Neste trabalho foi estudado o efeito dos parâmetros de síntese na resposta de polarização de híbridos Nafion-SiO2 como eletrólitos em células a combustível poliméricas (PEMFC) em elevadas temperaturas (até 130 °C). A fase inorgânica foi adicionada à matriz polimérica com o objetivo de aumentar a retenção de água na membrana em elevadas temperaturas (acima de 100 °C); melhorar as propriedades mecânicas do Nafion e favorecer cineticamente as reações eletródicas. As membranas foram preparadas a partir da incorporação in-situ de sílica em membranas comerciais de Nafion por rota sol-gel acompanhada de catálise ácida. Os parâmetros de síntese, tais como: concentração do catalisador ácido, natureza do solvente, temperatura e tempo de reação e concentração do precursor de silício (Tetraetil-Ortosilicato TEOS) foram avaliados em função do grau de incorporação e resposta de polarização. Os híbridos Nafion-SiO2 foram física e quimicamente caracterizados por gravimetria, termogravimetria (TG), microscopia eletrônica de varredura e espectroscopia de energia dispersiva de raios X (MEV-EDX), espectroscopia de impedância eletroquímica (EIS) e espalhamento de raios X em baixos ângulos (SAXS). Por fim, os híbridos sintetizados foram avaliados diretamente como eletrólitos em células PEM unitárias alimentadas com hidrogênio (H2) e oxigênio (O2) no intervalo de temperatura de 80 ºC a 130 ºC e a 130 ºC em condições de umidade relativa reduzida (75 e 50%). Resumidamente, o desempenho dos híbridos se mostrou fortemente dependente dos parâmetros de síntese, principalmente, o tipo de álcool utilizado e concentração inicial de TEOS. / In this work, the effect of sol-gel synthesis parameters on the preparation and polarization response of Nafion-SiO2 hybrids as electrolytes for proton exchange membrane fuel cells (PEMFC) operating at high temperatures (130 oC) was evaluated. The inorganic phase was incorporated in a Nafion matrix with the following purposes: to improve the Nafion water uptake at high temperatures (> 100 oC); to increase the mechanical strength of Nafion and; to accelerate the electrode reactions. The hybrids were prepared by an in-situ incorporation of silica into commercial Nafion membranes using an acid-catalyzed sol-gel route. The effects of synthesis parameters, such as catalyst concentration, sol-gel solvent, temperature and time of both hydrolysis and condensation reactions, and silicon precursor concentration (Tetraethylorthosilicate TEOS), were evaluated as a function on the incorporation degree and polarization response. Nafion-SiO2 hybrids were characterized by gravimetry, thermogravimetric analysis (TGA), scanning electron microscopy and X-ray dispersive energy (SEM-EDS), electrochemical impedance spectroscopy (EIS), and X-ray small angle scattering (SAXS). The hybrids were tested as electrolyte in single H2/O2 fuel cells in the temperature range of 80 130 oC and at 130 oC and reduced relative humidity (75% and 50%). Summarily, the hybrid performance showed to be strongly dependent on the synthesis parameters, mainly, the type of alcohol and the TEOS concentration.

The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance of the structure to the conditions of dry reforming of methane will be discussed.

The aim of the work is characterization of structure and magnetic properties of various CoFe2O4/SiO2 nanocomposites. Emphasis was put on the corelation of the magnetic properties with particle size (samples with different annealing temperature) and with strenght of the interparticle interactions (samples with different Fe/Si ratio or without silica matrix). Structure properties of all samples were determinated by powder x-ray diffraction, scanning and transmission electron microscopy. Magnetic properties were determinated by standard (temperature dependence of magnetization, magnetization isotherms) and advanced (a.c. susceptibility, memory effects) magnetic measurements. A sharp increase of the values of blocking temperature and coercivity with increase of strenght of the interparticle interactions and with increase of particle size was observed. Particle size determines the maximum value of coercivity and blocking temperature and strengh of the interparticle interactions shift this values in the interval determined by particle size.

In this work, SiO2, MWCNTs, MWCNTs:SiO2, MWCNTs-TiO2, and MWCNTs:TiO2:SiO2 nanomaterials were synthesized and characterized by the use of different techniques to ascertain novelty of the nanomaterials and also to establish their suitability for several electrical, electronic and magnetic based device applications. The results, in general, indicate that the nanocomposites were well prepared and the properties of MWCNTs can be tuned by introducing SiO2, TiO2, and a composite of SiO2 and TiO2 in its matrix. This tunability of properties leading to the suitability of the material for various applications has been explained in this work. / Physics

LiCoO₂thin films have been grown by pulsed laser deposition on stainless steel and SiO₂/Si substrates. The film deposited at 600°C in an oxygen partial pressure of 100mTorr shows an excellent crystallinity, stoichiometry and no impurity phase present. Microstructure and surface morphology of thin films were examined using a scanning electron microscope. The electrochemical properties of the thin films were studied with cyclic voltammetry and galvanostatic charge-discharge techniques in the potential range 3.0-4.2 V. The initial discharge capacity of the LiCoO2 thin films deposited on the stainless steel and SiO₂/Si substrates reached 23 and 27 µAh/cm², respectively. / Singapore-MIT Alliance (SMA)

This dissertation is focused on understanding heterogeneous metal catalysts supported on oxides using a model catalyst system of SiO2 thin film supported metal nano-clusters. The primary technique applied to this study is scanning tunneling microscopy (STM). The most important constituent of this model catalyst system is the SiO2 thin film, as it must be thin and homogeneous enough to apply electron or ion based surface science techniques as well as STM. Ultra-thin SiO2 films were successfully synthesized on a Mo(112) single crystal. The electronic and geometric structure of the SiO2 thin film was investigated by STM combined with LEED, Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The relationship between defects on the SiO2 thin film and the nucleation and growth of metal nano-clusters was also investigated. By monitoring morphology changes during thermal annealing, it was found that the metal-support interaction is strongly dependent on the type of metal as well as on the defect density of the SiO2 thin film. Especially, it was found that oxygen vacancies and Si impurities play an important role in the formation of Pd-silicide. By substituting Ti atoms into the SiO2 thin film network, an atomically mixed TiO2-SiO2 thin film was synthesized. Furthermore, these Ti atoms play a role as heterogeneous defects, resulting in the creation of nucleation sites for Au nano-clusters. A marked increase in Au cluster density due to Ti defects was observed in STM. A TiO2-SiO2 thin film consisting of atomic Ti as well as TiOx islands was also synthesized by using higher amounts of Ti (17 %). More importantly, this oxide surface was found to have sinter resistant properties for Au nano-clusters, which are desirable in order to make highly active Au nano-clusters more stable under reaction conditions.

In this study, The bottom electrode¡]TiN¡^, middle insulator ¡]Sn¡GSiO2¡^, and top electrode ¡]Pt¡^ were deposited respectively by sputtering technique for fabricating the resistive random access memory with metal-insulator-metal structure. Experimental results were indicated that Sn-dopped SiO2 RRAM could be operated over 105 times and retention time was kept stable at thermal stress up to 85 ¢J over 104 s. In the previous researches, we had known that the supercritical carbon dioxide¡]SCCO2¡^ fluids could efficiently to passivate the traps in the devices. The leakage current of dielectric film would be reduced significantly after SCCO2 fluids treatment. To improve the dielectric properties of Sn-dopped SiO2 films, the SCCO2 fluids technology was introduced in this study. After SCCO2 fluids treatment, the leakage current of devices was reduced significantly, because the HRS conduction mechanism was transformed from Poole-Frenkel conduction to Schottky emission and the LRS conduction mechanism was transformed from Ohmic conduction to Hopping conduction. Addtionally, RTA treatment was introduced to improve the Sn-dopped SiO2 films. It could also reduce leakage current of devices after RTA treatment. At last, we used constant current forming to find the process of electrons hopping conduction.

In this thesis, the resistance switching characteristic of Zn:SiO2 -based memory was studied. The resistive memory was fabricated by sputtering to deposit the Metal/Insulator/Metal (MIM) structure. The top and bottom layers were made by Pt and TiN respectively, and the insulator was Zn:SiO2 grown by co-sputtering with SiO2 and Zinc. We found that doping Zinc into SiO2 insulator induced the resistive switching characteristic. By the treatment of supercritical carbon dioxide (SCCO2) in Zn:SiO2 -based device,the operation current would decrease. In the result of x-ray electron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) , it showed that the defects in Zn:SiO2 thin-film were reduced. And the electric conduction mechanism of low resistance state made a change from ohmic conduction to hopping conduction. To emerge spontaneous phenomenon of hopping conduction, the memory devices were fabricated with a multi-layer structure. In Auger electron spectroscopy (AES), we found the signal of zinc, split into three different kinds of peaks, which met the multi-layer structure. From I-V sweep measurement, the multi-layer structure device could be appeared the spontaneous hopping conduction mechanism. In order to find out the initial state of electric conduction mechanism .We measured the device of Pt/Zn:SiO2/TiN with constant current forming. We found the initial state of electric conduction path out successfully, and it¡¦s operation current below 10 uA.

This dissertation is focused on understanding heterogeneous metal catalysts supported on oxides using a model catalyst system of SiO2 thin film supported metal nano-clusters. The primary technique applied to this study is scanning tunneling microscopy (STM). The most important constituent of this model catalyst system is the SiO2 thin film, as it must be thin and homogeneous enough to apply electron or ion based surface science techniques as well as STM. Ultra-thin SiO2 films were successfully synthesized on a Mo(112) single crystal. The electronic and geometric structure of the SiO2 thin film was investigated by STM combined with LEED, Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The relationship between defects on the SiO2 thin film and the nucleation and growth of metal nano-clusters was also investigated. By monitoring morphology changes during thermal annealing, it was found that the metal-support interaction is strongly dependent on the type of metal as well as on the defect density of the SiO2 thin film. Especially, it was found that oxygen vacancies and Si impurities play an important role in the formation of Pd-silicide. By substituting Ti atoms into the SiO2 thin film network, an atomically mixed TiO2-SiO2 thin film was synthesized. Furthermore, these Ti atoms play a role as heterogeneous defects, resulting in the creation of nucleation sites for Au nano-clusters. A marked increase in Au cluster density due to Ti defects was observed in STM. A TiO2-SiO2 thin film consisting of atomic Ti as well as TiOx islands was also synthesized by using higher amounts of Ti (17 %). More importantly, this oxide surface was found to have sinter resistant properties for Au nano-clusters, which are desirable in order to make highly active Au nano-clusters more stable under reaction conditions.

In recent years, even though the light output of GaN-related LED continues to increase, the brightness is still low compared to conventional lighting systems and it is necessary to further improve the light extraction of LEDs. In this study, the characteristics of LPD-SiO2 film and Al/SiO2/GaN MOS diode were investigated in advance of the formation of SiO2 micro structure for improving the oxide quality and controlling the deposition parameters. Temperature-difference method, post-annealing treatment, photochemical treatment, sulfurated treatment and etc. were used for the purposes of better properties of the MOS structure and the LED. To obtain higher light extraction efficiency of GaN LED, hemispherical SiO2 microlens was formed on the conventional and the flip-chip LEDs. The deposition mechanism had been developed to obtain the further improvements on the electrical and optical properties. The influences of epoxy encapsulation on the LEDs without and with microlens were also studied. Considering the refractive index of SiO2 is close to that of the epoxy, the enhancements of light extraction efficiency and angular optical distribution of GaN LED by using SiO2 microlens will be degraded after encapsulating. Therefore, we also tried to deposit ZnO film and rod on GaN LED by LPD method to maintain or further enhance the light extraction efficiency of GaN LEDs by the combining the micro structure and the epoxy encapsulation.