Tailoring the EB-PVD columnar microstructure to mitigate the infiltration of CMAS in 7YSZ thermal barrier coatings

The CMAS associated degradation of 7YSZ TBC layers is one of the serious problems in the aero engines that operate in dusty environments. CMAS infiltrates into TBC at high temperatures and stiffens the TBC which ultimately loses its strain tolerance and gets delaminated. The EB-PVD technique is used to coat TBCs exhibiting a columnar microstructure on parts such as blades and on vanes. By varying the EB-PVD process parameters, columnar morphology and porosity of the 7YSZ coating is changed and its effect on the CMAS infiltration behaviour is studied in detail. Two different TBC pore geometries were created and infiltration experiments were carried out at 1250 °C and 1225 °C for different time intervals. The 7YSZ coating with more ‘feathery’ features has resulted in higher CMAS resistance by at least by a factor of 2 than its less ‘feathery’ counterpart. These results are explained on the basis of a proposed physical model.     

Chemical compatibility of rare earth apatite with yttria-stabilized zirconia

The chemical compatibility of a series of rare earth apatite (RE-apatite), with Y₂O₃-stabilized ZrO₂ (YSZ) has been investigated. Three types of RE-apatite powders with different ionic radius (RE = Gd, Nd and La) were prepared, and bulks prepared from the powder mixtures of RE-apatite and YSZ were heat-treated at 1300 °C up to 100 h in this study. It was found that Gd-apatite reacted with YSZ and formed a reaction layer (Gd₂Si₂O₇) at the Gd-apatite/YSZ interface. Meanwhile, the intense Gd³⁺ diffusion resulted in the formation of Gd solid solutions in YSZ and much YSZ phase transformation. In contrary, as for Nd- or La-apatite/YSZ composite, which has larger ionic radius, no reaction product was observed at interface and there was less RE diffusion into YSZ as well as YSZ transformation. These results clearly indicated that large ionic radius of RE³⁺ could enhance the chemical compatibility of RE-apatite with YSZ.     

Effect of rare earth ions doping on the thermal properties of YAG transparent ceramics

Yttrium aluminium garnet doped with rare earth ions is one of the most common active media in solid state lasers. In high-power lasers, thermal management is crucial, requiring information on the thermal properties. In this work, the thermal diffusivity and conductivity of polycrystalline YAG ceramics doped with Yb and Er were measured by laser flash method at various temperatures ranging from room temperature to 900 °C. Transparent ceramic YAG samples were prepared by solid state reactive sintering of oxide powders under vacuum. Thermal diffusivity and conductivity showed similar trends, decreasing with increasing temperature as well as with the increase of dopant content from 0 to 20 at.%. The measured values were compared with literature data and empirical relations. Similar values were obtained both for Yb and Er doping. We thus suggest that the data of thermal diffusivity and conductivity of Yb:YAG may be used as a first approximation for Er:YAG.     

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.     

Repressing high-temperature radiative heat transfer in thermal barrier coatings

Photon diffusion in thermal barrier coatings (TBCs) significantly deteriorates the overall performance of gas turbines operating at high temperatures. This study presents the strategy of high-temperature photon suppression, based on a ceramic composite consisting of the second component with a smaller refractive index and controlled particle size. Using the Mie theory, it is theoretically demonstrated that controlling the second component particle size closer/equal to the infrared radiation wavelength region (1–5 μm) could reduce photon diffusion. Ceramic composites comprised of 8 wt.% yttria-stabilized zirconia (8YSZ, matrix) and corundum (second component) with different particle sizes were prepared. The total and the photon thermal conductivity of the 8YSZ/corundum composites are lower than pure 8YSZ by ∼48.9% and ∼96.4% at 1200°C, respectively. With the addition of corundum into 8YSZ, the thermal radiation transport of 8YSZ is significantly suppressed due to the photon scattering produced by the lower refractive index and proper particle size of the corundum. Besides, the fracture toughness and hardness of composites increased by ∼20% and ∼13%, respectively, compared to the 8YSZ. Composite with the corundum particles size of 1 μm displays the lowest values of total and photon thermal conductivity at high temperature.     

Effect of Ta5+ doping on the thermal physical properties of defective fluorite Y3NbO7 ceramics

The effects of substituting the B cation in A₃BO₇ ceramics on their thermal physical properties were investigated by applying a large mass difference. Y₃(Nb_1-xTa_x)O₇ (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) ceramics were synthesized, and their structural characteristics were determined. All the fabricated Y₃(Nb_1-xTa_x)O₇ ceramics showed defective fluorite structures and glass-like low thermal conductivity (1.18−2.04 W/m∙K at 25°C) because of the highly distorted crystal structure and significant mass difference. Substitution with Ta⁵⁺ enhanced the sintering resistance, leading to superior thermal-insulating performance via grain boundary scattering. Furthermore, the ceramics exhibited excellent coefficients of thermal expansion, implying the promising applicability of Y₃(Nb_1-xTa_x)O₇ as new thermal barrier materials. The effect of mass difference on the thermomechanical properties of the ceramics was examined, suggesting a simple strategy for engineering the chemical composition of new thermal barrier materials.     

Oxygen-vacancy-mediated microstructure and thermophysical properties in Zr3Ln4O12 for high-temperature applications

Yttria-stabilized zirconia (YSZ) has been considered as state-of-the-art material for high-temperature thermal barrier coatings, which provide thermal insulation to the superalloy components in gas turbines and jet engines. Oxygen vacancies induced by yttria substitutions are believed to be mainly responsible for the low thermal conductivity of YSZ due to their phonon scattering effect. However, high mobility of oxygen vacancies in YSZ leads to a rapid oxygen diffusion at high temperatures, therefore accelerates the failure of coatings by grain coarsening, sintering, and simultaneous oxidation of the underlying metallic bondcoat. In the present research, we further explored in the ZrO₂–Ln₂O₃ binary phase diagram and synthesized a series of ceramic materials with the chemical formula of Zr₃Ln₄O₁₂ (Ln = La, Gd, Y, Er, and Yb), in which more oxygen vacancies were involved and extremely low phonon thermal conductivities (1.3-1.6 W/m·K) were obtained, even approaching to the theoretical minimum. In addition, the mobility of these oxygen vacancies was remarkably suppressed by the lattice ordering with the decrease of Ln³⁺ radius, as confirmed by X-ray diffraction, Raman and transmission electron microscopy. Thus, the oxygen barrier property and sintering resistance were significantly enhanced accordingly, which makes Zr₃Ln₄O₁₂ compounds promising thermal barrier coating materials for next generation gas turbines and jet engines.     

Influence of solution-precursor plasma spray (SPPS) processing parameters on the mechanical and thermodynamic properties of 8 YSZ

8?mol% yttria stabilized zirconia (8YSZ) coatings are prepared by solution precursor plasma spray (SPPS) technique under different spray conditions. Phase analysis is performed using X-ray diffraction (XRD) and Electron back scattered diffraction (EBSD) techniques. Irrespective of the processing conditions and the heat treatment temperatures, all samples displayed cubic and tetragonal zirconia phases. Vertical and horizontal cracks appeared in the microstructural analysis of the coatings. Coating prepared under spray conditions having 40?mm distance between the spray gun and the sample exhibit high hardness, both at 0?h and 10?h heat treatment holding time. To explore the suitability of the coatings for the heat insulating applications, the thermal diffusivity and thermal conductivity are calculated. The coating with 42?mm distance between the spray gun and the sample displayed lowest thermal conductivity from 400 to 1200?℃.     

Microstructure and thermal properties of a promising thermal barrier coating: YTaO4

High temperature gas turbine sealing can increase the thermal efficiency of a gas turbine. In this paper, monoclinic phase YTaO₄ ceramics were fabricated via solid-state reaction. Phase composition and microstructures of the high-temperature-sintered YTaO₄ ceramics were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman Spectroscopy. Specific heat capacity rose gradually as temperature increased, due to volumetric expansion and phonon excitations. The thermal diffusivities and conductivities decreased significantly due to the effects of the porosity and phonon scattering. However, the thermal conductivities of the specimens were lower than that of 7–8 wt% yttria-stabilized zirconia (7-8YSZ), and YTaO₄ ceramics have better thermal stability than current (TBCs) material. The Vickers hardnesses of YTaO₄ ceramics as a function of sintering temperature were lower than that of 8YSZ, indicating YTaO₄ has better fracture toughness and thermal tolerance. The results demonstrate that YTaO₄ ceramics would be an excellent candidate for use as a thermal barrier coating material for high temperature gas turbines.     

Characterization of multi-scale synergistic toughened nanostructured YSZ thermal barrier coatings: From feedstocks to coatings

The nanostructured 8YSZ thermal barrier coatings were deposited by atmospheric plasma spraying onto K417 G nickel-based superalloy with high velocity oxygen fuel sprayed NiCoCrAlYCe bond-coat using as-prepared nanostructured t´-Zr_0.9Y_0.1O_1.95 feedstocks for the first time. The microstructure and mechanical properties of nanostructured and conventional 8YSZ coatings were comparatively investigated systematically. The results revealed that both coatings were composed of t´-Zr_0.9Y_0.1O_1.95 phase and the formation mechanism of t´ phase was elucidated. The nanostructured 8YSZ coatings demonstrated typical bi-modal microstructure, whereas the conventional 8YSZ coatings exhibited mono-modal microstructure. Furthermore, the bi-modal microstructure of nanostructured 8YSZ coatings was analysed by elastic modulus and nanohardness Weibull distribution plots. The high and low slopes in Weibull distribution plots corresponded to unmelted and melted regions of nanostructured 8YSZ coatings, respectively. The fracture toughness and bonding strength of nanostructured coatings were higher than that of conventional 8YSZ coatings. Finally the reasons were explained in detail.     

Development of thermal insulating material with low emissivity and high-temperature stability

In a previous study, we demonstrated that porous magnesium aluminate spinels, MgAl₂O₄, with two different pore size ranges (diameter = 0.05-1 μm and 1-5 μm) exhibited thermal conductivities of less than 0.3 W/(m K) in the high-temperature region of 1000°C-1500°C. In contrast, thermal insulating materials that are stable at even higher temperatures would offer further improved thermal efficiency and energy savings. Therefore, we investigated lanthanum hexaaluminate, LaAl₁₁O₁₈, with the expectation that its plate-like grain morphology would allow stable retention of its porosity at high temperatures. A process was developed for generating pores with the desired dimensions for use of the thermal insulating materials at high temperatures. The heat transfer behavior of these materials was evaluated via optical measurements. Herein, we report the structures and thermal properties of the obtained porous ceramics, including determination of the thermal emissivity measurements, to demonstrate their superior high-temperature thermal insulating properties.     

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.     

Microstructure analyses and thermophysical properties of nanostructured thermal barrier coatings

Nanostructured 8 wt% yttria partially stabilized zirconia coatings were deposited by air plasma spraying. Transmission electron microscopy, scanning electron microscopy, and X-ray diffraction were carried out to analyze the as-sprayed coatings and powders. Mercury intrusion porosimetry was applied to analyze the pore size distribution. Laser flash technique and differential scanning calorimetry were used to examine the thermophysical properties of the nanostructured coatings. The results demonstrate that the as-sprayed nanostructured zirconia coatings consist of the nonequilibrium tetragonal phase. The microstructure of the nanostructured coatings includes the initial nanostructure of powder and columnar grains. Moreover, micron-sized equiaxed grains were also exhibited in the nanostructured coatings. Their evolution mechanisms are discussed. The as-sprayed nanostructured zirconia coating shows a bimodal pore size distribution, and has a lower value of thermal conductivity than the conventional coating.     

Comparative study on thermal shock behavior of thick thermal barrier coatings fabricated with nano-based YSZ suspension and agglomerated particles

Two kinds of segmentation-crack structured YSZ thick thermal barrier coatings (TTBCs) were deposited by suspension plasma spraying (SPS) and atmospheric plasma spraying (APS) with nano-based suspension and agglomerated particles, respectively. The phase composition, microstructure evolution and failure behavior of both TBCs before and after thermal shock tests were systematically investigated. Microstructure of the APS coating exhibits typical segmentation-crack structure in the through-thickness direction, similar with the SPS coating. The densities of segmentation-crack in APS and SPS coatings were about 3 cracks mm⁻¹ and 4 cracks mm⁻¹_, respectively. The microstructure observation also showed that the columnar and equiaxed grains existed in the SPS coating. As for the thermal shock test, the spallation life of the APS TTBCs was 146 cycles, close to that of the SPS TTBCs (166 cycles). Failure of the APS coating is due to the spallation of fringe segments and splats.     

Wetting,infiltration and interaction behavior of CMAS towards columnar YSZ coatings deposited by plasma spray physical vapor

Thermal barrier coatings (TBCs) produced by electron beam physical vapor deposition (EB-PVD) or plasma spray (PS) usually suffer from molten calcium-magnesium-alumino-silicate (CMAS) attack. In this study, columnar structured YSZ coatings were fabricated by plasma spray physical vapor deposition (PS-PVD). The coatings were CMAS-infiltrated at 1250?°C for short terms (1, 5, 30?min). The wetting and spreading dynamics of CMAS melt on the coating surface was in-situ investigated using a heating microscope. The results indicate that the spreading evolution of CMAS melt can be described in terms of two stages with varied time intervals and spreading velocities. Besides, the PS-PVD columnar coating (～100?μm thick) was fully penetrated by CMAS melt within 1?min. After the CMAS attack for 30?min, the original feathered-YSZ grains (tetragonal phase) in both PS-PVD and EB-PVD coatings were replaced by globular shaped monoclinic ZrO₂ grains in the interaction regions.     

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.     

Hot corrosion and thermal shock resistance of Dense-CYSZ/YSZ bilayer thermal barrier coatings systems applied onto Ni-base superalloy

Bilayer thermal barriers coatings of Dense Ceria-Yttria-Stabilized Zirconia (D-CYSZ)/Yttria-Stabilized Zirconia (YSZ) were deposited onto Inconel 625 using atmospheric plasma spray (APS). The thickness of the d-CYSZ layer varied (0, 50, 100, and 150 μm), but the total thickness of the system was kept at 300 μm. The thermo-mechanical resistance of the multilayer system was evaluated through thermal shock tests, in which the bilayer systems evaluated exceeded 500 cycles with percentages of delamination of the coating below 20 % of the exposed area and showed higher thermomechanical resistance than a conventional YSZ system. Hot corrosion (HC) resistance of the bilayer system was evaluated using a salt mixture of 32 wt.% Na₂SO₄ and 68 wt.% V₂O₅ at 900 °C. The systems with a d-CYSZ layer showed higher resistance to HC, exhibiting fewer changes into the microstructure and presence of the monoclinic phase despite the presence of vertical cracks in the microstructure.     

Evaluation of microstructure evolution of thermal barrier YSZ coating after thermal exposure

Understanding the microstructural transformation of plasma sprayed (APS) yttria-stabilized zirconia (YSZ) after experiencing the thermal shocking cycles is practically important for the coating optimization in terms of structure and performance. In this study, thermal shocking tests were conducted on the YSZ coated piston crown. The microscopic morphology and structure alteration across the YSZ coating interface over the piston crown was characterized by the ex-situ techniques. The results revealed that the YSZ coating primarily consisted of a stable tetragonal phase, without the monoclinic phase even after 800 cycles of thermal shocking. As the thermal shocking test continued, the pore number within the YSZ coating gradually decreased due to their spontaneous closure and the grain size correspondingly increased. Some visible cracks parallel to the interface consisting of YSZ and bonding layer happened at the localized regions of the YSZ coating. The stress state of YSZ coating was from originally tensile to compressive after thermal exposure, which helped prolonging the service lifetime of YSZ coating. In particular, the thermal shock resistance of plasma sprayed YSZ coated piston crown in association with the varying microstructure was also discussed.     

Rare-earth-tantalate high-entropy ceramics with sluggish grain growth and low thermal conductivity

A series of rare-earth-tantalate high-entropy ceramics ((5RE_0.2)Ta₃O₉, where RE = five elements chosen from La, Ce, Nd, Sm, Eu and Gd) were prepared by conventional sintering in air at 1500 ^°C for 10 h. The (5RE_0.2)Ta₃O₉ high-entropy ceramics exhibit an orthogonal structure and sluggish grain growth. No phase transition occurs in the test temperature of 25–1200 ^°C. The thermal conductivities of all (5RE_0.2)Ta₃O₉ ceramics are in the range of 1.14–1.98 W m^?1 K^?1 at a test temperature of 25–500 ^°C, approximately half of that of YSZ. The sample of (Gd_0.2Ce_0.2Nd_0.2Sm_0.2Eu_0.2)Ta₃O₉ exhibits a low glass-like thermal conductivity with a value of 1.14 W m^?1 K^?1 at 25 ^°C. The thermal expansion coefficient of (5RE_0.2)Ta₃O₉ ceramics ranges from 5.6 × 10^?6 to 7.8 × 10^?6 K^?1 at 25–800 ^°C, and their fracture toughness is high (3.09–6.78 MPa·m^1/2). The results above show that (5RE_0.2)Ta₃O₉ ceramics could be a promising candidate for thermal barrier coatings.     

Multi-component strategy for remarkable suppression of thermal conductivity in strontium diyttrium oxide: The case of high-entropy Sr(Y0.2Sm0.2Gd0.2Dy0.2Yb0.2)2O4 ceramic

Anti-spinel oxide SrY₂O₄ has attracted extensive attention as a promising host lattice due to its outstanding high-temperature structural stability and large thermal expansion coefficient (TEC). However, the overhigh thermal conductivity limits its application in the field of thermal barrier coatings. To address this issue, a novel high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic was designed and synthesized for the first time via the solid-state method. It is found that the thermal conductivity of Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ is reduced to 1.61 W·m⁻¹·K⁻¹, 53 % lower than that of SrY₂O₄ (3.44 W·m⁻¹·K⁻¹) at 1500 °C. Furthermore, reasonable TEC (11.53 ×10⁻⁶ K⁻¹, 25 °C ∼ 1500 °C), excellent phase stability, and improved fracture toughness (1.92 ± 0.04 MPa·m^1/2) remained for the high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic, making it a promising material for next-generation thermal barrier coatings.