Cette thèse s’inscrit dans le domaine de la catalyse hétérogène pour des applications en raffinage et en pétrochimie. Plus particulièrement, nous avons choisi d’étudier le cas des catalyseurs d’hydrotraitement largement utilisés dans les procédés de conversion du pétrole en carburant. Ces catalyseurs sont constitués d’une phase métallique sulfurée supporté sur un support poreux inorganique.Dans ce travail, nous nous sommes particulièrement intéressés à la compréhension et la modélisation de la première étape de préparation d’un catalyseur d’hydrotraitement : l’étape d’imprégnation. Une méthodologie innovante basée sur la technique d’imagerie RMN qui permet d’observer operando le transport des précurseurs métalliques dans le support et sur la technique d’Imagerie Raman a été développée. Les résolutions spatiales et temporelles obtenues ont permis de valider cette méthodologie pour caractériser l’étape d’imprégnation en termes de phénomènes physiques (capillarité et diffusion) et chimiques (interaction de surface) et pour identifier les descripteurs clés de cette étape.En conclusion, ces travaux permettront un meilleur contrôle de l'étape d'imprégnation et donc du profil de distribution de la phase active, ce qui aura une forte répercussion sur la performance catalytique / The objective of this work is to characterize the impregnation step in terms of physical phenomena (capillarity and diffusion) and chemical phenomena (surface interaction) in order to identify the key descriptors of this step in order to improve the preparation hydrotreating catalysts. This involves monitor spatial and temporally the transport of the species in the impregnation solution within the porosity, more particularly in the case of Ni(Co)MoP/?-Al2O3 catalysts preparation.An original MRI approach has been developed to follow in-situ the impregnation step from a solution of mixed nature with more than one metal precursor in the presence of an additive. MRI provides access to the spatial distribution of all species within the catalyst with a spatial resolution of 39 × 39 µm. Raman imaging allows an identification of the chemical nature of the species in solution with a spatial resolution of 16.2 × 16.2 µm.First, the phenomena involved in the impregnation of model solutions composed of Ni (or Co), were studied by modifying the parameters of the solution. These experiments were then used as the basis for the development of a mathematical model to rationalize the impregnation step. In a second part, this study was extended to the preparation of hydrotreatment catalysts. Several phenomena have been evaluated here, notably the impact of the presence of phosphorus on the transport of Mo species, possible competition of adsorption between P, Co and Mo and the effect of the presence of citric acid.This study allows a better control of the impregnation step and thus of the distribution profile of the active phase, which has an impact on the catalytic performance

Ce doctorat porte sur la fonctionnalisation de silices colloïdales en vue de la rétention de micropolluants métalliques dans des effluents. Les nanoparticules et microparticules ouvrent des potentialités d’application dans de nombreux secteurs industriels (chimie, environnement, pharmacie...). Ainsi, ces travaux de recherche portent sur la synthèse et la caractérisation de matériaux composites submicroniques : il s’agit de silices colloïdales sur lesquelles sont greffés des silanes ou supportés des polysaccharides. Une des applications de ces travaux de recherche porte sur l’adsorption de métaux de transition sur ces composites en solution aqueuse. Dans le cadre de ce doctorat, les caractéristiques des composites sont définies par leur morphologie de surface, par l’étude des groupements fonctionnels présents, par détermination de leurs surfaces spécifiques ainsi qu’en solution aqueuse par détermination de leurs diamètres hydrodynamiques et de leurs potentiels zéta. Dans un premier temps, la fonctionnalisation de la silice a permis le greffage de groupements carboxyliques et amines dont tes taux de greffage obtenus ont été respectivement de 0,47 µmol/m² et 3,86 µmol/m². En présence de groupements amines, le potentiel  des composites est positif jusqu’ à pH 9 alors qu’il est négatif dès pH 3 pour des silices non fonctionnalisées. Dans un second temps, la silice est supportée par du chitosane dont le degré de désacétylation est de 77%. Conjointement, l’encapsulation de la silice est réalisées par du chitosane sur lequel des fonctions carboxyliques ont été greffées. La morphologie des particules est alors modifiée, leurs diamètres hydrodynamiques sont plus élevés et leurs potentiels  sont positifs jusqu’ à pH basique. La rétention d’ions métalliques (Cu(II) et Ni(II)) par ces composites à différents pH est ensuite étudiée. Pour chacun des cations métalliques, les capacités d’adsorption sont déterminées ainsi que les cinétiques d’adsorption. L’application de plusieurs modèles d’isotherme d’équilibre a été réalisée. Dans le cas de Cu(II), à pH 5, les meilleures capacités d’adsorption sont obtenues pour des silices supportées par du chitosane greffé : la capacité de rétention des ions Cu(II) est de 270 mg/g à pH 5. De même, c’est ce composite qui permet la meilleurs rétention des ions Ni(II) à pH 7 avec une capacité d’adsorption de 263 m/g. Concernant la cinétique, le modèle de réaction de surface du pseudo-second ordre s’applique bien aux résultats expérimentaux. / This study is focused on the preparation of three types of silica-based composites for the capture of Cu(II) and Ni(II) ions. The first strategy consists in coating chitosan on colloidal fumed silica after acidic treatment yielding the composite SiO2+CS. The second strategy can be separated into two routes: the first one involves surface grafting of silica with aminopropyltriethoxysilane to obtaining silica particles covered by amino groups (SiO2(NH2)). The second one involves in surface condensation of triethoxysilylbutyronitrile, followed by acidic hydrolysis of the surface-bound nitrile groups affording silica particles covered by carboxyl groups (SiO2(CO2H)). In the last step, chitosan has been grafted on the surface bound NH2 or -CO2H groups yielding the composites SiO2(NH2)+CS or SiO2(CO2H)+CS. The third strategy involves in the modified CS surface with -CO2H groups, followed by coating onto the non-modified silica nanoparticles to obtain the composite SiO2+CS(CO2H). The novel hybrid materials were characterized by IR spectroscopy, scanning electron microscopy, atomic force microscopy, and zeta potential measurements. Batch experiments were conducted to study the sorption performance of these composites for Cu(II) and Ni(II) removal from aqueous solution at optimum pH at 298 K. The kinetics were evaluated utilizing pseudo-first-order, pseudo-second-order, and intraparticle diffusion models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all types of adsorbents. The adsorption isotherms were evaluated utilizing Langmuir, Freundlich, and Temkin models. The best interpretation for equilibrium data was given by Langmuir isotherm model. This study demonstrates that the adsorption capacities for Cu(II) ion is more efficient for the SiO2+CS (256 mg g-1) compared to SiO2(NH2) (75 mg g-1). However, the carboxyl grafted CS-coated silica (SiO2+CS(CO2H) exhibited an excellent adsorption capacity (333 mg g-1). In case of Ni(II), based on Langmuir isotherm the maximum adsorption capacity found to be 182 mg g-1for SiO2+CS, and 210 mg g-1 for SiO2(CO2H) + CS. Using single-metal solutions, these adsorbents were found to have an affinity for metal ions in order as Cu(II) > Ni(II). The adsorption of Cu(II) ion by SiO2+CS was affected by the nature of the respective anion. Application of these composite materials to remove Cu(II) and Ni(II) from aqueous solution was shown to be more efficient than the adsorption capacities of many sorbents probed by other research groups.

Um den ständig steigenden Energiebedarf durch Kälteanlagen wie Kühlschränke oder Klimaanlagen zu verringern, sind in den vergangenen Jahren Kühlprozesse in den Mittelpunkt aktueller Forschungen gerückt, die auf Phasenumwandlungen in Festkörpern beruhen. Ein Beispiel dafür sind magnetokalorische Materialien, zu denen auch das in der vorliegenden Arbeit untersuchte Ni-Mn-Ga-Co gehört. In dieser Heusler-Legierung tritt eine Phasenumwandlung erster Ordnung von einer ferromagnetischen, kubischen Hochtemperaturphase (Austenit) in eine tetragonal verzerrte Tieftemperaturphase (Martensit) mit geringerer Magnetisierung auf. Der Unterschied in den Magnetisierungen beider Phasen erlaubt es auch, diese Phasenumwandlung durch ein Magnetfeld zu induzieren. Hierbei kühlt sich das Material durch eine Verringerung der Gitterentropie in dem System ab. Ein Nachteil von Phasenumwandlungen erster Ordnung ist die damit verbundene Hysterese. Außerdem lässt sich der magnetokalorische Effekt durch die scharfe Umwandlung nur in einem kleinen Temperaturbereich effektiv nutzen. Das Ziel dieser Arbeit besteht darin, anhand epitaktisch gewachsener Ni-Mn-Ga-Co-Schichten auf PMN-PT-Substraten zu untersuchen, ob und wie die Umwandlungstemperatur und damit auch die Hysterese der Heusler-Legierung durch mechanische Spannung beeinflusst werden kann. Dafür soll durch Anlegen eines elektrischen Feldes an das piezoelektrische Substrat die Ni-Mn-Ga-Co-Schicht reversibel mechanisch verspannt und die daraus resultierenden Veränderungen der strukturellen und magnetischen Eigenschaften untersucht werden. Im ersten Ergebnisteil wird zunächst gezeigt, dass epitaktische Ni-Mn-Ga-Co-Schichten auf PMN-PT wachsen können und diese einen strukturellen und magnetischen Phasenübergang zeigen. Eine Beeinflussung der bei Raumtemperatur vorliegenden Phase ist dabei über eine Variation der chemischen Zusammensetzung der Probe möglich. Im Anschluss werden die Auswirkungen eines angelegten elektrischen Feldes auf die strukturellen und magnetischen Eigenschaften analysiert. Röntgenuntersuchungen zeigen, dass die piezoelektrische Dehnung des Substrats vollständig auf das Ni-Mn-Ga-Co übertragen werden kann. Allerdings treten bei hohen Temperaturen aufgrund einer Phasenumwandlung im PMN-PT nichtlineare Dehnungseffekte auf. Eine Veränderung der Umwandlungstemperaturen durch die Dehnung des Ni-Mn-Ga-Co ist jedoch nicht möglich. Als wahrscheinliche Ursache dafür wird eine Besonderheit des martensitischen Gefüges der Ni-Mn-Ga-Co-Schichten diskutiert. Im Austenit wurde jedoch eine vollständig reversible Änderung der Magnetisierung um bis zu 7 % gemessen. Diese Magnetisierungsänderung bietet einen interessanten Anknüpfungspunkt für weitergehende Untersuchungen dieses Systems für multikalorische Anwendungen.

No description available.

Ce travail est peut être séparé en deux parties. Dans la première, nous rapportons l'étude menée sur un composé modèle d'hydroxyde de Nickel. La caractérisation de ce composé par diffraction X montre qu'il possède une cristallinité supérieure aux hydroxydes de nickel habituellement utilisés. L'observation au microscope électronique à balayage révèle que la poudre est constituée de grains hexagonaux, de dimension supérieure au micromètre, formés de monocristaux, eux aussi hexagonaux, empilés de façon très ordonnée. Les mesures électrochimiques montrent quant à elles que les composés modèles présentent des propriétés redox intéressantes. La morphologie très particulière de ce composé confère à cet hydroxyde de nickel un comportement de type monocristal en spectroscopie Raman. Des mesures in-situ, couplant voltamétrie cyclique et spectroscopie Raman, réalisées sur ce composé modèle, ont donc été mises en place. Les premiers résultats montrent que ces expériences pourraient nous aider à améliorer notre compréhension des mécanismes redox fondamentaux mis en jeu.Dans la deuxième partie, nous étudions le comportement électrochimique d'une électrode de nickel lorsque l'électrolyte (i.e. KOH 7N) est saturé en zinc. Des électrodes de type industriel ont été préparées à partir d'un hydroxyde de Nickel standard et non dopé, puis cyclées en condition galvanostatique. Les échantillons ainsi obtenus ont ensuite été caractérisés par MEB, DRX, IR et EXAFS. Cette dernière technique qui s'est avérée être la plus appropriée pour l'analyse de ces matériaux d'électrodes très hétérogènes nous a ainsi permis d'apporter des réponses pertinentes sur l'insertion du zinc dans la structure cristalline de Ni(OH)2. / This work may be separated in two parts. First, we report the study of a model compound of nickel hydroxide. X-ray diffraction shows that this compound has a better crystallinity than the standard nickel hydroxides used in commercial battery. Scanning Electron Microscopy revealed that the powder of this model hydroxide is composed of hexagonal grains whose dimension is larger than micrometer and who are formed of single-crystals, also hexagonal, stacked in a well ordered way. The electrochemical measurements show that this nickel hydroxide exhibit interesting redox properties. The particular morphology of the compound gives single-crystal type behavior in Raman spectroscopy. Therefore, in-situ measurements combining electrochemical measurements and Raman spectroscopy, performed on a single microscopic hexagonal plate, are proposed. Preliminary results emphasize that this experiment may help us to improve our understanding of the fundamental redox mechanism taking place in nickel hydroxide.Secondly, we study the electrochemical behavior of a nickel electrode in the presence of Zinc in the electrolyte. Industrial-type electrodes were prepared from a standard undoped nickel hydroxide. Then, samples obtained after electrochemical test were characterized by SEM, XRD, IR and EXAFS. The later which turned out to be the most appropriate for the analysis of our electrode materials, allowed us to get deeper insights in the insertion of zinc in the structure of Ni(OH)2.

No presente trabalho verificou-se a precisão de um critério que prevê composições de ligas vítreas aplicado ao sistema Zr-Ni-Cu. Este critério combina o parâmetro de instabilidade topológica (\'lâmbda\'), e o parâmetro termodinâmico (\'delta\' h) entre os elementos de liga. Os dois parâmetros correlacionam quantitativamente à composição química a tendência à formação de vidros metálicos. Este critério é uma ferramenta promissora e simples para guiar e reduzir o trabalho tedioso e intensivo de encontrar composições altas tendências a vitrificação em sistemas metálicos. Para comprovar a eficiência desta ferramenta, a metodologia foi calcular o parâmetro para o sistema de interesse e preparar ligas de acordo com algumas composições fornecidas. A metodologia de preparação das ligas seguiu a fusão a arco elétrico e subsequentemente o emprego das técnicas de resfriamento rápido, melt-spinning e splat-cooling, para a produção de fitas e discos metálicos respectivamente, e o coquilhamento para a produção de amostras maciças em forma de cunha. Para as amostras confeccionadas por melt-spinning e splat-cooling, verificou-se a precisão do critério de seleção através da quantificação das porcentagens de fases vítreas a partir de análises de difratogramas de raios-X e seus comportamentos térmicos a partir dos termogramas de análises por calorimetria exploratória diferencial (DSC). Já para as ligas coquilhadas em cunha, obtiveram-se alguns resultados com indícios de estruturas vítreas que foram caracterizadas por difração de raios-X e metalografia. Desta forma chegou-se à conclusão que o critério de seleção aplicado ao sistema Zr-Ni-Cu pode ser utilizado para o desenvolvimento de composições favoráveis à formação de vidro antes da produção das ligas. Conclui-se que o critério que combina o parâmetro de instabilidade topológica (\'lâmbda\' min) e o parâmetro termodinâmico (\'delta\' h) é uma ferramenta que pode ser utilizada como guia para encontrar as composições mais fáceis de formar vidro, reduzindo assim o trabalho experimental de tentativa e erro. / In the present work it was verified the accuracy of a proposed criterion to predict compositions of glassy alloys applied in the Zr-Ni-Cu system. This criterion combines the topological instability parameter (\'lâmbda\') and a thermodynamic parameter (\'delta\' h) among the alloying elements. The two parameters correlate quantitatively the chemical composition with the glass forming ability. This criterion is a promising and simple tool to guide and reduce the tedious and intensive work of finding good compositions of glasses in metallic systems. In an attempt to prove the efficiency of such tool, the methodology was to calculate the parameter for the system of interest and prepare alloys in accordance with the compositions provided by the tool. The methodology of preparation of the alloys followed the electric arc- melting and subsequent use of fast cooling techniques, melt-spinning and splat-cooling for the production of metallic ribbons and discs, respectively, and a wedge-shaped chiller mold to produce bulk metallic samples. For samples prepared from the melt-spinning and splat-cooling, it was verified the accuracy of the selection criteria by quantifying the percentage of glassy phases from X-ray diffractograms and their thermal behaviors from thermograms produced by differential scanning calorimetry (DSC). For alloys produced from the wedge-shaped mold, some results were obtained with evidence of vitreous structures that were characterized by X-ray diffraction and metallography. Therefore the conclusion is that the selection criteria applied to the system Zr-Ni-Cu can be used to develop favorable compositions for the formation of glasses before the production of the alloys. It is concluded that the selection criterion is a good tool and can be used as a guide to find the best glass forming alloys, thus reducing the experimental procedures of trial and error.

Submitted by Ricardo Cedraz Duque Moliterno (ricardo.moliterno@uefs.br) on 2016-09-06T20:52:55Z No. of bitstreams: 1 Disserta??o - texto completo PDF.pdf: 1916654 bytes, checksum: 5da1850898130e05e3a0797ecfea5037 (MD5) / Made available in DSpace on 2016-09-06T20:52:55Z (GMT). No. of bitstreams: 1 Disserta??o - texto completo PDF.pdf: 1916654 bytes, checksum: 5da1850898130e05e3a0797ecfea5037 (MD5) Previous issue date: 2015-03-13 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / This study has the main objective to investigate the replacement of the preposition in by ni, fairly frequent phenomenon in speech and sometimes in writing. From comparisons between varieties of Portuguese (Brazil and Africa), it is conjectured that this morphological change has to do with influences from some African languages which had contact with the Portuguese in the period of colonization / exploration of these places. In addition, note that the use of ni is performed by speakers from rural and urban, there is the hypothesis that possibly there is a continuum that explain its dissemination in Brazilian Portuguese. Thus, from the quantitative methodology Labovian inspiration, we analyze speech from the Portuguese rural, popular and cult of Feira de Santana to evaluate the hypothesis of a rural-urban continuum, taking into account the use of this morphological trait . The results of the rounds indicate that the rural Portuguese and worship favor the use of ni with the relative weighting of .65 and .52, respectively. The relative weight of .33 of popular Portuguese factor, in turn, indicates that this variety does not favor implementation of this variant. The fact that there are so discrepant values among them is explained from the historical and social characteristics of each language community. But what draws the most attention in this research is the analysis of the results of the linguistic variables corroborate the idea of a relationship between the Portuguese of Brazil and some African languages with regard to the use of ni. / O presente estudo tem o principal objetivo de investigar a substitui??o da preposi??o em por ni, fen?meno bastante recorrente na fala e, algumas vezes, na escrita. A partir de compara??es feitas entre variedades do portugu?s (do Brasil e da ?frica), conjectura-se que essa troca morfol?gica tenha a ver com influ?ncias de algumas l?nguas africanas que mantiveram contato com o portugu?s no per?odo da coloniza??o/explora??o desses lugares. Al?m disso, por notar que o uso do ni ? realizado por falantes da zona rural e da urbana, h? a hip?tese de que, possivelmente, exista um continuum que explique a sua difus?o no portugu?s brasileiro. Dessa forma, a partir da metodologia quantitativa de inspira??o laboviana, analisam-se falas do portugu?s rural, popular e culto de Feira de Santana a fim de avaliar a hip?tese da exist?ncia de um continuum rural-urbano, levando em considera??o o emprego desse tra?o morfol?gico. Os resultados das rodadas apontam que o portugu?s rural e culto favorecem o uso do ni com os pesos relativos de .65 e .52, respectivamente. O peso relativo de .33 do fator portugu?s popular, por sua vez, indica que essa variedade n?o favorece aplica??o dessa variante. O fato de haver valores t?o discrepantes entre elas ? explicado a partir das caracter?sticas hist?rico-sociais de cada comunidade lingu?stica. Todavia o que chama mais aten??o nesta pesquisa ? que os resultados da an?lise das vari?veis lingu?sticas corroboram a ideia de haver uma rela??o entre o portugu?s do Brasil e algumas l?nguas africanas no que diz respeito ao uso do ni.

This master’s thesis is focused on corrosion resistance of nickel-phosphorus coatings on magnesium alloy AZ91. In the theoretical part is summarized current knowledge about magnesium alloys and electroless deposition of Ni-P coatings including ongoing reactions. Theoretical part also lists all substances contained in the nickel bath and their specific use there. In the second half of theoretical part are discussed corrosion and immersion tests. Theoretical part is ended by review aimed towards the research in areas of immersion tests. Experimental part describes individual steps of pretreatment on magnesium alloy and then deposition of the Ni-P coating. Composition and morphology of deposited Ni-P coating and magnesium alloy were studied using energy dispersive spectroscopy. Experiment part also contains list of experiments trying to figure out ideal thickness of low-phosphorus coating which is able to protect magnesium alloy from corrosion. Master’s thesis is ended with the list of immersion tests and results which outcomes from them.

This thesis is involved in basical properties of electrode materials for alkaline accumulators. This thesis describes the possibilities of capacity stabilisation of nickel electrode to be stable for highest number of cycles. Thesis also consider modification of properties of electrode materials on the base of nickel hydroxide by using dopes (aluminum, manganese). Measuration proceeded on the thin film electrodes created by electrodeposition. Measuration of properties of electrodes proceeded by cyclic voltammetry and frequency analyzis.

This master's thesis is concerned with the influence of aluminate ions added in various concentrations into the structure of nicel hydroxide that creates Ni-Cd accumulators positive electrode active mass basis nowadays. Nicel hydroxide occurs in two basic modifications ? and ß. Nowadays used ß modification reaches low capacity in comparison with ? modification. The disadvantage of ? modification is its instability and gradual degradation to ß modification. The aim of this diploma paper is to select the optimal amount of aluminate additives into the structure of nicel hydroxide with regard to electrochemical efficiency, stability, and degradation degree of the accumulated layer.