New Thermal Barrier Coatings Based on Pyrochlore/YSZ Double-Layer Systems

Pyrochlore materials La₂Zr₂O₇ and Gd₂Zr₂O₇ have been used to produce thermal barrier coating systems by atmospheric plasma spraying. The materials have been applied as single-layer coatings with only a topcoat made of pyrochlore material. In addition, double-layer systems with a first layer of yttria-stabilized zirconia (YSZ) and a top layer made of pyrochlore material were produced. These systems have been tested in thermal cycling test rigs at surface temperatures between 1200-1450°C and the results were compared to the behavior of YSZ coatings. Single-layer coatings had a rather poor thermal cycling performance. On the other hand, double-layer systems showed similar results to YSZ coatings at temperatures below about 1300°C. At higher temperatures the double-layer coatings produced from our own powders revealed excellent thermal cycling behavior. At the highest test conditions, lifetime was thereby orders of magnitude better than that of YSZ coatings. Results indicate that an increase of the maximum surface temperature in gas turbines by at least 100 K becomes possible with the new coatings. Coatings produced from commercial powders showed a somewhat reduced performance.     

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.     

Thermal Barrier Coatings Design with Increased Reflectivity and Lower Thermal Conductivity for High-Temperature Turbine Applications

High reflectance thermal barrier coatings consisting of 7% Yittria-Stabilized Zirconia (7YSZ) and Al₂O₃ were deposited by co-evaporation using electron beam physical vapor deposition (EB-PVD). Multilayer 7YSZ and Al₂O₃ coatings with fixed layer spacing showed a 73% infrared reflectance maxima at 1.85 μm wavelength. The variable 7YSZ and Al₂O₃ multilayer coatings showed an increase in reflection spectrum from 1 to 2.75 μm. Preliminary results suggest that coating reflectance can be tailored to achieve increased reflectance over a desired wavelength range by controlling the thickness of the individual layers. In addition, microstructural enhancements were also used to produce low thermal conductive and high hemispherical reflective thermal barrier coatings (TBCs) in which the coating flux was periodically interrupted creating modulated strain fields within the TBC. TBC showed no macrostructural differences in the grain size or faceted surface morphology at low magnification as compared with standard TBC. The residual stress state was determined to be compressive in all of the TBC samples, and was found to decrease with increasing number of modulations. The average thermal conductivity was shown to decrease approximately 30% from 1.8 to 1.2 W/m-K for the 20-layer monolithic TBC after 2 h of testing at 1316°C. Monolithic modulated TBC also resulted in a 28% increase in the hemispherical reflectance, and increased with increasing total number of modulations.     

Dense Alumina–Zirconia Coatings Using the Solution Precursor Plasma Spray Process

For the first time, dense coatings have been made by the solution precursor plasma spray (SPPS) process. The conditions are described for the deposition of dense Al₂O₃–40 wt% 7YSZ (yttria-stabilized zirconia) coatings; the coatings are characterized and their thermal stability is evaluated. X-ray diffraction analysis shows that the as-sprayed coating is composed of α-Al₂O₃ and tetragonal ZrO₂ phases with grain sizes of 72 and 56 nm, respectively. The as-sprayed coating has a 95.6% density and consists of ultrafine splats (1–5 μm) and unmelted spherical particles (<0.5 μm). The lamellar structure, typical of conventional plasma-sprayed coatings, is absent at the same scale in the SPPS coating. The formation of a dense Al₂O₃–40 wt% 7YSZ coating is favored by the lower melting point of the eutectic composition, and resultant superheating of the molten particles. Phase and microstructural thermal stabilities were investigated by heat treatment of the as-sprayed coating at temperatures of 1000°–1500°C. No phase transformation occurs, and the grain size is still in the nanometer range after the 1500°C exposure for 2 h. The coating hardness increases from 11.8 GPa in the as-coated condition to 15.8 GPa following 1500°C exposure due to a decrease in coating porosity.     

Reaction Kinetics and Mechanisms between La0.65Sr0.3MnO3 and 8 mol% Yttria-Stabilized Zirconia

The reaction kinetics and mechanisms between 8 mol% yttria-stabilized zirconia (YSZ) and 30 mol% Sr-doped lanthanum manganite (La_0.65Sr_0.30MnO₃, LSM) with A-site deficiency for the application of planar solid oxide fuel cells (SOFCs) were investigated. The LSM/YSZ green tapes were cofired from 1200° to 1400°C for 1 to 48 h and then annealed at 1000°C for up to 1000 h. The results showed that the diffusion of manganese cations first caused the amorphization of YSZ, and then the formation of small La₂Zr₂O₇ (LZ) or SrZrO₃ (SZ) crystals if treated for a longer time at 1400°C. The ambipolar diffusion of the Mn–O pair, transported through the migration of oxygen vacancy, plays an important role in the formation of secondary phases. The diffusion of LSM to YSZ and substitution of Mn for Zr both result in the enhanced concentration of oxygen vacancy, leading to the formation of a void-free zone (VFZ). No additional reaction products in annealed LSM/YSZ specimens, treated at 1000°C for 1000 h, were detected. The interfacial reactions, detailed reaction kinetics, and mechanisms are reported.     

Degradation Mechanisms of ZrO2–8 wt% Y2O3/Ni-22Cr-10Al-1Y Thermal Barrier Coatings

Duplex ZrO₂–8 wt% Y₂O₃/Ni-22Cr-10Al-1Y thermal barrier coatings (TBCs) on Mar-M247 superalloy were tested under different operating conditions within the temperature range 1000° to 1150°C. Results of experiments in this study show that oxidation of bond coatings is the dominant TBC degradation mechanism whereas the operationally induced stresses exert a conjugate effect. The mechanisms of sintering and phase transformation of top coatings do not contribute to failure of TBCs within the temperature range studied. NiO and Ni(Cr,Al)₂O₄ grown on the surfaces of the bond coatings seem to accelerate spalling of the top coatings along a top coating/bond coating out-grown oxide interface. However, it is also concluded that the lifetime of TBCs is not directly related to a critical specific weight gain under thermal cycling conditions.     

High-Temperature Stability of Lanthanum Orthophosphate (Monazite) on Silicon Carbide at Low Oxygen Partial Pressures

The stability of lanthanum orthophosphate (LaPO₄) on SiC was investigated using a LaPO₄-coated SiC fiber at 1200°–1400°C at low oxygen partial pressures. A critical oxygen partial pressure exists below which LaPO₄ is reduced in the presence of SiC and reacts to form La₂O₃ or La₂Si₂O₇ and SiO₂ as the solid reaction products. The critical oxygen partial pressure increases from ∼0.5 Pa at 1200°C to ∼50 Pa at 1400°C. Above the critical oxygen partial pressure, a thin SiO₂ film, which acts as a reaction barrier, exists between the SiC fiber and the LaPO₄ coating. Continuous LaPO₄ coatings and high strengths were obtained for coated fibers that were heated at or below 1300°C and just above the critical oxygen partial pressure for each temperature. At temperatures above 1300°C, the thin LaPO₄ coating becomes morphologically unstable due to free-energy minimization as the grain size reaches the coating thickness, which allows the SiO₂ oxidation product to penetrate the coating.     

Novel Deposition of Columnar Y3Al5O12 Coatings by Electrostatic Spray-Assisted Vapor Deposition

A novel and cost-effective electrostatic spray-assisted vapor deposition (ESAVD) was used to deposit Y₃Al₅O₁₂ (YAG) coatings. Polycrystalline single-phase Y₃Al₅O₁₂ coatings were synthesized using the ESAVD method in an open atmosphere at 650°C, and then annealed at 700°–900°C for 1 h. The ESAVD process involves the decomposition and chemical reactions of charged aerosol in vapor phase. The low-temperature coating deposition characteristics of the ESAVD process using a suitable sol precursor decreases the reaction and crystallization temperatures for forming Y₃Al₅O₁₂ coatings. The microstructure of the Y₃Al₅O₁₂ coating prepared using the ESAVD method is columnar and such strain-resistance microstructure could be useful for thermal barrier coating applications.     

Phase Formation and Stability in Reactively Sputter Deposited Yttria-Stabilized Zirconia Coatings

Yttria-stabilized zirconia (YSZ) coatings were produced by reactively cosputtering metallic zirconium and yttrium targets in an argon and oxygen plasma using a system with multiple magnetron sputtering sources. Coating crystal structure and phase stability, as functions of Y₂O₃ content, substrate bias, and annealing temperature, were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results demonstrated that highly (111)-oriented tetragonal and cubic zirconia structures were formed in 2 and 4.5 mol% Y₂O₃ coatings, respectively, when the coatings were grown with an applied substrate bias. Conversely, coatings deposited with no substrate bias had random tetragonal and cubic structures. XRD analysis of annealed coatings showed that the cubic zirconia in 4.5 mol% Y₂O₃ coatings exhibited structural stability at temperatures up to 1200°C. Transformation of the tetragonal to monoclinic phase occurred in 2 mol% Y₂O₃ coating during high-temperature annealing, with the fraction of transformation dependent on bias potential and annealing temperature.     

Chemical Interactions between La-Sr-Mn-Fe-O-Based Perovskites and Yttria-Stabilized Zirconia

Orthoferrite-based perovskites are of interest as materials for the cathode in solid oxide fuel cells (SOFCs). Therefore, the chemical compatibility between perovskites of the composition (La_1−xSr_x)_zFe_1−yMn_yO_3−δ (0 # x # 0.3; 0.2 # y # 1; z = 0.90, 0.95, 1.00) and the solid electrolyte zirconia (ZrO₂) doped with 8 mol% yttria (Y₂O₃) (8YSZ) has been investigated. Powder mixtures of the two materials have been annealed at different temperatures. The formation of monoclinic ZrO₂ at 1000°C, as well as of La₂Zr₂O₇ and SrZrO₃ at 1400°C, has been determined in some samples. The reactions that are observed are discussed, with respect to the thermodynamic activities, tolerance factor, and oxygen-ion migration energies. Some perovskite compositions seem to be compatible with Y₂O₃-stabilized ZrO₂ (YSZ), thereby offering the possibility to use orthoferrite-based perovskites in SOFCs with a solid electrolyte made of YSZ.     

Intermediate Phase Development in Phosphorus-Doped Barium Titanate

In the present work, the phase formation and thermal evolution in phosphorus-doped BaTiO₃ have been studied using differential thermal analysis, X-ray diffractometry, scanning electron microscopy coupled with energy-dispersive spectroscopy, transmission electron microscopy, and high-temperature nuclear magnetic resonance. Phosphorus cations that are incorporated from ester phosphate form a surface layer that covers the BaTiO₃ particles. This layer acts as a reactive coating during sintering. Phosphorus-doped BaTiO₃ samples that have been treated at temperatures of 650°–900°C show the presence of crystalline Ba₂TiP₂O₉ and/or Ba₃(PO₄)₂ phases. The appearance of secondary phases is dependent on the cooling rate. Higher temperatures (900°–1200°C) result in the presence of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles. As a consequence, the remaining titanium-rich BaTiO₃ drives the formation of a liquid phase at temperatures >1200°C. In regard to the reported sintering behavior of P⁵⁺-doped BaTiO₃, the formation of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles could be the origin of the improved porosity coalescence and removal that is observed at the earlier stages of sintering.     

Stresses and Microstructural Development of Thermal Barrier Coatings Using AIP/D-gun Two-Step Processing

After depositing a Ni–32Co–20Cr–8Al–0.5Y–1Si–0.03B (wt%) bond coat on a Ni-base superalloy using arc ion plating (AIP), a ceramic top coat with hollow spherical powder of ZrO₂–8 wt%Y₂O₃ (HSP–YSZ) was deposited using detonation gun (D-gun) spraying. Thermal exposure behaviors of thermal barrier coatings (TBCs) were investigated at 1100°C. The thermal growth oxides (TGO) layer thickened and became more undulated during thermal exposure. Yttrium aluminum garnet (YAG) was observed within TGO, which produced thickness imperfections and thus aided to build up out-of-plane stresses. As a result, radial cracks initiated at the defects around TGO imperfections and separation developed through crack nucleation, propagation, and coalescence at the weaker TGO/bond coat interface. With further thermal exposure, coalescence of interfacial separations created a connected crack. The TBC detached and final failure occurred at the TGO/bond coat interface, leading to spallation of TBC when cooling to ambient. The stress distributions in the TGO layer with different thermal exposure times were also measured using luminescence spectroscopy. The stresses were independent of time after a transient period from θ-Al₂O₃ to α-Al₂O₃ scale. It is suggested that the lifetime of AIP/D-gun TBCs with an HSP–YSZ coat is controlled by the initiation and linking of a sub-critical interfacial crack.     

Yb2O3 and Gd2O3 doped strontium zirconate for thermal barrier coatings

Yb₂O₃ (10 mol%) and Gd₂O₃ (20 mol%) doped SrZrO₃ was investigated as a material for thermal barrier coating (TBC) applications. The thermal expansion coefficients (TECs) of sintered bulk Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 were recorded by a high-temperature dilatometer and revealed a positive influence on phase transformations of SrZrO₃ by doping Yb₂O₃ or Gd₂O₃. The results for the thermal conductivities of Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 indicated that both dopants can reduce the thermal conductivity of SrZrO₃. Mechanical properties (Young's modulus, hardness, and fracture toughness) of dense Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 showed lower Young's modulus, hardness and comparable fracture toughness with respect to YSZ. The cycling lifetimes of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ and Sr(Zr_0.8Gd_0.2)O_2.9/YSZ double layer coatings (DLC), which were prepared by plasma spraying, were comparable to that of YSZ at operating temperatures <1300 °C. However, the cycling lifetime of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ DLC was 25% longer, whereas Sr(Zr_0.8Gd_0.2)O_2.9/YSZ DLC had a shorter lifetime compared to the optimized YSZ coating at operating temperatures >1300 °C.     

Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: II, Diffusion Couples

Formation of secondary phases and diffusion of cations in diffusion couples of yttria-stabilized zirconia and lanthanum manganite substituted with 0 to 60 mol% strontium have been studied by scanning electron microscopy and energy dispersive X-ray spectroscopy. Only the primary phases were observed after 120 h at 1200°C, while formation of secondary phases was identified already after 1 h heat treatment at 1350°C. The phase composition of the reaction layer altered from La₂Zr₂O₇ to SrZrO₃ at increasing Sr content in La _x Sr_{1- x} MnO₃. The thickness of the reaction layer was increasing with heat treatment time. In diffusion couples of La_0.4Sr_0.6MnO₃ formation of manganese oxide was observed in the perovskite layer after 1 h heat treatment at 1350°C, while isolated grains of SrZrO₃ relatively deep inside the zirconia were observed after longer heat treatment time. Diffusion of Mn into zirconia was observed preferenced along grain boundaries in the early stage of the interface reaction.     

Residual Stress and Microstructural Evolution in Tantalum Oxide Coatings on Silicon Nitride

Due to its coefficient of thermal expansion (CTE) and phase stability up to 1360°C, tantalum oxide (Ta₂O₅) was identified and investigated as a candidate environmental barrier coating for silicon nitride-based ceramics. Ta₂O₅ coatings were plasma sprayed onto AS800, a silicon nitride ceramic from Honeywell International, and subjected to static and cyclic heat treatments up to 1200°C in air. Cross-sections from coated and uncoated substrates were polished and etched to reveal the effect of heat treatments on microstructure and grain size. As-sprayed coatings contained vertical cracks that healed after thermal exposure. Significant grain growth that was observed in the coatings led to microcracking due to the anisotropic CTE of Ta₂O₅. High-energy X-ray diffraction was used to determine the effect of heat treatment on residual stress and phases. The uncoated substrates were found to have a surface compressive layer before and after thermal cycling. Coating stresses in the as-sprayed state were found to be tensile, but became compressive after heat treatment. The microcracking and buckling that occurred in the heat-treated coatings led to stress relaxation after long heat treatments, but ultimately would be detrimental to the function of the coating as an environmental barrier by affording open pathways for volatile species to reach the underlying ceramic.     

Thermal Stability of Hexaaluminate Film Coated on SiC Substrate for High-Temperature Catalytic Application

A coating of barium hexaaluminate (Ba_0.75Al_11.0O_17.25) on an α-SiC substrate and the thermal stability of the formed film were investigated for a high-temperature catalytic application. The film prepared by sol coating consisted of BaAl₂Si₂O₈ and α-Al₂O₃ phases and always contained many cracks or exfoliations after heating at 1200C. A hexaaluminate porous film was successfully formed by slurry coating without void formation at the interface between the film and the substrate and exfoliation due to the formation of the intermediate layer after heating at 1200°C. The microstructure of the film remained unchanged, even after heating at 1300°C.     

Thermochemical Interaction of Thermal Barrier Coatings with Molten CaO–MgO–Al2O3–SiO2 (CMAS) Deposits

Thermal barrier coatings (TBCs) are increasingly susceptible to degradation by molten calcium–magnesium alumino silicate (CMAS) deposits in advanced engines that operate at higher temperatures and in environments laden with siliceous debris. This paper investigates the thermochemical aspects of the degradation phenomena using a model CMAS composition and ZrO₂–7.6%YO_1.5 (7YSZ) grown by vapor deposition on alumina substrates. The changes in microstructure and chemistry are characterized after isothermal treatments of 4 h at 1200°–1400°C. It is found that CMAS rapidly penetrates the open structure of the coating as soon as melting occurs, whereupon the original 7YSZ dissolves in the CMAS and reprecipitates with a different morphology and composition that depends on the local melt chemistry. The attack is minimal in the bulk of the coating but severe near the surface and the interface with the substrate, which is also partially dissolved by the melt. The phase evolution is discussed in terms of available thermodynamic information.     

A Crystalline Si3N4/Amorphous Si3N4 Composite

A composite consisting of elongated α-Si₃N₄ crystallites (5–50 (Am in diameter) embedded in an amorphous Si₃N₄ matrix was synthesized by chemical vapor deposition. The hardness and indentation fracture toughness of the amorphous matrix and of the composite have been evaluated at temperatures from ambient to 1200°C. It was found that the crystallites have relatively little influence on the hardness and indentation fracture toughness when the surrounding matrix is amorphous. However, a 1400°C heat treatment of the material results in a matrix consisting of small crystals (100 nm in diameter) surrounded by carbon-containing regions which appear to be amorphous in the TEM; TEM and EELS in nearby triple points revealed the presence of amorphous carbon. After heat treatment, the indentation fracture toughness at ambient and at 1200°C is increased due to extensive microcracking. The Vickers hardness at 1200°C also increased significantly as a result of the heat treatment. The relationship between the mechanical properties and the microstructure is discussed.     

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.     

Improved properties of scandia and yttria co-doped zirconia as a potential thermal barrier material for high temperature applications

Due to the limited temperature capability of current YSZ thermal barrier coating (TBC) material, considerable effort has been expended world-wide to research new candidates for TBC applications above 1200?°C. Our study suggested that Sc₂O₃ and Y₂O₃ co-doped ZrO₂ (ScYSZ) had excellent t’ phase stability even after annealed at 1500?°C for 336?h. The thermal expansion coefficient of ScYSZ was comparable to the value of YSZ. The thermal conductivity of fully dense ScYSZ was in the range of 2.13–1.91?W?m^?1?K^?1 (25–1300?°C), approximately 25% lower than that of YSZ. Although the fracture toughness of dense ScYSZ was slightly lower than YSZ, an evident decline in elastic modulus was found. Additionally, thermal cycling lifetime of plasma sprayed ScYSZ coating (914 cycles) at 1300?°C was about 2.6 times longer than its YSZ counterpart. The superior comprehensive properties confirm that ScYSZ is a prospective candidate material for high-temperature TBC application.