Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Molecular construction of oriented crystalline NaMnF3 and KMnF3 with perovskite structures at room temperature

In this work. we report the fabrication of high-quality (101)-oriented orthorhombic NaMnF3 and (100)-oriented cubic KMnF3 perovskites via an organic monolayer template at room temperature. The controlled crystallization under the organic monolayer template is explained in terms of the electrostatic interactions and beneficial lattice matching between the organic template and the ions undergoing nucleation. The present study is of great importance in the preparation of oriented perovskite materials as well as in the understanding of the mechanism for organic-template-directed crystallization.

Solvothermal synthesis of the complex fluorides KMgF3 and KZnF3 with the Perovskite structures

The complex fluorides KMgF3 and KZnF3 with Perovskite structures were solvothermally synthesised at 150-180degreesC and characterised by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy.

Hydrothermal synthesis of the complex fluorides LiBaF3 and KMgF3 with perovskite structures under mild conditions

The complex fluorides, LiBaF3 and KMgF3; which are isostructural with perovskite phases, are hydrothermally synthesized at 120-240 degrees C and characterized by powder X-ray diffraction, thermogravimetric analysis, IR spectroscopy and scanning electron microscopy.

(Ba3MTiMO9)-Ti-III-O-V (M-III = Fe, Ga, Y, Lu, M-V = Nb, Ta, Sb) perovskite oxides Synthesis, structure and dielectric properties

We describe the synthesis structures and dielectric properties of new perovskite oxides of the formula (Ba3MTiMO9)-Ti-III-O-V for M-III = Fe Ga Y Lu and M-V = Nb Ta Sb While M-V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M-III/Ti/M-V metal-oxygen octahedra are corner connected the M-V = Sb oxides show a distinct preference for the 6H structure where Sb-V/Ti-IV metal-oxygen octahedra share a common face forming (Sb Ti)O-9 dimers that are corner-connected to the (MO6)-O-III octahedra The preference of antimony oxides (Sb-V 4d(10)) for the 6H structure which arises from a special Sb-V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb-V/Ta-V d(0) atoms which prefer similar to 180 degrees Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M-V-O oxides in general The dielectric properties reveal a significant difference among Mill members All the oxides with the 3C structure excepting those with Mill = Fe show a normal low loss dielectric behaviour with epsilon = 20-60 in the temperature range 50-400 degrees C the M-III = Fe members with this structure (M-V = Nb Ta) display a relaxor-like ferroelectric behaviour with large E values at frequencies <= 1 MHz (50-500 degrees C) (C) 2010 Elsevier Masson SAS All rights reserved

AM(1-x)Al(x)O(3-x) (A=Na or K; M=Nb or Ta): New anion-deficient Perovskite oxides exhibiting oxide ion conduction

Anion-deficient perovskite oxides of the formula AM(1-x)Al(x)O(3-x) (A = Na or K; M = Nb or Ta) have been prepared for 0 < x less than or equal to 0.5. Diffraction experiments reveal that while the potassium compounds adopt orthorhombic/cubic perovskite structures similar to the parent KNbO3/KTaO3, the sodium compound, NaNb0.5Al0.5O2.5, possesses a brownmillerite/LaSr-CuAlO5-like superstructure. Al-27 NMR spectra show an exclusive tetrahedral oxygen coordination for AI(III) in Na-Nb0.5Al0.5O2.5 (I) and both tetrahedral and octahedral coordination for Al(III) in KNb0.5Al0.5O2.5 (II). The results suggest a long-range and short-range ordering of oxide ion vacancies in I and II respectively. Electrical conductivity measurements show a significant oxide ion conduction for KNb1-xAlxO3-x, with the conductivity increasing with x up to x = 0.5. The differences in the Arrhenius plots of the ionic conductivity of I and II have been rationalized in terms of the long-range and short-range ordering of oxide ion vacancies in the anion-deficient perovskite oxides.

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Lanthanum cobaltite black pigments with perovskite structure

In this work La1-xCaxCoO3 (x = 0-0.4) pigments were synthesized by the polymeric precursor method with heat treatments at 700, 800 and 900 C for 4 h. The powders were characterized by colorimetry, UV-vis spectroscopy and powder X-ray diffraction (XRD). The X-ray diffraction patterns showed the presence of a single phase perovskite, changing its structure from rhombohedral to cubic, when calcium was added to the lattice. All of the pigments had a black colour with a strong absorption over the whole of the visible spectrum as a consequence of the different oxidation states of cobalt and the high short-range disorder. The substitution of Ca2+ for La3+ did not influence the pigment colour but decreased its final cost. © 2013 Elsevier Ltd. All rights reserved.

Synthesis and structure of some interesting oxides of bismuth

Synthesis and structures of several new oxides containing bismuth are described. Three types of structures are common among the multinary oxides containing trivalent bismuth. They are the sillenite structure of γ-Bi2O3, the layered perovskite structure of Aurivillius phases and the pyrochlore structure. The influence of Bi3+∶6s 2 lone pair electrons is seen in all the three structures. In transition metal oxides containing trivalent bismuth,d o cations (Ti4+, Nb5+, W6+) stabilize the layered perovskite structure, while cations containing partially-filledd orbitals (V4+, Cr3+, Fe3+) favour pyrochlore-related structures. Ferroelectric distortion ofMO6 octahedra of thed o cations seems to play an important role in stabilizing layered perovskite structures.

Estudo DFT para a interação das moléculas de CO e NO com perovskitas de LaFePdO3 dopadas com Mn, Co e Ni

Recentemente, vem sendo desenvolvido o uso de catalisadores de metais preciosos suportados por óxidos do tipo perovskita em automóveis. Tais sistemas catalíticos são conhecidos como catalisadores Inteligentes. A tecnologia dos catalisadores inteligentes aponta para um novo futuro na catálise automotiva e surge como um promissor substituinte para os catalisadores convencionais. O entendimento dos principais fatores que levam a auto regeneração destes catalisadores é um passo fundamental no processo de evolução desta tecnologia. O mecanismo de auto regeneração é responsável diretamente pelo aumento considerável do tempo de vida útil destes catalisadores perante aos convencionais. Consequentemente, o seu custo é bem mais baixo comparado ao convencional. Outro fator relevante é a durabilidade estrutural e o grande número de possibilidade de combinações possíveis das perovskita que fazem delas excelentes estruturas para estudo. O objetivo do trabalho é entender o processo auto regenerativo do catalisador automotivo a base de perovskita dopadas com um átomo de cobalto, manganês e níquel e quando expostas a um ambiente com uma molécula de NO e CO , através da análise da interação desses átomos dopantes em relação a estrutura da perovskita e como se comportará o átomo de paládio ao entrar em contato com a molécula de NO e CO

Solvothermal synthesis of well-dispersed NaMgF3 nanocrystals and their optical properties

Complex metal fluoride NaMgF3 nanocrystals were successfully synthesized via a solvothermal method at a relatively low temperature with the presence of oleic acid, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, photoluminescence (PL) excitation and emission spectra, respectively. fit the synthetic process, oleic acid as a Surfactant played a Crucial role in confining the growth and solubility of the NaMgF3 nanocrystals. The as-prepared NaMgF3 nanocrystals have quasi-spherical shape with a narrow distribution. A possible formation mechanism of the nanocrystals was proposed based on the effect of oleic acid. The as-prepared NaMgF3 nanocrystals are highly crystalline and well-dispersed in cyclohexane to form stable and clear colloidal Solutions, which demonstrate a strong emission band centered at 400 nm in photoluminescence (PL) spectra compared with the cyclohexane solvent.

Optical spectroscopy properties of KMgF3 : Eu2+ nanocrystals and powder synthesized by microemulsion and solvothermal process

Nanocrystals and powders of KMgF3 doped with Eu2+ were synthesized by the microemulsion method and the solvothermal process, respectively. The emission and excitation spectra of KMgF3:Eu2+ phosphors were measured and compared with those of the samples synthesized through a solid. state reaction, Bridgman-Stockbarger method, and mild hydrothermal technique. The KMgF3: Eu2+ samples synthesized by means of the microemulsion method and the solvothermal process show only a sharp emission peak located at 360 nm, in the emission spectra, which arises from the f -> f(P-6(1/2)-> S-8(1/2)) transition of Eu2+. The broad emission bands appear at 420 nm,,which arises from Eu2+ <- O2- cannot be observed(in the mild hydrothermal and single crystal samples, the emission peak at 420 nm besides the emission of Eu2+ at 360 nm is observed). In the excitation spectrum of the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process, the excitation peaks show an intensive blue shift. The blue shift can he attributed to the lower oxygenic content in the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process.

Solvothermal synthesis of complex fluorides KCoF3 and KNiF3

Complex fluorides KCoF3 and KNiF3 with perovskite structures were solvothermally synthesized at 120-180 C and characterized by means of X-ray powder diffraction, scanning electron microscopy. thermogravimetric analysis and infrared spectroscopy.

Dielectric properties and microstructure of SrTiO3/BaTiO3 multilayer thin films prepared by a chemical route

Multilayer thin films with perovskite structures were produced by the polymeric precursor method. SrTiO3/BaTiO3 (STO/BTO) multilayers were deposited on Pt(111)/Ti/SiO2/Si(100) substrates by the spin-coating technique and heated in air at 700 degreesC. The microstructure and crystalline phase of the multilayered thin films were examined by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), resolution-high transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and X-ray diffraction. The SrTiO3/BaTiO3 multilayer thin films consisted of grainy structures with an approximate grain size of 60 nm. The multilayered thin films showed a very clear interface between the components. The SrTiO3/BaTiO3 multilayer thin films revealed dielectric constants of approximately 527 and loss tangents of 0.03 at 100 kHz. The dielectric constant calculated for this multilayer film system is the value of the sum of each individual component of the film, i.e. The total value of the sum of each SrTiO3 (STO) and BaTiO3 (BTO) layer. The multilayer SrTiO3/BaTiO3 obtained by the polymeric precursor method, also showed a ferroelectric behavior with a remanent polarization of 2.5 muC/cm(2) and a coercive field of 30 kV/cm. The multilayer films displayed good fatigue characteristics under bipolar stressing after application of 10(10) switching cycles. (C) 2001 Published by Elsevier B.V. B.V. All rights reserved.