Since metals in general, and steels in particular, are vital construction materials in our modern society, the corrosion protection of said materials is of great importance, both to ensure safety and to reduce costs associated to corrosion. Previously, chromium (VI) and other harmful substances were effectively used to provide corrosion protection to steel, but since their use was heavily regulated around year 2000, no coating has yet been developed that, in a fully satisfactory manner, replaces their corrosion protective properties.In this thesis, the use of hydrophobic and superhydrophobic surface coatings as part of corrosion protective coating systems has been studied. Since the corrosion mechanism relies on the presence of water to take place, the use of a superhydrophobic coating to retard the penetration of water to an underlying metal surface is intuitive. The evaluation of corrosion protective properties of the hydrophobic and superhydrophobic surfaces was performed using mainly contact angle measurements and electrochemical measurements in severely corrosive 3 wt% NaCl water solution.First, the differences in corrosion protection achieved when employing different hydrophobic wetting states were investigated using a model alkyl ketene dimer wax system. It was found that superhydrophobicity in the Lotus state is superior to the other states, when considering fairly short immersion times of less than ten days. This is due to the continuous air film that can form between such a superhydrophobic surface and the electrolyte, which can retard the transport of electrolyte containing corrosive ions to the metal surface to the point where the electrical circuit is broken. Since corrosion cannot occur unless an electrical current is flowing, this is a very efficient way of suppressing corrosion.An air layer on an immersed superhydrophobic surface is, however, not stable over long time, and to investigate long-term corrosion protection using hydrophobic coatings a polydimethylsiloxane formulation containing hydrophobic silica nanoparticles was developed. This system showed enhancement in corrosion protective properties with increasing particles loads, up until the point where the particle load instead causes the coating to crack (at 40 wt%). The conclusion is that the hydrophobicity of the matrix and filler, in combination with the elongatedivdiffusion path supplied by the addition of particles, enhanced the corrosion protection of the underlying substrate.To further understand how hydrophobicity and particle addition affect the corrosion protective properties of a coating a three layer composite coating system was developed. Using this coating system, consisting of a polyester acrylate base coating, covered by TiO2 particles (with diameter &lt; 100 nm) and finally coated with a thin hexamethyl disiloxane coating, it was found that both hydrophobicity and particles are needed to reach a great enhancement in corrosion protective properties also for this system. / Eftersom metaller, och då särskilt stål, är viktigta konstruktionsmaterial i vårt moderna samhälle är korrosionsskydd av stor betydelse, både för att garantera säkerhet och för att minska kostnader som uppkommer i samband med korrosion. Tidigare har sexvärt krom och andra skadliga ämnen använts för att på ett effektivt sätt skydda stål från korrosion, men efter att deras användning kraftigt reglerades runt år 2000 har ännu ingen beläggning utvecklats som helt kan ersätta krombeläggningarna med avseende på funktion.I denna avhandling har hydrofoba och superhydrofoba ytbeläggningar och deras möjliga applikation som en del av ett korrosionsskyddande beläggningssystem studerats. Eftersom korrosionsmekanismen är beroende av närvaron av vatten, är användandet av en superhydrofob beläggning för att fördröja transporten av vatten till den underliggande metallytan intuitiv. De korrosionsskyddande egenskaperna hos superhydrofoba ytbeläggningar utvärderades här främst med hjälp av kontaktvinkelmätningar och elektrokemisk utvärdering i korrosiv lösning bestående av 3 vikts% NaCl i vatten.Först undersöktes skillnaden i korrosionsskydd som uppnås vid användandet av ytbeläggningar med olika hydrofoba vätningsregimer med hjälp av ett modellsystem bestående av ett alkylketendimer vax. Det konstaterades att superhydrofobicitet i Lotusregimen är överlägset bättre än de andra hydrofoba vätningsregimerna, i alla fall när man ser till relativt korta exponeringstider, typiskt mindre än tio dagar. Detta beror på att den kontinuerliga luftfilm som kan bildas på en sådan typ av superhydrofob yta kan minska transporten av elektrolyt (som innehåller korrosiva joner) till metallytan till den grad att den elektriska kretsen bryts. Eftersom korrosion inte kan ske utan en sluten elektrisk krets är detta ett mycket effektivt sätt att förhindra korrosion från att ske.Ett luftskikt på en superhydrofob yta nedsänkt i vatten är dock inte stabilt under lång tid. För att undersöka möjligheten till korrosionsskydd under längre tid med hjälp av hydrofoba beläggningar utvecklades en hydrofob ytbeläggning bestående av polydimetylsiloxan och hydrofoba nanopartiklar av kiseldioxid. Detta system visade en förbättring av korrosionsskyddet vid ökat partikelinnehåll upp till den koncentration (40 wt%) där i stället sprickbildning i ytbeläggningen observerades. Från detta system kunde slutsatsen dras att matrisens och partiklarnasvihydrofobicitet i kombination med den längre diffusionsvägen som partiklarna orsakade förbättrade korrosionsskyddet av den underliggande metallen.För att ytterligare förstå hur hydrofobicitet och partikeltillsatser påverkar en ytbeläggnings korrosionsskyddande egenskaper har dessutom ett treskikts kompositbeläggningssystem utvecklats. Genom att använda detta beläggningssystem, som består av en basbeläggning av polyesterakrylat, ett lager TiO2-partiklar (med en diameter på &lt;100 nm) slutligen belagt med ett tunt ytskikt bestående av hexametyldisiloxan så kunde slutsatsen dras att både en hydrofob matris och partiklar behövs för att nå en markant förbättring av ytbeläggningens korrosionsskyddande egenskaper. / <p>QC 20151015</p>

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This thesis reports design and implementation of a MEMS based resonant mass sensor for cell detection applications. The main objective of the thesis is the real-time detection of captured cells inside liquid medium and obtaining the detection results by electronic means, without the aid of any external optical instruments. A new resonant mass sensor architecture is presented that has various advantages over its conventional counterparts. The device oscillates in the lateral direction, eliminating squeeze film damping. A thin parylene layer coated on the device prevents liquids from entering the narrow gaps of the device, further improving the quality factor. The resonator is embedded on the floor of a microchannel. A gold film on the proof mass facilitates antibody based cell capture on the device. Theoretical background regarding resonator operation is investigated. Various resonator designs are presented, taking into account design trade-offs, application v considerations, and fabrication limitations. The design procedure is verified with MATLAB Simulink modeling results and finite element simulations. A new process flow has been developed for resonator fabrication, combining SOI, glass, and polymer micromachining. Modifications have been done on the flow for the solution of problems encountered during device fabrication. Each device has a foot print area of 1.5 x 0.5 cm2. The majority of this area is occupied by fluidic connections and reservoirs. Resonance characterization results in air and water have shown that there is significant quality factor enhancement with the parylene coating method. The quality factor decreases to only 170 in water from 610 in air, when the resonator is coated with a thin layer of parylene. Uniformity and linearity tests revealed that the devices have a standard deviation of only 1.9% for different analyte capture sites and an R2 of 0.997 for mass loads as high as 2.7 ng. Detection of Saccharomyces cerevisiae type yeast cells has been done using the resonators. Mass measurement of single yeast cell (13 pg) and yeast clusters (102 pg) have been performed. Antibody and thiol-gold chemistry based Candida Albicans type bacteria capture and detection has also been made in both air and water environments. The mass of several captured bacterial cells in air has been measured as 95pg. Two bacterial cells have been captured on one device inside water and their mass has been measured as 85 pg. It is worthy to note that all mass measurements are consistent with theoretical expectations.

This thesis reports design and implementation of a MEMS based gravimetric resonator for cytometry applications. There are mainly two objectives of this thesis / to enable in-flow analysis and to perform closed loop operation that does not require any additional processing or equipment. A novel MEMS based resonator with in-flow capabilities is proposed for detection of agents inside micro channels. High resolution of mass detection inside micro channels is planned to be succeeded with lateral motion in the micro channel floor. The idea embedding lateral resonators emerges from decreasing squeeze film damping during the motion of the resonator. Lateral motion is supported by hydrophobic parylene coating to decrease the damping. Theory and design of the gravimetric resonators are explained and the fabrication flow is constructed and performed successfully by combining SOI, SOG and polymer micro fabrication techniques. Problems during the fabrication are overcome and optimized flow is presented. The devices have a foot print area of 1.5 x 0.5 cm2 which is mainly composed of reservoirs for fluidic connections. Ten types of devices are designed according to their mass sensitivities and compliances. Trade offs between frequency, injected current, and compliance are analyzed successfully by taking also the performance parameters of the interface electronics in to account. Test results reveal that single latex bead with 3 &micro / m diameter and 14.127 pg mass can be sensed successfully and mass sensitivity is measured to be 5.91 fg/Hz for this type of device.

Various potential methods and techniques for modifying surfaces to make themless sensitive to contamination have been researched for various applicationsbefore, to varying degrees of success. These are discussed in detail to potentiallyapply them in the automotive sector, to face the increasing technical cleanlinessrequirements, that are linked to more complexity in design and electrification. TheTheoretical background in dust adhesion and contact mechanics is discussed, withdevelopments in analytical and numerical methods highlighted. Then, someexamples of the surfaces in question are presented, and their topographiesmeasured. Potential techniques are identified from previous experimental research in otherfields, and their applicability and feasibility are discussed within the limits ofavailable data, then an attempt at a structured approach for choosing candidatesfor further experimental testing on a case by case basis is laid out, and suggestionsfor more comprehensive research into effective parameters and analytical methodsare made.

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. [...]