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.     

Evaluation of the hot corrosion behavior of thermal barrier coatings

Calcium silicate and yttria-stabilized ZrO₂/(MCrAlY) thermal barrier coating systems on air-cooled specimens were exposed to sodium-plus vanadium- doped Mach 0.3 combustion gases. The thermal barrier coating endurance was determined to be a strong inverse function of the ceramic coating thickness. Coating system durability was increased through the use of NiCrAlY and CoCrAlY bond coatings with high chronium and aluminum contents. Chemical and electron microprobe analyses supported the predictions of condensate compositions and the determination of their roles in causing spalling of the ceramic coatings.     

Characterization of the degraded microstructures of a platinum aluminide coating

The degradation of a platinum modified aluminide (PtAl) coating and a CMSX-4 superalloy substrate were investigated for cyclic and quasi-isothermal heating to 1200 °C. To accelerate the oxidation of the specimens, the thermally grown oxide (TGO) was removed at 10 h intervals. For up to 80 h of exposure, comparisons of specimens with periodic oxide removal and those without oxide removal were made. Qualitatively, the major changes to the bond coat were associated with phase changes from β-(Ni,Pt)Al to γ′-(Ni₃Al) and precipitate coarsening. This evolution was quantified through backscatter scanning electron microcopy and image analysis. With instrumented indentation, the room temperature coating modulus was also measured at 10 h intervals. Additional results include observations of differences in waviness of the bond coat surface for cyclic, quasi-isothermal, and true-isothermal heating, and observations of rafting near the substrate/coating interface. The differences between cyclic and quasi-isothermal heating indicate that stresses associated with cooling and heating significantly alter microstructural evolution.     

Benefits of Zr addition to oxidation resistance of a single-phase (Ni,Pt)Al coating at 1373 K

A single-phase (Ni,Pt)Al coating with lean addition of Zr was prepared by co-electroplating of Pt-Zr composite plating and subsequent gaseous aluminization treatments. Isothermal and cyclic oxidation behavior of the Zr-doped (Ni,Pt)Al coating samples was assessed at 1373 K in static air in comparison with plain nickel aluminide (NiAl) and normal (Ni,Pt)Al coatings. Results indicated that Zr-doped (Ni,Pt)Al coating demonstrated a lower oxidation rate constant and reduced tendency of oxide scale spallation as well as surface rumpling, in which the enhanced oxidation performance was mainly attributed to the segregation of Zr at oxide scale grain boundaries and the improved Young’s modulus of the coating. Besides, the addition of Zr effectively delayed oxide phase transformation of Al₂O₃ from θ phase to α phase in the early oxidation stage and coating degradation of β-NiAl to γ'-Ni₃Al in the stable oxidation stage.     

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.     

Cyclic Corrosion Behavior of Pt/Ru-Modified Bond Coatings Exposed to NaCl Plus Water Vapor at 1050°C

In the present investigation, Pt/Ru-modified bond coating consisted of 2 μm Pt+2 μm Ru was deposited on a nickel-based superalloy by electroplating method and followed by conventional Al pack cementation. The cyclic corrosion behavior of Pt/Ru-modified bond coating exposed to NaCl plus water vapor has been investigated under atmospheric pressure at 1050°C. The result shows that the cyclic corrosion life of Pt/Ru-modified bond coating is longer than that of the conventional Pt-modified aluminide coating in the presence of NaCl plus water vapor. The addition of Ru makes the coating possess the increased strength and suppress the rumpling behavior. The absence of rumpling may be responsible for the improved corrosion resistance of Pt/Ru-modified aluminide coating.     

The influence of protective coatings on thermal fatigue resistance of Udimet 710

A study was made to determine the influence of surface protective coatings on the thermal fatigue resistance of the nickel-base alloy Udimet⁷ 710 (U-710). Single- edge wedge-type specimens were thermally cycled between 80 and 1915°F in fluidized beds with an immersion time of 4 min in each bed. Thermal fatigue resistance was measured by determining the number of thermal cycles required for crack initiation. Crack propagation rates were also determined wherever possible. All the coatings employed in this study improved the thermal fatigue lifetime of U- 710. In terms of crack initiation resistance, plasma-sprayed CoCrAlY-type coatings were ranked the best and pack aluminide coatings the least effective. An inverse correlation was observed between the hardness of the coatings and the thermal fatigue lifetime. The pack aluminide coatings were not found to be beneficial from the point of view of crack propagation: although they delay crack initiation by eliminating substrate grain boundary crack initiation sites, once a crack starts it grows rapidly. In addition to oxidation resistance, the coating microstructure plays a crucial role in crack initiation and propagation. Voids aligned between columnar grains in a coating were found to be more detrimental than those uniformly distributed in the microstructure.     

Evaluation of the mechanical properties and environmental resistance of René 125 and X-40 superalloys coated with controlled composition reaction-sintered CoNiCrAlY

The application of MCrAlY-type coatings to high temperature turbine components is primarily provided by electron beam physical vapor deposition (PVD) processing. The process of coating with controlled composition reaction-sintered (CCRS) CoNiCrAlY was developed as a cost-effective alternative using only conventional equipment and processing techniques.The CCRS method involves a two-stage process, the first step consisting of the application of the modifier (CoNiCrY powder) onto the cleaned prepared surface in an appropriate slurry bisque. This is followed by pack processing in a controlled activity aluminum pack where reaction sintering occurs to form the final CoNiCrAlY composition.The CCRS CoNiCrAlY coating was applied to both nickel- and cobalt-base superalloys, René 125 and X-40, and to a limited number of mechanically alloyed MA754 specimens. Mechanical properties evaluated at ambient and elevated temperatures include tensile strength, strain tolerance and cycle fatigue. In addition, burner rig tests were conducted at 870°C (1600°F) and 927°C (1700°F) for hot corrosion resistance and at 1149°C (2100°F) for oxidation resistance. For each of the tests, specimens coated with PVD CoCrAlY, PVD NiCrAlY and CODEP B were evaluated under similar conditions in order to compare the performance of these coatings currently widely used.Generally, the results showed that the CCRS CoNiCrAlY coated specimens were equivalent, and in some cases superior, to the PVD and CODEP B coatings. The combination of 15–17 wt.% Al in the CoNiCrAlY coating relative to the PVD coating with 8–13 wt.% Al and the reaction sintering method produced a highly protective coating characterized by multiphase microstructure, ductility and inexpensive processing.     

Effect of Nickel Pre-Plated on Microstructure and Oxidation Behavior of Aluminized AISI 316 Stainless Steel

Aluminizing of nickel pre-plated AISI 316 is prepared by a high-activity pack at 1050 °C. The effect of initial nickel layer with different thicknesses on microstructure and oxidation behavior of coating is investigated. After aluminization, the surface microstructure of stainless steel mainly consists of β-(Fe, Ni)Al as matrix with β-FeAl + α -(Fe, Cr) precipitates and an inter-diffusion layer with γ phase. Aluminized coating on specimens with 10 and 20 µm primary thicknesses of the nickel layer includes three layers. The outer zone is made up of β-NiAl thin layer and a β-(Fe, Ni)Al layer. As the nickel layer increases to 50 and 100 µm, aluminide layers consist of outer and inner zone with β-NiAl and Ni₃Al phase, respectively. Oxidation tests at 950 °C show that the oxidation resistance of aluminide coatings improves and oxidation kinetics follows a sub-parabolic rate law by increase in thickness of initial nickel layer.     

The significance of thermal contact resistance in two-layer thermal-barrier-coated turbine vanes

A study was conducted to determine whether the thermal contact resistance (TCR) between layers is important in heat transfer through two-layer plasma-sprayed thermal barrier coatings (TBCs) applied to turbine vanes. The results obtained with a TBC system of an NiCrAlY bond and an yttria-stabilized zirconia ceramic showed that the TCR between the layers was negligible. This result also verified other results obtained with a different coating system of an NiCr bond and a calcia-stabilized zirconia ceramic.     

Failure processes within ceramic coatings at high temperatures

Plasma sprayed coatings have a complex structure which is produced by the overlaying of many molten or semi-molten particles in the diameter range of 20 to 120 μm. There is a need to characterize the failure behaviour of coatings and this has been carried out by using acoustic emission (AE) methodology. Coatings of NiCrAIY bond coat with a zirconia-12 wt% yttria overlay were applied to discshaped specimens of U-700 alloy. A waveguide of 1 mm diameter platinum was TIG welded to the specimen and allowed it to be suspended in a tubular furnace. The specimen was thermally cycled to 1150° C and the AE monitored. One method of examining the AE is from the viewpoint of the accumulative count data. It is also convenient to establish the temperatures for “initial” AE and “significant” AE (i.e., the temperature at which 100 counts is exceeded) so that coatings may be compared. Several other analyses have been carried out with the aim of establishing parameters which are related to the crack size and crack population. These studies have been used to postulate types of cracking mechanisms which may occur in plasma sprayed coatings during thermal cycling. It is shown that microcracking gave rise to a large amount of AE. However, this coating still survived more thermal cycles than a coating which exhibited macrocracking events. Data of this nature will be presented and the results discussed.     

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.     

Effect of thermal cycling on ZrO2Y2O3 thermal barrier coatings

A study was made of the comparative lifetimes of plasma-sprayed ZrO₂Y₂O₃ thermal barrier coatings on NiCrAlY bond coats on René 41 in short (4 min) and long (57 min) thermal cycles to 1040°C in a 0.3 Mach flame. Short cycles greatly reduced the life of the ceramic coating in terms of time at temperature as compared with longer cycles. The appearance of the failed coating indicated compressive failure. Failure occurred at the bond coat-ceramic coat junction. At heating rates greater than 550 kW m^?2, the calculated coating detachment stress was in the range of literature values of coating adhesive/cohesive strength. Methods are discussed for decreasing the effect of high heating rate by avoiding compressive stress.     

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.     

The effect of bond coat on mechanical properties of plasma-sprayed Al2O3 and Al2O3-13 wt% TiO2 coatings on AISI 316L stainless steel

In this study, Al₂O₃ and Al₂O₃-13 wt% TiO₂ were plasma sprayed onto AISI 316L stainless-steel substrate with and without Ni-5 wt% Al as bond coat layer. The coated specimens were characterized by optical microscopy, metallography and X-ray diffraction (XRD). Bonding strength of coatings were evaluated in accordance with the ASTM C-633 method. It was observed that the dominant phase was Al₂O₃ for both coatings. It was also found that the hardness of coating with bond coat was higher than that of coating without bond coat. Metallographic studies revealed that coating with bond coating has three different regions, which are the ceramic layer (Al₂O₃ or Al₂O₃-13 wt% TiO₂), the bond coating, and matrix, which is not affected by coating. The coating performed by plasma-spray process without bond coating has two zones, the gray one indicating the ceramic layer and the white one characterizing the matrix. No delamination or spalling was observed in coatings. However, there are some pinholes in coating layer, but they are very rare. The bonding strength of coatings with bond coat was higher than that of coating without bond coat. The strength of adhesion and cohesion was determined by means of a planemeter. It was seen that percentage of cohesion strength was higher than that of adhesion strength.     

A new way to produce Al + Cr coating on Ti alloy by vacuum fusing method and its oxidation resistance

An Al + Cr coating successfully produced by the vacuum fusing method was proposed for improving the oxidation resistance of Ti–6Al–4V alloy specimens. Unlike powder pack cementation, this technique was much more effective and cheap without the need for long time diffusion, and the Al concentration and the thickness of vacuum fusing coating layer could be controlled by adjusting powder mixing ratio and adding the immersed times, respectively. Compared with the specimen with an Cr-modified aluminide coating, the oxidation resistance of the specimens with vacuum fused Al + Cr coating was about two times than that of the specimens with Cr-modified aluminide coating. During oxidation, Cr additions suppressed metastable θ-alumina formation. It is only one phase -alumina scale that developed on the vacuum fused Al + Cr coating surface, while a single metastable θ-alumina scale formed on the Cr-modified aluminide coating surface.     

Nickel aluminide coating produced on γ-TiAl alloy by high activity aluminising process

Abstract

Ni aluminide diffusion coatings on the surface of γ-TiAl alloy were produced by electroplating a Ni layer followed by a single step high activity aluminising carried out in Ar+H₂ atmosphere with a mixture of Al, NH₄Cl and Al₂O₃ powders at 1000°C for 5 h. The effect of initial thickness for Ni layer on microstructure of produced Ni aluminide coating was highlighted. The thickness of initial Ni layer was changed to 4–20 μm. In the case of the Ni layer with thickness of 4 μm, only a little amount of NiAl phase was formed in a TiAl₃ matrix. However, the microstructure of coating, in the case of the Ni layer with thickness of 8 μm, consisted of an outer layer of two phases (NiAl+TiAl₃), an intermediate layer of TiAl₃ and an interdiffusion layer. For thicker initial Ni layers (16 and 20 μm), beside the latter coating microstructure, a continuous surface layer of NiAl phase was observed. Isothermal oxidation tests on these aluminide coatings reveal that the oxidation resistance of the aluminide coatings increases with increase in initial thickness of Ni layer.     

Observations of the spallation modes in an overlay coating and the corresponding thermal barrier coating system

Abstract

The oxidation dynamics of an overlay coating and the corresponding thermal barrier coating system are presented. The particular systems examined are composed of a nickel-based superalloy with an air plasma-sprayed NiCrAlY bond coat and the thermal barrier coating system consists of air plasmasprayed yttria stabilized zirconia layer. Failure can occur in these systems by crack propagation within the ceramic outer layer at the interface with the bond coat. Defects, such as microcracks and pores, are common in plasma-sprayed coatings and within the thermally grown oxide scales. These can act as initiation sites for cracks. The subsequent growth of these cracks can lead to loss of the outer protective materials. Considerable information is available by microscopic examination of sections through test specimens that have been held at temperature for varying amounts of time. By careful sample preparation it is possible to monitor the development of the oxide scale formed during high temperature testing and the sites of failure. Identification of the initiation sites and growth of cracks is important in understanding the spallation process. In this study, scanning electron microscopy is used to provide evidence of the processes involved in the two systems. A comparison of the two coating systems reveals the effect the outer ceramic layer has on the oxide scale growth, and the spallation processes crucial to the understanding of the failure mechanisms of these coating systems.     

Thermal cycling behaviour of thermal barrier coating systems based on first- and fourthgeneration Ni-based superalloys

Abstract

This study deals with the cyclic oxidation behaviour of thermal barrier coating systems. The systems consist of an yttria-stabilised zircona ceramic top coat deposited by EB-PVD, a β-(Ni,Pt)Al bond coat and a Ni-based superalloy. Two different superalloys are studied: a first-generation one and a fourthgeneration one containing Re, Ru and Hf. The aim of this work is to characterise the microstructural evolution of those systems and to correlate it to their resistance to spallation. Thermal cycling is carried out at 1100°C in laboratory air, with the number of cycles ranging between 10 and 1000. Each cycle consists of a 1 h dwell followed by forced-air cooling for 15 min down to room temperature. Among the main results of this work, it is shown that the MCNG-based system is significantly more resistant to spallation than the AM1-based one. Up to 50 cycles, both systems exhibit similar oxidation rate and phase transformations but major differences are observed after long-term ageing. In particular, a Ru-rich β-phase is formed in the bond coat of the MCNG-based system while the AM1- based one undergoes strong rumpling of the TGO/bond coat interface due to the loss of the thermal barrier coating.     

Experience with platinum aluminide coatings in land-based gas turbines

Hot-corrosion crucible tests with salt mixtures which simulated actual blade deposits were carried out to evaluate the potential of platinum-modified aluminide coatings for application in advanced industrial gas turbines. In comparison with simple aluminide coatings, a significantly improved resistance against hot corrosion at intermediate temperatures was found. At the highest turbine-operating temperature, coating life exceeds that of conventional plasma-sprayed NiCrSi coatings. Actual engine test results are presented which confirm the beneficial role of platinum. However, the susceptibility of platinum aluminide coatings to crack formation and propagation may make them unsuitable for application to rotating blades.