Phosphorylcholine (PC) based phospholipid bilayers have been explored as coating materials for various substrates due to their inherent resistance to non-specific protein adsorption. Phospholipids have been used for coatings in capillary electrophoresis (CE) to suppress electroosmotic flow (EOF) and to obtain better separation of proteins. Here, a series of investigations geared towards developing highly stable phospholipid based biomimetic stationary phases for chromatographic separations was performed.Fluid phospholipid bilayers lack the desired chemical and physical stability to serve as long-term coatings. In this work, highly stable phospholipid coatings generated via crosslinking polymerization of bis-SorbPC monomers were investigated. Reproducible EOF and migration times for model proteins were obtained for coated capillaries that were kept at room temperature for up to two months. Furthermore, the effects of surfactants, pH and capillary inner diameter (i.d.) on the stability of the lipid coating were investigated.In an alternate approach, stabilized phospholipid coatings for capillary electrophoresis were investigated via formation of hybrid monolayers. The capillary surface was chemically modified with a cyano group followed by deposition of phospholipid monomers. In this approach, marked enhancements in coating stability were attained with commercially available reagents. The hybrid coating was utilized for protein separations and gave efficiencies comparable to non-stabilized lipid coated capillaries.Fused silica capillaries were modified with phospholipid bilayers that were chemically tuned to introduce specific affinity binding agents, while minimizing nonspecific protein adsorption to the capillary wall. The wall of fused silica was functionalized with DOGS-NTA-Ni2+ lipid to present binding sites inside the capillary for 6xHis-tagged proteins. Fluorescence microscopy and changes in electrophoretic mobility were used to follow the interaction of the model proteins with the functionalized silica surface.The structural similarity of lipid vesicles to cell membranes made them attractive in developing stationary phases for both liquid chromatography and capillary electrophoresis to study interactions between analytes and phospholipid membranes. Stabilized PLB coated silica microspheres were prepared via polymerization of lipid monomers and displayed enhanced stability to extended storage and organic solvent. These highly stable microspheres, while minimizing nonspecific protein adsorption, were also functionalized with DOGS-NTA-Ni2+ and effectively bind 6xHis-EGFP proteins.

No description available.

Baigiamajame magistro darbe nagrinėjamos elektrolankiniu purškimu skirtingomis vielomis užpurkštos dangos. Atlikta terminio purškimo dangų, jų technologijų apžvalga ir analizė, pateikta dangų tyrimo metodika. Metalo paviršinis sluoksnis dengiamas siekiant pakeisti jo mechanines bei fizikines savybes, suteikti atsparumą išorės poveikiui ir pagerinti estetinį vaizdą. Atlikti nerūdijančio plieno, jūrinės bronzos bei jų kombinuotos dangų mikrostruktūros, mikrokietumo, dangos tamprumo modulio bei adhezijos tyrimai. Gauti rezultatai pateikti grafiškai. Išnagrinėjus praktinius ir skaitinius terminio purškimo dangų rezultatus, pateikiamos baigiamojo darbo išvados. Darbą sudaro 5 dalys: įvadas, literatūros šaltinių apžvalga ir analizė, elektrolankiniu purškimu gautų dangų tyrimai, išvados, literatūros sąrašas. Darbo apimtis – 59 p. teksto, 55 iliustr., 14 lent., 18 bibliografinių šaltinių. / In the final master thesis examined coatings by arc spraying with different solid wires. The review of thermal spray coatings technology and research methods are described. The metal surface coating was applied to modify it‘s mechanical and physical properties, also resistance to external impact and improve aesthetics view. The research of stainless steel, marine bronze and combined coating microstructures, microhardness modulus of elesticity and adhesion were carried out. The results are presented graphically. The experimental and numerical results of thermal spray coatings were analysed and conclusions were given. Structure of work: introduction, literature review and analysis, research of coatings by arc spraying, coclusions, references. Thesis consist of – 59 p. text, 55 pictures, 14 tables, 18 bibliografical entries.

Zinc and its alloys are among the most widely utilised metallic coatings for the sacrificial protection of steel. Although excellent in this mode of protection, these coatings are often less durable when subjected to environments of combined wear and corrosion due to their intrinsic relative softness and ductility. A possible and fast growing way of improving the durability of these coating is by the codeposition of inert particles into the zinc and zinc-alloy matrix. The main aim of this research was therefore to improve the durability of zinc and zinc-nickel coatings by the incorporation of inert particles via electrolytic codeposition methods. The first five chapters of this thesis comprise literature review on the electrodeposition of zinc, its alloys and composite electrodeposition in general. A major part of which was dedicated to the review of various conventional methods and parameters such as current density, agitation, temperature, solution composition, bath additives and pH usually investigated in electrodeposition. The experimental work was principally based on DC electrodeposition and was aimed at understanding the deposition behaviour of zinc and zinc-nickel electrodeposition baths, conditions which influence them and solution compatibility to the introduction of silica particles. A systematic study on the deposition behaviour of both zinc/silica and zinc-nickel/silica composite baths was carried out with particular interest on the rate of particle incorporation and the influence of particles on zinc-nickel alloy deposition. The complimentary codeposition behaviour of the nickel and silica particles was observed. The influence of bath additives such as N,N Dimethyldodecylamine (NND) and sodium nitrate on the rate of silica incorporation was also studied. Both additives were found to improve the rate of particle incorporation for the zinc/silica. The morphologies and compositions of the coatings were analysed with the use of SEM and FEGSEM. Corrosion performance studies were carried out in a neutral salt spray chamber and linear polarisation resistance methods used to determine barrier corrosion properties of the coatings. Anodic polarisation studies were also carried out. The results show an improvement in the corrosion performance of these coatings with the addition of silica particles Reciprocating wear tests were used to determine the wear behaviour of the coatings in terms of weight loss. Improvement in wear resistance was not observed in the zinc/silica coatings probably due to the high content of silica in the coatings. Lower silica contents may be required for the desired improvements. However, there were obvious improvements in the wear behaviour of the zinc-nickel/silica coatings due to the presence of the silica particles.

The purpose of the present PhD research project was to evaluate the feasibility of the electrodeposition of novel thin Ni composite coatings with lubricant particles from an additive-free Watts bath and their application as diffusion barrier layers in journal bearings for medium-speed diesel engines. Overall, the main objective was to develop thin Ni composite coatings with the following characteristics: • Improved tribological performance. • Good adhesion properties. • Good ‘anti-diffusion’ performance. Ultrasound was used in the preparation of pure Ni coatings and Ni composite coatings with lubricant particles under different conditions in order to understand how ultrasonic cavitation influences electrodeposition and characteristics of said Ni-based coatings. Two main studies were conducted related to this: 1. Study of the effect of ultrasonic power on the electrodeposition of pure Ni coatings to understand the influence of cavitation phenomena near the surface of the cathode on the properties of Ni deposits 2. Study of the effect of ultrasound on the production of Ni composite coatings to understand the influence of ultrasound in the dispersion of particles, the electrodeposition of Ni composite coatings and the properties of said Ni composite coatings. The influence of ultrasound on the dispersion of particles in the Watts bath was evaluated by observing the visual appearance of the resulting dispersions and analysing the particle size distribution of diluted solutions by laser diffraction-based particle sizing methods. The effect of ultrasound on the characteristics of Ni deposits and Ni composite coatings electrodeposited from the additive-free Watts bath was evaluated by different material characterization techniques: Abstract • X-Ray Diffraction (XRD) analysis was employed to observe the orientation of the Ni crystals that formed the coatings. • Field Ion Beam – Scanning Electron Microscopy (FIB-SEM) was employed to analyse the surface morphology and microstructure of the coatings. • Microhardness tests were performed to observe how the modification of the grain structure and the presence of particles may affect the hardness of the coatings. • Glow Discharge – Optical Emission Spectroscopy (GD-OES) was also employed to estimate the particle content in the Ni composite coatings.

De nombreuses pièces sont sujettes à des sollicitations de frottement à haute température dans le domaine de l’aéronautique. En effet, dans ce domaine, l’augmentation constante des puissances des réacteurs implique une augmentation de la température de fonctionnement des systèmes mécaniques et en particulier des contacts frottants. Cette augmentation de température a pour conséquence la diminution de la durabilité des matériaux lubrifiants solides actuellement utilisés pour ce type de contact. C’est pourquoi il est indispensable de sélectionner de nouveaux revêtements aux propriétés tribologiques à chaud améliorées. Dans cette optique, une thèse ayant pour sujet la durabilité de rotules aéronautiques d’attache mât-moteur de l’A380 soumises à des conditions extrêmes de fonctionnement en termes de température et de conditions glissement, a été effectuée au LTDS. Dans un premier temps, les endommagements de surface (abrasion, adhésion) des pièces réelles ont été analysés, à travers des analyses MEB/EDX du revêtement d’argenture déposé dans le contact entre les bagues intérieure et extérieure de la rotule. Des essais tribologiques en configuration classiquement utilisée, cylindre/plan (sur Cameron-Plint), ont ensuite été réalisés sur le revêtement d’argenture afin de comparer les endommagements observés in situ et sur banc. Dans le but de sélectionner un revêtement ou un couple de revêtements susceptibles de remplacer l’argenture dans le contact étudié, une dizaine de revêtements différents (couches accommodantes et couches dures) ont ensuite été testés individuellement en configuration cylindre/plan dans les mêmes conditions d’essai que dans le cas de l’argenture. Cette campagne d’essai a permis de dégager les plus performants/endurants tribologiquement. Parallèlement, un tribomètre original a été conçu au laboratoire afin de pouvoir simuler au mieux les conditions de contact réelles (sollicitations mécaniques, température de contact…). Ce tribomètre rotatif à haute température (TRHT), utilisable en configuration couronne/plan, permet d’appliquer simultanément au contact une force normale pouvant aller jusqu’à 50 kN, un mouvement rotatif alternatif, et une température de contact pouvant aller jusqu’à 1000°C grâce à un système de chauffage par induction. Les revêtements ayant démontré le meilleur comportement en termes de résistance à l’usure et au frottement au cours des essais en configuration cylindre/plan ont également été testés individuellement sur ce tribomètre en configuration couronne/plan. Les essais finaux ont été réalisés en interface complète, c'est-à-dire avec une couche accommodante déposée sur la pièce représentant la bague intérieure de la rotule, une couche dure déposée sur la pièce représentant la bague extérieure, et une couche à bas frottement (graisse ou vernis). Deux solutions de lubrification de ce type ont été déterminées pour le contact rotulé : une pour les rotules d’attache mât-moteur avant qui fonctionnent jusqu’à 160°C (CuNiIn + vernis Everlub / WC-C) et une pour les rotules d’attache mât-moteur arrière qui fonctionnent jusqu’à 570°C (stellite + vernisEverlub / TiHfCN). / In aeronautics tribology, mechanical parts are required to operate with increasing temperature. The increased functioning temperature of the contacts prone to friction and wear (such as bearings and other structural parts) is a direct consequence of the increasing power of jet engines. In the case of ball bearings, the substrate materials as well as the coating durability are affected by temperature. There is then a pressing need to introduce new coatings demonstrating effective tribological behaviour at high temperature. A PhD research subject was defined in partnership with Airbus Aerospace and SKF Aerospace and conducted at LTDS. The main goal of this research is to study the durability of ball bearings functioning under extreme conditions in terms of temperature and sliding friction. First, SEM/EDX analyses were done on the silver coating deposited in the contact between the ball bearings rings, in order to acknowledge the actual bearings surface damage. Tribological testing of the silver coating was then performed in a standard cylinder-on-flat configuration in order to compare in situ and experimental damages. More than ten different coatings (both soft and hard coatings, with solid lubrication properties and/or wear resistance properties) were then tested in the same configuration and conditions as the silver coating. These tests allowed us to identify the best suitable coatings for the application. An original test rig was also designed in the lab, in order to better simulate the bearings functioning conditions. This tribometer (TRHT) makes it possible to perform tests in ring-on-flat configuration (close contact) and to simultaneously apply a normal force up to 50 kN and a reciprocating rotating motion. Using this tribometer, the final tests were conducted on the best candidates among the different coatings, individually at first to assess their tribological behavior, and then in a configuration as close to reality as possible, with a hard coating covered ring and a soft coating covered flat, the contact between the two being greased or varnished. Finally, several possible solutions were determined, for two different functioning temperatures:160°C (CuNiIn + varnish Everlub / WC-C) and 570°C (stellite + varnish Everlub / TiHfCN).

The thermal conductivity of various porous thermal barrier coating (TBC) systems used in elevated temperature for industrial applications has been evaluated using a proposed six-phase model. These porous TBC systems rely on microstructural properties and yield different types of porosity. These microstructural properties can influence the thermal conductivity of TBC systems. The purpose of this thesis is to assess the thermal conductivity of TBC systems based on microstructural attributes, particularly the effect of different types of porosity. Thus, the first component of this thesis investigates the microstructural characterization of various TBC systems using image analysis (IA) technique. In this technique, scanning electron microscopy (SEM) and light optical microscopy (LOM) micrographs were used to measure the porosity level of different TBC materials. The volumetric fraction of porosity along with orientation, shape, and morphology have a considerable impact on the total thermal conductivity of TBCs. The second component of this thesis evaluates the thermal conductivity of these porous TBC systems by taking into account the effect of the heat treatment process. The IA results reveal that as long as the porosity content increases, the thermal conductivity decreases for all of the TBC materials studied in this thesis. Further, while the content of microcracks and non-flat porosity play a crucial role in reducing the thermal conductivity of TBC materials, the other types of porosity (open randomly oriented, penny-shaped, and interlamellar) exert less impact on the thermal conductivity of TBCs. Comparing the results of the proposed six-phase model to experimental values and finite element analysis (FEA) values showed a relatively good agreement. The proposed six-phase model can predict the thermal conductivity of porous microstructure of TBC systems close to real measured values; therefore, the proposed six-phase model may be utilized to fabricate the porous microstructure of TBCs.

The thesis comprises the two parts in each chapter: the first part focuses on the development and characterization of polyimide (PI) based composite coatings on a steel substrate. In order to improve the tribological performance of polyimide coatings, the fillers i.e. multi-walled carbon nanotubes (MWCNTs) and Graphene (GP) were added into PI and conducted friction test at elevated temperatures ranging from room temperature (RT) to 200°C. Also, the influence of fillers (MWCNTs and GP) materials into PI coatings surface, mechanical and tribological properties of polyimide composites coatings are measured. The addition of MWCNTs and GP reduces the friction coefficient as well as wear volume at elevated temperatures 50°C, 100°C and sometimes at 150°C. These temperatures play a vital role to form a lubrication layer in the contact interfaces at certain load and operating conditions. In these cases, three weight percentage (3wt%) of MWCNTs and GP into polyimide composites showed low friction and high wear-resistant as compared to other PI composites. Besides, by adding these two fillers into pure PI improved the mechanical properties such as micro-hardness and nanoindentation. The scanning electron microscope (SEM) was used to observe the wear mechanism of the composite coatings worn surfaces. The consequences expose that the fatigue wear mechanisms were predominant in the worn surfaces. Moreover, the thermal study of the polyimide composite coatings was conducted using thermal gravimetric (TG) to analyze the behavior of composite coatings at high temperatures. The results showed that the PI coatings with MWCNTs and GP have high thermal stability at 60% sample residue. In the second part-an epoxy coatings with filler materials e.g. hexagonal boron nitride (h-BN) and expanded graphite (EG) were made and conducted their tribological i.e. friction coefficient and wear performance. Also the perfect mixing ratio 4:1 (80 wt% base epoxy matrix and 20 wt% curing agent) was determined on the basis of stoichiometric ratio to cure the epoxy accurately. Therefore, seven samples with a various weight percentage (wt%) were prepared i.e. pure epoxy, epoxy with 5wt%, 10wt%, 15wt% of h-BN and EG. All the prepared samples ran at two different loading 2 N and 4 N conditions with 5 Hz frequency, 300 rpm and 30 minutes duration. The epoxy with h-BN showed low friction as compared to EG where EG has better wear-resistant behavior than h-BN.

Les réseaux de polymères interpénétrés (IPNs) combinent les propriétés de leurs différents composants. Ils possèdent une bonne résistance thermique, mécanique et chimique, et s’avèrent très intéressants pour pallier les inconvénients des réseaux homopolymères. Une méthode de synthèse rapide et efficace fait appel à la photopolymérisation. Les IPNs photopolymérisés sont donc très attractifs pour l’obtention de revêtements industriels présentant des propriétés de surface avancées. Cette thèse porte sur la réalisation de revêtements hydrophobes présentant des propriétés d’auto-régénération suite à un endommagement. Le concept mis en œuvre repose sur la ségrégation vers la surface de groupements fonctionnels liés chimiquement à un réseau IPN photopolymère, par différence de tension superficielle entre la surface et l’intérieur du matériau. L’auto-régénération de la fonctionnalité de surface nécessite une distribution homogène et une mobilité suffisante des groupements fonctionnels dans la matrice polymère. Des surfaces auto-régénérantes basées sur un réseau acrylate photopolymérisé ont d’abord été développées afin de démontrer la faisabilité du concept. Des IPNs photopolymérisés sous lumière UV et naturelle, combinant deux polymères (acrylates et époxydes) possédant des Tgs faibles et élevées (auto-régénération combinée avec résistance mécanique), et présentant des morphologies différentes ont ensuite été étudiés. Des surfaces auto-régénérantes possédant une Tg plus élevée compatible avec des applications industrielles ont été obtenues. / Interpenetrating polymer networks (IPNs) combine properties of their different components. They exhibit high mechanical strength, good thermal stability and chemical resistance. They are thus interesting to overcome the limitations of stand-alone networks. One of the easy and efficient ways to produce IPNs involves light curing. Considering these features, photocured IPNs are very attractive materials for functional polymeric surfaces in the coating industry. This thesis reports the development of hydrophobic coatings showing self-replenishing properties upon surface damage. This concept relies on the segregation of functional groups chemically bound to a light-cured IPN network towards the surface, thanks to the energy difference between surface and bulk. Surface functionality self-repairing mechanism requires a homogeneous distribution and a sufficient mobility of functional groups in the polymeric network. Self-replenishing hydrophobic surfaces based on a UV-cured acrylate network have been firstly developed in order to demonstrate the proof of concept. In a second part, UV and visible-light cured IPNs combining two polymers (acrylates and epoxides) with low and high Tgs (self-replenishing together with mechanical resistance), showing different morphologies have been investigated. Finally, self-replenishing hydrophobic surfaces with enhanced Tg more suitable for industrial applications have been obtained.

Ce travail porte sur l’étude de revêtements polysilazane (PSZ) élaborés dans le but d’inhiber l’adhésion des bactéries marines. Deux stratégies ont été étudiées : le greffage de chaînes poly(oxyde d’éthylène) (POE) (350, 750 ou 2000 g/mol) sur les chaînes PSZ par réactions d’hydrosilylation d’une part, et l’incorporation de composés du cuivre dans un film céramique issu de la pyrolyse d’un précurseur PSZ, d’autre part. Les conditions optimales de synthèse des PSZ greffés POE ont été définies afin de limiter notamment la réaction d’isomérisation de l’allyl-POE. La réticulation des PSZ greffés POE est alors effectuée par voie humide à température ambiante et procède par hydrolyse-condensation des fonctions alcoxysilane, SiH et SiN du précurseur PSZ. La prédominance des Si de type T3 (RSi(OSi)3) a été mise évidence par spectrométrie RMN du 29Si à l’état solide. La cristallisation des chaînes courtes de POE (350 g/mol) est totalement inhibée alors que l’aptitude des chaînes longues POE (750 et 2000 g/mol) à cristalliser est préservée. Le caractère hydrophile-hydrophobe et la capacité des films à inhiber l’adhésion bactérienne a été étudiée sur des revêtements à densités de greffons et à longueur de chaînes POE différentes. Les PSZs greffés POE 350g/mol avec un taux de greffage maximal conduisent à l’activité bactérienne la plus élevée de l’ensemble des revêtements étudiés.Les films céramiques incorporant du cuivre ont été préparés par pyrolyse d’un oligovinylsilazane en présence d’acétylacétonate de cuivre II sous atmosphère oxydante ou non oxydante. L’identification des phases des composés du cuivre a été effectuée par analyse DRX. L’environnement réducteur généré lors de la pyrolyse du PSZ favorise la formation d’espèces de cuivre (0) et cuivre (I) au détriment de cuivre (II). Les études bactériennes suggèrent que les cristaux CuO et Cu2O sont plus efficaces que le cuivre métal pour lutter contre l’adhésion bactérienne. / The objective of this work was to develop new polysilazane (PSZ) coatings which can inhibit the adhesion of marine bacteria. Two chemical strategies have been investigated: the grafting of poly(ethylene oxide) (POE) (350, 750, 2000 g/mol) on PSZ chains by hydrosilylation and the association of copper compounds with a pyrolized vinylsilazane matrix. The optimum conditions for grafting POE were defined to have a high selectivity toward olefin hydrosilylation. Crosslinking of POE-graft-PSZ was performed by moisture curing at room temperature. The main reactions occuring during curing are hydrolysis-condensation reactions of alkoxysilane, Si-H and Si-N functionalities. 29Si NMR in the solid state revealed the formation of a large amount of T3 Si [(RSi(OSi)3)]. The crystallization of short POE chains (350 g/mol) was found to be totally inhibited whereas long POE grafts (750 and 2000 g/mol) are still able to crystallize. The hydrophilic-hydrophobic properties and the antibactericidal activity of films with different graft density and POE chain length were studied. The POE (350 g/mol)-graft-PSZ with the greatest graft density were found to have the best antibactericidal activity. The incorporation of copper compounds in a pyrolized oligovinylsilazane was performed using copper acetylacetonate as a copper source. Pyrolysis was conducted in air or in Argon atmosphere. Identification of the copper phases was performed by XRD analysis. The reductive environment during thermal degradation of PSZ was found to favour the formation of copper (0) and copper (I) species relative to copper (II) species. The study of bacterial adhesion suggested that CuO and Cu2O crystals were more effective against bacterial adhesion than copper metal.