未来航空发动机热障涂层材料及制备技术

概述了未来航空发动机热障涂层最有前景的新材料、结构和制备工艺。新材料主要有改进型氧化钇稳定的氧化锆、A2B2O7型材料;新结构主要有双陶瓷层;新工艺主要为制备含垂直裂纹的热障涂层的改进大气等离子体喷涂、等离子喷涂-物理气相沉积、悬浮液等离子喷涂、电子束直接气相沉积。这些相互结合,必将促进高性能热障涂层的快速发展和应用,使其在未来航空发动机中发挥重要作用。     

Thermal cycling failure of new LaMgAl11O19/YSZ double ceramic top coat thermal barrier coating systems

New LaMgAl₁₁O₁₉ (LaMA)/YSZ double ceramic top coat thermal barrier coatings (TBCs) with the potential application in advanced gas-turbines and diesel engines to realize improved efficiency and durability were prepared by plasma spraying, and their thermal cycling failure were investigated. The microstructure evolutions as well as the crystal chemistry characteristics of LaMA coating which seemed to have strong influences on the thermal cycling failure of LaMA and the new double ceramic top coat TBCs based on LaMA/YSZ system were studied. For double ceramic top coat TBC system, interface modification of LaMA/YSZ by preparing thin composite coatings seemed to be more preferred due to the formations of multiple cracks during thermal cycling making the TBC to be more strain tolerant and as well as resulting in an improved thermal cycling property. The effects of the TGO stresses on the failure behavior of the TBCs were discussed through fluorescence piezo-spectroscopy analysis.     

地面重型燃气轮机及其热障涂层的研究进展与发展趋势

国际公认的重型燃气轮机制造尖端技术之一—热障涂层技术,高温下通常面临CMAS(CaO-MgO-Al₂O₃-SiO₂)腐蚀、氧化、相变与烧结等问题,其抗CMAS腐蚀性等关键性能极大地影响涂层寿命,提高热障涂层的性能刻不容缓。对重型燃气轮机用热障涂层的研究进展与发展趋势进行全面总结与分析。首先介绍国内外重型燃气轮机的现状及发展趋势、热障涂层的系统结构、材料和几种典型的制备工艺,然后针对高温下燃气轮机热障涂层遇到的一些问题,对其隔热性、抗氧化性及抗热震性等关键性能的研究进展进行综述,最后分类详述热障涂层的CMAS腐蚀机理及其防护研究进展。综述热障涂层的几种关键性能,提出热障涂层的性能与其材料、结构及制备工艺密切相关,据此总结归纳提高热障涂层性能的方法,为热障涂层性能的提高提供参考依据,以弥补燃气轮机热障涂层领域目前缺乏这类综述文章的不足。     

镍基合金涡轮叶片热障涂层研究进展

热障涂层技术是提升航空发动机性能的关键因素之一,随着航空发动机技术的发展,对热障涂层也提出了更高的要求。为适应镍基合金涡轮叶片热胀涂层的使用要求,热胀涂层的陶瓷面层发展出（YSZ+A2B2O7）结构涂层。热障涂层陶瓷面层常用的制备方法包括等离子喷涂技术和电子束物理气相沉积技术,金属粘结层常用的制备方法包括真空电弧镀技术和化学气相沉积技术。热障涂层低膨胀系数金属粘结层技术、热障涂层修复技术、新一代热障涂层材料、建立科学的热障涂层性能评价体系等是未来热障涂层的主要发展方向。     

Cyclic-Oxidation Behavior of Thermal-barrier Coatings Exposed to NaCl Vapor

A Ni–24Cr–6Al–0.7Y (NiCrAlY) coating was deposited on a nickel-base superalloy by low-pressure plasma spraying, and the top coating, ZrO₂ partially stabilized with Y₂O₃ (7.5 wt%), was deposited on the NiCrAlY coating by air-plasma spraying. The cyclic-oxidation behavior of the NiCrAlY + YSZ coating exposed to NaCl vapor was investigated under atmospheric pressure at 1,050 °C, 1,100 °C and 1,150 °C. The cyclic-oxidation life of the NiCrAlY + YSZ coating in the presence of NaCl vapor was shortened compared with that in air. The higher the temperature is, the shorter the cyclic oxidation life. The oxide scale formed at the interface between the bond coat and the ceramic layer after exposure to NaCl vapor consisted of voluminous and non-protective NiO, Al₂O₃ and NiCr₂O₄ spinel. The failure of the TBC exposed to NaCl vapor occurs within the top coat and close to the YSZ/thermal growth oxide interface. The failure mechanism has been discussed based on the experimental results and thermodynamics.     

Technical and Economical Aspects of Current Thermal Barrier Coating Systems for Gas Turbine Engines by Thermal Spray and EBPVD: A Review

The most advanced thermal barrier coating (TBC) systems for aircraft engine and power generation hot section components consist of electron beam physical vapor deposition (EBPVD) applied yttria-stabilized zirconia and platinum modified diffusion aluminide bond coating. Thermally sprayed ceramic and MCrAlY bond coatings, however, are still used extensively for combustors and power generation blades and vanes. This article highlights the key features of plasma spray and HVOF, diffusion aluminizing, and EBPVD coating processes. The coating characteristics of thermally sprayed MCrAlY bond coat as well as low density and dense vertically cracked (DVC) Zircoat TBC are described. Essential features of a typical EBPVD TBC coating system, consisting of a diffusion aluminide and a columnar TBC, are also presented. The major coating cost elements such as material, equipment and processing are explained for the different technologies, with a performance and cost comparison given for selected examples.     

Adhesion improvements of Thermal Barrier Coatings with HVOF thermally sprayed bond coats

Thermal barrier coatings (TBC) are an effective engineering solution for the improvement of in service performance of gas turbines and diesel engine components. The quality and further performance of TBC, likewise all thermally sprayed coatings or any other kind of coating, is strongly dependent on the adhesion between the coating and the substrate as well as the adhesion (or cohesion) between the metallic bond coat and the ceramic top coat layer. The debonding of the ceramic layer or of the bond coat layer will lead to the collapse of the overall thermal barrier system. Though several possible problems can occur in coating application as residual stresses, local or net defects (like pores and cracks), one could say that a satisfactory adhesion is the first and intrinsic need for a good coating. The coating adhesion is also dependent on the pair substrate-coating materials, substrate cleaning and blasting, coating application process, coating application parameters and environmental conditions. In this work, the general characteristics and adhesion properties of thermal barrier coatings (TBCs) having bond coats applied using High Velocity Oxygen Fuel (HVOF) thermal spraying and plasma sprayed ceramic top coats are studied. By using HVOF technique to apply the bond coats, high adherence and high corrosion resistance are expected. Furthermore, due to the characteristics of the spraying process, compressive stresses should be induced to the substrate. The compressive stresses are opposed to the tensile stresses that are typical of coatings applied by plasma spraying and eventually cause delamination of the coating in operational conditions. The evaluation of properties includes the studies of morphology, microstructure, microhardness and adhesive/cohesive resistance. From the obtained results it can be said that the main failure location is in the bond coat/ceramic interface corresponding to the lowest adhesion values.     

Study of microstructure and thermal shock behavior of two types of thermal barrier coatings

Gas turbines provide one of the most severe environments challenging material systems nowadays. Only an appropriate coating system can supply protection particularly for turbine blades. This study was made by comparison of properties of two different types of thermal barrier coatings (TBCs) in order to improve the surface characteristics of high temperature components. These TBCs consisted of a duplex TBC and a five layered functionally graded TBC. In duplex TBCs, 0.35 mm thick yittria partially stabilized zirconia top coat (YSZ) was deposited by air plasma spraying and ～0.15 mm thick NiCrAlY bond coat was deposited by high velocity oxyfuel spraying. ～0.5 mm thick functionally graded TBC was sprayed by varying the feeding ratio of YSZ/NiCrAlY powders. Both coatings were deposited on IN 738LC alloy as a substrate. Microstructural characterization was performed by SEM and optical microscopy whereas phase analysis and chemical composition changes of the coatings and oxides formed during the tests were studied by XRD and EDX. The performance of the coatings fabricated with the optimum processing conditions was evaluated as a function of intense thermal cycling test at 1100 °C. During thermal shock test, FGM coating failed after 150 and duplex coating failed after 85 cycles. The adhesion strength of the coatings to the substrate was also measured. Finally, it is found that FGM coating has a larger lifetime than the duplex TBC, especially with regard to the adhesion strength of the coatings.     

Ultrasonic Detection of Delamination and Material Characterization of Thermal Barrier Coatings

This article describes ultrasonic nondestructive evaluation (NDE) to detect the changes of material properties and provide early warning of delamination in thermal barrier coating (TBC) systems. NDE tests were performed on single-crystal René N5 superalloy coupons that were coated with a commercially available MCrAlY bond coat and an air plasma sprayed 7% yttria-stabilized zirconia (YSZ) top coat deposited by Air Plasma Spray method, as well as Haynes 230 superalloy coupons coated with MCrA1Y bond coat, and an electron beam physical vapor deposit of 7% YSZ top coat. The TBC coupons were subjected to either cyclic or isothermal exposure for various lengths of time at temperatures ranging from 900 to 1100?°C. The ultrasonic measurements performed on the coupons had provided an early warning of delamination along the top coat/TGO interface before exposure time, when delamination occurred. The material's property (Young??s modulus) of the top coat was estimated using the measured wave speeds. Finite element analysis (FEA) of the ultrasonic wave propagation was conducted on a simplified TBC system to verify experimental observations. The technique developed was also demonstrated on an as-manufactured turbine blade to estimate normalized top coat thickness measurements.     

Simultaneous synthesis by spark plasma sintering of a thermal barrier coating system with a NiCrAlY bond coat

As-fabricated thermal barrier coating (TBC) systems generally consist of a superalloy substrate, a MCrAlY bond coat (M = Ni, Co, Fe), and a ceramic (usually partially stabilized zirconia) top coat. The conventional methods for producing the two coating layers generally derive from thermal spray and physical vapor deposition techniques. Thermal exposure leads to the formation of an additional layer: the thermally grown oxide (TGO) between the bond coat and top coat. In the present work, a TBC system is synthesized through the application of spark plasma sintering (SPS), which provides not only the opportunity to synthesize all three layers at once, but the process is quite rapid and can produce dense layers. More specifically, this paper describes the application of this method to an yttria-stabilized ZrO₂ (YSZ) top coat and a NiCrAlY bond coat on a Ni-base Hastelloy X substrate. A one-micron thick Al₂O₃ TGO layer is also created from the reaction between an Al foil layer inserted in the stack prior to sintering and the ZrO₂ in the top coat. The effects of select process conditions are considered. The resulting multi-layer system is characterized with optical microscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray analysis (EDAX) and X-ray diffraction (XRD). Differential thermal analysis (DTA) is used to investigate the reaction between the Al foil and the YSZ top coat.     

Overview on advanced thermal barrier coatings

During the last decade a number of ceramic materials, mostly oxides have been suggested as new thermal barrier coating (TBC) materials. These new compositions have to compete with the state-of-the-art TBC material yttria stabilized zirconia (YSZ) which turns out to be difficult due to its unique properties. On the other hand YSZ has certain shortcomings especially its limited temperature capability above 1200 °C which necessitates its substitution in advanced gas turbines.In the paper an overview is tried on different new materials covering especially doped zirconia, pyrochlores, perovskites, and aluminates. Literature results and also results from our own investigations will be presented and compared to the requirements. Finally, the double-layer concept, a method to overcome the limited toughness of new TBC materials, will be discussed.     

A physics-based life prediction methodology for thermal barrier coating systems

A novel mechanistic approach is proposed for the prediction of the life of thermal barrier coating (TBC) systems. The life prediction methodology is based on a criterion linked directly to the dominant failure mechanism. It relies on a statistical treatment of the TBC’s morphological characteristics, non-destructive stress measurements and on a continuum mechanics framework to quantify the stresses that promote the nucleation and growth of microcracks within the TBC. The last of these accounts for the effects of TBC constituents’ elasto-visco-plastic properties, the stiffening of the ceramic due to sintering and the oxidation at the interface between the thermally insulating yttria stabilized zirconia (YSZ) layer and the metallic bond coat. The mechanistic approach is used to investigate the effects on TBC life of the properties and morphology of the top YSZ coating, metallic low-pressure plasma sprayed bond coat and the thermally grown oxide. Its calibration is based on TBC damage inferred from non-destructive fluorescence measurements using piezo-spectroscopy and on the numerically predicted local TBC stresses responsible for the initiation of such damage. The potential applicability of the methodology to other types of TBC coatings and thermal loading conditions is also discussed.     

High-temperature oxidation and hot corrosion behavior of two kinds of thermal barrier coating systems for advanced gas turbines

High-temperature oxidation and hot corrosion tests were conducted at 800 to 1100 °C under isothermal and thermal-cycle conditions for two kinds of thermal barrier coating (TBC) systems with different compositions of ceramic top coat: Y₂O₃-stabiIized zirconia (YSZ) and CaO-SiO₂-ZrO₂ (C₂S-CZ). Qualitative and quantitative failure analyses were carried out to clarify the failure mechanisms of TBC systems. In high-temperature oxidation up to 1100 °C, the YSZ-TBC system was subjected more easily to spalling of the ceramic top coat. This is attributed to the localized oxidation along the ceramic top coat/metallic (NiCrAlY) bond coat interface, as compared with the case of the C₂S-CZ-TBC system. Thus, the most significant oxidation damage resulted in the YSZ system under the thermal-cycle condition. On the other hand, for hot corrosion by Na₂SO₄-NaCI molten salt up to 1000 °C, the C₂S-CZ system was more reactive with the molten salt to form a new phase layer composed of both the metallic bond coat constituents, such as aluminum and chromium, and corrosive species such as oxygen at the inner region of the ceramic top coat. Furthermore, effects of both the heat treatment, in particular the atmosphere after plasma spraying, and the chromium content of the bond coat were investigated for each coating system.     

Recent Developments in the Field of Thermal Barrier Coatings

Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bondcoat and a ceramic, heat-isolative topcoat. Several recent research activities are concentrating on developing improved bondcoat or topcoat materials; for the topcoat especially, those with reduced thermal conductivity are investigated. Using advanced topcoat materials, the ceramic coating can be further divided into layers with different functions. One example is the double-layer system in which conventional yttria-stabilized zirconia (YSZ) is used as bottom and new materials such as pyrochlores or perovskites are used as topcoat layers. These systems demonstrated an improved temperature capability compared to standard YSZ. In addition, new functions are introduced within the TBCs. These can be sensorial properties that can be used for an improved temperature control or even for monitoring remaining lifetime. Further increased application temperatures will also lead to efforts for a further improvement of the reflectivity of the coatings to reduce the radiative heat transfer through the TBC.     

Plasma Spray-PVD: A New Thermal Spray Process to Deposit Out of the Vapor Phase

Plasma spray-physical vapor deposition (PS-PVD) is a low pressure plasma spray technology recently developed by Sulzer Metco AG (Switzerland). Even though it is a thermal spray process, it can deposit coatings out of the vapor phase. The basis of PS-PVD is the low pressure plasma spraying (LPPS) technology that has been well established in industry for several years. In comparison to conventional vacuum plasma spraying (VPS) or low pressure plasma spraying (LPPS), the new proposed process uses a high energy plasma gun operated at a reduced work pressure of 0.1 kPa (1 mbar). Owing to the high energy plasma and further reduced work pressure, PS-PVD is able to deposit a coating not only by melting the feed stock material which builds up a layer from liquid splats but also by vaporizing the injected material. Therefore, the PS-PVD process fills the gap between the conventional physical vapor deposition (PVD) technologies and standard thermal spray processes. The possibility to vaporize feedstock material and to produce layers out of the vapor phase results in new and unique coating microstructures. The properties of such coatings are superior to those of thermal spray and electron beam-physical vapor deposition (EB-PVD) coatings. In contrast to EB-PVD, PS-PVD incorporates the vaporized coating material into a supersonic plasma plume. Owing to the forced gas stream of the plasma jet, complex shaped parts such as multi-airfoil turbine vanes can be coated with columnar thermal barrier coatings using PS-PVD. Even shadowed areas and areas which are not in the line of sight of the coating source can be coated homogeneously. This article reports on the progress made by Sulzer Metco in developing a thermal spray process to produce coatings out of the vapor phase. Columnar thermal barrier coatings made of Yttria-stabilized Zircona (YSZ) are optimized to serve in a turbine engine. This process includes not only preferable coating properties such as strain tolerance and erosion resistance but also the simultaneous coverage of multiple air foils.     

Intermetallic Al-, Fe-, Co- and Ni-Based Thermal Barrier Coatings Prepared by Cold Spray for Applications on Low Heat Rejection Diesel Engines

Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bond coat and a ceramic heat insulating topcoat. They possess the desired low thermal conductivity, but at the same time they are very brittle and sensitive to thermal shock and thermal cycling due to the inherently low coefficient of thermal expansion. Recent research activities are focused on the developing of multilayer TBC structures obtained using cold spraying and following annealing. Aluminum intermetallics have demonstrated thermal and mechanical properties that allow them to be used as the alternative TBC materials, while the intermetallic layers can be additionally optimized to achieve superior thermal physical properties. One example is the six layer TBC structure in which cold sprayed Al-based intermetallics are synthesized by annealing in nitrogen atmosphere. These multilayer coating systems demonstrated an improved thermal fatigue capability as compared to conventional ceramic TBC. The microstructures and properties of the coatings were characterized by SEM, EDS and mechanical tests to define the TBC material properties and intermetallic formation mechanisms.     

粘结层预处理对PS-PVD沉积7YSZ热障涂层氧化行为的影响

目的提高PS-PVD沉积7YSZ热障涂层的抗高温氧化性能。方法采用等离子喷涂-物理气相沉积(PS-PVD)分别在未预处理和预处理(抛光+预氧化)的粘结层表面制备了柱状结构7YSZ热障涂层,并在大气环境下测试了柱状结构7YSZ热障涂层的950℃静态高温氧化性能。利用扫描电子显微镜、X射线衍射仪、能谱仪对高温氧化过程中的陶瓷层/粘结层界面形貌、TGO层结构演变进行表征。结果粘结层的抛光处理能够降低表面几何受力不均匀部位,抑制陶瓷层/TGO/粘结层界面处微裂纹的产生,同时粘结层的预氧化处理形成的薄而连续的TGO层能有效降低TGO的生长速度,抑制陶瓷层-粘结层之间的元素互扩散。柱状结构7YSZ涂层的高温氧化动力学曲线符合Wagner抛物线规律,粘结层未预处理和预处理的7YSZ热障涂层的氧化速率常数分别为0.101×10~(-12) cm~2/s和0.115×10~(-13) cm~2/s。结论粘结层预处理能有效改善等离子物理气相沉积7YSZ热障涂层的抗氧化性能。     

An evaluation of the electric arc spray and (HPPS) processes for the manufacturing of high power plasma spraying MCrAIY coatings

The high power plasma torch (PlazJet) can be used to spray refractory ceramics with high spray rates and deposition efficiency. It can provide dense and hard coating with high bond strengths. When manufacturing thermal barrier coatings, the PlazJet gun is well adapted to spraying the ceramic top coat but not the MCrAIY materials that are used as bond coat. Arc spraying can compete with plasma spraying for metallic coatings since cored wires can be used to spray alloys and composites. In addition, the high production rate of arc spraying enables a significant decrease in coating cost. This paper discusses the performances of the PlazJet gun, and a twin-wire are spray system, and compares the properties and cost of MCrAIY coatings made with these two processes. For arc spraying, the use of air or nitrogen as atomizing gas is also investigated.     

Thermo-Physical Properties and Thermal Shock Resistance of Segmented La2Ce2O7/YSZ Thermal Barrier Coatings

La₂Ce₂O₇ (LCO)/yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC) with segmentation crack structure was produced by atmospheric plasma spraying. Thermo-physical properties, such as thermal diffusivities and thermal conductivities, and thermal cycling performance of the segmented LCO/YSZ TBC were investigated. The thermal conductivity of the segmented coating was measured to be around 1.02 W/mK at 1200 °C, relatively lower than that of the non-segmented coating, respectively. The segmented LCO/YSZ TBC exhibited a thermal cycling lifetime of around 2100 cycles, improving the durability by nearly 50% as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Plasma-sprayed duplex and graded partially stabilized zirconia thermal barrier coatings: deposition process and properties

Atmospheric plasma spraying of duplex and graded ZrO₂ (8% Y₂O₃) thermal barrier coatings (TBCs) on Inconel 617 substrate with a NiCrAlY bond coat is described in terms of a deposition process of con-trolled coating structure. Special attention is devoted to the dominant spray parameters and the injector configuration for powder feeding, which play a fundamental role in graded coating deposition with con-trolled formation of a graded metal-ceramic (GMC) intermediate zone. The results of the graded coating spraying allow: (a) suppression of step-interface effects, (b) suppression of large differences (misfit) be-tween physical and mechanical constants of the coating and those of the substrate material, and (c) favor-able intergrowth of crystallites for a microstructurally integrated structure. Sprayed TBCs were investigated and compared with regard to their thermal cycling, oxidation behavior, and mechanical properties. The influence of crystal anisotropy changes on the resulting coating structure and properties is shown. On the basis of finite element (FE) calculations, the stress distribution within thermally cycled coating systems was analyzed. It is confirmed that the graded coating structure relaxes considerably the stresses resulting from the internal constraint due to thermal expansion difference between both metallic and ce-ramic materials. This stress distribution also decreases the gradient of elastic deformation and/or resid-ual stresses between the metal bond coat and top ceramic coating, and hence leads to a better thermal cycling behavior of the graded TBC systems. However, this advantage is not practical in every case, since the rapid oxidation of the metallic lamellae causes the ceramic phase in the GMC zone to undergo tensile stresses within a short thermal exposure time. The lifetime of duplex TBC systems that are under steady-state thermal load conditions is much higher than that of graded ones.