How effective would the implementation of biodiesel fuel in reducing emissions caused by automobiles and motorcycles in the densely populated regions? The goal of this research is targeted at determining the most proficient methods in depleting the harmful substances emitted from refueling stations and the efficiency of biodiesel fuel in emissions reduction. The initial stages in the research involved the use of aluminum oxide and molecular sieve, which would act as active metals for copper and manganese. Impregnation and solgel method of catalytic production were utilized with 12 sets of oxidized copper, and molecular sieve catalysts, totaling at 24 sets. With results from the primary testing, initial selection of impregnation production methods based on its conversion rate had a carrying capacity of 20% CuMn/ oxidized copper catalyst (Cu: Mn ratio at 1:1), and a 20% CuMn/molecular sieve catalyst (Cu: Mn ratio of 1:1) with the solgel method. The two exogenous tests were not only found to be the most efficient rate of conversion as base standards, but were also found to be the most competent method to date. Approximate calculations from the two catalytic testing showed that CuMn/oxidized copper catalyst conversion are less affected by variation in concentration density. Furthermore, the CuMn/oxidized copper and CuMn/molecular sieve catalysts faced a positive conversion rate when reacted with a decreased space velocity, but leveled off once it reached a specific level. Moreover, the two catalysts also faced an increased conversion rate when conducted with an increase in oxygen concentration, and reached maximized efficiency at 30% concentration. Secondary stage of the research focuses on operational efficiency of the biodiesel fuel, with emphasis on its pollutant emissions and economical standpoint. The initial testing concluded that not only did the fuel has a lower cost in reducing greenhouse gas emission than alternative energy sources, but it can also reduce SOx emissions by 7,200kg, 23 metric tons of PM10, and 262,400 metric tons of CO2 annually when applied with B2 fuel. Pollution reduction assessment indicated that if all diesel powered automobiles utilized the B10 biodiesel fuel, then it¡¦s estimated that it would have an annual THC reduction rate of 2.83x102 metric tons, 1.98x103 tons in COs, 4.56x103 in NOx, and 5.66x101 metric tons in PM gases. Furthermore, if the B20 fuel cells were incorporated, then it¡¦s estimated to have an annual reduction rate of 2.83x102 metric tons in THC, 2.83x103 metric tons of CO, 1.14x103 metric tons of NOx, and 1.16x102 metric tons of PM. Results from the beta stage testing indicated that if B10 fuel were incorporated into all diesel powered automobiles, with a budget of NT$1million would result in an annual reduction rate of 0.57 metric tons of THC, 9.12 metric tons of NOx, 0.11 metric tons of PM and a totaled 9.8 metric tons of reduction. Furthermore, if B20 were implemented, again with NT$1 million budget, we would expect to see annual reductions of 0.06 metric tons of THC, 0.25 metric tons of NOx, 2.51 tons of PM gases, totaling at 2.81 metric tons of reductions.

Le photochromisme est la propriété que possèdent certaines espèces chimiques de présenter une transformation réversible, induite par la lumière, entre deux états ayant des spectres d'absorption séparés. Suivant l'amplitude des modifications structurales photoinduites, la réaction peut se produire dans des milieux plus ou moins rigides. Dans ce travail, nous nous intéressons à la phase cristalline et plus particulièrement à l'étude des propriétés spectroscopiques de nano- et microcristaux de molécules organiques photochromes. Dans ce but, nous avons développé un banc de microspectroscopie avec une résolution de 500nm, nous permettant d'étudier des cristaux de taille submicrométrique. Lors de l'étude de monocristaux d'un diarylethene, nous avons observé un effet photomécanique original : la réaction photochrome s'accompagne dans ce cas de sauts pouvant mesurer jusqu'à 4mm pour des cristaux de taille micrométrique. D'autre part, lorsqu'on empêche les cristaux de sauter, on observe la formation d'un réseau de fractures parallèles et équidistantes à la surface des cristaux. Ces effets correspondent à la traduction macroscopique de l'accumulation de contraintes ponctuelles dans le cristal lors de la photoréaction. Nous défendons l'hypothèse selon laquelle sauts et fractures ont un antécédent commun : une déformation périodique de la surface qui pourrait être liée à une instabilité de Grinfeld.

Deux études distinctes mettant en oeuvre la détection et l'analyse de signaux spectroscopiques optiques de molécules individuelles- colorants ou molécules organiques- ont été menées.<br />Par microscopie grand champ de fluorescence, l'émission de molécules uniques de pérylène orange insérées dans un film solgel mince, par enregistrement de films d'une large zone de l'échantillon sur laquelle plus d'une centaine d'émetteurs individuels sont détectés, fournit des informations sur cette espèce et la matrice sondée. Pour exploiter les films, un outil logiciel a été développé. Les processus de photoblanchiment, la mobilité moléculaire, la nucléation des molécules excitées sont mis en évidence et discutés. On note une grande richesse des dynamiques temporelles d'émission, mais aussi des spectres qui reflètent notamment la reconformation proposée du pérylène orange excité. Il s'ensuit l'existence de nombreux nanoenvironnements différents dans la matrice poreuse.<br />Par microscopie confocale à balayage, le signal de diffusion Raman exaltée de surface de molécules uniques organique adsorbées sur des agrégats d'argent de morphologie complexe est exploité. Certains objets présentent une exaltation géante, estimée être de plus de 14 ordres de grandeur, ce qui permet l'enregistrement de spectres résolus en seulement une seconde. L'analyse chimique offerte permet de distinguer différentes espèces, et la présence nécessaire sur ces points chauds d'Ag+ est démontrée. Une caractérisation corrélée par microscopie électronique des agrégats actifs repérés met aussi en avant l'existence d'une morphologie privilégiée, avec de nombreuses protubérances de dimension nanométrique et interstices.

Surface chemical gradients are materials that exhibit continuous, gradually varying chemical or physical properties along and across the length of a substrate. As a result, each point on the gradient surface can represent an individual sample. They are broadly classified as chemical and physical gradients depending upon the properties that the gradient exhibits. A physical gradient involves a continuous variation of physical properties such as surface roughness and film porosity on the micrometer scale. Chemical gradients involve a gradual variation of chemical properties such as polarity, acidity and basicity, etc. Such gradients have found various applications in cell adhesion, nanoparticle absorption, etc. Because of the multitude of potential applications of acid-base gradient materials in separation science and biological applications, the main work of this dissertation work is focused on the preparation and fundamental, molecular level investigation of acid-base gradients on siloxane surfaces. In this work, we focused on the preparation and characterization of surface charge gradients. Charged gradients are gradients that contain charged functional groups that are spatially distributed along the length of the substrate. They can interact with each other or with other species in solution by electrostatic interactions. They can also play a key role in governing the interaction of macromolecules and bacteria on surfaces, the wetting of surfaces, the layer-by-layer (LBL) assembly of thin films, reactions in catalysis, and the separation of charged species in chromatography. Therefore, understanding localized interactions between surface functional groups and charged species in solution are particularly relevant to the development of surfaces resistant to biofouling, antimicrobial surfaces, catalytic surfaces, multi-layered composite thin films, and imprinted surfaces for chemical sensing and separations. Thus, it is of great of interest to develop methodologies to create and study heterogeneous and homogeneous charged surfaces with well-defined properties. There have been several different methods developed for the preparation of charged gradients. First a chemical gradient is prepared and then the chemical gradient is converted to charged gradient by a chemical approach. Silane-based methods for the preparation of chemical gradients are among those that are widely used because of the straightforwardness of the chemistry involved and also the availability of silanes with various chemical functionalities. A few of these silane based approaches such as the vapor-diffusion method and liquid diffusion method have been used for various applications so far. Most of these methods are only able to prepare surface chemical gradients for a specific application mainly because of their limitations in terms of gradient-length scale and chemistry involved. In this work, we used a procedure already developed in our lab to prepare chemical gradients from different functionalized alkoxysilanes; we call this procedure the ‘controlled-rate infusion method (CRI)’. This method can be adapted to different substrates and can form gradients at various length-scales, such as few hundred microns to tens of centimeters. The CRI method involves the infusion of an organoalkoxysilane solution into a container with a substrate mounted vertically so that time-dependent exposure along the substrate forms a gradient in chemical functionality from bottom to the top. The most important attribute of this method is that the local steepness of the gradient can be systematically controlled by simply changing the rate of infusion. The steepness of the gradient can also be changed at predefined positions along its length by programming the rate of infusion. CRI can also be used to prepare gradients containing multiple functionalities, termed multicomponent chemical gradients. The different chemical functionalities can be oriented in different directions to produce gradients where functionalities can be oriented along the same or opposed directions producing aligned and opposed multicomponent chemical gradients, respectively. In this work, the multicomponent gradients were converted to charge gradients via chemical reaction with 30% H2O2. Using controlled rate infusion and this technique, aligned or opposed multicomponent charge gradients containing NH3+, SO3- and SiO- groups were prepared. By infusing 3-aminopropyltriethoxysilane (APTEOS) and 3-mercaptopropyltriethoxysilane (MPTMOS) in the same or opposed direction, gradients containing charged species in different locations relative to each other along the length of the substrate were made. The gradient properties in each case were different and correlated to the way they were prepared i.e., where the gradients were oriented in an aligned or opposed fashion. Surface wettability and local surface charge, etc were found to be entirely different depending on the type of charge gradients (aligned and opposed). In another example, SiO- and NH3+ opposed gradients were prepared by infusing APTEOS on different base layers prepared from tetramethoxysilane (TMOS), phenyltrimethoxysilane (PTMOS), dimethyldimethoxysilane (DMDMOS) or octyltrimethoxysilane (OTMOS) followed by protonation of the surface amines. The gradient profiles and surface wettability were found to be independent of each other and dependent of the type of the base layer. In summary, this dissertation work focuses mainly on the preparation of multicomponent charge gradients and their molecular level characterization by a multitude of different analytical methods including XPS spectroscopy, tapping mode atomic force microscopy (TM-AFM), zeta potential measurement, and SCA and DCA measurements. CRI has incredible flexibility and adaptability, which was confirmed by extending it to different siloxane base films and creating gradients with different functionalities. Multicomponent charge gradients containing acid and base functionalities can be prepared and optimized for and acid base catalysis reactions such Michael addition as well as aldol, Henry, and Knoevenagel condensations.

With the digital systems moving towards higher frequencies, lower operating voltages and higher power, supplying the required current at the right voltage and at the right time to facilitate timely switching of the CMOS circuits becomes increasingly challenging. The board level power supply cannot meet these requirements directly due to the high inductance of the package interconnections. To overcome this problem, several thin film decoupling capacitors have to be placed on the IC or close to the IC in the package. Two approaches were pursued for high-k thin film decoupling capacitors. 1) Low cost sol-gel based thin film capacitors on organic board compatible Cu-foils 2) RF-sputtered thin film capacitors on silicon substrate for silicon compatible processes While sol-gel provides cost effective technology, sputtered ferroelectric devices are more compatible from manufacturing stand point with the existing technology. Nano-crystalline barium titanate and barium strontium titanate film capacitor devices were fabricated and characterized for organic and silicon substrates respectively. Sol-gel barium titanate films were fabricated first on a bare Cu-foil and then transferred to organic board through a standard lamination process. With process optimization and film doping, a capacitance density of 3 µF/cm2 was demonstrated with breakdown voltage greater than 12V. Leakage current characteristics, breakdown voltages, and electrical reliability of the devices were significantly improved through doping of the barium titanate films and modified film chemistry. Films and interfaces were characterized with high resolution electron microscopy, SEM, XRD, and DC leakage measurements. RF sputtering was selected for ferroelectric thin film integration on silicon substrate. Barium strontium titanate (BST) films were deposited on various electrodes sputtered on silicon substrates. The main focus was to improve interface stabilities for high-k thin films on Si to yield large-area defect-free devices. Effect of bottom electrode selection and barrier layers on device yield and performance were investigated carefully. High yield and high device performance was observed for certain electrode and barrier layer combination. A capacitance density up to 1 µF/cm2 was demonstrated with a breakdown voltage above 15 V on large area, 7 mm2, devices. These two techniques can potentially meet mid-high frequency future decoupling requirements.

Made available in DSpace on 2016-03-15T19:36:26Z (GMT). No. of bitstreams: 1 Renato Meneghetti Peres.pdf: 2481386 bytes, checksum: 4a0c9e9713ebe096dc1943b16d0149bd (MD5) Previous issue date: 2010-08-06 / Fundo Mackenzie de Pesquisa / Nanocomposites are nanometrical material particles embedded in a specific matrix. The degree of organization of the nanostructures and their properties depend on the nature of the organic and inorganic components of the structure that can generate synergic interactions. Polymeric nanocomposites are related to a class of hybrid materials where inorganic substances of nanometric dimensions are dispersed in a polymeric matrix. A small amount of inorganic material has a great effect on the structure performance. The nanoparticles of inorganic materials have high specific surface area that promotes the dispersion of the polymeric matrix and the properties depend on the homogeneity of the dispersion. The interaction reactions between the components can be observed on the material`s structure. The nanometrical material obtained by sol-gel process can be incorporated directly on the polymeric matrix. There is a tendency to a hard dispersion when a ceramic nanoscale particle is embedded in a polymeric matrix. This difficult can be attributed to a small spacement between the ceramic atomic planes to allow the passage of the polymeric chain between that. In this case, techniques can be used to the spacement to be enlarged with a organophilic agent action that enable a better addiction between the reinforcement and de matrix and make a influence in the mechanical, termical and rheological properties for the characterization by different techniques. In this work, the pseudoboehmite obtained by sol-gel process was treated by an octadecylamine solution to obtain a mix added to Nylon 6,12. After the mixing, the nanocomposite was dryed and processed to conformed the specimen used in the material caracterization. Mechanical, termical, reological, MEV and X-ray diffraction tests are done. The nanocomposite which contains pseudoboehmite and octadecylamine tests results were compared with the nanocomposite contained just pseduboehmite to compair and verify the octadecylamine treatment effect in the materials properties. / Nanocompósitos são materiais contendo partículas nanométricas dispersas em uma matriz específica. O grau de organização das nanoestruturas e suas propriedades dependem da natureza dos componentes orgânicos e inorgânicos de sua estrutura onde podem ocorrer interações sinérgicas. Os nanocompósitos poliméricos consistem em um grupo de materiais híbridos nos quais substâncias inorgânicas de dimensões nanométricas estão dispersas na matriz polimérica. Por possuírem alta área específica, uma pequena quantidade de nanocarga pode ocasionar um grande efeito no desempenho da estrutura, no entanto é importante observar que a dispersão do nanoreforço na matriz polimérica deve ocorrer da forma mais homogênea possível, promovendo as interações sinérgicas entre matriz e reforço ao longo de toda a estrutura do material. A obtenção de um reforço cerâmico por processo sol-gel, permite a obtenção de um produto com partículas de dimensões nanométricas, sendo que o mesmo pode ser incorporado à matriz polimérica. Ainda que em dimensões na escala nano, sempre que uma cerâmica é adicionada a um polímero, existe uma tendência à dificuldade na dispersão do material devido ao pequeno espaçamento entre os planos atômicos da cerâmica para que ocorra a passagem da cadeia polimérica entre estes planos. Neste caso, o emprego de técnicas de modificação da nanocarga, onde este espaçamento pode ser aumentado pela ação de um agente organofílico, possibilitando uma melhor acoplagem do reforço à matriz e influenciando diretamente nas propriedades mecânicas, térmicas e reológicas do material quando caracterizado pelas mais diversas técnicas. Neste trabalho, a pseudoboemita obtida por processo sol-gel foi tratada com uma solução de octadecilamina obtendo-se uma mistura adicionada ao Nylon 6,12. Após a mistura o nanocompósito foi seco e processado para conformação dos corpos-de-prova utilizados na caracterização do material. Realizou-se a caracterização por meio de ensaios mecânicos, térmicos, reológicos, MEV e Difração de Raios-X. Os resultados obtidos na caracterização do material contendo pseudoboemita e octadecilamina foram comparados aos resultados obtidos na adição apenas da pseudoboemita para comparação e verificação do efeito do tratamento com octadecilamina nas propriedades do material.

Thin film nanostructures may be defined as assemblies, arrays, or randomly distributed nanoparticles, nanowires, or nanotubes, which together form a layer of materials supported on a substrate surface. Because such nanostructures are supported on a substrate surface, their potential applications cover a wide area in optical, magnetic, electrochemical, electromagnetic, and optoelectronic devices. The focus of the present thesis is the development of methodologies to grow certain thin film nanostructures of some transition metal oxides (TMOs), including copper oxides and LixCoO2, through CVD, sol-gel, and electromagnetic radiation-mediated approaches. The work towards this objective can be divided into three parts: first, the design, synthesis, and systematic identification of novel metalorganic precursors of copper (monometallic) and Li and Co (bimetallic); second, the growth of nanostructured oxides thin films using these precursors; and third, the application of electromagnetic radiation to control or tailor the growth of as grown nanostructures. The underlying growth mechanisms substantiated by appropriate evidence have been put forward, wherever found relevant and intriguing. It may be added that the principal objective of the work reported here has been to explore the several ideas noted above and examine possibilities, rather than to study any specific one of them in significant detail. It is hoped earnestly that this has been accomplished to a reasonable extent. Chapter 1 reviews briefly the reports available in the literature on three specific methods of growing thin films nanostructures, namely chemical vapour deposition, sol-gel processing and light-induced approach. The objective of this chapter has been to provide the background of the work done in the thesis, and is substantiated with a number of illustrative examples. Some of the fundamental concepts involved, viz., plasmons and excitons, have been defined with illustration wherever found relevant in the context of the work. Chapter 2 describes the various techniques used for synthesis and characterisation of the metalorganic complexes as well as of the thin films. This chapters covers mostly experimental details, with brief descriptions of the working principles of the analytical procedures adopted, namely, infrared spectroscopy, mass spectroscopy, elemental analysis, and thermal analysis for characterisation of the metalorganic complexes. This is followed by a similarly brief account of techniques employed to characterize the thin films prepared in this work, viz., glancing incidence X-ray diffraction (GIXRD), field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), electrostatic force microscopy (EFM), transmission electron microscopy (TEM), glancing incidence infra-red spectroscopy (GIIR) and, UV-visible spectroscopy. The metalorganic chemical vapour deposition (MOCVD) systems built in house and used for growth of films are described in detail. The topics in the different sections of the chapter are accompanied by pertinent diagrams. Chapter 3 deals with the design, synthesis and characterisation of novel polynuclear complexes of copper and cobalt. Keeping in mind the various advantages such as low toxicity, ease of synthesis, non-pyrophoricity, and low temperature volatility, of environmentally benign complexes based on biologically compatible such as triethanolamine, diethanolamine, the objective has been to synthesize complexes containing triethanolamine and diethanolamine of transition metals such as cobalt and copper, and to investigate their applicability in MOCVD processes as a novel class of precursors. With the notion of ‘better’ and efficient design of precursors, an attempt has been made, through a semi-empirical modeling, to understand the correlation between volatility and various intrinsic molecular parameters such as lattice energy, vibrational-rotational energy, and internal symmetry. Chapter 4 discusses the growth of nanoporous Cu4O3-C composite films through the MOCVD process employing Cu4(deaH)(dea)(oAc)5.(CH3)2CO as the precursor. The various characteristic aspects of as-grown films, such as their crystallinity, morphology, and composition have been covered elaborately in various sections of this chapter. The chapter describes the efficient guiding and confining of light exploiting the photonic band gap of these nanoporous films, which indicates the potential usefulness of these and similar films as optical waveguides. A model described in the literature on absorbing photonic crystals, wherein a periodically modulated absorption entails an inevitable spatial modulation of dispersion, i.e., of the index contrast to open a photonic band gap, has been used to calculate the indices of refraction of one of these nanoporous films. The chapter also reports briefly the preliminary electrochemical investigations carried out on a typical film, examining the notion of its application as the anode in a Li-ion rechargeable battery. Chapter 5 describes the synthesis of nanocrystalline LixCoO2 films by the sol-gel method. Reports available in literature indicate that the various phases of LixCoO2 are extremely sensitive to processing temperature, making it difficult to control dimensionality of a given phase using temperature as one of process parameters. We have investigated the possibility of using incoherent light to tailor the particle size/shape of this material. The as-grown and irradiated films were characterised by X-ray diffraction, and by microscopic and spectroscopic techniques.Optical spectroscopy was carried out in order to gain insight into the physico-chemical mechanism involved in such structural and morphological transformation. Chapter 6 deals with the synthesis of self-assembled nanostructures from the pre-synthesized nanocrystals building blocks, through optical means of exciton formation and dissociation. It has been demonstrated that, upon prolonged exposure to (incoherent) ultraviolet-visible radiation, LixCoO2 nanocrystals self-assemble into acicular architectures, through intermediate excitation of excitons. Furthermore, it has been shown that such self-assembly occurs in nanocrystals, which are initially anchored to the substrate surface such as that of fused quartz. This new type of process for the self-assembly of nanocrystals, which is driven by light has been investigated by available microscopic and spectroscopic techniques. Chapter 7 describes the stabilisation of chemically reactive metallic lithium in a carbonaceous nanostructure, viz., a carbon nanotube, achieved through the MOCVD process involving a lithium-alkyl moiety. This moiety is formed in situ during deposition through partial decomposition of a metalorganic precursor synthesized in house, which contains both lithium and cobalt. It is surmised that the stabilization of metallic Li in the nanostructure in situ occurs through the partial decomposition of the metalorganic precursor. Quantitative X-ray photoelectron spectroscopy carried out on such a film reveals that as much as 33.4% metallic lithium is trapped in carbon. Lastly, Chapter 8 briefly highlights the outlook for further investigations suggested by the work undertaken for this thesis. Novel precursors derived from biologically compatible ligands can open up possibility of growing new type of micro/nano-structures, and of unusual phases in the CVD grown films. Furthermore, it is proposed that the novel method of growth and alignment of nanocrystals through irradiation with incoherent light, employed for the specific material LixCoO2, may be employed for various other metallic and semiconducting materials.