CN110670019A - Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof - Google Patents

Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof Download PDF

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CN110670019A
CN110670019A CN201910974710.7A CN201910974710A CN110670019A CN 110670019 A CN110670019 A CN 110670019A CN 201910974710 A CN201910974710 A CN 201910974710A CN 110670019 A CN110670019 A CN 110670019A
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CN110670019B (en
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鲜广
赵海波
鲜丽君
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Sichuan University
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Sichuan University
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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
    • C23C14/14—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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a crater wear resistant aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating which is composed of a CoNiCrAlY high-entropy alloy bonding layer and alpha-Cr2O3Oxide template layer, alpha-Al2O3The oxide core layer and the AlTiZrN nitride surface layer are integrated, the four sublayers are arranged from inside to outside, and the total thickness of the coating is 1-3 mu m. The preparation method comprises the following steps: heating and ion etching the substrate, and depositing a CoNiCrAlY layer on the substrate by using an arc evaporation plating process; then using cathode arc ion plating process to continuously and sequentially deposit alpha-Cr2O3Layer, alpha-Al2O3Layer and AlAnd a TiZrN layer. The oxide and nitride composite coating has excellent high-temperature oxidation resistance and high abrasion resistance, has good crater abrasion resistance under the conditions of high-speed cutting and dry cutting, has good process controllability, and is convenient for industrial production.

Description

Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof
Technical Field
The invention belongs to the technical field of surface coatings of cutting tools, and particularly relates to a crater wear resistant aluminum-titanium-zirconium-nitrogen-aluminum oxide multilayer composite coating and a preparation method thereof.
Background
The surface hardness of the cutting tool can be improved by times by preparing a thin coating on the surface of the cutting tool, and the service life of the cutting tool can be prolonged by times. The nitride hard coating is a widely used coating material on the surface of a cutting tool, such as TiN, TiAlN, CrAlN, TiAlCrN, TiAlSiN and the like, and the common property of the coating materials is that the coating materials have poor oxidation resistance under a high-temperature working state, and are easy to generate crater abrasion and even oxidation spalling failure. Currently, cutting technology is continuously advanced and developed, and particularly, high-speed cutting and dry cutting technologies are increasingly applied, and one problem faced by such cutting technologies is the increase of cutting temperature. Therefore, the application of nitride coated tools to new cutting techniques such as high speed cutting, dry cutting, etc. is challenging.
The advantage of an oxide coating is that the coating itself is an oxide, which does not have the problem of oxidation of the coating or which is oxidation resistant, which is more suitable for the operation of the tool at high temperatures. alpha-Al2O3The coating is an ideal tool surface coating material for cutting processing under high temperature condition due to compact structure, good chemical stability, good thermal stability and higher hardness and toughness, and is also the common alpha-Al contained in the tool coating prepared by the chemical vapor deposition method at present2O3The reason for (1). However, the chemical vapor deposition method is characterized in that the coating deposition temperature is high (600-1000 ℃), which causes changes to the properties of the blade body material, such as causing embrittlement of carbides in the cemented carbide blade and reduction of toughness, thereby causing the application of the blade in metal cutting (mainly milling) to be limited. The physical vapor deposition method is suitable for the surface coating of a wider range of cutters and other tools, dies and mechanical parts due to the low deposition temperature (< 550 ℃); the method deposits alpha-Al just because of the low deposition temperature2O3Is insufficient in energy, Al produced by physical vapor deposition2O3The coating is usually amorphous or other crystalline structure, and the ideal use effect is difficult to obtain.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a crater wear resistant aluminum-titanium-zirconium-nitrogen-aluminum oxide multilayer composite coating.
The invention also aims to provide a preparation method of the crater wear resistant aluminum-titanium-zirconium-nitrogen-aluminum oxide multilayer composite coating.
The crater wear resistant aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating is characterized in that the coating is an integral body formed by a high-entropy alloy bonding layer, an oxide template layer, an oxide core layer and a nitride surface layer, the four sublayers are arranged from inside to outside, and the total thickness of the coating is 1-3 mu m.
Wherein, in the coating, the high-entropy alloy bonding layer is CoaNibCrcAldYeThe thickness of the film is 50-200 nm, wherein a + b + c + d + e =1, the ranges of a, b, c, d and e are 0.15-0.4.
Wherein, in the coating, the oxide template layer is alpha-Cr2O3The thickness is 150-300 nm; the oxide core layer is alpha-Al2O3The thickness is 500-2000 nm; the nitride surface layer is AlTiN, and the thickness is 300-500 nm.
The invention provides a preparation method of the crater wear resistant aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating, which comprises the following steps:
A. loading the cleaned substrate material into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the substrate;
C. preparing a high-entropy alloy bonding layer by using an arc evaporation process;
D. preparing an oxide template layer by using a cathodic arc coating process;
E. preparing an oxide core layer by using a cathodic arc coating process;
F. and preparing the nitride surface layer by using a cathodic arc coating process.
In the step A, the vacuumizing and heating is to firstly vacuumize the back bottom to be below 0.03Pa, open an auxiliary heating device of a furnace wall to heat the substrate, and simultaneously open a rack rotating power supply to enable the substrate to rotate and revolve in the vacuum chamber until the temperature of the substrate reaches 380 ℃.
Wherein in the step B of the method, the ion etching is performedThe etching is to introduce argon into the vacuum chamber, adjust the argon flow to ensure that the pressure is 0.1-0.25 Pa, then apply-100 to-200V of direct current bias and-200 to-400V of pulse bias to the substrate, and utilize the ionized Ar+And etching the surface of the substrate for 30-90 min.
In the step C of the method, the working pressure of the prepared high-entropy alloy bonding by the arc evaporation process is 0.1-0.2 Pa, the arc current passing through the evaporation crucible is 180-220A, and the material placed in the evaporation crucible is CoaNibCrcAldYeThe high-entropy alloy has a + b + c + d + e =1, the value ranges of a, b, c, d and e are 0.15-0.4, and the evaporation time is 5-10 min.
In the step D, the working gas for preparing the oxide template layer by the cathodic arc coating process is Ar + O2The working pressure is 1.5-3.5 Pa, the working target material is a Cr arc target, the target current is 50-100A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 10-20 min.
In the step E, the working gas for preparing the oxide core layer by the cathodic arc coating process is Ar + O2The working pressure is 1.0-3.0 Pa, the working target material is an Al arc target, the target current is 80-120A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 40-150 min.
In the step F, the working gas for preparing the nitride surface layer by the cathodic arc coating process is N2The working pressure is 1.5-3.5 Pa, the working target material is an AlTiZr alloy arc target, the target current is 80-120A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 20-35 min.
Compared with the prior art, the invention has the following advantages:
1) the multi-layer composite coating of aluminum, titanium, zirconium, nitrogen and aluminum oxide for resisting crater wear is composed of four sublayers with different functions and components, firstly, compared with the traditional Cr and Ti pure metal bonding layer and TiAl alloy bonding layer, the high-entropy alloy bonding layer has higher obdurability, and can play a good role between the base material of the cutter and the surface coating materialThe bonding effect of the coating enables the coating to be firmly combined with the substrate; next, alpha-Cr is used2O3The oxide template layer is beneficial to Al2O3According to alpha-Cr2O3The epitaxial growth of the crystal structure solves the problem of preparing alpha-Al by a physical vapor deposition method due to low temperature2O3The problem of difficulty; thirdly, alpha-Al2O3The combination of the oxide core layer and the AlTiN nitride surface layer avoids the problems of low hardness and insufficient wear resistance of a pure oxide coating and the problems of poor high-temperature oxidation resistance, low chemical stability and low performance of obstructing the diffusion of element atoms inside and outside the pure nitride coating.
2) The invention provides a method for preparing a multi-layer composite coating of aluminum, titanium, zirconium, nitrogen and aluminum oxide, which is resistant to crater wear, and relates to a combined ion plating process which takes cathodic arc deposition as a main process and takes an evaporation plating process for preparing a bonding layer as an auxiliary process. Before coating, impurities adsorbed in the substrate material are released by heating, and meanwhile, the surface of the substrate is bombarded and etched by ionized Ar +, so that the combination of the coating and the substrate is enhanced; the high-entropy alloy material is evaporated by adopting an electric arc evaporation process, a high-entropy alloy bonding layer is deposited on the substrate, the bonding capacity of the coating and the substrate is further enhanced, the bonding layer is prepared by electric arc evaporation, the advantages of high deposition rate and almost unlimited size and shape of the evaporation raw material are that the evaporation raw material is weighed and then put into an evaporation crucible, and the bonding layer is deposited by adopting cathode electric arc ion plating, so that the evaporation raw material is required to be prepared into a target material with a certain shape and size; high ionization rate of particles and high ion energy in the process of cathode arc ion plating, and alpha-Al is easier to obtain than magnetron sputtering2O3. In the process of depositing the coating, the preparation of the multilayer composite coating is easy by switching different arc targets, and the operation process is simple and easy to master and control.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
Loading a cleaned cermet substrate into a plasma enhancementIn a vacuum chamber of the composite ion coating system, when the back bottom is vacuumized to 0.03Pa, an auxiliary heating device of a furnace wall is opened to heat the substrate, and a rotating power supply is turned on to enable the substrate to rotate ceaselessly until the temperature of the substrate reaches 380 ℃; introducing argon into the vacuum chamber, adjusting the flow of argon to ensure that the pressure is 0.16Pa, applying-200V DC bias and-400V pulse bias to the substrate, and utilizing ionized Ar+Etching the surface of the substrate for 60 min; closing substrate bias voltage and adjusting argon flow in sequence to ensure that working pressure is 0.18Pa, starting an evaporation plating main arc power supply to carry out evaporation coating, wherein the main arc current on a crucible is 180A, and the evaporation raw material is Co0.2Ni0.2Cr0.2Al0.2Y0.2Blocking, evaporating and depositing for 10 min; closing a main arc power supply, starting a Cr arc target, setting the target current to be 65A, introducing oxygen into the vacuum chamber, adjusting the flow of argon and oxygen to enable the working pressure to be 2.5Pa, applying bias voltage of-50V to the substrate, and depositing for 12 min; starting an Al arc target, setting the target current to be 80A, then closing a Cr arc target power supply, adjusting the gas flow, controlling the pressure to be 2.8Pa, and keeping the substrate bias constant to continue depositing for 120 min; starting the AlTiZr alloy arc target, setting the target current to be 100A, then closing an Al arc target power supply, introducing nitrogen, closing oxygen and argon, adjusting the gas flow, controlling the working pressure to be 2.0Pa, continuously keeping the substrate bias voltage unchanged, and finishing the deposition for 25 min. The prepared nitrogen oxide composite coating resisting crater wear consists of a CoNiCrAlY high-entropy alloy bonding layer and alpha-Cr2O3Oxide template layer, alpha-Al2O3The oxide core layer and the AlTiZrN nitride surface layer are composed of four sublayers, the combination of the sublayers and the coating and the substrate is good, and the product has good crater wear resistance under the high-speed turning condition.
Example 2
Putting a clean hard alloy substrate into a vacuum chamber of a plasma enhanced composite ion coating system, opening an auxiliary heating device of a furnace wall to heat the substrate when the back substrate is vacuumized to 0.03Pa, and simultaneously opening a rotating power supply to enable the substrate to rotate ceaselessly until the temperature of the substrate reaches 380 ℃; then argon is introduced into the vacuum chamberAdjusting the flow of argon gas to ensure that the pressure is 0.25Pa, and then applying a DC bias of-150V and a pulse bias of-350V to the substrate, using ionized Ar+Etching the surface of the substrate for 40 min; closing substrate bias voltage and adjusting argon flow in sequence to ensure that working pressure is 0.12Pa, starting an evaporation plating main arc power supply to carry out evaporation coating, wherein the main arc current on a crucible is 200A, and the evaporation raw material is Co0.2Ni0.2Cr0.2Al0.2Y0.2Blocking, evaporating and depositing for 6 min; closing a main arc power supply, starting a Cr arc target, setting the target current to be 80A, introducing oxygen into the vacuum chamber, adjusting the flow of argon and oxygen to enable the working pressure to be 3.0Pa, applying bias voltage of-70V to the substrate, and depositing for 15 min; starting an Al arc target, setting the target current to be 90A, then closing a Cr arc target power supply, adjusting the gas flow, controlling the pressure to be 2.5Pa, and keeping the substrate bias constant to continue depositing for 150 min; and starting the AlTiZr alloy arc target, setting the target current to be 120A, then closing an Al arc target power supply, introducing nitrogen, closing oxygen and argon, adjusting the gas flow, controlling the working pressure to be 3.0Pa, continuously keeping the substrate bias voltage unchanged, and finishing the deposition for 20 min. The prepared nitrogen oxide composite coating resisting crater wear consists of a CoNiCrAlY high-entropy alloy bonding layer and alpha-Cr2O3Oxide template layer, alpha-Al2O3The oxide core layer and the AlTiZrN nitride surface layer consist of four sublayers, the sublayers and the coating are well combined with the substrate, and the coating has good crater wear resistance under the dry milling condition.
Example 3
Loading a clean metal ceramic substrate into a vacuum chamber of a plasma enhanced composite ion coating system, opening an auxiliary heating device of a furnace wall to heat the substrate when the back substrate is vacuumized to 0.03Pa, and simultaneously opening a rotating power supply to enable the substrate to rotate ceaselessly until the temperature of the substrate reaches 380 ℃; introducing argon into the vacuum chamber, adjusting the flow of argon to ensure that the pressure is 0.16Pa, applying-200V DC bias and-400V pulse bias to the substrate, and utilizing ionized Ar+Etching the surface of the substrate for 90 min; closing substrate bias voltage and adjusting argon flow in sequence to ensure working pressureThe pressure is 0.2Pa, an evaporation plating main arc power supply is started to carry out evaporation coating, the main arc current on the crucible is 220A, and the evaporation raw material is Co0.2Ni0.2Cr0.2Al0.2Y0.2Blocking, evaporating and depositing for 6 min; closing a main arc power supply, starting a Cr arc target, setting the target current to be 90A, introducing oxygen into the vacuum chamber, adjusting the flow of argon and oxygen to enable the working pressure to be 3.5Pa, applying bias voltage of-30V to the substrate, and depositing for 10 min; opening an Al arc target, setting the target current to be 120A, then closing a Cr arc target power supply, adjusting the gas flow, controlling the pressure to be 3.0Pa, adjusting the substrate bias voltage to be-40V, and coating for 130 min; starting the AlTiZr alloy arc target, setting the target current to be 100A, then closing an Al arc target power supply, introducing nitrogen, closing oxygen and argon, adjusting the gas flow, controlling the working pressure to be 2.8Pa, adjusting the substrate bias voltage to be-50V, and finishing the deposition for 30 min. The prepared nitrogen oxide composite coating resisting crater wear consists of a CoNiCrAlY high-entropy alloy bonding layer and alpha-Cr2O3Oxide template layer, alpha-Al2O3The oxide core layer and the AlTiZrN nitride surface layer are composed of four sublayers, the combination of the sublayers and the coating and the substrate is good, and the product has good crater wear resistance under the high-speed turning condition.
Example 4
Putting a clean hard alloy substrate into a vacuum chamber of a plasma enhanced composite ion coating system, opening an auxiliary heating device of a furnace wall to heat the substrate when the back substrate is vacuumized to 0.03Pa, and simultaneously opening a rotating power supply to enable the substrate to rotate ceaselessly until the temperature of the substrate reaches 380 ℃; introducing argon into the vacuum chamber, adjusting the flow of argon to ensure that the pressure is 0.1Pa, applying-200V DC bias and-400V pulse bias to the substrate, and utilizing ionized Ar+Etching the surface of the substrate for 30 min; closing substrate bias voltage and adjusting argon flow in sequence to ensure that the working pressure is 0.2Pa, starting an evaporation plating main arc power supply to carry out evaporation coating, wherein the main arc current on a crucible is 205A, and the evaporation raw material is Co0.15Ni0.15Cr0.4Al0.15Y0.15Blocking, evaporating and depositing for 10 min; the main arc power supply is turned off, the Cr arc target is turned on,setting the target current as 70A, introducing oxygen into the vacuum chamber, adjusting the flow of argon and oxygen to make the working pressure be 1.5Pa, applying bias voltage of-80V to the substrate, and depositing for 15 min; starting an Al arc target, setting the target current to be 120A, then closing a Cr arc target power supply, adjusting the gas flow, controlling the pressure to be 3.0Pa, and continuously coating the film for 40min with the substrate bias voltage kept unchanged; starting the AlTiZr alloy arc target, setting the target current to be 80A, then closing an Al arc target power supply, introducing nitrogen, closing oxygen and argon, adjusting the gas flow, controlling the working pressure to be 1.5Pa, continuously keeping the substrate bias voltage unchanged, and finishing the deposition for 20 min. The prepared nitrogen oxide composite coating resisting crater wear consists of a CoNiCrAlY high-entropy alloy bonding layer and alpha-Cr2O3Oxide template layer, alpha-Al2O3The oxide core layer and the AlTiZrN nitride surface layer consist of four sublayers, the sublayers and the coating are well combined with the substrate, and the coating has good crater wear resistance under the dry milling condition.

Claims (10)

1. The multi-layer composite coating of aluminum, titanium, zirconium, nitrogen and aluminum oxide, which is resistant to crater wear, is characterized in that the coating is an integral body formed by a high-entropy alloy bonding layer, an oxide template layer, an oxide core layer and a nitride surface layer, the four sublayers are arranged from inside to outside, and the total thickness of the coating is 1-3 mu m.
2. The crater wear-resistant aluminum-titanium-zirconium-nitrogen-and-aluminum oxide multilayer composite coating according to claim 1, wherein the high-entropy alloy bonding layer is CoaNibCrcAldYeThe thickness of the film is 50-200 nm, wherein a + b + c + d + e =1, the ranges of a, b, c, d and e are 0.15-0.4.
3. The multi-layer composite coating of aluminum, titanium, zirconium, nitrogen and aluminum oxide for resisting crater wear of claim 1, wherein the oxide template layer is α -Cr2O3The thickness is 150-300 nm; the oxide core layer is alpha-Al2O3The thickness is 500-2000 nm; the nitridingThe surface layer is AlTiZrN with a thickness of 300-500 nm.
4. A preparation method of the crater wear resistant aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating according to any one of claims 1 to 3, characterized by comprising the following steps:
A. loading the cleaned substrate material into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the substrate;
C. preparing a high-entropy alloy bonding layer by using an arc evaporation process;
D. preparing an oxide template layer by using a cathodic arc coating process;
E. preparing an oxide core layer by using a cathodic arc coating process;
F. and preparing the nitride surface layer by using a cathodic arc coating process.
5. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-aluminum oxide multi-layer composite coating according to claim 4, wherein in the step A, the vacuumizing and heating are performed by firstly vacuumizing the back bottom to 0.03Pa or below, turning on an auxiliary heating device of a furnace wall to heat the substrate, and simultaneously turning on a rack rotating power supply to enable the substrate to perform rotation and revolution motions in the vacuum chamber until the temperature of the substrate reaches 380 ℃.
6. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-aluminum oxide multi-layer composite coating according to claim 4, wherein in the step B, argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is adjusted to ensure that the pressure is 0.1-0.25 Pa, then a direct current bias voltage of-100-200V and a pulse bias voltage of-200-400V are applied to the substrate, and ionized Ar is used+And etching the surface of the substrate for 30-90 min.
7. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-and-aluminum oxide multilayer composite coating according to claim 4, wherein the step C is carried outIn the preparation method, the working pressure of the high-entropy alloy bonding prepared by the arc evaporation process is 0.1-0.2 Pa, the arc current passing through the evaporation crucible is 180-220A, and the material placed in the evaporation crucible is CoaNibCrcAldYeThe high-entropy alloy has a + b + c + d + e =1, the value ranges of a, b, c, d and e are 0.15-0.4, and the evaporation time is 5-10 min.
8. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-and-aluminum oxide multi-layer composite coating according to claim 4, wherein in the step D, the working gas for preparing the oxide template layer by the cathodic arc coating process is Ar + O2The working pressure is 1.5-3.5 Pa, the working target material is a Cr arc target, the target current is 50-100A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 10-20 min.
9. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-and-aluminum oxide multilayer composite coating according to claim 4, wherein in the step E, the working gas for preparing the oxide core layer by the cathodic arc plating process is Ar + O2The working pressure is 1.0-3.0 Pa, the working target material is an Al arc target, the target current is 80-120A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 40-150 min.
10. The method for preparing the crater wear-resistant aluminum-titanium-zirconium-nitrogen-and-aluminum oxide multilayer composite coating according to claim 4, wherein in the step F, the working gas for preparing the nitride surface layer by the cathodic arc coating process is N2The working pressure is 1.5-3.5 Pa, the working target material is an AlTiZr alloy arc target, the target current is 80-120A, the bias voltage applied to the substrate is-30-80V, and the deposition time is 20-35 min.
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