Effect of scandia content on the thermal shock behavior of SYSZ thermal sprayed barrier coatings

Nanostructured 4SYSZ (scandia (3.5 mol%) yttria (0.5 mol%) stabilized zirconia) and 5.5 SYSZ (5 mol% scandia and 0.5 mol% yttria) thermal barrier coatings (TBCs) were deposited on nickel-based superalloy using NiCrAlY as the bond coat by plasma spraying process. The thermal shock response of both as-sprayed TBCs was investigated at 1000 °C. Experimental results indicated that the nanostructured 5.5SYSZ TBCs have better thermal shock performance in contrast to 4SYSZ TBCs due to their higher tetragonal phase content and higher fracture toughness of this coating     

Effect of molten V2O5 salt on the corrosion behavior of micro- and nano-structured thermal sprayed SYSZ and YSZ coatings

The corrosion resistance of micro-and nano-structured scandia and yttria codoped zirconia (nano-4 mol%SYSZ and micro-8.6SYSZ) and yttria doped zirconia (4YSZ) in the presence of molten vanadium oxide were investigated. To this end, duplex TBCs (thermal barrier coatings), composed of a bond coat (NiCrAlY) and a top coat (4SYSZ or 4YSZ), were deposited on the IN738LC Ni-based supper-alloy by atmospheric plasma spraying (APS). The corrosion studies of plasma sprayed TBCs were conducted in 25 mg V₂O₅ molten salt at 910 °C for different times. The nanostructured coating, as compared to its micro-structured counterpart, in spite of a further reaction with the V₂O₅ salt, showed a higher degradation resistance during the corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones. Finally, the corrosion resistance and degradation mechanism of SYSZ and YSZ coatings were compared with the presence of molten NaVO₃ and V₂O₅ salt, respectively.     

Structure-property relationship and design of plasma-sprayed La2Ce2O7/8YSZ composite coatings for gas turbine blades

Novel lanthanum-cerium oxide/8?wt% yttria partially stabilized zirconia (LC/8YSZ) thermal barrier coatings (TBCs) were deposited by supersonic atmospheric plasma spraying. The thermal insulation temperature and thermal shock resistance of LC/8YSZ double-ceramic-layer TBCs (DCL-TBCs) were quantitatively evaluated by a burner rig test. The results showed that the thermal insulation temperature increased with the increase of LC layer thickness in DCL-TBCs. When the thickness ratio between LC layer and 8YSZ layer was close to 1:1, the DCL-TBCs had the highest thermal shock resistance. LC/8YSZ thickness ratio significantly affected the energy release rate and the stress induced by thermal gradient or sintering. The sintering stress was found to be the main reason that caused the delamination of LC layer, however, the stress induced by thermal gradient resulted in the spallation of YSZ layer.     

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 and columnar growth characteristics of 7YSZ thermal barrier coatings fabricated by plasma spray physical vapor deposition

Thermal barrier coating (TBC) applications of 7 wt% yttria stabilized zirconia (7YSZ) must meet low thermal conductivity and excellent high temperature stability. However, the resulting morphology of 7YSZ TBCs fabricated by PS-PVD currently remains poorly studied. The present study addresses this issue by evaluating the microstructure, phase composition, grain distribution, and columnar crystal orientations of 7YSZ coatings fabricated by PS-PVD. The results demonstrate that the growth of YSZ columnar crystals exhibits an obvious preferred orientation [101] that is consistent throughout the entire coating cross-sectional area. The contents of tetragonal phase in the coating is 65.8 %, and the phase has a strongly preferred growth tendency toward <001> . The nano-indentation test shows that the microhardness of the coating increases gradually from bottom to top. In addition, the observed characteristics of 7YSZ particle are evaluated based on the results of numerical simulations of the temperature, velocity, and pressure fields in the plasma jet.     

Thermal shock performance and failure behavior of Zr6Ta2O17-8YSZ double-ceramic-layer thermal barrier coatings prepared by atmospheric plasma spraying

Zr₆Ta₂O₁₇ has higher fracture toughness, better phase stability, thermal insulation performance and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (8 YSZ, 7–8 wt%) at temperatures above 1200 °C. However, the thermal expansion coefficients between Zr₆Ta₂O₁₇ coating and bond coating do not match well. A double-ceramic-layer design is applied to alleviate the thermal stress mismatch. The Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer thermal barrier coatings (TBCs) are prepared by atmospheric plasma spraying (APS). During the thermal shock test, Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer TBCs exhibit a better thermal shock resistance than 8 YSZ and Zr₆Ta₂O₁₇ single-layer TBCs. The thermal shock performance and failure mechanism of TBCs in the thermal shock test are investigated and discussed in detail.     

Thermal cycling performances of multilayered yttria-stabilized zirconia/gadolinium zirconate thermal barrier coatings

Gadolinium zirconate (Gd₂Zr₂O₇, GZO) as an advanced thermal barrier coating (TBC) material, has lower thermal conductivity, better phase stability, sintering resistance, and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (YSZ, 6-8 wt%) at temperatures above 1200°C. However, the drawbacks of GZO, such as the low fracture toughness and the formation of deleterious interphases with thermally grown alumina have to be considered for the application as TBC. Using atmospheric plasma spraying (APS) and suspension plasma spraying (SPS), double-layered YSZ/GZO TBCs, and triple-layered YSZ/GZO TBCs were manufactured. In thermal cycling tests, both multilayered TBCs showed a significant longer lifetime than conventional single-layered APS YSZ TBCs. The failure mechanism of TBCs in thermal cycling test was investigated. In addition, the CMAS attack resistance of both TBCs was also investigated in a modified burner rig facility. The triple-layered TBCs had an extremely long lifetime under CMAS attack. The failure mechanism of TBCs under CMAS attack and the CMAS infiltration mechanism were investigated and discussed.     

Comparative study on effect of oxide thickness on stress distribution of traditional and nanostructured zirconia coating systems

Numerical based assessment of traditional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coating systems (TBCs) has been carried out with varying thickness of thermally grown oxide (TGO). Radial, axial and shear stresses are determined for both coatings and are presented in comparison with few novel and interesting results. Elastic strain energy for TGO failure assessment is determined from calculated stress within TGO for varying thickness. Radial stresses at TGO/bond coat interface and maximum axial stresses in nanostructured zirconia coatings are found to be lower than in traditional YSZ up to a critical TGO thickness of 6 –7 μm, after which stresses in nanostructured zirconia coatings increase considerably. However, radial compressive stresses in nanostructured TBCs are lower in all TGO thickness cases and shear stresses are slightly higher with relatively more prominent difference at high oxide thickness.     

Changes in high-temperature thermal properties of modified YSZ with various rare earth doping elements

To protect the high-temperature components of gas turbines, 6–8 wt.% yttria stabilised zirconia (YSZ) has been extensively used as a thermal barrier coating (TBC) material. However, its application is severely limited at high temperatures because of zirconia phase transition and sintering densification above 1200 °C. This study developed modified YSZ with enhanced high-temperature thermal properties owing to the addition of various rare-earth doping elements. Among the various rare earth-doped compositions, all the thermal properties were significantly improved in compositions containing scandium, gadolinium, and dysprosium. Furthermore, in the selected compositions, the high-temperature thermal properties were analysed under heat treatment conditions of 1300 °C, with a target turbine inlet temperature (TIT) of 1500 °C. The high-temperature phase stability of the tetragonal phase was significantly improved in the newly developed compositions, and they exhibited glass-like low thermal conductivity (～0.984 W/mK) due to the influence of lattice distortion caused by the differences in the substituent-ion mass and size, and the oxygen vacancies. Moreover, there was notable improvement in the thermal expansion coefficient (～11 × 10^?6/K) and resistance to high-temperature densification.     

Isothermal Oxidation Behavior of Gd2Zr2O7/YSZ Multilayered Thermal Barrier Coatings

Efficiency of a gas turbine can be increased by increasing the operating temperature. Yttria‐stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used in gas turbine applications. However, above 1200°C, YSZ undergoes significant sintering and CMAS (calcium magnesium alumino silicate) infiltration. New ceramic materials of rare earth zirconate composition such as gadolinium zirconate (GZ) are promising candidates for thermal barrier coating applications (TBC) above 1200°C. Suspension plasma spray of single‐layer YSZ, double‐layer GZ/YSZ, and a triple‐layer TBC comprising denser GZ on top of GZ/YSZ TBC was attempted. The overall coating thickness in all three TBCs was kept the same. Isothermal oxidation performance of the three TBCs along with bare substrate and bond‐coated substrate was investigated for time intervals of 10 h, 50 h, and 100 h at 1150°C in air environment. Weight gain/loss analysis was carried out by sensitive weighing balance. Microstructural analysis was carried out using scanning electron microscopy (SEM). As‐sprayed single‐layer YSZ and double‐layer GZ/YSZ showed columnar microstructure, whereas the denser layer in the triple‐layer TBC was not columnar. Phase analysis of the top surface of as‐sprayed TBCs was carried out using XRD. Porosity measurements were made by water intrusion method. In the weight gain analysis and SEM analysis, multilayered TBCs showed lower weight gain and lower TGO thickness compared to single‐layer YSZ.     

Effect of the Starting Microstructure on the Thermal Properties of As-Sprayed and Thermally Exposed Plasma-Sprayed YSZ Coatings

Thermal barrier coatings (TBCs) experience thermal gradients, excessive temperature, and high heat flux from hot gases in turbines during service. These extended thermal effects induce sintering and significant microstructure changes, which alter the resulting thermal conductivity of the TBCs. To study the effects of different starting microstructures on the sintering behavior, plasma-sprayed yttria-stabilized zirconia (YSZ) TBCs produced from different starting powders and process parameters were subjected to thermal aging at several temperatures and time intervals, after which their thermal conductivity was measured at room temperature. The thermal conductivity results were analyzed by introducing the Larson–Miller parameter, that describes the creep-like behavior of thermal conductivity increase with annealing temperature and time. One set of coatings was also annealed under the same conditions and the thermal conductivities were measured at elevated temperatures. The temperature-dependent thermal conductivity data were analyzed and used to predict the long-term thermal property behavior for a general YSZ coating design.     

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.     

Microstructure evolution of Al-modified 7YSZ PS-PVD TBCs in thermal cycle

The PS-PVD method was used to prepare 7YSZ thermal barrier coatings (TBCs) and NiCrAlY bond coatings on a DZ40 M substrate. To prevent oxidation of the coating, magnetron sputtering was used to modify the surface of TBCs with an Al film. To explore the stability of TBCs during thermal cycling, water quenching was performed at 1100 °C, and ultralong air cooling for 16,000 cycles was performed. The results showed that before water quenching and air cooling, the top surface structure of the 7YSZ TBCs changed. After water quenching, the surface of the Al film was scoured and broken, the surface peeled off layer-by-layer, and cracks formed at the interface between the thermally grown oxide and NiCrAlY. During air cooling of the thermal cycle, the Al film reacted with O₂ in the air to form a dense Al₂O₃ top layer that coated the cauliflower-like 7YSZ surface and maintained the feather-like shape. At the same time, the TGO layer between 7YSZ and NiCrAlY grew and cracked. The two thermal cycles of water quenching and air cooling led to different failure mechanisms of TBCs. Water quenching failure was caused by layer-by-layer failure of the 7YSZ top coat, while air cooling failure occurred due to the internal cracking of the TGO layer at the 7YSZ/NiCrAlY interface and the failure of the TGO/NiCrAlY interface.     

Synthesis and characteristics of nanocrystalline YSZ powder by polyethylene glycol assisted coprecipitation combined with azeotropic-distillation process and its electrical conductivity

Nanoscale 8 mol% yttria stabilized zirconia (YSZ) powders were prepared by polyethylene glycol (PEG-1540) assisted coprecipitation coupling with azeotropic distillation drying process. The role of PEG and azeotropic-distillation on the morphology and particle size of YSZ was studied. Thermogravimetry and X-ray diffraction results showed that azeotropic-distillation could reduce the formation temperature of YSZ phase. X-ray patterns of the YSZ powders revealed that the crystallite size of the powders increases with increasing calcination temperature, which is consistent with transmission electron microscopy observations. The sintering behavior and the ionic conductivity of the pellets prepared from YSZ powders calcined at 800 °C were also studied. At sintering temperatures ≥1400 °C, more than 99% of the relative density was obtained. The alternating-current impedance spectroscopy results showed that the YSZ pellet sintered at 1450 °C has ionic conductivity of 0.0726 S cm⁻¹ at 800 °C in air. The present work results have indicated that the PEG assisted coprecipitation combined with azeotropic-distillation drying process is an alternative method to synthesize yttria stabilized zirconia powders with a high sinterability and a good ionic conductivity.     

A novel way to fabricate highly porous fibrous YSZ ceramics with improved thermal and mechanical properties

Inspired by nest structure, highly porous fibrous yttria-stabilized zirconia (YSZ) ceramics were fabricated through tert-butyl alcohol (TBA)-based gel-casting process and pressureless sintering by using YSZ fibers as raw material and adding K₂SO₄ as removable sintering aid. Different sintering temperature and soaking time were investigated to achieve optimal thermal and mechanical properties. The results show that all specimens consist of crystallized t-YSZ phase. Fibers interconnect with good interfacial bonding on junctions. Under higher sintering temperature, porosity drops gradually while compressive strength increases significantly. With prolonged soaking time, there is no obvious change in porosity and compressive strength increases gradually. All specimens have uniformly distributed pores with average size of 30.2 μm and show good structural stability at high temperature. Ultra-low thermal conductivity is achieved and ductile fracture mode with high elongation makes it more applicable in high-temperature thermal insulating applications.     

Comparison of hot corrosion behaviors of plasma-sprayed nanostructured and conventional YSZ thermal barrier coatings exposure to molten vanadium pentoxide and sodium sulfate

The purpose of the current study was evaluation and comparison of hot corrosion behaviors of plasma-sprayed conventional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). Hot corrosion studies were performed on the surface of coatings in the presence of a molten mixture of V₂O₅+Na₂SO₄ at 1000 °C for 30 h. Results indicated that the hot corrosion mechanisms of conventional and nanostructured YSZ coatings were similar. The reaction between corrosive salt and Y₂O₃ produced YVO₄, leaching Y₂O₃ from YSZ and causing the detrimental phase transformation of zirconia from tetragonal to monoclinic. The nanostructured coating, as compared to its conventional counterpart, in spite of a further reaction with the corrosive salt, showed a higher degradation resistance during the hot corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones.     

Correlation between yttria stabilized zirconia particle size and morphological properties of NiO–YSZ films prepared by spray coating process

A systematic approach was taken to investigate the morphology of NiO–yttria stabilized zirconia (YSZ) films deposited by a spray coating process. The final morphological aspects of anode films were influenced by the particle size of YSZ powders and the milling time of the slurries used for film deposition. YSZ powders with average particle size of 17 and 52 nm were obtained from powders calcined at 800 and 1000 °C, respectively. The results obtained by rheological studies pointed out that slurries prepared from YSZ powders calcinated at 1000 °C and milling time of 20 h had more stability. All slurries presented thixotropic and pseudoplastic behaviors.     

Conductive and radiative heat transfer inhibition in YSZ photonic glass

A high temperature stable ceramic photonic structure is demonstrated with low thermal conductivity and suppressed external radiative heat transfer. The structure is based on a disordered arrangement of yttria-stabilized zirconia (YSZ) microparticles, called photonic glass (PhG). The prepared YSZ-PhG film exhibits low thermal conductivity of 0.03 Wm⁻¹K⁻¹ comparable to that of the air. The small point contacts of the adjacent YSZ particles are the main cause of such low thermal conductivity. After annealing at 1400 °C for 5 h, the solid thermal conductivity increased to 0.3 Wm⁻¹K⁻¹ at room temperature due to the thermally induced neck formation, associated with an increased contact area between adjacent particles. This thermal conductivity is still much lower than that of conventional YSZ thermal barrier coatings (TBCs) with approximately 1 Wm⁻¹K⁻¹. At the same time, the PhG structure is an efficient scatterer for thermal radiation in the wavelength range between 1 and 6 μm. In an only 100 μm thick structure an average reflection of 84% was obtained. At 1400 °C, the effective thermal conductivity is 0.2 Wm⁻¹K⁻¹. The presented structure is applicable to other oxides with even lower bulk thermal conductivity and can be considered for future TBCs.     

Enhanced thermal stability of high yttria concentration YSZ aerogels

Aerogels are a promising class of materials for lightweight, high-performance insulation. However, their high specific surface area contributes to rapid densification of the structure at elevated temperatures. Upon densification, the favorable properties of low thermal conductivity and low density are lost. Investigation of doped metal oxide systems presents a route to stabilization of porous structures at high temperatures and a platform to study parameters conducive to thermal stability. Our work focuses on yttria-stabilized zirconia (YSZ) aerogels prepared via a sol-gel method and supercritically dried. Yttria concentrations were studied from 0 to 50 mol% YO_1.5 to stabilize porosity to temperatures of 1200°C and develop an understanding of properties contributing to improved stability. Increased yttria content improved the thermal stability of the pore structure by reducing densification and suppressing crystallite growth, resulting in retention of the mesoporous structure to 1200°C. The improvement in thermal stability is related to associated reductions in specific surface energy and cation diffusivity at higher yttria concentrations. This work demonstrates that tuning thermodynamic and kinetic factors is a viable route to improved thermal stability in highly porous structures for use as insulation in extreme environments.     

Effect of physical vapor deposited Al2O3 film on TGO growth in YSZ/CoNiCrAlY coatings

Thermal barrier coatings (TBCs) comprising of yttria stabilized zirconia (YSZ) ceramic top coat and CoNiCrAlY metallic bond coat have been widely used in gas turbines. However, the developed oxides layer in the interface of the top and bond coats during thermal exposure of the TBCs always results in the destruction of the system. In order to restrain the growth of oxides layer and improve the thermal shock resistance of TBCs, a thin Al₂O₃ film was pre-deposited on CoNiCrAlY bond coat by physical vapor deposition (PVD) technology. After thermal exposure, morphologies and phase compositions of the thermal growth oxides (TGO) layer in the conventional and pre-deposited Al₂O₃ film TBCs were examined by scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS). The residual stresses in the coatings were analyzed using micro-Raman spectroscopy (LabRam-1B). It was found that TGO layer formed in the conventional TBCs was mainly composed of Al₂O₃, (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ + NiO (CSN), and (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ (CS), while in the treated TBCs, the formed TGO layer appeared more uniform and compact. The CSN and CS clusters, which are normally considered as a weakness for TBCs, were greatly limited. The residual stresses in the TBCs after thermal shock were also reduced by the deposition of Al₂O₃ film.