Polyaniline (PANI), when doped with small-molecule acids, is an attractive candidate for organic and polymer electronics because of its high electrical conductivity. Its utility as functional components in electrical devices, however, has been severely restricted because such PANI has limited processibility stemming from its limited solubility in common solvents. To overcome this barrier, we have developed water dispersible PANI that is template polymerized in the presence of a polymer acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or PAAMPSA. The polymer acid serves two roles: it acts as a dopant to render PANI conductive and excess water soluble pendant groups provide dispersibility of PANI in aqueous media. While the introduction of polymer acids renders the conducting polymer processible, such gain in processibility is often accompanied by a significant reduction in conductivity. As such, PANI that is doped with polymer acids has only seen limited utility in organic electronics. Given the promise of conducting polymers in organic electronics in general, this thesis focuses on the elucidation of processing-structure-property relationships of PANI-PAAMPSA with the aim of ultimately improving the electrical conductivity of polymer acid-doped PANI. By controlling the molecular weight and molecular weight distribution of the polymer acid template, we have improved the conductivity of PANI-PAAMPSA from 0.4 to 2.5 S/cm. The conductivity increases with decreasing molecular weight of PAAMPSA, and it further increases with narrowing the molecular weight distribution of PAAMPSA. Strong correlations between the structure and the conductivity of PANI-PAAMPSA are observed. In particular, the crystallinity of PANI increases with increasing the conductivity of PANI-PAAMPSA. Given that the crystallinity qualifies the molecular order in PANI-PAAMPSA, we observe a linear correlation between molecular order and macroscopic charge transport in PANI-PAAMPSA. PANI-PAAMPSA forms electrostatically stabilized sub-micron particles during polymerization due to strong ionic interactions between the sulfonic acid groups of PAAMPSA and aniline. When cast as films, the connectivity of these particles must play an important role in macroscopic conduction. The size and size distribution of PANI-PAAMPSA particles is strongly influenced by the molecular characteristics of polymer acid template. Templating the synthesis of PANI-PAAMPSA with a higher molecular weight PAAMPSA results in larger particles, and templating with a PAAMPSA having a larger molecular weight distribution results in a large size distribution in the particles. Because conduction in PANI-PAAMPSA films is governed by how these particles pack, the macroscopic conductivity of PANI-PAAMPSA films increases with increasing particle density, that is reducible from the molecular characteristics of PAAMPSA. Moreover, PANI-PAAMPSA particles are structurally and chemically inhomogeneous. The conductive portions of the polymer preferentially segregate to the particle surface. Conduction in these materials is therefore mediated by the particle surface and conductivity thus scales superlinearly with particle surface area per unit film volume. We further have improved the electrical conductivity of PANI-PAAMPSA by more than two orders of magnitude via post-processing solvent annealing with dichloroacetic acid (DCA). Since DCA is a good plasticizer for PAAMPSA and its pKa is lower than that of PAAMPSA (pKas of DCA and PAAMPSA are 1.21 and 2.41, respectively, at room temperature), DCA can effectively moderate the ionic interactions between PANI and PAAMPSA, thereby relaxing the sub-micron particulate structure arrested during polymerization. PANI-PAAMPSA can thus rearrange from a “compact coil” to an “extended chain” conformation upon exposure to DCA. Efficient charge transport is thus enabled through such “extended chain” PANI-PAAMPSA structure. DCA-treated PANI-PAAMPSA exhibits an average conductivity of 48 S/cm. The DCA treatment is not only specific to PANI-PAAMPSA. This treatment can also enhance the conductivity of commercially-available poly(ethylene dioxythiophene) that is doped with poly(styrene sulfonic acid), or PEDOT-PSS. Specifically, DCA-treated PEDOT-PSS exhibits a conductivity of 600 S/cm; this conductivity is the highest among polymer acid-doped conducting polymers reported so far. PANI-PAAMPSA can effectively function as anodes in organic solar cells (OSCs) whose active layer is a blend of poly(3-hexylthiophene), P3HT, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Specifically, the OSCs with PANI-PAAMPSA anodes exhibit an average short circuit current density of 1.95 mA/cm², open circuit voltage of 0.52 V, fill factor of 0.38, and efficiency of 0.39 %. The use of DCA-treated PANI-PAAMPSA as anodes increases device performance (i.e., short circuit current density and thereby efficiency) of OSCs by approximately two and a half fold. The OSCs with DCA-treated PANI-PAAMPSA anodes exhibit short circuit current density and efficiency as high as 4.95 mA/cm² and 0.97 %, respectively. We demonstrated several factors that govern the electrical conductivity of polymer acid-doped conducting polymers. Design rules, such as those illustrated in this study, can enable the development of conducting polymers that is not only easily processible from aqueous dispersions, but also sufficiently conductive for electronic applications, and should bring us closer to the realization of low-cost organic and polymeric electronics. / text

La vitrification des déchets nucléaires de hautes activités est une étape importante à maîtriser afin d’assurer leur confinement. Depuis 2010, un procédé de vitrification en creuset froid présentant de nombreux avantages est exploité à cet effet dans l’usine de La Hague. Cette technologie est basée sur la circulation de courants électromagnétiques directement dans la charge du creuset dont les parois sont refroidies. Grâce au gradient thermique créé entre ces parois refroidies et le bain de verre en fusion, une couche de verre solide appelée autocreuset est formée jouant le rôle de barrière anticorrosive et électriquement isolante. Du fait de leur composition et de leur microstructure complexes, l’étude des propriétés électriques et diélectriques des verres d’intérêt nucléaire et la compréhension des phénomènes mis en jeu sont nécessaires afin de maîtriser convenablement le fonctionnement du procédé en creuset froid ainsi que les simulations thermo-hydrauliques qui lui sont associées.L’étude présentée ici porte sur la description des phénomènes de mouvements de charges électriques à l’origine des propriétés électriques et diélectriques ayant lieu au sein de verres borosilicatés d’intérêt nucléaire. Des relations entre ces propriétés et la composition ainsi que la microstructure de ces verres sont également établies. Ces problématiques sont tout d’abord abordées dans le cas de deux verres technologiques inactifs de compositions complexes grâce à des caractérisations microstructurales et des mesures d’impédance complexe à l’état solide. Une description plus détaillée des phénomènes mis en jeu est réalisée grâce à la caractérisation de verres simplifiés à 5 oxydes (SiO2-B2O3-Na2O-CaO -RuO2 ou -MoO3) permettant ainsi une meilleure compréhension des mouvements de charges selon la fréquence du champ électrique, la température ainsi que la composition et la microstructure du matériau. / The vitrification of high-level nuclear waste is an important step to master in order to ensure their immobilization. Since 2010, a cold crucible induction melter is used in the La Hague plant due to its advantages. This process is based on electromagnetic currents directly induced on the load of the crucible whose walls are water-cooled. Thanks to the thermal gradient established between these cooled walls and the molten glass, a solid glass layer called self-crucible is created which protects the crucible from corrosion effects and acts as an electrical insulator. Due to their complex composition and microstructure, the study of electrical and dielectric properties of nuclear glasses and the understanding of the related phenomena are necessary in order to efficiently master the cold crucible process and the associated thermo-hydraulic simulations.This study is dealing with the description of the electric charge motion phenomena involving the electrical and dielectric properties of the nuclear borosilicate glasses. Relationships between these properties, the composition and the microstructure are also given. These issues are firstly broached through the investigation of two industrial inactive glasses of complex composition thanks to microstructure characterizations and complex impedance measurements in the solid-state. A more detailed description of the phenomena is performed thanks to the characterization of simplified glasses containing 5 oxides (SiO2-B2O3-Na2O-CaO -RuO2 or -MoO3) allowing a better understanding of the charge motion according to the electrical field frequency, the temperature, the composition and the microstructure of the material.

A agricultura de precisão é um ramo de pesquisa relativamente recente na área agrícola e que apresenta perspectivas promissoras na geração de novas técnicas de gerenciamento da lavoura otimizadoras de insumos e que permitam diminuição nos custos de produção. Técnicas como aplicação localizada de fertilizantes, defensivos agrícolas e melhor monitoramento de características dos solos e outros fatores de produção, fornecem informações que permitem um melhor gerenciamento da área a ser cultivada e em última instância resultam num maior rendimento econômico por área cultivada. Para que seja possível otimizar a produção agrícola utilizando essas técnicas algumas informações iniciais são necessárias. Entre essas uma das mais divulgadas é a utilização dos mapas de produtividade na avaliação da variabilidade espacial das lavouras. Pesquisas recentes tem relatado que conjugado a esse mapa outras camadas de informações podem e devem ser incorporadas, possibilitando desvendar os motivos da variabilidade espacial da produtividade em uma lavoura. Entre essas camadas existem os mapas de características físico-químicas do solo. Um conceito de mapeamento de fatores do solo é o monitoramento da condutividade elétrica do mesmo que permite inferir sobre elementos como textura, salinidade, teor de água, entre outros fatores. O presente trabalho estudou a técnica da mensuração desta característica e sua avaliação em solos brasileiros, verificando a correlação das leituras de condutividade elétrica do solo com parâmetros obtidos por análise laboratorial de amostras do mesmo e com a produtividade de culturas instaladas em três áreas experimentais. Além disso verificou-se a possibilidade de definição de unidades de gerenciamento do solo, que consigam com sucesso representar regiões homogêneas quanto a atributos que influenciam o desenvolvimento das culturas, utilizando a condutividade elétrica. Para realização desses objetivos técnicas diversas de análises foram utilizadas. Após a análise estatística descritiva dos conjuntos de dados procedeu-se com a análise geoestatística dos mesmos para avaliação do grau de dependência espacial das variáveis e obtenção dos mapas das distribuições espaciais das mesmas. De posse desses mapas foi possível efetuar a análise de correlação linear de Pearson entre as variáveis e em seguida a análise de componentes principais para verificar quais seriam as de maior influência sobre a variação do solo em cada uma das áreas monitoradas. Na última etapa a lógica fuzzy definiu as unidades de gerenciamento do solo e uma análise de variância avaliou a relevância dessas divisões. Os resultados indicaram a utilidade da condutividade elétrica, além de comprovarem a eficácia do procedimento realizado, devido a correlação da mesma com alguns atributos físico-químicos do solo, notadamente a elevada correlação com o conteúdo de argila em uma das áreas experimentais. / Precision Agriculture is a line of research relatively recent in the agricultural area and one that presents promising perspectives on the generation of new field management techniques that allow for cost reduction and input optimization. Techniques as variable rate application of fertilizers, agrochemical and better sensing of soil characteristics, and other production factors, give information that enables better management of fields being cultivated and result in greater economic revenue. For it to be possible to optimize agricultural production using these techniques some initial information are necessary. For one, there is the utilization of yield maps to evaluate the spatial variability of fields. Some researches demonstrated that, conjugated to those maps, other levels of information should be incorporated, permitting to reveal factors that explain spatial variability of yield in a field. Among these information there are physical-chemical soil characteristics maps. One of the concepts for mapping soil factors is sensing its electrical conductivity, which is related to soil characteristics such as texture, moisture, salinity and other. This research studied the measurement of the electrical conductivity of some types of Brazilian soils. Then, correlation of the electrical conductivity readings with soil parameters, obtained by laboratory analysis of soil samples, and with crop yields, cultivated on three experimental areas, was obtained. Besides that, it was verified the possibility of definition of soil management zones, using soil electrical conductivity, which can successfully represent homogeneous regions with regards to attributes that influence the development of crops. For accomplishing these objectives, several analysis techniques were used. After the descriptive statistics analysis of the data set, the geostatistical analysis was made for the evaluation of the variables’ degree of spatial dependence and then obtaining the maps with the spatial distribution of these same variables. In the possession of these maps, it was possible to verify Pearson’s linear correlation among all variables, followed by the principal components analysis to infer which of them had greater influence on soil variability in each of the experimental areas. Thenceforth, fuzzy logic was used to define the soil management zones and an analysis of variance evaluated the importance of the zone divisions made. Results showed the usefulness of electrical conductivity, besides corroborating the efficiency of the proceedings used, because of its correlation with some physical-chemical properties of the soil, especially high correlation with clay content in one of the experimental areas.

Compósitos de matriz metálica combinam diferentes classes de materiais a fim de obter novas propriedades, superiores às dos materiais originais. A adição de partículas cerâmicas (reforço) em ligas de cobre pode melhorar suas propriedades mecânicas sem gerar grande perda na condutividade elétrica. Este trabalho teve como objetivo processar e estudar a microestrutura e propriedades (condutividade elétrica, dureza e fratura) de compósitos à base de cobre reforçados com alumina e céria. As amostras foram processadas pela técnica de metalurgia do pó: pesagem, mistura (sem bolas por 30min a 46 rpm), compactação (uniaxial à frio com pressão de 1080 Mpa por 10s) e sinterização (800°C por 6h sob vácuo de 10-5 torr). As análises de MO, MEV, EDS e DRX (com refinamento Rietveld) indicaram boa coalescência das partículas, formando superfície continua e com baixa porosidade. A alumina formou regiões aglomeradas da ordem de 20 μm, a céria ficou finamente dispersa nos contornos de grão do cobre com algumas regiões aglomeradas, o cromo formou regiões de cerca de 100 μm e não teve distribuição completamente uniforme ao longo da matriz, a prata formou solução sólida com o cobre e, durante o resfriamento lento, formou precipitados menores do que 5 μm uniformemente dispersos no interior dos grãos de cobre. Os compósitos apresentaram condutividade elétrica entre 15 e 40 %IACS, dureza entre 62 e 88 HV5 e as fractografias apresentaram fratura mista e regiões indicando boa adesão matriz-reforço. Em relação ao cobre puro, foi observado efetivo aumento na dureza (cerca de 2x), porém, em todos os compósitos, o acréscimo da fase cerâmica acarretou na diminuição da condutividade elétrica. Os compósitos de Cu-8%(Al2O3, CeO2) foram os que apresentaram melhor equilíbrio entre essas duas propriedades, com condutividade de 40 e 38 %IACS e dureza de 63 e 69 HV5. / Metal matrix composites combine different classes of materials to obtain new properties, superior to those of the original materials. The addition of ceramic particles (reinforcement) in copper alloys could improve their mechanical properties without generating great loss in electrical conductivity. The aim of this work was to process and study the microstructure and properties (electrical conductivity, hardness and fracture) of copper-based composites reinforced with alumina and ceria. The samples were processed by the powder metallurgy technique: weighing, blending (no balls for 30 min at 46 rpm), compaction (cold uniaxial at 1080 MPa for 10s) and sintering (800°C for 6 h under vacuum of 10-5 torr). Analysis of OM, SEM, EDS and XRD (with Rietveld refinement) indicated good coalescence of the particles, forming continuous surface with low porosity. The alumina formed agglomerated regions with approximately 20 μm, the ceria was finely dispersed in the grain boundary of the copper with some agglomerated regions, the chromium formed regions of about 100 μm and have a non-uniform distribution throughout the matrix, the silver formed solid solution with copper and, during slow cooling, formed precipitates smaller than 5 μm, uniformly dispersed inside the copper grains. The composites presented electrical conductivity between 15 and 40 %IACS, hardness between 62 and 88 HV5 and the fractographs presented mixed fracture and regions indicating good matrix-reinforcement adhesion. In relation to pure copper, it was observed an increase in hardness (about 2x), however, in all the composites, the increase of the ceramic content led to a decrease in the electrical conductivity. The Cu-8%(Al2O3, CeO2) composites showed the best balance between these two properties, with conductivity of 40 and 38 %IACS and hardness of 63 and 69 HV5.

Les fils composites Cu/Nb étudiés ici sont d'excellents candidats pour les bobines non destructives générant des champs magnétiques pulsés intenses (B ≥ 100T). Ils sont fabriqués par Accumulative Drawing and Bundling (ADB) et sont constitué de renforts continus de Nb dans une matrice multi-échelles de Cu. Ces travaux rentrent dans le cadre du projet METAFORES (ANR-12-BS09-0002), visant l’évaluation des effets de taille et d’architecture sur les propriétés des conducteurs Cu/Nb. L’objectif principal consiste donc à caractériser leur microstructure et leurs propriétés à chaque étape de la fabrication par différentes techniques de caractérisation. Des essais mécaniques et électriques montrent une augmentation de la limite d’élasticité avec l’affinement de la microstructure tout en conservant une conductivité électrique adéquate. Les études de la texture globale par DRX ont mis en évidence trois composantes de texture de fibre dont deux pour la matrice de Cu (<111> et <100>) et une composante unique <110> pour le Nb. On retrouve ces trois composantes de texture dans les analyses locales (EBSD), cependant les proportions relatives des composantes du Cu varient en fonction du nombre de cycles ADB.Les essais de déformation in-situ sous neutrons ont mis en évidence des comportements élasto-plastique et purement élastique des familles de grains {111} du Cu et {110} du Nb respectivement, quels que soient les échantillons. Pour la famille {200} du Cu, le comportement mécanique varie en fonction du nombre de cycles ADB. Tous ces résultats viendront nourrir les simulations effectuées dans le cadre du projet METAFORES (Thèse de Tang Gu, ENSAM-Paris/Mines ParisTech). / High strength and high conductivity Cu/Nb composites studied here are very good candidates for the design of magnets generating high pulsed magnetic fields (B ≥ 100T). They are fabricated by Accumulative Drawing and Bundling (ADB) and are constituted with a multi-scale Cu matrix embedding continuous Nb filaments that are distributed in a controlled manner. This study is performed within the framework of the METAFORES project (ANR-12-BS09-0002) aiming at assessing size and architecture effects on properties of these Cu/Nb conductors. The main purpose is therefore to characterize the microstructure and properties of these conductors at different stages of the fabrication process. Mechanical and electrical results show an increase in yield strength while maintaining adequate electrical conductivity. Global texture studies confirm three fiber texture components: two for the Cu matrix (<111> and <100>) and a single component <110 > for Nb. These three texture components are also observed at the local scale analysis (EBSD); however the volume fractions of the Cu components locally depend on the number of ADB cycles.In-situ deformation tests under neutrons reveal elasticplastic and purely elastic behaviors of the {111} Cu and {110} Nb grains family respectively, whatever the samples. However, for the {200} Cu grains family, mechanical behavior strongly depends on the number of ADB cycles. These results will feed the simulations conducted in the METAFORES project (Thesis of Tang Gu, ENSAM-Paris / Mines ParisTech).

Cerâmicas elétricas de Ba2In2O5 foram preparadas pelo método convencional de mistura de óxidos, e pela mistura e cristalização dos nitratos metálicos, para verificar o efeito do tamanho inicial das partículas na transição de fase ordemdesordem e na condutividade elétrica. Foram feitas substituições utilizando os cátions Gd3+ e Er3+, para verificar o efeito destes cátions na condutividade elétrica do indato de bário. Foi também preparado o óxido de índio pela técnica de complexação de cátions, e as nanopartículas obtidas foram caracterizadas por diversas técnicas. As principais técnicas de caracterização utilizadas foram: análise térmica, espectroscopia de absorção na região do infravermelho com transformada de Fourier, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, difração de raios X convencional e utilizando radiação síncrotron, espalhamento de raios X a baixos ângulos, espectroscopia de energia dispersiva, espectroscopia Raman e medida da condutividade elétrica por espectroscopia de impedância. Os principais resultados mostraram que os tratamentos térmicos de calcinação e sinterização exercem forte influência na obtenção da fase Ba2In2O5. Fases espúrias são facilmente formadas no Ba2In2O5 também decorrentes da interação deste com a umidade. Um menor tamanho inicial de partículas favorece a redução na temperatura de transição de fase de segunda ordem. A introdução do Er, em teores relativamente baixos, produziu aumento na condutividade elétrica e simultânea redução na temperatura de transição de fase. Altos teores de Er e Gd dão origem a múltiplas fases. Na decomposição térmica do citrato de índio é formado um composto intermediário. A calcinação do citrato de índio produziu um material particulado com tamanho nanométrico, mesmo para temperaturas de até 900 ºC. / The Ba2In2O5 conducting ceramic was prepared by the conventional powder mixing technique and by the crystallization of a mixture of metallic nitrates. The main purpose of this work was to verify the particle size effect on the electrical conductivity and phase transition temperature of sintered ceramics. Gd3+ and Er3+ were used to study the effect of dopant cations in the electrical conductivity behavior of Ba2In2O5. Finally, indium oxide was prepared by the cation complexation technique, and the obtained nanoparticles were characterized by several techniques. The main characterization techniques used in this work were: thermal analyses, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy, energy dispersive X-ray analysis, conventional X-ray diffraction and non-conventional X-ray diffraction using síncroton radiation, small angle X-ray diffraction, Raman spectroscopy and electrical conductivity by impedance spectroscopy. The main results show that special care should be taken in order to obtain single phase Ba2In2O5 powders, especially with thermal treatments of calcination and sintering of powders and compacts. The temperature for the second order phase transition decreased with reduction of the initial particle size. An increase of the electrical conductivity along with decrease in the temperature for phase transition was observed for small amounts of Er. Large contents of both Gd and Er give rise to more complexes phases. An intermediate compound was formed during the thermal decomposition of indium citrate. Calcination of this precursor up to 900 ºC gave rise to nanosized particles.

O trabalho teve o objetivo de investigar técnicas de sensoriamento de solo e analisar o potencial de utilização das mesmas diretamente no campo. Quatro etapas distintas foram desenvolvidas para atender aos seguintes objetivos: a) comparar e avaliar o potencial de predição de atributos do solo de três espectrômetros portáteis (vis-NIR) em ambiente controlado; b) avaliar a predição em movimento de pH, P e K utilizando técnicas de sensoriamento óptico (reflectância vis-NIR) e eletroquímico (eletrodos íon-seletivos de pH e K) em uma área experimental com variabilidade induzida; c) montar e testar uma plataforma de campo com sensores elétricos, eletroquímicos e ópticos; d) avaliar o potencial de predição de textura do solo utilizando um equipamento portátil de espectroscopia de fluorescência de raios X. Na primeira etapa as leituras de reflectância espectral vis-NIR dos três equipamentos avaliados mostraram-se muito semelhantes, com coeficientes de correlação acima de 0,86 na faixa de 400 a 1800 nm. Quando comparados nesta região espectral os equipamentos produziram modelos de predição muito semelhantes, com leve superioridade para o sistema FieldSpec. Os modelos mostraram-se mais promissores para a predição da textura do solo em relação aos atributos químicos. Na segunda etapa as leituras de campo utilizando eletrodos íon-seletivos de pH e K apresentaram uma alta correlação com as análises de laboratório. As avaliações permitiram observar que condições de solo com baixa umidade prejudicam sensivelmente as leituras. Apesar da alta correlação, os valores de campo precisam ser corrigidos para a metodologia de laboratório desejada. Os modelos de predição de P, K e pH utilizando espectrometria vis-NIR no campo apresentaram baixa precisão. Os testes da Plataforma Multisensores de Solo (PMS) na terceira etapa demonstraram ser possível a utilização de sensores elétricos, eletroquímicos e ópticos em uma mesma plataforma. As leituras de condutividade elétrica aparente do solo (CEa) demonstraram que este parâmetro está relacionado com a textura, atuando como um indicador da variabilidade e possibilitando a identificação dos locais de transição de textura. O pH mensurado pela PMS exibiu correlações abaixo das verificadas na segunda etapa. No entanto, alguns resultados atípicos foram verificados, como a correlação maior entre pH em CaCl2 com a PMS do que em relação ao método em H2O. As leituras de reflectância vis-NIR utilizando a PMS apresentaram bons modelos de predição de areia e argila, permitindo a criação de mapas de alta resolução destes parâmetros. A espectroscopia de fluorescência de raios X portátil foi eficiente para estimar a textura do solo. Os teores de areia e argila foram estimados tanto por meio de regressões lineares simples como regressões múltiplas com valores de R2 acima de 0,60. O Fe total foi o principal elemento utilizado nesses modelos de regressão. / The objective of this work was to investigate soil sensing techniques and to analyze the potential for their use directly in the field. Four distinct steps were developed to meet the following objectives: a) to compare and evaluate the potential of predicting soil attributes with three portable spectrometers (vis-NIR) in a controlled environment; B) to evaluate the on-the-go prediction of pH, P and K using optical sensors (vis-NIR reflectance) and electrochemical techniques (ion-selective pH and K electrodes) in an experimental area with induced variability; C) assemble and test a field platform with electrical, electrochemical and optical sensors; D) to evaluate the potential of predicting soil texture using a portable X-ray fluorescence spectroscopy equipment. In the first step the vis-NIR spectral reflectance readings of the three equipments evaluated were very similar, with correlation coefficients above 0.86 in the 400 to 1800 nm range. When compared in this spectral region, the equipment produced very similar prediction models, with slight superiority for the FieldSpec system. The models showed to be more promising for the prediction of soil texture in relation to chemical attributes. In the second step the field readings using ion-selective pH and K electrodes presented a high correlation with the laboratory analyzes. The evaluations showed that soil conditions with low moisture significantly affect the readings. Despite the high correlation, the field values need to be corrected for the desired laboratory methodology. Prediction models of P, K and pH using field-vis-NIR spectrometry showed low precision. The tests of the Multisensors Soil Platform (MSP) in the third stage demonstrated that it is possible to use electric, electrochemical and optical sensors in the same platform. The electrical conductivity (EC) readings showed that this parameter was related with soil texture, acting as an indicator of variability and allowing the identification of texture transitions. The pH measured by MSP exhibited correlations below those verified in the second step. However, some atypical results were verified, such as the higher correlation between pH in CaCl2 and MSP than in H2O. The vis-NIR reflectance readings using the MSP resulted in good sand and clay prediction models, allowing the creation of high resolution maps of these parameters. Portable X-ray fluorescence spectroscopy was efficient for estimating soil texture. The sand and clay contents were estimated both by simple linear regressions and multiple regressions with R2 values above 0.60. Total Fe was the main element used in these regression models.

A intensificação da produção brasileira tem contribuído para a redução da importação de sementes de hortaliças devido, principalmente, à atuação de empresas multinacionais. O elevado valor comercial e o aumento da utilização de sementes híbridas têm justificado o uso de sementes de qualidade diferenciada, cuja oferta tem sido crescente. Neste contexto, o presente trabalho teve como objetivo estudar a eficiência de diferentes métodos para a avaliação do potencial fisiológico de sementes de rabanete (Raphanus sativus L.), visando à identificação dos mais promissores para a utilização em programas de controle de qualidade. Utilizaram-se lotes de três cultivares de rabanete, a saber: Gigante Siculo (4 lotes), Cometa (3 lotes) e Saxa (2 lotes). A avaliação da viabilidade e do vigor das sementes foi realizada mediante a condução de testes de germinação, primeira contagem de germinação, envelhecimento acelerado, deterioração controlada, condutividade elétrica, lixiviação de potássio e emergência de plântulas, sendo estudadas variações nos procedimentos para condução dos testes de envelhecimento acelerado, deterioração controlada, condutividade elétrica e lixiviação de potássio. Concluiu-se que o teste de envelhecimento acelerado com procedimento tradicional, destacando o binômio temperatura/período de exposição de 41ºC/48 horas, é suficientemente sensível para detectar diferenças entre lotes de sementes de rabanete. Os testes de condutividade elétrica e lixiviação de potássio podem constituir alternativas promissoras para a avaliação do vigor de sementes de rabanete, mas há necessidade de estudos adicionais para determinação dos procedimentos mais adequados para sua condução. / The increase in Brazilian production seeds has contributed to reduce the import of vegetable seeds mainly by international companies. The commercial value and the preferential use of hybrids instead of open pollinated cultivars has justified the demand for high quality seeds. In this context, this research was conducted with the objective to study the efficacy of different methods to evaluate the physiological potential of radish (Raphanus sativus L.) seeds. Three cultivars were evaluated: Siculo Giant (four lots), Comet (three lots) and Saxa (two lots). Seed viability and vigor seed lots were determined by germination, germination first count, accelerated aging, controlled deterioration, electrical conductivity, potassium leachate and seedling emergence tests, including alternative procedures for the accelerated aging, controlled deterioration, electrical conductivity and potassium leachate tests. It was concluded that traditional accelerated aging (48 hours/41ºC, was sensitive to identify different levels of physiological potential in the studied lots. The electrical conductivity and potassium leachate are promising options for vigor testing of radish seeds, but research is still necessary to define the most effective procedures to perform these tests.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-03-11T20:36:23Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) THAYS ALLANA OLCOSKI.pdf: 2638999 bytes, checksum: 786ecaaa8b03350890f4a8a81ad27819 (MD5) / Made available in DSpace on 2019-03-11T20:36:23Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) THAYS ALLANA OLCOSKI.pdf: 2638999 bytes, checksum: 786ecaaa8b03350890f4a8a81ad27819 (MD5) Previous issue date: 2018-10-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A mulita é a única fase cristalina formada no sistema SiO2-Al2O3, sendo um material refratário, com elevado ponto de fusão, excelente resistência ao choque térmico, resistividade elétrica e baixa condutividade térmica. Pode ser usada tanto em aplicações tradicionais quanto avançadas. Para a sua obtenção são necessárias elevadas temperaturas e longos tempos de sinterização, devido a necessidade de alta energia de ativação para ocorrer a difusão dos íons na rede da mulita. Para otimizar o processo, pode ser usado precursores em pó com tamanho de grãos submicrométricos ou usar aditivos de sinterização. Neste estudo foi usado como aditivo o MgO, para obter a mulita por sinterização reativa, a partir da mistura de Al(OH)3 e SiO2 coloidal, e da mistura de Al2O3 e SiO2 coloidal. Para verificar o seu efeito na mulitização e sinterização da mulita nessas composições, foram adicionadas 0,8; 1,6; 2,4; 3,1 e 3,9 % em peso de MgO. As composições foram sinterizadas à 1350, 1450 e 1550 ºC por 4 horas. Inicialmente as composições foram analisadas por dilatometria e análise térmica diferencial e termogravimétrica. E após sinterização foram analisadas por difração de raios X, fluorescência de raios X, medidas de densidade e porosidade aparentes, microscopia eletrônica de varredura, resistência à flexão em três pontos e espectroscopia de impedância. Pelos resultados obtidos, observou-se que a adição de MgO reduziu a temperatura de mulitização e a temperatura de sinterização das composições estudadas, de 1400 ºC para em torno de 1350 ºC. Além disso, observou-se que, quanto maior o teor de MgO e a temperatura de sinterização, maiores e mais anisotrópicos são os grãos de mulita formados e maior é a sua resistência a flexão. Sendo que a composição M5 sinterizada à 1550 ºC obteve o maior valor de resistência de 28 MPa. Houve uma redução drástica da porosidade à 1450 e 1550 ºC, ao contrário do que ocorreu à 1350 ºC, podendo ser observado nas imagens de MEV e pelos valores de porosidade aparente. Sendo que a composição M5 sinterizada à 1550 ºC obteve o menor valor de porosidade de 2 %, sendo que a composição M0 sinterizada na mesma temperatura obteve 13,1 %. As composições derivadas da mistura com alumina, obtiveram microestruturas mais densas, com menor porosidade e maior resistência à flexão. A composição MA1 sinterizada à 1450 ºC, obteve o maior valor de resistência no valor de 65,2 MPa, devido ao aparecimento da fase vítrea, que reforçou a sua microestrutura. Com o aumento da quantidade de MgO, houve a formação da fase espinélio, juntamente com a mulita, restando ainda α-alumina residual em algumas composições. No ensaio de espectroscopia de impedância, obteve-se apenas um semicírculo na representação de Nyquist, associado a contribuição apenas do interior do grão, com uma capacitância em torno de 10-11-10- 12 F. Notou-se que a condutividade elétrica do material é dependente da temperatura de ensaio, que quanto maior a temperatura maior a condutividade. Além do que, o aparecimento de fases como, espinélio, alumina e fase vítrea favoreceram a resistividade elétrica do material, consideravelmente. / The mullite is the only crystalline phase formed in the SiO2-Al2O3 system, being a refractory material with high melting point, excelente resistance to termal shock, electrical resistivity and low termal conductivity. It can be used traditional and advanced applications. High temperatures and long sintering times are required due to the high activation energy required to diffuse the ions in the mullite network. To optimize the process, power precursors with submicron grain size or using sintering additives. In this study, MgO was used to obtain the reactive sintering mullite from the mixture of Al(OH)3 and coloidal SiO2, and the mixture of Al2O3 and coloidal SiO2. To verify its effect on mulitization and sintering of mullite in these compositions, 0,8; 1,6; 2,4; 3,1 and 3,9 wt% MgO were added. The compositions were sintered at 1350, 1450 and 1550 ºC for 4 hours. Initially the compostions were analyzed by dilatometry and differential termal and thermogravimetric analysis. After sintering, they were analyzed by X ray diffraction, X ray fluorescence, apparent density and porosity measurements, scanning eléctron microscopy, three-point flexural strength and impedance spectroscopy. From the obtained results, it was observed that the addition of MgO reduced the mulitization temperature and the sintering temperature of the compositions studied, from 1400 ° C to around 1350 ° C. In addition, it has been observed that the higher the MgO contente and the sintering temperature, the larger and more anisotropic the mullite grains are formed and the greater their flexural strength. The composition M5 sintered at 1550 ºC obtained the highest resistance value of 28 MPa. There was a drastic reduction of porosity at 1450 and 1550 ºC, contrary to what happened at 1350 ºC, which can be observed in the SEM images and the values of apparent porosity. In which the composition M5 sintered at 1550 ºC obtained the lowest porosity value of 2%, and the composition M0 sintered at the same temperature obtained 13,1%. The composition MA1 sintered at 1450 ºC, obtained the highest value of resistance in the value of 65,2 MPa, due to the appearance of the glassy phase, which reinforced its microstructure. With the increase of the amount of MgO, there was formation of the spinel phase, together with the mullite, remaining residual α-alumina in some compositions. In the impedance spectroscopy test, only a semicircle was obtained in the Nyquist representation, associated with the contribution of only the interior of the grain, with a capacitance around 10-11-10-12 F. It was noted that the electrical conductivity of the material is dependent on the test temperature, that the higher the temperature the higher the conductivity. In addition, the appearance of phases such as spinel, alumina and vitreous phase favored the electrical resistivity of the material, considerably.

Les matériaux composites présentent un intérêt dans des secteurs de pointe tel que l’aéronautique du fait de leurs propriétés. Dans le cas des composites à matrice organique renforcés par des fibres longues, les propriétés dépendent non seulement du renfort et de la matrice mais également de l’interface fibre/matrice (F/M). Ce mémoire fait état de travaux menés pour incorporer des nanotubes de carbone (NTC) alignés directement sur des fibres de carbone (FC) tissées de manière sécurisée afin d’élaborer un composite à matrice thermodurcissable et thermoplastique et d’évaluer l’effet des NTC introduits à l’interface F/M sur les propriétés électriques et mécaniques des composites. Pour cela, le procédé de dépôt chimique en phase vapeur (CVD) à partir d’aérosol mixte toluène/ferrocène a été développé pour la croissance de NTC alignés sur les FC, avec comme objectif la mise en place d’une procédure permettant d’éviter toute manipulation intermédiaire des produits. Il consiste à réaliser la synthèse de NTC en deux étapes successives qui sont le dépôt préalable d’une couche céramique de type SiO2 à la surface des fibres de carbone suivi de la croissance de NTC. Ce procédé a été ajusté pour permettre une croissance homogène de NTC alignés sur tissus de FC de taille suffisante pour permettre la préparation de matériaux composites. Les matériaux obtenus à l’issu de chacune des étapes ont été caractérisés en utilisant des techniques physico-chimiques complémentaires afin de comprendre le rôle de la sous-couche oxyde sur la croissance des NTC. Nous avons en particulier mis en évidence que cette dernière est modifiée lors de la croissance de NTC conduisant à la formation d’un oxyde mixte suite à l’incorporation de l’élément fer dans la sous-couche de type SiO2. Celle-ci joue alors le rôle de couche barrière de diffusion et permet une croissance de NTC alignés, denses et longs à la surface de substrats carbonés (carbone vitreux ou tissus de fibres de carbone). En outre, pour limiter les risques de dissémination de NTC dans l’atmosphère lors des manipulations des tissus de fibres recouverts de NTC pour l’élaboration des composites, nous avons réalisé une fonctionnalisation de surface des NTC afin d’encapsuler ces derniers sur le renfort fibreux. Enfin des mesures des propriétés mécaniques et électriques ont été réalisées sur les tissus présentant différents traitements et sur les matériaux composites incluant ces tissus. / Because of their properties, composite materials have attracted considerable interests in advanced technology such as in aeronautic field because of their properties. In the case of organic composite reinforced with long fibres, the properties depend not only on the reinforcements and the matrix but also on the interface between the fibre and the matrix (F/M). This thesis deals with the work led to integrate securely aligned carbon nanotubes (CNT) directly on carbon fibres (CF) in order to assess their effects on electrical and mechanical properties at the F/M interface in thermosetting and thermoplastic composite. To include aligned CNT directly on carbon substrates, the catalytic chemical vapour deposition synthesis method of CNT has been developed which consists in carrying out the synthesis in two steps in the same synthesis equipment avoiding intermediate handling. First, a deposition of oxide ceramic layer based on SiO2 is performed followed by the growth of CNT. The process has been adjusted in order to achieve a homogeneous growth of aligned CNT along the carbon fibre cloth compatible with industrial requirement for composite elaboration. Each material obtained from the different steps has been characterized with complementary physical and chemical analysis techniques in order to understand the ceramic sub-layer role on the growth of CNT. In particular, it has been pointed out that during the growth of CNT the sub-layer is modified by the incorporation of iron in the ceramic layer based SiO2, leading to the formation of mixed oxide which plays the role of diffusion barrier layer resulting in the growth of aligned, dense and long CNT on carbon substrates (glassy carbon, carbon fibre cloth). Besides, to avoid the dispersion of CNT in the atmosphere during the handling step for the elaboration of composite, a surface functionalization of CNT has been performed to encapsulate them. Finally, electrical and mechanical properties have been measured on carbon clothes exposed to different treatments and on composites reinforced with these clothes.