Evolution of porosity,crack density,and CMAS penetration in thermal barrier coatings subjected to burner rig testing

Degradation of thermal barrier coatings (TBCs) in gas-turbine engines due to calcium–magnesium–aluminosilicate (CMAS) glassy deposits from various sources has been a persistent issue since many years. In this study, state of the art electron microscopy was correlated with X-ray refraction techniques to elucidate the intrusion of CMAS into the porous structure of atmospheric plasma sprayed (APS) TBCs and the formation and growth of cracks under thermal cycling in a burner rig. Results indicate that the sparse nature of the infiltration as well as kinetics in the burner rig are majorly influenced by the wetting behavior of the CMAS. Despite the obvious attack of CMAS on grain boundaries, the interaction of yttria-stabilized zirconia (YSZ) with intruded CMAS has no immediate impact on structure and density of internal surfaces. At a later stage the formation of horizontal cracks is observed in a wider zone of the TBC layer.     

Characterization of stress in a thermal barrier coating during CMAS corrosion using Ce3+ photoluminescence spectroscopy

The stress caused by calcium–magnesium–alumino–silicate (CMAS) corrosion is a critical factor in thermal barrier failure of thermal barrier coatings (TBCs). For the service safety of TBCs, it is important to characterize the stress inside TBCs during CMAS corrosion using a nondestructive and accurate method. In this study, photoluminescence spectroscopy technology was applied to characterize the stress in TBCs during CMAS corrosion. First, TBC specimens containing yttrium–aluminum–garnet doped with trace Ce³⁺ ions (YAG:Ce³⁺)/yttrium oxide partially stabilized zirconia double-ceramic-layer were prepared by atmospheric plasma spraying. Then, CMAS corrosion experiments were performed using the TBC specimens, and a mechanical model was derived based on Ce³⁺ photoluminescence spectroscopy to investigate the stress in the TBCs. Finally, the microstructure, extent of CMAS corrosion and stress field in TBC specimens, was characterized. The results reveal that the penetration of CMAS leads to local stress concentration and a nonlinear stress distribution from the outside surface to the inside of the YAG:Ce³⁺ layer. In addition, an increase in corrosion time, temperature, and CMAS concentration can significantly influence the evolution of the stress field in TBCs.     

A new approach to protect and extend longevity of the thermal barrier coating by an impermeable layer of silicon nitride

A sample representation of a gas turbine engine blade, consisting of a nickel superalloy substrate with a deposited thermal barrier coating (TBC), was covered with silicon nitride, Si₃N₄, as an impermeable layer using plasma enhanced chemical vapor deposition (PECVD). The silicon nitride layer was used to seal the topcoat of yttria-stabilized zirconia (YSZ) surface of the TBC to mitigate calcium–magnesium–aluminum–silicon oxide (CMAS) attack. CMAS testing was carried out on the covered and uncovered surfaces by melting a ratio of 25 mg/cm² of CMAS powder onto the surface of each sample in a furnace at 1100°C for 1 h. The conformal surface reaction of the sealed layer confirmed no cracking or delamination at high temperatures. Scanning electron microscopy (SEM) micrographs confirmed that the surface of YSZ was successfully sealed. The new coating of silicon nitride was shown to be a viable solution and technique to significantly block CMAS infiltration in porous thermal barrier coatings.     

Pore filling behavior of YSZ under CMAS attack: Implications for designing corrosion‐resistant thermal barrier coatings

To understand the pore filling behavior in thermal barrier coatings during calcium‐magnesium‐alumino‐silicate (CMAS) infiltration process, porous yttria‐stabilized zirconia pellets with different sizes of spherical pores were prepared to simulate thermal barrier coatings. The pores (D50 ranging from 6 to 77 μm) were introduced to the pellets using poly methyl methacrylate as pore forming agents. Then the pellets were sintered to remove the pore forming agents and to achieve a similar volume fraction of porosity with thermal barrier coatings. After CMAS infiltration, only some small pores in the CMAS‐infiltrated zones were filled by CMAS, whereas all large pores (larger than 13 μm) remained unfilled; besides, the results also show that even open pores can resist filling by CMAS. The reason may relate to pore diameters; if the diameter of a pore is relatively large, the pore surface will not be completely wetted by liquid CMAS, the liquid meniscus will be discontinuous, and therefore the pore cannot be filled. The key insight gained from this study is that introducing “CMAS‐proof” pores into thermal barrier coatings may be a potential way to mitigate CMAS damage.     

CMAS-Resistant Thermal Barrier Coatings (TBC)

Electron beam-physical vapor-deposited thermal barrier coatings (TBC) are susceptible to damage due to environmental contaminants such as calcium–magnesium–aluminum–silicon oxide systems (CMAS). This paper discusses various approaches of modifying TBC for enhanced protection against CMAS attack. Methodologies were explored with various coating systems maintaining functionality as nonwetting, sacrificial, and impervious to CMAS attack. In the brief isothermal (1260°C/10 min) tests, a nearly crack-free and reglazed Pd coating provided substantial protection from the CMAS attack. Approaches that provided some minor improvements need further optimization to better assess their viability.     

Isothermal Oxidation Behavior of Gd2Zr2O7/YSZ Multilayered Thermal Barrier Coatings

Efficiency of a gas turbine can be increased by increasing the operating temperature. Yttria‐stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used in gas turbine applications. However, above 1200°C, YSZ undergoes significant sintering and CMAS (calcium magnesium alumino silicate) infiltration. New ceramic materials of rare earth zirconate composition such as gadolinium zirconate (GZ) are promising candidates for thermal barrier coating applications (TBC) above 1200°C. Suspension plasma spray of single‐layer YSZ, double‐layer GZ/YSZ, and a triple‐layer TBC comprising denser GZ on top of GZ/YSZ TBC was attempted. The overall coating thickness in all three TBCs was kept the same. Isothermal oxidation performance of the three TBCs along with bare substrate and bond‐coated substrate was investigated for time intervals of 10 h, 50 h, and 100 h at 1150°C in air environment. Weight gain/loss analysis was carried out by sensitive weighing balance. Microstructural analysis was carried out using scanning electron microscopy (SEM). As‐sprayed single‐layer YSZ and double‐layer GZ/YSZ showed columnar microstructure, whereas the denser layer in the triple‐layer TBC was not columnar. Phase analysis of the top surface of as‐sprayed TBCs was carried out using XRD. Porosity measurements were made by water intrusion method. In the weight gain analysis and SEM analysis, multilayered TBCs showed lower weight gain and lower TGO thickness compared to single‐layer YSZ.     

Enhanced properties of Al-modified EB-PVD 7YSZ thermal barrier coatings

7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coating (TBC) prepared by electron beam-physical vapor deposition (EB-PVD) has been used in gas turbine engines for many years, where the TBC must successfully withstands the damage caused by a variety of environmental and mechanical aspects. The primary failure modes for TBC are oxidation of bond coating, particle erosion and CMAS (calcium-magnesium-alumina-silicates) corrosion. The lifetime of TBC associated with above three failure factors will be reduced significantly. In order to prolong the operation time, an alternative approach depositing Al film on 7YSZ TBC surface by magnetron sputtering is proposed. An α-Al₂O₃ overlay was in-situ synthesized on each 7YSZ column through reaction of Al and ZrO₂ during vacuum heat treatment. And the results indicate that the Al-modified EB-PVD 7YSZ TBC shows better oxidation resistance, as well as lower particulate erosion and CMAS corrosion.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part II,Interactions with Sand and Fly Ash

Based on the application of OB considerations (Part I) to various major thermal barrier coating (TBC) compositions and two types of important calcium–magnesium–alumino–silicates (CMAS)—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with high CMAS‐resistance potential, is chosen for studying molten‐CMAS/TBC interactions. It is demonstrated that 2ZrO₂·Y₂O₃(ss) air plasma sprayed (APS) TBCs are highly resistant to high‐temperature attack by both sand‐CMAS and fly‐ash‐CMAS. Despite the differences in the compositions of the two CMASs, the overall CMAS‐attack mitigation mechanisms in both cases appear to be similar, viz reaction between 2ZrO₂·Y₂O₃(ss) APS TBC and the CMAS, and the formation of main reaction products of Y‐depleted c‐ZrO₂ and nonstoichiometric Ca–Y apatite. Large differences in the OBs (ΔΛ) between the 2ZrO₂·Y₂O₃(ss) and the CMASs are good predictors of ready reaction between this TBC and these CMASs. While the details of the CMAS‐mitigation mechanisms can depend critically on various other aspects, the OB difference (ΔΛ) calculations could be used for the initial screening of CMAS‐resistant TBC compositions.     

Sintering of tricalcium phosphate–fluorapatite composites with zirconia

Zirconia (ZrO₂) addition effects on densification and microstructure of tricalcium phosphate–26.52 wt% fluorapatite composites were investigated, using X-ray diffraction, scanning electron microscopy and by analysis using ³¹P nuclear magnetic resonance. The tricalcium phosphate–26.52 wt% fluorapatite–zirconia composites densification increases versus temperature. At 1300 °C, the composites apparent porosity reaches 9% with 5 wt% zirconia. XRD analysis of the composites reveals the presence of tricalcium phosphate, fluorapatite and zirconia without any other structures. Above 1300 °C, the densification was hindered by grain growth and the formation of both intragranular porosity and new compounds. The ³¹P MAS-NMR analysis of composites sintered at various temperatures or with different percentages of zirconia reveals the presence of tetrahedral P sites. At 1400 °C, XRD analysis of the tricalcium phosphate–26.52 wt% fluorapatite–20 wt% zirconia composites shows the presence of calcium zirconate and tetracalcium phosphate. This result indicated that partial decomposition of tricalcium phosphate during sintering process of composites when 20 wt% or less ZrO₂ was added. Thus, zirconia reacts with tricalcium phosphate forming calcium zirconate and tetracalcium phosphate.     

Effect of CMAS Infiltration on Radiative Transport Through an EB-PVD Thermal Barrier Coating

One of the adverse effects of sand ingestion in gas turbines is that the thermal barrier coatings on the blades and vanes can be infiltrated at high temperatures by molten calcium–magnesium–aluminum–silicate (CMAS) and cause premature failure of the coating. To investigate the effect of CMAS penetration, the optical properties of a synthetic glass representative of CMAS are reported from 500 nm to 2.5 μm. Results are then presented to show that silicate infiltration of an electron beam-deposited TBC can increase radiative transport through the coating. The results are qualitatively consistent with a simple optical scattering model for radiative transport through a porous coating.     

Effect of test parameters in the exposure of Ca–Mg–Al–silicate on yttria stabilized zirconia

Jet engine components need protective coatings to function against both high-temperature and environmental effects. Ingested calcium–magnesium–aluminosilicates (CMAS) dust particulates are extremely detrimental to the life of the coatings. However, many methods exist to investigate the infiltration of CMAS into these coatings with each method exploring a different aspect of the degradation process. To probe the overlap in these methods, this study focuses on the effect of grain size, areal density, and aspect ratio on the infiltration of CMAS into yttria stabilized zirconia. The infiltration depths ranged from 6 up to 85 µm depending on the test conditions.     

Effects of CMAS penetration on the delamination cracks in EB-PVD thermal barrier coatings with curved interface

During the high-temperature operation of electron beam physical vapor deposited (EB-PVD) thermal barrier coating (TBC), the penetration of environmental calcium-magnesium-alumina-silicate (CMAS) compositions into the ceramic top-coat would affect the growth of delamination cracks. In this work, the effects of CMAS penetration on the delamination cracks in EB-PVD TBC with curved interface are investigated by finite element analysis. In the numerical model, the curved interface evolves as the cyclic displacement instability of the thermally grown oxide (TGO) layer. The penetration of CMAS into the columnar gaps of EB-PVD TBC mainly increases the in-plane modulus of TC layer. It is demonstrated that, with the increase of in-plane modulus in an intact TC, the level of tensile stress, which mainly occurs in the region above the curved interface and responsible for initiating the delamination cracks, presents a decrease; meanwhile, the level of shear stress, which mainly occurs in the region at the periphery of the curved zone to drive the delamination crack when it propagates into this region, presents a increase. Furthermore, the calculation of the strain energy release rate shows that, for the crack located above the curved interface, the increase of in-plane modulus in TC layer can prevent the accumulation of strain energy release rate, and therefore make it more difficult for delamination initiation. However, once the crack propagates into the flat periphery, CMAS penetration would begin to enhance its growth.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part I,Optical Basicity Considerations and Processing

The higher operating temperatures in gas‐turbine engines enabled by thermal barrier coatings (TBCs) engender new materials issues, viz silicate particles (sand, volcanic ash, fly ash) ingested by the engine melt on the hot TBC surfaces and form calcium–magnesium–alumino–silicate (CMAS) glass deposits. The molten CMAS glass degrades TBCs, leading to their premature failure. In this context, we have used the concept of optical basicity (OB) to provide a quantitative chemical basis for the screening of CMAS‐resistant TBC compositions, which could also be extended to environmental barrier coatings (EBCs). By applying OB difference considerations to various major TBC compositions and two types of important CMASs—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with the potential for high CMAS‐resistance, is chosen for this study. Here, we also demonstrate the feasibility of processing of 2ZrO₂·Y₂O₃(ss) air‐plasma sprayed (APS) TBC using commercially developed powders. The resulting TBCs with typical APS microstructures are found to be single‐phase cubic fluorite, having a thermal conductivity <0.9 W·(m·K)^?1 at elevated temperatures. The accompanying Part II paper presents results from experiments and analyses of high‐temperature interactions between 2ZrO₂·Y₂O₃(ss) APS TBC and the two types of CMASs.     

Thermal cycling performances of multilayered yttria-stabilized zirconia/gadolinium zirconate thermal barrier coatings

Gadolinium zirconate (Gd₂Zr₂O₇, GZO) as an advanced thermal barrier coating (TBC) material, has lower thermal conductivity, better phase stability, sintering resistance, and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (YSZ, 6-8 wt%) at temperatures above 1200°C. However, the drawbacks of GZO, such as the low fracture toughness and the formation of deleterious interphases with thermally grown alumina have to be considered for the application as TBC. Using atmospheric plasma spraying (APS) and suspension plasma spraying (SPS), double-layered YSZ/GZO TBCs, and triple-layered YSZ/GZO TBCs were manufactured. In thermal cycling tests, both multilayered TBCs showed a significant longer lifetime than conventional single-layered APS YSZ TBCs. The failure mechanism of TBCs in thermal cycling test was investigated. In addition, the CMAS attack resistance of both TBCs was also investigated in a modified burner rig facility. The triple-layered TBCs had an extremely long lifetime under CMAS attack. The failure mechanism of TBCs under CMAS attack and the CMAS infiltration mechanism were investigated and discussed.     

Molten silicate interactions with plasma sprayed thermal barrier coatings: Role of materials and microstructure

Ingestion of siliceous particulate debris into both propulsion and energy turbines has introduced significant challenges in harnessing the benefits of enhanced operation efficiencies through the use of higher temperatures and thermal barrier coatings (TBCs). The so-called CMAS (for calcium-magnesium alumino-silicate) particles can melt in the gas path at temperatures greater than 1200C, where they will subsequently impact the coating surface and infiltrate through the carefully engineered porosity or cracks in a TBC. Ultimately, this CMAS attack causes premature spallation through its solidification and stiffening the ceramic during cooling. It has been noted in recent years, that TBCs based on yttria stabilized zirconia (YSZ) are completely non-resistant to CMAS attack due to their lack of reactivity with infiltrant liquid. New TBC ceramics such as Gadolinium Zirconate (GZO) show promise of CMAS resistance through rapid reaction-induced crystallization and solidification of the infiltrant, leading to its arrested infiltration. In both situations, the microstructure (porosity, micro and macro cracks) can be important differentiators in terms of the infiltration and subsequent failure mechanisms. This paper seeks to examine the interplay among microstructure, material, and CMAS attack in different scenarios. To do so, different types of YSZ & GZO single and multilayer coatings were fabricated using Air Plasma Spray (APS) and exposed to CMAS through isothermal and gradient mechanisms. In each of the cases, beyond their unique interactions with CMAS, it was observed the inherent microstructure and character of the porosity of the coating will have an additional role on the movement of the melt. For instance, vertical cracks can provide pathways for accelerated capillaric flow of the melt into both YSZ and GZO coatings. Based on these observations multilayer coatings have been proposed and realized toward potentially reducing complete coating failure and supporting multiple CMAS attack scenarios.     

Laser surface modification of porous yttria stabilized zirconia against CMAS degradation

Here, we present a new combined freeze-casting and laser processing method for the design of yttria-stabilized zirconia (YSZ) based thermal-barrier coatings. YSZ ceramics with unidirectionally-aligned pore channels were created using the freeze-casting method. After sintering, top view and cross-sectional scanning electron microscopy (SEM) revealed the structural features of the preform, which exhibits a 74 ± 2% volume fraction of porosity and an average pore channel size of 30 ± 3 μm. The measured thermal conductivity of this porous structure was 0.27 ± 0.02 W/(m K), which is eight times lower than that of reported values for dense YSZ. Though high porosity is beneficial both from a structural and thermal response perspective, the open porosity could potentially be an issue from an application stand-point when evaluating the resistance of materials to calcium–magnesium–aluminum–silicon oxide (CMAS) attack. CMAS attack, which can originate from deposits of molten sand, ash, and dust, is one of the major causes of thermal barrier coating failure. Therefore, the surface of the porous samples was modified using a laser process to create a barrier to CMAS infiltration. SEM micrographs aided in determining the optimum laser parameters required to fully seal the surface using a laser treatment. The performance of the original porous and surface-modified YSZ was compared by conducting CMAS infiltration studies. Laser modification was shown to be a viable technique to significantly reduce CMAS infiltration in porous thermal barrier coatings.     

The Accelerating Effect of CaSO4 Within CMAS (CaO–MgO–Al2O3–SiO2) and Its Effect on the Infiltration Behavior in EB‐PVD 7YSZ

Infiltration and deposition of CaSO₄ in thermal barrier coatings (TBC) in addition to the CMAS deposits was found in many occasions on real aviation engines. The source and role of CaSO₄ on the degradation of TBC is not well understood. CaSO₄ containing CMAS was synthesized and a systematic study of its role on the CMAS infiltration behavior in EB‐PVD 7YSZ is presented in this work. Its influence on the melting and crystallization behavior of CMAS was studied with the help of differential scanning calorimetry. The decomposition of CaSO₄ into CaO and SO₃ was observed at 1050°C in laboratory air under the presence of CMAS using mass spectroscopy and in situ high‐temperature XRD. The same amount of CaO is brought into the CMAS system by means of adding CaCO₃, which will eventually decompose into CaO and CO₂ at 700°C. CMAS infiltration tests were carried out at different temperatures with and without CaSO₄/CaCO₃ and the results demonstrate that the sulfur has no direct effect on the aggressiveness of the anhydrite containing CMAS with regard to its infiltration behavior in EB‐PVD 7YSZ at high temperatures. The extra amount of calcia added to CMAS that is introduced by the evaporating species is responsible for enhanced infiltration of the deposits into the TBC.     

Melting and Crystallization of Silicate Systems Relevant to Thermal Barrier Coating Damage

The melting and crystallization behaviors of model calcium–magnesium–alumino‐silicate (CMAS) compositions relevant to the degradation of thermal barrier coatings (TBCs) were investigated. A primary goal was to establish a baseline for studies on CMAS reactions with TBC materials, reported separately, and their potential to mitigate degradation. Ternary calcium alumino‐silicate (CAS) compositions investigated melt below their equilibrium solidus owing to their metastable phase constitution. Additions of MgO or FeO_x have significant effects on the melting behavior, depending on the C:A:S proportions. Amorphization on cooling is commonplace, with MgO, AlO_1.5, and especially FeO_x promoting crystallization. The behaviors of amorphous and crystalline versions of the same CMAS are different and depend on heating/cooling rates, with attendant implications for their interaction with TBCs.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

CMAS corrosion behavior of a LaPO4 ceramic prepared by spark plasma sintering

At high temperatures in gas turbines, traditional yttria stabilized zirconia materials fail prematurely owing to CMAS (calcium–magnesium–alumina–silicate) corrosion. Thus, new materials need to be developed urgently. In this study, LaPO₄ powder was synthesized by chemical coprecipitation and heat treatment using lanthanum nitrate (La(NO₃)₃∙6H₂O) and ammonium dihydrogen phosphate (NH₄H₂PO₄) as starting materials, and LaPO₄ bulk was prepared by spark plasma sintering. The surface of the LaPO₄ bulk was coated with CMAS (CaO–MgO–Al₂O₃–SiO₂) powder, and the CMAS interaction with the LaPO₄ bulk at different temperatures was investigated. The phase and microstructure of the LaPO₄ powder and bulk, as well as the CMAS corrosion products, were characterized using X-ray diffraction and scanning electron microscope. The superior CMAS resistance of the LaPO₄ bulk was attributed to the low wettability of LaPO₄ by the CMAS melt and the development of dense layers of new corrosion products, which effectively protected the LaPO₄ bulk from CMAS infiltration.