Microstructure modification of EB-pvd gadolinium zirconate thermal barrier coatings and the effect on their resistance against siliceous CMAS melts

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Investigation of erosion behavior of EB-PVD-TBCs and sacrificial coatings after CMAS infiltration

Aero-engines operating in sand laden environments often encounter severe problems with thermal barrier coatings (TBCs) due to erosion damage. Since the turbine entry temperatures are raising, the life-time of TBC coatings as well as its thermal conductivity are additionally influenced by molten sand (calcium-magnesium-alumino-silicate/ CMAS). Few attempts have been made in understanding the combined impact of both erosion and CMAS effects [1,2]. Wellman and Nicholls [1] have found that a fully CMAS infiltrated electron-beam physical vapor deposited (EB-PVD) TBC behaves like a continuum during erosion and slightly improves its erosion behavior under room temperature compared to pure TBC. Development of CMAS resistant coatings has been a hot topic for the last two decades and one of the proposed method is the application of sacrificial oxide layers such as Al2O3, MgO, Sc2O3 et al. [3], on top of the TBCs. These sacrificial layers chemically react with the CMAS and modify the melting temperature or the viscosity of CMAS and thus the infiltration of CMAS into the TBC is inhibited. Since both damage mechanisms (erosion and corrosion) occur parallel and competitively in a turbine, this study focuses on deeper understanding of the erosion behavior of CMAS-infiltrated 7wt.-% yttria stabilized zirconia (7YSZ) TBCs. 400 µm thick 7YSZ coatings with two different microstructures were produced by EB-PVD. Additionally, sacrificial Al2O3 coatings were also applied on the top of 7YSZ by means of suspension plasma spraying (SPS) and suspension high velocity oxy-fuel spraying (SHVOF) using water-based suspensions. CMAS infiltration experiments were carried out at 1250 °C using different CMAS compositions and different infiltration times. Erosion tests were realized at room temperature in an in-house erosion test rig and evaluated partly by confocal microscopy. Microstructural examinations as well as crack identification before and after testing were carried out using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Infiltrated TBCs behaved as a continuum material during erosion exposure which lead mainly to surface spallation. Furthermore, the CMAS infiltration in the TBCs and partly the sintering effect at 1250 °C lead to a network of vertical cracks. These vertical cracks are weak areas where severe erosion occurs. The different TBC microstructures, infiltration times and CMAS compositions strongly influence the erosion behavior of the TBC. In case of alumina top coats the microstructure and especially the presence of porosity in the coating has strongly influenced the CMAS infiltration depth, the erosion behavior, and the stability of the entire coating system. [1] R.G. Wellman, J.R. Nicholls, Erosion, corrosion and erosion–corrosion of EB PVD thermal barrier coatings, Tribology International. 41 (2008) 657–662. doi:10.1016/j.triboint.2007.10.004. [2] S. Rezanka, D.E. Mack, G. Mauer, D. Sebold, O. Guillon, R. Vaßen, Investigation of the resistance of open-column-structured PS-PVD TBCs to erosive and high-temperature corrosive attack, Surface and Coatings Technology. 324 (2017) 222–235. doi:10.1016/j.surfcoat.2017.05.003. [3] A.K. Rai, R.S. Bhattacharya, D.E. Wolfe, T.J. Eden, CMAS-Resistant Thermal Barrier Coatings (TBC), International Journal of Applied Ceramic Technology. 7 (2010) 662–674. doi:10.1111/j.1744-7402.2009.02373.x

Investigation of CMAS resistance of SPS- and SHVOF-alumina topcoats on EB-PVD 7YSZ layers

Thermal barrier coatings (TBCs) undergo severe degradation by interaction with molten calcium-magnesium-aluminum-silicate (CMAS) minerals that are found mainly in volcanic ashes (VA) or desert sands. After the infiltration of the CMAS, chemical reactions, diffusion and phase transformation can lead to residual stress, cracks and spallation and thus significantly shorten the life-time of the components. As the state-of-the-art material 7 wt.-% Y2O3 stabilized ZrO2 (7YSZ) offers limited resistance to the CMAS attack, development of CMAS-resistant TBCs has undergone intense research during the last decades. One of the proposed approaches is the application of a sacrificial layer on top of the TBC which reacts with the molten CMAS/VA to crystalline phases and in this way inhibits further infiltration by sealing the gaps and pores. Al2O3 is one candidate for such a sacrificial layer which exhibits good CMAS resistance by formation of arresting phases. However, EB‑PVD Al2O3-topcoats suffer locally from cracks that arise from crystallization and sintering shrinkage, thereby providing only a discontinuous protection against CMAS infiltration due to their characteristic morphology. Even though the alumina is a candidate material, the coating density and the arrangement of porosity has been found to be a critical factor for restricting CMAS infiltration. In this work alumina coatings were sprayed on top of EB‑PVD 7YSZ TBCs using suspension plasma spraying (SPS) and suspension high velocity oxygen fuel spraying (SHVOF) starting from an aqueous suspension containing fine dispersed Al2O3 (d50 about 2.3 µm). The spray parameters were optimized in order to produce Al2O3 topcoats with homogeneous distributed porosity from very porous (porosity about 30 %) to denser (porosity about 10-15 %). These coatings were tested under CMAS attack by performing infiltration experiments at 1250 °C for different time intervals from 5 min to 10 hours. One Island volcanic ash from the Eyjafjallajökull volcano (IVA) and two types of synthetic CMAS compositions were tested in this study. The infiltration kinetics and reaction products were studied by SEM, energy-dispersive spectroscopy (EDS) and x-ray diffraction (XRD). It was observed that the microstructure and especially the presence of the porosity in the Al2O3 coatings strongly influenced the CMAS infiltration kinetics. Due to its high and non-uniform porosity, CMAS/VA melt infiltrated the 100 µm thick, very porous alumina SPS‑coating inhomogeneously and reached the subjacent 7YSZ layer already after one hour of annealing at 1250°C. Additionally, it was found that the infiltration kinetics varies also with the chemical composition of the CMAS/VA. Different crystalline phases such as anorthite, spinel or others were formed as reaction products of the SPS‑Alumina-TBC with the CMAS/VA-melt. The exact phases and its location depend on the used CMAS/VA composition. Furthermore, the annealing time has a major influence on the presence of the various phases. The infiltration kinetics of the SHVOF‑coatings was different due to a change in morphology. The current experiments clearly demonstrate that CMAS/VA mitigation depends on the interplay between morphology of the coating which dictates the driving force for infiltration, the reaction speed between alumina and the deposit, and the deposit chemistry

Microstructure modification of EB-pvd gadolinium zirconate thermal barrier coatings and the effect on their resistance against siliceous CMAS melts

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Development of EBCs and T/EBC multi-layer coatings: Challenges and implications

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Microstructure Modification of EB-PVD GZO TBCs and the effect on their Resistance against Siliceous CMAS melts

Gadolinium zirconate TBCs are proven to be very effective in restricting the CMAS attack by forming quick crystalline reaction products such as apatite and garnet that seal the porosity against infiltration. However, the microstructural effects on the efficacy of GZO against CMAS attack is less explored and especially the microstructures that are obtained by the Electron Beam-Physical Vapor Deposition method. Several distinct GZO microstructures are created by EB-PVD deposition method and assessed with regard to their microstructural characteristics. The response of elected microstructures to CMAS melts with different chemical compositions was studied for up to 50h at 1250°C. An optimized columnar microstructures with smaller intercolumnar gaps and long featherarms was found to significantly lower the CMAS infiltration compare to those microstructures created with standard parameters. The formation the reaction products such as Apatite, Fluorite, Garnet etc. was found to be strongly dependent on the CMAS melt composition as well as on the local microstructure. Garnet, which formed as a continuous layer on top of Apatite and Fluorite, is identified as a beneficial reaction product that improves the CMAS resistance, as it slows down the consumption of GZO, binds high amounts of CMAS and stabilizes the subjacent Apatite-Fluorite reaction layer

Investigation of CMAS Resistance of Sacrificial Suspension Sprayed Alumina Topcoats on EB-PVD 7YSZ Layers

Molten calcium-magnesium-aluminum-silicate (CMAS) mineral particles cause significant degradation of thermal barrier coatings (TBCs) in aero-engines. One approach to protect the TBC coating against the CMAS attack is the application of a sacrificial coating on top of the TBC coating. In this work, Al2O3 coatings were deposited on EB-PVD 7YSZ layers using suspension plasma spraying (SPS) and suspension high velocity oxy-fuel spraying (SHVOF), in order to produce sacrificial topcoats with two different microstructures and porosity levels. The coating systems were tested under CMAS attack with one natural volcanic ash and two artificial CMAS powders by conducting infiltration tests at 1250 °C in the time intervals between 5 min and 10 h. It was found that the porosity and morphology of suspension sprayed alumina topcoats, the chemical composition of the deposits and the infiltration conditions strongly influence the CMAS infiltration, reaction kinetics and formation of the reaction products. While the porous SPS coatings offer limited resistance against CMAS infiltration, the dense SHVOF coatings show promising CMAS sealing behavior. Among the formed reaction products, only (Fe, Mg) Al spinel acted as an efficient barrier against CMAS infiltration. However, the formation of uniform spinel layers strongly depends on the pore morphology of the sacrificial coating and the CMAS chemistry

Erosion behavior of CMAS/VA infiltrated EB-PVD Gd2Zr2O7 TBCs: Special emphasis on the effect of mechanical properties of the reaction products

Aero-engines operating in sand-laden (CMAS/CaO-MgO-Al2O3-SiO2) environments often encounter severe problems with thermal barrier coatings (TBCs) due to CMAS infiltration and erosion damage. This study focuses on a deeper understanding of the erosion behavior of CMAS-infiltrated EB-PVD Gd2Zr2O7 TBCs. The study includes isothermal infiltration of different CMAS and subsequent erosion tests at room temperature. In addition to the erosion behavior of the entire coating, the influence of different reaction products within the reaction layer on erosion failure was investigated by measuring the hardness and Young’s modulus of the individual phases using in-situ REM-Nanoindentation. It was found that a garnet layer above the reaction layer and spinel inclusions within a thick apatite/fluorite reaction layer, can improve the erosion resistance of this reaction layer by 30-40%. Furthermore, a correlation between the erosion behavior and the hardness vs. Young’s modulus relation, obtained from nanoindentation over the entire coating, was observed for a consistent microstructure

Microstructure Refinement of EB-PVD Gadolinium Zirconate Thermal Barrier Coatings to Improve Their CMAS Resistance

Rare-earth zirconates are proven to be very effective in restricting the CMAS attack against thermal barrier coatings (TBCs) by forming quick crystalline reaction products that seal the porosity against infiltration. The microstructural effects on the efficacy of Electron Beam-Physical Vapor Deposition gadolinium zirconate (EB-PVD GZO) against CMAS attack are explored in this study. Four distinct GZO microstructures were manufactured and the response of two selected GZO variants to different CMAS and volcanic ash melts was studied for annealing times between 10 min and 50 h at 1250°C. A significant variation in the microstructural characteristics was achieved by altering substrate temperature and rotation speed. A refined microstructure with smaller intercolumnar gaps and long feather arms lowered the CMAS infiltration by 56%-72%. Garnet phase, which formed as a continuous layer on top of apatite and fluorite, is identified as a beneficial reaction product that improves the CMAS resistance

Comparative study of EB-PVD gadolinium-zirconate and yttria-rich zirconia coatings performance against Fe-containing calcium-magnesium-aluminosilicate (CMAS) infiltration

This detailed study compare and contrast the calcium-magnesium-aluminosilicate (CMAS) infiltration resistance behavior of electron-beam physical vapor deposition (EB-PVD) produced gadolinium zirconate (GZO) and yttria rich zirconia (65YZ, 65 wt % Y2O3 rest zirconia) coatings. The infiltration kinetics, as well as the stability and protective nature of different reaction products, was studied by performing long term infiltration tests (up to 50 h) at 1250 °C. The results reveal that for the specific microstructures used in this study, 65YZ has a higher infiltration resistance and forms a thinner reaction layer compared to GZO. The analysis indicates that the better performance of 65YZ is associated with a synergetic reaction mechanism, which includes the formation of Carich apatite and a uniform layer of a garnet phase. The formation of apatite requires more rare-earth (RE) in the case of GZO than its 65YZ counterpart, meaning that more Gd would be dissolved before forming apatite crystals, which leads to higher consumption of the GZO layer compared to that of 65YZ. The implications of these mechanisms are discussed in detail concerning the tendency of garnet formation, equilibration of the apatite phase with Ca and RE content, and the effects of the reduction in viscosity due to the RE dissolution into the glass. However, microstructural differences in the coatings used in this study might also affect the diverging infiltration resistance and reaction kinetics and need to be considere