Combined pre-annealing and pre-oxidation treatment for the processing of thermal barrier coatings on NiCoCrAlY bond coatings

A combined pre-annealing and pre-oxidation treatment was developed for the processing of partially yttria stabilized (PYSZ) thermal barrier coatings (TBC) on top of NiCoCrAlY bond coatings (BC). To develop this pre-treatment, the influence of the oxygen potential during pre-annealing and pre-oxidation on the life span and failure mechanisms of the entire high temperature coating system upon thermal cycling was investigated. The results of this study showed that the service life of the coating system depended strongly on the composition and microstructure of the thermally grown oxide (TGO) after pre-oxidation. The longer life spans were obtained if the TGO thickened very slowly during thermal cycling due to a large α-Al₂O₃ grain size. Such a slow-growing TGO corresponded with a pre-treatment for which θ-Al₂O₃ was formed during pre-oxidation and for which the yttrium was located within a high density of pegs along the TGO/BC interface after pre-oxidation. If the yttrium was present on top of the TGO after pre-oxidation, a thick mixed alumina-zirconia layer formed upon thermal cycling. This mixed oxide layer contributed significantly to the total oxide layer thickness, resulting in short life spans. The formation of NiAl₂O₄ spinel in between the TBC and the α-Al₂O₃ should be avoided, since this can lead to premature failure along the spinel/α-Al₂O₃ interface.     

Hybrid intermetallic Ru/Pt-modified bond coatings for thermal barrier systems

NiAl-based bond coatings for thermal barrier coating (TBC) systems containing varying amounts of Ru and Pt have been investigated. The addition of Ru to bulk NiAl has shown substantial increases in the creep strength of these aluminide materials, while Pt-modifications are known to improve the oxidation resistance of NiAl. The oxidation and interdiffusion behavior of these hybrid Ru/Pt bond coat systems are compared to conventional Pt-modified aluminide bond coats. The Ru/Pt-modified aluminide bond coats demonstrate cyclic oxidation lives comparable to those of Pt-modified aluminide bond coatings. These hybrid Ru/Pt-modified bond coats exhibit better creep properties than traditional Pt-modified coatings and suppress the rumpling mechanism typically responsible for the spallation of TBC from Ni(Pt)Al bond coatings. The evolution of coating microstructures at various stages of cyclic life was studied, and phase equilibria issues relevant to the fabrication and oxidation behavior of these multilayer systems are discussed.     

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.     

热障涂层双层黏结层的高温氧化行为

采用箱式电阻炉研究了具有梯度热膨胀系数的（孔隙层+氧化层）双层黏结层结构热障涂层的高温氧化行为。采用气罩等离子喷涂在Inconel 738合金基材上制备60μm厚的孔隙层,通过超音速火焰喷涂（HVOF）在孔隙层上制备120μm厚的氧化层。在1000℃下对黏结层进行不同时间的高温氧化试验。结果表明,黏结层由孔隙层和氧化层组成;喷涂态孔隙层具有典型的层状结构,未出现明显氧化;喷涂态氧化层较为致密,内部弥散分布着细小的α-Al₂O₃颗粒;具有梯度热膨胀系数黏结层表面的热生长氧化物（TGO）生长速率显著低于传统黏结层,且不再遵循抛物线生长规律,而是以对数规律生长;由于生长速率缓慢,尽管在制备过程中消耗了部分Al元素,但在500 h范围内TGO仍然以α-Al₂O₃为主。      

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.     

Thermal modeling of various thermal barrier coatings in a high heat flux rocket engine

One- and two-dimensional thermal models were developed to predict the thermal response of tubes with and without thermal barrier coatings (TBCs) tested for short durations in a H₂/O₂ rocket engine. Temperatures were predicted using median thermophysical property data for traditional air plasma sprayed ZrO₂–Y₂O₃ TBCs, as well as air plasma sprayed and low pressure plasma sprayed ZrO₂–Y₂O₃/NiCrAlY cermet coatings. Good agreement was observed between predicted and measured metal temperatures. It was also shown that the variation in the reported values of the thermal conductivity of plasma sprayed ZrO₂–Y₂O₃ coatings can result in temperature differences of up to 180°C at the ceramic/metal interface. In contrast, accounting for the presence of the bond coat or radiation from the ceramic layer had only a small effect on substrate temperatures (<20°C). The thermal models were also used to show that for the short duration test conditions of this study, a 100 μm thick ZrO₂–Y₂O₃ coating would provide a metal temperature benefit of approximately 300°C over an uncoated tube while a 200 μm thick coating would provide a benefit greater than 500°C. The difference in the thermal response between tubes and rods was also predicted and used to explain the previously-observed increased life of TBCs on rods over that on tubes.     

Influence of thermal shock on insulation effect of nano-multilayer thermal barrier coatings

Thermal barrier coatings (TBCs) with nano-multilayer structure were investigated by thermal shock test. The change of insulation effect during thermal shock test was studied by in-situ temperature monitor with a thermal couple set into the substrate. Microstructure and electrical properties of TBCs were characterized by SEM and Impedance Spectroscopy, respectively. Initial increase in insulation effect was observed and related to the formation and growth of perpendicular microcracks in top coat and transversal microcracks in TGO. With thermal shock, the insulation effect decreased due to the further growth of microcracks in top coat and TGO which induced the failure 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.     

The development of new bond coat compositions for thermal barrier coating systems operating under industrial gas turbine conditions

Environmental and economic issues are driving the development of increasingly efficient gas turbines. An important step in achieving this is to engineer components which can operate with longer lifetimes and at higher metal temperatures. Inlet temperatures for gas turbines now exceed the melting temperatures of nickel-based superalloys (i.e. 1300–1350 °C). The use of advanced air cooling systems coupled with thermal barrier coatings (TBCs) reduces the temperature of the underlying superalloy substrate. The bond coating, an important part of the TBC system, oxidizes to form a slow growing protective oxide layer, while also providing adhesion between the ceramic topcoat and the substrate. NiCoCrAlY overlay coatings are some of the most commonly used bond coatings for industrial gas turbines and extensive research has been undertaken over many years to find the best bond coating composition.This paper reports upon the production of new, model bond coatings with a wide range of different compositions. The focus is on their oxidation behavior at a temperature typically experienced by bond coatings on industrial turbine blades (950 °C). A physical vapor deposition technique, magnetron sputtering, has been used to deposit a range of Ni–Co–Cr–Al coatings onto 10 mm diameter sapphire substrates. This was achieved through co-sputtering two targets: a Ni–10%Cr, Ni–20%Cr, Ni–50%Cr, Ni–20%Co–40%Cr or Ni–40%Co–20%Cr target and a pure Al target. About a hundred samples with varying compositions were produced by this method. The coatings were then oxidized in air for 500 h at 950 °C.All samples were assessed by measuring the change in coating thickness, using pre- and post-exposure metrology only, and also the change in specimen weight. This approach has shown that magnetron sputtering successfully deposited 20 to 30 μm thick coatings and allowed the calculation of oxide growth rates. Energy dispersive X-ray (EDX) analysis was used to characterize the exact composition of each sample. Additionally, X-ray diffraction (XRD) has been used to identify the major oxides formed during exposure. The selective growth of protective Cr₂O₃ or Al₂O₃ or other less protective mixed oxides (depending on the initial coating composition) was observed. This influenced the oxide scale growth rate, indicating which coatings produced more protective oxides and allowing future optimization of the bond coating composition, for service within the turbine section of industrial gas turbines to be planned.     

Thermal fatigue behavior of thermal barrier coatings with the MCrAlY bond coats by cold spraying and low-pressure plasma spraying

The thermal fatigue behavior of thermal barrier coatings (TBCs) with the NiCoCrAlTaY bond coats deposited by cold spraying and low-pressure plasma spraying (LPPS) was examined through thermal cyclic test. The TBCs were subjected to the pre-oxidation before the test in an Ar atmosphere. The results show that a more uniform TGO in both thickness and composition forms on the cold-sprayed bond coat than that deposited by LPPS. The TBCs with the cold-sprayed bond coat exhibit a longer thermal cyclic lifetime than that with the LPPS bond coat. The differences in oxidation behavior and thermal cyclic behavior between two TBCs were discussed based on the evident difference in the surface morphology of two MCrAlY bond coats deposited by cold spraying and LPPS.     

Mechanical property variations within thermal barrier coatings

The mechanical properties of nanostructured yttria stabilized zirconia (YSZ) coatings were investigated using an instrumented indentation technique. Coatings were produced using the Triple-Torch Plasma Reactor (TTPR) where three plasma jet plumes converge to form a single jet where powder is injected axially. Partially fused clusters of sub-micron particles are characteristic for the coating microstructure. Flattened particles, termed as splats that are typical for conventional YSZ coatings were not observed.The microstructure exhibits a low isotropy that is related to variations in mechanical properties that are measured in directions parallel (normal to the coating plane) and perpendicular to the spray direction (in the plane of the coating). The microstructure of the nanostructured coating, which is different from a conventional coating, has a significant effect on the anisotropy of the mechanical properties. The in-plane elastic modulus of the nanostructured coating is lower than the normal modulus, as opposed to a conventional YSZ coating where the ratio is inversed. Multiple indentations arranged in arrays were used to map the variation in mechanical properties. Indentation results obtained using spherical and Vickers indenters are compared.     

Mullite-rich plasma electrolytic oxide coatings for thermal barrier applications

A study has been undertaken of the characteristics exhibited by mullite-rich plasma electrolytic oxide coatings grown on aluminium alloys by using silicate-rich electrolytes. It is found that they can be grown at a higher rate, and to a greater thickness, than alumina PEO coatings on aluminium. The thermal conductivity of these coatings has been measured using a steady-state method. It is shown to be of the order of 0.5 W m^− 1 K^− 1, which may be compared with ∼ 1.5 W m^− 1 K^− 1 for pure alumina PEO coatings and ∼ 10-15 W m^− 1 K^− 1 for dense polycrystalline mullite. Coupled with excellent substrate adhesion and good mechanical properties, this relatively low conductivity makes these coatings attractive for thermal barrier applications. Furthermore, they are shown to exhibit a relatively low global stiffness (∼ 40 GPa), which will reduce the magnitude of thermally-induced stresses and improve the resistance to spallation during temperature changes.     

Thermal properties of oxides with magnetoplumbite structure for advanced thermal barrier coatings

Oxides having magnetoplumbite structure are promising candidate materials for applications as high temperature thermal barrier coatings because of their high thermal stability, high thermal expansion, and low thermal conductivity. In this study, powders of LaMgAl₁₁O₁₉, GdMgAl₁₁O₁₉, SmMgAl₁₁O₁₉, and Gd_0.7Yb_0.3MgAl₁₁O₁₉ magnetoplumbite oxides were synthesized by citric acid sol-gel method and hot-pressed into disk specimens. The thermal expansion coefficients (CTE) of these oxide materials were measured from room temperature to 1500 °C. The average CTE value was found to be ∼ 9.6 × 10^− 6/C. Thermal conductivity of these magnetoplumbite-based oxide materials was also evaluated using steady-state laser heat flux test method. The effects of doping on thermal properties were also examined. Thermal conductivity of the doped Gd_0.7Yb_0.3MgAl₁₁O₁₉ composition was found to be lower than that of the undoped GdMgAl₁₁O₁₉. In contrast, thermal expansion coefficient was found to be independent of the oxide composition and appears to be controlled by the magnetoplumbite crystal structure. Preliminary results of thermal conductivity testing at 1600 °C for LaMgAl₁₁O₁₉ and LaMnAl₁₁O₁₉ magnetoplumbite oxide coatings plasma-sprayed on NiCrAlY/Rene N5 superalloy substrates are also presented. The plasma-sprayed coatings did not sinter even at temperatures as high as 1600 °C.     

An investigation into the correlation between nano-impact resistance and erosion performance of EB-PVD thermal barrier coatings on thermal ageing

Nanomechanical testing (nano-impact and nanoindentation mapping) has been carried out on the top surfaces of as-received and aged 8 wt.% yttria stabilised zirconia (YSZ) thermal barrier coatings (TBCs) produced by electron-beam physical vapour deposition (EB-PVD). The correlation between the nanomechanical test results and the previously reported erosion resistance of the TBCs has been investigated. The experimental results revealed that aged TBCs on zirconia for 24 h at 1500 °C or on alumina for 100 h at 1100 °C resulted in large increases in their hardness (H), modulus (E), H/E and H³/E² ratios but their erosion resistance was reduced. Nano-impact tests showed a dramatic decrease in impact resistance following the ageing of these TBCs, which is consistent with the erosion results. The strong correlation between the nano-impact and erosion resistances has confirmed the premise that rapid laboratory impact tests must produce deformation with similar contact footprint to that produced in the erosion tests.     

真空热处理双粘结层热障涂层抗氧化性能

传统单层结构粘结层热障涂层抗氧化性能不足寿命短,采用超音速火焰喷涂(high velocity oXy-fuel,HVOF)和大气等离子喷涂(atmosphere plasma spray,APS)制备双层结构粘结层,对粘结层进行真空热处理,研究热障涂层的抗氧化性能.结果 显示,经过1050℃×3 h真空热处理,粘结层...     

Microcrack formation in plasma sprayed thermal barrier coatings

Air plasma sprayed ZrO₂–8wt%Y₂O₃ thermal barrier coatings were deposited under tightly controlled conditions. The lengths and orientations of the horizontal cracks and vertical cracks in these coatings were characterized in detail, and process/structure maps of the crack distribution as a function of particle and substrate states were constructed. A fully coupled thermo-mechanical finite element model was used to study the buildup of stresses during splat solidification, and to understand the effect of deposition conditions on crack formation during plasma spray deposition. The model also showed that surface roughness plays a key role in determining the magnitude of maximum stresses, and that only roughness features on the scale of splat thickness are important in providing locations of maximum stress concentration.     

Mechanical properties of solution-precursor plasma-sprayed thermal barrier coatings

The microstructure of thermal barrier coatings (TBCs) of 7 wt.% Y₂O₃ stabilized ZrO₂ (7YSZ) deposited using the solution-precursor plasma spray (SPPS) method has: (i) controlled porosity, (ii) vertical cracks, and (iii) lack of large-scale “splat” boundaries. An unusual feature of such SPPS TBCs is that they are well-adherent in ultra-thick forms (~ 4 mm thickness), where most other types of ultra-thick ceramic coatings fail spontaneously. Here a quantitative explanation is provided as to why as-deposited ultra-thick SPPS TBCs are so well-adherent. The mode II toughness of thin (0.2 mm) SPPS TBCs has been measured using the “barb” shear test, which is found to be 66 J m^− 2. Residual stresses in SPPS TBCs of thickness 0.2, 1.5, and 4.0 mm have been estimated using a microstructure-based object-oriented finite element (OOF) method. These stresses are found to be low, as a result of the strain-tolerant microstructure of the SPPS TBCs. The corresponding strain energy release rates that drive mode II cracks in the three different thickness SPPS TBCs have been found to be less than the mode II toughness.     

Effects of Ce and Si additions to CoNiCrAlY bond coat materials on oxidation behavior and crack propagation of thermal barrier coatings

In thermal barrier coating (TBC) systems, thermally grown oxide (TGO) forms at the interface between the top coat and the bond coat (BC) during service. Delamination or spallation at the interface occurs by the TGO formation and growth. Therefore, modifications of the BC materials are one means to inhibit the TGO formation and to improve the crack resistance of TBCs. In this study, morphologies of TGO were controlled by using Ce and Si additions to conventional CoNiCrAlY BC material. The evaluation of the crack resistance was carried out using acoustic emission methods under pure bending conditions. As a result, when the BCs of TBCs with Ce added were aged at 1373 K over 10 h, the morphologies of the TGO were changed drastically. The BC materials of TBCs coated with Ce added indicated an improved crack resistance with high-temperature exposure. It is expected that the morphologies can improve the crack resistance of TBCs. This article was originally published inBuilding on 100 Years of Success: Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, 2006.     

Monitoring delamination of plasma-sprayed thermal barrier coatings by reflectance-enhanced luminescence

Plasma-sprayed thermal barrier coatings (TBCs) present a challenge for optical diagnostic methods to monitor TBC delamination, because the strong scattering exhibited by plasma-sprayed TBCs severely attenuates light transmitted through the TBC. This paper presents a new approach that indicates delamination in plasma-sprayed TBCs by utilizing a luminescent sublayer that produces significantly greater luminescence intensity from delaminated regions of the TBC. Freestanding coatings were produced with either a Eu-doped or Er-doped yttria-stabilized zirconia (YSZ) luminescent layer below a plasma-sprayed undoped YSZ layer. A NiCr backing layer was added to represent an attached substrate in some sections. For specimens with a Eu-doped YSZ luminescent sublayer, luminescence intensity maps showed excellent contrast between unbacked and NiCr-backed sections. Discernable contrast between unbacked and NiCr-backed sections was not observed for specimens with a Er-doped YSZ luminescent sublayer, because luminescence from Er impurities in the undoped YSZ layer overwhelmed luminescence originating from the Er-doped YSZ sublayer.     

A design perspective on thermal barrier coatings

This article addresses the challenges for maximizing the benefit of thermal barrier coatings for turbine engine applications. The perspective is from the viewpoint of a customer, a turbine airfoil designer who is continuously challenged to increase the turbine inlet temperature capability for new products while maintaining cooling flow levels or even reducing them. This is a fundamental requirement for achieving increased engine thrust levels. Developing advanced material systems for the turbine flowpath airfoils, such as high-temperature nickel-base superalloys or thermal barrier coatings to insulate the metal airfoils from the hot flowpath environment, is one approach to solve this challenge. The second approach is to increase the cooling performance of the turbine airfoil, which enables increased flowpath temperatures and reduced cooling flow levels. Thermal barrier coatings have been employed in jet engine applications for almost 30 years. The initial application was on augmentor liners to provide thermal protection during afterburner operation. However, the production use of thermal barrier coatings in the turbine section has only occurred in the past 15 years. The application was limited to stationary parts and only recently incorporated on the rotating turbine blades. This lack of endorsement of thermal barrier coatings resulted from the poor initial duratbility of these coatings in high heat flux environments. Significant improvements have been made to enhance spallation resistance and erosion resistance, which has resulted in increased reliability of these coatings in turbine applications.