Embora o escoamento estratificado óleo-água seja comum na indústria do petróleo, existem poucos trabalhos na literatura sobre a estrutura ondulatória encontrada no escoamento em dutos ascendentes ou descendentes. O objetivo deste trabalho é entender e caracterizar as estruturas interfaciais ondulatórias em escoamentos estratificados óleo e água em dutos levemente inclinados e comparar com os resultados retirados da modelagem proposta. Uma primeira tentativa de modelar a onda interfacial óleo-água através da equação da energia bifásica unidimensional para regime permanente é apresentada e comparada aos resultados obtidos experimentalmente. Valores de comprimento de onda foram coletados para quatro ângulos de inclinação a partir da horizontal (-5º, -2º, 2º e 5º) e diversos pares de vazão de óleo e água. Os dados foram extraídos de frames de vídeos de alta resolução através de uma técnica manual. Um software baseado em LabView foi desenvolvido para possibilitar a automação da obtenção do comprimento de onda e amplitude. Os comprimentos de onda obtidos com a técnica automática foram comparados com os dados obtidos através da técnica manual. O mensuramento é bem satisfatório e sugere que a ferramenta experimental proposta possa ser aplicada para o estudo de qualquer padrão de escoamento óleo-água, onde uma estrutura ondulatória possa ser identificada. A validade da modelagem da onda interfacial proposta foi avaliada através da comparação entre os resultados teóricos e dados experimentais. A concordância observada é encorajadora. / Even though the oil-water stratified flow pattern has a common occurrence in the upstream oil industry, quite often in directional wells, there are only a few works in the literature dealing with its interfacial wavy structure. This work has the mean goal of comprehending a characterizing the interfacial wave structure in inclined water-oil stratified pipe flow, comparing it with the proposed model. A model, based on the steady-state one-dimensional two-phase flow energy equation is presented and compared to our experimental data. Wave lengths and amplitude data were collected at four inclinations from the horizontal (-5º, -2º, 2º and 5º) and several oil and water flow rates. The data were extracted form high-resolution video images through a manual technique. A LabView based software was developed in order to obtain the lengths and amplitude automatically. Wave length obtained from it were compared to the manual technique data. The satisfactory measurement suggests the applicability of the experimental tool to any water-oil pipe flow pattern, where a wave structure can be identified. The validity by the comparison between theoretical and experimental data. The agreement observed is promising.

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2015-10-28T11:36:30Z No. of bitstreams: 1 Daniel Gustavo Brusius Wilbert_.pdf: 4731645 bytes, checksum: 08c801a9545a481516dfe01632256d9c (MD5) / Made available in DSpace on 2015-10-28T11:36:30Z (GMT). No. of bitstreams: 1 Daniel Gustavo Brusius Wilbert_.pdf: 4731645 bytes, checksum: 08c801a9545a481516dfe01632256d9c (MD5) Previous issue date: 2015-07-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / O setor da construção civil é responsável por um grande impacto ambiental, destacando-se dois principais fatores, a quantidade de matéria-prima consumida e de resíduos gerados. Estes resíduos, em grande parte apresentam um grande potencial de reciclagem. Dentre estes resíduos, os de concreto apresentam um excelente potencial de utilização. Inúmeras pesquisas já comprovaram a viabilidade de utilização do Agregado Reciclado de Concreto (ARC). Porém, a menor qualidade do ARC em comparação aos agregados naturais, resultada em queda no desempenho destes concretos, principalmente nas propriedades de durabilidade. Como consequência ocorre um enfraquecimento da zona de transição entre a argamassa velha e a nova. Em função desta queda de desempenho ao se utilizar ARC, a presente pesquisa teve por objetivo a análise desta zona de transição, através do estudo da interface entre duas argamassas de concreto por meio da técnica de nanoindentação. Para esta análise foram moldados agregados reciclados de concretos modificados, todos no traço referência (sem adição), e posteriormente aplicada uma nova camada de argamassas com diferentes traços. Os traços variaram entre dois tipos de adição (Finos Basálticos – FB e Cinza da Casca de Arroz – CCA), em diferentes teores de adição ao cimento, 0, 5, 10 e 15% para os finos e 0, 5 7,5 e 10% para a CCA. Após cura de 63 dias, as amostras foram preparadas para a realização dos ensaios. Para a análise das medidas de nanoindentação na interface, foram propostos três métodos de análise. As propriedades macroestruturais foram avaliadas aos 28 dias, como módulo de elasticidade dinâmico, resistência à compressão, resistência à tração por compressão diametral e absorção de água por capilaridade. Os resultados demonstraram a melhora das propriedades macroestruturais das argamassas com 15% de FB e CCA em relação à referência. Foram identificadas alterações na região de interface entre as argamassas no traço com 15% de finos de basalto e em todos os traços com CCA, que apresentaram os melhores resultados. A comparação entre a região mais próxima à zona de transição resultou, para todos os traços, em valores semelhantes aos obtidos em regiões de pastas mais distantes à zona de transição, demonstrando que o uso de uma argamassa antiga na condição seca (simulando um agregado reciclado seco) melhorou as condições da zona de transição com a argamassa nova. / Construction is responsible for a large environmental impact, highlighting two main factors: consume of raw materials and generation of waste materials. By other hand, construction and demolition waste has a good potential of recycling. Many studies have demonstrated the viability of using recycled concrete coarse aggregate (RCA) in new concrete. However, due to the RCA’s properties, most results point to a lower durability of the concrete. It is also consensus that the main reasons for the lower quality of the new concrete are the mortar layer adhered to the natural aggregate and the weakening in the new Interfacial Transition Zone (ITZ) between the old and the new mortar. This study analyze the new interfacial transition zone in these concretes through nanoindentation. There were produced recycled concrete aggregates without addition of filler, and over these aggregates there were produced a new mortar layer with different mix compositions. There were used basaltic filler and rice husk ash-RHA in different levels of addition: 0, 5, 10 and 15% for the filler, and 0, 5, 7,5 and 10% for the ash. Their interfaces were evaluated using different methodologies. Modulus of elasticity, compressive strength, tensile strength and capillarity were determined. The use of fines improved the mortar properties in relation to the reference, especially those with 15% filler and the samples with RHA. The region near to the ITZ shows similar elastic moduli values to those obtained in the paste, in all mortars, proving that using dry recycled aggregates the new mortar loose water to the aggregates and increase their mechanical properties.

Ce travail vise à obtenir une morphologie cœur-peau directement lors du mélangeage à l’état fondu de polymères ternaires PLA/PBAT/PA. Le but final est d'améliorer la ténacité de l'acide polylactique (PLA). La morphologie des mélanges de polymères multi-phases est contrôlée par la thermodynamique du système. La morphologie des mélanges ternaires peut être prédite à partir des valeurs relatives des trois coefficients d'étalement caractérisant le triplet de polymères. Les coefficients d'étalement sont calculés à partir des valeurs des tensions interfaciales entre les composants binaires. La détermination des tensions interfaciales entre PLA, poly (butylène adipate-co-téréphtalate) (PBAT) et un copolyamide (PA) prédit une morphologie dispersée complexe dans la matrice PLA où les sous-inclusions PA sont partiellement encapsulées dans la phase PBAT. Cette morphologie a été obtenue par mélange à l'état fondu des trois composants, comme observé par les observations en microscopie électronique à balayage. Dans une seconde étape, une compatibilisation sélective a été utilisée pour modifier l'emplacement des sous-inclusions de PA. A cette fin, deux copolymères diblocs PBAT-b-PLA, PA-b-PBAT ont été synthétisés. La présence des copolymères diblocs nous permet de modifier la tension interfaciale des couples PLA/PBAT, PA/PBAT. Cette modification de l'équilibre de tension interfaciale modifie avec succès la morphologie, passant d’une semi-encapsulation à une encapsulation complète des sous-inclusions de PA dans les gouttes de PBAT. La performance mécanique de ce mélange ternaire a été évaluée. / This work aims at achieving direct core-shell morphologies in ternary PLA/PBAT/PA polymer blends by melt mixing. The final goal is to improve the toughness of polylactic acid (PLA). The morphology of multi-phase polymer blends is controlled by the thermodynamics of the system. The morphology of ternary blends can be predicted from the relative values of the three spreading coefficients characterizing the triplet of polymers. Spreading coefficients are calculated from the values of interfacial tensions between binary components. The determination of interfacial tensions between a PLA, a poly(butylene adipate-co-terephthalate) (PBAT) and a copolyamide (PA) predicts a complex dispersed morphology in the PLA matrix where PA subinclusions are partly encapsulated in the PBAT phase. This morphology was obtained by melt mixing the three components, as observed by scanning electron microscopy. In a second step, selective compatibilization was used to modify the PA sub-inclusion location. To this end, PBAT-b-PLA and PA-b-PBAT di-block copolymers were synthesized. The presence of the di-block copolymers enabled to modify the interfacial tension in PLA/PBAT and PA/PBAT. The modification of the interfacial tension balance was shown to successfully change the morphology from semi-encapsulation to full encapsulation of PA sub-inclusions in the PBAT drops. The mechanical performance of this ternary blend was evaluated.

<p>The thesis covers the following topics:</p> <p>1. aggregation and size effect on metal-polymer nanocomposite thermal interface materials</p> <p>2. diffusion limited cluster aggregation lattice simulation on thermal conductivty</p> <p>3. thermal interfacial resistance reduction between metal and dielectric materials by inserting an intermediate metal layer</p> <p>4. absence of coupled thermal interfaces in al2o3/ni/al2o3 sandwich structure</p> <p>5. ultra-efficient low-cost radiative cooling paints</p>

La formation d'émulsions eau-dans-huile stables est un problème majeur rencontré par les pétroliers au niveau de la production mais aussi du raffinage. Afin d'essayer de prévoir ce phénomène, Total a développé une méthode de classement des huiles qui permet, à partir de leurs propriétés physico-chimiques, de déterminer a priori leur capacité à former ou non des émulsions stables. Cependant, les mécanismes interfaciaux sous-jacents ainsi que l’influence des molécules tensioactives du brut sur la stabilité des émulsions n’est pas très clair. Notre travail a consisté à étudier la contribution des acides naphténiques et des asphaltènes dans les phénomènes observés. L’étude d’huiles réelles a permis d’établir un lien entre la stabilité des émulsions et la formation à l'interface d'un gel 2D. Les études menées sur les huiles réelles dont les acides naphténiques ont été extraits ont permis de montrer que ces derniers, en compagnie de leurs formes ionisées, les naphténates, ont la capacité de réduire la stabilité des émulsions en diminuant la résistance du gel interfacial, ou même en empêchant sa formation. Les expériences réalisées sur les huiles réelles dépourvues d’asphaltènes ont permis de confirmer le rôle stabilisant des asphaltènes. Les résultats obtenus suggèrent que les asphaltènes s’adsorbent sur le gel 2D déjà formé par des tensioactifs passés de l’huile vers l’eau et le rapprochent ainsi de sa transition vitreuse. La résistance du gel interfacial s'en trouve alors augmentée, ce qui conduit à la formation d'émulsions plus stables. En croisant le classement industriel des bruts opéré par Total et les résultats de l’étude, un mécanisme global, régi par la compétition entre les acides naphténiques, les naphténates et les asphaltènes à l’interface E/H est proposé pour expliquer les différences de stabilité observées avec les différentes huiles. Lorsque les acides et les naphténates sont suffisamment concentrés, ils empêchent la formation du gel interfacial et les émulsions sont peu stables. Lorsqu’ils sont moins concentrés le rôle des asphaltènes peut alors devenir prépondérant en donnant une cohésion plus importante au gel qui se rapproche de sa transition vitreuse, ce qui conduit en général au renforcement de la stabilité des émulsions formées. / Water-in-crude oil emulsions are a major issue for oil companies in both production and refining facilities. Thanks to physical and chemical characterizations, Total set a classification which allows the decision of a crude oil ability to create stable emulsions. However the interfacial mechanisms implied and the influence of the indigenous surfactants of crude oil remain unclear. Our work consists in studying the naphthenic acids and asphaltenes contribution to the w/o emulsion stability. The study of realistic crude oils enabled the discovery of a link between the emulsion stability with the formation of a very particular interfacial behavior: a two-imensional gel. Experiments with desacidified oils have proven the destabilizing ability of naphthenic acids and their ionized form, naphthenates. They actually decrease the interfacial gel strength and can even prevent the gel formation. Asphaltenes-free crude oils have permitted to confirm the stabilizing role of asphaltenes. Rather than adsorbing directly on the interface, asphaltenes seem to adsorb on the interfacial gel already formed. The gel strength is thus increased and lead to higher emulsion stability. Thanks to these results and the industrial classification of crude oil developed by Total, a global mechanism explaining the emulsion stability process has been proposed. This mechanism is governed by the competition between asphaltenes, naphthenates and naphthenic acids at the water/oil interface. If the concentration of naphthenic acids and naphthenates is high enough, the interfacial gel cannot be formed and the emulsions are unstable. If the crude oil is not acidic enough, the asphaltenes influence increases dramatically and implies the strengthening of the gel which becomes closer to his glass transition. This generally leads to the formation of more stable emulsions.

La performance mécanique des composites à matrice céramique repose en partie sur le contrôle de la liaison interfaciale et le choix des matériaux. Ces travaux s’intéressent au renforcement de la liaison interfaciale en traitant la surface des fibres SiC de dernière génération : les Hi-Nicalon S. L’objectif est d’établir une accroche chimique et/ou mécanique principalement avec l’interphase BN. Des composites modèles, minicomposites élaborés par voie CVI (Chemical Vapor Infiltration) sont utilisés comme base de travail. La quantification de la force de la liaison interfaciale s’effectue en évaluant l’énergie de liaisons interfaciales Gci issues d’essais de traction, et en calculant la contrainte de cisaillement τ par essais de pushout. Dans un premier temps, les fibres HNS dont les surfaces ont été légèrement modifiées, ont été testées avec l’interphase classique PyC. La liaison interfaciale sur minicomposites reste faible. Différentes traitements chimiques ont été effectués à la surface des fibres dans l’optique de renforcer la liaison interfaciale avec le BN, interphase plus résistance à l’oxydation que le PyC. Au préalable, les conditions d’élaborations de l’interphase BN ont été étudiées. / Mechanical properties of ceramic composites can be improved by controlling interfacial bonding and choosing materials. To enhance interfacial bonding, treatment on the last SiC fiber, Hi-Nicalon S surface are proposed in this work. The aim is to allow chemical and/or mechanical bonds mainly with BN interphase. For this, composites models, minicomposites are elaborated by CVI (Chemical Vapor Infiltration). Quantification of the strength of interfacial bonding is based by evaluating interfacial bonding energy Gci with tensile tests, and by calculating interfacial shear stress τ with push-out tests. Firstly, Hi-Nicalon S fibers whose surfaces have been slightly modified have been tested with classic interphase PyC. Interfacial bonding on minicomposites is weak. Different treatments have been performed on surface fibers to enhance interfacial bonding with BN, which have a better resistance oxidation than PyC. Before, elaboration parameters of BN interphase have been studied.

Esta pesquisa tem como finalidade desenvolver implantes de alumina com núcleo denso e superfície gradualmente porosa (FGM) recobertos com materiais bioativos - hidroxiapatita e biovidro. Materiais porosos são estudados como solução para a osseointegração, porém apresenta déficit nas suas propriedades mecânicas. Estruturas bifásicas foram desenvolvidas por pesquisadores com o propósito de promover crescimento tecidual, sem afetar significativamente sua propriedade mecânica, no entanto ocorre delaminação. Neste trabalho é proposta uma estrutura em gradiente funcional que visa aprimorar as propriedades mecânicas conjugadas com a sinalização celular e com integração óssea. O tamanho, a morfologia de poros e também a porosidade são parâmetros fundamentais para boa resposta tecidual e integração do implante, pois afetam a viabilidade e a afinidade celular. Para essa finalidade a busca por uma espessura efetiva de porosidade se faz fundamental para alto desempenho do implante. Peças de alumina porosas infiltradas com materiais bioativos foram fabricadas e estudadas in vivo, em tíbias de ratos da raça Wistar durante 14, 18, 21 e 28 dias, para investigar a qualidade do crescimento de tecido ósseo. O estudo com implantes porosos recobertos foi realizado para avaliar e padronizar a superfície porosa do gradiente funcional. Os animais foram analisados com densidade mineral óssea (DMO), as tíbias foram caracterizadas na interface osso-implante e nos poros com histologia, com EDS-line-scan, com radiografias e com ensaios de cisalhamento. Implantes de alumina com 70% de porosidade foram comparados com recobrimento bioativo e sem recobrimento in vivo e ex-vivo. Nos resultados, os implantes recobertos aceleram o processo de osseointegração. Essa característica foi mais evidente no período de 28 dias de implantação com aumento de 24% na tensão de cisalhamento. Após validar uma superfície porosa e osseointegrável para a superfície do gradiente funcional, foram aplicadas técnicas diferenciadas para manufaturar peças com núcleo denso e superfície com gradiente de porosidade. As peças com FGM foram manufaturadas com a utilização de duas técnicas, dipping e co-prensagem e foram analisadas com microscopia eletrônica de varredura. Com o método de manufatura de co-prensagem foram obtidas peças com superfície gradualmente porosa, com transição de densificação contínua, sem delaminação. Os implantes de alumina em gradiente funcional com 70 % de porosidade na superfície mais externa, recobertos por bioativos apresentam potencial para aplicações em implantes ósseos ou dentários. / The present thesis reports on the development of alumina implants with dense core and gradually porous surface (FGM) covered with bioactive materials, hydroxyapatite (HA) and bioactive glass. Porous materials have been studied to provide tissue ingrowth, however they strongly affect the mechanical properties of the implant. Biphasic structures have been developed by some researchers to promote tissue growth without affecting the mechanical properties, although delamination may occur. This study proposes a functional gradient structure to improve both the mechanical properties of the material and cell signaling. The size and morphology of the pores as well as their porosity are key parameters for good tissue response and implant integration, since they affect the viability and cell affinity, and an effective porosity thickness becomes essential for a high performance of the implant. Porous alumina implants coated with bioactive materials were fabricated and studied in vivo in rat tibia for 14, 18, 21, and 28 days to investigate the quality of bone tissue growth. The study of porous coated implants was performed to evaluate and standardize the porous surface of the functional gradient. The animals were examined with bone mineral density (BMD), the tibiae were characterized in the bone-implant interface and the pores were analyzed with histology, EDS line-scan, X-ray and shear tests. Alumina with 70% porosity was compared with and without bioactive coating in vivo and ex vivo. The results showed that the covered implants accelerated the osseointegration process. This characteristic is more evident within 28 days of deployment with a 24% increase in shear stress. After validating a porous and osteointegrated surface for the surface of the functional gradient, several techniques were applied to manufacture parts with dense core and surface with gradient of porosity. The pieces were manufactured with FGM using two techniques, dipping and co-pressing and were analyzed by scanning electron microscopy. The manufacturing method of co-pressing allowed obtaining pieces with gradually porous surface and continuous transition of densification without delamination. On the outermost surface, alumina implants with functional gradient and 70% porosity and coated with bioactive materials presented potential for application to bone or dental implants.

Due to their ability to confer enhanced surface properties without compromising the properties of the substrate, coatings have become ubiquitous in heavy industrial applications for corrosion, wear, and thermal protection, among others. Kinetic Metallization (KM), a solid-state impact consolidation and coating process, is well-suited for depositing industrial coatings due to its versatility, low substrate heat input, and low cost. The ability of KM coatings to adhere to the substrate is determined by the quality of the interface. The purpose of this study is to develop a model to predict the interfacial quality of KM coatings using known coating and substrate properties. Of the various contributions to adhesion of KM coatings, research suggests that the thermodynamic Work of Adhesion (WAD) is the most fundamental. It is useful to define interfacial quality in terms of the critical strain energy release rate (GC) at which coating delamination occurs. Studies show that GC for a given interface is related to WAD. This study attempts to develop a theoretical model for calculating WAD and understand the relationship between GC and WAD. For a bimetallic interface between two transition metals, WAD can be theoretically calculated using known electronic and physical properties of each metal: the molar volume, V, the surface energy, γ, and the enthalpy of alloy formation, ΔHinterface; ΔHinterface is a function of the molar volume, V, the work function, φ, and the electron density at the boundary of the Wigner-Seitz cell, nWS.WAD for Ni-Cu and Ni-Ti interfaces were 3.51 J/m2 and 4.55 J/m2, respectively. A modified Four-point bend testing technique was used to experimentally measure GC for Ni-Cu and Ni-Ti specimens produced by KM. These tests yielded mean G­C values of 50.92 J/m2 and 132.68 J/m2 for Ni-Cu and Ni-Ti specimens, respectively. Plastic deformation and surface roughness are likely the main reasons for the large discrepancy between GC and WAD. At the 95% confidence level, the mean GC of the Ni-Ti interface is significantly higher than that of the Ni-Cu interface. Further testing is recommended to better understand the relationship between WAD and GC.

L'exfoliation en phase liquide du graphite est l'une des méthodes les plus prometteuses pour augmenter la production et la disponibilité commerciale du graphène. Le processus d'exfoliation peut être décrit, de manière conceptuelle, en quatre étapes: le contact du graphite avec le liquide, l'intercalation du solvant entre les feuillets de graphène, la dispersion du matériau à deux dimension et sa stabilisation en phase liquide. Comme les liquides ioniques peuvent être facilement obtenus avec différentes structures moléculaires et donc des propriétés physicochimiques modulables, ils ont été utilisés dans cette thèse comme milieux liquides pour l'exfoliation du graphite. Notre objectif est d'optimiser l'exfoliation du graphite à travers la compréhension des mécanismes moléculaires et des interactions impliquées dans chaque étape du processus. Les énergies interfaciale graphite-liquide ont été calculées à partir de tensions de surface et d'angles de contact mesurées entre des liquides ioniques et du graphite pour déterminer l'affinité de différents liquides à la surface du graphite. Afin d'étudier cette interface liquide - solide, des simulations en dynamique moléculaire ont été menées pour analyser l'organisation des liquides ioniques à la surface du graphite. De même, l'énergie libre nécessaire pour créer des cavités au sein du liquide ionique a été calculée.Des simulations moléculaires ont également été réalisées pour modéliser l'exfoliation d'un feuillet de graphène à partir de graphite en apportant une vue microscopique de l'intercalation des molécules de solvant. L'énergie nécessaire à l'exfoliation a pu être calculée en présence de différents liquides. Des composés polyaromatiques ont été considérés comme des modèles pour le graphène car ils peuvent être facilement obtenus purs, sans variabilité de structure, défauts ou groupes fonctionnels non contrôlés. Les enthalpies de dissolution du naphtalène, anthracène et pyrène dans différents liquides ioniques ont été mesurées par calorimétrie en solution et liées à leur solubilité. L'organisation des ions autour de ces composés modèles a été étudiée par simulation moléculaire et spectroscopie Infra-Rouge.Après l'exfoliation, les échantillons de graphène en suspension dans différents liquides ioniques ont été caractérisés expérimentalement en termes de taille de feuillets (microscopie électronique à transmission et microscopie à force atomique), nombre de couches de graphène (microscopie à force atomique, spectroscopie Raman), concentration totale (spectroscopie UV-visible) et pureté du matériau exfolié (spectroscopie de photoélectrons~X). Vingt liquides ioniques différents à base de cations imidazolium, pyrrolidinium et ammonium et d'anions bis (trifluorométhylsulfonyl)imide, triflate, dicyanamide, tricyanométhanide et méthylsulfate ont été testés. Les interactions moléculaires permettant d'établir de règles de conception pour les liquides ioniques capables d'exfolier les matériaux carbonés ont été identifiées. Le cation pyrrolidinium a montré des résultats prometteurs dans toutes les étapes du processus d'exfoliation, par rapport au cation imidazolium ou ammonium. La sélection d'un grand anion flexible a réduit l'énergie interfaciale avec le graphite, dispersé les nanocarbones en augmentant l'entropie du système et stabilisé le graphite exfolié en plus grande quantité. Un petit anion tel que le triflate semble être favorable à l'obtention de graphène, même si la taille des couches et leur quantité sont réduites. Un liquide ionique ayant une partie apolaire importante facilitera l'insertion et la dispersion du nanomatériau de carbone. Pour la stabilisation du graphite, les interactions alkyle-π et π- π sont décisives. / The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. The exfoliation process can be conceptually described in four steps: the contact of the graphite with liquid, the intercalation of the solvent between layers, the dispersion of the two dimensional material, and its stabilization in the liquid-phase. Because ionic liquids can be easily obtained with chosen molecular structures and tunable physicochemical properties, they were used in this study as liquid media for the exfoliation of graphite. Our aim is to optimize the exfoliation of graphite through the understanding of the molecular mechanisms and of the interactions involved in each step of the process.The liquid-graphite interfacial energies from measured surface tensions and contact angles, between ionic liquids and pristine graphite surface, were used to determine the affinity of different liquids at the surface of graphite. In order to investigate this interface, molecular dynamics simulations were conducted to analyse the ordering of ionic liquids at the surface of graphite. The free energies necessary to create cavities inside the bulk ionic liquid have also been studied.Molecular simulations were also used to study the exfoliation of one graphene layer from a stack of graphite and hence provide a microscopic view of the intercalation of solvent molecules. The energies involved in the process have been calculated.Polyaromatic compounds were regarded as models for graphene as they can be easily obtained pure, without structure variability, defects or uncontrolled functional groups. Enthalpies of dissolution of polyaromatic hydrocarbons (naphthalene, anthracene and pyrene) in different ionic liquids were measured by solution calorimetry and related with their solubility. The ordering of the ions around this model compounds were studied by molecular simulation and spectroscopy Infra-Red.After exfoliation, samples of suspended graphene in different ionic liquids have been characterized experimentally in terms of flake size (using transmission electron microscopy and atomic force microscopy), number of layers (atomic force microscopy, spectroscopy Raman), total concentration (UV-visible spectroscopy) and purity of the exfoliated material (X-ray photoelectron spectrometry).Twenty different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate have been tested. The molecular interactions have been identified thus allowing the establishment of design rules for ionic liquids capable of exfoliating carbon materials. The pyrrolidinium cation has shown promising results in all the steps of exfoliation process, compared to the imidazolium or ammonium cation. Selecting a large and flexible anion reduced the interfacial energy with graphite, dispersed the nanocarbons by increasing the entropy of the system and stabilized the exfoliated graphite in larger quantity. A small anion such as triflate appears to be favorable for obtaining graphene, whereas the size of the layers and their quantity is reduced. An ionic liquid having an important apolar portion will facilitate the insertion and dispersion of graphene layers. For the stabilization of graphite, the alkyl-π et π -π interactions are decisive.

An experimental study of phase transitions of long-chain n-alkanes induced by the effect of interfaces is described. ¶ The phase behaviour of long-chain n-alkanes (carbon number 14, 16, 17, 18) adsorbed at isolated mica surfaces and confined between two mica surfaces has been studied in the vicinity of and down to several degrees below the bulk melting points, Tm. Using the Surface Force Apparatus we have measured the thickness of alkane films adsorbed from vapour (0.97 [equal to or greater-than] p/p[subscript o] [equal to or greater-than] 0.997), studied capillary condensation transition, subsequent growth of capillary condensates between two surfaces, and phase transitions in both the adsorbed films and the condensates. By measuring the growth rate of the capillary condensates we have identified a transition in the lateral mobility of molecules in the adsorbed films on isolated mica surfaces. This transition to greater mobility occurs slightly above Tm for n-hexadecane, n-heptadecane and n-octadecane but several degrees below Tm for n-tetradecane, and is accompanied by a change in wetting behaviour and a measurable decrease in adsorbed film thickness for n-heptadecane and n-octadecane. Capillary condensates that form below Tm remain liquid, but may freeze if the degree of confinement is reduced by separation of the mica surfaces. An increase in the area of the liquid-vapour interface relative to that of the liquid-mica interface facilitates freezing in the case of the long-chain alkanes, which show surface freezing at the liquid-vapour interface. ¶ Although thermodynamic properties of the surface freezing transition have been rather well documented, the kinetics involved in formation of such ordered monolayers has so far received very little attention. We studied the surface tension of n-octadecane as a function of temperature in the vicinity of Tm, using the static Wilhelmy plate and the dynamic maximum bubble pressure methods. The two methods give different results on cooling paths, where nucleation of the surface ordered phase is involved, but agree on heating paths, where both methods measure properties of the equilibrium surface phase. On cooling paths, the surface of bubbles may supercool below the equilibrium surface freezing temperature. The onset of surface freezing is marked by a sharp drop in the surface tension. The transition is accompanied by an increased stability of the films resulting in longer bubble lifetimes at the liquid surface, which suggests that the mechanical properties of the surfaces change from liquid-like to solid-like. Our results suggest occurrence of supercooling of the monolayer itself.