Les procédés de dépôt en phase vapeur sont particulièrement performants pour la synthèse de revêtements à propriétés contrôlées. Plus spécifiquement, ce travail de recherche porte sur l'élaboration de revêtements biocompatibles, sur alliage titane TiAl6V4, obtenus par pulvérisation magnétron en conditions réactives. Dans un premier temps, nous avons décrit les procédés de mise en forme des implants commerciaux pour pouvoir les reproduire au niveau du laboratoire. Dans un second, nous avons focalisé notre étude sur l'effet de la structure cristallographique de films de zircone sur leur caractère biocompatible à partir de cultures cellulaires de fibroblastes. Les résultats ainsi obtenus démontrent très nettement des différences de comportement entre des films de zircone monoclinique, quadratique ou cubique. Dans l'objectif d'apporter des éléments d'information permettant de discuter de ces effets, d'autres séries de revêtements céramiques ont été élaborées comme par exemple des oxydes de titane ou de zirconium amorphes, de l'oxyde d'yttrium, de l'oxyde d'aluminium ou encore du carbone amorphe. Les cultures cellulaires pratiquées sur ces échantillons ont permis de démontrer le caractère biocompatible de l'oxyde d'yttrium excluant ainsi tout effet nocif de cet élément dans les zircones dopées / The vapor deposition processes are particularly successful for the synthesis of coatings with tuneable properties. More specifically, this research deals with the development of biocompatible coatings on titanium alloys TA6V obtained by magnetron sputtering in reactive conditions. At first, we described the processes to design the commercial medical implants to be able to reproduce them within the laboratory. In the second, we focused our study on the effect of the crystallographic structure of zirconia-based coatings on their biocompatible character from cell cultures of fibroblasts. The results obtained demonstrate a significant variation of cell behavior for the three the zirconia structures: monoclinic, tetragonal or cubic. In the purpose to bring relevant information that allow discussing these effects, another series of ceramic coatings were developed as for instance amorphous oxides of titanium or zirconium, yttrium oxide,, aluminum oxide or amorphous carbon. The cell response on these samples demonstrates to the biocompatible properties of the yttrium oxide, excluding any harmful effect of this element in the doped zirconia

This work investigates the feasibility of the use of plasma spray deposition as a method of producing high performance polymer coatings. The work concentrates on the understanding of the processing of the plasma spraying of polymers, the behaviour of polymeric materials during deposition, and the study of process-structure-properties relationships. Processing modelling for the three stages of the evolution of a polymer deposit (droplet-splat-coating) has been carried out using heat transfer theory. A theoretical model is proposed which consists of three parts: the first part predicts the temperature profile of in-flight particles within plasma jet, the second part predicts the cooling of isolated splats impacting on a substrate and the third part, the heat transfer through the coating thickness. The heat transfer analysis predicts that the development of large temperature gradients within the particle is a general characteristics of polymers during plasma spraying. This causes difficulties for polymer particles to be effectively molten within the plasma jet without decomposition. The theoretical calculations have predicted the effect of processing parameters on the temperature, the degree of melting and decomposition of in-flight polymer particles. With the aid of the model, the conditions for the preparation of high integrity thermoplastic deposits have been established by the control of the plasma arc power, plasma spraying distance, feedstock powder injection, torch traverse speed and feedstock particle size. The optimal deposition conditions are designed to produce effective particle melting in the plasma, extensive flow on impact, and minimal thermal degradation. The experimental work on optimizing processing parameters has confirmed the theoretical predictions. Examination of polymer coating structures reveals that the major defects are unmelted particles, cracks and pores. Five major categories of pores have been classified. It also revealed a significant loss in crystallinity and the presence of a minor metastable phase in the plasma deposited polyamide coatings due to rapid solidification. The study has indicated that the molecular weight of a polymer plays an important role on the splat flow and coating structure. Under non-optimal deposition condition, substantial thermal degradation occurred for which a chain scission mechanism is proposed for plasma deposited polyamide coatings. There are difficulties in achieving cross-linking during plasma spray deposition of thermosets. The theoretical calculations predict that adequate cross-linking is unlikely in a coating deposited under normal conditions, but preheating the substrate to above the cross-linking temperature improves the degree of cross-linking of the coatings substantially. In addition, the coating thickness has a major effect on the degree of cross-linking of thermosets. The calculations also predict that lowering the thermal conductivity by applying a thermal barrier undercoat and using a faster curing agent to reduce time required for the cross-linking reaction can improve the degree of cross-linking of thermoset deposits. The experimental results for the degree of cross-linking and wear resistance confirmed these predictions.

No description available.

Les finitions poudres, utilisées avec succès dans l'industrie du métal, représentent aujourd'hui une alternative aux systèmes utilisés actuellement pour les substrats en bois. Cette technologie permet tout d'abord de répondre aux besoins des industriels de l'ameublement et de la menuiserie car elle est en parfait accord avec la Directive Européenne 1999/13/CEE sur la réduction des émissions des COV. De plus, l'arrivée sur le marché de formulations thermodurcissables à basse température et à polymérisation sous UV a permis d'appliquer cette technologie à des substrats thermosensibles tels que le bois et ses matériaux dérivés. Actuellement, la finition poudre donne de très bons résultats en termes de qualité sur le panneau de fibres (MDF). D'autres résultats prometteurs ont aussi été obtenus sur du contreplaqué ou du bois massif de hêtre. Etudier de près l'ensemble des facteurs influençant le procédé, en particulier la nature du support bois et sa préparation, les paramètres de poudrage et de cuisson sont les objectifs principaux l'optimisation de ce procédé à l'échelle industrielle. Par ailleurs, les interactions substrat-finition poudre, outre les caractéristiques chimiques des résines, semblent définir la qualité finale du système et sa durabilité vis-à-vis du vieillissement. Un axe supplémentaire de l'étude est de vérifier l'éventuelle fonctionnalisation des finitions poudres pour leur donner des rôles particuliers, comme par exemple l'apport d'une propriété antibactérienne ou l'adsorption de COV environnants / Powder coatings, successfully used in the metal industry, represent today an alternative to the systems currently used for wooden substrates. This technology allows first to respond to the needs of manufacturers of furniture and carpentry as it is in perfect agreement with the European Directive 1999/13/EEC on the reduction of VOC emissions. In addition, the arrival on the market of thermosetting formulations at low temperature or UV polymerization allows to apply this technology to heat-sensitive substrates such as wood and derivates. Currently, powder coating gives very good results in terms of quality on the fiberboard (MDF). Other promising results have also been obtained on plywood or solid beech. Study the factors influencing the process, in particular the nature of the substrate and its preparation, powdering and baking settings are the main objectives to optimize this process on an industrial scale. Furthermore, interactions substrate-powder coating, in addition to the chemical characteristics of resins, seem to define the final quality of the system and its durability against aging. An additional axis of the study is to verify the possible functionalization of powder coatings provide particular roles, such as for example the provision of an antibacterial property or the adsorption of surrounding VOC

Detonation gun coatings of tungsten carbide have been widely recognised as one of the most effective anti-wear coatings for oilfield applications. However, very little fundamental tribological information exists for the material, which hinders coating development and the evolution of correct specifications. This study redresses this problem by conducting adhesive, abrasive and erosive tests upon the coating and relating the findings to the coated microstructure. The intention has been to simulate the in-service behaviour of parallel gate valves, which are used primarily to control flow in remote locations where reliability and freedom from maintenance are essential. Although problems with such valves are rare, costs associated with replacement are exceptionally high and therefore a high research priority has been placed on valves of this type. Currently, new designs of valve are tested using a pipe loop rig at BP Research Centre. However, such tests are both expensive and time consuming and with the increasing desire to bring products to market more quickly an alternative is sought. Probably, the area offering most scope for improvement is in material specification of the sealing surfaces and this work sets out to produce a first stage selection procedure for candidate materials. Uniquely, the study has taken one component, systematically categorised its failure mechanisms using non-destructive replication techniques and then reproduced them in the laboratory. The failure analysis has pointed to three-body abrasion, erosion and adhesion being the dominant failure modes and therefore, a suite of tribo-test methods have been developed to replicate them These are namely reciprocating diamond-on-flat, slurry erosion and reciprocating pin-on-plate tests. The material studied was a proprietary detonation gun coating of tungsten carbide, LW45, which is currently the most popular seal facing material specified for gate valves. A conformal contact geometry was chosen for the reciprocating pin-on-plate tests and problems with alignment were overcome by using a pre-test running-in procedure with 1 μm metallographic paste. Wear of LW45 occurring during the pin-on-plate test was not affected by test speed over the range selected, but was highly dependent upon load. Four different categories ranging from minimal wear to catastrophic wear have been identified. Extensive post test analysis using optical and scanning electron microscopy has further classified the failure that occurs into two groups, termed mild and severe. In the mild regime wear occurs by preferential removal of the binder phase, which is minimised on further sliding by protruding carbide particles. Eventually sufficient binder is removed for carbide fall-out to occur, upon which the cycle is repeated. A greater wear volume is produced by the severe wear mechanism which is caused by the interlinking of cracks present within the microstructure of the coating. To ensure operation in the mild regime, continuous sliding under operating pressures of above 7.84 MPa should be avoided. Abrasive wear simulated by the diamond-on-flat test increased with load. However, the failure mechanisms produced were independent of load and consist of a combination of plastic deformation and brittle fracture with plastic deformation representing the rate controlling step in the wear process. Slurry erosion tests have shown that LW45 wears by a brittle erosive mechanism and is therefore best able to resist erosion at low impingement angles. The volume loss per particle impact for LW45 is proportional to the kinetic energy of the impinging particles. The failure mechanism involved the growth of cracks in the microstructure by a fatigue action eventually leading to crack interlinking and material fall out. For all wear conditions, it is suggested that the removal of microcracking from the coating microstructure will lead to significant improvements in wear performance. A simplified design guide has been produced that gives a weighted importance to the various failure modes attributable to the respective tests. A significant improvement in performance was recorded by LW45 in comparison to typical substrate materials such as AISI 410 and Ferralium F255 stainless steels.

Le système barrière thermique (BT) est utilisé pour protéger les aubes de turbines à gaz aéronautiques. Aux températures de fonctionnement, une des causes de l'endommagement du système barrière thermique est la dégradation de la couche céramique isolante en zircone yttriée (8YPSZ : ZrO2 - 4% mol. Y2O3) par corrosion. Celle-ci est due à des dépôts d'oxydes à base de Ca, Mg, Al, Si, appelés CMAS provenant de diverses particules ingérées par le moteur. A haute température (~1200°C), le CMAS fond et s'infiltre dans la microstructure poreuse de la BT, se rigidifie au refroidissement provoquant, à terme, la délamination de la BT. A haute température, la BT subit une corrosion chimique induisant sa dissolution dans le CMAS liquide. L'ensemble de ces deux phénomènes conduit à la perte d'intégrité de la barrière thermique. Le présent travail s'est focalisé sur la compréhension des mécanismes de dégradation chimique en vue de proposer une solution de protection contre l'infiltration par les CMAS. Après expertise d'aubes de turbines de retour de vol, une reproduction de la corrosion de la barrière thermique par un CMAS modèle de type CAS et une étude thermodynamique et cinétique de la dissolution de différents oxydes des systèmes ZrO2 - Y2O3 et ZrO2 - Nd2O3 ont été menées dans le verre silicaté CAS pour comprendre le processus de dissolution de Zr et Y et définir une nouvelle composition de barrière thermique anti-CMAS. Le comportement en corrosion par le CAS de matériaux céramiques denses de compositions ZrO2 - 12% mol Nd2O3 et Zr2Nd2O7 ainsi qu'un revêtement déposé par EB-PVD ((La, Nd)2Zr2O7) a été testée. Les résultats obtenus font apparaître que : i) le CAS réplique le mécanisme de corrosion en service, soit la dissolution-re-précipitation. ii) l'oxyde ZrO2 se dissout progressivement et forme le zircon (ZrSiO4) dans le verre CAS, dès 30 min iii) les dopants (Nd2O3 et Y2O3) conduisent à la formation très rapide, de la phase apatite X8Ca2(SiO4)6O2 (X = Nd ou Y) après réaction avec le verre silicaté. En plus de la phase apatite, Y2O3 forme la phase Ca3Y2Si6O18, qui est instable entre 1300°C et 1400°C. iv) les composés dopés au néodyme (ZrO2 - 12% mol Nd2O3 et Zr2Nd2O7) se dissolvent et conduisent, quasi-spontanément, à la phase apatite Nd8Ca2(SiO4)6O2 ainsi qu'à la re-précipitation de grains de ZrO2 appauvris en néodyme. v) malgré la présence de Y2O3, les composés ZrO2 - 4% mol Y2O3, ZrO2 - 10% mol Y2O3 ne conduisent qu'à la re-précipitation de la zircone appauvrie en Y2O3. L'absence de phases secondaires notamment, la phase apatite, pourrait expliquer l'infiltration facile du CMAS dans la microstructure de la barrière thermique en zircone yttriée. vi) l'inhibition avérée de l'infiltration du CAS dans la microstructure poreuse de couches céramiques de nouvelles compositions semble être due à la formation rapide d'une couche superficielle fine et dense, constituée de zircone appauvrie en dopant et de phase apatite / Thermal barrier coating (TBC) system is used to protect aeronautical gas turbine blades. At operating temperatures, one of the damaging causes of thermal barrier system is the degradation of the insulating ceramic layer in zirconia (8YPSZ: ZrO2 - 4 mol %. Y2O3) by corrosion. The corrosion is due to calcium - magnesium alumino-silicates (CMAS) deposits from various particles ingested by the engine. At high temperature (~ 1200°C), the molten CMAS infiltrates the porous microstructure of the thermal barrier leads to i) the chemical dissolution of the thermal barrier zirconia and ii) the delamination of the TBC after cracking at low temperature due to the mismatch of CTE of the solid oxides constituting the CMAS and TBC. This study has contributed to understanding the mechanisms of chemical degradation in order to propose a solution to protect against infiltration by CMAS. After expertise of ex-service turbine blades, a reproduction of the thermal barrier corrosion by model CMAS (CAS) and thermodynamic and kinetic study of the solubility of different oxides of both ZrO2-Y2O3 and ZrO2-Nd2O3 systems were performed in the silicate glass (CAS) in order to understand the mechanism of Zr and Y dissolution and to define a new composition of TBC. The corrosion by the CAS of dense ceramic (ZrO2 - 12 mol% Nd2O3 and Zr2Nd2O7) and of a EB-PVD coating (La, Nd)2Zr2O7)was studied. The results obtained show that: i) CAS replicates the corrosion mechanism, i.e. dissolution-re-precipitation reaction ii) ZrO2 oxide dissolves gradually and forms zircon (ZrSiO4) in the glass after 30 min iii) (Nd2O3 and Y2O3) oxides lead very rapidly to the apatite X8Ca2(SiO4)6O2 (X = Nd, Y) phase formation, after reaction with silicate glass. In addition to the apatite phase, Y2O3 forms Ca3Y2Si6O18 phase, which is unstable at 1300°C and 1400°C iv) the compounds doped with Nd2O3 (ZrO2 - 12 mol% Nd2O3 and Zr2Nd2O7) dissolve and form almost spontaneously, the apatite Nd8Ca2(SiO4)6O2 phase and the ZrO2 depleted in Nd2O3 grains v) Although Y2O3 is a constitutent of the compounds ZrO2 - 4 mol% Y2O3, ZrO2 - 10 mol% Y2O3, the chemical corrosion of these compounds leads only to the re-precipitation of zirconia depleted Y2O3. The absence of secondary phases, particularly the apatite phase may explain the easy CMAS infiltration in the microstructure of the 8YPSZ thermal barrier vi) inhibition of CAS infiltration into the porous microstructure of ceramic layers of new compositions seems to be due to the rapid formation of a thin and dense layer, consisting in Nd-depleted zirconia and apatite phase

No description available.

Ces travaux de thèse sont consacrés à l'élaboration de revêtement réfléchissant et diffusant par projection plasma d'arc soufflé. Par la sélection des paramètres opératoires et le contrôle de la microstructure des revêtements élaborés, la première partie de cette étude présente la mise en forme d'un revêtement bicouche (micro/nano-structuré) d'alumine possédant une réflectance supérieure à 90% sur la gamme UV-Visible. Le transfert nécessaire à la démonstration pour démontrer la faisabilité d'élaboration de pièces de plus grandes dimensions (0.25 m2) a été entrepris. Dans une seconde partie et à partir de l'exploration de la microstructure des revêtements et de leur physicochimie, l'amélioration de la réflectance dans le proche UV par la couche nanostructurée est explicitée d'une part par la nature de la phase cristallographique moins absorbante et d'autre part par la présence en nombre de pores de faibles dimensions. De plus, la caractérisation des propriétés radiatives des revêtements par inversion de l'Equation du Transfert Radiatif a permis d'obtenir des éléments de compréhension des phénomènes d'interaction rayonnement/matière. Enfin, une dernière partie a pour objectif de mettre en place les différents éléments nécessaires à la prédiction des propriétés optiques de revêtements mis en forme par projection plasma. Un modèle tridimensionnel a été proposé pour représenter numériquement la structure de chacune des couches micro- et nanostructurée à partir des analyses microstructurales. Le code de résolution des équations de Maxwell par méthode FDTD (Finite Difference Time Domain) a été validé et de premières simulations ont été réalisées / This study deals with the manufacturing of reflecting and scattering coatings by plasma spraying process. By the selection of operating parameters and the control of the coatings microstructure, the first part of this work presents the elaboration of a micro/nanostructured bilayer material in alumina with a reflectance up to 90 % in the near UV-Visible range of wavelength. The feasibility of larger pieces (0.25m2) is demonstrated and the different characterizations for inserting the material in the Laser MegaJoule are performed. In a second part, from characterizations of the microstructure (by SEM, Hg Porosimetry, USAXS) and the chemical composition (DRX, X fluorescence), the improvement of the reflectance in the near-UV thanks to the nanostructured layer is explained, on the one hand, by the less absorbing crystallographic phase and, on the other hand, by the smaller and numerous pores. Moreover, the characterization of the radiation properties by the Radiation Transfer Equation inversion brings new elements for understanding the phenomena during radiation/porous media interaction and to determine the spatial repartition of the scattering radiation. The aim of the last part is to set up the different tools which are necessary to compute simulations of plasma-sprayed coatings optical behavior. From the microstructure analysis, a tridimensional numerical representation of each layer is suggested. The resolution of Maxwell equations is performed by FDTD (Finite Difference Time Domain) method. The model is validated and some first simulations are realized

Répondant à une forte demande de sécurité, d’économie de poids et d’optimisation du volume utile, les réservoirs pour carburants sont actuellement généralement constitués d’une paroi barrière polymère multicouche visant à limiter les émissions de vapeurs dans l’atmosphère. Etre capable de prédire les perméabilités est primordial pour l’optimisation de telles structures. Grâce à des automates conçus au laboratoire, les mesures de sorption et de perméabilité ont été réalisées pour trois polymères leaders du domaine (PEHD, Liant et EVOH) et des mélanges modèles de carburants composés d’éthanol, d’iso-octane et de toluène. Les propriétés de sorption ont été modélisées par UNIQUAC et un nouveau modèle inédit SORPFIT. Les paramètres des lois de diffusion, de type TSVF2 ou Long généralisé, ont aussi été optimisés pour chaque polymère malgré une difficulté particulière pour l’EVOH. Une méthodologie originale a été ensuite proposée pour la prédiction des flux partiels des multicouches à partir des paramètres caractéristiques des monocouches correspondantes. Selon la nature et la disposition de chaque couche, deux cas de figures ont été identifiés : la limitation cinétique et la limitation thermodynamique du transfert, cette dernière étant estimée à partir des modèles de sorption initialement optimisés. La confrontation des calculs avec les mesures expérimentales réalisées pour des films bicouches et tricouches d’Arkema montre des prédictions très satisfaisantes. Cette approche est finalement étendue à la simulation de la perméabilité de structures multicouches plus complexes et plus représentatives des réservoirs pour carburants industriels / Responding to a strong demand for security, weight reduction and volume optimization, the fuel tanks are currently usually made of polymer multi-layer barriers in order to limit vapour emissions into the atmosphere. The prediction of their permeability remains a world-wide critical challenge for the multi-layer optimization. Thanks to original semi-automated experimental set-ups, sorption and permeability measurements were carried out for three leading polymer materials (HDPE, EVOH and Binder) and model fuel mixtures of ethanol, iso-octane and toluene. The modelling of the sorption properties was successfully achieved by the UNIQUAC model and a new model called SORPFIT. The parameters of the diffusion laws according to the TSVF2 or the generalized Long models were also optimized for each polymer despite some difficulty with EVOH. An original methodology was then proposed for predicting the partial fluxes of polymer multi-layers from the characteristic parameters of the corresponding mono-layers. Depending on the nature and disposition of each layer, two scenarios were identified: the kinetics limitation and the thermodynamics limitation of mass transfer, the latter being estimated from the sorption models initially optimized. The comparison of the calculated fluxes with the experimental data obtained for bi-layer and tri-layer films provided by the world-wide industrial company Arkema showed that the predictions were very satisfying. This approach was then extended to the simulation of the permeability of more complex multi-layer structures which are more representative of commercial fuel tanks