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In several types of coating processes a solid substrate is removed at a controlled velocity U from a liquid bath. The shape of the liquid meniscus and the thickness of the coating layer depend on U. These dependencies have to be understood in detail for non-volatile liquids to control the deposition of such a liquid and to lay the basis for the control in more complicated cases (volatile pure liquid, solution with volatile solvent). We study the case of non-volatile liquids employing a precursor film model that describes partial wettability with a Derjaguin (or disjoining) pressure. In particular, we focus on the relation of the deposition of (i) an ultrathin precursor film at small velocities and (ii) a macroscopic film of thickness h ∝ U^(2/3) (corresponding to the classical Landau Levich film). Depending on the plate inclination, four regimes are found for the change from case (i) to (ii). The different regimes and the transitions between them are analysed employing numerical continuation of steady states and saddle-node bifurcations and simulations in time. We discuss the relation of our results to results obtained with a slip model. In connection with evaporative processes, we will study the pinning of a droplet due to a sharp corner. The approach employs an evolution equation for the height profile of an evaporating thin film (small contact angle droplet) on a substrate with a rounded edge, and enables one to predict the dependence of the apparent contact angle on the position of the contact line. The calculations confirm experimental observations, namely that there exists a dynamically produced critical angle for depinning that increases with the evaporation rate. This suggests that one may introduce a simple modification of the Gibbs criterion for pinning that accounts for the non-equilibrium effect of evaporation.

Geological Carbon Storage (GCS) is considered as one of the key techniques to reduce the rate of atmospheric emissions of CO2 and thereby to contribute to controlling the global warming. A successful application of a GCS project requires the capability of the formation to trap CO2 for a long term. In this context, processes related to CO2 trapping and also possible leakage of CO2 to the near surface environment need to be understood. The overall aim of this thesis is to understand the flow and transport of CO2 through porous media in the context of geological storage of CO2. The entire range of scales, including the pore scale, the laboratory scale, the field experiment scale and the industrial scale of CO2 injection operation are addressed, and some of the key processes investigated by means of experiments and modeling.  First, a numerical model and laboratory experimental setup were developed to investigate the CO2 gas flow, mimicking the system in the near-surface conditions in case a leak from the storage formation should occur. The system specifically addressed the coupled flow and mass transport of gaseous CO2 both in the porous domain as well as the free flow domain above it. The comparison of experiments and modelling results showed a very good agreement indicating that the model developed can be applied to evaluate monitoring and surface detection of potential CO2 leakage. Second, the field scale CO2 injection test carried out in a shallow aquifer in Maguelone, France was analyzed and modeled. The results showed that Monte Carlo simulations accounting for the heterogeneity effects of the permeability field did capture the key observations of the monitoring data, while a homogeneous model could not represent them. Third, a numerical model based on phase-field method was developed and model simulations carried out addressing the effect of wettability on CO2-brine displacement at the pore-scale. The results show that strongly water-wet reservoirs provide a better potential for the dissolution trapping, due to the increase of interface between CO2 and brine with very low contact angles. The results further showed that strong water-wet conditions also imply a strong capillary effect, which is important for residual trapping of CO2. Finally, numerical model development and model simulations were carried out to address the large scale geological storage of CO2 in the presence of impurity gases in the CO2 rich phase. The results showed that impurity gases N2 and CH4 affected the spatial distribution of the gas (the supercritical CO2 rich phase), and a larger volume of reservoir is needed in comparison to the pure CO2 injection scenario. In addition, the solubility trapping significantly increased in the presence of N2 and CH4.

Le renfort des matériaux composites via la croissance de nanotubes de carbone (NTC) directement à la surface des renforts textiles permet d'augmenter certaines propriétés des composites. La méthode flamme est la technique facilement industrialisable à la continue qui permet de réaliser la croissance des NTC sur des textiles. Cependant un procédé à la continue va engendrer des contraintes sur les renforts, ainsi le but de ces travaux de doctorat est de déterminer le comportement des textiles après la croissance de NTC, sous différentes contraintes de type industrielles, et d'évaluer leur influence sur la mise en œuvre et les propriétés des matériaux composites. Ces travaux ont mis en évidence la formation d'un film de transfert dès le début du frottement de surfaces textiles recouvertes de NTC contre une pièce métallique ou un autre textile de même nature. De plus, la présence des NTC a permis de mettre en évidence un comportement spécifique en indentation. La mouillabilité des surfaces avec une résine époxy n'est en revanche pas influencée par la présence des NTC, si ce n'est que très faiblement dans la dynamique du mouillage. Il a été montré que les conditions de croissance des NTC, notamment la nature du catalyseur, avaient une influence sur la résistance à long terme du film de transfert formé après frottement, sur l'adhésion des NTC sur les fibres de renfort, ainsi que sur la dynamique du mouillage avec de la résine époxy. Finalement, des matériaux composites ont été fabriqués avec des renforts avant et après usure de la surface présentant des NTC, dans le but d'étudier son influence sur les propriétés des composites. L'usure, se traduisant par la transformation des NTC en film de transfert, n'influence ni les propriétés électriques des matériaux, ni les propriétés mécaniques en flexion 3 points. / Reinforcement of composite materials with carbon nanotubes (CNTs) grafted on textiles provides an increase in the properties of the composites. The flame method is the most rapid and the easiest industrialized technique to realize the growth of CNTs on textile surfaces. At an industrial scale, some strains will be applied between the CNTs’ growth step and the composite processing, which can cause damage on the CNTs and alter the positive contribution of the CNTs to the properties of composites. That is why the aim of this study is to determine the effect of different industrial stresses on the CNTs behaviour and their influence on the composite processing and composite properties. In this work, we highlighted the formation of a transfer film, composed of CNTs, during the friction of the CNTs against metallic pieces or against the same fabric. The presence of the CNTs shows a particular behaviour in indentation. However, the wettability with an epoxy resin is not influenced by the CNTs, except a little in the dynamic of the wettability. It has been shown that the growth condition of the CNTs, particularly the catalyst, has an influence on the long term resistivity of the transfer film formed by the friction, on the adhesion of the CNTs on the fibres and on the dynamic of the wettability with an epoxy resin. Finally, composite materials composed of CNTs growth fabrics before and after the wear of the surface, were manufactured in order to study the influence of the wear on the properties of the composite material. It appears that, the wear, causing the formation of the transfer film, has no influence on the electrical and flexural properties of the composite material.

The study is focused on study of surface and interfacial properties of oil at high temperatures, to understand the mechanisms of heat transfer and oil absorption during frying

Ce travail de thèse de doctorat vise à l’élaboration de surfaces poreuses hiérarchiquement structurées à partir de copolymères aux structures bien définies ainsi qu’à l’étude de leurs propriétés. La chimie des polymères, en constante évolution, a permis dans ce travail de thèse la synthèse de copolymères diblocs de natures diverses par des techniques de polymérisation radicalaire contrôlée tout aussi variées. En effet, la polymérisation radicalaire contrôlée par les nitroxydes (NMP), par transfert d’atome (ATRP), par transfert réversible d’addition/fragmentation (RAFT) et par le Cu(0) ont été utilisées pour la synthèse de copolymères diblocs associant un bloc de poly(styrène) à divers blocs d’acrylates ou de 4-vinylpyridine. Intimement associée à un procédé d’élaboration basé sur l’évaporation de solvant, nommé figure de souffle (trad. Breath Figure), la synthèse de ces copolymères a permis l’élaboration de surfaces poreuses hiérarchiquement structurées aux échelles du micro et nanomètre. Les différentes phases ont conféré à ces matériaux des propriétés particulières d’adhésion, de mouillabilité ou encore de bioactivité. Ces recherches doctorales ont bénéficié de la double compétence du laboratoire en chimie et en physico-chimie des polymères. En effet, des techniques de microscopie (optique, à force atomique ou électronique), de diffusion de rayonnement (neutrons et rayon-X aux petits angles) ainsi que des tests de pégosité et de mouillabilité ont permis l’étude de la structuration des films ainsi que l’étude de leurs propriétés de surface. / The present studies aim at designing hierarchically structured porous surface from copolymers with well defined structures. As a science in constant evolution, polymer chemistry, enable the synthesis of diblock copolymers with different natures by the mean of various radical controlled polymerization techniques. Indeed, radical controlled polymerization with nitroxyde (NMP), by atom transfer (ATRP), by reversible addition/fragmentation transfer (RAFT) or by Cu(0) were used for the synthesis of diblock copolymers based on polystyrene and different acrylates or 4-vinylpyridine blocks. The intimately association between a fast solvent evaporation process named the Breath Figure and the synthesis of the copolymers enable the production of hierarchically structured materials from micro to nanoscale. The nature of the different blocks confers adhesion, wettability or bioactivity properties to these materials. These researches benefit from the chemistry and physico-chemistry laboratory competences. Indeed, microscopy techniques (optical, atomic force and electronic), scattering (small angle neutron or X-ray) as well as tack or wettability measurements enable the complete characterization of films structuration and point up their properties.

La nucléation, la croissance et la dissociation des hydrates de gaz au voisinage d’un ménisque eau – gaz dans des capillaires de verre sont étudiées par vidéo-microscopie et spectroscopie Raman à température, pression, mouillabilité et géométrie du substrat contrôlées. Dans ce travail, deux hydrates simples de structure I (hydrate de CO2 et hydrate de CH4), deux hydrates simples de structure II (N2 et Cyclopentane) et un hydrate double (cyclopentane + CO2) sont examinés. En baissant la température bien au-dessous de 0 °C, i.e., sous un fort sous-refroidissement, tous ces hydrates, excepté l’hydrate de cyclopentane, nucléent sans que la glace soit formée. L’hydrate forme d’abord une croûte polycristalline sur le ménisque eau-molécule invitée (guest). Ensuite, il se propage rapidement à partir de ce ménisque dans l’eau sous forme de fibres ou dendrites et le long de la paroi capillaire sous forme d’une croûte fine et polycristalline appelée ”halo”. Sur un substrat hydrophile, ce halo avance du côté de la phase invitée, alimenté par une couche d’eau entre le halo et la paroi interne du capillaire. Symétriquement, sur un verre hydrophobe (traité au silane), le halo et une couche de la phase invitée se propagent du côté eau. Aucun halo n’est observé sur un substrat de mouillabilité intermédiaire. La croissance et la morphologie du halo d’hydrate et l’épaisseur de sa couche sous-jacente d’eau (ou de phase invitée) dépendent fortement du sous-refroidissement. Grâce au faible volume du capillaire utilisé et à la vitesse rapide de refroidissement, la limite de métastabilité de l’hydrate de CO2 est approchée pour différentes pressions et mouillabilité. Le régime des faibles sous-refroidissements est également étudié : une nouvelle morphologie d’hydrate de CO2 est découverte pour des sous-refroidissements inférieurs à 0,5 °C, constituée d’un cristal creux, générée au niveau du ménisque eau – guest et avançant du côté guest le long du verre, alimenté par une épaisse couche d’eau prise en sandwich entre le verre et ce cristal. Une nouvelle procédure est proposée pour détermination des conditions d’équilibre des hydrates de gaz dans une large plage de température et de pression, y compris l’extension métastable de la ligne triphasique (eau liquide – hydrate – guest) jusqu’à des températures bien inférieures à 0 °C. Enfin, les mécanismes par lesquels le CO2 et le cyclopentane agissent en synergie pour former l’hydrate de structure II sont discutés. / The nucleation, growth and dissociation of gas hydrate across a water – gas meniscus in glass capillaries are investigated by means of video-microscopy and confocal Raman spec- troscopy under controlled temperature, pressure, cooling rate and substrate wettability and geometry. Structure I and II hydrates are examined, with the following guest molecules: CO2, CH4, N2, cyclopentane, and cyclopentane + CO2. By lowering the temperature well below 0 °C, i.e., under strong subcooling, all these hydrates but the cyclopentane hydrate nucleate without forming ice on the liquid water – guest meniscus, which is rapidly covered with a polycrystalline crust. The hydrate then propagates from this meniscus as fast-growing fibers or dendrites in bulk water and as a thin polycrystalline crust, or halo, along the capillary wall. On water-wet substrates, this halo advances on the guest side of the meniscus, fed by a water layer sandwiched between the halo and glass. Symmetrically, on guest-wet (silane-treated) glass, the halo and an underlying guest layer grow on the water side of the interface. No halo is observed on intermediate-wet glass. The hydrate halo growth and morphology and the thickness of its underlying water (or guest) layer strongly depend on subcooling. Thanks to the small capillary volume and the rapid temperature descent, the metastability limit of CO2 hydrate is approached for various pressures and substrate wettabilities. The low subcooling regime is investigated as well: a novel CO2 hydrate morphology is discovered for subcoolings below 0.5 °C, which consist of a hollow hydrate crystal originating from the water – guest meniscus and advancing on the guest side along glass, fed by a thick water layer sandwiched between glass and this crystal. A new procedure is proposed to determine gas hydrate dissociation conditions in a large temperature and pressure range, including the metastable extension of the three-phase (liquid water – hydrate - guest) down to temperatures well below 0 °C. Finally, the mechanisms by which CO2 and cyclopentane synergistically act to form the structure II hydrate are discussed.

Les alliages métalliques complexes (CMAs) sont des composés intermétalliques dont la structure cristallographique diffère de celle des alliages conventionnels par le nombre conséquent d'atomes dans la maille (jusqu'à plusieurs milliers d'atomes), généralement arrangés sous forme d'agrégats atomiques de haute symétrie. Ils sont prometteurs pour un certain nombre d'applications technologiques, en particulier les revêtements fonctionnels, en raison de leurs propriétés de surface uniques. Cette thèse a pour objectif, à la fois la détermination de la structure et des propriétés électroniques d’une surface d’un CMA de la famille des clathrates intermétalliques, et des propriétés de mouillage intrinsèques de plusieurs CMAs à base d’aluminium. Dans une première partie, nous nous sommes intéressés aux surfaces de bas indice (100) et (110) du clathrate Ba8Au5.25Ge40.75. Leurs structures atomiques et électroniques ont été déterminées en combinant des expériences de sciences des surfaces et des calculs basés sur la théorie de la fonctionnelle de la densité. La structure tridimensionnelle de Ba8Au5.25Ge40.75, formée d'un réseau de deux types de cages (structure hôte) à base de germanium et d’or, qui emprisonnent les atomes de Ba, induit une nanostructuration de la surface contrôlée par son orientation, puisque le type de cages préservées à la surface diffère pour les surfaces (100) et (110). Dans les deux cas, les atomes de Ba qui protrudent à la surface, ont un rôle primordial pour la stabilité de surface : ils assurent un transfert de charge qui sature les liaisons pendantes des atomes de germanium en surface. Dans une seconde partie, les propriétés intrinsèques de mouillage de plusieurs CMAs à base d’aluminium, ont été déterminées par une approche couplant des mesures de microscopie et des calculs ab initio. Expérimentalement, les angles de contact de gouttes de plomb (métal sonde) sur plusieurs surfaces de CMAs ont été systématiquement mesurés. Les angles précédents étant fonction, entre autres, de l’énergie interfaciale, des calculs d'énergie interfaciale ont été menés, d’une part avec un substrat d’un métal simple, Al(111), et d’autre part sur un substrat de CMA, Al13Co4(100). Les résultats obtenus mettent en évidence une forte influence de la structure de l’interface sur l’énergie interfaciale / Complex metallic alloys (CMAs) are intermetallic compounds possessing a large unit cell containing several tens to hundreds of atoms. Their structure can be described alternatively by the packing of highly symmetric atomic clusters. Clathrate (or cage) compounds are a new class of CMAs having a crystal structure described by a complex arrangement of covalently-bonded cages. The Ba8Au5.25Ge40.75 type-I clathrate is one such cage compound, whose bulk properties have been (and still are) extensively explored for thermoelectric applications. In fact, it is possible to tune the compound electronic structure by a fine control of its bulk composition. Regarding the properties of the Ba8Au5.25Ge40.75 surface, information remains scarce if not inexistent. However, it is known that the surfaces of CMAs often exhibit interesting surface properties. To this end, we have studied two low-index surfaces: BaAuGe(100) and BaAuGe(110) by a combination of experimental (XPS; LEED; STM) and computational (DFT) methods. Experimental results show no evidence for surface segregation and LEED patterns are consistent with (1x1) bulk terminations with no surface reconstruction. The interplay between the 3D nano-caged structure and 2D surfaces is investigated. We demonstrate that the surface structures of the two surfaces considered preserve the bulk structure cages in addition to an ordered arrangement of surface Ba atoms. The two surfaces are formed by a breakage of highly directional covalent bonds present within the framework, hence leading to destabilizing dangling bonds. Ab initio calculations show that the surface structure is stabilized through electron charge transfer from protruding Ba to surface Ge and Au atoms, saturating the dangling bonds. This charge-balance mechanism lifts the possible surface reconstruction envisaged. We reveal how the surface nanostructuration is surface orientation dependent. The results indicate that the surface electronic structure of BaAuGe(110) is impacted by the Au surface concentration. The surface models for BaAuGe(100) and BaAuGe(110) present a metallic character and low work function values, useful for further applications. Such structurally complex surfaces may also be used as templates for novel nanoscale architectures. Further in this work, we also applied the state-of-the-art surface science techniques to investigate the wetting properties of Al-based CMAs. In these experiments, chemically inert Pb element was used as a metal probe. Systematic analysis is done to find the correlation between the wetting properties and the electronic structure properties of these CMAs. Interfacial energy calculations have been performed to model the Pb/CMA interface based on few approaches reported in literature. We have tested these approaches on a moiré patterned Pb(111)/Al(111) interface. This interface is found to be controlled by geometric factors. Hence, an acquired understanding was applied to Pb deposited on Al13Co4(100) (Al-rich side) interface

La faible densité et les propriétés mécaniques remarquables des composites polymères en font des matériaux de choix pour remplacer les métaux. Cependant, leurs propriétés physicochimiques rendent leurs surfaces peu adhésives pour divers types de revêtements. Pour améliorer l’adhérence de revêtements métalliques sur des substrats de PEEK, et pour mieux comprendre les mécanismes de l’adhésion, les propriétés de surface du matériau ont été modifiées par des procédés physiques en voie sèche.D’une part, cette étude montre que les traitements par plasma oxydants (à basse pression, ou à pression atmosphérique) permettent d’améliorer la mouillabilité de la surface et l’adhérence de revêtements métalliques, par l’augmentation de la polarité de la surface, quantifiée par XPS. D’autre part, cette étude montre que l’ablation laser infrarouge à impulsion femtoseconde permet la gravure d’un motif dense, induisant de meilleures tenues mécaniques de l’assemblage. Enfin, cette étude montre que la modification de la chimie et de la topographie combinées améliore davantage ce potentiel d’adhérence.Le but de cette étude est d’ouvrir une voie vers un modèle décrivant les mécanismes de l’adhésion, influencés par la chimie de surface et la géométrie d’un motif, en s’appuyant sur un modèle mécanique permettant de décrire la dynamique des contraintes se propageant au travers de l’interface, en tenant compte des propriétés mécaniques des matériaux. / Thanks to their low densities and good mechanical properties, polymer composites are good candidates for metal alloys substitutes. However, their physicochemical properties limit their adhesion potential towards several types of coatings. In order to improve metallic thin films adhesion on PEEK substrates, and to better comprehend adhesion mechanisms, dry-phase methods have been used to alter the surface properties of the material.First, this study shows that oxidative plasma treatments (at low or at atmospheric pressure) improve the wettability and the practical adhesion of metallic coatings, by an increase of the polar component of the surface, as measured by XPS. Second, this study shows that dense patterns etched by an infrared femtosecond laser allow good practical adhesion of the metallic thin films on the substrate. Finally, this study shows that the modification of both surface chemistry and the surface topography at the same time further improves the practical adhesion of the metallic thin films.The goal of this study is to propose a route towards a model describing the combined influence of surface texture and chemistry, with the support of a mechanical model describing the dynamics of the stress dissipation through the interface while taking into account the mechanicals properties of the interfacial materials.

Surfactants both change the wettability and lower the interfacial tension by various degrees depending on the type of surfactant and how it interacts with the specific oil. Ultra low IFT means almost zero capillary pressure, which in turn indicates little oil should be produced from capillary imbibition when the surfactant reduces the IFT in naturally fractured oil reservoirs that are mixed-wet or oil-wet. What is the transport mechanism for the surfactant to get far into the matrix and how does it scale? Molecular diffusion and capillary pressure are much too slow to explain the experimental data. Recent dynamic laboratory data suggest that the process is faster when a pressure gradient is applied compared to static tests. A mechanistic chemical compositional simulator was used to study the effect of pressure gradient on chemical oil recovery from naturally fractured oil reservoirs for several different chemical processes (polymer, surfactant, surfactant-polymer, alkali-surfactant-polymer flooding). The fractures were simulated explicitly by using small gridblocks with fracture properties. Both homogeneous and heterogeneous matrix blocks were simulated. Microemulsion phase behavior and related chemistry and physics were modeled in a manner similar to single porosity reservoirs. The simulations indicate that even very small pressure gradients (transverse to the flow in the fractures) are highly significant in terms of the chemical transport into the matrix and that increasing the injected fluid viscosity greatly improves the oil recovery. Field scale simulations show that the transverse pressure gradients promote transport of the surfactant into the matrix at a feasible rate even when there is a high contrast between the permeability of the fractures and the matrix. These simulations indicate that injecting a chemical solution that is viscous (because of polymer or foam or microemulsion) and lowers the IFT as well as alters the wettability from mixed-wet to water-wet, produces more oil and produces it faster than static chemical processes. These findings have significant implications for enhanced oil recovery from naturally fractured oil reservoirs and how these processes should be optimized and scaled up from the laboratory to the field. / text