CN115679264B

CN115679264B - Metal-ceramic composite impact-resistant high-entropy coating of die-casting die and preparation method thereof

Info

Publication number: CN115679264B
Application number: CN202211679647.2A
Authority: CN
Inventors: 李建军; 范鹏; 朱恩光; 梁晖; 方佳洁
Original assignee: Ikd Co ltd
Current assignee: Ningbo Zhongye Precision Parts Co ltd
Priority date: 2022-12-27
Filing date: 2022-12-27
Publication date: 2023-03-31
Anticipated expiration: 2042-12-27
Also published as: CN115679264A

Abstract

The invention discloses a metal-ceramic composite impact-resistant high-entropy coating of a die-casting die and a preparation method thereof, wherein the surface of a die matrix comprises a ZrCr layer, a TiVNbHfZrCr/ZrCr metal nano layer, a TiVNbHfZrCrN ceramic nano layer and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film from inside to outside; the TiVNbHfZrCr is metal, the TiVNbHfZrCrN is ceramic, and the TiVNbHfZrCrN are used for constructing a multilayer film, so that the toughness of the metal and the high hardness of the ceramic can be fully exerted, and the coating not only has high hardness, but also has good toughness and has good tolerance capability when being subjected to impact load. In terms of structure, the nano structure of the metal-ceramic enables the stress of the coating to be well released, reduces the internal stress of the coating and enables the structure of the coating to be stable during long-term work.

Description

Metal-ceramic composite impact-resistant high-entropy coating of die-casting die and preparation method thereof

Technical Field

The invention relates to a surface treatment technology of a die-casting die, in particular to a metal-ceramic composite impact-resistant high-entropy coating of the die-casting die and a preparation method thereof.

Background

In the die-casting process, because a die cavity bears the sharp heat action of the incandescent molten alloy at the initial stage of each die-casting cycle, the working surface can generate compressive thermal stress; after the die casting is finished, a lubricant is sprayed into the die to carry out rapid cooling, so that tensile stress is generated on the surface of the die. Under the action of the alternating thermal stress, thermal fatigue microcracks are generated on the surface of the die, and along with the increase of the number of die-casting cycles, the microcracks rapidly expand and sometimes expand towards the center to form cracks. If the surrounding of the crack is accompanied by the scouring and corrosion of the molten alloy to the mold cavity, the surface of the mold can be further damaged, and finally the mold can be cracked early and even scrapped. The problems of high product rejection rate, low production efficiency, even damage to a die and the like caused by die sticking, erosion and corrosion in the die-casting process are always the difficult problems troubling various die-casting enterprises. The most important technical means for prolonging the service life of the die is to coat the surface of the die-casting die.

The nano multilayer film is a multilayer structure formed by alternately depositing and growing two or more materials with different components or structures in a direction vertical to the one dimension of the film in a nano-scale. High hardness due to the super-hard effect and high toughness due to a multilayer structure are one of the important research directions of the current wear-resistant and impact-resistant coating. The high-toughness coating material has high crack formation resistance and crack propagation resistance under the action of stress, and the nano multilayer structure can cause crack deflection and dissipate impact energy due to the existence of a large number of interfaces, so that the high-toughness coating material has a good effect of improving the toughness and the erosion resistance of the coating.

The high-entropy protective coating deposited on the surface of the die not only has the functions of abrasion resistance, corrosion resistance and high hardness, but also can greatly improve the die release performance of die castings without die sticking because the coating is not compatible or reacts with metal solutions such as aluminum, zinc and the like. The high-entropy alloy and the coating thereof are hot spots for research in the field of materials in recent years, have the characteristics of excellent strength, toughness, corrosion resistance, wear resistance and the like, and are rapidly applied and developed in the field of surface engineering. By designing high-entropy alloy coatings of different systems, an efficient preparation process method is developed, and the high-entropy alloy coating is applied to the field of surface engineering and is expected to become an ideal means for strengthening the surfaces of key parts of wear-resistant, corrosion-resistant, heat-resistant and other extreme environment equipment. Compared with the traditional alloy coating, the high-entropy alloy coating generally has higher hardness and strength, the high-entropy alloy is subjected to solid solution strengthening and second phase strengthening caused by hard compounds, the plastic deformation resistance of the coating is effectively enhanced, and the residual compressive stress generated in the preparation process of the high-entropy coating and the film is beneficial to further improvement of the tribological performance of the high-entropy coating and the film.

The high-temperature-resistant nano multilayer self-lubricating coating for the die-casting core-pulling with the authorization notice number of CN112501571B comprises a bonding layer, a transition layer, a SiTiC-DLC coating and a high-temperature-resistant self-lubricating layer which are sequentially attached to the outside of the die-casting core-pulling, wherein the bonding layer is a pure SiB layer, the transition layer is a SiBN layer, and the high-temperature-resistant self-lubricating layer is a SiTiC-DLC/BTiC-DLC nano multilayer film formed by SiTiC-DLC and BTiC-DLC. The coating structurally combines a diamond-like coating doped with multiple elements, has a gradient structure, and has the gradual change characteristic in components, so that the coating has good toughness and lower stress. In addition, due to the composite doping of the silicon element, the boron element and the titanium, the coating has high hardness and temperature resistance.

For example, the ultrahard nano composite coating for the die-casting aluminum trimming die with the authorization publication number of CN112095080B sequentially comprises a bonding layer, a transition layer, a supporting layer, a hardening layer and a lubricating layer from inside to outside, wherein the bonding layer is a pure Ti layer, the transition layer is a TiN transition metal ceramic layer, the supporting layer is an AlTiSiN/TiN nano multilayer film, the hardening layer is an AlTiSiCN/TiCN nano multilayer film, and the lubricating layer is an AlTiSiC/TiC nano multilayer film. The coating realizes a gradient structure by using nitride, forms a gradually changed structure and components, is metallurgically combined with a matrix, has good adhesive force, improves the aluminum liquid erosion resistance of the die-casting die, and can obtain good lubricating property because the AlTiSiC and the TiC are diamond-like carbon coatings rich in carbon.

The research of the high-entropy alloy coating mainly focuses on high-entropy carbide and nitride coatings, and the ceramic coatings are slightly poor in toughness, cannot fully exert the excellent performance of the high-entropy coating, and can be further improved in impact resistance.

Disclosure of Invention

The invention provides a metal-ceramic composite impact-resistant high-entropy coating of a die-casting die. The metal-ceramic nano structure is used for constructing the multilayer film, so that the toughness of metal and the high hardness of ceramic can be fully exerted, and the coating not only has high hardness, but also has good toughness and good endurance capacity when being subjected to impact load.

The technical scheme adopted by the invention for solving the technical problems is as follows: the die-casting die metal-ceramic composite impact-resistant high-entropy coating comprises a ZrCr layer, a TiVNbHfZrCr/ZrCr metal nano layer, a TiVNbHfZrCrN ceramic nano layer and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film from inside to outside of the surface of a die matrix.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is formed by a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers in an alternating mode, the thickness of the TiVNbHfZrCr monolayers is 5-20 nanometers, the thickness of the TiVNbHfZrCrN monolayers is 5-30 nanometers, and the modulation period of a coating is 10-50 nanometers.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the TiVNbHfZrCr/ZrCr metal nano layer is formed by a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers in an alternating mode, the thickness of the TiVNbHfZrCr single layers is 5-10 nanometers, the thickness of the ZrCr single layers is 5-20 nanometers, and the modulation period is 10-30 nanometers.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the coating hardness is 3000-3500HV.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the thickness of the ZrCr layer is 20-30 nanometers, the thickness of the TiVNbHfZrCr/ZrCr metal nano-layer is 1000-3000 nanometers, the thickness of the TiVNbHfZrCrN ceramic nano-layer is 500-2000 nanometers, and the thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multi-layer film is 1000-5000 nanometers.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die comprises the following steps:

step one, carrying out arc discharge plasma etching on the die-casting die;

secondly, bombarding ZrCr on the ZrCr target to the surface of the die-casting die in a high-energy manner by using an arc ion plating method to prepare a ZrCr layer;

sequentially starting a ZrCr target and a TiVNbHfZrCr target, and alternately depositing a TiVNbHfZrCr monolayer and a ZrCr monolayer to form a TiVNbHfZrCr/ZrCr metal nano-layer consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of ZrCr monolayers;

step four, closing the ZrCr target, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form a TiVNbHfZrCrN ceramic nano-layer;

and fifthly, starting the TiVNbHfZrCr target, starting nitrogen at intervals, and alternately depositing TiVNbHfZrCr single layers and TiVNbHfZrCrN single layers layer by layer to form the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHZrCr single layers and a plurality of TiVNbHfZrCrN single layers.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: step two is carried out under the condition of 0.3-0.5Pa, -500V to-800V.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: step three is carried out under the condition of 0.5-3Pa, -100V to-250V.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the fourth step is carried out under the conditions of 2-5Pa and-150-250V.

The invention adopts a further preferable technical scheme for solving the technical problems as follows: the fifth step is carried out under the conditions of 2-5Pa, -150 to-250V.

Compared with the prior art, the invention has the advantages that the TiVNbHfZrCr is metal, the TiVNbHfZrCrN is ceramic, and the TiVNbHfZrCrN and the TiVNbHfZrCr are used for constructing the multilayer film, so that the toughness of the metal and the high hardness of the ceramic can be fully exerted, and the coating not only has high hardness, but also has good toughness and has good endurance capacity when being subjected to impact load. In terms of structure, the nano structure of the metal-ceramic enables the stress of the coating to be well released, reduces the internal stress of the coating and enables the structure of the coating to be stable during long-term work.

Drawings

The present invention will be described in further detail below with reference to the drawings and preferred embodiments, but those skilled in the art will appreciate that the drawings are only drawn for the purpose of illustrating the preferred embodiments and should not be taken as limiting the scope of the present invention. Furthermore, unless specifically stated otherwise, the drawings are merely schematic representations based on the concept of a composition or construction of the object being described and may include exaggerated displays and are not necessarily drawn to scale.

FIG. 1 is a schematic view of an apparatus for preparing a metal-ceramic composite impact-resistant high-entropy coating of a die-casting mold according to the present invention;

FIG. 2 is a schematic view of a composite structure of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die provided by the invention.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Those skilled in the art will appreciate that the description is illustrative only, and is not to be construed as limiting the scope of the invention.

FIG. 1 shows the apparatus used in the first to sixth embodiments, in which the vacuum chamber is surrounded by furnace walls, and the size of the vacuum chamber is 1000X1000mm. The vacuum chamber is provided with a vacuumizing port 4, and the vacuumizing unit vacuumizes the vacuum chamber through the vacuumizing port 4. The furnace door is provided with an etching source 1 and an auxiliary anode 9, four corners of the vacuum chamber are provided with heaters 7, the heating power is 10-30 kilowatts, and the heating efficiency is improved. The arc targets were mounted on the furnace wall, the first ZrCr target 2 and the second ZrCr target 6, the first TiVNbHfZrCr target 3 and the second TiVNbHfZrCr target 8, respectively, were mounted, and the samples were mounted on the work holder 5. The layout greatly increases the plasma density in the vacuum chamber, and the workpiece is completely immersed in the plasma. The deposition rate, the hardness and the adhesive force of the coating are greatly improved. Because the target structure is optimized, the magnetic field distribution is more uniform, the electric arc is uniformly burnt on the target surface, and the uniformity of the coating is improved. In the first to sixth embodiments, the arc ion plating technology is similar to the existing coating equipment, and meanwhile, the coating equipment is simple in structure, easy to control and good in industrial application prospect.

Examples one through six are further illustrated below. In the first to sixth embodiments, different process parameters are utilized to prepare the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die on the surface of the die-casting die, so that the erosion resistance of the die is improved.

Example one

Starting the equipment shown in the figure 1, starting the heater 7, adjusting the temperature of the vacuum chamber to 400 ℃, introducing argon, starting the etching source 1 and the auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. The ion etching cleaning is also carried out before the coating preparation so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove the oxide and other contaminants on the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

Ion etching cleaning is a prerequisite for adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting a ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the condition of 0.3Pa and-500V, so that a ZrCr layer with the thickness of 20 nanometers is deposited as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the condition of 0.5Pa and-100V, the thickness of the TiVNbHfZrCr single layer is 5 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 5 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 10 nanometers, and the total thickness of the TiVNbHfZrCr/ZrCr layer is 1000 nanometers. The TiVNbHfZrCr/ZrCr metal nano-layer is used as a transition layer, and aims to reduce the component difference between a substrate and a surface coating by mainly utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr metal components are relatively close, and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 2Pa and-150V by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form the TiVNbHfZrCrN ceramic nano layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 500 nanometers, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the conditions of 2Pa and-150V, and alternately depositing a TiVNbHfZrCr monolayer and a TiVNbHfZrCrN monolayer layer by layer, namely forming the TiVNbHfZrCrN monolayer when the nitrogen is introduced, forming the TiVNbHfZrCr monolayer when the nitrogen is not introduced, and forming the TiVNbHZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers by repeating the process. The single-layer thickness of the TiVNbHfZrCr is 5 nanometers, the single-layer thickness of the TiVNbHfZrCrN is 5 nanometers, and the modulation period of the coating is 10 nanometers. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 1000 nanometers. And naturally cooling after the preparation to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

As shown in fig. 2, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die comprises a ZrCr layer 20, a TiVNbHfZrCr/ZrCr metal nano-layer 30, a TiVNbHfZrCrN ceramic nano-layer 40 and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano-multilayer film 50 from the inside to the outside of the surface of a die matrix 10. In the figure, the number of the single layer of TiVNbHfZrCr and the single layer of TiVNbHfZrCr of the metal nanolayer 30 of TiVNbHfZrCr/ZrCr is merely an example to indicate that the structure is a multilayer alternate stacking structure, and is not a real number. The same is true for the illustration of the TiVNbHfZrCr/TiVNbHfZrCrN high entropy metal-ceramic nano-multilayer film 50 in the same figure.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment has the following characteristics and advantages: first, compared with the conventional die casting mold coating, the impact resistant coating is constructed by using the TiVNbHfZrCr metal layer and the TiVNbHfZrCrN ceramic layer, so that the coating has high hardness and high toughness. Secondly, the embodiment combines the high-entropy metal coating and the high-entropy nitride ceramic coating, which is an innovative attempt and can fully exert the performance advantages of the high-entropy coating material. Thirdly, compared with the conventional arc ion plating technology, the multilayer structure technology is adopted in the embodiment to inhibit the growth of columnar crystals and improve the density of the coating, so that the corrosion resistance and the wear resistance of the coating are improved greatly; fourthly, in the embodiment, the TiVNbHfZrCrN with good temperature resistance is compounded, so that the advantage of good high-temperature stability can be exerted, the coating and the high-temperature aluminum liquid cannot react, and the coating has good anti-adhesion, wear-resisting and impact-resisting effects. To sum up, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment improves the binding force between the coating and the substrate, and is provided with a binding layer, a transition layer and other structures. The aim of the multilayer structure is mainly to create a composition gradient and a hardness gradient, which allows a high hardness of the coating with low internal stresses. The die-casting die has good binding force, wear resistance, temperature resistance, impact resistance and adhesion resistance, can ensure long-term stable work of the die-casting die, greatly improves the performance of the die-casting die, stabilizes the processing quality, improves the processing efficiency and reduces the production cost of manufacturers.

Example two

Starting the equipment shown in the figure 1, starting a heater 7, adjusting the temperature of a vacuum chamber to 600 ℃, introducing argon, starting an etching source 1 and an auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. The ion etching cleaning is also carried out before the coating preparation so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove the oxide and other contaminants on the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

Ion etching cleaning is a prerequisite for adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting a ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the condition of 0.5Pa and-800V, so that a ZrCr layer with the thickness of 30 nanometers is deposited as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by utilizing electric arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the conditions of 3Pa and-250V, the thickness of the TiVNbHfZrCr single layer is 10 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 10 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano-layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 20 nanometers, and the total thickness of the TibHfZrCr/ZrCr layer is 3000 nanometers. The TiVNbHfZrCr/ZrCr metal nano-layer is used as a transition layer, and aims to reduce the component difference between a substrate and a surface coating by mainly utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr are relatively close in metal components and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 5Pa and-250V by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form the TiVNbHfZrCrN ceramic nano layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 2000 nm, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the condition of 5 Pa-250V, and alternately depositing TiVNbHfZrCr monolayers and TiVNbHfZrCrN monolayers layer by layer, namely forming the TiVNbHfZrCrN monolayers when the nitrogen is introduced, forming the TiVNbHfZrCr monolayers when the nitrogen is not introduced, and repeating the process to form the TiVNbHZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers. The single-layer thickness of the TiVNbHfZrCr is 20 nanometers, the single-layer thickness of the TiVNbHfZrCrN is 30 nanometers, and the modulation period of the coating is 50 nanometers. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 5000 nanometers. And naturally cooling after the preparation to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

As shown in fig. 2, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die comprises a ZrCr layer 20, a TiVNbHfZrCr/ZrCr metal nano-layer 30, a TiVNbHfZrCrN ceramic nano-layer 40 and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano-multilayer film 50 from the inside to the outside of the surface of a die matrix 10. In the figure, the number of the TiVNbHfZrCr single layer and the TiVNbHfZrCr single layer of the TiVNbHfZrCr/ZrCr metal nano layer 30 is only an example to indicate that the single layer is a multilayer alternate stacked structure, and is not a real number. The same is true for the illustration of the TiVNbHfZrCr/TiVNbHfZrCrN high entropy metal-ceramic nano multilayer film 50 in the same figure.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment has the following characteristics and advantages: first, compared with the conventional die casting mold coating, the impact resistant coating is constructed by using the TiVNbHfZrCr metal layer and the TiVNbHfZrCrN ceramic layer, so that the coating has high hardness and high toughness. Secondly, the embodiment combines the high-entropy metal coating and the high-entropy nitride ceramic coating, which is also an innovative attempt, and can fully exert the performance advantages of the high-entropy coating material. Thirdly, compared with the conventional arc ion plating technology, the multilayer structure technology is adopted in the embodiment to inhibit the growth of columnar crystals and improve the density of the coating, so that the corrosion resistance and the wear resistance of the coating are improved greatly; fourthly, in the embodiment, the TiVNbHfZrCrN with good temperature resistance is compounded, so that the advantage of good high-temperature stability can be exerted, the coating and the high-temperature aluminum liquid cannot react, and the coating has good anti-adhesion, wear-resisting and impact-resisting effects. To sum up, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment improves the binding force between the coating and the substrate, and is provided with a binding layer, a transition layer and other structures. The aim of the multilayer structure is mainly to create a composition gradient and a hardness gradient, which allows a high hardness of the coating with low internal stresses. The die-casting die has good binding force, wear resistance, temperature resistance, impact resistance and adhesion resistance, can ensure long-term stable work of the die-casting die, greatly improves the performance of the die-casting die, stabilizes the processing quality, improves the processing efficiency and reduces the production cost of manufacturers.

EXAMPLE III

Starting the equipment shown in the figure 1, starting the heater 7, adjusting the temperature of the vacuum chamber to 500 ℃, introducing argon, starting the etching source 1 and the auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. Ion etching cleaning is also carried out before the coating preparation, so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove oxides and other contaminants from the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

Ion etching cleaning is a prerequisite for adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting the ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the conditions of 0.4Pa and-600V, so that a ZrCr layer with the thickness of 25 nanometers is deposited as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by utilizing electric arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the conditions of 1Pa and-150V, the thickness of the TiVNbHfZrCr single layer is 10 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 20 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano-layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 30 nanometers, and the total thickness of the TibHfZrCr/ZrCr layer is 1500 nanometers. The TiVNbHfZrCr/ZrCr metal nano layer is used as a transition layer, and the purpose is mainly to reduce the component difference between a matrix and a surface coating by utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr are relatively close in metal components and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 3Pa and-150V by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the target is deposited on the surface of a die-casting mold to form the TiVNbHfZrCrN ceramic nano-layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 2000 nm, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the condition of 4 Pa-200V, and alternately depositing TiVNbHfZrCr monolayers and TiVNbHfZrCrN monolayers layer by layer, namely forming the TiVNbHfZrCrN monolayers when the nitrogen is introduced, forming the TiVNbHfZrCr monolayers when the nitrogen is not introduced, and repeating the process to form the TiVNbHZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers. The single layer thickness of TiVNbHfZrCr is 10 nanometers, the single layer thickness of TiVNbHfZrCrN is 10 nanometers, and the modulation period of the coating is 20 nanometers. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 2000 nm. And naturally cooling after the preparation is finished to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

As shown in fig. 2, the metal-ceramic composite impact-resistant high-entropy coating of the die casting mold comprises a ZrCr layer 20, a TiVNbHfZrCr/ZrCr metal nano-layer 30, a TiVNbHfZrCrN ceramic nano-layer 40, and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano-multilayer film 50 from the inside to the outside of the surface of a mold substrate 10. In the figure, the number of the single layer of TiVNbHfZrCr and the single layer of TiVNbHfZrCr of the metal nanolayer 30 of TiVNbHfZrCr/ZrCr is merely an example to indicate that the structure is a multilayer alternate stacking structure, and is not a real number. The same is true for the illustration of the TiVNbHfZrCr/TiVNbHfZrCrN high entropy metal-ceramic nano-multilayer film 50 in the same figure.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment has the following characteristics and advantages: first, compared with the conventional die casting mold coating, the impact resistant coating is constructed by using the TiVNbHfZrCr metal layer and the TiVNbHfZrCrN ceramic layer, so that the coating has high hardness and high toughness. Secondly, the embodiment combines the high-entropy metal coating and the high-entropy nitride ceramic coating, which is an innovative attempt and can fully exert the performance advantages of the high-entropy coating material. Thirdly, compared with the conventional arc ion plating technology, the multilayer structure technology is adopted in the embodiment to inhibit the growth of columnar crystals and improve the density of the coating, so that the corrosion resistance and the wear resistance of the coating are improved greatly; fourthly, in the embodiment, the TiVNbHfZrCrN with good temperature resistance is compounded, so that the advantage of good high-temperature stability can be exerted, the coating and the high-temperature aluminum liquid cannot react, and the coating has good anti-adhesion, wear-resisting and impact-resisting effects. To sum up, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment improves the binding force between the coating and the substrate, and is provided with a binding layer, a transition layer and other structures. The aim of the multilayer structure is mainly to create a composition gradient and a hardness gradient, which allows a high hardness of the coating with low internal stresses. The high-strength wear-resistant and anti-adhesion wear-resistant die-casting die has good binding force, wear resistance, temperature resistance, impact resistance and adhesion resistance, can ensure long-term stable work of the die-casting die, greatly improves the performance of the die-casting die, stabilizes the processing quality, improves the processing efficiency and reduces the production cost of manufacturers.

Example four

Starting the equipment shown in the figure 1, starting the heater 7, adjusting the temperature of the vacuum chamber to 450 ℃, introducing argon, starting the etching source 1 and the auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. Ion etching cleaning is also carried out before the coating preparation, so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove the oxide and other contaminants on the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

Ion etching cleaning is a prerequisite for adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting a ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the condition of 0.35Pa and-550V, so that a ZrCr layer with the thickness of 30 nanometers is deposited as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by utilizing electric arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the conditions of 1.5Pa and-150V, the thickness of the TiVNbHfZrCr single layer is 5 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 5 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano-layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 10 nanometers, and the total thickness of the TiVNbHfZrCr/ZrCr layer is 1500 nanometers. The TiVNbHfZrCr/ZrCr metal nano-layer is used as a transition layer, and aims to reduce the component difference between a substrate and a surface coating by mainly utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr are relatively close in metal components and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 2.5Pa and-175V by using an arc ion plating method, reacting with the nitrogen, and then bombarding at high energy until the TiVNbHfZrCrN target is deposited on the surface of a die-casting mold to form the TiVNbHfZrCrN ceramic nano-layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 550 nanometers, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the conditions of 2.5Pa and-150V, and alternately depositing a TiVNbHfZrCr monolayer and a TiVNbHfZrCrN monolayer layer by layer, namely forming the TiVNbHfZrCrN monolayer when the nitrogen is introduced, forming the TiVNbHfZrCr monolayer when the nitrogen is not introduced, and forming the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers by repeating the process. The single layer thickness of TiVNbHfZrCr is 5 nm, the single layer thickness of TiVNbHfZrCrN is 10nm, and the modulation period of the coating is 15 nm. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 1500 nanometers. And naturally cooling after the preparation is finished to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment has the following characteristics and advantages: first, compared with the conventional die casting mold coating, the impact resistant coating is constructed by using the TiVNbHfZrCr metal layer and the TiVNbHfZrCrN ceramic layer, so that the coating has high hardness and high toughness. Secondly, the embodiment combines the high-entropy metal coating and the high-entropy nitride ceramic coating, which is an innovative attempt and can fully exert the performance advantages of the high-entropy coating material. Thirdly, compared with the conventional arc ion plating technology, the multilayer structure technology is adopted in the embodiment to inhibit the growth of columnar crystals and improve the density of the coating, so that not only is the corrosion resistance of the coating improved, but also the wear resistance is greatly improved; fourthly, the TiVNbHfZrCrN with good temperature resistance is compounded, so that the advantage of good high-temperature stability can be exerted, the coating and the high-temperature aluminum liquid cannot react, and the coating has good anti-adhesion, wear-resisting and impact-resisting effects. To sum up, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment improves the binding force between the coating and the substrate, and is provided with a binding layer, a transition layer and other structures. The aim of the multilayer structure is mainly to create a composition gradient and a hardness gradient, which allows a high hardness of the coating with low internal stresses. The high-strength wear-resistant and anti-adhesion wear-resistant die-casting die has good binding force, wear resistance, temperature resistance, impact resistance and adhesion resistance, can ensure long-term stable work of the die-casting die, greatly improves the performance of the die-casting die, stabilizes the processing quality, improves the processing efficiency and reduces the production cost of manufacturers.

EXAMPLE five

Starting the equipment shown in the figure 1, starting the heater 7, adjusting the temperature of the vacuum chamber to 550 ℃, introducing argon, starting the etching source 1 and the auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. Ion etching cleaning is also carried out before the coating preparation, so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove oxides and other contaminants from the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

The ion etching cleaning is a precondition for the adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting the ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the conditions of 0.45Pa and-650V, so that a ZrCr layer with the thickness of 20 nanometers is deposited to be used as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by utilizing electric arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the conditions of 2.5Pa and-185V, the thickness of the TiVNbHfZrCr single layer is 15 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 10 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 25 nanometers, and the total thickness of the TiVNbHfZrCr/ZrCr layer is 2500 nanometers. The TiVNbHfZrCr/ZrCr metal nano layer is used as a transition layer, and the purpose is mainly to reduce the component difference between a matrix and a surface coating by utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr are relatively close in metal components and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 3Pa and-175V by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form the TiVNbHfZrCrN ceramic nano layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 1200 nm, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano-layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the condition of 5 Pa-150V, and alternately depositing TiVNbHfZrCr monolayers and TiVNbHfZrCrN monolayers layer by layer, namely forming the TiVNbHfZrCrN monolayers when the nitrogen is introduced, forming the TiVNbHfZrCr monolayers when the nitrogen is not introduced, and repeating the process to form the TiVNbHZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers. The single-layer thickness of the TiVNbHfZrCr is 20 nanometers, the single-layer thickness of the TiVNbHfZrCrN is 20 nanometers, and the modulation period of the coating is 40 nanometers. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 4000 nanometers. And naturally cooling after the preparation to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

As shown in fig. 2, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die comprises a ZrCr layer 20, a TiVNbHfZrCr/ZrCr metal nano-layer 30, a TiVNbHfZrCrN ceramic nano-layer 40 and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano-multilayer film 50 from the inside to the outside of the surface of a die matrix 10. In the figure, the number of the single layer of TiVNbHfZrCr and the single layer of TiVNbHfZrCr of the metal nanolayer 30 of TiVNbHfZrCr/ZrCr is merely an example to indicate that the structure is a multilayer alternate stacking structure, and is not a real number. The same is true for the illustration of the TiVNbHfZrCr/TiVNbHfZrCrN high entropy metal-ceramic nano multilayer film 50 in the same figure.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment has the following characteristics and advantages: first, compared with the conventional die casting mold coating, the impact resistant coating is constructed by using the TiVNbHfZrCr metal layer and the TiVNbHfZrCrN ceramic layer, so that the coating has high hardness and high toughness. Secondly, the embodiment combines the high-entropy metal coating and the high-entropy nitride ceramic coating, which is also an innovative attempt, and can fully exert the performance advantages of the high-entropy coating material. Thirdly, compared with the conventional arc ion plating technology, the multilayer structure technology is adopted in the embodiment to inhibit the growth of columnar crystals and improve the density of the coating, so that not only is the corrosion resistance of the coating improved, but also the wear resistance is greatly improved; fourthly, the TiVNbHfZrCrN with good temperature resistance is compounded, so that the advantage of good high-temperature stability can be exerted, the coating and the high-temperature aluminum liquid cannot react, and the coating has good anti-adhesion, wear-resisting and impact-resisting effects. To sum up, the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die prepared by the embodiment improves the binding force between the coating and the substrate, and is provided with a binding layer, a transition layer and other structures. The aim of the multilayer structure is mainly to create a composition gradient and a hardness gradient, which allows a high hardness of the coating with low internal stresses. The high-strength wear-resistant and anti-adhesion wear-resistant die-casting die has good binding force, wear resistance, temperature resistance, impact resistance and adhesion resistance, can ensure long-term stable work of the die-casting die, greatly improves the performance of the die-casting die, stabilizes the processing quality, improves the processing efficiency and reduces the production cost of manufacturers.

Example six

Starting the equipment shown in the figure 1, starting a heater 7, adjusting the temperature of a vacuum chamber to 480 ℃, introducing argon, starting an etching source 1 and an auxiliary anode 9, and carrying out arc discharge plasma etching on the die-casting die. The ion etching cleaning is also carried out before the coating preparation so as to further improve the bonding force of the coating and the substrate. The ion etching technique is mainly used to remove oxides and other contaminants from the surface of the die casting mold, so that a clean surface is obtained during the coating preparation. Compared with general glow cleaning and chemical cleaning, the method has high etching efficiency and higher etching efficiency and cleaning effect than glow discharge.

Ion etching cleaning is a prerequisite for adhesion. However, the subsequent preparation process is also a necessary supplement for obtaining high adhesion, and an ion bombardment method is generally adopted to further improve the adhesion. After the plasma etching is finished, starting a ZrCr target, and bombarding ZrCr on the ZrCr target to the surface of a die-casting die at high energy by using an arc ion plating method under the condition of 0.4Pa and-700V, so that a ZrCr layer with the thickness of 30 nanometers is deposited as a bonding layer. The ion bombardment process is a high-energy non-equilibrium state process, and the heat generated by bombardment is used for generating diffusion between the coating and the substrate. In the patent, zrCr metal on a ZrCr target is evaporated at high temperature by utilizing electric arc discharge and moves to the surface of a die-casting die at high speed under the action of high bias voltage, negative high pressure is added on the surface of the die-casting die, the high pressure has an accelerating effect on ionized ZrCr ions, the accelerated ZrCr ions can impact the surface of the die-casting die at high speed, high temperature can be generated in the impacting process, the ZrCr ions can form metallurgical bonding with a die-casting die matrix, and the general diffusion depth reaches 5-10nm.

After a ZrCr layer is prepared to be used as a bonding layer, the pressure and the voltage are adjusted, a TiVNbHfZrCr target is started to deposit a TiVNbHfZrCr single layer under the condition of 2Pa and-250V, the thickness of the TiVNbHfZrCr single layer is 10 nanometers, then the TiVNbHfZrCr target is closed, the ZrCr target is started again, a ZrCr single layer is deposited on the TiVNbHfZrCr single layer, the thickness of the ZrCr single layer is 10 nanometers, the TiVNbHfZrCr target or the ZrCr target is started at intervals in sequence, a TiVNbHfZrCr/ZrCr metal nano layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers is formed alternately, the modulation period is 20 nanometers, and the total thickness of the TibHfZrCr/ZrCr layer is 2000 nanometers. The TiVNbHfZrCr/ZrCr metal nano layer is used as a transition layer, and the purpose is mainly to reduce the component difference between a matrix and a surface coating by utilizing the change of components, reduce lattice mismatch, reduce internal stress and easily obtain a thicker coating. Particularly, the ZrCr alloy and the TiVNbHfZrCr are relatively close in metal components and can be well compatible.

And on the basis of the TiVNbHfZrCr/ZrCr layer, closing the ZrCr target, starting the TiVNbHfZrCr target all the time, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature under the conditions of 3Pa and-150V by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form the TiVNbHfZrCrN ceramic nano layer. The thickness of the TiVNbHfZrCrN ceramic nano layer is 2000 nm, and the formed nitride is used as a hardening layer to gradually improve the hardness of the coating and improve the wear resistance of the coating. Meanwhile, the compatibility between the TiVNbHfZrCrN ceramic nano layer and the TiVNbHfZrCr/ZrCr transition layer is good, and the coating stress is reduced.

Based on a high-entropy nitride hardening layer TiVNbHfZrCrN ceramic nano-layer. Starting a TiVNbHfZrCr target, starting nitrogen at intervals under the condition of 5 Pa-150V, and alternately depositing TiVNbHfZrCr monolayers and TiVNbHfZrCrN monolayers layer by layer, namely forming the TiVNbHfZrCrN monolayers when the nitrogen is introduced, forming the TiVNbHfZrCr monolayers when the nitrogen is not introduced, and repeating the process to form the TiVNbHZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers. The single-layer thickness of the TiVNbHfZrCr is 10 nanometers, the single-layer thickness of the TiVNbHfZrCrN is 10 nanometers, and the modulation period of the coating is 20 nanometers. The total thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 1000 nanometers. And naturally cooling after the preparation to obtain the TiVNbHfZrCr/TiVNbHfZrCrN die-casting die metal-ceramic composite impact-resistant high-entropy coating.

As shown in fig. 2, the metal-ceramic composite impact-resistant high-entropy coating of the die casting mold comprises a ZrCr layer 20, a TiVNbHfZrCr/ZrCr metal nano-layer 30, a TiVNbHfZrCrN ceramic nano-layer 40, and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano-multilayer film 50 from the inside to the outside of the surface of a mold substrate 10. In the figure, the number of the TiVNbHfZrCr single layer and the TiVNbHfZrCr single layer of the TiVNbHfZrCr/ZrCr metal nano layer 30 is only an example to indicate that the single layer is a multilayer alternate stacked structure, and is not a real number. The same is true for the illustration of the TiVNbHfZrCr/TiVNbHfZrCrN high entropy metal-ceramic nano multilayer film 50 in the same figure.

The coatings prepared in the first to sixth examples were subjected to hardness tests, and the hardness of the coatings ranged from 3000 to 3500HV.

The metal-ceramic composite impact-resistant high-entropy coating of the die-casting die and the preparation method thereof provided by the invention are described in detail, specific examples are applied to explain the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the invention and the core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims

1. The metal-ceramic composite impact-resistant high-entropy coating of the die casting die is characterized by comprising a ZrCr layer, a TiVNbHfZrCr/ZrCr metal nano layer, a TiVNbHfZrCrN ceramic nano layer and a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film from the inside to the outside of the surface of a die matrix;

the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is formed by a plurality of TiVNbHfZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers in an alternating mode, the thickness of the TiVNbHfZrCr monolayers is 5-20 nanometers, the thickness of the TiVNbHfZrCrN monolayers is 5-30 nanometers, and the modulation period of a coating is 10-50 nanometers;

the TiVNbHfZrCr/ZrCr metal nano-layer is formed by a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers in an alternating mode, the thickness of each TiVNbHfZrCr single layer is 5-10 nanometers, the thickness of each ZrCr single layer is 5-20 nanometers, and the modulation period is 10-30 nanometers;

the thickness of the ZrCr layer is 20-30 nanometers, the thickness of the TiVNbHfZrCr/ZrCr metal nano layer is 1000-3000 nanometers, the thickness of the TiVNbHfZrCrN ceramic nano layer is 500-2000 nanometers, and the thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 1000-5000 nanometers.

2. The die casting mold metal-ceramic composite impact-resistant high-entropy coating of claim 1, characterized in that the coating hardness is 3000-3500HV.

3. The preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die is characterized by comprising the following steps of:

step one, carrying out arc discharge plasma etching on the die-casting die;

secondly, bombarding ZrCr on the ZrCr target to the surface of the die-casting die in a high-energy mode by an arc ion plating method to prepare a ZrCr layer, wherein the thickness of the ZrCr layer is 20-30 nanometers;

step three, starting the ZrCr target and the TiVNbHfZrCr target in sequence, alternately depositing TiVNbHfZrCr single layers and ZrCr single layers to form a TiVNbHfZrCr/ZrCr metal nano-layer consisting of a plurality of TiVNbHfZrCr single layers and a plurality of ZrCr single layers,

the thickness of the TiVNbHfZrCr single layer is 5-10 nanometers, the thickness of the ZrCr single layer is 5-20 nanometers, the modulation period is 10-30 nanometers, and the thickness of the TiVNbHfZrCr/ZrCr metal nano layer is 1000-3000 nanometers;

closing the ZrCr target, introducing nitrogen, evaporating the TiVNbHfZrCr target at high temperature by using an arc ion plating method, reacting with the nitrogen, and bombarding at high energy until the TiVNbHfZrCr target is deposited on the surface of a die-casting die to form a TiVNbHfZrCrN ceramic nano-layer, wherein the thickness of the TiVNbHZrCrN ceramic nano-layer is 500-2000 nanometers;

and fifthly, starting the TiVNbHfZrCr target, starting nitrogen at intervals, and alternately depositing TiVNbHfZrCr monolayers and TiVNbHfZrCrN monolayers layer by layer to form a TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film consisting of a plurality of TiVNbHZrCr monolayers and a plurality of TiVNbHfZrCrN monolayers, wherein the thickness of the TiVNbHfZrCr monolayer is 5-20 nanometers, the thickness of the TiVNbHfZrCrN monolayer is 5-30 nanometers, the modulation period of the coating is 10-50 nanometers, and the thickness of the TiVNbHfZrCr/TiVNbHfZrCrN high-entropy metal-ceramic nano multilayer film is 1000-5000 nanometers.

4. The preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die as claimed in claim 3, wherein the second step is carried out under the conditions of 0.3-0.5Pa, -500V to-800V.

5. The preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die as claimed in claim 3, characterized in that the third step is carried out under the conditions of 0.5-3Pa, -100V to-250V.

6. The preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die as claimed in claim 3, wherein the fourth step is carried out under the conditions of 2-5Pa, -150 to-250V.

7. The preparation method of the metal-ceramic composite impact-resistant high-entropy coating of the die-casting die as claimed in claim 3, characterized in that the fifth step is carried out under the conditions of 2-5Pa, -150 to-250V.