CN112695282B - Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof - Google Patents
Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof Download PDFInfo
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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
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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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
- C23C14/0021—Reactive sputtering or evaporation
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- C23C14/54—Controlling or regulating the coating process
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- 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
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Abstract
The invention discloses a protective coating for resisting corrosion of medium-high temperature water vapor and a preparation method and application thereof. The protective coating comprises a Cr layer as a bonding layer, a CrC layer as a diffusion barrier layer and a CrAl layer as a connecting layer which are sequentially laminated in the thickness direction of the protective coating x Layer and Cr as a surface functional layer 2 And an AlC layer. The preparation method comprises the following steps: the method comprises the steps of sequentially depositing a Cr layer, a CrC layer, a Cr layer and a Cr-Al-C film layer on the surface of a substrate by adopting an arc ion plating technology to form a Cr/CrC/Cr/Cr-Al-C multilayer film coating, and then carrying out medium-low temperature annealing to obtain the protective coating. The invention adopts the arc ion plating technology, controls Cr and CrAl targets and the flow of introduced hydrocarbon gas, combines with subsequent heat treatment, has simple and controllable process and industrialized production, and the prepared coating has excellent medium and high temperature water vapor corrosion resistance and can solve the problem of water vapor corrosion of the alloy under medium and high temperature conditions.
Description
Technical Field
The invention relates to a protective coating, in particular to a protective coating for resisting medium-high temperature water vapor corrosion, a preparation method and application thereof, and belongs to the technical field of surface treatment.
Background
Vapor corrosion is an important factor that seriously jeopardizes the safe operation of nuclear power plants. On one hand, the water vapor in the pipeline has serious corrosion effect on stainless steel under the conditions of high temperature and high pressure after long-term operation in a harsh loop environment, so that a loose oxide layer is generated on the inner wall of the pipeline, the effective wall thickness of the steel is reduced, the wall surface property is changed, and the safe operation of the loop pipeline is influenced. The light one can cause the loss of power factors of the nuclear power station and reduce the operation efficiency of the nuclear power station, and the heavy one can cause the breakage of parts such as a recirculation pipeline and the like in a reactor, so that the nuclear power station is shut down and replaced, thereby causing huge economic loss, or causing the occurrence of nuclear radiation leakage accidents, thereby threatening the life safety of people. On the other hand, in a Fudao nuclear power station accident of 3 Yuan-Nissan in 2011, due to the fact that cooling water is in shortage under the accident working condition, corrosion reaction occurs between the Zr alloy cladding and water vapor, and a large amount of hydrogen and heat are generated through violent exothermic reaction, so that a reactor core is melted and exploded, nuclear fuel leaks, and great negative effects are caused to the society and the environment. In addition, the steam corrosion also seriously threatens the safe operation of industrial boilers, power generation facilities and waste incineration devices, and is a difficult problem which needs to be solved urgently in industry. The application of a coating resistant to medium-high temperature water vapor corrosion on the surface of a metal material through an advanced surface engineering technology is a key for solving the problems, and the search for a coating system resistant to medium-high temperature water vapor corrosion is always a key focus of attention in the scientific research and industrial industries.
The MAX phase is a novel ternary layered metalloid ceramic material, wherein M is an early transition metal, typically Cr, ti, V and the like; a is a main group element, such as Al, si, etc. commonly used; x is C or N. MAX phase belongs to P63/mmc space group, and its crystal structure is formed from M close-packed 6 X octahedron layers and A atomic layers are alternately arranged. The unique layered structure enables the MAX phase to have the excellent properties of metal and ceramic, such as excellent electrical conductivity and thermal conductivity, good thermal shock resistance and damage tolerance, lower hardness and better machinability; high elastic modulus and high-temperature strength, excellent oxidation resistance and corrosion resistance, and the like. This series of excellent properties makes the MAX phase material one of the ideal candidate coating materials for metal surface protection in harsh environments. Especially Cr 2 In the AlC system, the Cr and Al contained in the system can simultaneously generate stable protective oxide Cr 2 O 3 And Al 2 O 3 Can impart Cr 2 Strong protective performance of AlC.
However, cr 2 The problem of chemical compatibility of the AlC MAX phase coating and the interfaces of substrates such as zirconium alloy, stainless steel and the like is a key factor of coating failure in the high-temperature steam service process, and the coating is widely concerned at home and abroad. For MAX phase coatings on Zr alloy surfaces, e.g. Cr 2 AlC and Ti 2 AlC and the like, al is easy to diffuse to a Zr matrix at high temperature, and a hard and brittle Zr-Al intermetallic compound is formed. In addition to chemical compatibility, the mismatch in thermal and mechanical properties of the coating and the alloy matrix is also a critical factor in premature failure of the coating. For example, zr alloy has a thermal expansion coefficient of about 6X 10 6 K -1 The coefficient of thermal expansion of the MAX phase coating is generally higher than 8.0 x 10 6 K -1 Especially Cr 2 The coefficient of thermal expansion of the AlC coating is as high as 12 x 10 6 K -1 . The hardness of the alloy is 3 to 5GPa in terms of mechanics 2 The hardness of the AlC coating is 15-20 GPa. Therefore how to treat Cr 2 The AlC MAX phase coating is subjected to interface regulation, meets the long-acting protection effect in medium-high temperature steam environment, and has wide scientific and application values.
Disclosure of Invention
The invention mainly aims to provide a protective coating for resisting corrosion of medium-high temperature water vapor and a preparation method thereof, thereby overcoming the defects in the prior art.
It is also an object of the present invention to provide the use of said protective coating against corrosion by medium and high temperature water vapor.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a protective coating for resisting corrosion of medium-high temperature water vapor, which comprises a Cr layer serving as a bonding layer, a CrC layer serving as a diffusion barrier layer and a CrAl layer serving as a connecting layer which are sequentially laminated in the thickness direction of the protective coating x Layer and Cr as a surface functional layer 2 And an AlC layer.
The embodiment of the invention also provides a preparation method of the protective coating for resisting corrosion of medium-high temperature water vapor, which comprises the following steps: by usingThe arc ion plating technology comprises the steps of sequentially depositing a Cr layer, a CrC layer, a Cr layer and a Cr-Al-C film layer on the surface of a substrate to form a Cr/CrC/Cr/Cr-Al-C multilayer film coating, and then carrying out medium and low temperature annealing treatment to obtain Cr/CrC/CrAl x /Cr 2 And the AlC coating is the protective coating for resisting the corrosion of the medium-high temperature water vapor.
In some preferred embodiments, the preparation method comprises: adopting an arc ion plating technology, taking a pure Cr target as a cathode target material and taking protective gas as working gas, and depositing and forming a Cr layer on the surface of the substrate, wherein the adopted arc source current is 60-80A, the bias voltage of the substrate is-80-150V, and the air pressure of the working gas is 0.8-1.5 Pa.
In some preferred embodiments, the preparation method comprises: adopting an arc ion plating technology, taking a pure Cr target as a cathode target material, taking hydrocarbon gas as working gas, and continuously depositing on the surface of the substrate deposited with the Cr layer to form a CrC layer so as to obtain a Cr/CrC composite coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 1-2 Pa.
In some preferred embodiments, the preparation method comprises: depositing a Cr layer on the surface of the Cr/CrC composite coating by adopting an arc ion plating technology and taking a pure Cr target as a cathode target material and protective gas as working gas to obtain the Cr/CrC/Cr composite coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 0.8-1.5 Pa.
In some preferred embodiments, the preparation method comprises: depositing a Cr-Al-C layer on the surface of the Cr/CrC/Cr composite coating by adopting an arc ion plating technology and taking a CrAl target as a cathode target material and a mixed gas of a hydrocarbon gas and a protective gas as a working gas to obtain a Cr/CrC/Cr/Cr-Al-C multilayer coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 1-2 Pa.
The embodiment of the invention also provides application of the protective coating for resisting corrosion of medium-high temperature steam in the field of substrate surface protection in medium-high temperature steam environment.
Further, the temperature of the medium-high temperature steam environment is 300-1300 ℃.
The embodiment of the invention also provides a device which comprises a substrate, wherein the substrate is also provided with the protective coating for resisting the corrosion of the medium-high temperature water vapor.
Compared with the prior art, the invention at least has the following beneficial effects:
1) The invention realizes the design of the protective coating for resisting medium and high temperature water vapor corrosion through the design of the multilayer coating, the service life of the protective coating is obviously prolonged compared with the service life of the conventional coating, and the Cr/CrC/CrAl for resisting the medium and high temperature water vapor corrosion x /Cr 2 The AlC multilayer film coating has a four-layer structure, wherein the bonding layer Cr layer endows the coating with high bonding strength so as to avoid premature spalling failure of the coating in the service process, and the diffusion barrier layer CrC layer can avoid Cr in the high-temperature corrosion process 2 High-activity Al in AlC coating diffuses to the substrate, the thermal stability of the coating is improved, and CrAl is connected with the layer x The layer can improve the CrC diffusion barrier layer and the surface Cr 2 Bonding strength of AlC layer, surface functional layer Cr 2 The AlC coating mainly plays a role in resisting water vapor corrosion. In conclusion, the four layers of coatings have synergistic functions, so that the coating has long service life and reliable medium and high temperature water vapor protection performance;
2) The invention adopts the electric arc ion plating technology, is obtained by controlling the use of Cr and CrAl targets and the flow of the introduced hydrocarbon gas and combining with the subsequent heat treatment, has simple preparation process, simple and easily controlled operation process, is easy for large-area uniform deposition and more beneficial to industrial production application, and the prepared coating has excellent medium-high temperature water vapor corrosion resistance and can solve the water vapor corrosion problem of alloys (titanium alloy, zirconium alloy, stainless steel and the like) under medium-high temperature conditions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows Cr/CrC/CrAl in an exemplary embodiment of the invention x /Cr 2 The preparation flow schematic diagram of the AlC multilayer film protective coating;
FIG. 2 shows Cr/CrC/CrAl in an exemplary embodiment of the invention x /Cr 2 The cross section of the AlC multilayer film protective coating is schematic;
FIG. 3 shows Cr/CrC/CrAl in example 1 of the present invention x /Cr 2 The cross-sectional shape of the AlC multilayer film protective coating is shown;
FIG. 4 shows Cr/CrC/CrAl in example 1 of the present invention x /Cr 2 XRD phase structure diagram of AlC multilayer film protective coating;
FIG. 5 shows Cr/CrC/CrAl in example 1 of the present invention x /Cr 2 The sectional appearance graph of the AlC multilayer film protective coating after being oxidized and corroded for 30min at 1200 ℃;
FIG. 6 is CrAl in comparative example 1 of the present invention x /Cr 2 The cross-sectional topography of the AlC coating;
FIG. 7 shows CrAl in comparative example 1 of the present invention x /Cr 2 A surface topography map of the AlC coating after oxidation corrosion;
FIG. 8 is CrC/Cr in comparative example 2 of the present invention 2 And the sectional morphology of the AlC coating after oxidation corrosion.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made long-term research and extensive practice to provide the technical scheme of the present invention, which mainly realizes a protective coating design for resisting medium-high temperature water vapor corrosion through a multilayer coating design, and the service life of the protective coating is significantly prolonged compared with the service life of the existing coating. The technical solution, its implementation and principles, etc. will be further explained as follows.
As one aspect of the technical scheme of the invention, the invention relates to a protective coating for resisting medium-high temperature water vapor corrosion, which comprises 4 layers, wherein a bonding layer, a diffusion barrier layer, a connecting layer and a surface functional layer are sequentially arranged from a substrate to the surface growth direction and respectively correspond to a Cr layer, a CrC layer and a CrAl layer x Layer and Cr 2 And an AlC layer.
In some preferredIn examples, the Cr layer, crC layer and CrAl layer x Sum of layer thickness and Cr 2 The thickness ratio of the AlC layer is 4: 5-1: 1.
Further, the thickness of the Cr layer is 0.5-2.5 μm, the thickness of the CrC layer is 1-5 μm, and the CrAl layer is x The thickness of the layer is 0.5-2.5 μm, and the Cr is 2 The thickness of the AlC layer is 3-11 μm.
In some preferred embodiments, the total thickness of the protective coating layer resisting corrosion of medium and high temperature water vapor is 5-20 μm.
In some preferred embodiments, the connecting layer CrAl x The atomic ratio of Cr to Al in the layer is 1: 1-2: 1.
In some preferred embodiments, the Cr is 2 Cr in AlC layer 2 The phase purity of AlC MAX phase is more than 90wt%, and the Cr is 2 The atomic ratio of Cr, al and C in the AlC layer (Cr: al: C) is 2: 1.
In conclusion, the invention provides Cr/CrC/CrAl resisting medium-high temperature steam corrosion x /Cr 2 The AlC multilayer film coating has a four-layer structure, wherein the bonding layer Cr layer endows the coating with high bonding strength so as to avoid premature spalling failure of the coating in the service process, and the diffusion barrier layer CrC layer can avoid Cr in the high-temperature corrosion process 2 High-activity Al in AlC coating diffuses to the substrate, the thermal stability of the coating is improved, and CrAl is connected with the layer x The layer can improve the CrC diffusion barrier layer and the surface functional layer Cr 2 Bonding strength of AlC layer, surface functional layer Cr 2 The AlC coating mainly plays a role in resisting water vapor corrosion.
As another aspect of the technical solution of the present invention, it relates to a method for preparing the above-mentioned protective coating layer for resisting corrosion by medium-high temperature water vapor, which comprises: adopting an arc ion plating technology to deposit a Cr layer, a CrC layer, a Cr layer and a Cr-Al-C film layer on the surface of a matrix in sequence to form a Cr/CrC/Cr/Cr-Al-C multilayer film coating, and then carrying out medium-low temperature annealing treatment to obtain Cr/CrC/CrAl x /Cr 2 And the AlC coating is the protective coating for resisting the corrosion of the medium-high temperature water vapor.
In some embodiments, the method of making further comprises: and before depositing the Cr layer on the surface of the substrate, etching the substrate by using ionized argon ions.
Further, the etching treatment adopts process conditions including: the pressure of the chamber is 0.2-0.6 Pa, the Ar flow is 20-60 sccm, the current of the anode ion source is 0.1-0.3A, and the etching time is 10-40 min.
In some embodiments, the method of making specifically comprises: and depositing a Cr layer on the surface of the substrate by adopting an arc ion plating technology and taking a pure Cr target as a cathode target material and protective gas as working gas, wherein the adopted arc source current is 60-80A, the bias voltage of the substrate is-80-150V, and the gas pressure of the working gas is 0.8-1.5 Pa.
In some embodiments, the method of making specifically comprises: adopting an arc ion plating technology, taking a pure Cr target as a cathode target material, taking hydrocarbon gas as working gas, and continuously depositing on the surface of the substrate deposited with the Cr layer to form a CrC layer so as to obtain a Cr/CrC composite coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 1-2 Pa.
In some embodiments, the method of making specifically comprises: depositing a Cr layer on the surface of the Cr/CrC composite coating by adopting an arc ion plating technology and taking a pure Cr target as a cathode target material and protective gas as working gas to obtain the Cr/CrC/Cr composite coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 0.8-1.5 Pa. Wherein,
in some embodiments, the method of making specifically comprises: depositing a Cr-Al-C layer on the surface of the Cr/CrC/Cr composite coating by adopting an arc ion plating technology and taking a CrAl target as a cathode target material and a mixed gas of hydrocarbon gas and protective gas as a working gas to obtain a Cr/CrC/Cr/Cr-Al-C multilayer coating; the current of the adopted arc source is 60-80A, the bias voltage of the matrix is-80 to-150V, and the air pressure of the working gas is 1-2 Pa.
In some embodiments, the method of making specifically comprises: placing the Cr/CrC/Cr/Cr-Al-C multilayer film coating in annealing equipment for medium and low temperature annealing treatment to obtain Cr/CrC/CrAl x /Cr 2 An AlC coating layer; wherein, the process conditions of the medium and low temperature annealing treatment comprise: the annealing temperature is 300-800 ℃, the annealing time is 10-1000 h, the annealing atmosphere is a vacuum atmosphere or a protective atmosphere, and the vacuum degree under the vacuum atmosphere is 1.0 multiplied by 10 -3 Pa～3.0×10 -2 Pa, the pressure under the protective atmosphere is one atmosphere.
In some embodiments, the method of making further comprises: before the matrix is etched, the matrix is sequentially cleaned by adopting an oil removing agent, alcohol and acetone and dried.
In some more specific embodiments, the preparation method of the protective coating resisting corrosion by medium-high temperature water vapor adopts an arc ion plating technology, and specifically comprises the following steps:
(1) Cleaning and drying the matrix in a degreasing agent, alcohol and acetone in sequence, and then putting the matrix into a vacuum coating chamber;
(2) Introducing argon gas into the vacuum cavity through an anode ion source before film coating, and etching the substrate in the step (1) by utilizing ionized argon ions;
(3) Depositing a bonding layer Cr layer, a diffusion barrier layer CrC layer and a connecting layer Cr layer in sequence by using a pure Cr target, wherein the deposition of the diffusion barrier layer CrC layer is carried out in a hydrocarbon gas atmosphere, and the deposition of the pure Cr layer is carried out in a protective gas atmosphere; using a CrAl target with the atomic ratio of 1:1 as a deposition target material, and depositing a Cr-Al-C film in the mixed atmosphere of hydrocarbon gas and protective gas by a technology, wherein the four layers of coatings are deposited by an arc ion plating technology, and the Cr/CrC/Cr/Cr-Al-C multilayer film coating is deposited on the surface of a substrate;
(4) The deposited Cr/CrC/Cr/Cr-Al-C multilayer film coating is placed in an annealing furnace for medium and low temperature annealing to obtain Cr/CrC/CrAl x /Cr 2 And (4) AlC coating.
In some specific embodiments, the etching process in step (2) is specifically: setting the pressure of the chamber to be 0.2-0.6 Pa, the Ar flow to be 20-60 sccm, the anode ion source current to be 0.1-0.3A and the etching time to be 10-40 min.
In some embodiments, during the deposition of the bonding layer Cr layer, the diffusion barrier layer CrC layer, the bonding layer Cr layer and the surface Cr-Al-C layer in step (3), the arc source current is 60 to 80A, and the substrate bias voltage is-80 to-150V.
In some specific embodiments, when the bonding layer Cr layer and the connection layer Cr layer are deposited in step (3), the gas introduced into the chamber is a protective gas, and the pressure of the protective gas is 0.8 to 1.5Pa; the gas introduced during the deposition of the CrC diffusion barrier layer is hydrocarbon gas, preferably CH 4 Or C 2 H 2 And the air pressure is 1 to 2Pa.
Further, the protective gas may be an inert gas, preferably argon (Ar), but is not limited thereto.
Further, the thickness of the bonding layer Cr layer is 0.5-2.5 μm.
Furthermore, the thickness of the Cr layer of the connecting layer is 0.5-2.5 μm.
Further, the thickness of the diffusion impervious layer CrC layer is 1-5 mu m.
In some specific embodiments, the gas introduced during the deposition of the surface Cr-Al-C layer in step (3) is a mixture of hydrocarbon gas and protective gas, and the gas pressure is 1 to 2Pa, wherein the hydrocarbon gas is CH 4 Or C 2 H 2 In any one of the above, the hydrocarbon gas accounts for 2 to 10% by volume.
Further, the protective gas may be an inert gas, preferably argon (Ar), but is not limited thereto.
Further, the thickness of the surface functional layer Cr-Al-C layer is 3-11 μm.
In some specific embodiments, the deposited Cr/CrC/Cr/Cr-Al-C multilayer film coating in the step (4) is placed in an annealing furnace for medium and low temperature annealing to obtain Cr/CrC/CrAl x /Cr 2 An AlC multilayer film; the annealing process is completed under the protection of vacuum or protective gas, the annealing temperature is 300-800 ℃, and the annealing time is 10-1000 h; the degree of vacuum under the vacuum annealing condition was 1.0X 10 -3 Pa～3.0×10 -2 Pa; the annealing pressure under the protective gas protection condition is one atmosphere.
Further, the annealing temperature is preferably 500-800 ℃; the annealing time is preferably 3 to 100 hours.
Further, the protective gas may be an inert gas, preferably argon (Ar), but is not limited thereto.
Further, the material of the substrate may include, but is not limited to, titanium alloy, zirconium alloy, or stainless steel.
As another aspect of the technical scheme of the invention, the invention relates to a protective coating which is prepared by the method and resists the corrosion of medium-high temperature water vapor.
As another aspect of the technical scheme of the invention, the invention relates to the application of the protective coating resisting the corrosion of the medium-high temperature water vapor in the field of substrate surface protection under the medium-high temperature water vapor environment.
Further, the temperature of the medium-high temperature steam environment is 300-1300 ℃.
Further, the base material is not limited, and may be titanium alloy, zirconium alloy, stainless steel, or the like, but is not limited thereto.
In another aspect, the present invention relates to a device comprising a substrate, said substrate further being provided with the above-mentioned protective coating against corrosion by medium and high temperature water vapor.
Further, the base material is not limited, and may be titanium alloy, zirconium alloy, stainless steel, or the like, but is not limited thereto.
In a more specific embodiment of the invention, the protective coating is resistant to corrosion by medium and high temperature water vapor (i.e., cr/CrC/CrAl) x /Cr 2 AlC multilayer film coating) is shown in fig. 1.
Cr/CrC/CrAl of the present example x /Cr 2 The preparation method of the AlC multilayer film coating comprises the following specific steps:
(1) Cleaning and drying the matrix in a degreasing agent, alcohol and acetone in sequence, and then putting the matrix into a vacuum coating chamber;
(2) Introducing argon into the vacuum cavity through an anode ion source before film coating, and etching the substrate in the step (1) by utilizing ionized argon ions;
(3) Depositing a bonding layer Cr layer, a diffusion barrier layer CrC layer and a connecting layer Cr layer in sequence by using a pure Cr target, wherein the deposition of the diffusion barrier layer CrC layer is carried out in a hydrocarbon gas atmosphere, and the deposition of the pure Cr layer is carried out in an Ar gas atmosphere; using a CrAl target with the atomic ratio of 1:1 as a deposition target material, and depositing a Cr-Al-C film in a mixed atmosphere of hydrocarbon gas and Ar gas by a technology, wherein the four layers of coatings are deposited by an arc ion plating technology, and the Cr/CrC/Cr/Cr-Al-C multilayer film coating is deposited on the surface of a substrate;
(4) The deposited Cr/CrC/Cr/Cr-Al-C multilayer film coating is placed in an annealing furnace for medium and low temperature annealing to obtain Cr/CrC/CrAl x /Cr 2 And (4) AlC coating.
Cr/CrC/CrAl prepared above x /Cr 2 The AlC multilayer film coating has a 4-layer structure as shown in fig. 2.
In summary, according to the technical scheme, the invention adopts the arc ion plating technology, and Cr and CrAl targets are used and CH is introduced by controlling 4 The flow of gas is obtained by combining with subsequent heat treatment, the operation process of the preparation process is simple and easy to control, large-area uniform deposition is easy to realize, the coating can be applied to industrial production, the prepared coating has excellent medium and high temperature water vapor corrosion resistance, and the problem of water vapor corrosion of alloys (titanium alloy, zirconium alloy, stainless steel and the like) under medium and high temperature conditions can be solved.
The technical solutions of the present invention are described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
Putting the cleaned and dried Zr alloy substrate into a vacuum cavity, firstly, putting the cleaned and dried Zr alloy substrate into the vacuum cavityIntroducing 40sccm argon gas into the vacuum cavity, setting the current of the linear anode ion source to be 0.2A and the pressure of the cavity to be 0.4Pa, and etching the substrate for 30min by utilizing ionized argon ions; then depositing a Cr binding layer by adopting an arc ion plating technology, wherein a target material is a Cr target, the negative bias of a substrate is-150V, the arc current is 70A, the Ar gas pressure is 1.0Pa, and the deposition thickness is 1.5 mu m; then introducing a reaction gas CH 4 ，CH 4 The air pressure is 1.5Pa, the arc current is 70A, the bias voltage is-100V, and a CrC diffusion impervious layer is deposited with the thickness of 4.5 mu m; introducing Ar gas, wherein the pressure of the Ar gas is 1.0Pa, the arc current is 70A, the bias voltage is-100V, and the deposition thickness is 2.0 mu m; fourthly, depositing a Cr-Al-C coating by adopting an arc ion plating technology, wherein the target material is a CrAl composite target, the current is 70A, and the reaction gases are Ar and CH when depositing a Cr-Al-C single layer 4 The pressure of the cavity is 1.5Pa, the proportion of the hydrocarbon reaction gas to the total gas flow is 10%, the negative bias of the substrate is-150V, and the thickness of the coating is about 10 mu m. For deposited Cr/CrC under vacuum condition x Heat treating the/Cr/Cr-Al-C multilayer coating with a vacuum degree of 2.0X 10 -3 Pa, the annealing temperature is 620 ℃, and the annealing time is 10h.
Cr/CrC/CrAl prepared in this example x /Cr 2 The AlC multilayer film coating has a compact four-layer structure, the cross-sectional shapes of which are shown in figure 3, and a Cr layer, a CrC layer and CrAl x The sum of the thickness of the three layers is 8 mu m, cr 2 The thickness of the AlC coating was about 10 μm, with a thickness ratio of 4: 5.Cr 2 The atomic ratio of Cr to Al to C of the AlC layer is close to 2:1 2 Removing Cr from AlC layer 2 A small amount of Al is contained in addition to AlC MAX phase 4 C 3 And Cr 3 C 2 Impurity phase, performing Rietveld fine correction calculation on the phase structure by TOPAS software, and performing Cr refining calculation 2 The AlC phase was 91wt.%, and the XRD phase structure is shown in fig. 4. After being corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the multilayer coating is 8.9mg/cm 2 While the corrosion weight gain of the Zr alloy matrix under the same conditions is 88.9mg/cm 2 The weight of the Zr alloy substrate is increased by 1/10, and the water vapor resistance of the Zr alloy substrate is obviously improved. Cr/CrC/CrAl after steam corrosion x /Cr 2 The cross-sectional shape analysis of the AlC multilayer coating shows thatThe coating is kept complete, the oxidation corrosion is slight, and only the surface layer generates thinner Al 2 O 3 Layers as shown in fig. 5.
Example 2
Putting the cleaned and dried Zr alloy substrate into a vacuum cavity, firstly introducing argon gas of 20sccm into the vacuum cavity, setting the current of a linear anode ion source to be 0.1A and the pressure of a cavity to be 0.6Pa, and etching the substrate for 40min by utilizing ionized argon ions; then depositing a Cr binding layer by adopting an arc ion plating technology, wherein a target material is a Cr target, the negative bias of a substrate is-100V, the arc current is 60A, the Ar gas pressure is 1.5Pa, and the deposition thickness is 0.5 mu m; then introducing a reaction gas CH 4 ，CH 4 The air pressure is 1Pa, the arc current is 60A, the bias voltage is-150V, and a CrC diffusion impervious layer is deposited with the thickness of 1 mu m; introducing Ar gas, wherein the pressure of the Ar gas is 1.5Pa, the arc current is 60A, the bias voltage is-150V, and the deposition thickness is 2.5 mu m; fourthly, depositing a Cr-Al-C coating by adopting an arc ion plating technology, wherein the target material is a CrAl composite target, the current is 60A, and the reaction gases are Ar and CH when depositing a Cr-Al-C single layer 4 The pressure of the cavity is 2Pa, the proportion of the hydrocarbon reaction gas in the total gas flow is 5 percent, the negative bias of the substrate is-100V, and the thickness of the coating is about 4 mu m. For deposited Cr/CrC under vacuum condition x Heat treating the/Cr/Cr-Al-C multilayer coating at a vacuum of 1.0X 10 -3 Pa, the annealing temperature is 800 ℃, and the annealing time is 100h.
Cr/CrC/CrAl prepared in this example x /Cr 2 The AlC multilayer film coating has a dense four-layer structure, which differs from the structure of the coating obtained in example 1 in that: cr layer, crC layer and CrAl in the present example x Sum of layer thickness and Cr 2 The thickness ratio of the AlC layer is 1:1. After being corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the multilayer coating is 8.4mg/cm 2 The result shows that the coating has better water vapor resistant protection performance.
Example 3
Putting the cleaned and dried Zr alloy substrate into a vacuum cavity, firstly introducing argon gas of 60sccm into the vacuum cavity, setting the current of a linear anode ion source to be 0.3A and the pressure of the cavity to be 0.2Pa, and reducing the pressure of the cavity to be equal to the pressure of the linear anode ion sourceEtching the matrix for 10min by using ionized argon ions; then depositing a Cr bonding layer by adopting an arc ion plating technology, wherein a target material is a Cr target, the negative bias voltage of a matrix is-80V, the arc current is 80A, the Ar gas pressure is 0.8Pa, and the deposition thickness is 2.5 mu m; then introducing a reaction gas C 2 H 2 ，C 2 H 2 The air pressure is 2Pa, the arc current is 80A, the bias voltage is-80V, and a CrC diffusion impervious layer is deposited with the thickness of 5 mu m; thirdly, introducing Ar gas, wherein the pressure of the Ar gas is 0.8Pa, the arc current is 80A, the bias voltage is-80V, and the deposition thickness is 0.5 mu m; fourthly, depositing a Cr-Al-C coating by adopting an arc ion plating technology, wherein the target material is a CrAl composite target, the current is 80A, and the reaction gases are Ar and C when depositing a Cr-Al-C single layer 2 H 2 The pressure of the cavity is 1Pa, the proportion of the hydrocarbon reaction gas in the total gas flow is 2 percent, the negative bias of the substrate is-80V, and the thickness of the coating is about 11 mu m. For deposited Cr/CrC under vacuum condition x the/Cr/Cr-Al-C multilayer coating is subjected to heat treatment, the vacuum degree is 3.0 x 10 -3 Pa, annealing temperature of 300 ℃ and annealing time of 1000h.
Cr/CrC/CrAl prepared in this example x /Cr 2 The AlC multilayer film coating has a dense four-layer structure, which differs from the structure of the coating obtained in example 1 in that: the thickness of the Cr bonding layer in this example was 2.5 μm. After being corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the multilayer coating is 9.2mg/cm 2 The result shows that the coating has better water vapor resistant protection performance.
Example 4
This example differs from example 1 only in that: the thickness of the Cr bond layer in this example was 0.5. Mu.m. After the multilayer coating is subjected to steam corrosion at 1200 ℃ for 30min, the corrosion weight gain of the multilayer coating is 8.9mg/cm 2 The result shows that the coating has better water vapor resistant protective performance.
Example 5
This example only differs from example 1 in that: the thickness of the CrC diffusion barrier layer in this example was 1 μm. After being corroded for 30min by water vapor at 300 ℃, the corrosion weight gain of the multilayer coating is 8.2mg/cm 2 The result shows that the coating has better water vapor resistant protection performance.
Example 6
This example differs from example 1 only in that: the thickness of the CrC diffusion barrier layer in this example was 5 μm. After being corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the multilayer coating is 8.5mg/cm 2 The result shows that the coating has better water vapor resistant protection performance.
Example 7
This example differs from example 1 only in that: cr in the present example 2 The thickness of the AlC layer was 3 μm. After being corroded for 30min by water vapor at 1300 ℃, the corrosion weight gain of the multilayer coating is 9.6mg/cm 2 The result shows that the coating has better water vapor resistant protection performance.
Comparative example 1
Putting the cleaned and dried Zr alloy substrate into a vacuum cavity, firstly introducing 40sccm of argon into the vacuum cavity, setting the current of a linear anode ion source to be 0.2A and the negative bias voltage of the substrate to be-200V, and etching the substrate for 30min by utilizing ionized argon ions; then depositing a Cr bonding layer by adopting an arc ion plating technology, wherein the target material is a Cr target, the arc current is 70A, the Ar gas pressure is 1.0Pa, and the deposition thickness is 2.5 mu m; then depositing a Cr-Al-C coating by adopting an arc ion plating technology, wherein the target material is a CrAl composite target, the current is 70A, and the reaction gases are Ar and CH when depositing a Cr-Al-C single layer 4 The pressure of the cavity is 1.5Pa, the proportion of the hydrocarbon reaction gas to the total gas flow is 10 percent, the negative bias of the substrate is-150V, and the thickness of the coating is about 10 mu m. Heat treating the deposited Cr/Cr-Al-C multilayer coating under vacuum condition with vacuum degree of 2.0 × 10 -3 Pa, the annealing temperature is 620 ℃, the annealing time is 10h, and CrAl is formed after annealing x /Cr 2 And the AlC is a two-layer structure coating.
CrAl prepared by this comparative example, as shown in FIG. 6 x /Cr 2 The AlC coating has a compact two-layer structure, crAl x Layer thickness of 2.5 μm, cr 2 The AlC coating thickness was about 10 μm, with a thickness ratio of 1: 4. After the double-layer coating is corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the double-layer coating is 34.6mg/cm 2 Significantly higher than the oxidative weight gain in example 1. For CrAl after corrosion x /Cr 2 Surface topography analysis of AlC coatingNow, the coating exhibits microcracks during corrosion (as shown in FIG. 7) which act as rapid internal diffusion paths for corrosive ions, probably due to Cr 2 Al is quickly diffused in the AlC coating in the corrosion process, so that the coating is not matched with the substrate.
Comparative example 2
Putting the cleaned and dried Zr alloy substrate into a vacuum cavity, firstly introducing 40sccm of argon into the vacuum cavity, setting the current of a linear anode ion source to be 0.2A and the negative bias voltage of the substrate to be-200V, and etching the substrate for 30min by utilizing ionized argon ions; then depositing a CrC diffusion impervious layer by adopting an arc ion plating technology, wherein the target material is a Cr target and CH 4 The gas pressure is 1.5Pa, the arc current is 70A, the bias voltage is-100V, and the thickness is 2.5 μm; then depositing a Cr-Al-C coating by adopting an arc ion plating technology, wherein the target material is a CrAl composite target, the current is 70A, and the reaction gases are Ar and CH when depositing a Cr-Al-C single layer 4 The pressure of the cavity is 1.5Pa, the proportion of the hydrocarbon reaction gas to the total gas flow is 10%, the negative bias of the substrate is-150V, and the thickness of the coating is about 10 mu m. For CrC deposited under vacuum x the/Cr-Al-C multilayer coating is subjected to heat treatment with the vacuum degree of 2.0 x 10 - 3 Pa, the annealing temperature is 620 ℃, and the annealing time is 10h.
CrC/Cr prepared by the comparative example 2 After the AlC coating is subjected to steam corrosion at 1200 ℃ for 30min, the corrosion weight gain is 15.6mg/cm 2 Also higher than the oxidative weight gain in example 1. CrC/Cr after steam corrosion 2 The cross-sectional shape analysis of the AlC coating shows that the CrC diffusion impervious layer and the Cr are separated 2 The AlC layer cracks directly (as shown in FIG. 8) and the coating oxidizes internally, probably due to the CrC diffusion barrier and Cr 2 The coefficient of thermal expansion and the mechanical property of the AlC layers are not matched.
Comparative example 3
This comparative example differs from example 1 in that: the comparative example is divided into three layers, i.e. lacking the surface functional layer Cr 2 The AlC layer is corroded by water vapor at 1200 ℃ for 30min to increase weight by 31.5mg/cm 2 Significantly higher than the corrosion gain of example 1. The results show that the corrosion rate increases significantly in the absence of a surface functional layerThe protection effect is greatly reduced.
The aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the invention.
Throughout this specification, where compositions are described as having, containing, or comprising specific components, or where processes are described as having, containing, or comprising specific process steps, it is contemplated that compositions taught by the present invention also consist essentially of, or consist of, the recited components, and that processes taught by the present invention also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "include," have, has "and the like are generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (22)
1. A preparation method of a protective coating resisting corrosion of medium-high temperature water vapor is characterized by comprising the following steps: adopting an arc ion plating technology to deposit a Cr layer, a CrC layer, a Cr layer and a Cr-Al-C film layer on the surface of a matrix in sequence to form a Cr/CrC/Cr/Cr-Al-C multilayer film coating, and then carrying out medium-low temperature annealing treatment to obtain Cr/CrC/CrAl x /Cr 2 An AlC coating, namely obtaining a protective coating resisting medium and high temperature water vapor corrosion, wherein the protective coating resisting medium and high temperature water vapor corrosion comprises a Cr layer serving as a bonding layer, a CrC layer serving as a diffusion barrier layer and a CrAl layer serving as a connecting layer which are sequentially laminated in the thickness direction of the protective coating x Layer and Cr as a surface functional layer 2 And an AlC layer.
2. The method of claim 1, further comprising: before depositing a Cr layer on the surface of the substrate, firstly, etching the substrate by ionized argon ions; the etching treatment adopts the following process conditions: the pressure of the cavity is 0.2 to 0.6Pa, the flow rate of Ar is 20 to 60sccm, the current of the anode ion source is 0.1 to 0.3A, and the etching time is 10 to 40min.
3. The method according to claim 1, comprising: depositing a Cr layer on the surface of the substrate by adopting an arc ion plating technology and taking a pure Cr target as a cathode target material and protective gas as working gas, wherein the adopted arc source current is 60 to 80A, the substrate bias voltage is-80 to-150V, and the working gas pressure is 0.8 to 1.5Pa; the thickness of the Cr layer is 0.5 to 2.5 mu m.
4. The method according to claim 3, comprising in particular: adopting an arc ion plating technology, taking a pure Cr target as a cathode target material, taking hydrocarbon gas as working gas, and continuously depositing on the surface of the substrate deposited with the Cr layer to form a CrC layer so as to obtain a Cr/CrC composite coating; wherein the adopted arc source current is 60 to 80A, the bias voltage of the substrate is-80 to-150V, and the working gas pressure is 1 to 2Pa.
5. The method of manufacturing according to claim 4, characterized in that: the hydrocarbon gas comprises CH 4 Or C 2 H 2 。
6. The method of claim 4, wherein: the thickness of the CrC layer is 1 to 5 mu m.
7. The preparation method according to claim 4, characterized by specifically comprising: depositing a Cr layer on the surface of the Cr/CrC composite coating by adopting an arc ion plating technology and taking a pure Cr target as a cathode target material and protective gas as working gas to obtain the Cr/CrC/Cr composite coating; wherein the adopted electric arc source current is 60 to 80A, the matrix bias voltage is-80 to-150V, the working gas pressure is 0.8 to 1.5Pa, and the thickness of the Cr layer is 0.5 to 2.5 mu m.
8. The preparation method according to claim 7, characterized by specifically comprising:
depositing a Cr-Al-C layer on the surface of the Cr/CrC/Cr composite coating by adopting an arc ion plating technology and taking a CrAl target as a cathode target material and a mixed gas of a hydrocarbon gas and a protective gas as a working gas to obtain a Cr/CrC/Cr/Cr-Al-C multilayer coating; wherein the adopted arc source current is 60 to 80A, the bias voltage of the substrate is-80 to-150V, and the working gas pressure is 1 to 2Pa.
9. The method for producing according to claim 8, characterized in that: the hydrocarbon gas comprises CH 4 Or C 2 H 2 。
10. The method of claim 8, wherein: the volume percentage of hydrocarbon gas in the mixed gas is 2% -10%.
11. The method of claim 8, wherein: the thickness of the Cr-Al-C layer is 3 to 11 mu m.
12. The preparation method according to claim 1, characterized by specifically comprising: placing the Cr/CrC/Cr/Cr-Al-C multilayer film coating in annealing equipment for medium and low temperature annealing treatment to obtain Cr/CrC/CrAl x /Cr 2 An AlC coating layer; wherein, the process conditions of the medium and low temperature annealing treatment comprise: the annealing temperature is 300 to 800 ℃, the annealing time is 10 to 1000 hours, the annealing atmosphere is a vacuum atmosphere or a protective atmosphere, and the vacuum degree in the vacuum atmosphere is 1.0 multiplied by 10 -3 Pa~3.0×10 -2 Pa, the pressure under the protective atmosphere is one atmosphere.
13. The method of manufacturing according to claim 12, wherein: the annealing temperature of the medium and low temperature annealing treatment is 500 to 800 ℃.
14. The production method according to any one of claims 3, 7, 8, and 12, characterized in that: the protective gas is inert gas, and the protective atmosphere is inert gas atmosphere.
15. The method for producing as claimed in claim 14, wherein: the inert gas is argon.
16. The method of claim 2, further comprising: before the matrix is etched, sequentially cleaning the matrix by adopting an oil remover, alcohol and acetone, and drying;
and/or the material of the substrate comprises titanium alloy, zirconium alloy or stainless steel.
17. The production method according to claim 1, characterized in that: the Cr layer, the CrC layer and the CrAl layer x Sum of layer thickness and Cr 2 The thickness ratio of the AlC layer is 4 to 1.
18. The method of claim 1, wherein: the total thickness of the protective coating resisting medium-high temperature water vapor corrosion is 5 to 20 micrometers.
19. The production method according to claim 1, characterized in that: the CrAl x The atomic ratio of Cr to Al in the layer is 1 to 1; and/or the Cr 2 Cr of AlC layer 2 The purity of AlC phase is more than 90wt percent, and the Cr phase 2 The atomic ratio of Cr, al and C in the AlC layer is 2.
20. Use of the protective coating which is prepared by the preparation method of any one of claims 1 to 19 and resists medium and high temperature steam corrosion in the field of matrix surface protection in medium and high temperature steam environment, wherein the temperature of the medium and high temperature steam environment is 300 to 1300 ℃.
21. A device comprising a substrate, characterized in that: the substrate is also provided with a protective coating which is resistant to corrosion of medium and high temperature water vapor and is prepared by the preparation method of any one of claims 1 to 19.
22. The apparatus of claim 21, wherein: the material of the substrate comprises titanium alloy, zirconium alloy or stainless steel.
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