CMAS-Resistant Plasma Sprayed Thermal Barrier Coatings Based on Y2O3-Stabilized ZrO2 with Al3+ and Ti4+ Solute Additions

The higher operating temperatures in gas-turbine engines made possible by thermal barrier coatings (TBCs) are engendering a new problem: environmentally ingested airborne silicate particles (sand, ash) melt on the hot TBC surfaces and form calcium-magnesium-alumino-silicate (CMAS) glass deposits. The molten CMAS glass degrades the TBCs, leading to their premature failure. Here, we demonstrate the use of a commercially manufactured feedstock powder, in conjunction with air plasma spray process, to deposit CMAS-resistant yttria-stabilized zirconia-based TBCs containing Al³⁺ and Ti⁴⁺ in solid solution. Results from the characterization of these new TBCs and CMAS/TBCs interaction experiments are presented. The CMAS mitigation mechanisms in these new TBCs involve the crystallization of the anorthite phase. Raman microscopy is used to generate large area maps of the anorthite phase in the CMAS-interacted TBCs demonstrating the potential usefulness of this method for studying CMAS/TBCs interactions. The ubiquity of airborne sand/ash particles and the ever-increasing demand for higher operating temperatures in future high efficiency gas-turbine engines will necessitate CMAS resistance in all hot-section components of those engines. In this context, the versatility, ease of processing, and low cost offered by the process demonstrated here could benefit the development of these new CMAS-resistant TBCs.     

Novel thermal barrier coatings that are resistant to high-temperature attack by glassy deposits

Airborne sand particles that deposit on thermal barrier coatings (TBCs) in gas-turbine engines melt and form calcium–magnesium–aluminosilicate (CMAS) glass, which attacks the TBCs. A new approach for mitigating CMAS attack on TBCs is presented, where up to 20 mol.% Al₂O₃ and 5 mol.% TiO₂ in the form of a solid solution is incorporated into Y₂O₃-stabilized ZrO₂ (YSZ) TBCs. The fabrication of such TBCs with engineered chemistries is made possible by the solution-precursor plasma spray (SPPS) process, which is uniquely suited for depositing coatings of metastable ceramics with extended solid-solubilities. Here, the TBC serves as a reservoir of Al and Ti solutes, which are incorporated into the molten CMAS glass that is in contact with the TBC. This results in the crystallization of the CMAS glass and the attendant arrest of the penetrating CMAS front. This approach could also be used to mitigate attack by other types of foreign deposits (salt, ash, and contaminants) on TBCs.     

等离子蒸发沉积热障涂层抗CMAS附着研究进展

热障涂层是先进航空发动机核心热端部件高压涡轮叶片的关键技术,随着发动机服役温度的不断提高,一种主要化学成分为CaO-MgO-Al2O3-SiO2(简称CMAS)的环境沉积物对叶片的危害日益严重,不仅堵塞叶片表面气膜冷却孔,影响叶片冷效,而且导致热障涂层早期剥落失效,服役寿命大幅度降低。高温熔融CMAS在涂层表面的附着过程及防护方法是目前热障涂层研究领域的热点和难点。本文针对新型的等离子蒸发沉积技术,梳理了近年来国内外学者在热障涂层抗CMAS附着、渗入和腐蚀方面的最新研究成果,指出了涂层抗CMAS侵蚀研究的发展方向。     

Composition effects of thermal barrier coating ceramics on their interaction with molten Ca–Mg–Al–silicate (CMAS) glass

Systematic studies have been performed to investigate the composition effects of ZrO₂-based thermal barrier coating (TBC) ceramics on their interactions with molten Ca–Mg–Al–silicate (CMAS) glass. Porous ceramic pellets (～15% porosity), instead of actual TBCs, are used in these model studies, where the penetration of molten CMAS into the pellets is investigated. This study involves a total of six compositions of ZrO₂-based ceramics: two containing low solute (Y³⁺ or Gd³⁺) concentration, three with high concentration of solute (Y³⁺, Gd³⁺ or Yb³⁺), and one containing a combined intermediate concentration of Y³⁺+Al³⁺+Ti⁴⁺ solutes. While both the type of the solute and its concentration in the ZrO₂-based TBC ceramics have been found to influence the extent of molten CMAS penetration into the pellets, the solute concentration has the most dramatic effect. In particular, molten CMAS penetration is almost completely suppressed in porous TBC ceramic pellets containing a high concentration of Y³⁺ solute (Y₂Zr₂O₇). Possible mechanisms governing these effects are presented, together with a discussion of guidelines for the chemical design of CMAS-resistant zirconate TBC ceramics. Generally, for a TBC ceramic to be highly effective against CMAS attack it must interact vigorously with the molten CMAS, which must result in the rapid crystallization of the refractory oxide phase(s) that form a sealing layer, arresting further penetration of the molten CMAS. The porous ceramic pellets approach used here could be developed into rapid-screening methodologies for the discovery of CMAS-resistant TBC ceramic compositions, and to study the effect of composition of CMAS glasses on their interactions with TBC ceramics of specific compositions.     

Higher Temperature Thermal Barrier Coatings with the Combined Use of Yttrium Aluminum Garnet and the Solution Precursor Plasma Spray Process

Gas-turbine engines are widely used in transportation, energy and defense industries. The increasing demand for more efficient gas turbines requires higher turbine operating temperatures. For more than 40 years, yttria-stabilized zirconia (YSZ) has been the dominant thermal barrier coating (TBC) due to its outstanding material properties. However, the practical use of YSZ-based TBCs is limited to approximately 1200 °C. Developing new, higher temperature TBCs has proven challenging to satisfy the multiple property requirements of a durable TBC. In this study, an advanced TBC has been developed by using the solution precursor plasma spray (SPPS) process that generates unique engineered microstructures with the higher temperature yttrium aluminum garnet (YAG) to produce a TBC that can meet and exceed the major performance standards of state-of-the-art air plasma sprayed YSZ, including: phase stability, sintering resistance, CMAS resistance, thermal cycle durability, thermal conductivity and erosion resistance. The temperature improvement for hot section gas turbine materials (superalloys & TBCs) has been at the rate of about 50 °C per decade over the last 50 years. In contrast, SPPS YAG TBCs offer the near-term potential of a > 200 °C improvement in temperature capability.     

CMAS corrosion of EB PVD TBCs: Identifying the minimum level to initiate damage

Over the last decade a significant amount of research has been conducted into the durability of thermal barrier coatings (TBCs) focusing mainly on issues of oxidation, erosion and foreign object damage (FOD). However, as the performance and durability of TBCs has improved the temperatures at which they operate has increased. This increase in temperature has resulted in another lifing issue for EB PVD TBCs, namely that of CMAS attack. Calcium–magnesium–alumino-silicate (CMAS) attack occurs when atmospheric dust that has deposited on the surface of turbine blades melts and wicks into the columns of the TBC. This occurs at temperatures above 1240–1260 °C and results in the degradation of the columnar microstructure of the TBCs. Due to the fact that TBCs operate in a temperature gradient CMAS only infiltrates part of the coating before solidifying.There are a number of issues associated with CMAS attack, both chemical and mechanical. From a chemical point of view CMAS attack of electron beam (EB) physical vapour deposited (PVD) TBCs can be considered as a form of corrosion; when there is a lot of excess CMAS on the surface of a coated component Yttria diffuses out of the TBC into the molten CMAS resulting in a t′ to monoclinic phase transformation in the yttria stabilised zirconia (YSZ), CMAS attack also results in localised melting and subsequent re-precipitation of the coating resulting in a loss of the defined columnar microstructure. While from a mechanical point of view the CMAS, once re-solidified, reduces the strain compliance of the EB PVD and can result in spallation of the TBC on cooling. Furthermore, current studies have indicated that small amount of CMAS infiltration significantly increases the erosion rate of EB PVD TBCs.This paper covers various aspects of CMAS attack of EB PVD TBCs, specifically looking at minimum levels of CMAS required to initiate damage, as well as investigating it from an erosion–corrosion perspective.     

Thermal barrier coating experience in gas turbine engines at Pratt & Whitney

Pratt & Whitney has accumulated more than three decades of experience with thermal barrier coatings (TBCs). These coatings were originally developed to reduce surface temperatures of combustors of JT8D gas turbine engines to increase the thermal fatigue life of the components. Continual improvements in de-sign, processing, and properties of TBCs have extended their applications to other turbine components, such as vanes, vane platforms, and blades, with attendant increases in performance and component du-rability. Plasma-spray-based generation I (Gen I) combustor TBCs with 7 wt % yttria partially stabilized zirconia deposited by air plasma spray (APS) on an APS NiCoCrAlY bond coat continues to perform ex-tremely well in all product line engines. Durability of this TBC has been further improved in Gen II TBCs for vanes by incorporating low-pressure chamber plasma-sprayed NiCoCrAl Y as a bond coat. The modi-fication has improved TBC durability by a factor of 2.5 and altered the failure mode from a “black fail-ure” within the bond coat to a “white failure” within the ceramic. Further improvements have been accomplished by instituting a more strain-tolerant ceramic top layer with electron beam/physical vapor deposition (EB-PVD) processing. This Gen III TBC has demonstrated exceptional performance on rotating airfoils in high-thrust-rated engines, improving blade durability by three times through elimination of blade creep, fracture, and rumpling of metallic coatings used for oxi-dation protection of the airfoil surfaces. A TBC durability model for plasma-sprayed as well as EB-PVD systems is proposed that involves the accumulation of compressive stresses during cyclic thermal expo-sure. The model attempts to correlate failure of the various TBCs with elements of their structure and its degradation with thermocyclic exposure.     

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.     

大气等离子喷涂热障涂层CMAS防护层成分及厚度优化

目的优化热障涂层(TBCs)CMAS(CaO-MgO-Al_2O_3-SiO_2)阻抗层的成分和厚度,使其能有效阻抗CMAS沉积物的腐蚀,并同时与热障涂层有较高的结合力。方法首先利用多孔无压烧结陶瓷块体研究了不同含量Al_2O_3和8YSZ(8wt.%氧化钇稳定氧化锆)均匀混合后在高温(1250℃)条件下对CMAS沉积物的防护作用。采用扫描电子显微镜(SEM)、能谱仪(EDS)以及X射线衍射(XRD)仪,分析研究了CMAS腐蚀层的显微结构、腐蚀深度及反应产物。其次,基于最优成分,利用大气等离子喷涂(APS)制备了具有8YSZ/Al_2O_3陶瓷层的热障涂层。对CMAS腐蚀厚度进行分析测量,提出CMAS阻抗层的厚度。结果 Al_2O_3的添加可以有效地阻碍CMAS的渗入,并且Al_2O_3含量越多,防护效果越好。但是CMAS的渗入深度和氧化铝的添加量呈非线性关系。结合TBC陶瓷层的热学性能和力学性能的要求,本实验中最佳的TBCs复合陶瓷层组分为70wt%8YSZ+30wt%Al_2O_3。基于实验结果,提出YSZ/Al_2O_3复合陶瓷层(50μm)-YSZ陶瓷层(150μm)的双层TBC陶瓷层结构,并综合计算出复合陶瓷层的热膨胀系数为9.93×10-6℃-1以及双层TBC陶瓷层的热导率为2.4 W/(m·K)。最后对Al_2O_3减缓CMAS腐蚀的机理进行了量化分析。结论 YSZ/Al_2O_3复合阻抗层的最优成分为70wt%8YSZ+30wt%Al_2O_3,厚度为50μm,能有效阻碍高温下CMAS腐蚀。     

Thermal barrier coatings for industrial gas turbine applications: An industrial note

Thermal barrier coatings (TBCs) have been used in high-thrust aircraft engines for many years to pro-vide thermal protection and increase engine efficiencies. TBC life requirements for aircraft engines are typically less than those required for industrial gas turbines. This paper describes current and future ap-plications of TBCs in industrial gas turbine engines. Early testing and applications of TBCs are reviewed. Areas of concern from the engine designer’s and materials engineer’s perspective are identified and evaluated. This paper focuses on the key factors that are expected to influence utilization of TBCs in ad-vanced industrial gas turbine engines. It is anticipated that reliable, durable, and highly effective coating systems will be produced that will ultimately improve engine efficiency and performance.     

Application of Plasma-Sprayed Complex Perovskites as Thermal Barrier Coatings

In an effort to improve the performance of heat engines at high temperatures, advanced surface coatings have been developed from complex perovskites. Materials of Ba(Mg_1/3Ta_2/3)O₃ and La(Al_1/4Mg_1/2Ta_1/4)O₃ composition were synthesized and applied as ceramic topcoats of thermal barrier coating (TBC) systems by atmospheric plasma spraying (APS) in single layer and in double-layer combination with conventional yttria stabilized zirconia (YSZ). Microstructural and phase analyses reveal that plasma spraying of complex perovskites is accompanied with the formation of vertical crack networks and secondary oxide phases which influence the failure mechanism of the TBCs. The low value of fracture toughness for the complex perovskites and the thermally grown oxide at the topcoat-bondcoat interface of the TBCs are, however, the major factors which lead to the coating failure on thermal cycling at about 1250 °C.     

Editorial

Thermal Barrier Coatings (TBCs) in current gas turbine engines routinely deliver metal tempera-ture reductions of 50 to 80°C under normal conditions and as much as 140°C temperature reduc-tions in hot spots (Ref 1). This temperature reduction can be used to lower metal component tem-peratures under constant operating conditions to achieve longer life, or to increase the performance of the engine through higher operating temperatures while maintaining constant life of the component, as indicated by the horizontal arrows in Fig. 1. A middle road of longer life and increased engine performance/efficiency is also possible. The choice of how to use the thermal benefits derived from TBCs is critical, especially if the intent is to follow the high economic pay-off path of increasing the operating temperatures to increase engine efficiency. In this case, large increases in operating temperature and engine efficiency are possible with the insulating capabil-ity of TBCs. The problem is that if the temperatures are increased to take full advantage of the TBC insulating ability, and a large frac-tion of the coating spalls, the remaining bare metallic component would be subjected to high temperatures and unacceptably rapid deg-radation (Fig. 1). Obviously, the risk of coating failure must be balanced against the benefit of coating use.     

PVD TBC experience on GE aircraft engines

The higher performance levels of modern gas turbine engines present significant challenges in the reli-ability of materials in the turbine. The increased engine temperatures required to achieve the higher per-formance levels reduce the strength of the materials used in the turbine sections of the engine. Various forms of thermal barrier coatings have been used for many years to increase the reliability of gas turbine engine components. Recent experience with the physical vapor deposition process using ceramic material has demonstrated success in extending the service life of turbine blades and nozzles. Engine test results of turbine components with a 125 μm (0.005 in.) PVD TBC have demonstrated component operating tem-peratures of 56 to 83 °C (100 to 150 °F) lower than non-PVD TBC components. Engine testing has also revealed that TBCs are susceptible to high angle particle impact damage. Sand particles and other engine debris impact the TBC surface at the leading edge of airfoils and fracture the PVD columns. As the impacting continues, the TBC erodes in local areas. Analysis of the eroded areas has shown a slight increase in temperature over a fully coated area ; however, a significant temperature reduc-tion was realized over an airfoil without TBC.     

Failure Mechanism for Thermal Fatigue of Thermal Barrier Coating Systems

Thick thermal barrier coatings (TBCs), consisting of a CoNiCrAlY bond coat and yttria-partially stabilized zirconia top coat with different porosity values, were produced by air plasma spray (APS). The thermal fatigue resistance limit of the TBCs was tested by furnace cycling tests (FCT) according to the specifications of an original equipment manufacturer (OEM). The morphology, residual stresses, and micromechanical properties (microhardness, indentation fracture toughness) of the TBC systems before and after FCT were analyzed. The thermal fatigue resistance increases with the amount of porosity in the top coat. The compressive in-plane stresses increase in the TBC systems after thermal cycling; nevertheless the increasing rate has a trend contrary to the porosity level of top coat. The data suggest that the spallation happens at the TGO/top coat interface. The failure mechanism of thick TBCs was found to be similar to that of conventional thin TBC systems made by APS.     

Low Thermal Conductivity Yttrium Aluminum Garnet Thermal Barrier Coatings Made by the Solution Precursor Plasma Spray: Part II—Planar Pore Formation and CMAS Resistance

Low thermal conductivity in yttrium aluminum garnet (YAG)-based thermal barrier coatings (TBCs) made by solution precursor plasma spray (SPPS) can be achieved by creating planar arrays of porosity called inter-pass boundaries (IPBs) as shown in Part I. In the current work, the mechanism of IPBs formation is studied through analysis of precursor entrainment and collection of single/raster step deposition patterns. It is concluded that the IPBs are formed by trapping precursor that under/over penetrates the plasma jet. CMAS interaction tests on SPPS YAG TBCs with heavy IPBs show an improvement of 123X and 15X over APS YSZ and SPPS YAG-light IPBs TBCs, respectively. It is demonstrated that the exceptional coating performance is because of the engineered heavy IPBs which branch out from the vertical cracks and run parallel to the surface. The CMAS melt gets drawn in the IPBs due to the capillary forces, leading to a shallow infiltration depth. The IPBs have a porosity of 70%, thus act as reservoirs for CMAS. Based on the favorable results, an alternate CMAS mitigation strategy is proposed that solely relies on microstructural features instead of the conventional approach where a vigorous reaction between CMAS-TBCs is desirable to form secondary phases.     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。     

Thermal stability and mechanical properties of thick thermal barrier coatings with vertical type cracks

The thermal stability and failure mechanism of thick thermal barrier coatings (TBCs) with and without vertical type cracks were investigated through the cyclic thermal exposure and thermal-shock tests. The TBC systems with thickness of about 2000 µm in the top coat were prepared by an air plasma spray (APS) on the bond coat of about 150 µm in thickness prepared by APS. The adhesive strength values of the as-prepared TBCs with and without vertical type cracks were determined to be 24.7 and 11.0 MPa, respectively, indicating the better interface stability in the TBC with vertical type cracks. The TBC with vertical type cracks shows a better thermal durability than that without vertical type cracks in the thermal cyclic exposure and thermal-shock tests. The hardness values of the as-prepared TBCs with and without vertical type cracks were found to be 6.6 and 5.3 GPa, respectively, which were increased to 9.5 and 5.5 GPa, respectively, after the cyclic thermal exposure tests. These results indicate that the vertical type cracks developed in the top coat are important in improving the lifetime performance of thick TBC in high temperature environment.     

Strain analysis of plasma sprayed thermal barrier coatings under mechanical stress

The stiffness of air plasma sprayed (APS) thermal barrier coatings (TBCs) was determined from bending experiments combining strain analysis on a microstructural level with macroscopic mechanical parameters. Tests were performed with freestanding and attached TBCs, the latter either loaded in tension or in compression. Relationships are derived, which describe the TBC stiffness in a multilayer composite (attached TBC) and for a bimodular material that possess a lower stiffness in tension than in compression (stand-alone TBC). The increase of in-plane stiffness with increasing compressive stress emphasizes the importance of the spraying defects for the elastic response of the coating.     

Failure of Thermal Barrier Coatings Subjected to CMAS Attack

The effect of environmental deposits, such as calcium-magnesium-alumino-silicate (CMAS), on thermal barrier coatings (TBCs) of commercial grade was investigated in laboratory scale. A controlled CMAS infiltration was achieved through exposure of coatings to calibrated cement tape composites containing synthetic glass powder representative of CMAS. Tube furnace and cyclic thermal shock simulation equipment were utilized to melt the synthesized CMAS tape on coating surfaces. The resulting premature failures of coatings were investigated through study of the thermomechanical and thermochemical interactions between the coatings and CMAS deposit. It was found that the porous nature of the thermal-sprayed TBCs make them vulnerable to CMAS attack even before discernible chemical reaction starts. Possible mitigation approaches are proposed for a better coating life under such severe circumstances.     

Structure and durability evaluation of YSZ + Al2O3 composite TBCs with APS and HVOF bond coats under thermal cycling conditions

Plasma sprayed thermal barrier coatings (TBCs) are applied to gas turbine components for providing thermal insulation and oxidation resistance. The TBC systems currently in use on superalloy substates typically consists of a metallic MCrAlY based bond coat and an insulating Y₂O₃ partially stabilized ZrO₂ as a ceramic top coat (ZrO₂ 7–8 wt.% Y₂O₃). The oxidation of bond coat underlying yttria stabilized zirconia (YSZ) is a significant factor in controlling the failure of TBCs. The oxidation of bond coat induces to the formation of a thermally grown oxide (TGO) layer at the bond coat/YSZ interface. The thickening of the TGO layer increases the stresses and leads to the spallation of TBCs. If the TGO were composed of a continuous scale of Al₂O₃, it would act as a diffusion barrier to suppress the formation of other detrimental mixed oxides during the extended thermal exposure in service, thus helping to protect the substrate from further oxidation and improving the durability. The TBC layers are usually coated onto the superalloy substrate using the APS (Atmospheric plasma spray) process because of economic and practical considerations. As well as, HVOF (High velocity oxygen fuel) bond coat provides a good microstructure and better adhesion compared with the APS process. Therefore, there is a need to understand the cycling oxidation characteristic and failure mode in TBC systems having bond coat prepared using different processes. In the present investigation, the growth of TGO layers was studied to evaluate the cyclic oxidation behavior of YSZ/Al₂O₃ composite TBC systems with APS-NiCrAlY and HVOF-NiCrAlY bond coats. Interface morphology is significantly effective factor in occurrence of the oxide layer. Oxide layer thickening rate is slower in APS bond coated TBCs than HVOF bond coated systems under thermal cycle conditions at 1200 °C. The YSZ/Al₂O₃ particle composite systems with APS bond coat have a higher thermal cycle life time than with the HVOF bond coating.