Fracture of plasma-sprayed thick thermal barrier coatings under multiaxial stress states

Failure behaviour of free‐standing plasma‐sprayed coatings was investigated under combined axial and shear loading. Thin‐walled tubular specimens were loaded with various combinations of tension/compression and torsion. This allows the failure surface to be established for loading situations where the two principal stresses are of opposite signs. Specimens failed in one of the two modes, a tensile failure perpendicular to the maximum principal stress or a compression shear failure through the thickness. Failure data were adequately described by the maximum principal stress theory. Stress–strain curves fall within a single scatter band depending on the failure mode. In situ deformation tests showed that the mechanism was microcrack closing and sliding in compression and microcrack opening, coalescence and the development of new microcracks in tension.     

EB-PVD热障涂层对高温合金基体断裂特征影响的研究

采用EB－PVD方法在K3合金上（包括铸态和经标准热处理两种状态）沉积了由NiCoCrAlY金属粘结层和YSZ涂层顶层组成的双层结构的热障涂层,对未涂层和涂层试样的拉伸性能进行了评估,并分析了涂层的制备和中间处理过程中的基体的微观结构的变化。结果表明,在热障涂层的沉积以及中间处理过程中（真空前处理及后处理）,基体的铸态组织得到改善,产生了析出强化,使得在铸态K3合金基体上沉积热障兴层后基体的拉伸强度由800MPa提高到1050MPa,而在经过标准热处理的合金基体上沉积热障涂层对基体的力学性能几乎没有影响。     

Erosion of thermal barrier coatings

Abstract

Thermal barrier coatings have been used within gas turbines for over 30 years to extend the life of hot section components. Thermally sprayed ceramics were the first to be introduced and are widely used to coat combustor cans, ductwork, platforms and more recently turbine aerofoils of large industrial engines. The alternative technology, electron beam physical vapour deposition,(EB-PVD) has a more strain-tolerant columnar microstructure and is the only process that can offer satisfactory levels of spall resistance, erosion resistance and surface finish retention for aero-derivative engines.

Whatever technology is used, the thermal barrier must remain intact throughout the turbine life. Erosion may lead to progressive loss of TBC thickness during operation, raising the metal surface temperatures and thus shortening component life. Ballistic damage can lead to total TBC removal.

This paper reviews the erosion behaviour of both thermally sprayed and EB-PVD TBCs relating the observed behaviour to the coating microstructure. A model for the erosion of EB-PVD ceramics is presented that permits the prediction of erosion rates. The model has been validated using a high velocity erosion gas gun rig, both on test coupons and samples removed from coated components. The implications of erosion on component life are discussed in the light of experimental results and the model predictions.     

Understanding of degradation-resistant behavior of nanostructured thermal barrier coatings with bimodal structure

Nanostructured thermal barrier coatings (TBCs) often provide high degradation resistance, as well as extended lifetime. However, the underlying mechanism has not been fully understood. In this study, the sintering characteristics of nanostructured yttria-stabilized zirconia (YSZ) coatings were investigated, and compared with those of the conventional YSZ coatings. Multiscale characterizations of the changes in microstructures and properties were performed. Results showed that the enhanced high-performance durability was mainly attributed to different sintering mechanisms of lamellar zones and nanozones. Sintering characteristics of the lamellar zones were similar to those of the conventional coatings. Stage-sensitive healing of two-dimensional (2D) pores dominated the sintering behavior of the lamellar zones. However, the differential densification rates between nanozones and lamellar zones of the nanostructured TBCs led to the formation of coarse voids. This counteractive effect, against healing of 2D pores, was the main factor contributing to the retardation of the performance degradation of bimodal TBCs during thermal exposure. Based on the understanding of the performance-degradation resistance, an outlook towards TBCs with higher performances was presented.     

On debonding of graded thermal barrier coatings

Thermal barrier coatings generally consist of a metallic substrate which is the primary structural component, a metallic bond coat which serves as oxygen diffusion barrier, a very thin layer of thermally grown oxide and a ceramic top coat that provides the main thermal shielding. Homogeneous ceramic coatings as top coats appear to have certain undesirable features such as high residual and thermal stresses, generally low toughness and relatively poor bonding strength. The new concept of compositional grading of the top coat may help to overcome some of these shortcomings by eliminating the material property discontinuities. A common mode of failure in thermal barrier coatings seems to be the debonding of the top coat. In this study the related interface crack problem for a graded ceramic/metal top coat is considered. It is assumed that the thermophysical properties of the top coat continuously vary between that of the bond coat at the top coat-bond coat interface and that of the ceramic at and near the free surface. The main objective of the study is to examine the influence of the material nonhomogeneity parameters and relative dimensions on the stress intensity factors and the crack opening displacements.     

热传导对双陶瓷热障涂层隔热效果影响研究

为了更好地设计双陶瓷热障涂层结构,考察在制备和服役过程中热导率的变化对隔热效果的影响,建立了双陶瓷热障涂层半透明数学模型,采用有限元ANSYS软件模拟了稳态隔热效果.结果表明:顶层陶瓷层的热导率增大降低了隔热效果,且随顶层厚度增加隔热效果降低幅度增大;第2层陶瓷层的热导率增大降低了隔热效果,且随顶层厚度增加隔热效果降低幅度减小;陶瓷层半透明且衰减系数很小时,顶层厚度增加,隔热效果先快速后缓慢增加至不变甚至略有降低,且远低于相同条件下不透明时.顶层陶瓷层热导率变化对隔热效果影响大于第2层陶瓷层.     

双陶瓷层热障涂层的隔热行为有限元模拟研究

基于热传导、热对流和热辐射理论建立了双陶瓷层热障涂层不透明和半透明物理模型,采用有限元ANSYS软件模拟了稳态温度场。结果表明双陶瓷层在不透明时,随总厚度或顶层厚度增加,顶层上表面温度近似线性增加,第2层和粘结层上表面温度近似线性降低。在陶瓷层半透明条件下,衰减系数对各层温度有一定影响。在衰减系数很大时,各层温度与不透明情况类似;在衰减系数较小时,顶层上表面温度略低于不透明时,第2层上表面温度略高于不透明时,粘结层上表面温度先快速后缓慢降低并保持不变,且远高于不透明时,界面反射能降低各层温度。     

Measurements of the thermal gradient over EB-PVD thermal barrier coatings

Conventional two-layered structure thermal barrier coatings (TBCs), graded thermal barrier coatings (GTBCs) and graded thermal barrier coatings with micropores were prepared onto superalloy DZ22 tube by electron beam physical vapor deposition (EB-PVD). Thermal gradient of the TBCs was evaluated by embedding two thermal couples in the surfaces of the tube and the top coat at different surrounding temperatures with and without cooling gas flowing through the tube. The results showed that higher thermal gradient could be achieved for the GTBCs with micropores compared to the two-layered structure TBCs and GTBCs. However, after the samples were heated at 1050°C, the thermal gradient for the GTBCs with or without micropores decreased with the increase of heating time. On the other hand, the thermal gradient for the TBCs increased with the increase of heating time. Cross-section observations by scanning electron microscopy showed that the change in microstructure was the main reason for the change of the thermal gradient.     

The role of transient oxides during deposition and thermal cycling of thermal barrier coatings

Abstract

High temperature coating systems, consisting of a René N5 superalloy, a Ni–23Co–23Cr–19Al–0.2Y (at.%) bond coating (BC) and a partially yttria stabilised zirconia (PYSZ) thermal barrier coating (TBC), were thermally cycled to failure for three different pre-oxidation treatments performed for 1 h at 1373 K and a partial oxygen pressure (pO₂) of 20 kPa, 100 Pa and 0.1 Pa, respectively. These pre-treatments resulted in the formation of different thermally grown oxide (TGO) layers prior to TBC deposition with respect to the presence of the transient oxides NiAl₂O₄, θ-Al₂O₃, and Y₃Al₅O₁₂ at the TGO surface. The TGO microstructures after TBC deposition and thermal cycling were investigated with a variety of analytical techniques and compared with those after pre-oxidation. For all pre-oxidation treatments, a double-layered TGO developed on the BC during thermal cycling. The TGO adjacent to the TBC consisted of small Zr-rich oxide crystallites embedded in an Al₂O₃ matrix when the TGO surface after pre-oxidation comprised of Y₃Al₅O₁₂ plus α-Al₂O₃. When the TGO surface constituted of θ-Al₂O₃, the Zr-rich oxide crystallites were embedded in a NiAl₂O₄ spinel layer after thermal cycling. Zr was absent in the oxide layer when the TGO surface prior to TBC deposition was composed of NiAl₂O₄ spinel. The TGO contiguous to the BC consisted in all cases of α-Al₂O₃ with Y₃Al₅O₁₂ crystallites. The roughness of the α-Al₂O₃/BC interface increased for a higher density of Y-rich oxide protrusions (i.e. pegs) along this interface.     

Residual stress measurement by Piezospectroscopy of cross sections through thermal barrier coatings

Abstract

Piezo-spectroscopic measurements of the residual stress in the TGO have been demonstrated on cross sections through thermally cycled TBC systems with high spatial resolution (approximately 2 × 2 × 5 µm). The residual stress is perturbed by relaxation at the free surface, but this can be taken into account in an approximate way. This relaxation has a range approximately equal to the YSZ thickness indicating that the YSZ imposes significant mechanical constraint on the TGO despite its low modulus.

The measurements have shown that the non-planar morphology of the TGO induces large deviations from the thermo-elastic equi-biaxial stress expected for a planar TGO. The mean level of compressive residual stress is reduced by relaxation due to bending of the non-planar TGO, in agreement with elastic FEM analysis of sinusoidal TGO morphology. However, the real morphology is not sinusoidal and in some locations the local curvature is extremely high. In these regions the residual stress is observed to become tensile and as high as 1 GPa. The failure mechanism is by nucleation and growth of local damaged regions caused by these tensile stresses (which are evident as low stress regions on analysis through the YSZ) into larger regions that eventually become unstable to large-scale buckling and spalling.     

掺杂纳米CeO2对ZrO2-Y2O3热障涂层隔热性能的影响

以纳米ZrO₂-8 wt%Y₂O₃(YSZ)和在纳米ZrO_2-8wt%Y₂O₃中分别掺杂25wt%和50wt%纳米CeO₂团聚处理后作为隔热层材料,NiCrAlY(Ni-25Cr-5Al-0.5Y,wt %)作为粘结层材料,用等离子喷涂(APS)方法在GH30高温合金表面制备三种材料体系的热障涂层(TBC) 。通过扫描电镜(SEM)和X射线衍射仪(XRD)对掺杂了25wt%纳米CeO₂涂层的微观组织结构进行分析研究,测定了三种材料涂层在室温和 300、500、700℃时的热导率,并在相同边界条件下测试了它们的隔热性能。结果表明：掺杂纳米CeO₂涂层组成相为稳定的t相(t-ZrO₂、t-Zr_0.82Y_0.18O_1.91、t-Zr_0.82Ce_0.18O₂)和c相(c-CeO₂) , 涂层中存在闭合的孔隙和微裂纹;掺杂纳米CeO₂能够降低涂层的热导率,并且隔热性能随CeO₂含量的增加而提高。对于 400μm厚的CeO₂/ZrO₂-Y₂O₃涂层(CYZ , 掺杂25wt%CeO₂)对基体产生的温降比纳米YSZ涂层提高了10.7%,当CeO₂的含量从25wt%提高到50wt%时,隔热性能也提高了7.1%。     

Interfacial fracture characteristic and crack propagation of thermal barrier coatings under tensile conditions at elevated temperatures

Thermal barrier coatings (TBCs) have been extensively used in aircraft engines for improved durability and performance for more than fifteen years. In this paper, thermal barrier coating system with plasma sprayed zirconia bonded by a MCrAlY layer to SUS304 stainless steel substrate was performed under tensile tests at 1000°C. The crack nucleation, propagation behavior of the ceramic coatings in as received and oxidized conditions were observed by high-performance camera and discussed in detail. The relationship of the transverse crack numbers in the ceramic coating and tensile strain was recorded and used to describe crack propagation mechanism of thermal barrier coatings. It was found that the fracture/spallation locations of air plasma sprayed (APS) thermal barrier coating system mainly located within the ceramic coating close to the bond coat interface by scanning electron microscope (SEM) and energy dispersive X-Ray (EDX). The energy release rate and interface fracture toughness of APS TBCs system were evaluated by the aid of Suo–Hutchinson model. The calculations revealed that the energy release rate and fracture toughness ranged, respectively, from 22.15 J m⁻² to 37.8 J m⁻² and from 0.9 MPa m^1/2 to 1.5 MPa m^1/2. The results agree well with other experimental results.     

Corrosion of thermal barrier coatings by vanadium and sulfur compounds

Abstract

Hot corrosion studies of two plasma-sprayed coatings, yttria-stabilized zirconia and calcium silicate, were undertaken in order to compare the performance of these materials for use as thermal barrier coatings in high-temperature combustion environments. The coatings were tested in contact with vanadium pentoxide at 1,000°C and, also, under conditions in which they were exposed to sulfur-containing compounds at 900°C or 1,000°C. The samples were subsequently characterized by scanning electron microscopy and X-ray diffraction analysis to identify the effects of these tests on the microstructure and composition. The results indicate that reactions with V₂O₅ lead to a disruptive phase transformation in zirconia that rapidly degrades the coating. For calcium silicate, the reactions with V₂O₅ appear to be more limited and less disruptive so that the coating is much more slowly degraded by the vanadium compounds. Exposure to SO_x and sulfate salts at high temperature caused rapid degradation of the calcium silicate coatings through a reaction involving the formation of CaSO₄. Under similar conditions, the yttria-stabilized zirconia coatings experienced much less attack.     

Failure aspects of thermal barrier coatings

Abstract

The paper describes aspects of thermal barrier coating (TBC) microstructure and the physical and mechanical properties which they influence. The stress-strain behaviour of air plasma sprayed (APS) TBCs is discussed, including the role of residual stresses. Failure phenomena as well as the TMF behaviour of TBC coated nickel base superalloys are described. The role of bond coat oxidation on TBC life is discussed as well as some mechanical properties of vacuum plasma sprayed MCrAlY-bond coatings. Finally, life prediction methodologies are addressed and discussed in terms of a critical strain accumulation concept. From this is derived an equation which covers time dependent effects such as bond coat oxidation and sintering. The paper concludes with a brief summary of the evolution of TBCs in aero and industrial gas turbines, and the failure modes in each. In particular the increased importance of erosion, in industrial gas turbines, due to water injection is highlighted.     

Microstructural characterization of the failures of thermal barrier coatings on Ni-base superalloys

Abstract

Typical thermal barrier coating (TBC) systems consist of a nickel-base superalloy substrate coated with a MCrAlY or diffusion aluminide bond coat, onto which is deposited a yttria-stabilized zirconia (YSZ) TBC. The bond coats are usually deposited via diffusion aluminizing processes or low pressure plasma spray processes (LPPS). The YSZ can be deposited by air plasma spraying (APS) or electron beam physical vapor deposition (EBPVD). A layer of thermally-grown oxide (TGO), which is usually alumina, forms between the bond coat and YSZ during TBC deposition and subsequent high-temperature exposure. The conventional wisdom is that APS coatings tend to fail in the YSZ and that EBPVD coatings tend to fail at the interface between the TGO and bond coat. However, current research has shown that the situation is much more complex and that the actual fracture path can be a function of the type of bond coat, the type of high-temperature exposure, and coating process parameters. This paper describes the results of a study of the failure of state-of-the-art EBPVD TBCs deposited on NiCoCrAlY and platinum-modified diffusion aluminide bond coats. The failure times and fracture morphology are described as a function of bond coat type. The failure times were found to be a strong function of temperature for both bond coats. The failure for NiCoCrAlY bond coats was found to initiate at defects in the coating, particularly at the TGO/YSZ interface, but the fracture propagated primarily along the TGO–bond coat interface. The failure times and morphologies for platinum-modified diffusion aluminide bond coats depended strongly on bond coat surface preparation. The mechanisms for failure of the two bond coats are described. Also, the effects of modifications to the bond coats and variations in processing parameters on these mechanisms are presented.     

Measurement of thermal diffusivity and anisotropy of plasma-sprayed coatings

The thermal diffusivity of free-standing tungsten and zirconia plasma-sprayed coatings was measured in the directions parallel and perpendicular to their surface. The parallel thermal diffusivity was evaluated by a double-sensing Laplace-transform technique and compared to the perpendicular values obtained by the (lash technique. Ratios between the parallel and the perpendicular thermal diffusivity values were in the range of 1.1 to 1.5 for zirconia and 4 to 6 for tungsten. The results are discussed in terms of the coating thickness and microstructure.On leave from Laboratoire d'Énergetique et de Méchanique Théorique et Appliquée, B.P. 160, 54504 Vandoeuvre les Nancy, France.     

Fracture behavior under mixed-mode loading of ceramic plasma-sprayed thermal barrier coatings at ambient and elevated temperatures

The fracture behavior under modes I and II loading of ceramic plasma-sprayed thermal barrier coatings was determined in air at 25 and 1316 °C in asymmetric four-point flexure. The mode I fracture toughness was found to be K_Ic = 1.15 ± 0.07 and 0.98 ± 0.13 MPa , respectively, at 25 and 1316 °C. The respective ‘nominal’ mode II fracture toughness values were K_IIc = 0.73 ± 0.10 and 0.65 ± 0.04 MPa . The empirical mixed-mode fracture criterion best described the coatings’ fracture behavior under mixed-mode loading. The angle of crack propagation was in reasonable agreement with the minimum strain energy density criterion.     

CMAS环境下电子束物理气相沉积热障涂层的热循环行为及失效机制

航空发动机涡轮叶片工作时表面经常产生CaO-MgO-Al₂O₃-SiO₂(简称CMAS)等沉积物。本文中研究了电子束物理气相沉积(EB-PVD)制备ZrO₂热障涂层(TBCs)在CMAS环境下的热循环行为及失效机制。结果表明, 在1200℃热冲击条件下, 表面涂覆CMAS的热障涂层的热循环寿命低于100次, 而未涂覆CMAS的涂层寿命达到500次以上, CMAS 的存在加速了热障涂层的剥落失效。在1200℃经过210次循环后, ZrO₂陶瓷层与CMAS之间形成了约8 μm厚的互反应区, 其形成主要与CMAS中Ca²⁺内扩散有关。CMAS环境下热障涂层陶瓷层产生大量横向裂纹, 涂层的失效主要以陶瓷层片状剥落为主。     

Performance of thermal barrier coatings in industrial gas turbine conditions

Abstract

The effect of aerofoil geometry on the oxidative degradation mechanisms experienced by thermal barrier coatings (TBCs) used on industrial turbine blades has been investigated. Modified aerofoil-shaped samples (CMSX4 coated with high-velocity oxy-fuel sprayed AMDRY 995 and air plasma sprayed TBC) were oxidised at five temperatures in furnaces from 900 to 1000°C. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterise details of the microstructural evolution of the thermally grown oxide and to monitor inter-diffusion between the bond coating and substrate. Additionally, a novel non-destructive examination technique (flash thermography) was used to detect and track the spread of cracks beneath the TBCs. Multiple samples cracking in identical locations suggested an effect of geometry in the failure of coatings. Furthermore, it was observed that coating curvature influenced spinel formation.     

Characterization of thermally cycled alumina scales

Abstract

Cross-sectional transmission electron microscopy was used to characterize the alumina scales formed on several Ni-base alumina-formers. The alumina scale microstructure of Ni–20at%Cr–19Al–0.05Y after 100, 1 h cycles at 1,100°C was compared to an isothermally-grown scale. Despite being near the onset of mass loss in cyclic testing, very few defects were noted in either scale microstructure. The more adherent scales that form on Hf-doped NiAl and Ni–49at%Al–2Cr were also characterized. With the addition of Cr, the formation of α-Cr precipitates at the metal–oxide interface coincided with increased long-term scale spallation. No similar precipitation mechanism was observed to be associated with scale spallation on NiCrAlY.