CN112391601A - Thermal barrier coating and method for producing the same - Google Patents
Thermal barrier coating and method for producing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
Abstract
The invention provides a thermal barrier coating and a preparation method thereof, which can improve the bonding force between TGO and a bonding layer and improve the oxidation resistance of the bonding layer. The preparation method of the thermal barrier coating comprises the steps of generating a bonding layer on the surface of a substrate through chemical vapor deposition or physical vapor deposition; injecting/depositing Zr and/or Hf elements to the shallow surface of the bonding layer by using PIII & D to generate an in-situ modified layer; and generating a top layer on the in-situ modified layer.
Description
Technical Field
The invention relates to a thermal barrier coating and a preparation method thereof.
Background
In order to improve the fuel economy and the working thrust, the inlet temperature of a turbine of an aeroengine is gradually increased and far exceeds the allowable use temperature of the traditional nickel-based single crystal superalloy. Thermal Barrier Coating (TBC) is widely applied to high-temperature end components such as high-pressure turbine blades and the like, is used for isolating component substrates and high-temperature gas, resists high-temperature oxidation and corrosion, reduces the surface temperature of the substrates, improves the working efficiency of unit bodies such as turbines and the like, prolongs the service life of the unit bodies, and saves the operating cost of aero-engines.
Thermal barrier coatings are typically composed of two parts: the outer layer in contact with the combustion gases, called the Top Coat (TC), is mainly a ceramic insulating material, the common component being yttrium oxide(Y2O3) Stabilized zirconium dioxide (ZrO)2) Or rare earth oxides, whose function is to insulate against heat; the intermediate layer between the facing and the substrate is called a Bond Coat (BC), and is usually composed of MCrAlY (M ═ Ni, Co or NiCo) and nial (pt), which functions to relieve thermal stress and resist corrosion oxidation of the substrate and ceramic layers due to thermal mismatch.
In service of the thermal barrier coating, the following processes can occur: a protective TGO layer (thermal growth oxides, e.g. Al) of only a few microns thickness is formed between the adhesive layer and the facing layer2O3Etc.) and the thickness is gradually increased, Al element and the like in the adhesive layer are consumed; the bonding layer and the matrix are mutually diffused, active elements in the bonding layer are diffused to the matrix, matrix refractory elements are diffused to the bonding layer, and basic characteristics of the bonding layer and the matrix material are changed; thermal stress build-up occurs due to mismatch of thermal expansion coefficients of the bond coat, TGO and face coat, with wrinkling, cracking and peeling of the TGO layer. Thus, the bond coat plays a critical role in service and failure of the thermal barrier coating.
Research shows that a small amount or trace of trace elements added into the bonding layer can promote alpha-Al2O3Generating, improving the bond between TGO and bond coat, avoiding or retarding spinel structure (Ni, Co) (Cr, Al) in TGO2O4Oxides are formed which are prone to crack initiation under high and low temperature cycling and lead to coating failure. In addition, the surface stress state of the bonding layer has a large influence on crack propagation, and surface tensile stress is generally considered to be more likely to cause rapid crack propagation and merging, so that the coating is cracked and fails.
The conventional preparation processes of thermal barrier coatings commonly used in industry include thermal spraying, electroplating, chemical vapor infiltration, ion plating, electron beam physical vapor deposition and the like. Therefore, trace elements are added/synthesized to materials such as powder for spray coating, plating solution, target material for deposition, and the like, in order to be incorporated into the coating layer. For example, 0.2-1.5% of Y element is added into NiCrAl powder, and a NiCrAlY bonding layer is prepared by a plasma spraying process. In general, the conventional process method generally has the problem that trace elements are easy to diffuse to the matrix, so that the matrix performance is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a thermal barrier coating, which can improve the bonding force between TGO and a bonding layer and improve the oxidation resistance of the bonding layer.
It is another object of the present invention to provide a thermal barrier coating.
The preparation method of the thermal barrier coating comprises the following steps:
generating a bonding layer on the surface of the substrate through chemical vapor deposition or physical vapor deposition;
injecting/depositing Zr and/or Hf elements to the shallow surface of the bonding layer by using PIII & D to generate an in-situ modified layer; and
and generating a surface layer on the in-situ modified layer.
In one embodiment, the bond coat is MCrAlY (M ═ Ni, Co, or NiCo), NiAl, and NiPtAl.
In one embodiment, the in-situ modification layer is formed by applying Zr PIII & D, Hf PIII & D, Zr/Hf binary PIII & D, Zr PIII & D first and Hf PIII & D second or Hf PIII & D first and Zr PIII & D second to the surface of the bond coat.
In one embodiment, when PIII & D is used, pure Zr and pure Hf metals are used as cathode targets with a purity of not less than 99.99%.
In one embodiment, the thickness of the in-situ modification layer is 0 to 500 nm.
In one embodiment, when using PIII & D, the Zr and Hf element content of the bond coat surface is adjusted by the cathode trigger frequency, cathode trigger pulse width, implant/deposition voltage, implant/deposition frequency, or implant deposition time parameters.
In one embodiment, in the in-situ modification layer, the Zr content is controlled to be in the range of 0 to 20 at.%, and the Hf content of the surface of the adhesive layer is controlled to be in the range of 0 to 20 at.%.
The thermal barrier coating according to the invention is obtained with any of the methods described.
The thermal barrier coating is applied to a substrate and comprises a surface layer in contact with the outside and a bonding layer between the surface layer and the substrate, wherein the bonding layer is provided with an in-situ modification layer, the thickness of the in-situ modification layer is 0-500 nm, and Zr and/or Hf elements are doped in the in-situ modification layer.
In the thermal barrier coating, in the in-situ modification layer, the Zr content is within the range of 0-20 at.%, and the Hf content on the surface of the bonding layer is within the range of 0-20 at.%.
The beneficial effects are as follows:
zr and Hf elements are distributed in the depth range of the shallow surface of the bonding layer, the integral performance of the bonding layer and the base body is not changed, the bonding force of TGO and the bonding layer is improved while the integral composition, structure and performance of the bonding layer and the base body are not influenced, and the oxidation resistance of the bonding layer is improved;
secondly, Zr and Hf elements are effectively introduced into the bonding layer to promote alpha-Al2O3Generating and reducing the wrinkles of the adhesive layer;
regulating and controlling the surface stress state of the bonding layer to enable the bonding layer to be in a compressive stress state, and prolonging the service life of the coating;
for adding microelements in hot spraying, electroplating, chemical vapor infiltration, ion plating and electron beam physical vapor deposition, the Zr and Hf element content can be conveniently and accurately controlled by the scheme, repeated development and verification of novel powder, electroplating solution and target materials are avoided, and the coating development efficiency is improved.
Drawings
The above and other features, properties and advantages of the present invention will become more apparent from the following description of the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a bond coat modification schematic of a thermal barrier coating.
Detailed Description
The following discloses many different embodiments or examples for implementing the subject technology described. Specific examples of components and arrangements are described below to simplify the present disclosure, but these are merely examples and do not limit the scope of the invention. For example, if a first feature is formed over or on a second feature described later in the specification, this may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features are formed between the first and second features, such that the first and second features may not be in direct contact. Additionally, reference numerals and/or letters may be repeated among the various examples throughout this disclosure. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. Further, when a first element is described as being coupled or coupled to a second element, the description includes embodiments in which the first and second elements are directly coupled or coupled to each other, as well as embodiments in which one or more additional intervening elements are added to indirectly couple or couple the first and second elements to each other.
Plasma immersion ion implantation and deposition (PIII & D) is a surface modification technique that uses high-pressure ion beams to accelerate and act on a material to be modified, and changes the properties of the shallow surface composition, structure, and the like of the material. The literature, "plasma immersion ion implantation deposition techniques and applications", explains the technical terminology in detail, and PIII & D are mainly of three types: (1) an ion implantation type; (2) film deposition type; (3) and (4) injecting a deposition type.
The method for preparing the thermal barrier coating of the following embodiment comprises the following steps: generating a bonding layer on the surface of the substrate through chemical vapor deposition or physical vapor deposition; injecting Zr and/or Hf elements to the shallow surface of the bonding layer by using PIII & D to generate an in-situ modified layer; and generating a top layer on the in-situ modified layer. The improvement is mainly characterized in that in the second step, Zr and/or Hf elements are injected to the shallow surface of the bonding layer by using PIII & D to generate an in-situ modified layer, the second step is described in detail later, and the first step and the third step are not described in detail. FIG. 1 shows a schematic diagram of a modified bonding layer structure, wherein 10 represents a substrate, 20 represents a bonding layer, and 25 represents an in-situ modified layer.
In the following embodiment, PIII & D is used for carrying out surface modification on the bonding layer of the thermal barrier coating, Zr and/or Hf elements are injected to the shallow surface of the bonding layer, the surface composition, the structure and the stress state of the bonding layer are changed, and the performance is optimized to different degrees.
More specifically, as an example, the following process scheme may be employed.
1) Pretreatment of
Ultrasonic cleaning of the part with the adhesive layer is performed using organic solvents including, but not limited to, ethanol, acetone, or isopropanol. And (3) placing the parts subjected to ultrasonic cleaning in an oven for drying, wherein the temperature of the oven is not higher than 100 ℃.
2) Surface modification
And clamping the part by using a proper tool clamp, and shielding the uncoated area of the part. Placing the part on a vacuum cavity target table of the equipment, and vacuumizing until the vacuum degree is higher than 5 multiplied by 10-3Pa, starting the target platform to rotate. Starting the high voltage of the cathode, triggering the cathode, starting the high voltage (0.5 kV-100 kV) of the target platform, and implementing the modification process. And stopping the process after the set time is reached. In the step, the part is placed in a vacuum cavity and connected with high pressure, a plasma sheath layer is formed around the part, Zr + and Hf + ions triggered by Zr cathode and Hf cathode target materials are introduced into the vacuum cavity and accelerated by the plasma sheath layer to form high-energy ion beams, the high-energy ion beams interact with the surface of the bonding layer until the ions stop moving, the surface components, the structure and the stress state of the bonding layer are changed, and the performance is optimized in different degrees.
3) Post-treatment
After the injection/deposition is completed, the cathode trigger is turned off, and the target table high voltage is turned off. Argon is input into the vacuum cavity, a radio frequency power supply is started to ionize the argon, a target table bias voltage (voltage 0 (more than 0) to 2000V) is started, and the modification process is implemented. And stopping the process after the set time is reached.
In the foregoing processes, the bonding layer includes, but is not limited to, MCrAlY (M ═ Ni, Co, or NiCo), NiAl, and NiPtAl, and the preparation process of the bonding layer includes chemical vapor deposition and physical vapor deposition. As a recommended scheme, NiAl or NiPtAl is selected as the bonding layer.
In the foregoing process, Zr PIII & D (PIII & D injection/deposition Zr element), Hf PIII & D (PIII & D injection/deposition Hf element), Zr/Hf binary PIII & D (PIII & D simultaneous injection/deposition Hf, Zr element), Zr-PIII & D first and Hf-PIII & D second or Hf-PIII & D first and Zr-PIII & D second can be performed on the surface of the bond coat.
In the process, pure metal Zr and pure metal Hf are used as cathode target materials, and the purity is not lower than 99.99%.
In the above process, the Zr content on the surface of the bonding layer can be controlled within the range of 0 (more than 0) to 20 at.%, and the Hf content on the surface of the bonding layer can be controlled within the range of 0 to 20 at.%.
In the process, the components, the structures and the performances of the depth of 0 (more than 0) to 500nm of the surface of the bonding layer can be regulated and controlled, and the in-situ modified layer within 500nm can be formed.
In the step 2), the content of Zr element and Hf element on the surface of the bonding layer can be adjusted through parameters such as cathode trigger frequency, cathode trigger pulse width, injection/deposition voltage, injection/deposition frequency, injection deposition time and the like.
In the foregoing process, the post-treatment step may or may not be carried out.
The process only modifies the components, structure and performance of an in-situ modification layer (usually in the depth range of hundreds of nanometers) of the bonding layer, so that trace elements are not easy to diffuse to a substrate to influence the performance of the substrate, and the overall components, structure and performance of the bonding layer and the substrate are not influenced. In the service process of the modified bonding layer, the bonding force between the TGO layer and the bonding layer and the oxidation resistance of the bonding layer are improved, the wrinkle of the bonding layer is improved and delayed, and the surface stress of the bonding layer is compressive stress.
In conclusion, Zr and/or Hf elements are controllably introduced to the shallow surface of the bonding layer by the process to form an in-situ modified layer, so that the bonding force between the TGO and the bonding layer is improved, the oxidation resistance of the bonding layer is improved, and the wrinkles of the bonding layer in the service process of the coating are reduced while the integral composition, structure and performance of the bonding layer and the substrate are not influenced.
As a recommended proposal, Zr/Hf binary PIII is selected&D, selecting process parameters including vacuum degree of 1 multiplied by 10-3Pa～10×10-3Pa, the high voltage of the target table is 0.5kV to 100kV, the injection/deposition pulse width is 50 to 2000 microseconds, the injection/deposition frequency is 5 to 20Hz, the cathode source trigger pulse width is 200 to 3000 microseconds, and the injection/deposition time is 15 to 180 minutes.
The proposed solution has the following characteristics:
1) the Zr and Hf elements are effectively introduced into the bonding layer, the generation of alpha-Al 2O3 is promoted, and the wrinkles of the bonding layer are reduced;
2) the Zr and Hf elements are distributed in the depth range of 500 nanometers on the shallow surface of the bonding layer, the integral performance of the bonding layer and the base body is not changed, the trace elements are effectively applied, and the relative cost is reduced;
3) the Zr and Hf element content can be conveniently and accurately controlled, repeated development and verification of novel powder, electroplating solution and target materials are avoided, and the coating development efficiency is improved;
4) the surface stress state of the bonding layer can be regulated and controlled to be in a pressure stress state, so that the service life of the coating is prolonged
Although the present invention has been disclosed in terms of the preferred embodiment, it is not intended to limit the invention, and variations and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. Therefore, any modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope defined by the claims of the present invention, unless the technical essence of the present invention departs from the content of the present invention.
Claims (10)
1. A method for preparing a thermal barrier coating is characterized in that,
generating a bonding layer on the surface of the substrate through chemical vapor deposition or physical vapor deposition;
injecting/depositing Zr and/or Hf elements to the shallow surface of the bonding layer by using PIII & D to generate an in-situ modified layer; and
and generating a surface layer on the in-situ modified layer.
2. The method of claim 1, wherein the bond coat is MCrAlY (M ═ Ni, Co, or NiCo), NiAl, and NiPtAl.
3. The method of claim 1, wherein the step of forming the in-situ modified layer comprises applying Zr PIII & D, Hf PIII & D, Zr/Hf binary PIII & D, Zr PIII & D first and Hf PIII & D second, or Hf PIII & D first and Zr PIII & D second to the bond coat surface.
4. The method according to claim 1, wherein when PIII & D is used, pure Zr and pure Hf metals are used as the cathode target material, and the purity is not less than 99.99%.
5. The method according to claim 1, wherein the in-situ modification layer has a thickness of 0 to 500 nm.
6. The method of claim 1, wherein the Zr element and Hf element content of the surface of the bond coat is adjusted by a cathode trigger frequency, a cathode trigger pulse width, an implant/deposition voltage, an implant/deposition frequency, or an implant deposition time parameter when using PIII & D.
7. The method according to claim 1, wherein in the in-situ modification layer, the Zr content is controlled to be in the range of 0 to 20 at.%, and the Hf content of the surface of the adhesive layer is controlled to be in the range of 0 to 20 at.%.
8. A thermal barrier coating, characterized in that it is obtained with a method according to any one of claims 1 to 7.
9. A thermal barrier coating is applied on a substrate and comprises a surface layer in contact with the outside and a bonding layer between the surface layer and the substrate, wherein the bonding layer is provided with an in-situ modification layer, the thickness of the in-situ modification layer is 0-500 nm, and Zr and/or Hf elements are doped in the in-situ modification layer.
10. The thermal barrier coating of claim 9, wherein in the in situ modified layer, the Zr content is in the range of 0 to 20 at.% and the bond coat surface Hf content is in the range of 0 to 20 at.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910748464.3A CN112391601A (en) | 2019-08-14 | 2019-08-14 | Thermal barrier coating and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910748464.3A CN112391601A (en) | 2019-08-14 | 2019-08-14 | Thermal barrier coating and method for producing the same |
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| Publication Number | Publication Date |
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| CN112391601A true CN112391601A (en) | 2021-02-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118074A (en) * | 1993-10-22 | 1995-05-09 | Mitsubishi Heavy Ind Ltd | Method for joining ceramic to metal |
| US6153313A (en) * | 1998-10-06 | 2000-11-28 | General Electric Company | Nickel aluminide coating and coating systems formed therewith |
| US20090035601A1 (en) * | 2007-08-05 | 2009-02-05 | Litton David A | Zirconium modified protective coating |
| CN104228183A (en) * | 2014-07-28 | 2014-12-24 | 中国科学院重庆绿色智能技术研究院 | Composite coating on surface of magnesium alloy structural component and preparation method of composite coating |
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2019
- 2019-08-14 CN CN201910748464.3A patent/CN112391601A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118074A (en) * | 1993-10-22 | 1995-05-09 | Mitsubishi Heavy Ind Ltd | Method for joining ceramic to metal |
| US6153313A (en) * | 1998-10-06 | 2000-11-28 | General Electric Company | Nickel aluminide coating and coating systems formed therewith |
| US20090035601A1 (en) * | 2007-08-05 | 2009-02-05 | Litton David A | Zirconium modified protective coating |
| CN104228183A (en) * | 2014-07-28 | 2014-12-24 | 中国科学院重庆绿色智能技术研究院 | Composite coating on surface of magnesium alloy structural component and preparation method of composite coating |
Non-Patent Citations (1)
| Title |
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| 王铁军 等, 西安交通大学出版社 * |
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Application publication date: 20210223 |