Thermal barrier coating, preparation method and application

Abstract

The invention discloses a thermal barrier coating, a preparation method and application. The thermal barrier coating comprises a bonding layer, a YSZ ceramic layer and a GYbZ ceramic surface layer which are sequentially arranged in a stacked mode. The GYbZ ceramic surface layer contains (Gd < 0.9 > Yb < 0.1 >) < 2 > Zr2O7; the YSZ ceramic layer contains yttrium oxide stabilized zirconium oxide; the YSZ ceramic layer and the GYbZ ceramic surface layer are respectively provided with a columnar crystal structure. And (Gd0. 9Yb0. 1) 2Zr2O7 is adopted as the ceramic surface layer, so that the CMAS corrosion resistance of the thermal barrier coating can be improved. Due to the columnar crystal structure, the thermal barrier coating has high strain tolerance, internal overall stripping is converted into layer-by-layer stripping of the surface layer, the GYbZ ceramic surface layer is high in phase stability, the thermal expansion coefficient better matched with YSZ and low heat conductivity at high temperature are achieved, stress between layers in the thermal barrier coating is smaller, and the service life of the coating is greatly prolonged.

Description

Technical Field

[0001] This application belongs to the field of thermal barrier coating technology, and relates to a thermal barrier coating, its preparation method and application. Background Technology

[0002] Aero engines are hailed as the "heart" of aircraft and are also the core power source for various high-end defense equipment such as ships, missiles, and rockets. To meet the continuous demands for higher performance in modern aviation, improving the thrust-to-weight ratio of engines has become a key technological direction. With the continuous increase in thrust-to-weight ratio, engine exhaust temperatures, especially turbine inlet temperatures, also rise significantly, placing more stringent requirements on the thermal protection capabilities of materials. Therefore, coating the surface of high-temperature alloy substrates with thermal barrier coatings (TBCs) has become a necessary means to extend service life and ensure operational safety.

[0003] However, in the high-temperature operating environment of engines, tiny silicate particles are ubiquitous in the air, primarily originating from atmospheric dust, volcanic ash, and sandstorms. These particles are typically composed of oxides such as CaO, MgO, Al2O3, and SiO2, collectively referred to as CMAS. Under the influence of high-temperature, high-speed airflow, CMAS particles readily react with or physically erode thermal barrier coatings, leading to coating structural damage, decreased chemical stability, and even peeling failures. This significantly shortens the coating's lifespan and poses a potential threat to the reliability of engine operation. Therefore, there is an urgent need to develop coating materials with excellent mechanical properties, particularly those resistant to the thermal shock of CMAS particles. Summary of the Invention

[0004] Therefore, it is necessary to provide a thermal barrier coating, its preparation method, and its application to improve the thermal barrier coating's resistance to thermal shock from CMAS particles.

[0005] In some embodiments, a thermal barrier coating is provided, comprising an adhesive layer, a YSZ ceramic layer, and a GYbZ ceramic surface layer stacked sequentially.

[0006] The GYbZ ceramic surface layer contains (Gd) 0.9 Yb 0.1 )2Zr2O7;

[0007] The YSZ ceramic layer contains yttrium oxide-stabilized zirconium oxide.

[0008] The YSZ ceramic layer and the GYbZ ceramic surface layer each have a columnar crystal structure.

[0009] In some embodiments, the width of the columnar crystal structure in the YSZ ceramic layer is 2μm to 4μm.

[0010] In some embodiments, the width of the columnar crystal structure in the GYbZ ceramic surface layer is 3μm to 8μm.

[0011] In some embodiments, the thickness of the YSZ ceramic layer and the GYbZ ceramic surface layer are each independently 100 μm to 150 μm.

[0012] In some embodiments, the adhesive layer contains NiPtAl, and the thickness of the adhesive layer is 20 μm to 50 μm.

[0013] In some embodiments, a method for preparing the thermal barrier coating is provided, including a step of preparing an adhesive layer, a step of preparing a YSZ ceramic layer, and a step of preparing a GYbZ ceramic surface layer; wherein,

[0014] In the step of preparing the adhesive layer, an adhesive layer is prepared on the surface of the substrate;

[0015] In the step of preparing the YSZ ceramic layer, the YSZ ceramic layer is deposited on the surface of the adhesive layer on the side away from the substrate by electron beam physical vapor deposition;

[0016] In the step of preparing the GYbZ ceramic surface layer, the GYbZ ceramic surface layer is deposited on the surface of the YSZ ceramic layer away from the adhesive layer by electron beam physical vapor deposition.

[0017] In some embodiments, in the provided method for preparing a thermal barrier coating, the adhesive layer is prepared by using an impact Ni-electroplating Pt-aluminizing process to prepare the adhesive layer containing NiPtAl.

[0018] In some embodiments, the method for preparing the thermal barrier coating, in the step of preparing the YSZ ceramic layer, satisfies one or more of the following conditions:

[0019] (1) The electron gun voltage for electron beam physical vapor deposition is 10KV~20KV;

[0020] (2) The target heating current for electron beam physical vapor deposition is 0.8 A to 1.4 A;

[0021] (3) The working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400 cm 3 / min;

[0022] (4) At a vacuum degree of 1×10 -3 Pa ~ 1×10 -2 The YSZ ceramic layer was prepared under Pa conditions;

[0023] (5) The temperature of the matrix is ​​600℃~1000℃; and

[0024] (6) The rotation speed of the substrate is 10 r / min to 20 r / min.

[0025] In some embodiments, the method for preparing the thermal barrier coating, in the step of preparing the GYbZ ceramic surface layer, satisfies one or more of the following conditions:

[0026] (1) The electron gun voltage for electron beam physical vapor deposition is 10KV~20KV;

[0027] (2) The target heating current for electron beam physical vapor deposition is 0.8 A to 1.4 A;

[0028] (3) The working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400 cm 3 / min;

[0029] (4) At a vacuum degree of 1×10 -3 Pa ~ 1×10 -2 The GYbZ ceramic surface layer was prepared under Pa conditions;

[0030] (5) The temperature of the matrix is ​​800℃~1000℃; and

[0031] (6) The rotation speed of the substrate is 20 r / min to 30 r / min.

[0032] In some embodiments, the thermal barrier coating or the thermal barrier coating prepared by the preparation method is provided for use in the manufacture of engines.

[0033] The provided thermal barrier coating comprises a YSZ ceramic layer and a GYbZ ceramic top layer, exhibiting a columnar crystalline structure. It utilizes (Gd...) 0.9 Yb 0.1 GYbZ, as a ceramic topcoat, enhances the thermal barrier coating's resistance to CMAS corrosion. When CMAS penetrates the coating at high temperatures (>1200℃), GYbZ reacts with CMAS to form a high-melting-point crystalline phase (such as the apatite phase Gd8Ca2(SiO4)6O2), consuming CMAS while forming a dense reaction barrier layer, effectively preventing significant infiltration of CMAS along the columnar crystal gaps of the coating. The columnar crystal structure gives the thermal barrier coating a high strain tolerance, transforming overall internal peeling into layer-by-layer peeling of the surface. The GYbZ ceramic topcoat has high phase stability and a thermal expansion coefficient that matches YSZ better, as well as low thermal conductivity at high temperatures, resulting in lower stress between layers in the thermal barrier coating and significantly extending the coating's lifespan. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments and examples of this application, and to more completely understand this application and its beneficial effects, the accompanying drawings used in the description of the embodiments or examples will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of this application. Those skilled in the art can obtain other drawings based on these drawings without any creative effort.

[0035] Figure 1 The diagram shows a thermal barrier coating in some embodiments, where 100 is a GYbZ ceramic surface layer, 200 is a YSZ ceramic layer, 300 is an adhesive layer, and 400 is a substrate.

[0036] Figure 2 The microstructure of the thermal barrier coating section in Example 1;

[0037] Figure 3 This is a macroscopic morphology image of the surface of the thermal barrier coating in Example 1 after 1000 cycles of gas thermal shock.

[0038] Figure 4 This is a macroscopic morphology image of the surface of the thermal barrier coating in Example 1 after 2000 cycles of gas thermal shock.

[0039] Figure 5 This is a macroscopic surface morphology diagram of the thermal barrier coating CMAS coupled with gas thermal shock after 120 cycles in Example 1.

[0040] Figure 6 This is a macroscopic morphology image of the surface of the thermal barrier coating CMAS coupled with gas thermal shock 400 times in Example 1. Detailed Implementation

[0041] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0042] It should be noted that when a component is said to be "fixed to" another component, it can be directly attached to the other component or there may be an intervening component. When a component is said to be "connected to" another component, it can be directly connected to the other component or there may be an intervening component.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0044] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0045] The terms "and / or," "or / and," and "and / or" as used in this application encompass any one of two or more related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and "a combination of A and B."

[0046] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0047] The terms “combinations thereof,” “any combination thereof,” and “any combination thereof” as used in this application include all suitable combinations of any two or more of the listed items.

[0048] In this application, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0049] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0050] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0051] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0052] In this invention, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0053] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0054] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0055] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0056] In this application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass-volume percentage.

[0057] In this application, "room temperature" generally refers to 5℃~30℃, and more preferably 25±5℃.

[0058] In this application, "YSZ" in the context refers to yttrium-stabilized zirconium oxide.

[0059] In some embodiments, a long-life thermal barrier coating is provided that combines excellent thermal shock resistance and excellent CMAS resistance, and the provided thermal barrier coating meets the service requirements under actual engine operating conditions.

[0060] In some embodiments, a thermal barrier coating is provided, comprising an adhesive layer, a YSZ ceramic layer, and a GYbZ ceramic surface layer stacked sequentially.

[0061] GYbZ ceramic surface layer contains (Gd) 0.9 Yb 0.1 )2Zr2O7;

[0062] The YSZ ceramic layer contains yttrium oxide-stabilized zirconium oxide;

[0063] The YSZ ceramic layer and the GYbZ ceramic surface layer each have a columnar crystal structure.

[0064] The coefficient of thermal expansion (CTE) of Gd₂Zr₂O₇ is approximately 8.5~9.5×10⁻⁶. -6 K -1 (1200℃), while the CTE of YSZ is approximately 11×10 -6 K -1 Yb 3+ After doping, (Gd 0.9 Yb 0.1 The CTE of 2Zr2O7 (GYbZ) was increased to 11.86 × 10⁻⁶. -6 K -1 (1200℃). Low thermal conductivity is an essential property of thermal barrier coatings. The thermal conductivity of Gd2Zr2O7 increases significantly at high temperatures (~1600℃), reaching as high as 1.16 W / m. -1 K -1 In contrast (Gd 0.9 Yb 0.1 The thermal conductivity of 2Zr2O7 at 1600℃ is only 0.8 W / m. -1 K -1 It can suppress high-temperature radiative thermal conductivity and effectively suppress the increase of high-temperature thermal conductivity of the coating.

[0065] The provided thermal barrier coating comprises a YSZ ceramic layer and a GYbZ ceramic top layer. It utilizes Yb-modified gadolinium zirconate (Gd... 0.9 Yb 0.1 (2Zr2O7, GYbZ) is used as a ceramic surface layer, which improves the resistance to CMAS corrosion while taking into account the thermal expansion coefficient that is more compatible with YSZ and the lower thermal conductivity.

[0066] In some embodiments, the width of the columnar crystal structure in the YSZ ceramic layer in the provided thermal barrier coating is 2μm to 4μm. For example, the width of the columnar crystal structure in the YSZ ceramic layer can be 2μm, 3μm, 4μm, etc., or it can be a range composed of any two of the aforementioned values.

[0067] In some embodiments, the width of the columnar crystal structure in the GYbZ ceramic surface layer of the provided thermal barrier coating is 3μm to 8μm. For example, the width of the columnar crystal structure in the GYbZ ceramic surface layer can be 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, etc., or it can be a range composed of any two of the aforementioned values.

[0068] In some embodiments, the thickness of the YSZ ceramic layer and the GYbZ ceramic surface layer in the provided thermal barrier coating is independently 100 μm to 150 μm. For example, the thickness of the YSZ ceramic layer and the GYbZ ceramic surface layer can be independently 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, etc., or it can be a range composed of any two of the aforementioned values.

[0069] In some embodiments, the provided thermal barrier coating contains NiPtAl in the adhesive layer, and the thickness of the adhesive layer is 20μm to 50μm. For example, the thickness of the adhesive layer can be 20μm, 30μm, 40μm, 50μm, etc., or it can be a range composed of any two of the aforementioned values.

[0070] The material used for the GYbZ ceramic surface layer is (Gd) 0.9 Yb 0.1 GYbZ ceramic topcoat has high phase stability and a thermal expansion coefficient that is more compatible with YSZ, as well as low thermal conductivity at high temperatures. This improves the thermal barrier coating's resistance to CMAS corrosion while maintaining a better thermal expansion coefficient and lower thermal conductivity compared to YSZ. The thermal expansion coefficient of the GYbZ ceramic topcoat is more compatible with that of the YSZ ceramic layer, resulting in lower stress between layers in the thermal barrier coating.

[0071] Using (Gd) 0.9 Yb 0.1 GYbZ, as a ceramic topcoat, can enhance the thermal barrier coating's resistance to CMAS corrosion. When CMAS penetrates the coating at high temperatures (>1200℃), GYbZ reacts with CMAS to form a high-melting-point crystalline phase (such as the apatite phase Gd8Ca2(SiO4)6O2), consuming CMAS while forming a dense reaction barrier layer, effectively preventing CMAS from penetrating significantly into the columnar intergranular spaces of the coating.

[0072] In some embodiments, a method for preparing a thermal barrier coating is provided, including a step of preparing an adhesive layer, a step of preparing a YSZ ceramic layer, and a step of preparing a GYbZ ceramic surface layer; wherein,

[0073] In the step of preparing the adhesive layer, an adhesive layer is prepared on the surface of the substrate;

[0074] In the step of preparing the YSZ ceramic layer, the YSZ ceramic layer is deposited on the surface of the binder layer away from the substrate by electron beam physical vapor deposition;

[0075] In the step of preparing the GYbZ ceramic surface layer, the GYbZ ceramic surface layer is deposited on the surface of the YSZ ceramic layer away from the binder layer by electron beam physical vapor deposition.

[0076] A columnar crystalline structure coating constructed using electron beam physical vapor deposition (EB-PVD) can reduce thermal mismatch stress within the coating during thermal shock cycling. The EB-PVD-prepared coating exhibits a vertically growing columnar crystalline structure. The columnar crystals are connected by nanoscale pores or weakly bonded grain boundaries. During thermal cycling, due to the difference in coefficients of thermal expansion (CTE) between layers and between layers and the substrate, transverse tensile stress is generated within the coating. The weak bonding interfaces between the columnar crystals allow for minute relative sliding or local separation (high strain tolerance), effectively releasing stress and preventing crack propagation within the coating, enabling it to withstand greater strain without cracking. The provided thermal barrier coating possesses a columnar crystalline structure, which gives it high strain tolerance, transforming overall internal peeling into layer-by-layer surface peeling, significantly extending the coating's lifespan.

[0077] In some embodiments, in the provided method for preparing a thermal barrier coating, the bonding layer preparation step employs an impact Ni-electroplating Pt-aluminizing process to prepare a bonding layer containing NiPtAl.

[0078] In some embodiments, in the method for preparing the thermal barrier coating, the electron gun voltage of the electron beam physical vapor deposition in the step of preparing the YSZ ceramic layer is 10KV~20KV. For example, the electron gun voltage can be 10KV, 11KV, 12KV, 13KV, 14KV, 15KV, 16KV, 17KV, 18KV, 19KV, 20KV, etc., or it can be a range composed of any two of the aforementioned values.

[0079] In some embodiments, in the provided method for preparing the thermal barrier coating, in the step of preparing the YSZ ceramic layer, the target heating current for electron beam physical vapor deposition is 0.8 A to 1.4 A. For example, the target heating current can be 0.8 A, 0.9 A, 1.0 A, 1.1 A, 1.2 A, 1.3 A, 1.4 A, etc., or it can be a range composed of any two of the aforementioned values.

[0080] In some embodiments, in the method for preparing the thermal barrier coating, during the step of preparing the YSZ ceramic layer, the working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400 cm 3 / min, for example, the oxygen flow rate can be 300 cm. 3 / min, 350 cm 3 / min, 400 cm 3 / min, etc., can also be a range composed of any two of the aforementioned values.

[0081] In some embodiments, in the provided method for preparing a thermal barrier coating, the step of preparing the YSZ ceramic layer is carried out under a vacuum of 1×10⁻⁶. -3 Pa ~ 1×10 -2 YSZ ceramic layers are prepared under Pa conditions, for example, a vacuum degree of 1×10⁻⁶. -3 Pa, 2×10 -3 Pa, 3×10 -3 Pa, 4×10 -3 Pa, 5×10 -3 Pa, 6×10 -3 Pa, 7×10 -3 Pa, 8×10 -3 Pa, 9×10 -3 Pa, 1×10 -2 Pa, etc., can also be a range consisting of any two of the aforementioned values.

[0082] In some embodiments, in the method for preparing the thermal barrier coating, the temperature of the substrate in the step of preparing the YSZ ceramic layer is 600℃~1000℃. For example, the temperature of the substrate can be 600℃, 700℃, 800℃, 900℃, 1000℃, etc., or it can be a range composed of any two of the aforementioned values.

[0083] In some embodiments, in the method for preparing the thermal barrier coating, the rotation speed of the substrate in the step of preparing the YSZ ceramic layer is 10 r / min to 20 r / min. For example, the rotation speed of the substrate can be 10 r / min, 15 r / min, 20 r / min, etc., or it can be a range composed of any two of the aforementioned values.

[0084] In some embodiments, in the method for preparing the thermal barrier coating, the electron gun voltage of the electron beam physical vapor deposition in the step of preparing the GYbZ ceramic surface layer is 10KV~20KV. For example, the electron gun voltage can be 10KV, 12KV, 14KV, 16KV, 18KV, 20KV, etc., or it can be any range of two of the aforementioned values.

[0085] In some embodiments, in the method for preparing the thermal barrier coating, the target heating current for electron beam physical vapor deposition in the step of preparing the GYbZ ceramic surface layer is 0.8 A to 1.4 A. For example, the target heating current can be 0.8 A, 0.9 A, 1.0 A, 1.1 A, 1.2 A, 1.3 A, 1.4 A, etc., or it can be a range composed of any two of the aforementioned values.

[0086] In some embodiments, in the method for preparing the thermal barrier coating, during the step of preparing the GYbZ ceramic surface layer, the working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400 cm 3 / min, for example, the oxygen flow rate can be 300 cm. 3 / min, 350 cm 3 / min, 400 cm 3 / min, etc., can also be a range composed of any two of the aforementioned values.

[0087] In some embodiments, in the method for preparing the thermal barrier coating, the step of preparing the GYbZ ceramic surface layer is carried out under a vacuum of 1×10⁻⁶. -3 Pa ~ 1×10 -2 GYbZ ceramic surface layer was prepared under Pa conditions;

[0088] In some embodiments, in the method for preparing the thermal barrier coating, the temperature of the substrate in the step of preparing the GYbZ ceramic surface layer is 800℃~1000℃. For example, the temperature of the substrate can be 800℃, 850℃, 900℃, 950℃, 1000℃, etc., or it can be a range composed of any two of the aforementioned values.

[0089] In some embodiments, in the method for preparing the thermal barrier coating, during the step of preparing the GYbZ ceramic surface layer, the rotational speed of the substrate is 20 r / min to 30 r / min. For example, the rotational speed of the substrate can be 20 r / min, 25 r / min, 30 r / min, etc., or it can be a range composed of any two of the aforementioned values. In some embodiments, in the method for preparing the thermal barrier coating, during the step of preparing the adhesive layer, a NiPtAl-containing adhesive layer is prepared using an impact Ni plating-Pt electroplating-aluminizing process.

[0090] In some embodiments, in the method for preparing the thermal barrier coating, in the step of preparing the adhesive layer, the substrate is placed in an aqueous nickel source solution for impact plating to obtain a nickel-plated substrate, and the nickel-plated substrate is placed in an aqueous platinum source solution for electroplating, annealing, and vapor-phase aluminizing to obtain an adhesive layer containing NiPtAl.

[0091] In some embodiments, the method for preparing the thermal barrier coating further includes a pretreatment step on the surface of the substrate.

[0092] In some implementations, the surface of the substrate is pretreated by wet sandblasting.

[0093] In some implementations, the wet blasting parameters include: a pressure of 0.2 MPa to 0.5 MPa and a time of 1 min to 5 min.

[0094] In some embodiments, the application of a thermal barrier coating or a thermal barrier coating prepared by a preparation method is provided in the manufacture of an engine. In some embodiments, the engine is an aero-engine.

[0095] The following are specific embodiments. They are intended to provide a more detailed description of this application to help those skilled in the art and researchers better understand it. The technical conditions described do not constitute any limitation on this application. Any modifications made within the scope of the claims of this application are protected by the claims.

[0096] Unless otherwise stated, all raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. Experimental methods not specifying particular conditions in the examples were performed under conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0097] Example 1

[0098] This embodiment provides a thermal barrier coating. The preparation method of the provided thermal barrier coating is as follows:

[0099] The surface of the single-crystal superalloy IC21 was wet-blasted using white corundum sand with a particle size of 180-220 mesh and a content of 25%, under an air pressure of 0.3 MPa and a water pressure of >2 Kg / cm³. 2 The blowing distance was 240 mm. Subsequently, the sample was ultrasonically cleaned with distilled water and acetone for 10 min and 20 min respectively, and then dried.

[0100] The pretreated sample was placed in a 100 ml / L dilute hydrochloric acid solution for 30 s for surface activation. After rinsing, it was immersed in a nickel chloride solution for 1 min of Ni impact plating. Subsequently, it was placed in a Pt plating solution, powered by a constant current power supply, with a clean TiPt mesh as the anode. The current density during electroplating was 1 ASD, and after 30 min, the Pt plating thickness reached 20 μm. Then, it was plated under vacuum at 1050 ℃ (< 5 × 10⁻⁶). -3 Annealing (Pa) for 2 h. The annealed samples were then subjected to vapor-phase aluminizing using a mixture of FeAl powder (Al content 49 wt.%) and 2 wt.% NH4Cl. Under a closed, inert environment, a high-temperature, low-activity aluminizing process was employed, heating to 1050 ℃ (heating rate less than 8 ℃ / min) and holding for 5 h, followed by furnace cooling to obtain a β-(Ni,Pt)Al binder layer with a thickness of 20–30 μm.

[0101] The sample with the obtained β-(Ni, Pt)Al binder layer was suspended above the target using a metal wire. A YSZ ceramic layer and a GYbZ ceramic surface layer were sequentially deposited on the binder layer surface using EB-PVD. The target material used for preparing the YSZ ceramic layer was YSZ, and the sample was placed at a depth of 1×10⁻⁶. -2 Coating deposition was performed in a coating chamber under vacuum conditions of 20 kV, with an electron gun voltage of 20 kV and a target heating current of 1.3 A. During deposition, the sample was first preheated to 900 °C within the chamber, and the oxygen flow rate was 300 cm⁻¹. 3 The sample rotation speed was 15 r / min, and a YSZ ceramic layer was obtained. The target material was then changed to (Gd... 0.9 Yb 0.1 GYbZ ceramic surface layer was prepared using 2Zr2O7, and the sample was in a 1×10⁻⁶ range. -2 Coating deposition was performed in a coating chamber under vacuum conditions of 20 kV, with an electron gun voltage of 20 kV and a target heating current of 1.3 A. During deposition, the sample was first preheated to 900 °C within the chamber, and the oxygen flow rate was 300 cm⁻¹. 3 The sample rotation speed was 20 r / min, and the GYbZ ceramic surface layer was obtained.

[0102] The obtained thermal barrier coating was structurally characterized using the following method:

[0103] The microstructure of the thermal barrier coating cross-section was observed using scanning electron microscopy (SEM), and the results are as follows: Figure 2 As shown, from Figure 2As can be seen, the obtained thermal barrier coatings, specifically the YSZ ceramic layer and the GYbZ ceramic surface layer, possess columnar crystal structures. The thickness of the β-(Ni,Pt)Al single-phase coating is 27.8±0.12 μm, the thickness of the YSZ ceramic layer is 144.1±0.57 μm, and the thickness of the GYbZ ceramic surface layer is 136.9±0.48 μm. The width of the columnar crystal structure in the YSZ ceramic layer is 3.16±0.78 μm, and the width of the columnar crystal structure in the GYbZ ceramic surface layer is 5.63±1.57 μm.

[0104] Performance testing

[0105] (1) 1350 ℃ gas thermal shock test

[0106] The thermal barrier coating was subjected to a 1350℃ thermal shock test on a high-temperature gas thermal shock tester. A high-temperature flame was generated by the combustion of a mixture of methane and oxygen, and the thermal barrier coating was subjected to the 1350℃ gas thermal shock test. At the start of the cycle, the sample surface temperature was raised from room temperature to 1350±50℃ within 90 seconds and held for 300 seconds, then lowered to room temperature within 60 seconds, while maintaining the substrate temperature below 1050℃ throughout the entire cycle. After every 100 cycles, the sample was visually inspected, and the coating surface condition was recorded. When more than 20% of the coating on the sample surface peeled off, it was considered to have failed; the number of cycles at this point is the coating life.

[0107] The macroscopic morphology of the coating surface obtained in Example 1 under different gas thermal shock cycles is shown in the following figures. Figure 3 , Figure 4 As shown. It can be seen that after 1000 thermal shocks of the gas ( Figure 3 Only the center of the coating showed spot-like peeling, and the peeling occurred layer by layer; after 2000 cycles ( Figure 4 The area of ​​GYbZ surface layer peeling has expanded but the substrate has not been exposed, and the coating structure remains intact, proving that the coating structure has a lifespan of more than 2,000 gas thermal shock cycles and has excellent high-temperature thermal shock resistance.

[0108] (2) CMAS coupled gas thermal shock test

[0109] The CMAS corrosion-coupled gas thermal shock treatment involves preparing a suspension of CMAS and ethanol (3 wt.%) and spraying it onto the sample surface to ensure uniform deposition of CMAS particles. The spraying rate is set to 0.02 g / cycle. During spraying, the sample must be placed horizontally with the nozzle directly facing the sample surface, ensuring complete coverage. After each spray, allow the sample to stand for a few minutes to allow the ethanol to evaporate before continuing spraying until the CMAS coating thickness reaches 20 mg / cm³. 2After spraying, the sample was mounted on a thermal shock device, and a gas thermal shock test was conducted according to standard procedures. A high-temperature flame was generated by the combustion of a mixture of methane and oxygen, and the thermal barrier coating was subjected to a 1350°C gas thermal shock test. At the start of the cycle, the sample surface temperature was raised from room temperature to 1350±50°C within 90 seconds and held for 300 seconds, then lowered to room temperature within 60 seconds, while maintaining the substrate temperature below 1050°C throughout the entire cycle. After every 100 cycles, the sample was visually inspected, and the coating surface condition was recorded. When more than 20% of the coating on the sample surface peeled off, it was considered a failure, and the number of cycles at this point was the coating life. The macroscopic morphology of the coating surface obtained in the example under different CMAS coupled gas thermal shock cycles is shown in the figure below. Figure 5 , Figure 6 As shown. It can be seen that after 120 cycles of CMAS-coupled gas thermal shock ( Figure 5 Only after 400 cycles did peeling begin to appear in the center of the coating; Figure 6 The peeling area expanded but did not expose the substrate. A large amount of GYbZ surface layer still existed, and the coating structure remained intact, proving that the coating structure has a thermal shock resistance life of more than 400 cycles against CMAS coupled gas and has excellent resistance to molten CMAS thermal shock.

[0110] Comparative Example 1

[0111] This comparative example provides a thermal barrier coating. Compared to the thermal barrier coating in Example 1, this thermal barrier coating does not have a columnar crystal structure and does not have a GYbZ ceramic surface layer. The preparation method is similar to that in Example 1, except that an atmospheric plasma spraying (APS) method is used to prepare the YSZ monolayer ceramic layer TBCs, the thickness of which is approximately 150 μm, and no GYbZ ceramic surface layer is prepared.

[0112] The sample's service life was 130 cycles under 1250 °C gas thermal shock and 4 cycles under CMAS coupled gas thermal shock tests. Its service life is significantly shorter than that of the embodiments described in this application.

[0113] Comparative Example 2

[0114] This comparative example provides a thermal barrier coating with a columnar crystalline structure and no GYbZ ceramic surface layer. The preparation method is similar to that in Example 1, except that no GYbZ ceramic surface layer is deposited.

[0115] The specimen's lifespan was 410 cycles under 1200 °C gas thermal shock and 50 cycles under 1300 °C CMAS coupled gas thermal shock tests.

[0116] Combined with the CMAS coupled gas thermal shock experiments in the examples and comparative examples, it can be seen that both the columnar crystalline thermal barrier coating and the deposition of a GYbZ ceramic surface layer on the ceramic surface are beneficial to improving the coating's resistance to CMAS thermal shock. This demonstrates that the double-ceramic-layer columnar structure coating provided by the present invention has better resistance to CMAS thermal shock.

[0117] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0118] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A thermal barrier coating, characterized in that, It includes an adhesive layer, a YSZ ceramic layer, and a GYbZ ceramic surface layer stacked in sequence; The GYbZ ceramic surface layer contains (Gd) 0.9 Yb 0.1 )2Zr2O7; The YSZ ceramic layer contains yttrium oxide-stabilized zirconium oxide. The YSZ ceramic layer and the GYbZ ceramic surface layer each have a columnar crystal structure.

2. The thermal barrier coating according to claim 1, characterized in that, The width of the columnar crystal structure in the YSZ ceramic layer is 2μm~4μm.

3. The thermal barrier coating according to claim 1, characterized in that, The width of the columnar crystal structure in the GYbZ ceramic surface layer is 3μm~8μm.

4. The thermal barrier coating according to any one of claims 1 to 3, characterized in that, The thickness of the YSZ ceramic layer and the GYbZ ceramic surface layer are each independently 100μm to 150μm.

5. The thermal barrier coating according to any one of claims 1 to 3, characterized in that, The adhesive layer contains NiPtAl, and the thickness of the adhesive layer is 20μm~50μm.

6. The method for preparing the thermal barrier coating according to any one of claims 1 to 5, characterized in that, This includes the steps of preparing the adhesive layer, preparing the YSZ ceramic layer, and preparing the GYbZ ceramic surface layer; among which, In the step of preparing the adhesive layer, an adhesive layer is prepared on the surface of the substrate; In the step of preparing the YSZ ceramic layer, the YSZ ceramic layer is deposited on the surface of the adhesive layer on the side away from the substrate by electron beam physical vapor deposition; In the step of preparing the GYbZ ceramic surface layer, the GYbZ ceramic surface layer is deposited on the surface of the YSZ ceramic layer away from the adhesive layer by electron beam physical vapor deposition.

7. The method for preparing a thermal barrier coating according to claim 6, characterized in that, In the step of preparing the adhesive layer, the adhesive layer containing NiPtAl is prepared by impact plating Ni-electroplating Pt-aluminizing process.

8. The method for preparing a thermal barrier coating according to claim 6, characterized in that, In the process of preparing the YSZ ceramic layer, one or more of the following conditions must be met: (1) The electron gun voltage for electron beam physical vapor deposition is 10KV~20KV; (2) The target heating current for electron beam physical vapor deposition is 0.8 A to 1.4 A; (3) The working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400cm 3 / min; (4) At a vacuum degree of 1×10 -3 Pa ~ 1×10 -2 The YSZ ceramic layer was prepared under Pa conditions; (5) The temperature of the matrix is ​​600℃~1000℃; and (6) The rotation speed of the substrate is 10 r / min to 20 r / min.

9. The method for preparing a thermal barrier coating according to any one of claims 6 to 8, characterized in that, In the process of preparing the GYbZ ceramic surface layer, one or more of the following conditions must be met: (1) The electron gun voltage for electron beam physical vapor deposition is 10KV~20KV; (2) The target heating current for electron beam physical vapor deposition is 0.8 A to 1.4 A; (3) The working gas for electron beam physical vapor deposition includes oxygen, and the oxygen flow rate is 300 cm⁻¹. 3 / min~400cm 3 / min; (4) At a vacuum degree of 1×10 -3 Pa ~ 1×10 -2 The GYbZ ceramic surface layer was prepared under Pa conditions; (5) The temperature of the matrix is ​​800℃~1000℃; and (6) The rotation speed of the substrate is 20 r / min to 30 r / min.

10. The application of the thermal barrier coating according to any one of claims 1 to 5 or the thermal barrier coating prepared by the preparation method according to any one of claims 6 to 9 in the manufacture of an engine.

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