Effect of morphology on thermal conductivity of EB-PVD PYSZ TBCs

Partially yttria stabilized zirconia (PYSZ) based thermal barrier coatings (TBC) manufactured by electron beam-physical vapour deposition (EB-PVD) protect turbine blades, working under severe service conditions in aero engines and stationary turbines. These coatings show a high strain tolerance relying on their unique morphology which is comprised of weakly bonded, preferred-oriented columns, voids between feather-like sub-columns and, finally, of intra-columnar closed pores.The results obtained in this work demonstrate that variation of the EB-PVD process parameters alters the resulting columnar morphology and porosity of the coatings. The physical properties and, most importantly, thermal conductivity, are greatly affected by these morphological alterations. This study investigates three morphologically different EB-PVD PYSZ TBC top coats in terms of the spatial and geometrical characteristics of their porosity and correlates those with the thermal conductivity values measured in as-coated state and after heat treatment at 1100 °C for 1 h and 100 h. Changes in the open and closed porosity caused by heat-treatment are characterized by small-angle neutron scattering (SANS), Brunauer-Emmett-Teller Method (BET) and scanning electron microscope (SEM). Correlation of shape and surface-area changes in all porosity types of the analysed coatings revealed that the thermal conductivity of these coatings is influenced primarily by size and shape distribution of the pores and secondarily by the pore surface-area available at the cross section perpendicular to the heat flux.     

Effect of heat treatment on the thermal conductivity of plasma-sprayed thermal barrier coatings

The effect of heat treatment on the thermal conductivity of plasma-sprayed Y₂O₃ stabilized ZrO₂ (YSZ) and Al₂O₃ coatings was investigated. A heat treatment of 1300 °C in flowing argon for 50 h was found to significantly increase the thermal conductivity of the coatings when compared to measurements in the assprayed condition. Transmission electron microscopy (TEM) examination of the microstructures of the coatings in the as-sprayed and heat-treated conditions revealed that sintering of microcracks at the splat interfaces was the main cause for the increase in thermal conductivity. In the YSZ coatings, complete closure of microcracks was frequently observed. In contrast, microcrack closure in the Al₂O₃ coatings was characterized by the isolated necking of particles across a microcrack rather than complete closure. A model for thermal conductivity in a solid containing oriented penny-shaped cracks was used to explain the observed increase in thermal conductivity after heat treatment.     

Failure mechanism of EB-PVD thermal barrier coatings on NiAl substrate

Yttria stabilized zirconia（YSZ） was deposited on the line cut β-NiAl substrate by electron-beam physical vapour deposition（EB-PVD）, and the cyclic oxidation behaviors of thermal barrier coatings on β-NiAl substrate were investigated in 1 h thermal cycles at 1 200 ℃ in air. The results show that the samples fail after 80-100 cycles. Sub-interface cavitations in the substrate develop due to depletion of Al in forming thermally grown oxides（TGOs）. The collapse and closing up of cavities result in the ragged YSZ/TGO/substrate interface. Since the specific crack trajectories are quite sensitive to local geometry, cracks along the YSZ/TGO/substrate interfaces ultimately lead to YSZ spallation.     

Effect of thermal treatment on the effective thermal conductivity of YPSZ coatings

Thermally sprayed coatings present effective properties strongly different from those of the primary bulk material. In particular, the actual thermal conductivity of Yttria Partially Stabilized Zirconia (YPSZ) coatings is typically twice lower than the thermal conductivity of dense YPSZ. The architecture of the porous network plays a major role on this decrease: thin inter-lamellar cracks act as thermal resistance and contribute to decrease the effective thermal conductivity more efficiently than globular pores.From this situation, an in-house code has been developed since a few years: this code implements a finite difference method to perform calculations directly on micrographs of coating cross-sections obtained by SEM. Each pixel of the intermediate binary picture is interpreted as a cell of integration of the heat conduction equation. A thermal gradient is applied between the top and bottom edges and a system of linear equations is formed and solved, providing the thermal flux flowing through the structure and the corresponding effective thermal conductivity.In the present study, the case of YPSZ coatings before and after thermal treatment was considered. The numerical results are in rather good agreement with experimental data: the thermal treatment tends to close a part of the thinnest pores, thus providing a decrease of the pore level and an increase of the effective thermal conductivity of the produced coatings.     

High temperature properties of thermal barrier coatings obtained by detonation spraying

NiCrAlY/YPSZ and NiCrAlY/NiAl/YPSZ thermal barrier coatings (TBCs) were successfully deposited by detonation spraying. The results indicated that the detonation sprayed TBCs included a uniform ceramic coat containing a few microcracks and a bond coat with a rough surface. The lamellar structure and the presence of cracks and impurities could reduce the thermal conductivity of the ceramic coat. Oxidation kinetics at 1000–1150 °C of detonation sprayed TBCs have been measured and discussed. The role of a Ni–Al intermediate layer in improving the oxidation resistance of duplex TBCs has also been studied.     

Miniaturized bend tests on partially stabilized EB-PVD ZrO2 thermal barrier coatings

The elastic properties of thermal barrier coatings (TBCs) are important for modelling the lifetime of these coatings. A new test setup has been developed to measure the system modulus of electron-beam enhanced physical vapour deposited (EB-PVD) TBC coatings by miniaturized bend tests.Due to the brittleness, low stiffness and small thickness of the top coat and its complex microstructure, it is difficult to measure its Young's modulus by standard mechanical testing. For this reason, a special sample material has been prepared which consists of a 1 mm thick layer of EB-PVD TBC. This material was isothermally heat treated for different times at 950 °C, 1100 °C and 1200 °C and then tested in a specially developed miniaturized bend test. The bend test setup permits mechanical tests with a high resolution in stress and strain, where the strain is measured by digital image correlation. So the stiffness of the free-standing TBC samples could be measured with a high accuracy and the sintering behaviour of the EB-PVD TBC and the consequent rise of Young's modulus could be determined. The results show a significant increase of the system modulus with heat treatment time and temperature caused by sintering of the coating. An activation energy of 220 kJ/mol for the process has been determined.In addition, the material was tested by nanoindentation in order to measure Young's modulus on a local scale, and the porosity of the samples was determined by quantitative image analysis.     

The effect of pre-oxidation atmosphere on the durability of EB-PVD thermal barrier coatings with CoNiCrAlY bond coats

The effects of pre-oxidation heat treatment on oxidation behavior and thermal cycle life of electron-beam physical deposited (EB-PVD) thermal barrier coatings (TBCs) with CoNiCrAlY bond coats were investigated as a function of the pO₂ of the pre-oxidation atmosphere. The pO₂ of the pre-oxidation atmosphere was controlled by using a solid-state electrochemical oxygen pump system. The purity and microstructure of the continuous Al₂O₃ layer formed on the bond coat during pre-oxidation at 1050 °C were highly influenced by the pO₂ of the atmosphere. High purity α-Al₂O₃ with large grain size was formed on the bond coats under a pO₂ of 10^− 12-10^− 9 Pa, which resulted in a lower growth rate of TGO and longer lifetime.     

Thermal conductivity of nanoporous ZrO2-4 mol% Y2O3 multilayer coatings fabricated by EB-PVD

The effect of multilayer configurations on the thermal conductivity of 4 mol% Y₂O₃⁻ stabilized ZrO₂ coatings fabricated by EB-PVD has been investigated. The deposited coating layers consist of columnar grains containing nano-sized pores. Multilayer specimens are found to contain many pores at the interfaces between layers. The density and thermal conductivity of the multilayer coatings decreases with increasing number of coating layers for one to six layers. The thermal conductivities of coatings deposited onto rotating substrates are lower than those of coatings deposited on stationary substrates. The decreased thermal conductivity of multilayer coatings is ascribed to the increased total porosity resulting from an increase in the number of interface pores concomitant with the formation of non-uniform interfaces between layers, which causes increased phonon scattering.     

Effect of heat treatment at 900 °C on microstructural and mechanical properties of thermal barrier coatings

The effect of heat treatment at 900 °C in air on the microstructural and mechanical properties of electron beam physical vapour deposited thermal barrier coatings (TBCs) was investigated in this work. To clarify this effect, the phase and the microstructure of the zirconia ceramic top coat (TC) before and after the treatment were first characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) respectively. The changes in Young's modulus and hardness of the TC before and after the treatment were then measured by indentation tests at room temperature. The delamination behavior, especially the evolution of the interfacial load capacity between the ceramic TC and the thermally grown oxide (TGO), was finally examined by the finite element analysis with surface-based cohesive behavior. Correlations between the changes in microstructure and mechanical properties were also discussed. Results showed that after the treatment neither the phase transformation from the tetragonal zirconia to the monoclinic nor the transformation to the cubic was detected, whereas the TC sintered. The combined effect of the sintering related densification and the cracks formed during the treatment led to an initial increase and a subsequent decrease in Young's modulus and hardness of the TC with increasing treatment time. The interfacial load capacity increased with increasing Young's modulus of the TC and increasing thickness of the TGO.     

Effects of annealing on the microstructure and the mechanical properties of EB-PVD thermal barrier coatings

The effects of thermal annealing at 1000 °C in air on the microstructure and the mechanical properties (Young's modulus and hardness) of thermal barrier coatings consisting of a 4 mol% Y₂O₃ partially stabilized ZrO₂ top coat and a NiCoCrAlY bond coat, deposited by electron beam physical vapour deposition on nickel-based superalloy IN 625, have been investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), image analysis and nanoindentation. During annealing, the ceramic top coat undergoes sintering and recrystallization. These processes lead to stress relaxation, an increase of the intra-columnar porosity and the number of large pores as measured by image analysis of SEM micrographs. An increase of the grain size of the γ-phase in the bond coat, accompanied by changes in the morphology of γ-grains with annealing time, is also observed. Correlations between these microstructural changes in the top coat and the bond coat and their mechanical properties are established and discussed.     

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...     

DD90单晶高温合金热障涂层抗氧化及热循环性能

在第3代单晶高温合金DD90上制备热障涂层,采用超音速火焰喷涂(HVOF)制备NiCrAlY+NiCoCrAlTaY双层结构的粘结层,大气等离子喷涂(APS)制备YSZ和MSZ/YSZ结构的陶瓷层。在1150℃抗氧化试验中,YSZ涂层增重量明显高于MSZ涂层。在1200℃热循环250次后,2种涂层没有发生明显相变,MSZ涂层抗烧结性更优异。2种涂层TGO主要由Al₂O₃及少量尖晶石结构的混合氧化物组成。双层粘结层减少了Al元素向基材的扩散,而Cr元素由于浓度梯度扩散导致拓扑密堆(tcp)相的析出及二次反应区(SRZ)深度的增加。     

Thermal conductivity and elastic modulus evolution of thermal barrier coatings under high heat flux conditions

Laser high heat flux test approaches have been established to obtain critical properties of ceramic thermal barrier coatings (TBCs) under near-realistic temperature and thermal gradients that may be encountered in advanced engine systems. Thermal conductivity change kinetics of a thin ceramic coating were continuously monitored in real time at various test temperatures. A significant thermal conductivity increase was observed during the laser-simulated engine heat flux tests. For a 0.25 mm thick ZrO₂-8% Y₂O₃ coating system, the overall thermal conductivity increased from the initial value of 1.0 W/m K to 1.15, 1.19, and 1.5 W/m K after 30 h of testing at surface temperatures of 990, 1100, and 1320 °C, respectively, Hardness and elastic modulus gradients across a 1.5 mm thick TBC system were also determined as a function of laser testing time using the laser sintering/creep and microindentation techniques. The coating Knoop hardness values increased from the initial hardness value of 4 GPa to 5 GPa near the ceramic/bond coat interface and to 7.5 GPa at the ceramic coating surface after 120 h of testing. The ceramic surface modulus increased from an initial value of about 70 GPa to a final value of 125 GPa. The increase in thermal conductivity and the evolution of significant hardness and modulus gradients in the TBC systems are attributed to sintering-induced microporosity gradients under the laser-imposed high thermal gradient conditions. The test techniques provide a viable means for obtaining coating data for use in design, development, stress modeling, and life prediction for various TBC applications.     

Application of USAXS analysis and non-interacting approximation to determine the influence of process parameters and ageing on the thermal conductivity of electron-beam physical vapor deposited thermal barrier coatings

Electron-beam physical vapor deposited (EB-PVD) thermal barrier coatings (TBCs) display a lower thermal conductivity compared with the deposited bulk material. This effect is achieved due to the presence of pores within these films. The spatial and geometrical characteristics of the porosity influence directly the magnitude of the achieved reduction of the thermal conductivity. In this work, three EB-PVD coating containing different microstructures were manufactured by varying the manufacturing process parameters during the deposition process. Their corresponding thermal conductivities were measured via the laser flash analysis method (LFA) in both the as-coated state and after ageing (1100 °C/100 h). Analysis of the pore formation during processing was carried out by ultrasmall-angle X-ray scattering (USAXS). This technique is supported with a computer based modeling developed by researchers at Advanced Photon Source (APS) in ANL, USA, and in National Institute of Standards and Technology (NIST), USA. The model enables the characterization of the size, shape, volume and orientation of each of the pore populations in EB-PVD TBCs. The effect of these spatial and geometrical characteristics of the porosity on the thermal conductivity of the EB-PVD coatings were studied via a non-interacting approximation based on Maxwell's model. Results of LFA measurements and the applied approximation indicate an interrelation between the microstructure and the thermal properties of the analyzed EB-PVD coatings. Microstructures containing a higher volume fraction of fine anisotropic intra-columnar pores, and larger voids between feather-arms oriented at lower angles toward the substrate plane correspond to lower thermal conductivity values. Inter-columnar gaps do no significantly contribute to lowering the thermal conductivity due to their orientation parallel to the heat flux and their lower volume fraction compared with the volume occupied by the primary columns. On heat treatment, the deepest section of the gaps between feather-arms break-up into arrays of nano-sized low aspect ratio voids. The anisotropic, elongated intra-columnar pores evolve toward low aspect ratio shapes that are less effective in reducing the thermal conductivity.     

Influence of heat treatment on nanocrystalline zirconia powder and plasma-sprayed thermal barrier coatings

Nanostructured zirconia top coat was deposited by air plasma spray and NiCoCrAlTaY bond coat was deposited on Ni substrate by low pressure plasma spray.Nanostructured and conventional thermal barrier coatings were heat-treated at temperature varying from 1050 to 1 250oC for 2-20 h.The results show that obvious grain growth was found in both nanostructured and conventional thermal barrier coatings(TBCs)after high temperature heat treatment.Monoclinic/tetragonal phases were transformed into cubic phase in the agglomerated nano-powder after calcination.The cubic phase content increased with increasing calcination temperature.Calcination of the powder made the yttria distributed on the surface of the nanocrystalline particles dissolve in zirconia when grains grew.Different from the phase constituent of the as-sprayed conventional TBC which consisted of diffusionlesstransformed tetragonal,the as-sprayed nanostructured TBC consisted of cubic phase.     

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.     

Effects of deposition conditions on composition and thermal cycling life of lanthanum zirconate coatings

Lanthanum zirconate (La₂Zr₂O₇, LZ) coatings were prepared under four different deposition conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphology, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of pyrochlore, and the existence of excess La₂O₃ is also observed. The deviation could be reduced by properly controlling the electron beam current or by changing the ingot composition. Meanwhile, when the electron beam current was 500 - 600 mA, the thermal cycling life of the coating is superior to other coatings.     

Oxidation and thermal fatigue of EB-PVD thermal barrier coatings on tube superalloy substrate

Two-layer structure thermal barrier coatings （TBCs） （NiCoCrAIY （bond coat）＋（6%-8%, mass fraction） Y2O3-stabilized ZrO2（YSZ top coat）） were deposited by electron beam physical vapor deposition （EB-PVD） on tube superalloy substrates. The samples were investigated by isothermal oxidation and thermal shock tests. It is found that the mass gains of the substrate with and without TBCs are 0.165 and 7.34 mg/cm^2, respectively. So the TBCs system is a suitable protection for the substrate. In thermal shock tests the vertical cracks initiate at the top coat and grow into the bond coat, causing the oxidation of the bond coat along the cracks. Failure of the TBCs system occurs by the spallation of the YSZ from the bond coat, and some micro-cracks are found at the location where the fragment of the YSZ top coat spalled from.     

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.