Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Investigation on bi-layer coating with La2(Ti0.2Zr0.2Sn0.2Ce0.2Hf0.2)2O7/YSZ prepared by laser cladding

Thermal barrier coatings are an effective technology for improving the high-temperature performance of hot section components in gas turbine engine. Due to their excellent properties, high-entropy oxides are considered to be promising materials for thermal barrier coatings. Laser cladding is a coating preparation technology and the top coat prepared by laser cladding technology has an important application value for thermal barrier coatings. In this work, to improve the thermal cycling behavior of the La₂(Ti_0.2Zr_0.2Sn_0.2Ce_0.2Hf_0.2)₂O₇ high-entropy oxide coating, a bi-layer coating with the La₂(Ti_0.2Zr_0.2Sn_0.2Ce_0.2Hf_0.2)₂O₇ high-entropy oxide layer and the YSZ layer was designed and fabricated by laser cladding on the NiCoCrAlY alloy surface. The microstructure, phase and mechanical properties of the coating were analyzed by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and micro-hardness and nanoindentation tests, respectively. The results show that a bi-layer La₂(Ti_0.2Zr_0.2Sn_0.2Ce_0.2Hf_0.2)₂O₇/YSZ coating was successfully prepared by the laser cladding method, and shows good bonding at the interface between the layers. The high-entropy oxide layer maintains a relatively stable defective fluorite structure and its microstructure exists in the stable cellular and dendrite crystalline state after laser cladding. The high-entropy oxide layer prepared by laser cladding showed an average elastic modulus of 167 GPa and an average hardness of 1022.8HV in nanoindentation tests. Thermal cycling of the coating was carried out at 1050 °C. Failure of the bi-layer coating occurred after 60 thermal cycles at 1050 °C. Thermal stresses between different layers are calculated during thermal cycling. Due to its excellent mechanical properties, the bi-layer coating with the La₂(Ti_0.2Zr_0.2Sn_0.2Ce_0.2Hf_0.2)₂O₇ high-entropy oxide and YSZ layers is expected to become an effective high-entropy oxide thermal barrier coating.     

A simple non-destructive method to indicate the spallation and damage degree of the double-ceramic-layer thermal barrier coating of La2(Zr0.7Ce0.3)2O7 and 8YSZ:Eu

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and Eu³⁺-doped zirconia, which was partially stabilised by 8 wt% yttria (8YSZ:Eu), were prepared by atmospheric plasma spraying. A thermal cycling test was carried out. The 8YSZ:Eu sublayer exposed during thermal cycling could produce visible luminescence under ultraviolet (UV) illumination, providing an indication of the spallation and damage degree of the coating. The result shows that the application of a Eu³⁺-doped luminescence sublayer can be a very simple and useful non-destructive technique to indicate the spallation and damage degree of DCL coatings.     

Effect of multi-component rare-earth doping on maintaining structure stability of RE2Zr2O7 (RE = La,Sm, Gd,Y, Yb) coatings under thermal cycling

Inspired by the high entropy effects of high-entropy components, a novel high-entropy rare-earth zirconate (La_1/5Gd_1/5Y_1/5Sm_1/5Yb_1/5)₂Zr₂O₇ (HEC-LZ) was designed and successfully synthesized in this work. In addition, two binary rare-earth doped zirconates (RE-LZ), (La_1/3Sm_1/3Yb_1/3)₂Zr₂O₇ (LSYZ) and (La_1/3Gd_1/3Y_1/3)₂Zr₂O₇ (LGYZ), were proposed using the same rare-earth elements for comparison. The thermal barrier coatings with LZ-based ceramic top layer were prepared by spray granulation, solid-phase synthesis and atmospheric plasma spraying techniques. The as-synthesized LZ-based ceramics are all dominated by the pyrochlore phase. Under 1000 °C, the thermal cycling performances of the three coatings were studied. The microstructure evolution and crack expansion during the failure process were investigated in detail. The strengthening mechanism and the cause of coating spallation are proposed in combination with mechanical properties and thermal matching analysis. The results showed that compared with the undoped LZ coating, the thermal shock life of LGYZ coating, LSYZ coating and HEC-LZ coating is improved by nearly 46%, 27% and 57%, respectively. Due to the characteristics of high randomness, HEC-LZ ceramic has a large lattice distortion than RE-LZ ceramics, resulting in a higher coefficient of thermal expansion and fracture toughness, which contributes to maintaining the structure stability of coatings under thermal stress.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

A novel high-entropy (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 ceramic aerogel with ultralow thermal conductivity

Here, we report a novel high-entropy rare earth zirconate (HE-REZ) (Sm_0.2Eu_0.2Tb_0.2Dy_0.2Lu_0.2)₂Zr₂O₇ ceramic aerogel prepared through a sol-gel template method and high-temperature calcination followed by 3-D-structure reconstruction. The structural evolution and crystallisation behaviour of the prepared aerogel were characterised through scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results indicated that the as-prepared HE-REZ ceramic aerogels had a typical nanoporous structure. The HE-REZ ceramic aerogels thermally treated at 900 °C presented an ultralow room temperature thermal conductivity of 0.031 W/(m·K), high specific surface areas of 443.26 m²/g and a relatively high strength of 12.95 MPa. The effects of different calcination temperatures on the microstructure of the samples were also investigated. Therefore, the excellent insulation performance of these unique HE-REZ ceramic aerogels indicate that they can be used as high-temperature insulators for hypersonic vehicles in the future.     

Thermal cycling behavior of nanostructured 8YSZ，SZ/8YSZ and 8CSZ/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The nanostructured single-ceramic-layer (SCL) 8YSZ thermal barrier coatings (TBCs), double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZ)/8YSZ and SZ doped with 8 wt% CeO₂ nanoscale particles (8CSZ)/8YSZ TBCs were fabricated by atmospheric plasma spraying (APS) on nickel-based superalloy substrates with NiCoCrAlY as the bond coating. The thermal cycling behavior of the three as-sprayed TBCs was investigated systematically at 1000 ℃ and 1200 ℃. The results reveal that the thermal cycling lifetime of the nanostructured DCL 8CSZ/8YSZ TBCs is the longest among them, which is largely due to the fact that the intermediate layer buffer effect of the DCL structure, more porosity and improvement of thermal expansion coefficient from doping CeO₂ nanoparticles can relieve thermal stress to a great extent at elevated temperature. The failure mechanism of the nanostructured TBCs has been discussed in detail.     

Investigating the thermal,mechanical and thermal cyclic properties of plasma-sprayed Al2O3-7YSZ/7YSZ double ceramic layer TBCs

Double ceramic layer (DCL) TBCs consisting of a top 20 wt.% Al₂O₃-7YSZ layer and a bottom 7YSZ layer were desirably designed to achieve preferable performance while the thermal, mechanical and thermal cyclic properties were comprehensively investigated. Compared to the conventional 7YSZ TBCs, the thermal insulation properties of the DCL coating were significantly improved due to the increased oxygen vacancy concentration induced by Al₂O₃ addition while the thickness of the thermally grown oxides was diminished by the decreased oxygen diffusion rate. Furthermore, the improved fracture toughness of the DCL coating also prolonged the thermal cyclic life.     

Preparation and characterization of nanostructured La2Zr2O7 feedstock used for plasma spraying

The nanostructured La₂Zr₂O₇ (LZ) feedstock with high density, suitable size distribution and nearly spherical morphology which can be used for plasma spraying was prepared by spray drying in this study. The spray drying process was discussed. In addition, the formation mechanism of feedstock with hollow shell structure was discussed by finite element method in this paper. The double ceramic layer (DCL) LZ/YSZ (yttria stabilized zirconia) thermal barrier coatings were prepared using the as prepared LZ feedstock. The average grain size computed by Scherrer formulation, the observation of powder size by Transmission Electron Microscope (TEM) and “single splat” deposition experiment indicate that the as prepared LZ feedstock is nanostructured feedstock.     

Superposed structure of double-ceramic layer based on YSZ/LaMgAl11O19 thermal barrier coating

The superposed structure of double ceramic layer (SDCL) could be an effective means to develop long-life thermal barrier coating (TBC) at high temperatures. In this study, YSZ/LaMgAl₁₁O₁₉ TBC system with double-ceramic layer (DCL) and SDCL structures were prepared on nickel-based superalloy substrates by atmospheric plasma spraying. The thermal cycling behavior of the coatings was investigated using a furnace at 1000 °C and burner-rig facility at 1375 ± 25 °C on the coating surface. Results showed that the thermal cycle life of the SDCL structure was increased by 7.2% for the furnace and 13.2% for the burner-rig facility compared with that of the DCL structure. The relatively long thermal cycle life of the SDCL structure was attributed to the blocking of the propagation of cracks in the LMA layers by the YSZ ceramic layer and the release of residual thermal stresses by the formation of cracks in the LMA layers.     

Thermal cycling and hot corrosion behavior of a novel LaPO4/YSZ double-ceramic-layer thermal barrier coating

LaPO₄ powders were produced by a chemical co-precipitation and calcination method. The ceramic exhibited a monazite structure, kept phase stability at 1400?°C for 100?h, and had low thermal conductivity (~ 1.41?W/m?K, 1000?°C). LaPO₄/Y₂O₃ partially stabilized ZrO₂ (LaPO₄/YSZ) double-ceramic-layer (DCL) thermal barrier coatings (TBCs) were fabricated by air plasma spray. The LaPO₄ coating contained many nanozones. Thermal cycling tests indicated that the spallation of LaPO₄/YSZ DCL TBCs initially occurred in the LaPO₄ coating. The failure mode was similar to those of many newly developed TBCs, probably due to the low toughness of the ceramics. LaPO₄/YSZ DCL TBCs were highly resistant to V₂O₅ corrosion. Exposed to V₂O₅ at 700–900?°C for 4?h, La(P,V)O₄ formed as the corrosion product, which had little detrimental effect on the coating microstructure. At 1000?°C for 4?h, a minor amount of LaVO₄ was generated.     

Thermal Stability of Lanthanum Zirconate Plasma-Sprayed Coating

Lanthanum zirconate (La₂Zr₂O₇, LZ) is a newly proposed material for thermal barrier coatings (TBCs). The thermal stability of LZ coating was studied in this work by long-term annealing and thermal cycling. After long-term annealing at 1400°C or thermal cycling, both LZ powder and plasma-sprayed coating still kept the pyrochlore structure, and a preferred crystal growth direction in the coating was observed by X-ray diffraction. A considerable amount of La₂O₃ in the powder was evaporated in the plasma flame, resulting in a nonstoichiometric coating. Additionally, compared with the standard TBC material yttria-stabilized zirconia (YSZ), LZ coating has a lower thermal expansion coefficient, which leads to higher stress levels in a TBC system.     

Influence of the intermixed interfacial layers on the thermal cycling behaviour of atmospheric plasma sprayed lanthanum zirconate based coatings

In application as a thermal barrier coating (TBC), yttria stabilised zirconia (YSZ) approaches some limits of performance. To further enhance the efficiency of gas turbines, higher temperature capability and a longer lifetime of the coating are needed for the next generation of TBCs. Pyrochlore oxides of general composition, A₂B₂O₇, where A is a 3⁺ cation (La to Lu) and B is a 4⁺ cation (Zr, Hf, Ti, etc.) have high melting point, fair coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high temperature thermal barrier coatings. Among those oxide materials lanthanum zirconate (LZ/La₂Zr₂O₇) offers very attractive properties. This work describes the fabrication, microstructure and high temperature (1280 °C) thermal cycling behaviour of lanthanum zirconate coatings with five different coating architectures, deposited using atmospheric plasma spray process. The coating architecture which had five layers with two intermixed interlayers had much longer life time than other considered architectures. The coatings were characterised using X-ray diffraction, energy dispersive spectrometry, optical and scanning electron microscopy, before and after thermal cycling tests, to study the coating failure mechanisms.     

Thermal cycling behavior of plasma-sprayed yttria-stabilized zirconia thermal barrier coating with La0.8Ba0.2TiO3−δ top layer

In this study, a La_0.8Ba_0.2TiO_3?δ (LBT) upper layer was deposited on an yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC) through atmospheric plasma spraying. The thermal cycling behaviors of the YSZ single-ceramic-layer and LBT–YSZ double-ceramic-layer coatings at 1000 °C were investigated through a water quenching method. Moreover, phases, microstructural evolution, and elemental distributions were studied through by X-ray diffraction and scanning electron microscopy–energy-dispersive X-ray spectroscopy. The results showed that the thermal cycling lifetime of the LBT–YSZ coating was 27% higher than that of conventional YSZ coating. The conventional YSZ coating failed after 251 cycles because of the joining of the continuous horizontal and vertical cracks caused by the formation of thermal growth oxides and the bending effect of the single-ceramic-layer structure. The thermal cycling behavior of the LBT–YSZ coating was different from that of the YSZ coating at the edge and center. Although the former was similar to the failure behavior of the YSZ coating, the cracks in the vertical direction were deflected as a result of the bending effect of the double-ceramic-layer structure during quenching. This deflection led to the formation of slope cracks with longer propagation paths and slope spallation zones. The latter showed small-debris spallation on top of the LBT upper layer due to the lower fracture toughness of the LBT, which protected the central coating from the structural damage of the ceramic coating. These two behaviors would either release the thermal stress or increase the crack-propagation energy requirement in the ceramic coating, consequently improving the thermal cycling lifetime of the LBT–YSZ coating. In summary, depositing an LBT upper layer could potentially improve the thermal cycling lifetimes of TBCs.     

Mechanical properties of lanthanum zirconate-based composite thermal barrier coatings

Lanthanum zirconate is a promising candidate material for thermal barrier coating (TBC) applications due to its low thermal conductivity and high temperature phase stability. However, its application is limited by thermal durability caused by low fracture toughness and low coefficient of thermal expansion. We recently developed LZ/8YSZ composite TBC systems using blended LZ and 8YSZ powders, which have demonstrated excellent thermal cycling performance. In this study, the mechanical properties of the composite TBCs were characterised using both nanoindentation and Vicker’s microhardness tests. The nanoindentation results show that both Young’s modulus and nanohardness increase with increasing 8YSZ content, suggesting the mechanical properties can be tailored by changing the volume ratio of 8YSZ. The ratios of Young’s modulus to nanohardness remain constant, ～18, irrespective to the coating’s composition. The microhardness results show the same dependence with 8YSZ content, which is confirmed by the analytic models based on composite theory.     

Thermal cycling behaviour of plasma sprayed lanthanum zirconate based coatings under concurrent infiltration by a molten glass concoction

Thermal barrier coatings (TBCs) used in gas-turbine engines afford higher operating temperatures, resulting in enhanced efficiencies and performance. However, during aero engine operation, environmentally ingested airborne particles, which includes mineral debris, sand dust and volcanic ashes get ingested by the turbine with the intake air. As engine temperatures increase, the finer debris tends to adhere to the coating surface and form calcium magnesium alumino-silicate (CMAS) melts that penetrate the open void spaces in the coating. Upon cooling at the end of an operation cycle, the melt freezes and the infiltrated volume of the coating becomes rigid and starts to spall by losing its ability to accommodate strains arising from the thermal expansion mismatch with the underlying metal. The state-of-the-art ZrO₂-7-weight% Y₂O₃ (YSZ) coatings are susceptible to the aforementioned degradation. Rare-earth zirconates have generated substantial interest as novel thermal barrier coatings (TBC) based primarily on their intrinsically lower thermal conductivity and higher resistance to sintering than YSZ. In addition, the pyrochlore zirconates are stable as single phases at up to their melting point. La₂Zr₂O₇ (LZ) is one among such candidates. Hence, the present study focusses on the comparison of cyclic molten CMAS infiltration behaviour of the base metal Inconel 738 (BM), the bond coat NiCrAlY (BC), the duplex YSZ, the LZ coating and a five layered coated specimen with LZ as top layer. Among those coatings mentioned above, the five layer coated specimen showed excellent CMAS infiltration resistance under thermal cycling conditions.     

Experimental investigation of Al2O3/8YSZ and CeO2/8YSZ plasma sprayed thermal barrier coating on diesel engine

In this research work, aluminium oxide/yttria stabilized zirconia (20%Al₂O₃/80%8YSZ) and ceria/yttria stabilized zirconia (20%CeO₂/80%8YSZ) were coated through atmospheric plasma spray technique (APS) as thermal barrier coating (TBC) over CoNiCrAlY bond coat on aluminium alloy (Al-13%Si) substrate piston crown material and their thermal cycling behavior were studied experimentally. Thermal cycle test of both samples were conducted at 800?°C. Microstructural, phase and elemental analysis of the TBC coatings were experimentally investigated. The performance, combustion and emission characteristics of Al₂O₃/8YSZ, CeO₂/8YSZ TBC coated and uncoated standard diesel engine were experimentally investigated. The test results revealed that CeO₂/8YSZ based TBC has an excellent thermal cycling behavior in comparison to the Al₂O₃/8YSZ based TBC. The spallation of the Al₂O₃/8YSZ TBC occurred mainly due to the formation of thermally grown oxide (TGO), and growth of residual stresses at top coating and bond coating interface. The experimental results also revealed that the increase of brake thermal efficiency and reduction of specific fuel consumption for both TBC coated engine. Further reduction of HC, CO and smoke and increase of NOx emission were recorded for both TBC coated engine compared to the standard diesel engine.     

LZC/YSZ DCL TBCs by EB-PVD: Microstructure,low thermal conductivity and high thermal cycling life

Thermal barrier coatings (TBCs) with low thermal conductivity have triggered tremendous attention due to their promising application in the gas turbine engines. Albeit recent studies have investigated double ceramic layers (DCL) with pyrochlore (A₂B₂O₇) phase, it still remains a big challenge for controlling element content and investigating the relationship between the complex hierarchical architectures and their thermal performances. Here we describe a series of DCL La₂O₃-ZrO₂-CeO₂ (LZC)/Y₂O₃-stabilized ZrO₂ (YSZ) coating under different current of electron beam by electron beam-physical vapor deposition (EB-PVD). The formation of hierarchical architecture with feathery microstructure and intra-columnar have been investigated in detail. The DCL coatings achieve a high thermal cycling life and relatively low thermal conductivity at controlling current of electron beam from 1.0 A to 1.3 A. This work may open new opportunities to rationally design other promising TBCs.     

Thermal behaviour of multilayer and functionally-graded YSZ/Gd2Zr2O7 coatings

Zirconates with pyrochlore structure, such as Gd₂Zr₂O₇, are new promising thermal barrier coatings because of their very low thermal conductivity and good chemical resistance against molten salts. However, their coefficient of thermal expansion is low, therefore their thermal fatigue resistance is compromised. As a solution, the combination of yttria-stabilised zirconia (YSZ) and Gd₂Zr₂O₇ can reduce the thermal contraction mismatch between the thermal barrier coating parts.In the present study, two possible designs have been performed to combine YSZ/Gd₂Zr₂O₇. On the one hand, a multilayer coating was obtained where YSZ layer was deposited between a Gd₂Zr₂O₇ layer and a bond coat. On the other hand, a functionally-graded coating was designed where different layers with variable ratios of YSZ/Gd₂Zr₂O₇ were deposited such that the composition gradually changed along the coating thickness.Multilayer and functionally-graded coatings underwent isothermal and thermally-cycled treatments in order to evaluate the oxidation, sintering effects and thermal fatigue resistance of the coatings. The YSZ/Gd₂Zr₂O₇ multilayer coating displayed better thermal behaviour than the Gd₂Zr₂O₇ monolayer coating but quite less thermal fatigue resistance compared to the conventional YSZ coating. However, the functionally-graded coating displays a good thermal fatigue resistance. Hence, it can be concluded that this kind of design is ideal to optimise the behaviour of thermal barrier coatings.     

Rare-earth high-entropy aluminate-toughened-zirconate dual-phase composite ceramics for advanced thermal barrier coatings

Superb toughening is achieved by incorporating a secondary ferroelastic phase in high-entropy rare-earth zirconate 5RE₂Zr₂O₇ (HZ). Here, we report an enhancement of 64% in fracture toughness through the addition of 30mol% high-entropy rare-earth aluminate 5REAlO₃ (HA) to the HZ matrix (30HA). The aforementioned rare-earth elements RE are La, Sm, Eu, Gd, and Yb. The present dual-phase composite ceramic 30HA has a large fracture toughness of 2.77 ± 0.14 MPa m^1/2, along with excellent high-temperature phase stability, resulting in good usage for potential thermal barrier coating applications. Particularly, the fracture toughness of the dual-phase composite ceramics at first increases to a maximum and then drops suddenly, as the mole fraction of HA increases from 0 to 50%. A clear definition of fitting parameters and their physical significance is provided for a better interpretation of the experimental data. The present toughening mechanism sheds light on microstructure engineering in high-entropy ceramics for excellent mechanical properties.