Cyclic thermogravimetry of TBC systems

The previously developed cyclic thermogravimetry analysis (CTGA) method is applied to the cyclic oxidation at 1100 °C of ZrO2–Y2O3/NiPtAl or NiCoCrAlYTa/single crystal nickel-base AM3 superalloy TBC systems. Cyclic thermogravimetry with fast heating and cooling and high accuracy in mass measurement allows to measure oxidation kinetics of the bond coating and also to detect and quantify the occurrence of the top coating cracking and spalling. The resulting data could be used later on, for time of life modelling of TBC systems

Etude de l'influence du platine sur le comportement en oxydation d'un système barrière thermique comprenant une sous-couche NiCoCrAlYTa

La résistance à l'écaillage d'un système barrière thermique est fonction de la composition et microstructure des matériaux constituant le système, ainsi que des procédés utilisés pour son élaboration. Cette thèse s'intéresse à l'influence d'une couche de platine déposée à la surface du dépôt NiCoCrAlYTa (sous-couche) sur le comportement en oxydation du système barrière thermique. Une étude approfondie est d'abord menée afin d'identifier les atouts et points faibles en oxydation cyclique d'un système comprenant un revêtement NiCoCrAlYTa. La formation d'une couche d'oxyde composée non exclusivement d'alumine et l'importante rugosité de la sous-couche, favorisant les défauts au sein de la barrière thermique, accélèrent l'écaillage de la barrière thermique. Parallèlement, la présence de carbures de tantale au sein du dépôt ne suffit pas à stopper le titane qui diffuse depuis le superalliage jusqu'à la couche d'oxyde et dégrade le système. Le platine ayant déjà démontré son effet très bénéfique sur les dépôts aluminures de nickel, il apparaît comme prometteur pour améliorer le comportement en oxydation du revêtement NiCoCrAlYTa. L'étude de son influence débute par une analyse fine de deux sous-couches NiCoCrAlYTa modifié platine : la première comprend un revêtement NiCoCrAlYTa obtenu par co-dépôt électrolytique, la seconde un dépôt NiCoCrAlYTa élaboré par projection plasma sous vide. Cette caractérisation, par diffraction des rayons X et microscopie électronique à balayage et en transmission, met en évidence la présence de martensite en surface du revêtement, conséquence de la diminution de l'activité de l'aluminium par le platine. Elle révèle également la forte influence du procédé utilisé pour l'élaboration du dépôt NiCoCrAlYTa sur la microstructure obtenue après le traitement thermique de diffusion. Des essais d'oxydation isotherme et de préoxydation sont ensuite réalisés sur la sous-couche dont le revêtement NiCoCrAlYTa est élaboré par co-dépôt électrolytique. Les couches d'oxydes formées sont analysées par diffraction des rayons X, spectroscopie Raman et fluorescence. Grâce à l'ajout de platine, qui entraîne l'augmentation de la teneur en aluminium dans la zone externe du revêtement, l'oxydation sélective de l'aluminium est favorisée. Cela se traduit par une diminution de la cinétique d'oxydation et une augmentation de la résistance à l'écaillage de la couche d'oxyde. Cependant, les carbures de tantale se décomposent lors du traitement thermique de diffusion puis lors de l'oxydation, laissant le titane libre de diffuser depuis le superalliage jusqu'à l'oxyde. De l'oxyde de titane est en effet détecté par spectroscopie Raman en petite quantité dans de la couche d'oxyde (avec l'AM3 comme substrat). Un autre point important sur la composition du superalliage est la présence d'élément réactif qui permet de diminuer la croissance de la couche d'oxyde. Concernant les essais de préoxydation, les résultats obtenus indiquent la nécessité d'une faible pression partielle d'oxygène afin de promouvoir la formation d'alumine-α. Le platine, quant à lui, ne favorise pas la formation d'alumine de transition. Des essais d'oxydation cyclique sur des systèmes barrière thermique sont ensuite menés. L'effet bénéfique du platine sur l'oxydation sélective de l'aluminium est confirmé, ce qui entraîne une augmentation de la durée de vie en cyclage. Cependant, la décomposition des carbures de tantale est de nouveau observée. Une diffusion très importante de titane depuis le superalliage jusqu'à l'oxyde est ainsi notée pour les systèmes barrière thermique comprenant une sous-couche modifiée platine avec un dépôt NiCoCrAlYTa obtenu par projection plasma sous vide. Dans le cas de système avec une sous-couche modifiée platine comprenant un dépôt NiCoCrAlYTa élaboré par co-dépôt électrolytique, le problème majeur est la présence de pores en surface et d'une certaine porosité à l'intérieur du revêtement. L'oxydation des pores en surface ainsi que le cyclage thermique provoque la pénétration de l'oxyde puis sa propagation catastrophique dans le revêtement. Les résultats obtenus permettent de dégager les points importants de l'élaboration d'un système barrière thermique. Il est alors recommandé que le superalliage contienne un élément réactif mais peu de titane. Le dépôt NiCoCrAlYTa nécessaire à la fabrication de la sous-couche doit être dense et la préparation de surface, avant et après le dépôt de platine, doit permettre d'obtenir une faible rugosité de surface avant le dépôt de la barrière thermique. Enfin, les paramètres (température, pression partielle d'oxygène, sablage) lors de la première oxydation du système doivent être contrôlés de manière à favoriser la formation d'alumine-α. ABSTRACT : The resistance to spallation of a thermal barrier coating system depends on the composition and the microstructure of the materials constituting the system, as well as on the processes used for its manufacturing. This PhD is interested in the influence of a Pt layer deposited on the surface of the NiCoCrAlYTa coating (bond coating) on the oxidation behavior of the thermal barrier coating system. A thorough study is first carried out in order to define the assets and the weak points under cyclic oxidizing conditions of a system composed of a NiCoCrAlYTa coating. The formation of an oxide layer not only composed of alumina and the great roughness of the bond coating, favoring defects within the thermal barrier, speed up the thermal barrier spallation. At the same time, the presence of tantalum carbides within the coating is not sufficient to prevent titanium from diffusing from the bond coating toward the oxide layer and from degrading the system. Platinum having already demonstrated its beneficial effect on nickel aluminide coatings, it seems promising in order to improve the oxidation resistance of the NiCoCrAlYTa coating. The study of its influence starts by a thorough analyses of two Pt-modified NiCoCrAlYTa bond coatings: the first one is composed of a NiCoCrAlYTa coating made by composite electroplating, the second one is composed of a NiCoCrAlYTa coating manufactured by vacuum plasma spray. This characterization, done using X-ray diffraction and secondary and transmission electron microscopy, highlights the presence of martensite at the coating surface, consequence of the decrease in the aluminium activity by platinum. It also reveals the strong influence of the process used to manufacture the NiCoCrAlYTa coating on the microstructure obtained after diffusion heat treatment. Preoxidation and isothermal oxidation tests are then carried out on the systems for which the NiCoCrAlYTa coating is made by composite electroplating. The oxide layers that formed are analyzed by X-ray diffraction, Raman spectroscopy and fluorescence. With Pt addition, that leads to an increase in the aluminium concentration in the external part of the coating, the selective oxidation of aluminium is favored. This results in a decrease in the oxidation kinetics and an increase in the resistance to spallation of the oxide layer. However, tantalum carbides decompose during the diffusion heat treatment and then during the oxidation, making the titanium free to diffuse from the superalloy toward the oxide. Indeed, titanium oxide is identified in small quantity in the oxide layer by Raman spectroscopy (with AM3 as substrate). Another relevant point on the superalloy composition is the presence of reactive elements that leads to a decrease in the oxide layer growth. Concerning the preoxidation tests, the obtained results indicate the necessity of a low oxygen partial pressure so as to promote the α-alumina formation. As for platinum, it does not favor the formation of transient alumina. Cyclic oxidation tests on thermal barrier coating systems are then carried out. The beneficial effect of platinum on the selective oxidation of aluminum is confirmed, that leads to longer lifetimes under thermal cycling. However, the tantalum carbides decomposition is observed once again. A great titanium diffusion from the superalloy toward the oxide is noticed for the thermal barrier coating systems composed of a platinum modified bond coating with a NiCoCrAlYTa deposit made by vacuum plasma spraying. In the case of systems composed of a Pt modified bond coating with a NiCoCrAlYTa deposit manufactured by composite electroplating, the main issue is the presence of pores at the surface and of a porosity within the coating. The pores oxidation at the surface as well as the thermal cycling result in the oxide penetration and then its disastrous propagation within the coating. The obtained results reveal the relevant points concerning the manufacturing of thermal barrier coating systems. It is recommended to use a reactive element containing superalloy that has very little titanium. The NiCoCrAlYTa coating required for the bond coating manufacturing has to be dense and the surface preparation, before and after the Pt deposit, has to lead to a surface with a low roughness before the deposition of the thermal barrier coating. Finally, the parameters during the first oxidation of the system (temperature, oxygen partial pressure, grit blasting), has to be done in order to favor α-alumina formatio

Inhibited aluminization of an ODS FeCr alloy

Aluminide coatings are of interest for fusion energy applications both for compatibility with liquid Pb-Li and to form an alumina layer that acts as a tritium permeation barrier. Oxide dispersion strengthened (ODS) ferritic steels are a structural material candidate for commercial reactor concepts expected to operate above 600 °C. Aluminizing was conducted in a laboratory scale chemical vapor deposition reactor using accepted conditions for coating Fe- and Ni base alloys. However, the measured mass gains on the current batch of ODS Fe-14Cr were extremely low compared to other conventional and ODS alloys. After aluminizing at two different Al activities at 900 °C and at 1100 °C, characterization showed that the ODS Fe-14Cr specimens formed a dense, primarily AlN layer that prevented Al uptake. This alloy batch contained a higher (> 5000 ppma) N content than the other alloys coated and this is the most likely reason for the inhibited aluminization. Other factors such as the high O content, small (~ 140 nm) grain size and Y-Ti oxide nano-clusters in ODS Fe-14Cr also could have contributed to the observed behavior. Examples of typical aluminide coatings formed on conventional and ODS Fe- and Ni-base alloys are shown for comparison

Characterization of TBC systems with NiPtAl or NiCoCrAlYTa bond coatings after thermal cycling at 1100°C: a comparative study of failure mechanisms

During service, TBC can suffer degradation by CMAS, FOD, erosion or spallation. Whereas the first three are due to foreign particles, the last one is related to thermal cycling. When subjected to high temperature exposures followed by rapid coolings under oxidizing conditions, a TBC system undergoes morphological changes and stress development. This will initiate cracks which propagate and finally lead to failure by spallation. Consequently, the aim of the present study is to understand better the mechanisms responsible for such spallation events. Two kinds of TBC systems with different bond coatings (NiCoCrAlYTa or Pt-modified nickel aluminide bond coatings) are thermally cycled. Subsequently, SEM investigations on TBC systems after spallation concentrate on failure path, defect, morphological and microstructural changes to propose way for improving TBC system lifetime

Beneficial Effect of Pt and of Pre-Oxidation on the Oxidation Behaviour of an NiCoCrAlYTa Bond-Coating for Thermal Barrier Coating Systems

The oxidation behaviour of a thermal barrier coating (TBC) system is a major concern as the growth of the thermally grown oxide (TGO) layer on the bondcoating creates stresses that greatly favour the thermal barrier spallation. To delay the loss of the thermal protection provided, research has focused on the bondcoating composition and microstructure as well as on the parameters required for a suitable pre-oxidation treatment before the deposition of the ceramic top coat. Platinum is known to enhance the oxidation/corrosion resistance of MCrAlY coatings. The effect of Pt on the oxidation behaviour of a NiCoCrAlYTa coating was assessed in this study. In addition, pre-oxidation treatments were conducted to determine if the oxidation behaviour of the modified NiCoCrAlYTa coating could be further improved

Effect of modification by Pt and manufacturing processes on the microstructure of two NiCoCrAlYTa bond coatings intended for thermal barrier system applications

Few studies have already shown that Pt influences the diffusion of aluminium and therefore the microstructure of β-NiAl or γ-Ni/γ′-Ni3Al materials. Besides, several works have revealed that the addition of Pt to MCrAlY (M = Ni and/or Co) improves the oxidation/corrosion behavior of the material. Nevertheless, very few data have been published on the microstructure of such modified MCrAlYs. Then, the present work deals with the addition of Pt to two NiCoCrAlYTa coatings that differ by their manufacturing process. Characterization is carried out in order to understand the influence of Pt diffusion but also the effect of the manufacturing process on the final microstructure. The collected data from XRD, SEM, EDS and TEM analyses reveal that an Al uphill diffusion occurs during heat treatment due to the presence of the Pt layer. The Al diffusion from the NiCoCrAlYTa bulk to the Pt-rich surface is so extensive that no more β-phase remains within the core of the coating. Pt may also dissolve TaC, precipitates largely present in the non-modified NiCoCrAlYTa coatings. In addition to Pt, the microstructure of the NiCoCrAlYTa prior to Pt deposition and heat treatment, dependent on the NiCoCrAlYTa manufacturing process, greatly influences the final microstructure

Relevance of other parameters than carbon activity in defining the severity of a metal dusting environment

Two metal dusting experiments were carried out at 570 °C on 800HT and HR120 alloys, for more than 6000 h. The tests were designed to run at different total pressures and gas velocities but similar carbon activities and oxygen partial pressures. For a given alloy, shorter average incubation times and larger mass losses were observed at high pressure. For both tests, HR120 alloy underwent greater mass losses and exhibited a higher pit density. For nearly all samples, pit densities greatly differed between both sides of the specimens. Therefore, the carbon and oxygen activities alone are not sufficient to evaluate the aggressiveness of a metal dusting environment. Greater degradation was the result of the association of a higher gas velocity with a higher total pressure and a finer alloy grain size

Chromium and iridium effects on the short-term interdiffusion behaviour between Pt rich γ-γ′ bond-coatings and a Ni-Al-Cr alloy

The interdiffusion behaviour of a 5 μm thick layer of Pt deposited by electroplating on a γ-Ni-12Al-10Cr model alloy was studied in order to assess the effect of Cr. Heat treatments were performed for 1 min up to 1 h at 1100 °C under argon. Cr addition increased the uphill diffusion of Al to the surface when compared with Pt/γ-(Ni,Al) systems. Al and Cr had a positive chemical interaction in presence of Pt, as shown by the positive values of the DAlCrNi and DCrAlNi diffusion coefficients determined by modelling. Pt had a negative chemical interaction with Al and with Cr in such a way that Pt decreased their activities. According to the diffusion coefficient values, Pt had a greater influence on the Al activity than on the Cr one. Similarly, 2 μm of Pt and 3 μm of Pt-25Ir were deposited by electroplating on the same model alloy to investigate the effect of Ir. Heat treatments were performed in the same conditions as for Cr. Iridium slowed down the interdiffusion when compared with systems with Pt only. Iridium diffused slower toward the substrate than Pt and a lower Pt + Ir flux toward the substrate was found. As voids formed at the interdiffusion zone/substrate interface due to Kirkendall effect, this lower inward Pt + Ir flux resulted in a lower outward vacancy flux and then Ir reduced Kirkendall voids formation. Moreover, Ir decreased the Pt effect on Al activity by dilution or even gave an opposite contribution to the Pt one. This reduced the uphill diffusion of Al, delaying the α-NiPtAl phase formation. Diffusion paths of each model system were also identified after 15 min at 1100 °C and all highlighted the α-NiPtAl phase formation and its aptitude to be used in TBC systems

Mechanistic-Based Lifetime Predictions for High-Temperature Alloys and Coatings

Increasing efficiency is a continuing goal for all forms of power generation from conventional fossil fuels to new renewable sources. However, increasing the process temperature to increase efficiency leads to faster degradation rates and more components with corrosion-limited lifetimes. At the highest temperatures, oxidation-resistant alumina-forming alloys and coatings are needed for maximum lifetimes. However, lifetime models accurate over the extended application durations are not currently available for a wide range of candidates and conditions. Increased mechanistic understanding and relevant long-term data sets will assist in model development and validation. Current progress is outlined for applying a reservoir-type model to Fe-base alloys and coatings. However, more work is needed to understand environmental effects, such as the presence of H2O, and to extend the current model to NiCrAl and NiCr alloys. As the critical performance factors are better understood, it will be easier to evaluate new materials in laboratory screening experiments

Étude de l'influence du platine sur le comportement en oxydation d'un système barrière thermique comprenant une sous-couche NiCoCrAlYTa

La résistance à l'écaillage d'un système barrière thermique est fonction de la composition et microstructure des matériaux constituant le système, ainsi que des procédés utilisés pour son élaboration. Cette thèse s'intéresse à l'influence d'une couche de platine déposée à la surface du dépôt NiCoCrAlYTa (sous-couche) sur le comportement en oxydation du système barrière thermique. Une étude approfondie est d'abord menée afin d'identifier les atouts et points faibles en oxydation cyclique d'un système comprenant un revêtement NiCoCrAlYTa. La formation d'une couche d'oxyde composée non exclusivement d'alumine et l'importante rugosité de la sous-couche, favorisant les défauts au sein de la barrière thermique, accélèrent l'écaillage de la barrière thermique. Parallèlement, la présence de carbures de tantale au sein du dépôt ne suffit pas à stopper le titane qui diffuse depuis le superalliage jusqu'à la couche d'oxyde et dégrade le système. Le platine ayant déjà démontré son effet très bénéfique sur les dépôts aluminures de nickel, il apparaît comme prometteur pour améliorer le comportement en oxydation du revêtement NiCoCrAlYTa. L'étude de son influence débute par une analyse fine de deux sous-couches NiCoCrAlYTa modifié platine : la première comprend un revêtement NiCoCrAlYTa obtenu par co-dépôt électrolytique, la seconde un dépôt NiCoCrAlYTa élaboré par projection plasma sous vide. Cette caractérisation, par diffraction des rayons X et microscopie électronique à balayage et en transmission, met en évidence la présence de martensite en surface du revêtement, conséquence de la diminution de l'activité de l'aluminium par le platine. Elle révèle également la forte influence du procédé utilisé pour l'élaboration du dépôt NiCoCrAlYTa sur la microstructure obtenue après le traitement thermique de diffusion. Des essais d'oxydation isotherme et de préoxydation sont ensuite réalisés sur la sous-couche dont le revêtement NiCoCrAlYTa est élaboré par co-dépôt électrolytique. Les couches d'oxydes formées sont analysées par diffraction des rayons X, spectroscopie Raman et fluorescence. Grâce à l'ajout de platine, qui entraîne l'augmentation de la teneur en aluminium dans la zone externe du revêtement, l'oxydation sélective de l'aluminium est favorisée. Cela se traduit par une diminution de la cinétique d'oxydation et une augmentation de la résistance à l'écaillage de la couche d'oxyde. Cependant, les carbures de tantale se décomposent lors du traitement thermique de diffusion puis lors de l'oxydation, laissant le titane libre de diffuser depuis le superalliage jusqu'à l'oxyde. De l'oxyde de titane est en effet détecté par spectroscopie Raman en petite quantité dans de la couche d'oxyde (avec l'AM3 comme substrat). Un autre point important sur la composition du superalliage est la présence d'élément réactif qui permet de diminuer la croissance de la couche d'oxyde. Concernant les essais de préoxydation, les résultats obtenus indiquent la nécessité d'une faible pression partielle d'oxygène afin de promouvoir la formation d'alumine-a. Le platine, quant à lui, ne favorise pas la formation d'alumine de transition. Des essais d'oxydation cyclique sur des systèmes barrière thermique sont ensuite menés. L'effet bénéfique du platine sur l'oxydation sélective de l'aluminium est confirmé, ce qui entraîne une augmentation de la durée de vie en cyclage. Cependant, la décomposition des carbures de tantale est de nouveau observée. Une diffusion très importante de titane depuis le superalliage jusqu'à l'oxyde est ainsi notée pour les systèmes barrière thermique comprenant une sous-couche modifiée platine avec un dépôt NiCoCrAlYTa obtenu par projection plasma sous vide. Dans le cas de système avec une sous-couche modifiée platine comprenant un dépôt NiCoCrAlYTa élaboré par co-dépôt électrolytique, le problème majeur est la présence de pores en surface et d'une certaine porosité à l'intérieur du revêtement. L'oxydation des pores en surface ainsi que le cyclage thermique provoque la pénétration de l'oxyde puis sa propagation catastrophique dans le revêtement. Les résultats obtenus permettent de dégager les points importants de l'élaboration d'un système barrière thermique. Il est alors recommandé que le superalliage contienne un élément réactif mais peu de titane. Le dépôt NiCoCrAlYTa nécessaire à la fabrication de la sous-couche doit être dense et la préparation de surface, avant et après le dépôt de platine, doit permettre d'obtenir une faible rugosité de surface avant le dépôt de la barrière thermique. Enfin, les paramètres (température, pression partielle d'oxygène, sablage) lors de la première oxydation du système doivent être contrôlés de manière à favoriser la formation d'alumine-a.The resistance to spallation of a thermal barrier coating system depends on the composition and the microstructure of the materials constituting the system, as well as on the processes used for its manufacturing. This PhD is interested in the influence of a Pt layer deposited on the surface of the NiCoCrAlYTa coating (bond coating) on the oxidation behavior of the thermal barrier coating system. A thorough study is first carried out in order to define the assets and the weak points under cyclic oxidizing conditions of a system composed of a NiCoCrAlYTa coating. The formation of an oxide layer not only composed of alumina and the great roughness of the bond coating, favoring defects within the thermal barrier, speed up the thermal barrier spallation. At the same time, the presence of tantalum carbides within the coating is not sufficient to prevent titanium from diffusing from the bond coating toward the oxide layer and from degrading the system. Platinum having already demonstrated its beneficial effect on nickel aluminide coatings, it seems promising in order to improve the oxidation resistance of the NiCoCrAlYTa coating. The study of its influence starts by a thorough analyses of two Pt-modified NiCoCrAlYTa bond coatings: the first one is composed of a NiCoCrAlYTa coating made by composite electroplating, the second one is composed of a NiCoCrAlYTa coating manufactured by vacuum plasma spray. This characterization, done using X-ray diffraction and secondary and transmission electron microscopy, highlights the presence of martensite at the coating surface, consequence of the decrease in the aluminium activity by platinum. It also reveals the strong influence of the process used to manufacture the NiCoCrAlYTa coating on the microstructure obtained after diffusion heat treatment. Preoxidation and isothermal oxidation tests are then carried out on the systems for which the NiCoCrAlYTa coating is made by composite electroplating. The oxide layers that formed are analyzed by X-ray diffraction, Raman spectroscopy and fluorescence. With Pt addition, that leads to an increase in the aluminium concentration in the external part of the coating, the selective oxidation of aluminium is favored. This results in a decrease in the oxidation kinetics and an increase in the resistance to spallation of the oxide layer. However, tantalum carbides decompose during the diffusion heat treatment and then during the oxidation, making the titanium free to diffuse from the superalloy toward the oxide. Indeed, titanium oxide is identified in small quantity in the oxide layer by Raman spectroscopy (with AM3 as substrate). Another relevant point on the superalloy composition is the presence of reactive elements that leads to a decrease in the oxide layer growth. Concerning the preoxidation tests, the obtained results indicate the necessity of a low oxygen partial pressure so as to promote the a-alumina formation. As for platinum, it does not favor the formation of transient alumina. Cyclic oxidation tests on thermal barrier coating systems are then carried out. The beneficial effect of platinum on the selective oxidation of aluminum is confirmed, that leads to longer lifetimes under thermal cycling. However, the tantalum carbides decomposition is observed once again. A great titanium diffusion from the superalloy toward the oxide is noticed for the thermal barrier coating systems composed of a platinum modified bond coating with a NiCoCrAlYTa deposit made by vacuum plasma spraying. In the case of systems composed of a Pt modified bond coating with a NiCoCrAlYTa deposit manufactured by composite electroplating, the main issue is the presence of pores at the surface and of a porosity within the coating. The pores oxidation at the surface as well as the thermal cycling result in the oxide penetration and then its disastrous propagation within the coating. The obtained results reveal the relevant points concerning the manufacturing of thermal barrier coating systems. It is recommended to use a reactive element containing superalloy that has very little titanium. The NiCoCrAlYTa coating required for the bond coating manufacturing has to be dense and the surface preparation, before and after the Pt deposit, has to lead to a surface with a low roughness before the deposition of the thermal barrier coating. Finally, the parameters during the first oxidation of the system (temperature, oxygen partial pressure, grit blasting), has to be done in order to favor a-alumina formation.TOULOUSE-INP (315552154) / SudocSudocFranceF