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CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / FundaÃÃo de Amparo à Pesquisa do Estado do Amazonas / Esta tese està composta de quatro partes distintas. Na primeira parte, vamos dar uma nova caracterizaÃÃo da esfera euclidiana como a Ãnica variedade Riemanniana compacta com curvatura escalar constante e admitindo um campo de vetores conforme nÃo trivial que à tambÃm Ricci conforme. Na segunda parte, provaremos algumas propriedades dos quase sÃlitons de Ricci, as quais permitem estabelecer condiÃÃes de rigidez desses objetos, bem como caracterizar as estruturas de quase sÃlitons de Ricci gradiente na esfera euclidiana. ImersÃes isomÃtricas tambÃm serÃo consideradas; classificaremos os quase sÃlitons de Ricci imersos em formas espaciais, atravÃs de uma condiÃÃo algÃbrica sobre a funÃÃo sÃliton. AlÃm disso, vamos caracterizar, atravÃs de uma condiÃÃo sobre o operador de umbilicidade, as hipersuperfÃcies n-dimensionais de uma forma espacial, com curvatura mÃdia constante, tendo duas curvaturas principais distintas e com multiplicidades p e n - p. Na terceira parte, provaremos um resultado de rigidez e algumas fÃrmulas integrais para uma mÃtrica m-quasi-Einstein generalizada compacta. Na Ãltima parte, vamos apresentar uma relaÃÃo entre a curvatura gaussiana e o Ãngulo de contato de superfÃcies imersas na esfera euclidiana tridimensional,a qual permite concluir que a superfÃcie à plana, se o Ãngulo de contato for constante. AlÃm disso, deduziremos que o toro de Clifford à a Ãnica superfÃcie compacta com curvatura mÃdia constante tendo tal propriedade. / This thesis is composed of four distinct parts. In the first part, we shall give a new characterization of the Euclidean sphere as the only compact Riemannian manifold with constant scalar curvature carrying a conformal vector eld non-trivial which is also Ricci conformal. In the second part, we shall prove some properties of almost Ricci solitons, which allow us to establish conditions for rigidity of these objects, as well as characterize the structures of gradient almost Ricci soliton in Euclidean sphere. Isometric immersions also will be considered, we shall classify almost Ricci solitons immersed in space forms, through algebraic condition on soliton function. Furthermore, we characterize under a condition of the umbilicity operator, n-dimensional hypersurfaces in a space form with constant mean curvature, admitting two distinct principal curvatures with multiplicities p and n - p. In the third part, we prove a result of rigidity and some integral formulae for a compact generalized m-quasi-Einstein metric. In the last part, we present a relation between the Gaussian curvature and the contact angle of surfaces immersed in Euclidean three-dimensional sphere, which allows us to conclude that such a surface is at provided its contact angle is constant. Moreover, we deduce that Clifford tori are the unique compact surfaces with constant mean curvature having such property.

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Des réseaux polymères supramoléculaires ont été préparés à partir de deux types d’interactions supramoléculaires différentes, ionique et par liaisons hydrogène. Les interactions ioniques ont été introduites dans des P(BMA-co-MA) par l’introduction de CaCO3 comme charge capable de se décomposer partiellement pour former des cation Ca2+. La présence de Ca2+ a été confirmée par diffraction de rayons X par l’observation d’un pic ionique caractéristique. Les interactions par liaisons hydrogène ont été introduites selon deux approches. L’une a été de préparer d’abord un monomère supramoléculaire avec un motif DA (donneur-accepteur) pour ensuite le copolymériser en polymères supramoléculaires P(MAAM-co-St) et P(MAP-co-St) par polyaddition. Par l'autre approche, le polymère supramoléculaire a été synthétisé par polycondensation de PUU, monomères contenant des liaisons hydrogène multiples. La présence de liaisons hydrogène intermoléculaires a mise en évidence par IRTF qualitativement, et la constante d’association Kass a été calculée par 1H-RMN pour les motifs d’association. Des tests solubilité ont indiqué que la génération d'interactions supramoléculaires dans les polymères conduit à des réticulations. En conséquence, les matériaux sont renforcés et présentent une meilleure thermo-résistance et des modules plus élevés lorsque la fraction motifs supramoléculaire est augmentée. En outre, Des analyses rhéologiques ont été réalisées pour étudier la viscoélasticité et la thermo-réversibilité de ces systèmes physiquement réticulé / Supramolecular polymer networks are prepared basing on two different supramolecular interactions, ionic interaction and hydrogen bonds interaction. Ionic interaction was introduced in P(BMA-co-MA) with CaCO3 as a filler. The presence of Ca2+ is confirmed with X-ray diffraction by the apperence of specific ionic peak. The hydrogen bond interaction was introduced by two approaches. One is to first prepare a supramolecular monomer bearing DA moiety then supramolecular polymer P(MAAM-co-St) and P(MAP-co-St) are prepared by polyaddition. In the other approach, the supramolecular polymer is synthesized by one-step PUU polycodensation from the reagent containing multiple-hydrogen-bond sequence. The presence of intermolecular hydrogen bonds is detected by FTIR qualitatively, and the strengh, quantified as Kass, is calculated by 1H-NMR for different moieties respectively. Solubility tests indicate that the introduction of supramolecular interaction in the traditional polymers leads to the crosslinking in different extents. Consequently, materials are strengthened showing better thermo-endurence property and higher modulus when the content of supramolecular moiety is increased. Furthermore, rheological analysis is performed to investigate the viscoelasticity and to track the thermo reversibility

La complexité des mécanismes de transport en nanofiltration (NF) nécessite ledéveloppement d’outils de modélisation fiables permettant de comprendre et d’optimiser lesopérations de séparation en NF.La présente étude comprend deux volets. Le premier porte sur la rétention d’un soluténeutre – le poly(éthylène glycol) à 600 g mol-1 (PEG) – seul et en présence d’ions, par unemembrane organique de NF (polyamide). Les résultats obtenus montrent que la rétention dusoluté neutre chute en présence d’ions et ce, d’autant plus que la concentration du sel estélevée. Ce phénomène ne peut être expliqué par le seul phénomène de déshydratation dusoluté neutre par les ions environnants. Un phénomène supplémentaire de gonflement de porea été mis en évidence et corrélé à la densité de charge membranaire. La contribution des deuxphénomènes à la chute du taux de rejet du PEG a été évaluée pour différents sels à plusieursconcentrations.Le deuxième volet du travail est consacré à (i) l’évaluation de la constante diélectrique desolutions à l’intérieur de nanopores (ep) d’une membrane organique de NF (polyamide) àpartir de mesures de potentiel de membrane et (ii) la validation de cette méthode. Les valeursobtenues s’avèrent être inférieures à celle de la solution externe (effet du confinement) etdiminuer avec l’augmentation de la proportion en ions calcium du mélange (effet structurantdes ions). L’accord entre les constantes diélectriques ep déterminées à partir de mesures depotentiel de membrane et de taux de rejet ionique (mélanges ternaires) valide la cohérence dumodèle de transport utilisé (exclusion stérique, électrique et diélectrique aux interfaces) etmontre que les mesures de potentiel de membrane peuvent être envisagées pour l’évaluationcorrecte de la constante diélectrique à l’intérieur de nanopores / The complexity of transport mechanisms in nanofiltration (NF) requires the developmentof reliable modelling tools for understanding and optimizing the separation process.This study is composed of two parts. The first one focuses on the retention of a neutralsolute – poly(ethylene glycol) 600 g mol-1 (PEG) – in single solute solutions and in thepresence of mineral salts by an organic NF membrane (polyamide). Results show that PEGrejection is significantly lower in mixed-solute solutions and that rejection rate drop increaseswith salt concentration. This phenomenon cannot be imputed to only the partial dehydrationof PEG molecules by surrounding ions (salting-out effect). The additional hypothesis whichwas considered in the present work is an increase in the effective pore size (pore swelling).This hypothesis was supported by electrokinetics charge density data. The contribution ofpore swelling and salting-out to the overall decrease in the rejection rate of PEG wasevaluated for different salts at various concentrations.The second part of this study deals with (i) the determination of the dielectric constantinside pores (ep) of an NF organic membrane from membrane potential measurements and (ii)the validation of this technique. Membrane potential data were analyzed by means of theSEDE (steric, electric and dielectric exclusion) transport model. ep values were found to besmaller than the bulk value and to decrease when sodium ions were replaced by calcium ions.The agreement between ep values obtained from membrane potential measurements and thosecalculated from ion rejection rate data (ternary mixtures) highlights the global coherence ofthe transport model used and shows that membrane potential measured with electrolytemixtures can be used to determine the dielectric constant inside pores with no requirement ofadditional rejection rate measurements.

Les électrolytes liquides, composés d’un sel dissous dans un solvant, interviennent dans la composition des batteries et font l’objet de nombreuses études afin d’améliorer leurs performances et leur sécurité. Parmi toutes les propriétés essentielles d’un électrolyte, la plus importante est sa conductivité ionique, qui influe sur les performances de la batterie. Pour un sel donné, la conductivité est elle-même principalement déterminée par les propriétés physico-chimiques du solvant comme sa constante diélectrique ou sa viscosité. L’objectif de cette étude est de développer des modèles permettant d’estimer des propriétés d’intérêt des électrolytes liquides, afin d’offrir un gain de temps aux chimistes, qui pourront éliminer les compositions inadéquates du point de vue de telle ou telle propriété. La première partie de cette étude présente une méthode pour estimer la conductivité d’un électrolyte, constitué d’un sel LiPF6 dans un mélange de solvants. Cette méthode s’appuie sur de nouvelles équations, pour estimer les paramètres de l’équation de Casteel-Amis, à partir de propriétés physico-chimiques du mélange de solvants, dont la constante diélectrique. La seconde partie présente a par ailleurs permis de développer une méthode pour estimer la constante diélectrique d’un solvant pur, à partir de sa structure chimique. Cette méthode s’appuie sur de nouveaux modèles additifs qui permettent d’estimer les paramètres de l’équation de Kirkwood-Fröhlich. Parmi ces modèles, deux d’entre eux permettent l’estimation de la densité et de l’indice de réfraction d’un composé liquide à température ambiante. L’ensemble des modèles développés sont utilisables via une interface utilisateur. / Liquid electrolytes, composed of a salt dissolved in a solvent, are used in the composition of batteries and are the subject of numerous studies to improve their performance and safety. Of all the essential properties of an electrolyte, the most important is its ionic conductivity, which influences the battery's performance. For a given salt, the conductivity itself is mainly determined by the physico-chemical properties of the solvent such as its dielectric constant or its viscosity. The objective of this study is to develop models to estimate properties of interest of liquid electrolytes, in order to offer time savings to chemists, who will be able to eliminate inadequate compositions from the point of view of such or such property. The first part of this study presents a method to estimate the conductivity of an electrolyte, consisting of a LiPF6 salt in a solvent mixture. This method is based on new equations, to estimate the parameters of the Casteel-Amis equation, based on the physico-chemical properties of the solvent mixture, including the dielectric constant. The second part also presents a method to estimate the dielectric constant of a pure solvent, based on its chemical structure. This method is based on new additive models that estimate the parameters of the Kirkwood-Fröhlich equation. Two of these models estimate the density and refractive index of a liquid compound at room temperature. All the models developed can be used via a user interface.

A broca-da-cana, Diatraea saccharalis (Fabricius, 1794) (Lepidoptera: Crambidae) vem se constituindo, em uma importante praga do milho, com relatos de surtos populacionais em diversas partes do país. Devido ao aumento de sua importância, em milho, nos últimos anos, a presente pesquisa teve como objetivos: (a) determinar os limites térmicos e a temperatura ótima de desenvolvimento de D. saccharalis; (b) validar as constantes térmicas (K), para fase de ovo e período lagarta-pupa estimadas em laboratório, nas condições de campo, levando-se em consideração as condições microclimáticas; (c) avaliar os danos e consequente perda na produção de grãos provocadas pelo ataque de diferentes densidades larvais de D. saccharalis em dois estádios fenológicos de milho e (d) determinar o raio e área de dispersão de Trichogramma galloi Zucchi, 1988 (Hymenoptera: Trichogrammatidae) em milho visando ao controle de D. saccharalis. Os resultados obtidos mostram que o limiar térmico inferior de desenvolvimento (Tb) de D. saccharalis foi de14; 13 e 12°C para as fases de ovo, larva e pupa, respectivamente; as faixas de temperatura ótima de desenvolvimento (Topt), estimadas experimentalmente, foram de 30 a 32°C para as fases de ovo e larva e de 28 a 30°C para a fase de pupa; o limiar térmico superior (Tmáx) foi de 35,4ºC para a fase de larva, estimada pelo modelo de Logan-6 e que ficou dentro da faixa térmica determinada experimentalmente, que indicou também, para este parâmetro, a faixa térmica de 36 a 38ºC para a fase de ovo e de 32 a 34ºC para a fase de pupa. As previsões em campo de eclosão das lagartas e emergência dos adultos (período lagarta-pupa) podem ser feitas com as constantes térmicas (K) obtidas em laboratório [76,5 graus-dias (GD) para a fase de ovo e 476,2 GD para o período lagarta-pupa], desde que sejam utilizados os dados de temperatura obtidos com a estação meteorológica automática e dados de microclima, para a fase de ovo e período lagarta-pupa, respectivamente. Os danos e as perdas na produção provocado por D. saccharalis independem do estádio fenológico das plantas de milho, porém a redução na produção de grãos é proporcional ao número de lagartas por planta utilizadas nas infestações, sendo essas reduções de 11; 17; 28 e 39% para 50; 100; 150 e 200 lagartas por planta. O raio de dispersão de T. galloi foi de 11,8 e 12,1 m, sendo a área de dispersão de 176m2 e187m2, com as plantas de milho nos estádios v4-6 e v6-8, respectivamente. / The sugarcane borer Diatraea saccharalis (Fabricius, 1794) (Lepidoptera: Crambidae) has become an important pest of corn in Brazil, with reports of outbreaks in many parts of the country in recent years. In view of this situation, this study aimed to: (a) determine the thermal limits of D. saccharalis; (b) determine the thermal constants (K) for the egg stage and caterpillar-pupa period estimated in field conditions, taking into consideration the microclimate conditions; (c) evaluate the damage and consequent production losses caused by infestation at different larval densities of D. saccharalis at two phenological stages of corn; and (d) determine the dispersal radius and area of Trichogramma galloi Zucchi, 1988 (Hymenoptera: Trichogrammatidae) in corn, aiming to control D. saccharalis. The results showed that the lower threshold temperature (Tt) of D. saccharalis was 14, 13 and 12 ºC for the egg, larval and pupal stages, respectively. Optimal temperature ranges (Topt), estimated experimentally, were 30 to 32 ºC for the egg and larval stages and 28 to 30 ºC for the pupal stage. The upper threshold temperature (Tmax) was 35.4 ºC for the larval stage estimated by the Logan-6 model. This was within the thermal range determined experimentally, which also indicated the thermal range for Tmax of 36 to 38 ºC for the egg stage and 32 to 34 ºC for the pupal stage. Larval hatching and adult emergence (caterpillar-pupa period) in the field can be predicted with thermal constants (K) obtained in the laboratory (76.5 degree-days) (DD) for the egg stage and 476.2 DD for the caterpillar-pupa period), provided that temperature data obtained from the automatic station and microclimate data for the egg stage and caterpillar-pupa period, respectively, are used. The damage caused by D. saccharalis was independent of the phenological stage of the corn plants, but the reduction in grain production was proportional to the number of larvae per plant used in the infestation, with reductions of 11, 17, 28 and 39% for 50, 100, 150 and 200 caterpillars per plant. The dispersal radius of T. galloi was 11.8 and 12.1 m, and the dispersal area was 176 m2 and 187 m2 with corn plants in the V4-6 and V6-8 stages, respectively.

Este trabalho tem como objetivo a produção e caracterização elétrica de filmes finos de telureto com nanopartículas de ouro para aplicações em microeletrônica. Filmes finos foram produzidos por magnetron sputtering a partir de alvos de telureto cerâmico e de ouro metálico. Foi desenvolvida metodologia adequada para a nucleação das nanopartículas de ouro por meio de tratamento térmico. Foram nucleadas nanopartículas de ouro a fim de que fossem observadas as influências nas propriedades elétricas. Os filmes foram depositados sobre substrato de silício e, para as medidas elétricas, ilhas de alumínio foram depositadas sobre o filme, utilizando-se os processos convencionais de microeletrônica: limpeza química, deposição por sputtering e evaporação. Com a finalidade de verificar a nucleação das nanopartículas metálicas, foram realizadas análises por Microscopia Eletrônica de Transmissão que indicaram a presença de nanopartículas metálicas, cristalinas, aproximadamente esféricas e com tamanho médio aproximado entre 1,5 e 5 nm. Outras técnicas de caracterização usadas foram microscopia de força atômica, perfilometria e extração de curvas da capacitância e condutância em função da tensão. Foram produzidos filmes com diversas espessuras com e sem nanopartículas de ouro. Por meio das medidas de capacitância em função da tensão foi possível determinar a influência das nanopartículas metálicas na constante dielétrica (k). Os resultados obtidos mostram aumento do valor de k de aproximadamente 70%, na presença de nanopartículas de ouro. Cabe ressaltar o resultado obtido para os filmes com espessura de 32,8 nm, para os quais o valor da constante dielétrica varia de 9,4 para 12,2, para tratamentos de 10 e 20 h, respectivamente. O material estudado tem possíveis aplicações em microeletrônica como dielétrico em capacitores e transistores MOS, e como camada de passivação em dispositivos de potência. / This work has the objective of production and electrical characterization f tellurite thin films containing gold nanoparticles for microelectronic applications. Thin films have been produced by magnetron sputtering from ceramic tellurite and metallic gold targets. It was developed an appropriate methodology for the gold nanoparticles nucleation by means of heat treatment. Gold nanoparticles were nucleated in order to be observed the influence on the electrical properties. The films were deposited on silicon substrate and, to the electrical measurements, aluminium islands were deposited on the film, using the conventional processes of microelectronics: chemical cleaning, deposition by sputtering and evaporation. With purpose to check the metallic nanoparticles nucleation, transmission electron microscopy measurements were performed and indicated the presence of crystalline metallic nanoparticles, with spherical shape and with average size between 1.5 and 5 nm. Other characterization techniques were used as atomic force microscopy, profilometry and electrical measurements to obtain the capacitance and conductance curves. Films have been produced with different thicknesses with and without gold nanoparticles. From capacitance measurement, it was possible to determine the metallic nanoparticles influence on the dielectric constant (k). The results obtained showed the increase of k of about 70% with the presence of gold nanoparticles. We have to remark the results obtained for thin films with 32.8 nm thickness with k varying from 9.4 to 12.2, for heat treatments during 10 and 20 h, respectively. The material studied has possible applications in microelectronics as high-k dielectrics for capacitors and transistors MOS, and as passivation layer for power devices.