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.     

Microstructural,mechanical and thermal shock properties of triple-layer TBCs with different thicknesses of bond coat and ceramic top coat deposited onto polyimide matrix composite

In this study, a triple-layer thermal barrier coating (TBC) of Cu-6Sn/NiCrAlY/YSZ was deposited onto a carbon-fiber reinforced polyimide matrix composite. Effects of different thicknesses of YSZ ceramic top coat and NiCrAlY intermediate layer on microstructural, mechanical and thermal shock properties of the coated samples were examined. The results revealed that the TBC systems with up to 300 µm top coat thicknesses have clean and adhesive coating/substrate interfaces whereas cracks exist along coating/substrate interface of the TBC system with 400 µm thick YSZ. Tensile adhesion test (TAT) indicated that adhesion strength values of the coated samples are inversely proportional to the ceramic top coat thickness. Contrarily, thermal shock resistance of the coated samples enhanced with increase in thickness of the ceramic coating. Investigation of the TBCs with different thicknesses of NiCrAlY and 300 µm thick YSZ layers revealed that the TBC system with 100 µm thick NiCrAlY layer exhibited the best adhesion strength and thermal shock resistance. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

Gradient thermal cycling behavior of a thermal barrier coating system constituted by NiCoCrAlY bond coat and pure metastable tetragonal nano-4YSZ top coat

Pure metastable tetragonal (t’) phase 4YSZ top coats with thickness of 100 and 200 μm were deposited on NiCoCrAlY-coated second generation single crystal superalloy by air plasma spray (APS). The two thermal barrier coatings were evaluated under gradient thermal cycling test using gas mixture of propane and oxygen. After flame shock test, the values of Young's modulus, hardness and degree of densification all exhibited a gradient distribution across YSZ thickness. In contrast to intensive sintering at surface of 200 μm 4YSZ coating, the TBC sample with 4YSZ layer of 100 μm underwent poor oxidation at interface of YSZ and bond coat, forming a duplex oxide scale: (Ni,Co)(Cr,Al)₂O₄ spinel over Al₂O₃, which promoted the delamination at the top-coat/bond-coat interface. The resistance against gradient thermal cycling, the phase stability of 4YSZ and the failure mechanism of the TBCs, were discussed correlating to the effects of YSZ thickness.     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

Thermal stability and sintering behavior of plasma sprayed nanostructured 7YSZ, 15YSZ and 5.5SYSZ coatings at elevated temperatures

Nanostructured scandia, yttria doped zirconia (5.5SYSZ), 7 wt% yttria stabilized zirconia (7YSZ) and 15YSZ thermal barrier coatings (TBCs) were produced by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal stability and sintering behavior of the three as-sprayed TBCs at 1480 °C were investigated. The results indicated that the thermal stability of SYSZ and TBCs was longer than the 7YSZ TBCs due to higher amount of tetragonal phase. Furthermore, the results demonstrated that the nanostructured 7YSZ coating exhibits higher sintering resistance than 5.5SYSZ TBC.     

Failure mechanisms of magnesia alumina spinel abradable coatings under thermal cyclic loading

Abradable coatings have been used in low- and high-pressure sections of jet engine compressors for more than 40 years. Today, they are also used in the high-pressure turbine of jet engines and are gaining more interest for applications in industrial gas turbines. They minimise the clearance between the rotating blade tips and the stationary liners. Aside from being abradable, the coatings have to be mechanically stable and withstand high thermo-mechanical loadings. A typical material used in engines today is yttria-stabilised zirconia (YSZ). This material advantageously combines a suitable thermal conductivity with a high thermal expansion coefficient, but shows a temperature capability limited to 1200 °C in long-term applications. Typical abradable coating thicknesses are above 1 mm. With increasing coating thickness and limited cooling efficiency leading to high surface temperatures, there is a risk of premature failure. As a result, new ceramic materials have been developed with better high-temperature capability. The present work investigates an atmospheric plasma sprayed ceramic double-layer coating system composed of 7YSZ as an intermediate layer and magnesia alumina spinel as a top layer.This double-layer system was sprayed onto disc-shaped Inconel 738 superalloy substrates, which were coated with a vacuum plasma sprayed MCrAlY bondcoat. The lifetime of the coating system was assessed via thermal gradient cycling testing with surface temperatures above 1400 °C. During cycling, the samples showed a typical failure mechanism with exfoliation of thin coating lamellae starting from the coating surface. This failure mechanism was not observed in thermal barrier or abradable coatings in the past. The failure mechanism was analysed and mismatch stress calculations were carried out.     

Optimized sol–gel thermal barrier coatings for long-term cyclic oxidation life

New promising thermal barrier coatings (TBCs) processed by the sol–gel route are deposited onto NiPtAl bond coated superalloy substrates using the dip and/or spray coating technique. In this study, the optimization of the process, including an appropriate heat treatment prone to densify the yttria-stabilized-zirconia (YSZ) top-coat and leading to the sintering and the development of a resulting crack network, is investigated. In particular, relevant information on internal strain evolution during the heat treatment are obtained using in situ synchrotron X-rays diffraction and confirm a stabilization of the TBC through the occurrence of the micro-cracks that beneficially releases the in-plane sintering stress. Such TBCs are subsequently reinforced using additional material brought within the cracks using sol–gel spray coating. The effect of various process parameters, such as the pre-oxidation of the bond-coat, on the sol gel TBCs consolidation and their cyclic oxidation resistance enhancement, is presented. Reinforced sol–gel TBCs are successfully oxidized up to more than one thousand 1 h-cycles at 1100 °C, without any detrimental spallation.     

A study of damage evolution in high purity nano TBCs during thermal cycling: A fracture mechanics based modelling approach

This work concerns the study of damage evolution in a newly developed high purity nano 8YSZ thermal barrier coating during thermal cyclic fatigue tests (TCF). TCF tests were conducted between 100 °C–1100 °C with a hold time of 1 h at 1100 °C, first till failure and later for interrupted tests. Cross section analysis along the diameter of the interrupted test samples revealed a mixed-type failure and that the most of the damage occurred towards the end of the coating’s life. To understand the most likely crack growth mechanism leading to failure, different crack growth paths have been modelled using finite element analysis. Crack growing from an existing defect in the top coat towards the top coat/TGO interface has been identified as the most likely mechanism. Estimated damage by the model could predict the rapid increase in the damage towards the end of the coating’s life.     

Degradation of plasma-sprayed yttria-stabilized zirconia coatings via ingress of vanadium oxide

V₂O₅ reaction and melt infiltration in plasma-sprayed 7 wt% Y₂O₃–ZrO₂ (YSZ) coatings were investigated at temperatures ranging from 750 °C to 1200 °C using SEM and TEM combined with EDS. The interlamellar pores and intralamellar cracks, common in plasma-sprayed materials, provide pathway for the molten species. The microstructure of the contaminated coatings is therefore the result of the interplay between the dissolution/reaction rates of the V₂O₅ with YSZ coating and the infiltration rates of the molten species. Near the coating surface, the reaction front proceeds in a planar fashion, via dissolution of the lamella and precipitation of fine-grained reaction products composed of ZrV₂O₇ (for reactions at 750 °C and below), m-ZrO₂ and YVO₄. The thickness of this planar reaction zone or PRZ was found to increase as reaction time and temperature increased. The melted V₂O₅ was observed to infiltrate along the characteristic microstructure of plasma-sprayed coatings, i.e. the interconnected pores and cracks, and react with the YSZ. The thickness of this melt infiltrated reaction zone or MIRZ ranged from 5 μm for reactions at 750 °C for 30 min to 130 μm for reactions at 1000 °C for 90 min. At 1200 °C, only a PRZ was observed (i.e. the thickness of the MIRZ was nominally zero), suggesting that the dissolution reaction within the pores/cracks and subsequent formation of reaction products may limit infiltration. Fifty-hour heat-treatments at 1000 °C and 1200 °C prior to reaction with the V₂O₅ at 800 °C for 90 min were used to change the microstructural features of the coating, such as crack connectivity and pore size. The heat-treatment at 1000 °C was found most deleterious to the coating due to large cracks created via a desintering process that afforded deep penetration of the molten V₂O₅.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

Reducing sintering temperature of yttria stabilized zirconia through addition of lithium nitrate and alumina

Reducing sintering temperature of yttria stabilized zirconia (YSZ) has been achieved through doping with alumina and lithium nitrate at levels below 1 mol%. Sintering experiments of pure and doped samples have been conducted with the same profile using an optical dilatometer. All samples exhibited anisotropic sintering over a wide range of temperatures but final shrinkage values were comparable in axial and radial directions. Sintering temperature has been reduced by as much as 110 °C. We believe that the reduction in sintering temperatures is due to viscous flow in the first stage sintering. Bimetallic doping (mixture of alumina and lithium nitrate doping) is more effective in reducing sintering temperature than single doping possibly due to better distribution of doping material throughout the matrix material. Separate sintering experiments for 5 h have been conducted at 1250 °C and 1170 °C on doped 8 mol% and 3 mol% YSZ, respectively, and have shown that near full density (～96%) is reachable.     

An evaluation of plasma-sprayed coatings based on Al2O3 and Al2O3–13 wt.% TiO2 with bond coat on pure titanium substrate

In this study, the effects of bond coat on the properties of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ coatings, which is plasma sprayed onto a commercial pure titanium substrate with and without Ni–5 wt.% Al (METCO 450 NS) as bond coating layer were investigated in terms of microhardness, bonding strength and surface roughness. Optical and scanning electron microscopy (SEM) examinations revealed that there is a uniform coating layer with no spalling and delamination. However, there is a little amount of porosity. The results indicated that the application of bond coat layer in the plasma spraying of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ on pure titanium substrate has increased the hardness and bonding strength of coatings. While the adhesive bonding is dominant without bond coat, the cohesive bonding is dominant with the application of the bond coating layer. It has been observed that percentage of cohesion strength was about three times higher than that of adhesion strength.     

Kinetic and thermodynamic effects of manganese as a densification aid in yttria-stabilized zirconia

This work demonstrates the role of Mn as an effective sintering aid in Yttria-Stabilized-Zirconia (YSZ) is a result of the concomitant reduction of activation energies and change of interfacial energies caused by Mn segregation. Kissinger analyses of the heat of sintering showed a decrease in activation energy from 219.9 kJ/mol for YSZ to 103.4 kJ/mol for YSZ containing 3-mol% Mn. Direct microcalorimetry analyses showed that the average surface and grain boundary energies of YSZ decreased from 0.94 and 0.71 J/m², respectively, to 0.70 and 0.17 J/m² for 3-mol% Mn doped YSZ. The decrease in the ratio between surface and grain boundary energies indicates an increase in dihedral angle from 137.5° to 166.6°, meaning an increase in sintering stress. Segregation of manganese to grain boundaries was experimentally observed and is discussed to be responsible for both kinetic and thermodynamic changes in the system while suggesting interconnection by the thermodynamic extremal principle.     

Mechanisms governing the thermal shock and tensile fracture of PS-PVD 7YSZ TBC

Thermal barrier coating (TBC) system including NiCoCrAlYTa metallic bond coating and 7YSZ (7 wt%Y₂O₃-ZrO₂) ceramic top coating was deposited on nickel-based superalloy by plasma spray-physical vapor deposition (PS-PVD). Thermal shock property of 7YSZ TBC was characterized by water-quenching test at 1100 ℃ and its failure behaviors were investigated in detail. Besides, tensile test was performed for TBC sample and its cross-sectional fracture microstructure was studied as well. The results showed that after water-quenching test lots of pitting spallation took place in TBC surface, but no obvious microcracks were observed. Additionally, the tensile test indicated that fracture occurred in 7YSZ coating near the interface of ceramic-bond coating. After conduction of water-quenching and tensile testing, a lot of spherical particles and nano-sized agglomerated clusters were observed in the quasi-columnar structured 7YSZ coating. These lead to the formation of weak inter-column bonding and the failure of PS-PVD 7YSZ TBC. Moreover, in order to better understand the failure process, a deposition mechanism of coating was proposed.     

Thermal cycling failure of the multilayer thermal barrier coatings based on LaMgAl11O19/YSZ

Thermal cycling failure of three multilayer TBCs based on LaMgAl₁₁O₁₉ (LaMA)/YSZ was comparatively investigated by using the burner-rig testing method in this work. Results indicate that through optimizing the weight ratio and thickness of the intermediate LaMA/YSZ composite layers, a five-layer TBC with much improved thermal cycling life of 11,749 cycles at 1372 °C surface and 1042 °C bond coat testing temperature has been realized. While, thermal cycling lifetimes of the tri- and six-layer TBCs were 7439 and 7804 cycles at surface/bond coat testing temperatures of 1378 °C/1065 °C and 1367 °C/1056 °C, respectively. Factors related to the 60 wt.% LaMA + 40 wt.% YSZ (60LaMA + 40YSZ) intermediate composite layer with the highest thermal expansion coefficient than other composite layers generating higher internal stress level to the tri- and six-layer TBCs, different bond coat temperature and TGO growth, as well as long-term stability of the LaMA coating during thermal cycling tests, were characterized and compared to understand the different thermal cycling lifetime and failure modes among such three multilayer TBCs.     

Fabrication of yttria-stabilized-zirconia thick coatings via slurry process with pressure infiltration

Yttria-stabilized-zirconia (YSZ) coatings with thicknesses up to 420 μm have been prepared using a novel slurry process with pressure infiltration. Binary-sized particle slurries (binary-slurries), composed of nano-particle slurry (nano-slurry) and micro-sized preformed particles, were cast on metal substrates to form coatings. After sintering at 1150 °C for 1 h, preformed particles were cemented with nano-particles to form a porous YSZ coating. Subsequently, the nano-slurry was infiltrated into the porous coatings under pressure. The infiltrated nano-slurry filled the pores, and was sintered together with the porous coating, resulting in an increase in both density and mechanical properties of the coating. After 5–6 infiltration cycles, the coating reached 82% theoretic density and micro-hardness of 3.7 GPa. Such coatings could be used as thermal barrier coatings for high temperature applications.     

Constrained sintering and cracking of air plasma sprayed thermal barrier coatings: Experimental observation and modeling

The development of vertical cracks in air plasma sprayed (APS) thermal barrier coatings (TBCs) during thermal cycling and constrained sintering under a temperature gradient is investigated. Microstructural analysis shows that the development of the vertical cracks is associated with multiple processes, including sintering during the hold period and cleavage during cooldown. Inspired by the experimental observations, an image-based sintering model is used to simulate the development of vertical cracks as the coating sinters while constrained by a substrate. The computational results show that microstructural imperfections can develop into vertical cracks, which then propagate toward the interface. A simple analytical model is presented for the threshold level of in-plane stress for the onset of propagation of a vertical crack during constrained sintering. By combining the results of these different modeling approaches, the cross-coupling of the material and geometric parameters, and how this determines the sintering response (microstructure evolution) and vertical crack formation is evaluated. In addition, the growth of vertical cracks by a cleavage mechanism during cooldown is examined and the coupling between sintering, cleavage crack growth, and TBC lifetime is explored.     

Porosity analysis and oxidation behavior of plasma sprayed YSZ and YSZ/LaPO4 abradable thermal barrier coatings

In this research, the high temperature oxidation behavior, porosity, and microstructure of four abradable thermal barrier coatings (ATBCs) consisting of micro- and nanostructured YSZ, YSZ-10%LaPO₄, and YSZ-20%LaPO₄ coatings produced by atmospheric (APS) method were evaluated. Results show that the volume percentage of porosity in the coatings containing LaPO₄ was higher than the monolithic YSZ sample. It was probably due to less thermal conductivity of LaPO₄ phases. Furthermore, the results showed that the amount of the remaining porosity in the composite coatings was higher than the monolithic YSZ at 1000 °C for 120 h. After 120 h isothermal oxidation, the thickness of thermally growth oxide (TGO) layer in composite coatings was higher than that of YSZ coating due to higher porosity and sintering resistance of composite coatings. Finally, the isothermal oxidation resistance of conventional YSZ and nanostructured YSZ coating was investigated.     

Vertical crack distribution effect on the TBC delamination induced by crack growth from the ceramic surface and near the interface

The propagation of vertical crack on the surface of thermal barrier coatings (TBCs) may affect the interface cracking and local spallation. This research aims to establish a TBC model incorporating multiple cracks to comprehensively understand the effects of vertical crack distribution on the coating failure. The continuous TGO growth and ceramic sintering are together introduced in this model. The influence of the vertical crack spacing and non-uniform distribution on the stress state, crack driving force, and dynamic propagation is examined. Moreover, the influence of coating thickness on the crack growth driving is also explored. The results show that large spacing will lead to early crack propagation. The uniform distribution of vertical cracks can delay the spallation. When the spacing is less than 4 times ceramic coat thickness, the cracking driving force will come in a steady-state stage with the increase of vertical crack length. Prefabrication of vertical cracks with spacing less than 0.72 mm on the coating surface can greatly decrease the strain energy. The results in this study will contribute to the construction of an advanced TBC system with long lifetime.