The thermal conductivity of various porous thermal barrier coating (TBC) systems used in elevated temperature for industrial applications has been evaluated using a proposed six-phase model. These porous TBC systems rely on microstructural properties and yield different types of porosity. These microstructural properties can influence the thermal conductivity of TBC systems. The purpose of this thesis is to assess the thermal conductivity of TBC systems based on microstructural attributes, particularly the effect of different types of porosity. Thus, the first component of this thesis investigates the microstructural characterization of various TBC systems using image analysis (IA) technique. In this technique, scanning electron microscopy (SEM) and light optical microscopy (LOM) micrographs were used to measure the porosity level of different TBC materials. The volumetric fraction of porosity along with orientation, shape, and morphology have a considerable impact on the total thermal conductivity of TBCs. The second component of this thesis evaluates the thermal conductivity of these porous TBC systems by taking into account the effect of the heat treatment process. The IA results reveal that as long as the porosity content increases, the thermal conductivity decreases for all of the TBC materials studied in this thesis. Further, while the content of microcracks and non-flat porosity play a crucial role in reducing the thermal conductivity of TBC materials, the other types of porosity (open randomly oriented, penny-shaped, and interlamellar) exert less impact on the thermal conductivity of TBCs. Comparing the results of the proposed six-phase model to experimental values and finite element analysis (FEA) values showed a relatively good agreement. The proposed six-phase model can predict the thermal conductivity of porous microstructure of TBC systems close to real measured values; therefore, the proposed six-phase model may be utilized to fabricate the porous microstructure of TBCs.

Dans cette thèse on étudie le comportement des ondes électromagnétiques lorsqu'elles rencontrent un matériau négatif, c'est-à-dire un matériau dont la permittivité électrique et/ou la perméabilité magnétique est négative. On se focalise ici sur le cas où seulement la permittivité change de signe. En dimension deux, les équations de Maxwell en régime harmonique se réduisent à deux sous-problèmes scalaires plus aisés à traiter. L'un de ces sous-problèmes autorise la propagation d'ondes de surface, appelées plasmons de surface, à l'interface entre le matériau négatif et le diélectrique, ce qui le rend particulièrement intéressant pour les applications. On se concentre sur ce sous-problème et en particulier sur sa partie principale qui correspond à une équation de conductivité. Cependant, comme la permittivité change de signe les outils classiques comme le Théorème de Lax-Milgram sont mis en défaut. Dans le premier chapitre, on introduit des outils utiles à la compréhension du reste de la thèse. On décrit en particulier comment l'étude l'équation de conductivité fait naturellement intervenir l'opérateur de Poincaré-Neumann dont le spectre encode les rapports de permittivité qui permettent l'existence des plasmons de surface. On présente une formulation intégrale et une formulation variationnelle de l'opérateur de Poincaré-Neumann et le lien qui existe entre ces deux formulations. Le second chapitre de ce manuscrit s'intéresse au caractère bien posé de l'équation de conductivité lorsque la permittivité change de signe. En utilisant des méthodes d'équations intégrales on propose une condition suffisante pour que ce problème soit bien posé. Dans le troisième chapitre de cette thèse, on se concentre sur le calcul numérique du spectre de l'opérateur de Poincaré-Neumann à l'aide des méthodes d'éléments finis. On s'intéresse à la convergence des valeurs propres calculées numériquement vers les valeurs propres théoriques. Dans le dernier chapitre, on étudie le problème de transmission des ondes électromagnétiques dans une couche métallique de permittivité négative sous l'angle des fonctions de Green. En particulier on s'intéresse au comportement de la fonction de Green pour ce problème lorsque l'épaisseur de la couche métallique tend vers zéro. / In this thesis, we study the behaviour of electromagnetic waves when interacting with a negative material. Such a material has a negative electric permittivity and/or magnetic permeability. Here we only focus on negative permittivity materials. In dimension two, Maxwell's equations in harmonic regime reduce to a couple of scalar, easier to tackle, sub-problems. One of these sub-problems allows surface waves to propagate along the interface between a negative material and a dielectric, which makes it very interesting for the applications. Such surface waves are called surface plasmons. Here, we focus on this sub-problem and more specifically on its main part which is a conductivity equation. Yet, as the permittivity sign changes between the negative material and the dielectric, it is not allowed to use the classical Lax-Milgram framework. In the first chapter, we introduce tools which are useful to understand the rest of this thesis. In particular, we describe how studying conductivity equation leads us to deal with the Poincar{'e}-Neumann operator. The spectrum of this operator encodes permittivity ratios that allow surface plasmons to propagate. We propose both the integral formulation and the variational formulation of this operator, and we explain the link existing in-between. In the second chapter of this thesis, we focus on the well-posedness property of the conductivity equation when permittivity sign changes. Using integral equation methods, we propose a sufficient well-posedness condition for this problem. In the third chapter, we deal with the numerical computation of the Poincaré-Neumann operator spectrum using finite element methods. We are interested in the convergence of numerically computed eigenvalues to the theoretical ones. In the last chapter, we study the electromagnetic wave transmission problem in a metallic layer with a negative permittivity from the Green's function point of view. In particular, we investigate the Green's function behaviour when the metallic layer thickness goes to zero.

Le groupe Montupet est un spécialiste de la conception et de la production de pièces de fonderie en aluminium usinées pour l’automobile. Les moules métalliques utilisés pour la réalisation de culasses automobiles en aluminium sont protégés par un revêtement appelé le poteyage. La principale fonction du revêtement de poteyage est de protéger l’outillage en acier de la corrosion chimique de l’alliage. Du fait de ses propriétés thermiques, une autre fonction du poteyage est la modulation des échanges thermiques entre le moule et la pièce en cours de solidification dont dépend fortement la microstructure finale de l’alliage. Le procédé utilisé aujourd’hui pour l’application du poteyage sur les parois du moule en acier consiste à projeter manuellement une barbotine au moyen d’un pistolet. Ce procédé ne permet pas d’obtenir la répétabilité des caractéristiques des couches déposées nécessaire au contrôle des gradients de solidification locaux. De plus, les outillages actuels souffrent de l’insuffisance de la protection du poteyage, ce qui conduit à une usure prématurée ayant un coût important et conduisant à des diminutions du rendement de l’outil industriel. Dans le cadre du projet PROOF de robotisation de l’étape de poteyage, les objectifs suivants ont été fixés. Il s’agit de mieux définir ce que devraient être les propriétés physicochimiques du poteyage. L’objectif à long terme est de réaliser une rupture technologique par l’application d’un revêtement permanent ou de longue durée de vie. Dans un premier temps, ces travaux présentent une caractérisation complète de la nature physico-chimique des suspensions des poteyages utilisés actuellement ainsi que l’étude de leur comportement en pulvérisation. Dans un second temps, après que des revêtements aient été produits par projection plasma sous air (APS), il est apparu nécessaire de comparer leurs propriétés thermiques à celles des revêtements de poteyage. Des valeurs de diffusivité thermiques ont été mesurées, les valeurs de conductivités thermiques des revêtements étudiés ont ensuite été calculées puis confirmées expérimentalement. La dernière partie de ces travaux s’attache à présenter les outils mis en place en usine afin de tester les revêtements créés par projection plasma et de vérifier leur adéquation (thermique et chimique notamment) avec la coulée de pièces en alliage d’aluminium. Ces essais en conditions réelles ou semi-réelles permettent la comparaison de l’efficacité de tous les revêtements étudiés. / Montupet is specialized in the manufacture of aluminium foundry components for the automotive industry. The metallic molds used for aluminium cylinder heads are protected by a specific coating called die coating. The main objective of this die coating is to protect the steel tool from chemical corrosion of the liquid alloy. Because of its thermal properties, another of its aims is the adjustment of the thermal exchanges between the mold and the solidifying aluminium, which strongly affects the final microstructure of the alloy. The process used nowadays to coat the die coating on the steel mold walls consists in spraying manually a suspension. However, this process does not allow to obtain reproducible characteristics of the coated layers necessary to control the local solidification gradients. Furthermore, the current tools suffer from the inadequate protection of the die coating, which leads to premature wear resulting in important costs and a decrease of the efficiency of the industrial tool. In the frame of the PROOF project, aiming in the automatisation of the die coating projection, several objectives were set: better know what should be the physico-chemical properties of the die coating and realize a technological jump by creating a long-life or even permanent coating. Firstly, this work shows a complete characterization of the physico-chemical state of the suspensions used nowadays as well as the study of their behavior during spraying. Then, once the coatings were produced by Air Plasma Spraying (APS), it appeared necessary to compare their thermal properties to the ones measured on the die coatings. Hence, thermal diffusivity values have been measured. Afterwards thermal conductivity of the studied coatings have been calculated and finally experimentally checked. Eventually, this work shows the tools developed within the company in order to test the plasma coatings and to check their thermal and chemical compatibility to the process of aluminium casting. These trials in real or semi-real conditions allow the efficiency comparison of the whole studied coatings.

L’élévation de la température est l’un des principaux paramètres limitant la puissance nominale des machines électriques. La température atteinte au niveau des bobinages, peut avoir de graves conséquences sur le système d’isolation des enroulements et peut ainsi réduire la durée de vie des machines électriques. Le travail de recherche effectué dans cette thèse s’attache à l’extraction de modèles thermiques simplifiés permettant la prédiction des niveaux d’échauffement. Nous avons alors mis en place une démarche basée sur une méthode numérique (Finite Intgeration Technique) qui permet une identification naturelle des grandeurs du modèle thermique. Cette démarche nécessite d’homogénéiser le bobinage en le remplaçant par un seul matériau homogène équivalent permettant de reproduire le même comportement thermique du cas réel du bobinage. Pour ce faire, plusieurs techniques d’homogénéisation ont été employées. Nous nous sommes également intéressés aux différentes configurations des conducteurs dans l’encoche en vue d’obtenir une meilleure évacuation de la chaleur dans le bobinage des machines électriques. La démarche proposée dans ce travail a pout objectif d’obtenir des modèles thermiques simplifiés qui peuvent être réduit à un seul nœud pour calculer la température du point chaud. La validité des modèles est évaluée par comparaison aux éléments finis en considérant deux formes géométriques de l’encoche : une encoche simple puis une encoche de géométrie plus complexe que l’on retrouve dans une machine à commutation de flux. / The temperature rise is one of the main parameters limiting the power of electrical machine. In fact in the stator windings the temperature rise decreases the performances of its insulation system and it can reduce the life time of the motors and it may even lead to the motor failure. Appropriate models of the windings are necessary to find the hot spot of the machine. The work proposed in this thesis focuses on the extraction of simplified thermal models in order to evaluate the temperature distribution. An approach based on a numerical method (Finite Integration Technique) has been developed allowing the identification of the thermal model parameters. As a first step the homogenization of the winding is necessary to obtain the thermal model of the stator slot which has a complex heterogeneous structure requiring careful modeling. The objective is then to replace the conductors and the resin by one homogenous material that reproduces a similar thermal behavior. Several homogenization techniques are used to determine the effective thermal conductivity of the composite material. We are also interested to study different configurations or distributions of the conductors in the slot to limit heat dissipation in the windings of electrical machines. The second part of this thesis presents a method, based on the Finite Integration Technique (FIT) for the discretization that gives us an equivalent thermal model allowing the evaluation of transient temperature evolutions in the slot with low calculation cost.

L’exploration lunaire représente une part importante de l'activité des agences spatiales nationales. Les scientifiques se sont intéressés aux interactions de la surface lunaire avec le plasma environnant et les appareils envoyés sur place. Les observations ont mis en évidence la présence de régolithe, formant une épaisse couche de poussières à la surface, et il a été constaté que ces particules sont très abrasives et tranchantes. Elles représentent un risque matériel important pour les équipements envoyés sur la Lune et la nécessité de comprendre les origines de leur transport est incontournable pour le bon déroulement des futures missions. Le mouvement de ces poussières peut, entre autres, être issu de phénomènes électrostatiques, particulièrement présents aux frontières ombre/lumière. Les observations d'un nuage de poussières au-dessus de la surface lunaire en sont la preuve. Cependant, les mécanismes à l'origine de ce nuage sont peu connus. Il est donc nécessaire de comprendre les interactions entre les poussières et l'environnement lunaire afin de prévenir la pollution d'appareils se trouvant à la surface. L'objectif de la thèse est de comprendre et de modéliser la charge et le transport électrostatique des poussières aux interfaces ombre/lumière. Le dispositif DROP a été développé afin d'observer le transport électrostatique de poussières et permettre une compréhension physique de cette dynamique. Les tests effectués ont permis de dégager les paramètres les plus importants dans la dynamique des poussières. Ils ont également rendu possible l'adaptation d'un modèle numérique préexistant qui a été contraint afin de le rendre plus représentatif de la situation lunaire. / The lunar exploration represents a major part of all national space agencies activities. The scientists have studied the interactions of the lunar surface with the surrounding plasma but also with equipment sent on the lunar surface. Observations have shown the presence of regolith particles covering the surface of the Moon. This layer of dust grains can be several meters thick and these dust particles are very abrasive and adhesive. They are an important risk for equipment sent on the Moon. Thus, the understanding of the origins of dust grains transport is vital to successfully plan future missions. e lunar dust dynamics can be produced by electrostatic phenomena, especially at boundaries between shadowed and unlit regions. Observations of a dust Cloud above the lunar surface are evidence of this dynamic. However, the mechanisms causing this dust Cloud are unknown. It is thus necessary to understand the interactions between dust grains and the lunar environment in order to prevent the pollution of equipment on the lunar surface. The objective of this PhD thesis is the understanding and the modelling of dust particles charge and electrostatic transport near boundaries between shadow and light. An experimental device has been developed to observe dust grains electrostatic transport and to allow a physical understanding of this dynamic. The tests allowed to highlight the most important parameters in the behavior of dust particles. They also led to the adaptation of a numerical model pre-existing and enabled to constraint the parameters used in the model in order to make it more accurate.

Um grande crescimento no interesse por microdispositivos eletroforéticos tem sido observado nos últimos anos. Vantagens atrativas como baixo consumo de reagentes e diminutos tempos de analise são verificados. Microdispositivos fabricados usando toner de impressora e folhas de transparência (poliéster) vem a somar valores como baixo custo e simplicidade de confecção à técnica de micro-separação eletroforética. Entretanto, a aplicação analítica utilizando esse tipo de microdispositivo tem sido pouco explorada. <br />Neste trabalho o uso de microchips eletroforéticos fabricados em poliéster-toner (PT) é utilizado para a determinação simultânea do herbicida glifosato e seu maior metabólito, AMPA (ácido aminometilfosfônico). Em um primeiro momento, o trabalho apresenta o desenvolvimento de uma metodologia no qual utiliza condutometria sem contato (C4D) como sistema de detecção, aliada à separação eletroforética em microchips de PT. Vários parâmetros que regem uma boa confiabilidade analítica, tanto quanto otimizam a sensibilidade do sistema foram avaliados. <br />Em um segundo momento, ainda aliada à microchips de PT, a técnica de cronoamperometria foi utilizada como sistema de detecção. Nessa etapa do projeto estudos eletroquímicos foram inicialmente realizados em eletrodos convencionais de ouro e cobre, buscando averiguar qual metal apresenta maior sensibilidade para o herbicida glifosato. Tendo o metal cobre como melhor escolha, eletrodos planares foram construídos a partir da combinação das tecnologias da produção de máscaras de toner, e placas de circuito impresso como fonte de cobre. <br />Em ambas as metodologias desenvolvidas, picos bem resolvidos foram encontrados para os analitos em estudo. Tempos menores que 80 s foram gastos entre o processo de separação e detecção; uma boa repetibilidade também foi encontrada. Os valores de limite de detecção (LD) utilizando C4D foram 60,8 e 74,8 &micro;mol L-1 para glifosato e AMPA respectivamente. Como esperado, menores valores de LD foram obtidos na detecção amperométrica, com 1,88 &micro;mol L-1 para glifosato e 16,45 &micro;mol L-1 para AMPA. A aplicabilidade dos métodos foi verificada através da analise do herbicida e seu metabólito em amostras de água. Etapas de derivatização e pré-concentração off-line não foram usadas nesse trabalho, dessa forma os dois métodos desenvolvidos apresentaram como principais vantagens o extremo baixo custo, e a simplicidade de uso. / A large increase in interest in electrophoretic microdevices has been observed in recent years. Advantages attractive as low reagent consumption and low analytical time are checked. Microdevices fabricated using printer toner and polyester transparency sheets are the sum values as low cost and simplicity of the technique of making micro-electrophoretic separation. However, the analytical application using this type of microdevice has been little explored. <br />In this work the use of microchip electrophoresis fabricated on polyester-toner (PT) is used for the simultaneous determination of the herbicide glyphosate and its major metabolite, AMPA (aminomethylphosphonic acid). In a first moment, the work presents the development of a methodology in which the use capacitively coupled contactless conductivity detection (C4D) for determination of analytes is employed, coupled with electrophoretic separation in PT microchips. Several parameters that govern a good analytical reliability and with the intuit of optimizing the sensitivity of the system were evaluated. <br />In a second time and still allied to the PT microchips, the technique of chronoamperometry was used for detection. Electrochemical studies were initially conducted in conventional electrodes of gold and copper, looking for determine which metal is more sensitive to detect the herbicide glyphosate. Having the best choice planar copper electrodes were constructed from a combination of technologies for the production of toner masks, and printed circuit boards. <br />In both, C4D and chronoamperometric detection methodologies, well-resolved peaks were found for the glyphosate and AMPA. Time analysis of less than 80s were found including the separation and detection processes, and a good analytical repeatability was also found. The limits of detection (LOD) using C4D were 60,8 and 74,8 &micro;mol L-1 respectively for glyphosate and AMPA. As expected, lower LOD were obtained in the amperometric detection methodology, 1.9 &micro;mol L-1 for glyphosate, and 16.5 &micro;mol L-1 for AMPA. The applicability of the methods was tested by analyzing the herbicide and its metabolite in fortified water samples. Steps of derivatization and preconcentration off-line were not applied in this work, so the two methods showed as main advantages very low cost and time analysis, and simplicity of application.

A introdução de cálcio e lítio como aditivos de sinterização na céria: 10% mol gadolínia foi investigada com o intuito de verificar sua influência na densificação e condutividade elétrica das cerâmicas sinterizadas. Pós contendo de 0 a 1,5% mol do metal foram preparados tanto por reação em estado sólido quanto pela co-precipitação dos oxalatos. As principais técnicas de caracterização utilizadas foram análise térmica, difração de raios X, microscopia eletrônica de varredura e medida da condutividade elétrica por espectroscopia de impedância. Os resultados obtidos mostraram que cerâmicas densas podem ser obtidas utilizando ambos os aditivos. O aumento no teor do aditivo resulta em aumento na densificação. A forma de adição, por reação em estado sólido ou por coprecipitação exerce influência na condutividade elétrica. A adição de cálcio promove maior crescimento dos grãos que o lítio. A condutividade elétrica das amostras contendo o segundo aditivo é inferior à da céria-gadolínia pura. Ambos os aditivos exercem influência na condutividade intergranular. Adição de cálcio resulta também em diminuição da condutividade intragranular. Os aditivos favorecem a exudação do gadolínio. / In this work, the use of calcium and lithium as sintering aid to gadolinia-doped ceria was systematically investigated. The main purpose was to verify the influence of these additives on the densification and electrical conductivity of sintered ceramics. Powder compositions containing up to 1.5 mol% (metal basis) of calcium or lithium were prepared by both solid state reaction and oxalate coprecipitation methods. The main characterization techniques were thermal analyses, X-ray diffraction, scanning electron microscopy and electrical conductivity by impedance spectroscopy. Both additives promoted densification of gadolinia-doped ceria. The densification increases with increasing the additive content. Different effects on microstructure and electrical conductivity result from the method of preparation, e.g., solid state reaction or coprecipitation. Calcium addition greatly enhances the grain growth compared to lithium addition. The electrical conductivity of specimens containing a second additive is lower than that of pure gadolinia-doped ceria. Both additives influence the intergranular conductivity and favor the exudation of gadolinium out of the solid solution.

A solução sólida céria-samária é uma das principais candidatas para aplicação como eletrólito sólido em células a combustível de óxido sólido, devido sua alta condutividade iônica em temperaturas intermediárias (500-750 ºC) de operação. Um dos problemas ainda não solucionados com relação a este material é sua relativamente baixa sinterabilidade. Nesse trabalho foi utilizado o método de sinterização em duas etapas visando melhorar a densificação com reduzido tamanho médio de grãos. Soluções sólidas comercial e obtida por mistura de óxidos de composição Ce0,8Sm0,2O1,9 foram utilizadas. Para fins comparativos também foi utilizado o método denominado sinterização em duas etapas tradicional que visa a obtenção de amostras densas independentemente do tamanho médio de grãos. Resultados de densidade aparente e retração linear revelaram que ambos os tipos de amostras têm comportamento distinto. Para a solução sólida comercial, a retração total até 1400 ºC foi de ~18%. Só foram obtidos resultados de densidade significativos ao utilizar temperaturas elevadas (igual ou superior a 1300 ºC). Para o material obtido por mistura de óxidos não foi possível atingir densidades maiores que 90% da densidade teórica. A sinterização em duas etapas tradicional produziu amostras densas, da mesma forma, que a não-tradicional, mas com tamanhos de grãos consideravelmente maiores. Amostras sinterizadas por ambos os processos foram analisadas por espectroscopia de impedância para a determinação da condutividade elétrica em função da temperatura, e não apresentaram variação significativa nas condutividades intra e intergranular. A sinterização em duas etapas não resultou em melhorias na densificação e nem na condutividade elétrica das amostras. Entretanto, a redução obtida no tamanho médio de grãos pode melhorar as propriedades mecânicas. / Samaria-doped ceria solid solution has been proposed to be used as solid electrolyte in Solid Oxide Fuel Cells due to its high ionic conductivity at intermediate temperatures (500-750 ºC). One of the main problems related to this solid solution is the relatively low sinterability. In this work, sintering of powder compacts was carried out by the two-step sintering method to improve the densification with simultaneous reduction of the mean grain size. Samaria-doped ceria, both commercial and prepared by solid state reactions, with composition Ce0.8Sm0.2O1.9 were investigated. For comparison purposes, the traditional two-step sintering method, by which dense specimens are produced, was also utilized. Apparent density and linear shrinkage results showed distinct features depending on the type of specimen. Total linear shrinkage for commercial solid solution up to ~ 1400 ºC was 18%, but high density values were obtained only for sintering experiments conducted at high temperatures ( 1300 ºC). Specimens prepared by solid state reactions did not attain density values higher than 90% of the theoretical one. The traditional method produced dense specimens as well as the two-step sintering, although the grain size was considerably higher in the former. Specimens sintered by the two methods were used for electrical conductivity measurements. No significant variation in both the grain and the grain boundary conductivities was obtained. The two-step sintering did not allow any improvement in the densification and in the electrical conductivity of samaria-doped ceria. However, the decrease in the mean grain size may contribute to improve the mechanical properties of this solid solution.

Os efeitos decorrentes da adição de NiO na densificação, na microestrutura e na condutividade elétrica da zircônia totalmente estabilizada com ítria foram sistematicamente estudados. Zircônia-8% mol de ítria (8YSZ) comercial e acetato, trihidróxi-carbonato, nitrato e óxido de níquel foram utilizados como materiais de partida. Os teores de Ni variaram entre 0,5% e 5% em mol e as composições foram preparadas por mistura dos materiais precursores a partir das concentrações estequiométricas. Estudos de densificação realizados por meio de medidas de densidade geométrica e dilatometria revelaram que a retração total até 1400ºC varia de ~16 até ~20% dependendo do precursor de níquel. No segundo estágio de sinterização a retração linear aumentou com o aumento no teor do aditivo (precursor: trihidróxi-carbonato de níquel). No estágio inicial de sinterização a energia de ativação para a difusão via contornos de grão varia de acordo com o precursor de níquel utilizado sendo menor para o óxido e maior para o trihidróxi-carbonato. No estágio secundário de sinterização prevalece a sinterização volumétrica. Neste estágio, as temperaturas de máxima retração são independentes do precursor de níquel, exceto para o acetato. O tamanho médio de cristalito variou com o tipo de precursor empregado sendo menor para o trihidróxi-carbonato e maior para o óxido de níquel. O limite de solubilidade do NiO determinado por difração de raios X é 1,48% em mol a 1350ºC. Para teores acima do limite de solubilidade o aditivo permanece aleatoriamente distribuído como uma fase secundária na forma de NiO. O principal efeito do aditivo na microestrutura é aumentar o tamanho médio de grãos. Os resultados de medidas elétricas revelaram que a adição de NiO não produz alterações significativas na condutividade intragranular da 8YSZ para diversos tempos de sinterização, exceto quando o precursor é o óxido de níquel, para o qual a condutividade elétrica aumenta com o tempo de sinterização evidenciando a dificuldade na formação de solução sólida, quando o material precursor possui tamanho de cristalito superior ao da matriz. Entretanto, a condutividade intragranular nas amostras preparadas com o trihidróxi-carbonato de nickel é pouco inferior à das demais amostras. Nas amostras sinterizadas por 15 h a 1350ºC um terceiro semicírculo foi associado com a formação de fase tetragonal na 8YSZ, devido à aceleração pelo níquel na cinética da transformação de fase cúbica para tetragonal. A condutividade intergranular varia com o tempo de sinterização devido à diminuição na fração de interfaces (contornos de grão) que ocorre com o aumento no tamanho médio de grãos. A condutividade intergranular microscópica da 8YSZ não varia significativamente com a adição de NiO. / The effects produced by NiO addition to yttria fully-stabilized zirconia were systematically investigated. Commercial zirconia-8 mol% yttria, nickel acetate, nitrate, trihydroxicarbonate and nickel oxide were used as starting materials. The NiO content varied from 0.5 to 5 mol%, and the compositions were prepared by mechanically mixing the starting materials in the stoichiometric proportions. Densification studies carried out by density and dilatometry measurements revealed that the maximum shrinkage (~16-~20%) depends on the type of nickel precursor. In the second sintering stage the linear shrinkage increased with increasing NiO content (precursor: nickel trihydroxi-carbonate). In the first sintering stage, the activation energy for grain boundary diffusion changed according to the additive precursor, being lower for the oxide and higher for the trihydroxi-carbonate. In the second stage, when the major part of porosity is eliminated, the maximum shrinkage rate temperatures were found to be independent on the precursor except when nickel acetate is used. The solubility limit at 1350ºC is 1.48% as determined by X-ray diffraction. Above the solubility limit the excess NiO is retained as a second randomly distributed phase. The main effect of the additive in the ceramic microstructure is to increase the average grain size. The electrical measurements showed that the additive did not produce any significant effect in the grain conductivity irrespective of the sintering time, except when the precursor material was nickel oxide. In this case, the grain conductivity increased with increasing sintering time. This effect is attributed to the crystallite size of the nickel oxide precursor, which is higher than that of 8YSZ, slowing down the formation of solid solution. However, the grain conductivity of samples prepared with nickel trihydroxi-carbonate precursor is slightly lower than those of other samples. The samples sintered for 15 h exhibited an additional semicircle in the impedance diagram, which is assigned to the tetragonal phase of zirconia-yttria, resulting from thermal decomposition of the cubic structure. Hence, NiO additive accelerates the kinetics of cubic-to-tetragonal phase transformation in 8YSZ. The grain boundary conductivity depends on the sintering time due to reduction of the fraction of interfaces as a consequence of grain growth. The microscopic grain boundary conductivity of 8YSZ does not vary with NiO addition.

Este trabalho apresenta os resultados da preparação e caracterização de eletrólitos poliméricos a partir de DNA-CTMA e DNA-DODA com adição de 7, 9, 10 e 11% (m/m) de LiClO4 e/ou LiI/I2. O objetivo é usar estes eletrólitos poliméricos em pequenas células solares sensibilizadas com corante (DSSC). O DNA com a massa molecular de 5,41x108 &plusmn; 1179,6 g/mol foi usado para a síntese de complexos de DNA-CTMA e DNA-DODA através da reação de substituição de DNA com os agentes surfactantes: CTMA e DODA. As amostras na forma de filmes foram caracterizadas por espectroscopia de impedância, difração de raios-X, UV-Vis, FT-IR e análises térmicas (DSC e TGA). Os espectros de FT-IR confirmaram a obtenção dos complexos de DNA-CTMA e DNA-DODA. A espectroscopia no UV/Vis revelou a presença de absorção em 260 nm atribuída às transições eletrônicas &pi;- &pi;* das bases nitrogenadas do DNA. As análises térmicas dos complexos de DNA-CTMA e DNA-DODA mostraram a estabilidade térmica de 226&deg;C e 232&deg;C e a transição vítrea de -67&deg;C e -40,0&deg;C, respectivamente. A difração de raios-X das amostras permitiu a determinação da porcentagem de cristalinidade sendo entre 43,74 e 63,20% para DNA-CTMA e entre 49,4 e 76,25% para DNA-DODA. Os filmes foram submetidos às medidas de condutividade iônica revelando os melhores resultados de 8,21x10-4 S/cm a 25&deg;C para as amostras de DNA-CTMA com 10% (m/m) de LiClO4 e 2,87x10-4 S/cm para o DNA-DODA com 10% (m/m) de LiClO4. Os eletrólitos de DNA-CTMA com 9 e 10 % (m/m) de LiI/I2 e DNA-DODA com 9 e 10% (m/m) de LiI/I2 foram aplicados em pequenas células solares mostrando a eficiência de 0,14, 0,31, 0,177 e 0,66% respectivamente, valores considerados promissores para futuros estudos. / The present work describes the preparation and characterization of polymeric electrolytes of DNA-CTMA and DNA-DODA with addition of 7, 9, 10 and 11% (m/m) LiClO4 and/or LiI/I2. The objective is use of these polymer electrolytes in dye sensitized solar cells (DSSC). The DNA with molecular weight of 5,41x108 &plusmn; 1179,6 g/mol was used to synthesize DNA-CTMA and DNA-DODA complexes by substitution reaction. The obtained samples in the film form were then characterized by impedance spectroscopy, X-ray diffraction, UV-Vis, FT-IR and thermal analyses (DSC and TGA). The FT-IR spectra confirmed both, DNA-CTMA and DNA-DODA complexes obtaining. The UV-Vis spectroscopy of the samples evidenced an absorption band at 260 nm attributed to electronic transitions &pi;-&pi; * of DNA nitrogenous bases. The TGA and DSC analyses shoved a thermal stability of the DNA-CTMA and DNA-DODA samples of 226&deg;C and 232&deg;C and, glass transition of -67&deg;C and -40&deg;C, respectively. The X-ray diffraction allowed determining the crystallinity of 43.74 to 63.20% for the samples of DNA-CTMA and 49.4 to 76.25% for the DNA-DODA. The films were subjected to ionic conductivity measurements showing the best results of 8.21x10-4 S/cm at 25&deg;C for the DNA-CTMA with 10% (w/w) of LiClO4 and of 2.87x10-4 S/cm for DNA-DODA with 10% (w/w) of LiClO4. Finally the electrolytes of DNA-CTMA with 9 and 10% (m/m) of LiI/I2 and of DNA-DODA 9 and 10% (m/m) of LiI/I2 were applied in small solar cells exhibiting the efficiency of 0,14, 0,31, 0,177 and 0,66%, respectively. The obtained results are promising for future investigations.