Oxidation and Hot Corrosion of Gadient Thermal Barrier Coatings Prepared by EB—PVD

The performances of gradient thermal barrier coatings (GTBCs)produced by EB-PVD were evaluated by isothermal oxidation and cyclic hot corrosion(HTHC) tests.Compared with conventional two-layered TBCs, the GTBCs exhibite better resistance to not only oxidation but also hot-corrosion.Adense Al2O3 layer in the GTBCs effectively prohibites inward diffusion of Oand S and outward diffusion of Al and Cr during the tests.On the other hand ,an “inlaid“ interface ,resulting from oxidation of the Al along the columnar grains of the bond coat,enhances the adherence of Al2O3 layer.Failure of the GTBC finally occurred by cracking at the interface between the bond coat and Al2O3 layer, due to the combined effect of sulfidation of the bond coat and thermal cycling.     

A study on gradient thermal barrier coatings by EB-PVD in a cyclic high-temperature hot-corrosion environment

Gradient thermal barrier coatings (GTBCs) have been produced by electron beam physical vapor deposition (EB-PVD). Their performance was evaluated by isothermal oxidation and cyclic high-temperature hot-corrosion tests. It is found that the GTBCs exhibited better resistance to high-temperature oxidation and cyclic high-temperature hot-corrosion (HTHC) than traditional two-layered TBCs. A dense Al₂O₃ layer on the bond coat of GTBCs can effectively prohibit inward diffusion of oxidants such as O and S and outward diffusion of Al and Cr. On the other hand, an inlaid interface, the formation of which resulted from the oxidation of Al diffusion into the gaps between the columns of bond coat during the fabrication of the GTBCs, contributes to reinforce the adherence of the Al₂O₃ layer to the bond coat. During fluxing of the Al₂O₃ layer, S and O diffused into the bond coat. Cracks developed in the surface layer of bond coat by the combined effect of sulfidation of the bond coat and thermal cycling, and finally led to failure of the GTBC.     

Einfluss einer PVD‐Al‐Zwischenschicht auf die Eigenschaften eines thermisch gespritzten Wärmedämmschichtsystems nach Temperaturwechselbelastung

Thermal barrier coatings (TBC) generally consist of a metallic bond coat (BC) and a ceramic top coat (TC). Co–Ni–Cr–Al–Y metallic super alloys and Yttria stabilised zirconia (YSZ) have been widely used as bond coat and top coat for thermal barrier coatings systems, respectively. As a result of long‐term exposure of thermal barrier coatings systems to oxygen‐containing atmospheres at high temperatures, a diffusion of oxygen through the porous ceramic layer occurs and consequently an oxidation zone is formed in the interface between ceramic top coat and metallic bond coat. Alloying components of the BC layer create a so‐called thermally grown oxides layer (TGO). One included oxide type is α‐Al₂O₃. α‐Al₂O₃ lowers oxygen diffusion and thus slows down the oxidation process of the bond coat and consequently affects the service life of the coating system positively. The distribution of the alloying elements in the bond coat layer, however, generally causes the formation of mixed oxide phases. The different oxide phases have different growth rates, which cause local stresses, micro‐cracking and, finally, delamination and failure of the ceramic top coat layer. In the present study, a thin Al inter‐layer was deposited by DC‐Magnetron Sputtering on top of the Co–Ni–Cr–Al–Y metallic bond coat, followed by thermal spraying of yttria‐stabilised zirconia (YSZ) as a top coat layer. The deposited Al inter‐layer is meant to transform under operating conditions into a closed layer with high share of α‐Al₂O₃ that slows down the growth rate of the resulting thermally grown oxides layer. Surface morphology and microstructure characteristics as well as thermal cycling behaviour were investigated to study the effect of the intermediate Al layer on the oxidation of the bond coat compared to standard system. The system with Al inter‐layer shows a smaller thermally grown oxides layer thickness compared to standard system after thermal cycling under same conditions.     

Influence of Water Vapor on the Isothermal Oxidation Behavior of Thermal Barrier Coatings

The oxidation of specimens with thermal barrier coating (TBC) consisted of nickel-base superalloy, low-pressure plasma sprayed Ni-28Cr-6AI-0.4Y (wt pct) bond coating and electron beam physical vapor deposited 7.5 wt pct yttria stabilized zirconia (YSZ) top coating was studied at 1050℃ respectively in flows of 02, and mixture of O2 and 5%H2O under atmospheric pressure. The thermal barrier coating has relatively low oxidation rate at 1050℃ in pure O2. Oxidation rate of thermal barrier coating in the atmosphere of O% and 5%H2O is increased The oxidation kinetics obeys almost linear law after long exposure time in the presence of 5% water vapor. Oxide formed along the interface between bond coat and top coat after oxidation at 1050℃ in pure O2 consisted of Al2O3, whereas interfacial scales formed after oxidation at 1050℃ in a mixture of O2 and 5%H2O were mainly composed of Ni(AI,Cr)2O4,NiO and AI2O3. It is suggested that the effect of water vapor on the oxidation of the NiCrAlY coating may be attributed     

TGO对热障涂层失效的作用分析

热生长氧化物(TGO)的形成与长大是热障涂层失效的根本原因。先在IC10高温合金基体上超音速火焰喷涂(HVOF)NiCoCrAlTaY粘结层(BC层),再等离子喷涂二元稀土氧化物稳定氧化锆Sc2O3-Y2O3-ZrO2,喷涂样在1 100℃恒温氧化,利用扫描电镜(SEM)、能谱仪对断面形貌、成分进行分析,讨论了TGO的形成机理及其与热障涂层失效的关系。结果表明:随着恒温氧化时间增加,TGO层底部的Al含量下降,上部、中间弥散颗粒及底部的Ni含量均增加,上部、中间弥散颗粒中Cr含量均减少;喷涂样氧化140 h后,TGO层由靠近陶瓷层的富(Cr,Al)2O3层、弥散其间的富Ni颗粒和靠近BC层的Al2O3层组成;TGO的生长速度先由Al与O2化学反应速度决定,接着受BC层金属元素扩散速度影响,最后由化学反应速度和扩散速度共同控制;减少TGO中的有害氧化物含量以降低涂层内的应力,可有效提高涂层的使用寿命。     

Microstructural changes to metal bond coatings on gas turbine alloys with time at high temperature

Complex coating systems are required to protect nickel-based super alloys from high temperature oxidation and corrosion. Industrial gas turbine blades and heat shields are generally plasma sprayed with a metal bond coating containing nickel, chromium, cobalt, aluminium and yttrium, and then an external thermal barrier coating of yttria-stabilised zirconia is applied. In this study, samples of an IN939 alloy heat shield with both a metal bond coat and a ceramic thermal barrier coating have been heated in air at high temperature for up to 2000 hours to assess the long term stability of the metal bond coat. Polished sections of the heat treated samples were examined by SEM and EDX to determine microstructural changes. The Ni-Cr-Co-Al-Y coating was found to be a very effective barrier against oxidation; the only apparent oxidation being the growth of an alumina layer between the bond coat and ceramic thermal barrier coating. With time, the growth of the Ni₃Al phase in the metallic bond coat was observed, with extensive diffusion of other elements to and from the bond coat.     

Effect of the thickness of plasma-sprayed coating on bond strength and thermal fatigue characteristics

NiCrAlY bond coat and ZrO2–8 wt% Y2O3 top coat with various thicknesses were deposited on Hastelloy X by plasma spraying. Residual stress was calculated by the finite element method (FEM) to explain the variations in the bond strength and thermal fatigue characteristics with the thickness of the bond coat and top coat. The bond strength of thermal barrier coatings (TBCs) increased with decreasing maximum residual stress in the y-direction of the top coat. The thermal fatigue characteristics increased with decrease of the maximum principal residual stress of the top coat and the thickness of oxidation layer of the bond coat.     

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.     

Degradation of thermal barrier coatings due to thermal cycling up to 1150°C

The degradation of thermal barrier coatings (TBCs) due to thermal cycling up to 1150°C has been studied. During thermal cycling, the bond coat in the TBCs was oxidised to form an alumina and a mixed oxide layer between the top coat of yttria stabilised zirconia (YSZ) and the bond coat of MCrAlY alloy. The mixed oxide layer mainly consists of -Cr₂O₃ and (Ni,Co)(Cr,Al)₂O₄ spinel phases, which are formed above the -alumina layer. Interestingly, the alumina layer gradually disappeared during the oxidation while the content of chromium in the mixed oxide increased with increasing oxidation time. As the oxidation accelerated after the disappearance of the alumina layer, cracks initiated and propagated in the mixed oxide layer near the YSZ. Eventually, the crack propagation induced the spallation of some YSZ top coatings after the 2000 h oxidation.     

Effect of platinum on the oxide-to-metal adhesion in thermal barrier coating systems

An investigation was conducted to determine the role of Pt in a thermal barrier coating system deposited on a nickel-base superalloy. Three coating systems were included in the study using a layer of yttria-stabilized zirconia as a model top coat, and simple aluminide, Pt-aluminide, and Pt bond coats. Thermal exposure tests at 1,150 °C with a 24-h cycling period to room temperature were used to compare the coating performance. Additional exposure tests at 1,000, 1,050, and 1,100 °C were conducted to study the kinetics of interdiffusion. Microstructural features were characterized by scanning electron microscopy and transmission electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction. Wavelength dispersive spectroscopy was also used to qualitatively distinguish among various refractory transition metals. Particular emphasis was placed upon: (i) thermal stability of the bond coats, (ii) thickening rate of the thermally grown oxide, and (iii) failure mechanism of the coating. Experimental results indicated that Pt acts as a “cleanser” of the oxide-bond coat interface by decelerating the kinetics of interdiffusion between the bond coat and superalloy substrate. This was found to promote selective oxidation of Al resulting in a purer Al₂O₃ scale of a slower growth rate increasing its effectiveness as “glue” holding the ceramic top coat to the underlying metallic substrate. However, the exact effect of Pt was found to be a function of the state of its presence within the outermost coating layer. Among the bond coats included in the study, a surface layer of Pt-rich γ′-phase (L1₂ superlattice) was found to provide longer coating life in comparison with a mixture of PtAl₂ and β-phase.     

IBAD钼膜与Al_2O_3(0001)单晶界面的HREM研究

采用中等能量离子束辅助沉积（IBAD）技术在单晶Al2O3（0001）基片上沉积钼膜，通过HREM等分析手段，在原子尺度上，对于钼膜及其与Al2O3单晶基体界面的显微结构进行了研究。结果表明：钼膜的晶粒呈细小柱状或纤维状，平均晶粒尺寸约为8nm，钼膜的致密度较高，膜内存在非晶组织。在钼膜与Al2O3单晶基片之间存在厚约10～15nm的非晶过渡层，在界面处未发现原子的长程扩散。非晶过渡层与钼膜界面处存在台阶，增加了钼膜的形核点。     

The effect of bond coat oxidation on the microstructure and endurance of a thermal barrier coating system

Abstract

Isothermal oxidation tests have been carried out on a thermal barrier coating (TBC) system consisting of a nickel-based superalloy, CoNiCrAlY bond coat applied by HVOF and yttria-stabilised zirconia (YSZ) top coat applied by EB-PVD. Bond coat microstructure, coating cracking and failure were characterised using high resolution scanning electron microscopy complemented with compositional analyses using energy dispersive X-ray spectrometry. A protective alumina layer formed during the deposition of the YSZ top coat and this grew with sub-parabolic kinetics during subsequent isothermal oxidation at temperatures in the range 950 to 1150°C. After short exposures at 1050°C and final cooling, small sub-critical cracks were found to exist within the YSZ but adjacent to bond coat protuberances. Their formation is related to the development of local tensile strains associated with the growth of an alumina layer (TGO) on the non-planar bond coat surface. However, for the specimens examined, these cracks did not propagate, in contrast to other TBC systems, and final spallation was always found to have occurred at the bond coat/TGO interface. This shows that the strain energy within the TGO layer made a significant contribution to the delamination process.     

HP40Nb钢热浸镀Al-Si高温氧化行为及组织研究

为提高高温抗氧化性能,对HP40Nb钢进行了热浸镀Al-10%(质量分数)Si,并进行不同温度扩散处理,研究了不同扩散处理试样在1000℃条件下的高温氧化行为,通过SEM,EDS和XRD分析了经不同扩散处理后的渗层在高温氧化过程中的组织结构变化.结果表明:经800℃/4h扩散处理,渗层由内层(NiAl+ Cr3 Si)...     

Improving thermal barrier coatings by laser remelting

Thermal barrier coatings are extensively used to protect metallic components in applications where the operating conditions include aggressive environment at high temperatures. These coatings are usually processed by thermal spraying techniques and the resulting microstructure includes thin and large splats, associated with the deposition of individual droplets, with porosity between splats. This porosity reduces the oxidation and corrosion resistance favouring the entrance of aggressive species during service. To overcome this limitation, the top coat could be modified by laser glazing reducing surface roughness and sealing open porosity. ZrO2(Y2O3) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The top coat was laser remelted and a densified ceramic layer was induced in the top surface of the ceramic coating. This layer inhibited the ingress of aggressive species and delayed bond coat oxidation.     

Comparative performance of selected bond coats in advanced thermal barrier coating systems

An investigation was carried out to determine the comparative performance of selected bond coats representing the diffusion aluminides and overlays in thermal barrier coating systems. Emphasis was placed upon oxidation behavior, thermal stability, and failure mechanism. Isothermal oxidation tests were carried out attemperatures in the range of 1000 °C to 1150 °C. Scanning electron microscopy combined with energy dispersive x-ray spectroscopy, x-ray diffraction, and transmission electron microscopy were used to characterize the coating microstructure. Among the bond coats examined, overlays exhibited the best performance followed by Pt-aluminides and simple alunimides for a given alloy substrate. However, for all types of bond coats, failure of the coating system occurred by decohesion of the oxide scale at the oxide-bond coat interface. All bond coats examined were found to be degraded by oxidation and interdiffusion with the alloy substrate permitting the formation of non-protective oxide scale near the bond coat surface. Platinum as well as active elements such as Hf and Y were identified as key elements in improving the performance of thermal barrier coating systems.     

Aluminum Coatings for Steel

Aluminum coated steel possesses excellent oxidation and corrosion resistance in sulfur and marine: environments and can substitute for expensive alloy of steels. Hot dip aluminizing (HAD) and pack cementation calorizing (CAL) are dealt with in detail. IN HDA coats, some alloying action takes place, when the substrate is dipped in molten Al at 973 K for 1-2 minutes. The coat consists of an outer pure Al layer, followed by a hard intermetallic layer consisting of FeAl₃ and Fe₂Al₅, forming a serrated interface with the base. Isothermal holding of such samples at 773-933 K for 10 minutes leads to further diffusion and phase changes. This improves resistance to thermal shock and bending. In CAL coats, the process parameters (1173-1223 K/2-4 h and pack composition), were optimized, resulting in appreciable alloying. The surface layer consists of Fe3Al and FeAl, which is comparable to the inner alloy layer of HDA coats. The structures/ property correlation is carried out for both coatings and the results compared.     

Failure mechanism of a thermal barrier coating system on a nickel-base superalloy

An investigation was carried out to determine the failure mechanism of a thermal barrier coating system on an Ni-base superalloy. The coating system consisted of an outer layer of yttria-stabilized zirconia (top coat), and an inner layer of Pt-aluminide (bond coat). Specimens were exposed at 1010 and 1150 °C with a 24-h cycling period to room temperature. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction were used in microstructural characterization. Spallation of the oxide scale developed by the bond coat was found to be the mode of failure. Experimental results indicated that the breakdown of oxide was affected by internal oxidation of Hf diffusing from the alloy substrate into the bond coat surface developing localized high levels of stress concentration at the oxide–bond coat interface. It was concluded that the cause of failure was degradation of thermal stability of the bond coat accelerating its oxidation rate and permitting outward diffusional transport of elements from the substrate.     

Crack propagation studies and bond coat properties in thermal barrier coatings under bending

Ceramic based thermal barrier coatings (TBC) are currently considered as a candidate material for advanced stationary gas turbine components. Crack propagation studies under bending are described that were performed on plasma sprayed ZrO₂, bonded by MCrAlY layer to Ni base superalloy. The crack propagation behaviour of the coatings at room temperature in as received and oxidized conditions revealed a linear growth of the cracks on the coating till the yield point of the super alloy was reached. High threshold load at the interface between the ceramic layer and the bond coat was required to propagate the crack further into the bond coat. Once the threshold load was surpassed the crack propagated into the brittle bond coat without an appreciable increase in the load. At temperatures of 800°C the crack propagated only in the TBC (ceramic layer), as the ductile bond coat offered an attractive sink for the stress relaxation. Effects of bond coat oxidation on crack propagation in the interface region have been examined and are discussed.     

Modification of NiCoCrAlY with Pt: Part Ⅱ. Application in TBC with pure metastable tetragonal(t’) phase YSZ and thermal cycling behavior

A thermal barrier coating system comprising Pt-modified NiCoCrAlY bond coating and nanostructured 4mol.% yttria stabilized zirconia(4YSZ, hereafter) top coat was fabricated on a second generation Ni-base superalloy. Thermal cycling behavior of NiCoCrAlY-4 YSZ thermal barrier coatings(TBCs) with and without Pt modification was evaluated in ambient air at 1100?C up to 1000 cycles, aiming to investigate the effect of Pt on formation of thermally grown oxide(TGO) and oxidation resistance. Results indicated that a dual layered TGO, which consisted of top(Ni,Co)(Cr,Al)_2O_4 spinel and underlying α-Al_2O_3, was formed at the NiCoCrAlY/4 YSZ interface with thickness of 8.4μm, accompanying with visible cracks at the interface. In contrast, a single-layer and adherent α-Al_2O_3 scale with thickness of 5.6μm was formed at the interface of Pt-modified NiCoCrAlY and 4 YSZ top coating. The modification of Pt on NiCoCrAlY favored the exclusive formation of α-Al_2O_3 and the reduction of TGO growth rate, and thus could effectively improve overall oxidation performance and extend service life of TBCs. Oxidation and degradation mechanisms of the TBCs with/without Pt-modification were discussed.     

Ti/Al_2O_3界面的光电子能谱研究

用X射线光电子谱（XPS）和俄歇电子能谱（AES）研究了Ti／Al_2O_3界面形成的过程。研究表明，活性金属Ti在室温下能与衬底Al2O3（1102）形成约20nm强结合的界面区。从Al，O，Ti的光电子谱形状变化以及它们随着Ti覆盖度的增加而出现结合能位移表明，在界面处形成的反应层中，最初几个单层的Ti很容易被Al2O3表面的活性氧所氧化，从而使Ti／Al2O3界面逐步由具有更强相互作用的TiOx／Al2O3界面所代替，并形成由多相混合体［Ti-O相，（Ti，Al）2O3相以及金属Al相］所组成的界面区。就是说，Ti通过Al—O键的O2-离子转移其电子给Al3 并使它还原成金属Al，从而形成Ti－O键所致。本文用AES强度剖面分析观察到了这种被还原的Al。