Estudio de materiales cerámicos de alta constante dielétrica basados en CaCu3Ti4O12

Tesis doctoral inédita. Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Inorgánica. Fecha de lectura: 16-12-201

Effect of the Synthesis Route on the Microstructure and the Dielectric Behavior of CaCu3Ti4O12 Ceramics

CaCu3Ti4O12 (CCTO) was prepared by a conventional synthesis (CS) and through reaction sintering, in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of CCTO have been studied by XRD, FE-SEM, EDS, AFM, and impedance spectroscopy to correlate structure, microstructure, and electrical properties. Samples prepared by reactive sintering show very similar dielectric behavior to those prepared by CS. Therefore, it is possible to prepare CCTO by means of a single-step processing method

Dielectric behaviour of Hf-doped CaCu3Ti4O12 ceramics obtained by conventional synthesis and reactive sintering

CaCu3(Ti4xHfx)O12 ceramics (JC = 0.04, 0.1 and 0.2) were prepared by conventional synthesis (CS) and through reactive sintering (RS), in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of Hf-doped CCTO (CCTOHf) have been studied by XRD, FE-SEM, AFM, Raman and impedance spectroscopy (IS) in order to correlate the structure, microstructure and the electrical properties. Samples prepared by reactive sintering show slightly higher dielectric constant than those prepared by conventional synthesis in the same way than the pure CCTO. Dielectric constant and dielectric losses decrease slightly increasing Hf content. For CCTOHf ceramics with x> 0.04 for CS and x> 0.1 for RS, a secondary phase HfTi04 appears. As expected, the reactive sintering processing method allows a higher incorporation of Hf in the CCTO lattice than the conventional synthesis one

Towards materials with enhanced electro-mechanical response: CaCu3Ti4O12-polydimethylsiloxane composites

We describe a straightforward production pathway of polymer matrix composites with increased dielectric constant for dielectric elastomer actuators (DEAs). Up to date, the approach of using composites made of high dielectric constant ceramics and insulating polymers has not evidenced any improvement in the performance of DEA devices, mainly as a consequence of the ferroelectric nature of the employed ceramics. We propose here an unexplored alternative to these traditional fillers, introducing calcium copper titanate (CCTO) CaCu3Ti4O12, which has a giant dielectric constant making it very suitable for capacitive applications. All CCTO-polydimethylsiloxane (PDMS) composites developed display an improved electro-mechanical performance. The largest actuation improvement was achieved for the composite with 5.1 vol% of CCTO, having an increment in the actuation strain of about 100% together with a reduction of 25% in the electric field compared to the raw PDMS matrix

Dielectric behaviour of Hf-doped CaCu₃Ti₄O₁₂ ceramics obtained by conventional synthesis and reactive sintering

CaCu₃ (Ti₄₋ₓ Hfₓ )O₁₂ ceramics ( x  = 0.04, 0.1 and 0.2) were prepared by conventional synthesis (CS) and through reactive sintering (RS), in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of Hf-doped CCTO (CCTOHf) have been studied by XRD, FE-SEM, AFM, Raman and impedance spectroscopy (IS) in order to correlate the structure, microstructure and the electrical properties. Samples prepared by reactive sintering show slightly higher dielectric constant than those prepared by conventional synthesis in the same way than the pure CCTO. Dielectric constant and dielectric losses decrease slightly increasing Hf content. For CCTOHf ceramics with x  > 0.04 for CS and x  > 0.1 for RS, a secondary phase HfTiO₄ appears. As expected, the reactive sintering processing method allows a higher incorporation of Hf in the CCTO lattice than the conventional synthesis one.Facultad de Ciencias Exacta

Resolución estructural en 3D de electrocerámicas mediante microscopía Raman confocal

Las propiedades de los materiales cerámicos son una combinación entre las propiedades intrínsecas, definidas por los granos cristalinos, y las propiedades extrínsecas, como son bordes de grano y fases secundarias. La relación entre estos dos elementos produce en muchas ocasiones, la presencia de propiedades inusuales que son la base de muchos materiales electrocerámicos. Sirvan como ejemplo algunos materiales tipo como son: varistores cerámicos, termistores, materiales con coeficiente de resistividad positivo, sensores de borde de grano, etc. En un material electrocerámico con respuesta funcional la correlación entre estructura-microestructura -propiedades es una constante, tanto en la etapa de diseño en laboratorio como en la etapa de producción industrial. El empleo de Microscopía Raman Confocal (MRC) se propone como una metodología relevante para el estudio de los factores que afectan a dichas correlaciones en materiales electrocerámicos. La técnica de MRC constituye una potente herramienta que permite determinar no solo la estructura sino las interacciones entre los elementos microestructurales. La correlación entre estas variables con las propiedades funcionales y la posibilidad de determinar las mismas en condiciones de operación, abren unas posibilidades que hasta la fecha solo estaban en la imaginación de los científicos. En esta presentación se resumen brevemente algunos de los principios relacionados con la técnica de Microscopía Raman Confocal, que junto con ejemplos seleccionados permiten visualizar aspectos relacionados con: la orientación de cristales, identificación fases cristalinas; resolución de nanoestructuras e interfases; determinación y dinámica de dominios ferroeléctricos; presencia de tensiones mecánicas; fenómenos de conducción,... sobre diferentes materiales cerámicos. Los trabajos mostrados son ejemplos de alta resolución en 3D de materiales funcionales como son los materiales electrocerámicos

Nonlinear I–V electrical behaviour of doped CaCu3Ti4O12 ceramics

In this work a comparative study of undoped CaCu3Ti4O12 (CCTO) and doped with Fe3+(CCTOF) and Nb5+(CCTON) ceramics, was aimed to modify the electronic transport.XRDpatterns, FE-SEM microstructural analysis, impedance spectroscopy and I–V response curves were afforded to correlate the microstructure with the nonlinear I–V behaviour. The appearance of nonlinear behaviour in doped CCTO samples has been correlated with the ceramic microstructure that consists in n-type semiconductor grains, surrounded by a grain boundary phase based on CuO. The presence of this secondary grain boundary phase is the responsible of the assisted liquid phase sintering in CCTO ceramics. Doped samples showed cleaner grain boundaries than CCTO and nonlinearity in the I–V response.Peer reviewe

Nonlinear I–V electrical behaviour of doped CaCu3Ti4O12 ceramics

In this work a comparative study of undoped CaCu3Ti4O12 (CCTO) and doped with Fe3+(CCTOF) and Nb5+(CCTON) ceramics, was aimed to modify the electronic transport.XRDpatterns, FE-SEM microstructural analysis, impedance spectroscopy and I–V response curves were afforded to correlate the microstructure with the nonlinear I–V behaviour. The appearance of nonlinear behaviour in doped CCTO samples has been correlated with the ceramic microstructure that consists in n-type semiconductor grains, surrounded by a grain boundary phase based on CuO. The presence of this secondary grain boundary phase is the responsible of the assisted liquid phase sintering in CCTO ceramics. Doped samples showed cleaner grain boundaries than CCTO and nonlinearity in the I–V response.Peer reviewe

Enhancement of UV absorption behavior in ZnO–TiO2 composites

The ultraviolet–visible, UV–vis, absorption edge behaviour of semiconductor oxides as TiO2 and ZnO promotes their use as inorganic UV filters for sunscreens. In cosmetics, the use of nanoparticles is favoured because of their higher yield and lower whiteness. However, the particle size effect in the UV absorption is unclear. For this reason, the performances of nano and microsized TiO2 and ZnO are evaluated in both the UV–vis spectroscopy and the Sun Protection Factor, SPF, value. In order to cover the UV range completely by using inorganic filters a new composite is attempted by dry nanodispersion methodology in which TiO2 nanoparticles are dispersed onto ZnO microparticles. The new composite shows superior UV absorbing properties and ca. 60% SPF value due to a synergism between components that resulted in extended UV coverage and reduction of the total amount of nanoparticles required in the sunscreens. In addition, nanoparticles are effectively anchored onto microparticles avoiding the presence of free nanoparticles