Application of Plasma-Sprayed Complex Perovskites as Thermal Barrier Coatings

In an effort to improve the performance of heat engines at high temperatures, advanced surface coatings have been developed from complex perovskites. Materials of Ba(Mg_1/3Ta_2/3)O₃ and La(Al_1/4Mg_1/2Ta_1/4)O₃ composition were synthesized and applied as ceramic topcoats of thermal barrier coating (TBC) systems by atmospheric plasma spraying (APS) in single layer and in double-layer combination with conventional yttria stabilized zirconia (YSZ). Microstructural and phase analyses reveal that plasma spraying of complex perovskites is accompanied with the formation of vertical crack networks and secondary oxide phases which influence the failure mechanism of the TBCs. The low value of fracture toughness for the complex perovskites and the thermally grown oxide at the topcoat-bondcoat interface of the TBCs are, however, the major factors which lead to the coating failure on thermal cycling at about 1250 °C.     

Atmospheric Plasma Spraying of High Melting Temperature Complex Perovskites for TBC Application

High melting materials have always been very attractive candidates for materials development in thermal barrier coating (TBC) applications. Among these materials, complex perovskites with Ba(Mg_1/3Ta_2/3)O₃ and La(Al_1/4Mg_1/2T_1/4)O₃ compositions have been developed and deposited in TBC systems by atmospheric plasma spraying. Spray parameters were optimized and in-flight particle temperatures were recorded using Accuraspray-g3 and DPV 2000. Plasma sprayed coatings were found to undergo non-stoichiometric decomposition of components which could have contributed to early failure of the coatings. Particle temperature diagnostics suggest that gun power of ~15 kW or lower where majority of the particles have already solidified upon impact to the substrate could probably prevent the decomposition of phases. Additionally, it has been found that the morphology of the powder feedstock plays a critical role during atmospheric plasma spraying of complex perovskites.     

Fabrication and Characteristics of YSZ�CYSZ/Al2O3 Double-Layer TBC

A novel YSZ?CYSZ/Al₂O₃ (YSZ means 6 wt% yttria partially stabilized zirconia) double-layer thermal barrier coating was fabricated using composite sol?Cgel and pressure filtration microwave sintering (PFMS) technologies. In this double-layer coating, the top layer was YSZ ceramics with a thickness of about 150 ??m and the bottom layer was composed of micro-sized YSZ particles packed by nano-sized ??-Al₂O₃ films and had a thickness of about 10 ??m. Cyclic oxidation tests indicated that this coating possessed superior properties to resist oxidation of alloy and spallation of coating. These beneficial effects could be mainly attributed to that, the alloy substrate could be sealed completely by ??-Al₂O₃ phase and the thermal stress could be decreased by means of better thermal matching and nano/micron structure in YSZ/Al₂O₃ layer. Moreover, thermal insulation capability tests indicated that the thermal barrier effect was improved due to the application of YSZ/Al₂O₃ layer. YSZ/Al₂O₃ layer could be considered as a promising bond coat in TBCs.     

Development and Optimization of Tailored Composite TBC Design Architectures for Improved Erosion Durability

Rare-earth pyrochlores, RE₂Zr₂O₇, have been identified as potential thermal barrier coating (TBC) materials due to their attractive thermal properties and CMAS resistance. However, they possess a low fracture toughness which results in poor erosion durability/foreign object damage resistance. This research focuses on the development of tailored composite air plasma spray (APS) TBC design architectures utilizing a t′ Low-k secondary toughening phase (ZrO₂-2Y₂O₃-1Gd₂O₃-1Yb₂O₃; mol.%) to enhance the erosion durability of a hyper-stoichiometric pyrochlore, NZO (ZrO₂-25Nd₂O₃-5Y₂O₃-5Yb₂O₃; mol.%). In this study, composite coatings have been deposited with 30, 50, and 70% (wt.%) t′ Low-k toughening phase in a horizontally aligned lamellar morphology which enhances the toughening response of the coating. The coatings were characterized via SEM and XRD and were tested for erosion durability before and after isothermal heat treatment at 1100 °C. Analysis with mixing laws indicated improved erosion performance; however, a lack of long-term thermal stability was shown via isothermal heat treatments at 1316 °C. An impact stress analysis was performed using finite element analysis of a coating cross section, representing the first microstructurally realistic study of mechanical properties of TBCs with the results correlating well with observed behavior.     

Microstructure and Thermomechanical Properties of Atmospheric Plasma-Sprayed Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating

In this study, a Yb₂O₃ coating was fabricated by the atmospheric plasma spray technique. The phase composition, microstructure, and thermal stability of the coating were examined. The thermal conductivity and thermal expansion behavior were also investigated. Some of the mechanical properties (elastic modulus, hardness, fracture toughness, and flexural strength) were characterized. The results reveal that the Yb₂O₃ coating is predominantly composed of the cubic Yb₂O₃ phase, and it has a dense lamellar microstructure containing defects. No mass change and exothermic phenomena are observed in the thermogravimetry and differential thermal analysis curves. The high-temperature x-ray diffraction results indicate that no phase transformation occurs from room temperature to 1500 °C, revealing the good phase stability of the Yb₂O₃ coating. The coefficient of thermal expansion of the Yb₂O₃ coating is (7.50-8.67)?×?10^?6 K^?1 in the range of 200-1400 °C. The thermal conductivity is about 1.5 W m^?1 K^?1 at 1200 °C. The Yb₂O₃ coating has excellent mechanical properties and good damage tolerant. The unique combination of these properties implies that the Yb₂O₃ coating might be a promising candidate for T/EBCs applications.     

Thermal barrier coating bonded by (Al2O3–Y2O3)/(Y2O3-stabilized ZrO2) laminated composite coating prepared by two-step cyclic spray pyrolysis

Thermal barrier coating bonded by (Al₂O₃–Y₂O₃)/(Y₂O₃-stabilized ZrO₂) (YSZ) laminated coating has been developed on Ni-based superalloy by two-step cyclic pyrolysis. It is demonstrated, from cyclic oxidation tests at 1100 °C, that YSZ top coat and alloy substrate can be bonded together effectively by the (Al₂O₃–Y₂O₃)/YSZ laminated coating, showing good resistance to oxidation, cracking, spallation and buckling. These beneficial effects can be attributed to the sealing effect of the designed multi-sealed compact bond coat with α-Al₂O₃ layers, the decrease of thermal stresses, the increase of fracture toughness in such bond coat and no interdiffusion between the substrate and bond coat.     

Proposal of self-healing coatings for nuclear fusion applications

Avoiding cracks in ceramic coatings is one of the most important problems to be solved for the thermally sprayed tritium permeation barriers in fusion reactor. In this paper, a self-healing composite coating composed of TiC + mixture (TiC/Al₂O₃) + Al₂O₃ was developed to address this problem. The coating was deposited on certain martensitic steel by plasma spraying. The morphology and phase of the coating were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the porosity was analyzed by using Image Pro software. The thermal shock resistance test and residual stress measurement of the coating were also performed. In the experiment, NiAl + TiC + mixture (TiC/Al₂O₃) + Al₂O₃ and mixture (TiC/Al₂O₃) + Al₂O₃ films were also fabricated and studied respectively. The results showed that the TiC + mixture (TiC/Al₂O₃) + Al₂O₃ coating exhibited the best mechanical integrity and self-healing ability among the three samples with the porosity decreased by 90% after heat-treatment under normal atmosphere. The oxidation/expansion of TiC in the coating played an important role in the sealing of pores. This self-healing coating made by thermal spraying is proposed as a good candidate for tritium permeation barrier in fusion reactors.     

Thermochemical compatibility of ytterbia–(hafnia/silica) multilayers for environmental barrier coatings

Environmental barrier coating (EBC) systems consisting of multiple layers tailored to address individual protection needs may offer improved performance relative to conventional architectures. If the requirements of thermochemical and thermomechanical compatibility are met, the deposition of a segmented thermal barrier coating on a dense rare earth silicate EBC could provide additional thermal protection and resistance to attack by molten deposits. The thermochemical compatibility between silicates in the YbO_1.5–SiO₂ system and phases in the YbO_1.5–HfO₂ system was investigated by equilibrating powder compacts of selected ternary compositions; diffusion couples were used to simulate interactions at the layer interfaces in the proposed architectures. The deduced 1500 °C ternary isothermal section reveals that the ordered δ-Yb₄Hf₃O₁₂ and H₃–Yb₆HfO₁₁ phases are only compatible with ytterbium monosilicate (Yb₂SiO₅) EBC. Implementation of these hafnates in contact with ytterbium disilicate (Yb₂Si₂O₇) leads to interfacial reactions that facilitate layer debonding. The results provide criteria to guide the design of future thermal/environmental barrier coating architectures.     

Comparison of Single-Phase and Two-Phase Composite Thermal Barrier Coatings with Equal Total Rare-Earth Content

Rare-earth zirconates have been the focus of advanced thermal barrier coating research for nearly two decades; however, their lack of toughness prevents a wide-scale adoption due to lack of erosion and thermal cyclic durability. There are generally two methods of improving toughness: intrinsic modification of the coating chemistry and extrinsic modification of the coating structure. This study compares the efficacy of these two methods for a similar overall rare-earth content via the air plasma spray process. The extrinsically toughened coatings were comprised of a two-phase composite containing 30 wt.% Gd₂Zr₂O₇ (GZO) combined with 70 wt.% of a tougher t′ low-k material (ZrO₂-2Y₂O₃-1Gd₂O₃-1Yb₂O₃; mol.%), while a single-phase fluorite with the overall rare-earth content equivalent to the two-phase composite (13 mol.% rare-earth) was utilized to explore intrinsically toughened concept. The coatings were then characterized via x-ray diffraction, energy-dispersive spectroscopy, and scanning electron microscopy, and their performance was evaluated via erosion, thermal conductivity, thermal annealing (500 h), and thermal cycling. It was shown that the extrinsic method provided an improved erosion and thermal conductivity response over the single phase, but at the expense of high-temperature stability and cyclic life.     

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.     

Development and Investigation on New Composite and Ceramic Coatings as Possible Abradable Seals

To improve gas turbine performance, it is possible to decrease back flow gases in the high-temperature combustion region of the turbo machine by reducing the shroud/rotor gap. Thick and porous thermal barrier coating (TBC) systems and composite CoNiCrAlY/Al₂O₃ coatings made by air plasma spray and composite NiCrAlY/graphite coatings made by laser cladding were studied as possible high-temperature abradable seal on shroud. Oxidation and thermal fatigue resistance of the coatings were assessed by means of isothermal and cyclic oxidation tests. Tested CoNiCrAlY/Al₂O₃ and NiCrAlY/graphite coatings after 1000 h at 1100 °C do not show noticeable microstructural modification. The oxidation resistance of the new composite coatings satisfied original equipment manufacturer (OEM) specifications. Thick and porous TBC systems passed the thermal fatigue test according to the considered OEM procedures. According to the OEM specifications for abradable coatings, the hardness evaluation suggests that these kinds of coatings must be used with abrasive-tipped blades. Thick and porous TBC coating has shown good abradability using tipped blades.     

Evolution of thermal properties of EB-PVD 7YSZ thermal barrier coatings with thermal cycling

During high-temperature exposure, the microstructure of thermal barrier coatings evolves, leading to increased thermal conductivity. We describe the evolution in the thermal properties of a 7 wt.% Y₂O₃ stabilized ZrO₂ electron beam-physical vapor deposited (EB-PVD) thermal barrier coating with thermal cycling between room temperature and 1150 °C until failure. The thermal diffusivity and conductivity of the coating were evaluated non-destructively based on the analysis of its photothermal infrared emission. Although the coating density does not increase significantly with thermal cycling, the thermal diffusivity and conductivity of the coating increased substantially, particularly during the first 20 1 h cycles. The values then approach a limiting value. Complementary Raman spectroscopy suggests that the increase is accompanied by a reduction in the defect concentration in the coating and that there is also a correlation between the width of the Raman lines and the thermal conductivity.     

Thermo-Physical Properties and Thermal Shock Resistance of Segmented La2Ce2O7/YSZ Thermal Barrier Coatings

La₂Ce₂O₇ (LCO)/yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC) with segmentation crack structure was produced by atmospheric plasma spraying. Thermo-physical properties, such as thermal diffusivities and thermal conductivities, and thermal cycling performance of the segmented LCO/YSZ TBC were investigated. The thermal conductivity of the segmented coating was measured to be around 1.02 W/mK at 1200 °C, relatively lower than that of the non-segmented coating, respectively. The segmented LCO/YSZ TBC exhibited a thermal cycling lifetime of around 2100 cycles, improving the durability by nearly 50% as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Air Plasma-Sprayed Yttria and Yttria-Stabilized Zirconia Thermal Barrier Coatings Subjected to Calcium-Magnesium-Alumino-Silicate (CMAS)

Yttria (Y₂O₃) and zirconia (ZrO₂) stabilized by 8 and 20 wt.%Y₂O₃ thermal barrier coatings (TBCs) subjected to calcium-magnesium-alumino-silicate (CMAS) have been investigated. Free-standing Y₂O₃, 8 and 20 wt.%YSZ coatings covered with synthetic CMAS slurry were heated at 1300 °C in air for 24 h in order to assess the effect of Y₂O₃ on the corrosion resistance of the coatings subjected to CMAS. The microstructures and phase compositions of the coatings were characterized by SEM, EDS, XRD, RS, and TEM. TBCs with higher Y₂O₃ content exhibited better CMAS corrosion resistance. Phase transformation of ZrO₂ from tetragonal (t) to monoclinic (m) occurred during the interaction of 8YSZ TBCs and CMAS, due to the depletion of Y₂O₃ in the coating. Some amounts of original c-ZrO₂ still survived in 20YSZ TBCs along with a small amount of m-ZrO₂ that appeared after reaction with CMAS. Furthermore, Y₂O₃ coating was found to be particularly highly effective in resisting the penetration of molten CMAS glass at high temperature (1300 °C). This may be ascribed to the formation of sealing layers composed of Y-apatite phase [based on Ca₄Y₆ (SiO₄)₆O and Y_4.67(SiO₄)₃O] by the high-temperature chemical interactions of Y₂O₃ coating and CMAS glass.     

A2Zr2O7型稀土锆酸盐热障涂层研究进展

综述了国内外稀土锆酸盐热障涂层在制备技术,纳米涂层,涂层结构及涂层的热物理性能、力学性能及热腐蚀性能等方面的研究成果,讨论了稀土锆酸盐热障涂层在每个方面研究存在的不足。指出未来应该进一步改善稀土锆酸盐涂层的制备工艺及后处理工艺,提高涂层的结合强度,延长涂层的服役寿命,改善涂层耐腐蚀、抗烧结等性能;开发新的涂层制备工艺,重点研究各类纳米稀土锆酸盐涂层的性能;进一步提高涂层的隔热效果、服役温度及工作寿命。     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.     

Failure of physical vapor deposition/plasma-sprayed thermal barrier coatings during thermal cycling

ZrO₂-7 wt.% Y₂O₃ plasma-sprayed (PS) coatings were applied on high-temperature Ni-based alloys precoated by physical vapor deposition with a thin, dense, stabilized zirconia coating (PVD bond coat). The PS coatings were applied by atmospheric plasma spraying (APS) and inert gas plasma spraying (IPS) at 2 bar for different substrate temperatures. The thermal barrier coatings (TBCs) were tested by furnace isothermal cycling and flame thermal cycling at maximum temperatures between 1000 and 1150 °C. The temperature gradients within the duplex PVD/PS thermal barrier coatings during the thermal cycling process were modeled using an unsteady heat transfer program. This modeling enables calculation of the transient thermal strains and stresses, which contributes to a better understanding of the failure mechanisms of the TBC during thermal cycling. The adherence and failure modes of these coating systems were experimentally studied during the high-temperature testing. The TBC failure mechanism during thermal cycling is discussed in light of coating transient stresses and substrate oxidation.     

Phase and Microstructure Evolution and Toughening Mechanism of a Hierarchical Architectured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating under High Temperature

In recent years, numerous techniques have been developed to mimic nacre-like hierarchical architectures in order to improve the damage tolerance of materials. We present herein a simple strategy to fabricate such a hierarchical architectured Al₂O₃–Y₂O₃ composite coating via atmospheric plasma spraying. The evolution of the phase and microstructure of the Al₂O₃–Y₂O₃ composite coating were characterized under conditions of high-temperature exposure in air at 800-1350 °C. The hardness and porosity of several typical coatings were determined. In situ formation of dense hierarchical architectured Al₂O₃–YAG composite coating with improved hardness was achieved after heat treatment at 1350 °C. Compared with Al₂O₃ coating, elevated toughness was found for the hierarchical architectured Al₂O₃–YAG composite coating, which can be ascribed to the distribution of YAG phase that contributed to crack termination and deflection, and microbridging. After thermal aging treatment at 1350 °C, the hierarchical architectured Al₂O₃–YAG composite coating was quite stable after 100 h of thermal exposure. Furthermore, the Al₂O₃–Y₂O₃ composite coating exhibited superior sintering resistance compared with the Al₂O₃ coating.     

Enhancement of Functional Ceramic Coating Performance by Gas Tunnel Type Plasma Spraying

A high-precision plasma system has been pursued for advanced thermal processing. The gas tunnel type plasma jet device developed by the author exhibits high energy density and also high efficiency. Among its various applications is the plasma spraying of ceramics such as Al₂O₃ and ZrO₂. The performance of these ceramic coatings is superior to conventional ones. Properties such as the mechanical and chemical properties of the zirconia coatings were reported in previous studies. In this study, the enhancement of the performance of functional ceramic coatings by the gas tunnel type plasma spraying method was carried out using different powders. Results show that the alumina/zirconia composite system exhibited improvements of mechanical properties and corrosion resistance. The alumina/zirconia composite coating has the potential for use as a high functionally graded thermal barrier coating. Another application of the gas tunnel type plasma is for surface modification of metals. As an example, TiN films were formed in 5 s and, thick TiN coatings were easily obtained by gas tunnel type plasma reactive spraying.     

Neodymium-cerium oxide as new thermal barrier coating material

Neodymium-cerium oxide (Nd₂Ce₂O₇) was proposed as a new thermal barrier coating material in this work. Monolithic Nd₂Ce₂O₇ powder was prepared by the solid-state reaction at 1400 °C. The phase composition, thermal stability and thermophysical properties of Nd₂Ce₂O₇ were investigated. Nd₂Ce₂O₇ with fluorite structure was thermally stable in the temperature range of interest for TBC applications. The results indicated that the thermal expansion coefficient (TEC) of Nd₂Ce₂O₇ was higher than that of YSZ (6-8 wt.% Y₂O₃ + ZrO₂) and even more interesting was the TEC change as a function of temperature paralleling that of the superalloy bond coat. Moreover, the thermal conductivity of Nd₂Ce₂O₇ is 30% lower than that of YSZ, which was discussed based on the theory of heat conduction. Thermal barrier coating of Nd₂Ce₂O₇ was produced by atmospheric plasma spraying (APS) using the spray-dried powder. The thermal cycling was performed with a gas burner test facility to examine the thermal stability of the as-prepared coating.