Thèses sur le sujet « Zirconia yttria coatings »

Yttria-stabilized-zirconia (YSZ) coatings have been fabricated on metallic (Fecralloy) substrates using a colloidal processing technique, namely electrophoretic deposition (EPD). The deposition of YSZ particles has been examined as a function of EPD conditions and suspension properties.

Yttria stabilized zirconia (YSZ) coatings were produced from a YSZ suspension in acetylacetone (ACAC) using electrophoretic deposition (EPD) and then consolidated via the natural drying and isothermal sintering with the constraint of the metal substrates. Before EPD, the operational pH of the suspension was adjusted by addition of acetic acid or organic bases. The effect of suspension pH on the deposition of EPD coatings was studied with respect to the suspension stability, coating density and microstructure both for a mono-sized system and micro-nano binary systems. The constrained drying process of the deposits was examined via the measurement of the critical cracking thickness (CCT). The sinterability of coatings was evaluated by micro-hardness and microstructure. For a mono-sized (0.26μm) suspension, results showed that the zeta potential had a high positive value on both sides of the isoelectric point (IEP). This probably resulted from the adsorption of base molecules triethanolamine (TEA), detected by fourier transform infrared spectroscopy. Three alkalis with different molecular structure were compared and the effect of their molecule length on the interparticle repulsion was discussed. Accordingly, the double layer thickness of the particles can be estimated. Based on this, particle interactions were estimated for different pH suspensions. The reduced particle coagulation increased the packing density of the EPD coatings from 38 % at pH 7.4 to 53 % at pH 8.4. Therefore, subsequent sintering of coatings was promoted. After sintering at 1200 °C, coatings made in pH 8.4 suspensions obtained a much higher hardness and had fewer big pores than coatings fabricated in pH 7.4 suspensions. The CCT of the latter is slightly higher than the former which might be ascribed to its particle network structure. In a binary suspension composed of the coarse (1μm) and fine (with average size of 100 nm or 10 nm, content varied in 0-30 wt. % to the powder mixture) YSZ powders, interactions between different species can be tuned by the zeta potential of individual component. Binary particles can be well dispersed at pH 4 when both of the coarse and fine powders reached their highest zeta potentials. Heterocoagulation occurred between them to form a haloing structure with fine powders covered on the coarse particle surfaces when they exhibited zeta potentials of the opposite sign at pH 8.6. Particle interactions were estimated and the microstructures of the binary coatings were examined to discuss how the different fine particle sizes influenced the particle packing after EPD. At pH 4, there existed a “stability window” for the 10 nm fines at 10 wt. % whereas no noticeable the border of the window can be observed for 100 nm fines within the measuring range. 10 nm and 100 nm fine powders gave similar overall densities of binary EPD coatings which were independent of the fine powder content. For heterocoagulation coatings made at pH 8.6, although the adsorption of fine particles reduce the agglomeration of coarse powder, the low zeta potential of the halos led to a loose structure of the “skeleton” ( the packing of the coarse powder) in the final binary coatings. 10 nm fine powders was observed to give a higher CCT and denser particle packing than 100 nm fine powders especially in a pre-saturated heterocoagulated binary coatings at 20 wt. % fine powder content. In order to further improve the sintering of the EPD coatings at low temperature sintering, a layer of CuO was applied on the coarse powder surface. With the addition of 30 wt. % fine powders, the hardness of EPD coatings after sintering 2 hours at 1150°C increased from 6 to 61 Vickers. With the presence of CuO, the hardness values were enhanced by 2.5-4.25 times. The density measurements indicated that the CuO layer not only served as a sintering aid, the CuO layer also helped with the binary particle packing particularly in the heterocoagulation condition because of the stronger particle interactions between the fine powders and CuO modified coarse powders. It seems that CuO had no significant impact on the cracking resistance of the binary coatings during drying, however t-m phase transformation was observed during sintering possibly due to the liquid phase induce by CuO.

A thermal barrier coating (TBC) is used as thermal protection of metallic components exposed to hot gas streams in e.g. gas turbine engines. Due to a high thermal expansion coefficient, low thermal conductivity, chemical- and thermal stability, yttria stabilized zirconia (YSZ) is the most widely used material for TBCs today. In the work presented in this master thesis an aqueous nitrate precursor solution was prepared and deposited on stainless steel substrates by spray pyrolysis to produce 8YSZ coatings (8 mol% of Y2O3 in ZrO2). The precursor solution concentration and deposition parameters, including set-point temperature and volume sprayed, were optimized to produce continuous and crack-free green coatings.The deposited green coatings were characterized by scanning electron microscopy, thermogravimetry and Fourier transform infrared spectroscopy to study the influence of substrate temperature on the microstructure of the green coatings. A substantial change in microstructure was observed for the green coatings in a certain temperature range indicating that a minimum deposition temperature was necessary to obtain crack-free green coatings.Heat treatment was necessary to decompose the nitrate species in the deposited film. During heat treatment, vertical cracks were introduced into the coatings due to the nitrate decomposition. The cracking behavior of the coatings was studied for different drying times and conditions, and it was found that the crack propagation can be controlled to obtain the preferred size and geometry of the cracks. Due to built-up stresses in the coating, which can exceed the fracture toughness of the material, it was found that there was a maximum film thickness achievable before spallation of the coating for a given precursor solution. Therefore, the possibility of spraying multi-layered coatings was investigated. The introduction of a second layer showed that it was possible to double the thickness of the coating.

Electrophoretic deposition (EPD) has been used to produce the yttria-stabilized zirconia (YSZ) coatings on metal substrates. Sintering of YSZ with and without doping has been carried out at 1150 °C for 2hrs. The properties of these coatings have been examined in light of thermal barrier applications. For EPD, the green density increases with an initial increase in the HCl concentration and the EPD time. This suggests that particle packing was influenced by a time dependent re-arrangement, in addition to the initial suspension dispersion state. The green density peaks at a electrical conductivity of around 10×10-4 S/m achieved by an 0.5 mM HCl addition for the 20 g/l suspensions with the EPD time of around 8 ~10 minute. For sintered coatings, the HCl concentration had a marked effect on the neck size to grain size ratio of the 8 mol% yttria-stabilized zirconia (8YSZ) coatings. The presence of ZrCl4 and ZrOCl2, and a high concentration of oxygen vacancies at the grain boundaries are believed to promote neck growth in the early stage of sintering at 1150 °C. During sintering of 3 mol% and 8 mol% yttria-stabilized zirconia (3YSZ and 8YSZ) at 1150 ºC for 2hrs, the densification rate substantially increased with a small amount of Fe2O3 addition (0.5 mol%) to the 3YSZ/8YSZ deposits. A more pronounced graingrowth was present in the Fe2O3 doped 8YSZ deposits. The increased Zr4+ diffusion coefficient is mainly responsible to the rapid densification rate of the Fe2O3 doped 3YSZ/8YSZ deposits. A small grain growth observed in the Fe2O3 doped 3YSZ deposits is attributed to the Fe3+ segregation at grain boundary. A small amount of CeO2 doping was found to substantially inhibit the densification rate of the doped 3YSZ deposits with a minor grain growth. Fe2O3 doping reduced the thermal conductivities of 3YSZ/8YSZ. It is found that Rayleigh-type phonon scattering due to the mass difference alone is inadequate to explain the thermal conductivity of Fe2O3 doped YSZ systems. The lattice strain effects due to the ionic radius difference could more effectively reduce thermal conductivity of the Fe2O3-doped 3YSZ. A decrease in the growth rate of the TGO scale with the increasing Fe2O3 additions was observed for the oxidized FeCrAlY metal substrates with the Fe2O3-doped 3YSZ coating, which was found to be attributed to the early formation of the stable and dense α-Al2O3 phase due to the presence of Fe3+ ions.

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.

Yttria-stabilized zirconia has long been the favoured refractory material for demanding applications such as thermal barrier coatings on turbine components. Its low thermal conductivity, relatively high thermal expansion coefficient, and good fracture toughness are most useful parameters when acute thermal cycles are considered. In recent years however, the demand for higher turbine operating temperatures has led to novel and innovative research in improving the thermal conductivity and sintering resistance of thermal barrier coatings. Rareearth doped zirconia, rare-earth zirconates, and lanthanum hexa-aluminate have all been proposed as candidate materials for the next generation of thermal barrier coatings. Drawn from research conducted during 2003-2005, this study focuses on dysprosia as a ternary dopant to yttria-stabilized zirconia, examining the relationship of dopant content with overall thermal conductivity and sintering behaviour under cyclic thermal loading between room temperature and 1100°C. Air plasma spray deposition technique was employed for coatings deposition. Based on existing published works, this study is prefaced with four hypotheses: 1. increasing levels of dysprosia would likely result in lower overall thermal conductivity; 2. best improvement occurs at about 10 mol% total dopant (Dy + Y); 3. addition of dysprosia is also likely to increase sintering resistance during thermal cycling, since Dy cation radius is larger than Zr; 4. higher dopant concentrations, between 10 mol% and 50 mol%, should increasingly lead to shorter coating life under thermal cycling. As-sprayed coating heat capacity, thermal diffusivity, and porosity were measured by differential scanning calorimetry, laser flash method, and image analyses, respectively. Post-cycle coating porosity levels were compared against data for as-sprayed coatings. A theoretical model for estimating the thermal conductivity of plasma sprayed zirconia coatings was derived and constructed from previous works by other researchers. Experimental data and theoretical model presented in this study offer positive confirmations for the hypotheses, with the exceptions that the greatest reduction in thermal conductivity was seen at 15 mol% total dopant and that increased levels of dysprosia did not result in continued reductions in thermal conductivity. Literature data suggests long range ordering of oxygen vacancies could be a contributing factor in this trend.

Plasma sprayed Thermal Barrier Coating systems (TBCs) are commonly used for thermal protection of components in modern gas turbine application such as power generation, marine and aero engines. The material that is most commonly used in these applications is Yttria Partially Stabilized Zirconia (YPSZ) because of this ceramic’s favourable properties, such as low thermal conductivity, phase stability to high temperature, and good erosion resistance. The coating microstructures in YPSZ coatings are highly heterogeneous, consisting of defects such as pores and cracks of different sizes which determine the coating’s final thermal and mechanical properties, and the service lives of the coatings. Determination of quantitative microstructure–property correlations is of great interest as experimental procedures are time consuming and expensive. Significant attention has been given to this field, especially in last fifteen years. The usual approach for modelling was to describe various microstructural features in some way, so as to determine their influence on the overall thermal conductivity of the coating. As the analytical models over-simplified the description of the defects, various numerical models were developed which incorporated real microstructure images.This thesis work describes two modelling approaches to further investigate the relationships between microstructure and thermal conductivity of TBCs. The first modelling approach uses a combination of a statistical model and a finite element model which could be used to evaluate and verify the relationship between microstructural defects and thermal conductivity. The second modelling approach uses the same finite element model along with a coating morphology generator, and can be used to design low thermal conductivity TBCs. A tentative verification of both the approaches has been done in this work.

There has been an urge for increasing the efficiency in advanced gas turbine engines. To fulfill these needs the inlet gas temperatures should be increased in the gas turbine engines, thermal barrier coatings (TBCs) have gained significant applications in increasing the gas inlet temperatures. Insulating characteristics of ceramic TBCs allow the operation at up to 150~250 °C higher gas temperatures. Because of the severe turbine engine operating conditions that include high temperature, steep temperature gradient, thermal cycling, oxidation and hot-corrosion, TBCs can fail by spallation at the interface between the metal and ceramic. The lack of understanding in failure mechanisms and their prediction warrant a development of non-destructive evaluation technique that can monitor the quality and degradation of TBCs. In addition, the development of NDE technique must be based on a robust correlation to the characteristics of TBC failure. The objective of this study is to develop electrochemical impedance spectroscopy (EIS) as a Non-destructive evaluation (NDE) technology for application to TBCs. To have a better understanding of the multilayer TBCs using EIS they were divided into individual layers and EIS were performed on them. The individual layers included polycrystalline ZrO2-7~8 wt.%Y?O? (YSZ) (topcoat) of two different densities were subjected to sintering by varying the sintering temperature and holding time for three different thickness and hot extruded NiAl alloy buttons which were subjected to isothermal oxidation with varying temperature and time. NiAl is as similar to the available commercial bondcoats used in TBCs. Then degradation monitoring with electrolyte penetration was carried out on electron beam physical vapor deposited (EB-PVD) TBCs as a function of isothermal exposure. Quality control for air plasma sprayed TBCs were carried out as a function of density, thickness and microstructure. Dense vertically cracked TBCs were tested as a function of vertical crack density and thickness. Electrochemical impedance response was acquired from all specimens at room temperature and analyzed with an AC equivalent circuit based on the impedance response as well as multi-layered structure and micro-constituents of specimens. Physical and microstructural features of these specimens were also examined by optical and electron microscopy. The EIS measurement was carried out in a three-electrode system using a standard Flat Cell (K0235) from Princeton Applied Research and IM6e BAS ZAHNER TM frequency response analyzer. The electrolyte employed in this investigation was 0.01M (molar) potassium Ferri/Ferro Cyanide [(K?Fe(CN)?/K?Fe(CN)?x3H?O)]. The thickness and density were directly related to the resistance and capacitance of the polycrystalline YSZ with varying thickness and open pores. As the effective thickness of the YSZ increased with sintering time and temperature, the resistance of the YSZ (R[subscript YSZ]) increased proportionally. The variation in capacitance of YSZ (C[subscript YSZ]) with respect to the change in porosity/density and thickness was clearly detected by EIS. The samples with high porosity (less dense) exhibited large capacitance, C[subscript YSZ]), compared to those with less porosity (high density), given similar thickness. Cracking in the YSZ monoliths resulted in decrease of resistance and increase in capacitance and this was related to the electrolyte penetration. Growth and spallation of TGO scale on NiAl alloys during isothermal oxidation at various temperatures and holding time was also correlated with resistance and capacitance of the TGO scale. With an increase in the TGO thickness, the resistance of the TGO (R[subscript TGO]) increased and capacitance of the TGO (C[subscriptTGO]) decreased. This trend in the resistance and capacitance of the TGO changed after prolonged heat treatment. This is because of the spallation of the TGO scale from the metal surface. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO, excluding the abrupt changes associated with the failure. As a function of isothermal exposure for EB -PVD TBCs, initial increase in the resistance of YSZ with thermal exposure was observed perhaps due to the high temperature sintering of YSZ. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO. An explanation based on electrolyte penetration into sub-critical damage is proposed for the gradual decrease in the resistances of YSZ and TGO with prolonged thermal exposure. Observation of exposed metallic bond coat surface on the fracture surface, which readily provides conduction, was related to the abrupt and large increase in the capacitance of YSZ and TGO. A direct relation between the resistance of the YSZ (R[subscript YSZ]) and density of the YSZ was observed for APS TBCs with varying topcoat density. APS TBCs with varying topcoat chemistry and thickness were tested and directly related to resistance of topcoat. With the increase in the topcoat thickness, the capacitance decreased and the resistance increased. The higher values of C[subscript CAT] and R[subscript CAT] compared to that of CYSZ and RYSZ were related to the higher dielectric constant and resistivity of CaTiO?. Dense vertically cracked TBCs were tested with varying crack density were tested and the variation in the resistance was related indirectly to the cracks and directly to the difference in the thickness of the topcoat. EB-PVD TBCs with varying density (dense and columnar) were tested and the variation in resistance was attributed to the dense structure and columnar structure of the topcoat with columnar structure having lower resistance because of more electrolyte penetration through the columnar structure. From this study, EIS showed a potential as a NDE technique for quality assurance and lifetime remain assessment of TBCs. Future work should continue on developing a mathematical model to study the impedance curves and come up with a model for individual layers of TBC and then sum them up to get the multilayered TBC response. The flexible instrument probe of EIS needs to be designed and tested for field evaluation of TBCs.
M.S.
Department of Mechanical, Materials and Aerospace Engineering
Engineering and Computer Science
Mechanical, Materials and Aerospace Engineering

In this work, X-ray techniques have been used to study coatings of zirconia and yttria doped zirconia. The experimental techniques used were laboratory-based X-ray diffraction (XRD) and synchrotron radiation based small-angle X-ray scattering techniques in both transmission mode; small-angle X-ray scattering (SAXS), and reflection mode; grazing-incidence small-angle x-ray scattering (GISAXS). By using XRD and (GI)SAXS measurements, information has been gained about the crystal structure of the coatings, and about the size- and surface structure of the scattering particles, respectively. Two types of in situ experiments were performed; in situ dipping-and-heating cycles, and in situ incremental heating. SAXS was used for the measurements on the former, whilst both SAXS and GISAXS was used for the latter. The coatings have been studied at various stages during calcination, and a novel methodology used for tracing the morphology quantitatively in systems subject to change, is presented here. This type of measurement and methodology is important, for example, in understanding mechanisms of corrosion and catalysis or ageing of materials. I found that the coatings transform from polymeric gels to particulate films featuring agglomeration and Ostwald ripening, as the sample is heated. The yttria concentration was found to influence the size- and the surface structure of the scattering particles; the more yttria, the smaller particles. When the samples were heated, I found that the particles within the coatings with higher yttria concentration gets a rougher surface structure at lower temperature than the particles in the lower yttria concentration coatings.

Since the mid 1970's the U.S. Navy has used Yttria-stabilized zirconia ( YSZ ) as thermal barrier coatings for hot stage gas turbine components. Use of low cost, high contaminant, fuels has led to shortened component life from failure of YSZ coatings due to corrosive attack by vanadium and other combustion oxides. The object of this investigation was to determine the reactivity of adding alpha-Al203 to Current YSZ ceramics for creation of a ceramic composite which could improve mechanical properties and show improved durability to corrosive chemical attack. Ten powder samples of Zro2(8)Mol%YzO3, alpha-Al2O3, and V20s5 of varying compositions were annealed at 900 deg C for 100 hours. X-Ray Diffraction analysis utilizing a standard 'search and match' method was used to determine the phases present in the reacted powder samples. Peak intensity comparisons between reacted and un-reacted samples allowed for a quantitative determination for the reactivity of a-A1203 with the YSZ system exposed to V2O3. This investigation indicated that alpha-Al2O3 is non-reactive in all YSZ samples exposed to V205 at 900 deg C. Ceramic, Alpha alumina, YSZ, Vanadia, Surface-induced coating (SIC), PSZ, XRD, SEM

Combustion chemical vapor deposition (combustion CVD) is a thin film deposition process that uses a flame created by the ignition of an aerosol containing precursors dissolved in a flammable solvent. Combustion CVD is a relatively new technique for creating thin film oxide coatings. Combustion CVD has been successfully used to deposit high quality thin oxide films for potential applications such as thermal barrier coatings, dielectric thin films, composite interlayer coatings, etc. The present work involved developing the optimum parameters for deposition of thin films of yttria-stabilized zirconia (YSZ), alumina (Al₂O₃), and YSZ-alumina composites followed by a determination of the mechanical properties of the films (measured using nanoindentation) as a function of composition. The optimized parameters for deposition of YSZ, alumina, and YSZ-alumina composites onto single crystal a-plane alumina involved using an organic liquid as the flammable solvent and Y 2-ethylhexanoate, Zr 2-ethylhexanoate and Al acetylacetonate as the metal precursors at a 0.002 M concentration delivered at 4 ml/min at flame temperatures of 155 ℃ and substrate temperatures of 105 ℃. The resulting films were grown with deposition rates of ~ 1.5 μm/hr. Measurement of the mechanical properties (hardness, elastic modulus and fracture toughness) of the films was performed using a mechanical properties microprobe called the Nanoindenter®. In order to obtain valid results from nanoindentation, the combustion CVD films were optimized for minimum surface roughness and grown to a thickness of approximately 0.8 μm. With the penetration depth of the indenter at approximately 150 nm, the 800 nm thickness of the film made influences of the substrate on the measurements negligible. The hardnesses and elastic moduli of the YSZ-alumina films did not vary with the composition of the film. The fracture toughness, however, did show a dependence on the composition. It was found that second phase particles of alumina grown into a YSZ matrix increased the fracture toughness of the films (on average, 1.76 MPa• m⁰.⁵ for 100% YSZ to 2.49 MPa• m⁰.⁵ for 70 mol% YSZ/30 mol% alumina). Similarly, second phase particles of YSZ grown into an alumina matrix also increased the fracture toughness (on average, 2.20 MPa• m⁰.⁵ for 100% alumina to 2.45 MPa• m⁰.⁵ for 37.2 mol% YSZ/62.8 mol% alumina). Modeling of the fracture toughness of the YSZ-alumina films was successfully achieved by using the following toughening mechanisms: crack deflection from the second phase particles, grain bridging around the particles, and residual stress from the CTE mismatch between the film and the substrate and between the second phase particles and the matrix of the film.

La projection plasma consiste à faire fondre un matériau dans un jet de plasma et à le projeter à grande vitesse en direction d’un substrat pour y former un revêtement. Ce jet de plasma est généré par une torche à plasma d’arc suite à la formation d’un arc électrique entre deux électrodes. Les torches à plasma dites conventionnelles sont largement utilisées, mais leur design conduit à des instabilités de l’arc électrique et du jet de plasma pouvant affecter le traitement thermocinétique des particules. Des torches à plasma dites segmentées ont alors été développées : grâce à la présence d’un étage supplémentaire entre les deux électrodes, elles sont plus stables et plus puissantes. Cependant, certains aspects du fonctionnement d’une torche segmentée restent peu explorés. L’objectif de ces travaux est d’approfondir l’étude sur le comportement de la torche à plasma segmentée SinplexProTM, de son fonctionnement statique à la dynamique de l’arc électrique, jusqu’à l’étude des caractéristiques des particules en vol et des microstructures des dépôts
Plasma spraying consists in melting a material in a plasma jet and to spray it at high speed towards a substrate to form a coating. The plasma jet is generated by a plasma torch following the formation of an electric arc between two electrodes. Conventional plasma torches are widely used, but their design leads to electric arc and plasma jet instabilities and may affect the thermokinetic treatment of he injected particles. Then, cascaded-anode plasma torches were developed: thanks to the presence of an additional stage between the two electrodes, they are more stable and more powerful. However, some aspects of the operating of a cascaded-anode plasma torch remain unexplored. The aim of this work is to deepen the understanding of the cascaded-anode plasma torch SinplexProTM behavior, from statics operation to the electric arc dynamics, up to the study of in-flight particles characteristics and coatings microstructures

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

Les principaux objectifs de ces travaux de thèse sont d'une part d'optimiser le protocole d'élaboration des barrières thermiques (BT) issues de la voie sol-gel et d'autre part de caractériser l'adhérence de ces barrières thermiques mais aussi de proposer des pistes en vue d'augmenter la durée de vie de celles-ci. Tout d'abord, une première étude a porté sur le choix et la validation d'un nouvel agent dispersant pour optimiser la formulation du sol chargé permettant la mise en forme des barrières thermiques. Ainsi, ce changement de dispersant a généré une microstructure conduisant à une augmentation significative de la durée de vie du système en oxydation cyclique mais a aussi permis de simplifier le protocole d'élaboration puisque l'étape de colmatage, jusqu'alors nécessaire, a été supprimée. L'étude paramétrique de la microstructure surfacique des barrières thermiques a montré que le réseau de microfissures formé initialement restait stable en fonction du vieillissement avec la création d'un sous-réseau microfissuré. Pour comprendre les mécanismes d'endommagement des barrières thermiques sol-gel et les confronter à ceux des barrières thermiques industrielles EB-PVD, la méthode d'indentation interfaciale a été retenue pour sonder l'interface revêtement/substrat. Ainsi des valeurs de ténacités apparentes ont pu être déterminées afin de comparer les adhérences des BTSG et des BTEB-PVD. A partir de ces résultats, des modèles phénoménologiques d'endommagement ont été imaginés. Pour les BTEB-PVD, l'initiation et la propagation de fissures restent localisées à l'interface barrière thermique/sous-couche de liaison, d'un coté ou de l'autre de l'oxyde de croissance selon les conditions, alors que pour les BTSG, l'endommagement est induit par la libération d'énergie élastique stockée dans le système qui augmente en fonction du vieillissement
The main objectives of this PhD are first to improve and optimise the elaboration protocol of thermal barrier coatings (TBC) manufactured by the sol-gel route and then to characterise their adhesion and investigate the possibility to enhance their lifetime. A preliminary study is focused on the selection and validation of a new dispersing agent to optimise the composite sol formulation before shaping TBC. Indeed, the new dispersant induced a microstructure allowing to significantly increase the cyclic oxidation lifetime of the system but also to simplify the elaboration process as the reinforcement step was suppressed. The parametric study of TBC surface microstructure proved that the initial micro-cracks network remained stable during ageing including the formation of a crack sub-network. To understand the damage mechanisms of sol-gel TBC and to compare them to those corresponding to industrial EB-PVD TBC, the method of interfacial indentation was developed to investigate the subtrate/top-coat interface. The apparent toughness values were determined to compare both BTSG and BTEB-PVD adhesions. From these results, phenomenological models for damage mechanisms were proposed. For BTEB-PVD, crack initiation and propagation are located at the top-coat/bond-coat interface, either on one side or the other side of the thermally grown oxide (TGO) depending of the conditions. For BTSG, the damage is a consequence of the release of the elastic strain energy stored in the system, increasing with the ageing temperature

Dans le but d’évaluer la performance et de comprendre les mécanismes d'usure, à haute température, de matériaux céramiques, de compositions chimiques différentes (Al2O3, base ZrO2, mullite), à différentes échelles de structure (finement structuré, microstructuré et submillimétrique) et de configurations différentes (monocouche, bicouche et en volume), des revêtements céramiques ont été réalisés par projection plasma à pression atmosphérique sur un substrat céramique silico-alumineux. Les revêtements d’Al2O3, de ZrO2-Al2O3 et de ZrO2- Y2O3 correspondant à la configuration monocouche ont été élaborés avec deux échelles de structure : finement structurée et microstructurée. Tandis que les revêtements de mullite/Al2O3, mullite/ ZrO2-Al2O3 et mullite/ ZrO2-Y2O3 correspondant à la configuration bicouche, ont été réalisés avec la couche supérieure (top coat) de mullite microstructurée sur les sous-couches (bond coat) finement structurés et microstructurés. Les revêtements ont été comparés à des réfractaires électrofondus d’Al2O3 et d’AZS correspondant à la configuration en volume à l’échelle submillimétrique, utilisés comme références en raison de leur grande résistance à l’usure à haute température dans les industries de fabrication du verre et des ciments. Tous les matériaux céramiques ont été exposés à des conditions d’usure par contact glissant (5 N, 20000 tours et 0,10 m.s-1) avec un tribomètre de type bille sur disque à des températures de 25, 500, 750 et 1000 °C. Les résultats indiquent que l’usure des revêtements d’Al2O3, de ZrO2- Al2O3 et de ZrO2-Y2O3 à 25 et 1000 °C est due à une déformation ductile, avec des taux d’usure respectifs de l’ordre de 10-4-10-6 et 10-4-10-5 mm3.N-1.m-1, tandis qu’à 500 et 750 °C l’usure se fait par déformation fragile avec des taux d’usure de l’ordre de 10-3-10-4 mm3.N-1.m-1 pour les deux températures. La résistance à l’usure a été trouvée légèrement supérieure dans les revêtements finement structurés principalement en raison de la ténacité plus élevée. Pour les deux réfractaires électrofondus en volume à échelle submillimétrique, l’usure par déformation ductile est prépondérante à 1000 °C, avec des taux d’usure de l’ordre de 10-4 mm3.N-1.m-1. Pour les systèmes bicouches de mullite, l’usure par déformation fragile a été observée à toutes les températures évaluées, avec des taux d’usure de l’ordre de 10-3-10-4 mm3.N-1.m-1, sans montrer aucune amélioration du fait de la présence d’une sous-couche céramique. En cherchant des solutions plus économiques et pour d’autres applications, le comportement tribologique à haute température a également été étudié sur des revêtements d’Al2O3 finement structurés et microstructurés, réalisés par projection à la flamme oxyacétylénique, plus économique que la projection plasma, ainsi que sur les mêmes revêtements d’Al2O3 réalisés par projection plasma sur un substrat métallique d’Inconel 718, couramment utilisé dans les industries spatiale et aéronautique. Dans les deux cas, les résultats étaient similaires à ceux obtenus par projection plasma sur un substrat réfractaire
In order to evaluate and to understand the wear performance and mechanisms at high temperatures that take place when different chemical compositions (Al2O3, ZrO2, mullite), scales (finely structured, microstructured and submillimetric) and configurations (single layer, bilayer and volume) interact, atmospheric plasma sprayed coatings manufactured on a silicoaluminous ceramic substrate were used. The Al2O3, ZrO2-Al2O3 and ZrO2-Y2O3 coatings correspond to the monolayer configuration, as well as the finely and microstructured scales, while the Mullite/Al2O3, Mullite/ ZrO2-Al2O3 and of Mullite/ ZrO2-Y2O3 correspond to the bilayer configuration, where the outer mullite layer is microstructured and the sub-layers can correspond to finely and microstructured scales. In the same way, the Al2O3 and AZS commercial refractories correspond to the volume configuration and the submillimeter scale, taking into account that these have also been used as references because of the high resistance to wear that they show in glass and cement industries. Subsequently, these ceramic materials were subjected to sliding contact wear conditions (5 N, 20000 rpm and 0,10 ms-1) with a ball on disk tribometer at temperatures of: 25, 500, 750 and 1000 °C. The results indicate that the wear of the Al2O3, ZrO2-Al2O3 and ZrO2-Y2O3 coatings at 25 and 1000 ° C was by ductile deformation, showing wear rates of the order of 10-4-10- 6 and 10-4-10-5 mm3.N-1.m-1 respectively, while at 500 and 750 °C was by brittle deformation with wear rates of the order of 10-3-10-4 mm3.N-1.m-1 for both temperatures, finding a slightly higher wear resistance in finely structured coatings due primarily to toughness. Regarding the two electro-melted volume refractories at submillimetric scale, they showed wear by ductile deformation only at 1000 °C, showing wear rates of the order of 10-4 mm3.N-1.m-1. On the other hand, the mullite bilayer systems showed wear by brittle deformation at all evaluated temperatures, with wear rates of the order of 10-3-10-4 mm3.N-1.m-1, without showing any improvement at all because of the presence of the sub-layers. Finally, aiming to seek more economical options, as well as to give other applications to the materials studied, it has also been determined the influence on wear at high temperature of Al2O3 coatings, finely and microstructured, manufactured by the chep technique of oxy-flame spraying, as well as the same Al2O3 coatings manufactured by plasma spraying on a metallic substrate of Inconel 718, which is used by the space and aerospace industries, obtaining for both cases comparable and similar results to all those obtained previously
Con el fin de evaluar el desempeño y comprender los mecanismos de desgaste de materiales cerámicos que se producen a alta temperatura cuando diferentes composiciones químicas (Al2O3, base ZrO2, mullita), diferentes escalas de estructura (finamente estructurado, microestructurado y submilimétrico) y diferentes configuraciones (mono-capa, bi-capa y en volumen) interactúan, fueron realizados recubrimientos cerámicos por proyección térmica de plasma sobre un sustrato cerámico silico-aluminoso. Los recubrimientos de Al2O3, ZrO2-Al2O3 y ZrO2-Y2O3 corresponden con la configuración mono-capa y con las escalas finamente estructurada y microestructurada. Mientras que los recubrimientos de mullita/Al2O3, mullita/ ZrO2-Al2O3 y mullita/ ZrO2-Y2O3 corresponden con la configuración bi-capa, donde la capa superior de los recubrimientos es de mullita microstructurada y las subcapas pueden ser finamente estructuradas y microestructuradas. Dichos recubrimientos fueron comparados con refractarios electrofundidos de Al2O3 y AZS correspondientes con la configuración en volumen y con la escala submilimétrica, los cuales también fueron utilizados como referencias debido a sus altas resistencias al desgaste a altas temperaturas en industrias tales como: la del vidrio y el cemento. Todos los materiales cerámicos fueron sometidos a condiciones de desgaste por contacto deslizante (5 N, 20000 vueltas y 0,10 m.s-1) con un tribómetro de tipo bola-disco a temperaturas de 25, 500, 750 y 1000 °C. Los resultados indican que el desgaste en los recubrimientos de Al2O3 y base ZrO2 a 25 y 1000 °C fue por deformación dúctil, con tasas de desgaste de 10-4-10-6 et 10-4-10-5 mm3.N-1.m-1 respectivamente, mientras que a 500 y 750 °C el desgaste fue por deformación frágil con tasas de desgaste del orden de 10-3-10-4 mm3.N- 1.m-1 para ambas temperaturas y ambos materiales. La resistencia al desgaste en los recubrimientos finamente estructurados fue ligeramente superior debido principalmente a la mayor tenacidad tenacidad a la fractura. Para los dos refractarios electrofundidos en volumen a escala submilimétrica, el desgaste por deformación dúctil fue detectado solo a 1000 °C, con tasas de desgaste del orden de 10-4 mm3.N-1.m-1. Para los sistemas bi-capa de mullita, el desgaste por deformación frágil se observó a todas las temperaturas evaluadas, con tasas de desgaste del orden de 10-3-10-4 mm3.N-1.m-1, sin mostrar ninguna mejora debido a la presencia de una subcapa cerámica. Finalmente, en aras de buscar tanto soluciones más económicas como otras aplicaciones, el comportamiento tribológico a alta temperatura se estudió también en recubrimientos de Al2O3 finamente estructurados y microestructurados, realizados mediante proyección térmica de llama oxiacetilénica, más económica que la proyección de plasma, así como sobre los mismos recubrimientos de Al2O3 realizados mediante proyección de plasma sobre un sustrato metálico de Inconel 718, utilizado comúnmente en las industrias espacial y aeronáutica. En ambos casos, los resultados fueron similares a los obtenidos por plasma o por sustrato refractario

Les dépôts de YSZ, élaborés par projection plasma, sont des céramiques réfractaires généralement utilisées pour les applications de barrières thermiques (TBC). Sa faible conductivité thermique associée à sa bonne résistance mécanique assure aux TBC de hautes performances et de bons rendements. La structure et la microstructure complexe sont à l'origine de ces propriétés mécaniques, et celles doivent être contrôlées. Tout comme les céramiques denses la YSZ se dégrade en température et sous vapeur d'eau.La dégradation des propriétés mécaniques dans le temps (module d'élasticité et contrainte à rupture)est accélérée par la température. Pour cette étude les propriétés ont été évaluées en flexion 3 points à température ambiante. Les observations structurales et microstructurales ont été réalisées respectivement par DRX et microscopie électronique à balayage au cours du vieillissement. Un model analytique a pu être proposé pour prédire le comportement du matériau dans le temps sous humidité
Yttria Stabilized Zirconia (YSZ) coatings, deposited by plasma sprayed process, are refractory ceramics mostly used as the Thermal Barrier Coating (TBC) applications. The low YSZ thermal conductivity associated to the good mechanical resistance ensures a high performances and efficiencies of these TBC. The structure and the complex microstructure are responsible for the mechanical properties and must be controlled. Like brittle ceramic materials, the YSZ is affected by degradation at low temperature due to water vapor. Material ageing results from the progressive degradation of the mechanical properties (such as fracture strength and Young’s modulus), which seem to decrease in time and accelerate depending on temperature. In this study, the mechanical properties have been evaluated by means of three-point bending tests at room temperature. The observations of the structure and the microstructure are respectively investigated by X-ray diffraction and SEM-technique with material ageing. An analytical model is suggested in order to predict the evolution of the properties under humidity atmosphere

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.

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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

Lors de cette etude, nous avons mis au point et optimise les conditions d'elaboration de revetements ceramique oxyde et cermet a l'aide d'un procede de projection par canon a detonation : le korund. Les mesures experimentales de pression et de celerite de l'onde de detonation nous permettent de conclure a la validite de la representation de la detonation se propageant a l'interieur du fut du korund et de l'ecoulement des produits de detonation en aval de cette onde, respectivement a l'aide des modeles chapman-jouguet (c. J. ) et taylor zeldovich (t. Z. ). L'optimisation de la composition, de la microdurete, de la rugosite, de la porosite et de l'adherence-cohesion d'un certain nombre de revetements, dont l'alumine, la zircone-yttriee et le cermet carbure de tungstene-cobalt (wc-co), a ete rendue possible par l'etude des parametres de l'installation korund. Les revetements obtenus par ce procede sont generalement tres denses et tres adherents (a titre d'exemple : porosite = 1 a 2 % ; adherence cohesion 40 a 75 mpa). Leurs caracteristiques mecaniques ont ete etudiees par le biais d'essais de flexion 3 ou 4 points qui ont montre que la rupture interfaciale substrat-revetement est mixte adhesive-cohesive. La comparaison des proprietes, et notamment de la resistance a l'erosion des revetements obtenus par differents procedes de projection hypersonique, a mis en evidence le tres bon comportement des revetements optimises durant cette etude.

Sélectionner des traitements de surface pour l’industrie nécessite de prendre en compte :les propriétés à conférer au substrat, la nature et la géométrie de celui-ci et les caractéristiques du milieu extérieur. Certaines combinaisons de ces paramètres rendent difficile la sélection d’un traitement unique, d’où le recours à des multitraitements de surface. Dès lors, se posent les questions suivantes :

- Utiliser des multitraitements de surface peut se faire en scindant les différentes requêtes en sous-ensembles, de manière à ce que chaque traitement réponde à l’un d’eux. Dans quel ordre ces requêtes doivent-elles être introduites par rapport au substrat ?

- Comment sélectionner les traitements de surface répondant à chaque requête individuelle ?

- Comment classer des multitraitements en termes d’adéquation au problème posé ?

Dans ce travail, les première et troisième questions sont abordées, en explorant les requêtes concernant habituellement les dispositifs de moulage de l’aluminium :

- Résistance aux contraintes d’origine thermique.

- Résistance à la corrosion par les métaux fondus.

- Résistance au frottement.

L’analyse de la bibliographie relative aux traitements de surface utilisés dans ces systèmes a été analysée et des « architectures »-types ont été identifiées (chapitre 3). On prévoit, par exemple, un traitement conférant la résistance à la fatigue superficielle, ainsi qu’un revêtement étanche et résistant à l’aluminium fondu. Une barrière thermique est parfois préconisée.

Pour chacune des architectures, des traitements de surface individuels peuvent être sélectionnés. Un « facteur de performance » permettant de classer les solutions par rapport au problème de la fatigue thermique a été construit (chapitre 4) et discuté dans deux situations :

- Lorsqu’un revêtement est présent, et que les contraintes d’origine thermique (différence de dilatation thermique couche-substrat) menacent de le rompre lors de l’immersion dans un milieu corrosif à haute température. Des essais de corrosion dans de l’aluminium fondu ont été réalisés sur un acier revêtu par du nitrure de chrome dopé à l’aluminium, synthétisé par déposition physique en phase vapeur (chapitre 5 – collaboration :Inasmet).

- Lorsque des variations thermiques rapides menacent de rompre le substrat et la (les) couches. Des essais de fatigue thermique ont été réalisés sur de l’acier à outils pour travail à chaud non traité, boruré ou recouvert d’un multitraitements (zircone yttriée / NiCrAlY / boruration / acier). Le revêtement en zircone yttriée a été obtenu par projection par plasma. L’essai de fatigue thermique a été modélisé et le facteur de performance, discuté (chapitre 6).

Au chapitre 7, les architectures-types ont été introduites dans une méthodologie de sélection des multi-traitements de surface, qui a été appliquée dans deux cas :

- Celui des moules de fonderie, devant résister à la fatigue thermique et à la corrosion par l’aluminium fondu. Le facteur de performance a été extrapolé à d’autres situations qu’aux chapitres 5 et 6. Les solutions habituellement proposées pour résoudre ce problème sont retrouvées.

- Celui de deux pièces en acier frottant l’une contre l’autre en présence d’aluminium fondu.

To select surface treatments, one must account for the required functional properties, the substrate features and the solicitations the substrate must endure. Certain combinations of these parameters make it difficult to select a single surface treatment, a reason why several successive treatments are preferred. To select them, one needs to determine:

- How to divide the several requests into groups and how to stack up these groups from the substrate to the outer surface, so that each treatment deals with one specific group of requests/properties.

- How to select individual layers for each group of properties.

- How to rank the multi-treatments in terms of relevance for a given application.

In this work, one tries to answer the first and the third questions, by studying the case of aluminium foundry, in which the industrial devices frequently face the following solicitations:

- Thermal stress (thermal fatigue, thermal expansion mismatch).

- Presence of corrosive molten metal.

- Sliding wear.

In the literature, several “standard” architectures are proposed (chapter 3), like a diffusion layer reducing superficial fatigue plus a corrosion barrier layer. A thermal barrier coating is also sometimes proposed.

For each of these architectures, one can select individual treatments. To rank them, one devised a “performance index” for thermal stress (chap.4), which is discussed for two cases:

- For large differences between layer and substrate thermal expansion coefficients, when both are put into contact with a high temperature corrosive medium, the layer may be damaged. One discusses this case by examining the corrosion caused by molten aluminium for a steel substrate coated by anticorrosive chromium nitride doped with aluminium. The layer is produced by physical vapour deposition (chap. 5 – cooperation: Inasmet).

- Repeated fast surface temperature transients can also damage the substrate and/or the layer by thermal fatigue. One conducted thermal fatigue tests with samples of hot work tool steel, respectively untreated, simply borided and protected by a multilayer. In the last case, top coat is yttria stabilised zirconia, followed by a nickel superalloy and then a borided layer (undercoat). One synthesized the zirconia coating by plasma spray and one modelled the thermal fatigue (chap. 6).

In chap. 7, architectures from chap. 2 are introduced in a multi-treatment selection routine, which is applied in two cases:

- Foundry moulds for molten aluminium, withstanding both thermal fatigue and corrosion. The devised performance index is extrapolated beyond the tests of chap. 5 and 6 to treatments for this industrial application, thereby quantifying their respective merits.

- A foundry device exposed to molten metal and sliding wear.

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

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.

QC 20170821

Indiana University-Purdue University Indianapolis (IUPUI)
Zirconia (ZrO2) is an important ceramic material with a broad range of applications. Due to its high melting temperature, low thermal conductivity, and high-temperature stability, zirconia based ceramics have been widely used for thermal barrier coatings (TBCs). When TBC is exposed to thermal cycling during real applications, the TBC may fail due to several mechanisms: (1) phase transformation into yttrium-rich and yttrium-depleted regions, When the yttrium-rich region produces pure zirconia domains that transform between monoclinic and tetragonal phases upon thermal cycling; and (2) cracking of the coating due to stress induced by erosion. The mechanism of erosion involves gross plastic damage within the TBC, often leading to ceramic loss and/or cracks down to the bond coat. The damage mechanisms are related to service parameters, including TBC material properties, temperature, velocity, particle size, and impact angle. The goal of this thesis is to understand the structural and mechanical properties of the thermal barrier coating material, thus increasing the service lifetime of gas turbine engines. To this end, it is critical to study the fundamental properties and potential failure mechanisms of zirconia. This thesis is focused on investigating the structural and mechanical properties of zirconia. There are mainly two parts studied in this paper, (1) ab initio calculations of thermodynamic properties of both monoclinic and tetragonal phase zirconia, and monoclinic-to-tetragonal phase transformation, and (2) image-based finite element simulation of the indentation process of yttria-stabilized zirconia. In the first part of this study, the structural properties, including lattice parameter, band structure, density of state, as well as elastic constants for both monoclinic and tetragonal zirconia have been computed. The pressure-dependent phase transition between tetragonal (t-ZrO2) and cubic zirconia (c-ZrO2) has been calculated using the density function theory (DFT) method. Phase transformation is defined by the band structure and tetragonal distortion changes. The results predict a transition from a monoclinic structure to a fluorite-type cubic structure at the pressure of 37 GPa. Thermodynamic property calculations of monoclinic zirconia (m-ZrO2) were also carried out. Temperature-dependent heat capacity, entropy, free energy, Debye temperature of monoclinic zirconia, from 0 to 1000 K, were computed, and they compared well with those reported in the literature. Moreover, the atomistic simulations correctly predicted the phase transitions of m-ZrO2 under compressive pressures ranging from 0 to 70 GPa. The phase transition pressures of monoclinic to orthorhombic I (3 GPa), orthorhombic I to orthorhombic II (8 GPa), orthorhombic II to tetragonal (37 GPa), and stable tetragonal phases (37-60 GPa) are in excellent agreement with experimental data. In the second part of this study, the mechanical response of yttria-stabilized zirconia under Rockwell superficial indentation was studied. The microstructure image based finite element method was used to validate the model using a composite cermet material. Then, the finite element model of Rockwell indentation of yttria-stabilized zirconia was developed, and the result was compared with experimental hardness data.