Zirconium-rich cr-zr-n alloy coating, coated product, use in hard coating, and preparation method

Abstract

The present application relates to a zirconium-rich Cr-Zr-N alloy coating, a coated product, a use, and a preparation method. The Cr-Zr-N alloy coating contains a Cr-Zr-N alloy material having the chemical formula of (CrxZryNz)Ma, wherein M is a doping element, x, y, z, and a are each independently an atomic ratio, 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, and 0≤a / (x+y+z+a)≤0.05.

Description

Zirconium-rich Cr-Zr-N alloy coating, coated article, application in hard coating and preparation method

[0001] This application claims priority to the Chinese patent application No. CN2023107465738, filed on June 21, 2023, and entitled “Zirconium-rich Cr-Zr-N alloy coating, coated article, application in hard coating and preparation method”, the content of which is hereby incorporated by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of alloy coating, further relates to the technical field of zirconium-containing coating, in particular to a zirconium-rich Cr-Zr-N alloy coating, a coated article, an application in hard coating and a preparation method. BACKGROUND

[0003] With the rapid development of modern science and technology, in order to improve the surface performance of various materials and parts, hard coating emerges as the times require. Hard coating has high hardness, and plays an increasingly important role in the fields of 3C digital products, mechanical processing, die manufacturing, geological drilling, textile industry and aerospace, etc.

[0004] Metal nitrides generally have high melting point and hardness, good thermal stability, excellent oxidation resistance and other characteristics. Nitrides of transition metals such as titanium, chromium, vanadium, niobium, zirconium and hafnium are often used as strengthening coatings on tool surfaces to improve hardness. The most common and earliest studied and most widely used are titanium nitride coatings (TiN coatings) and chromium nitride coatings (CrN coatings). Among them, TiN coating has the advantages of high hardness, good toughness, good chemical stability and beautiful color, and has been successfully applied in the tool industry, and has been hailed as “a revolution in tools”. In addition to being used as a functional coating, TiN coating can also be used as a decorative coating; compared with TiN coating, CrN coating has a lower friction coefficient, better high-temperature resistance and corrosion resistance, and a higher sputtering yield, which is conducive to mass industrial production. In addition, the internal stress of CrN coating is lower, resulting in a lower hardness value than TiN coating.

[0005] With the wide application of coating products, the coating substrate has entered the era of light alloys, such as aluminum alloys. However, these light alloy materials have weak corrosion resistance, which puts new requirements on the corrosion resistance of hard coatings. The protective coating on the substrate surface not only needs to have high hardness, but also needs to have excellent corrosion resistance. However, for traditional single-metal nitride coatings, the internal stress of the coating is large, and defects occur during coating growth, resulting in poor corrosion resistance despite the high hardness. Therefore, the development of alloy nitride coatings is timely.

[0006] However, the existing alloy nitride coating is generally difficult to meet the requirements of high hardness and high corrosion resistance at the same time.

[0007] SUMMARY

[0008] According to various embodiments and various aspects of the present application, one aspect of the present application provides a zirconium-rich Cr-Zr-N alloy coating. Other aspects of the present application also provide a coated article, an application in hard coating, and a preparation method.

[0009] In a first aspect of the present application, a zirconium-rich Cr-Zr-N alloy coating is provided, which contains a Cr-Zr-N alloy material having a chemical formula of (Cr x Zr y N z )M a , M is a doping element, wherein x, y, z and a are each independently an atomic ratio, 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, and 0≤a / (x+y+z+a)≤0.05.

[0010] In some embodiments, 64.5-y≤x≤93.8-y and 15.0≤x≤1.93y-23.4.

[0011] In some embodiments, 15.0≤x≤53.8, 33.7≤y≤78.8 and 6.2≤z<28.0. In some of them, 72-y<x≤93.8-y and 15.0≤x<2.5y-44.6.

[0012] In some embodiments, based on any suitable embodiment described above, the sum of x, y and z is 100.

[0013] In some embodiments, based on any suitable embodiment described above, the Cr-Zr-N alloy coating satisfies the following two characteristics:

[0014] The X-ray diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has a peak in the range of diffraction angle 2θ(°) of 30°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 30°-50° satisfies ≥2°;

[0015] The selected area electron diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has a diffraction peak in the range of 30°-50° in the radial intensity profile corresponding to the selected area electron diffraction pattern, and the half-height width of at least one diffraction peak in the range of 30°-50° satisfies , and ​

[0016] In some embodiments, based on any suitable embodiment described above, the thickness of the Cr-Zr-N alloy coating is d min ~ 6 μm, wherein d min is selected from 10 nm ~ 50 nm.

[0017] In some embodiments, d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm or 50 nm.

[0018] In some embodiments, based on any suitable embodiment described above, the doping element is a non-metallic element, a metallic element or a combination thereof;

[0019] The non-metallic element includes one or more of O, C, B, Si and Ar;

[0020] The metallic element includes one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

[0021] In some embodiments, 0 ≤ a / (x+y+z+a) ≤ 0.02.

[0022] In a second aspect of the present application, a coated article is provided, comprising a substrate and the Cr-Zr-N alloy coating according to the first aspect of the present application; wherein the Cr-Zr-N alloy coating is located on at least one side of the substrate.

[0023] In some embodiments, the surface material of the substrate is one of an alloy, a single-element metal and an inorganic non-metallic material;

[0024] Optionally, the material type of the alloy includes one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based;

[0025] Optionally, the single-element metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium;

[0026] Optionally, the inorganic non-metallic material includes one or more of ceramic and glass.

[0027] In some embodiments, the surface material of the substrate is one of a light alloy or one of a stainless steel alloy;

[0028] Optionally, the light alloy includes one or more of titanium alloy, aluminum alloy and magnesium alloy.

[0029] In some embodiments, the coated article satisfies one or more of the following characteristics:

[0030] The Cr-Zr-N alloy coating layer is in direct contact with the substrate or is provided with a transition layer;

[0031] The Cr-Zr-N alloy coating layer is on the surface of the coated article or the side of the Cr-Zr-N alloy coating layer away from the substrate is further provided with a surface layer, which is a single-layer structure or a multi-layer structure.

[0032] In a third aspect of the present application, use of the Cr-Zr-N alloy coating layer of the first aspect of the present application as at least part of a hard coating, or use of the coated article of the second aspect of the present application in the preparation of a product having a hard coating is provided.

[0033] In some embodiments, the hard coating is also a corrosion-resistant coating.

[0034] In a fourth aspect of the present application, a method for preparing a Cr-Zr-N alloy coating layer is provided, which comprises the following steps: using a vapor deposition technique to deposit the constituent elements of the Cr-Zr-N alloy coating layer on at least a part of the surface of a substrate according to a preset atomic ratio, thereby forming the Cr-Zr-N alloy coating layer of the first aspect of the present application.

[0035] In some embodiments, the method for preparing the Cr-Zr-N alloy coating layer comprises the following steps: under the condition of introducing a mixed gas comprising argon and a nitrogen-containing gas, using one or more targets comprising chromium and zirconium to sputter deposit the constituent elements of the Cr-Zr-N alloy coating layer on at least a part of the surface of the substrate, thereby forming the Cr-Zr-N alloy coating layer.

[0036] In some embodiments, the method for preparing satisfies one or more of the following characteristics:

[0037] The temperature for sputter deposition is 30°C to 330°C;

[0038] The total gas pressure of the mixed gas comprising argon and a nitrogen-containing gas is 0.3 Pa to 1.2 Pa;

[0039] The target comprises a chromium target, and the power density of the chromium target is 1.3 W / cm 2 to 6.7 W / cm 2 ;

[0040] The target comprises a zirconium target, and the power density of the zirconium target is 0.8 W / cm 2 to 7.9 W / cm 2 ;

[0041] The target material comprises an alloy target comprising at least two metal elements in the Cr-Zr-N alloy coating; optionally, the target material comprises a chromium-zirconium-based alloy target, and the power density of the chromium-zirconium-based alloy target is 4 W / cm 2 ~ 6 W / cm 2 ;

[0042] The bias voltage of the substrate is -150 V to -20 V;

[0043] The sputtering deposition time is 10 min to 150 min;

[0044] The nitrogen-containing gas is nitrogen, and the gas flow of the nitrogen is 8 sccm to 52 sccm;

[0045] The nitrogen-containing gas is nitrogen, and the gas amount ratio of argon and nitrogen in the mixed gas is (2-6):1.

[0046] In a fifth aspect of the present application, a Cr-Zr-N alloy material is provided, which is defined as in the first aspect of the present application.

[0047] The details of one or more embodiments of the present application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the application will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF DRAWINGS

[0048] In order to more clearly illustrate the technical solutions in the embodiments or examples of the present application, and more completely understand the present application and its beneficial effects, the drawings needed to be used in the description of the embodiments or examples will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without any creative effort. It should be noted that the drawings are drawn in a simplified form, and are only used to conveniently and clearly assist in the description of the present application. The various sizes of each component shown in the drawings are arbitrarily shown, which can be accurate or can not be drawn according to the actual proportion. For example, in order to make the drawing clearer, the size of some components is appropriately exaggerated in some places of the drawing. Unless otherwise specified, the components in the drawing are not drawn according to the scale. The present application does not limit each size of each component.

[0049] In the following description, the same reference numbers in the drawings represent the same parts.

[0050] Figure 1 is a structural schematic diagram of a plated product comprising an exemplary zirconium-rich Cr-Zr-N alloy coating in an embodiment of the present application, comprising a substrate and an exemplary Cr-Zr-N alloy coating of the present application;

[0051] Figure 2 is a schematic diagram of the structure of several coated products in several embodiments of this application: (A) includes a substrate, a transition layer and an exemplary Cr-Zr-N alloy coating of this application; (B) includes a substrate, a transition layer, an exemplary Cr-Zr-N alloy coating of this application and a surface layer; (C) includes a substrate, an exemplary Cr-Zr-N alloy coating of this application and a surface layer.

[0052] Figure 3 is a schematic diagram of an apparatus for preparing the Cr-Zr-N alloy coating of this application in one embodiment of the present application;

[0053] Figure 4 shows the Cr prepared in Example 1 of this application. 53.8 Zr 40.0 N 6.2 SEM cross-sectional view of the alloy coating;

[0054] Figure 5 shows the Cr prepared in Example 1 of this application. 53.8 Zr 40.0 N 6.2 XRD diffraction pattern (A), selected area electron diffraction pattern (B), and radial intensity profile (C) of the alloy coating;

[0055] Figure 6 shows the Cr prepared in Example 2 of this application. 34.5 Zr 30.0 N 35.5 SEM cross-sectional view of the alloy coating;

[0056] Figure 7 shows the Cr prepared in Example 2 of this application. 34.5 Zr 30.0 N 35.5 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0057] Figure 8 shows the Cr prepared in Example 3 of this application. 15.0 Zr 78.8 N 6.2 SEM cross-sectional view (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0058] Figure 9 shows the Cr prepared in Example 4 of this application. 15.0 Zr 49.5 N 35.5 SEM cross-sectional view of the alloy coating;

[0059] Figure 10 shows the Cr prepared in Example 4 of this application. 15.0 Zr 49.5 N 35.5XRD pattern (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating;

[0060] Figure 11 is a Cr 29.7 Zr 50.1 N 20.2 SEM cross-section of the alloy coating;

[0061] Figure 12 is a Cr 29.7 Zr 50.1 N 20.2 XRD pattern of the alloy coating;

[0062] Figure 13 is a Cr 88.9 Zr 11.1 SEM cross-section of the alloy coating;

[0063] Figure 14 is a Cr 37.8 Zr 16.2 N 46 SEM cross-section of the alloy coating;

[0064] Figure 15 is a Cr 37.8 Zr 16.2 N 46 XRD pattern (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating;

[0065] Figure 16 is a Cr 39.6 Zr 19.4 N 41 XRD pattern (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating.

[0066] In the XRD pattern, the horizontal axis is 2Θ, in °, and the vertical axis is X-ray diffraction intensity, in a.u.; according to the selected area electron diffraction pattern (SAED) of the alloy coating, the radial intensity profile thereof is obtained, expressed in the form of characteristic atomic spacing (d)-diffraction intensity, with d as the horizontal axis, in angstrom The vertical axis is electron diffraction intensity, in a.u.

[0067] In the XRD pattern and the radial intensity profile of the SAED pattern, a.u. has the known meaning in the art.

[0068] In some SEM images, some cross-section delamination occurred when the silicon wafer was brittle fractured during the preparation of the cross-section sample to be observed, but it did not affect the observation and analysis of the cross-section morphology. The positions of different structural layers in the substrate and protective coating can be determined according to the thickness of the corresponding structural layer.

[0069] Reference signs: 1 is a vacuum cavity, 2 is a sample table, 3 is a direct current anode, 4 is a chromium target (also referred to as a Cr target), 5 is a zirconium target (also referred to as a Zr target);

[0070] 100 is a substrate, 200 is a transition layer (also referred to as a transition film layer), 300 is a Cr-Zr-N alloy coating, and 400 is a surface layer (also referred to as a surface film layer).

[0071] In the present application, unless otherwise specified, the chromium target 4 is a Cr target for RF-assisted direct current cathode electric conduction, and the zirconium target 5 is a Zr target for RF-assisted direct current cathode electric conduction. DETAILED DESCRIPTION

[0072] The present application will be further described below in conjunction with the drawings, embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and are not used to limit the scope of the present application, and the purpose of providing these embodiments and examples is to make the understanding of the disclosed content of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein, and those skilled in the art can make various modifications or changes without departing from the spirit of the present application, and the equivalent forms obtained thereby also fall within the protection scope of the present application. For example, the features described or illustrated as part of an embodiment can be combined in another embodiment in a suitable manner to produce a new embodiment. In addition, in the following description, a large number of details are given in order to provide a more complete understanding of the present application, and it should be understood that the present application can be implemented without one or more of these details.

[0073] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the embodiments and examples and are not intended to limit the present application.

[0074] Terminology

[0075] Unless otherwise stated or contradictory, the terms or phrases used herein have the following meanings:

[0076] The selection scope of the terms "and / or", "or / and", "and / or" used in the present application includes any one of two or more relevant listed items, and also includes any and all combinations of the relevant listed items. For example, "A and / or B" includes three parallel schemes of A, B and "combination of A and B".

[0077] In the present application, "multiple", "various", "multiple times" and the like, if not specifically limited, refer to more than two or equal to two in number. For example, "one or more" means one or more than two.

[0078] In the present application, if not otherwise stated, "one or more" means any one of the listed items or any combination of the listed items. Similarly, in other cases where "one or more" is used to represent "one or more", the same understanding is made if not otherwise stated.

[0079] As used herein, "combination thereof", "any combination thereof", "any combination manner thereof" and the like include all suitable combination manners of any two or more of the listed items.

[0080] In the present application, "suitable", "suitable", "any suitable manner" and the like in "suitable combination manner", "suitable manner", "any suitable manner" and the like are subject to the implementation of the technical solutions of the present application, the solution of the technical problems of the present application, and the realization of the expected technical effects of the present application.

[0081] In the present application, "preferably", "better", "better", "as appropriate" are only to describe the better effect of the implementation mode or embodiment, and it should be understood that it does not constitute a limitation on the protection scope of the present application. If there are multiple "preferably" in a technical solution, if not specifically stated, and there is no contradictory relationship or mutual restriction, each "preferably" is independent.

[0082] In the present application, "further", "more further", "in particular", "for example", "such as", "example", "for example" and the like are used for description purposes, indicating that the technical solutions before and after are related in terms of coverage, but should not be understood as a limitation on the previous technical solution, nor should it be understood as a limitation on the protection scope of the present application. In the present application, if not otherwise stated, A (such as B) means that B is one non-limiting example of A, and it can be understood that A is not limited to B.

[0083] In the present application, "optionally", "optional", "option" means optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "options" in a technical solution, unless otherwise specified, and there is no contradiction or mutual restriction, each "option" is independent of each other. In the present application, "optionally contains", "optionally includes" and the like, means "contains or does not contain". "Optional component X" means that component X exists or does not exist.

[0084] In the present application, the terms "first", "second", "third", "fourth" and the like in "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are only for description purposes, and cannot be understood as indicating or implying relative importance or quantity, nor can it be understood as implying the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration description, and should be understood as not constituting a closed limitation on the quantity.

[0085] The terms "contains", "includes" and "comprises" used in the present application are synonymous and are inclusive or open-ended, and do not exclude additional, unrecited members, elements or method steps.

[0086] In the present application, the technical features described in an open-ended manner include both closed technical solutions consisting of listed features and open technical solutions including listed features.

[0087] In the present application, with respect to a numerical interval (i.e. a numerical range), unless otherwise specified, the distribution of optional values within the numerical interval is considered to be continuous, and includes both numerical endpoints (i.e. the minimum value and the maximum value) of the numerical interval, as well as every value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, including both endpoint integers of the numerical range and every integer between the two endpoints, it is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges encompassed therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad interpretation of percentage intervals, ratio intervals, value intervals, etc.

[0088] Unless otherwise specified, "about" herein means within a certain range around the number, and the fluctuation range can vary depending on the type and value of the number. For example, it is allowed to fluctuate within a range of ±2%, ±1%, ±0.5% and the like of the number. For example, about 2° can mean selected from 2° ± 0.02° and the like.

[0089] The temperature parameters in the present application, if not particularly limited, allow for constant temperature treatment as well as for variations within a certain temperature interval. It is to be understood that the constant temperature treatment allows for fluctuations within the accuracy of the instrument control. Fluctuations within a range of, for example, ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed. The temperature unit °C refers to "degrees Celsius".

[0090] In the present application, the term "room temperature" generally refers to 4°C to 35°C, for example 20°C ± 5°C. In some embodiments of the present application, "room temperature" refers to 10°C to 30°C. In some embodiments of the present application, "room temperature" refers to 20°C to 30°C.

[0091] In the present application, the term "room temperature" generally refers to 4°C to 35°C, for example 20°C ± 5°C. In some embodiments of the present application, "room temperature" refers to 10°C to 30°C. In some embodiments of the present application, "room temperature" refers to 20°C to 30°C.

[0092] In the present application, units relating to data ranges, if only the right end point is followed by a unit, it means that the units of the left end point and the right end point are the same. For example, 3-5h means that the units of the left end point "3" and the right end point "5" are both h (hours), which have the same meaning as 3h-5h. In addition, similar descriptions related to temperature, size and other parameters are also applicable to the above understanding.

[0093] All documents mentioned in the present application are incorporated by reference into the present application as if each document were individually incorporated by reference. Unless and to the extent that the contents of the documents conflict with the purpose and / or technical solutions of the present application, the documents referred to in the present application are incorporated by reference in their entirety. When the present application refers to the documents, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the documents are also incorporated by reference. When the present application refers to the documents, the examples and preferred modes of the relevant technical features referred to are also incorporated by reference into the present application, but are limited to the extent that the present application can be implemented. It should be understood that when the contents of the documents conflict with the description in the present application, the present application is given priority or is modified adaptively according to the description in the present application.

[0094] The mass or weight of the relevant components mentioned in the embodiments or examples of the present application can not only refer to the detailed content of each component, but also represent the proportional relationship between the mass or weight of each component. Therefore, as long as the content of the relevant components in the embodiments or examples of the present application is enlarged or reduced in proportion, it is within the scope disclosed by the embodiments or examples of the present application. The mass or weight mentioned in the embodiments or examples of the present application can be micrograms (μg), milligrams (mg), grams (g), kilograms (kg) and other units commonly known in the chemical field.

[0095] In this application, unless specifically stated otherwise, the steps involved in the method flow are not strictly limited in execution order, and can be executed in other orders than described. Also, any one step can include multiple sub-steps or multiple stages, which do not necessarily have to be executed at the same time, but can be executed at different times, and the execution order does not necessarily have to be sequential, but can be alternated or simultaneous with other steps or sub-steps or stages of other steps.

[0096] In describing a position relationship, unless otherwise specified, when an element such as a layer, film or substrate is referred to as "on" another film layer, it can be directly on the other film layer or there can be an intervening film layer. Further, when a layer is referred to as being "under" another layer, it can be directly under the other layer, or there can be one or more intervening layers. It is also understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or there can be one or more intervening layers.

[0097] In the case of using "include", "have", and "contain" described in this document, it is intended to cover non-exclusive inclusion, unless the explicit limiting language such as "only", "consisting of", etc. is used, another component can also be added.

[0098] Unless otherwise mentioned, the singular form of the terms can include the plural form and cannot be understood as having a quantity of one.

[0099] In this application, the exemplary description involving "in some embodiments (or examples)", "in an embodiment (or example)", etc. can cover but is not limited to the following meanings: these schemes can be combined with other schemes in a suitable manner to form new technical schemes.

[0100] In order to improve the hardness of the coating, the conventional alloy coating mainly uses the alloy nitride coating designed with rich nitrogen. The alloy nitride coating mainly uses the combination of different metal elements to form a coating with different microstructures to achieve different functional characteristics. The conventional alloy coating mainly uses the design with rich nitrogen to improve the hardness of the coating, and the atomic percentage of nitrogen element is usually higher than 40%. In addition, in order to improve the hardness, the conventional multi-element alloy coating also involves the addition of zirconium to improve the hardness to a certain extent. However, since zirconium is a large-size atom, its metal activity is higher than that of titanium, and its price is higher than that of titanium, so titanium is generally used to replace zirconium in alloy research and development, and the content of zirconium in the conventional alloy is usually not high, generally less than 10%.

[0101] The inventors of the present application found through a large number of investigations and experimental analyses that the traditional hard coating (such as TiN) is prone to form columnar crystals in the process of nucleation and crystallization growth, usually has a columnar crystal structure, and a high content of columnar crystals promotes the formation of a highly ordered structure arranged in a direction, and a large number of intercrystalline gap defects caused by crystallization exist in the highly ordered structure, mainly in the form of penetrating columnar gaps, and there are shadows between the columnar crystals in the corresponding scanning electron microscope (SEM) cross-section view. It is speculated that these penetrating columnar gaps may cause the alloy coating to be insufficiently dense. The inventors of the present application speculate that the traditional ordered structure arranged in a direction is prone to cause the coating to be insufficiently dense, thus limiting the improvement of hardness; on the other hand, under corrosion conditions, the corrosion medium can quickly penetrate the coating through the penetrating gaps and react with the substrate, thus causing the corrosion resistance of the alloy coating to be insufficiently ideal.

[0102] In addition, the alloy materials on the market at present mainly use anodic oxidation, magnetron sputtering and other means for surface protection. For example, aluminum alloys mainly use anodic oxidation for surface protection, and the working principle is as follows: the aluminum alloy material is placed in a strong acid or strong alkali solution to form oxides and metal or alloy coatings on the surface to form surface protection. Since the solution is a strong acid or strong alkali, the hardness of the product formed by this method is low, and in addition, a large amount of wastewater, waste liquid and waste gas is generated in the production process, which is not conducive to environmental protection.

[0103] The present application adopts a zirconium-rich alloy design and selects the element composition and ratio to form a new alloy nitride coating with a high content of zirconium, which is a Cr-Zr-N alloy coating. The alloy coating realizes a new alloy function: the zirconium-rich Cr-Zr-N alloy coating provided by the present application not only has high hardness characteristics, but also endows the alloy coating with excellent corrosion resistance much higher than that of traditional hard coatings, and is a hard coating with excellent corrosion resistance and high hardness.

[0104] According to various embodiments and various examples of the present application, one aspect of the present application provides a zirconium-rich Cr-Zr-N alloy coating, the Cr-Zr-N alloy material in the Cr-Zr-N alloy coating is rich in zirconium, the Cr-Zr-N alloy coating not only has high hardness, but also has excellent corrosion resistance, and can be used as a protective coating or part of a plated product. The present application also provides plated products, applications in hard coatings and preparation methods.

[0105] The Cr-Zr-N alloy material in the zirconium-rich Cr-Zr-N alloy coating provided by the present application mainly contains Cr, Zr and N, and the three elements have a specific relative atomic ratio (Cr x Zr y N z), 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, the Cr-Zr-N alloy coating has a highly disordered atomic distribution and a fully dense atomic arrangement on the basis of the aforementioned zirconium-rich chemical composition, and the coating structure is dense, thus having high hardness characteristics and excellent scratch resistance, and can reduce the occurrence of scratches or weaken scratch damage. In addition, the special structure of the Cr-Zr-N alloy coating also reduces or avoids the through-column seams in traditional hard coatings, thereby greatly improving the corrosion resistance of the Cr-Zr-N alloy coating. The Cr-Zr-N alloy coating provided in the present application has both high hardness and excellent corrosion resistance.

[0106] In the coated product, the position of the Cr-Zr-N alloy coating provided in the present application can be flexibly set, which can directly contact the substrate or not, and can be used as a surface layer or as an intermediate film layer between the substrate and other surface layers. The Cr-Zr-N alloy coating provided in the present application can provide excellent corrosion resistance while effectively resisting scratches and scratches in different positions. The Cr-Zr-N alloy coating provided in the present application can provide a high-brightness surface when used on the surface of a coated product, and the coating has both aesthetic decoration and protection.

[0107] The Cr-Zr-N alloy coating provided in the present application can be used as at least a part of a hard coating, and can be used as a surface film layer, an intermediate film layer or a bottom film layer of a hard coating. The aforementioned coated product can be an intermediate product or a final product, and various products with a hard coating can be further prepared. The hard coating not only has high hardness characteristics, but also can provide excellent corrosion resistance as a corrosion-resistant coating.

[0108] The Cr-Zr-N alloy coating provided in the present application can be applied to a variety of substrates, and the substrate materials include but are not limited to alloys, elemental metals, inorganic non-metallic materials (such as silicon wafers, ceramics, glass) and various substrates.

[0109] The preparation method of the Cr-Zr-N alloy coating provided in the present application is simple, easy to operate, green and environmentally friendly, and has the advantages of quantification, high efficiency and good repeatability, and is suitable for industrial application.

[0110] The Cr-Zr-N alloy coating provided in the present application can have high hardness characteristics and excellent corrosion resistance in the case of a relatively thin thickness, thereby saving raw materials, simplifying the process, shortening the production cycle and significantly reducing the cost.

[0111] In the first aspect of the present application, a zirconium-rich Cr-Zr-N alloy coating is provided, which contains alloy materials mainly containing Cr, Zr and N, and the relative atomic ratio of Cr xZr y N z ), 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, the zirconium-rich Cr-Zr-N alloy coating has a high content of zirconium and is optimized by the ratio of the three elements, and has high hardness and excellent corrosion resistance, and can be used as at least part of the hard coating of the coated product.

[0112] In some embodiments, a zirconium-rich Cr-Zr-N alloy coating is provided, the Cr-Zr-N alloy coating comprising a Cr-Zr-N alloy material having a chemical formula of (Cr x Zr y N z )M a , wherein x, y, and z are each independently an atomic ratio, 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, M is a doping element, a is the atomic ratio of the M element, and a is 0 or a positive number.

[0113] In some embodiments, a zirconium-rich Cr-Zr-N alloy coating is provided, the Cr-Zr-N alloy coating comprising a Cr-Zr-N alloy material having a chemical formula of (Cr x Zr y N z )M a , wherein x, y, and z are each independently an atomic ratio, 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, M is a doping element, a is the atomic ratio of the M element, and 0≤a / (x+y+z+a)≤0.05.

[0114] The Cr-Zr-N alloy coating provided by an aspect of the present application can also be referred to as "the Cr-Zr-N alloy coating of the present application", "the Cr-Zr-N alloy coating of the present application", "the exemplary Cr-Zr-N alloy coating of the present application", or "the Cr-Zr-N alloy coating provided by the present application", and includes but is not limited to the Cr-Zr-N alloy coating provided by the first aspect. Each of the above-mentioned references should be understood in a non-limiting manner, and is not understood as limiting the scope of the present application, for example, the scope of the present application is not limited to "the Cr-Zr-N alloy coating of the present application". The description of "the Cr-Zr-N alloy coating of the present application" and the like involved in the present application is understood in a non-limiting manner as the exemplary Cr-Zr-N alloy coating provided by an aspect of the present application, and does not limit the scope of the Cr-Zr-N alloy coating provided by the present application.

[0115] In the present application, unless otherwise specified, "Cr-Zr-N alloy" and "CrZrN alloy" both represent an alloy containing Cr element, Zr element and N element, and other alloying elements are allowed to be contained, and the two can be used interchangeably.

[0116] In the present application, unless otherwise specified, "Cr-Zr-N alloy material" represents an alloy material containing chromium (Cr) element, zirconium (Zr) element and nitrogen (N) element. In the Cr-Zr-N alloy material involved in the present application, the three elements of Cr, Zr and N have the specific atomic ratio x:y:z as described above. In the present application, the form of the Cr-Zr-N alloy material is not particularly limited, and can be, but is not limited to, an alloy coating.

[0117] In the present application, unless otherwise specified, the "atomic ratio" of two or more elements represents the ratio of the number of atoms.

[0118] In the present application, unless otherwise specified, "Cr-Zr-N ternary alloy" and "CrZrN ternary alloy" both represent an alloy composed of Cr element, Zr element and N element.

[0119] In the zirconium-rich Cr-Zr-N alloy coating provided in the present application, the Cr-Zr-N alloy material mainly contains Cr, Zr and N three elements, and the three elements have a specific relative atomic ratio Cr x Zr y N z , 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, the Cr-Zr-N alloy coating has a highly disordered atomic distribution and a fully dense atomic arrangement on the basis of the aforementioned zirconium-rich chemical composition, the coating structure is dense, thus having high hardness characteristics, excellent scratch resistance, and can reduce the occurrence of scratches or weaken scratch damage. In addition, the special structure of the Cr-Zr-N alloy coating also reduces or avoids the penetrating column seam in the traditional hard coating, thereby greatly improving the corrosion resistance of the Cr-Zr-N alloy coating. The Cr-Zr-N alloy coating provided in the present application has both high hardness and excellent corrosion resistance.

[0120] Since zirconium is a large-size atom, it has high atomic activity and is easy to alloy and nitride, and its nitride or alloy nitride will exhibit higher hardness. By increasing the element content of zirconium in the alloy coating, on the one hand, the hardness of the alloy coating is effectively improved, and on the other hand, a specific atomic ratio of Cr and N elements in the Cr-Zr-N alloy material is formed, which can form a highly disordered atomic distribution and a fully dense atomic arrangement during the deposition process of preparing the coating, further improve the hardness of the coating, and also reduce or avoid the penetrating column seam, thereby significantly improving the corrosion resistance of the alloy coating.

[0121] The high-hardness coating has high hardness, low friction coefficient, and wear resistance, and when applied to a substrate such as a metal substrate or an alloy substrate, the high-hardness effect can be achieved, so that the coating has extremely strong high-hardness and wear resistance, and is particularly suitable for structural parts that have high hardness requirements and are prone to wear in the fields of 3C digital products, mechanical processing, mold manufacturing, geological drilling, textile industry, aerospace, tool surface, and the like. For example, in the field of portable 3C products such as mobile phone shell parts, the shell surface needs to be protected by high-hardness coating to increase the service life of the product. For another example, in the field of molds and cutters, the wear resistance of the mold or cutter can be effectively increased by increasing the high-hardness alloy coating, and the durability of the alloy tool can also be prolonged. For another example, in the field of aerospace, the shell of the device is prone to wear due to overheating friction with air at high speed, and the service life of the shell can be increased by increasing the high-hardness alloy coating on the surface of the shell.

[0122] The corrosion-resistant coating needs to have self-inertness and sufficient isolation. The "self-inertness" can be expressed as that the coating material has sufficient inertness and is not easy to chemically react with the corrosion medium in the service environment. The "sufficient isolation" can be expressed as that the coating structure is sufficiently dense, so that the substrate is fully isolated from the use environment, and the reaction between the substrate and the corrosion medium therein is prevented or delayed, so as to achieve the purpose of corrosion resistance.

[0123] The traditional hard coating is usually in a nanocrystalline state and has a high content of columnar crystals, and a large number of through pores are usually present in the coating, which on the one hand reduces the density of the coating and affects the hardness characteristics, and on the other hand leads to poor corrosion resistance.

[0124] The Cr-Zr-N alloy coating provided in the present application has a "highly disordered and fully dense" characteristic structure, contains a small amount of through pores or no through pores, and the coating structure is dense. Among them, the three atoms of Cr, Zr and N with different radii have a special atomic ratio, which is beneficial to the condensation of atoms into a highly disordered state during deposition, and then tightly packed in a highly disordered state. The dual characteristics of "highly disordered distribution" and "fully dense arrangement" of atoms in the coating make the alloy coating easy to grow densely and improve the hardness of the coating, and also inhibit the formation of a large number of continuous through gaps, thereby forming an effective isolation between the substrate and the corrosion environment, and significantly improving the corrosion resistance. In addition, a higher Zr content is also beneficial to improving the chemical inertness of the coating in the corrosion environment, thereby synergistically and preferably improving the corrosion resistance of the Cr-Zr-N coating of the present application.

[0125] In the Cr-Zr-N alloy coating of the present application, based on the special atomic ratio of Cr, Zr and N, Cr and N are introduced to form a zirconium-rich Cr-Zr-N alloy coating in the case of high Zr content, which not only makes Cr and Zr easy to form strong bond energy, and is conducive to the rapid growth of Cr-Zr alloy with suitable atomic ratio during deposition, in addition, the addition of appropriate amount of nitrogen also further promotes the re-nucleation of Cr-Zr alloy to form the Cr-Zr-N alloy of the present application, by improving the compactness of the coating nucleation, the hardness and corrosion resistance of the coating can be improved. Among them, in terms of atomic size, the atomic radius of Cr is 1.25 angstrom The atomic radius of Zr is The atomic radius of N is Cr and Zr atomic size is close, and the size of N atom is small, in the nucleation process, a small amount of small size N atom can penetrate into the pores of large size Cr and Zr metal crystal grains with suitable atomic ratio, achieving better hole filling effect, making the atomic arrangement more compact, and at the same time, the growth defects of thin film columnar crystal structure can be inhibited, so as to better improve the hardness and corrosion resistance of the coating.

[0126] In some embodiments, 64.5-y≤x≤93.8-y and 15.0≤x≤1.93y-23.4. At this time, Cr, Zr and N can form a better synergistic effect, which is more conducive to improving the excellent comprehensive performance of high hardness and high corrosion resistance of the alloy coating.

[0127] In some embodiments, 15.0≤x≤53.8, 33.7≤y≤78.8 and 6.2≤z<28.0, further, the following formula can be met: 72-y<x≤93.8-y and 15.0≤x<2.5y-44.6. At this time, the atomic ratio of Cr, Zr and N is conducive to forming a more compact, higher hardness and higher corrosion resistance alloy coating.

[0128] In some embodiments, based on any suitable embodiment described above, the sum of x, y and z is 100. At this time, x, y and z correspond to the atomic percentage of Cr, Zr and N respectively. At this time, the atomic ratio of Cr, Zr and N is constrained in a more suitable range, so that the formed Cr-Zr-N alloy coating is conducive to obtaining a more compact structure, and is conducive to realizing higher coating hardness and better corrosion resistance.

[0129] In some embodiments, x can be any of the following values or selected from the interval between any two of the following values: 15.0, 20.0, 25.0, 29.7, 30.0, 34.5, 35.0, 40.0, 41.3, 45.0, 47.1, 52.0, 53.8, etc., under the condition that the ratio relationship of 15.0≤x≤53.8, 30.0≤y≤78.8 and 6.2≤z≤35.5 is met and x+y+z=100.

[0130] In some embodiments, y can be any of the following values or selected from the interval between any two of the following values: 30.0, 33.2, 35.0, 35.1, 40.0, 45.0, 49.5, 50.0, 50.1, 55.0, 60.0, 65.0, 70.0, 75.0, 78.8, etc., under the condition that the ratio relationship of 15.0≤x≤53.8, 30.0≤y≤78.8 and 6.2≤z≤35.5 is met and x+y+z=100.

[0131] In some embodiments, z can be any of the following values or selected from the interval between any two of the following values: 6.2, 10.0, 10.1, 13.0, 15.0, 20.0, 20.2, 25.0, 25.5, 30.0, 35.5, etc., under the condition that the ratio relationship of 15.0≤x≤53.8, 30.0≤y≤78.8 and 6.2≤z≤35.5 is met and x+y+z=100.

[0132] In some embodiments, based on any of the foregoing suitable embodiments, the Cr-Zr-N alloy coating satisfies the following two characteristics:

[0133] The X-ray diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has a peak in the range of diffraction angle 2θ(°) of 30°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 30°-50° satisfies ≥2°;

[0134] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating, there is a diffraction peak in the range of , and the half-height width of at least one diffraction peak in the range of

[0135] The means for structural characterization of the Cr-Zr-N alloy coating in the present application can also be used to characterize the Cr-Zr-N alloy material provided in the present application, and the Cr-Zr-N alloy material can not be limited to the form of a coating, but can be an independent raw material, such as an alloy sheet, an alloy plate, etc.

[0136] The Cr-Zr-N alloy coating provided in the present application is not strictly divided by traditional perfect single crystal or sufficient amorphous state, but focuses on the close packing degree of atomic arrangement, which is closely related to the disorder of atomic arrangement and the suitable mismatch degree of atomic size on the basis of the specific atomic ratio of Cr, Zr and N. The highly dense Cr-Zr-N alloy coating provided in the present application has high hardness and excellent corrosion resistance in performance, and simultaneously satisfies at least one wide peak (further, there can be no sharp peak, i.e. all wide peaks) in the range of diffraction angle 2θ(°) of 30°-50° in the XRD pattern and at least one wide peak (further, there can be no sharp peak, i.e. all wide peaks) in the radial intensity profile of the selected area electron diffraction pattern.

[0137] In the present application, whether the constituent atoms of the alloy coating have the "highly disordered" state is evaluated by XRD technology. More specifically, the XRD pattern of the Cr-Zr-N alloy coating shows wide and slow bulges, which are called "wide peaks" of the 2θ(°) diffraction peaks. By the half-width value of the wide peak, the length of atomic ordered arrangement can be obtained by using the Scherrer formula. The calculation method is: D=Kλ / (β·cosθ), wherein D is the length of atomic ordered arrangement (representing the grain size in crystalline materials), K is the Scherrer constant, λ is the X-ray wavelength, β is the half-width value of the diffraction peak (Full Width at Half Maximum, FWHM), and θ is the diffraction angle. It can be seen that the half-width FWHM is inversely proportional to the length D of atomic ordered arrangement, and the shorter the length D of atomic ordered arrangement, the higher the disorder of atomic distribution. Therefore, the degree of disordered distribution of atoms can be reflected by the half-width FWHM of the diffraction peak in a specific range of the XRD pattern: the wider the half-width FWHM, the shorter the length of atomic ordered arrangement, and the more disordered the overall atomic distribution; the aforementioned "wide peak" of wide and slow bulges can reflect the highly disordered distribution of atoms in the whole material.

[0138] Generally speaking, the higher the atomic ordered arrangement, the stronger the crystallinity, and the easier it is to form large-size grains in a longer distance, and the narrower the diffraction peak in the XRD pattern, and high crystallinity often accompanies sharp peaks. In the alloy coating of the present application, the three atoms of Cr, Zr and N can be arranged in a highly disordered manner in the Cr-Zr-N alloy coating, so as to show wide and slow bulges (wide peaks) in the XRD pattern of the Cr-Zr-N alloy coating, and at least one peak in the range of diffraction angle 2θ(°) of 30°-50° is a "wide peak".

[0139] ​In the present application, unless otherwise specified, a "broad peak" in the XRD pattern can be defined as a peak with a full width at half maximum (FWHM) of ≥ 2°. The FWHM of the broad peak can further be ≥ 2.2°, still further ≥ 2.23°, still further ≥ 2.25°, still further ≥ 2.3°, still further ≥ 3°, still further ≥ 3.5°, still further ≥ 3.92°, still further ≥ 4°, still further ≥ 5°. The FWHM of any "broad peak" in the XRD pattern can independently be any of the following values, can be greater than or equal to any of the following values, can be greater than or equal to any of the following values and less than or equal to 10°, can be selected from the interval defined by any two of the following values: 2°, 2.23°, 2.25°, 2.5°, 3°, 3.5°, 3.52°, 3.92°, 4°, 4.5°, 5°, 5.5°, 5.56°, 6°, 6.5°, 7°, 7.5°, 8.42°, 8.5°, 9°, 9.5°, etc. As non-limiting examples, it can be selected from any of the following ranges: 2°-10°, 2°-9.5°, 2°-9°, 2.2°-8.5°, 2.20°-8.45°, 2.23°-8.42°, etc.

[0140] In the present application, unless otherwise specified, a "sharp peak" in the X-ray diffraction (XRD) pattern refers to a diffraction peak with a full width at half maximum (FWHM) of < 2°.

[0141] In more detail, the Cr-Zr-N alloy coating provided in the present application has an XRD pattern with peaks in the range of diffraction angle 2θ(°) of 30°-50°, and at least one of the diffraction peaks in the XRD pattern is a broad peak. The special microstructure state of "at least one peak being a broad peak" can be expressed as "having at least one 2θ(°) diffraction peak in the range of 30°-50° with a FWHM of ≥ 2°" or "at least one 2θ(°) diffraction peak in the range of 30°-50° has a FWHM of ≥ 2°". The determination of whether the condition "having at least one 2θ(°) diffraction peak in the range of 30°-50° with a FWHM of ≥ 2°" is satisfied can be performed as follows: if the FWHM of a 2θ(°) diffraction peak in the XRD pattern is ≥ 2°, it is determined to be a "broad peak"; if the FWHM of a 2θ(°) diffraction peak is < 2°, it is determined to be a sharp peak. For a given 2θ(°) position, it can be any of the three states of no peak, broad peak or sharp peak. The broad peak characteristic of the characteristic diffraction peaks of the Cr-Zr-N alloy coating provided in the present application is more obvious in the X-ray diffraction (XRD) pattern.

[0142] In contrast, in the conventional Cr-Zr-N alloy coating with a high content of columnar crystals, the diffraction peaks in the range of diffraction angle 2θ(°) of 30°-50° are usually sharp peaks with a FWHM of < 2°, and no broad peak appears.

[0143] In the present application, XRD patterns of the alloy coating can be obtained by using conventional instruments and methods in the art. For example, a German Bruker D8 Advance XRD diffractometer can be used.

[0144] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has peaks in the range of diffraction angle 2θ(°) of 30°-50°, and at least one 2θ(°) diffraction peak in the range of 30°-50° is a wide peak, the half-height width value of which can be referred to the examples in the context; for example, the half-height width of the wide peak is ≥2.23°, then at least one 2θ(°) diffraction peak in the range of 30°-50° satisfies ≥2.23°.

[0145] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has 1 wide peak in the range of diffraction angle 2θ(°) of 30°-50°, the half-height width value of which can be referred to the examples in the context.

[0146] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has 2 or more wide peaks in the range of diffraction angle 2θ(°) of 30°-50°, the half-height width value of each of which can be independently referred to the examples in the context.

[0147] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has all 2θ(°) diffraction peaks in the range of diffraction angle 2θ(°) of 30°-50° as wide peaks, i.e. there is no sharp peak, the half-height width value of each of which can be independently referred to the examples in the context.

[0148] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has peaks in the range of diffraction angle 2θ(°) of 30°-50°, and the half-height width of each of the 2θ(°) diffraction peaks in the range of 30°-50° independently satisfies ≥2°, further can independently satisfy ≥2.2°, further can independently satisfy ≥2.23°, further can independently satisfy ≥2.25°, further can independently satisfy ≥2.3°, further can independently satisfy ≥3°, further can independently satisfy ≥3.5°, further can independently satisfy ≥4°, further can independently satisfy ≥5°.

[0149] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of the present application has and only has 1 diffraction peak in the range of diffraction angle 2θ(°) of 30°-50°, and it is a wide peak.

[0150] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating is obtained by Cu target Kα ray.

[0151] In the present application, the XRD pattern of the alloy coating can be obtained by using the following instrument and method: using a German Bruker D8 Advance XRD diffractometer, in a θ-2θ mode, using a Cu target Kα ray, wavelength λ is 0.15406 nm, the X-ray tube is controlled at 40 kV and 40 mA, the scanning range is 20°-80°, and the precise scanning measurement is carried out with a step of 0.01°.

[0152] The half-height width value can be obtained by using the conventional analysis method in the art (including but not limited to the analysis software provided by the instrument supplier). For example, the step of obtaining the half-height width value can include: first, correcting the diffraction peak, which can include: smoothing, subtracting the background, removing the Kα2 line, and subtracting the instrument broadening, etc., after fitting the diffraction peak with a Pseudo-Voigt function, the half-height width value of the diffraction peak is obtained.

[0153] The analysis software is not particularly limited, and non-limitingly, the EDP2XRD software (version 1.0.0, copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) can be used to process the spectrum data, for example, the following method can be used: first, perform scale correction, then determine the center of the diffraction ring transmission spot, then convert into an XRD spectrum (wherein the electron wavelength is 0.00251 nanometers (nm), and the X-ray wavelength is 0.154 nanometers; after subtracting the straight-line background from the diffraction peak, and then fitting with a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0154] Regarding the characterization of the atomic close-packed degree in the alloy coating, the traditional XRD pattern cannot well characterize it, because when detecting physical vapor deposition (PVD) films or coatings at an atomic scale (such as a diameter <3 nm), the XRD method often lacks resolution due to the relatively large wavelength (>0.1 nm) of X-rays, and is not suitable for PVD films or coatings with low order degree (such as grains or amorphous with a diameter <3 nm).

[0155] In the present application, whether the coating constituent atoms reach "sufficiently dense packing" is evaluated by selected area electron diffraction (SAED). Electron wave is selected because its wavelength is significantly smaller (<0.01 nm), thus higher resolution. In more detail, if there is only a continuous diffraction ring with uniform brightness on the SEAD pattern, and the diffraction ring is relatively wide, it indicates that the atoms in the coating are densely packed in a highly random mixed manner. To quantitatively characterize, the SAED pattern can be converted into a characteristic atomic spacing (d)-radial intensity profile, where the characteristic atomic spacing (d) is taken as the horizontal coordinate, and the diffraction intensity is taken as the vertical coordinate. If the diffraction ring in the SEAD is relatively wide, the corresponding half-height width of the radial intensity profile is relatively wide, reflecting the stronger atomic packing in the alloy coating.

[0156] In the present application, the atomic radius of Cr atom is The atomic radius of Zr atom is The atomic radius of N atom is The three atoms with different diameters have a suitable atomic size mismatch, and can form a sufficiently dense packing structure under the condition of a higher degree of random mixing. During the growth of PVD thin films or alloy coatings, the atomic sufficiently dense packing in the Cr-Zr-N alloy coating makes the alloy coating easy to grow densely, and can inhibit the formation and growth of columnar crystals due to local ordering, thereby making it difficult for continuous through-type pores to form in large quantities. Therefore, the half-height width of the radial intensity profile can be used as a characteristic parameter of the sufficiently dense packing structure of the alloy coating to reflect the atomic packing in the alloy coating. The larger the value of the half-height width, the better the atomic packing in the alloy coating. In short, the present application uses the half-height width of the radial intensity profile of SAED as a characteristic parameter of atomic sufficiently dense packing, which is in line with scientific principles and has scientific nature.

[0157] When the half-height width of the radial intensity profile is greater than a certain threshold value, the atoms in the coating can achieve sufficiently dense packing. According to the inventors' extensive experimental exploration, in the present application, the threshold value of the half-height width of the SAED-radial intensity profile for judging whether the atomic sufficiently dense packing is achieved is determined as That is, when the half-height width value The atomic sufficiently dense packing can be achieved.

[0158] In the present application, the transmission electron microscope (TEM) technique can be used to obtain the characteristic atomic spacing (d) radial intensity profile of the alloy coating sample.

[0159] In the present application, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating can be denoted as SAED-radial intensity profile, and can also be denoted as the characteristic interatomic distance-intensity quantitative atlas of the selected area electron diffraction pattern (SAED pattern). The selected area electron diffraction pattern obtained by the transmission electron microscopy technique can be denoted as TEM selected area electron diffraction pattern, and can also be denoted as TEM-SAED pattern. The SAED-radial intensity profile obtained by the transmission electron microscopy technique can also be denoted as TEM-SAED-radial intensity profile.

[0160] In the present application, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating (including the Cr-Zr-N alloy coating of the present application) can be obtained according to the selected area electron diffraction pattern (SAED) of the alloy coating by using the conventional instruments and methods in the art. The radial intensity profile is expressed in the form of characteristic interatomic distance (d)-diffraction intensity, with d as the horizontal coordinate and in angstrom unit The vertical coordinate is the electron diffraction intensity (intensity).

[0161] In the present application, in the radial intensity profile of the SAED pattern, the half-height width value of the diffraction peak is judged as a wide peak; and the half-height width value of the diffraction peak is judged as a sharp peak. For a specific characteristic interatomic distance, it can be any one of the three states of no peak, sharp peak or wide peak. In the radial intensity profile, the wide peak characteristic of the characteristic diffraction peak of the Cr-Zr-N alloy coating provided in the present application is more obvious. In the radial intensity profile of the selected area electron diffraction pattern (SAED pattern), “wide peak” refers to a diffraction peak with a half-height width , and “sharp peak” refers to a diffraction peak with a half-height width .

[0162] In the present application, in relation to the radial intensity profile or SAED-radial intensity profile, if not otherwise specified, the TEM technique can be used.

[0163] In the present application, in the radial intensity profile corresponding to the SAED pattern, “wide peak” can be defined as a half-height width satisfying The half-height width of the wide peak can be further more further can be more further can be more further can be more further can be

[0164] In the present application, the half-height width data in the radial intensity profile corresponding to the selected area electron diffraction pattern can be obtained by using (but not limited to) the following transmission electron microscopy (TEM) method:

[0165] TEM sample preparation: The sample was thinned using a Helios 5CX Focused Ion Beam (FIB) from Themo Fisher Limited to obtain an electron transparent, TEM observable planar sample.

[0166] SAED image acquisition: A Talos F200x Transmission Electron Microscope (TEM) from Themo Fisher Limited was used to acquire the selected area electron diffraction pattern (SAED) of the sample, with an electron accelerating voltage of 200 kilo-volt (kV) and a selected area aperture diameter of 900 nm. Based on the selected area electron diffraction pattern (SAED), a radial intensity profile was obtained, and the half-height width of the diffraction peak was obtained by assigning an integral half-height width.

[0167] According to the principle that the half-height width of the diffraction peak in the radial intensity profile corresponds to the width of the diffraction ring in the selected area electron diffraction pattern (SAED), the selected area electron diffraction pattern (SAED) of the alloy coating can be converted into the corresponding radial intensity profile.

[0168] As known by those skilled in the art, the larger the width of the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing degree of atoms, and thus the more sufficient the atomic close packing in the Cr-Zr-N alloy coating of the present application. The half-height width of the diffraction peak in the radial intensity profile is a quantitative indicator of the width of the diffraction ring, and the larger the half-height width, the more sufficient the atomic close packing.

[0169] In some embodiments, the selected area electron diffraction pattern (SAED) of the Cr-Zr-N alloy coating of the present application is obtained using a transmission electron microscope (TEM) characterization technique with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0170] In some embodiments, the radial intensity profile of the selected area electron diffraction pattern (SAED) of the Cr-Zr-N alloy coating of the present application has at least one diffraction peak with a half-height width of in the range of 0.1 nm to 0.3 nm. in the range of 0.1 nm to 0.3 nm.

[0171] The radial intensity profile of the Cr-Zr-N alloy coating provided by the present application has a half-height width of the diffraction peak in the range of 0.1 nm to 0.3 nm. The half-height width of the diffraction peak in the radial intensity profile of the Cr-Zr-N alloy coating provided by the present application has an upper limit value due to the atomic close packing limit, and a non-limiting example of the upper limit value is

[0172] In the present application, the half-height width of the "wide peak" in the radial intensity profile corresponding to the SAED pattern can be any of the following values, can be greater than or equal to any of the following values, and can be greater than or equal to any of the following values and less than or equal to the aforementioned upper limit value (such as ) can each independently be selected from any one of the following ranges: etc. As non-limiting examples, the half-width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any one of the following ranges: etc.

[0173] In some embodiments, the radial intensity profile of the Cr-Zr-N alloy coating has: a half-width of the diffraction peak in the range of 0.5-2.0°

[0174] In some embodiments, the radial intensity profile of the Cr-Zr-N alloy coating has: a half-width of the diffraction peak in the range of 0.5-2.0° can each independently be any one of the following values, can each independently be greater than or equal to any one of the following values, and / or can each independently be selected from any one of the following ranges: etc. As non-limiting examples, the half-width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any one of the following ranges: etc.

[0175] In some embodiments, the radial intensity profile of the SAED pattern corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating has: one broad peak in the range of 0.5-2.0°, the half-width of which can be found in the examples above and below.

[0176] In some embodiments, the radial intensity profile of the SAED pattern corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating has: two or more broad peaks in the range of 0.5-2.0°, the half-width of which can each independently be found in the examples above and below.

[0177] In some embodiments, the radial intensity profile of the SAED pattern corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating has: all diffraction peaks in the range of 0.5-2.0°, the half-width of which satisfies: as defined above and below.

[0178] In some embodiments, the characteristic interatomic distance of the Cr-Zr-N alloy coating is obtained using TEM diffraction data; wherein the TEM diffraction test of the alloy coating is performed using an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0179] In some embodiments, the TEM test employs an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm to obtain a selected area electron diffraction (SAED) pattern of the Cr-Zr-N alloy coating.

[0180] With respect to the internal mechanism analysis of the Cr-Zr-N alloy coating provided in the present application having high hardness and excellent corrosion resistance, the present inventors have found through a large number of experimental explorations that, for the Cr-Zr-N alloy coating, when the following two conditions are simultaneously satisfied: (1) at least one broad peak in the XRD diffraction pattern in the diffraction angle 2θ(°) range of 30°-50°, and (2) at least one broad peak in the radial intensity profile of the selected area electron diffraction pattern in the range of 30°-50°, the prepared Cr-Zr-N alloy coating has high hardness characteristics and excellent corrosion resistance. If only the XRD diffraction pattern in the diffraction angle 2θ(°) range of 30°-50° has at least one broad peak, but there is no broad peak in the radial intensity profile of the SAED pattern in the range of 30°-50°, the prepared Cr-Zr-N alloy coating can have poor corrosion resistance, for example, the corresponding aluminum alloy substrate sample can not pass the 24h or 48h salt spray corrosion resistance test. If the radial intensity profile of the SAED pattern has at least one broad peak in the range of 30°-50°, but there is no broad peak in the XRD diffraction pattern in the diffraction angle 2θ(°) range of 30°-50°, the Cr-Zr-N alloy coating can also have poor corrosion resistance.

[0181] In some embodiments, based on any suitable embodiment described above, the thickness of the Cr-Zr-N alloy coating is d min ~ 6μm, wherein d min may be selected from the range of 10nm-50nm, d min may also be any one of the following thicknesses, or selected from the range consisting of any two of the following thicknesses: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, etc.; for example, the thickness of the Cr-Zr-N alloy coating can be 25nm-6μm, 30nm-6μm, 40nm-6μm, 50nm-6μm, 1.0μm-2.5μm, 1.0μm-2.0μm, etc. The size unit μm represents "micrometer", and "nm" represents "nanometer".

[0182] ​By controlling the thickness of the Cr-Zr-N alloy coating of the present application, the high hardness characteristics and / or corrosion resistance of the alloy protective coating can be better fully utilized. The thicker the Cr-Zr-N alloy coating, the more conducive to improving the hardness and / or corrosion resistance of the alloy coating. The Cr-Zr-N alloy coating provided by the present application can have high hardness characteristics and high corrosion resistance at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs. Compared with traditional Zr-containing alloy coatings, the Cr-Zr-N alloy coating of the present application can provide a more compact structure and achieve better high hardness characteristics and corrosion resistance at the same thickness.

[0183] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 10 nm to 6 μm.

[0184] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 25 nm to 6 μm.

[0185] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 1 μm to 2.5 μm.

[0186] In addition, when the thickness of the alloy coating is thin, the plated film product formed can also exhibit a silver-white metallic color close to the color of the substrate metal, which is conducive to achieving an aesthetic and decorative effect without changing the color of the substrate.

[0187] The Cr-Zr-N alloy coating provided by the embodiments of the present application can or can not have doping of other elements, which can be flexibly selected according to the additional functional requirements of the alloy material and / or the alloy coating. It can be understood that in the present application, when the doping elements are present, the types and amounts of the doping elements are limited so as not to affect the high hardness and corrosion resistance of the Cr-Zr-N alloy coating.

[0188] In the present application, the chemical formula of the Cr-Zr-N alloy material contained in the Cr-Zr-N alloy coating can be written as (Cr x Zr y N z )M a wherein x, y and z are each independently atomic ratios and positive numbers, M is a doping element, and a is the atomic ratio of the M element and is 0 or a positive number. During nucleation, N atoms can penetrate into the pores of large-size Cr and Zr metal grains, achieving a good pore-filling effect, making the atomic stacking of the coating more compact, and also inhibiting the growth defects of the thin film columnar crystal structure, thereby improving the corrosion resistance of the coating.

[0189] When a is 0, the Cr-Zr-N alloy material does not contain a doping element, corresponding to a Cr-Zr-N ternary alloy material. When a > 0, the Cr-Zr-N alloy material contains a doping element, wherein a / (x+y+z) is equal in value to the "relative atomic percentage of the doping element to Cr, Zr, and N", and a / (x+y+z+a) is equal in value to the "atomic percentage of the doping element in the Cr-Zr-N alloy material". The "relative atomic percentage of the doping element M to Cr, Zr, and N" refers to the ratio of the number of atoms of the doping element M to the sum of the number of atoms of Cr, Zr, and N in the material, expressed in percentage.

[0190] Unless otherwise specified, the Cr-Zr-N alloy material involved in each embodiment of the present application mainly contains Cr, Zr, and N, and further, the sum of the atomic ratios of the three elements accounts for ≥ 95% of the sum of the atomic ratios of all elements in the Cr-Zr-N alloy material (corresponding to 0≤a / (x+y+z+a)≤0.05, and further, for example, 0≤a / (x+y+z)≤0.05), and further, for example, ≥ 98% (corresponding to 0≤a / (x+y+z+a)≤0.02, and further, for example, 0≤a / (x+y+z)≤0.02), and still further, for example, a Cr-Zr-N ternary alloy material (at this time, a = 0). By limiting the content of the doping element, the influence of the doping element on the highly disordered and densely packed arrangement of atoms in the Cr-Zr-N alloy coating of the present application can be minimized, which is conducive to reducing the number of elements required for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Zr, and N to form a denser coating, and facilitating the realization of higher hardness and better corrosion resistance.

[0191] In some embodiments, a / (x+y+z) = 0. At this time, it corresponds to a Cr-Zr-N ternary alloy material, which is simple in composition and easy to prepare and manipulate. The Cr-Zr-N ternary alloy coating formed at this time can obtain a dense structure and achieve high hardness and high corrosion resistance.

[0192] In some embodiments, 0 < a / (x+y+z+a) ≤ 0.05. a / (x+y+z+a) can also be any of the following values, or less than or equal to any of the following values but greater than 0, or selected from a numerical range consisting of any two of the following values: 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, etc.

[0193] In some embodiments, 0 < a / (x+y+z) < 0.05. a / (x+y+z) can also be any of the following ratios, or less than or equal to any of the following ratios but greater than 0, or selected from a numerical interval formed by any two of the following ratios: 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, etc.

[0194] In some preferred embodiments, 0 < a / (x+y+z+a) < 0.02, further for example 0 < a / (x+y+z+a) < 0.02, 0 < a / (x+y+z+a) < 0.01, 0 < a / (x+y+z+a) < 0.01, 0 < a / (x+y+z+a) < 0.01, etc. In some embodiments, 0 < a / (x+y+z) < 0.02, further for example 0 < a / (x+y+z) < 0.02, 0 < a / (x+y+z) < 0.01, 0 < a / (x+y+z) < 0.01, 0 < a / (x+y+z) < 0.01, etc. At this time, the doping element can be controlled at a relatively low content, and the influence of the doping element on the atomic highly disordered and fully close-packed arrangement in the Cr-Zr-N alloy coating can be minimized, which is conducive to reducing the doping element or reducing the difficulty of doping, simplifying the preparation process, promoting the collaborative deposition of Cr-Zr-N to form a denser coating, and being conducive to achieving higher hardness and better corrosion resistance.

[0195] In some embodiments, the doping element is a non-metallic element, a metallic element, or a combination thereof, which can be flexibly selected according to the additional functional requirements of the Cr-Zr-N alloy coating. It can be understood that in the present application, when the doping element is contained, the type and doping amount of the doping element are limited to being able to form the Cr-Zr-N alloy coating structure of the present application and not affecting the realization of excellent high hardness and corrosion resistance.

[0196] Non-limitingly, the non-metallic element can include one or more of O, C, B, Si, and Ar. Non-limitingly, the metallic element can include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0197] It should be noted that in any of the embodiments of the context of the present application, the Cr-Zr-N alloy coating and the Cr-Zr-N alloy material provided by the present application allow the presence of unavoidable impurities introduced during the preparation process. The "unavoidable impurities" are not intentionally added impurities, and the main reason for their presence is that they are unintentionally brought in during the preparation process. Non-limiting examples of "unavoidable impurities" include C, O and other elements present in the air, which can also come from the composition of the raw materials or equipment. The atomic content of "unavoidable impurities" in the Cr-Zr-N alloy coating is usually trace or micro, which can be generally ignored, such as less than 0.01% atomic content. Taking the technical solution of "Cr-Zr-N alloy coating composed of Cr element, Zr element and N element" as an example, in theory, the Cr-Zr-N alloy coating is composed of Cr, Zr and N elements, but trace or micro amounts of other elements such as C and O may be introduced during the preparation process in addition to the three elements Cr, Zr and N.

[0198] In one aspect of the present application, a Cr-Zr-N alloy material can also be provided, which is as defined in the first aspect of the present application.

[0199] In the second aspect of the present application, a coated product is provided, which comprises a substrate 100 and a Cr-Zr-N alloy coating (such as the Cr-Zr-N alloy coating 300 shown in Figure 1) described in the first aspect of the present application; wherein the Cr-Zr-N alloy coating is located on at least one side of the substrate. The Cr-Zr-N alloy coating can exist in the protective coating of the coated product, and endow the protective coating with high hardness and excellent corrosion resistance.

[0200] The Cr-Zr-N alloy coating provided by the present application can be located on one side or both sides of the substrate.

[0201] In some embodiments, the surface material of the substrate is one of an alloy, a single-element metal and an inorganic non-metallic material. Non-limitingly, the material type of the alloy can include one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based. Non-limitingly, the single-element metal can be any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium. Non-limitingly, the inorganic non-metallic material can include one or more of ceramic and glass. Non-limitingly, the inorganic non-metallic material can include a silicon wafer.

[0202] Further, the Cr-Zr-N alloy coating provided by the present application can be applied to a variety of substrates, and the material of the substrate includes but is not limited to alloys, single-element metals and other materials, and can also be used for inorganic non-metallic materials (such as silicon wafers, ceramics, glass) and other types of substrates.

[0203] In some embodiments, the surface material of the substrate is one of light alloys; optionally, the light alloys can include one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0204] In some embodiments, the surface material of the substrate is one of light alloys; further, the light alloys can include one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0205] In some embodiments, the surface material of the substrate is one of stainless steel alloys. Further, the stainless steel alloys can be any one of austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, etc.

[0206] In some embodiments, the coated product satisfies one or more of the following characteristics:

[0207] The Cr-Zr-N alloy coating layer is in direct contact with the substrate (in which case there is no transition layer) or is provided with a transition layer, further, the transition layer can be a single-layer structure or a multi-layer structure (i.e. one or more structural layers can be formed between the Cr-Zr-N alloy coating layer provided in the present application and the substrate);

[0208] The Cr-Zr-N alloy coating layer is on the surface of the coated product or the side of the Cr-Zr-N alloy coating layer away from the substrate is further provided with a surface layer, further, the surface layer can be a single-layer structure or a multi-layer structure (i.e. one or more structural layers can be further formed on the Cr-Zr-N alloy coating layer provided in the present application).

[0209] In the present application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably, both referring to the structural layer between the substrate and the Cr-Zr-N alloy coating layer provided in the present application, which has a transition property, and can be a single-layer structure or a multi-layer structure.

[0210] In the present application, unless otherwise specified, "surface layer" and "surface film layer" have the same meaning and can be used interchangeably, both referring to the structural layer on the surface of the coated product, which is on the side of the Cr-Zr-N alloy coating layer provided in the present application away from the substrate, and can be a single-layer structure or a multi-layer structure.

[0211] In some embodiments, the Cr-Zr-N alloy coating layer 300 is in direct contact with the substrate 100 (in which case there is no transition layer).

[0212] In some embodiments, the Cr-Zr-N alloy coating layer 300 is provided with a transition layer 200 between the substrate 100.

[0213] In some embodiments, the Cr-Zr-N alloy coating layer 300 is on the surface of the coated product.

[0214] In some embodiments, the Cr-Zr-N alloy coating 300 is further provided with a surface layer 400 on the side away from the substrate 100.

[0215] Figure 1 is a schematic structural diagram of a coated article including an exemplary Cr-Zr-N alloy coating of the present application, including a substrate 100 and a Cr-Zr-N alloy coating 300.

[0216] Figure 2 is a schematic structural diagram of a coated article in several embodiments of the present application: (A) including a substrate 100, a transition layer 200 and a Cr-Zr-N alloy coating 300; (B) including a substrate 100, a transition layer 200, a Cr-Zr-N alloy coating 300 and a surface layer 400; (C) including a substrate 100, a Cr-Zr-N alloy coating 300 and a surface layer 400.

[0217] In the coated article, the position of the Cr-Zr-N alloy coating provided by the present application can be flexibly set, which can be in direct contact with the substrate, or not in direct contact with the substrate, and can be used as a surface layer, or can be located between the substrate and other surface layers as an intermediate film layer. The Cr-Zr-N alloy coating of the present application in different positions can effectively resist scratches and scratches while providing excellent corrosion resistance.

[0218] When the Cr-Zr-N alloy coating of the present application is located on the surface of the coated article (at this time, the Cr-Zr-N alloy coating of the present application is used as a surface layer of the coated article), the highly dense structure of the alloy coating can also obtain better coating reflection characteristics, and further provide the coated article with a surface having high brightness, so that the coating has both aesthetic decoration and protection. When testing the chroma value of the alloy coating, the sample to be tested uses a substrate material suitable for actual application, and the improvement degree of the density and other properties of the alloy coating on the substrate is detected. The L value, a value and b value of the sample can be tested by using a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan, the light receiving system selects F2 light source, and the average value is taken after testing 6 matrix points of each sample. Among them, the L value represents the brightness value, the a value represents the red and green chroma value, and the b value represents the yellow and blue chroma value. The larger the L value, the higher the brightness, which indicates that the surface of the coating is more dense. The mechanism is as follows: the spectrophotometer is incident light on the surface of the measured sample, forming a reflection, and a reflectivity curve can be obtained. The amplitude of the curve can reflect the density of the material, which can be characterized by the L value, and the higher the density of the same material, the larger the L value displayed.

[0219] According to the difference of the main component of the substrate, the coated product can be any one of light alloy product, stainless steel product, single-element metal, inorganic non-metallic substrate product (such as ceramic substrate product, silicon substrate product, glass substrate product) and the like, indicating that the main component of the substrate is light alloy, stainless steel, single-element metal and the like. Non-limitingly, the light alloy product can include but is not limited to aluminum alloy product, titanium alloy product, magnesium alloy product and the like. Non-limitingly, the stainless steel product can include but is not limited to austenitic stainless steel, ferritic stainless steel, martensitic stainless steel. Non-limitingly, the single-element metal product can include but is not limited to zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium, further such as copper, aluminum, iron, silver and chromium.

[0220] In the third aspect of the present application, the application of the Cr-Zr-N alloy coating described in the first aspect of the present application is provided.

[0221] The application field of the Cr-Zr-N alloy coating described in the first aspect of the present application includes but is not limited to the application field of traditional hard coating, such as but not limited to 3C digital product, automobile parts or accessories, mechanical processing, mold manufacturing, geological drilling, textile industry and aerospace product or technical field.

[0222] The examples of the hard coating and its applicable field in the third aspect of the present application can also refer to the foregoing first aspect.

[0223] In some embodiments, the application of the Cr-Zr-N alloy coating described in the first aspect of the present application as at least a part of the hard coating, or the application of the coated product described in the second aspect of the present application in the preparation of products with hard coating is provided. Further, the hard coating is also a corrosion-resistant coating. As a non-limiting example, the product with hard coating can be a structural part with high hardness requirement and easy to wear in the fields of 3C digital product, mechanical processing, mold manufacturing, geological drilling, textile industry and aerospace, tool surface and the like.

[0224] The Cr-Zr-N alloy coating provided in the present application can be used as at least a part of the hard coating, can be used as a protective coating of a single structure layer, can be used as a layer in a multi-layer structure protective coating, and can be used as a surface film layer, an intermediate film layer or a bottom film layer of the hard coating. The foregoing coated product can be an intermediate product or a final product, which can be further prepared into various products with hard coating. The hard coating not only has high hardness characteristics, but also can provide excellent corrosion resistance as a corrosion-resistant coating.

[0225] Among them, the final product can be directly used or sold. The intermediate product can be further processed or assembled with other elements into a new product.

[0226] In some embodiments, the protective duration in salt spray corrosion test can be ≥ 24 hours, i.e. the Cr-Zr-N alloy coating can pass the 24-hour test, and most of the embodiments can pass the 48-hour test, for example, when the Cr-Zr-N alloy coating is formed on the surface of an aluminum alloy substrate. The ASTM B117 salt spray test method can be used, and reference can be made to the example section below. The protective duration in salt spray corrosion test of conventional hard coatings is generally difficult to reach 8 hours under the same test conditions.

[0227] When the Cr-Zr-N alloy coating is used for protection, it can also provide better hardness and corrosion resistance than conventional protective layers under the same thickness, so that high hardness characteristics and excellent corrosion resistance can be achieved under a thinner thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing the cost.

[0228] In a fourth aspect of the present application, a method for preparing the Cr-Zr-N alloy coating includes the following steps: using a gas deposition technique to deposit the constituent elements of the Cr-Zr-N alloy coating on at least a part of the surface of the substrate according to a preset atomic ratio, to form the Cr-Zr-N alloy coating described in the first aspect of the present application.

[0229] The method for preparing the Cr-Zr-N alloy coating provided by the present application is simple, easy to operate, green and environmentally friendly, and has the advantages of quantification, high efficiency, and good repeatability, and is suitable for industrial application.

[0230] The definition of the substrate can be involved in the second aspect of the present application.

[0231] In some embodiments, the gas deposition technique is a physical vapor deposition technique. Further, the physical vapor deposition technique can be realized by one or more of the following methods: vacuum evaporation, sputtering, arc plasma plating, ion plating, and molecular beam epitaxy.

[0232] In one embodiment, the physical vapor deposition method is magnetron sputtering plating.

[0233] In some embodiments, the constituent elements of the Cr-Zr-N alloy coating are deposited on at least a part of the surface of the substrate according to a preset atomic ratio by using a sputtering plating (such as magnetron sputtering plating) technique.

[0234] The device shown in FIG. 3 includes a vacuum chamber 1, a sample stage 2, a direct current anode 3, a chromium target 4, and a zirconium target 5. The chromium target 4 is a chromium target for radio frequency assisted direct current cathode electric conduction, and the zirconium target 5 is a zirconium target for radio frequency assisted direct current cathode electric conduction. The drawing is not drawn in a 1:1 ratio, and the relative sizes of the elements are only drawn in the drawing by way of example for the purpose of understanding the present application, but are not necessarily drawn in true proportion, and the proportion in the drawing does not constitute a limitation on the present application. The Cr-Zr-N alloy coating of the present application can be formed by forming a reactive sputtering with a N2-containing gas (such as Ar / N2mixed gas) in the vacuum chamber 1.

[0235] In some embodiments, the method for preparing the Cr-Zr-N alloy coating includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen-containing gas, using one or more targets including chromium and zirconium to sputter deposit the constituent elements of the Cr-Zr-N alloy coating on at least a part of the surface of the substrate to form the Cr-Zr-N alloy coating. The nitrogen-containing gas can be, but is not limited to, nitrogen, and in this case, the gas ratio of argon to nitrogen in the mixed gas can be (2-6):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, etc. Selecting nitrogen as the nitrogen-containing gas and controlling the content of nitrogen can further adjust the performance of the Cr-Zr-N alloy coating of the present application.

[0236] The target material can include one or more of a chromium target, a zirconium target, and an alloy target. The alloy target includes at least two metal elements in the Cr-Zr-N alloy coating. The atomic ratio of the metal elements in the alloy target can be the same as or close to the atomic ratio of the corresponding metal elements in the Cr-Zr-N alloy coating. In some embodiments, the alloy target is a chromium-zirconium-based alloy target, which at least includes chromium and zirconium, such as a CrZr alloy target, a CrZrN alloy target, etc. In some examples, the atomic ratio of Cr and Zr in the chromium-zirconium-based alloy target (such as the CrZr alloy target) is 65%:35%. In some examples, the atomic ratio of Cr and Zr in the chromium-zirconium-based alloy target (such as the CrZr alloy target) is 55%:45%. In some embodiments, the alloy target includes all the metal elements in the Cr-Zr-N alloy coating. Examples of the alloy target can be found in Example 2 and Example 11 below.

[0237] In the present application, unless otherwise specified, the "chromium-zirconium-based alloy target" at least includes chromium and zirconium, and can or can not include other elements. When including other elements, it can be understood that the chemical composition in the target material should generally be within the range of the preset chemical formula (Cr x Zr y N z )M a For example, the chromium-zirconium-based alloy target can be a chromium-zirconium-nitrogen alloy target (i.e., a CrZrN alloy target) composed of chromium, zirconium, and nitrogen.

[0238] In some embodiments, a Cr-Zr alloy target can be used to replace the Cr target 4 in FIG. 3, and installed at the position of the original Cr target 4 in FIG. 3.

[0239] In some embodiments, the method for preparing the Cr-Zr-N alloy coating layer by sputtering deposition (e.g., magnetron sputtering deposition) includes the following steps: under the condition of introducing a mixed gas containing argon and a nitrogen-containing gas, using a Cr target and a Zr target or using a Cr-Zr alloy target (i.e., a CrZr alloy target), sputtering and depositing the constituent elements of the Cr-Zr-N alloy coating layer on at least a portion of the surface of the substrate to form the Cr-Zr-N alloy coating layer.

[0240] In some embodiments, the method for preparing the Cr-Zr-N alloy coating layer by sputtering deposition (e.g., magnetron sputtering deposition) includes the following steps: under the condition of introducing a mixed gas containing argon and a nitrogen-containing gas, using a Cr target and a Zr target or using a Cr-Zr alloy target (i.e., a CrZr alloy target), sputtering and depositing the constituent elements of the Cr-Zr-N alloy coating layer on at least a portion of the surface of the substrate to form the Cr-Zr-N alloy coating layer.

[0241] In some embodiments, the cleaning process for the substrate includes the following steps: placing the substrate in water for ultrasonic cleaning for 10 minutes to 15 minutes, vacuum drying the cleaned substrate for 15 minutes to 20 minutes, and placing the dried substrate on a sample stage of a sputtering deposition device (e.g., a magnetron sputtering deposition device). The sample stage can be a rotatable sample stage.

[0242] In one embodiment, the cleaning process for the substrate includes the following steps: placing the substrate in deionized water (DI water) for ultrasonic cleaning for 10 minutes to 15 minutes, placing the cleaned substrate in a vacuum oven for baking for 15 minutes to 20 minutes, and placing the baked substrate on a rotatable sample stage in a vacuum chamber.

[0243] In some embodiments, after the step of cleaning the substrate, before the step of sputtering and depositing the constituent elements of the Cr-Zr-N alloy coating layer on at least a portion of the surface of the substrate, a transition layer is formed on at least a portion of the surface of the cleaned substrate, for example, by depositing the constituent elements of the transition layer on at least a portion of the surface of the cleaned substrate.

[0244] In some embodiments, after forming the Cr-Zr-N alloy coating layer of the present application on one side of the substrate, a surface layer can be further deposited and formed. The surface layer can be a single-layer structure or a multi-layer structure.

[0245] In some embodiments, the sputtering deposition temperature is 30°C to 330°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 150°C, 200°C, 250°C, 300°C, 330°C, etc.

[0246] In some embodiments, the total pressure of the mixture containing argon and nitrogen is 0.3 Pa to 1.2 Pa; for example, 0.3 Pa, 0.5 Pa, 0.8 Pa, 1 Pa, 1.2 Pa, etc. The pressure unit Pa refers to "Pascal".

[0247] In some embodiments, sputtering is performed using radio frequency assisted DC sputtering. Compared to other preparation methods, this can further improve the performance of the alloy coating formed by sputtering deposition.

[0248] In some embodiments, the target material includes a chromium target with a power density of 1.3 W / cm². 2 ~6.7W / cm 2 Unit: W / cm² 2 It refers to "tiles per square centimeter".

[0249] In some embodiments, the target material includes a zirconium target with a power density of 0.8 W / cm². 2 ~7.9W / cm 2 .

[0250] In some embodiments, the target material includes a chromium target and a zirconium target, with the chromium target having a power density of 1.3 W / cm². 2 ~6.7W / cm 2 Furthermore, the power density of the zirconium target is 0.8 W / cm². 2 ~7.9W / cm 2 .

[0251] In some embodiments, the target material includes a chromium-zirconium-based alloy target with a power density of 4 W / cm². 2 ~6W / cm 2 .

[0252] In some implementations, the substrate bias voltage is -150V to -20V; for example, -150V, -120V, -100V, -90V, -80V, -60V, -50V, -40V, -30V, -20V, etc. The unit V refers to "volt".

[0253] In some embodiments, the flow rate of the nitrogen-containing gas can be 8-52 sccm, such as 8 sccm, 10 sccm, 20 sccm, 25 sccm, 30 sccm, 40 sccm, 50 sccm, 52 sccm, etc. Further, the nitrogen-containing gas is nitrogen. The unit sccm (standard cubic centimeter per minute) is a flow rate unit used to characterize the flow rate of a gas.

[0254] In some embodiments, the sputtering deposition time is 10-150 min, such as 10 min, 15 min, 30 min, 45 min, 60 min, 90 min, 100 min, 120 min, etc. The thickness of the Cr-Zr-N alloy coating of the present application can be regulated by adjusting the deposition time, and the longer the deposition time, the greater the thickness of the Cr-Zr-N alloy coating.

[0255] In some embodiments, the base vacuum of the vacuum chamber used is ≤ 5.0 x 10 -4 Pa. This pressure setting can ensure the collision of sputtering particles with gas molecules, while also reducing the entry of impurities in the gas molecules during deposition, thereby improving the corrosion resistance, purity, and adhesion of the Cr-Zr-N alloy coating of the present application.

[0256] It can be understood that the argon and nitrogen-containing gas can be introduced into the vacuum chamber through a single path or mixed through a mixing cylinder before entering the chamber, thereby reducing the impurity content of the Cr-Zr-N alloy coating of the present application and improving its performance.

[0257] In some embodiments, "loading the constituent elements of the Cr-Zr-N alloy coating on at least a portion of the surface of the substrate in a predetermined atomic ratio by using a sputtering coating (such as a magnetron sputtering coating) technique" includes the following steps: 1. introducing a mixed gas containing argon and a nitrogen-containing gas into the vacuum chamber, maintaining the pressure in the vacuum chamber 1 at 0.3-1.2 Pa (such as 0.5-0.8 Pa), turning on the bias voltage, setting it to -150 V to -20 V, setting the power density of the chromium target 4 to 1.3-6.7 W / cm 2 , 2 , setting the power density of the zirconium target 5 to 0.8-7.9 W / cm 2 , 2 , and depositing a Cr-Zr-N alloy coating on at least a portion of the surface of the substrate after cleaning treatment; further, the Cr-Zr-N alloy coating with different film thicknesses can be prepared by controlling the film formation time.

[0258] In the fifth aspect of the present application, a Cr-Zr-N alloy material is provided, which can be defined as in the first aspect of the present application, and can also be the Cr-Zr-N alloy material in any of the embodiments described in the context. As mentioned above, the Cr-Zr-N alloy material has a suitable atomic size mismatch degree and a special atomic ratio, and can be "highly disordered and fully dense" with a high degree of random mixing, thereby forming the Cr-Zr-N alloy coating of the present application.

[0259] In some embodiments, the Cr-Zr-N alloy material satisfies the following two characteristics:

[0260] The X-ray diffraction pattern of the Cr-Zr-N alloy material has a peak in the range of diffraction angle 2θ(°) of 30°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 30°-50° satisfies ≥2°;

[0261] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material, there is a diffraction peak in the range of , and the half-height width of at least one diffraction peak in the range of

[0262] Further, the XRD test results and the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material can also refer to the description of the X-ray diffraction pattern and the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating in the present application, and the corresponding optional and preferred modes can also be applicable to the Cr-Zr-N alloy material.

[0263] Some embodiments are provided below.

[0264] The embodiments of the present application will be described in detail below with reference to the examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods not specified in the following examples are preferably referred to the guidelines given in the present application, and can also be carried out according to the experimental manuals or conventional conditions in the art, or according to the conditions suggested by the manufacturers, or according to the known experimental methods in the art.

[0265] In the following examples, the measurement parameters of the raw material components may, without specific instructions, have slight deviations within the weighing accuracy range. The temperature and time parameters allow for acceptable deviations caused by instrument testing accuracy or operation accuracy.

[0266] Test methods:

[0267] 1. Hardness test of alloy coating

[0268] When testing the hardness of the alloy coating, the sample to be tested uses a substrate that is suitable for practical application,

[0269] The surface material of the "substrate suitable for practical application" can include but is not limited to: aluminum alloy, stainless steel, copper sheet.

[0270] In the following examples, unless otherwise specified, when testing the hardness of the alloy coating, the aluminum alloy and stainless steel are used as the substrate, and the alloy coating is deposited on the aluminum alloy and stainless steel using the preset preparation parameters to obtain the sample to be tested for testing the hardness of the alloy coating. This is mainly because during the nanoindentation test, the probe penetrates the sample to be tested, forming a strong pressure, at which time the substrate is required to have a certain toughness. If a brittle silicon wafer is used, cracking may occur during the test, resulting in inaccurate test results. Alloy materials have excellent toughness and are more suitable as the tested substrate for nanoindentation testing. At the same time, using alloy materials as the substrate to measure nano-hardness is more universal in the field of nano-hardness parameter characterization in the coated field.

[0271] The hardness of each film or coating is tested using a nanoindenter model NHT3 produced by Anton-Paar of Austria, which is configured with a tetrahedral Berkvich indenter, with a penetration depth of 100 nm, and the load changes with the penetration depth. After testing 5 matrix points for each sample, the average value is taken.

[0272] 2. Salt spray corrosion resistance test of alloy coating

[0273] When testing the salt spray corrosion resistance of the alloy coating, the sample to be tested uses a substrate that is suitable for practical application, and the improvement of the corrosion resistance of the alloy coating on the substrate is detected. The surface material of the "substrate suitable for practical application" can include but is not limited to: aluminum alloy, stainless steel.

[0274] The ASTM B117 salt spray test standard is used, with a solution pH value of 6.5-7.2, and a solution chemical composition of sodium chloride (NaCl), deionized water, and sodium hydroxide (NaOH).

[0275] A 12-hour period can be used as a sub-period for the salt spray corrosion resistance test.

[0276] The test period of the alloy coating prepared on substrates of different materials can be different, for example:

[0277] The test period of the sample with an aluminum alloy substrate is 48h or 24h;

[0278] The test period of the sample with a stainless steel substrate is 144h or 96h;

[0279] The test period of the sample with a copper sheet substrate is 12h.

[0280] The standard for passing (OK) the salt spray corrosion resistance test is that after the sample is tested, the appearance is free of corrosion, discoloration, and rust.

[0281] The standard for failing (NG) the salt spray corrosion resistance test is that after the sample is tested, the appearance is corroded, discolored, or rusted.

[0282] 3. Morphology and composition test analysis of alloy coating

[0283] The sample to be tested is a silicon wafer as a substrate.

[0284] The test method of scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX) is used

[0285] Morphology analysis: a scanning electron microscope of Regulus 8230 produced by Hitachi Company is used.

[0286] Composition analysis: an X-ray energy dispersive spectrometer (EDX) attached to the scanning electron microscope of Regulus 8230 produced by Hitachi Company is used, and the relative intensity of all elements is corrected by ZAF method.

[0287] Test parameters: the acceleration voltage of the electron is 15 kilovolts (kV), the beam current is 10 microamperes (μA), the magnification of the sample is 200 times, and 10 points of each sample are tested and averaged.

[0288] 4. X-ray diffraction (XRD) test of alloy coating

[0289] When the XRD test of the alloy coating is performed, a silicon wafer is used as a substrate.

[0290] 4.1. Calculation of half-height width value of diffraction peak in XRD spectrum

[0291] A German Bruker D8 Advance XRD diffractometer is used, in θ-2θ mode, using Cu target Kα ray, wavelength λ is 0.15406 nanometers (nm), X-ray tube is controlled at 40 kilovolts (kV) and 40 milliamperes (mA), scanning range is 20°-80°, and precise scanning measurement is performed with a step of 0.01°.

[0292] The steps for obtaining the half-height width value are: first, the diffraction peak is corrected, including: smoothing, background subtraction, removal of Kα2 line, and subtraction of instrument broadening, etc., and after the diffraction peak is fitted with Pseudo-Voigt function, the half-height width value of the diffraction peak is obtained.

[0293] The EDP2XRD software (version 1.0.0, copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) was used to process the pattern data: first, the ruler correction was performed, then the center of the diffraction ring transmission spot was determined, and then the XRD pattern was converted (wherein the electron wavelength was 0.00251 nanometer, and the X-ray wavelength was 0.154 nanometer; after the diffraction peak was subtracted from the straight line background and then fitted by the Voigt function, the half-height width value of the corresponding diffraction peak was obtained.

[0294] 4.2. Determine whether the XRD pattern of the alloy coating forms a broad peak

[0295] The method for determining whether there is a broad peak in the XRD diffraction pattern in the diffraction angle 2θ(°) range of 30°-50°: in the XRD pattern, if the half-height width value of the 2θ(°) diffraction peak is ≥2°, it is determined to be a broad peak; if the half-height width value of the 2θ(°) diffraction peak is <2°, it is determined to be a sharp peak.

[0296] For a specified 2θ(°) position, it can be any one of the three states of no peak, sharp peak or broad peak.

[0297] 5. TEM test

[0298] When performing the TEM test of the alloy coating, a silicon wafer was used as the substrate.

[0299] 5.1. The half-height width data in the diffraction ring of the TEM diffraction pattern were obtained by the following method:

[0300] TEM sample preparation: a Helios 5CX model focused ion beam (FIB) of Thermo Fisher Corporation was used to thin the sample to obtain an electron-transparent, TEM-observable planar sample.

[0301] SAED image acquisition: a Talos F200x model transmission electron microscope (TEM) of Thermo Fisher Corporation was used to obtain the selected area electron diffraction pattern (SAED) of the sample, with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0302] Radial intensity profile acquisition: The SAED pattern data obtained above was processed using EDP2XRD software (version 1.0.0, copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney). First, the scale was corrected, then the center of the diffraction ring transmission spot was determined, and finally converted into a radial intensity profile (with an electron wavelength of 0.00251 nm and an X-ray wavelength of 0.154 nm), with the characteristic atomic spacing as the horizontal coordinate and the diffraction intensity as the vertical coordinate.

[0303] The step of obtaining the half-height width value is as follows: after the diffraction peak is subtracted from the straight line background and then fitted with a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0304] 5.2. Method for determining whether the radial intensity profile of the TEM selected area electron diffraction pattern has a wide peak in the range of 0.1-0.2 nm: If the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is greater than 0.2 nm, it is determined to be a wide peak; if the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is less than 0.1 nm, it is determined to be a sharp peak. For a specific characteristic atomic spacing, it can be any one of the three states of no peak, sharp peak or wide peak.

[0305] 6. Colorimetric value test of alloy coating

[0306] When testing the colorimetric value of the alloy coating, the sample to be tested uses a substrate suitable for actual application to detect the improvement degree of the compactness and other properties of the alloy coating on the substrate. The surface material of the "substrate suitable for actual application" can include but is not limited to: aluminum alloy, stainless steel.

[0307] The L value, a value and b value of the sample were tested by a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan, with F2 light source selected for the light receiving system, and the average value was taken after testing 6 matrix points for each sample.

[0308] Among them, the L value represents the brightness value, the a value represents the red or green chroma value, and the b value represents the yellow or blue chroma value. The a value represents the red-green color of the object, with a positive value indicating a red chroma value and a negative value indicating a green chroma value. The b value represents the yellow-blue color of the object, with a positive value indicating a yellow chroma value and a negative value indicating a blue chroma value.

[0309] ​​The greater the L value, the higher the brightness, and the more compact the coating surface. The mechanism is as follows: the spectrophotometer is incident light on the surface of the measured sample, forming a reflectivity curve, the amplitude of which can reflect the density of the material, which can be characterized by the L value, and the higher the compactness of the same material, the greater the L value.

[0310] In the following examples, DI water refers to deionized water.

[0311] The stainless steel sheets, aluminum alloy sheets and silicon sheets in each of the following examples and comparative examples have the same material, respectively.

[0312] In the following examples, the target material is sputtered by a radio frequency assisted direct current sputtering method.

[0313] In the following examples, in the XRD pattern and the SAED-radial intensity profile, "only one wide peak" refers to only one characteristic peak, and the peak is a wide peak, unless otherwise specified.

[0314] Example 1.

[0315] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr 53.8 Zr 40.0 N 6.2 .

[0316] Pre-treatment: the stainless steel sheets, aluminum alloy sheets and silicon sheets with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes (min), dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes. The size unit mm refers to "millimeter", and cm refers to "centimeter".

[0317] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by using plasma etching.

[0318] Deposition of Cr-Zr-N alloy coating: the sample stage turntable was turned on and the rotation speed was set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 8 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the furnace pressure was kept at 0.7 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 4.2 W / cm 2 , and the power density of the Zr target was set to 3.5 W / cm 2, and a Cr-Zr-N alloy coating was deposited, with the film thickness being controlled to be 2500 nm by controlling the film forming time.

[0319] The samples with stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance test, hardness test and color value test, and the samples with silicon sheets as substrates were subjected to SEM and composition analysis, XRD analysis and TEM test.

[0320] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 53.8 Zr 40.0 N 6.2 .

[0321] The hardness value of the aluminum alloy substrate sample was 16.1 GPa, and the hardness value of the stainless steel substrate sample was 18.3 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protection properties.

[0322] The cross-sectional SEM characterization of the test sample can be seen from FIG. 4, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 5. The SEM test results show that the Cr-Zr-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 30°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 30°-50° of the XRD diffraction pattern is all ≥2°, wherein there is only one wide peak with a half-height width of 8.42° in the range of 30°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0323] The color value test results are as follows: the color value of the aluminum alloy substrate sample is L: 77.02, a: 0.52, b: 4.99; the color value of the stainless steel substrate sample is L: 79.36, a: 0.40, b: 4.49, which is silver white in color.

[0324] Example 2.

[0325] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating is Cr 34.5 Zr 30.0 N 35.5 , and the preparation method is as follows:

[0326] In this embodiment, the target material is a chromium-zirconium alloy target, and the original chromium target 4 in FIG. 3 is replaced with a CrZr alloy target with an atomic percentage ratio of 55%:45%.

[0327] Pre-treatment: stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, and kept for 15 minutes at room temperature (about 30°C).

[0328] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0329] Deposition of Cr-Zr-N alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the CrZr alloy target was powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set to 42 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.8 Pa, the bias voltage was turned on and set to -100 V, and the power density of the CrZr alloy target was set to 5.0 W / cm 2 , and the Cr-Zr-N alloy coating was deposited by controlling the film formation time to make the obtained film thickness 2000 nm.

[0330] The stainless steel sheet and aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance test, hardness test and color value test were performed, and the silicon sheet was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed.

[0331] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 34.5 Zr 30.0 N 35.5 .

[0332] The hardness value of the aluminum alloy substrate sample was 21.7 GPa, and the hardness value of the stainless steel substrate sample was 22.1 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, and has excellent protection properties.

[0333] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 6, and the XRD diffraction pattern, TEM- SAED pattern and radial intensity profile can be seen in Figure 7. The SEM test results show that the Cr-Zr-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 30°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 30°-50° of the XRD diffraction pattern is all ≥2°, and there is only one wide peak with a half-height width of 3.52° in the range of 30°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0334] The chroma value test results: the test chroma value of the aluminum alloy substrate sample is L: 74.20, a: 0.55, b: 7.68; the test chroma value of the stainless steel substrate sample is L: 77.26, a: 0.42, b: 7.11, which is silver white in color.

[0335] Example 3.

[0336] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating is Cr 15.0 Zr 78.8 N 6.2 , and the preparation method is as follows:

[0337] Pre-treatment: the stainless steel sheet, aluminum alloy sheet and silicon sheet samples with an aspect ratio of 50mmx50mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, and heated to 150°C for 15 minutes.

[0338] Plasma cleaning: Ar gas was introduced, the furnace pressure was maintained at 2.0 Pa, the bias voltage was turned on and set to -800V, and plasma cleaning was performed for 20 minutes, the purpose of which was to remove small impurities on the surface of the sample by plasma etching.

[0339] Deposition of Cr-Zr-N alloy coating: the sample stage turntable was turned on and the rotation speed was set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power source, Ar and N2 gas was introduced, the N2 gas flow was set to 8sccm, the gas flow ratio of Ar:N2 was maintained at 6:1, the furnace pressure was maintained at 0.7 Pa, the bias voltage was turned on and set to -100V, the power density of the Cr target was set to 1.3W / cm 2 , and the power density of the Zr target was set to 7.9W / cm 2, and a Cr-Zr-N alloy coating was deposited. By controlling the film forming time, the thickness of the obtained film was 2500 nm.

[0340] The salt spray corrosion resistance test, hardness test and color value test were performed on the samples with stainless steel sheet and aluminum alloy sheet as the substrate, and the SEM and composition analysis, XRD analysis and TEM test were performed on the samples with silicon sheet as the substrate.

[0341] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 15.0 Zr 78.8 N 6.2 .

[0342] The hardness value of the aluminum alloy substrate sample was 20.6 GPa, and the hardness value of the stainless steel substrate sample was 22.8 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample could pass the 48 h test, and the stainless steel substrate sample could pass the 144 h test, which had excellent protection properties.

[0343] The SEM cross-section characterization of the test sample was performed, and the SEM graph of the cross-section morphology, TEM-SAED graph and radial intensity profile graph can be referred to FIG. 8. The SEM test results showed that the Cr-Zr-N alloy coating structure was dense, and no penetrating column seam was observed; the XRD test results showed that the XRD diffraction graph had a wide peak in the range of 30°-50° of the diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 30°-50° of the XRD diffraction graph was all ≥2°, wherein there was only one wide peak with a half-height width of 3.92° in the range of 30°-50°; the radial intensity profile graph of the TEM selected area electron diffraction pattern had only one wide peak in the range of , and the half-height width value was

[0344] The color value test results: the color value of the aluminum alloy substrate sample was L: 74.29, a: 0.53, b: 6.38; the color value of the stainless steel substrate sample was L: 75.65, a: 0.47, b: 6.31, which was bright silver white color.

[0345] Example 4.

[0346] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating was Cr 15.0 Zr 49.5 N 35.5 , and the preparation method was as follows:

[0347] Pre-treatment: the stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were respectively placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating film machine, and the vacuum chamber was vacuumed to 5 x 10 -4Pa, heated to 150℃, and kept for 15 minutes;

[0348] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0349] Deposition of Cr-Zr-N alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 42 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.8 Pa, the bias voltage was turned on and set at -100 V, and the power density of the Cr target was set at 1.3 W / cm 2 , the power density of the Zr target was set at 5 W / cm 2 , and the Cr-Zr-N alloy coating was deposited by controlling the film formation time, and the obtained film thickness was 2200 nm.

[0350] The stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and the salt spray corrosion resistance test, the hardness test and the color value test were performed, and the silicon wafer was used as the substrate of the sample, and the SEM and composition analysis, XRD analysis and TEM test were performed.

[0351] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 15.0 Zr 49.5 N 35.5 .

[0352] The hardness value of the aluminum alloy substrate sample was 21.2 GPa, and the hardness value of the stainless steel substrate sample was 22.6 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample could pass the 48 h test, and the stainless steel substrate sample could pass the 144 h test, and had excellent protection properties.

[0353] The cross-sectional SEM characterization of the test sample was performed, the cross-sectional morphology could be referred to FIG. 9, and the XRD diffraction pattern, the TEM-SAED pattern and the radial intensity profile could be referred to FIG. 10. The SEM test results showed that the Cr-Zr-N alloy coating structure was dense, and no penetrating column seam was observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of 30°-50° of the diffraction angle 2θ(°), and the half-height width value of the 2θ(°) diffraction angle in the range of 30°-50° of the XRD diffraction pattern was all ≥2°, and there was only one wide peak with a half-height width of 2.23° in the range of 30°-50°; there was only one wide peak in the radial intensity profile of the TEM selected area electron diffraction pattern in the range of , and the half-height width value was

[0354] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 75.25, a: 0.52, and b: 6.48; the colorimetric value of the stainless steel substrate sample is L: 76.95, a: 0.41, and b: 6.04, which is bright silver white.

[0355] Example 5.

[0356] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating is Cr 29.7 Zr 50.1 N 20.2 , and the preparation method is as follows:

[0357] Pre-treatment: the stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm are respectively placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0358] Plasma cleaning: Ar gas is introduced, the pressure in the furnace body is kept at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes, which aims to remove small impurities on the surface of the sample by plasma etching.

[0359] Deposition of Cr-Zr-N alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Zr target are powered by a radio frequency assisted direct current power source, Ar and N2 gases are introduced, the N2 gas flow is set to 24 sccm, the gas flow ratio of Ar:N2 is kept at 3:1, the pressure in the furnace body is kept at 0.6 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 2.6 W / cm 2 , the power density of the Zr target is set to 5 W / cm 2 , the Cr-Zr-N alloy coating is deposited, and the film thickness is controlled to be 2500 nm.

[0360] The stainless steel sheet and the aluminum alloy sheet are used as the substrate of the sample, and the salt spray corrosion resistance test, hardness test and colorimetric value test are performed, and the silicon sheet is used as the substrate of the sample, and the SEM and composition analysis, XRD analysis and TEM test are performed.

[0361] According to the composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 29.7 Zr 50.1 N 20.2 .

[0362] The hardness value of the aluminum alloy substrate sample was 19.5 GPa, and the hardness value of the stainless steel substrate sample was 21.7 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, having excellent protection properties.

[0363] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in FIG. 11, and the XRD diffraction pattern can be seen in FIG. 12. The SEM test results show that the Cr-Zr-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that in the XRD diffraction pattern, the diffraction angle 2θ(°) in the range of 30°-50° is a wide peak, that is, the half-height width value of the diffraction angle 2θ(°) in the range of 30°-50° in the XRD diffraction pattern is all ≥2°, and there is only one wide peak with a half-height width of 5.66° in the range of 30°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has at least one wide peak in the range of 30°-50°.

[0364] Colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample was L: 76.13, a: 0.52, b: 5.88; the colorimetric value of the stainless steel substrate sample was L: 78.01, a: 0.42, b: 5.07, showing a bright silver-white color.

[0365] Example 6.

[0366] In this example, the substrate surface is attached with a double-layer thin film structure, including a Cr-Zr-N alloy coating with chemical composition of Cr 15.0 Zr 78.8 N 6.2 and a surface layer with chemical composition of TiN, which is denoted as Cr-Zr-N / TiN. At this time, the substrate surface is attached with a multi-layer thin film structure, wherein the Cr-Zr-N alloy coating provided by the present application serves as an intermediate layer therebetween, located between the substrate and the surface layer. The preparation method is as follows:

[0367] Pre-treatment: the stainless steel sheet, aluminum alloy sheet and silicon sheet samples with an aspect ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0368] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, the purpose of which was to remove small impurities on the surface of the sample by plasma etching.

[0369] ​Deposition of the Cr-Zr-N alloy coating of this application: The sample stage rotation was turned on, the rotation speed was set to 6 revolutions per minute, and the distance between the sample stage and the target surface was adjusted to 8 cm. The Cr and Zr targets were powered by an RF-assisted DC power supply. Ar and N2 gases were introduced, with the N2 gas flow rate set to 8 sccm. The gas volume was set to maintain an Ar:N2 gas ratio of 6:1, and the furnace pressure was maintained at 0.7 Pa. The bias voltage was turned on and set to -100 V. The power density of the Cr target was set to 1.3 W / cm². 2 The power density of the Zr target was set to 7.9 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0370] Surface deposition: Replace the Zr target in the furnace with a Ti target, turn on the sample stage rotation rack, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Ti target with a DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 10 sccm, maintain the Ar:N2 gas ratio at 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5 W / cm³. 2 A TiN coating was deposited, and by controlling the film deposition time, a film thickness of 100 nm was obtained.

[0371] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0372] Component analysis revealed that the component was Cr. 15.0 Zr 78.8 N 6.2 The alloy coating surface is coated with a TiN coating (as a surface layer).

[0373] The hardness value of the aluminum alloy substrate sample was 12.2 GPa, and the hardness value of the stainless steel substrate sample was 14.5 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample passed the test for 48 hours, and the stainless steel substrate sample passed the test for 144 hours, demonstrating excellent protective properties.

[0374] The test sample underwent SEM cross-sectional testing. The SEM results showed that the Cr-Zr-N alloy coating had a dense structure.

[0375] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 55.75, a: 6.65, b: 12.92, and the colorimetric values ​​of the stainless steel substrate sample are L: 56.23, a: 6.82, b: 13.21, exhibiting a golden yellow color.

[0376] Example 7.

[0377] In this example, the substrate surface is attached with a three-layer film structure, which includes a transition layer (as a bottom coating layer), a Cr-Zr-N alloy coating layer containing Cr-Zr-N alloy material, and a surface layer on the surface in sequence from the substrate surface, and the three-layer film structure is denoted as Cr / Cr-Zr-N / TiN, wherein the transition layer is a Cr layer, the chemical composition of the Cr-Zr-N alloy coating layer is Cr 15.0 Zr 78.8 N 6.2 , and the chemical composition of the surface layer is TiN. The preparation method is as follows:

[0378] Pre-treatment: the stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm are respectively placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating film machine, the vacuum chamber is vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0379] Plasma cleaning: Ar gas is introduced, the pressure in the furnace body is kept at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0380] Deposition of bottom coating layer (transition layer): the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target is powered by a radio frequency assisted direct current power supply, Ar gas is introduced, the Ar gas flow is set to 42 sccm, the pressure in the furnace body is kept at 0.5 Pa, the bias voltage is turned on and set to -100 V, and the power density of the Cr target is set to 5 W / cm 2 , the Cr bottom coating layer is deposited, and the film thickness is 300 nm by controlling the film forming time.

[0381] Deposition of Cr-Zr-N alloy coating layer (middle coating layer) of the application: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Zr target are powered by a radio frequency assisted direct current power supply, Ar and N2 gases are introduced, the N2 gas flow is set to 8 sccm, the gas flow ratio of Ar:N2 is set to 6:1, the pressure in the furnace body is kept at 0.7 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 1.3 W / cm 2 , the power density of the Zr target is set to 7.9 W / cm 2 , the Cr-Zr-N alloy coating layer is deposited, and the film thickness is 1000 nm by controlling the film forming time.

[0382] Deposition of surface layer: replace the Zr target in the furnace with a Ti target, turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use a direct current power supply to supply electricity to the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 10 sccm, set the gas flow ratio to maintain an Ar:N2 gas flow ratio of 3:1, maintain the pressure in the furnace at 0.5 Pa, turn on the bias voltage and set it to -100 V, and set the power density of the Ti target to 5 W / cm2. 2 Deposition of TiN coating, by controlling the film formation time, the obtained film thickness is 100 nm.

[0383] Use stainless steel sheet, aluminum alloy sheet as the substrate of the sample, carry out salt spray corrosion resistance test, hardness test and color value test, use silicon wafer as the substrate of the sample, carry out SEM and composition analysis, XRD analysis and TEM test.

[0384] Through composition analysis, there are three layers of thin film structure on the surface of the substrate, and the chemical composition components are Cr (transition layer), Cr 15.0 Zr 78.8 N 6.2 (Cr-Zr-N alloy coating of the present application) and TiN (surface layer), and the three-layer thin film structure is Cr / Cr-Zr-N / TiN.

[0385] The hardness value of the aluminum alloy substrate sample is 13.8 GPa, and the hardness value of the stainless steel substrate sample is 15.4 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protection characteristics.

[0386] SEM cross-section test is carried out on the test sample. The SEM test results show that the Cr-Zr-N alloy coating structure is dense.

[0387] Color value test results: the color value of the aluminum alloy substrate sample is L: 53.49, a: 7.07, b: 13.81, and the color value of the stainless steel substrate sample is L: 55.73, a: 7.35, b: 14.50, which presents golden yellow color.

[0388] Example 8.

[0389] In this example, the chemical composition components of the Cr-Zr-N alloy coating are Cr 15.0 Zr 78.8 N 6.2 , and the preparation method is as follows:

[0390] Pre-treatment: place the copper sheet and silicon wafer samples with a length-width ratio of 50 mm x 50 mm into DI water for ultrasonic cleaning for 15 minutes, dry them in an oven, and then place them in the vacuum chamber of the plating machine, vacuum the vacuum chamber to 5 x 10-4 Pa, heated to 150°C, and kept for 15 minutes.

[0391] Plasma cleaning: Ar gas was introduced to keep the pressure in the furnace at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 minutes to remove small impurities on the surface of the sample by plasma etching.

[0392] Deposition of the Cr-Zr-N alloy coating according to the present application: the sample stage turntable was turned on and set at a rotation speed of 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 8 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the pressure in the furnace was kept at 0.7 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 1.3 W / cm 2 , the power density of the Zr target was set at 7.9 W / cm 2 , and the Cr-Zr-N alloy coating was deposited by controlling the film deposition time to obtain a film thickness of 1000 nm.

[0393] The copper sheet was used as the substrate of the sample for salt spray corrosion resistance test, hardness test and colorimetric value test, and the silicon wafer was used as the substrate of the sample for SEM and composition analysis, XRD analysis and TEM test.

[0394] According to the composition analysis, the composition of the Cr-Zr-N alloy coating on the surface of the substrate was Cr 15.0 Zr 78.8 N 6.2 . The hardness value of the copper substrate sample was 8.9 GPa. In the salt spray corrosion resistance test, the copper substrate sample could pass the 12-hour test and had certain protective properties.

[0395] The SEM test results showed that the alloy coating structure was dense and no through columnar joint was observed.

[0396] The colorimetric value of the copper substrate sample was L: 74.78, a: 0.56, b: 6.58, and the color was bright silver white.

[0397] Example 9. The thickness of the Cr-Zr-N alloy coating was about 50 nm

[0398] The chemical composition of the Cr-Zr-N alloy coating was Cr 29.7 Zr 50.1 N 20.2 , and the only difference was that the thickness of the Cr-Zr-N alloy coating was adjusted to 50 nm.

[0399] The hardness value of the aluminum alloy substrate sample was 9.1 GPa, and the hardness value of the stainless steel substrate sample was 9.8 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, having excellent protection properties.

[0400] The color value test results are as follows: the color value of the aluminum alloy substrate sample is L: 77.23, a: 0.51, and b: 5.98, and the color value of the stainless steel substrate sample is L: 78.81, a: 0.41, and b: 5.27, showing a bright silver-white color.

[0401] Example 10. The Cr-Zr-N alloy coating layer has a thickness of about 6 μm

[0402] The chemical composition of the Cr-Zr-N alloy coating layer is Cr 29.7 Zr 50.1 N 20.2 , and the only difference is that the thickness of the Cr-Zr-N alloy coating layer is adjusted to 6000 nm.

[0403] The hardness value of the aluminum alloy substrate sample is 23.8 GPa, and the hardness value of the stainless steel substrate sample is 25.2 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, having excellent protection properties.

[0404] The color value test results are as follows: the color value of the aluminum alloy substrate sample is L: 75.23, a: 0.55, and b: 6.08, and the color value of the stainless steel substrate sample is L: 76.81, a: 0.42, and b: 5.57, showing a bright silver-white color.

[0405] Example 11. The Cr-Zr-N alloy coating layer contains a doping element

[0406] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating layer containing a doping element is Cr 34.5 Zr 30.0 N 30.5 C5, at this time, the atomic ratio of Cr, Zr, and N is normalized to 100, and the atomic ratio of Cr, Zr, and N is about 36.32:31.58:32.11, and the atomic percentage of the doping element C in the Cr-Zr-N alloy coating layer is 5%. The preparation method is as follows:

[0407] In this embodiment, the target material is a chromium-zirconium alloy target, and the original chromium target (original Cr target) at the position of the chromium target 4 in FIG. 3 is replaced with a CrZr alloy target with an atomic percentage ratio of 55%:45%.

[0408] Pre-treatment: stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50mm x 50mm were put into DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then put into a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0409] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0410] Deposition of the Cr-Zr-N alloy coating according to the present application: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the CrZr alloy target was powered by a radio frequency assisted direct current power supply, Ar, C2H2 and N2 gases were introduced, the flow rate of N2 gas was set to 35 sccm, the flow rate of C2H2 gas was set to 6 sccm, the gas flow rate was set to keep the gas flow rate ratio of Ar:(C2H2+N2) at 2:1, the pressure in the furnace body was kept at 0.8 Pa, the bias voltage was turned on and set to -100 V, and the power density of the CrZr alloy target was set to 4.5 W / cm 2 , and the Cr-Zr-N alloy coating according to the present application (which is a carbon-doped Cr-Zr-N alloy coating) was deposited, and the film thickness was 2500 nm by controlling the film deposition time.

[0411] The stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance test, hardness test and color value test were performed. The silicon sheet was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed.

[0412] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 34.5 Zr 30.0 N 30.5 C5.

[0413] The hardness value of the aluminum alloy substrate sample was 21.2 GPa, and the hardness value of the stainless steel substrate sample was 21.8 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample could pass the 48h test, and the stainless steel substrate sample could pass the 144h test, which had excellent protection properties.

[0414] In the XRD diffraction pattern, there were at least 1 broad peak in the range of diffraction angle 2θ (°) 30°-50°, and in the radial intensity profile of the TEM selected area electron diffraction pattern, there were at least 1 broad peak in the range of .

[0415] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 73.80, a: 0.59, b: 6.78, and the colorimetric value of the stainless steel substrate sample is L: 76.16, a: 0.42, b: 6.71, which is bright silver white color.

[0416] According to the experimental exploration results of the inventors, when other non-metallic doping elements (such as Si, B, O, etc.) or metallic doping elements (such as Al) are used, a higher hardness can also be provided when the atomic ratio of the doping element is appropriate (such as 4at%, 2at%), and excellent corrosion resistance is also provided. In some embodiments, the aluminum alloy substrate sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test in the salt spray corrosion resistance test experiment. There is at least one wide peak in the XRD diffraction pattern in the range of diffraction angle 2θ(°) 30°-50°, and the radial intensity profile of the TEM selected area electron diffraction pattern has at least one wide peak in the range of 30°-50°.

[0417] “at%” means atomic percentage, which is a quantity.

[0418] Example 12.

[0419] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating is Cr 53.8 Zr 30 N 16.2 The element composition does not meet the following combination formula: 64.5-y≤x≤93.8-y and 15.0≤x≤1.93y-23.4.

[0420] The preparation method is as follows:

[0421] Pre-treatment: stainless steel sheets, aluminum alloy sheets and silicon sheets with an aspect ratio of 50mm×50mm are placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5×10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0422] Plasma cleaning: Ar gas is introduced, the furnace pressure is kept at 2.0Pa, the bias voltage is turned on and set to -800V, and plasma cleaning is performed for 20 minutes, which aims to remove small impurities on the surface of the sample by plasma etching.

[0423] ​Deposition of Cr-Zr-N alloy coating of the application: open the sample stage turret, set the rotation speed to 6 rounds per minute, adjust the sample stage to the target surface distance to 8 cm, Cr target, Zr target with RF assisted DC power supply, Ar and N2 gas, N2 gas flow is set to 18 sccm, set the gas ratio to keep Ar:N2 ratio to 3:1, keep the pressure in the furnace body to 0.7 Pa, open the bias voltage, set to -100 V, set the power density of the Cr target to 4.5 W / cm 2 , set the power density of the Zr target to 2.7 W / cm 2 , deposit the Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1000 nm.

[0424] Use stainless steel sheet, aluminum alloy sheet as the substrate of the sample, carry out salt spray corrosion resistance test, hardness test and color value test. Use silicon wafer as the substrate of the sample, carry out SEM and composition analysis, XRD analysis and TEM test.

[0425] Through composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 53.8 Zr 30 N 16.2 .

[0426] The hardness value of the aluminum alloy substrate sample is 11.1 GPa, and the hardness value of the stainless steel substrate sample is 12.3 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the 24h test (not pass the 48h test), and the stainless steel substrate sample can pass the 96h test (not pass the 144h test), which has good but not excellent corrosion resistance.

[0427] The XRD diffraction pattern has at least one broad peak in the range of diffraction angle 2θ(°) 30°-50°, and the radial intensity profile of the TEM selected area electron diffraction pattern has at least one broad peak in the range of .

[0428] The color value test results: the color value of the aluminum alloy substrate sample is L: 77.52, a: 0.68, b: 4.12, and the color value of the stainless steel substrate sample is L: 79.34, a: 0.51, b: 3.74, which is silver white color.

[0429] In addition, the inventors of the application have found through a large number of experimental explorations that for the Cr-Zr-N alloy coating of the application, when the following two conditions are met simultaneously: (1) the XRD diffraction pattern has at least one broad peak in the range of diffraction angle 2θ(°) 30°-50°, and (2) the radial intensity profile of the TEM selected area electron diffraction pattern has at least one broad peak in the range of When there is at least one wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating has high hardness characteristics and excellent corrosion resistance. If only the XRD diffraction pattern has at least one wide peak in the range of 30° to 50°, but the radial intensity profile of the TEM-SAED pattern of the Cr-Zr-N alloy coating has no wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating may have poor corrosion resistance, for example, the corresponding aluminum alloy substrate sample may not pass the 24h salt spray corrosion resistance test. When there is at least one wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating has high hardness characteristics and excellent corrosion resistance. If only the XRD diffraction pattern has at least one wide peak in the range of 30° to 50°, but the radial intensity profile of the TEM-SAED pattern of the Cr-Zr-N alloy coating has no wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating may have poor corrosion resistance, for example, the corresponding aluminum alloy substrate sample may not pass the 24h salt spray corrosion resistance test. When there is at least one wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating has high hardness characteristics and excellent corrosion resistance. If only the XRD diffraction pattern has at least one wide peak in the range of 30° to 50°, but the radial intensity profile of the TEM-SAED pattern of the Cr-Zr-N alloy coating has no wide peak in the range of 30° to 50°, the prepared Cr-Zr-N alloy coating may have poor corrosion resistance, for example, the corresponding aluminum alloy substrate sample may not pass the 24h salt spray corrosion resistance test.

[0430] Comparative Example 1.

[0431] In this comparative example, the chemical composition of the alloy coating is Cr 88.9 Zr 11.1 The preparation method is as follows:

[0432] Pre-treatment: stainless steel sheets, aluminum alloy sheets and silicon sheet samples with an aspect ratio of 50mm x 50mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0433] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0434] Deposition of Cr-Zr alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by radio frequency assisted direct current power supply, Ar gas was introduced, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 6.7 W / cm 2 , the power density of the Zr target was set to 0.8 W / cm 2 , and the Cr-Zr alloy coating was deposited. By controlling the film formation time, the obtained film thickness was 1900 nm.

[0435] The stainless steel sheets and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance test, hardness test and color value test. The silicon sheet was used as the substrate sample for SEM and composition analysis test.

[0436] The composition of the alloy coating on the surface of the substrate was Cr 88.9 Zr 11.1 .

[0437] The hardness value of the test sample was 18.5 GPa for the aluminum alloy substrate sample and 19.6 GPa for the stainless steel substrate sample. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48 h test (NG, protection duration < 24 h), and the stainless steel substrate sample failed the 144 h test (NG, protection duration < 48 h), and the protection performance was poor.

[0438] SEM cross-section testing was performed on the test sample, and the cross-section morphology can be seen in FIG. 13. The SEM test results showed that the alloy coating film had crystallization defects, the structure was not dense, and there were obvious gaps.

[0439] The colorimetric value test results were as follows: the colorimetric value of the aluminum alloy substrate sample was L: 83.21, a: -0.21, and b: 0.88, and the colorimetric value of the stainless steel substrate sample was L: 85.05, a: -0.25, and b: 0.79, which was a silver-white color.

[0440] Comparative Example 2.

[0441] In the present comparative example, the chemical composition of the alloy coating was Cr 37.8 Zr 16.2 N 46 , and the preparation method was as follows:

[0442] Pre-treatment: stainless steel sheets, aluminum alloy sheets, and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

[0443] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was maintained at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0444] Deposition of alloy coating: the sample stage turntable was turned on and the rotation speed was set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set to 52 sccm, the gas flow ratio of Ar:N2 was maintained at 2:1, the pressure in the furnace body was maintained at 0.9 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 3.5 W / cm 2 , and the power density of the Zr target was set to 1.8 W / cm 2, a Cr-Zr-N alloy coating was deposited, and by controlling the film forming time, the thickness of the obtained film was 1000 nm.

[0445] The samples with stainless steel sheet and aluminum alloy sheet as the substrate were subjected to salt spray corrosion resistance test, hardness test and color value test, and the samples with silicon sheet as the substrate were subjected to SEM and composition analysis, XRD analysis and TEM test.

[0446] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 37.8 Zr 16.2 N 46 .

[0447] The hardness value of the aluminum alloy substrate sample was 16.6 GPa, and the hardness value of the stainless steel substrate sample was 18.1 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48 h test (NG, protection time < 24 h), and the stainless steel substrate sample failed the 144 h test (NG, protection time < 48 h), and the protection performance was poor.

[0448] The cross-sectional SEM test of the test sample showed that the cross-sectional morphology could be seen from FIG. 14, and the test results of XRD diffraction pattern, TEM selected area electron diffraction pattern and radial intensity profile could be seen from FIG. 15. The SEM test results showed that the alloy coating film structure was loose, and there were obvious penetrating column seams. The XRD test results showed that there were two peaks in the XRD diffraction pattern in the range of 30°-50°, and both were sharp peaks (half-height width value < 2° 2θ peak), wherein the half-height widths of the two sharp peaks in the range of 30°-50° were 0.66° and 1.24°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern had two peaks in the range of , and the half-height widths were , that is, there were two sharp peaks.

[0449] The color value test results: the color value of the aluminum alloy substrate sample was L: 61.87, a: 0.57, b: 4.45, and the color value of the stainless steel substrate sample was L: 67.38, a: 0.49, b: 4.29, and the color was dark and did not have metallic luster.

[0450] Comparative Example 3.

[0451] In this comparative example, the film structure was TiN, and the chemical composition of the alloy coating was TiN.

[0452] To make the coating of this comparative example, the Zr target in the furnace body was replaced with a Ti target, and the preparation method was as follows:

[0453] Pre-treatment: stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0454] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0455] Deposition of TiN coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Ti target was powered by a direct current source, Ar and N2 gases were introduced, the N2 gas flow was set to 10 sccm, the gas flow ratio of Ar:N2 was kept at 3:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Ti target was set to 5 W / cm 2 , a TiN alloy coating was deposited, and the film thickness was 200 nm by controlling the film deposition time.

[0456] Stainless steel sheet and aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance test, hardness test and color value test were performed.

[0457] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was TiN.

[0458] The hardness value of the aluminum alloy substrate sample was 3.8 GPa, and the hardness value of the stainless steel substrate sample was 4.3 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48 h test (NG, protection time < 12 h), and the stainless steel substrate sample failed the 144 h test (NG, protection time < 24 h).

[0459] The color value test results: the color value of the aluminum alloy substrate sample was L: 57.95, a: 6.45, b: 13.95, and the color value of the stainless steel substrate sample was L: 59.33, a: 6.92, b: 13.91, which was golden yellow in color.

[0460] Comparative Example 4.

[0461] In this comparative example, the chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 , and the preparation method was as follows:

[0462] Pre-treatment: stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine. The vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0463] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0464] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Zr target were powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 45 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.8 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 4.6 W / cm 2 , the power density of the Zr target was set to 2.2 W / cm 2 , and a Cr-Zr-N alloy coating was deposited. By controlling the film formation time, the thickness of the alloy coating film obtained was 1400 nm.

[0465] Stainless steel sheet and aluminum alloy sheet were used as the substrate of the sample for salt spray corrosion resistance test, hardness test and color value test. Silicon wafer was used as the substrate of the sample for SEM and composition analysis, XRD analysis and TEM test.

[0466] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 39.6 Zr 19.4 N 41 .

[0467] The hardness value of the aluminum alloy substrate sample was 15.4 GPa, and the hardness value of the stainless steel substrate sample was 17.2 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection time < 12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection time < 24 hours), and did not have the protection characteristics of the substrate.

[0468] The SEM test result shows that the alloy coating film has crystallization defects, the structure is not dense, and there is obvious through column joint. The XRD diffraction pattern, TEM selected area electron diffraction pattern and radial intensity profile of the alloy coating can be referred to (A), (B) and (C) in FIG. 16. The XRD test result shows that there are two peaks in the XRD diffraction pattern in the range of 30°-50° of diffraction angle 2θ (°), and both are sharp peaks (half-height width value < 2° of 2θ peak), wherein the half-height widths of the two sharp peaks in the range of 35°-40° are 1.87° and 1.02° respectively. The radial intensity profile of the TEM selected area electron diffraction pattern has two peaks in the range of , , i.e. there is one sharp peak.

[0469] The chroma value test result: the chroma value of the aluminum alloy substrate sample is L: 64.71, a: 0.58, b: 4.15, and the chroma value of the stainless steel substrate sample is L: 66.38, a: 0.49, b: 4.27, which is silver white in color.

[0470] Comparative Example 5. Alloy coating thickness 50 nm

[0471] The method is basically the same as that of Comparative Example 4, the chemical composition of the alloy coating is Cr 39.6 Zr 19.4 N 41 , and the difference is that the thickness of the alloy coating is changed from 1400 nm to 50 nm.

[0472] The hardness value of the aluminum alloy substrate sample is 9.1 GPa, and the hardness value of the stainless steel substrate sample is 9.8 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample fails to pass the 48 h test (NG, protection time < 12 h), and the stainless steel substrate sample fails to pass the 144 h test (NG, protection time < 24 h), which does not have the protection characteristics for the substrate.

[0473] Comparative Example 6. Alloy coating thickness 1000 nm

[0474] The method is basically the same as that of Comparative Example 4, the chemical composition of the alloy coating is Cr 39.6 Zr 19.4 N 41 , and the difference is that the thickness of the alloy coating is changed from 1400 nm to 1000 nm.

[0475] The hardness value of the aluminum alloy substrate sample was 16.5 GPa, and the hardness value of the stainless steel substrate sample was 17.9 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration <12h), and the stainless steel substrate sample failed the 144h test (NG, protection duration <24h), and did not have the protection characteristics for the substrate.

[0476] Comparative Example 7. Alloy coating thickness 2500 nm

[0477] The chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 , except that the thickness of the alloy coating was changed from 1400 nm to 2500 nm.

[0478] The hardness value of the aluminum alloy substrate sample was 20.5 GPa, and the hardness value of the stainless steel substrate sample was 21.1 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration <12h), and the stainless steel substrate sample failed the 144h test (NG, protection duration <24h), and did not have the protection characteristics for the substrate.

[0479] Comparative Example 8. Alloy coating thickness 6000 nm

[0480] The chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 , except that the thickness of the alloy coating was changed from 1400 nm to 6000 nm.

[0481] The hardness value of the aluminum alloy substrate sample was 22.1 GPa, and the hardness value of the stainless steel substrate sample was 23.7 GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration <12h), and the stainless steel substrate sample failed the 144h test (NG, protection duration <24h), and did not have the protection characteristics for the substrate.

[0482] Comparative Examples 9-11. No protective coating

[0483] The aluminum alloy bare chip, the stainless steel bare chip, and the copper bare chip were respectively used for the salt spray corrosion resistance test, and it was found that obvious corrosion occurred within 12 hours.

[0484] Result analysis:

[0485] The Cr, Zr, and N elements in the Cr-Zr-N alloy coating provided in the present application satisfy a certain atomic ratio, and are rich in zirconium.

[0486] The Cr-Zr-N alloy coating (Examples 1-12) provided in the present application can be used as a protective coating itself or a part of a protective coating, both of which can provide higher hardness and excellent corrosion resistance.

[0487] According to the salt spray corrosion resistance test results, the Cr-Zr-N alloy coating (Examples 1-12) provided in the present application can all bring excellent corrosion resistance to the substrate; among them, Examples 1-5 and 8-12 are single-layer film structures, and the Cr-Zr-N alloy coating provided in the present application directly provides surface protection for the substrate; Example 6 is a double-layer film structure, and the Cr-Zr-N alloy coating provided in the present application serves as a lower protective layer, and a surface layer (TiN coating) is further attached to the surface of the side of the Cr-Zr-N alloy coating away from the substrate, which serves as a surface decorative coating (located in the upper layer); the Cr-Zr-N alloy coating of Example 7 is a three-layer film structure, which includes a transition layer (as a bottom coating), a Cr-Zr-N alloy coating and a TiN coating on the surface from the surface of the substrate; the Cr-Zr-N alloy coating in Example 11 contains a certain atomic percentage of doping elements (≤5at%); the element composition in Example 12 does not meet the following combination formula: “64.5-y≤x≤93.8-y and 15.0≤x≤1.93y-23.4”.

[0488] Examples 1-7 and 9-11 all use aluminum alloy substrates and stainless steel substrates, and the Cr-Zr-N alloy coating on the aluminum alloy surface can pass the 48h salt spray corrosion resistance test, and on the stainless steel surface can pass the 144h salt spray corrosion resistance test. Example 8 uses a copper substrate, and the copper substrate (which is a more active alloy than aluminum alloy) can pass the 12h salt spray corrosion resistance test. In Example 12, the Cr-Zr-N alloy coating on the aluminum alloy surface can pass the 24h salt spray corrosion resistance test (but does not pass the 48h test), and on the stainless steel surface can pass the 96h salt spray corrosion resistance test (but does not pass the 144h test).

[0489] The alloy coating provided in the present application can be used independently as a single-layer film, or can be located in a multi-layer composite film, such as one of the layers, which can be used as a surface layer (exposed), a bottom coating (contacting the substrate), or an intermediate layer (between the bottom coating and the surface layer).

[0490] According to the XRD test and TEM selected area electron diffraction test results, the Cr-Zr-N alloy coating (Examples 1-12) provided in the present application has at least one broad peak (further, all broad peaks, and the half-height width is all ≥2°) in the XRD diffraction pattern in the range of 30°-50° of diffraction angle 2θ (°), and the radial intensity profile of the TEM selected area electron diffraction pattern is in the range of 30°-50° of diffraction angle 2θ (°). The Cr-Zr-N alloy coating in each of the embodiments has at least one wide peak (further, all are wide peaks, each with a half-height width of ≥2°), and the atomic arrangement of the Cr-Zr-N alloy coating is "highly disordered and fully dense", which is consistent with the highly dense structure in the SEM morphology characterization result.

[0491] In addition, the Cr-Zr-N alloy coating provided in the present application, when located on the surface of the protective coating (Examples 1-5, 8-12), can also provide a higher brightness value for the corresponding plated product.

[0492] The substrates of Comparative Examples 9-11, without the protective coating, are not resistant to salt spray corrosion, and obvious corrosion occurs within 12 hours.

[0493] The alloy coating film of Comparative Example 1 lacks N element, the alloy coating films of Comparative Examples 2 and 4 have a high N element content, and Comparative Example 3 does not have a Cr-Zr-N alloy coating (Comparative Example 3 is a TiN coating), and it is found that Comparative Examples 1-4 all have corrosion resistance test failure (NG).

[0494] For the alloy coatings of different thicknesses in Comparative Examples 5-8, the hardness and corrosion resistance are significantly inferior to the Cr-Zr-N alloy coatings of the same thickness provided in the present application. Among them, Comparative Example 8 has a thickness as high as 6000 nm (6 microns), and the hardness is high, but the corrosion resistance is still poor. It is speculated that the reason may be that the film structure is not dense, there are gaps, such as through-column gaps, which cause the corrosion solution to quickly pass through the gaps and contact the substrate, thereby causing the coating to fail in corrosion resistance. Increasing the thickness of the coating can increase the hardness of the coating, but the structural defects still exist. The Cr-Zr-N alloy coating provided in the present application can have high hardness and excellent corrosion resistance at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing the cost. In the case of a thin alloy coating, the plated product formed can also present a silver-white metallic color close to the color of the substrate metal, which is beneficial to achieve an aesthetic and decorative effect without changing the color of the substrate.

[0495] Each of the technical features of the above embodiments and examples can be combined in any suitable manner. In order to make the description concise, not all possible combinations of the technical features in the above embodiments and examples are described, but as long as the combination of the technical features does not exist contradictory, it should be considered within the scope of the present disclosure.

[0496] The above-mentioned embodiments and examples only express several embodiments of the present application, and are used to understand the technical scheme of the present application in detail, but cannot be understood as a limitation on the protection scope of the present application. It should be pointed out that, for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application. In addition, it should be understood that, after reading the above teaching content of the present application, the skilled in the art can make various modifications or modifications to the present application, and the equivalent forms obtained are also within the protection scope of the present application. It should also be understood that, on the basis of the technical scheme provided by the present application, the skilled in the art can obtain the technical scheme through logical analysis, reasoning or limited test, which is within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application should be based on the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A zirconium-rich Cr-Zr-N alloy coating, wherein, The Cr-Zr-N alloy coating contains a Cr-Zr-N alloy material, the chemical formula of the Cr-Zr-N alloy material is (Cr x Zr y N z )M a , M is a doping element, wherein x, y, z and a are each independently an atomic ratio, 15.0≤x≤53.8, 30.0≤y≤78.8, 6.2≤z≤35.5, and 0≤a / (x+y+z+a)≤0.

05.

2. The Cr-Zr-N alloy coating according to claim 1, wherein 64.5 ≤ x ≤ 93.8 - y and 15.0 ≤ x ≤ 1.93y - 23.

4.

3. The Cr-Zr-N alloy coating of claim 1, wherein, 15.0 ≤ x ≤ 53.8, 33.7 ≤ y ≤ 78.8 and 6.2 ≤ z < 28.

0.

4. The Cr-Zr-N alloy coating according to claim 3, wherein 72 - y < x ≤ 93.8 - y and 15.0 ≤ x < 2.5y - 44.

6.

5. The Cr-Zr-N alloy coating according to any one of claims 1 to 4, wherein The sum of x, y and z is 100.

6. The Cr-Zr-N alloy coating according to any one of claims 1 to 5, wherein The Cr-Zr-N alloy coating satisfies the following two characteristics: The X-ray diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has a peak in the range of diffraction angle 2θ (°) of 30°-50°, and the half-height width of at least one 2θ (°) diffraction peak in the range of 30°-50° satisfies ≥2°; The selected area electron diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating corresponds to a radial intensity profile plot with characteristic interatomic distances as the abscissa and diffraction intensity as the ordinate, in which have diffraction peaks within a range, and the half-height width of at least one diffraction peak in the range satisfies 7. The Cr-Zr-N alloy coating according to any one of claims 1 to 6, wherein The thickness of the Cr-Zr-N alloy coating is d min ~ 6 μm, wherein d min is selected from 10 nm ~ 50 nm.

8. The Cr-Zr-N alloy coating according to claim 7, wherein d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, or 50 nm.

9. The Cr-Zr-N alloy coating according to any one of claims 1 to 8, wherein The doping element is a non-metallic element, a metallic element or a combination thereof; The non-metallic element includes one or more of O, C, B, Si and Ar; The metallic element includes one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

10. The Cr-Zr-N alloy coating according to any one of claims 1 to 9, wherein 0 ≤ a / (x+y+z+a) ≤ 0.

02.

11. A coated article comprising a substrate and a Cr-Zr-N alloy coating according to any one of claims 1 to 11; wherein, The Cr-Zr-N alloy coating is located on at least one side of the substrate.

12. The coated article of claim 11, wherein, The surface material of the substrate is one of an alloy, a single-element metal and an inorganic non-metallic material; Optionally, the material type of the alloy includes one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based; Optionally, the single-element metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium; Optionally, the inorganic non-metallic material includes one or more of ceramic and glass.

13. The coated article of claim 11 or 12, wherein, The surface material of the substrate is one of a light alloy or one of a stainless steel alloy; Optionally, the light alloy includes one or more of titanium alloy, aluminum alloy and magnesium alloy.

14. The coated article of any of claims 11-13, wherein, The coated product satisfies one or more of the following characteristics: The Cr-Zr-N alloy coating is in direct contact with the substrate or is provided with a transition layer; The Cr-Zr-N alloy coating is located on the surface of the coated product or the side of the Cr-Zr-N alloy coating away from the substrate is further provided with a surface layer, which is a single-layer structure or a multi-layer structure.

15. Use of the Cr-Zr-N alloy coating according to any one of claims 1-10 as at least a part of a hard coating, or use of the coated product according to claims 11-14 in the preparation of a product having a hard coating.

16. The use according to claim 15, wherein, The hard coating is also a corrosion-resistant coating.

17. A method for preparing a Cr-Zr-N alloy coating, comprising the following steps: using a gas deposition technique to deposit the constituent elements of the Cr-Zr-N alloy coating on at least a part of the surface of a substrate according to a preset atomic ratio, thereby forming the Cr-Zr-N alloy coating according to any one of claims 1-10.

18. The production method according to claim 17, wherein The Cr-Zr-N alloy coating is prepared by sputtering deposition of constituent elements of the Cr-Zr-N alloy coating on at least a part of the surface of the substrate using one or more targets comprising chromium and zirconium under the condition of supplying a mixed gas comprising argon and a nitrogen-containing gas.

19. The production method according to claim 18, wherein The preparation method satisfies one or more of the following features: The temperature for sputtering deposition is 30-330°C; The total gas pressure of the mixed gas comprising argon and a nitrogen-containing gas is 0.3-1.2 Pa; The target material includes a chromium target having a power density of 1.3 W / cm 2 ~ 6.7 W / cm 2 ; The target material includes a zirconium target having a power density of 0.8 W / cm 2 ~ 7.9 W / cm 2 ; The target material includes an alloy target including at least two metal elements in the Cr-Zr-N alloy coating; optionally, the target material includes a chromium-zirconium-based alloy target with a power density of 4 W / cm 2 ~ 6 W / cm 2 ; The bias voltage for the substrate is -150 to -20 V; The time for sputtering deposition is 10-150 min; The nitrogen-containing gas is nitrogen, and the gas flow rate of the nitrogen is 8-52 seem; The nitrogen-containing gas is nitrogen, and the ratio of the gas amount of argon to that of nitrogen in the mixed gas is (2-6):

1.

20. A Cr-Zr-N alloy material, wherein, The Cr-Zr-N alloy material is as defined in any one of claims 1-6, 9-10.

Images