CN115110030A - Cerium-doped high-entropy alloy nitride coating and preparation method thereof - Google Patents
Cerium-doped high-entropy alloy nitride coating and preparation method 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
- 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
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- 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
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
Abstract
The invention relates to a cerium-doped high-entropy alloy nitride coating and a preparation method thereof, belonging to the technical field of high-entropy alloy coatings. The cerium-doped high-entropy alloy nitride coating disclosed by the invention is composed of the following elements in percentage by mass: 7-10% of Ti, 5-13% of Al, 10-14% of Cr, 14-22% of Nb, 8-11% of V, 0.7-1.5% of Ag, 10-31% of Ce and 19-23% of N. The cerium-doped high-entropy alloy nitride coating contains cerium element Ce, and due to the active physical and chemical properties, the cerium element Ce can change the positions of element atoms in the high-entropy alloy in crystal lattices, so that the high-entropy alloy coating can exert a thermodynamic high-entropy effect, a dynamic slow diffusion effect, a serious distortion effect of a crystal lattice structure and a performance cocktail effect to a greater extent, and the high-entropy alloy coating is promoted to show higher hardness and elastic modulus and more excellent tribological performance.
Description
Technical Field
The invention relates to a cerium-doped high-entropy alloy nitride coating and a preparation method thereof, belonging to the technical field of high-entropy alloy coatings.
Background
The bearing is a key part in the aerospace equipment, and the dry running performance of the bearing under the working condition of oil loss lubrication is an important guarantee for the safe operation of the aerospace equipment. In the past decades, the successful application of sulfide solid self-lubricating coatings to mechanical parts such as bearings has become an important way to improve the service performance of mechanical moving parts. However, sulfide coatings have the disadvantage of being susceptible to oxidative failure, which limits their use in aerospace.
The high-entropy alloy coating is one of potential important functional materials in the 21 st century because of having higher strength and hardness and excellent mechanical, physical and electrical advantages such as oxidation resistance, corrosion resistance and friction resistance. Because atoms of each element of the high-entropy alloy occupy lattice positions randomly, the high-entropy thermodynamic effect, the dynamic slow diffusion effect, the severe distortion effect of the lattice structure and the cocktail effect on performance are shown, so that the high-entropy alloy shows a plurality of excellent performances under the synergistic action of a plurality of mechanisms. Potential engineering applications of high-entropy alloy coatings on the surfaces of precision bearings are of great interest to numerous internationally scholars. Chinese patent application document CN108411272A discloses a preparation method of an AlCrCuFeNi-based high-entropy alloy coating for bearings, which comprises the following steps: the high-entropy alloy coating is formed on the surface of the bearing by using AlCrCuFeNi series high-entropy alloy as a target material and adopting a magnetron sputtering process. The frictional wear performance of the coating prepared by the method still cannot meet the use requirements in the field of bearings.
Disclosure of Invention
The invention aims to provide a cerium-doped high-entropy alloy nitride coating, which is used for solving the problem that the friction and wear properties of the conventional high-entropy alloy coating cannot meet the use requirements in the field of bearings.
The invention also aims to provide a preparation method of the cerium-doped high-entropy alloy nitride coating.
In order to achieve the purpose, the technical scheme adopted by the cerium-doped high-entropy alloy nitride coating is as follows:
a cerium-doped high-entropy alloy nitride coating is composed of the following elements in percentage by mass: 7-10% of Ti, 5-13% of Al, 10-14% of Cr, 14-22% of Nb, 8-11% of V, 0.7-1.5% of Ag, 10-31% of Ce and 19-23% of N.
The cerium-doped high-entropy alloy nitride coating contains cerium element Ce, and due to the active physical and chemical properties, the cerium element Ce can change the positions of element atoms in the high-entropy alloy in crystal lattices, so that the high-entropy alloy coating can exert thermodynamic high-entropy effect, dynamic slow diffusion effect, severe distortion effect of crystal lattice structure and performance cocktail effect to a greater extent, and the high-entropy alloy coating is promoted to show higher hardness and elastic modulus and more excellent tribological performance; in addition, Ag has a self-lubricating effect and is beneficial to improving the mechanical and tribological properties of the cerium-doped high-entropy alloy nitride coating.
Preferably, the cerium-doped high-entropy alloy nitride coating consists of the following elements in percentage by mass: 7.82-9.97% of Ti, 5.87-12.55% of Al, 10.81-13.16% of Cr, 14.34-21.32% of Nb, 8.28-10.78% of V, 0.76-1.29% of Ag, 10.25-30.42% of Ce and 19.39-22.61% of N.
Preferably, the cerium-doped high-entropy alloy nitride coating is formed by deposition through a magnetron sputtering method.
Preferably, the cerium-doped high-entropy alloy nitride coating is deposited on a coating substrate; the coating substrate comprises a base material and a transition layer coated on the base material; the cerium-doped high-entropy alloy nitride coating is deposited on the transition layer of the coating substrate. The cerium-doped high-entropy alloy nitride coating is deposited on the transition layer, so that the binding force between the cerium-doped high-entropy alloy nitride coating and the base material can be improved.
Preferably, the matrix material is a metal matrix or a Si matrix. Preferably, the metal matrix is 9Cr18 or GCr 15.
Preferably, the transition layer is a chromium layer. Preferably, the transition layer is formed by deposition on the base material by magnetron sputtering.
Preferably, the thickness of the transition layer is 100-200 nm. When the thickness of the transition layer is 100-200 nm, the binding force between the base material and the cerium-doped high-entropy alloy nitride coating can be improved.
Preferably, the thickness of the cerium-doped high-entropy alloy nitride coating is 1-2.5 μm. When the thickness of the cerium-doped high-entropy alloy nitride coating is 1-2.5 mu m, the compactness of the coating can be improved, and the coating is ensured to have good performance.
The preparation method of the cerium-doped high-entropy alloy nitride coating adopts the technical scheme that:
a preparation method of a cerium-doped high-entropy alloy nitride coating comprises the following steps:
(1) providing a coated substrate; the coating substrate comprises a base material and a transition layer coated on the base material;
(2) depositing a cerium-doped high-entropy alloy nitride coating on the transition layer of the coating substrate; the cerium-doped high-entropy alloy nitride coating comprises the following elements in percentage by mass: 7-10% of Ti, 5-13% of Al, 10-14% of Cr, 14-22% of Nb, 8-11% of V, 0.7-1.5% of Ag, 10-31% of Ce and 19-23% of N.
The cerium-doped high-entropy alloy nitride coating prepared by the preparation method of the cerium-doped high-entropy alloy nitride coating has high hardness, elastic modulus and excellent wear resistance. The hardness and the elastic modulus of the cerium-doped high-entropy alloy nitride coating prepared by the invention can respectively reach 18.8GPa and 162.9GPa to the maximum extent, and the ratio (H/E value) of the hardness to the elastic modulus is 0.09-0.12, so that the cerium-doped high-entropy alloy nitride coating has excellent wear resistance.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the cerium-doped high-entropy alloy nitride coating consists of the following elements in percentage by mass: 7.82-9.97% of Ti, 5.87-12.55% of Al, 10.81-13.16% of Cr, 14.34-21.32% of Nb, 8.28-10.78% of V, 0.76-1.29% of Ag, 10.25-30.42% of Ce and 19.39-22.61% of N.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the transition layer is a chromium layer. Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the thickness of the transition layer is 100-200 nm.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the transition layer is formed by deposition on the base material in a magnetron sputtering mode.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the matrix material is a metal matrix or a Si matrix. Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the metal matrix is 9Cr18 or GCr 15.
Preferably, before the transition layer is deposited on the base material, the base material is sequentially subjected to ultrasonic cleaning by using ethanol and acetone, and then the transition layer is deposited on the ultrasonically cleaned base material. Preferably, the ultrasonic cleaning of the base material with ethanol is carried out for 30 min. Preferably, the time for ultrasonic cleaning of the base material with acetone is 20 min.
Preferably, the method for depositing and forming the transition layer on the base material by adopting a magnetron sputtering mode comprises the following steps: and placing the base material in a vacuum reaction cavity, taking a metal target as a target material and inert gas as a sputtering atmosphere, and depositing a transition layer on the base material, wherein the base material deposited with the transition layer is the coating substrate.
Preferably, in the method for forming the transition layer on the base material by deposition in a magnetron sputtering mode, the temperature of the base material is 200-350 ℃. For example, in the method for depositing and forming the transition layer on the base material by adopting a magnetron sputtering mode, the temperature of the base material is 300 ℃. Preferably, in the method for depositing and forming the transition layer on the base material by adopting a magnetron sputtering mode, the bias voltage of the base material is 0-50V. For example, in the method of depositing the transition layer on the substrate material by magnetron sputtering, the bias voltage of the substrate material is 0V.
Preferably, after the substrate material is placed in the vacuum reaction cavity, the vacuum reaction cavity is first evacuated to make the vacuum degree in the vacuum reaction cavity reach 5 × 10 -4 And Pa, introducing inert gas into the vacuum reaction cavity, and depositing on the base material to form a transition layer.
Preferably, the metal target is a chromium target. Preferably, in the method for forming the transition layer by deposition on the base material by magnetron sputtering, the inert gas is argon. Preferably, in the method for forming the transition layer on the substrate material by deposition in a magnetron sputtering manner, the flow rate of the inert gas is 10-30 sccm. For example, in the method of depositing and forming the transition layer on the substrate material by using the magnetron sputtering method, the flow rate of the inert gas is 20 sccm. Preferably, in the method for depositing and forming the transition layer on the base material by adopting a magnetron sputtering mode, the sputtering deposition pressure is 0.2-0.6 Pa. For example, in the method of forming the transition layer on the base material by magnetron sputtering, the sputtering deposition pressure is 0.3 Pa. Preferably, the sputtering power of the metal target is 150 to 200W. For example, the sputtering power of the metal target is 200W. Preferably, the sputtering time for depositing and forming the transition layer on the base material is 20-30 min. For example, the sputtering time for depositing the transition layer on the base material is 20 min.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the cerium-doped high-entropy alloy nitride coating is formed by depositing on the transition layer by a magnetron sputtering method.
It can be understood that after the transition layer is deposited on the base material by adopting the magnetron sputtering method, the cerium-doped high-entropy alloy nitride coating can be continuously deposited on the transition layer by adopting the same magnetron sputtering device, the base material deposited with the transition layer can also be stored for later use, and the cerium-doped high-entropy alloy nitride coating is deposited on the transition layer by adopting the magnetron sputtering method when needed in later period.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the magnetron sputtering method comprises the following steps: placing the coated substrate in a vacuum reaction chamber to contain N 2 Sputtering the metal-based target material in a sputtering atmosphere to deposit a cerium-doped high-entropy alloy nitride coating on the transition layer; said group containing N 2 Gas from N 2 And an inert gas.
Preferably, in the method for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer by adopting a magnetron sputtering method, the temperature of the coating substrate is 200-350 ℃. For example, in a method for depositing a cerium-doped high-entropy alloy nitride coating on a transition layer by a magnetron sputtering method, the temperature of the coating substrate is 300 ℃.
Preferably, the metal-based target is a Ce-Ag alloy target and a TiAlCrNbV high-entropy alloy target. The Ce-Ag alloy target and the TiAlCrNbV high-entropy alloy target are used as deposition sources, so that the preparation process can be simplified, and the uniformity of Ti, Al, Cr, Nb and V in the prepared coating can be improved.
Preferably, the atomic number ratio of Ce to Ag in the Ce-Ag alloy target is (0.9-1.1): 0.9-1.1. For example, the atomic number ratio of Ce to Ag in the Ce-Ag alloy target is 1: 1. The Ce-Ag alloy target is used as a Ce source, so that Ce can be prevented from being oxidized.
Preferably, the atomic number ratio of Ti, Al, Cr, Nb and V in the TiAlCrNbV high-entropy alloy target material is (0.9-1.1): (0.9-1.1): 0.9-1.1). For example, the atomic number ratio of Ti, Al, Cr, Nb and V in the TiAlCrNbV high-entropy alloy target material is 1:1:1:1: 1. When the atomic number ratio of Ti, Al, Cr, Nb and V in the TiAlCrNbV high-entropy alloy target material is 1:1:1:1:1, the uniformity of Ti, Al, Cr, Nb and V in the prepared high-entropy alloy nitride coating is improved.
Preferably, the purity of the Ce-Ag alloy target material is 99.99%. Preferably, the purity of the TiAlCrNbV high-entropy alloy target is 99.99%.
Preferably, the sputtering power of the Ce-Ag alloy target is 50-180W. Preferably, the sputtering power of the TiAlCrNbV high-entropy alloy target is 120-180W. Preferably, the sputtering power of the Ce-Ag alloy target is 50-150W. Further preferably, the sputtering power of the Ce — Ag alloy target is 100W. Further preferably, the sputtering power of the TiCrNbAlV alloy target is 150W.
Preferably, the Ce-Ag alloy is sputtered using a direct current power supply. Preferably, the TiAlCrNbV alloy is sputtered by using a radio frequency power supply.
Preferably, in the method for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer, the sputtering time is 120-180 min. For example, in the method for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer, the sputtering time is 180 min.
Preferably, in the method for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer, the sputtering deposition pressure is 0.2-0.6 Pa. Further preferably, in the method for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer, the sputtering deposition pressure is 0.3-0.5 Pa. For example, in a method for depositing a cerium-doped high-entropy alloy nitride coating on a transition layer, a sputtering deposition pressure of 0.3Pa is used.
Preferably, containing N 2 The flow rate of the gas is 25-70 sccm. Preferably, containing N 2 N in gas 2 The flow rate of (2) is 15 to 40 sccm. E.g. containing N 2 N in gas 2 The flow rate of (2) is 20 sccm. Preferably, containing N 2 The inert gas in the gas is argon. Preferably, containing N 2 The flow rate of the inert gas in the gas is 10-30 sccm. E.g. containing N 2 The flow rate of the inert gas in the gas was 20 sccm.
Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the thickness of the cerium-doped high-entropy alloy nitride coating is 1-2.5 μm. Preferably, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the thickness of the cerium-doped high-entropy alloy nitride coating is 2-2.4 μm. For example, in the preparation method of the cerium-doped high-entropy alloy nitride coating, the thickness of the cerium-doped high-entropy alloy nitride coating is 2.0 μm.
Drawings
FIG. 1 is an XRD spectrum of a high entropy alloy nitride coating prepared by example 5 and a comparative example in experimental example 1;
FIG. 2 is a schematic diagram of the appearance and morphology of the cerium-doped high-entropy alloy nitride coating prepared in example 4 in Experimental example 2 after a friction test at room temperature;
FIG. 3 is a schematic diagram of the appearance and the morphology of the cerium-doped high-entropy alloy nitride coating prepared in example 5 in Experimental example 2 after a friction test at room temperature;
FIG. 4 is a schematic diagram of the appearance and morphology of the cerium-doped high-entropy alloy nitride coating prepared in example 6 in Experimental example 2 after a friction test at room temperature;
FIG. 5 is a schematic diagram of the appearance and appearance of the cerium-doped high-entropy alloy nitride coating prepared in example 8 in Experimental example 2 after a friction test at 500 ℃;
fig. 6 is an XPS spectrum of the high entropy alloy nitride coating prepared in example 5.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The purity of the Ce-Ag alloy target used in the embodiment and the comparative example of the invention is 99.99 percent, and the atomic number ratio of Ce to Ag in the Ce-Ag alloy target is 1: 1; the purity of the TiAlCrNbV high-entropy alloy target is 99.99%, and the atomic number ratio of Ti, Al, Cr, Nb and V in the TiAlCrNbV high-entropy alloy target is 1:1:1:1: 1. The TiAlCrNbV alloy is prepared from Ti, Al, Cr, Nb and V by a powder metallurgy method. The preparation method of the Ce-Ag alloy comprises the following steps: the Ce and the Ag with the atomic ratio of 1:1 are prepared by a smelting method.
The specific embodiment of the cerium-doped high-entropy alloy nitride coating is as follows:
example 1
The cerium-doped high-entropy alloy nitride coating of the embodiment is composed of the following elements in percentage by mass: 9.97 percent of Ti9.55 percent of Al, 13.16 percent of Cr, 21.32 percent of Nb, 10.78 percent of V, 0.76 percent of Ag, 10.25 percent of Ce and 21.21 percent of N. The thickness of the cerium-doped high-entropy alloy nitride coating layer of the embodiment is 2.4 μm.
Example 2
The cerium-doped high-entropy alloy nitride coating of the embodiment is composed of the following elements in percentage by mass: 7.82 percent of Ti7, 5.87 percent of Al, 10.81 percent of Cr, 16.43 percent of Nb, 8.43 percent of V, 0.82 percent of Ag, 30.42 percent of Ce and 19.39 percent of N. The thickness of the cerium-doped high-entropy alloy nitride coating layer of the embodiment is 2.0 μm.
Example 3
The cerium-doped high-entropy alloy nitride coating of the embodiment is composed of the following elements in percentage by mass: 8.12% of Ti, 6.34% of Al, 12.41% of Cr, 14.34% of Nb, 8.28% of V, 1.29% of Ag, 26.61% of Ce and 22.61% of N. The thickness of the cerium-doped high-entropy alloy nitride coating layer of the embodiment is 2.2 μm.
Secondly, the specific embodiment of the preparation method of the cerium-doped high-entropy alloy nitride coating is as follows:
example 4
The preparation method of the cerium-doped high-entropy alloy nitride coating of the embodiment is a preparation method of the cerium-doped high-entropy alloy nitride coating of embodiment 1, and specifically includes the following steps:
(1) firstly, ultrasonically cleaning a metal base material and a monocrystalline silicon piece (Si base material) which are 9Cr18 in an ultrasonic cleaner for 30min by using ethanol, then ultrasonically cleaning the metal base material and the Si base material in the ultrasonic cleaner for 20min by using acetone, and then drying the ultrasonically cleaned metal base material and the Si base material to obtain the pretreated metal base material and the Si base material.
(2) Placing the pretreated metal matrix material and Si matrix material in a vacuum reaction cavity of a magnetron sputtering machine, vacuumizing the vacuum reaction cavity to make the pressure of the vacuum reaction cavity 5 multiplied by 10 -4 Pa, introducing working gas argon with the flow of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, heating the pretreated metal base material and the Si base material to 300 ℃, then opening a chromium target baffle, taking the chromium target as a target material without applying base body bias voltage, exciting the chromium target by using a direct current power supply with the power of 200W, forming stable glow, sputtering and depositing on the surfaces of the pretreated metal base material and the Si base material to form a chromium transition layer, wherein the sputtering and depositing time is 20min, and the thickness of the transition layer formed by depositing on the surfaces of the pretreated metal base material and the Si base material is 200 nm. The resulting metal substrate with the chromium transition layer deposited thereonThe material and the Si matrix material are coating substrates.
Then, simultaneously opening the Ce-Ag alloy target baffle and the TiAlCrNbV high-entropy alloy target baffle, introducing nitrogen with the flow rate of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, then exciting the Ce-Ag alloy target by using a radio frequency power supply, exciting the TiAlCrNbV high-entropy alloy target by using a direct current power supply, controlling the sputtering power of the Ce-Ag alloy target to be 50W and the sputtering power of the TiAlCrNbV high-entropy alloy target to be 150W, keeping the temperature of a coating substrate to be 300 ℃, forming a cerium-doped high-entropy alloy nitride coating on the chromium transition layer by sputtering and depositing the Ce-Ag alloy target and the TiAlCrNbV high-entropy alloy target on the chromium transition layer through co-sputtering, wherein the co-sputtering time is 180min, and the thicknesses of the cerium-doped high-entropy alloy nitride coating deposited on the transition layer on the surface of the metal matrix material and the transition layer on the surface of the Si matrix material are both 2.4 mu m.
Example 5
The preparation method of the cerium-doped high-entropy alloy nitride coating of the embodiment is a preparation method of the cerium-doped high-entropy alloy nitride coating of the embodiment 2, and specifically includes the following steps:
(1) firstly, ultrasonically cleaning a metal base material and a monocrystalline silicon piece (Si base material) which are 9Cr18 in an ultrasonic cleaner for 30min by using ethanol, then ultrasonically cleaning the metal base material and the Si base material in the ultrasonic cleaner for 20min by using acetone, and then drying the ultrasonically cleaned metal base material and the Si base material to obtain the pretreated metal base material and the Si base material.
(2) Placing the pretreated metal matrix material and Si matrix material in a vacuum reaction cavity of a magnetron sputtering machine, vacuumizing the vacuum reaction cavity to make the pressure of the vacuum reaction cavity 5 multiplied by 10 -4 Pa, introducing working gas argon with the flow of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, heating the pretreated metal base material and the Si base material to 300 ℃, opening a chromium target baffle, taking the chromium target as a target material without applying base body bias voltage, exciting the chromium target by using a direct current power supply with the power of 200W to form stable glow, sputtering and depositing on the surfaces of the pretreated metal base material and the Si base material to form a chromium transition layer, and sputtering and depositing to form a chromium transition layerThe time of (2) is 20min, and the thickness of the transition layer formed by deposition on the surface of the pretreated metal base material and the surface of the Si base material is 200 nm. The obtained metal matrix material and Si matrix material deposited with the chromium transition layer are coating substrates.
Then simultaneously opening the Ce-Ag alloy target baffle and the TiAlCrNbV high-entropy alloy target baffle, introducing nitrogen with the flow of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, then exciting the Ce-Ag alloy target by using a radio frequency power supply, exciting the TiAlCrNbV high-entropy alloy target by using a direct current power supply, controlling the sputtering power of the Ce-Ag alloy target to be 100W and the sputtering power of the TiAlCrNbV high-entropy alloy target to be 150W, keeping the temperature of a coating substrate to be 300 ℃, forming a cerium-doped high-entropy alloy nitride coating by sputtering and depositing on the chromium transition layer through co-sputtering of the Ce-Ag alloy target and the TiAlCrNbV high-entropy alloy target, wherein the co-sputtering time is 180min, and the thicknesses of the cerium-doped high-entropy alloy coating deposited on the transition layer on the surface of the metal matrix material and the transition layer on the surface of the Si matrix material are both 2.0 mu m.
Example 6
The preparation method of the cerium-doped high-entropy alloy nitride coating of the embodiment is a preparation method of the cerium-doped high-entropy alloy nitride coating of embodiment 3, and specifically includes the following steps:
(1) firstly, ultrasonically cleaning a metal base material and a monocrystalline silicon piece (Si base material) which are 9Cr18 in an ultrasonic cleaner for 30min by using ethanol, then ultrasonically cleaning the metal base material and the Si base material in the ultrasonic cleaner for 20min by using acetone, and then drying the ultrasonically cleaned metal base material and the Si base material to obtain the pretreated metal base material and the Si base material.
(2) Placing the pretreated metal matrix material and Si matrix material in a vacuum reaction cavity of a magnetron sputtering machine, vacuumizing the vacuum reaction cavity to make the pressure of the vacuum reaction cavity 5 multiplied by 10 -4 Pa, introducing working gas argon with the flow of 20sccm, controlling the pressure of the vacuum reaction cavity to be 0.3Pa, heating the pretreated metal substrate material and the Si substrate material to 300 ℃, opening a chromium target baffle, taking the chromium target as a target material, applying no substrate bias voltage, and using workExciting a chromium target by a direct current power supply with the rate of 200W to form stable glow, and then sputtering and depositing on the surfaces of the pretreated metal base material and the Si base material to form a chromium transition layer, wherein the sputtering and depositing time is 20min, and the thicknesses of the transition layers formed on the surfaces of the pretreated metal base material and the Si base material by deposition are both 200 nm. The obtained metal matrix material and Si matrix material deposited with the chromium transition layer are coating substrates.
Then, simultaneously opening the Ce-Ag alloy target baffle and the TiAlCrNbV high-entropy alloy target baffle, introducing nitrogen with the flow rate of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, then exciting the Ce-Ag alloy target by using a radio frequency power supply, exciting the TiAlCrNbV high-entropy alloy target by using a direct current power supply, controlling the sputtering power of the Ce-Ag alloy target to be 150W and the sputtering power of the TiAlCrNbV high-entropy alloy target to be 150W, keeping the temperature of a coating substrate to be 300 ℃, forming a cerium-doped high-entropy alloy nitride coating on the chromium transition layer by sputtering and depositing the Ce-Ag alloy target and the TiAlCrNbV high-entropy alloy target on the chromium transition layer through co-sputtering, wherein the co-sputtering time is 180min, and the thicknesses of the cerium-doped high-entropy alloy nitride coating deposited on the transition layer on the surface of the metal matrix material and the transition layer on the surface of the Si matrix material are both 2.2 mu m.
Comparative example 1
The preparation method of the high-entropy alloy nitride coating of the comparative example specifically comprises the following steps:
(1) firstly, ultrasonically cleaning a metal base material and a monocrystalline silicon piece (Si base material) which are 9Cr18 in an ultrasonic cleaner for 30min by using ethanol, then ultrasonically cleaning the metal base material and the Si base material in the ultrasonic cleaner for 20min by using acetone, and then drying the ultrasonically cleaned metal base material and the Si base material to obtain the pretreated metal base material and the Si base material.
(2) Placing the pretreated metal matrix material and Si matrix material in a vacuum reaction cavity of a magnetron sputtering machine, vacuumizing the vacuum reaction cavity to make the pressure of the vacuum reaction cavity 5 multiplied by 10 -4 Pa, then introducing working gas argon with the flow of 20sccm, controlling the pressure of the vacuum reaction cavity to be 0.3Pa, and heating the pretreated metal matrix material and the Si matrix materialAnd opening a chromium target baffle plate when the temperature is 300 ℃, taking the chromium target as a target material, not applying matrix bias, exciting the chromium target by using a direct current power supply with the power of 200W to form stable glow, sputtering and depositing on the surfaces of the pretreated metal matrix material and the Si matrix material to form a chromium transition layer, wherein the sputtering and depositing time is 20min, and the thicknesses of the transition layers formed by deposition on the surfaces of the pretreated metal matrix material and the Si matrix material are both 200 nm. The obtained metal matrix material and Si matrix material deposited with the chromium transition layer are coating substrates.
Then simultaneously opening the Ag target baffle and the TiAlCrNbV high-entropy alloy target baffle, introducing nitrogen with the flow rate of 20sccm, controlling the pressure of a vacuum reaction cavity to be 0.3Pa, exciting the Ag target by using a radio frequency power supply, exciting the TiAlCrNbV high-entropy alloy target by using a direct current power supply, controlling the sputtering power of the Ag alloy target to be 100W and the sputtering power of the TiAlCrNbV high-entropy alloy target to be 150W, keeping the temperature of a coating substrate to be 300 ℃, forming a high-entropy alloy nitride coating by sputtering and depositing on the chromium transition layer through co-sputtering of the Ag target and the TiAlCrNbV high-entropy alloy target, wherein the co-sputtering time is 180min, and the thicknesses of the high-entropy alloy nitride coating deposited on the transition layer on the surface of the metal substrate material and the transition layer on the surface of the Si substrate material are both 2.1 mu m.
The high-entropy alloy nitride coating prepared by the comparative example consists of the following elements in percentage by mass: 12.45% of Ti12.45%, 5.26% of Al, 9.98% of Cr, 19.34% of Nb, 6.81% of V, 6.7% of Ag and 39.47% of N.
Comparative example 2
The preparation method of the high-entropy alloy nitride coating of the present comparative example is different from the preparation method of the high-entropy alloy nitride coating of example 5 only in that the Ce-Ag alloy target is replaced with the La-Ag alloy target in step (2) of the present comparative example.
Comparative example 3
The preparation method of the high-entropy alloy nitride coating of the comparative example specifically comprises the following steps:
(1) the method comprises the steps of firstly carrying out ultrasonic cleaning on a metal base material and a monocrystalline silicon piece (Si base material) which are made of GCr15 for 10min by using acetone in an ultrasonic cleaner, and then drying the metal base material and the Si base material which are subjected to ultrasonic cleaning to obtain a pretreated metal base material and a pretreated Si base material.
(2) Placing the pretreated metal matrix material and Si matrix material in a vacuum reaction cavity of a magnetron sputtering machine, vacuumizing the vacuum reaction cavity to make the pressure of the vacuum reaction cavity be 3.2 multiplied by 10 -3 Pa, introducing working gas argon with the flow of 20sccm, controlling the pressure of the vacuum reaction cavity to be 0.1Pa, then carrying out back splash cleaning on the substrate and the target material for 30min, wherein the target current is 1.25A, and the substrate bias voltage is-400V. And opening a chromium target baffle, applying matrix bias voltage to 110V by taking a chromium target as a target material, exciting the chromium target by using a direct current power supply with target current of 1.25A to form stable glow, and sputtering and depositing on the surfaces of the pretreated metal matrix material and the Si matrix material to form a chromium bottom layer, wherein the sputtering and depositing time is 20 min. The obtained metal matrix material and Si matrix material deposited with the chromium transition layer are coating substrates. Then introducing nitrogen with the flow of 6sccm, and continuously bombarding the surface of the substrate for 20min to form a CrN transition layer.
Then opening an AlCrCuFeNi high-entropy alloy target baffle, introducing nitrogen with the flow of 6sccm, controlling the pressure of a vacuum reaction cavity to be 0.1Pa, exciting the AlCrCuFeNi high-entropy alloy target by using a direct-current power supply, controlling the sputtering current of the high-entropy alloy target to be 1.25A, and forming a high-entropy alloy nitride coating by sputtering and depositing on the CrN transition layer through co-sputtering of the AlCrCuFeNi high-entropy alloy target, wherein the co-sputtering time is 60min, and the thicknesses of the high-entropy alloy nitride coating deposited on the transition layer on the surface of the metal matrix material and the transition layer on the surface of the Si matrix material are both 1.2 mu m.
Comparative example 4
The preparation method of the high-entropy alloy nitride coating of the comparative example is different from the preparation method of the high-entropy alloy nitride coating of the comparative example 3 only in that in the step (2) of the preparation method of the high-entropy alloy nitride coating of the comparative example, after a CrN transition layer is formed on a metal substrate material and a Si substrate material, a Ce-Ag target baffle and an AlCrCuFeNi high-entropy alloy target baffle are opened at the same time, nitrogen with the flow of 6sccm is introduced, the pressure of a vacuum reaction cavity is controlled to be 0.1Pa, a Ce-Ag target is excited by a radio frequency power supply, an AlCrCuFeNi high-entropy alloy target is excited by a direct current power supply, the target current of the Ce-Ag alloy target is controlled to be 1A, the sputtering current of the AlCrCuFeNi high-entropy alloy target is controlled to be 1.25A, the high-entropy alloy nitride coating is formed on the CrN transition layer by co-sputtering deposition of the Ce-Ag target and the AlCrCuFeNi high-entropy alloy target, the co-sputtering time is 60min, the thickness of the high-entropy alloy nitride coating deposited on the transition layer on the surface of the metal base material and the transition layer on the surface of the Si base material is 1.02 mu m.
Experimental example 1
In order to determine the microstructure of the prepared coating, the structures of the high-entropy alloy nitride coatings prepared in example 5 and comparative example 1 were characterized using an XRD scanner, and the results are shown in fig. 1. As can be seen from FIG. 1, the combination of the prior studies shows that the high-entropy alloy crystals are formed by solid solution of various elements with each other to form a single disordered BCC (body centered cubic) or FCC (face centered cubic) structure in the absence of main elements. The high entropy alloy nitride coatings prepared in comparative example 1 and example 5 have a single FCC solid solution structure, since AlN, CrN, NbN, TiN, AgN, and VN are all FCC structures. The high-entropy alloy nitride coating prepared in the comparative example 1 has a steamed bread-like wide bulge diffraction peak on the left side of 43 degrees, and has an amorphous structure, which indicates low crystallinity; the diffraction peak of the (111) crystal plane of the high-entropy alloy nitride coating prepared in example 5 is shifted to the left and broadened, which shows that with the addition of Ce or CeAg, the particle bombardment is enhanced, the crystallinity is improved, and the preferential growth along the (111) crystal plane is more obvious. Both coatings exhibited a diffraction peak of (200) crystal plane at 43 °, and the diffraction peak of (200) crystal plane of the high-entropy alloy nitride coating prepared in example 5 was enhanced as compared with the XRD pattern of the high-entropy alloy nitride coating prepared in comparative example 1, indicating that the preferred orientation of the coating was gradually changed from (111) crystal plane to (200) crystal plane. The analytical reason is that this is related to the lowest strain energy of the (111) crystal plane and the lowest surface energy of the (200) crystal plane, and due to the difference of the Ce atomic radius from other elements, the lattice distortion energy is increased, and the increase of the surface adatom mobility causes the coating to grow along the crystal plane with the lowest surface energy of the (200) crystal plane, improving the microstructure of the coating.
Experimental example 2
In order to evaluate the mechanical properties of the high-entropy alloy nitride coatings prepared in examples 4 to 6 and comparative examples 1 to 4, the hardness, elastic modulus, and wear resistance of the high-entropy alloy nitride coatings prepared in examples 4 to 6 and comparative examples 1 to 4, respectively, were tested. Wherein, an iNano nanoindenter is adopted to analyze the hardness and the elastic modulus of the coating, and a Berkovich indenter is selected to carry out hardness test. The test load adopted during the test of the iNano nanoindenter is 50mN, and the maximum indentation depth does not exceed 1/10 of the film thickness. The wear resistance is characterized by a friction coefficient and a wear rate, the friction coefficient is obtained by testing through a high-temperature friction wear testing machine, and the friction test adopts the following parameters: the friction radius is 5mm, the diameter of the counter grinding ball is 6mm, the rotating speed is 336r/min, and the normal load is 10N; the wear rate is calculated according to the formula W ═ V/F × L (where V is the wear scar wear volume, F is the normal load applied by the friction test, and L is the friction stroke length). The friction test is dry friction, the temperature adopted in the friction test is room temperature or 500 ℃, and after the friction test, the appearance of the high-entropy alloy nitride coating prepared in the embodiment 4-6 after the friction test is observed by adopting a scanning electron microscope.
In order to ensure the accuracy of the test results of the wear resistance, the hardness and the elastic modulus, the high-entropy alloy nitride coating deposited on the surface of the metal base material is used for testing the wear resistance, the high-entropy alloy nitride coating deposited on the surface of the Si base material is used for testing the hardness and the elastic modulus, and the Si base is adopted as a hardness test to ensure the accuracy of the hardness test of the coating because the nano-indenter is calibrated by using the Si base.
The test results of hardness, elastic modulus and wear resistance of the high-entropy alloy nitride coatings prepared in examples 4 to 6 and comparative examples 1 to 4 are shown in tables 1 to 2, and the appearance of the high-entropy alloy nitride coatings prepared in examples 4 to 6 after a friction test are shown in fig. 2 to 5, wherein fig. 2 to 4 are the appearance and the appearance of the high-entropy alloy nitride coatings prepared in examples 4 to 6 after the friction test at room temperature, and fig. 5 is the appearance and the appearance of the high-entropy alloy nitride coatings prepared in example 5 after the friction test at 500 ℃.
TABLE 1 hardness and elastic modulus of high entropy alloy nitride coatings prepared in examples 4-6 and comparative examples 1-4
Note: H/E represents the ratio of the hardness and the elastic modulus of the high-entropy alloy nitride coating.
TABLE 2 wear resistance at room temperature and 500 ℃ of high entropy alloy nitride coatings prepared in examples 4-6 and comparative examples 1-4
The results show that the ratio (H/E value) of the hardness and the elastic modulus of the high-entropy alloy nitride coatings prepared in examples 4-6 and comparative example 4 is larger than that of the high-entropy alloy nitride coatings prepared in comparative examples 1-3, and the high-entropy alloy nitride coatings doped with the rare earth element Ce have higher plastic deformation resistance. In addition, the wear loss of the high-entropy alloy nitride coatings prepared in examples 4 to 6 at room temperature is smaller than that of the high-entropy alloy nitride coatings prepared in comparative examples 1 to 4 at room temperature, which shows that the high-entropy alloy nitride coatings can have better tribological properties by doping rare earth elements. Further comparing the tribological properties at room temperature and high temperature, it is found that the friction coefficient and the wear loss of the coating at high temperature are both reduced, especially the friction coefficient and the wear loss of the high-entropy alloy nitride coating prepared in example 5 are minimal, and it is analytically known that the mechanism for improving the friction property of the coating is that the oxide formed in friction, cerium oxide and Ag produce a synergistic lubrication effect, the oxide formed at high temperature and its lubrication phase effectively reduce the friction and wear of the coating, and the friction and wear are relatively large due to insufficient oxide generated in the friction process at room temperature.
When the metal matrix material of 9Cr18 in the preparation method of the cerium-doped high-entropy alloy nitride coating layer of example 5 was replaced with the metal matrix material of GCr15, the friction coefficient and the wear loss of the prepared cerium-doped high-entropy alloy nitride coating layer at room temperature and 500 ℃ were the same as those of the cerium-doped high-entropy alloy nitride coating layer prepared in example 5, respectively.
Experimental example 3
Since the high-entropy alloy nitride coating prepared in example 5 has better tribological properties at high temperature than at room temperature, to further confirm the excellent high-temperature tribological properties of the high-entropy alloy nitride coating prepared in example 5, the valence state of the high-entropy alloy nitride coating is characterized by XPS, and the result is shown in FIG. 6, wherein the XPS spectrum of Ce in FIG. 6 shows that CeO exists in the high-entropy alloy nitride coating prepared in example 5 2 . Therefore, during the wear test, CeO having a layered structure formed on the surface of the high-entropy alloy nitride coating layer prepared in example 5 2 、Ce 2 O 3 And soft metal Ag existing on the surface jointly form a synergistic lubrication effect, so that the frictional wear of the coating is reduced, and Ag and CeO are generated 2 、Ce 2 O 3 Synergistic lubricating effect with other oxides.
Claims (10)
1. The cerium-doped high-entropy alloy nitride coating is characterized by consisting of the following elements in percentage by mass: 7-10% of Ti, 5-13% of Al, 10-14% of Cr, 14-22% of Nb, 8-11% of V, 0.7-1.5% of Ag, 10-31% of Ce and 19-23% of N.
2. The cerium-doped high-entropy alloy nitride coating of claim 1, wherein the thickness of the cerium-doped high-entropy alloy nitride coating is 1 to 2.5 μm.
3. A preparation method of a cerium-doped high-entropy alloy nitride coating is characterized by comprising the following steps: (1) providing a coated substrate; the coating substrate comprises a base material and a transition layer coated on the base material; (2) depositing a cerium-doped high-entropy alloy nitride coating on the transition layer of the coating substrate; the cerium-doped high-entropy alloy nitride coating comprises the following elements in percentage by mass: 7-10% of Ti, 5-13% of Al, 10-14% of Cr, 14-22% of Nb, 8-11% of V, 0.7-1.5% of Ag, 10-31% of Ce and 19-23% of N.
4. The method for preparing a cerium-doped high-entropy alloy nitride coating according to claim 3, wherein the transition layer is a chromium layer; the thickness of the transition layer is 100-200 nm; the thickness of the cerium-doped high-entropy alloy nitride coating is 1-2.5 mu m.
5. The method for preparing a cerium-doped high-entropy alloy nitride coating layer according to claim 4, wherein the thickness of the transition layer is 200 nm; the thickness of the cerium-doped high-entropy alloy nitride coating is 2-2.4 mu m.
6. The method for preparing a cerium-doped high-entropy alloy nitride coating layer according to claim 3, wherein the transition layer is formed by deposition on a base material by means of magnetron sputtering.
7. The method for preparing the cerium-doped high-entropy alloy nitride coating layer according to any one of claims 3 to 6, wherein the cerium-doped high-entropy alloy nitride coating layer is formed by deposition on the transition layer by a magnetron sputtering method; the magnetron sputtering method comprises the following steps: placing the coated substrate in a vacuum reaction chamber to contain N 2 Sputtering the metal-based target material in a sputtering atmosphere to deposit a cerium-doped high-entropy alloy nitride coating on the transition layer; said group containing N 2 Gas from N 2 And an inert gas.
8. The method for preparing a cerium-doped high-entropy alloy nitride coating according to claim 7, wherein the metal-based target is a Ce-Ag alloy target and a TiAlCrNbV high-entropy alloy target; the atomic number ratio of Ce to Ag in the Ce-Ag alloy target material is (0.9-1.1) to (0.9-1.1); the TiAlCrNbV high-entropy alloy target material comprises (0.9-1.1) atomic number ratios of Ti, Al, Cr, Nb and V, (0.9-1.1) atomic number ratios of (0.9-1.1).
9. The method for preparing the cerium-doped high-entropy alloy nitride coating of claim 8, wherein the sputtering power of the Ce-Ag alloy target is 50-150W; the sputtering power of the TiAlCrNbV high-entropy alloy target is 120-180W; containing N 2 N in gas 2 The flow rate of (2) is 15-40 sccm; the sputtering deposition pressure for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer is 0.2-0.6 Pa.
10. The method for preparing a cerium-doped high-entropy alloy nitride coating of claim 9, wherein the atomic number ratio of Ce to Ag in the Ce-Ag alloy target is 1: 1; the atomic number ratio of Ti, Al, Cr, Nb and V in the TiAlCrNbV high-entropy alloy target material is 1:1:1:1: 1; the sputtering power of the TiAlCrNbV high-entropy alloy target is 150W; containing N 2 N in gas 2 The flow rate of (2) is 20 sccm; the sputtering deposition pressure for depositing the cerium-doped high-entropy alloy nitride coating on the transition layer is 0.3 Pa.
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| CN115505876A (en) * | 2022-09-29 | 2022-12-23 | 中国科学院兰州化学物理研究所 | Gold-nickel-nitrogen ternary composite conductive lubricating coating and preparation method and application thereof |
| CN115505876B (en) * | 2022-09-29 | 2023-11-17 | 中国科学院兰州化学物理研究所 | Gold-nickel-nitrogen ternary composite conductive lubricating coating and preparation method and application thereof |
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