Conventional yttria stabilized zirconia (YSZ) are widely used in the gas turbine to protect the substrate material from high temperature. But the common YSZ top coatings have limitations at higher temperature (above 1200 ℃) due to significant phase transformation and intensified sintering effect. Among the list of pyrochlores, gadolinium zirconate offer very attractive properties like low thermal conductivity, high thermal expansion coefficient and CMAS resistance. However, a lower fracture toughness than YSZ and tendency to react with alumina (thermal grown oxide) can lead to lower lifetime. Therefore, multi-layered thermal barrier coating approach was attempted and compared with single layer system. Single layer (YSZ) was processed by suspension plasma spraying (SPS). Double layer coating system comprising of YSZ as the bottom ceramic layer and gadolinium zir-conate as the top ceramic coat was processed by SPS. Also, a triple layer coating system with denser gadolinium zirconate on top of double layer system, was sprayed. Denser gado-linium zirchonate acts as the sealing layer and arrest the CMAS penetration. Isothermal oxidation performance of the sprayed coating systems including bare substrate and sub-strate with bond coat were investigated for a time period of 10hr, 50hr and 100hr at 1150℃ in air environment. Weight gain was observed in all the systems investigated. Microstruc-tural analysis was carried out using optical microscopy, SEM/EDS. Phase analysis was done using X-ray diffraction (XRD). Porosity measurement was made by water impregna-tion method. It was observed that multi-layered thermal barrier coating systems of YSZ/GZ and YSZ/GZ/GZ(dense) showed lower weight gain and TGO thickness than the single layer YSZ for all exposure time (10hr, 50hr & 100hr). The triple layer system had lower weight gain and TGO thickness compared to double layer system due to lower po-rosity content. Also, from the porosity measurement data, it could be seen that sintering effect is more dominant at 10 hr. of oxidation for all the coatings systems.

Yttria Stabilized Zirconia (YSZ) is the standard ceramic top coat material used for TBC application. Above 1200°C, issues such as CMAS (Calcium Magnesium Alumino Silicates) infiltration susceptibility, phase instability and high sintering rates limits its long durability. Therefore, new materials which can overcome these challenges without compromising the other requirements for TBCs are highly desirable. Gadolinium zirconate is one such material which has shown promising results for CMAS infiltration resistance. In this work, a relatively new TBC processing route, suspension plasma spray (SPS) has been employed to deposit gadolinium zirconate based TBCs. The primary aim of this study was to deposit two different coating systems (layered and composite) of gadolinium zirconate and YSZ composition using SPS technique and evaluate their thermal cyclic fatigue life performance. The layered system was a triple layered TBC with YSZ as the base layer, relatively porous GZ as the intermediate layer and dense GZ as the top layer. The blended TBC system comprised of a thin YSZ layer, an intermediate GZ+YSZ thick layer and dense GZ top layer. In the thermal cyclic fatigue test at 1100°C and 1200°C, it was observed that blended TBC had a lower thermal cyclic life than the layered TBC. It was shown that SPS is a promising technique to deposit columnar microstructure TBCs.

Grâce à l'utilisation d'un porteur liquide, la projection plasma de suspension (SPS) permet la fabrication de revêtements finement structurés. Comme pour la projection plasma conventionnelle (APS), les microstructures des revêtements SPS peuvent être adaptées en contrôlant les conditions de projection. Cependant, le procédé SPS est plus compliqué que le procédé APS par son nombre de paramètres modifiables.Cette thèse vise à apporter une compréhension plus fondamentale de la relation entre les paramètres du procédé SPS et les propriétés des revêtements YSZ en identifiant des modèles génériques basés sur l’utilisation de méthodes statistiques mathématiques pour l'étude de l'influence et de la sensibilité de paramètres individuels.Des expériences systématiques ont été menées pour étudier l'influence de six paramètres (puissance du plasma, charge massique de suspension, taille de la poudre, distance de projection, pas de projection et rugosité du substrat) sur la microstructure des revêtements qui ont aussi été analysés en terme de propriétés d’usage (mécanique, thermique, tribologique, etc.). La porosité des revêtements a fait l’objet d’une étude approfondie et les mesures ont été réalisées par trois techniques différentes : la méthode par analyse d’images, la transmission RX et la méthode USAXS (Ultra-Small Angle X-ray Scattering). Des analyses multivariées sur les données expérimentales recueillies ont été effectuées et plusieurs modèles mathématiques ont été proposés afin de prédire les propriétés des revêtements et guider ensuite vers une optimisation de la microstructure du revêtement en vu d'applications spécifiques.Dans ce contexte d'optimisation des performances mécaniques et tribologiques de ces revêtements céramiques, différentes quantités et tailles de poudre h-BN ont été ajoutées dans la suspension YSZ. Les revêtements composites YSZ / h-BN ont été fabriqués et leur analyse a montré une nette réduction du coefficient de frottement et du taux d'usure lorsque la taille et la quantité de poudre d’ajout sont optimisées l'une avec l'autre. Trois mécanismes d’usure ont finalement été identifiés et seront discutés. / Thanks to the using of liquid carrier, suspension plasma spray (SPS) enables the manufacture of finely structured coatings. As for conventional plasma spraying (APS), the microstructures of SPS coatings can be tailored by controlling the spray conditions. However, SPS is more complicated than APS due to its number of modifiable parameters.This thesis aims to provide a more fundamental understanding of the relationship between SPS process parameters and the properties of YSZ coatings by identifying generic models based on the use of mathematical statistical methods for the study of influence and sensitivity of the individual parameters.Systematic experiments were carried out to study the influence of six parameters (plasma power, suspension mass load, powder size, projection distance, projection step and substrate roughness) on the microstructure of coatings which were also analyzed in terms of the properties (mechanical, thermal, tribological, etc.). The porosity of the coatings was studied in detail and the measurements were carried out using three different techniques: the image analysis method, the X-ray transmission and the USAXS (Ultra-Small Angle X-ray Scattering) method. Multivariate analyzes of the collected experimental data were performed and several mathematical models were proposed to predict the properties of the coatings and then guide towards an optimization of the microstructure of the coating for specific applications.In this context of optimizing the mechanical and tribological performance of ceramic coatings, different amounts and sizes of h-BN powder have been added in the YSZ suspension. The YSZ/h-BN composite coatings were manufactured by SPS process and their analysis showed a clear reduction in the coefficient of friction and the wear rate when the size and the amount of addition powder are optimized together. Three wear mechanisms have finally been identified and been discussed.

Yttria stabilized zirconia (YSZ) is the state of the art ceramic top coat material used for TBC applications. The desire to achieve a higher engine efficiency of agas turbine engine by increasing the turbine inlet temperature has pushed YSZ toits upper limit. Above 1200°C, issues such as poor phase stability, high sinteringrates, and susceptibility to CMAS (calcium magnesium alumino silicates) degradation have been reported for YSZ based TBCs. Among the new materials,gadolinium zirconate (GZ) is an interesting alternative since it has shown attractive properties including resistance to CMAS attack. However, GZ has a poor thermo-chemical compatibility with the thermally grown oxide leading to poor thermal cyclic performance of GZ TBCs and that is why a multi-layered coating design seems feasible.This work presents a new approach of depositing GZ/YSZ multi-layered TBCs by the suspension plasma spray (SPS) process. Single layer YSZ TBCs were also deposited by SPS and used as a reference.The primary aim of the work was to compare the thermal conductivity and thermal cyclic life of the two coating designs. Thermal diffusivity of the YSZ single layer and GZ based multi-layered TBCs was measured using laser flash analysis (LFA). Thermal cyclic life of as sprayed coatings was evaluated at 1100°C, 1200°C and 1300°C respectively. It was shown that GZ based multi-layered TBCs had a lower thermal conductivity and higher thermal cyclic life compared to the single layer YSZ at all test temperatures. The second aim was to investigate the isothermal oxidation behaviour and erosion resistance of the two coating designs. The as sprayed TBCs were subjected toisothermal oxidation test at 1150°C. The GZ based multi-layered TBCs showed a lower weight gain than the single layer YSZ TBC. However, in the erosion test,the GZ based TBCs showed lower erosion resistance compared to the YSZ singlelayer TBC. In this work, it was shown that SPS is a promising production technique and that GZ is a promising material for TBCs.

Gas turbine engine efficiency needs to be raised in order to decrease fuel consumption, greenhouse gas emissions, and expenses. Efficiency may be improved in two ways: by reducing engine weight and raising intake temperatures. At intake temperature, conventional nickel-based alloys are already on the verge of failure, meaning there is a need and demand of materials which can withstand higher temperatures. Silicon Carbide Ceramic Matrix Composites (SiC CMCs) are being investigated as a potential replacement for superalloys due to their superior physical properties, such as their low weight and high melting point (approximately one-third of superalloys' weight). However, using SiC CMCs has a serious disadvantage. The mass recession of the SiC is caused by the volatilization of silicon hydroxide, which is caused by oxidation and reactivity with water vapor under the working conditions of gas turbine engines. Therefore, a shielding layer is used to prevent oxidation of the SiC CMCs. This protective coating (EBC) goes by the name of Environmental Barrier Coating. Thermal spray techniques such as atmospheric plasma spray and suspension plasma spray, which employ powder as the feedstock, are used to deposit EBC on SiC CMCs. For EBC to perform well, the coating must be crystalline, reasonably thick to sustain harsh environment, and devoid of cracks. EBC was deposited in order to look at how the spray parameters affected the microstructure. SEM pictures were used to quantify the coating's porosity and the severity of the cracks. To investigate the production of thermally grown oxide (TGO) in the coating and substrate and check how EBCs perform under thermal cyclic fatigue loading, a thermal cyclic fatigue test was conducted. The XRD analysis is performed to ascertain the proportion of crystalline and amorphous phases in the coating, which unfortunately is still in the process to be completed. In the as-sprayed coating samples we can see that when there are more amount and larger pores, we see less number of cracks and vice versa. The effect of spray parameters can be seen on the coatings. Comparing to SPS trial 1, the SPS trial 2 coatings are denser with less number of cracks and has good adhesion. Still the SPS trial 2 coating did not achieve better microstructure in terms of density, and cracks compared to the APS coatings but further looking into the parameters, more desirable coatings can be achieved. After TCF testing, a layer of TGO was seen at the bond coat/topcoat interface, and there was no failure of the coating seen.

En tant que technologie de projection thermique avancée, la projection plasma sous basse pression (LPPS) permet d'obtenir des revêtements de haute qualité et peut combler l'écart d'épaisseur entre les technologies de projection thermique conventionnelles et les procédés de couche mince standard. En outre, LPPS permet de construire des revêtements uniformes avec diverses microstructures; le dépôt a lieu non seulement à partir des éclaboussures liquides, mais aussi à partir des amas nanométriques ainsi que de la phase vapeur en fonction des conditions opérationnelles. Afin de continuer à améliorer et à développer le procédé LPPS, cette recherche vise à le combiner avec les procédés émergents de projection plasma en suspension et de projection plasma réactif. Il devait à la fois fournir deux nouveaux processus intégrés et réaliser des revêtements à structure fine avec des microstructures uniques et des performances élevées.Une torche à plasma bi-cathode (laboratoire LERMPS, UTBM, France) à mode d'injection axiale a été conçue et construite pour le LPPS, dont la puissance maximale en entrée du plasma a pu atteindre 80 kW. En utilisant cette nouvelle torche, soit la suspension à très fines particules, soit les poudres micrométriques ont pu être injectées dans le centre du plasma à basse pression. En conséquence, le transfert de chaleur et de masse entre le jet de plasma et les matériaux pulvérisés a été amélioré.La torche à plasma bi-cathode axiale a été appliquée d'abord pour pulvériser deux types de charges de YSZ, y compris la suspension de YSZ et les poudres agglomérées de YSZ. Les résultats ont indiqué que tous les revêtements YSZ présentaient des structures relativement denses en raison de la grande vitesse des particules sous faibles pressions. Les revêtements ont été composés des particules fondues, des particules agglomérées ainsi que du dépôt en phase vapeur. Il a été constaté que le degré de vaporisation de YSZ a été augmenté en utilisant une taille de particule plus fine, une pression ambiante plus basse, une distance de pulvérisation plus longue et une puissance de plasma plus élevée. En outre, tous les revêtements YSZ ont subi une transformation de phase significative d'une phase monoclinique à une phase tétragonale, et le degré de transformation était proportionnel au degré de vaporisation. Cependant, les propriétés mécaniques des revêtements résultants ont des comportements opposés. Les revêtements YSZ préparés à partir des particules agglomérées, qui avaient une plus grande taille de gouttelettes et moins de dépôt en phase vapeur, présentaient une dureté et un module de Young plus élevés que les revêtements YSZ fabriqués à partir d'une suspension fine.Une autre torche à plasma à haute énergie O3CP (Oerlikon Metco, Suisse) a été utilisée pour synthétiser in situ les revêtements de TiN sur des alliages de Ti-6Al-4V par projection de plasma réactive à très basse pression. Les poudres de Ti pur ont été pulvérisées dans une atmosphère de N2 sous une puissance de plasma d'entrée de 120 kW. Les revêtements TiN hybrides structurés ont été synthétisés, ce qui n'était pas le cas auparavant avec d'autres procédés de projection thermique. Il est connu que la réaction de nitruration se produisait non seulement dans le jet de plasma mais aussi sur le substrat. De plus, avec l'augmentation de la distance de pulvérisation, l'effet de nitruration a été affaibli et la structure hybride du revêtement de TiN a changé de laminaire dense en colonne poreuse, en function du degré de vaporisation supérieur, de la concentration de réactive inférieure et du substrat plus froid.. Néanmoins, ils ont également permis d'améliorer les propriétés mécaniques du substrat Ti-6Al-4V. / As an advanced thermal spray technology, low-pressure plasma spray (LPPS) allows obtaining high-quality coatings and can bridge the thickness gap between conventional thermal spray technologies and standard thin film processes. Moreover, LPPS permits to build uniform coatings with various microstructures; deposition takes place not only from liquid splats but also from nano-sized clusters as well as from the vapor phase depending on operational conditions. In order to further improve and develop the LPPS process, this research aims to combine it with the emerging suspension plasma spray and reactive plasma spray processes. It was expected to both provide two novel integrated processes and achieve fine-structured coatings with unique microstructures and high performance.A bi-cathode plasma torch (LERMPS lab, UTBM, France) with an axial injection mode was designed and built for LPPS, whose maximum input plasma power was able to reach to 80 kW. By using this new torch, either the very fine-particle suspension or the micro-sized powders was able to be injected into the plasma center under low pressures. As a result, the heat and mass transfer between the plasma jet and the sprayed materials were enhanced.The axial bi-cathode plasma torch was applied firstly to spray two kinds of YSZ feedstocks, including the YSZ suspension and the YSZ agglomerated powders. The results indicated that all the YSZ coatings exhibited relatively dense structures due to the high velocity of particles under low pressures. The coatings were composed of the melted particles, the agglomerated particles as well as the vapor deposition. It was found that the vaporization degree of YSZ was increased by using smaller particle size, lower ambient pressure, longer spraying distance and higher plasma power. In addition, all the YSZ coatings undergone a significant phase transformation from a monoclinic phase to a tetragonal phase, and the transformation degree was proportional to the vaporization degree. However, the mechanical properties of the resulting coatings had the opposite behaviors. The YSZ coatings prepared from the agglomerated particles, which had a bigger droplet size and less vapor deposition, showed a higher hardness and Young's modulus than the YSZ coatings fabricated from fine suspension did.Another high-energy plasma torch O3CP (Oerlikon Metco, Switzerland) was employed to in-situ synthesize the TiN coatings on Ti-6Al-4V alloys by reactive plasma spray under very low pressure. The pure Ti powders were sprayed into an N2 atmosphere under an input plasma power of 120 kW. The hybrid structured TiN coatings were synthesized, which was not previously achieved with other thermal spraying processes. It was known that the nitriding reaction occurred not only in the plasma jet but also on the substrate. Additionally, with increasing spraying distance, the nitriding effect was weakened, and the hybrid structure of TiN coating changed from dense laminar to porous columnar, according to the higher vaporization degree, lower reactant concentration and colder substrate. Nevertheless, they also were able to improve the mechanical properties of the Ti-6Al-4V substrate.