Optical and structural properties of PbI(2) thin films

Lead iodide thin films were fabricated using the spray pyrolysis technique. Milli-Q water and N.N-dimethylformamide were used as solvents under varying deposition conditions. Films as thick as 60 mu m were obtained. The optical and structural properties of the samples were investigated using Photoluminescence, Raman scattering, X-ray diffraction, and Scanning electron microscopy. In addition, the study included also the electronic properties which were investigated by measuring the dark conductivity as a function of temperature. The deposition technique seems to be promising for the development of thick films to be used in medical imaging.

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Non-leachable highly luminescent ordered mesoporous SiO2 spherical particles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Materiais meso-estruturados luminescentes

Pós-graduação em Química - IQ

Application of a hybrid blocking layer in dye-sensitized solar cells

In dye-sensitized solar cells a blocking layer between the transparent electrode and the mesoporous titanium dioxide film is used to prevent short-circuits between the hole-conductor and the front electrode. The conventional approach is to use a compact layer of titanium dioxide prepared by spin coating or spray pyrolysis. The thickness of the blocking layer is critical. On one hand, the layer has to be thick enough to cover the rough substrate completely. On the other hand, the serial resistance increases with increasing film thickness, because the layer acts as an ohmic resistance itself. In this thesis an amphiphilic diblock copolymer is used as a functional template to produce an alternative, hybrid blocking layer. The hybrid blocking layer is thinner than the conventional, compact titanium dioxide film and thereby possesses a higher conductivity. Still, this type of blocking layer covers the rough electrode material completely and avoids current loss through charge recombination. The novel blocking layer is prepared using a tailored, amphiphilic block copolymer in combination with sol-gel chemistry. While the hydrophilic poly(ethylene oxide) part of the polymer coordinates a titanium dioxide precursor to form a percolating network of titania particles, the hydrophobic poly(dimethylsiloxane) part turns into an insulating ceramic layer. With this technique, crack-free films with a thickness down to 24 nm are obtained. The presence of a conductive titanium dioxide network for current flow, which is embedded in an insulating ceramic material, is validated by conductive scanning force microscopy. This is the first time that such a hybrid blocking layer is implemented in a solar cell. With this approach the efficiency could be increased up to 27 % compared to the conventional blocking layer. Thus, it is demonstrated that the hybrid blocking layer represents a competitive alternative to the classical approach.

Propiedades ópticas y estructurales de nanoestructuras de Zn(Cd)(Mg)O

En la presente tesis doctoral se ha realizado un estudio utilizando diferentes técnicas de crecimiento (RPE-MOCVD y spray pyrolysis) y estructuras (nanohilos, pozos y puntos cuánticos y capas) con el objetivo de desarrollar dispositivos que cubran desde el rango visible hasta el ultravioleta. Es por esta razón por la que se han elegido materiales basados en ZnO, debido a la posibilidades que estos ofrecen para variar su bandgap en un amplio rango de energías. Prueba de ello es que en este estudio se ha conseguido cubrir un rango espectral desde 1.86 hasta 4.11 eV, estudiandose además fenómenos físicos como son la difusión e incorporaci ón de la aleación o la adsorción de gases en la super_cie, lo que ha permitido la fabricación de diferentes fotodetectores de gran sensibilidad. Por todo ello, los resultados obtenidos en esta tesis suponen una gran contribución al conocimiento de las propiedades físicas de las aleaciones de Zn(Cd)O y Zn(Mg)O para potenciales aplicaciónes en dispositivos que operen en el rango visible y ultravioleta del espectro, respectivamente. En esta memoria se da en primer lugar una visión de las propiedades de materiales basados en ZnO, entrando en detalle en una de las ventajas que este presenta, la facilidad que tiene este material para formar nanoestructuras. En el capítulo 3 se dan los conceptos teóricos necesarios para comprender las propiedades ópticas de este tipo de materiales, mostrando también los resultados más reseñables obtenidos en ZnO. En los capítulos referentes a los resultados se pueden diferenciar dos grandes bloques. En el primer bloque de resultados se han analizado nanohilos y pozos cuánticos de Zn(Cd)O crecidos por la técnica de RPE-MOCVD (Capítulos 4 y 5). En el segundo se expondrá el estudio realizado sobre capas y puntos cuánticos de Zn(Mg)O crecidos por la técnica spray pyrolysis como se describe en mayor detalle a continuación. Nanohilos y pozos cuánticos de Zn(Cd)O crecidos por RPE-MOCVD Teóricamente aleando el ZnO con CdO es posible disminuir el valor del band- gap desde 3.37 eV hasta 0.95 eV, cubriendo por completo el espectro visible. El desarrollo del ternario Zn(Cd)O permitiría la fabricación de heteroestructuras y pozos cuánticos, muy importantes en el desarrollo de dispositivos optoelectrónicos que cubran la parte visible del espectro. Sin embargo, la diferencia de estructura cristalina entre estos dos materiales junto a la baja solubilidad del Cd y su alta presión de vapor, di_culta la obtención de material de alta calidad cristalina con alto contenido en Cd. En esta tesis doctoral se ha realizado una completa caracterización óptica y estructural de nanohilos de Zn(Cd)O credidos por la técnica de RPE-MOCVD. Estos nanohilos tinene unas longitudes comprendidas entre 1 y 3 _m y diámetros entre 100 y 200 nm. La concentración máxima introducida de Cd en estas estructuras ha sido de hasta un 54% manteniendo la estructura wurtzita del ZnO, siendo este el mayor contenido de Cd introducido hasta la fecha en nanostructuras basada en ZnO. Este hecho se traduce en una variación de la energía de emisión entre 3.31 y 1.86 eV con el aumento en Cd. El uso de diferentes técnicas de alta resoluci ón de caracterización estructural ha permitido demostrar la presencia de una sola fase estructural wurtzita sin observarse ningún indicio de separación de fases ni acumulación de Cd a lo largo del nanohilo para todos los contenidos de Cd. Con el propósito de fabricar dispositivos en nanohilos individuales, parte de esta tesis doctoral ha estado dedicada a estudiar el impacto que el recocido térmico tiene en las propiedades ópticas y eléctricas de nanohilos de Zn(Cd)O. El recocido térmico es un proceso clave en la optimización de dispositivos, ya sea para la obtenci ón de contactos óhmicos, reducción de defectos o difusión de dopantes por ejemplo. En este estudio se ha observado una mejora muy signi_cativa de las propiedades de emisión de los nanohilos cuando estos eran recocidos a temperaturas mayores que la de crecimiento (300 oC). En las muestras con Cd se ha observado además que el recocido también produce un desplazamiento de la emisión hacia mayores energías debido a una reducción homogénea del contenido de Cd. Medidas de fotoluminiscencia con resolución temporal muestran el impacto que tiene la localización del excitón en las _uctuaciones de potencial, debidas a una distribución estadística del Cd, en la dinámica de los portadores. Comparando el tiempo de vida de los portadores entre los nanohilos recocidos y sin recocer se ha observado un aumento de este parámetro en las estructuras recocidas. Este aumento es fundamentalmente debido a una reducción de centros de recombinación no radiativa asociados a defectos presentes a lo largo del nanohilo. Además, se ha estudiado la evolución de los tiempos de vida de los portadores en función de la temperatura, registrándose una menor estabilidad con la temperatura de los tiempos de vida en las muestras recocidas. Este resultado sugiere que el recocido térmico consigue reducir parte del desorden de la aleación en la estructura. Tras haber caracterizados los nanohilos se desarrollaron una serie de procesa dos para la fabricación de dispositivos basados en nanohilos individuales. Se fabricaron en concreto fotodetectores sensibles al UV, en los que se observó también la alta sensibilidad que muestran a la adsorción de gases en la super_cie, incrementada por la gran relación super_cie/volúmen característica de las nanoestructuras. Estos procesos de adsorción observados tienen un impacto directo sobre las propiedades ópticas y electricas de los dispositivos como se ha demostrado. Por ello que en esta tesis se hayan estudiado en detalle este tipo de procesos, ideando maneras para tener un mayor control sobre ellos. Finalmente se crecieron estructuras de pozos cuántico de ZnCdO/ZnO en nanohilos con contenidos de Cd nominales de 54 %. Las medidas ópticas realizadas mostraron como al aumentar la anchura del pozo de 0.7 a 10 nm, la emisión relacionada con el pozo se desplazaba entre 3.30 y 1.97 eV. Este gran desplazamiento representa el mayor obtenido hasta la fecha en pozos cuánticos de ZnCdO/ZnO. Sin embargo, al caracterizar estructuralmente estas muestras se observó la presencia de procesos de difusión de Cd entre el pozo y la barrera. Como se ha podido medir, este tipo de procesos reducen sustancialmente la concentración de Cd en el pozo al difundirse parte a la barrera. cambiando completamente la estructura de bandas nominal de estas estructuras. Este estudio demuestra la importancia del impacto de los procesos de difusión en la interpretación de los efectos de con_namiento cuántico para este tipo de estructuras. Capas y puntos cuánticos de Zn(Mg)O crecidos por spray pyrolysis La técnica de spray pyrolysis, debido a su simplicidad, bajo coste y capacidad de crecer sobre grandes áreas conservando una alta calidad cristalina presenta un gran interés en la comunidad cientí_ca para el potencial desarrollo de dispositivos comerciales. En esta tesis se ha estudiado las propiedades ópticas y eléctricas de capas y puntos cuánticos de Zn(Mg)O crecidos por esta técnica. Al contrario que pasa con el Cd, al introducir Mg en la estructura wurtzita de ZnO se consigue aumentar el bandgap del semiconductor. Sin embargo, al igual que pasa con el CdO, la diferencia de estructura cristalina entre el ZnO y el MgO limita la cantidad de Mg que se puede incorporar, haciendo que para una cierta concentración de Mg aparezcan el fenómeno de separación de fases. En esta tesis se ha conseguido incorporar hasta un contenido de Mg del 35% en la estructura wurtzita del ZnO utilizando la técnica de spray pyrolysis, resultado que representa la mayor concentración de Mg publicada hasta la fecha. Este hecho ha posibilitado variar la energía del borde de absorción desde 3.30 a 4.11 eV. En estas capas se ha realizado una completa caracterización óptica observándose una diferencia entre las energías del borde de absorción y del máximo de emisión creciente con el contenido en Mg. Esta diferencia, conocida como desplazamiento de Stokes, es debida en parte a la presencia de _uctuaciones de potencial producidas por un desorden estadístico de la aleación. Se han fabricado fotodetectores MSM de alta calidad utilizando las capas de Zn(Mg)O previamente caracterizadas, observándose un desplazamiento del borde de absorción con el aumento en Mg desde 3.32 a 4.02 eV. Estos dispositivos muestran altos valores de responsividad (10-103 A/W) y altos contrastes entre la responsividad bajo iluminación y oscuridad (10-107). Estos resultados son en parte debidos a la presencia de mecanismos de ganancia y una reducción de la corriente de oscuridad en las muestras con alto contenido de Mg. Utilizando esta misma técnica de crecimiento se han crecido puntos de Zn(Mg)O con concentraciones nominales de Mg entre 0 y 100 %, con dimensiones medias entre 4 y 6 nm. Las medidas estructurales realizadas muestran que hasta un valor de Mg de 45 %, los puntos están compuestos por una única fase estructural, wurtzita. A partir de esa concentración de Mg aparece una fase cúbica en los puntos, coexistiendo con la fase hexagonal hasta una concentración nominales del 85 %. Para concentraciones mayores de Mg, los puntos muestran una única fase estructural cúbica. Medidas de absorción realizadas en estos puntos de Zn(Mg)O muestran un desplazamiento del borde de absorción entre 3.33 y 3.55 eV cuando la concentraci ón de Mg en los puntos aumenta hasta el 40 %. Este desplazamiento observado es debido solamente a la fase wurtzita del Zn(Mg)O donde se incorpora el Mg. ABSTRACT This PhD theis presents a study using di_erent growth techniques (RPEMOCVD and spray pyrolysis) and structures (nanowires, quantum dots and wells and layers) in order to develop devices that extend from the visible to the ultraviolet range. For this reason ZnO based materials have been choosen, because they o_er the possibility to tunne the bandgap in this energy range. Proof of this is that this study has managed to cover a spectral range from 1.86 to 4.11 eV, also being studied physical phenomena such as di_usion and incorporation of alloy or adsorption of gases on the surface, allowing the develop di_erent highly sensitive photodetectors. Therefore, the results obtained in this thesis are a great contribution two large blockso the knowledge of the physical properties of alloys Zn(Cd)O and Zn(Mg)O for potential applications in devices that operate in the visible and ultraviolet range, respectively. In the _rst chapter, the general properties of ZnO-based materials are presented, showing the facilities that these kind of materials o_er to obtain di_erent nanoestructures. In Chapter 3, optical theoretical concepts are given to understand the optical properties of these materials, also showing the most signi_cant results of ZnO. In the chapters related with the results, two blocks could be distinguish. In the _rst one, Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD have been analyzed (Chapters 4 and 5). The second block of results shows the study performed in Zn(Mg)O _lms and quantum dots grown by spray pyrolysis. Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD In summary, the results of the PhD thesis are a great contribution to the knowledge of the physical properties of Zn(Cd)O and Zn(Mg)O alloys and their application for high performance devices operating in the visible and UV ranges, respectively. The performance of the device is still limited due to alloy solubility and p-doping stability, which opens a door for future research in this _eld. Theoretically, annealing ZnO with CdO allows to reduce the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. The development of ZnCdO alloys allows the fabrication of heterostructures and quantum wells, necessary for the development of high performance optoelectronic devices. However, the di_erent crystal structures between CdO and ZnO and the low solubility of Cd and its high vapor pressure, hinders the growth of ZnCdO alloys with high Cd contents. In this PhD thesis Zn(Cd)O nanowires have been optically and structurally characterized, obtaining a maximum Cd content of 54% while maintaining their wurtzite structure. This Cd content, which allows lowering the bandgap down to 1.86 eV, is the highest concentration ever reported in nanostructures based on ZnO. The combination of optical and structural characterization techniques used during this thesis has allowed the demonstration of the presence of a single wurtzite structure, without observing any indication of phase separation or Cd accumulation along the nanowire. Annealing processes are essential in the fabrication of optoelectronic devices. For this reason, a complete study of the annealing e_ects in the optical and electrical properties of Zn(Cd)O nanowires has been performed. In the _rst place, annealing nanowires at higher temperatures than their growth temperature (300 oC) allows a signi_cant improvement of their emission properties. However, in the samples that contain Cd a shift in the emission towards higher energies has been observed due to a homogeneous reduction of the Cd content in the nanowires. Time resolved photoluminescence measurements show the impact of the exciton localization in the potential _uctuations due to a statistical alloy disorder. An increase in the carrier lifetime has been obtained for the annealed nanowires. This increase is mainly due to the reduction of non-radiative recombination centers associated with the defects present in the material. Furthermore, temperature dependent time resolved photoluminescence measurements suggest a reduction of the alloy disorder in the annealed samples. In this thesis, single nanowire photodetectors with a high responsivity in the UV range have been demonstrated. Due to the high surface/volume ratio, these structures are very sensitive to gas adsorption at the surface, which largely de_nes the optical and electrical properties of the material and, therefore, of the device. With the aim of obtaining time stable devices, the dynamic adsorption-desorption processes have been studied, developing di_erent approaches that allow a higher control over them. Finally, ZnCdO/ZnO quantum wells have been grown with a nominal Cd concentration of 54% inside the well. The performed optical measurements show that increasing the well width from 0.7 to 10 nm, shifts the emission related with the well from 3.30 to 1.97 eV. This result represents the highest shift reported in the literature. However, a detailed structural characterization shows the presence of di_usion phenomena which substantially reduce the concentration of Cd in the well, while increasing it in the barrier. This type of phenomena should be considered when ac curately interpretating the quantum con_nement e_ects in Zn(Cd)O/ZnO quantum wells. Theoretically, annealing ZnO with CdO allows to decrease the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. Zn(Mg)O _lms and quantum dots grown by spray pyrolysis Due to its simplicity, low-cost and capacity to grow over large areas conserving a high crystal quality, spray pyrolysis technique presents a great interest in the scienti_c community for developing comercial devices. In this thesis, a complete study of the optical and structural properties of Zn(Mg)O _lms and quantum dots grown by spray pyrolysis has been performed. Contrary to Zn(Cd)O alloys, when introducing Mg in the ZnO wurtzite structure an increase in the bandgap in obtained. Once again, the di_erence in the crystal structure of ZnO and MgO limits the amount of Mg that can be introduced before phase separation appears. In this PhD thesis, a maximum Mg content of 35% has been incorporated in the wurtzite structure using spray pyrolysis. This variation in the Mg content translates into an increase of the absorption edge from 3.30 to 4.11 eV. Up to this date, this result represents the highest Mg content introduced by spray pyrolysis in a ZnO wurzite structure reported in the literature. The comparison of the emission and absorption spectra shows the presence of an increasing Stokes shift with Mg content. This phenomenon is partialy related with the presence of potential _uctuations due to an statistic alloy disorder. MSM photodetectors have been processed on previously characterized Zn(Mg)O _lms. These devices have shown a shift in the absorption edge from 3.32 to 4.02 eV with the increase in Mg content, high responsivity values (10-103 A/W) and high contrast ratios between illuminated and dark responsivities (10-107). These values are explained by the presence of a gain mechanism and a reduction of dark current in the ZnMgO samples. Zn(Mg)O quantum dots have also been grown using spray pyrolysis with Mg concentrations between 0 and 100% and with average widths ranging 4 to 6 nm. Structural measurements show that at a Mg concentration of 45% the cubic phase appears, coexisting with the hexagonal phase up to an 85% concentration of Mg content. From 85% onwards the quantum dots show only the cubic phase. Absorption measurements performed in these structures reveal a shift in the absorption edge from 3.33 to 3.55 eV when the Mg content increases up to 40 %.

Biossensores de pH, ureia e glicose utilizando a microeletrônica de filmes finos de AZO e TIO2

Este trabalho apresenta o desenvolvimento de biossensores de pH, ureia e glicose, utilizando óxidos como plataforma para a parte seletiva. Os filmes finos de óxidos condutores foram produzidos por diferentes técnicas de deposição, como spin-coat, dip-coat, spray-pyrolysis e casting. Os materiais fabricados foram AZO e TiO2, ambos depositados sobre substratos de FTO, ITO ou vidro hidroflilizado. O número de camadas foi variado para cada técnica e as caracterizações morfológicas e estruturais foram feitas por MEV, DRX e FTIR. As caracterizações elétricas foram feitas por EGFET e voltametria cíclica. Os filmes foram testados como sensores de pHs na faixa de 2 a 8. O filme depositado com AZO em substrato de FTO pela técnica de spray-pyrolysis apresentou melhor resposta, com sensibilidade de 31,7 mV/pH entre toda a faixa de pHs do 2 ao 8. Já para os filmes de TiO2, o filme produzido por dip-coat com 5 camadas em substrato de FTO apresentou sensibilidade de 37,8 mV/pH entre a faixa de pHs de 2 a 8. Paralelamente, os filmes tiveram suas superfícies funcionalizadas com proteínas como urease ou glicose oxidase. Neste caso, os dispositivos foram testados entre as concentrações de 5 a 200 mg/dL de ureia e glicose. Como biossensor de ureia, o filme de TiO2 depositado por spin-coat com 5 camadas em substrato de FTO apresentou a maior sensibilidade, com valor 3,32 mV/(mg/dL) entre as concentrações de 5 a 120 mg/dL. Para os filmes estudados como biossensores de glicose, o melhor resultado também foi obtido pelo filme de TiO2 depositado por spin-coat com 5 camadas em substrato de FTO, apresentando sensibilidade em torno de 6,18 mV/(mg/dL) entre as concentrações de 5 a 200 mg/dL. Alguns resultados encontrados foram iguais ou melhores aos encontrados na literatura vigente, mesmo que os dispositivos ainda são passíveis de otimização.

Investigations on the structural, optical and magnetic properties of nanostructured cerium oxide in pure and doped forms and its polymer nanocomposites

In recent years, nanoscience and nanotechnology has emerged as one of the most important and exciting frontier areas of research interest in almost all fields of science and technology. This technology provides the path of many breakthrough changes in the near future in many areas of advanced technological applications. Nanotechnology is an interdisciplinary area of research and development. The advent of nanotechnology in the modern times and the beginning of its systematic study can be thought of to have begun with a lecture by the famous physicist Richard Feynman. In 1960 he presented a visionary and prophetic lecture at the meeting of the American Physical Society entitled “there is plenty of room at the bottom” where he speculated on the possibility and potential of nanosized materials. Synthesis of nanomaterials and nanostructures are the essential aspects of nanotechnology. Studies on new physical properties and applications of nanomaterials are possible only when materials are made available with desired size, morphology, crystal structure and chemical composition. Cerium oxide (ceria) is one of the important functional materials with high mechanical strength, thermal stability, excellent optical properties, appreciable oxygen ion conductivity and oxygen storage capacity. Ceria finds a variety of applications in mechanical polishing of microelectronic devices, as catalysts for three-way automatic exhaust systems and as additives in ceramics and phosphors. The doped ceria usually has enhanced catalytic and electrical properties, which depend on a series of factors such as the particle size, the structural characteristics, morphology etc. Ceria based solid solutions have been widely identified as promising electrolytes for intermediate temperature solid oxide fuel cells (SOFC). The success of many promising device technologies depends on the suitable powder synthesis techniques. The challenge for introducing new nanopowder synthesis techniques is to preserve high material quality while attaining the desired composition. The method adopted should give reproducible powder properties, high yield and must be time and energy effective. The use of a variety of new materials in many technological applications has been realized through the use of thin films of these materials. Thus the development of any new material will have good application potential if it can be deposited in thin film form with the same properties. The advantageous properties of thin films include the possibility of tailoring the properties according to film thickness, small mass of the materials involved and high surface to volume ratio. The synthesis of polymer nanocomposites is an integral aspect of polymer nanotechnology. By inserting the nanometric inorganic compounds, the properties of polymers can be improved and this has a lot of applications depending upon the inorganic filler material present in the polymer.

Chemical and physical effects of ultrasound: sonoluminescence and materials

When a liquid is irradiated with ultrasound, acoustic cavitation (the formation, growth, and implosive collapse of bubbles in liquids irradiated with ultrasound) generally occurs. This is the phenomenon responsible for the driving of chemical reactions (sonochemistry) and the emission of light (sonoluminescence). The implosive collapse of bubbles in liquids results in an enormous concentration of sound energy into compressional heating of the bubble contents. Therefore, extreme chemical and physical conditions are generated during cavitation. The study of multibubble sonoluminescence (MBSL) and single-bubble sonoluminescence (SBSL) in exotic liquids such as sulfuric acid (H2SO4) and phosphoric acid (H3PO4) leads to useful information regarding the intracavity conditions during bubble collapse. Distinct sonoluminescing bubble populations were observed from the intense orange and blue-white emissions by doping H2SO4 and H3PO4 with sodium salts, which provides the first experimental evidence for the injected droplet model over the heated-shell model for cavitation. Effective emission temperatures measured based on excited OH• and PO• emission indicate that there is a temperature inhomogeneity during MBSL in 85% H3PO4. The formation of a temperature inhomogeneity is due to the existence of different cavitating bubble populations: asymmetric collapsing bubbles contain liquid droplets and spherical collapsing bubbles do not contain liquid droplets. Strong molecular emission from SBSL in 65% H3PO4 have been obtained and used as a spectroscopic probe to determine the cavitation temperatures. It is found that the intracavity temperatures are dependent on the applied acoustic pressures and the thermal conductivities of the dissolved noble gases. The chemical and physical effects of ultrasound can be used for materials synthesis. Highly reactive species, including HO2•, H•, and OH• (or R• after additives react with OH•), are formed during aqueous sonolysis as a consequence of the chemical effects of ultrasound. Reductive species can be applied to synthesis of water-soluble fluorescent silver nanoclusters in the presence of a suitable stabilizer or capping agent. The optical and fluorescent properties of the Ag nanoclusters can be easily controlled by the synthetic conditions such as the sonication time, the stoichiometry of the carboxylate groups to Ag+, and the polymer molecular weight. The chemical and physical effects of ultrasound can be combined to prepare polymer functionalized graphenes from graphites and a reactive solvent, styrene. The physical effects of ultrasound are used to exfoliate graphites to graphenes while the chemical effects of ultrasound are used to induce the polymerization of styrene which can then functionalize graphene sheets via radical coupling. The prepared polymer functionalized graphenes are highly stable in common organic solvents like THF, CHCl3, and DMF. Ultrasonic spray pyrolysis (USP) is used to prepare porous carbon spheres using energetic alkali propiolates as the carbon precursors. In this synthesis, metal salts are generated in situ, introducing porous structures into the carbon spheres. When different alkali salts or their mixtures are used as the precursor, carbon spheres with different morphologies and structures are obtained. The different precursor decomposition pathways are responsible for the observed structural difference. Such prepared carbon materials have high surface area and are thermally stable, making them potentially useful for catalytic supports, adsorbents, or for other applications by integrating other functional materials into their pores.

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Effect of liquid precursor pyrolysis on phase selection in the MgO-MgAl2O4 system

Aqueous solutions of Al and Mg nitrates have been spray pyrolysed at 673 K to synthesize powders with compositions varying between MgO and MgAl2O4. This has been carried out with the aim of studying phase selection and phase evolution in this system. The powders have been subsequently heat treated and the sequence of phases characterised by X-ray diffraction and transmission electron microscopy. Metastable extensions of the different phase fields have been calculated based on functions which predict the equilibrium phase diagram accurately. The appearance of phases is closely related to the temperature and to the non-stoichiometry in different compositional ranges of the system. The sequence of phase evolution has been correlated to the thermodynamics of nucleation in the system.

Synthesis and characterization of Y0.9-xGdxEu0.1BO3 phosphors by spray drying process

Y0.9-xGdxEu0.1BO3 phosphors were synthesized by spray drying (SD) method, and the results were compared with those by conventional solid state (SS) and citrate gel (GC) methods. The PL intensity of phosphors increases with the increase of x value in Y0.9-xGdxEu0.1BO3 (prepared by SD) due to an energy migration process like Gd3+ - (Gd3+)(n) - Eu3+ occurred in the material. Compared with the latter two methods, the phosphor particles prepared by spray drying method have a better morphology, such as homogeneous size (about 1similar to3 mum) with spherical shape and smooth surface. Furthermore, the spray drying-derived phosphors have higher photoluminescence (PL) intensity than those by citrate gel method, but still a little lower than those by the solid state method.