photoelectrode exhibits an energy conversion efficiency of 0.183% under one sun illumination. This work provide further insight for improving the efficiency of utilization of solar energy by using a new composite perovskite oxides material, which may be promising rational categories of material for solar conversion and storage devices. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Microstructure and gas sensitive properties of alpha-Fe2O3-MO2 (M: Sn and Ti) materials prepared by ball milling

    DEFF Research Database (Denmark)

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

    1998-01-01

    Metastable alpha-Fe2O3-MO2 (M: Sn and Ti) solid solutions can be synthesized by mechanical alloying. The alloy formation, microstructure, and gas sensitive properties of mechanically milled alpha-Fe2O3-SnO2 materials are discussed. Tin ions in alpha-Fe2O3 are found to occupy the empty octahedral...... holes in the alpha-Fe2O3 lattice. This interstitial model can also describe the structure of alpha-Fe2O3-TiO2 solid solutions. Finally, a correlation of gas sensitive properties with microstructure of alpha-Fe2O3-SnO2 materials is presented....

  3. Solid state compatibility in the ZnO-rich region of ZnO-Bi2O3-Sb2O3 and ZnO-Bi2O3-Sb2O5 systems

    Directory of Open Access Journals (Sweden)

    Jardiel, T.

    2010-04-01

    Full Text Available The obtaining of ZnO-Bi2O3-Sb2O3 (ZBS based varistor thick films with high non-linear properties is constrained by the bismuth loss by vaporization that takes place during the sintering step of these ceramics, a process which is yet more critical in the thick film geometry due to its inherent high are/volume ratio. This volatilization can be controlled to a certain extent by modifying the proportions of the Bi and/or Sb precursors. Obviously this requires a clear knowledge of the different solid state compatibilities in the mentioned ZBS system. In this sense a detailed study of the thermal evolution of the ZnO-Bi2O3-Sb2O3 and ZnO-Bi2O3-Sb2O5 systems in the ZnO-rich region of interest for varistors, is presented in this contribution. A different behaviour is observed when using Sb2O3 or Sb2O5 as starting precursor, which should be attributed to the oxidation process experimented by Sb2O3 compound during the heating. On the other hand the use of high amounts of Bi in the starting formulation leads to the formation of a liquid phase at lower temperatures, which would allow the use of lower sintering temperatures.La obtención de varistors en lámina gruesa basados en ZnO-Bi2O3-Sb2O3 (ZBS y con propiedades altamente no-lineales está limitada por la perdida de bismuto por volatilización durante la sinterización de estos cerámicos, un proceso que es todavía más crítico en la geometría de lámina gruesa debido a su elevada relación área/volumen inherente. Dicha volatilización puede ser no obstante controlada hasta cierta extensión modificando las proporciones de los precursores de Bi y/o Sb. Obviamente ello conlleva un amplio conocimiento de las diferentes compatibilidades en estado sólido en el mencionado sistema ZBS. En este sentido, en la presente contribución se presenta un estudio detallado de la evolución térmica de los sistemas ZnO-Bi2O3-Sb2O3 y ZnO-Bi2O3-Sb2O5 en la región rica en ZnO de interés para varistores. Como

  4. Optical evidences for an intermediate phase in relaxor ferroelectric Pb(In1/2Nb1/2O3-Pb(Mg1/3Nb2/3O3-PbTiO3 single crystals

    Directory of Open Access Journals (Sweden)

    Xiaolong Zhang

    2016-02-01

    Full Text Available The mechanism of low-temperature structural transformation and evolution of polar nano-structures in relaxor ferroelectric Pb(In1/2Nb1/2O3-Pb(Mg1/3Nb2/3O3-xPbTiO3 (x = 0.33, 0.35, and 0.42 single crystals have been investigated with the aid of temperature dependent low-wavenumber Raman scattering (LWRS and photoluminescence (PL spectra. The E(TO1 phonon mode reveals the characteristic relaxational polarization fluctuations associated with the reorientation of either polar nano-regions or polar nano-domains. It was found that these mechanisms are not independent and they can be ascribed to the phonon localization. In addition, a short-range monoclinic phase (Mc can be found below 250 K in the tetragonal phase region by LWRS, which is always associated with the morphotropic phase boundary (MPB and excellent electromechanical properties. It is interesting that PL spectra confirm these results. The present work indicates that external field modulation and change of composition can result in the monoclinic phase and co-existence of multi-phase.

  5. Structures and magnetic properties of rare earth double perovskites containing antimony or bismuth Ba{sub 2}LnMO{sub 6} (Ln=rare earths; M=Sb, Bi)

    Energy Technology Data Exchange (ETDEWEB)

    Otsuka, Shumpei, E-mail: m-nis-s-o@ec.hokudai.ac.jp; Hinatsu, Yukio

    2015-07-15

    A series of double perovskite-type oxides Ba{sub 2}LnMO{sub 6} (Ln=lanthanides; M=Sb, Bi) were synthesized and their structures were studied. The Ln and M are structurally ordered in the rock-salt type at the B-site of the perovskite ABO{sub 3}. For Ba{sub 2}PrBiO{sub 6} and Ba{sub 2}TbBiO{sub 6}, it has been found that the disordering between Ln ion and Bi ion occurs at the B-site of the double perovskite and both the Pr (Tb) and Bi exist in two oxidation state in the same compound from the analysis of the X-ray diffraction and magnetic susceptibility data. Magnetic susceptibility measurements show that all these compounds are paramagnetic and have no magnetic ordering down to 1.8 K. - Graphical abstract: Tolerance factor for Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) plotted against the ionic radius of Ln{sup 3+}. We have found that there is a clear relation between crystal structures and tolerance factors. - Highlights: • The Ln and M ions are structurally ordered in the rock-salt type at the B-site. • The disordering between Pr (Tb) ion and Bi ion occurs at the B-site. • Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) have no magnetic ordering down to 1.8 K.

  6. Crystal Growth and Characterization of (Bi0.5Na0.5)TiO3-BaTiO3 Single Crystals Obtained by a Top-Seeded Solution Growth Method under High-Pressure Oxygen Atmosphere

    Science.gov (United States)

    Onozuka, Hiroaki; Kitanaka, Yuuki; Noguchi, Yuji; Miyayama, Masaru

    2011-09-01

    A single crystal of ferroelectric 0.88(Bi,Na)TiO3-0.12BaTiO3 (BNT-BT) solid solution with tetragonal P4mm structure was grown by a top-seeded solution growth (TSSG) method at a high oxygen pressure (PO2 ) of 0.9 MPa. The crystals exhibited a large remanent polarization (Pr) of 54 µC/cm2, which leads to a spontaneous polarization estimated to be 54 µC/cm2. The large Pr compared with that of crystals grown at PO2 = 0.1 MPa is suggested to originate from a low oxygen vacancy concentration. The high-PO2 TSSG method is demonstrated to be effective for obtaining large-sized, high-quality BNT-BT crystals.

  7. Luminescence and light yield of (Gd.sub.2./sub.Y)(Ga.sub.3./sub.Al.sub.2./sub.)O.sub.12./sub.:Pr.sup.3+./sup. single crystal scintillators

    Czech Academy of Sciences Publication Activity Database

    Lertloypanyachai, P.; Pathumrangsan, N.; Sreebunpeng, K.; Pattanaboonmee, N.; Chewpraditkul, W.; Yoshikawa, A.; Kamada, K.; Nikl, Martin

    2017-01-01

    Roč. 468, Jun (2017), s. 369-372 ISSN 0022-0248 R&D Projects: GA ČR GA16-15569S Institutional support: RVO:68378271 Keywords : (Gd 2 Y)(Ga 3 Al 2 )O 12 :Pr 3+ * photoelectron yield * luminescence * scintillation Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.751, year: 2016

  8. Surface reactivity and hydroxyapatite formation on Ca5MgSi3O12 ceramics in simulated body fluid

    Science.gov (United States)

    Xu, Jian; Wang, Yaorong; Huang, Yanlin; Cheng, Han; Seo, Hyo Jin

    2017-11-01

    In this work, the new calcium-magnesium-silicate Ca5MgSi3O12 ceramic was made via traditional solid-state reaction. The bioactivities were investigated by immerging the as-made ceramics in simulated body fluid (SBF) for different time at body temperature (37 °C). Then the samples were taken to measure X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), X-ray energy-dispersive spectra (EDS), and Fourier transform infrared spectroscopy (FT-IR) measurements. The bone-like hydroxyapatite nanoparticles formation was observed on the ceramic surfaces after the immersion in SBF solutions. Ca5MgSi3O12 ceramics possess the Young's modulus and the bending strength and of 96.3 ± 1.2 GPa and 98.7 ± 2.3 MPa, respectively. The data suggest that Ca5MgSi3O12 ceramics can quickly induce HA new layers after soaking in SBF. Ca5MgSi3O12 ceramics are potential to be used as biomaterials for bone-tissue repair. The cell adherence and proliferation experiments are conducted confirming the reliability of the ceramics as a potential candidate.

  9. Random-site cation ordering and dielectric properties of PbMg.sub.1/3./sub.Nb.sub.2./3./sub.O.sub.3./sub.-PbSc.sub.1/2./sub.Nb.sub.1/2./sub.O.sub.3./sub

    Czech Academy of Sciences Publication Activity Database

    Raevski, I. P.; Prosandeev, S. A.; Emelyanov, S. M.; Savenko, F. I.; Zakharchenko, I. N.; Bunina, O. A.; Bogatin, A. S.; Raevskaya, S. I.; Sahkar, E. V.; Jastrabík, Lubomír

    2003-01-01

    Roč. 53, - (2003), s. 475-487 ISSN 1058-4587 R&D Projects: GA MŠk LN00A015 Institutional research plan: CEZ:AV0Z1010914 Keywords : cation ordering * dielectric properties * relaxors Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.608, year: 2003

  10. Study on preparation of orange-emitting phosphor Y3Mg2AlSi2O12: Ce3+ for wLED

    Directory of Open Access Journals (Sweden)

    Yan Shirun

    2017-12-01

    Full Text Available Ce3+-doped garnet-structured orange-emitting phosphor Y3Mg2AlSi2O12:Ce3+ was prepared by sol-gel combustion using urea as a fuel.Effects of the reduction temperature,Ce3+ doping concentration on the structure,morphology,and photoluminescence property of the as-prepared phosphor were investigated by X-ray diffraction(XRD,scaning electron microscope(SEM,photoluminescence spectroscopy and UV-Vis reflection spectroscopy.The crystallinities,morphologies,and photoluminescence properties of the phosphors prepared by sol-gel combustion and solid-state reaction were compared.The reasons causing different performance of the phosphors were discussed.

  11. Phase relationships in the BaO-Ga2O3-Ta2O5 system and the structure of Ba6Ga21TaO40.

    Science.gov (United States)

    Cao, Jiang; Yu, Xiaodi; Kuang, Xiaojun; Su, Qiang

    2012-07-16

    Phase relationships in the BaO-Ga(2)O(3)-Ta(2)O(5) ternary system at 1200 °C were determined. The A(6)B(10)O(30) tetragonal tungsten bronze (TTB) related solution in the BaO-Ta(2)O(5) subsystem dissolved up to ~11 mol % Ga(2)O(3), forming a ternary trapezoid-shaped TTB-related solid solution region defined by the BaTa(2)O(6), Ba(1.1)Ta(5)O(13.6), Ba(1.58)Ga(0.92)Ta(4.08)O(13.16), and Ba(6)GaTa(9)O(30) compositions in the BaO-Ga(2)O(3)-Ta(2)O(5) system. Two ternary phases Ba(6)Ga(21)TaO(40) and eight-layer twinned hexagonal perovskite solid solution Ba(8)Ga(4-x)Ta(4+0.6x)O(24) were confirmed in the BaO-Ga(2)O(3)-Ta(2)O(5) system. Ba(6)Ga(21)TaO(40) crystallized in a monoclinic cell of a = 15.9130(2) Å, b = 11.7309(1) Å, c = 5.13593(6) Å, β = 107.7893(9)°, and Z = 1 in space group C2/m. The structure of Ba(6)Ga(21)TaO(40) was solved by the charge flipping method, and it represents a three-dimensional (3D) mixed GaO(4) tetrahedral and GaO(6)/TaO(6) octahedral framework, forming mixed 1D 5/6-fold tunnels that accommodate the Ba cations along the c axis. The electrical property of Ba(6)Ga(21)TaO(40) was characterized by using ac impedance spectroscopy.

  12. Synthesis and superstructure of La sub(2/3) (Mg sub(1/2)W sub(1/2))O/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Torii, Y [Government Industrial Research Inst., Nagoya (Japan)

    1979-10-01

    A new perovskite La sub(2/3)(Mg sub(1/2)W sub(1/2))O/sub 3/ having an orthorhombic multiple-cell was synthesized. The lattice constants were a = 7.8157(5) A, b = 7.8344(6) A and c = 2 x 7.9067(6) A. The superstructure was found to be due to a NaCl-type ordering of B ions as well as an ordering of A-site vacancies.

  13. Non-stoichiometry in the KMo2P3O12-tunnel structure: The oxide K0.75MoNbP3O12

    International Nuclear Information System (INIS)

    Leclaire, A.; Borel, M.M.; Grandin, A.; Raveau, B.

    1990-01-01

    K 0.75 MoNbP 3 O 12 , M r =503.009, orthorhombic, Pbcm, a=8.8518 (5), b=9.1453 (11), c=12.5174 (11) A, V=1013.3 (3) A 3 , Z=4, D x =3.300 Mg m -3 , λ(Mo Kα)=0.71073 A, μ=3.13 mm -1 , F(000)=953, T=294 K, R=0.029, wR=0.033 for 1235 observed reflections. This compound is isostructural with KMo 2 P 3 O 12 -type oxides. Its framework is built up from MoO 6 octahedra and PO 4 tetrahedra which delimit tunnels running along b. Different from KMo 2 P 3 O 12 , the tunnels are partly occupied by the potassium ions which are distributed at random. (orig.)

  14. Synthesis and physical properties of the CuFe{sub 2−x}Mn{sub x}O{sub 4} (0 ≤ x ≤ 2) solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Helaïli, N. [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, U.S.T.H.B., BP 32 El-Alia, 16111 Algiers (Algeria); Centre of Research in Physical and Chemical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Bessekhouad, Y., E-mail: ybessekhouad@yahoo.fr [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, U.S.T.H.B., BP 32 El-Alia, 16111 Algiers (Algeria); National Veterinary High School, BP 161-El Harrach, Algiers (Algeria); Bachari, K. [Centre of Research in Physical and Chemical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Trari, M. [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, U.S.T.H.B., BP 32 El-Alia, 16111 Algiers (Algeria)

    2014-12-15

    The CuFe{sub 2−x}Mn{sub x}O{sub 4} (0 ≤ x ≤ 2) solid solutions have been prepared by direct solid state reaction and the dependence of optical, electrical and electrochemical properties on the composition has been investigated. All samples exhibited the formation of a unique cubic phase irrespective of the composition with crystallite sizes on the order of 44 nm. Mn is localized in both octahedral and tetrahedral sites, and forms Mn{sup 3+}–O{sup 2−} complexes. The CuFe{sub 2−x}Mn{sub x}O{sub 4} system exhibits a p-type conductivity with indirect transition band gaps that decrease from 1.54 to 1.28 eV. Charge transport occurs either between Fe{sup 2+}/Fe{sup 3+} or Mn{sup 2+}/Mn{sup 3+} ions in B-sites according to the x value, and the conduction mechanism is controlled by small polaron hopping with a thermal activation of the mobility (μ), which is in the order of ∼10{sup −5} cm{sup 2} V{sup −1}s{sup −1} and does not depend on x. The conduction bands are particularly affected by the Mn introduction and the potentials can shift by as much as 0.5 eV. Finally, the CuFe{sub 2−x}Mn{sub x}O{sub 4} system was used as a bulk electrode in a photoelectrochemical cell and as a microphotoelectrode for H{sub 2}-production. CuFe{sub 1.6}Mn{sub 0.4}O{sub 4} demonstrates the best quantum conversion efficiency in terms of electricity (η = 0.21) and H{sub 2}-production (η{sup ∗} = 1.59). - Highlights: • The CuFe{sub 2−x}Mn{sub x}O{sub 4} (0 ≤ x ≤ 2) solid solutions have been prepared by solid state reaction. • CuFe{sub 2−x}Mn{sub x}O{sub 4} system exhibits p-type conductivity with indirect transition band gaps. • The charge transport occurs either between Fe{sup 2+}/Fe{sup 3+} or Mn{sup 2+}/Mn{sup 3+} ions in B-sites. • CuFe{sub 1.6}Mn{sub 0.4}O{sub 4} demonstrates the best quantum conversion efficiency {η"∗(H_2) = 1.59}.

  15. Synthesis and structure of a pink pigment in the system Zr02-TiO2-SnO2-Cr2O3

    International Nuclear Information System (INIS)

    Zygadlo, M.

    1979-01-01

    The mechanism has been discussed of the formation of this pigment in the ceramic glazes and the results are communicated of the experiment to synthetize this pigment and to test it by the thermographic, X-ray and electron-microsonde methods. It has been found that the pink pigment is the result of dispersion of Cr 2 O 3 upon the grain areas of Zr0 2 , TiO 2 and SnO 2 : it is not a solid solution of Cr 2 O 3 in these oxides as has been earlier suggested. (author)

  16. Hexa-μ-acetato-1:2κ4O,O′;1:2κ2O:O;2:3κ4O,O′;2:3κ2O:O-bis(4,4′-dimethyl-2,2′-bipyridine-1κ2N,N′;3κ2N,N′-2-calcium-1,3-dizinc

    Directory of Open Access Journals (Sweden)

    Md. Alamgir Hossain

    2013-12-01

    Full Text Available In the centrosymmetric trinuclear ZnII...CaII...ZnII title complex, [CaZn2(CH3COO6(C12H12N22], the CaII ion lies on an inversion centre and is octahedrally coordinated by six acetate O atoms. The ZnII ion is coordinated by two N atoms from a bidentate dimethylbipyridine ligand and three O atoms from acetate ligands bridging to the CaII ion, leading to a distorted square-pyramidal coordination sphere. The Zn...Ca distance is 3.4668 (5 Å.

  17. Effect of Al2O3 on the sintering of garnet-type Li6.5La3Zr1.5Ta0.5O12

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuxing; Yan, Pengfei; Xiao, Jie; Lu, Xiaochuan; Zhang, Ji-Guang; Sprenkle, Vincent L.

    2016-10-01

    It is widely recognized that Al plays a dual role in the fabrication of garnet-type solid electrolytes, i.e., as a dopant that stabilizes the cubic structure and a sintering aid that facilitates the densification. However, the sintering effect of Al2O3 has not been well understood so far because Al is typically “unintentionally” introduced into the sample from the crucible during the fabrication process. In this study, we have investigated the sintering effect of Al on the phase composition, microstructure, and ionic conductivity of Li6.5La3Zr1.5Ta0.5O12 by using an Al-free crucible and intentionally adding various amounts of γ-Al2O3. It was found that the densification of Li6.5La3Zr1.5Ta0.5O12 occurred via liquid-phase sintering, with evidence of morphology change among different compositions. Among all of the compositions, samples with 0.05 mol of Al per unit formula of garnet oxide (i.e., 0.3 wt% Al2O3) exhibited the optimal microstructure and the highest total ionic conductivity of 5 10-4 S cm-1 at room temperature.

  18. Family of defect-dicubane Ni4Ln2 (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 complexes: rare Tb(III) and Ho(III) examples showing SMM behavior.

    Science.gov (United States)

    Zhao, Lang; Wu, Jianfeng; Ke, Hongshan; Tang, Jinkui

    2014-04-07

    Reactions of Ln(III) perchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2 complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d-4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2 (5) complex containing diamagnetic Y(III) atoms was also isolated to assist the magnetic studies. Interestingly, complexes 2 and 3 exhibit SMM characteristics and 4 shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni-Y species suggests that the Ln ions' contribution to the slow relaxation must be effectual as previously observed in other Ni-Dy samples. However, the observation of χ″ signals with zero dc field for the Ni-Tb and Ni-Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni-Tb and Ni-Ho complexes.

  19. High-temperature thermoelectric properties of the β-As2−xBixTe3 solid solution

    Directory of Open Access Journals (Sweden)

    J.-B. Vaney

    2016-10-01

    Full Text Available Bi2Te3-based compounds are a well-known class of outstanding thermoelectric materials. β-As2Te3, another member of this family, exhibits promising thermoelectric properties around 400 K when appropriately doped. Herein, we investigate the high-temperature thermoelectric properties of the β-As2−xBixTe3 solid solution. Powder X-ray diffraction and scanning electron microscopy experiments showed that a solid solution only exists up to x = 0.035. We found that substituting Bi for As has a beneficial influence on the thermopower, which, combined with extremely low thermal conductivity values, results in a maximum ZT value of 0.7 at 423 K for x = 0.017 perpendicular to the pressing direction.

  20. Exploring the critical dependence of adsorption of various dyes on the degradation rate using Ln3+-TiO2 surface under UV/solar light

    International Nuclear Information System (INIS)

    Devi, L. Gomathi; Kumar, S. Girish

    2012-01-01

    Graphical abstract: The surface reactive acidic sites enhances on doping with rare earth ions which facilitates efficient adsorption of the dye molecules on the catalyst surface. In addition, the nature of the dopant, its concentration and electronic configuration additionally contributes to the overall efficiency. Highlights: ► The degradation of structurally different anionic dyes under different pH conditions is reported. ► Pre adsorption of pollutant on catalyst surface is vital for efficient photocatalysis. ► Adsorption of dye on the catalyst surface depends on the substituent's attached to it. ► The dopant with half filled electronic configuration served as shallow traps for charge carriers. - Abstract: The degradation of structurally different anionic dyes like Alizarin Red S (ARS) Amaranth (AR), Brilliant Yellow (BY), Congo Red (CR), Fast Red (FR), Methyl Orange (MO), and Methyl Red (MR) were carried out using Ln 3+ (Ln 3+ = La 3+ , Ce 3+ and Gd 3+ ) doped TiO 2 at different pH conditions under UV/solar light. All the anionic dyes underwent rapid degradation at acidic pH, while resisted at alkaline conditions due to the adsorptive tendency of these dyes on the catalyst surface at different pH conditions. Gd 3+ (0.15 mol%)-TiO 2 exhibited better activity compared to other photocatalyst ascribed to half filled electronic configuration of Gd 3+ ions. It is proposed that Ln 3+ serves only as charge carrier traps under UV light, while it also act as visible light sensitizers under solar light. Irrespective of the catalyst and excitation source, the dye degradation followed the order: AR > FR > MO > MR > ARS > BY > CR. The results suggest that pre-adsorption of the pollutant is vital for efficient photocatalysis which is dependent on the nature of the substituent's group attached to the dye molecule.

  1. Crystallization of pyroxene phases and physico-chemical properties of glass-ceramics based on Li{sub 2}O–Cr{sub 2}O{sub 3}–SiO{sub 2} eutectic glass system

    Energy Technology Data Exchange (ETDEWEB)

    Salman, S.M.; Salama, S.N.; Abo-Mosallam, H.A., E-mail: abomosallam@yahoo.com.au

    2015-01-15

    The crystallization characteristics, crystalline phase assemblages and solid solution phases developed due to thermally crystallized glasses based on the Li{sub 2}SiO{sub 3}–Li{sub 2}Si{sub 2}O{sub 5}–LiCrSi{sub 2}O{sub 6} (1028 ± 3 °C) eutectic glass system by replacing some trivalent oxides instead of Cr{sub 2}O{sub 3} were investigated. The microhardness and chemical durability of the glass-ceramics were also determined. Lithium meta and disilicate (Li{sub 2}SiO{sub 3} and Li{sub 2}Si{sub 2}O{sub 5}), lithium gallium silicate (LiGaSiO{sub 4}), and varieties of pyroxene phases, including Cr-pyroxene phase, i.e. lithium-kosmochlor (LiCrSi{sub 2}O{sub 6}), lithium aluminum silicate (LiAlSi{sub 2}O{sub 6}), lithium indium silicate (LiInSi{sub 2}O{sub 6}) and pyroxene solid solution of Li-aegerine type [Li (Fe{sub 0.5}, Cr{sub 0.5}) Si{sub 2}O{sub 6}] were the main crystalline phases formed in the crystallized glasses. There is no evidence for the formation of solid solution or liquid immiscibility gaps between LiAlSi{sub 2}O{sub 6} or LiInSi{sub 2}O{sub 6} phases and LiCrSi{sub 2}O{sub 6} phase. However, LiCrSi{sub 2}O{sub 6} and LiFeSi{sub 2}O{sub 6} components were accommodated in the pyroxene structure under favorable conditions of crystallization to form monomineralic pyroxene solid solution phase of the probably formula [Li (Fe{sub 0.5}, Cr{sub 0.5}) Si{sub 2}O{sub 6}]. The type and compatibility of the crystallized phases are discussed in relation to the compositional variation of the glasses and heat-treatment applied. The microhardness values of the crystalline materials ranged between 5282 and 6419 MPa while, the results showed that the chemical stability of the glass-ceramics was better in alkaline than in acidic media. - Highlights: • Glass ceramics based on Li{sub 2}O–Cr{sub 2}O{sub 3}–SiO{sub 2} eutectic (1028 ± 3 °C) glass were prepared. • LiCrSi{sub 2}O{sub 6} and LiFeSi{sub 2}O{sub 6} phases form monomineralic pyroxene solid

  2. The influence of SiO2 Addition on 2MgO-Al2O3-3.3P2O5 Glass

    DEFF Research Database (Denmark)

    Larsen, P.H.; Poulsen, F.W.; Berg, Rolf W.

    1999-01-01

    2MgO-Al2O3-3.3P2O5 glasses with increasing amounts of SiO2 are considered for sealing applications in Solid Oxide Fuel Cells (SOFC). The change in chemical durability under SOFC anode conditions and the linear thermal expansion is measured as functions of the SiO2 concentration. Raman spectroscopy...... analysis of the glasses reveals no sign of important changes in the glass structure upon SiO2 addition. Some increase in glass durability with SiO2 concentration is reported and its cause is discussed....

  3. Effect of La2O3 content on wear resistance of alumina ceramics

    Institute of Scientific and Technical Information of China (English)

    WU Tingting; ZHOU Jian; WU Bolin; LI Wenjie

    2016-01-01

    In order to improve the wear resistance, a kind of alumina ceramic with good wear resistance was created in an Al2O3-CaCO3-SiO2-MgO-La2O3 (ACSML) system. The effects of La2O3 content on sintering temperature, bulk density, and wear rate were investigated. The wear rate of sample was as low as 0.0393‰. The wear resistance of the sample containing La2O3 has im-proved 43% than that of the sample without La2O3. Appropriate La2O3 doping could inhibit grain growth, enhance density, and purify grain boundary. La2O3 could diffuse into Al2O3 to form a solid solution and react with Al2O3 to form high-aluminum low-lanthanum complex oxides. The combination among Al2O3, the solid solution layer, and the layer of high-aluminum low-lanthanum complex oxides combined closely, which could improve grain boundary cohesion. Besides, the homogeneous distributions of elements made uniform structure. Finally, the wear resistance of alumina ceramic was improved.

  4. Reaction of (CP(2)asterisk-lnH)(2) (ln=Y, La) and CP(2)asterisk-Y(2-C(6)H(4)CH(2)NMe(2)) with esters and amides and molecular-structure of [CP(2)asterisk-Y(mu- ocme=chc(oet)o)](2)

    NARCIS (Netherlands)

    Deelman, B.J; Wierda, F.; Meetsma, A.; Teuben, J.H

    1995-01-01

    The activation of esters and amides by (Cp(2)*LnH)(2) [Ln = Y (1a), Ln = La (1b), Cp*=C(5)Me] and Cp(2)*Y(2-C(6)H(4)CH(2)NMe(2)) (2) is described. Compounds 1a and 1b react with ethyl acetate to form Cp(2)*YOEt (3a) and Cp(2)*LaOEt (30). With 1a and ethyl benzoate a 1:1 mixture of 3a and

  5. A comparative Moessbauer study of the Nd1+xBa2-x(Cu0.9757Fe0.03)3Oz solid solution: the role of low-temperature treatment

    International Nuclear Information System (INIS)

    Goodilin, E A; Peryshkov, D V; Presniakov, I A; Didenko, K V; Tretyakov, Yu D

    2004-01-01

    Local structure features of the Nd 1+x Ba 2-x (Cu 0.97 57 Fe 0.03 ) 3 O z solid solution with various oxygen contents and cation compositions were examined for the first time by Moessbauer spectroscopy to explore the effects of cation disorder in the cases of the anomalous pseudocubic x = 0 phase, the x = 0.6 tetragonal solid solution with Nd stochastically substituting Ba and also the x = 0.9 orthorhombic phase with superstructurally ordered Nd and Ba. A new spectral component characterized by an isomer shift δ = 0 mm s -1 and quadrupole splitting Δ = 0 mm s -1 was found for all the cases, evidencing the formation of associated defects such as 'Fe(IV) Cu1 O 6 -Nd Ba ' and confirming antistructural disordering of Nd 3+ and Ba 2+ in low-T c NdBa 2 Cu 3 O z samples

  6. General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y).

    Science.gov (United States)

    Geng, Fengxia; Matsushita, Yoshitaka; Ma, Renzhi; Xin, Hao; Tanaka, Masahiko; Izumi, Fujio; Iyi, Nobuo; Sasaki, Takayoshi

    2008-12-03

    The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water

  7. Structural and photoluminescence study of Er-Yb codoped nanocrystalline ZrO{sub 2}-B{sub 2}O{sub 3} solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Salas, P. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, A.P. 1-1010, Queretaro 76000 (Mexico); Borja-Urby, R. [Grupo de Espectroscopia de Materiales Avanzados y nanoestructurados (EMANA), Centro de Investigaciones en Optica, A. C., Loma del Bosque 115, Col. Lomas del Campestre, C.P. 37150 Leon, Gto. (Mexico); Diaz-Torres, L.A., E-mail: ditlacio@cio.mx [Grupo de Espectroscopia de Materiales Avanzados y nanoestructurados (EMANA), Centro de Investigaciones en Optica, A. C., Loma del Bosque 115, Col. Lomas del Campestre, C.P. 37150 Leon, Gto. (Mexico); Rodriguez, G. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, A.P. 1-1010, Queretaro 76000 (Mexico); Vega, M. [Centro de Geociencias, Universidad Nacional Autonoma de Mexico, A.P. 1-1010, Queretaro 76000 (Mexico); Angeles-Chavez, C. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas 152, A.P. 14-805, 07730 Mexico, DF (Mexico)

    2012-09-20

    Codoped Er{sup 3+} and Yb{sup 3+} nanocrystalline ZrO{sub 2}-B{sub 2}O{sub 3} phosphor obtained by a modified sol-gel method is demonstrated. The addition of up to 2.5 mol% B{sub 2}O{sub 3} to nanocrystalline ZrO{sub 2}:Yb(2%), Er(1%) keep the tetragonal rare-earth stabilized ZrO{sub 2} phase; whereas higher B{sub 2}O{sub 3} content destabilize the tetragonal phase, leading to the tetragonal to monoclinic transition with no tetragonal ZrO{sub 2} phase segregation. Visible upconversion of the luminescent active ions, Er{sup 3+} and Yb{sup 3+}, depend strongly on B{sub 2}O{sub 3} content. The PL intensity is strongly quenched for high B{sub 2}O{sub 3} content due to increasing multiphonon relaxation processes related to B-O and B-O-B vibronic modes.

  8. Phase relations in crystalline ceramic nuclear waste forms the system UO/sub 2 + x/-CeO2-ZrO2-ThO2 at 12000C in air

    International Nuclear Information System (INIS)

    Pepin, J.G.; McCarthy, G.J.

    1981-01-01

    Steady-state phase relations in the system UO/sub 2 + x/-CeO 2 -ZrO 2 -ThO 2 were determined for application to phase relations in the high-level crystalline ceramic nuclear waste form Supercalcine-Ceramics. Samples were treated at 1200 0 C at an oxygen partial pressure of 0.21 atm and a total pressure of 1 atm. Phase assemblages were found to be composed of cubic solid solutions of the flourite structure type, solid solutions based on ZrO 2 , and orthorhombic solid solutions based on U 3 O 8

  9. Homogeneity and microstructure study of Gd2O3-UO2 pellets

    International Nuclear Information System (INIS)

    Pan Ying; Gao Dihua; Guo Yibai; Zhu Shuming

    1994-10-01

    The microstructure of Gd 2 O 3 -UO 2 pellets (0∼10 wt%) prepared in different conditions, the homogeneity distribution of Gd 2 O 3 in the pellets and the lattice parameter of solid solution are studied by metalloscope, WDS, EDAX, SEM-image processing system, XRD and image analyzer. The theoretical density has been calculated. The effect of size and content of Gd 2 O 3 particles, the blend process, the sintering temperature and time, and the sintering atmosphere on the microstructure of Gd 2 O 3 pellets and the homogeneity of Gd 2 O 3 in the pellets are studied. (16 refs., 10 figs., 8 tabs.)

  10. High ion conductive Sb2O5-doped β-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries

    Science.gov (United States)

    Xie, Dongjiu; Chen, Shaojie; Zhang, Zhihua; Ren, Jie; Yao, Lili; Wu, Linbin; Yao, Xiayin; Xu, Xiaoxiong

    2018-06-01

    The combination of high conductivity and good stability against Li is not easy to achieve for solid electrolytes, hindering the development of high energy solid-state batteries. In this study, doped electrolytes of Li3P1-xSbxS4-2.5xO2.5x are successfully prepared via the high energy ball milling and subsequent heat treatment. Plenty of techniques like XRD, Raman, SEM, EDS and TEM are utilized to characterize the crystal structures, particle sizes, and morphologies of the glass-ceramic electrolytes. Among them, the Li3P0.98Sb0.02S3.95O0.05 (x = 0.02) exhibits the highest ionic conductivity (∼1.08 mS cm-1) at room temperature with an excellent stability against lithium. In addition, all-solid-state lithium batteries are assembled with LiCoO2 as cathode, Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 as the bi-layer electrolyte, and lithium as anode. The constructed solid-state batteries delivers a high initial discharge capacity of 133 mAh g-1 at 0.1C in the range of 3.0-4.3 V vs. Li/Li+ at room temperature, and shows a capacity retention of 78.6% after 50 cycles. Most importantly, the all-solid-state lithium batteries with the Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 electrolyte can be workable even at -10 °C. This study provides a promising electrolyte with the improved conductivity and stability against Li for the application of all-solid-state lithium batteries.

  11. Epitaxial growth of Er, Ti doped LiNbO3 films prepared by sol-gel method

    International Nuclear Information System (INIS)

    Takahashi, Makoto; Yoshiga, Tsuyoshi; Kajitani, Naofumi; Takeda, Yuki; Sato, Shoji; Wakita, Koichi; Ohnishi, Naoyuki; Hotta, Kazutoshi; Kurachi, Masato

    2006-01-01

    Erbium (Er 3+ ) doped lithium niobate (LiNbO 3 ) thick films were deposited on z-cut congruent LiNbO 3 (LN) substrate by the sol-gel method from the 0.20 mol/dm 3 precursor solution containing various Er 3+ concentration and 0.10 mol/dm 3 poly(vinyl alcohol) (PVA), and their crystal characteristics were evaluated. The Er 3+ concentration in the LN film was controlled by the Er 3+ concentration in the starting solution. The orientation relationships between Er doped LN films and substrates were determined by X-ray diffraction, Raman spectroscopy, and transmission electron microscopy, and (006) oriented Er doped LN epitaxial layers with parallel epitaxial relationships could be grown on the z-cut LN wafer. Moreover, it was made clear from the electron beam diffraction measurements that the film came to be polycrystalline, when the Er concentration was over 3 mol%. The refractive index of Er-doped LN films decreased with increasing Er concentration. 1.5 mol% Ti: 1.0 mol% Er LN films, which acted as a waveguide, were prepared by our so-gel method. It showed the 1530 nm emission by 980 nm excitation, which was considered to be due to the Er 3+ corresponding to the 4 I 13/2 → 4 I 15/2 transition. (author)

  12. Monte Carlo simulations for describing the ferroelectric-relaxor crossover in BaTiO3-based solid solutions

    International Nuclear Information System (INIS)

    Padurariu, Leontin; Enachescu, Cristian; Mitoseriu, Liliana

    2011-01-01

    The properties induced by the M 4+ addition (M = Zr, Sn, Hf) in BaM x Ti 1-x O 3 solid solutions have been described on the basis of a 2D Ising-like network and Monte Carlo calculations, in which BaMO 3 randomly distributed unit cells were considered as being non-ferroelectric. The polarization versus temperature dependences when increasing the M 4+ concentration (x) showed a continuous reduction of the remanent polarization and of the critical temperature corresponding to the ferroelectric-paraelectric transition and a modification from a first-order to a second-order phase transition with a broad temperature range for which the transition takes place, as commonly reported for relaxors. The model also describes the system's tendency to reduce the polar clusters' average size while increasing their stability in time at higher temperatures above the Curie range, when a ferroelectric-relaxor crossover is induced by increasing the substitution (x). The equilibrium micropolar states during the polarization reversal process while describing the P(E) loops were comparatively monitored for the ferroelectric (x = 0) and relaxor (x = 0.3) states. Polarization reversal in relaxor compositions proceeds by the growth of several nucleated domains (the 'labyrinthine domain pattern') instead of the large scale domain formation typical for the ferroelectric state. The spatial and temporal evolution of the polar clusters in BaM x Ti 1-x O 3 solid solutions at various x has also been described by the correlation length and correlation time. As expected for the ferroelectric-relaxor crossover characterized by a progressive increasing degree of disorder, local fluctuations cause a reducing correlation time when the substitution degree increases, at a given temperature. The correlation time around the Curie temperature increases, reflecting the increasing stability in time of some polar nanoregions in relaxors in comparison with ferroelectrics, which was experimentally proved in

  13. Chemical and structural changes in Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) lanthanide nickelates as a function of oxygen partial pressure at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Flura, Aurélien; Dru, Sophie; Nicollet, Clément; Vibhu, Vaibhav; Fourcade, Sébastien; Lebraud, Eric; Rougier, Aline; Bassat, Jean-Marc; Grenier, Jean-Claude, E-mail: grenier@icmcb-bordeaux.cnrs.fr

    2015-08-15

    The chemical stability of lanthanide nickelates Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) has been studied in the temperature range 25–1300 °C, either in air or at low pO{sub 2} (down to 10{sup −4} atm). Thermal gravimetry analysis (TGA) measurements coupled with X-ray diffraction (XRD) characterization have shown that all compounds retain their K{sub 2}NiF{sub 4}-type structure in these conditions, while remaining over-stoichiometric in oxygen up to 1000 °C. Only Nd{sub 2}NiO{sub 4+δ} starts to decompose into Nd{sub 2}O{sub 3} and NiO above 1000 °C, at pO{sub 2}=10{sup −4} atm. In addition, a careful analysis of the lanthanide nickelates structural features has been performed by in situ XRD, as a function of temperature and pO{sub 2}. For all compounds, a structural transition has been always observed in the temperature range 200–400 °C, in air or at pO{sub 2}=10{sup −4} atm. In addition, their cell volume did not vary upon the variation of the oxygen partial pressure. Therefore, these materials do not exhibit a chemical expansion in these conditions, which is beneficial for a fuel cell application as cathode layers. Additional dilatometry measurements have revealed that a temperature as high as 950 °C for Pr{sub 2}NiO{sub 4+δ} or 1100 °C for La{sub 2}NiO{sub 4+δ} and Nd{sub 2}NiO{sub 4+δ} has to be reached in order to begin the sintering of the material particles, which is of primary importance to obtain an efficient electronic/ionic conduction in the corresponding designed cathode layers. Besides, excellent matching was found between the thermal expansion coefficients of lanthanide nickelates and SOFC electrolytes such as 8wt% yttria stabilized zirconia (8YSZ) or Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} (GDC), at least from 400 °C up to 1400 °C in air or up to 1200 °C at pO{sub 2}=10{sup −4} atm. - Graphical abstract: This study reports the good chemical stability of oxygen overstoichiometric Ln2NiO4+δ(Ln = La, Pr or Nd) at high temperatures

  14. Synthesis, structure and phase separation of a new 12R-type perovskite-related oxide Ba3NdMn2O9

    International Nuclear Information System (INIS)

    Yang, H.; Tang, Y.K.; Yao, L.D.; Zhang, W.; Li, Q.A.; Li, F.Y.; Jin, C.Q.; Yu, R.C.

    2007-01-01

    A new 12R-type perovskite-related oxide, Ba 3 NdMn 2 O 9 , has been prepared by traditional solid-state reaction method and the presence of chemical phase separation phenomenon has been revealed by transmission electron microscopy. The perfect grains of the compound have an average chemical composition of Ba 4 NdMn 3 O 12 (mainly for cationic ratio) according to the characterization by TEM-EDX. In this perfect 12R-type structure with composition Ba 4 NdMn 3 O 12 , the Nd cations are located in the corner-sharing octahedra, whereas the Mn cations are located in the face-sharing octahedra, leading to a remarkable cation ordering. Superstructure modulation was found to be a common phenomenon in the 12R polytype and the modulated areas were revealed by both EDX and EELS to be Nd rich compared to the perfect areas. This result together with the previous work [A.F. Fuentes, K. Boulahya, U. Amador, J. Solid State Chem. 177 (2004) 714] has shown that, for the rare-earth-containing Ba-RE-Mn-O systems (RE being rare-earth elements), the composition Ba 4 REMn 3 O 12 (mainly for cationic ratio) is required for the formation of perfect 12R polytype

  15. Low temperature synthesis of non-crystaline solids of the system SrO-SiO2

    International Nuclear Information System (INIS)

    Yamane, M.; Kojima, T.

    1981-01-01

    Non-crystalline solids within the liquid-liquid immiscibility region in the system SrO-SiO 2 have been prepared from a gel obtained by the hydrolysis of silicon tetramethoxide with an aqueous solution of strontium nitrate. The gel which was porous and translucent at room temperature increased in transparency with heating due to the collapse of micropores until it became completely clear. The gel became opaque again due to the precipitation of α-quartz at higher temperatures. The critical temperatures below which clear solids were obtained fell on a line connecting the glass transition temperatures of vitreous silica and those of SrO-SiO 2 glass prepared by melting. The density and refractive index of the pore-free, clear glassy solid, changed continuously with the SrO content along lines connecting those of vitreous silica and SrO-SiO 2 glasses of high SrO content prepared by melting. The maximum amount of Sr 2+ which could be introduced using an aqueous solution as the starting material corresponded to a composition of 10 SrO x 90 SiO 2 by weight. (orig.)

  16. Dielectric, piezoelectric properties of MnO2-doped (K0.5Na0.5)NbO3–0.05LiNbO3 crystal grown by flux-Bridgman method

    International Nuclear Information System (INIS)

    Liu, Ying; Xu, Guisheng; Liu, Jinfeng; Yang, Danfeng; Chen, Xiaxia

    2014-01-01

    Highlights: • KNN–0.05LN based single crystals were grown by flux-Bridgman method. • Dielectric, piezoelecrc and ferroelectric properties were studied. • The effect of MnO 2 doping on the crystals' properties. • Dielectric and other properties were improved due to MnO 2 doping. - Abstract: Lead-free potassium sodium niobate piezoelectric single crystals substituted with lithium and then doped with MnO 2 (K 0.5 Na 0.5 )NbO 3 –0.05LiNbO 3 –yMnO 2 (y = 0%, 1.0% and 1.5%) (abbreviated as KNN–0.05LN–yMnO 2 ) have been grown by flux-Bridgman method using KCl–K 2 CO 3 eutectic composition as the flux. Their actual composition as well as the dielectric and piezoelectric properties were studied. Their actual composition deviated from the ratio of the raw materials due to different segregation coefficients of K and Na. The orthorhombic–tetragonal (T o–t ) and tetragonal–cubic phase transition temperature (the Curie temperature T c ) of the single crystal appears at 186 °C and 441 °C, respectively, for KNN–0.05LN–1.0%MnO 2 , shift to higher temperatures compared with that of pure KNN–0.05LN crystals, according to the dielectric permittivity versus temperature loops. The KNN–0.05LN–1.0%MnO 2 (001) plate shows higher piezoelectric coefficient d 33 and dielectric permittivity ε r when compared with pure KNN–0.05LN crystal, being on the order of 226 pC/N and 799 (161 pC/N and 530 for KNN–0.05LN), respectively. These excellent properties show that MnO 2 dopant is effective in improving KNN–0.05LN based piezoelectric crystals

  17. Characteristics of transfer of europium ions from phosphoric acid solution into the CaSO4·O.5H2O solid phase

    International Nuclear Information System (INIS)

    Berdonosova, D.G.; Burlakova, E.V.; Yasenkova, M.A.; Ivanov, L.N.; Melikhov, I.V.

    1989-01-01

    The mechanism of formation of the precipitated CaSO 4 ·0.5H 2 O phase was studied in detail; the precipitation was performed at 80 degree, equimolar solutions of Ca(H 2 PO 4 ) 2 and H 2 SO 4 in phosphoric acid of 38% concentration being used. The availability of detailed information on the mechanism of formation of CaSO 4 ·0.5H 2 O precipitates determined the choice of conditions of study of capture of rare earths. In particular, H 3 PO 4 of 38% P 2 O 5 concentration was used as the medium of formation of the calcium sulfate precipitate. Europium was chosen as the rare earth. Its behavior in the liquid and solid phases was studied by radiometric and luminescence methods. The radionuclide 152 Eu is convenient as a radioactive tracer while luminescence of europium is structure-sensitive; therefore, europium is often used in physicochemical investigations as a luminescent probe. It follows from the data that most of the europium captured by the precipitate during coagulation of the ultramicrocrystals is retained firmly by the solid phase. Therefore, in order to diminish capture of europium (and other rare earths) by the precipitate coagulation of the latter should be prevented

  18. Nanocrystalline (U0.5Ce0.5)O2±x solid solutions through citrate gel-combustion

    Science.gov (United States)

    Maji, D.; Ananthasivan, K.; Venkata Krishnan, R.; Balakrishnan, S.; Amirthapandian, S.; Joseph, Kitheri; Dasgupta, Arup

    2018-04-01

    Nanocrystalline powders of (U0.5Ce0.5)O2±x solid solutions were synthesized in bulk (100-200 g) through the citrate gel combustion. The fuel (citric acid) to oxidant (nitrate) mole ratio (R) was varied from 0.1 to 1.0. Two independent lots of the products obtained through the gel-combustion were calcined at 973 K in air and in a mixture of argon containing 8% H2 respectively. All these powders were characterized for their bulk density, X-ray crystallite size, specific surface area, size distribution of the particles, porosity as well as residual carbon. The morphology and microstructures of these powders were studied by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) respectively. Nanocrystalline single phase fluorite solid solutions having a typical crystallite size of about (7-15 nm) were obtained. These powders were highly porous comprising cuboidal flaky agglomerates. The combustion mixture with an 'R' value of 0.25 was found to undergo volume combustion and was found to yield a product that was distinctly different. The systematic investigation on synthesis and characterization of nanocrystalline UCeO2 is reported for the first time.

  19. Synthesis, Structure, and Magnetism of Tris(amide) {Ln[N(SiMe3)2]3}1- Complexes of the Non-Traditional +2 Lanthanide Ions.

    Science.gov (United States)

    Ryan, Austin Jack; Darago, Lucy E; Balasubramini, Sree Ganesh; Chen, Guo P; Ziller, Joseph W; Furche, Filipp; Long, Jeffrey R; Evans, William J

    2018-02-28

    A new series of Ln2+ complexes has been synthesized that overturns two previous generalizations in rare-earth metal reduction chemistry: that amide ligands do not form isolable complexes of the highly-reducing non-traditional Ln2+ ions and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR2)3 (R = SiMe3) complexes in THF under Ar with M = K or Rb in the presence of 2.2.2-cryptand (crypt) forms crystallographically-characterizable [M(crypt)][Ln(NR2)3] complexes not only for the traditional Tm2+ ion and the configurational crossover ions, Nd2+ and Dy2+, but also for the non-traditional Gd2+, Tb2+, Ho2+, and Er2+ ions. Crystallographic data as well as UV-visible, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4fn5d1 configurations for Ln2+ ions in this tris(silylamide) ligand environment. The Dy2+ complex, [K(crypt)][Dy(NR2)3], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 µB. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The effect of Mn substitution on the structure and magnetic properties of Se(Cu sub 1 sub - sub x Mn sub x)O sub 3 solid solution

    CERN Document Server

    Escamilla, R; Rosales, M I; Moran, E C; Alario-Franco, M A

    2003-01-01

    The effects of Mn substitution on the structure and magnetic properties of the SeMO sub 3 (M = Cu sub 1 sub - sub 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] octahe...

  1. Mechanism and microstructures in Ga2O3 pseudomartensitic solid phase transition.

    Science.gov (United States)

    Zhu, Sheng-Cai; Guan, Shu-Hui; Liu, Zhi-Pan

    2016-07-21

    Solid-to-solid phase transition, although widely exploited in making new materials, challenges persistently our current theory for predicting its complex kinetics and rich microstructures in transition. The Ga2O3α-β phase transformation represents such a common but complex reaction with marked change in cation coordination and crystal density, which was known to yield either amorphous or crystalline products under different synthetic conditions. Here we, via recently developed stochastic surface walking (SSW) method, resolve for the first time the atomistic mechanism of Ga2O3α-β phase transformation, the pathway of which turns out to be the first reaction pathway ever determined for a new type of diffusionless solid phase transition, namely, pseudomartensitic phase transition. We demonstrate that the sensitivity of product crystallinity is caused by its multi-step, multi-type reaction pathway, which bypasses seven intermediate phases and involves all types of elementary solid phase transition steps, i.e. the shearing of O layers (martensitic type), the local diffusion of Ga atoms (reconstructive type) and the significant lattice dilation (dilation type). While the migration of Ga atoms across the close-packed O layers is the rate-determining step and yields "amorphous-like" high energy intermediates, the shearing of O layers contributes to the formation of coherent biphase junctions and the presence of a crystallographic orientation relation, (001)α//(201[combining macron])β + [120]α//[13[combining macron]2]β. Our experiment using high-resolution transmission electron microscopy further confirms the theoretical predictions on the atomic structure of biphase junction and the formation of (201[combining macron])β twin, and also discovers the late occurrence of lattice expansion in the nascent β phase that grows out from the parent α phase. By distinguishing pseudomartensitic transition from other types of mechanisms, we propose general rules to predict the

  2. Ce2O3-SO3-H2O system at 150 and 200 deg C

    International Nuclear Information System (INIS)

    Belokoskov, V.I.; Trofimov, G.V.; Govorukhina, O.A.

    1978-01-01

    The solubility, solid phase composition and crystal characteristics in the Ce 2 O 3 -SO 3 -H 2 O system have been studied in a broad range of sulfuric acid concentrations (25 to 80% SO 3 ) at temperatures from 150 to 200 deg C. It has been established that in the system the equilibrium had been reached after 15 to 20 days. At 150 deg C, Ce 2 (SO 4 ) 3 x2H 2 O, Ce 2 (SO 4 ) 3 xH 2 O sulfates and Ce 2 (SO 4 ) 3 x3H 2 SO 4 acid salt crystallize in the system. At 200 deg C, the same sulfates crystallize in the system, except that the bisaturation points of the system are shifted, with respect to 150 deg C, into the region of higher SO 3 concentration and correspond to solutions with a SO 3 concentration of 57.8 and 65%. The solubility of cerium(3) at 150 deg C is about 0.5% Ce 2 O 3 . An increase in temperature up to 200 deg C leads to a slightly higher solubility of cerium sulfates

  3. Physical properties of iodate solutions and the deliquescence of crystalline I2O5 and HIO3

    Directory of Open Access Journals (Sweden)

    B. J. Murray

    2010-12-01

    Full Text Available Secondary aerosol produced from marine biogenic sources in algal-rich coastal locations will initially be composed of iodine oxide species, most likely I2O5, or its hydrated form HIO3, formed as a result of iodine gas-phase chemistry. At present, there is no quantitative hygroscopic data for these compounds and very little data available for iodate solutions (HIO3 and I2O5 share a common aqueous phase. With increased interest in the role of such aerosol in the marine atmosphere, we have conducted studies of (i the deliquescence behaviour of crystalline HIO3 and I2O5 at 273–303 K, (ii the efflorescence behaviour of aqueous iodate solution droplets, and (iii properties (water activity, density, and viscosity of subsaturated and saturated iodate solutions. The deliquescence of I2O5 crystals at 293 K was observed to occur at a relative humidity (DRH of 80.8±1.0%, whereas for HIO3, a DRH of 85.0±1.0% was measured. These values are consistent with measured water activity values for saturated I2O5 and HIO3 solutions at 293 K of 0.80±0.01 and 0.84±0.01 respectively. At all temperatures, DRH values for HIO3 crystals were observed to be higher than for those of I2O5. The temperature-dependent DRH data, along with solubility and water activity data were used to evaluate the enthalpy of solution (ΔHsol for HIO3 and I2O5. A ΔHsol value of 8.3±0.7 kJ mol−1 was determined for HIO3 which is consistent with a literature value of 8.8 kJ mol−1. For I2O5, we report for the first time its solubility at various temperatures and ΔHsol = 12.4±0.6 kJ mol−1. The measured water activity values confirm that aqueous iodate solutions are strongly non-ideal, consistent with previous reports of complex ion formation and molecular aggregation.

  4. In2Mo3O12: A low negative thermal expansion compound

    International Nuclear Information System (INIS)

    Marinkovic, Bojan A.; Ari, Monica; Jardim, Paula Mendes; Avillez, Roberto R. de; Rizzo, Fernando; Ferreira, Fabio Furlan

    2010-01-01

    Orthorhombic In 2 Mo 3 O 12 has low negative linear coefficient of thermal expansion (α l = -1.85 x 10 -6 o C -1 ) as evaluated by X-ray powder diffraction using a synchrotron facility. The linear coefficient of thermal expansion for orthorhombic In 2 Mo 3 O 12 is directly dependent on the inherent volume distortion parameter (υ) of InO 6 . This finding strongly corroborates the recently proposed relationship between the linear coefficient of thermal expansion in A 2 M 3 O 12 compounds (α l ) and the distortion level of AO 6 polyhedra. With the increase of inherent distortion parameter (υ) of AO 6 polyhedra, the linear coefficient of thermal expansion becomes more negative. Another important feature of AO 6 polyhedra, including InO 6 , is that their distortion increases as a function of temperature. Orthorhombic In 2 Mo 3 O 12 is stable in the studied temperature range, 370-760 o C.

  5. Cu4Pr6(MoO4)11-Pr2(MoO4)3 system

    International Nuclear Information System (INIS)

    Arzumanyan, G.A.

    1982-01-01

    Existence boundaries and Dalton compositions (CuPr(MoO 4 ) 2 , CuPr 3 (MoO 4 ) 5 ) of solid solutions that in the mojority are of shcheelite dsitored structure have been determined in the Cu 4 Pr 6 (MoO 4 ) 11 -Pr 2 (MoO 4 ) 3 system. It has been revealed that regions of homogeneity near the CuPr(MoO 4 ) 2 composition have a horseshoeshaped profile

  6. New Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 Quaternary Ceramics: Morphotropic Phase Boundary Design and Electrical Properties.

    Science.gov (United States)

    Luo, Nengneng; Zhang, Shujun; Li, Qiang; Xu, Chao; Yang, Zhanlue; Yan, Qingfeng; Zhang, Yiling; Shrout, Thomas R

    2016-06-22

    Four series of Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 (PMN-PIN-PZ-PT) quaternary ceramics with compositions located at the morphotropic phase boundary (MPB) regions were prepared. The MPBs of the multicomponent system were predicted using a linear combination rule and experimentally confirmed by X-ray powder diffraction and electrical measurement. The positions of MPBs in multicomponent systems were found in linear correlation with the tolerance factor and ionic radii of non-PT end-members. The phase structure, piezoelectric coefficient, electromechanical coupling coefficient, unipolar strains, and dielectric properties of as-prepared ceramics were systematically investigated. The largest d33s were obtained at S36.8, L37.4, M39.6, and N35.8, with the corresponding values of 580, 450, 420, and 530 pC/N, respectively, while the largest kps were found at S34.8, L37.4, M39.6, and N35.8, with the respective values of 0.54, 0.50, 0.47, and 0.53. The largest unipolar strain Smax and high-field piezoelectric strain coefficients d33* were also observed around the respective MPB regions. The rhombohedral-to-tetragonal phase transition temperature Trt increased with increasing PIN and PZ contents. Of particular importance is that high Trt of 140-197 °C was achieved in the M series with PZ and PIN contents being around 0.208 and 0.158, which will broaden the temperature usage range.

  7. Measurement of the transport properties of (Sb2Te3)sub(0.75)(Bi2Te3)sub(0.25) solid solution with addition of Tl2Te3

    International Nuclear Information System (INIS)

    Sher, A.

    1983-03-01

    The thermoelectric parameters of the solid solution (Sb 3 Te 3 )sub(0.75)(Bi 2 Te 3 )sub(0.25) in the presence of a low concentration of Tl 3 Te 3 were examined. The electrical conductivity, thermal conductivity, Seebeck coefficient and Hall constant were measured on samples which represent the upper parts of the ingots, in the temperature range 10K-300K. The lattice thermal conductivity, carrier, mobility, effective mass and carrier concentration were calculated from the measured parameters. The variation of the carrier mobility with temperature was similar in all the measured samples. At temperatures higher than 80K the mobility was proportional to Tsup(-33/2). At lower temperatures the mobility approached a saturation value which decreased with increasing Tl 2 Te 3 concentration. At about room temperature, the mobility was already not proportional to Tsup(x). Increasing the Tl 2 Te 3 or Sb 2 Se 3 concentration resulted in a lower deviation from the Tsup(x) dependence and a slower increase in the lattice thermal conductivity with decreasing temperature. Addition of Tl 2 Te 3 to the solid solution resulted in minor improvement in the thermoelectric quality which depends on the mobility, effective mass and lattice thermal conductivity. The thermoelectric properties were nearly the same as those obtained by addition of Sb 2 Se 3 to the solid solution. The addition of Tl 2 Te 3 annuled an effect of increasing carrier concentration with decreasing temperature. It resulted in a slower decrease in the Seebeck coefficient. (H.K.)

  8. 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.

  9. Doping with lead of single crystals of solid solutions of Sbsub(1,5)Bisub(0,5)Tlsub(3)-Bisub(2)Sesub(3)

    International Nuclear Information System (INIS)

    Abrikosov, N.Kh.; Ivanova, L.D.; Polikarpova, N.V.; Galechyan, M.G.

    1984-01-01

    By the Czochralski method with liquid phase additional feeding single crystals of solid solutions of the Sbsub(1.5)Bisub(0.5)Tesub(3)-Bisub(2)Sesub(3) system with 0, 10 and 15 mol.% of Bi 2 Se 3 content doped with lead up to 1.37 at/cm 3 are grown. Lead content in crystals and alloys is determined by the atom-abmethod using the scale of standard solutions. It has been found that the effective coefficient of lead distribution in investigated solutions is approximately 0.5. It is shown that lead addition leads to increase of electric conductivity and heat conductivity and decrease of thermoelectric coeffcient at the expense of current carriers concentration growth, the lead in crystals of solid solutions of the Sbsub(1.5)Bisub(0.5)Tesub(3)-Bisub(2)Sesub(3) system being a single charge acceptor

  10. Effect of Fe2O3 on the sintering and stabilization of ZrO2-MgO system

    International Nuclear Information System (INIS)

    Longo, E.; Paskocimas, C.A.; Ambrosecchia, J.R.; Weffort, L.C.; Baldo, J.B.; Leite, L.R.; Varela, J.A.

    1990-01-01

    Through X-ray diffraction, it was studied the influence of the iron oxide (Fe 2 O 3 ) as a mineralizer in the development of partially stabilized zirconia phases (cubic/tetragonal) within the system ZrO 2 -MgO. In the preparation of the studied compositions it was utilized a Brazilian comercial zirconia powder and different precursors for the MgO and Fe 2 O 3 additives. It was observed that the main effect of iron oxide consisted on the speed up of the solid solution formation process of Mg + 2 in the Zr +4 sub-lattice, as well as being a very effective sintering agent. (author) [pt

  11. The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

    Science.gov (United States)

    Bernstein, Max; Sandford, Scott; Cruikshank, Dale

    2005-01-01

    Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the

  12. 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)

  13. Study of solubility in Ca(NO3)2-Ln(NO3)3-H2O systems at 25 deg C (Ln-Ce,Pr,Nd)

    International Nuclear Information System (INIS)

    Shevchuk, V.G.; Dryuchko, A.G.; Bunyakina, N.V.; Storozhenko, D.A.

    1983-01-01

    The isothermal method has been used to study solubility in the systems calcium nitrate-cerium (praseodymium, neodymium) nitrate water at 25 deg C. The systems are attributed to eutonic type. Formations of complex compounds and solid solutions are not disclosed

  14. The phase diagram of KNO3-KClO3

    International Nuclear Information System (INIS)

    Zhang Xuejun; Tian Jun; Xu Kangcheng; Gao Yici

    2004-01-01

    The binary phase diagram of KNO 3 -KClO 3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO 3 ) 1-x (ClO 3 ) x (0 3 ) 1-x (ClO 3 ) x (0.90 3 -based solid solutions and KClO 3 -based solid solutions phase, respectively. For KNO 3 -based solid solutions, KNO 3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO 3 by ClO 3 -radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO 3 -based (α) phase and KClO 3 -based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent

  15. Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

    Institute of Scientific and Technical Information of China (English)

    CAI Tiejun; LIAO Yuchao; PENG Zhenshan; LONG Yunfei; WEI Zongyuan; DENG Qian

    2009-01-01

    The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.

  16. Thermal analysis and prediction of phase equilibria in the TiO2-Bi2O3 system

    International Nuclear Information System (INIS)

    Lopez-Martinez, Jaqueline; Romero-Serrano, Antonio; Hernandez-Ramirez, Aurelio; Zeifert, Beatriz; Gomez-Yanez, Carlos; Martinez-Sanchez, Roberto

    2011-01-01

    A thermodynamic study on the TiO 2 -Bi 2 O 3 system was carried out using differential thermal analysis (DTA) and X-Ray diffraction (XRD) techniques covering the composition range from 65 to 90 mol% Bi 2 O 3 . From the XRD results the only two intermediate compounds in the Bi 2 O 3 rich region were Bi 4 Ti 3 O 12 and Bi 12 TiO 20 . The Bi 4 Ti 3 O 12 phase presents the well known plate-like morphology. The experimentally determined phase transition temperatures with DTA technique were compared with thermodynamic calculated results and good agreement was obtained. The DTA results also showed that the limit of the peritectic reaction between liquid and Bi 4 Ti 3 O 12 occurs approximately at 90 mol% Bi 2 O 3 . The phase diagram of the TiO 2 -Bi 2 O 3 system was calculated using a quasichemical model for the liquid phase. The thermodynamic properties of the intermediate compounds were estimated from the data of TiO 2 and Bi 2 O 3 pure solids. In this manner, data for this binary system have been analysed and represented with a small adjustable parameter for the liquid phase.

  17. Ca Mn exchange between grossular and MnCl2 solutions at 2 kbar and 600°°C: reaction mechanism and evidence for non-ideal mixing in spessartine-grossular garnets

    Science.gov (United States)

    Gavrieli, I.; Matthews, Alan; Holland, J. B.

    1996-10-01

    The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich ( X gt Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln KD versus X gt Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters Δ G° (600 °C, 2 kbar)=-8.0±0.8 kJ/mol and w gt CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w gt CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar.

  18. Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

    Science.gov (United States)

    Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

    2018-02-19

    The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 22 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

  19. The investigation of YAlO{sub 3}-NdAlO{sub 3} system, synthesis and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Szysiak, A., E-mail: agnieszka.szysiak@itme.edu.pl [Institute of Electronic Materials Technology, Wolczynska 133, 01-919 Warsaw (Poland); Klimm, D.; Ganschow, S. [Leibniz Institute for Crystal Growth, Max-Born Str. 2, 12489 Berlin (Germany); Mirkowska, M.; Diduszko, R.; Lipinska, L. [Institute of Electronic Materials Technology, Wolczynska 133, 01-919 Warsaw (Poland); Kwasniewski, A. [Leibniz Institute for Crystal Growth, Max-Born Str. 2, 12489 Berlin (Germany); Pajaczkowska, A. [Institute of Electronic Materials Technology, Wolczynska 133, 01-919 Warsaw (Poland)

    2011-09-01

    Highlights: {center_dot} The system YAlO{sub 3}-NdAlO{sub 3} is pseudo-binary. {center_dot} Both end members show high mutual solubility >25% in the solid phase. {center_dot} A solid solution Y{sub 0.8}Nd{sub 0.2} melts azeotropic ca. 20{sup o} below pure YAP. {center_dot} All YAP-rich solid solutions have the 2-phase region between solidus and liquidus. - Abstract: The pseudo-binary phase diagram of the YAlO{sub 3} (YAP)-NdAlO{sub 3} (NAP) system was determined by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) measurements. High purity nanocrystalline powders and small single crystals of Y{sub 1-x}Nd{sub x}AlO{sub 3} (0 {<=} x {<=} 1) have been produced successfully by modified sol-gel (Pechini) and micro-pulling-down methods, respectively. Both end members show high mutual solubility >25% in the solid phase, with a miscibility gap for intermediate compositions. A solid solution with x {approx} 0.2 melts azeotropic ca. 20{sup o} below pure YAP. Such crystals can be grown from the melt without segregation. The narrow solid/liquid region near the azeotrope point could be measured with a 'cycling' DTA measurement technique.

  20. Structural and electrical properties of Na{sub 1/2}La{sub 1/2}TiO{sub 3} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Barik, S K; Mahapatra, P K [Vidyasagar University, Department of Physics and Technophysics, Midnapur, West Bengal (India); Choudhary, R N.P. [Department of Physics and Meteorology, I.I.T. Kharagpur (India)

    2006-11-15

    Na{sub 1/2}La{sub 1/2}TiO{sub 3} (NLT) ceramic was prepared by a high-temperature solid-state reaction technique. A preliminary structural analysis (XRD) suggested the formation of a single-phase orthorhombic structure. SEM micrograph of the material showed uniform grain distribution on the surface of the sample. The dielectric permittivity and the loss tangent of the sample were measured in a frequency range from 1 kHz to 1 MHz and a temperature range 28 C to 525 C. Electrical properties of the material were studied using an ac impedance spectroscopic technique. Detailed analysis of the impedance spectrum suggested that the electrical properties of the material are strongly temperature dependant. The Nyquist plots clearly showed the presence of both bulk and grain boundary effect in the compound. The activation energy was estimated to be 1.1 eV from the temperature variation of dc conductivity. The a.c. conductivity spectrum suggests a typical signature of ion conducting system. (orig.)