CN112695282A - 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 PDF

Info

Publication number
CN112695282A
CN112695282A CN202011481521.5A CN202011481521A CN112695282A CN 112695282 A CN112695282 A CN 112695282A CN 202011481521 A CN202011481521 A CN 202011481521A CN 112695282 A CN112695282 A CN 112695282A
Authority
CN
China
Prior art keywords
layer
crc
coating
medium
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011481521.5A
Other languages
Chinese (zh)
Other versions
CN112695282B (en
Inventor
汪爱英
王振玉
柯培玲
阮海涛
李忠昌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN202011481521.5A priority Critical patent/CN112695282B/en
Publication of CN112695282A publication Critical patent/CN112695282A/en
Application granted granted Critical
Publication of CN112695282B publication Critical patent/CN112695282B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C14/24—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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a protective coating for resisting medium-high temperature water vapor corrosion 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 coatingxLayer and Cr as a surface functional layer2And an AlC layer. The preparation method comprises the following steps: adopting an arc ion plating technology to sequentially deposit a Cr layer, a CrC layer, a Cr layer and Cr-Al-And C film layer, forming Cr/CrC/Cr/Cr-Al-C multilayer film coating, and then carrying out medium and 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

Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof
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 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-packed6X 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 Cr2In the AlC system, the Cr and Al contained in the system can simultaneously generate stable protective oxide Cr2O3And Al2O3Can impart Cr2Strong protective performance of AlC.
However, Cr2The chemical compatibility problem of the AlC MAX phase coating and the interface of the basal bodies such as zirconium alloy, stainless steel and the like is a key factor of the coating failure in the high-temperature water vapor service process, and the coating is widely concerned at home and abroad. For MAX phase coatings on Zr alloy surfaces, e.g. Cr2AlC and Ti2AlC 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 106K-1The coefficient of thermal expansion of the MAX phase coating is generally higher than 8.0 x 106K-1Especially Cr2The coefficient of thermal expansion of the AlC coating is as high as 12 x 106K-1. From the mechanical aspect, the hardness of the alloy is 3-5 GPa, and Cr2The hardness of the AlC coating is 15-20 GPa. Therefore how to treat Cr2The AlC MAX phase coating is subjected to interface regulation and control, and the long-acting protection effect under the medium-high temperature steam environment is metHas wide scientific and application value.
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 achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a protective coating for resisting medium-high temperature water vapor corrosion, 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 coatingxLayer and Cr as a surface functional layer2And 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: 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/CrAlx/Cr2And 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: 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 substrate bias voltage is-80-150V, and the working gas pressure 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 substrate is-80-150V, 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-80-150V, 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 substrate is-80-150V, 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 medium-high temperature water vapor corrosion in the field of substrate surface protection in medium-high temperature water vapor environments.
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 has at least 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 corrosionx/Cr2The 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 process2High-activity Al in AlC coating diffuses to the substrate, the thermal stability of the coating is improved, and CrAl is connected with the layerxThe layer can improve the CrC diffusion barrier layer and the surface Cr2Bonding strength of AlC layer, surface functional layer Cr2The AlC coating mainly plays a role in resisting water vapor corrosion. In conclusion, the four layers of coatings cooperate to make the coating have the whole functionThe protective performance of the medium and high temperature water vapor is long in service life and reliable;
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 description of the embodiments or 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 for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Cr/CrC/CrAl in an exemplary embodiment of the inventionx/Cr2The preparation flow schematic diagram of the AlC multilayer film protective coating;
FIG. 2 shows Cr/CrC/CrAl in an exemplary embodiment of the inventionx/Cr2A schematic cross-sectional view of an AlC multilayer film protective coating;
FIG. 3 shows Cr/CrC/CrAl in example 1 of the present inventionx/Cr2The sectional morphology of the AlC multilayer film protective coating is shown;
FIG. 4 shows Cr/CrC/CrAl in example 1 of the present inventionx/Cr2XRD phase structure diagram of AlC multilayer film protective coating;
FIG. 5 shows Cr/CrC/CrAl in example 1 of the present inventionx/Cr2The 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 inventionx/Cr2The cross-sectional morphology of the AlC coating;
FIG. 7 shows CrAl in comparative example 1 of the present inventionx/Cr2A surface topography map of the AlC coating after oxidation corrosion;
FIG. 8 shows CrC/Cr in comparative example 2 of the present invention2And 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 layerxLayer and Cr2And an AlC layer.
In some preferred embodiments, the Cr layer, CrC layer, and CrAl layerxSum of layer thickness and Cr2The thickness ratio of the AlC layer is 4:5 to 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 isxThe thickness of the layer is 0.5-2.5 μm, and the Cr is2The thickness of the AlC layer is 3-11 μm.
In some preferred embodiments, the total thickness of the protective coating resisting corrosion of medium and high temperature water vapor is 5-20 μm.
In some preferred embodiments, the connecting layer CrAlxThe atomic ratio of Cr to Al in the layer is 1:1 to 2: 1.
In some preferred embodiments, the Cr is2Cr in AlC layer2The phase purity of AlC MAX phase is more than 90 wt%, and the Cr is2The atomic ratio of Cr, Al and C in the AlC layer (Cr: Al: C) is 2:1: 1.
In conclusion, the invention provides Cr/CrC/CrAl resisting medium-high temperature water vapor corrosionx/Cr2The AlC multilayer film coating has a four-layer structure, wherein the bonding layer Cr layer endows the coating with high bonding strength to avoidThe coating is prevented from being peeled off and failed in the service process too early, and the diffusion barrier layer CrC layer can prevent Cr from being corroded in the high-temperature corrosion process2High-activity Al in AlC coating diffuses to the substrate, the thermal stability of the coating is improved, and CrAl is connected with the layerxThe layer can improve the CrC diffusion barrier layer and the surface functional layer Cr2Bonding strength of AlC layer, surface functional layer Cr2The AlC coating mainly plays a role in resisting water vapor corrosion.
In another aspect, the present invention relates to a method for preparing the above protective coating against corrosion by 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/CrAlx/Cr2And 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: before depositing the Cr layer on the surface of the matrix, the matrix is etched by ionized argon ions.
Further, the etching treatment adopts process conditions including: the pressure of the chamber is 0.2-0.6 Pa, the flow rate of Ar 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 substrate bias voltage is-80-150V, and the working gas pressure 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 substrate is-80-150V, 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-80-150V, and the air pressure of the working gas is 0.8-1.5 Pa. Wherein the content of the first and second substances,
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 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 substrate is-80-150V, 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/CrAlx/Cr2An 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 in the vacuum atmosphere is 1.0 multiplied by 10-3Pa～3.0×10-2Pa, 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 for 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 an oil removing 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 an 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 protective gas by a technology, wherein the four layers of deposited coatings are all 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) placing the deposited Cr/CrC/Cr/Cr-Al-C multilayer film coating in an annealing furnace for medium and low temperature annealing to obtain Cr/CrC/CrAlx/Cr2And (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 connection layer Cr layer and the surface Cr-Al-C layer in the 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 1.5 Pa; the gas introduced during the deposition of the CrC diffusion barrier layer is hydrocarbon gas, preferably CH4Or C2H2And the air pressure is 1-2 Pa.
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 the step (3) is hydrocarbon gas and protectionThe gas mixture of the sex gases has a pressure of 1-2 Pa, wherein the hydrocarbon gas is CH4Or C2H2In 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 mu m.
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/CrAlx/Cr2An 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 10-3Pa～3.0×10-2Pa; 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 3-100 h.
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/Cr2AlC multilayer film coating) is shown in fig. 1.
Cr/CrC/CrAl of this examplex/Cr2The preparation method of the AlC multilayer film coating comprises the following specific steps:
(1) cleaning and drying the matrix in an oil removing 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 an Ar gas atmosphere; using a CrAl target with an 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) placing the deposited Cr/CrC/Cr/Cr-Al-C multilayer film coating in an annealing furnace for medium and low temperature annealing to obtain Cr/CrC/CrAlx/Cr2And (4) AlC coating.
Cr/CrC/CrAl prepared abovex/Cr2The 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 controlling4The flow of the gas is obtained by combining with the subsequent heat treatment, the operation process of the preparation process is simple and easy to control, and large-area uniform deposition is easy to realizeThe coating prepared by the method has excellent medium-high temperature water vapor corrosion resistance, and can solve the problem of water vapor corrosion of alloys (titanium alloy, zirconium alloy, stainless steel and the like) under medium-high temperature conditions.
The technical solutions of the present invention will be 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 any inventive step based on the embodiments of the present invention, are within the 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 introducing argon gas of 40sccm into the vacuum cavity, setting the current of a linear anode ion source to be 0.2A and the pressure of a 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 voltage 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 CH4，CH4The 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 layer4The 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. For deposited Cr/CrC under vacuum conditionxHeat treating the/Cr/Cr-Al-C multilayer coating with a vacuum degree of 2.0X 10-3Pa, the annealing temperature is 620 ℃, and the annealing time is 10 h.
Cr/CrC/CrAl prepared in this examplex/Cr2The AlC multilayer film coating has a compact four-layer structure, the cross-sectional morphology of the AlC multilayer film coating is shown in figure 3, and the Cr layer, the CrC layer and the CrAl layer arexThe sum of the thickness of the three layers is 8 mu m, Cr2The AlC coating thickness was about 10 μm, with a thickness ratio of 4: 5. Cr (chromium) component2The atomic ratio of Cr to Al to C of the AlC layer is close to 2:1:1, and Cr2Removing Cr from AlC layer2In addition to AlC MAX phase, it also contains a small amount of Al4C3And Cr3C2Impurity phase, performing Rietveld fine correction calculation on the phase structure by TOPAS software, and performing Cr refining calculation2The AlC phase was 91 wt.%, 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/cm2While the corrosion weight gain of the Zr alloy matrix under the same conditions is 88.9mg/cm21/10 for increasing the weight of the substrate, the water vapor resistance of the Zr alloy substrate is obviously improved. Cr/CrC/CrAl after steam corrosionx/Cr2The cross section morphology analysis of the AlC multilayer coating shows that the coating is kept complete, the oxidation corrosion is slight, and only the surface layer generates thinner Al2O3Layers 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 voltage of a matrix 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 CH4，CH4The 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 layer4The pressure of the cavity is 2Pa, the proportion of the hydrocarbon reaction gas in the total gas flow is 5 percent,the substrate was negatively biased at-100V and the coating thickness was about 4 μm. For deposited Cr/CrC under vacuum conditionxHeat treating the/Cr/Cr-Al-C multilayer coating at a vacuum of 1.0X 10-3Pa, the annealing temperature is 800 ℃, and the annealing time is 100 h.
Cr/CrC/CrAl prepared in this examplex/Cr2The 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 examplexSum of layer thickness and Cr2The 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/cm2The 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 a cavity to be 0.2Pa, and etching the substrate for 10min 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 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 C2H2，C2H2The 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; 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 layer2H2The 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 conditionxHeat treating the/Cr/Cr-Al-C multilayer coating with a vacuum degree of 3.0X 10-3Pa, the annealing temperature is 300 ℃, and the annealing time is 1000 h.
Cr/CrC/CrAl prepared in this examplex/Cr2The AlC multilayer film coating has compact fourThe layer structure differs from that 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/cm2The 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 being corroded for 30min by water vapor at 1200 ℃, the corrosion weight gain of the multilayer coating is 8.9mg/cm2The result shows that the coating has better water vapor resistant protection performance.
Example 5
This example differs from example 1 only 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/cm2The 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/cm2The 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 example2The 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/cm2The 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 argon gas of 40sccm 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 binding layer by adopting an arc ion plating technology, wherein a 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 Cr-A by arc ion plating technologyl-C coating, CrAl composite target as target material, 70A current, Ar and CH as reaction gas when depositing Cr-Al-C single layer4The 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 × 10-3Pa, the annealing temperature is 620 ℃, the annealing time is 10h, and CrAl is formed after annealingx/Cr2And the AlC is a two-layer structure coating.
CrAl prepared by this comparative example, as shown in FIG. 6x/Cr2The AlC coating has a compact two-layer structure, CrAlxLayer thickness of 2.5 μm, Cr2The 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/cm2Significantly higher than the oxidative weight gain in example 1. For CrAl after corrosionx/Cr2Surface topography analysis of the AlC coating revealed that the coating exhibited microcracks during corrosion (as shown in FIG. 7) which were rapid interdiffusion pathways for corrosive ions, probably due to Cr2Al 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 argon gas of 40sccm 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 CH4The 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 layer4The 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. For deposited Cr/CrC under vacuum conditionxHeat treating the/Cr/Cr-Al-C multilayer coating with a vacuum degree of 2.0X 10-3Pa, the annealing temperature is 620 ℃, and the annealing time is 10 h.
CrC/Cr prepared by the comparative example2After the AlC coating is subjected to steam corrosion at 1200 ℃ for 30min, the corrosion weight gain is 15.6mg/cm2Also higher than the oxidative weight gain in example 1. CrC/Cr after steam corrosion2The cross-sectional shape analysis of the AlC coating shows that the CrC diffusion impervious layer and the Cr are separated2The AlC layer cracks directly (as shown in FIG. 8) and the coating undergoes internal oxidation, probably due to the CrC diffusion barrier and Cr2The 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 Cr2The corrosion weight gain of the AlC layer is 31.5mg/cm after the AlC layer is subjected to steam corrosion at 1200 ℃ for 30min2Significantly higher than the corrosion gain of example 1. The result shows that the corrosion rate is obviously increased and the protection effect is greatly reduced after the surface functional layer is lacked.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only 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 disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is 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 (10)

1. The protective coating is characterized by comprising a Cr layer serving as a bonding layer, a CrC layer serving as a diffusion barrier layer and CrAl layer serving as a connecting layer which are sequentially stacked in the thickness direction of the protective coating for resisting medium-high temperature water vapor corrosionxLayer and Cr as a surface functional layer2And an AlC layer.
2. The protective coating against corrosion by medium and high temperature water vapor according to claim 1, characterized in that: the Cr layer, the CrC layer and the CrAl layerxSum of layer thickness and Cr2The thickness ratio of the AlC layer is 4:5 to 1: 1; preferably, the thickness of the Cr layer is 0.5-2.5 μm, and the thickness of the CrC layerThe degree of the CrAl is 1-5 mu mxThe thickness of the layer is 0.5-2.5 μm, and the Cr is2The thickness of the AlC layer is 3-11 mu m; and/or the total thickness of the protective coating resisting the corrosion of the medium-high temperature water vapor is 5-20 mu m.
3. The protective coating against corrosion by medium and high temperature water vapor according to claim 1, characterized in that: the CrAlxThe atomic ratio of Cr to Al in the layer is 1: 1-2: 1; and/or, the Cr2The phase purity of the AlC layer is more than 90 wt%, and the Cr layer is2The atomic ratio of Cr, Al and C in the AlC layer is 2:1: 1.
4. A method for the preparation of a protective coating against corrosion by medium and high temperature water vapor according to any of claims 1 to 3, characterized in that it 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/CrAlx/Cr2And the AlC coating is the protective coating for resisting the corrosion of the medium-high temperature water vapor.
5. The method of claim 4, further comprising: before depositing a Cr layer on the surface of the matrix, firstly, etching the matrix by ionized argon ions; preferably, the etching process adopts process conditions including: the pressure of the chamber is 0.2-0.6 Pa, the flow rate of Ar is 20-60 sccm, the current of the anode ion source is 0.1-0.3A, and the etching time is 10-40 min.
6. The preparation method according to claim 4, characterized by specifically 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 60-80A, the substrate bias voltage is-80-150V, and the working gas pressure is 0.8-1.5 Pa; preferably, the protective gas comprises an inert gas, preferably argon; preferably, the thickness of the Cr layer is 0.5-2.5 μm;
and/or the preparation method specifically comprises the following steps: 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 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; preferably, the hydrocarbon gas comprises CH4Or C2H2(ii) a Preferably, the thickness of the CrC layer is 1-5 μm.
7. The method according to claim 6, 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 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; preferably, the thickness of the Cr layer is 0.5-2.5 μm;
preferably, the preparation method specifically comprises the following steps:
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 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; preferably, the hydrocarbon gas comprises CH4Or C2H2(ii) a Preferably, the volume percentage of the hydrocarbon gas in the mixed gas is 2-10%; preferably, the protective gas comprises an inert gas, preferably argon; preferably, the thickness of the Cr-Al-C layer is 3-11 μm.
8. The preparation method according to claim 4, 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/CrAlx/Cr2An AlC coating layer; wherein the medium-low temperature annealing partThe technological conditions include: the annealing temperature is 300-800 ℃, preferably 500-800 ℃, the annealing time is 10-1000 h, the annealing atmosphere is a vacuum atmosphere or a protective atmosphere, and the vacuum degree in the vacuum atmosphere is 1.0 multiplied by 10-3Pa～3.0×10-2Pa, the pressure under the protective atmosphere is one atmosphere; preferably, the protective atmosphere comprises an inert gas atmosphere, preferably an argon atmosphere;
and/or, the preparation method further comprises the following steps: 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.
9. Use of a protective coating against corrosion by medium and high temperature water vapor according to any one of claims 1 to 3 in the field of protection of the surface of a substrate in medium and high temperature vapor environments; preferably, the temperature of the medium-high temperature steam environment is 300-1300 ℃.
10. A device comprising a substrate, characterized in that: the substrate is also provided with a protective coating layer which resists the corrosion of the medium-high temperature water vapor and is defined in any one of claims 1 to 3; preferably, the material of the substrate comprises titanium alloy, zirconium alloy or stainless steel.
CN202011481521.5A 2020-12-15 2020-12-15 Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof Active CN112695282B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011481521.5A CN112695282B (en) 2020-12-15 2020-12-15 Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011481521.5A CN112695282B (en) 2020-12-15 2020-12-15 Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112695282A true CN112695282A (en) 2021-04-23
CN112695282B CN112695282B (en) 2022-10-28

Family

ID=75508308

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011481521.5A Active CN112695282B (en) 2020-12-15 2020-12-15 Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112695282B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068946A (en) * 2022-01-14 2022-02-18 长沙理工大学 MAX-phase multilayer composite protective coating for sulfur electrode current collector of sodium-sulfur battery and preparation method thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101048530A (en) * 2004-11-26 2007-10-03 山特维克知识产权股份有限公司 Coated product and method of its production
CN102787300A (en) * 2011-05-18 2012-11-21 中国核动力研究设计院 Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface
US20140044944A1 (en) * 2012-08-07 2014-02-13 Kia Motors Corporation Coating material for aluminum die casting mold and method of manufacturing the coating material
CN107620033A (en) * 2016-07-14 2018-01-23 中国科学院宁波材料技术与工程研究所 A kind of preparation method of high-purity strong fine and close MAX phases coating
CN107815643A (en) * 2017-09-14 2018-03-20 上海新弧源涂层技术有限公司 A kind of nano laminated coating for high-temperature service and preparation method thereof
CN108728793A (en) * 2018-06-16 2018-11-02 江西省科学院应用物理研究所 A kind of tough anti-corrosion CrAlN/Cr2AlC multilayer coatings and preparation method thereof
CN108950480A (en) * 2018-08-22 2018-12-07 中国科学院力学研究所 It a kind of high-ductility abrasion-proof composite coating and is deposited onto heat and makees method in convex mold
CN109295425A (en) * 2018-09-28 2019-02-01 深圳市奥美特纳米科技有限公司 Cr/CrN/CrAlSiN/CrAlTiSiN nanometer multilayer Gradient Film and preparation method thereof
CN110904413A (en) * 2019-11-08 2020-03-24 西安浩元航空科技有限公司 Method for processing superhard coating on surface of aluminum alloy section hot extrusion die
CN111519157A (en) * 2020-06-23 2020-08-11 中国科学院宁波材料技术与工程研究所 Preparation method and application of Cr-Al-C series MAX phase coating
CN111748782A (en) * 2019-03-29 2020-10-09 中国科学院宁波材料技术与工程研究所 MAX phase coating and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101048530A (en) * 2004-11-26 2007-10-03 山特维克知识产权股份有限公司 Coated product and method of its production
CN102787300A (en) * 2011-05-18 2012-11-21 中国核动力研究设计院 Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface
US20140044944A1 (en) * 2012-08-07 2014-02-13 Kia Motors Corporation Coating material for aluminum die casting mold and method of manufacturing the coating material
CN107620033A (en) * 2016-07-14 2018-01-23 中国科学院宁波材料技术与工程研究所 A kind of preparation method of high-purity strong fine and close MAX phases coating
CN107815643A (en) * 2017-09-14 2018-03-20 上海新弧源涂层技术有限公司 A kind of nano laminated coating for high-temperature service and preparation method thereof
CN108728793A (en) * 2018-06-16 2018-11-02 江西省科学院应用物理研究所 A kind of tough anti-corrosion CrAlN/Cr2AlC multilayer coatings and preparation method thereof
CN108950480A (en) * 2018-08-22 2018-12-07 中国科学院力学研究所 It a kind of high-ductility abrasion-proof composite coating and is deposited onto heat and makees method in convex mold
CN109295425A (en) * 2018-09-28 2019-02-01 深圳市奥美特纳米科技有限公司 Cr/CrN/CrAlSiN/CrAlTiSiN nanometer multilayer Gradient Film and preparation method thereof
CN111748782A (en) * 2019-03-29 2020-10-09 中国科学院宁波材料技术与工程研究所 MAX phase coating and preparation method thereof
CN110904413A (en) * 2019-11-08 2020-03-24 西安浩元航空科技有限公司 Method for processing superhard coating on surface of aluminum alloy section hot extrusion die
CN111519157A (en) * 2020-06-23 2020-08-11 中国科学院宁波材料技术与工程研究所 Preparation method and application of Cr-Al-C series MAX phase coating

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
P. A. MILOSERDOV等: "High Temperature Synthesis of Cast Cr2AlC at an Inert Gas Overpressure", 《INORGANIC MATERIALS》 *
ZHENYU WANG等: "High-performance Cr2AlC MAX phase coatings: Oxidation mechanisms in the 900–1100°C temperature range", 《CORROSION SCIENCE》 *
ZILONG ZHAO等: "Effect of CrAl interlayer on adhesion strength of CrAlN coating", 《SURFACE ENGINEERING》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068946A (en) * 2022-01-14 2022-02-18 长沙理工大学 MAX-phase multilayer composite protective coating for sulfur electrode current collector of sodium-sulfur battery and preparation method thereof

Also Published As

Publication number Publication date
CN112695282B (en) 2022-10-28

Similar Documents

Publication Publication Date Title
CN111172503B (en) Zirconium alloy cladding surface multilayer composite coating and preparation method thereof
CN108728793B (en) Tough corrosion-resistant CrAlN/Cr2AlC multilayer film coating and preparation method thereof
CN109560289B (en) Metal bipolar plate, preparation method thereof and fuel cell
CN102787300A (en) Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface
CN111826616B (en) Nuclear fuel cladding coating and preparation method thereof
JP2021502564A (en) Zirconium alloy cladding with improved high temperature oxidation resistance and its manufacturing method
CN112695282B (en) Protective coating resisting corrosion of medium-high temperature water vapor and preparation method and application thereof
CN110791730A (en) Preparation method of zirconium alloy cladding surface composite coating for nuclear fuel
CN109355611A (en) A kind of preparation method for composite ceramic coat for zirconium alloy cladding
CN109207953A (en) Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process
CN114657509A (en) Ceramic-metal multilayer composite coating resistant to corrosion of liquid lead-bismuth alloy and preparation method thereof
CN110499494A (en) It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof
CN116926489A (en) Preparation method of zirconium alloy surface gradient composite coating for cores
CN112795875A (en) Nuclear fuel zirconium alloy cladding element
CN112663001A (en) Titanium alloy blade protective coating and preparation method thereof
CN116043222A (en) High-temperature-resistant corrosion-resistant protective coating containing multilayer structure and preparation method thereof
CN114059017A (en) Protective coating and preparation method thereof, product and preparation method thereof, and application of product in medium-temperature salt spray corrosion environment
CN113106394B (en) Composite coating resistant to corrosion of high-temperature liquid lead-bismuth alloy and preparation method thereof
CN115961259B (en) High-toughness corrosion-resistant MAX-phase multilayer composite coating and preparation method and application thereof
CN115679263B (en) Corrosion-resistant coating and cladding material for nuclear reactor and preparation method thereof
CN110760751A (en) Method for improving liquid metal corrosion resistance of martensite heat-resistant steel
KR20200037652A (en) Metal film coated having excellent oxidation resistance at high temperature and corrosion resistance and the steel sheet, and method for manufacturing the same
CN115305444B (en) Zirconium alloy-based AlCrNbTiZr high-entropy alloy coating resistant to high-temperature water corrosion and preparation method thereof
CN115142029B (en) Preparation method of corrosion-resistant Cr-based multi-layer structure composite coating
CN115821208B (en) Accident-resistant high-entropy alloy coating for nuclear fuel cladding pipe and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant