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International audience; In this work, a structural characterization of sputtered silica films was carried out using Raman spectroscopy. Due to the low cross-section and the thinness of the silica layer, its Raman signature is dwarfed by that of the glass substrate and is therefore difficult to extract. Overcoming these limitations represents an experimental challenge and requires the development of specific analysis strategies. For this purpose, an integrated approach for extracting and interpreting the Raman signature of amorphous silica films deposited on a soda-lime glass substrate was developed, based on three distinct methods: delamination of the sputtered silica film, creating a reflective mask substrate by depositing a metallic silver coating on the glass substrate and applying a numerical signal analysis (Non-negative matrix factorization) to the multidimensional dataset acquired through depth profile acquisitions on silica films directly deposited on a glass substrate. The reliability of each proposed method is demonstrated for the extraction of the silica thin film Raman spectra. These various methods can be easily extended to other materials, either crystalline or amorphous. Furthermore, we discuss the advantages and the limits of each approach.Applying this methodology allowed us to highlight the structural differences between sputtered silica thin film and bulk vitreous silica glass (v-SiO2). Magnetron sputtering film deposition is shown to form dense silica glass layers, with an estimated densification ratio, measured by x-ray reflectivity, equal to 7%. At the medium distance range, the network connectivity change in v-SiO2 is expressed by an unusually high population of three-membered rings leading to a more compact structure. The short-range order transformation was also studied by deriving the intertetrahedral angle decrease. The present results could be a step towards advanced investigation to gain insights into the structure of films at the atomic level.

Structural properties of aqueous Na-silicates at both room and high temperature (below 500°C) have been investigated to better understand the microscopic evolution of structure and the macroscopic phenomenon of foaming. NMR spectroscopy has provided a direct quantification of structural units defined as Qn. Solid-state NMR along with Raman spectroscopy has indicated the extent of local structural reorganization on heating the silicates. Heating an aqueous Na-silicate leads to structural changes due to the removal of water, where the quantity of leftover water in the system obeys an Arrhenian evolution with an activation energy of 30 kJ.mol−1. TGA, NMR and Raman measurements suggest that the structure becomes similar to the one of hydrated silicate glasses studied in geochemistry. Increasing the Na concentration results in a larger quantity of water retained after a pre-drying treatment, which correlates with a lower softening temperature of the material and is, macroscopically, related to foaming of the silicate.

International audience; The effect of temperature on multicomponent chemical diffusion in liquids of the quaternary system CaO−Na 2 O−Al 2 O 3 −SiO 2 has been studied. Diffusion-couple experiments were performed around a central composition of 64.5 wt%SiO 2 , 13.3 wt%Na 2 O, 10.8 wt%CaO, 11.4 wt%Al 2 O 3. Experiments were performed for three temperatures far above the glass transition (1200, 1280 and 1360 • C), as well as 30 • C above the glass transition. Strong multidiffusive effects were observed for all temperatures, with significant uphill diffusion of calcium, demonstrating that uphill diffusion happens close to the glass transition as well as at high temperature. For each temperature, we determined the diffusion matrix of the system and quantified its eigenvectors and eigenvalues, which correspond formally to (respectively) exchanges between ions, and associated diffusion coefficients. Little variation of the eigen-vectors of the diffusion matrix was observed as a function of temperature, with a dominant eigenvector corresponding to the exchange of sodium with calcium, the two other eigenvectors corresponding to the exchange of calcium with network formers. For the temperature range 1200-1360°C, the eigenvalues of the diffusion matrix have an Arrhe-nian temperature dependence, with an activation energy consistent with electrical conductivity for the exchange of sodium and calcium, and an activation energy consistent with viscosity for eigenvectors involving network formers. Multicomponent diffusion close to the glass transition is characterized by the same eigenvectors as at higher temperature , but some diffusion profiles are asymmetric due to strong viscosity contrasts resulting in concentration-dependent eigenvalues. Moreover, we observe some departure from Eyring relation close to the glass transition, with diffusion eigenvalues several orders of magnitude greater than the Eyring prediction. Highlights-Multicomponent diffusion matrices were determined experimentally around a central composition of 64.5 wt%SiO 2 , 13.3 wt%Na 2 O, 10.8 wt%CaO, 11.4 wt%Al 2 O 3 , for three superliquidus temperatures and 30 degrees above the glass transition.-Eigenvalues of the diffusion matrix were found to be Arrhenian down to 30 degrees above the glass transition.-Eigenvalues of exchanges involving network formers are in good agreement with Eyring's law at superliquidus temperatures, but a departure from Eyring's law is observed close to the glass transition.

International audience; This article focuses on the numerical study of the evaporation of sessile dropletsusing a Volume-Of-Fluid (VOF) method in the free-software Basilisk. We con-sider pure liquid droplets forming a spherical-cap onto a smooth or rough andnon-corrosive substrate and we investigate two different modes of evaporation:the unpinned mode where the contact angle is constant and the pinned modewhere the wetting area is constant. The numerical method used to implementthe contact angle and for the reconstruction of the interface is fully described,especially for the pinned mode where we propose a new VOF implementation.In the unpinned mode, we perform parametric studies and we show the influenceof the relative humidity and the contact angle on the evaporation process. Forall the explored parameters, the simulations predict that the volume decreaseslinearly with time, which matches the signature behaviour of evaporating un-pinned droplets, irrespective of the geometrical parameters. In the pinned mode,the contact angle analysis indicates a linear decrease in time which was expectedaccording to the theory and validated with some experiments we performed.

International audience; We report a detailed structural investigation of Ca-Na aluminosilicate glasses containing 0-20 wt% ZrO2 using X-ray absorption spectroscopy, Raman spectroscopy and 27 Al and 29 Si NMR. The X-ray absorption spectroscopy data reveal that Zr is predominantly present in ZrO6 octahedra but a significant Zr coordination change occurs with increasing ZrO2 content. Though Al and Zr are competing to be surrounded by charge balancing cations, 27 Al NMR data do not show the presence of high-coordinated Al species; thus charge-balancing cations are preferentially localized close to AlO4 tetrahedra rather than Zr polyhedra, explaining the increase in Zr coordination number that ultimately leads to limit Zr solubility in glasses. Raman and 29 Si NMR data indicates that Zr atoms are linked to the silicate network with a trend for higher degree of network connectivity at high zirconia content. Change in network connectivity and in Zr environment provide insights to understand chemical durability or crystallization in glasses.

International audience; High temperature cation mobilities, based on the multicomponent diffusion method, have been coupled with a structural investigation in the Na2O-CaO-Al2O3-SiO2-ZrO2 (NCASZ) system at 1200°C and 1250°C. From structural investigation using X-ray absorption spectroscopy (XANES), zirconium was determined in six-fold coordinated sites in the reduced glass composition range of our study and no significant structural changes have been evidenced compared to a quaternary Na2O-CaO-Al2O3-SiO2 (NCAS) glass with a similar composition. Additionally, the diffusion experiments revealed that adding zirconium in the quaternary melt has no influence on the dominant eigenvectors that correspond to exchange between calcium and sodium. Despite the expected mobility decrease resulting from a viscosity increase upon the addition of zirconium, the dominant eigenvalue calculated in this study is higher when Zr is introduced in the melt structure. This result strongly suggests that the sodium mobility is enhanced by the presence of Zr, which is explained by a change in the structural role of sodium from network modifier associated to Q3(Si) sites in NCAS melts to charge compensator associated with [ZrO6] 2-sites in NCASZ melts. This modification generates lower bond strengths between sodium and other cations in the melt, thus favoring an enhancement in mobility. Moreover, the diffusion matrix was applied to predict diffusion profiles between zirconium-bearing crystals and melts. We observed that even far from the composition field used for the matrix determination, predictions of zirconium diffusion profiles may be relevant and demonstrate the potential of this approach to evaluate crystal/melt dissolution behavior.; Les mobilités de cation à haute température, basées sur la méthode de diffusion multicomposante, ont été couplées à une étude structurale dans le système Na2O-CaO-Al2O3-SiO2-ZrO2 (NCASZ) à 1200°C et 1250°C. À partir d’une étude structurale utilisant la spectroscopie d’absorption des rayons X (XANES), le zirconium a été déterminé dans des sites de ccoordinence 6 dans la gamme de composition réduite de notre étude et aucun changement structurel significatif n’a été démontré par rapport à un verre quaternaire Na2O-CaO-Al2O3-SiO2 (NCAS) avec une composition similaire. En outre, les expériences de diffusion ont révélées que l’ajout de zirconium dans la fonte quaternaire n’a aucune influence sur les vecteurs propres dominants qui correspondent à l’échange entre le calcium et le sodium. Malgré la diminution prévue de la mobilité résultant d’une augmentation de la viscosité lors de l’ajout de zirconium, la valeur propre dominante calculée dans cette étude est plus élevée lorsque Zr est introduit dans la structure du liquide. Ce résultat suggère fortement que la mobilité en sodium est renforcée par la présence de Zr, ce qui s’explique par un changement dans le rôle structurel du sodium depuis un rôle de modificateur de réseau associé aux sites Q3(Si) dans les liquides NCAS vers un rôle de compensateur de charge associé aux sites [ZrO6]2- dans les liquides NCASZ. Cette modification génère des forces de liaison plus faibles entre le sodium et d’autres cations dans le liquide, favorisant ainsi une amélioration de la mobilité. En outre, la matrice de diffusion a été appliquée pour prédire les profils de diffusion entre les cristaux porteurs de zirconium et les liquides. Nous avons observé que même loin du champ de composition utilisé pour la détermination de la matrice de diffusion, les prédictions des profils de diffusion du zirconium peuvent être pertinentes et démontrer le potentiel de cette approche pour évaluer le comportement de dissolution à l'interface cristal/liquide.

Under suitable conditions, an immersed granular bed can be destabilized by local thermal forcing and the induced buoyant force. The destabilization is evident from the triggering and establishment of a dense fluid-like granular plume. Varying the initial granular layer average height $h$, a time series of the free layer surface is extracted, allowing us to dynamically compute the underlying volume of the granular layer. Different observed phenomena, namely the initial interface deformation, the lowering of the average granular interface (i.e. decrease of the granular layer volume) and the emission of a plume, are analysed. We show that the phenomenon is mainly driven by heat transfer, for large $h$ and also involves a variable height thermal boundary condition and Darcy flow triggering, for small $h$. Simple modelling with no adjustable parameters not only allows us to capture the observed scaling power laws but is also in quantitative agreement with the obtained experimental data.

International audience; Periodic arrays of anisotropic silver nanoparticles having peculiar optical properties are fabricated at a macroscopic scale. The proposed scalable method is based on temperature‐assisted solid‐state dewetting of a continuous thin layer deposited on a silica substrate patterned by the nanoimprint technique. The resulting nanoparticles are shaped like diamonds and are half‐embedded into the patterned silica. A period‐dependent optimum in film thickness for the quality of spatial organization is found and discussed in terms of thermodynamics and, for the first time, in terms of the role of grains in the dewetting process. The optical properties of the arrays are driven by not only simply the particle shape but also the lattice period and the degree of order. A surface lattice resonance that disperses with the underlying period is evidenced experimentally and confirmed by optical simulations. The opportunity to fabricate and tune such an assembly of plasmonic particles on transparent substrate opens interesting perspectives for not only fundamental photonics but also potential optical applications.

Author(s): Sauret, Alban; Somszor, Katarzyna; Villermaux, Emmanuel; Dressaire, Emilie | Abstract: During the transport of colloidal suspensions in microchannels, the deposition of particles can lead to the formation of clogs, typically at constrictions. Once a clog is formed in a microchannel, advected particles form an aggregate upstream from the site of the blockage. This aggregate grows over time, which leads to a dramatic reduction of the flow rate. In this paper, we present a model that predicts the growth of the aggregate formed upon clogging of a microchannel. We develop an analytical description that captures the time evolution of the volume of the aggregate, as confirmed by experiments performed using a pressure-driven suspension flow in a microfluidic device. We show that the growth of the aggregate increases the hydraulic resistance in the channel and leads to a drop in the flow rate of the suspensions. We then derive a model for the growth of aggregates in multiple parallel microchannels where the clogging events are described using a stochastic approach. The aggregate growths in the different channels are coupled. Our work illustrates the critical influence of clogging events on the evolution of the flow rate in microchannels. The coupled dynamics of the aggregates described here for parallel channels is key to bridge clogging at the pore scale with macroscopic observations of the flow rate evolution at the filter scale.

International audience; Silicone elastomers such as polydimethylsiloxane (PDMS) are convenient materials routinely used in laboratories that combine ease of preparation, flexibility, transparency, and gas permeability. However, these elastomers are known to contain a small fraction of uncrosslinked low-molecular-weight oligomers, the effects of which are not completely understood, particularly when used in contact with liquids. Here, we show that triple lines involving air, water, and PDMS elastomers are responsible for the contamination of water–air interfaces by uncrosslinked silicone oligomers through a capillarity-induced extraction mechanism. We investigate both the case of static and moving contact lines and study various geometries ranging from partially immersed PDMS plates to water droplets or air bubbles deposited on PDMS plates, all involving air–water–elastomer triple lines. We demonstrate experimentally that the contamination timescale is strikingly shorter for moving contact lines than in the static case. Eventually, we propose a simple poroelastic model capturing the main features of contamination observed in experiments.

Band alignment at the interface between evaporated silver films and Zn- or O-terminated polar orientations of ZnO is explored by combining soft and hard x-ray photoemissions on native and hydrogenated surfaces. Ultraviolet photoemission spectroscopy (UPS) is used to track variations of work function, band bending, ionization energy, and Schottky barrier during silver deposition. The absolute values of band bending and the bulk position of the Fermi level are determined on continuous silver films by hard x-ray photoemission spectroscopy (HAXPES) through a dedicated modeling of core levels. Hydrogenation leads to the formation of $\ensuremath{\sim}0.3$ monolayer of donorlike hydroxyl groups on both ZnO-O and ZnO-Zn surfaces and to the release of metallic zinc on ZnO-Zn. However, no transition to an accumulation layer is observed. On bare surfaces, silver adsorption is cationic on $\text{ZnO}(000\overline{1})\text{-O}$ [anionic on ZnO(0001)-Zn] at the earliest stages of growth as expected from polarity healing before adsorbing as a neutral species. UPS and HAXPES data appear quite consistent. The two surfaces undergo rather similar band bendings for all types of preparation. The downward band bending of ${V}_{bb,\text{ZnO-O}}=\ensuremath{-}0.4$ eV and ${V}_{bb,\text{ZnO-Zn}}=\ensuremath{-}0.6$ eV found for the bare surfaces is reinforced upon hydrogenation (${V}_{bb,\text{ZnO-O}+\mathrm{H}}=\ensuremath{-}1.1$ eV, ${V}_{bb,\text{ZnO-Zn}+\mathrm{H}}=\ensuremath{-}1.2$ eV). At the interface with Ag, a unique value of band bending of $\ensuremath{-}0.75$ eV is observed. While exposure to atomic hydrogen modulates strongly the energetic positions of the surface levels, a similar Schottky barrier of 0.5--0.7 eV is found for thick silver films on the two surfaces.

International audience; A flexible fiber carrying a liquid drop may coil inside the drop thereby creating a drop-on-fiber system with an ultra-extensible behaviour. During compression, the excess fiber is spooled inside the droplet and capillary forces keep the system taut, while during elongation, the fiber is gradually released and if a large number of spools is uncoiled a high stretchability is achieved. This mechanical behaviour is of interest for stretchable connectors but information, may it be electronic or photonic, usually travels through stiff functional materials and high Young's modulus, leading to large bending rigidity, prevents in-drop coiling. Here we overcome this limitation by attaching a beam of soft elastomer to the functional fiber, thereby creating a composite system which exhibits in-drop coiling and carries information while being ultra-extensible. We present a simple model to explicate the underlying mechanics of the addition of the soft beam and we show how it favors in-drop coiling. We illustrate the method with a two-centimeter long micronic PEDOT:PSS conductive fiber joined to a PVS soft beam, showing the system conveys electricity throughout a 1900% elongation.

Silicon nitride is widely used in glass industry embedded in stacks of thin layers applied to functionalize glass for thermal, optical (antireflection) or self-cleaning applications. The deposition of these layers is made by magnetron sputtering on large surfaces with a great versatility. However, nanometric pores can be produced in these amorphous layers deposited with this technique which is detrimental for the durability of the products containing theses layers. This PhD thesis presents the development of a multiscale approach in order to characterize this nano-porosity combining two techniques: Transmission Electron Microscopy (TEM/STEM) and Electrochemical Impedance Spectroscopy (EIS). This analysis route is applied to study silicon nitride layers of different thicknesses. Furthermore, the impact of several parameters like the deposition pressure, the nitrogen partial pressure or the nature of the seed layer has been investigated.The nano-porosity of these layers is strongly dependent on the deposition conditions: pressure and thickness seem to be crucial for their nanostructure. For most of the cases, the morphology of this silicon nitride layer is divided in two main areas: a homogeneous area near the substrate and a columnar structure in the upper part of the layer. A quantitative description of the columnar area porosity is proposed and includes the estimation of the pores diameter and density, their change in morphology with the layer thickness, their percolation and the substrate accessible surface at the bottom of the through pores., Le nitrure de silicium est largement utilisé dans l’industrie verrière au sein d’empilements de couches minces permettant de fonctionnaliser le vitrage. Le dépôt de ces couches est réalisé par pulvérisation cathodique magnétron sur une large gamme de surfaces. Cette technique de dépôt génère cependant des pores nanométriques dans ces couches amorphes au détriment de la durabilité des produits au sein desquels elles sont employées. Cette thèse de doctorat présente le développement d’une approche multi-échelles de la caractérisation de cette nano-porosité en se basant sur l’association de deux techniques : la Microscopie Electronique en Transmission (TEM/STEM) et la Spectroscopie d’Impédance Electrochimique (EIS). Cette démarche est appliquée à l’étude de couches de nitrure de silicium de différentes épaisseurs. Par ailleurs, l’impact de certains paramètres comme la pression de dépôt, la pression partielle en azote ou encore la nature de la sous-couche de croissance a été investigué.La nano-porosité de ces couches est fortement dépendante des conditions de dépôt utilisées : la pression et l’épaisseur semblent déterminantes sur leur nanostructure. Dans la plupart des cas la morphologie de ces couches de nitrure de silicium se divisent en deux principales zones dans l’épaisseur : une couche homogène proche du substrat et une structure colonnaire occupant la partie supérieure de la couche. Une description quantitative de la porosité de cette zone colonnaire est proposée et comprend l’estimation du diamètre et de la densité des pores, l’évolution de leur morphologie dans l’épaisseur, leur percolation, ou encore la surface accessible en fond des pores traversant la couche.

This thesis focuses on the bubbles population that appears between two glass pieces when heated at 1100 °C without any reactive raw materials. Understanding the mechanisms involved in the transition from dissolved gas to gas is still a fundamental issue of materials science. Industrially, bubbles are the major sources of defects in the final glass product and the amount of recycled glass introduced in glass furnaces will likely increase.We have studied the life of a bubble at different times, from its creation to its growth behavior, and to its rise in the molten glass. We show that homogeneous nucleation cannot exist in molten glass because chemical reactions are not able to generate the needed supersaturations by themselves. Thus, right after glass transition, glass flow is responsible for the entrapment of gas pockets, which then become natural precursors of bubbles.We model the supersaturation at the interface between two glasses, and we show its influence over the number of stable nuclei that can form bubbles.We also model the growth dynamic by using the same characterization of glasses' oxidation states than for nucleation. We experimentally show that bubbles located at the interface between a reduced glass and an oxidized glass grow faster than bubbles located in an oxidized glass only. The main effect of the interaction between the two glasses is to move the sulfur equilibrium towards the formation of gaseous SO2.Finally, using X-rays and an optical flow algorithm, we present a new experimental setup which measure velocity fields in an opaque medium to assess bubbles ability to promote glass mixing., L'objectif de cette thèse est l'étude de la population de bulles générée entre deux morceaux de verre mis en contact et portés à 1100 °C sans matières premières. Comprendre la transition gaz dissous/gaz est un sujet scientifique majeur, par ailleurs les bulles sont le principal défaut dans les verres industriels et la quantité de verre recyclé introduite dans les fours est destinée à augmenter. Nous étudions la vie d'une bulle de sa nucléation à sa remontée dans le verre fondu en passant par sa croissance. Nous montrons que la nucléation homogène n'existe pas dans un verre car les réactions chimiques ne génèrent pas les sursaturations suffisantes. L'écoulement du verre après la transition vitreuse enferme des poches de gaz qui sont les précurseurs naturels des bulles. Nous modélisons la sursaturation à l'interface entre deux verres et montrons son influence sur le nombre de nuclei stables qui forment des bulles. Nous modélisons la dynamique de croissance des bulles en utilisant la même caractérisation de l'état d'oxydation que pour la nucléation. Nous constatons que la croissance des bulles à l'interface entre un verre réduit et un verre oxydé est plus rapide que celle des bulles situées dans un verre oxydé seul. Nous attribuons cette accélération à l'interaction entre les verres qui décale l'équilibre du soufre vers la formation de SO2 gazeux. Pour finir, nous présentons un montage expérimental qui permet de mesurer des champs de vitesse dans du verre grâce à l'utilisation de rayons X et à un algorithme de flot optique. Cette mesure permet d'évaluer la capacité d'une population de bulles à favoriser le mélange du verre au début de la fusion.

International audience; Multicomponent chemical diffusion has been investigated in the SiO2-Na2O-B2O3 system for melts with an average composition (mol.%) of 68SiO2-18B2O3-14Na2O. Three diffusion couples were studied at 5 different temperatures between 700 °C and 1100 °C. The extended form of Fick's second law was used to fit the data, derive the diffusion matrix at each temperature, and quantify eigenvectors and eigenvalues. The results reveal diffusive mechanisms in chemical space (i.e. eigenvectors) that appear constant over the temperature range studied. The principal eigenvector is characterized by an exchange between silicon and sodium, while the secondary eigenvector corresponds to an exchange between silicon and boron made possible by sodium. Eigenvalues vary considerably with temperature, but do not follow an Arrhenian law. This behavior has been attributed to the structural changes of the borosilicate network with temperature. The diffusion data are then compared with viscosity and ionic conductivity measurements, revealing close links between viscosity and chemical diffusion.

International audience; The resuspension and dispersion of particles occur in industrial fluid dynamic processes as well as environmental and geophysical situations. In this paper, we experimentally investigate the ability to fluidize a granular bed with a vertical gradient of temperature. Using laboratory experiments with a localized heat source, we observe a large entrainment of particles into the fluid volume beyond a threshold temperature. The buoyancy-driven fluidized bed then leads to the transport of solid particles through the generation of particle-laden plumes. We show that the destabilization process is driven by the thermal conductivity inside the granular bed and demonstrate that the threshold temperature depends on the thickness of the granular bed and the buoyancy number, i.e., the ratio of the stabilizing density contrast to the destabilizing thermal density contrast.

International audience; The present study focuses on the optical properties of functionalized surfaces and how the surface geometry impacts them. Physical measurements of reflected light are required to understand the visual aspect of such surfaces. Bidirectional Reflection Distribution Function (BRDF) is evaluated in order to identify and understand physical effects induced by different surface functionalization. BRDF measurements of high angular resolution allow us to observe diffraction phenomenon at an unusual scale. Experimental results were compared to theoretical calculation, and then diffraction effect was confirmed. This study stresses that diffractive phenomenon could have an impact on visual aspect even for simple pattern geometry. In the same way, if more complex periodic patterns are considered, as multistate periodicity pattern for example, it could rise to important modification of surface visual aspect.

International audience; Wet granular aggregates are common precursors of construction materials, food, and health care products. The physical mechanisms involved in the mixing of dry grains with a wet substrate are not well understood and dicult to control. Here, we study experimentally the accretion of dry grains on a wet granular substrate by measuring the growth dynamics of the wet aggregate. We show that this aggregate is fully saturated and its cohesion is ensured by the capillary depression at the air-liquid interface. The growth dynamics is controlled by the liquid fraction at the surface of the aggregate and exhibits two regimes. In the viscous regime, the growth dynamics is limited by the capillary-driven flow of liquid through the granular packing to the surface of the aggregate. In the capture regime, the capture probability depends on the availability of the liquid at the saturated interface, which is controlled by the hydrostatic depression in the material. We propose a model that rationalizes our observations and captures both dynamics based on the evolution of the capture probability with the hydrostatic depression.

International audience; We report an unexpected behavior in wetting dynamics on soft silicone substrates: the dynamics of aqueous droplets deposited on vertical plates of such elastomers exhibits two successive speed regimes. This macroscopic observation is found to be closely related to microscopic phenomena occurring at the scale of the polymer network: we show that uncrosslinked chains found in most widely used commercial silicone elastomers are responsible for this surprising behavior. A direct visualization of the uncrosslinked oligomers collected by water droplets is performed, evidencing that a capillarity-induced phase separation occurs: uncrosslinked oligomers are extracted from the silicone elastomer network by the water-glycerol mixture droplet. The sharp speed change is shown to coincide with an abrupt transition in surface tension of the droplets, when a critical surface concentration in uncrosslinked oligomer chains is reached. We infer that a droplet shifts to a second regime with a faster speed when it is completely covered with a homogeneous oil film.

Square arrays of gold (Au) hemispheroids deposited on a UV-transparent glass substrate reveal a rich optical response when investigated by spectroscopic Mueller Matrix Ellipsometry. Two samples were studied; the first consisted of hemispheroids of parallel radius of 58 nm and height 30 nm with lattice constant 210 nm; the corresponding parameters for the second sample were 38 nm, 20 nm and 125 nm, respectively. By a full azimuthal rotation of the samples, we observe all the Rayleigh anomalies corresponding to grazing diffracted waves, with strong resonances for co-polarization scattered light near the high symmetry points and cross-polarization scattered light around the Localized Surface Plasmon Resonance. Polarization-conversion becomes particularly important at grazing incidence, and the cross-polarization follows the Rayleigh lines. The optical response (neglecting polarization conversion) is modelled in the quasi-static approximation using the so-called Bedeaux-Vlieger formalism, and the Finite Element Method using COMSOL. The direct inversion of the effective (substrate dependent) dielectric function is discussed.

International audience; The transport of suspensions of microparticles in confined environments is associated with complex phenomena at the interface of fluid mechanics and soft matter. Indeed, the deposition and assembly of particles under flow involve hydrodynamic, steric and colloidal forces, and can lead to the clogging of microchannels. The formation of clogs dramatically alters the performance of both natural and engineered systems, effectively limiting the use of microfluidic technology. While the fouling of porous filters has been studied at the macroscopic level, it is only recently that the formation of clogs has been considered at the pore-scale, using microfluidic devices. In this review, we present the clogging mechanisms recently reported for suspension flows of colloidal particles and for biofluids in microfluidic channels, including sieving, bridging and aggregation of particles. We discuss the technological implications of the clogging of microchannels and the schemes that leverage the formation of clogs. We finally consider some of the outstanding challenges involving clogging in human health, which could be tackled with microfluidic methods.

In this PhD thesis, the scratch mechanisms during sliding contact on thin layers with low adhesion have been investigated with a ball on plane tribometer that allows in-situ microscopic observations. In this work, experiments were carried out on glass/ZnO/Ag/ZnO/Si3N4 model stacks and the impact of several parameters was studied: force, size of the ball, thickness of the overcoat, adhesion and friction coefficient.We have shown that the scratch process has three successive phases: initiation, development and steady state. Initiation begins with transverse cracks in the stack followed by delamination due to crack bifurcation at the interface above the silver layer. Only the characteristic size of these phenomena depends on parameters such as the thickness of the layer or its adhesion. After initiation, a phenomenon of pleating occurs even if confined under the contact and leads to the building of a pile of debris at the front of the contact zone by accumulation. Finally, in steady state, the scratch is only driven by the interaction between the pile of debris and the layers. It has been shown that the complexity of this interaction makes quasi-impossible any measure of adhesion based on the post mortem characteristics of the scratch.Finally, it has been shown that it is possible to improve the scratch resistance of a stack by patterning its silver layer at nanoscale. The origin of this improvement derives from an increase of adhesion due to pinning effect which has been demonstrated by using cleavage experiments., Dans cette thèse, les mécanismes de rayures en contact glissant sur des empilements de couches minces de faible adhésion ont été étudiés grâce à un tribomètre bille/plan à vision in-situ. Dans le cadre de ce travail, des expériences ont été menées sur un empilement modèle : verre/ZnO/Ag/ZnO/Si3N4 et l'impact de plusieurs paramètres a été étudié : force, taille de la bille, épaisseur de la surcouche, adhésion et coefficient de frottement.Nous avons montré que la rayure se déroule en trois phases successives : initiation, développement et régime stationnaire. L'initiation débute par une fissuration transverse de l’empilement suivi par un délaminage due à la bifurcation de la fissure à l’interface au-dessus de l’argent. Seule la taille caractéristique de ces phénomènes dépend de paramètres comme l'épaisseur des couches ou l'adhésion. Après l'initiation, un phénomène de plissage en milieu confiné se produit et permet de débuter la construction d'un tas de débris à l’avant du frotteur par accumulation. Finalement, en régime stationnaire, on constate que la rayure est uniquement pilotée par l’interaction entre le tas de débris et la couche. On a montré que la complexité de cette interaction rend toute mesure d’adhésion à partir des caractéristiques post-mortem de la rayure quasi-impossible.Finalement, il a été montré qu'il est possible d'améliorer la résistance à la rayure d’un empilement en texturant à l'échelle nanométrique sa couche d'argent. L’origine de cette amélioration vient d’une augmentation de l'adhésion par un effet de piégeage qui a été étudié à l'aide d'expériences de clivage.

International audience; Various materials are made of long thin fibers that are randomly oriented to form a complex network in which drops of wetting liquid tend to accumulate at the nodes. The capillary force exerted by the liquid can bend flexible fibers, which in turn influences the morphology adopted by the liquid. In this paper, we investigate through a model situation the role of the fiber flexibility on the shape of a small volume of liquid on a pair of crossed flexible fibers. We characterize the liquid morphologies as we vary the volume of liquid, the angle between the fibers, and the length of the fibers. The drop morphologies previously reported for rigid crossed fibers, i.e., a drop, a column and a mixed morphology, are also observed on flexible crossed fibers with modified domains of existence. In addition, at small tilt angles between the fibers, a new behavior is observed: the fibers bend and collapse. Depending on the volume of liquid, a thin column with or without a drop is reported on the collapsed fibers. Our study suggests that the fiber flexibility adds a rich variety of behaviors that may be important for some applications.

The crucial role of hydrodynamic pinch-off instabilities is evidenced in the coarsening stage of viscous liquids. The phase separation of a barium borosilicate glass melt is studied by in-situ synchrotron X-Ray tomography at high temperature. The high viscosity contrast between the less viscous phase and the more viscous phase induces a topological symmetry breaking: capillary breakups occur preferentially in the less viscous phase. As a result, contrasting morphologies are obtained in the two phases. This symmetry breaking is illustrated on three different glass compositions , corresponding to different volume fractions of the two phases. In particular, a fragmentation phenomenon, reminiscent of the end-pinching mechanism proposed by Stone et al. [1, 2] is evidenced in the less viscous phase.

This work considers a nearly spherical bubble and a nearly flat free surface interacting under buoyancy at vanishing Bond number Bo. For each perturbed surface, the deviation from the unperturbed shape is asymptotically obtained at leading order on Bo. The task appeals to the normal traction exerted on the unperturbed surface by the Stokes flow due to a spherical bubble translating toward a flat free surface. The free surface problem is then found to be well-posed and to admit a solution in closed form when gravity is still present in the linear differential equation governing the perturbed profile through a term proportional to Bo. In contrast, the bubble problem amazingly turns out to be over-determined. It however becomes well-posed if the requirement of horizontal tangent planes at the perturbed bubble north and south poles is discarded or if the term proportional to Bo is omitted. Both previous approaches turn out to predict for a small Bond number, quite close solutions except in the very vicinity of the bubble poles. The numerical solution of the proposed asymptotic analysis shows in the overlapping range Bo=O(0.1) and for both the bubble and the free surface perturbed shapes, a good agreement with a quite different boundary element approach developed in Pigeonneau and Sellier [“Low-Reynolds-number gravity-driven migration and deformation of bubbles near a free surface,” Phys. Fluids 23, 092102 (2011)]. It also provides approximated bubble and free surface shapes whose sensitivity to the bubble location is examined.

International audience; Two-phase flows driven by the interfacial dynamics is studied with a phase-field model to tract implicitly interfaces. The phase field obeys the Cahn-Hilliard equation. The fluid dynamics is described with the Stokes equations with an additional source term in the momentum equation taking into account the capillary forces. A discontinuous Galerkin finite element method is used to solve the coupled Stokes/Cahn-Hilliard equations. The Cahn-Hilliard equation is treated as a system of two coupled equations corresponding to the advection-diffusion equation for the phase field and a non-linear elliptic equation for the chemical potential. First, the variational formulation of the Cahn-Hilliard equation is presented. A numerical test is achieved showing the optimal-order in error bounds. Second, the variational formulation in discontinuous Galerkin finite element approach of the Stokes equations is recalled in which the same space of approximation is used for the velocity and the pressure with an adequate stabilization technique. Finally, numerical simulations describing the capillary rising in a tube is presented.

International audience; Numerical simulations of two-phase flows driven by viscosity (e.g. for bubble motions in glass melting process) rely on the ability to efficiently compute the solutions to discretized Stokes equations. When using boundary element methods to track fluid interfaces, one usually faces the problem of solving linear systems with a dense matrix with a size proportional to the system number of degrees of freedom. Acceleration techniques, based on the compression of the underlying matrix and efficient matrix vector products are known (Fast Multipole Method, H-matrices, etc.) but are usually rather cumbersome to develop. More recently, a new method was proposed, called the " Sparse Cardinal Sine Decomposition " , in the context of acoustic problems to tackle this kind of problem in some generality (in particular with respect to the Green kernel of the problem). The proposed contribution aims at showing the potential applicability of the method in the context of viscous flows governed by Stokes equations.

International audience; Nuclear Magnetic Resonance and Raman spectra are often noisy, especially for distributed environments. Singular Value Decomposition (SVD) and low-rank approximation are useful tools to denoise spectra. However, processing time can be significantly different depending on which algorithm we use. Java, Matlab and Python were used to compare computation time either from Central Processing Unit (CPU) and Graphics Processing Unit (GPU).

National audience; Singular Value Decomposition (SVD) is a mathematical tool that can be used to remove noise from spectra. In this article, we used it on Nuclear Magnetic Resonance and Raman spectra. The results proved that this technique can be very efficient, either on a single 1D spectrum or on an array of spectra and that it can be easily generalised. We compared execution time on a few processors and graphic cards with Java, Matlab and Python. Impressive differences were seen, probably due to the used optimisations. Execution time is now short enough to apply SVD on continuous experiments.

International audience; We experimentally study the rate of chaotic mixing in viscoplastic fluids, by using a rod-stirring protocol with a rotating vessel. Only a limited zone localized around the stirring rods is highly sheared at a given time. Using a dyed spot as initial condition, we measure the decay of concentration fluctuations of dye as mixing proceeds. The mixing rate is found to be proportional to the volume of highly-sheared fluid during a rotation period of the rods, and inversely proportional to the number of rotations of the rods over a rotation of the vessel. Thanks to numerical simulations and experimental measurements, we relate the volume of highly-sheared fluid to the parameters of the flow. We propose a quantitative two-zone model for the mixing rate taking into account the geometry of the highly-sheared zone, as well as the rate at which fluid is renewed inside this zone. For all experiments, the model predicts correctly the scaling of the exponential mixing rates during a first rapid stage, and a second slower one.

International audience; The plastic behavior of silicate glasses has emerged as a central concept for the understanding of glass strength. Here we address the issue of shear-hardening in amorphous silica. Using in situ SEM mechanical testing with a high stiffness device, we have been able to compress silica pillars to large strains while directly monitoring radial strain. The sizeable increase of pillar cross-section during compression directly demonstrates the significant role of homogeneous shear flow. From the direct evaluation of the cross section, we have also measured true stress-strain curves. The results demonstrate that silica predominantly experiences plastic shear flow but that there is no shear-induced hardening. The consequence of this finding for our understanding of glass strength is discussed.

International audience; We consider the possibility of monitoring silver solid-state dewetting with in situ ellipsometry. We first study the optical response of partially dewetted samples in correlation with their morphological structure measured by Atomic Force Microscopy (AFM). We find that the main features observed in microscopy are identifiable in ellipsometry spectra. Then, we analyse the dielectric function extracted from in situ measurements to predict the progression in the dewetting process. We also identify two different behaviours leading to different final states.

International audience; We have carried out wetting experiments on textured surfaces with high aspect ratio asperities in the Wenzel state. When inclination is imparted to the asperities, we observe a strictly unidi-rectional spreading opposite to the direction in which the asperities point. The advancing contact angle decreases markedly as inclination increases. A crude numerical analysis successfully accounts for this behaviour, highlighting the interplay between Gibbs pinning at the top of the structures and imbibition along the valleys between them. In Gibbs pinning non-linearities play a major role and we find that simple line averaging-i.e. a rule of mixture-cannot account for this evolution except for weak surface perturbations, i.e. large inclinations.

This thesis focuses on the physical and chemical transformations undergone by a granula glass batch during the glass making process. Industrial window or container glass batches are complex mixtures, that we approached by the ternary oxide system SiO2-CaO-Na2O. Industrial raw materials, namely silica sand, limestone and sodium carbonate, are used. This simplification makes it possible to study the coupling between the granular microstructure and the physical and chemical transformations during the heating. Indeed, the multiple possible reaction paths propagate the heterogeneity of the granular batch to the glass. To support our study of the ternary system, two sub-system are investigated. On one hand, reactions between sodium disilicate and 4 calcium-bearing species (CaCO3, CaO, CaSiO3, Ca2SiO4) show the formation of successive layers of crystalline intermediate species between the dissolving grains and the molten silicate. On the other hand, sodium calcium mixed carbonate is synthesized ex situ and characterized. Its formation in a ternary glass batch is observed in situ, and its reactivity with silica is studied. In a ternary soda-lime glass batch, X-ray in situ and ex situ microtomography reveals the significance of wetting and degassing phenomena in orienting the grains towards a reaction path. Conversion of a limited depth of limestone grains into mixed carbonate for a short time is notably witnessed. This mechanism is strongly dependent on the grains surrounding limestone particles. Finally, we use an innovative deconvolution procedure to measure the impact of granulometry and the nature of calcium-bearing raw materials on the final glass homogeneity.; L'objectif de cette thèse est d'étudier les transformations physico-chimiques lors de l'élaboration d'un verre à partir d'un mélange granulaire. Les mélanges vitrifiables industriel formant des verres de vitrage ou de conditionnement sont approchés par le système à trois oxydes SiO2-CaO-Na2O, apportés sous forme de sable, de calcaire et de carbonate de sodium. Cette simplification permet d'étudier le lien entre microstructrure de l'empilement granulaire et transformations pendant le chauffage. La variété des chemins réactionnels entre les grains de matières premières transmet en effet l'hétérogénéité du mélange au verre. Le système ternaire est décomposé en deux sous-systèmes. D'une part, les réactions entre le disilicate de sodium et 4 porteurs de calcium (CaCO3, CaO, CaSiO3, Ca2SiO4) révèlent la formation de couches d'espèces cristallines entre le grain calcique en cours de dissolution et le silicate fondu. D'autre part, la synthèse ex situ de carbonate mixte de calcium et de sodium est réalisée. Ce produit est analysé et caractérisé ; son apparition in situ dans un mélange ternaire est observée, et sa réaction avec la silice est étudiée. Dans un mélange vitrifiable silico-sodocalcique, la tomographie X in situ et post mortem montre l'importance de phénomènes transitoires de mouillage et de dégagement gazeux qui orientent les réactions chimiques. En particulier, un mécanisme local et de courte durée convertit une profondeur limitée des grains de calcaire en carbonate mixte. Enfin, l'homogénéité du verre obtenu à 1300°C est étudiée à l'aide d'une méthode de déconvolution de spectres Raman innovante, pour plusieurs granulométries et espèces porteuses de calcium.

International audience; Novel statistical analysis and machine learning algorithms are proposed for the deconvolution and interpretation of Raman spectra of silicate glasses in the Na 2 O-CaO-SiO 2 system. Raman spectra are acquired along diffusion profiles of three pairs of glasses centered around an average composition of 69. 9 wt. % SiO 2 , 12. 7 wt. % CaO , 16. 8 wt. % Na 2 O. The shape changes of the Raman spectra across the compositional domain are analyzed using a combination of principal component analysis (PCA) and sparse non-negative matrix factorization (NMF). This procedure yields components accounting for the observed changes , as well as their mixing proportions , without any direct prior assumption as to their actual shape , number or position. These methods are applied separately to the Q band (wavenumbers in the range 850 – 1400 cm −1) , the main band (200 – 850 cm −1) and to the whole spectra (200 – 1400 cm −1). Compositional profiles obtained by Electron Probe Micro-Analysis (EPMA) are then used to relate spectral components to structural entities. Spectral components extracted from a Q band analysis and a complete spectral analysis show significant similarities both in terms of shape of the components and their mixing proportions. This result implies a link between Q n species and the shift of the medium-range network features in the main band of the Raman spectra. To illustrate the possibilities of the method , a linear regression model is used to relate the proportions of spectral components derived from the Raman spectra to chemical composition. This model can be used to determine the composition of different glasses inside the investigated compositional domain with reasonable accuracy .

International audience; Transport of liquid drops in fibrous media occurs in various engineering systems such as fog harvesting or cleaning of textiles. The ability to tune or to control liquid movement can increase the system efficiency and enable new engineering applications. In this Letter, we experimentally investigate how partially wetting drops on a single fiber can be manipulated by vibrating the fiber. We show that a sliding motion along the fiber or a dripping of the drop can be triggered by standing waves. We identify the conditions on the drop volume, the fiber tilt angle and the amplitude and frequency of oscillations to observe these different behaviors. Finally, we experimentally illustrate that vibrations can be used to control the transport and the collection of water drops along a fiber using a combination of the sliding and dripping transitions.

International audience; The transport, dispersion and resuspension of particles occur in industrial fluid dynamical processes as well as environmental and geophysical situations. Whereas the resuspension of an immersed granular bed by fluid flows such as vortices or shear flows has been the focus of many studies, the ability to fluidize particles with a vertical gradient of temperature remains poorly understood. Using laboratory experiments with a localized heat source, we observe that a massive entrainment of particles into the fluid volume occurs beyond a threshold temperature. The buoyancy driven fluidized bed then leads to the transport of solid particles through the generation of particle-laden plumes. We show that the destabilization process is driven by the thermal conductivity inside the granular bed and demonstrate that the threshold temperature depends on the thickness of the granular bed and the buoyancy number, i.e. the ratio of the stabilizing density contrast to the destabilizing thermal density contrast.

International audience; We characterize the different morphologies adopted by a drop of liquid placed on two randomly oriented fibers, which is a first step toward understanding the wetting of fibrous networks. The present work reviews previous modeling for parallel and touching crossed fibers and extends it to an arbitrary orientation of the fibers characterized by the tilting angle and the minimum spacing distance. Depending on the volume of liquid, the spacing distance between fibers and the angle between the fibers, we highlight that the liquid can adopt three different equilibrium morphologies: (1) a column morphology in which the liquid spreads between the fibers, (2) a mixed morphology where a drop grows at one end of the column or (3) a single drop located at the node. We capture the different morphologies observed using an analytical model that predicts the equilibrium configuration of the liquid based on the geometry of the fibers and the volume of liquid.

International audience; In this paper, we study analytically the flow in a rotating container subjected to an azimuthal forcing. We show that this mechanical forcing generates a correction to the solid body rotation called mean zonal flow, similar to the time oscillation of the rotation rate of an axisymmetric container. This axisymmetric correction induced by nonlinear effects in the Ekman layers modifies the solid body rotation of the fluid in the container. At the leading order, the contribution in the bulk is shown to be an azimuthal flow which scales as the square of the amplitude of the multipolar deformation and is independent of the Ekman number. We also show that the mean zonal flow depends on the symmetry of the angular forcing n and the ratio of the angular rate of the deformation to the angular rate of the cylinder ΩR = Ωorb /Ωspin. We found that for an elliptical forcing, n = 2, the rotation rate of the zonal flow does not depend on the radial position. In addition, the angular rate is found to be asymmetric with respect to ΩR. These scalings are similar to the time harmonic forcing in a cylinder. The particular case of a tidal forcing is also considered.

We perform experiments on the sloshing dynamics of liquids in a rectangular container submitted to an impulse. We show that when foam is placed on top of the liquid the oscillations of the free interface are significantly damped. The ability to reduce sloshing and associated splashing could find applications in numerous industrial processes involving liquid transport., Accepted for publication in Journal of Visualization

When a container is set in motion, the free surface of the liquid starts to oscillate or slosh. Such effects can be observed when a glass of water is handled carelessly and the fluid sloshes or even spills over the rims of the container. However, beer does not slosh as readily as water, which suggests that foam could be used to damp sloshing. In this work, we study experimentally the effect on sloshing of a liquid foam placed on top of a liquid bath. We generate a monodisperse two-dimensional liquid foam in a rectangular container and track the motion of the foam. The influence of the foam on the sloshing dynamics is experimentally characterized: only a few layers of bubbles are sufficient to significantly damp the oscillations. We rationalize our experimental findings with a model that describes the foam contribution to the damping coefficient through viscous dissipation on the walls of the container. Then we extend our study to confined three-dimensional liquid foam and observe that the behavior of 2D and confined 3D systems are very similar. Thus we conclude that only the bubbles close to the walls have a significant impact on the dissipation of energy. The possibility to damp liquid sloshing using foam is promising in numerous industrial applications such as the transport of liquefied gas in tankers or for propellants in rocket engines., Comment: 17 pages, accepted in Physics of Fluids

International audience; We investigate experimentally the drying of a small volume of perfectly wetting liquid on two crossed fibers. We characterize the drying dynamics for the three liquid morphologies that are encountered in this geometry: drop, column and a mixed morphology, in which a drop and a column coexist. For each morphology, we rationalize our findings with theoretical models that capture the drying kinetics. We find that the evaporation rate significantly depends upon the liquid morphology and that the drying of the liquid column is faster than the evaporation of the drop and the mixed morphology for a given liquid volume. Finally, we illustrate that shearing a network of fibers reduces the angle between them, changes the morphology toward the column state, and therefore enhances the drying rate of a volatile liquid deposited on it.

The axisymmetric gravity-driven dynamics of a bubble rising toward a free surface is addressed for gas-liquid interfaces having unequal surface tensions. The liquid flow is governed by the Stokes equations which are here solved using a boundary element method in axisymmetric configuration. Within this framework, two dimensionless numbers arise: the Bond number Bo1 based on the surface tension of the bubble interface and the surface tension ratio ˆ γ comparing the free surface and bubble surface tensions. Under a careful and discussed selection of the code key settings (number of boundary elements, initial bubble location, and distance beyond which the free surface is truncated), it has been possible to numerically and accurately track in time the bubble and free surface shapes for several values of (Bo1, ˆ γ). The long-time shapes are found to deeply depend upon both Bo1 and ˆ γ and also to compare well with the shapes predicted in Princen and Mason [“Shape of a fluid drop at a fluid-liquid interface. II. Theory for three-phase systems,” J. Colloid. Sci. 20, 246–266 (1965)] using a hydrostatic model in which both surfaces are touching. Similarly, the drainage dynamics of the liquid film thickness between the bubble and the free surface depends on (Bo1, ˆ γ). The long-time film thickness exponentially decays in time and a so-called thinning rate α for which the numerical behaviors and a simple model reveal two basic behaviors: (i) at small Bond number, α behaves as 1/Bo1 and (ii) at large Bond number, α is nearly constant. In addition, it is found that in the entire range of the quantity χ = (1 + ˆ γ)Bo1/(2 ˆ γ), the thinning rate α is well approximated by the function 1/(18 χ) + α∞ with α∞ ≈ 0.158. Such a result also permits one to estimate the typical drainage time versus the initial bubble radius a, the liquid density ρ and viscosity μ, the gravity and the free surface, and bubble surface tensions.

When droplets impact fibrous media, the liquid can be captured by the fibers or contact then break away. Previous studies have shown that the efficiency of drop capture by a rigid fiber depends on the impact velocity and defined a threshold velocity below which the drop is captured. However, it is necessary to consider the coupling of elastic and capillary effects to achieve a greater understanding of the capture process for soft substrates. Here, we study experimentally the dynamics of a single drop impacting on a thin flexible fiber. Our results demonstrate that the threshold capture velocity depends on the flexibility of fibers in a non-monotonic way. We conclude that tuning the mechanical properties of fibers can optimize the efficiency of droplet capture., Comment: Soft Matter (2015)

International audience; The temporal evolution of mechanical energy and spatially-averaged crack speed are both monitored in slowly fracturing artificial rocks. Both signals display an irregular burst-like dynamics, with power-law distributed fluctuations spanning a broad range of scales. Yet, the elastic power released at each time step is proportional to the global velocity all along the process, which enables defining a material-constant fracture energy. We characterize the intermittent dynamics by computing the burst statistics. This latter displays the scale-free features signature of crackling dynamics, in qualitative but not quantitative agreement with the depinning interface models derived for fracture problems. The possible sources of discrepancies are pointed out and discussed.

This thesis is devoted to the bubble(s) and solid particle(s) interactions near the surface of a liquid subject to gravity. Such case occurs during industrial glass process when bubbles and impurities, driven by gravity, gather below the surface of the liquid molten glass. The present work numerically investigates, in the viscous flow regime, the evolution in time of each interface (bubbles and molten glass surface) shape together with the thickness of the film occurring between two closes surfaces (drainage phenomenon). On each interface a competition takes place between different forces: the capillary one modeled by the interface uniform surface tension, the gravity one and the viscous one due to the liquid flow. The relative magnitude of these effects is estimated using the Bond number (comparing the gravity term to the capillary term) and the capillary number (comparing the viscous term to the capillary term) which are of the same order for particles with negligible inertia. The surface tension effect has been then quantified and discussed in a large range of Bond number for one bubble, several bubble(s) and clusters made of bubble(s) and solid particle(s)., La thèse porte sur les interactions entre des bulles et/ou des particules solides situées à proximité de la frontière d'un liquide soumis à l'action de la pesanteur. Cette situation est notamment rencontrée pour les bains de verre liquide dans lesquels les bulles et les impuretés se concentrent sous l'action de la seule gravité au voisinage immédiat de la surface du verre. Ce travail étudie numériquement, dans le cadre des écoulements visqueux, l'évolution temporelle de la déformation de chaque interface (bulle(s) et surface du verre) et de l'épaisseur du film liquide entre deux surfaces proches (phénomène de drainage). Sur chaque interface interviennent des forces capillaires (mesurées par la tension de surface uniforme), des forces de pesanteur et enfin des forces visqueuses dues à l'écoulement. L'importance relative de ces efforts est mesurée par le nombre de Bond (comparant termes de gravité et termes capillaires) et le nombre capillaire (comparant termes visqueux et termes capillaires) qui pour nos particules d'inertie négligeable sont du même ordre de grandeur. L'influence des tensions de surface et du nombre de Bond a ainsi été mise en évidence et commentées dans les cas d'une seule bulle, de plusieurs bulles et enfin de bulles et de sphères solides.

This manuscript deals with the coupled diffusion in an industrial glass system containing four oxides (SiO2, Al2O3, CaO, Na2O). The temperature range extends from the glass transition temperature (650°C) to the liquidus (1200°C). The first results concern the macroscopic nature of diffusion. The matrix containing the diffusion coefficients quantifies the mobility of the components and highlights many interactions between them. Other information can be obtained at the microscopic scale. The exchange equations summarize the main diffusion paths followed by the system in reactions form. All the data from the literature are processed and they seem to converge towards preferential diffusion paths. Hypothesis about the mechanisms of diffusion of the species are proposed. The results obtained at low temperatures open a discussion of the relationship between transport properties and diffusion. The study of the structure of the material was based on Raman spectroscopy. Diffusion experiments provide a large number of glass compositions, which allowed us to develop a statistical tool for handling spectra. The spectral components thus obtained are discussed in the light of the many observations described in the literature. This approach allowed us to interpret the components through correlations between their relative intensities and the composition of the material and by studying their evolution along the diffusion profiles. The possibility of a Raman spectroscopy technique for quantifying species is discussed., Cette thèse traite de la diffusion couplée dans un système verrier industriel contenant quatre oxydes (SiO2, Al2O3, CaO, Na2O). La gamme de températures considérée s’étend de la transition vitreuse (650°C) au liquidus (1200°C). Les premiers résultats concernent la nature macroscopique de la diffusion. La matrice des coefficients de diffusion permet de quantifier la mobilité des composants et met en évidence de nombreuses interactions entre eux. D’autres informations sont obtenues à l’échelle microscopique. Les équations d’échanges synthétisent les principaux chemins de diffusion suivis au sein du système sous la forme de réactions. L’ensemble des données de la littérature est traité et semble converger vers des chemins de diffusion préférentiels. Des hypothèses sur les mécanismes de la diffusion des espèces sont proposées. Les résultats obtenus à basse température permettent de discuter les liens entre propriétés de transport et diffusion. L’étude de la structure du matériau s’est appuyée sur la spectroscopie Raman. Les expériences de diffusion donnent accès à un grand nombre de compositions verrières, permettant ainsi de développer un outil statistique de traitement des spectres. Les composantes spectrales ainsi obtenues sont discutées à la lumière des nombreuses observations décrites dans la littérature. Cette démarche permet également d’interpréter les composantes au travers des corrélations entre leurs intensités relatives et la composition du matériau ainsi qu’en étudiant leur évolution le long des profils de diffusion. La possibilité de faire de la spectroscopie Raman une technique de quantification des espèces est discutée.

III–V semiconductors are materials of interest for energy production and lighting. However, these materials are difficult to grow by heteroepitaxy because of their lattice and thermal expansion coefficient mismatches with substrates. The resulting dislocations are extremely detrimental to their electronic properties. Nanostructures like nanowires relax efficiently the strain, thanks to their lateral free surfaces. Thus, they improve the material quality compared to planar thin films.In this PhD thesis, we demonstrate that a [111] fiber-textured polycristalline silicon layer film can be an efficient thin film substrate for oriented nanowire growth on an amorphous support. Such a film can be obtained by using the aluminum-induced crystallization of amorphous silicon. The optical and physical properties of the substrate are conserved by using a very thin Si layer (less than 10-nm thick).For many applications, organizing the nanowires in an array can be favorable. We demonstrate that this goal can be achieved by using small single crystal Si platelets (up to 100 nm in diameter). In a first time, the crystallization of these “nano-substrates” is comprehensively studied in order to define precise fabrication recipes. In a second time, we prove the concept of nanowire growth on these thin lithographed crystals.; Les semiconducteurs III–V sont des matériaux de choix pour la production d’électricité ou pour l’éclairage. En revanche, ce sont des matériaux difficiles à mettre en oeuvre sous la forme de couches minces bidimensionnelles par hétéro-épitaxie en raison des forts écarts de paramètres de mailles et de coefficient d’expansion thermique avec les substrats. Il en résulte notamment de nombreuses dislocations très préjudiciables pour les propriétés de ces semiconducteurs. Une manière pour réduire cette quantité de défauts est d'utiliser le semiconducteur sous la forme de nanostructures, telles que les nanofils.Nous démontrons dans cette thèse de doctorat qu’un film polycristallin de silicium, s’il est doté d’une texture de fibre [111], est un candidat de choix pour jouer le rôle de substrat couche mince pour la croissance épitaxiale de nanofils orientés, sur un support amorphe. Un tel film peut être obtenu à grande échelle par cristallisation du silicium amorphe induite par l’aluminium. L’utilisation d’une couche très mince (moins de 10 nm) permet alors de profiter avantageusement des propriétés optiques du substrat.Pour de nombreuses applications, il peut être profitable de pouvoir localiser les nanofils selon un schéma prédéfini. Nous démontrons que cet objectif peut être réalisé grâce à l’emploi de plaquettes monocristallines de Si de quelques dizaines de nanomètres de diamètre. La cristallisation de ces véritables nano-substrats est tout d’abord étudiée en détails afin d’élaborer une recette robuste de fabrication. Dans un second temps, nous démontrons le concept de croissance de nanofils sur ces minces cristaux lithographiés.

International audience; Straight cracks are observed in thin coatings under residual tensile stress, resulting into the classical network pattern observed in china crockery, old paintings, or dry mud. Here, we present a novel fracture mechanism where delamination and propagation occur simultaneously, leading to the spontaneous self-replication of an initial template. Surprisingly, this mechanism is active below the standard critical tensile load for channel cracks and selects a robust interaction length scale on the order of 30 times the film thickness. Depending on triggering mechanisms, crescent alleys, spirals, or long bands are generated over a wide range of experimental parameters. We describe with a simple physical model, the selection of the fracture path and provide a configuration diagram displaying the different failure modes.

Granular media, dry and wet, are ubiquitous in natural environment and industry. However, how to mix a liquid in a granular medium is still an open question. More precisely, the mechanisms implied in the mixing and the related physics are not known. How will evolve a heterogeneous system containing highly saturated areas and dry areas, whose properties are very different? This work starts with the study of the erosion mechanism of a wet cohesive granular medium by a dry flow. The first part focuses on the dynamics of the process in a tumbler. We have showed that the liquid properties have a special influence on the capillary bridges rupture dynamics. On the other hand, fluctuations of the stress applied by the flow have proved to be crucial in this phenomenon. An inclined channel setting for the granular erosion has revealed an instability, based on the coupling between erosion and the shape of the interface. We have determined the conditions of occurrence of this instability, and described the morphology of the created structures. Finally, we have studied the accretion mechanism, involved in the liquid transport by the creation of new capillary bridges, allowing to agglomerate grains., Les milieux granulaires, secs et humides, sont omniprésents dans la nature et également dans l'industrie. Néanmoins, à ce jour la façon dont est obtenue un mélange de liquide avec un matériau granulaire est mal connue. En particulier, on ignore les mécanismes permettant de réaliser le mélange, et la physique qui les gouverne. Comment un système hétérogène avec des zones riches en liquide et d'autres sèches, aux propriétés très différentes, va-t-il évoluer ? Ce travail commence par l'étude du mécanisme d'érosion d'un milieu granulaire humide et cohésif par un écoulement sec. Une première partie traite de la dynamique de ce processus dans une géométrie de tambour tournant. Nous avons pu observer que les propriétés des liquides impliqués ont une influence particulière sur la dynamique de rupture des ponts capillaires. Par ailleurs, les fluctuations de contrainte de l'écoulement se sont révélées cruciales dans ce phénomène. La mise en œuvre de l'érosion granulaire dans une géométrie de canal incliné a permis d'observer un phénomène d'instabilité basé sur le couplage entre l'érosion et la forme de l'interface. Nous avons déterminé les conditions d'existence de cette instabilité, et détaillé la morphologie des structures créées. Enfin nous avons étudié le mécanisme d'accrétion, qui participe au transport du liquide par la création de nouveaux ponts capillaire permettant l'agglomération de grains.