The general objective of this thesis is to conduct experiments on sphere free-falling in liquid that advance our understanding of the drag reduction on solids moving in liquid by means of lubricating gas layers and attached streamlined air cavities. Part I of the thesis investigates the effect of thin air layers, naturally sustained on superhydrophobic surfaces, on the terminal velocity and drag force of metallic spheres free- falling in water. The surface of 20 mm to 60 mm steel or tungsten-carbide spheres is rendered superhydrophobic by a simple coating process that uses a commercially available hydrophobic agent. By comparing the free-fall of unmodified spheres and superhydrophobic spheres, in a 2.5 meters tall water tank, it is demonstrated that even a very thin air layer (~ 1 – 2 μm) that covers the freshly dipped superhydrophobic sphere, can reduce the drag force on the spheres by up to 80 %, at Reynolds numbers 105 to 3×105, owing to an early drag crisis transition. Part II of the thesis investigates the drag reduction by means of the dynamic Leidenfrost vapor-layer sustained on the surface of heated metallic spheres free-falling in a fluorocarbon liquid, FC-72 (perfluorohexane). In these experiments we employed two tall liquid tanks: a 3 meter tall 14 cm wide tank and a 2 meter tall 20 × 20 cm cross-section tank with a heater device. These tanks are significantly larger than the tanks used in prior studies and allow us to track the extended fall trajectories and to compare the drag on room-temperature no-vapor-layer spheres to that of heated Leidenfrost vapor-layer spheres. Analysis of the extended free-fall trajectories and acceleration, based on the sphere dynamic equation of motion, enables the accurate evaluation of the vapor-layer-induced drag reduction, without the need for extrapolation. We demonstrate that the drag on the Leidenfrost sphere in FC-72, can be as low as CD = 0.04 ± 0.01, or an order of magnitude lower than the values for the no-vapor-layer spheres in the subcritical Reynolds number range. This drag reduction extends into the supercritical Reynolds number range. The analysis method developed herein, to describe the sphere trajectories, can be applied in other related studies. Part III of the thesis examines a recently demonstrated phenomenon of the formation of stable-streamlined gas cavity following the impact of a heated Leidenfrost sphere on a liquid surface or a superhydrophobic sphere on water. The sphere encapsulated in a teardrop-shaped gas cavity was found to have near-zero hydrodynamic drag due to the self-adjusting streamlined shape and the free-slip boundary condition on the cavity interface. Here it is shown that such cavities can be formed following the water impact from a sufficient height of non-superhydrophobic spheres with water contact angles between 30° and 120°. In this case the streamlined cavity is attached just above the sphere’s equator, instead of entirely wrapping the sphere. Nevertheless, this sphere with attached cavity has near-zero drag and predetermined free-fall velocity in compliance with the Bernoulli law of potential flow. Last, the effect of surfactant addition to the water solution is investigated. The shape and fall velocity of the sphere with streamlined cavity formation were unaffected by the addition of low-surface-modulus synthetic surfactants, but was destabilised when a solution containing high-surface-modulus surfactants, such as soaps were used.

The possibility of using supercritical carbon dioxide (scCO2) as the primary solvent in a spray process for producing superhydrophobic surfaces have been examined in this work. Using scCO2 as solvent will have considerably lower environmental impact compared to an organic solvent since scCO2 is considered a green solvent as it is non-toxic, non-flammable and recyclable. To be able to work at the pressures needed to reach the supercritical state of carbon dioxide, a high-pressure technique called rapid expansion of supercritical solutions (RESS) has been used to produce the coatings. Fluorinated compounds are often used when producing superhydrophobic coatings due to their intrinsic water repellent properties, but generally these compound do not degrade in nature. Due to this, a wax and a biodegradable polymer have been used as the coating materials in this work. Two RESS set-ups were used to spray a polymer from solutions of scCO2 and acetone. The first system was based on a continuous flow of the solvent mixture and the polymer particles were collected on silica surfaces. Some of the coatings had superhydrophobic properties and the limitation with this technique was the loss of particles between the nozzle and the surface. In the second set-up, RESS was combined with electrostatic deposition (ED) to improve the particle collection. Different processing parameters were examined and most of the RESS-ED sprayed surfaces were superhydrophobic. This was demonstrated by high contact angles against water, low contact angle hysteresis and low tilt angles at which a water droplet rolls off the surface. It was also shown that the surface structures created when spraying using RESS-ED induced the important two-level roughness that was needed to achieve superhydrophobicity. A semi-continuous process for scaling-up the RESS system when spraying the wax has been developed. Temperature and pressure was investigated to find the highest solubility of the wax in scCO2, and 250 bar and 67 °C resulted in the largest amount of sprayed wax. It was also shown that the system is suitable for spray-coating the wax on different substrates such as glass, paper, aluminium etc. since all of these surfaces showed superhydrophobic properties. The wear resistance of the coatings were examined by different methods. Scratch resistance, vertical compression and the friction between the surface and a finger were analysed. The polymer coated surfaces showed a larger robustness compared with the wax surfaces in the scratch tests. The superhydrophobicity was lost for the wax coatings exposed to compression loads above 59 kPa and in the frictions test, one finger stroke over the coating destroyed the surface roughness. Finally, the wax surfaces were investigated as coating barriers to protect steel from corrosion. The superhydrophobic coating was stable up to 10 days before corrosion of the steel started. / <p>QC 20140922</p>

Magnesium and its alloys have many interesting properties and thanks to them it can be used in many applications (transport industry, medicine etc.). Disadvantage of these materials is their high corrosion rate. For this reason, there is an effort to achieve high corrosion resistance through different modifications of magnesium and its alloys. In recent years the superhydrophobization of the surface seem to be an attractive solution for this question. This type surface modification minimalize contact between the surface and water. In this diploma thesis the superhydrophobic surface was created on the magnesium alloy AZ91. The first step included pretreatment of AZ91 surface by etching in solution of SnCl2 or ZnCl2. Next step was superhydrophobization in the ethanolic solution of stearic acid. The surface morphology and elemental analysis of the superhydrophobic coating were explored by use of scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS). The adhesion properties of the coating on the AZ91 were analysed by means of scratching test. Contact and sliding angles were measured for superhydrophobic coatings. Electrochemical characterization of the coatings was determined using potentiodynamic polarization (PD) and electrochemical impedance spectroscopy (EIS). Finally, the analysis of composition and the functional groups was made using Fourier-transform infrared spectroscopy (FTIR) and the phase composition analysis was performed using X-ray diffraction (XRD). The results show that the coatings prepared by etching did not lead to good corrosion properties, even though the value of contact angle was about 150 °. The reduction of corrosion resistance could be caused by not obtaining required surface morphology or insufficient binding of stearic acid in the form of stearate to the sample surface.

No description available.

Functional coatings produced using scalable and cost-effective processes such as electrodeposition and etching lead to the creation of random roughness at multiple length scales on the surface. The first part of thesis work aims at developing a fundamental mathematical understanding of multiscale coatings by presenting a fractal model to describe wettability on such surfaces. These surfaces are described with a fractal asperity model based on the Weierstrass-Mandelbrot function. Using this description, a model is presented to evaluate the apparent contact angle in different wetting regimes. Experimental validation of the model predictions is presented on various hydrophobic and superhydrophobic surfaces generated on several materials under different processing conditions. Superhydrophobic surfaces have myriad industrial applications, yet their practical utilization has been severely limited by their poor mechanical durability and longevity. Toward addressing this gap, the second and third parts of this thesis work present low cost, facile processes to fabricate superhydrophobic copper and zinc-based coatings via electrodeposition. Additionally, systematic studies are presented on coatings fabricated under different processing conditions to demonstrate excellent durability, mechanical and underwater stability, and corrosion resistance. The presented processes can be scaled to larger, durable coatings with controllable wettability for diverse applications. Apart from their use as superhydrophobic surfaces, the application of multiscale coatings in photo-thermal conversion systems as solar selective coatings is explored in the final part of this thesis. The effects of scale-independent fractal parameters of the coating surfaces and heat treatment are systematically explored with respect to their optical properties of absorptance, emittance, and figure of merit (FOM). / Master of Science

Lors de la polymérisation en suspension du chlorure de vinyle, il se forme sur les parois un dépôt de polychlorure de vinyle (PVC). Ce phénomène, nommé encroûtement, génère des problèmes car il limite la production de PVC et affecte la qualité du produit final. Dans ce contexte, un projet FUI (Fond Unique Interministériel) intitulé «Ecoating», a été financé dans le cadre d’une collaboration entre plusieurs partenaires industriels et universitaires (INEOS ChlorVinyls, Mäder Research, Avenir Group, LPIM, ESPCI-ParisTech). Deux thèses ont vu le jour au LPIM, avec pour but de développer un revêtement (photo)polymère aux propriétés anti-encroûtement durables qui permettrait d’améliorer la qualité du PVC produit, d’augmenter les quantités produites et ainsi d’améliorer la compétitivité des usines de PVC. Cette thèse s’inscrit dans le développement d’un vernis photopolymère répondant au cahier des charges. Pour éviter l’encroûtement des réacteurs, il est nécessaire de stopper une étape du mécanisme d’encroûtement comme l'adsorption sur les parois du réacteur d’un copolymère nommé Acvagen Graft Copolymer (AGC). Ce copolymère est très actif dans le phénomène d’encroûtement (site de nucléation) et se trouve principalement dans la phase aqueuse du milieu réactionnel. La stratégie de recherche élaborée dans ce projet a été basée sur le développement d'un revêtement photopolymère présentant une faible affinité pour l'eau et devant adhérer à la surface des réacteurs pour éviter la formation de croûte. Les polymères à base de fluoroacrylates ont été les premiers candidats choisis dans cette étude du fait que leurs propriétés exceptionnelles (faible énergie de surface, stabilité chimique et haute hydrophobicité...) pouvaient éviter l'adsorption de l'AGC sur les parois du réacteur, et par conséquent le développement de la croûte. Une recherche bibliographique a été réalisée pour comprendre le comportement particulier de ces molécules qui migrent vers la surface du film et s’organisent en surface pour donner des surfaces hydrophobes. Des mélanges de résines fluoroacryliques modèles ont été testés pour évaluer le caractère hydrophobe du revêtement, comprendre la migration des molécules de fluor vers l’interface en fonction de la nature de substrat et aussi déterminer l’influence de l’ajout d’additifs fluorés au mélange sur les propriétés globales du film. Cette étude nous a permis de comprendre l’influence de l’additif fluoré sur les propriétés chimiques et physiques du film. À l’échelle du laboratoire des tests d’immersion de ces revêtements déposés sur l’acier inoxydable ont étés réalisés dans l’eau chaude (80°C) afin de caractériser leur caractère hydrophobe en fonction du vieillissement dans l’eau chaude ainsi que l’adhésion du film au substrat. Nous avons observé une diminution de l'hydrophobicité de la surface du film au cours du temps lors d’une immersion. [...] / Our scientific approach has explored different strategies to develop a durable UV-cured coating with antifouling properties to prevent the crust formation. Firstly, the potential of fluoroacrylate photocurable coatings was exhaustively investigated. Indeed, their outstanding properties (low surface energy, chemical stability and high hydrophobicity...) could limit the adsorption of the AGC on the reactor walls and further encrusting. A bibliographic research highlighted the behavior of fluorinated monomers on film surface and the parameters affecting the hydrophobic properties. Different fluorinated monomers were selected. At low concentration, they provide hydrophobic surfaces on 316L stainless steel, the reference substrate. However, a decrease of the films surface hydrophobicity in hot water was observed with time, and was attributed to a disorganization of the fluorinated chains on the coating surface. An optimization of the amount of fluoroacrylate monomer was performed by confocal Raman microscopy (CRM) to promote the fluorinated chains stability on the surface before and after immersion in hot water at 80°C. The beneficial effect was found maximal at a concentration ranging from 1 to 1.8 wt%. However, even after this optimization, a decrease of the film surface hydrophobicity was observed for increased immersion time in hot water. Therefore, optimized fluoroacrylate monomer concentration was combined with alternated thermal/immersion post-treatment and has conducted to more stable photocured films. This result was attributed to a rigidification of the fluorinated chains on the film surface limiting thus, the extent of their disorganization. After this study realized at a laboratory scale, we tested the photocured coating in the VCM pilot reactor. A surface cleaning, an increase of the stainless steel roughness by shot blasting and the use of alkoxysilanes as coupling agents were implemented in order to enhance the adhesion properties of the photopolymer film on stainless steel. In addition, the use of a fluorinated monomer containing a heteroatom improved the rigidification when associated with the alternated thermal/immersion post-treatment. The crust formation was limited during four successive polymerizations in the VCM pilot reactor. A durable anti-fouling UV-coating could be not obtained due to some swelling phenomena resulting from the lack of coating adhesion or some abrasion occurring from small PVC pellets during the PVC polymerization.A second part of this project was dedicated to superhydrophobic coatings. Indeed, reducing interaction with water should lead to a better protection of the substrate. A literature review on the superhydrophobic surfaces has shown that the contact with hot water generally strongly affects their antiwetting properties and induces a large contact angle decrease. [...]