CN115233173A - Hard wear-resistant anti-oxidation high-entropy alloy coating and preparation method thereof - Google Patents
Hard wear-resistant anti-oxidation high-entropy alloy coating and preparation method thereof Download PDFInfo
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- CN115233173A CN115233173A CN202210825310.1A CN202210825310A CN115233173A CN 115233173 A CN115233173 A CN 115233173A CN 202210825310 A CN202210825310 A CN 202210825310A CN 115233173 A CN115233173 A CN 115233173A
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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
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- 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
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- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
The invention belongs to the field of metal or alloy surface treatment, and particularly relates to a hard wear-resistant oxidation-resistant high-entropy alloy coating and a preparation method thereof. The high-entropy alloy coating is made of (AlCrTiVZr) 100‑X N X The high-entropy alloy coating has a columnar crystal structure and is coated on the surface of a product to be protected. The invention adopts high-power radio frequency magnetron technology, adopts an AlCrTiVZr target as a sputtering source and high-purity nitrogen as reaction gas in a reactive magnetron sputtering mode, and prepares hard wear-resistant and oxidation-resistant (AlCrTiVZr) on the surface of a steel sheet by controlling the volume flow of the high-purity nitrogen 100‑X N X And (4) coating. The hard wear-resistant and oxidation-resistant high-entropy alloy coating prepared by the invention has the performances of high hardness, high interface bonding strength, excellent wear resistance, high-temperature oxidation resistance and the like.
Description
Technical Field
The invention belongs to the field of metal or alloy surface treatment, and particularly relates to a hard wear-resistant oxidation-resistant high-entropy alloy coating and a preparation method thereof.
Background
In the actual industrial production and application process, some cutters, dies and mechanical parts are difficult to be used for a long time under the severe conditions of high speed, high temperature, dry friction, impact, heavy load and the like, and often fail due to factors such as surface abrasion, corrosion, high temperature oxidation and the like, and an important and effective method for preventing the failures is coating technology. Although the traditional coatings prepared by electroplating, chemical plating and other technologies, such as chromium coatings and titanium coatings, can solve the partial problems of surface abrasion, corrosion and the like of tool parts, the coatings are easy to crack and fall off in the service process of the tool parts due to high brittleness and poor oxidation resistance, the preparation cost is high, the environmental pollution in the preparation process is serious, and the requirements of modern industrial production and application cannot be met. Therefore, the improvement and development of new coating processes and new technologies have become important tasks and difficulties in the field of protective coatings for metal and alloy surfaces.
In recent decades, the magnetron sputtering technology has been developed rapidly, and the coating prepared therefrom has the advantages of excellent performance, simple process, no environmental pollution, etc., and thus is a mainstream protective coating preparation technology. In order to solve the problems of large brittleness, poor oxidation resistance and the like of the traditional electroplating and chemical plating coatings, in recent decades, magnetron sputtering technology is adopted to prepare binary coating systems such as TiN, crN and the like and multi-component coating systems such as TiAlN, tiCrN and the like, the coating systems have high hardness, good wear resistance and oxidation resistance, can effectively reduce the damage to the surfaces of tool parts and components and improve the service life of the tool parts and components, but the coating systems still have the following defects, so that the coating systems cannot be widely applied to the field of surface protection of metals and alloys.
(1) The component elements of the coating system and the component elements of the substrate have larger difference, so that the component elements have larger difference of thermal expansion coefficients, the expansion degrees of the coating and the substrate are greatly different at high temperature, and larger internal stress can be generated in the coating, so that the coating is easy to crack and fall off;
(2) Although these coating systems, such as TiN, crN, etc., have extremely high hardness and good wear resistance, they have insufficient strength and unstable structure at high temperatures of 1000 ℃ or higher, so that they have great disadvantages in high-temperature oxidation resistance and ablation impact resistance.
Disclosure of Invention
The invention aims to provide a hard wear-resistant oxidation-resistant high-entropy alloy coating for metal and alloy surfaces and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: a hard wear-resistant oxidation-resistant high-entropy alloy coating is made of (AlCrTiVZr) 100-X N X The high-entropy alloy coating has a columnar crystal structure and is coated on the surface of a product to be protected.
Furthermore, the to-be-protected product is made of steel or alloy steel.
Furthermore, the thickness of the high-entropy alloy coating is 0.5-10 um.
The preparation method of the coating is characterized in that the AlCrTiVZr target is used as a sputtering source, high-purity nitrogen is used as reaction gas, and the coating is prepared in a reaction magnetron sputtering mode.
The method specifically comprises the following steps:
step (1): pretreating the surface of a product to be protected;
step (2): placing the product in a sputtering chamber of magnetron sputtering equipment, vacuumizing, and arranging a magnetron sputtering AlCrTiVZr high-entropy alloy target in the sputtering chamber;
and (3): treating the product to be protected by using a magnetron sputtering high-entropy alloy target, and introducing high-purity nitrogen as reaction gas to obtain a product with a surface deposited with (AlCrTiVZr) 100-X N X The product of the coating.
Further, the pretreatment in the step (1) is specifically as follows: the abrasive paper is subjected to coarse grinding, fine grinding and fine grinding, and then polished, and the polished steel sheet is subjected to ultrasonic cleaning with alcohol.
Further, the step (2) of evacuating specifically comprises: vacuumizing the sputtering chamber to make the background pressure of the sputtering chamber reach 3 x 10 < -5 > to 1 x 10 < -3 > Pa; and (3) starting a baking lamp in the sputtering chamber to bake the sputtering chamber during vacuumizing, wherein the baking temperature is preferably 100-150 ℃, and the baking time is preferably 30 +/-5 min.
Further, pre-sputtering is performed before the step (3), and the pre-sputtering specifically comprises the following steps: introducing high-purity argon gas for pre-sputtering and cleaning the surface of the AlCrTiVZr target material; the preferred volume flow of the high-purity argon gas is 20 plus or minus 3sccm; when the pre-sputtering is carried out, the time of the pre-sputtering is 10 +/-2 min.
Further, the step (3) is specifically as follows: the working pressure of the sputtering chamber is 2 multiplied by 10 -1 ～6×10 -1 Pa, introducing high-purity argon and high-purity nitrogen, and setting the power of the magnetron sputtering high-entropy alloy target, wherein the volume flow of the high-purity argon is 20 +/-2 sccm, and the volume flow of the high-purity nitrogen is 2-50 sccm; the sputtering power is 50W-500W, and the sputtering time is 0.5 h-10 h.
Further, the AlCrTiVZr high-entropy alloy target is prepared by adopting a powder metallurgy process, and the purity of the AlCrTiVZr high-entropy alloy target is more than 99.6%.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
the invention mainly designs the components of the high-entropy alloy target, determines that the component of the high-entropy alloy target is AlCrTiVZr, adopts the magnetron sputtering preparation technology, and regulates and controls the volume flow and sputtering power of high-purity nitrogen of reaction gas, thereby regulating and controlling the components and the thickness of the hard wear-resistant and oxidation-resistant (AlCrTiVZr) 100-XNX coating, so that the prepared hard wear-resistant and oxidation-resistant (AlCrTiVZr) 100-XNX coating not only has stronger bonding force with a steel sheet, but also has the performances of high hardness, high interface bonding strength, excellent wear resistance, high-temperature oxidation resistance and the like, and the basis for designing the components of the high-entropy alloy target comprises the following aspects:
(1) The Cr, ti, V and Zr are refractory metal elements, have high melting point and good high-temperature strength, and have good corrosion resistance to molten alkali metal and steam, and the addition of the Al element can make up the poor high-temperature oxidation resistance of the elements, so that the prepared (AlCrTiVZr) 100-XNX coating has good strength, high-temperature oxidation resistance and corrosion resistance at high temperature;
(2) Al, cr, ti, V and Zr are all nitriding forming elements and can form a strong Me-N bond with nitrogen atoms, and the formation of the bond can increase the lattice distortion degree of the coating, so that the hardness, the elastic modulus and the wear resistance of the (AlCrTiVZr) 100-XNX coating are improved;
(3) The chemical components of the substrate contain Cr, V and other elements, and the AlCrTiVZr system is similar to the chemical components of the substrate, so that the thermal expansion coefficient of the prepared (AlCrTiVZr) 100-XNX coating is similar to that of the substrate, and the interface bonding strength between the (AlCrTiVZr) 100-XNX coating and the substrate is improved.
Drawings
FIG. 1 is a graph comparing the hardness of hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coatings produced in example 3 of the present invention with steel sheet.
FIG. 2 is a graph comparing the load-depth curves of hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coatings made in example 3 of the invention with steel sheets.
FIG. 3 is a comparison of the XRD of the hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coating produced in inventive example 3 with steel sheet.
FIG. 4 is a scanning electron micrograph of the thickness of a hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coating made in example 3 of the present invention.
FIG. 5 is a graph of a frictional wear test at 25 ℃ of a hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coating made in example 3 of the present invention, with a test pressure of 15N, a test time of 30min, and a frictional length of 5mm.
FIG. 6 is a graph of a frictional wear test at 300 ℃ for a hard wear-resistant, oxidation-resistant (AlCrTiVZr) 100-XNX coating made in example 3 of the present invention, with a test pressure of 15N, a test time of 30min, and a frictional length of 5mm.
Fig. 7 is an interfacial bonding strength-scratch test chart of hard wear-resistant, oxidation-resistant (AlCrTiVZr) 100-XNX coatings prepared in example 3 of the present invention, in which the test type is progressive, an indenter diameter of 400um is used, an initial pressure is 0.03N, a loading rate is 1.5N/min, a pressure at which the coating is broken is 6N, and an interfacial bonding strength = a pressure at which the coating is broken/a contact area of the indenter and the coating.
FIG. 8 is a high temperature oxidized appearance of the hard wear resistant, oxidation resistant (AlCrTiVZr) 100-XNX coating made in example 3 of this invention after being naturally cooled to room temperature after being heat insulated at 900 ℃ for 5 hours with steel sheet.
Detailed Description
The present invention is described in further detail below with reference to the attached drawing figures.
A preparation method of a hard wear-resistant oxidation-resistant high-entropy alloy coating for the surfaces of metals and alloys comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
The preparation method specifically comprises the following steps: the high-power radio frequency magnetron sputtering technology is adopted, a steel sheet after ultrasonic cleaning treatment is placed in a reaction cavity, an AlCrTiVZr target is used as a sputtering source, high-purity nitrogen is used as reaction gas, and hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the steel sheet 100-X N X Coating wherein the sputtering chamber background pressure is 3X 10 -5 ～1×10 -3 Pa, baking temperature of 100-150 ℃, baking time of 30min, and volume flow of high-purity argon of 20sccm, the pre-sputtering time is 10min, and the working pressure of the sputtering chamber is 2 multiplied by 10 -1 ～6×10 -1 Pa, the volume flow of the high-purity nitrogen is 2-50sccm, the sputtering power of the AlCrTiVZr target is 50-500W, and the sputtering time is 0.5-10 h.
High-purity argon is used as protective gas. The target distance between the steel sheet and the AlCrTiVZr target is 10-15 cm. The mesh number of the used sand paper is 180 meshes, 320 meshes, 600 meshes, 1000 meshes, 1500 meshes, 2000 meshes and 4000 meshes. The tools used for polishing the steel sheet are a metallographic polishing flannelette and a grinding and polishing machine. The ultrasonic cleaning time is 10min. The dimensions of the steel sheet were 10 mm. Times.10 mm. Times.1 mm and 20 mm. Times.20 mm. Times.1 mm.
Example 1 in this example, the substrate is a steel sheet with dimensions of 20mm x 1mm, with hard wear-resistant, oxidation-resistant (AlCrTiVZr) deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 9 multiplied by 10 -4 ～1×10 -3 Pa, baking temperature of 100-150 ℃, baking time of 30min, volume flow of high-purity argon of 20sccm, pre-sputtering time of 10min, and working pressure of sputtering chamber of 5 multiplied by 10 -1 ～6×10 -1 Pa, the volume flow of high-purity nitrogen gas is 2sccm, the sputtering power of the AlCrTiVZr target is 100W, and the sputtering time is 10h.
Example 2
In this example, the substrate is a steel sheet with dimensions of 20mm by 1mm, and the hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 5 multiplied by 10 -5 ～6×10 -5 Pa, baking temperature of 100-150 ℃, baking time of 30min, volume flow of high-purity argon of 20sccm, pre-sputtering time of 10min, and working pressure of sputtering chamber of 2 x 10 -1 ～3×10 -1 Pa, the volume flow of high-purity nitrogen gas is 20sccm, the sputtering power of the AlCrTiVZr target is 150W, and the sputtering time is 4h.
Example 3
In this example, the substrate is a steel sheet with dimensions of 20mm by 1mm, and the hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 4 multiplied by 10 -4 ～5×10 -4 Pa, baking temperature of 100-150 deg.C for 30min, high-purity argon gas volume flow of 20sccm, pre-sputtering time of 10min, and sputtering chamber working pressure of 4.5 × 10 -1 ～5.5×10 -1 Pa, the volume flow of high-purity nitrogen is 4sccm, the sputtering power of the AlCrTiVZr target is 250W, and the sputtering time is 2.5h.
The hard wear and oxidation resistant (AlCrTiVZr) made in this example 100-X N X A summary of the properties of the parts of the coating is as follows:
example 4
In this example, the substrate is a steel sheet with dimensions of 20mm by 1mm, and the hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 1 x 10 -4 ～2×10 -4 Pa, baking temperature of 100-150 ℃, baking time of 30min, volume flow of high-purity argon of 20sccm, pre-sputtering time of 10min, and working pressure of sputtering chamber of 2.5 multiplied by 10 -1 ～3.5×10 -1 Pa, the volume flow of high-purity nitrogen is 30sccm, the sputtering power of the AlCrTiVZr target is 250W, and the sputtering time is 6h.
Example 5
In this example, the substrate is a steel sheet with dimensions of 20mm by 1mm, and the hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, and introducing high-purity nitrogen as reaction gas during treatment to obtain the alloy with hard wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 8 multiplied by 10 -5 ～9×10 -5 Pa, baking temperature of 100-150 ℃, baking time of 30min, volume flow of high-purity argon of 20sccm, pre-sputteringThe shooting time is 10min, and the working pressure of the sputtering chamber is 4 multiplied by 10 -1 ～5×10 -1 Pa, the volume flow of high-purity nitrogen is 40sccm, the sputtering power of the AlCrTiVZr target is 350W, and the sputtering time is 8h.
Example 6
In this example, the substrate is a steel sheet with dimensions of 20mm by 1mm, and the hard wear-resistant and oxidation-resistant (AlCrTiVZr) is deposited on the surface of the substrate 100-X N X The preparation method of the coating comprises the following steps:
the steel sheet is subjected to coarse grinding, fine grinding and fine grinding processes on abrasive paper with different meshes, then polished, and then the polished steel sheet is subjected to ultrasonic cleaning by using alcohol. The coarse grinding, the fine grinding and the cleaning process aim at removing impurities such as rust, oil dirt and the like on the surface of the steel sheet;
the steel sheet after ultrasonic cleaning treatment is placed in a sputtering chamber of magnetron sputtering equipment, a magnetron sputtering high-entropy alloy target is arranged in the sputtering chamber, and the magnetron sputtering high-entropy alloy target is an AlCrTiVZr high-entropy alloy target.
Treating the steel sheet subjected to ultrasonic cleaning treatment by using the magnetron sputtering high-entropy alloy target, introducing high-purity nitrogen as reaction gas during treatment, and obtaining the alloy with hard, wear-resistant and oxidation-resistant surface deposited (AlCrTiVZr) 100-X N X Coated steel sheet.
Magnetron sputtering parameters: the background pressure of the sputtering chamber is 3 multiplied by 10 -5 ～4×10 -5 Pa, baking temperature of 100-150 ℃, baking time of 30min, volume flow of high-purity argon of 20sccm, pre-sputtering time of 10min, and working pressure of sputtering chamber of 2 x 10 -1 ～3×10 -1 Pa, the volume flow of high-purity nitrogen gas is 50sccm, the sputtering power of the AlCrTiVZr target is 500W, and the sputtering time is 1h.
Hard wear-resistant and oxidation-resistant (AlCrTiVZr) prepared by the invention 100-X N X The coating is a coating with high hardness and good combination with the surface of the steel sheet, has good performances of abrasion resistance, high-temperature oxidation resistance and the like, and can meet the protection requirements of abrasion resistance and high-temperature oxidation resistance of a plurality of parts. For example, as a wear-resistant coating on the surface of cutting tools,because the hardness of the prepared hard ablation-resistant coating can reach more than 19GPa, the interface bonding strength of the coating and the substrate can also reach more than 100 MPa.
Claims (10)
1. The hard wear-resistant oxidation-resistant high-entropy alloy coating is characterized in that the high-entropy alloy coating is made of (AlCrTiVZr) 100-X N X The high-entropy alloy coating has a columnar crystal structure and is coated on the surface of a product to be protected.
2. Coating according to claim 1, characterized in that the material of the product to be protected is steel or alloy steel.
3. A coating according to claim 2, wherein the thickness of the high entropy alloy coating is between 0.5um and 10um.
4. The method for preparing a coating as claimed in any of claims 1 to 3, characterized in that the coating is prepared by reactive magnetron sputtering using AlCrTiVZr target as a sputtering source and high-purity nitrogen as a reaction gas.
5. The method according to claim 4, characterized in that it comprises in particular the steps of:
step (1): pretreating the surface of a product to be protected;
step (2): placing the product in a sputtering chamber of magnetron sputtering equipment, vacuumizing, and arranging a magnetron sputtering AlCrTiVZr high-entropy alloy target in the sputtering chamber;
and (3): treating the product to be protected by using a magnetron sputtering high-entropy alloy target, and introducing high-purity nitrogen as reaction gas to obtain a product with a surface deposited with (AlCrTiVZr) 100-X N X The product of the coating.
6. The method according to claim 5, wherein the pretreatment in step (1) is specifically: the abrasive paper is subjected to coarse grinding, fine grinding and fine grinding, and then polished, and the polished steel sheet is subjected to ultrasonic cleaning with alcohol.
7. The method according to claim 5, wherein the evacuation in step (2) is specifically: vacuumizing the sputtering chamber to make the background pressure of the sputtering chamber reach 3 x 10 < -5 > to 1 x 10 < -3 > Pa; and (3) starting a baking lamp in the sputtering chamber to bake the sputtering chamber during vacuumizing, wherein the baking temperature is preferably 100-150 ℃, and the baking time is preferably 30 +/-5 min.
8. The method according to claim 5, characterized in that step (3) is preceded by a pre-sputtering, in particular: introducing high-purity argon gas for pre-sputtering and cleaning the surface of the AlCrTiVZr target material; the preferred volume flow of the high-purity argon gas is 20 plus or minus 3sccm; when the pre-sputtering is carried out, the time of the pre-sputtering is 10 +/-2 min.
9. The method according to claim 5, wherein step (3) is specifically: the working pressure of the sputtering chamber is 2 multiplied by 10 -1 ～6×10 -1 Pa, introducing high-purity argon and high-purity nitrogen, and setting the power of the magnetron sputtering high-entropy alloy target, wherein the volume flow of the high-purity argon is 20 +/-2 sccm, and the volume flow of the high-purity nitrogen is 2-50 sccm; the sputtering power is 50W-500W, and the sputtering time is 0.5 h-10 h.
10. The method as claimed in claim 9, wherein the AlCrTiVZr high-entropy alloy target is prepared by a powder metallurgy process, and the purity of the AlCrTiVZr high-entropy alloy target is more than 99.6%.
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| CN202210825310.1A Pending CN115233173A (en) | 2022-07-14 | 2022-07-14 | Hard wear-resistant anti-oxidation high-entropy alloy coating and preparation method thereof |
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| CN116024480A (en) * | 2023-01-10 | 2023-04-28 | 昆明理工大学 | High-entropy alloy material and preparation method thereof |
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