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.     

The influence of bondcoat and topcoat mechanical properties on stress development in thermal barrier coating systems

A finite-element study has been undertaken to investigate the stress development within a TBC system consisting of an EB-PVD YSZ topcoat and a Pt-aluminized diffusion bondcoat. Particular attention has been paid to the role of variables such as the elastic anisotropy within the topcoat, interface roughness, variation in creep strength of the bondcoat and the volumetric strains associated with the formation of the thermally grown oxide (TGO). Bond coat oxidation and thermal loading during cooling give rise to significant tensile stresses within the topcoat and tensile tractions at the TGO interfaces. Bondcoat creep, as distinct from yield and plastic behaviour, was the dominant stress relaxation process, and strong bondcoats (in creep) tended to show higher tensile stress levels. Another important factor determining thermal barrier coating stress levels was the level of elastic anisotropy of the topcoat: an elastic isotropic yttria-stabilized zirconia gave rise to considerably higher stresses than a transversely isotropic topcoat.     

Influence of Surface Finish on the Cyclic Oxidation Lifetime of an EB-PVD TBC, Deposited on PtAl and Pt-diffused Bondcoats

Thermal barrier coatings (TBCs) are well established as protective systems for gas turbine hot path components, due to their ability, with substrate cooling, to reduce the maximum surface temperature experienced by the metal component. However, when subject to high temperature oxidation, cyclic heating and cooling during service, TBCs degrade in both thermal protection capability and mechanical stability as a result of a combined thickening of the alumina-thermally grown oxide and sintering of the ceramic top coat. Eventually the ceramic top coat spalls from the metallic substrates. The detailed failure mechanisms for the TBC often are complicated, reflecting a balance between defects introduced into the TBC during manufacture and service and the stored energy generated in the TBC as a result of cyclic thermal exposure. It has been shown that the surface finish influences the residual stress in the thermally grown oxide and thus the stored energy. In this study, the influence of substrate surface finish, prior to bondcoat manufacture, on the cyclic oxidation lifetime is examined. Two EB-PVD TBC systems, a zirconia 8 wt% yttria topcoat on a platinum aluminide bondcoat and a zirconia 8 wt% yttria topcoat on a platinum diffused γ+γ′ bondcoat have been studied. For these two systems, various substrate surface finishes have been investigated, including ground, grit blasted and polished and grit blasted surfaces. The lifetime data for these cyclic oxidation tests of EB-PVD TBCs on these two diffusion bondcoats, platinum aluminide and platinum diffused, on CMSX4, have been analysed statistically for the various surface finishes. It is shown that the variability in measured lifetime can be modelled using Weibull statistics. The role of surface finish on the Weibull model parameters, characteristic life (η) and Weibull modulus (β), are discussed in this paper and hence the role surface finish plays on the likelihood of early, short life, TBC failure. Based on this analysis a more optimised surface finish is recommended to extend TBC lifetimes with diffusion based bondcoats. Further, the platinum diffusion bondcoat is shown to outperform the platinum aluminide system once the substrate surface finish has been optimised.     

Ceramic Top Coats of Plasma-Sprayed Thermal Barrier Coatings: Materials,Processes, and Properties

The ceramic top coat has a major influence on the performance of the thermal barrier coating systems (TBCs). Yttria-partially-stabilized zirconia (YSZ) is the top coat material frequently used, and the major deposition processes of the YSZ top coat are atmospheric plasma spraying and electron beam physical vapor deposition. Recently, also new thermal spray processes such as suspension plasma spraying or plasma spray-physical vapor deposition have been intensively investigated for TBC top coat deposition. These new processes and particularly the different coating microstructures that can be deposited with them will be reviewed in this article. Furthermore, the properties and the intrinsic–extrinsic degradation mechanisms of the YSZ will be discussed. Following the TBC deposition processes and standard YSZ material, alternative ceramic materials such as perovskites and hexaaluminates will be summarized, while properties of pyrochlores with regard to their crystal structure will be discussed more in detail. The merits of the pyrochlores such as good CMAS resistance as well as their weaknesses, e.g., low fracture toughness, processability issues, will be outlined.     

TGO Growth and Crack Propagation in a Thermal Barrier Coating

In thermal barrier coating (TBC) systems, a continuous alumina layer developed at the ceramic topcoat/bond coat interface helps to protect the metallic bond coat from further oxidation and improve the durability of the TBC system under service conditions. However, other oxides such as spinel and nickel oxide, formed in the oxidizing environment, are believed to be detrimental to TBC durability during service at high temperatures. It was shown that in an air-plasma-sprayed (APS) TBC system, postspraying heat treatments in low-pressure oxygen environments could suppress the formation of the detrimental oxides by promoting the formation of an alumina layer at the ceramic topcoat/bond coat interface, leading to an improved TBC durability. This work presents the influence of postspraying heat treatments in low-pressure oxygen environments on the oxidation behavior and durability of a thermally sprayed TBC system with high-velocity oxy-fuel (HVOF)-produced Co-32Ni-21Cr-8Al-0.5Y (wt.%) bond coat. Oxidation behavior of the TBCs is evaluated by examining their microstructural evolution, growth kinetics of the thermally grown oxide (TGO) layers, and crack propagation during low-frequency thermal cycling at 1050 °C. The relationship between the TGO growth and crack propagation will also be discussed.     

Thermal shock testing of thermal barrier coating/bondcoat systems

Various methods of thermal shock testing are used by aircraft and industrial gas turbine engine (IGT) manufacturers to characterize new thermal barrier coating systems in the development stage as well as for quality control. The cyclic furnace oxidation test (FCT), widely used in aircraft applications, stresses the ceramic/bondcoat interface, predominantly through thermally grown oxide (TGO) growth stress. The jet engine thermal shock (JETS) test, derived from a burner rig test, creates a large thermal gradient across the thermal barrier coating (TBC), as well as thermomechanical stress at the interface. For IGT applications with long high-temperature exposure times, a combination of isothermal preoxidation and thermal shock testing in a fluidized bed reactor may better represent the actual engine conditions while both types of stress are present. A comparative evaluation of FCT, JETS, and a combined isothermal oxidation and fluidized bed thermal shock test has been conducted for selected ceramic/bondcoat systems. The results and the failure mechanisms as they relate to the TBC system are discussed. A recommendation on the test method of choice providing best discrimination between the thermal shock resistance of the ceramic layer, the ceramic/bondcoat interface, and even substrate related effects, is given. This paper was presented at the 2nd International Surface Engineering Congress sponsored by ASM International, on September 15–17, 2003, in Indianapolis, Indiana, and appeared on pp. 520–29.     

Pre-oxidation and TGO growth behaviour of an air-plasma-sprayed thermal barrier coating

In thermal barrier coating (TBC) systems, spinel and nickel oxide formed in an oxidizing environment are believed to be detrimental to TBC durability during service at high temperatures. The present study shows that in an air-plasma-sprayed (APS) TBC with Co–32Ni–21Cr–8Al–0.5Y (wt.%) bond coat, pre-oxidation treatments in low-pressure oxygen environments can suppress the formation of the detrimental oxides by promoting the formation of an Al₂O₃ layer at the ceramic topcoat/bond coat interface. The development of the thermally grown oxide (TGO) layer generally exhibits a three-stage growth phenomenon that resembles high temperature creep. The pre-oxidation treatments reduce the growth rate and extend the steady-state growth stage, leading to an improved durability. Crack propagation in the TBC proceeds via opening and growth of pre-existing discontinuities in the ceramic topcoat, assisted by crack nucleation and growth associated with the TGO. Crack propagation during thermal cycling appeared to be controlled by TGO growth, and the maximum crack length and TGO thickness generally have a power law relationship.     

Failure Analysis of Multilayered Suspension Plasma-Sprayed Thermal Barrier Coatings for Gas Turbine Applications

Improvement in the performance of thermal barrier coatings (TBCs) is one of the key objectives for further development of gas turbine applications. The material most commonly used as TBC topcoat is yttria-stabilized zirconia (YSZ). However, the usage of YSZ is limited by the operating temperature range which in turn restricts the engine efficiency. Materials such as pyrochlores, perovskites, rare earth garnets are suitable candidates which could replace YSZ as they exhibit lower thermal conductivity and higher phase stability at elevated temperatures. The objective of this work was to investigate different multilayered TBCs consisting of advanced topcoat materials fabricated by suspension plasma spraying (SPS). The investigated topcoat materials were YSZ, dysprosia-stabilized zirconia, gadolinium zirconate, and ceria–yttria-stabilized zirconia. All topcoats were deposited by TriplexPro-210^TM plasma spray gun and radial injection of suspension. Lifetime of these samples was examined by thermal cyclic fatigue and thermal shock testing. Microstructure analysis of as-sprayed and failed specimens was performed with scanning electron microscope. The failure mechanisms in each case have been discussed in this article. The results show that SPS could be a promising route to produce multilayered TBCs for high-temperature applications.     

Resonant-based identification of the elastic properties of layered materials: Application to air-plasma sprayed thermal barrier coatings

This work introduces a resonant-based, mixed numerical–experimental method for the determination of the in-plane elastic properties of the constituent materials of laminates. This non-destructive method identifies elastic properties from the resonant frequencies of beam-shaped layered specimens, using a set of finite element models. The method is demonstrated on a thermal barrier coating system made of NiCoCrAlY bondcoat and yttria-stabilised zirconia topcoat deposited by air-plasma spraying on stainless steel. The stainless steel was found to be elastically anisotropic, while both bondcoat and topcoat exhibited in-plane isotropy. Moreover, the topcoat Poisson's ratio approached zero, and the bondcoat properties varied with the coating thickness. Scanning electron microscopy was used to correlate the identified elastic properties with the coating microstructure.     

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。     

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.     

Influence of Bondcoat Spray Process on Lifetime of Suspension Plasma-Sprayed Thermal Barrier Coatings

Development of thermal barrier coatings (TBCs) manufactured by suspension plasma spraying (SPS) is of high commercial interest as SPS has been shown capable of producing highly porous columnar microstructures similar to the conventionally used electron beam–physical vapor deposition. However, lifetime of SPS coatings needs to be improved further to be used in commercial applications. The bondcoat microstructure as well as topcoat–bondcoat interface topography affects the TBC lifetime significantly. The objective of this work was to investigate the influence of different bondcoat deposition processes for SPS topcoats. In this work, a NiCoCrAlY bondcoat deposited by high velocity air fuel (HVAF) was compared to commercial vacuum plasma-sprayed NiCoCrAlY and PtAl diffusion bondcoats. All bondcoat variations were prepared with and without grit blasting the bondcoat surface. SPS was used to deposit the topcoats on all samples using the same spray parameters. Lifetime of these samples was examined by thermal cyclic fatigue testing. Isothermal heat treatment was performed to study bondcoat oxidation over time. The effect of bondcoat deposition process and interface topography on lifetime in each case has been discussed. The results show that HVAF could be a suitable process for bondcoat deposition in SPS TBCs.     

Evolution of Residual Stresses in PS-PVD Thermal Barrier Coatings on Thermal Cycling

Plasma spray-physical vapor deposition (PS-PVD) is an advanced technique to fabricate quasi-columnar structured thermal barrier coatings (TBCs) with excellent thermal cyclic lifetime. In this study, PS-PVD TBCs were investigated via burner rig test. The residual stresses in both of the topcoat layer and the thermally grown oxide (TGO) scale were measured non-destructively using Raman spectroscopy and Cr³⁺ photoluminescence piezo-spectroscopy, respectively. Evolution of the microstructures and distribution of residual stresses in such kind structured TBCs before and after thermal cycling test were investigated. The accumulated tensile stress in the as-sprayed ceramic topcoat changed to compressive state after 100 cycles and then gradually increased. In addition, the mapping compressive stresses in the TGO measured through the ceramic topcoat surface decreased rapidly and then essentially maintained at a relatively stable state with further testing. Moreover, the pre-heating of the bondcoat could significantly affect the stress distribution in the TGO, in contrast, no obviously influence on the stresses in the YSZ topcoat.     

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.     

航空发动机涡轮叶片热障涂层研究现状

热障涂层是一种可以有效保障航空发动机涡轮叶片正常工作，同时显著提高其工作效率和服役时间的表面防护技术。热障涂层的性能在很大程度上影响叶片的承温和抗腐蚀能力，进而间接影响航空发动机的服役性能。涂层性能主要受其结构和材料2个方面的影响。介绍了涂层结构的优缺点和研究进展，当前常见的结构形式有双层结构、多层结构和梯度结构；介绍了粘结层材料的研究进展；对陶瓷层材料的研究进展进行了详述，如YSZ的掺杂改性、A₂B₂O₇型化合物、钙钛矿结构材料以及近年来兴起的几种高熵陶瓷材料，其中高熵陶瓷材料包括：高熵稀土钽酸盐、铝酸盐、锆/铪酸盐、磷酸盐、硅酸盐以及高熵稀土氧化物，分别从热导率、热膨胀系数、断裂韧性、热循环寿命和抗腐蚀能力等方面对其进行介绍；概述了热障涂层常见的几种失效形式如：TGO失效、CMAS腐蚀以及高温烧结，并且对其发生机理进行简要的介绍；展望了热障涂层未来的发展趋势和方向。     

Evolution of Lamellar Interface Cracks During Isothermal Cyclic Test of Plasma-Sprayed 8YSZ Coating with a Columnar-Structured YSZ Interlayer

The failure of plasma-sprayed thermal barrier coatings (TBC) usually occurs through spalling of ceramic coating. The crack evolution during thermal cycling of TBC is directly associated with its spalling. In this paper, the cracks in TBC along the direction of the interface between ceramic coating and bond coat were examined from cross-section of TBC experienced different numbers of thermal cycle, and crack number and the total length of cracks were measured to aim at understanding the failure mechanism. TBC consists of cold-sprayed NiCoCrAlTaY bond coat on IN738 superalloy and double layered plasma-sprayed 8YSZ with a columnar grain structured YSZ interlayer of about 20 μm thick and about 230 μm lamellar YSZ. With each isothermal cyclic test, the TBC samples were kept at 1150 °C for 26 min hold and then cooled down to a temperature less than 80 °C in 4 min by air forced cooling. Results showed that cracks propagated primarily within lamellar-structured YSZ over the columnar YSZ along lamellar interface. The measurement from the cross-section revealed that crack number and total crack length apparently increased with the increase of the number of thermal cycle. It was found that cracks with a length less than a typical size of 200 μm accounted for the majority of cracks despite the number of thermal cycle during the test. A crack initiation and propagation model for plasma-sprayed TBC is proposed with a uniform distribution of circular cracks. The propagatable cracks form homogeneously within plasma-sprayed porous YSZ coating at the early stage of thermal cycling and propagate at an identical rate during thermal cycling. Only a few of large cracks are formed before most cracks reach to the critical size for multi-cracks linking-up. The propagation of most cracks to the critical size will leads to the rapid crack bridging and subsequent spalling of top ceramic TBC.     

A chromia forming thermal barrier coating system

Conventional thermal barrier coating (TBC) systems consist of an insulating ceramic topcoat, a bond coat for oxidation protection and the underlying superalloy designed to combat the oxidising conditions in aero‐ and land‐based gas turbines. Under high‐temperature oxidation, the use of an alumina forming bond coat is warranted, thus all current TBC systems are optimised for the early formation of a dense, protective thermally grown oxide (TGO) of alumina. This also offers protection against Type I hot corrosion but a chromia layer gives better protection against Type II corrosion and intermediate temperatures, the conditions found in land‐based gas turbines. In this paper the authors present the first known results for a chromia forming TBC system. Tests have been performed under oxidising conditions, up to 1000 h, at temperatures between 750 °C and 900 °C, and under Type I (900 °C) and Type II (700 °C) hot corrosion conditions up to 500 h. Under all these conditions no cracking, spallation or degradation was observed. Examination showed the formation of an adherent, dense chromia TGO at the bond coat / topcoat interface. These initial results are very encouraging and the TGO thicknesses agree well with comparable results reported in the literature.     

温度梯度热循环下纳米7YSZ陶瓷层结构演变

目的采用低温超音速等离子喷涂(LT-HVOF)在镍基高温合金基体(K417)上制备了NiCoCrAlYTa粘结层,使用大气等离子喷涂(APS)在粘结层上制备了纳米7%Y_2O_3-ZrO_2(7YSZ)陶瓷涂层,以获得温度梯度热循环下纳米陶瓷层的结构演变机制。方法通过燃气热冲击实验仪对热障涂层模拟真实服役条件下温度梯度热循环的工作环境,采用一维稳态热传导模型计算了热障涂层中各涂层界面的温度,探讨了在热驱动作用下等径晶粒和非等径晶粒的扩散长大机制。结果热循环次数为40次时,涂层近表面出现了烧结致密化现象,而陶瓷层底部涂层保持原来的结构。热循环次数增加到460次时,整个陶瓷层断面都发生了烧结致密化现象。结论温度是涂层烧结致密化的主导因素。涂层中当等大晶粒接触形成弯曲颈时,由于弯曲颈只受水平方向静压力作用,晶粒中原子扩散速率慢,导致晶粒长大速率较慢;而当非等大晶粒接触形成弯曲颈时,在晶粒接触弯曲颈处存在一偏大晶粒方向的剪切力,其导致晶粒向弯曲颈扩散速率增加,晶粒长大速率较快。     

氧化锆粉体的制备及其在热障涂层中的应用

分别描述了纳米氧化锆粉体与空心球氧化锆粉体的制备工艺，分析了不同工艺影响氧化锆产物形态、结构、粒度等方面的因素，并将2种粉末制备的涂层分别与传统微结构涂层进行性能对比。在分析由不同氧化锆粉末制备而成的涂层性能时，除了工艺参数外，更多的是考虑初始氧化锆粉末对涂层性能所带来的影响。期待在未来的研究中，能够优化现有或者探索出更优异的制粉工艺，研究出性能更加优良的新型粉末，以期能够提高热障涂层的性能，满足高精尖领域在未来的使用需求。最后，针对不同制粉工艺及不同粉末制备涂层的发展方向进行了展望。