<p>Coatings are frequently applied on gas turbine components inorder to restrict surface degradation such as corrosion andoxidation of the structural material or to thermally insulatethe structural material against the hot environment, therebyincreasing the efficiency of the turbine. However, in order toobtain accurate lifetime expectancies and performance of thecoatings system it is necessary to have a reliableunderstanding of the mechanical properties and failuremechanisms of the coatings.</p><p>In this thesis, mechanical and fracture behaviour have beenstudied for a NiAl coating applied by a pack cementationprocess, an air-plasma sprayed NiCoCrAlY bondcoat, a vacuumplasma-sprayed NiCrAlY bondcoat and an air plasma-sprayed ZrO₂+ 6-8 % Y₂O₃topcoat. The mechanical tests were carried out ata temperature interval between room temperature and 860oC.Small punch tests and spherical indentation were the testmethods applied for this purpose, in which existing bending andindentation theory were adopted for interpretation of the testresults. Efforts were made to validate the test methods toensure their relevance for coating property measurements. Itwas found that the combination of these two methods givescapability to predict the temperature dependence of severalrelevant mechanical properties of gas turbine coatings, forexample the hardness, elastic modulus, yield strength, fracturestrength, flow stress-strain behaviour and ductility.Furthermore, the plasma-sprayed coatings were tested in bothas-coated and heat-treated condition, which revealedsignificant difference in properties. Microstructuralexamination of the bondcoats showed that oxidation with loss ofaluminium plays an important role in the coating degradationand for the property changes in the coatings.</p><p><b>Keywords:</b>small punch test, miniaturised disc bendingtests, spherical indentation, coatings, NiAl, APS-NiCoCrAlY,VPS-NiCrAlY, mechanical properties</p>

L'évaluation de la résistance interfaciale des systèmes barrière thermique EB-PVD est primordiale afin de pouvoir contrôler la production d'aubes de turbine revêtues et d'améliorer la compréhension des phénomènes d'écaillage de la céramique qui se produisent en fonctionnement. L'essai d'adhésion par choc laser LASAT qui s'appuie sur la propagation bidimensionnelle des ondes de choc (le phénomène LASAT-2D) consiste à mesurer le diamètre de fissure interfaciale pour différents tirs effectués à densité de puissance laser croissante. L'application de l'essai LASAT sur une pièce industrielle nécessite d'effectuer le choc du côté revêtu de céramique. Un adhésif vinylique protecteur ainsi qu'un milieu de confinement par adhésif transparent sont utilisés afin de générer un choc en surface de la céramique. La propagation de l'onde de choc est étudiée à travers des expériences spécifiques ainsi qu'une simulation numérique. La fissuration de l'interface est révélée par la présence d'une tache qui est mesurée par observation optique du dessus de la céramique. La reproductibilité de l'essai LASAT appliqué côté céramique est établie. Dans l'optique de valider un protocole de contrôle non destructif, le cyclage thermique est utilisé pour évaluer la nocivité d'une zone choquée présentant ou non des fissures. La présence de fissures à l'interface entre l'alumine et la zircone ne diminue pas la durée de vie à écaillage d'aubes de turbines lors du cyclage thermique. La tenue mécanique initiale de la céramique est comparée de manière qualitative et quantitative pour différents échantillons et qualitativement pour plusieurs aubes de turbine. L'évolution de la résistance interfaciale en fonction du cyclage thermique est étudiée. On démontre également sur plusieurs échantillons une corrélation entre l'adhérence initiale mesurée par LASAT et la durée de vie à écaillage par cyclage thermique. / The assessment of the interface strength of EB-PVD thermal barrier coating (TBC) is a key issue to control the production and better understand the ceramic spallation that will occur during life duration of coated turbine blades. The Laser Shock Adhesion Test (LASAT) involving bi-dimensional shock wave propagation, namely the LASAT-2D, consists in measuring the interfacial crack diameter when implementing a set of laser shocks with increased laser power densities. Applying the LASAT onto an industrial blade requires implementing the laser shock onto the ceramic side. A protective vinylic adhesive tape and a confinement by transparent adhesive tape are used to generate the shock on the ceramic. Shock wave propagation is studied through specific experiments and a numerical simulation. The interfacial crack is revealed by the presence of a spot that could be measured on a top-view optical image of the ceramic. Reproductibility of the LASAT applied on the coated side of the TBC is thereby established. Harmfulness of a loaded area with and without cracks is investigated thanks to thermal cycling in order to validate a non-destructive protocol. The presence of cracks at the interface between alumina and zirconia does not reduce the life duration of coated turbine blades in thermal cycling. Initial adhesion strength is compared both qualitatively and quantitatively for different samples and qualitatively for some turbine blades. Evolution of the interface strength with thermal cycling is presented. A correlation between initial adhesion and time of spallation of the ceramic is demonstrated on different samples.

La réparation des revêtements barrières thermiques endommagés par fissuration entraine des coûts de maintenance très élevés. Dans cette étude, qui s’inscrit dans le cadre du projet Européen FP7-SAMBA, il a été proposé d’utiliser des particules de MoSi2(B), revêtues d’une couche d’alumine, comme agent cicatrisant. L’oxydation de celles-ci doit entrainer la formation de silice amorphe qui s’écoule dans la fissure puis réagit avec la barrière thermique en zircone yttriée pour former du zircon. Cette étude traite dans un premier temps de l’élaboration par Spark Plasma Sintering (SPS) de composites modèles composés de zircone yttriée et de particules de MoSi2(B) non revêtues. Les propriétés mécaniques (ténacité, dureté, module d’Young) et thermiques (conductivité thermique, coefficient de dilatation) de ces composites ont été déterminées. Les travaux se sont ensuite orientés vers l’étude du comportement en oxydation cyclique à 1100 °C sous air de ces composites par thermogravimétrie cyclique. La modélisation de l’oxydation de ces composites mais aussi de systèmes multi-couches MoSi2(B)/YPSZ modèles a permis de déterminer les mécanismes et les cinétiques de formation de la silice et du zircon. Une augmentation significative des cinétiques de formation de ces oxydes a été observée lorsque le bore est ajouté dans le MoSi2 ce qui peut être potentiellement très bénéfique pour la cicatrisation des fissures. L'utilisation du procédé SPS a permis de réaliser des systèmes barrières thermiques auto-cicatrisants sur substrats en superalliages à base de nickel revêtus à partir de zircone yttriée et de particules de MoSi2(B) elles-mêmes revêtues d’une couche d’alumine. La pré-oxydation des substrats revêtus favorise la croissance d’une couche d’alumine qui empêche la formation de siliciures par réaction entre les particules et la sous-couche. Ces revêtements présentent une bonne résistance à l’endommagement en cyclage thermique. Les observations post-mortem de ces systèmes mettent en évidence la cicatrisation locale de fissures par formation de silice et de zircon. Bien qu’il ne soit pas possible aujourd’hui de dire si la présence de ces particules augmente ou non la durée de vie de la barrière thermique, par manque de systèmes de référence, ces observations très encourageantes démontrent expérimentalement la validité du concept d’auto-cicatrisation des barrières thermiques proposé dans le cadre de ce projet. / Repair of thermal barrier coatings (TBC) systems damaged by cracking leads to significant maintenance costs. In this project (FP7-SAMBA), it was proposed to use MoSi2(B) particles, coated with an alumina shell, as healing agent for TBCs. Healing particles intercepted by cracks will oxidize preferentially, leading to the formation of amorphous SiO2, which flows into cracks and subsequently reacts with the TBC leading to the formation of a load bearing ZrSiO4 phase. In this study model composite materials were prepared from mixtures of yttria partially stabilized zirconia (YPSZ) and uncoated MoSi2(B) particles by using Spark Plasma Sintering (SPS) technique. Mechanical (toughness, hardness, Young modulus) and thermal (conductivity, coefficient of thermal expansion) properties of these materials were determined. Then, cyclic thermogravimetry analysis (CTGA) was used to study the oxidation behavior of these materials at 1100 °C in air. Kinetics of silica and zircon formations were determined through modelling of the oxidation of composite materials but also the oxidation of multi-layer YPSZ/MoSi2(B) materials. Boron addition was shown to significantly increase silica and zircon formation rates which could be very beneficial for the healing of the cracks. Then, SPS technique was used to sinter self-healing thermal barrier coatings on bond coated Ni-based superalloys from mixtures of YPSZ and Al2O3-coated MoSi2(B) particles. The pre-oxidation of coated substrates was shown to prevent the detrimental formation of silicides by the reaction of MoSi2(B) particles and the bond coat. Good results were obtained upon thermal cycling and post-mortem observations highlight local healing of cracks. At this time, it is too early to quantify the potential effect of the particles on the TBC lifetime due to a lack of reference systems and statistics. However, these observations demonstrate, experimentally, the validity of the self-healing mechanism proposed in the framework of this project.

Le procédé de dépôt physique en phase vapeur assisté par plasma thermique (PS-PVD) consiste à évaporer le matériau sous forme de poudre à l’aide d’un jet de plasma d’arc soufflé pour produire des dépôts de structures variées obtenus par condensation de la vapeur et/ou dépôt des nano-agrégats. Dans le procédé de PS-PVD classique, l’intégralité du traitement du matériau est réalisée dans une enceinte sous faible pression, ce qui limite les phénomènes d’évaporation ou nécessite d’utiliser des torches de puissance importante. Dans ce travail, une extension du procédé de PS-PVD conventionnel à un procédé à deux enceintes est proposée puis explorée par voie de modélisation et de simulation numérique : la poudre est évaporée dans une enceinte haute pression (105 Pa) reliée par une tuyère de détente à une enceinte de dépôt basse pression (100 ou 1 000 Pa), permettant une évaporation énergétiquement plus efficace de poudre de Zircone Yttriée de granulométrie élevée, tout en utilisant des torches de puissance raisonnable. L’érosion et le colmatage de la tuyère de détente peuvent limiter la faisabilité d’un tel système. Aussi, par la mise en oeuvre de modèles numériques de mécaniquedes fluides et basé sur la théorie cinétique de la nucléation et de la croissance d’agrégats, on montre que, par l’ajustement des dimensions du système et des paramètres opératoires ces deux problèmes peuvent être contournés ou minimisés. En particulier, l’angle de divergence de la tuyère de détente est optimisé pour diminuer le risque de colmatage et obtenir le jet et le dépôt les plus uniformes possibles à l'aide des modèles susmentionnés, associés à un modèle DSMC (Monte-Carlo) du flux de gaz plasmagène raréfié. Pour une pression de 100 Pa, les résultats montrent que la barrière thermique serait formée par condensation de vapeur alors que pour 1 000 Pa, elle serait majoritairement formée par dépôt de nano-agrégats. / Plasma Spray Physical Vapor Deposition (PS-PVD) aims to substantially evaporate material in powder form by means of a DC plasma jet to produce coatings with various microstructures built by vapor condensation and/or by deposition of nanoclusters. In the conventional PS-PVD process, all the material treatment takes place in a medium vacuum atmosphere, limiting the evaporation process or requiring very high-power torches. In the present work, an extension of conventional PS-PVD process as a two-chamber process is proposed and investigated by means of numerical modeling: the powder is vaporized in a high pressure chamber (105 Pa) connected to the low pressure (100 or 1,000 Pa) deposition chamber by an expansion nozzle, allowing more energetically efficient evaporation of coarse YSZ powders using relatively low power plasma torches. Expansion nozzle erosion and clogging can obstruct the feasibility of such a system. In the present work, through the use of computational fluid dynamics, kinetic nucleation theory and cluster growth equations it is shown through careful adjustment of system dimensions and operating parameters both problems can be avoided or minimized. Divergence angle of the expansion nozzle is optimized to decrease the clogging risk and to reach the most uniform coating and spray characteristics using the aforementioned approaches linked with a DSMC model of the rarefied plasma gas flow. Results show that for 100 Pa, the thermal barrier coating would be mainly built from vapor deposition unlike 1,000 Pa for which it is mainly built by cluster deposition.

The diploma thesis is focused on the study of the thermal sprayed coating consisting of the NiCrAlY alloy bond layer and the partially stabilized zirconium oxide (8YSZ) top layer on the AZ91 magnesium alloy. The theoretical part deals with the structure of the alloy AZ91, NiCrAlY and partially stabilized zirconia. Furthermore, the methods of thermal spraying and the function and properties of thermal barrier coatings are summarized. The experimental part deals with the characterization of the thermal sprayed coating and the AZ91 alloy in terms of elemental, structural and phase composition. Optical and electron microscopy, EDS and XRD analysis were used for characterization. Electrochemical properties were investigated in~3.5% sodium chloride solution by potentiodynamic polarization. The mechanical properties (hardness, coefficient of friction) of the substrate and coating were measured using a hardness tester and tribological tests.

Etwa 27000 Flugzeuge durchqueren täglich den Luftraum über Europa. Dieser weiter steigende Flugverkehr erfordert neue Richtlinien für die Luftfahrzeuge. Im Besonderen stehen CO2- und NOX-Emission, Kerosinverbrauch und Lärmbelastung unter Optimierungsbedarf. Diese Anforderungen wurden bis 2050 vom Advisory Council for Aerospace Research in Europe (kurz: ACARE) festgelegt und werden wissenschaftlich unterstützt [3, 4]. Um diese Ziele zu erreichen, gibt es verschiedene Forschungsprogramme, Clean Sky ist ein EU-Technologieprogramm davon. In diesem Projekt werden sechs Demonstrator-Programme entwickelt, von denen MTU Aero Engines eines gestaltet. Im Rahmen dieses Projektes wurde eine Weiterentwicklung des Getriebefan (Geared Turbofan-GTF) erreicht, bei dem Fan und Niederdruckturbine durch ein Getriebe voneinander entkoppelt sind. Durch die optimierte Drehzahl beider Komponenten (vergrößerter Fan - langsamer, Niederdruckturbine (LPT) - schneller) wird die Turbinenleistung gesteigert und gleichzeitig die Geräuschemission minimiert. Entwickelt wurde der GTF von Pratt & Whitney in Kooperation mit MTU Aero Engines. Herkömmliche Varianten sehen vor, dass die Niederdruckturbine u.a. den Fan antreibt und zwar nur so schnell, dass der äußere Radius des Fans die zulässige Geschwindigkeit nicht überschreitet. Die herkömmlich verwendeten Nickelbasislegierungen in der Niederdruckturbine haben mit 8 g/cm3 eine zu hohe Dichte um einige Anforderungen im ACARE wirtschaftlich erfüllen zu können. Bereits 1967 hat die US Airforce das große Potential zur Gewichtsreduzierung durch Titanaluminid-Legierungen (TiAl-Legierungen) mit einer Dichte von rund 4 g/cm3 im Hochtemperaturbereich der Flugzeugtriebwerke erkannt. Zwischen 1980 und 1990 entwickelte das General Electric-Forschungscenter die gamma-TiAl-Legierung Ti-48Al-2Cr-2Nb, welche als erste kommerzielle Titanaluminidlegierung in der Niederdruckturbine von Flugzeugtriebwerken eingesetzt wurde. Eine weitere Legierung dieser Werkstoffgruppe kam erst ca. 15 Jahre später zum Einsatz, die TNM-Legierung. Wie man an diesem Beispiel sehen kann, dauert die Integration neuer Werkstoffe in der Luftfahrt aufgrund der notwendigen Vorversuche und Sicherheitsaspekte teilweise 20 Jahre. Seit September 2014 kommt im Triebwerk PW1100G GTF von Pratt & Whitney die geschmiedete Version der TNM-Legierung zum Einsatz. MTU Aero Engines AG München baut hierfür die Niederdruckturbine. Durch die hervorragenden Hochtemperatureigenschaften der gamma-TiAl-Legierungen wie z.B. thermische Stabilität der Mikrostruktur, Resistenz gegen Titanfeuer und hohe spezifische Fes-tigkeit, konnten sich die Titanaluminide in Konkurrenz zu den Nickelbasislegierungen sehr gut platzieren. Deswegen werden die beiden gamma-TiAl-Legierungen (Ti-48Al-2Cr-2Nb, TNMTM) bereits in den letzten Stufen der Niederdruckturbine eingesetzt. Ein Nachteil der gamma-Titanaluminide ist die begrenzte Oxidationsbeständigkeit über 750 °C, wodurch das Einsatzfeld als Hochtemperaturwerkstoff stark begrenzt wird. Um das Anwen-dungspotential der gamma-Titanaluminide weiter zu steigern und auch bei Temperaturen über 750 °C einzusetzen, ist eine Steigerung der Oxidationsbeständigkeit notwendig. Die Oxidationsbeständigkeit kann durch das Aufbringen von Oxidationsschutzschichten wie z.B. Al2O3 erreicht werden. Welche neben der Korrosionsbeständigkeit auch die thermisch-mechanischen Anforderungen des Substrat-Schicht-Verbundes sicherstellen müssen. Zur Erhöhung der Temperaturbelastbarkeit von gamma-TiAl-Schaufeln können zur thermischen Isolation keramische Wärmedämmschichten (WDS) aufgebracht werden. Aufgrund der WDS können höhere Prozesstemperaturen realisiert und die Lebensdauer des Grundwerkstoffs verlängert werden. Die Lebensdauer der Wärmedämmschichten und das Betriebsverhalten werden unter anderem durch eine gute Haftung auf dem Untergrund, eine niedrige Wärmeleitfähigkeit und einen thermisch stabilen Phasenaufbau bestimmt. Die Kombination aus Oxidationsschutz und Wärmedämmung wird bereits für Nickelbasislegierungen in der Brennkammer und Hochdruckturbine der Flugzeugtriebwerke eingesetzt. Um gamma-Titanaluminide in weitere Stufen der Niederdruckturbine oder Hochdruckturbine einzubringen, müssen diese Temperaturen von mindestens 900 °C aushalten und erfordern ebenso Beschichtungen zum Oxidations- und Wärmeschutz. Diese Schutzschichten finden für gamma-Titanaluminide bisher jedoch noch keine Anwendung.

Konventionelle Wärmedämmschichtensysteme bestehen aus einer Yttriumoxid-stabilisierten Zirkoniumdioxid-Deckschicht auf einer MCrAIY Haftschicht; wobei M für Co, Ni oder CoNi steht. Während der Nutzung bildet sich durch die Kombination von Wärme und Sauerstoff die Reaktionszone in der BC/TC-Grenzfläche. Diese Reaktionszone besteht aus thermisch wachsenden Übergangsmetalloxiden. In dieser Dissertation wurde das Phänomen der Bildung von TGO in TBC-Systemen betrachtet. Co32Ni21Cr8Al0.5Y Haftschichten wurden mithilfe des Verfahrens des atmosphärischen Plasmaspritzens (APS) auf Inconel 600 Substrate aufgebracht. Jm nächsten Schritt wurden durch DC-Magnetronsputter dünne Aluminumschichten auf die Oberfläche aufgetragen. Schließlich wurde YSZ TC mittels APS auf die Oberfläche gespritzt. Die beiden TBC-Systeme wurden zur Unterscheidung des Einflusses der thermischen Auslagerung unterschiedlich lange ausgelagert, um das thermochemischen Transformationsverhalten der Al-Zwischenschicht zu bestimmen. Die Schichtlebensdauer wurde unter thermischer Zyklierung mit einer definierten Verweilzeit untersucht. Das veränderte TBC-System mit der Al-Zwischenschicht (Al TBC) wurden mit dem TBC-System ohne Al-Zwischenschicht (R TBC) verglichen. Die Ergebnisse zeigen, dass das Hinzufügung der Al-Schichte in der BC/TC Grenzfläche nützlich für die Bildung der kontinuierlichen α Al2O3-Schicht während der Vorbereitungsphase der Wärmebehandlung ist. Diese dichte α Al2O3-Schicht bildet offensichtlich eine Durchgangsbarriere für den Sauerstoff während des Lebensdauertests. Dies hat Potential für die Verringerung der Bildung schädlicher Oxide. Der Ansatz ist nützlich für die Verlängerung der stabilen Wachstumsphase von TGO. In der Folge ermöglicht dies eine höhere Lebensdauer von Al-TBC-Systemen im Vergleich zu R-TBC-Systemen für die betrachteten thermischen Bedingungen und Zyklierungen.:Table of contents 1 Introduction 1 2 Motivation and overall interest 3 3 State of science and technology 5 3.1 Thermal barrier coating (TBC) systems 5 3.1.1 Substrate material 6 3.1.2 Ceramic top coating 6 3.1.3 Metallic bond coating 8 3.1.4 Thermally grown oxides (TGO) 12 3.1.5 Approaches on controlled TGO formation 15 3.1.6 Failure modes of TBC systems 17 3.2 Thermal spray technology 20 3.2.1 Atmospheric plasma spray (APS) technique 20 3.2.2 Formation sequence of the coating 21 3.2.3 Structure of the coating 22 3.3 Technology of thin layer deposition 23 3.4 Conclusions from the state of science and technology 24 4 Scientific objectives and work program 26 5 Experimental procedure 30 5.2 Material selection 30 5.3 Feedstock materials and thermal spray powders 32 5.4 Process selection 33 5.5 Specification of the scientific instruments 33 5.6 Detailed experimental procedure 34 5.6.1 Characterization of thermal spray powders 34 5.6.2 Preparation and characterization of overlaid coatings 35 5.6.3 Thermal treatment of TBC systems 39 5.6.4 Characterization of heat treated coating systems 40 5.6.5 Evaluation of TGO thickness and crack propagation 41 6 Results and discussions 43 6.1 Thermal spray powders and as sprayed coatings 43 6.1.1 Thermal spray powders 43 6.1.1.1 CoNiCrAlY thermal spray powder 43 6.1.1.2 ZrO2 – 8 %Y2O3 thermal spray powders 47 6.1.2 As-sputtered Al layer 50 6.1.2.1 Microstructure features 50 6.1.2.2 Elemental and phase composition analyses 50 6.1.3 As-sprayed coating systems 51 6.1.3.1 Bare and Al-covered CoNiCrAlY coatings 51 6.1.3.2 As-sprayed TBC systems 55 6.2 TBC systems after thermal treatment with different spans of dwell time 58 6.2.1 Thermal treatment with 5 and 30 min dwell time 58 6.2.2 Thermal treatment with 60 and 120 min dwell time 67 6.3 Lifetime test of TBC systems 68 6.3.1 Features in the cross section microstructure 68 6.3.2 Phase composition analyses 71 6.3.3 Elemental and Raman analyses 72 6.3.4 Features in the BC/TC of TBC systems after 80 thermal cycles 87 6.4 Thickness of TGO in the TBC systems 89 6.5 Length of cracks in the TC of the TBC systems 91 6.6 Relation between thickness of TGO and length of cracks 93 6.7 Discussion of loading condition and failure mode 95 6.8 Lifetime prediction of the TBC systems 97 6.9 Oxidation model of the TBC systems 98 7 Complementary work with discussion 100 7.1 Oxidation behavior of the TBC systems based on slow heating and cooling rates 100 7.1.1 Thickness of TGO and length of cracks 108 7.1.2 Raman analyses 112 7.1.3 Oxidation model of the TBC systems 116 7.2 Effect of Al content in the metallic coating 118 8 Complementary discussion 121 8.1 Effect of temperature on the oxidation behavior 121 8.2 Effect of deposition technique for metallic coating on the oxidation behavior 122 8.3 Effect of deposition technique for ceramic coating on the oxidation behavior 122 9 Summary and conclusion 124 10 References 128 / Conventional thermal barrier coating (TBC) systems consist of yttria-stabilized zirconia (YSZ) top coat (TC) on a MCrAlY bond coat (BC), where “M” stands for Co, Ni or CoNi. During their service under a combined heat and oxygen load, a reaction zone forms in the BC/TC interface. This reaction zone consists of thermally grown transition metal oxides (TGO). In the present thesis work, a phenomena related to the TGO formation is introduced. Co32Ni21Cr8Al0.5Y BC was overlaid by atmospheric plasma spraying (APS) technique on Inconel 600 substrates. Thin Al layers were deposited subsequently by DC-Magnetron sputtering on top. Finally, YSZ TC was sprayed by APS technique on the Al layers. The TBC systems were subjected to different thermal treatment procedures in order to investigate the thermo-chemical transformation behaviour of the Al-interlayer. The lifetime of the coatings was investigated under thermal cycling loading with dwell time. The altered TBC systems with Al interlayers (Al-TBC) were compared with the reference TBC systems without Al interlayers (R-TBC). The results show, that the addition of Al layers in the BC/TC interfaces is useful to form a continuous α-Al2O3 layer during the preliminary stage of heat treatment. The in-situ formed dense α-Al2O3 layer obviously acts as a diffusion barrier for oxygen during lifetime test. This has the potential to reduce the formation rate of detrimental oxides. This approach is beneficial to prolong the steady-state growth stage of the TGO, hence allows a higher lifetime for the Al-TBC systems in comparison to the R-TBC systems for the applied thermal loads.:Table of contents 1 Introduction 1 2 Motivation and overall interest 3 3 State of science and technology 5 3.1 Thermal barrier coating (TBC) systems 5 3.1.1 Substrate material 6 3.1.2 Ceramic top coating 6 3.1.3 Metallic bond coating 8 3.1.4 Thermally grown oxides (TGO) 12 3.1.5 Approaches on controlled TGO formation 15 3.1.6 Failure modes of TBC systems 17 3.2 Thermal spray technology 20 3.2.1 Atmospheric plasma spray (APS) technique 20 3.2.2 Formation sequence of the coating 21 3.2.3 Structure of the coating 22 3.3 Technology of thin layer deposition 23 3.4 Conclusions from the state of science and technology 24 4 Scientific objectives and work program 26 5 Experimental procedure 30 5.2 Material selection 30 5.3 Feedstock materials and thermal spray powders 32 5.4 Process selection 33 5.5 Specification of the scientific instruments 33 5.6 Detailed experimental procedure 34 5.6.1 Characterization of thermal spray powders 34 5.6.2 Preparation and characterization of overlaid coatings 35 5.6.3 Thermal treatment of TBC systems 39 5.6.4 Characterization of heat treated coating systems 40 5.6.5 Evaluation of TGO thickness and crack propagation 41 6 Results and discussions 43 6.1 Thermal spray powders and as sprayed coatings 43 6.1.1 Thermal spray powders 43 6.1.1.1 CoNiCrAlY thermal spray powder 43 6.1.1.2 ZrO2 – 8 %Y2O3 thermal spray powders 47 6.1.2 As-sputtered Al layer 50 6.1.2.1 Microstructure features 50 6.1.2.2 Elemental and phase composition analyses 50 6.1.3 As-sprayed coating systems 51 6.1.3.1 Bare and Al-covered CoNiCrAlY coatings 51 6.1.3.2 As-sprayed TBC systems 55 6.2 TBC systems after thermal treatment with different spans of dwell time 58 6.2.1 Thermal treatment with 5 and 30 min dwell time 58 6.2.2 Thermal treatment with 60 and 120 min dwell time 67 6.3 Lifetime test of TBC systems 68 6.3.1 Features in the cross section microstructure 68 6.3.2 Phase composition analyses 71 6.3.3 Elemental and Raman analyses 72 6.3.4 Features in the BC/TC of TBC systems after 80 thermal cycles 87 6.4 Thickness of TGO in the TBC systems 89 6.5 Length of cracks in the TC of the TBC systems 91 6.6 Relation between thickness of TGO and length of cracks 93 6.7 Discussion of loading condition and failure mode 95 6.8 Lifetime prediction of the TBC systems 97 6.9 Oxidation model of the TBC systems 98 7 Complementary work with discussion 100 7.1 Oxidation behavior of the TBC systems based on slow heating and cooling rates 100 7.1.1 Thickness of TGO and length of cracks 108 7.1.2 Raman analyses 112 7.1.3 Oxidation model of the TBC systems 116 7.2 Effect of Al content in the metallic coating 118 8 Complementary discussion 121 8.1 Effect of temperature on the oxidation behavior 121 8.2 Effect of deposition technique for metallic coating on the oxidation behavior 122 8.3 Effect of deposition technique for ceramic coating on the oxidation behavior 122 9 Summary and conclusion 124 10 References 128

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.

Reducing the heat losses in heavy-duty diesel engines is of importance for improving engine efficiency and reducing CO2 emissions. Depositing thermal barrier coatings (TBCs) onto engine components has been demonstrated to have great potential to reduce heat loss from the combustion chamber as well as from exhaust components. The overall aim of this thesis is to evaluate the thermal cycling lifetime and thermal insulation properties of TBCs for the purpose of reducing heat losses and thermal fatigue in heavy-duty diesel engines. In the thermal cycling test inside exhaust manifolds, nanostructured yttria-stabilized zirconia (YSZ) performed best, followed by YSZ with conventional microstructure and then La2Zr2O7. Forsterite and mullite could not withstand the thermal cycling conditions and displayed large cracks or spallation. Two sol-gel composite coatings displayed promising thermal cycling performance results in a furnace test under similar conditions. Thermal cycling testing of YSZ coatings having different types of microstructure, in a furnace at temperatures up to 800°C, indicated that the type of microstructure exerted a great influence. For the atmospheric plasma sprayed coatings, a segmented microstructure resulted in the longest thermal cycling lifetime. An even longer lifetime was seen for a plasma spray–physical vapour deposition (PS-PVD) coating. In situ heat flux measurements inside the combustion chamber indicated that plasma-sprayed Gd2Zr2O7 was the TBC material providing the largest heat flux reduction. This is explained by a combination of low thermal conductivity and high reflectance. The plasma-sprayed YSZ and La2Zr2O7 coatings provided very small heat flux reductions. Long-term testing indicated a running-in behaviour of YSZ and Gd2Zr2O7, with a reduction in heat flux due to the growth of microcracks in YSZ and the growth of macrocracks in Gd2Zr2O7. / <p>QC 20170821</p>

The durability of Thermal Barrier Coatings (TBCs) used on the turbine blades of aircraft and power generation engines has been known to be affected by sand particle ingression comprised of Calcium-Magnesium-Alumina-Silicate (CMAS). Previous studies have shown that these effects present themselves through variations in the thermomechanical and thermochemical properties of the coating. This study investigated the impact of CMAS ingression on the Yttria Stabilized Zirconia Topcoat (YSZ) and Thermally Grown Oxide (TGO) strain in sprayed Thermal Barrier Coating (TBC) samples of varying porosity with and without CMAS ingression. In-Situ Synchrotron X-ray Diffraction measurements were taken on the sample under thermal loading conditions from which the YSZ and TGO peaks were identified and biaxial strain calculations were determined at high temperature. Quantitative strain results are presented for the YSZ and TGO during a thermal cycle. In-plane strain results for YSZ near the TGO interface for a complete thermal cycle are presented, for a 6% porous superdense sample with CMAS infiltration. The outcomes from this study can be used to understand the role of CMAS on the strain tolerance of the TBC coating. It is well known that under engine operational conditions the development of the TGO layer, with large critical stresses, has been linked to failure of the coating. The growth of the TGO manifests as undulations in a series of peaks and troughs. Understanding the mechanics of the oxide layer at these locations provides significant information with respect to the failure mechanisms of the TBC coating. This study investigated the stress at the peak and trough of a TGO undulation for a cycled Dense Vertically Cracked (DVC) plasma sprayed TBC sample through photo-luminescence (PL) spectroscopy. High resolution nanoscale stress maps were taken nondestructively in the undulation of the TGO. Preliminary results from first line mapping of TGO peak and trough scan, at a resolution of 200 nm, have shown a non-uniform TGO stress variation. The results obtained from this study can be used to understand the stress variation in the peak and trough of a DVC sample's TGO undulation and how it contributes to the life of the TBC coating.