Estudio de las estructuras cristalinas y de las transiciones de fase en nuevos materiales de wolframio (SrM2+W6+O) y de antimonio (AM3+Sb5+O) con estructura de perovskita doble.

Los óxidos mixtos con estructura tipo perovskita doble A2BBO6 presentan gran interés desde el punto de vista científico y tecnológico debido a la gran variedad de propiedades que poseen: superconductoras, catalíticas, magnéticas y magnetorresistentes, por ejemplo. La temperatura es un variable que permite modificar la simetría de la estructura cristalina y, consecuentemente, las propiedades físicas del material. El trabajo describe la síntesis, caracterización estructural y de las transiciones de fase en nuevos materiales de dos familias de perovskitas dobles: la familia de wolframio (Sr2M2+W6+O6) y la familia de antimonio (A2M3+Sb5+O6). Se ha llevado a cabo la síntesis de 29 compuestos, 22 de ellos sintetizados por primera vez. Los compuestos se han caracterizado mediante técnicas de difracción de rayos X y de neutrones, determinando su estructura cristalina a temperatura ambiente, así como las posibles transiciones de fase a bajas y altas temperaturas, y en algunos casos, también las estructuras de altas y bajas temperaturas. Los materiales de la familia de wolframio estudiados en este trabajo presentan un ordenamiento total entre los cationes M2+ y W6+ en los sitios B y B de la perovskita doble (A2BBO6); y presentan, además, una única secuencia de transiciones de fase a altas temperaturas: P21/n -> I4/m -> Fm3m. Las temperaturas de las transiciones de fase observadas en estos compuestos en función del factor de tolerancia (t), muestran una tendencia general de disminución según t se aproxima a 1. En esta familia, se observa, también, que el rango de existencia de la fase tetragonal intermedia es más amplio para valores de t mayores. Con respecto de la familia de antimonio, el ordenamiento catiónico en los sitios A y B, de una parte, y en los sitios B y B de otra, depende del tamaño de los cationes. Los compuestos de esta familia presentan una gran variedad de grupos espaciales a temperatura ambiente: P2_1 /n, I2/m, I4/m, R-3 y Fm-3m. Además, dependiendo de la diferencia entre los tamaños de los cationes M^3+ y Sb^5+ , los compuestos presentan dos secuencias de transiciones de fase en todo el rango de temperatura: P21/n->I2/m->I4/m->Fm-3m, la misma que en la familia del wolframio pero con una simetría intermedia monoclínica I2/m (compuestos con cationes M^3+ de tamaños similares al del Sb^5+ ); y P21/n -> R-3 -> Fm-3m, con una simetría intermedia trigonal en vez de tetragonal, como en la familia del wolframio (compuestos con cationes M3+ de tamaños mayores que el del Sb5+ ). En esta familia, las temperaturas de las transiciones de fase disminuyen conforme aumenta t.

Materiales tipo perovskita Pr???Ca?Fe?.?Co?.?O? para su potencial aplicación como cátodo en celdas de combustible de óxido sólido.

Tesis (Maestría en Ciencias con Orientación en Química de los Materiales) UANL, 2012.

Materiales tipo perovskita Ln?Bi???Fe?.??M?.??O? (Ln: Pr, Nd; M: Co, Mn, Sc; x= 0-0.15) para su potencial aplicación en memorias magnetoeléctricas.

Tesis (Maestría en Ciencias con Orientación en Química de los Materiales) UANL, 2012.

Caracterização morfológica e microestrutural da perovskita BaCexPr1-xO3 sintetizada a partir do método de complexação combinando EDTA/Citrato

In this study, binary perovskite (BaCexO3) were doped with praseodymium (Pr) to obtainment of the ternary material BaCexPr1-xO3. This material was synthesized by the complexation method combining EDTA/Citrate with the stoichiometric ratio of the element Praseodymium ranging from x = 0.1 to x = 0.9 in order to determine the influence of this rare earth element on the morphology and microstructure of the final powder. At first the material was synthesized based on the route proposed by literature (Santos, 2010), and then characterized by SEM and XRD, besides being refined by the Rietveld method. In the material that had lowest residual parameter, S, and lowest average size of crystal, pH variation of synthesis solution was made in order to identify the influence of this parameter on the morphology and microscopy of the final powder. The results show that addition of praseodymium did not directly influence the crystallographic and lattice parameters, keeping even the same orthorhombic structure of the binary material BaCexO3, according to Yamanaka et al (2003). Material type BaCe0,2Pr0,8O3 had lowest residual parameter (S=1.4) and lowest average size of crystallite (26.4 nm), being used as reference in the pH variation of synthesis solution for 9, 7, 5 and 3, respectively. Variation of this parameter showed that when the synthesis solution pH was decreased to below 11, there was an increase in the average size of crystals, for pH 9, about 58.3%, for pH 7 (30.3 %), for pH 2 (2.3%) and for pH 3 (42%), indicating that the value initially used and quoted by Santos (2010) was the most coherent

Propriedades física de molécilas orgânicas e compostos do tipo perovskita CdSiO3 e CaPbO3

In the first part of this work our concern was to investigate the thermal effects in organic crystals using the theory of the polarons. To analyse such effect, we used the Fröhlich s Hamiltonian, that describes the dynamics of the polarons, using a treatment based on the quantum mechanics, to elucidate the electron-phonon interaction. Many are the forms to analyzing the polaronic phenomenon. However, the measure of the dielectric function can supply important information about the small polarons hopping process. Besides, the dielectric function measures the answer to an applied external electric field, and it is an important tool for the understanding of the many-body effects in the normal state of a polaronic system. We calculate the dielectric function and its dependence on temperature using the Hartree-Fock decoupling method. The dieletric function s dependence on the temperature is depicted by through a 3D graph. We also analyzed the so called Arrhenius resistivity, as a functionof the temperature, which is an important tool to characterize the conductivity of an organic molecule. In the second part we analyzed two perovskita type crystalline oxides, namely the cadmium silicate triclinic (CdSiO3) and the calcium plumbate orthorhombic (CaPbO3), respectively. These materials are normally denominated ABO3 and they have been especially investigated for displaying ferroelectric, piezoelectric, dielectrics, semiconductors and superconductors properties. We found our results through ab initio method within the functional density theory (DFT) in the GGA-PBE and LDA-CAPZ approximations. After the geometry optimization for the two structure using the in two approximations, we found the structure parameters and compared them with the experimental data. We still determined further the angles of connection for the two analyzed cases. Soon after the convergence of the energy, we determined their band structures, fundamental information to characterize the nature of the material, as well as their dielectrics functions, optical absorption, partial density of states and effective masses of electrons and holes

Estudo da estabilização da fase perovskita PMN em filmes ultrafinos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Medidas de condutividade A.C. e constante dielétrica na perovskita dupla Ca1.2 La0.8 FeIrO6

This work introduces the results from the performing of impedance spectroscopy on the transition metals oxide Ca1.2La0.8FeIrO6. It was sought to understand the behavior of one sample from its impedance spectra for different AC voltages and temperature values and if an applied external magnetic field at room temperature would cause some change on it. The results revealed that the Ca1.2La0.8FeIrO6 at high temperatures shows conductive and inductive behavior and that the resistance increases with frequency, phenomenon known as Kelvin effect. At 150 K, the spectrum real part no longer consists with the theoretical prediction of Kelvin effect, starting to be influenced by the utilized voltages, condition that inexists on theory. At low temperatures (10, 20, 30 K) it was observed resistive and capacitive behavior, being possible on these conditions, associate to the sample a paralel RC circuit in series with a contact resistance with a fitting from the ZSim software. This fitting allowed the obtaining of capacitance, DC resistance and contact resistance values. The application of a 700G magnetic field at room temperature didn't cause changes on the spectra

Estabilização da fase perovskita e propriedades estruturais de filmes finos relaxores do sistema PLZT

Pós-graduação em Ciência dos Materiais - FEIS

Desenvolvimento de células solares de perovskita baseadas em filmes de óxidos nanoestruturados

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desenvolvimento de células solares de perovskita baseadas em filmes de óxidos nanoestruturados

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

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)

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 colectivas: las amplitudes de los modos que describen la distorsión de la fase prototipo. Los resultados generales para la serie SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni) a temperatura ambiente se ha recogido en un diagrama en el que se han indicado las amplitudes de los modos que transforman de acuerdo a las irreps en función del factor de tolerancia, ya que todos ellos cristalizan en la misma fase monoclínica (P21/n); y a temperaturas altas se ha construido un diagrama de fase. Los materiales SrLnFeRuO6 ( Ln=La,Pr,Nd) y CaLn2CuTi2O9 cristalizan en la fase ortorrómbica Pbnm a temperatura ambiente; mientras que BaLn2CuTi2O9 tienen una estructura más simétrica, I4/mcm. A altas temperaturas se han identificado las transiciones de fase inducidas por el cambio de temperatura.A temperaturas bajas se han analizado las estructuras magnéticas de algunos de los compuestos mediante difracción de neutrones.

Efeito magnetocalórico em sistemas ferrimagnéticos

Nesta tese, o efeito magnetocalórico é estudado teoricamente partindo de um hamiltoniano modelo que leva em conta uma rede magnética formada por diversas sub-redes magnéticas acopladas. No hamiltoniano são consideradas as interações de troca, Zeeman e magnetoelástica. Primeiramente, o hamiltoniano é apresentado em sua forma generalizada para R sub-redes magnéticas e a influência dos parâmetros do modelo na temperatura de Nèel e na temperatura de compensação é analisada no sistema com duas sub-redes magnéticas. Encontramos que, dependendo dos parâmetros de troca, arranjos ferrimagnético, antiferromagnético e ferromagnéticos podem ser obtidos. O efeito magnetocalórico foi sistematicamente estudado para diversos arranjos possíveis, posteriormente foi estudado em compostos reais do tipo R3Fe5O12 (RIG), sistema formado por três sub-redes magnéticas. Retornando ao sistema com duas sub-redes magnéticas foi analisada a influência da interação magnetoelástica no efeito magnetocalórico nos arranjos ferrimagnéticos obtidos previamente. Aplicando este modelo para uma estrutura cúbica do tipo perovskita, estudamos o efeito magnetocalórico nos compostos EuZrO3 e EuTiO3. Uma metodologia para a obtenção da magnetização de uma amostra policristalina foi apresentada e ainda estudamos o efeito magnetocalórico anisotrópico de natureza antiferromagnética.

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

Caracterização microestrutural e elétrica de La(FexNi1-x)O3 sintetizado pelo método da gelatina

The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment