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.     

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.     

等离子喷涂热障涂层热震失效过程及残余应力分析

采用等离子喷涂技术在高温合金上制备了热障涂层(粘接层为NiCoCrAlY,陶瓷层为ZrO2-8%Y2O3),利用扫描电镜(SEM)、拉曼光谱(RFS)等试验手段研究了热障涂层热震失效的过程及残余应力大小和分布状态。结果表明:150次热循环后,陶瓷层和热生长氧化物(TGO)生成裂纹,其中陶瓷层的裂纹已扩展至TGO;350次热循环后,出现贯通陶瓷层与金属过渡层的纵向裂纹,涂层局部出现剥离,剥离位置位于TGO与陶瓷层界面;拉曼光谱(RFS)分析结果显示TGO内应力水平分布不均,局部厚大区和凸凹处残余应力较大,是裂纹萌生、扩展的主要部位。     

Stress Analysis and Failure Mechanisms of Plasma-Sprayed Thermal Barrier Coatings

Yttria-stabilized zirconia coatings were deposited by plasma spraying and heat-treated at 1100 °C for 50, 100, 150, and 200 h in air, respectively. Mechanical properties including microhardness and Young’s modulus were evaluated using the nanoindentation test. Residual stresses in the ceramic topcoat and the thermally grown oxide (TGO) layer were measured using Raman spectroscopy and photoluminescence piezo-spectroscopy (PLPS) techniques, respectively. The results showed that both the modulus and hardness increased with the thermal exposure time up to 100 h and then gradually decreased. The accumulated tensile stress in the as-sprayed topcoat changed to compressive stress after thermal exposure, and the compressive stress in the topcoat increased with an increase of thermal exposure time up to 150 h. The average compressive stresses in the TGO layer were higher than that of the cross-sectional topcoat, and the measured in-plane compressive stress increased firstly and then gradually decreased with increasing exposure time. The local interface geometry strongly affect the nature and evolution of hydrostatic stresses in the TGO. Finally, the crack initiation and propagation at the topcoat/TGO/bondcoat interface has been discussed with respect to the residual stresses in the plasma-sprayed TBC system.     

Development of residual stress and damage in thermal barrier coatings

Photo-luminescence piezo-spectroscopy through the electron beam deposited (EBPVD) yttria-stabilised zirconia (YSZ) thermal barrier coating has been used to study the evolution of residual stress due to the alumina thermally grown oxide (TGO) formed on Pt-Al bond coats on CMSX-4 substrates. The coated specimens were thermally cycled between room temperature and 1150 °C, holding for 1 h at the top temperature. The experiments explored the effects of two different bond coat surface finishes (normal and polished) and thickness of YSZ from 70 to 270 μm.In most cases the mean TGO stress was found to gradually decrease with thermal cycling in agreement with previously published results. This is mainly due to rumpling increasing the waviness of the TGO and hence the ability to relieve stress by bending. For the same reason, the TGO residual stress in specimens with polished bond coats was higher initially than in those with a normal surface finish. Stress mapping showed that there are regions, approximately 100 μm in size, where the stress is particularly low (< 1 GPa compressive) and these were attributed to local TGO damage or delamination. The incidence of these low stress “events” increased markedly just before coating spallation. The failure was in the TGO, or in the YSZ close to the TGO, probably as a result of weakening in this region by the damage induced by rumpling and driven by the stored energy in the YSZ.     

On the interfacial degradation mechanisms of thermal barrier coating systems: Effects of bond coat composition

Thermal barrier coating (TBC) systems based on an electron beam physical vapour deposited, yttria-stabilized zirconia (YSZ) top coat and a substrate material of CMSX-4 superalloy were identically prepared to systematically study the behaviour of different bond coats. The three bond coat systems investigated included two β-structured Pt–Al types and a γ–γ′ type produced by Pt diffusion without aluminizing. Progressive evolution of stress in the thermally grown aluminium oxide (TGO) upon thermal cycling, and its relief by plastic deformation and fracture, were studied using luminescence spectroscopy. The TBCs with the LT Pt–Al bond coat failed by a rumpling mechanism that generated isolated cracks at the interface between the TGO and the YSZ. This reduced adhesion at this interface and the TBC delaminated when it could no longer resist the release of the stored elastic energy of the YSZ, which stiffened with time due to sintering. In contrast, the TBCs with Pt diffusion bond coats did not rumple, and the adhesion of interfaces in the coating did not obviously degrade. It is shown that the different failure mechanisms are strongly associated with differences in the high-temperature mechanical properties of the bond coats.     

Thermal cyclic performance of NiAl/alumina-stabilized zirconia thermal barrier coatings deposited using a hybrid arc and magnetron sputtering system

In the present work, a hybrid arc/sputter deposition system is used to deposit alumina-stabilized zirconia (ASZ) thermal barrier coatings. An initial NiAl bond coat is deposited on the nickel super alloy substrates, in the same coating system, by arc ion plating alone. The as-deposited ASZ coatings have a dense columnar structure. From X-ray diffractometry (XRD), it is found that the as-deposited ASZ films are almost entirely tetragonal. This is believed to result from the relatively high concentration of aluminum (10 at.%) in the ASZ films. Thermal testing is carried out over numerous cycles, each consisting of 30 and 10 min at 1100 °C and ambient, respectively. During thermal testing, a significant amount of the tetragonal phase is transformed to monoclinic. Furthermore a significant number of cracks, both parallel and perpendicular to the substrate surface, are found to occur in the ASZ layer as a result of tensile and compressive thermal stresses. Although a thermally grown oxide (TGO) layer between the top and bond coat, and Kirkendall voids in the interfacial region between substrate and bond coat occur in this coating system, the failure occurs principally as a result of parallel cracks which form just above the TGO. After 200 thermal cycles, a great portion of the topcoat has failed. The formation of cracks, and the subsequent coating failure, is likely to result from the dense coatings being unable to accommodate the thermal stresses parallel to the surface during the cycling tests.     

On TGO creep and the initiation of a class of fatigue cracks in thermal barrier coatings

The initiation of a class of fatigue cracks observed in thermal barrier coatings (TBCs) subjected to thermal gradient mechanical fatigue testing is investigated. The coating system is based on a NiCoCrAlY bond coat and a partially yttria stabilized zirconia top coat. To explain the development of the cracks of interest, the thermo-mechanical response of the bond coat and the thermally grown oxide (TGO) is examined and quantified through finite element analyses. The models include non-linear and time-dependent behavior such as creep, TGO growth stress, and thermo-mechanical cyclic loading. The simulations suggest that stress-redistribution due to creep can lead to tensile stresses in the TGO during TGMF testing that are large enough to initiate the cracks investigated.     

Thermal Failure of Nanostructured Thermal Barrier Coatings with Cold-Sprayed Nanostructured NiCrAlY Bond Coat

Nanostructured thermal barrier coatings (TBCs) were deposited by plasma spraying using agglomerated nanostructured YSZ powder on Inconel 738 substrate with cold-sprayed nanostructured NiCrAlY powder as bond coat. The isothermal oxidation and thermal cycling tests were applied to examine failure modes of plasma-sprayed nanostructured TBCs. For comparison, the TBC consisting of conventional microstructure YSZ and conventional NiCrAlY bond coat was also deposited and subjected to the thermal shock test. The results showed that nanostructured YSZ coating contained two kinds of microstructures; nanosized zirconia particles embedded in the matrix and microcolumnar grain structures of zirconia similar to those of conventional YSZ. Although, after thermal cyclic test, a continuous, uniform thermally grown oxide (TGO) was formed, cracks were observed at the interface between TGO/BC or TGO/YSZ after thermal cyclic test. However, the failure of nanostructured and conventional TBCs mainly occurred through spalling of YSZ. Compared with conventional TBCs, nanostructured TBCs exhibited better thermal shock resistance.     

热障涂层界面化合物与残余应力演变研究

用超音速氧燃料热喷涂在铁基合金上制备热障涂层粘结层,用大气等离子热喷涂技术制备陶瓷层。研究了高温氧化后其界面化合物和残余应力的演变。结果表明,随着高温氧化的进行,TGO和BC/基体界面均有氧化物生成,但生长形貌和趋势并不一致。TGO由Al2O3层与尖晶石层组成;BC/基体界面氧化物为单一Al2O3,且存在层状和块状两种形貌。合金的热化学动力学引起元素Co和Ni向基底扩散比较严重,Al元素扩散止于界面氧化物层,基本不向铸铁基底扩散,Fe元素会向粘结层方向扩散。TGO残余应力的演化分为0~15 h和15~100 h 2个阶段,且残余应力与TGO的凹凸生长形貌及其物相组成密切相关;而BC/基体界面单一氧化物的残余应力基本稳定,不受其生长形貌影响。     

Oxidation Control with Chromate Pretreatment of MCrAlY Unmelted Particle and Bond Coat in Thermal Barrier Systems

MCrAlY alloy bond coat is widely used in thermal barrier coating (TBC) systems to protect substrates from high-temperature oxidizing environments. However, failure of the ceramic topcoat can occur due to a thermally grown oxide (TGO) that grows at the interface between the bond coat and the topcoat. In this study, the effect of chromate treatment was investigated. Prior to topcoat deposition, a thin film of Cr₂O₃ was formed on the bond coat surface. High-temperature oxidation tests were carried out, and the oxidation rates were determined by inspection of cross sections. Similar oxidation tests were carried out using MCrAlY powder material assumed to be unmelted particles. As a result, the chromate-treated bond coat showed outstanding oxidation resistance. Calculations that take into account the oxidation of particles in the topcoat indicated the generation of internal stress to cause local fracture of the topcoat.     

The influence of coating compliance on the delamination of thermal barrier coatings

Low relative density yttria stabilized zirconia (YSZ) thermal barrier coatings have been deposited on NiCoCrAlY over-lay bond-coated Hastelloy-X substrates by an electron beam-directed vapor deposition (EB-DVD) method. The coatings have been applied to both roughened and smooth bond coat surfaces. During thermal cycling, those deposited on roughened surfaces spalled by delamination with the failure located in the YSZ layer close to the thermally-grown oxide (TGO). The cracks were initiated at “corn kernel” defects in the YSZ layer by a bond coat rumpling mechanism. Coatings applied to smooth bond coat surfaces had much longer (factor of two) spallation lifetimes and delamination occurred at the bond coat/TGO interface by the nucleation and coalescence of interfacial voids. In both cases, the delamination lifetime decreased with coating density and significantly exceeded the lifetimes of higher density coatings made by conventional electron beam deposition methods. The enhanced life of the more porous coatings is consistent with an increased compliance. This reduces the YSZ layers stored strain energy contribution to the driving force for interface delamination.     

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。     

Evolution of stress and morphology in thermal barrier coatings

Residual stress in the thermally grown oxide (TGO) in thermal barrier coatings (TBCs) was measured by photoluminescence piezospectroscopy (PLPS) and stress maps created to track local stress changes as a function of thermal cycling. The local stress images were observed to be correlated with morphological features on the metal surface that were purposely introduced during specimen preparation. Local stress relaxation and morphological evolution with thermal cycling were studied using the stress maps combined by post-mortem SEM examination. It was found that the morphology in the specimen having an initial polished surface was quite stable, while that in the specimen with a rough surface was unstable. The average residual stress in the specimen with the unstable morphology decreased with thermal cycling and it eventually failed along TGO/YSZ interface. The specimen with stable morphology maintained a high TGO stress throughout the thermal cycling process and failed along TGO/bond coat interface. The rough surface was also found to give rise to the formation of transition alumina (θ-Al₂O₃) in the TGO which was correlated with a reduced TGO stress.     

Characterisation of residual stress and interface degradation in TBCs by photo-luminescence piezo-spectroscopy

Residual stress in the TGO in two different TBC systems, one with a Pt aluminide (β structure) bond coat and another with a Pt diffusion (γγ′ structure) bond coat, were studied using photo-luminescence piezo-spectroscopy (PLPS). The luminescence spectra and TGO morphology were investigated progressively with thermal cycling at 1135 °C. The two TBC systems were found to have distinctly different TGO residual stresses and different failure modes. Several stress relaxation mechanisms were found to be operative in the Pt aluminide system, while no stress relaxation was evident in the Pt diffusion system until close to the end of life (spallation). Luminescence spectral shape evolution has been quantitatively analysed and correlated with TBC system degradation processes. Both TBC systems showed clear spectral shape changes as a result of the formation of interface cracks when they reached approximately 75% lifetime. Characteristic spectral shape changes in response to different types of interface crack were demonstrated experimentally. The correlation between spectral shape evolution and interface degradation opens a new avenue for studies of degradation and lifetime assessment of TBCs.     

Influence of thermal cycle on surface evolution and oxide formation in a superalloy system with a NiCoCrAlY bond coat

A material system comprising a NiCoCrAlY bond coat deposited on a superalloy substrate has been subjected to thermal cycling. The assessment contrasts the influence of simple and stepwise (intermediate temperature hold) thermal cycles on the undulation of the surface and on the evolution of residual compressive stress in the thermally-grown oxide (TGO) layer. Stress-mapping of the TGO was performed using luminescence spectroscopy. Regions of interest were cross-sectioned using focused ion beam techniques to enable sub-surface examination by scanning electron microscopy. The investigation revealed that the surface develops undulations upon stepwise cycling, but not for either simple cycling or isothermal exposure (at comparable TGO thickness). This behavior has been related to the rapid creep displacements occurring in the bond coat during the intermediate temperature hold, because it is subject to large stress at this temperature. When the undulations attain sufficient amplitude, creep cracks form along the ridges, causing the stress to locally relax. For situations that do not cause undulations, areas of reduced residual compression appear in the TGO. Yttria-rich particles were invariably present in these regions.     

Influence of TGO Composition on the Thermal Shock Lifetime of Thermal Barrier Coatings with Cold-sprayed MCrAlY Bond Coat

NiCoCrAlTaY bond coat was deposited by cold spraying to assemble thermal barrier coatings (TBCs). The microstructure of the cold-sprayed bond coat was examined using scanning electron microscopy. TBCs consisting of cold-sprayed bond coat and plasma-sprayed YSZ were pretreated at different conditions to form different thermally grown oxides (TGOs) before thermal cycling test. The influence of the TGO composition on the thermal cyclic lifetime was quantitatively examined through the measurement of the coverage ratio of the mixed oxides on the bond coat surface. The results showed that the bond coat exhibited a dense oxidation-free microstructure, and TGOs in different morphologies and constituents were present after thermal cyclic test. The formation of TGOs was significantly influenced by pretreatment conditions. Two kinds of TGO were detected on the surface of bond coat after the spallation of YSZ coatings. One is the α-Al₂O₃-based TGO and the other is the mixed oxide. It was found that the thermal cyclic lifetime is inversely proportional to the coverage ratio of the mixed oxides formed at the bond coat/YSZ interface. The high coverage ratio of the mixed oxide on the interface leads to the early spalling of YSZ coating.     

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.     

热生长下热障涂层残余应力及失效分析

针对典型热障涂层结构以界面开裂和涂层剥落为主要失效模式,考虑界面凹凸微观形貌特征,借助材料转换的方法实现氧化生长,利用粘弹塑性有限元法,研究了氧化层热生长和蠕变等因素对热障涂层残余应力的影响,并从应力应变循环演化的角度对热障涂层系统中微裂纹的萌生位置进行了预测。结果表明,随着氧化层厚度的增大,垂直于界面方向的残余应力迅速增大;材料蠕变对热障涂层系统应力释放作用显著;从残余应力和应变演化的角度进行评价,结构中的微裂纹会率先出现在粘接层凸峰以及陶瓷层/氧化层/黏结层界面的中间位置,仿真分析结果与试验结果一致。     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.