Thermal barrier coating resistant to CMAS corrosion and preparation method thereof

Abstract

The invention provides a CMAS corrosion resistant thermal barrier coating and a preparation method thereof.The CMAS corrosion resistant thermal barrier coating comprises a metal bonding layer, an yttria-stabilized zirconia layer and a multi-component rare earth zirconate layer, and the yttria-stabilized zirconia layer and the multi-component rare earth zirconate layer are sequentially arranged on the metal bonding layer. The multi-component rare earth cerate layer and / or the CMAS barrier layer are / is sequentially arranged on the multi-component rare earth zirconate layer; the multi-component rare earth zirconate layer comprises multi-component rare earth zirconate, the chemical formula of the multi-component rare earth zirconate is (nRE1 / n) 2Zr2O7, RE is any n of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and n is not smaller than 10; the CMAS barrier layer includes an anti-corrosion oxide having an optical basicity of 0.55 to 0.68. The CMAS corrosion resistant thermal barrier coating disclosed by the invention realizes high thermal insulation, sintering resistance and CMAS corrosion resistance, reduces the surface temperature of a matrix alloy, and improves the sintering resistance and CMAS corrosion resistance of ceramics.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal barrier coating materials, and in particular relates to a thermal barrier coating resistant to CMAS corrosion, a preparation method thereof, and an application thereof. Background Art

[0002] As the thrust-to-weight ratio of aircraft engines continues to increase, the turbine inlet temperature has far exceeded the tolerance limit of the most advanced high-temperature alloys. As an effective thermal protection technology, thermal barrier coatings (TBCs) can significantly reduce the surface temperature of the base alloy and provide erosion and corrosion resistance, thereby extending blade life and improving the engine's thrust-to-weight ratio and operating efficiency. Yttria-stabilized zirconia (YSZ) is currently the most widely used TBCs ceramic top layer material. However, due to the continuous increase in aircraft engine operating temperatures (>1250°C), YSZ faces a series of problems such as high-temperature sintering, phase transformation, and corrosion from molten silicate environmental deposits (CaO-MgO-Al2O3-SiO2, CMAS), and has gradually become unable to meet high-temperature protection requirements. Therefore, the development of new high-insulation, sintering-resistant, and CMAS-corrosion-resistant thermal barrier coating materials and structures has become one of the key technologies in the development of new generation engines.

[0003] Rare earth zirconates and cerates (A2B2O7, where A is a rare earth element and B is Zr or Ce) are considered promising materials for the top layer of TBCs due to their high melting point, sintering resistance, low thermal conductivity, and high-temperature structural stability. However, single-component rare earth zirconates and cerates suffer from shortcomings such as low thermal expansion coefficient, poor fracture toughness, and insufficient resistance to CMAS corrosion, making them unable to fully meet the requirements for long-life service in extreme environments.

[0004] Therefore, the development of thermal barrier coating materials and their structures that can meet the needs of high thrust-to-weight ratio engines under complex working conditions is of great significance to the development of this field. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and provide a thermal barrier coating resistant to CMAS corrosion, which achieves high thermal insulation, sintering resistance and CMAS corrosion resistance, is beneficial to reducing the surface temperature of the base alloy, and improves the sintering resistance and CMAS corrosion resistance of the ceramic.

[0006] The present invention is achieved through the following technical solutions:

[0007] The application discloses a thermal barrier coating resistant to CMAS corrosion, which comprises a metal bonding layer, a yttrium-stabilized zirconia layer and a multi-component rare earth zirconate layer arranged on the metal bonding layer in sequence, and a multi-component rare earth cerate layer and / or a CMAS barrier layer arranged on the multi-component rare earth zirconate layer in sequence; the multi-component rare earth zirconate layer comprises multi-component rare earth zirconate with a chemical formula of (nRE 1 / n )2Zr2O7, wherein RE is any n kinds of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and n is not less than 10; and the CMAS barrier layer comprises corrosion-resistant oxides with an optical basicity of 0.55-0.68.

[0008] The thermal barrier coating resistant to CMAS corrosion provided by the application has the multi-component rare earth zirconate with a component number not less than 10, so that the lattice distortion degree and ion confusion degree in the system are improved, the thermal conductivity of the system is reduced, the high-temperature sintering performance is improved, the CMAS corrosion resistance is improved, the chemical reaction consumption mechanism of the thermal barrier coating is slowed down by arranging the rare earth cerate layer and / or the CMAS barrier layer on the multi-component rare earth zirconate layer, the corrosion and consumption of the thermal barrier coating caused by CMAS are slowed down, the high heat insulation, sintering resistance and CMAS corrosion resistance are realized, the surface temperature of the base alloy is reduced, and the sintering resistance and CMAS corrosion resistance of the ceramic are improved.

[0009] Further, the multi-component rare earth cerate layer comprises multi-component rare earth cerate with a chemical formula of (nRE 1 / n )2Ce2O7, wherein n is not less than 8, and RE is any n kinds of combinations of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0010] Further, in the multi-component rare earth cerate, the chemical formula is (nRE 1 / n )2Ce2O7, n is not less than 8, and RE comprises Ho, Er, Tm, Yb, Lu, Sc, Tb and Dy; the more the component number of the rare earth cerate is, the better the heat insulation and CMAS corrosion resistance are; and when the components are selected, the elements with smaller optical basicity of rare earth oxides are preferentially selected as the components, so that the CMAS corrosion resistance is better.

[0011] Further, the thickness of the rare earth zirconate layer is 20-800 microns.

[0012] Further, the thickness of the rare earth cerate layer is 20-400 microns, and the thickness of the CMAS barrier layer is 5-50 microns.

[0013] Further, the corrosion-resistant oxides with low optical basicity comprise at least one of magnesium oxide, cobalt oxide, silicon oxide and aluminum oxide.

[0014] Furthermore, the metal bonding layer includes at least one of MCrAlY and PtAl.

[0015] The present invention also provides a method for preparing the above-mentioned thermal barrier coating resistant to CMAS corrosion, comprising the following steps:

[0016] preparing a yttria-stabilized zirconia layer on the metal bonding layer;

[0017] spraying or depositing a multi-component rare earth zirconate layer on the yttria-stabilized zirconia layer: weighing rare earth oxide and zirconium dioxide according to the chemical formula of the multi-component rare earth zirconate layer, uniformly mixing the rare earth oxide and zirconium dioxide to obtain a first mixed powder, sintering the first mixed powder to obtain a multi-component rare earth zirconate; and depositing the first mixed powder on the yttria-stabilized zirconia layer by plasma spraying, physical vapor deposition, electrophoretic deposition, or molten salt electrophoretic deposition to form a multi-component rare earth zirconate layer;

[0018] A multi-component rare earth cerate layer and / or the CMAS barrier layer are prepared on the multi-component rare earth zirconate layer.

[0019] Furthermore, in the step of sintering the first mixed powder to obtain multi-component rare earth zirconate, the sintering temperature of the first mixed powder is 1200-1700°C.

[0020] Furthermore, in the step of preparing the multi-component rare earth cerate and / or the CMAS barrier layer on the multi-component rare earth zirconate layer, when preparing the multi-component rare earth cerate layer, rare earth oxide and cerium dioxide are weighed according to the chemical formula of the multi-component rare earth cerate, the rare earth oxide and cerium dioxide are uniformly mixed to obtain a second mixed powder, the second mixed powder is sintered in an environment of 1200-1700° C. to obtain a multi-component rare earth cerate powder, and the multi-component rare earth cerate powder is deposited on the multi-component rare earth zirconate layer by plasma spraying, physical vapor deposition, electrophoretic deposition, or molten salt electrophoretic deposition to form a multi-component rare earth cerate layer;

[0021] When preparing the CMAS barrier layer, the anti-corrosion oxide powder of the CMAS barrier layer is sprayed or deposited on the multi-component rare earth zirconate layer, or the anti-corrosion oxide powder is sprayed or deposited on the multi-component rare earth cerate layer.

[0022] For better understanding and implementation, the present invention is described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of the structure of the thermal barrier coating resistant to CMAS corrosion in Example 1.

[0024] Figure 2Flowchart of the method for preparing a thermal barrier coating against CMAS corrosion according to Example 2.

[0025] Figure 3 The (16RE of Example 3 1 / 16 )XRD pattern of 2Zr2O7 sintered block.

[0026] Figure 4 The (16RE of Example 3 1 / 16 )Surface EBSD map of 2Zr2O7 sintered block.

[0027] Figure 5 (10RE of Example 3 1 / 10 )XRD pattern of sintered bulk of 2Ce2O7.

[0028] Figure 6 (10RE of Example 3 1 / 10 )EBSD map of sintered bulk of 2Ce2O7.

[0029] Figure 7 (10RE of Example 3 1 / 10 )Ce2O7 cross-sectional SEM image of a sintered block after being corroded under a molten CMAS film at 1400℃ for 50h. DETAILED DESCRIPTION

[0030] The following is a further detailed description of the embodiments of the present invention in conjunction with the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the embodiments of the present invention and are not intended to limit the embodiments of the present invention. It should also be noted that, for ease of description, the accompanying drawings only illustrate portions of the embodiments of the present invention, rather than all structures.

[0031] Furthermore, the terms "first," "second," "third," etc., in the specification and claims are used solely for descriptive purposes to distinguish between identical technical features. They are not to be construed as indicating or implying relative importance, or as implicitly specifying the number of technical features, nor do they necessarily describe a sequential or chronological order. The terms are interchangeable where appropriate. Thus, a feature specified as "first" or "second" may explicitly or implicitly include at least one of those features.

[0032] Similarly, the terms "fixed" and "connected" used in the specification and claims should not be construed as limited to direct connections. Thus, the expression "device A is connected to device B" should not be limited to devices or systems in which device A is directly connected to device B. Rather, it means that a path exists between device A and device B, which may include other devices or tools.

[0033] Example 1

[0034] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, Figure 1 The thermal barrier coating resistant to CMAS corrosion is shown in the structural diagram, please refer to Figure 1 The thermal barrier coating resistant to CMAS corrosion comprises a metal bonding layer 1, a yttria-stabilized zirconia layer 2 and a multi-component rare earth zirconate layer 3 arranged on the metal bonding layer 1 in sequence, and a multi-component rare earth cerate layer 4 and / or a CMAS barrier layer 5 arranged on the multi-component rare earth zirconate layer 3 in sequence.

[0035] The rare earth ceramic layer comprises the multi-component rare earth zirconate layer 3, wherein the multi-component rare earth zirconate layer 3 comprises multi-component rare earth zirconate with a chemical formula of (nRE 1 / n )2Zr2O7, RE is any n kinds of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and n is not less than 10.

[0036] The CMAS barrier layer 5 comprises corrosion-resistant oxide with an optical basicity of 0.55-0.68.

[0037] In the thermal barrier coating resistant to CMAS corrosion, the number of components of the multi-component rare earth zirconate is not less than 10, the degree of lattice distortion and the degree of ion confusion in the system are improved, the thermal conductivity of the system is reduced, the high-temperature sintering resistance and the CMAS corrosion resistance are improved, the CMAS corrosion of the thermal barrier coating is slowed down due to the chemical reaction consumption mechanism of the thermal barrier coating, the rare earth cerate layer 4 and / or the CMAS barrier layer 5 are arranged on the multi-component rare earth zirconate layer 3, the high thermal insulation, the sintering resistance and the CMAS corrosion resistance are realized, the surface temperature of the base alloy is reduced, and the sintering resistance and the CMAS corrosion resistance of the ceramic are improved.

[0038] The thermal barrier coating resistant to CMAS corrosion is applied to a metal surface, and the thermal barrier coating resistant to CMAS corrosion has low thermal conductivity, so that the temperature of the metal surface is reduced.

[0039] In an embodiment, the multi-component rare earth zirconate with a large number of components is selected as the thermal insulation layer, for example, the multi-component rare earth zirconate with 16 components, 15 components, 14 components, 13 components or 12 components is selected, and the rare earth element with a large ion radius difference is selected, so that the thermal insulation and the sintering resistance are improved. The more the number of components is, the higher the degree of atomic confusion in the system is, and thus the better the sintering resistance and the CMAS corrosion resistance are; the more the number of components is, the larger the ion radius difference is, so that the phonon scattering is more serious, and thus the thermal conductivity of the material is reduced, and the more the number of components is, the better the CMAS corrosion resistance is.

[0040] In the present embodiment, the multi-component rare earth cerate layer 4 comprises multi-component rare earth cerate with a chemical formula of (nRE 1 / n )2Ce2O7, n is not less than 8, and RE is any n combination of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The more the component number of the rare earth cerate, the better the heat insulation and CMAS corrosion resistance, such as 15-component, 14-component, 13-component, 12-component, 11-component, 10-component multi-component rare earth cerate. Since CMAS is a glass body at high temperature, its optical basicity is 0.63, which belongs to weak acidic melt, and thus has corrosive effect on the alkaline substances with relatively large optical basicity, similar to acid-base neutralization reaction, and the larger the optical basicity difference between the two, the stronger the reactivity. Therefore, the oxide with similar optical basicity to CMAS and stable at high temperature and capable of forming a dense layer is selected as the barrier layer 5 between CMAS and the thermal barrier coating, which can prevent the direct penetration of CMAS and prevent the acid-base neutralization reaction between CMAS and the barrier layer, thereby protecting the thermal barrier coating.

[0041] In one embodiment, the multi-component rare earth cerate comprises (La 1 / 10 Sm 1 / 10 Eu 1 / 10 Gd 1 / 10 Tb 1 / 10 Ho 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 Sc 1 / 10 )2Zr2O7, (Nd 1 / 10 Sm 1 / 10 Gd 1 / 10 Dy 1 / 10 Y 1 / 10 Ho 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Zr2O7, (La 1 / 11 Sm 1 / 11 Eu 1 / 11 Gd 1 / 11 Tb 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, (La 1 / 11 Nd 1 / 11 Sm 1 / 11 Gd1 / 11 Gy 1 / 11 Y 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, (La 1 / 12 Sm 1 / 12 Eu 1 / 12 Gd 1 / 12 Tb 1 / 12 Dy 1 / 12 Ho 1 / 12 Er 1 / 12 Tm 1 / 12 Yb 1 / 12 Lu 1 / 12 Sc 1 / 12 )2Zr2O7, (La 1 / 12 Pr 1 / 12 Nd 1 / 12 Gd 1 / 12 Tb 1 / 12 Dy 1 / 12 Y 1 / 12 Ho 1 / 12 Er 1 / 12 Tm 1 / 12 Yb 1 / 12 Lu 1 / 12 )2Zr2O7, (Pr 1 / 13 Nd 1 / 13 Sm 1 / 13 Eu 1 / 13 Tb 1 / 13 Dy 1 / 13 Y 1 / 13 Ho 1 / 13 Er 1 / 3Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 Sc 1 / 13 )2Zr2O7, (La 1 / 13 Ce 1 / 13 Pr 1 / 13 Nd 1 / 13 Sm 1 / 13 Eu 1 / 13 Dy 1 / 13 Y 1 / 13 Ho 1 / 13 Er 1 / 3 Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 )2Zr2O7, (La 1 / 14 Pr 1 / 14 Nd 1 / 14 Sm1 / 14 Eu 1 / 14 Gd 1 / 14 Tb 1 / 14 Dy 1 / 14 Ho 1 / 14 Er 1 / 14 Tm 1 / 14 Yb 1 / 14 Lu 1 / 14 Sc 1 / 14 )2Zr2O7, (La 1 / 14 Pr 1 / 14 Nd 1 / 14 Sm 1 / 14 Eu 1 / 14 Gd 1 / 14 Y 1 / 14 Dy 1 / 14 Ho 1 / 14 Er 1 / 14 Tm 1 / 14 Yb 1 / 14 Lu 1 / 14 Sc 1 / 14 )2Zr2O7, (La 1 / 15 Ce 1 / 15 Pr 1 / 15 Nd 1 / 15 Sm 1 / 15 Eu 1 / 15 Gd 1 / 15 Tb 1 / 15 Dy 1 / 15 Y 1 / 15 Ho 1 / 15 Er 1 / 15 Tm 1 / 15 Yb 1 / 15 Lu 1 / 15 )2Zr2O7, (La 1 / 15 Pr 1 / 15 Nd 1 / 15 Sm 1 / 15 Eu 1 / 15 Gd 1 / 15 Tb 1 / 15 Dy 1 / 15 Y 1 / 15 Ho 1 / 15 Er 1 / 15 Tm 1 / 15 Yb 1 / 15 Lu 1 / 15 Sc 1 / 15 )2Zr2O7, (La 1 / 15 Ce 1 / 15 Pr 1 / 15 Nd 1 / 15 Sm 1 / 15 Eu 1 / 15 Tb1 / 15 Dy 1 / 15 Y 1 / 15 Ho 1 / 15 Er 1 / 15 Tm 1 / 15 Yb 1 / 15 Lu 1 / 15 Sc 1 / 15 )2Zr2O7、(La 1 / 16 Ce 1 / 16 Pr 1 / 16 Nd 1 / 16 Sm 1 / 16 Eu 1 / 16 Gd 1 / 16 Tb 1 / 16 Dy 1 / 16 Y 1 / 16 Ho 1 / 16 Er 1 / 16 Tm 1 / 16 Yb 1 / 16 Lu 1 / 16 Sc 1 / 16 )One of the 2Zr2O7.

[0042] In this embodiment, the multi-component rare earth cerate has the chemical formula (nRE 1 / n )2Ce2O7, n is not less than 8, RE includes Ho, Er, Tm, Yb, Lu, Sc, Tb and Dy. The more components of rare earth cerate, the better the thermal insulation and CMAS corrosion resistance. When selecting components, it is preferred to select elements with smaller optical basicity of rare earth oxide as components, which have better CMAS corrosion resistance. For example, (Ho 1 / 8 Er 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 Sc 1 / 8 Tb 1 / 8 Dy 1 / 8 )2Ce2O7.

[0043] In one embodiment, the multi-component cerate comprises (Sm 1 / 8 Eu 1 / 8 Gd 1 / 8 Dy 1 / 8 Ho 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7、

[0044] (La 1 / 8 Nd 1 / 8 Tb 1 / 8 Y 1 / 8 Er 1 / 8Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7、

[0045] (Pr 1 / 8 Sm 1 / 8 Gd 1 / 8 Tb 1 / 8 Y 1 / 8 Er 1 / 8 Tm 1 / 8 Yb 1 / 8 )2Ce2O7、

[0046] (La 1 / 9 Gd 1 / 9 Tb 1 / 9 Y 1 / 9 Er 1 / 9 Tm 1 / 9 Yb 1 / 9 Lu 1 / 9 Sc 1 / 9 )2Ce2O7、

[0047] (La 1 / 9 Eu 1 / 9 Gd 1 / 9 Dy 1 / 9 Er 1 / 9 Tm 1 / 9 Yb 1 / 9 Lu 1 / 9 Sc 1 / 9 )2Ce2O7、

[0048] (Nd 1 / 9 Eu 1 / 9 Gd 1 / 9 Tb 1 / 9 Dy 1 / 9 Y 1 / 9 Er 1 / 9 Tm 1 / 9 Yb 1 / 9 )2Ce2O7、

[0049] (La 1 / 10 Eu 1 / 10 Gd 1 / 10 Tb 1 / 10 Dy 1 / 10 Y 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Ce2O7、

[0050] (La 1 / 10 Pr 1 / 10 Nd 1 / 10 Gd 1 / 10 Dy 1 / 10Y 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Ce2O7、

[0051] (La 1 / 10 Sm 1 / 10 Gd 1 / 10 Tb 1 / 10 Dy 1 / 10 Y 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Sc 1 / 10 )2Ce2O7、

[0052] (Gd 1 / 10 Tb 1 / 10 Dy 1 / 10 Y 1 / 10 Ho 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 Sc 1 / 10 )2Ce2O7、

[0053] (Nd 1 / 11 Sm 1 / 11 Eu 1 / 11 Gd 1 / 11 Tb 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Ce2O7、

[0054] (La 1 / 11 Pr 1 / 11 Sm 1 / 11 Gd 1 / 11 Dy 1 / 11 Y 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Ce2O7、

[0055] (La 1 / 12 Nd 1 / 12 Sm 1 / 12 Gd 1 / 12 Tb 1 / 12 Y 1 / 12 Ho 1 / 12 Er 1 / 12 Tm1 / 12 Yb 1 / 12 Lu 1 / 12 Sc 1 / 12 )2Ce2O7、

[0056] (La 1 / 12 Pr 1 / 12 Nd 1 / 12 Gd 1 / 12 Dy 1 / 12 Y 1 / 12 Ho 1 / 12 Er 1 / 12 Tm 1 / 12 Yb 1 / 12 Lu 1 / 12 Sc 1 / 12 )2Ce2O7、

[0057] (La 1 / 13 Nd 1 / 13 Sm 1 / 13 Eu 1 / 13 Gd 1 / 13 Dy 1 / 13 Y 1 / 13 Ho 1 / 13 Er 1 / 3 Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 Sc 1 / 13 )2Ce2O7、(La 1 / 13 Ce 1 / 13 Pr 1 / 13 Nd 1 / 13 Sm 1 / 13 Gd 1 / 13 Dy 1 / 13 Y 1 / 13 Ho 1 / 13 Er 1 / 3 Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 )2Ce2O7、(La 1 / 14 Pr 1 / 14 Nd 1 / 14 Sm 1 / 14 Eu 1 / 14 Gd 1 / 14 Y 1 / 14 Dy 1 / 14 Ho 1 / 14 Er 1 / 14 Tm 1 / 14 Yb 1 / 14 Lu 1 / 14 Sc 1 / 14 )2Ce2O7、

[0058] (La 1 / 14 Pr 1 / 14 Nd1 / 14 Sm 1 / 14 Eu 1 / 14 Gd 1 / 14 Tb 1 / 14 Dy 1 / 14 Ho 1 / 14 Er 1 / 14 Tm 1 / 14 Yb 1 / 14 Lu 1 / 14 Sc 1 / 14 )2Ce2O7、

[0059] (La 1 / 15 Pr 1 / 15 Nd 1 / 15 Sm 1 / 15 Eu 1 / 15 Gd 1 / 15 Tb 1 / 15 Dy 1 / 15 Y 1 / 15 Ho 1 / 15 Er 1 / 15 Tm 1 / 15 Yb 1 / 15 Lu 1 / 15 Sc 1 / 15 )2Ce2O7.

[0060] In the present embodiment, the rare earth zirconate layer 3 has a thickness of 20-800 μm.

[0061] In the present embodiment, the rare earth cerate layer 4 has a thickness of 20-400 μm, and the CMAS barrier layer 5 has a thickness of 5-50 μm.

[0062] The multi-component rare earth zirconate layer 3 is sequentially provided with a multi-component rare earth cerate layer 4 and / or a CMAS barrier layer 5, and the total thickness is 200-1000 μm.

[0063] Specifically, in one embodiment, the multi-component rare earth zirconate layer 3 is sequentially provided with a multi-component rare earth cerate layer 4 and a CMAS barrier layer 5, wherein the multi-component rare earth zirconate layer 3 has a thickness of 20-400 μm, the multi-component rare earth cerate layer 4 has a thickness of 20-400 μm, and the CMAS barrier layer 5 has a thickness of 5-50 μm.

[0064] In another embodiment, the multi-component rare earth zirconate layer 3 is provided with a CMAS barrier layer 5, wherein the multi-component rare earth zirconate layer 3 has a thickness of 20-800 μm, and the CMAS barrier layer 5 has a thickness of 5-50 μm.

[0065] In another embodiment, the multi-component rare earth cerate layer 4 is disposed on the multi-component rare earth zirconate layer 3, wherein the thickness of the multi-component rare earth zirconate layer 3 is 20-400 μm, and the thickness of the multi-component rare earth cerate layer 4 is 20-400 μm.

[0066] In the present embodiment, the low optical basicity corrosion-resistant oxide includes at least one of magnesium oxide, cobalt oxide, silicon oxide and aluminum oxide. The oxide close to the optical basicity (0.63) of CMAS is selected as the CMAS barrier layer 5 to improve the CMAS corrosion resistance, for example, the optical basicity of magnesium oxide is 0.68, the optical basicity of aluminum oxide is 0.61, the optical basicity of cobalt oxide is 0.55, and the optical basicity of mullite is 0.58.

[0067] In the present embodiment, the metal bonding layer 1 includes at least one of MCrAlY or PtAl.

[0068] In the present embodiment, the yttria-stabilized zirconia layer 2 is a 6%-8% yttria-stabilized zirconia layer 2.

[0069] In the CMAS corrosion-resistant thermal barrier coating of the present embodiment, the yttria-stabilized zirconia layer 2 can reduce the problem of mismatching of the thermal expansion coefficients between the metal bonding layer 1 and the multi-component rare earth zirconate layer 3, the multi-component rare earth zirconate layer 3 with 10 or more components has lower thermal conductivity and grain growth rate, and can improve the heat insulation performance and sintering resistance of the ceramic layer of the thermal barrier coating; the multi-component rare earth cerate layer 4 with 8 or more components has lower thermal conductivity and excellent sintering resistance and CMAS corrosion resistance, and can improve the CMAS corrosion resistance of the thermal barrier coating; the CMAS barrier layer 5 composed of the oxide ceramic with low optical basicity at the outermost layer can completely prevent the penetration of CMAS into the ceramic top layer, and improve the problem of poor thermal barrier coating corrosion and thermal cycle performance caused by CMAS penetration. The thermal physical properties of each coating in the thermal barrier coating are well matched, which can effectively alleviate the coating thermal cycle stress and CMAS corrosion problem, greatly prolong the service life of the coating, and has important application value in the field of thermal barrier coatings, and can be applied in the field of engines and the like to improve the efficiency and service life of the engine.

[0070] Example 2

[0071] The present embodiment provides a method for preparing the CMAS corrosion-resistant thermal barrier coating of embodiment 1, Figure 2 which is a flowchart of the method for preparing the CMAS corrosion-resistant thermal barrier coating, please refer to Figure 2 The method for preparing the CMAS corrosion-resistant thermal barrier coating includes the following steps:

[0072] Step S1: preparing a yttria-stabilized zirconia layer 2 on the metal bonding layer 1:

[0073] Step S2: Spraying or depositing a multi-component rare earth zirconate layer 3 on the yttria stabilized zirconia layer 2:

[0074] According to the chemical formula of the multi-component rare earth zirconate layer 3 and the multi-component rare earth cerate layer 4, the nano or sub-micron scale rare earth oxide and zirconia are weighed according to the stoichiometric ratio, the rare earth oxide and zirconia are uniformly mixed to obtain a first mixed powder, and the first mixed powder is sintered to obtain a multi-component rare earth zirconate.

[0075] The first mixed powder is sprayed or deposited on the yttria stabilized zirconia layer 2 to form the multi-component rare earth zirconate layer 3.

[0076] The sintering temperature of the first mixed powder is 1200-1700°C.

[0077] Step S3: Preparing a multi-component rare earth cerate layer 4 and / or the CMAS barrier layer 5 on the multi-component rare earth zirconate layer 3:

[0078] When preparing the multi-component rare earth cerate layer 4, the nano or sub-micron scale rare earth oxide and ceria are uniformly mixed to obtain a second mixed powder, which is further uniformly mixed by ball milling; the second mixed powder is sintered in a 1200-1700°C environment to obtain a multi-component rare earth cerate powder; and the multi-component rare earth cerate powder is sprayed or deposited on the multi-component rare earth zirconate layer 3 to form the multi-component rare earth cerate layer 4.

[0079] When preparing the CMAS barrier layer 5, the powder of the corrosion-resistant oxide of the CMAS barrier layer 5 is sprayed or deposited on the multi-component rare earth zirconate layer 3, or the powder of the corrosion-resistant oxide is sprayed or deposited on the multi-component rare earth cerate layer 4.

[0080] Example 3

[0081] The embodiment provides an anti-CMAS corrosion thermal barrier coating, which comprises a metal bonding layer 1 and, sequentially arranged on the metal bonding layer 1, a yttria stabilized zirconia layer 2, a 16-component rare earth zirconate layer 3, a 10-component rare earth cerate layer 4 and a CMAS barrier layer 5.

[0082] The embodiment also provides a method for preparing an anti-CMAS corrosion thermal barrier coating, which comprises the following steps:

[0083] Step S1: Preparing a yttria stabilized zirconia layer 2 on the metal bonding layer 1: preparing a yttria stabilized zirconia layer 2 on the metal bonding layer 1 by plasma spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition.

[0084] Step S2: Spraying or depositing a multi-component rare earth zirconate layer 3 on the yttria stabilized zirconia layer 2:

[0085] La2O3, Ce2O3, Pr6O 11 , Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Y2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Sc2O3 and ZrO2 in stoichiometric ratio to obtain a first mixed powder;

[0086] The first mixed powder is ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace at 1600 °C for 5 h to obtain a 16-component rare earth zirconate powder with a chemical formula of (16RE 1 / 16 )2Zr2O7.

[0087] The 16-component rare earth zirconate is sprayed or deposited on the yttria stabilized zirconia layer 2 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition to form a multi-component rare earth zirconate layer 3.

[0088] Step S3: Preparing a multi-component rare earth cerate layer 4 and / or the CMAS barrier layer 5 on the multi-component rare earth zirconate layer 3:

[0089] Gd2O3, Tb2O3, Dy2O3, Y2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Sc2O3 and CeO2 in stoichiometric ratio to obtain a second mixed powder; the second mixed powder is ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace at 1700 °C for 5 h to obtain a 10-component rare earth cerate powder with a chemical formula of (10RE 1 / 10 )2Ce2O7.

[0090] The multi-component rare earth cerate is sprayed or deposited on the 16-component rare earth zirconate layer 3 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition to form a multi-component rare earth cerate layer 4.

[0091] When preparing the CMAS barrier layer 5, the powder of the corrosion-resistant oxide of the CMAS barrier layer 5 is sprayed or deposited on the 10-component rare earth cerate layer 4 to obtain the CMAS barrier layer 5.

[0092] The above 16-component rare earth zirconate is characterized, and the 16-component rare earth zirconate (16RE 1 / 16 )2Zr2O7 is sintered at 1600 °C under a pressure of 30 MPa for 0.5 h to obtain a (16RE 1 / 16 )2Zr2O7 sintered block,Figure 3 is the XRD pattern of the sintered bulk of (16RE 1 / 16 )2Zr2O7, Figure 4 is the surface EBSD pattern of the sintered bulk of (16RE 1 / 16 )2Zr2O7, please refer to Figures 3-4 It can be seen that the 16-element rare earth zirconate ceramic is a single-phase fluorite structure, and the average grain size thereof is about 8.4 μm. The thermal conductivity thereof at 1200℃ is measured to be 0.98 W·m 1 ·K 1 The grain growth rate thereof after 200h of thermal exposure at 1400℃ is measured to be 0.46 nm / h, and the corrosion reaction layer thickness thereof after 50h of corrosion under the molten CMAS film at 1300℃ is 134.5 μm, indicating that the CMAS corrosion resistance of the 16-element rare earth zirconate ceramic (16RE 1 / 16 )2Zr2O7 is poor, and the 16-element rare earth zirconate ceramic (16RE 1 / 16 )2Zr2O7 cannot be directly used as the ceramic top layer material of the thermal barrier coating.

[0093] The 10-element rare earth cerate described above is characterized. The 10-element rare earth cerate (10RE 1 / 10 )2Ce2O7 is ball milled at 400 rpm for 24h, sieved through a 300 mesh sieve, and tablet-pressed for forming, and then (10RE 1 / 10 )2Ce2O7 sintered bulk is obtained by sintering at 1600℃ for 12h, Figure 5 is the XRD pattern of the sintered bulk of (10RE 1 / 10 )2Ce2O7, Figure 6 is the EBSD pattern of the sintered bulk of (10RE 1 / 10 )2Ce2O7, Figure 7 is the cross-sectional SEM pattern of the sintered bulk of (10RE 1 / 10 )2Ce2O7 after 50h of corrosion under the molten CMAS film at 1400℃.

[0094] Please refer to Figures 5-6 It can be seen that the 10-element ceramic is a single-phase fluorite structure, and the average grain size thereof is about 9.7 μm. The thermal conductivity thereof at 1200℃ is measured to be 1.03 W·m -1 ·K -1 Please refer to Figure 7 The corrosion reaction layer thickness thereof after 50h of corrosion under the molten CMAS film at 1400℃ is 11.2 μm, indicating that the 10-element ceramic has good CMAS corrosion resistance.

[0095] Therefore, the multi-component rare earth zirconate layer 3 with more than 10 components has lower thermal conductivity and grain growth rate, which can improve the thermal insulation performance and sintering resistance of the thermal barrier coating ceramic layer. The multi-component rare earth cerate layer 4 with more than 8 components has lower thermal conductivity and excellent sintering resistance and CMAS corrosion resistance, which can improve the CMAS corrosion resistance of the thermal barrier coating. Combining multi-component rare earth zirconate and multi-component rare earth cerate can achieve high thermal insulation, sintering resistance and CMAS corrosion resistance.

[0096] Example 4

[0097] This embodiment provides a thermal barrier coating resistant to CMAS corrosion, comprising a metal bonding layer 1 and a yttria-stabilized zirconia layer 2, a 14-component rare earth zirconate layer 3, a 12-component rare earth cerate layer 4 and a CMAS barrier layer 5 sequentially arranged on the metal bonding layer 1.

[0098] Step S1: preparing a yttria-stabilized zirconia layer 2 on the metal bonding layer 1: preparing a yttria-stabilized zirconia layer 2 on the metal bonding layer 1 by plasma spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition.

[0099] Step S2: spraying or depositing a multi-component rare earth zirconate layer 3 on the yttria-stabilized zirconia layer 2:

[0100] Weigh Pr6O according to the stoichiometric ratio 11 , Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Y2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Sc2O3 and ZrO2 to obtain a first mixed powder;

[0101] The first mixed powder was ball-milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace and kept at 1600 ° C for 10 h to obtain a 14-component rare earth zirconate powder with the chemical formula (14RE 1 / 14 )2Zr2O7.

[0102] A 14-component rare earth zirconate is deposited on the yttria-stabilized zirconia layer 2 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoresis to form a multi-component rare earth zirconate layer 3 .

[0103] Step S3: preparing a multi-component rare earth cerate layer 4 and the CMAS barrier layer 5 on the multi-component rare earth zirconate layer 3:

[0104] Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Y2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Sc2O3 and CeO2 in stoichiometric ratio to obtain a second mixed powder; ball milling the second mixed powder at 380 rpm for 12 h, drying, and then placing it in a muffle furnace, and keeping it at 1700°C for 5 h to obtain a 12-component rare earth cerate powder, with a chemical formula of (12RE 1 / 12 )2Ce2O7.

[0105] Spraying or depositing the multi-component rare earth cerate on the 12-component rare earth zirconate layer 3 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition to form a multi-component rare earth cerate layer 4.

[0106] When preparing the CMAS barrier layer 5, the powder of the corrosion-resistant oxide of the CMAS barrier layer 5 is sprayed or deposited on the 12-component rare earth cerate layer 4 to obtain the CMAS barrier layer 5.

[0107] Characterizing the 14-component rare earth zirconate as described above, sintering the 14-component rare earth zirconate (14RE 1 / 14 )2Zr2O7 at 1550°C under a pressure of 60 MPa for 0.5 h to obtain a (14RE 1 / 14 )2Zr2O7 sintered block, and analyzing the phase composition thereof to be a single-phase fluorite structure. The thermal conductivity thereof at 1200°C is measured to be 1.04 W·m- 1 ·K- 1 The grain growth rate thereof after 200 h of thermal exposure at 1400°C is measured to be 0.55 nm / h.

[0108] Characterizing the 12-component rare earth cerate as described above, ball milling the 12-component rare earth cerate (12RE 1 / 12 )2Ce2O7 powder at 400 rpm for 24 h, sieving through a 300-mesh sieve, tabletting, and then sintering at 1550°C for 12 h to obtain a (12RE 1 / 12 )2Ce2O7 sintered block, and measuring the thermal conductivity thereof at 1200°C to be 1.08 W·m- 1 ·K- 1 The corrosion reaction layer thickness thereof after 50 h of corrosion under a molten CMAS film at 1400°C is 13.5 μm.

[0109] Example 5

[0110] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, comprising a metal bonding layer 1 and a yttria-stabilized zirconia layer 2, an 14-component rare earth zirconate layer 3, a 12-component rare earth cerate layer 4 and a CMAS barrier layer 5 which are sequentially arranged on the metal bonding layer 1.

[0111] Step S1: preparing the yttria-stabilized zirconia layer 2 on the metal bonding layer 1: the yttria-stabilized zirconia layer 2 is prepared on the metal bonding layer 1 by plasma spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition.

[0112] Step S2: spraying or depositing the multi-component rare earth zirconate layer 3 on the yttria-stabilized zirconia layer 2:

[0113] La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Lu2O3, Sc2O3 and ZrO2 in stoichiometric proportions to obtain a first mixed powder;

[0114] The first mixed powder is ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace for heat preservation at 1600 ℃ for 10 h to obtain an 11-component rare earth zirconate powder, the chemical formula of which is (11RE 1 / 11 )2Zr2O7.

[0115] The 11-component rare earth zirconate is sprayed, deposited or electrophoretically deposited on the yttria-stabilized zirconia layer 2 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition to form the multi-component rare earth zirconate layer 3.

[0116] Step S3: preparing the multi-component rare earth cerate layer 4 and / or the CMAS barrier layer 5 on the multi-component rare earth zirconate layer 3:

[0117] La2O3, Pr6O 11 , Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Y2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Sc2O3 and CeO2 in stoichiometric proportions to obtain a second mixed powder; the second mixed powder is ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace for heat preservation at 1500 ℃ for 10 h to obtain a 15-component rare earth cerate powder, the chemical formula of which is (15RE 1 / 15 )2Ce2O7.

[0118] The multi-component rare earth cerate is sprayed, deposited or electrophoretically deposited on the 15-component rare earth zirconate layer 3 by ion spraying, physical vapor deposition, electrophoretic deposition or molten salt electrophoretic deposition to form the multi-component rare earth cerate layer 4.

[0119] When preparing the CMAS barrier layer 5, the anti-corrosion oxide powder of the CMAS barrier layer 5 is sprayed or deposited on the 15-component rare earth cerate layer 4 to obtain the CMAS barrier layer 5.

[0120] The 11-component rare earth zirconate described above is characterized. The 11-component rare earth zirconate (11RE 1 / 11 )2Zr2O7 is sintered at 1600℃ under a pressure of 45MPa for 0.5h to obtain a sintered (11RE 1 / 11 )2Zr2O7 bulk body, and analysis of the phase composition thereof shows that it has a pyrochlore and fluorite dual-phase structure. The thermal conductivity thereof at 1200℃ is measured to be 0.96W·m- 1 ·K- 1 The grain growth rate thereof after 200h of thermal exposure at 1400℃ is measured to be 1.23nm / h.

[0121] The 15-component rare earth cerate described above is characterized. The 15-component rare earth cerate (15RE 1 / 15 )2Ce2O7 is ball milled at 400rpm for 24h, sieved through a 300-mesh sieve, and tablet-pressed, and then sintered at 1650℃ for 5h to obtain a sintered (15RE 1 / 15 )2Ce2O7 bulk body, and the thermal conductivity thereof at 1200℃ is measured to be 0.95W·m- 1 ·K- 1 The corrosion reaction layer thickness thereof after 50h of corrosion under a molten CMAS film at 1400℃ is 12.7μm.

[0122] Example 6

[0123] The present embodiment provides a CMAS corrosion-resistant thermal barrier coating, comprising a metal bonding layer 1 and, sequentially disposed on the metal bonding layer 1, an 8% yttria-stabilized zirconia layer 2, a 16-component rare earth zirconate layer 3, and a 13-component rare earth cerate layer 4.

[0124] In the present embodiment, the metal bonding layer 1 is a NiCrAlY layer, which is disposed on the surface of a single-crystal nickel-based high-temperature alloy and prepared by plasma spraying to obtain a 100μm-thick NiCrAlY layer. The yttria-stabilized zirconia layer 2 has a thickness of 60μm.

[0125] The chemical formula of the 16-component rare earth zirconate layer 3 is (La 1 / 16 Ce 1 / 16 Pr 1 / 16 Nd 1 / 16 Sm 1 / 16 Eu 1 / 16 Gd 1 / 16 Tb 1 / 16 Dy1 / 16 Y 1 / 16 Ho 1 / 16 Er 1 / 16 Tm 1 / 16 Yb 1 / 16 Lu 1 / 16 Sc 1 / 16 )2Zr2O7, thickness of 200 μm.

[0126] 13-component rare earth cerate layer 4 has a chemical formula of (La 1 / 13 Nd 1 / 13 Sm 1 / 13 Eu 1 / 13 Gd 1 / 13 Tb 1 / 13 Dy 1 / 13 Ho 1 / 13 Er 1 / 13 Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 Sc 1 / 13 )2Ce2O7, thickness of 30 μm.

[0127] Example 7

[0128] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, which comprises a metal bonding layer 1 and an 8% yttria stabilized zirconia layer 2, a 13-component rare earth zirconate layer 3 and an 11-component rare earth cerate layer 4 arranged on the metal bonding layer 1 in sequence.

[0129] In the embodiment, the metal bonding layer 1 is a NiCrAlY layer, which is arranged on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying to obtain a 80 μm NiCrAlY layer. The yttria stabilized zirconia layer 2 has a thickness of 100 μm.

[0130] 13-component rare earth zirconate layer 3 has a chemical formula of (Pr 1 / 13 Nd 1 / 13 Sm 1 / 13 Eu 1 / 13 Tb 1 / 13 Dy 1 / 13 Y 1 / 13 Ho 1 / 13 Er 1 / 3 Tm 1 / 13 Yb 1 / 13 Lu 1 / 13 Sc 1 / 13 )2Zr2O7, thickness of 300 μm.

[0131] 11-component rare earth cerate layer 4 has a chemical formula of (Sm 1 / 11 Eu 1 / 11Gd 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Ce2O7, 46 pm thick.

[0132] Example 8

[0133] The present embodiment provides a CMAS corrosion resistant thermal barrier coating, comprising a metallic bond coat 1 and an 8% yttria stabilized zirconia layer 2, an 11 -component rare earth zirconate layer 3 and a CMAS barrier layer 5 disposed in sequence on the metallic bond coat 1.

[0134] In the present embodiment, the metallic bond coat 1 is a NiCrAlY layer, which is disposed on the surface of a single crystal nickel-based superalloy and is prepared by plasma spraying to obtain a 90 pm thick NiCrAlY layer. The yttria stabilized zirconia layer 2 is 80 pm thick.

[0135] The 11 -component rare earth zirconate layer 3 has a chemical formula of (Pr 1 / 11 Nd 1 / 11 Sm 1 / 11 Eu 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, 350 pm thick, which is disposed on the 8% yttria stabilized zirconia layer 2 by electrophoretic deposition.

[0136] The CMAS barrier layer 5 comprises 20 pm of magnesium oxide.

[0137] Example 9

[0138] The present embodiment provides a CMAS corrosion resistant thermal barrier coating, comprising a metallic bond coat 1 and an 8% yttria stabilized zirconia layer 2, an 11 -component rare earth zirconate layer 3 and a CMAS barrier layer 5 disposed in sequence on the metallic bond coat 1.

[0139] In the present embodiment, the metallic bond coat 1 is a NiCrAlY layer, which is disposed on the surface of a single crystal nickel-based superalloy and is prepared by plasma spraying to obtain a 120 pm thick NiCrAlY layer. The yttria stabilized zirconia layer 2 is 150 pm thick.

[0140] 11-component rare earth zirconate layer 3 has a chemical formula of (Pr 1 / 11 Nd 1 / 11 Sm 1 / 11 Eu 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, and a thickness of 280 μm.

[0141] The CMAS barrier layer 5 includes 30 μm of cobalt oxide.

[0142] Example 10

[0143] The present embodiment provides a CMAS corrosion resistant thermal barrier coating, which includes a metallic bond coat 1 and a 6% yttria stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3, an 8-component rare earth cerate layer 4 and a CMAS barrier layer 5 sequentially disposed on the metallic bond coat 1.

[0144] In the present embodiment, the metallic bond coat 1 is a NiCrAlY layer, which is disposed on the surface of a single crystal nickel-based superalloy, and a 120 μm NiCrAlY layer is prepared by plasma spraying. The yttria stabilized zirconia layer 2 has a thickness of 50 μm.

[0145] 11-component rare earth zirconate layer 3 has a chemical formula of (Sm 1 / 11 Eu 1 / 11 Gd 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, and a thickness of 120 μm.

[0146] The CMAS barrier layer 5 includes 10 μm of mullite.

[0147] Example 11

[0148] The present embodiment provides a CMAS corrosion resistant thermal barrier coating, which includes a metallic bond coat 1 and a 6% yttria stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3, an 8-component rare earth cerate layer 4 and a CMAS barrier layer 5 sequentially disposed on the metallic bond coat 1.

[0149] In this embodiment, the metallic bond coat 1 is a PtAl layer, which is prepared by plasma spraying to a thickness of 60 μm for disposition on the surface of a single-crystal nickel-based superalloy. The yttria-stabilized zirconia layer 2 has a thickness of 60 μm.

[0150] 10-component rare earth zirconate layer 3 has a chemical formula of (La 1 / 10 Sm 1 / 10 Eu 1 / 10 Gd 1 / 10 Tb 1 / 10 Ho 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 Sc 1 / 10 )2Zr2O7, and has a thickness of 200 μm.

[0151] 8-component rare earth cerate layer 4 has a chemical formula of (Sm 1 / 8 Eu 1 / 8 Gd 1 / 8 Dy 1 / 8 Ho 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7, and has a thickness of 130 μm.

[0152] The CMAS-resistant barrier layer 5 includes cobalt oxide having a thickness of 50 μm.

[0153] Example 12

[0154] The present embodiment provides a CMAS-resistant thermal barrier coating, which includes a metallic bond coat 1 and, sequentially disposed on the metallic bond coat 1, a 6% yttria-stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3, an 8-component rare earth cerate layer 4, and a CMAS-resistant barrier layer 5.

[0155] In this embodiment, the metallic bond coat 1 is a PtAl layer, which is prepared by plasma spraying to a thickness of 50 μm for disposition on the surface of a single-crystal nickel-based superalloy. The yttria-stabilized zirconia layer 2 has a thickness of 60 μm.

[0156] 10-component rare earth zirconate layer 3 has a chemical formula of (La 1 / 10 Sm 1 / 10 Eu 1 / 10 Gd 1 / 10 Tb 1 / 10 Ho 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 Sc 1 / 10)2Zr2O7, 400 pm thick.

[0157] 8-component rare earth cerate layer 4 has a chemical formula of (La 1 / 8 Eu 1 / 8 Gd 1 / 8 Dy 1 / 8 Ho 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7, 50 pm thick.

[0158] CMAS-resistant barrier layer 5 includes cobalt oxide with a thickness of 5 pm.

[0159] Example 13

[0160] The embodiment provides a CMAS-resistant thermal barrier coating, which comprises a metal bonding layer 1 and a 6% yttria-stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3, an 8-component rare earth cerate layer 4 and a CMAS-resistant barrier layer 5 arranged on the metal bonding layer 1 in sequence.

[0161] In the embodiment, the metal bonding layer 1 is a PtAl layer, which is arranged on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying to obtain a PtAl layer with a thickness of 100 pm. The yttria-stabilized zirconia layer 2 has a thickness of 60 pm.

[0162] 10-component rare earth zirconate layer 3 has a chemical formula of (Nd 1 / 10 Sm 1 / 10 Gd 1 / 10 Dy 1 / 10 Y 1 / 10 Ho 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Zr2O7, 130 pm thick.

[0163] 8-component rare earth cerate layer 4 has a chemical formula of (La 1 / 8 Nd 1 / 8 Tb 1 / 8 Y 1 / 8 Er 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7, 200 pm thick.

[0164] CMAS-resistant barrier layer 5 includes magnesium oxide with a thickness of 50 pm.

[0165] Example 14

[0166] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, which comprises a metal bonding layer 1 and a 6% yttria-stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3 and an 8-component rare earth cerate layer 4 arranged on the metal bonding layer 1 in sequence.

[0167] In the embodiment, the metal bonding layer 1 is a PtAl layer, which is arranged on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying to obtain a PtAl layer with a thickness of 100 μm. The yttria-stabilized zirconia layer 2 has a thickness of 100 μm.

[0168] The chemical formula of the 10-component rare earth zirconate layer 3 is (Nd 1 / 10 Sm 1 / 10 Gd 1 / 10 Dy 1 / 10 Y 1 / 10 Ho 1 / 10 Er 1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Zr2O7, and has a thickness of 400 μm.

[0169] The chemical formula of the 8-component rare earth cerate layer 4 is (La 1 / 8 Nd 1 / 8 Tb 1 / 8 Y 1 / 8 Er 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7, and has a thickness of 400 μm.

[0170] Example 15

[0171] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, which comprises a metal bonding layer 1 and a 6% yttria-stabilized zirconia layer 2, a 10-component rare earth zirconate layer 3 and an 8-component rare earth cerate layer 4 arranged on the metal bonding layer 1 in sequence.

[0172] In the embodiment, the metal bonding layer 1 is a PtAl layer, which is arranged on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying to obtain a PtAl layer with a thickness of 100 μm. The yttria-stabilized zirconia layer 2 has a thickness of 400 μm.

[0173] The chemical formula of the 10-component rare earth zirconate layer 3 is (Nd 1 / 10 Sm 1 / 10 Gd 1 / 10 Dy 1 / 10 Y 1 / 10 Ho 1 / 10 Er1 / 10 Tm 1 / 10 Yb 1 / 10 Lu 1 / 10 )2Zr2O7, thickness of 20 pm.

[0174] 8-component rare earth cerate layer 4 has a chemical formula of (La 1 / 8 Nd 1 / 8 Tb 1 / 8 Y 1 / 8 Er 1 / 8 Tm 1 / 8 Yb 1 / 8 Lu 1 / 8 )2Ce2O7, thickness of 20 pm.

[0175] Example 16

[0176] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, comprising a metal bonding layer 1 and an 8% yttria-stabilized zirconia layer 2, an 11-component rare earth zirconate layer 3 and a CMAS barrier layer 5 arranged on the metal bonding layer 1 in sequence.

[0177] In the embodiment, the metal bonding layer 1 is a NiCrAlY layer, which is arranged on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying to obtain a NiCrAlY layer with a thickness of 120 pm. The yttria-stabilized zirconia layer 2 has a thickness of 20 pm.

[0178] The 11-component rare earth zirconate layer 3 has a chemical formula of (Sm 1 / 11 Eu 1 / 11 Gd 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, thickness of 800 pm.

[0179] The CMAS barrier layer 5 comprises cobalt oxide with a thickness of 50 pm.

[0180] Example 17

[0181] The embodiment provides a thermal barrier coating resistant to CMAS corrosion, comprising a metal bonding layer 1 and an 8% yttria-stabilized zirconia layer 2, an 11-component rare earth zirconate layer 3 and a CMAS barrier layer 5 arranged on the metal bonding layer 1 in sequence.

[0182] In this embodiment, the metallic bond coat 1 is a NiCrAlY layer, which is provided on the surface of a single-crystal nickel-based superalloy and is prepared by plasma spraying to obtain a 120-μm-thick NiCrAlY layer. The yttria-stabilized zirconia layer 2 has a thickness of 20 μm.

[0183] 11 The chemical formula of the rare earth zirconate layer 3 is (Sm 1 / 11 Eu 1 / 11 Gd 1 / 11 Tb 1 / 11 Dy 1 / 11 Ho 1 / 11 Er 1 / 11 Tm 1 / 11 Yb 1 / 11 Lu 1 / 11 Sc 1 / 11 )2Zr2O7, and has a thickness of 800 μm.

[0184] The CMAS barrier layer 5 includes 5-μm-thick cobalt oxide.

[0185] Comparative Example 1

[0186] This comparative example provides a thermal barrier coating, which is similar to Example 5 in terms of main components, except that the rare earth zirconate layer is a 6-component rare earth zirconate layer, and the cerate layer is a 6-component cerate layer.

[0187] The preparation method is similar to that of Example 5, except that:

[0188] Step S2:

[0189] La2O3, Nd2O3, Gd2O3, Dy2O3, Ho2O3, Tm2O3 and ZrO2 are weighed according to the stoichiometric ratio, the mixed oxides are ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace and heat-treated at 1500 °C for 5 h to obtain (6RE 1 / 6 )2Zr2O7.

[0190] Step S3:

[0191] Nd2O3, Gd2O3, Y2O3, Er2O3, Yb2O3, Lu2O3 and CeO2 are weighed according to the stoichiometric ratio, the mixed oxides are ball milled at 380 rpm for 12 h, dried, and then placed in a muffle furnace and heat-treated at 1600 °C for 8 h to obtain (6RE 1 / 6 )2Ce2O7.

[0192] The 6-component rare earth zirconate is characterized, and the above (6RE 1 / 6 )2Zr2O7 is sintered at 1600 °C and a pressure of 40 MPa for 0.5 h to obtain (6RE1 / 6 )2Zr2O7sintered bulk, the thermal conductivity of which was measured to be 1.82 W·m- 1 ·K- 1 The grain growth rate of (6RE 1 / 6 )2Zr2O7was measured to be 4.8 nm / h after 200 h of thermal exposure at 1400℃, and the corrosion reaction layer thickness was 264.8 μm after 50 h of corrosion under the molten CMAS film at 1300℃, indicating that the thermal barrier performance, sintering resistance and CMAS corrosion resistance of (6RE

[0193] The 6-component rare earth cerate was characterized, and the above (6RE 1 / 6 )2Ce2O7raw powder was ball milled at 400 rpm for 24 h, sieved through a 300 mesh sieve, and tablet-pressed and formed, and then sintered at 1600℃ for 6 h to obtain (6RE 1 / 6 )2Ce2O7sintered bulk, the thermal conductivity of which was measured to be 1.78 W·m- 1 ·K- 1 The corrosion reaction layer thickness was 23.6 μm after 50 h of corrosion under the molten CMAS film at 1400℃, indicating that the thermal conductivity and CMAS corrosion resistance of the 6-component cerate were poorer than those of the multi-component in Examples 2-4.

[0194] Comparative Example 2

[0195] The present comparative example provides a thermal barrier coating, comprising a metal bonding layer and an 8% yttria-stabilized zirconia layer and a 7-component rare earth zirconate layer sequentially disposed on the metal bonding layer.

[0196] The metal bonding layer was a 100 μm NiCrAlY layer, which was disposed on the surface of a single-crystal nickel-based superalloy and prepared by plasma spraying. The yttria-stabilized zirconia layer had a thickness of 120 μm.

[0197] The chemical formula of the 7-component rare earth zirconate layer was (La 1 / 6 Nd 1 / 6 Smd 1 / 6 Dy 1 / 6 Ho 1 / 6 Tm 1 / 6 )2Zr2O7, and the thickness was 280 μm.

[0198] Comparative Example 3

[0199] The comparative example provides a thermal barrier coating, comprising a metallic bond coat and a 5-component rare earth zirconate layer. The metallic bond coat is a 100 pm layer of NiCrAlY, prepared by plasma spraying, for disposing on the surface of a single-crystal nickel-based superalloy.

[0200] The chemical formula of the 5-component rare earth zirconate layer is (La 1 / 5 Gd 1 / 5 Ho 15 Tmr 1 / 5 Lu 1 / 5 )2Zr2O7, with a thickness of 320 pm.

[0201] Comparative Example 4

[0202] The comparative example provides a thermal barrier coating, comprising a metallic bond coat and a 5-component rare earth zirconate layer and a 5-component rare earth cerate layer disposed in sequence on the metallic bond coat. The metallic bond coat is a 100 pm layer of NiCrAlY, prepared by plasma spraying, for disposing on the surface of a single-crystal nickel-based superalloy.

[0203] The chemical formula of the 5-component rare earth zirconate layer is (La 15 Sm 1 / 5 Gd 1 / 5 Er 1 / 5 Lu 1 / 5 )2Zr2O7, with a thickness of 150 pm.

[0204] The chemical formula of the 5-component rare earth cerate layer is (Gd 15 Dy 1 / 5 Y 1 / 5 Ho 1 / 5 Lu 1 / 5 )2Ce2O7, with a thickness of 150 pm.

[0205] Comparative Example 5

[0206] The comparative example provides a thermal barrier coating, comprising a metallic bond coat and a 14-component rare earth zirconate layer disposed on the metallic bond coat. The metallic bond coat is a 100 pm layer of NiCrAlY, prepared by plasma spraying, for disposing on the surface of a single-crystal nickel-based superalloy.

[0207] The chemical formula of the 14-component rare earth zirconate layer is (La 1 / 14 Pr 1 / 14 Nd 1 / 14 Sm 1 / 14 Eu 1 / 14 Tb 1 / 14 Dy 1 / 14 Y 1 / 14 Ho 1 / 14 Er1 / 4 Tm 1 / 14 Yb 1 / 14 Lu 1 / 14 Sc 1 / 14 )2Zr2O7, thickness of 300 μm.

[0208] The anti-CMAS corrosion thermal barrier coatings of Examples 6-10 and the thermal barrier coatings of Comparative Examples 2-5 were characterized, and tested for cyclic oxidation (55 min / 5 min) and corrosion under a molten CMAS film at 1400℃ (50 h), and the results are shown in Table 1.

[0209] Table 1. Cyclic oxidation performance and CMAS penetration depth test table

[0210] Coating used Cycles to failure CMAS reaction thickness / pm Example 6 465 16.4 Example 7 561 13.5 Example 8 539 -- Example 9 498 -- Example 10 435 3.4 Comparative Example 2 162 675.5 Comparative Example 3 95 539.4 Comparative Example 4 116 46.8 Comparative Example 5 57 278.5

[0211] As can be seen from Table 1, the anti-CMAS corrosion thermal barrier coatings prepared in the present application have much better cyclic life and CMAS corrosion resistance than the thermal barrier coatings using high-entropy / multi-component rare earth zirconate as the ceramic top layer alone, due to the effects of the yttria-stabilized zirconia layer and the multi-component rare earth cerate layer, the multi-component rare earth zirconate layer and / or the CMAS barrier layer. In Examples 8-9, no corrosion was detected, and thus there was no loss of the reaction layer thickness.

[0212] The present application is not limited to the above-described embodiments, and various modifications or changes can be made to the present application without departing from the spirit and scope of the present application, and the present application is intended to include such modifications and changes if they fall within the scope of the claims of the present application and equivalent technology.

Claims

1. A thermal barrier coating resistant to CMAS corrosion, characterized by: It comprises a metal bonding layer, a yttria-stabilized zirconia layer and a multi-component rare earth zirconate layer sequentially disposed on the metal bonding layer, and a multi-component rare earth cerate layer and / or a CMAS barrier layer sequentially disposed on the multi-component rare earth zirconate layer; The multi-component rare earth zirconate layer comprises a multi-component rare earth zirconate, the chemical formula of which is (nRE 1 / n )2Zr2O7, RE is any n types selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and n is not less than 10; The CMAS barrier layer includes a corrosion-resistant oxide having an optical basicity of 0.55-0.

68.

2. The thermal barrier coating for resisting CMAS corrosion according to claim 1, characterized in that: The multi-component rare earth cerate layer comprises a multi-component rare earth cerate, the chemical formula of which is (nRE 1 / n )2Ce2O7, n is not less than 8, and RE is any n combinations of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

3. The thermal barrier coating for resisting CMAS corrosion according to claim 2, characterized in that: The multi-component rare earth cerate has the chemical formula (nRE 1 / n )2Ce2O7, n is not less than 8, RE includes Ho, Er, Tm, Yb, Lu, Sc, Tb and Dy.

4. The thermal barrier coating for resisting CMAS corrosion according to claim 1, characterized in that: The thickness of the rare earth zirconate layer is 20-800 μm.

5. The thermal barrier coating for resisting CMAS corrosion according to claim 1, characterized in that: The thickness of the rare earth cerate layer is 20-400 μm; the thickness of the CMAS barrier layer is 5-50 μm.

6. The thermal barrier coating for resisting CMAS corrosion according to claim 1, characterized in that: The corrosion-resistant oxide with low optical basicity includes at least one of magnesium oxide, cobalt oxide, silicon oxide and aluminum oxide.

7. The thermal barrier coating for resisting CMAS corrosion according to claim 1, characterized in that: The metal bonding layer includes at least one of MCrAlY and PtAl.

8. A method for preparing the thermal barrier coating resistant to CMAS corrosion according to any one of claims 1 to 7, characterized in that: The following steps are involved: preparing a yttria-stabilized zirconia layer on the metal bonding layer; spraying or depositing a multi-component rare earth zirconate layer on the yttria-stabilized zirconia layer: weighing rare earth oxide and zirconium dioxide according to the chemical formula of the multi-component rare earth zirconate, uniformly mixing the rare earth oxide and zirconium dioxide to obtain a first mixed powder, sintering the first mixed powder to obtain the multi-component rare earth zirconate; and depositing the first mixed powder on the yttria-stabilized zirconia layer by plasma spraying, physical vapor deposition, electrophoretic deposition, or molten salt electrophoretic deposition to form the multi-component rare earth zirconate layer; A multi-component rare earth cerate layer and / or the CMAS barrier layer are prepared on the multi-component rare earth zirconate layer.

9. The method for preparing a thermal barrier coating resistant to CMAS corrosion according to claim 8, wherein: In the step of sintering the first mixed powder to obtain multi-component rare earth zirconate, the sintering temperature of the first mixed powder is 1200-1700°C.

10. The method for preparing a thermal barrier coating resistant to CMAS corrosion according to claim 8, characterized in that: In the step of preparing the multi-component rare earth cerate and / or the CMAS barrier layer on the multi-component rare earth zirconate layer, when preparing the multi-component rare earth cerate layer, rare earth oxide and cerium dioxide are weighed according to the chemical formula of the multi-component rare earth cerate, the rare earth oxide and cerium dioxide are uniformly mixed to obtain a second mixed powder, the second mixed powder is sintered in an environment of 1200-1700° C. to obtain a multi-component rare earth cerate powder, and the multi-component rare earth cerate powder is deposited on the multi-component rare earth zirconate layer by plasma spraying, physical vapor deposition, electrophoretic deposition, or molten salt electrophoretic deposition to form a multi-component rare earth cerate layer; When preparing the CMAS barrier layer, the anti-corrosion oxide powder of the CMAS barrier layer is sprayed or deposited on the multi-component rare earth zirconate layer, or the anti-corrosion oxide powder is sprayed or deposited on the multi-component rare earth cerate layer.

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