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.     

Mechanical Properties/Database of Plasma-Sprayed ZrO2-8wt% Y2O3 Thermal Barrier Coatings

Mechanical behavior of free-standing, plasma-sprayed ZrO₂-8wt% Y₂O₃ thermal barrier coatings, including strength, fracture toughness, fatigue, constitutive relation, elastic modulus, and directionality, have been determined under various loading-specimen configurations. This paper presents and describes a summary of mechanical properties of the plasma-sprayed coating material to provide them as a design database.     

Homogeneous ZrO2–Al2O3 Composite Prepared by Nano-ZrO2 Particle Multilayer-Coated Al2O3 Particles

ZrO₂–Al₂O₃ nanocomposite particles were synthesized by coating nano-ZrO₂ particles on the surface of Al₂O₃ particles via the layer-by-layer (LBL) method. Polyacrylic acid (PAA) adsorption successfully modified the Al₂O₃ surface charge. Multilayer coating was successfully implemented, which was characterized by ξ potential, particle size. X-ray diffraction patterns showed that the content of ZrO₂ in the final powders could be well controlled by the LBL method. The powders coated with three layers of nano-ZrO₂ particles, which contained about 12 wt% ZrO₂, were compacted by dry press and cold isostatically pressed methods. After sintering the compact at 1450°C for 2 h under atmosphere, a sintered body with a low pore microstructure was obtained. Scanning electron microscopy micrographs of the sintered body indicated that ZrO₂ was well dispersed in the Al₂O₃ matrix.     

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.     

Ta2O5/Nb2O5 and Y2O3 Co-doped Zirconias for Thermal Barrier Coatings

Zirconia doped with 3.2–4.2 mol% (6–8 wt%) yttria (3–4YSZ) is currently the material of choice for thermal barrier coating topcoats. The present study examines the ZrO₂-Y₂O₃-Ta₂O₅/Nb₂O₅ systems for potential alternative chemistries that would overcome the limitations of the 3–4YSZ. A rationale for choosing specific compositions based on the effect of defect chemistry on the thermal conductivity and phase stability in zirconia-based systems is presented. The results show that it is possible to produce stable (for up to 200 h at 1000°–1500°C), single (tetragonal) or dual (tetragonal + cubic) phase chemistries that have thermal conductivity that is as low (1.8–2.8W/m K) as the 3–4YSZ, a wide range of elastic moduli (150–232 GPa), and a similar mean coefficient of thermal expansion at 1000°C. The chemistries can be plasma sprayed without change in composition or deleterious effects to phase stability. Preliminary burner rig testing results on one of the compositions are also presented.     

Phase Relationships in the ZrO2-Sc2O3 and ZrO2-In2O3 Systems

Zirconia-rich subsolidus phase relationships in the ZrO₂–Sc₂O₃ and ZrO₂–In₂O₃ systems were investigated. Phase inconsistencies in the ZrO₂–Sc₂O₃ system resulted from a diffusionless cubic-to-tetragonal ( t' ) phase transformation not being recognized in the past. Through three different measuring techniques, along with microstructural observations, the solubility limits of the tetragonal and cubic phases were determined.     

Phase Equilibria in the Pseudoternary System ZrO2−Y2O3−Cr2O3 at 1600°C in Air

The pseudoternary system ZrO₂-Y₂O₃-Cr₂O₃ was studied at 1600°C in air by the quenching method. Only one intermediate compound, YCrO₃, was observed on the Y₂O₃−Cr₂O₃ join. ZrO₂ and Y₂O₃ formed solid solutions with solubility limits of 47 and 38 mol%, respectively. The apex of the compatibility triangle for the cubic ZrO₂, Cr₂O₃, and YCrO₃ three-phase region was located at =17 mol% Y₂O₃ (83 mol% ZrO₂). Below 17 mol% Y₂O₃, ZrO₂ solid solution coexisted with Cr₂O₃. Cr₂O₃ appears to be slightly soluble in ZrO₂(ss).     

Al2O3–ZrO2–SiO2 Ternary Glasses for Molybdenum Oxidation Barriers

The wettability of binary and ternary glasses belonging to SiO₂–Al₂O₃–ZrO₂ diagram has been studied using the sessile drop technique at 1750° and 1800°C. The ternary SiO₂–Al₂O₃–ZrO₂ (90–5–5 wt%) glass has proved to be well appropriated as a molybdenum oxidation barrier coating. The addition of 5 wt% of MoO₂ slightly improves its wettablity at higher temperatures without affecting its oxidation barrier properties. The Mo comes into the glass network as a mixture of Mo⁵⁺, Mo⁴⁺, and Mo⁶⁺. After oxidation at 1000°C in oxygen atmosphere, the molybdenum remains in the glass network as Mo⁶⁺.     

Novel Mg2Zr5O12/Mg2Zr5O12–ZrO2–MgF2 Gradient Layer Coating on Magnesium Formed by Microarc Oxidation

A novel Mg₂Zr₅O₁₂-based coating on magnesium was formed by microarc oxidation (MAO) in a K₂ZrF₆-containing electrolyte. The structure of the coating was examined by X-ray diffraction using the grazing angle method, scanning electron microscopy, and transmission electron microscopy. The friction and wear properties of the MAO-coated and -uncoated Mg samples were evaluated in a ball-on-disk testing system. The corrosion resistance of the coating in a 3.5% NaCl solution was investigated by the potentiodynamic polarization test. The coating is relatively dense and composed of a Mg₂Zr₅O₁₂–ZrO₂–MgF₂ inner layer and a nanocrystalline Mg₂Zr₅O₁₂ outer layer with a maximum hardness of 1240 Hv. The friction coefficient of the coating against Si₃N₄ is 0.35 under a dry-sliding condition. The corrosion resistance of the magnesium substrate is improved considerably by MAO treatment. The corrosion potential of the Mg₂Zr₅O₁₂-coated sample is −1.43 V with a current density as low as 7.06 × 10⁻⁸ A/cm². It is expected that the coating can considerably protect magnesium from wear and corrosion.     

Rapid Rate Sintering of Nanocrystalline ZrO2−3 mol% Y2O3

Conventional ramp-and-hold sintering with a wide range of heating rates was conducted on submicrometer and nanocrystalline ZrO₂–3 mol% Y₂O₃ powder compacts. Although rapid heating rates have been reported to produce high density/fine grain size products for many submicrometer and smaller starting powders, the application of this technique to ZrO₂–3 mol% Y₂O₃ produced mixed results. In the case of submicrometer ZrO₂–3 mol% Y₂O₃, neither densification nor grain growth was affected by the heating rate used. In the case of nanocrystalline ZrO₂–3 mol% Y₂O₃, fast heating rates severely retarded densiflcation and had a minimal effect on grain growth. The large adverse effect of fast heating rates on the densification of the nanocrystalline powder was traced to a thermal gradient/differential densification effect. Microstructural evidence suggests that the rate of densification greatly exceeded the rate of heat transfer in this material; consequently, the sample interior was not able to densify before being geometrically constrained by a fully dense shell which formed at the sample exterior. This finding implies that rapid rate sintering will meet severe practical constraints in the manufacture of bulk nanocrystalline ZrO₂–3 mol% Y₂O₃ specimens.     

Structure of Incoherent ZrO2/Al2O3 Interfaces

High-resolution electron microscopy was used to image incoherent ZrO₂/Al₂O₃ interfaces in ZrO₂-toughened Al₂O₃ containing intragranular ZrO₂. These particles are generally spherical but are sometimes faceted. High-resolution electron micrographs provide atomic-level information on the interfacial structure. For spherical particles, both ledgelike images and misfit dislocation-like images accommodated the lattice misfit, depending on the orientation of the interface, while faceted particles imply at least one low-energy ZrO₂/Al₂O₃ interface.     

In Situ Synthesis of ZrO2/ZrW2O8 Composites With Near-Zero Thermal Expansion

In this paper, ZrO₂ and WO₃ were used as the raw materials to prepare ZrO₂/ZrW₂O₈ composites by in situ reaction method and the thermal expansion property of the composites was studied. This novel method included a heating step up to 1473 K for 24 h, which combines the synthesizing and sintering of ZrW₂O₈. The result indicates that ZrO₂/ZrW₂O₈ composite shows near-zero thermal expansion when the weight ratio of ZrO₂ and WO₃ is 2.5:1. Compared with composites prepared previously by non-reactive sintering of ZrO₂ and ZrW₂O₈, the composites show higher relative density and lower porosity.     

Homogeneous Fabrication of Al2O3–ZrO2–SiC Whisker Composite by Surface-Induced Coating

Al₂O₃–ZrO₂–SiC whisker composites were prepared by surface-induced coating of the precursor for the ZrO₂ phase on the kinetically stable colloid particles of Al₂O₃ and SiC whisker. The fabricated composites were characterized by a uniform spatial distribution of ZrO₂ and SiC whisker phases throughout the Al₂O₃ matrix. The fracture toughness values of the Al₂O₃–15 vol% ZrO₂–20 vol% SiC whisker composites (∼12 MPa.m^1/2) are substantially greater than those of comparable Al₂O₃–SiC whisker composites, indicating that both the toughening resulting from the process zone mechanism and that caused by the reinforced SiC whiskers work simultaneously in hot-pressed composites.     

Subsolidus Equilibria in the System ZrO2-WO3-P2O5

The existence of stable and metastable forms of 2ZrO₂·P₂O₅ and the subsolidus phase relations in the system ZrO₂-ZrP₂O₇ were confirmed before investigation of the ternary system. The synthesis and thermal behavior of ZrW₂O₈ were reinvestigated, and the system WO₃-P₂O₅ was examined cursorily. A ternary compound, 2ZrO₂·WO₃·P₂O₅, was found, and compatibility triangles for the system between 1105° and 1150°C were established. The ternary compound is compatible with ZrO₂, WO₃, and three binary compounds, giving rise to five composition triangles. In addition, ZrP₂O₇, WO₃, and "W₂O₃(PO₄)₂" were compatible.     

Microstructural Characterization of ZrO2 Particles Prepared by Reaction of Gaseous ZrCl4 with Fe2O3

The microstructure of ZrO₂ fine particles produced by a novel synthesis method at 450° and 950°C has been studied. The fundamentals of the synthesis method, which involves both chemical and diffusion phenomena, are presented. The method is based on mass transport through the gaseous phase between metallic zirconium and Fe₂O₃ powder. The mass-transporting chemical species are zirconium and iron chlorides. This article focuses on the microstructure and structure of ZrO₂ particles formed by the reaction between gaseous ZrCl₄ and solid Fe₂O₃, which is a relevant reaction step that occurs during the synthesis process. The resulting ZrO₂ crystals grown on Fe₂O₃ particles have been analyzed using transmission electron microscopy. Microstructural characterization has been complemented by X-ray diffractometry analysis. Tetragonal-ZrO₂ is produced at 450°C and monoclinic-ZrO₂ single crystals are produced at 950°C.     

Effect of Nb2O5 Alloying on Thermal Expansion Anisotropy of 2 mol% Y2O3-Stabilized Tetragonal ZrO2

Tetragonal ZrO₂ ( t -ZrO₂) solid solutions were prepared with addit ons of 2 mol% Y₂O₃ plus up to 0.45 mol% Nb₂O₅. The thermal expansion coefficients in both the a- and c -axis lattice directions increased with Nb₂O₅ alloying and the thermal expansion in the c -axis direction was greater than that in the a -axis direction over the entire composition range. This anisotropic thermal expansion behavior was related to the 4-fold coordination of Nb⁵⁺ with oxygen ions in t -ZrO₂ solid solutions in the system ZrO₂–Y₂O₃–Nb₂O₅. The fracture toughness continuously increased with Nb₂O₅ alloying and suggested that the c/a axial ratio is a more significant factor than the internal stress that arises from the thermal expansion anisotropy, in the determination of the transformability of t -ZrO₂ in this system.     

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.     

Control of the Interfacial Reactions in Nb-Toughened MoSi2

Toughening of MoSi₂ for high-temperature applications can be achieved by incorporating ductile refractory-metal reinforcements, provided that a coating is applied to prevent interdiffusion and reaction between the matrix and the reinforcements. In the present study, three different coating techniques for applying a thin Al₂O₃ film on Nb reinforcements as a diffusion barrier have been studied. The techniques consisted of (i) sol-gel coating; (ii) physical vapor deposition (PVD); (iii) hot dipping in molten Al, followed by anodizing Al to form Al₂O₃. The processing parameters for the techniques were evaluated and the effectiveness of each coating as a diffusion barrier was assessed. For the present MoSi₂ matrix which contains SiO₂, PVD coatings provided the most effective diffusion barrier for processing MoSi₂/Nb composites.     

Phase Relations and Ordering in the Systems MgO-Y2O3-ZrO2 and CaO-MgO-ZrO2

The phase relations in the systems MgO-Y₂O₃-ZrO₂ and CaO-MgO-ZrO₂ were established at 1220° and 1420°C. The system MgO-Y₂O₃-ZrO₂ possesses a much-larger cubic ZrO₂ solid solution phase field than the system CaO-MgO-ZrO₂ at both temperatures. The ordered δ phase (Zr₃Y₄O₁₂) was found to be stable in the system ZrO₂-Y₂O₃ at 1220°C. Two ordered phases φ₁ (CaZr₄O₉) and φ₂ (Ca₆Zr₁₉O₄₄) were stable at 1220°C in the system ZrO₂-CaO. At 1420°C no ordered phase appears in either system, in agreement with the previously determined temperature limits of the stability for the δ, φ₁, and φ₂ phases. The existence of the compound Mg₃Y_zO₆ could not be confirmed.     

Thermal Expansions and Chemical Durabilities of Yttria–Aluminosilicate Glasses Containing Na2O and ZrO2

Properties of glasses in the system Y₂O₃–Al₂O₃–SiO₂ containing Na₂O and ZrO₂ were investigated. The difference between the thermal expansion coefficients (Δα) at temperatures above T _g and those below T _g, microhardness, density, and chemical durability were measured in relation to the Al₂O₃/Y₂O₃ molar ratio. These glasses were found to have a smaller value of Δα than that of a commercial coating glass.