CN113817985B

CN113817985B - Nano multilayer composite coating and preparation method and application thereof

Info

Publication number: CN113817985B
Application number: CN202111400075.5A
Authority: CN
Inventors: 谭志
Original assignee: Wuhan Zhongwei Chuangfa Industrial Research Institute Co ltd
Current assignee: Vitalink Industry Shenzhen Co ltd
Priority date: 2021-11-24
Filing date: 2021-11-24
Publication date: 2022-03-18
Anticipated expiration: 2041-11-24
Also published as: CN113817985A

Abstract

The invention relates to a nano multilayer composite coating and a preparation method and application thereof. The nano multilayer composite coating comprises Cr-B-N layers (the chemical composition is Cr)_mB_nN_1‑m‑n) And a Ti-Al-B-N layer (chemical composition of Ti)_xAl_yB_zN_{1‑x‑y‑z}) M, n, x, y and z are atomic percent, m is more than or equal to 0.4 and less than or equal to 0.6, n is more than or equal to 0.2 and less than or equal to 0.3, x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.1 and less than or equal to 0.5, z is more than or equal to 0.2 and less than or equal to 0.4, and x + y + z is less than 1. B is beneficial to forming a fibrous crystal structure by Cr-B-N, and the density and the toughness are improved; and B and TiAl alloy easily form strong metal bonds, so that the TiAl alloy is not easy to crystallize, and the film is in a layer-by-layer tiled growth mode in the growth process of the film, so that the high internal stress of the film, which is formed by crystal orientation growth, is reduced, the toughness and the density are improved, and the nano multilayer composite coating has high hardness and high toughness.

Description

Nano multilayer composite coating and preparation method and application thereof

Technical Field

The invention relates to the technical field of coating, in particular to a nano multilayer composite coating and a preparation method and application thereof.

Background

The decorative coating refers to coating treatment on the surface of a substrate to obtain a desired decorative effect. The nano-structure coating has attracted extensive academic attention due to unique physical and chemical properties, such as high hardness, high temperature resistance, wear resistance and the like, and also belongs to decorative coating films. However, the nano-structure coating has the problems of large stress, high interface energy and the like due to the fact that factors such as grain size inconsistency, unidirectional growth, crystal gaps and the like can occur in the film growth process, so that the nano-structure coating is designed in academia and has the main characteristic that two or more than two phases of materials are overlapped and accumulated layer by layer to form a film, the thickness of a single-layer film is controlled to be 5-10nm, the problems of stress, strain, crystal gaps and the like in the crystal growth process are solved, and various surface properties of the coating are improved.

At present, a nano-multilayer film with a metal ceramic composite structure is reported, wherein the nano-multilayer film is composed of a TiAlN/CrN structure, and a metal sublayer [ TiAl/Cr ] is obtained through a manufacturing process design]Spaced between the ceramic sublayer [ TiAlN/CrN]Thereby obtaining the cutter coating with high hardness and high toughness. Or a nano-structure consisting of CrN/AlCrNThe multilayer film is optimized in process, and the nano multilayer coating can be used as a hard coating of a supporting layer, so that the cutter coating with high hardness and high bonding force is applied. In addition, a TiAlN/CrN nano multilayer coating manufacturing method suitable for Ti alloy cutting is also reported, and the method eliminates a coarse columnar crystal structure through process optimization and improves the mechanical property and fracture toughness of a cutting coating. However, TiN, CrN, Al are commonly used for nano-multilayer film design_mCr_nN、Ti_mAl_nThe easily crystallizable materials such as N are designed for the purpose of seeking a high hardness effect, but due to the easy crystallizability of these materials, the film has higher internal stress in the growth process, which directly causes the defects of high brittleness, easy fracture and the like of the film, and simultaneously, columnar crystals are easily formed in the crystal growth process, and the surface unevenness is easily caused by the defects among crystal columns, so the surface roughness of the film is further influenced, which also determines that the nano multilayer film structure is only suitable for cutter type coating structures, for the application fields requiring high hardness, low surface roughness and high toughness of the film, the current nano-multilayer film is not suitable, such as the decorative film field of 3C products, besides a certain hardness (usually more than or equal to 15 GPa), the film also has excellent toughness and lower surface roughness, so that a user can have good use experience.

Therefore, the traditional nano-structure multilayer film mainly optimizes a certain kind of defects through a process, and parameter requirements in the field of decorative coating cannot be met, so that the application scene of the nano-structure multilayer film is limited.

Disclosure of Invention

Based on this, the object of the present invention is to provide a nano-multilayer composite coating having high hardness, low surface roughness and high toughness at the same time.

The technical scheme is as follows:

a nanometer multilayer composite coating comprises Cr-B-N layers and Ti-Al-B-N layers which are alternately stacked;

the chemical composition of the Cr-B-N layer is Cr_mB_nN_1-m-nThe chemical composition of the Ti-Al-B-N layer is Ti_xAl_yB_zN_1-x-y-z；

m, n, x, y and z are atomic percentages, and m, n, x, y and z satisfy:

0.4≤m≤0.6，0.2≤n≤0.3，0.1≤x≤0.5，0.1≤y≤0.5，0.2≤z≤0.4，x+y+z＜1。

in one embodiment, x is more than or equal to 0.1 and less than or equal to 0.3, y is more than or equal to 0.1 and less than or equal to 0.3, and z is more than or equal to 0.2 and less than or equal to 0.3.

In one embodiment, the number of alternating layers is greater than or equal to 2.

In one embodiment, the ratio of the thickness of the single layer of the Cr-B-N layer to the thickness of the single layer of the Ti-Al-B-N layer is 1: (0.5-1).

In one embodiment, the thickness of the Cr-B-N layer of a single layer is 5nm-10 nm; and/or

The thickness of the single Ti-Al-B-N layer is 5nm-10 nm; and/or

The total thickness of the nano multilayer composite coating is 1.5-2.5 mu m.

In one embodiment, the Cr-B-N layer has a fibrous crystalline structure and the Ti-Al-B-N layer has an amorphous structure.

The invention also provides a preparation method of the nano multilayer composite coating, which comprises the following steps:

providing a substrate, a Cr source, a B source, an N source, a Ti source and an Al source, and alternately depositing Cr-B-N layers and Ti-Al-B-N layers on the substrate in a physical vapor deposition mode to form the nano multilayer composite coating in a combined mode.

In one embodiment, the number of the alternately laminated cycles is more than or equal to 2, and the preparation method of the nano multilayer composite coating further comprises the following steps:

performing the step of alternately depositing the Cr-B-N layer and the Ti-Al-B-N layer on the substrate in the physical vapor deposition mode once or more times so as to alternately deposit the Cr-B-N layer and the Ti-Al-B-N layer which are stacked on the substrate in sequence, and combining to form the nano multilayer composite coating reaching the preset thickness;

wherein the Cr-B-N layer and the Ti-Al-B-N layer deposited each time are in different positions relative to the substrate.

In one embodiment, the physical vapor deposition is at least one of vacuum evaporation, magnetron sputter coating, arc plasma coating, ion coating, and molecular beam epitaxy.

In one embodiment, the physical vapor deposition is a magnetron sputtering coating, and the magnetron sputtering coating comprises:

providing a target material containing Cr and B, a target material containing Ti, Al and B, introducing Ar and N-containing gas, and alternately depositing a Cr-B-N layer and a Ti-Al-B-N layer on the substrate to form the nano multilayer composite coating in a combined manner.

In one embodiment, the preparation method of the nano multilayer composite coating comprises the following steps:

providing a substrate, a target material containing Cr and B, and introducing Ar and N₂Sputtering and depositing the Cr-B-N layer on the substrate, providing a target material containing Ti, Al and B, and introducing Ar and N₂And sputtering and depositing the Ti-Al-B-N layer on the Cr-B-N layer.

performing one or more times of the above steps of providing the target material containing Cr and B, and introducing Ar and N₂Sputtering and depositing the Cr-B-N layer on the substrate, providing a target material containing Ti, Al and B, and introducing Ar and N₂The step of forming the Ti-Al-B-N layer on the Cr-B-N layer through sputtering deposition is combined, so that the Cr-B-N layer and the Ti-Al-B-N layer which are stacked are sequentially and alternately deposited on the substrate, and a nano multi-layer composite coating reaching the preset thickness is formed through combination;

providing a substrate, a target material containing Ti, Al and B, and introducing Ar and N₂Sputtering and depositing the Ti-Al-B-N layer on the substrate, providing a target material containing Cr and B, and introducing Ar and N₂In the above Ti-sputter depositing said Cr-B-N layer on said Al-B-N layer.

performing one or more times of the steps of providing the target material containing Ti, Al and B, and introducing Ar and N₂Sputtering and depositing the Ti-Al-B-N layer on the substrate, providing a target material containing Cr and B, and introducing Ar and N₂The Ti-Al-B-N layer and the Cr-B-N layer are sequentially and alternately deposited on the substrate in a stacked mode through the combination of the steps of forming the Cr-B-N layer through sputtering deposition, and the nano multi-layer composite coating reaching the preset thickness is formed through combination;

wherein the Ti-Al-B-N layer and the Cr-B-N layer deposited each time are in different positions relative to the substrate.

In one embodiment, the process conditions for forming the Cr-B-N layer by each sputter deposition include:

the power densities of the target materials containing Cr and B are respectively and independently 3.0W/cm²-7.2W/cm²The bias voltage of the matrix is-100V- (-5) V respectively and the background vacuum degree is less than or equal to 5.0 x 10^-4Pa comprising said Ar and said N₂The total pressure of the mixed gas atmosphere is 0.5Pa to 0.8Pa, and the Ar and the N are respectively and independently₂The gas quantity ratios are respectively (3-6): 1.

in one embodiment, the process conditions for forming the Ti-Al-B-N layer by each sputter deposition include:

the power densities of the target materials containing Ti, Al and B are respectively and independently 3.0W/cm²-7.2W/cm²The bias voltage of the matrix is-100V- (-5) V respectively and the background vacuum degree is less than or equal to 5.0 x 10^-4Pa comprising said Ar and said N₂The total pressure of the mixed gas atmosphere is 0.5Pa to 0.8Pa, and the Ar and the N are respectively and independently₂The gas quantity ratios are respectively (3-6): 1.

in one embodiment, before the step of alternately depositing the Cr-B-N layer and the Ti-Al-B-N layer on the substrate by means of physical vapor deposition to form the nano multi-layer composite coating in combination, the method further comprises the steps of cleaning the substrate and depositing a buffer film on the substrate after the cleaning treatment.

The invention also provides a coated product which comprises a substrate and the nano multilayer composite coating, or the coated product comprises the substrate and the nano multilayer composite coating prepared by the preparation method, wherein the nano multilayer composite coating is arranged on the substrate.

In one embodiment, the coated article is an electronic device or an ornament.

The invention has the following beneficial effects:

the nano multilayer composite coating provided by the invention comprises Cr-B-N layers and Ti-Al-B-N layers which are alternately stacked, and is a multi-phase alloy composite nano multilayer film. Specifically, the invention adds B into CrN and TiAlN to form Cr-B-N, Ti-Al-B-N through a composition design method, wherein in Cr-B-N, the reaction potential energy is different in the process of film growth because the atomic radius of B is 0.91A and the atomic radius of N is 0.71A, and the Cr-B-N is more favorable for forming a fibrous crystal structure after the B is added. Secondly, on the chemical property, B, Cr and N can form a stronger bond, and as the content of B is gradually increased, part of B can replace the position of N to form Cr-B-N solid solution, thus the technical defect that the traditional nitride (such as CrN) is easy to grow into columnar crystal is suppressed, the crystal grain is more refined, the intercrystalline gap is smaller, the stress is effectively reduced, the crystal is not easy to break, meanwhile, the density of Cr-B-N is increased, the film roughness is reduced, the film surface is smoother, and the advantages of high hardness and wear resistance of CrN are kept. In Ti-Al-B-N, because B and TiAl alloy are easy to form strong metal bond, the Ti-Al-B-N material is difficult to crystallize in the film forming process, a single-layer film of the Ti-Al-B-N material is in an amorphous structure (also called glass state or amorphous state), and is difficult to grow along the crystal orientation in the film growing process, but is represented as a layer-by-layer tiled growth mode, so that the high internal stress of the film formed by crystal orientation growth is effectively reduced, the toughness is improved, and the film is difficult to break. Furthermore, the surface of the single-layer film layer is more flat, so that the subsequent deposited multi-layer film layer is more flat due to the fact that the shadow effect is reduced, a multi-layer structure formed by overlapping the Cr-B-N single-layer films and the Ti-Al-B-N single-layer films for multiple times can form a large number of interfaces, crack expansion of the coating during bearing is inhibited, and the nano multi-layer film has high toughness.

Therefore, the nano multilayer composite coating with high hardness, high density, low surface roughness, low internal stress and high toughness can be manufactured by optimizing the composition and multilayer compounding of the coating, is wear-resistant and not easy to break, prolongs the service life of the product, and has smoother surface and further increases the commercial application scenes compared with the traditional single-phase alloy nitride nano multilayer film. Meanwhile, the coating also has excellent corrosion resistance, and can be widely applied to the field of surface decoration or protection of devices and sample pieces, particularly the field of 3C product decoration coating.

In addition, the preparation method of the nano multilayer composite coating has the advantages of wide operability, controllable process parameters, easiness in mass production, good repeatability, environmental friendliness and suitability for industrial application.

Drawings

FIG. 1 is a schematic diagram of an apparatus for producing a nano-multilayer composite coating according to the present invention;

FIG. 2 is a cross-sectional view of a composite film plated on a substrate according to an embodiment of the present invention.

Detailed Description

The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

It should be noted that in the description of the present invention, for the terms of orientation, there are terms such as "central", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise" and the like indicating the orientation and positional relationship based on the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and should not be construed as limiting the specific scope of the present invention.

In describing positional relationships, unless otherwise specified, when an element such as a layer, film or substrate is referred to as being "on" another layer, it can be directly on the other layer or intervening layers may also be present. Further, when a layer is referred to as being "under" another layer, it can be directly under, or one or more intervening layers may also be present. It will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present.

Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.

In the present invention, at least one means any one, any two, or any two or more.

Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.

Furthermore, the drawings are not 1: 1 and the relative dimensions of the various elements in the figures are drawn for illustrative purposes only to facilitate understanding of the invention and are not necessarily drawn to scale, and are not to scale.

In the invention, the Cr-B-N layer which is closer to the direction of the matrix and is prepared for the first time is taken as a first Cr-B-N layer, the Cr-B-N layer which is farther from the direction of the matrix and is prepared for the second time is taken as a second Cr-B-N layer, and the like.

Similarly, in the invention, the Ti-Al-B-N layer which is closer to the substrate direction and is prepared for the first time is used as the first Ti-Al-B-N layer, the Ti-Al-B-N layer which is farther from the substrate direction and is prepared for the second time is used as the second Ti-Al-B-N layer, and the like.

The technical scheme of the invention is as follows:

m, n, x, y and z are atomic percentages, and m, n, x, y and z satisfy:

according to the invention, B is added into CrN and TiAlN to form Cr-B-N, Ti-Al-B-N by a component design method, in Cr-B-N, because the atomic radius of B is 0.91A and the atomic radius of N is 0.71A which are approximate, but the valence is greatly different from that of N element, the reaction potential energy is different in the process of film growth, and the Cr-B-N is more favorable for forming a fibrous crystal structure after the B is added. Secondly, on the chemical property, B, Cr and N can form a stronger bond, and as the content of B is gradually increased, part of B can replace the position of N to form Cr-B-N solid solution, so that the technical defect that the traditional nitride (such as CrN) is easy to grow into columnar crystal is overcome, the crystal grain is more refined, the intercrystalline gap is smaller, the stress is effectively reduced, meanwhile, the density of Cr-B-N is increased, the film roughness is reduced, the film surface is smoother, and the advantage that CrN has high hardness is kept. In Ti-Al-B-N, because B and TiAl alloy are easy to form strong metal bond, the Ti-Al-B-N material is difficult to crystallize in the film forming process, a single-layer film of the Ti-Al-B-N material is in an amorphous structure (also called glass state or amorphous state), and is difficult to grow along the crystal orientation in the film growing process, but is represented as a layer-by-layer tiled growth mode, so that the high internal stress of the film formed by crystal orientation growth is effectively reduced, the toughness is improved, meanwhile, the density of the Ti-Al-B-N film is also improved by the layer-by-layer tiled growth mode, the roughness is reduced, the surface of the film is more flat, and the advantage of high hardness of TiAlN is kept. Furthermore, the surface of the single-layer film layer is more flat, so that the subsequent deposited multi-layer film layer is more flat due to the fact that the shadow effect is reduced, a multi-layer structure formed by overlapping the Cr-B-N single-layer films and the Ti-Al-B-N single-layer films for multiple times can form a large number of interfaces, crack expansion of the coating during bearing is inhibited, and the nano multi-layer film has high toughness.

In one embodiment, the thickness of the Cr-B-N layer and the Ti-Al-B-N layer is 5nm-10 nm. This thickness range is advantageous for the nano-multilayer composite coating to have high flexibility while having high hardness. After the thickness of the single-layer film is reduced, when the nano multi-layer composite coating with the same preset thickness is prepared, the number of layers of the Cr-B-N layer and the Ti-Al-B-N layer is increased, the surface of the single-layer film is more smooth, the subsequent deposited multi-layer film is more smooth due to the fact that the shadow effect is reduced, the Cr-B-N and Ti-Al-B-N single-layer films are overlapped and combined for multiple times to form a multi-layer structure, interfaces with more numbers can be formed, crack expansion of the coating during bearing is better inhibited, and the coating has higher toughness.

In one embodiment thereof, the total thickness of the nano-multilayer composite coating is 1.5 μm to 2.5 μm.

It is understood that in the present invention, the order of the Cr-B-N layer and the Ti-Al-B-N layer may be interchanged, such as with respect to a substrate, the nano multilayer composite coating is arranged on the substrate and can be in a structure of Cr-B-N/Ti-Al-B-N/Cr-B-N/Ti-Al-B-N … …/Cr-B-N/Ti-Al-B-N or Ti-Al-B-N/Cr-B-N/Ti-Al-B-N/Cr-B-N … …/Ti-Al-B-N/Cr-B-N.

As can be understood, for the nano multilayer composite coating with the alternating lamination cycle number being more than or equal to 2, the preparation method also comprises the following steps:

performing the step of alternately depositing the Cr-B-N layer and the Ti-Al-B-N layer on the substrate in a magnetron sputtering coating mode once or more times so as to alternately deposit the Cr-B-N layer and the Ti-Al-B-N layer which are stacked on the substrate in sequence, and combining to form a nano multilayer composite coating reaching the preset thickness;

(1) The preparation method for firstly depositing the Cr-B-N layer on the substrate and then depositing the Ti-Al-B-N layer comprises the following steps:

For the preparation method of directly depositing the Cr-B-N layer on the substrate firstly and then depositing the Ti-Al-B-N layer, the position of the Cr-B-N layer deposited each time relative to the substrate is different, namely, the Cr-B-N layer deposited for the first time is on the substrate and is directly connected with the substrate, the Cr-B-N layer formed for the second time and later is on the Ti-Al-B-N layer and is not directly connected with the substrate, and the distance between the Cr-B-N layer and the substrate is gradually increased along with the increase of the number of the Ti-Al-B-N layers.

(2) The preparation method for depositing the Ti-Al-B-N layer on the substrate and then depositing the Cr-B-N layer comprises the following steps:

providing a substrate, a target material containing Ti, Al and B, and introducing Ar and N₂Sputtering and depositing the Ti-Al-B-N layer on the substrate, providing a target material containing Cr and B, and introducing Ar and N₂And sputtering and depositing the Cr-B-N layer on the Ti-Al-B-N layer.

In the same way, for the preparation method of directly depositing the Ti-Al-B-N layer on the substrate firstly and then depositing the Cr-B-N layer, the position of the Ti-Al-B-N layer deposited each time relative to the substrate is different, namely, the Ti-Al-B-N layer deposited for the first time is on the substrate and is directly connected with the substrate, the Ti-Al-B-N layer formed for the second time and later is on the Cr-B-N layer and is not directly connected with the substrate, and the distance between the Ti-Al-B-N layer and the substrate is gradually increased along with the increase of the number of the Cr-B-N layers.

In one embodiment, the time for depositing the nano-multilayer composite coating on the substrate is 30min to 180 min.

in one embodiment, in each step of forming the Cr-B-N layer by sputter deposition, the Cr and B-containing target materials are Cr-B composite target materials or a combination of Cr and B targets.

in one embodiment, in the step of forming the Ti-Al-B-N layer by sputter deposition, the target materials containing Ti, Al, and B are each independently a Ti-Al-B composite target material, a combination of a Ti-B composite target material and an Al target, a combination of a Ti-Al composite target material and a B target, a combination of an Al-B composite target material and a Ti target, or a combination of a Ti target, an Al target, and a B target.

In one embodiment, the material of the substrate may be an alloy, a ceramic or a glass.

In one embodiment, before the step of alternately depositing the Cr-B-N layer and the Ti-Al-B-N layer on the substrate by physical vapor deposition to form the nano multi-layer composite coating, a cleaning treatment (such as chemical cleaning and plasma etching cleaning) is performed on the substrate, and a buffer film is deposited on the substrate after the cleaning treatment. The buffer film is used for improving the binding force between the ceramic coating and a device or a workpiece, and the material of the buffer film can be one or a combination of more of Ti, Al, B and Cr.

In one embodiment, the thickness of the buffer film is 300nm-700 nm. Preferably 300nm to 600 nm.

Preferably, the buffer film is Cr_pB_q-Ti_αAl_βB_γThe composite buffer film comprises p, q, alpha, beta and gamma in atomic percentage, wherein the p, q, alpha, beta and gamma satisfy the conditions that p is more than or equal to 0.5 and less than or equal to 0.7, q is more than or equal to 0.3 and less than or equal to 0.5, alpha is more than or equal to 0.22 and less than or equal to 0.52, beta is more than or equal to 0.18 and less than or equal to 0.58, gamma is more than or equal to 0.3 and less than or equal to 0.5, p + q =1, and alpha + beta + gamma = 1. Further, the Cr is_pB_q-Ti_αAl_βB_γThe thickness of the composite buffer film is 300nm to 700nm, and more preferably 400nm to 600 nm.

For the preparation method of depositing the buffer film on the substrate, then depositing the Cr-B-N layer on the buffer film and then depositing the Ti-Al-B-N layer, the difference of the position of the Cr-B-N layer deposited each time relative to the substrate means that the Cr-B-N layer deposited for the first time is on the buffer film and is directly connected with the buffer film, the Cr-B-N layer formed for the second time and later is on the Ti-Al-B-N layer and is not directly connected with the buffer film, and the distance between the Cr-B-N layer and the substrate is gradually increased along with the increase of the number of the Ti-Al-B-N layers.

In the same way, for the preparation method that the buffer film is firstly deposited on the substrate, then the Ti-Al-B-N layer is deposited on the buffer film, and then the Cr-B-N layer is deposited, the difference of the position of the Ti-Al-B-N layer deposited each time relative to the substrate means that the Ti-Al-B-N layer deposited for the first time is on the buffer film and is directly connected with the buffer film, the Ti-Al-B-N layer formed for the second time and later is on the Cr-B-N layer and is not directly connected with the buffer film, and the distance between the Ti-Al-B-N layer and the substrate is gradually increased along with the increase of the number of the Cr-B-N layers.

In one embodiment, the method for preparing the nano multilayer composite coating comprises the following steps:

a. placing the sample on a sample table at room temperature, and vacuumizing to 5.0 × 10^-4Pa, heating to 330 ℃;

b. introducing Ar, adjusting the amount of Ar, keeping the pressure at 2.0Pa, starting the rotating frame, and carrying out plasma cleaning on the sample;

c. regulating the amount of Ar, keeping the pressure at 0.5Pa-0.8Pa, and opening the bias voltage to-100V- (-5V);

d. simultaneously turning on Ti_αAl_βB_γTarget and Cr_pB_qA target for fabricating a bottom buffer film layer;

e. introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio is (3-6): 1, the pressure is controlled to be 0.5Pa-0.8Pa, the rotating frame is opened, the sample platform rotates along with the rotating frame and passes through the Cr_pB_qTarget and Ti_αAl_βB_γTarget production of Ti_xAl_yB_zN_1-x-y-z/Cr_mB_nN_1-m-nNano multilayer sub-layers until film forming is finished;

f. cooling to room temperature, aerating to normal pressure, and taking out the sample.

Preferably, the nano multilayer composite coating of the present invention is prepared by using a magnetron sputtering device with multiple target positions and a closed magnetic field, and the schematic diagram of the device is shown in fig. 1, wherein 1 is a cavity, 2 is a magnetron target, and 3 is a sample stage (or sample holder), wherein A, B, C, D, E, F represents the position of the magnetron target head.

In one embodiment, the preparation of the nano-multilayer composite coating by using the apparatus shown in fig. 1 comprises the following steps:

(1) the workpiece or device to be coated is arranged on a sample table 3 which can rotate or revolve around the center of the cavity, and the coating surface of the workpiece is right opposite to the magnetic control target surface.

(2) And cleaning the device or the workpiece, including chemical cleaning and etching cleaning by using plasma.

(3) A plurality of Ti_αAl_βB_γTarget and Cr_pB_qThe target is arranged on the magnetic control target 2 according to a certain distance, and the distance between the sample stage 3 and the target 2 is adjusted to be 7-10 cm, so that the plated workpiece or device can be positioned in a magnetic field control range.

(4) The radio frequency auxiliary direct current power supply and the corresponding Ti_αAl_βB_γTarget and Cr_pB_qThe targets are connected.

(5) Evacuating the chamber 1 when the background vacuum is below 5 x 10^-4Below Pa, charging Ar and N₂By selectively turning on one or more Ti, while maintaining a furnace gas pressure of 0.5Pa-0.8Pa_αAl_βB_γTarget and Cr_pB_qTarget and controlling revolution speed of sample stage, and depositing the device or workpiece on the sample stage 3 to obtain Ti_xAl_yB_zN_1-x-y-zAnd Cr_mB_nN_1-m-nThe nano multilayer composite coating is formed by alternately laminating and combining, wherein the revolution speed of the sample table, the position and the number of the opened target materials and the components of the target materials can influence the thickness and the component composition of each layer in one period layer and the number of the whole period layers. During deposition, the workpiece is negatively biased.

Fig. 2 is a cross-sectional view of the structure of a composite thin film plated on a substrate according to an embodiment of the present invention, which includes a buffer film 6 (bottom buffer film) and a nano multi-layer

composite coating

7, 701, 703, and 705 constituting one coating structure of the nano multi-layer composite coating, such as a Cr-B-N layer, and 702 and 704 constituting another coating structure of the nano multi-layer composite coating, such as a Ti-Al-B-N layer.

It is understood that the high toughness and high hardness nanolayered multilayer composite coatings described herein can be applied to the surface protection of various substrates (devices or workpieces). In one embodiment, the material of the device or workpiece may be an alloy, ceramic, or glass.

In one embodiment, the coated article is an electronic device or an ornament.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

In examples 1 to 10 and comparative examples 3 to 7, Ti was added_αAl_βB_γThe target was mounted at A, C, E target positions shown in FIG. 1, and Cr was added_pB_qThe targets were mounted at B, D, F shown in FIG. 1, and the samples were set on the revolving turret 3. In comparative examples 1 and 2, Ti_αAl_βThe target was mounted at the A, C, E target position shown in FIG. 1, and Cr targets having a purity of 99.9% were mounted at the B, D, F position shown in FIG. 1, respectively, and the sample was placed on the revolving turret 3.

Coating composition testing of the present invention the coating composition and its distribution were analyzed using an M-ray energy spectrometer (EDM) of FEI Quanta (TM) 250 FEG. Selecting an area of not less than 30mm for each sample²And area, the average value of its composition is measured.

The coating is characterized by adopting a Nigri S-4800 scanning electron microscope (SEM, emission gun voltage is 8KV), the section morphology characteristics of the coating are observed, the growth structure of the coating is observed, and the surface roughness test is judged by adopting GB/T1031-.

The hardness test method of the coating of the invention comprises the following steps: the hardness of each film was tested using an NHT3 nanoindenter model manufactured by Anton-Paar, Austria, equipped with a tetrahedral Berkvich indenter, set the indentation depth to 100nm, the load varied with indentation depth, and 5 matrix points were measured for each sample and averaged.

The hundred-lattice test method comprises the following steps: the toughness of the coating is determined using the ISO2409-1992 standard.

The vibration testing method comprises the following steps: adding 15L of new ceramsite into a Rosler vibration wear-resistant tester, pouring 200ml of purified water, wherein the ceramsite is conical, the diameter of the ceramsite is 3mm, the height of the ceramsite is 9mm, the vibration time is 4 hours, taking out a sample, cleaning the sample by using 50% IPA and a paper towel, visually inspecting the sample, slowly rotating the sample at a distance of 130mm-150mm from eyes and 1m-1.5m from a light source, and visually inspecting the surface of the sample.

The salt spray corrosion resistance test method comprises the following steps: the corrosion resistance is tested by adopting a program circulating type salt water sprayer, the laboratory temperature is 35 ℃ plus or minus 2 ℃, the temperature of a saturated bucket is 47 ℃ plus or minus 2 ℃, the pH value of the solution is 6.5-7.2, and the test period of each sample is 72 hours.

Example 1

The embodiment provides a nano multilayer composite coating and a preparation method thereof.

This example uses Ti_αAl_βB_γTarget and Cr_pB_qA target wherein α is 0.32, β is 0.38, γ is 0.3, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percent.

The preparation method of the nano multilayer composite coating of the embodiment specifically comprises the following steps:

1) pretreatment: putting the sample into acetone solution for ultrasonic cleaning for 15 minutes, then putting into alcohol solution for ultrasonic cleaning for 15 minutes, and performing nitrogen N₂Drying, placing in a vacuum chamber of a film coating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, and keeping the temperature for 15 minutes;

2) plasma cleaning: introducing Ar gas, keeping the pressure of the furnace body at 2.0Pa, starting bias voltage, setting the pressure at-900V, and carrying out plasma cleaning for 20 minutes to remove micro impurities on the surface of the sample by using plasma etching;

3) a bottom layer buffer film: starting the rotating frame, setting the rotating speed to be 12 circles per minute, and enabling the rotating frame to sequentially pass through Cr_pB_qTarget and Ti_αAl_βB_γTarget, Cr_pB_qTarget and Ti_αAl_βB_γThe targets are powered by radio frequency auxiliary direct current power supply, Ar gas is introduced, the pressure in the furnace body is kept at 0.5Pa, the bias voltage is started and set to-100V, and Cr is added_pB_qTarget and Ti_αAl_βB_γThe target set power is 5W/cm²Preparing a buffer film with the film thickness of 500nm by controlling the film forming time;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB_γThe target power was adjusted to 4.5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB_γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 1 was tested to have Ti_0.3Al_0.3B_0.2N_0.2/Cr_0.6B_0.2N_0.2The structural cross section of the composite coating is shown in FIG. 2, and the composite coating comprises a bottom buffer film 6 and nano

multilayer composite coatings

7, 701, 703 and 705 are Cr-B-N layers, and 702 and 704 are Ti-Al-B-N layers. The hardness of the nano multilayer composite coating prepared by the embodiment is 25GPa, the Baige test is 1 grade, the toughness is good, the nano multilayer composite coating can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 30 nm.

Example 2

This example uses Ti_αAl_βB _γTarget and Cr_pB_qA target wherein α is 0.32, β is 0.38, γ is 0.3, p is 0.5, q is 0.5, and α, β, γ, p and q are atomic percent.

1) pretreatment: ultrasonic cleaning the sample in acetone solution for 15 min, ultrasonic cleaning in alcohol solution for 15 min, and treating with N₂After dryingPlacing into a vacuum chamber of a film coating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, and keeping the temperature for 15 minutes;

3) a bottom layer buffer film: starting the rotating frame, setting the rotating speed to be 12 circles per minute, and enabling the rotating frame to sequentially pass through Cr_pB_qTarget and Ti_αAl_βB _γTarget, Cr_pB_qTarget and Ti_αAl_βB _γThe targets are powered by radio frequency auxiliary direct current power supply, Ar gas is introduced, the pressure in the furnace body is kept at 0.5Pa, the bias voltage is started and set to-100V, and Cr is added_pB_qTarget and Ti_αAl_βB _γThe target set power is 5W/cm²Preparing a buffer film with the film thickness of 500nm by controlling the film forming time;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6.5W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 2 has Ti component_0.3Al_0.3B_0.2N_0.2/Cr_0.4B_0.3N_0.3The hardness is 24GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Example 3

This example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, wherein α is 0.52, β is 0.18, γ is 0.3, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percentages.

1) pretreatment: ultrasonic cleaning the sample in acetone solution for 15 min, ultrasonic cleaning in alcohol solution for 15 min, and treating with N₂Drying, placing in a vacuum chamber of a film coating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, and keeping the temperature for 15 minutes;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.3W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 3 was tested to have Ti_0.5Al_0.1B_0.2N_0.2/Cr_0.6B_0.2N_0.2The hardness is 21GPa, the Baige test is 1 grade, the toughness is good, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 30 nm.

Example 4

This example uses Ti_αAl_βB _γTarget and Cr_pB_qTarget, wherein α is 0.52, β is 0.18, γ is 0.3, p is 0.5, q is 0.5, and α, β, γ, p and q are atomic percentages.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6.5W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.3W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 4 was tested to have Ti_0.5Al_0.1B_0.2N_0.2/Cr_0.4B_0.3N_0.3The hardness is 19GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Example 5

This example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, wherein α is 0.12, β is 0.58, γ is 0.3, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percentages.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.8W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 5 was tested to have Ti_0.1Al_0.5B_0.2N_0.2/Cr_0.6B_0.2N_0.2The hardness is 21GPa, the Baige test is 1 grade, the toughness is good, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Example 6

This example uses Ti_αAl_βB_γTarget and Cr_pB_qA target wherein α is 0.12, β is 0.58, γ is 0.3, p is 0.5, q is 0.5, and α, β, γ, p and q are atomic percent.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6.5W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.8W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and the Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure is formed by stacking layer by layer, and the nano composite multilayer structure is prepared by controlling the total film forming timeThe nano multilayer composite coating with the total film thickness of 2.5 mu m is obtained.

The nano multi-layer composite coating prepared in example 6 was tested to have Ti_0.1Al_0.5B_0.2N_0.2/Cr_0.4B_0.3N_0.3The hardness is 19GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Example 7

This example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, wherein α is 0.27, β is 0.33, γ is 0.4, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percent.

2) deposition of nano-particlesMultilayer film sublayer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 7 was tested to have Ti_0.2Al_0.2B_0.4N_0.2/Cr_0.6B_0.2N_0.2The hardness is 18GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Example 8

This example uses Ti_αAl_βB_γTarget and Cr_pB_qA target wherein α is 0.27, β is 0.33, γ is 0.4, p is 0.5, q is 0.5, and α, β, γ, p and q are atomic percent.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6.5W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 8 was tested to have Ti_0.25Al_0.25B_0.3N_0.2/Cr_0.4B_0.3N_0.3The hardness is 17GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 15 nm.

Example 9

This example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, wherein α is 0.22, β is 0.28, γ is 0.5, p is 0.5, q is 0.5, and α, β, γ, p and q are atomic percentages.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 7.1W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.6W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 5nm, the thickness of the single-layer Ti-Al-B-N film is 5nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 9 was tested to have Ti_0.2Al_0.2B_0.4N_0.2/Cr_0.4B_0.3N_0.3The hardness is 15GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 15 nm.

Example 10

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 3.3W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 3.5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 5nm, the thickness of the single-layer Ti-Al-B-N film is 5nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in example 10 was tested to have Ti_0.25Al_0.25B_0.3N_0.2/Cr_0.6B_0.2N_0.2The hardness is 17GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Comparative example 1

This comparative example provides a nano-multilayer composite coating and a method of making the same.

This comparative example used Ti_αAl_βThe target and the Cr target, wherein alpha is 0.46, beta is 0.54, alpha and beta are atomic percent, and the purity of the Cr target is 99.9%.

The preparation method of the nano multilayer composite coating of the comparative example is as follows:

1) pretreatment: putting the sample into acetone solution for ultrasonic cleaning for 15 minutes, then putting into alcohol solution for ultrasonic cleaning for 15 minutes, blowing and drying, putting into a vacuum chamber of a film plating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, and keeping the temperature for 15 minutes;

3) a bottom layer buffer film: starting the rotating frame, setting the rotating speed to be 12 circles per minute, and enabling the rotating frame to sequentially pass through the Cr target and the Ti target_αAl_βTarget, Cr target and Ti_αAl_βThe targets are powered by a radio frequency auxiliary direct current power supply, and Ar gas is introduced to ensureThe pressure in the holding furnace body is 0.5Pa, the opening bias is set to-100V, and the Cr target and the Ti are added_αAl_βThe target set power is 5W/cm²Preparing a buffer film with the film thickness of 500nm by controlling the film forming time;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept to be 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and the Cr target power is adjusted to be 5W/cm²Is prepared from Ti_αAl_βThe target power was adjusted to 3.8W/cm²At the moment, the thickness of the single-layer Cr-N film is 10nm, the thickness of the single-layer Ti-Al-N film is 7nm, and the single-layer Cr-N film and the single-layer Ti-Al-N film sequentially pass through a Cr target and Ti_αAl_βTarget, and form Cr-N/Ti-Al-N/Cr-N …/Ti-Al-N/Cr-N nano composite multilayer structure by layer-by-layer superposition, and by controlling the total film-forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in the comparative example 1 has Ti component through testing_0.4Al_0.4N_0.2/Cr_0.8N_0.2The hardness is 25GPa, the Baige test is 4 grade, the toughness is poor, the 4h vibration test and the 72h corrosion resistance test cannot be passed, and the surface roughness Ra is less than or equal to 300 nm.

Comparative example 2

3) a bottom layer buffer film: starting the rotating frame, setting the rotating speed to be 12 circles per minute, and enabling the rotating frame to sequentially pass through the Cr target and the Ti target_αAl_βTarget, Cr target and Ti_αAl_βThe targets are powered by radio frequency auxiliary direct current power supply, Ar gas is introduced, the pressure in the furnace body is kept at 0.5Pa, the bias voltage is started and set to-100V, and the Cr targets and the Ti targets are_αAl_βThe target set power is 5W/cm²Preparing a buffer film with the film thickness of 500nm by controlling the film forming time;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 4:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and the Cr target power is adjusted to be 5.5W/cm²Is prepared from Ti_αAl_βThe target power was adjusted to 4.2W/cm²At the moment, the thickness of the single-layer Cr-N film is 10nm, the thickness of the single-layer Ti-Al-N film is 7nm, and the single-layer Cr-N film and the single-layer Ti-Al-N film sequentially pass through a Cr target and Ti_αAl_βTarget, and form Cr-N/Ti-Al-N/Cr-N …/Ti-Al-N/Cr-N nano composite multilayer structure by layer-by-layer superposition, and by controlling the total film-forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in the comparative example 2 has Ti component through testing_0.35Al_0.35N_0.3/Cr_0.6N_0.4The hardness is 22GPa, the Baige test is 4 grade, the toughness is poor, the 4h vibration test and the 72h corrosion resistance test cannot be passed, and the surface roughness Ra is less than or equal to 350 nm.

Comparative example 3

This comparative example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, α is 0.32, β is 0.38, γ is 0.3, p is 0.83, q is 0.17, and α, β, γ, p and q are atomic percent.

1) pretreatment: putting the sample into acetone solution for ultrasonic treatmentCleaning for 15 min, ultrasonic cleaning with alcohol solution for 15 min, and treating with N₂Drying, placing in a vacuum chamber of a film coating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, and keeping the temperature for 15 minutes;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 5W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.5W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in the comparative example 3 has Ti component after test_0.3Al_0.3B_0.2N_0.2/Cr_0.8B_0.1N_0.1The hardness is 22GPa, the Baige test is 3 grades, the toughness is poor, and the 4h vibration test and the 72h resistance can not be passedAnd (4) testing corrosion, wherein the surface roughness Ra is less than or equal to 260 nm.

Comparative example 4

This comparative example uses Ti_αAl_βB _γTarget and Cr_pB_qTarget, α is 0.32, β is 0.38, γ is 0.3, p is 0.2, q is 0.8, and α, β, γ, p and q are atomic percent.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 10W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.5W/cm²Film thickness of the monolayer Cr-B-N at this time10nm and a single layer of Ti-Al-B-N with a thickness of 7nm, successively passing through Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in the comparative example 4 has Ti component through testing_0.3Al_0.3B_0.2N_0.2/Cr_0.15B_0.7N_0.15The hardness is 9GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

Comparative example 5

This comparative example uses Ti_αAl_βB _γTarget and Cr_pB_qTarget, α is 0.85, β is 0.1, γ is 0.05, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percent.

3) a bottom layer buffer film: starting the rotating frame, setting the rotating speed to be 12 circles per minute, and enabling the rotating frame to sequentially pass through Cr_pB_qTarget and Ti_αAl_βB _γTarget, Cr_pB_qTarget and Ti_αAl_βB _γThe targets are powered by a radio frequency auxiliary direct current power supply, Ar gas is introduced, the pressure in the furnace body is kept at 0.5Pa, and the furnace body is openedStarting bias voltage, set to-100V, to Cr_pB_qTarget and Ti_αAl_βB _γThe target set power is 5W/cm²Preparing a buffer film with the film thickness of 500nm by controlling the film forming time;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.3W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and the nanometer composite multilayer structure of Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N is formed by stacking layer by layer, and the nanometer multilayer composite coating with the total film thickness of 2.5 mu m is prepared by controlling the total film forming time.

The nano multi-layer composite coating prepared in the comparative example 5 has Ti component after test_0.8Al_0.03B_0.02N_0.15/Cr_0.6B_0.2N_0.2The hardness is 24GPa, the Baige test is 4 grades, the toughness is poor, the 4h vibration test and the 72h corrosion resistance test cannot be passed, and the surface roughness Ra is less than or equal to 300 nm.

Comparative example 6

This comparative example uses Ti_αAl_βB_γTarget and Cr_pB_qTarget, α is 0.05, β is 0.9, γ is 0.05, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percent.

1) pretreatment: ultrasonic cleaning the sample in acetone solution for 15 min, ultrasonic cleaning in alcohol solution for 15 min, and treating with N₂Drying, placing in a vacuum chamber of a film coating machine, and vacuumizing the vacuum chamber to 5 x 10^-4Pa, heating to 330 ℃, keeping the temperature for 15 minutesA clock;

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 4.1W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget, and form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-Al-B-N/Cr-B-N nano composite multilayer structure layer by layer, and by controlling the total film forming time, the nano multilayer composite coating with the total film thickness of 2.5 μm is prepared.

The nano multi-layer composite coating prepared in the comparative example 6 has Ti component after test_0.04Al_0.8B_0.02N_0.14/Cr_0.6B_0.2N_0.2The hardness is 25GPa, the Baige test is 4 grade, the toughness is poor, the 4h vibration test and the 72h corrosion resistance test cannot be passed, and the surface roughness Ra is less than or equal to 300 nm.

Comparative example 7

This comparative example uses Ti_αAl_βB _γTarget and Cr_pB_qTarget, α is 0.15, β is 0.15, γ is 0.7, p is 0.7, q is 0.3, and α, β, γ, p and q are atomic percent.

2) depositing a nano multilayer film sub-layer: introduction of N₂And keeping Ar: n is a radical of₂The gas quantity ratio of (3) is 5:1, the pressure in the furnace is kept at 0.5Pa, the sample table rotates along with the rotating frame at the speed of 12 circles per minute, and Cr is added_pB_qThe target power was adjusted to 6W/cm²Is prepared from Ti_αAl_βB _γThe target power was adjusted to 9W/cm²At the moment, the thickness of the single-layer Cr-B-N film is 10nm, the thickness of the single-layer Ti-Al-B-N film is 7nm, and the single-layer Cr-B-N film and the single-layer Ti-Al-B-N film are sequentially subjected to Cr_pB_qTarget and Ti_αAl_βB _γTarget laminated one by one to form Cr-B-N/Ti-Al-B-N/Cr-B-N …/Ti-The nano-composite multilayer structure of Al-B-N/Cr-B-N is used for preparing a nano-multilayer composite coating with the total film thickness of 2.5 mu m by controlling the total film forming time.

The nano multi-layer composite coating prepared in the comparative example 7 has Ti component through testing_0.12Al_0.1B_0.6N_0.18/Cr_0.6B_0.2N_0.2The hardness is 10GPa, the Baige test is 0 grade, the toughness is excellent, the steel can pass a 4h vibration test and a 72h corrosion resistance test, and the surface roughness Ra is less than or equal to 20 nm.

It can be seen that the nano multilayer composite coatings prepared in the embodiments 1 to 10 of the present invention can pass the 72h corrosion prevention test, the 4h vibration wear resistance test and the 1 st-level above hundred grid test, have hardness higher than 15GPa, surface roughness less than or equal to 30nm, and even reach the level less than or equal to 15nm, and the above results fully demonstrate that the nano multilayer composite coatings provided by the present invention have high hardness, high surface density, low surface roughness, high toughness and excellent corrosion resistance.

In comparative example 1, the composition of the nano-multilayer composite coating was Ti_0.4Al_0.4N_0.2/Cr_0.8N_0.2In comparative example 2, the composition of the nano multi-layer composite coating was Ti_0.35Al_0.35N_0.3/Cr_0.6N_0.4The comparative example 1 and the comparative example 2 do not contain B, and both the comparative example 1 and the comparative example 2 cannot pass a 72h corrosion prevention test, a 4h vibration abrasion resistance test and a grade 1 or more hundred grid test, have rough surfaces, and are analyzed because the films of the comparative example 1 and the comparative example 2 have columnar crystal structures, so that the compactness of the films is weak, and the importance of B is fully explained.

In comparative examples 3-7, by changing the proportion of each element in the Ti-Al-B-N or Cr-B-N layer in the nano multi-layer composite coating, the prepared nano multi-layer composite coating can not pass a 72-hour corrosion resistance test, a 4-hour vibration wear resistance test, a high hardness (more than or equal to 15 GPa) and a more than 1-grade Baige test at the same time; in addition, the nano-multilayer composite coating layers of comparative examples 3, 5 and 6 had very rough surfaces. The above results fully illustrate the importance of the composition of the elements in the Ti-Al-B-N or Cr-B-N layer.

In summary, it can be seen that if the nano-multilayer composite coating is designed to include alternate stackingA Cr-B-N layer and a Ti-Al-B-N layer arranged, the Cr-B-N layer having a chemical composition of Cr_mB_nN_1-m-nThe chemical composition of the Ti-Al-B-N layer is Ti_xAl_yB_zN_1-x-y-z(ii) a m, n, x, y and z are atomic percent, m is more than or equal to 0.4 and less than or equal to 0.6, n is more than or equal to 0.2 and less than or equal to 0.3, x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.1 and less than or equal to 0.5, z is more than or equal to 0.2 and less than or equal to 0.4, and x + y + z is less than 1, so that the nano multilayer composite coating can be endowed with high hardness, high toughness, low surface roughness and excellent corrosion resistance.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the patent of the present invention shall be subject to the content of the appended claims, and the description and the attached drawings can be used for explaining the content of the claims.

Claims

1. The nano multilayer composite coating is characterized by comprising Cr-B-N layers and Ti-Al-B-N layers which are alternately stacked;

m, n, x, y and z are atomic percentages, and m, n, x, y and z satisfy:

2. the nanolayered multilayer composite coating of claim 1, wherein 0.1. ltoreq. x.ltoreq.0.3, 0.1. ltoreq. y.ltoreq.0.3, 0.2. ltoreq. z.ltoreq.0.3.

3. The nanolayered multilayer composite coating of claim 1, wherein the number of alternating lamination cycles is greater than or equal to 2.

4. The nanolayered multilayered composite coating of claim 1, wherein the ratio of the thickness of the Cr-B-N layer and the Ti-Al-B-N layer is 1: (0.5-1).

5. The nanolayered multilayered composite coating of claim 4, wherein a single layer of the Cr-B-N layer has a thickness of 5nm to 10 nm; and/or

The thickness of the single Ti-Al-B-N layer is 5nm-10 nm; and/or

The total thickness of the nano multilayer composite coating is 1.5-2.5 mu m.

6. The nanolayered multilayer composite coating of any one of claims 1 to 5, wherein the Cr-B-N layer has a fibrous crystalline structure and the Ti-Al-B-N layer has an amorphous structure.

7. A method for producing a nano-multilayer composite coating according to any one of claims 1 to 6, characterized by comprising the steps of:

8. The method for preparing nano multilayer composite coating according to claim 7, wherein the number of the alternately laminated cycles is not less than 2, and the method for preparing nano multilayer composite coating further comprises:

9. The method of any one of claims 7 to 8, further comprising a step of subjecting the substrate to a cleaning treatment and depositing a buffer film on the substrate after the cleaning treatment, prior to the step of alternately depositing the Cr-B-N layer and the Ti-Al-B-N layer on the substrate by physical vapor deposition to form the nano multi-layer composite coating in combination.

10. The method for preparing a nano-multilayer composite coating according to any one of claims 7 to 8, wherein the physical vapor deposition is a magnetron sputtering coating, and the magnetron sputtering coating comprises:

providing a target material containing Cr and B, a target material containing Ti and Al, introducing Ar and N-containing gas, and alternately depositing a Cr-B-N layer and a Ti-Al-B-N layer on the substrate to form the nano multilayer composite coating in a combined manner.

11. A coated article comprising a substrate and the nano-multilayer composite coating according to any one of claims 1 to 6, or comprising a substrate and the nano-multilayer composite coating prepared by the preparation method according to any one of claims 7 to 10, wherein the nano-multilayer composite coating is provided on the substrate.

12. The coated article of claim 11, wherein the coated article is an electronic device or a decorative article.