CN115595532A - Multilayer structure hard coating and preparation method and application thereof - Google Patents
Multilayer structure hard coating and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000005498 polishing Methods 0.000 claims description 8
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- 239000002356 single layer Substances 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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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
- C23C14/0641—Nitrides
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Abstract
The invention relates to the technical field of surface engineering and numerical control cutter cutting, and provides a multilayer structure hard coating and a preparation method and application thereof. The multilayer structure hard coating deposited by adopting the arc ion plating technology has at least three layers of structures, and comprises a bottom coating Al tightly combined with a substrate a Cr 1‑a N, middle layer coating m { Al b Ti c Me 1‑b‑c N+n(Al a Cr 1‑a N/Al b Ti c Me 1‑b‑c N)+Al a Cr 1‑a N+l(Al a Cr 1‑a N/Al b Ti c Me 1‑b‑c N) } and top coating Al b Ti c Me 1‑b‑c N, introduction of alloy elements Me (W, mo and V) can reduce friction coefficient of the coating and improve toughness of the coatingThe alloy has good toughness while maintaining high hardness under the optimization of the structure and the action of an alloy element Me.
Description
Technical Field
The invention relates to the technical field of surface engineering and numerical control cutter cutting, in particular to a multilayer structure hard coating and a preparation method and application thereof.
Background
The application of the hard coating in the field of cutting of numerical control tools has been in history for decades, but with the continuous improvement of the material performance of workpieces, the requirement on the performance of the coating is higher and higher, and the application of the traditional hard coating is limited to a certain extent. The hard coating begins to evolve in the direction of alloying and structuring.
The (Ti, al) N coating and the (Al, cr) N coating are used as common nitride coatings and have wider application in the field of numerical control cutter cutting. In the machining of stainless steel, for example, the wear forms of the tool are mainly adhesive wear, diffusion wear and abrasive wear. The (Ti, al) N coating has higher friction coefficient, leads to faster increase of cutting temperature in the cutting process, is beneficial to the development of adhesion abrasion and diffusion abrasion, and leads to quicker failure of the cutter. In addition, the coating has poor toughness, a cutter frequently undergoes rapid cooling in the water-cooling cutting process, the toughness of the coating is required to a certain degree, the poor high-temperature oxidation resistance can directly cause the coating to lose effectiveness at a low temperature, and the application is limited to a certain degree. The (Al, cr) N coating has great advantages in high-temperature oxidation resistance, but the coating has large friction coefficient, is not beneficial to chip removal in the cutting process, can cause heat accumulation due to unsmooth chip removal, and is more serious in adhesion and abrasion, so that the service life of the cutter is shortened. The addition of a metal element having lubricity, such as W, mo, V, etc., to the coating layer can surely improve the wear resistance and toughness of the (Ti, al) N coating layer. Such metallic elements can form oxides of magneli phase with lubricating properties at high temperatures, but such oxides are unstable at high temperatures as described in patents CN108866480B and CN110907433a, and are liable to volatilize at high temperatures, thus leading to a drastic reduction in the high temperature wear resistance. Furthermore, as described in "Effect of Mo on the thermal stability, oxidation resistance, and tribo-mechanical properties of arc imaged Ti-Al-N coatings", the addition of such elements also reduces the high temperature oxidation resistance of (Ti, al) N, and the more the amount added, the worse the high temperature oxidation resistance of the coating. Therefore, the invention combines the advantages of the (Al, cr) N coating and the (Ti, al) N coating, adds a small amount of metal elements with lubricating property, designs a multi-layer structure coating, maintains the advantages and the performance of the (Ti, al) N coating and the (Al, cr) N coating, and overcomes one or more performance defects of the coating.
Disclosure of Invention
The invention provides a multilayer structure hard coating, a preparation method and application thereof, and aims to solve the problems in the background art.
In order to achieve the above objects, embodiments of the present invention provide a multi-layered hard coating having at least a three-layered structure including a primer coating Al closely bonded to a substrate a Cr 1-a N, middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1-a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) } and top coating Al b Ti c Me 1-b-c N, the multilayer structure hard coating adopts a structuring means, and Al with high-temperature oxidation resistance is introduced a Cr 1-a The atomic percentage of Al atoms in the N coating is more than or equal to 0.2 and less than or equal to 0.8; al (aluminum) b Ti c Me 1-b-c The atomic percentage of Al atoms in N is more than or equal to 0.4 and less than or equal to 0.7, the atomic percentage of Ti atoms is more than or equal to 0.3 and less than or equal to 0.6,2 and less than or equal to 16, m is more than or equal to 50 and less than or equal to N, and l is less than or equal to 100.
Preferably, the multilayer structure hard coating adopts an alloying method to introduce an alloy element Me, me is at least one of W, mo and V, and Al b Ti c Me 1-b-c The N coating can generate an oxide with lubricating property in the friction process, so that the friction coefficient of the existing coating is effectively reduced, and the wear resistance is improved.
Preferably, the total thickness of the multilayer structure hard coating is 1.5-4.0 μm; the bottom layer coating Al a Cr 1- a N is a single-layer coating structure, and the thickness of N is 0.2-1.0 μm; the top layer coating Al b Ti c Me 1-b-c N is a single-layer coating structureThe thickness is 0.2-1.0 μm; the middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1- a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) is a multilayer structure, the thickness is 0.8-2.5 mu m, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
More preferably, the intermediate layer coating m { Al } b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1- a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) } from Al b Ti c Me 1-b-c N、n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)、Al a Cr 1-a N and l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) four layers of coatings are formed by sequential alternate deposition, m, N and l are alternate deposition times, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
More preferably, the first layer of Al of the intermediate layer b Ti c Me 1-b-c The thickness of the N coating is 0.02-0.07 mu m; second layer n (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b- c The thickness ratio of the N layer is 0.2-3; third layer of Al a Cr 1-a The thickness of the coating of N is 0.02-0.07 μm; fourth layer l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b-c The thickness ratio of the N layers is 0.2-3, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to l is less than or equal to 100.
Based on one general inventive concept, the present invention also provides a method for preparing the multilayer structure hard coating, comprising the steps of:
s1, grinding, sand blasting, polishing, ultrasonic cleaning and drying a substrate;
s2, starting a cathode arc ion plating machine, and carrying out ion cleaning on the surface of the substrate;
s3, depositing a bottom coating on the surface of the substrate by adopting an ion plating technology;
s4, depositing a middle layer coating on the bottom layer coating by adopting an ion plating technology;
and S5, depositing a top coating on the middle coating by adopting an ion plating technology to obtain the multilayer structure hard coating.
Preferably, the ion cleaning in step S2 specifically includes: putting the substrate in a vacuum chamber of an ion plating machine, vacuumizing and heating until the temperature is stabilized at 400-600 ℃ and the vacuum degree is lower than 1.0 multiplied by 10 -3 Pa, filling argon into the vacuum chamber until the pressure is 2.0-5.0 Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200-500V and the current of the ion source of 100-200A, and performing Ar ion glow cleaning on the substrate.
Preferably, the specific parameters of the bottom layer coating deposited in step S3 are: the arc current of the AlCr alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm; the specific parameters for depositing the middle layer coating in the step S4 are as follows: the arc current of the AlCr alloy target material and the AlTiMe alloy target material is 100-200A, the negative bias voltage of a substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, the rotating speed of a workpiece rotating stand is 1.0-3.0 rpm, wherein the alternation of layers is realized by the switching on and off of the target material; the specific parameters of the top coating deposited in the step S5 are as follows: the arc current of the AlTiMe alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm.
Preferably, the substrate is a numerical control blade prepared from hard alloy or ceramic material; the purity of the alloy target in the deposition process is not less than 99.96%.
The invention also provides application of the multilayer structure hard coating in the fields of cutter cutting and surface protection coating.
The scheme of the invention has the following beneficial effects:
(1) The invention adopts the multilayer structure hard coating deposited by the arc ion plating technology, and introduces the alloy elements Me (W, mo and V), so that the friction coefficient of the coating can be reduced, and the toughness of the coating can be improved.
(2) The multilayer structure hard coating prepared by the invention keeps higher hardness (shown in the following table 1) and has good toughness (shown in the attached figures 1-6) under the effects of structure optimization and alloy element Me.
(3) Compared with the traditional (Ti, al) N coating, the multilayer structure hard coating prepared by the invention is suitable for higher cutting speed and feed amount, widens the application range of the cutter, and prolongs the service life of the cutter.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a comparison graph of the micro-indentation morphology at a coating load of 100gf in example 1 of the present invention;
FIG. 2 is a comparison graph of the micro-indentation morphology at a coating load of 200gf for example 1 of the present invention;
FIG. 3 is a comparison graph of the micro-indentation morphology at a coating load of 100gf for example 2 of the present invention;
FIG. 4 is a comparison graph of the micro-indentation morphology at a coating load of 200gf for example 2 of the present invention;
FIG. 5 is a comparison graph of the micro-indentation morphology at a coating load of 100gf for example 3 of the present invention;
FIG. 6 is a comparison graph of the micro-indentation morphology at a coating load of 200gf for example 3 of the present invention;
FIG. 7 is a comparative micro-indentation morphology of 100gf coating load in comparative example 1 of the present invention;
FIG. 8 is a comparative micro-indentation morphology of coating load of 200gf in comparative example 1 of the present invention;
FIG. 9 is a comparative micro-indentation morphology of 100gf coating load in comparative example 2 of the invention;
FIG. 10 is a comparative micro-indentation morphology of coating load of 200gf in comparative example 2 of the present invention.
Detailed Description
To make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The (Ti, al) N coating and the (Al, cr) N coating are used as common nitride coatings and have wide application in the field of numerical control cutter cutting. In the machining of stainless steel, for example, the wear forms of the tool are mainly adhesive wear, diffusion wear and abrasive wear. The friction coefficient of the (Ti, al) N coating is high, so that the cutting temperature is increased quickly in the cutting process, the development of adhesion abrasion and diffusion abrasion is facilitated, and the cutter is quickly failed. In addition, the coating has poor toughness, a cutter frequently undergoes rapid cooling in the water-cooling cutting process, the toughness of the coating is required to a certain degree, the poor high-temperature oxidation resistance can directly cause the coating to lose effectiveness at a low temperature, and the application is limited to a certain degree. The (Al, cr) N coating has great advantages in high-temperature oxidation resistance, but the coating has large friction coefficient, is not beneficial to chip removal in the cutting process, can cause heat accumulation due to unsmooth chip removal, and is more serious in adhesion and abrasion, so that the service life of the cutter is shortened.
The invention provides a multilayer structure hard coating, and a preparation method and application thereof, aiming at the existing problems.
Embodiments of the present invention provide a multi-layered hard coating having at least a three-layered structure including a primer coating Al closely bonded to a substrate a Cr 1-a N, middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1-a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) } and top coating Al b Ti c Me 1-b-c N, the multilayer structure hard coating adopts a structuring means, and Al with high-temperature oxidation resistance is introduced a Cr 1-a The atomic percentage of Al atoms in the N coating is more than or equal to 0.2 and less than or equal to 0.8; al (Al) b Ti c Me 1-b-c The atomic percentage of Al atoms in N is more than or equal to 0.4 and less than or equal to 0.7, the atomic percentage of Ti atoms is more than or equal to 0.3 and less than or equal to c and less than or equal to 0.6,2 and less than or equal to 16, m is more than or equal to 50 and less than or equal to N, and l is less than or equal to 100.
Preferably, the multilayer structure hard coating adopts an alloying method to introduce an alloy element Me, wherein Me is at least one of W, mo and V, so that Al is added b Ti c Me 1-b-c The N coating can generate an oxide with lubricating property in the friction process, so that the friction coefficient of the existing coating is effectively reduced, and the wear resistance is improved.
Preferably, the total thickness of the multilayer structure hard coating is 1.5-4.0 μm; the bottom layer coating Al a Cr 1- a N is a single-layer coating structure, and the thickness of N is 0.2-1.0 μm; the top coating Al b Ti c Me 1-b-c N is a single-layer coating structure, and the thickness of N is 0.2-1.0 μm; the middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1- a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) is a multilayer structure, the thickness is 0.8-2.5 mu m, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
More preferably, the intermediate layer coating m { Al } b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1- a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) } from Al b Ti c Me 1-b-c N、n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)、Al a Cr 1-a N and l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) four layers of coatings are formed by sequential alternate deposition, m, N and l are alternate deposition times, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
More preferably, the first layer of Al of the intermediate layer b Ti c Me 1-b-c The thickness of the N coating is 0.02-0.07 μm; second layer n (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b- c The thickness ratio of the N layer is 0.2-3; third layer of Al a Cr 1-a The thickness of the coating of N is 0.02-0.07 μm; fourth layer l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b-c The thickness ratio of the N layers is 0.2-3, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
Based on one general inventive concept, the present invention also provides a method for preparing the multilayer-structure hard coating, comprising the following steps:
s1, grinding, sand blasting, polishing, ultrasonic cleaning and drying a matrix;
s2, starting a cathode arc ion plating machine, and carrying out ion cleaning on the surface of the substrate;
s3, depositing a bottom coating on the surface of the substrate by adopting an ion plating technology;
s4, depositing a middle layer coating on the bottom layer coating by adopting an ion plating technology;
and S5, depositing a top coating on the middle coating by adopting an ion plating technology to obtain the multilayer structure hard coating.
Preferably, the ion cleaning in step S2 specifically includes: putting the substrate in a vacuum chamber of an ion plating machine, vacuumizing and heating until the temperature is stabilized at 400-600 ℃ and the vacuum degree is lower than 1.0 multiplied by 10 -3 Pa, filling argon into the vacuum chamber until the pressure is 2.0-5.0 Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200-500V and the current of the ion source of 100-200A, and performing Ar ion glow cleaning on the substrate.
Preferably, the specific parameters of the bottom layer coating deposited in step S3 are: the arc current of the AlCr alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm; the specific parameters for depositing the middle layer coating in the step S4 are as follows: the arc current of the AlCr alloy target material and the AlTiMe alloy target material is 100-200A, the negative bias voltage of a substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, the rotating speed of a workpiece rotating stand is 1.0-3.0 rpm, wherein the alternation of layers is realized by the switching on and off of the target material; the specific parameters of the top coating deposited in the step S5 are as follows: the arc current of the AlTiMe alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm.
Preferably, the substrate is a numerical control blade prepared from hard alloy or ceramic material; the purity of the alloy target in the deposition process is not less than 99.96%.
The invention also provides application of the multilayer structure hard coating in the fields of cutter cutting and surface protection coating.
Example 1:
a multilayer hard coating comprises a bottom coating Al closely combined with a substrate 0.7 Cr 0.3 N, coating Al on the bottom layer 0.7 Cr 0.3 Middle layer coating on N4 Back Al 0.60 Ti 0.32 W 0.02 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N)+Al 0.7 Cr 0.3 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N) } and top coating Al on the middle coating 0.60 Ti 0.32 W 0.02 And N, wherein the substrate is a numerical control blade made of hard alloy materials.
The preparation method of the multilayer structure hard coating specifically comprises the following steps:
(1) Grinding, sand blasting and polishing the substrate, putting the substrate on a production line, carrying out ultrasonic cleaning for 20min by using an alkaline cleaning agent, then baking for 20min at 150 ℃, cooling, clamping on a rotating frame, and placing the rotating frame in a vacuum chamber.
(2) Vacuumizing and heating until the temperature is stabilized at 520 deg.C and the vacuum degree is 1.0 × 10 -3 And Pa, filling argon into the vacuum chamber until the pressure is 3.5Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200V and the current of the ion source of 180A, and performing Ar ion glow cleaning on the substrate for 45min.
(3) Depositing primer coating Al 0.7 Cr 0.3 The specific parameters of N are as follows: the arc current of the AlCr alloy target material is 150A, the negative bias of the substrate is 60V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 18min.
(4) Deposited intermediate layer coating 4 back Al 0.60 Ti 0.32 W 0.02 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N)+Al 0.7 Cr 0.3 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N) } specific parameters are: the AlCr alloy target material and the arc current are 150AThe arc current of the target material is 200A, the negative bias of the substrate is 150V, the nitrogen gas pressure is 4.0Pa, the deposition temperature is 520 ℃, and the rotating speed of the workpiece rotating stand is 1.6rpm: wherein a first coating Al is deposited 0.60 Ti 0.32 W 0.08 N, starting the AlTiW alloy target material, and setting the deposition time to be 5min; depositing a second coating 100 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N), starting an AlCr alloy target material, and depositing for 6min; depositing a third coating Al 0.7 Cr 0.3 N, closing the AlTiW alloy target material, and depositing for 6min; depositing a fourth coating 100 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.02 N), starting the AlTiW alloy target material, wherein the deposition time is 4min, and the above four layers are alternately deposited for 4 times.
(5) Depositing a top coating Al 0.60 Ti 0.32 W 0.02 The specific parameters of N are as follows: the arc current of the AlTiW alloy target material is 200A, the negative bias of the substrate is 60V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 50min.
(6) And closing the AlTiW alloy target, closing the gas, closing the bias power supply, closing the vacuum pump, and taking out the substrate after the vacuum chamber is cooled to below 200 ℃.
Wherein the purities of the AlTiW and AlCr alloy target materials are both 99.97%.
Example 2:
a multilayer hard coating comprises a bottom coating Al closely combined with a substrate 0.7 Cr 0.3 N, coating Al on the bottom layer 0.7 Cr 0.3 Middle layer coating on N4 Back Al 0.60 Ti 0.32 W 0.04 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N)+Al 0.7 Cr 0.3 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N) } and top coating Al on the middle coating 0.60 Ti 0.32 W 0.04 And N, wherein the substrate is a numerical control blade made of hard alloy materials.
The preparation method of the multilayer structure hard coating specifically comprises the following steps:
(1) Grinding, sand blasting and polishing the substrate, putting the substrate on a production line, carrying out ultrasonic cleaning for 20min by using an alkaline cleaning agent, and then baking for 20min at 150 ℃. After cooling, the glass is clamped on a rotating frame and placed in a vacuum chamber.
(2) Vacuum-pumping and heating until the temperature is stabilized at 520 deg.C and the vacuum degree is 1.0 × 10 -3 And Pa, filling argon into the vacuum chamber until the pressure is 3.5Pa, starting a bias power supply, starting a direct current negative bias voltage of 200V, starting an ion source with the current of 180A, and performing Ar ion glow cleaning on the substrate for 45min.
(3) Depositing primer coating Al 0.7 Cr 0.3 The specific parameters of N are as follows: the arc current of the AlCr alloy target material is 150A, the negative bias of the substrate is 60V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 18min.
(4) Deposited intermediate layer coating 4 back Al 0.60 Ti 0.32 W 0.04 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N)+Al 0.7 Cr 0.3 N+100(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N) are as follows: the arc current of the AlCr alloy target and the arc current of the AlTiW alloy target are 150A, the arc current of the AlTiW alloy target is 200A, the negative bias of a substrate is 150V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, and the rotating speed of a workpiece rotating stand is 1.6rpm: wherein a first coating Al is deposited 0.60 Ti 0.32 W 0.04 N, starting the AlTiW alloy target material, and setting the deposition time to be 5min; depositing a second coating 100 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N), starting an AlCr alloy target material, and depositing for 6min; depositing a third coating Al 0.7 Cr 0.3 N, closing the AlTiW alloy target material, and depositing for 6min; depositing a fourth coating 100 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.04 N), starting the AlTiW alloy target material, wherein the deposition time is 4min, and the above four layers are alternately deposited for 4 times.
(5) The specific parameters for depositing the top coating Al0.60Ti0.32W0.04N are as follows: the arc current of the AlTiW alloy target material is 200A, the negative bias of the substrate is 60V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 50min.
(6) And closing the AlTiW alloy target, closing the gas, closing the bias power supply, closing the vacuum pump, and taking out the substrate after the vacuum chamber is cooled to below 200 ℃.
Wherein the purities of the AlTiW and AlCr alloy target materials are both 99.97%.
Example 3:
a multilayer hard coating comprises a bottom coating Al closely combined with a substrate 0.7 Cr 0.3 N, coating Al on the bottom layer 0.7 Cr 0.3 Middle layer coating 8 f on N 0.60 Ti 0.32 W 0.08 N+60(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N)+Al 0.7 Cr 0.3 N+60(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N) } and top coating Al on the middle coating 0.60 Ti 0.32 W 0.08 And N, wherein the substrate is a numerical control blade made of hard alloy materials.
The preparation method of the multilayer structure hard coating specifically comprises the following steps:
(1) Grinding, sand blasting and polishing the substrate, putting the substrate on a production line, carrying out ultrasonic cleaning for 20min by using an alkaline cleaning agent, and then baking for 20min at 150 ℃. After cooling, the glass is clamped on a rotating frame and placed in a vacuum chamber.
(2) Vacuumizing and heating until the temperature is stabilized at 520 deg.C and the vacuum degree is 1.0 × 10 -3 And Pa, filling argon into the vacuum chamber until the pressure is 3.5Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200V and the current of the ion source of 180A, and performing Ar ion glow cleaning on the substrate for 45min.
(3) Depositing primer coating Al 0.7 Cr 0.3 The specific parameters of N are as follows: the arc current of the AlCr alloy target material is 150A, and the negative bias of the substrateThe pressure was 60V, the nitrogen pressure was 4.0Pa, the deposition temperature was 520 deg.C, the rotation speed of the workpiece turret was 1.6rpm, and the deposition time was 18min.
(4) Deposited intermediate layer coating 8 spherical Al 0.60 Ti 0.32 W 0.08 N+60(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N)+Al 0.7 Cr 0.3 N+60(Al 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N) are as follows: the arc current of the AlCr alloy target and the arc current of the AlTiW alloy target are 150A, the arc current of the AlTiW alloy target is 200A, the negative bias of the substrate is 150V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, and the rotating speed of the workpiece rotating stand is 1.6rpm: wherein a first coating Al is deposited 0.60 Ti 0.32 W 0.08 N, starting the AlTiW alloy target material, and depositing for 5min; depositing a second coating 60 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N), starting an AlCr alloy target material, and depositing for 3min; depositing a third coating Al 0.7 Cr 0.3 N, closing the AlTiW alloy target material, and depositing for 6min; depositing a fourth coating 60 (Al) 0.7 Cr 0.3 N/Al 0.60 Ti 0.32 W 0.08 N), starting the AlTiW alloy target material, wherein the deposition time is 2min, and the above four layers are alternately deposited for 8 times.
(5) Depositing a top coating Al 0.60 Ti 0.32 W 0.08 The specific parameters of N are as follows: the arc current of the AlTiW alloy target material is 200A, the negative bias of the substrate is 60V, the nitrogen pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 50min.
(6) And closing the AlTiW alloy target, closing the gas, closing the bias power supply, closing the vacuum pump, and taking out the substrate after the vacuum chamber is cooled to below 200 ℃.
Wherein the purities of the AlTiW and AlCr alloy target materials are both 99.97%.
Comparative example 1:
the (Ti, al) N is a single-layer structure coating, wherein the substrate is a numerical control blade prepared from a hard alloy material.
The preparation method of the (Ti, al) N coating specifically comprises the following steps:
(1) Grinding, sand blasting and polishing the substrate, putting the substrate on a production line, carrying out ultrasonic cleaning for 20min by using an alkaline cleaning agent, and then baking for 20min at 150 ℃. After cooling, the glass is clamped on a rotating frame and placed in a vacuum chamber.
(2) Vacuumizing and heating until the temperature is stabilized at 520 deg.C and the vacuum degree is 1.0 × 10 -3 And Pa, filling argon into the vacuum chamber until the pressure is 3.5Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200V and the current of the ion source of 180A, and performing Ar ion glow cleaning on the substrate for 45min.
(3) The specific parameters for depositing the (Ti, al) N coating are: the arc current of the AlTi (atomic ratio Al: ti =67 = 33) alloy target material is 200A, the negative bias voltage of the substrate is 80V, the nitrogen gas pressure is 3.5Pa, the deposition temperature is 500 ℃, the rotating speed of the workpiece rotating stand is 1.6rpm, and the deposition time is 160.2min.
(4) And (3) closing the AlTi alloy target material, closing the gas, closing the bias power supply, closing the vacuum pump, and taking out the substrate after the vacuum chamber is cooled to below 200 ℃.
Wherein the purity of the AlTi alloy target material is 99.96 percent.
Comparative example 2:
the (Al, cr) N is a single-layer structure coating, wherein the matrix is a numerical control blade prepared from a hard alloy material.
The preparation method of the (Al, cr) N coating specifically comprises the following steps:
(1) Grinding, sand blasting and polishing the substrate, putting the substrate on a production line, carrying out ultrasonic cleaning for 20min by using an alkaline cleaning agent, and then baking for 20min at 150 ℃. After cooling, the glass is clamped on a rotating frame and placed in a vacuum chamber.
(2) Vacuumizing and heating until the temperature is stabilized at 520 ℃ and the vacuum degree is 1.0 multiplied by 10 < -3 > Pa, then filling argon gas until the pressure in the vacuum chamber is 3.5Pa, starting a bias power supply, starting a direct current negative bias voltage of 200V, starting an ion source, wherein the current of the ion source is 180A, and performing Ar ion glow cleaning on the substrate for 45min.
(3) The specific parameters for depositing the (Al, cr) N coating are as follows: the arc current of the AlCr (atomic ratio Al: cr = 70) alloy target material is 150A, the negative bias voltage of the substrate is 150V, the nitrogen gas pressure is 4.0Pa, the deposition temperature is 520 ℃, the rotating speed of the workpiece rotating stand is 2.0rpm, and the deposition time is 140min.
(4) And closing the AlCr alloy target material, closing the gas, closing the bias power supply, closing the vacuum pump, and taking out the substrate after the vacuum chamber is cooled to be below 200 ℃.
Wherein the purity of the AlCr alloy target material is 99.97 percent.
Test examples:
hardness tests were performed on the coatings prepared in examples and comparative examples, respectively, using a nanoindenter, and the hardness data of the obtained coatings are shown in table 1.
TABLE 1 hardness data for coatings prepared in examples and comparative examples
| Coating layer | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Nano hardness [ GPa ]] | 34.2±2.3 | 31.7±2.5 | 37.1±2.9 | 36.8±2.0 | 35.6±3.0 |
As can be seen from table 1, the hardness of the multi-layered hard coated cutting tool of the present application was increased by about 5% to 15% compared to the hardness of the comparative coated cutting tool, indicating that the multi-layered hard coating of the present application has a higher hardness.
The coatings prepared in the examples and the comparative examples are respectively subjected to toughness characterization by a micro Vickers hardness tester, and the microscopic impression morphology of the coatings is observed by a scanning electron microscope. The obtained microscopic indentation morphology of the coating is shown in fig. 1 to 10, and at a load of 100gf, annular cracks appeared around the indentations of the coating of comparative example 1, while no cracks appeared around the indentations of the coatings of comparative example 2 and examples 1 to 3. At a load of 200gf, cracks occurred around the indentations of the coatings of comparative examples 1 to 2 and example 1, while cracks did not occur around the indentations of the coatings of examples 2 and 3. The results show that the toughness of the coatings obtained in the examples is improved by the combined effect of alloying and structuring, and that the toughness of the coatings prepared in examples 2 and 3 is relatively better.
The friction coefficients of the coatings obtained in examples and comparative examples were characterized by using a reciprocating frictional wear apparatus, and the friction coefficients of the resulting coatings are shown in table 2 below, in which the average friction coefficient of the coating of comparative example 1 in the stable friction stage was about 0.67, the friction coefficient of the coating of comparative example 2 was 0.71, and the friction coefficients of the coatings of examples 1 to 3 were 0.60, 0.53, and 0.49, respectively. The results show that the friction coefficient of the coating obtained in the examples is reduced by alloying.
Table 2: coefficient of friction of coatings prepared in examples and comparative examples
| Coating layer | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Coefficient of friction | 0.67 | 0.71 | 0.60 | 0.53 | 0.49 |
The multilayer structure hard coating cutter of the embodiment and the comparative example coated cutter are processed under the same cutting processing condition, and the specific cutting parameters are as follows: the model number of the blade is WNMG080408, the processing material is 304 stainless steel, the cutting speed Vc =240m/min, the feed Fz =0.25mm/rev, the cutting depth ap =1.0mm, and the cooling mode is water cooling. And when the uniform abrasion of the rear face of the blade reaches 0.2mm or the cutter has edge breakage, judging that the blade is failed. The cutting results are shown in table 3:
table 3: cutting life of the example and comparative example tools
| Coated cutting tool | Flank wear width | Cutting time |
| Comparative example 1 | 0.345mm | 10.5min |
| Comparative example 2 | 0.296mm | 10.5min |
| Example 1 | 0.278mm | 13.5min |
| Example 2 | 0.233mm | 13.5min |
| Example 3 | 0.216mm | 15.0min |
As can be seen from table 3, the cutting life of the multilayer-structure hard coating tool of the present application was improved by about 30% to 50% as compared to the cutting life of the comparative example-structure hard coating tool, and the amount of wear of the flank face was also relatively small, indicating that the multilayer-structure hard coating of the present application has excellent cutting performance.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The multilayer hard coating is characterized by comprising a bottom coating Al tightly combined with a substrate a Cr 1-a N, middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1-a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b- c N) } and top coating Al b Ti c Me 1-b-c N, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to 0.7,0.3 and less than or equal to c and less than or equal to 0.6,2 and less than or equal to 16, m is more than or equal to 50 and less than or equal to N, and l is less than or equal to 100.
2. The multilayer-structure hard coating according to claim 1, wherein the total thickness of the multilayer-structure hard coating is 1.5 to 4.0 μm; the bottom layer coating Al a Cr 1-a N is a single-layer coating structure, and the thickness of N is 0.2-1.0 μm; the top coating Al b Ti c Me 1-b-c N is a single-layer coating structure, and the thickness of N is 0.2-1.0 μm; the middle layer coating m { Al b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1-a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) is a multilayer structure, the thickness is 0.8-2.5 mu m, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
3. The multilayer hard coating according to claim 1, wherein the intermediate layer coating m { Al } b Ti c Me 1-b-c N+n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)+Al a Cr 1-a N+l(Al a Cr 1-a N/Al b Ti c Me 1-b-c N) } from Al b Ti c Me 1-b-c N、n(Al a Cr 1-a N/Al b Ti c Me 1-b-c N)、Al a Cr 1-a N and l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) four layers of coatings are formed by sequential alternate deposition, m, N and l are alternate deposition times, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to 100.
4. The multilayer hard coating according to claim 3, wherein the first Al layer of the intermediate layer b Ti c Me 1-b-c The thickness of the N coating is 0.02-0.07 μm; second layer n (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b-c The thickness ratio of the N layer is 0.2-3; third layer of Al a Cr 1-a The thickness of the coating of N is 0.02-0.07 μm; fourth layer l (Al) a Cr 1-a N/Al b Ti c Me 1-b-c N) has a coating thickness of 0.01 to 0.05 μm, and Al a Cr 1-a N layer and Al b Ti c Me 1-b-c The thickness ratio of the N layers is 0.2-3, wherein a is more than or equal to 0.2 and less than or equal to 0.8,0.4 and less than or equal to b is more than or equal to 0.7,0.3 and less than or equal to c is more than or equal to 0.6,2 and less than or equal to m is more than or equal to 16, N is more than or equal to 50 and less than or equal to l is less than or equal to 100.
5. The multilayer hard coating according to claim 1, wherein Me is at least one of W, mo and V.
6. The method for producing a multilayer-structured hard coating according to any one of claims 1 to 5, comprising the steps of:
s1, grinding, sand blasting, polishing, ultrasonic cleaning and drying a substrate;
s2, starting a cathode arc ion plating machine, and carrying out ion cleaning on the surface of the substrate;
s3, depositing a bottom coating on the surface of the substrate by adopting an ion plating technology;
s4, depositing a middle layer coating on the bottom layer coating by adopting an ion plating technology;
and S5, depositing a top coating on the middle coating by adopting an ion plating technology to obtain the multilayer structure hard coating.
7. The preparation method according to claim 6, wherein the ion cleaning in step S2 is specifically performed by: placing the substrate awayVacuumizing and heating the vacuum chamber of the sub-coating machine until the temperature is stabilized at 400-600 ℃ and the vacuum degree is lower than 1.0 multiplied by 10 -3 Pa, filling argon into the vacuum chamber until the pressure is 2.0-5.0 Pa, starting a bias power supply, starting an ion source with the direct current negative bias of 200-500V and the current of the ion source of 100-200A, and performing Ar ion glow cleaning on the substrate.
8. The preparation method according to claim 6, wherein the specific parameters for depositing the primer coating in the step S3 are as follows: the arc current of the AlCr alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm; the specific parameters for depositing the middle layer coating in the step S4 are as follows: the arc current of the AlCr alloy target material and the AlTiMe alloy target material is 100-200A, the negative bias voltage of a substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, the rotating speed of a workpiece rotating stand is 1.0-3.0 rpm, wherein the alternation of layers is realized by the switching on and off of the target material; the specific parameters of the top coating deposited in the step S5 are as follows: the arc current of the AlTiMe alloy target material is 100-200A, the negative bias of the substrate is 40-200V, the nitrogen pressure is 2.0-5.0 Pa, the deposition temperature is 400-600 ℃, and the rotating speed of the workpiece rotating stand is 1.0-3.0 rpm.
9. The preparation method according to claim 6, wherein the substrate is a numerically controlled blade made of cemented carbide or a ceramic material; the purity of the alloy target in the deposition process is not less than 99.96%.
10. Use of the multilayer-structured hard coating according to any one of claims 1 to 5 or the multilayer-structured hard coating obtained by the production method according to any one of claims 6 to 9 in the fields of tool cutting and surface protective coating.
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