Low-nitrogen alloy coating, cr-zr-n alloy material, use in hard corrosion-resistant coating, and preparation method

Abstract

The present application relates to a low-nitrogen alloy coating, a Cr-Zr-N alloy material, the use in a hard corrosion-resistant coating, and a preparation method. The alloy coating comprises a Cr-Zr-N alloy material, which mainly comprises three elements, i.e. Cr, Zr and N, wherein Cr, Zr and N have a specific relative atomic ratio (CrxZryNz, wherein 41.3≤x≤61.4, 33.2≤y≤40.0, and 5.4≤z≤25.5).

Description

Application and preparation method of low-nitrogen alloy coating, Cr-Zr-N alloy material, and hard corrosion-resistant coating

[0001] Related applications

[0002] This application claims priority to Chinese patent application number CN202310746562X, filed on June 21, 2023, entitled “Application and preparation method of low-nitrogen alloy coating, Cr-Zr-N alloy material, hard corrosion-resistant coating”, the entire text of which is hereby incorporated by reference. Technical Field

[0003] The present application relates to the field of metal nitrogen coating technology, and further to the field of alloy coating technology, in particular to the application and preparation method of low-nitrogen alloy coatings, Cr-Zr-N alloy materials, and hard corrosion-resistant coatings, and also to coated products. Background Art

[0004] With the rapid development of modern science and technology, hard coatings have emerged to improve the surface properties of various materials and components. Hard coatings, with their high hardness, are playing an increasingly important role in fields such as 3C digital products, machining, mold manufacturing, geological drilling, the textile industry, and aerospace.

[0005] Metal nitrides generally have the characteristics of high melting point and hardness, good thermal stability, and excellent oxidation resistance. Nitrides of transition metals such as titanium, chromium, vanadium, niobium, zirconium, and hafnium are often used as reinforcing coatings on tool surfaces to increase hardness. The most common, earliest studied, and most widely used coatings are titanium coatings (TiN coatings) and chromium coatings (CrN coatings). Among them, TiN coatings have the advantages of high hardness, good toughness, good chemical stability, and gorgeous color. They have been successfully applied in the tool industry and have been hailed as "a revolution in tools." In addition to being used as functional coatings, TiN coatings can also be used as decorative coatings. Compared with TiN coatings, CrN coatings have a lower friction coefficient, better high temperature and corrosion resistance, and a higher sputtering yield, which is conducive to large-scale industrial production. In addition, the internal stress of CrN coatings is lower, resulting in their hardness values ​​being lower than those of TiN coatings.

[0006] In addition, with the widespread application of coating products, coating substrates have entered the era of light alloys, such as aluminum alloys. However, these light alloy materials have weak corrosion resistance. As a result, new requirements are put forward for the corrosion resistance of hard coatings, requiring the protective coating on the substrate surface to have not only high hardness characteristics but also excellent corrosion resistance. However, for traditional single-metal nitride coatings, due to the large internal stress of the coating and the defects during the coating growth process, although it has high hardness characteristics, it has the problem of poor corrosion resistance. In view of this, the research and development of alloy coatings is timely.

[0007] In order to maintain high hardness characteristics, traditional alloy coatings mostly use nitrogen-rich alloy coatings, and the atomic percentage of nitrogen is usually higher than 40%. Alloy coatings mainly use different metal element compositions to form coatings with different microstructures to achieve different functional characteristics. The purpose of nitrogen-rich design of alloy nitrides is to achieve nitridation of metal elements in nitride alloys through a large or excessive ratio of N elements, forming a nitride-rich system with a high content of crystals to increase the hardness of the coating. However, although nitrogen-rich crystalline coatings improve hardness, they are not corrosion-resistant, especially in the application of light alloy surface protective coatings with corrosion resistance requirements.

[0008] Therefore, it is necessary to further develop new hard corrosion-resistant coating technologies.

[0009] Summary of the Invention

[0010] According to various embodiments and examples of the present application, one aspect of the present application provides a low-nitrogen alloy coating and a Cr-Zr-N alloy material as its main component. Other aspects of the present application also provide a method for preparing the low-nitrogen alloy coating and a coated product including the alloy coating, as well as applications in hard, corrosion-resistant coatings.

[0011] In a first aspect of the present application, a low-nitrogen alloy coating is provided, wherein the alloy coating comprises a Cr-Zr-N alloy material, wherein 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, 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5, and 0≤a / (x+y+z+a)≤0.05.

[0012] In some embodiments, the sum of x, y, and z is 100.

[0013] In some embodiments, 1.8y-19.7≤x≤-1.1y+98.5.

[0014] In some embodiments, based on any of the foregoing suitable embodiments, the alloy coating satisfies the following two characteristics:

[0015] The X-ray diffraction pattern of the Cr-Zr-N alloy material or the alloy coating has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and the half-maximum width of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2°;

[0016] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material or the alloy coating, the characteristic atomic distance is taken as the abscissa and the diffraction intensity is taken as the ordinate. There is a diffraction peak in the range of The half-height width of at least one diffraction peak within the range satisfies ≥

[0017] In some embodiments, the X-ray diffraction pattern of the alloy coating has a half-width at least one 2θ (°) diffraction peak within the range of 30° to 50° that satisfies ≥3.5°.

[0018] In some embodiments, in the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating, The half-height width of at least one diffraction peak in the range meets

[0019] In some embodiments, based on any of the above suitable embodiments, the thickness of the alloy coating is d min ~6μm, where d min Selected from 10nm to 50nm.

[0020] In some embodiments, d min 10nm, 20nm, 25nm, 30nm, 40nm or 50nm.

[0021] In some embodiments, based on any of the foregoing suitable embodiments, the doping element is a non-metallic element, a metallic element, or a combination thereof;

[0022] The non-metallic elements include one or more of O, C, B, Si and Ar;

[0023] The metal elements include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

[0024] In some embodiments, a=0 or 0

[0025] In a second aspect of the present application, a Cr—Zr—N alloy material is provided, which is as defined in the first aspect of the present application.

[0026] In a third aspect of the present application, a coated product is provided, comprising a substrate and the alloy coating according to the first aspect of the present application; wherein the alloy coating is located on at least one side of the substrate.

[0027] In some embodiments, the surface material of the substrate is one of an alloy, a single metal and an inorganic non-metallic material;​

[0028] 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;

[0029] Optionally, the elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium;

[0030] Optionally, the inorganic non-metallic material includes one or more of ceramics and glass.

[0031] In some embodiments, the surface material of the substrate is one of light alloys or one of stainless steel alloys;

[0032] Optionally, the light alloy includes one or more of titanium alloy, aluminum alloy and magnesium alloy.

[0033] In some embodiments, the coated article satisfies one or more of the following characteristics:

[0034] The alloy coating is in direct contact with the substrate or is provided with a transition film layer;

[0035] The alloy coating is located on the surface of the coated product or a surface film layer is provided on the side of the alloy coating away from the substrate. The surface film layer is a single-layer structure or a multi-layer structure.

[0036] In the fourth aspect of the present application, there is provided the use of the Cr-Zr-N alloy material described in the second aspect of the present application in the preparation of a hard corrosion-resistant coating, or the use of the alloy coating described in the first aspect of the present application as at least a part of a hard corrosion-resistant coating, or the use of the coated product described in the third aspect of the present application in the preparation of a product having a hard corrosion-resistant coating.

[0037] In the fifth aspect of the present application, a method for preparing an alloy coating is provided, which includes the following steps: using vapor deposition technology to deposit the constituent elements of the alloy coating on at least a portion of the surface of the substrate according to a preset atomic ratio to form the alloy coating described in the first aspect of the present application.

[0038] In some embodiments, the method for preparing the alloy coating includes the following steps: under the condition of introducing a mixed gas comprising argon and nitrogen-containing gas, using one or more target materials comprising chromium and zirconium, sputtering and depositing the constituent elements of the alloy coating on at least a portion of the surface of the substrate to form the alloy coating.

[0039] In some embodiments, the preparation method meets one or more of the following characteristics:

[0040] The temperature of sputtering deposition is 30℃~330℃;

[0041] The total gas pressure of the mixed gas comprising argon and nitrogen-containing gas is 0.5 Pa to 0.9 Pa;

[0042] The target material includes a chromium target, and the power density of the chromium target is 3.5W / cm 2 ~6.7W / cm 2 ;

[0043] The target material includes a zirconium target, and the power density of the zirconium target is 0.8W / cm 2 ~3.5W / cm 2 ;

[0044] The target material includes an alloy target, and the alloy target includes at least two metal elements in the alloy coating; optionally, the target material includes a chromium-zirconium based alloy target, and the power density of the chromium-zirconium based alloy target is 4W / cm 2 ~6W / cm 2 ;

[0045] The bias voltage of the substrate is -150V to -20V;

[0046] The sputtering deposition time is 10 min to 150 min;

[0047] The nitrogen-containing gas is nitrogen gas, and the gas flow rate of the nitrogen gas is 5 sccm to 52 sccm;

[0048] The nitrogen-containing gas is nitrogen, and the gas volume ratio of argon to nitrogen in the mixed gas is (2-6):1.

[0049] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions in the implementation methods or examples of the present application and to more completely understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for use in the description of the implementation methods or examples. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work. It should also be noted that the drawings are all drawn in a simplified form and are only used to conveniently and clearly assist in explaining the present application. The various dimensions of each component shown in the drawings are arbitrarily shown and may be accurate or not drawn to scale. For example, in order to make the illustrations clearer, the dimensions of the components are appropriately exaggerated in some places in the drawings. Unless otherwise specified, the components in the figures are not drawn to scale. This application does not limit every dimension of every component.

[0051] In the following description, the same reference numerals denote the same parts.

[0052] FIG1 is a schematic structural diagram of a coated article according to one embodiment of the present application, including a substrate and an exemplary alloy coating according to the present application;

[0053] FIG2 is a schematic diagram of the structure of a film-coated article in several embodiments of the present application; (A) includes a substrate, a transition film layer, and an exemplary alloy coating of the present application; (B) includes a substrate, a transition film layer, an exemplary alloy coating of the present application, and a surface film layer; (C) includes a substrate, an exemplary alloy coating of the present application, and a surface film layer;

[0054] FIG3 is a schematic diagram of an apparatus for preparing an alloy coating in one embodiment of the present application;

[0055] FIG4 is a graph showing the Cr prepared in Example 1 of the present application. 61.4 Zr 33.2 N 5.4 SEM cross-sectional image of the alloy coating;

[0056] Figure 5 shows the Cr prepared in Example 1 of this application. 61.4 Zr 33.2 N 5.4 XRD diffraction pattern (A), selected area electron diffraction pattern (B), and lattice spacing-intensity quantitative map (C) of the alloy coating;

[0057] Figure 6 shows the Cr prepared in Example 2 of this application. 53.8 Zr 40.0 N 6.2 SEM cross-sectional image of the alloy coating;

[0058] Figure 7 shows the Cr prepared in Example 2 of this application. 53.8 Zr 40.0 N 6.2 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile corresponding to SEAD pattern (C) of the alloy coating;

[0059] FIG8 is a graph showing the Cr prepared in Example 3 of the present application. 41.3 Zr 33.2 N 25.5 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile corresponding to SEAD pattern (C) of the alloy coating;

[0060] Figure 9 shows the Cr prepared in Example 4 of this application. 54.8 Zr 35.1 N 10.1XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile corresponding to SEAD pattern (C) of the alloy coating;

[0061] FIG10 is a graph showing the Cr prepared in Comparative Example 1 of this application. 88.9 Zr 11.1 SEM cross-sectional image of the alloy coating;

[0062] FIG11 is a graph showing the Cr prepared in Comparative Example 2 of this application. 37.8 Zr 16.2 N 46 SEM cross-sectional image of the alloy coating;

[0063] FIG12 is a graph showing the Cr prepared in Comparative Example 2 of this application. 37.8 Zr 16.2 N 46 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile corresponding to SEAD pattern (C) of the alloy coating;

[0064] FIG13 is a graph showing the Cr prepared in Comparative Example 4 of this application. 39.6 Zr 19.4 N 41 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.

[0065] In the XRD diffraction pattern, the horizontal axis is 2θ, the unit is °, and the vertical axis is the X-ray diffraction intensity (intensity), the unit is au; according to the selected area electron diffraction pattern (SAED) of the alloy coating, the corresponding radial intensity profile is obtained, which is expressed in the form of characteristic atomic spacing (d)-diffraction intensity, with d as the horizontal axis and the unit is angstrom The vertical axis represents the electron diffraction intensity (intensity), with the unit being au.

[0066] In the XRD diffraction pattern and the radial intensity profile corresponding to the SAED pattern, au has a well-known meaning in the art.

[0067] Some SEM images show some delamination during cross-sectional sample preparation due to brittle fracture of the silicon wafer, but this does not affect the observation and analysis of the cross-sectional morphology. The positions of the different structural layers in the substrate and protective coating can be determined based on their thickness.

[0068] Description of reference numerals: 1 is a vacuum chamber, 2 is a sample stage, 3 is a DC anode, 4 is a chromium target (also denoted as Cr target), and 5 is a zirconium target (also denoted as Zr target);

[0069] 100 is a substrate, 200 is a transition film layer (also called a transition layer), 300 is an alloy coating, and 400 is a surface film layer (also called a surface layer).

[0070] In the present application, unless otherwise specified, the chromium target 4 is a Cr target with radio frequency assisted direct current cathode power supply, and the zirconium target 5 is a Zr target with radio frequency assisted direct current cathode power supply. DETAILED DESCRIPTION

[0071] The present application will be described in further detail below in conjunction with the accompanying 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. The purpose of providing these embodiments and examples is to make the understanding of the present application disclosure 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. Those skilled in the art can make various changes or modifications without violating the connotation of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, the features described or described as part of one embodiment can be combined in another embodiment in a suitable manner to produce a new embodiment. In addition, in the description below, a large amount of details are given in order to provide a more comprehensive understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing embodiments and examples only and are not intended to limit this application.

[0073] the term

[0074] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0075] As used herein, the terms "and / or," "or / and," and "and / or" include any one of two or more of the listed items, as well as any and all combinations of the listed items. "Any and all combinations" include any combination of two, any more, or all of the listed items. For example, "A and / or B" includes A, B, and the combination of A and B.

[0076] In this application, "plurality", "multiple", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0077] In this application, unless otherwise specified, "one or more" means any one of the listed items or any combination of the listed items. Similarly, "one or more" and other expressions that mean "one or more" are also understood in the same way unless otherwise specified.

[0078] As used herein, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0079] In this document, the "suitable" in "suitable combination", "suitable method", "any suitable method", etc. is based on the ability to implement the technical solution of this application, solve the technical problems of this application, and achieve the expected technical effects of this application.

[0080] Herein, the terms "preferred," "better," "more preferred," and "suitable" are used solely to describe preferred implementations or examples and should not be construed as limiting the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0081] In this application, the terms "further," "further," "particularly," "for example," "such as," "example," and "for example" are used for descriptive purposes to indicate that the preceding and following technical solutions are related in terms of the content covered, but should not be construed as limiting the preceding technical solution or the scope of protection of this application. In this application, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0082] In this application, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel options of "with" or "without". If multiple "optional" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent. In this application, descriptions such as "optionally contain" and "optionally include" mean "containing or not containing". "Optional component X" means the presence or absence of component X.

[0083] In this application, the terms "first," "second," "third," "fourth," etc. in "the first aspect," "the second aspect," "the third aspect," "the fourth aspect," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0084] As used in this application, the terms "comprising," "including," and "comprising" are synonymous and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps.

[0085] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0086] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval only refers to an integer in the numerical interval, including the two endpoint integers of the numerical range and each integer between the two endpoints is equivalent to directly enumerating each integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0087] As used herein, unless otherwise specified, "about" means within a certain range above or below the number. This range may vary depending on the type and value of the number. For example, a range of ±2%, ±1%, ±0.5%, or the like is permitted. For example, "about 2°" may mean within a range selected from 2° ±0.02°, etc.

[0088] Unless otherwise specified, temperature parameters in this application allow for both constant temperature processing and temperature fluctuations within a certain temperature range. It should be understood that constant temperature processing allows for temperature fluctuations within the accuracy of instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted. The temperature unit °C refers to degrees Celsius.

[0089] In this application, the term "room temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of this application, "room temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" refers to 20°C to 30°C.

[0090] In this application, the term "normal temperature" generally refers to 20°C to 35°C, for example, 20°C to 35°C. In some embodiments of this application, "normal temperature" refers to 30°C to 35°C. In some embodiments of this application, "normal temperature" refers to 30°C.

[0091] In this application, when referring to a data range, if the unit is followed only by the right endpoint, it means that the units of the left and right endpoints are the same. For example, "3-5h" means that the units of the left endpoint "3" and the right endpoint "5" are both hours, which has the same meaning as "3h-5h". Similar descriptions of other parameters such as temperature and size also apply to the above understanding.

[0092] All documents mentioned in this application are cited as references in this application, just as each document is cited as a reference individually. Unless they conflict with the invention purpose and / or technical solution of this application, the cited documents involved in this application are cited in their entirety and for all purposes. When cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be adaptively amended according to the description in this application.

[0093] 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 of the mass or weight between the components. Therefore, as long as the content of the relevant components in the embodiments or examples of the present application is proportionally enlarged or reduced, it is within the scope disclosed in the embodiments or examples of the present application. The mass or weight in the embodiments or examples of the present application can be units known in the chemical industry such as micrograms (μg), milligrams (mg), grams (g), and kilograms (kg).

[0094] In this application, if a method flow involves multiple steps, unless otherwise specified herein, there is no strict order restriction on the execution of these steps, and they can be executed in an order other than the order described. Moreover, any step can include multiple sub-steps or multiple stages, and these sub-steps or stages do not necessarily need to be completed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be executed in turn, alternating, or simultaneously with other steps or parts of sub-steps or stages of other steps.

[0095] When describing positional relationships, unless otherwise specified, when an element, such as a layer, film, or substrate, is referred to as being "on" another layer, it can be directly on the other layer or intervening layers may also be present. Furthermore, when a layer is referred to as being "under" another layer, it can be directly under or one or more intervening layers may also be present. It will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or one or more intervening layers may also be present.

[0096] Where “including,” “having,” and “comprising” are used herein, it is intended to cover a non-exclusive inclusion, and another component may also be added unless a clear limiting term such as “only,” “consisting of,” etc. is used.

[0097] Unless mentioned otherwise, terms in the singular may include plural forms and should not be construed as having one number.

[0098] In this application, exemplary descriptions such as "in some embodiments (or examples)" and "in one embodiment (or example)" may include but are not limited to the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0099] With the widespread application of coating products, coating substrates have entered the era of light alloys, such as aluminum alloys. However, these light alloy materials often lack hardness and have weak corrosion resistance. As a result, new requirements are put forward for the hardness and corrosion resistance of protective coatings. The protective coating on the substrate surface must not only have high hardness characteristics but also excellent corrosion resistance. However, for traditional single-metal nitride coatings, due to the large internal stress of the coating and the defects during the coating growth process, although it has high hardness characteristics, it has the problem of poor corrosion resistance.

[0100] In order to improve the hardness of the coating, traditional alloy coatings mostly adopt nitrogen-rich design. The atomic percentage of nitrogen in traditional nitrogen-rich alloy coatings is usually higher than 40%. The purpose of nitrogen-rich design is to achieve nitridation of metal elements in nitride alloys through a large amount or excessive N element ratio, forming a nitride-rich system with a high content of crystallization to increase the hardness of the coating. However, although the nitrogen-rich crystalline coating improves the hardness, its corrosion resistance is insufficient, especially in the application of light alloy surface protective coatings with corrosion resistance requirements. In addition, the high nitrogen content in the nitrogen-rich alloy coating will also weaken the metallic properties of the coating, resulting in high internal stress and poor toughness of the coating.

[0101] Through extensive research and experimental analysis, the inventors of this application have discovered that traditional alloy coatings (such as TiN, etc.) are prone to forming columnar crystals during the nucleation and crystallization growth process, and usually have a columnar crystal structure. Moreover, a high content of columnar crystals will promote the formation of a directional arrangement into a highly ordered structure. In the highly ordered structure, there are a large number of crystals causing inter-crystal gap defects, which are mainly manifested as through-column gaps. The corresponding scanning electron microscope (SEM) cross-sectional images show shadows between the columnar crystals, and it is speculated that these through-column gaps may lead to insufficient density of the alloy coating. The inventors of this application speculate that the traditional directional arrangement of the ordered structure easily leads to insufficient density of the coating, thereby limiting the hardness improvement; on the other hand, under corrosive conditions, the corrosive medium can quickly penetrate the coating through the through-column gaps and react with the substrate, thereby causing the corrosion resistance of the alloy coating to be less than ideal.

[0102] Furthermore, alloy materials currently on the market primarily utilize methods such as anodic oxidation and magnetron sputtering for surface protection. For example, aluminum alloys are primarily protected by anodic oxidation, which involves placing the aluminum alloy material in a strong acid or alkaline solution to form an oxide and metal and alloy coating on the surface, creating a protective surface. Because the solution is a strong acid or alkaline solution, this method produces a product with low hardness. Furthermore, the production process generates a large amount of wastewater, waste liquid, and exhaust gas, which is detrimental to the environment.

[0103] In this application, by optimizing the element ratio, a low-nitrogen alloy coating was discovered, which simultaneously exhibits high hardness and excellent corrosion resistance. Furthermore, by alloying with a low nitrogen content, the metal content in the alloy material is relatively higher. Compared with traditional nitrogen-rich alloy coatings, the low-nitrogen alloy coating provided by this application has excellent metallic properties, with low internal stress and strong toughness. This gives the alloy coating provided by this application excellent bonding strength and durability.

[0104] According to various embodiments and examples of the present application, one aspect of the present application provides a low-nitrogen alloy coating and its main component, a Cr-Zr-N alloy material, both of which can be used for at least a portion of a hard, corrosion-resistant coating and as a protective film layer in coated products, exhibiting both high hardness and excellent corrosion resistance, as well as excellent durability. Other aspects of the present application also provide methods for preparing the low-nitrogen alloy coating and coated products including the alloy coating, as well as applications in hard, corrosion-resistant coatings.

[0105] The alloy coating provided by the present application is different from the traditional nitrogen-rich design and has a low nitrogen design. The Cr-Zr-N alloy material contained in the low nitrogen alloy coating mainly contains three elements: Cr, Zr and N, and these three elements have a specific relative atomic ratio (Cr x Zr y Nz ), 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5. Based on the low-nitrogen design, the alloy coating has formed a highly disordered atomic distribution and a sufficiently dense atomic arrangement through the optimization of the ratio of the three elements. The coating has a dense structure and high hardness and excellent corrosion resistance. It not only has excellent scratch resistance and can reduce the generation of scratches or weaken scratch damage, but also reduces or avoids the penetrating column cracks in traditional hard coatings, thereby greatly improving the corrosion resistance of the alloy coating.

[0106] The Cr-Zr-N alloy material in the alloy coating has the ability to form a highly disordered distribution and a sufficiently dense arrangement of the constituent atoms. The Cr, Zr, and N atoms are highly disordered. Based on the highly disordered atomic distribution, the atoms contained in the alloy coating can form a sufficiently dense arrangement, so that the alloy coating has a dense structure, and also reduces or avoids the penetrating column cracks in traditional high-hardness alloy coatings. Therefore, the alloy coating of the present application has high hardness characteristics, can reduce the occurrence of surface scratches, and also has excellent corrosion resistance.

[0107] In the present application, the metal content in the alloy material is relatively higher through the alloying ratio with low nitrogen content. Compared with the traditional nitrogen-rich alloy coating, the low-nitrogen alloy coating provided by the present application also has excellent metallic properties, and has the characteristics of low internal stress and strong toughness of the alloy coating, so that the alloy coating provided by the present application has good bonding strength and excellent durability.

[0108] In the coated product, the position of the alloy coating provided by the present application can be flexibly set. It can directly contact the substrate or not directly contact the substrate. It can serve as a surface film layer or be located between the surface film layers of the substrate and other structures and serve as an intermediate film layer. When serving as an intermediate film layer, other film layers are also provided on the outside of the alloy coating, so that the alloy coating of the present application does not need to serve as a surface film layer. The alloy coatings of the present application in different positions can effectively resist scratches and scrapes while also providing excellent corrosion resistance. When the alloy coating provided by the present application is used as a surface film layer of a coated product, it can provide a high-brightness surface, so that the coating has both beautiful decoration and protective functions.

[0109] The alloy coating provided herein can be used as at least a portion of a hard, corrosion-resistant coating, including as a surface layer, an intermediate layer, or a base layer. The coated product can be an intermediate or final product, and can be further fabricated into various products having a hard, corrosion-resistant coating. This hard, corrosion-resistant coating not only exhibits high hardness but also provides excellent corrosion resistance.

[0110] The alloy coating provided in this application can be applied to a variety of substrates, and the materials of the substrates include but are not limited to alloys, elemental metals, inorganic non-metallic materials (such as silicon wafers, ceramic glass) and other substrates.

[0111] The preparation method of the alloy coating provided in the present application is simple, easy to operate, green and environmentally friendly, and also has the advantages of being quantifiable, highly efficient and reproducible, and is suitable for industrial applications.

[0112] The alloy coating provided in this application can have both high hardness and excellent corrosion resistance at a relatively thin thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs.

[0113] In a first aspect of the present application, a low nitrogen alloy coating is provided, wherein the alloy coating comprises a Cr-Zr-N alloy material, mainly comprising three elements: Cr, Zr and N, and Cr, Zr and N have a specific relative atomic ratio (Cr x Zr y N z ), 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5. This alloy coating has a low-nitrogen design and, through the optimized ratio of the three elements, combines high hardness with excellent corrosion resistance. It can be used as at least part of a hard, corrosion-resistant coating on coated products.

[0114] In some embodiments, a low nitrogen alloy coating is provided, the alloy coating comprising 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 , wherein x, y and z are each independently an atomic ratio, 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5, M is a doping element, a is the atomic ratio of the M element, and a is 0 or a positive number.

[0115] In some embodiments, a low nitrogen alloy coating is provided, the alloy coating comprising 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 , wherein x, y and z are each independently an atomic ratio, 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5, M is a doping element, a is the atomic ratio of the M element, and 0≤a / (x+y+z+a)≤0.05.

[0116] The alloy coating provided in one aspect of the present application may also be referred to as the "alloy coating of the present application," the "alloy coating of the present application," the "alloy coating provided in the present application," or the "exemplary alloy coating of the present application," and includes but is not limited to the alloy coating provided in the first aspect. Each of the above citations should be understood in a non-restrictive manner and is not to be construed as limiting the scope of the present application. For example, the scope of the present application is not limited to the "alloy coating of the present application." Descriptions such as the "alloy coating of the present application" in this application are to be understood in a non-restrictive manner as referring to the exemplary alloy coating provided in one aspect of the present application and are not to limit the scope of the alloy coating provided in the present application.

[0117] The alloy coating provided in this application is an alloy coating containing Cr, Zr and N elements, also referred to as a Cr-Zr-N alloy coating.

[0118] In this application, unless otherwise specified, “Cr—Zr—N alloy” and “CrZrN alloy” both refer to alloys containing Cr, Zr and N elements, and may contain other alloying elements, and the two can be used interchangeably.

[0119] In this application, unless otherwise specified, "Cr-Zr-N alloy material" refers to an alloy material containing chromium (Cr), zirconium (Zr), and nitrogen (N). In the Cr-Zr-N alloy material referred to in this application, the three elements Cr, Zr, and N have the aforementioned specific atomic ratio x:y:z. In this application, the form of the Cr-Zr-N alloy material is not particularly limited and may be, but is not limited to, an alloy coating.

[0120] The means of structural characterization of the Cr-Zr-N alloy coating in this application can also be used to characterize the Cr-Zr-N alloy material provided in this application, and the Cr-Zr-N alloy material may not be limited to the coating form, but may be an independent raw material, such as an alloy sheet, alloy plate, etc.

[0121] In this application, unless otherwise specified, the "atomic ratio" of two or more elements means the ratio by atomic number.

[0122] In the present application, unless otherwise specified, "Cr-Zr-N ternary alloy" and "CrZrN ternary alloy" both refer to an alloy composed of three elements: Cr, Zr, and N.

[0123] The alloy coating provided by the present application is different from the traditional nitrogen-rich design and has a low nitrogen design. The Cr-Zr-N alloy material contained in the low nitrogen alloy coating mainly contains three elements: Cr, Zr and N, and these three elements have a specific relative atomic ratio (Cr x Zr y N z), 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5. Based on the low-nitrogen design, the alloy coating has formed a highly disordered atomic distribution and a sufficiently dense atomic arrangement through the optimization of the ratio of the three elements. The coating has a dense structure and high hardness and excellent corrosion resistance. It not only has excellent scratch resistance and can reduce the generation of scratches or weaken scratch damage, but also reduces or avoids the penetrating column cracks in traditional hard coatings, thereby greatly improving the corrosion resistance of the alloy coating.

[0124] Furthermore, by alloying with a low nitrogen content, the metal content in the alloy material is relatively higher. Compared with the traditional nitrogen-rich alloy coating, the low nitrogen alloy coating provided by the present application has excellent metallic properties, and has the characteristics of low internal stress and strong toughness of the alloy coating. When the alloy coating of the present application is applied to a substrate (such as a metal or alloy surface), it has the characteristics of low internal stress and high toughness, and its metallic properties cause the thermal expansion coefficient to be closer to that of the metal or alloy substrate relative to the traditional nitrogen-rich alloy coating, so that the coating of the present application has excellent bonding strength and durability, and is particularly suitable for application in the fields of 3C digital products, aerospace, and automobiles, etc., on the surface of metal or alloy parts to increase their durability.

[0125] Corrosion-resistant coatings must be inherently inert and fully isolated. "Intrinsically inert" means the coating material is sufficiently inert to not react chemically with the corrosive media in the service environment. "Full isolation" means the coating structure is sufficiently dense to fully isolate the substrate from the service environment, preventing or delaying any reaction between the substrate and the corrosive media, thereby achieving corrosion resistance.

[0126] Traditional nitrogen-rich alloy coatings (such as TiN) are usually nanocrystalline and often have a high content of columnar crystals. The high content of columnar crystals leads to a large number of through-holes, which reduces the density of the coating, affects the hardness and leads to poor corrosion resistance.

[0127] The alloy coating provided by the present application has a characteristic structure of "highly disordered and fully densely packed", contains very few through-holes or no through-holes, and has a dense coating structure. Among them, the three atoms of Cr, Zr and N with very different radii have a special atomic ratio, which is conducive to making the atoms condense into a highly disordered state during deposition, and then densely stacked in a highly disordered state. The dual characteristics of highly disordered and fully densely packed atoms in the coating make the alloy coating easy to grow densely and improve the hardness of the coating. It can also inhibit the formation of a large number of continuous through-holes, thereby forming an effective isolation between the substrate and the corrosive environment, significantly improving the corrosion resistance, and thus multiple factors synergistically and preferably improve the hardness and corrosion resistance of the alloy coating of the present application. Among them, it is speculated that there is the following mechanism: during the nucleation process, N atoms can penetrate into the pores of large-sized Cr and Zr metal grains, achieving a better pore filling effect, making the coating atoms stack more densely, and better inhibiting the growth defects of the thin film columnar crystal structure, and better improving the corrosion resistance of the coating.

[0128] In the alloy coating of the present application, based on the special atomic ratio of Cr, Zr and N, Zr and Cr elements are introduced under low nitrogen content to form Cr-Zr-N alloy, with a higher Cr content, followed by a lower Zr content, and a lower N content. On the one hand, Cr and Zr are easy to form stronger bond energy, which is beneficial to promote the rapid growth of Cr-Zr alloy with a suitable atomic ratio during the deposition process. On the other hand, by adding low-content nitrogen, while achieving high metallic properties of the coating, the re-nucleation of the Cr-Zr alloy can be promoted to form the Cr-Zr-N alloy of the present application, thereby improving the density of the coating nucleation, improving the coating hardness and corrosion resistance, and also helping to improve the durability of the coating on the substrate surface. Among them, in terms of atomic size, the Cr atomic radius is The atomic radius of Zr is The atomic radius of N is The atomic sizes of Cr and Zr are close, while the atomic size of N is smaller. During the nucleation process, an appropriate amount of small-sized N atoms can penetrate into the pores of large-sized Cr and Zr metal grains with appropriate atomic ratios, achieving a better pore-filling effect and making the atomic arrangement denser. At the same time, it can inhibit the growth defects of the columnar crystal structure of the film, thereby better improving the hardness and corrosion resistance of the coating.

[0129] In some embodiments, the sum of x, y, and z is 100, i.e., x+y+z=100. In this case, x, y, and z correspond to the atomic percentages of the three elements Cr, Zr, and N, respectively. In this case, the ratio of the three atoms of Cr, Zr, and N is constrained within a more appropriate range, and the content relationship between the three elements of Cr, Zr, and N is more optimized, which is more conducive to the Cr, Zr, and N atoms in the alloy coating being arranged in a highly disordered and fully dense manner, so that the formed alloy coating is conducive to obtaining a denser structure, which is conducive to achieving higher coating hardness and better corrosion resistance.

[0130] In some embodiments, based on any of the aforementioned suitable embodiments, x, y, and z further satisfy the following formula: 1.8y-19.7≤x≤-1.1y+98.5. When the atomic ratio of Cr, Zr, and N satisfies the above formula, the synergistic alloying effect between the three elements facilitates the arrangement of highly disordered atoms in a more densely packed manner, thereby forming a denser structure, better suppressing growth defects in the thin film columnar crystal structure, and further enhancing the combined properties of high hardness and high corrosion resistance of the alloy coating.

[0131] In some embodiments, the alloy coating satisfies the following two characteristics:

[0132] The X-ray diffraction pattern of the Cr-Zr-N alloy material or alloy coating has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and the half-maximum width of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥ 2°;

[0133] In the radial intensity profile corresponding to the selected area electron diffraction pattern of Cr-Zr-N alloy material or alloy coating, the characteristic atomic distance is taken as the horizontal axis and the diffraction intensity is taken as the vertical axis. There is a diffraction peak in the range of The half-height width of at least one diffraction peak within the range satisfies ≥

[0134] The means of structural characterization of the Cr-Zr-N alloy coating in this application can also be used to characterize the Cr-Zr-N alloy material provided in this application, and the Cr-Zr-N alloy material may not be limited to the coating form, but may be an independent raw material, such as an alloy sheet, alloy plate, etc.

[0135] The alloy coating provided by the present application is not clearly divided into the traditional perfect single crystal or fully amorphous state, but focuses on the degree of close packing of atomic arrangement. Based on the specific atomic ratio of Cr, Zr and N, the close packing degree is closely related to the disorder of the atomic arrangement and the appropriate mismatch of the atomic size. The highly dense alloy coating provided by the present application has both high hardness and excellent corrosion resistance in terms of performance. In terms of structure, it also satisfies the following requirements: there is at least one broad peak (furthermore, there may be no sharp peak, that is, all are broad peaks) in the diffraction angle 2θ (°) range of 30° to 50° in the XRD pattern, and the radial intensity profile of the selected area electron diffraction pattern is There is at least one broad peak in the range (further, there may be no sharp peaks, that is, all are broad peaks).

[0136] In this application, whether the constituent atoms of the alloy coating have a "highly disordered" state is evaluated by XRD technology. In more detail, the XRD pattern of the alloy coating shows wide and gentle ridges, and these "wide and gentle ridges" are called "broad peaks" of the 2θ (°) diffraction peak. The half-height width of the broad peak is used to obtain the length of the orderly arrangement of atoms using the Scherrer formula. The calculation method is: D = Kλ / (β·cosθ), where D is the length of the orderly arrangement of atoms (representing the grain size in crystalline materials), K is the Scherrer constant, λ is the wavelength of X-rays; β is the half-height width of the diffraction peak (referring to the width value at half the height of the diffraction peak, Full Width at Half Maximum, FWHM), and θ is the diffraction angle. It can be seen that the half-height width FWHM is inversely proportional to the length D of the orderly arrangement of atoms, and the shorter the length D of the orderly arrangement of atoms, the higher the disorder of the atomic distribution. Therefore, the half-width (FWHM) of the diffraction peak within a specific range in the XRD pattern can be used to reflect the degree of disordered distribution of atoms: the wider the half-width (FWHM), the shorter the length of the ordered arrangement of atoms, and the more disordered the overall atomic distribution; the aforementioned wide and gently raised "broad peak" can reflect the highly disordered distribution of atoms in the material as a whole.

[0137] Generally speaking, the higher the atomic order and the stronger the crystallinity, the easier it is to form large grains over a longer distance, and the narrower the diffraction peak in the XRD pattern. High crystallinity is often accompanied by sharp peaks. However, in the alloy coating of the present application, the Cr, Zr, and N atoms can be arranged in a highly disordered manner throughout the alloy coating, resulting in a wide and gentle ridge (broad peak) in the XRD pattern of the alloy coating, with at least one peak being a "broad peak" within the diffraction angle 2θ (°) range of 30° to 50°.

[0138] In this application, unless otherwise specified, a "broad peak" in an XRD pattern may be defined as having a half-height width ≥ 2°. The half-height width of the broad peak may further be ≥ 2.2°, further ≥ 2.23°, further ≥ 2.25°, further ≥ 2.3°, further ≥ 3°, further ≥ 3.5°, further ≥ 3.92°, further ≥ 4°, further ≥ 5°, further ≥ 5.54°, and further ≥ 6.05°. The half-height width 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 ​​(except 10°) and less than or equal to 10°, and can also be selected from an interval consisting of any two of the following values: 2°, 2.5°, 3°, 3.5°, 4°, 4.5°, 5°, 5.5°, 5.54°, 6°, 6.05°, 6.5°, 7°, 7.5°, 8.42°, 8.5°, 8.85°, 9°, 9.25°, 9.5°, 10°, etc. As a non-limiting example, it can be selected from any of the following ranges: 2° to 10°, 2° to 9.5°, 2° to 9.25°, 3.5° to 10°, 3.5° to 9.5°, 3.5° to 9.25°, 5.5° to 9.5°, 5.54° to 9.25°, etc.

[0139] In this application, unless otherwise specified, a “sharp peak” in an X-ray diffraction (XRD) pattern refers to a diffraction peak with a half-height width < 2°.

[0140] In more detail, the alloy coating provided in the present application has an XRD pattern with a peak within the diffraction angle 2θ (°) range of 30° to 50°, and at least one of the diffraction peaks in the XRD pattern is a broad peak. The special microstructural state in which at least one peak is a "broad peak" can be expressed by "having at least one 2θ (°) diffraction peak with a half-height width ≥ 2° within the range of 30° to 50°" or "having at least one 2θ (°) diffraction peak with a half-height width ≥ 2° within the range of 30° to 50°." The following method can be used to determine whether the "having at least one 2θ (°) diffraction peak with a half-height width ≥ 2° within the range of 30° to 50°" is met: in the XRD pattern, if the half-height width of the 2θ (°) diffraction peak is ≥ 2°, it is judged as a "broad peak"; if the half-height width of the 2θ (°) diffraction peak is < 2°, it is judged as a sharp peak. For a given 2θ(°) position, it can be any of the three states: peakless, broad, or sharp. In the X-ray diffraction (XRD) diagram, the characteristic diffraction peak of the alloy coating provided in the present application has a more obvious broad peak characteristic.

[0141] In traditional alloy coatings with a high content of columnar crystals, the diffraction peaks in the diffraction angle 2θ (°) range of 30° to 50° often appear as sharp peaks with a half-height width < 2°, and no broad peaks appear.

[0142] In the present application, conventional instruments and methods in the art may be used to obtain the XRD pattern of the alloy coating, for example, a German Bruker D8 Advance XRD diffractometer may be used.

[0143] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and at least one 2θ (°) diffraction peak in the range of 30° to 50° is a broad peak. The half-height width of the broad peak can refer to the examples in the context; taking the half-height width of the broad peak ≥3.5° as an example, at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥3.5°; taking the half-height width of the broad peak ≥

[0144] Taking 5.54° as an example, at least one 2θ(°) diffraction peak in the range of 30° to 50° satisfies ≥5.54°.

[0145] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has a broad peak within a diffraction angle 2θ (°) range of 30° to 50°. The half-maximum width of the broad peak can be found in the examples above and below.

[0146] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has two or more broad peaks within a diffraction angle 2θ (°) range of 30° to 50°, and the half-height widths of these broad peaks can be independently referred to in the examples above.

[0147] In some embodiments, in the X-ray diffraction pattern of the alloy coating of the present application, all 2θ(°) diffraction peaks within the diffraction angle 2θ(°) range of 30° to 50° are broad peaks, that is, there are no sharp peaks. The half-height widths of these broad peaks can be independently referred to the examples in the context.

[0148] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and the half-height width of the 2θ (°) diffraction peak in the range of 30° to 50° independently satisfies ≥ 2°, and further can independently satisfy ≥

[0149] 2.19°, further can each independently satisfy ≥2.2°, further can each independently satisfy ≥2.3°, further can each independently satisfy ≥3°, further can each independently satisfy ≥3.5°, further can each independently satisfy ≥4°, further can each independently satisfy ≥5°, further can each independently satisfy ≥5.54°, further can each independently satisfy ≥6.05°.

[0150] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has only one diffraction peak within the diffraction angle 2θ (°) range of 30° to 50°, and the diffraction peak is a broad peak.

[0151] In some embodiments, the X-ray diffraction pattern of the alloy coating of the present application has two diffraction peaks within a diffraction angle 2θ (°) range of 30° to 50°, and both are broad peaks.

[0152] In some embodiments, the X-ray diffraction pattern of the alloy coating is obtained using Cu target Kα radiation.

[0153] In this application, the following instruments and methods can be used to obtain the XRD pattern of the alloy coating: using a German Bruker D8 Advance XRD diffractometer, in θ-2θ mode, using Cu target Kα rays, a wavelength λ of 0.15406 nanometers (nm), the X-ray tube is controlled at 40 kilovolts (kV) and 40 milliamperes (mA), the scanning range is 20° to 80°, and precise scanning measurements are performed with a step size of 0.01°.

[0154] The FWHM value can be obtained using conventional analytical methods in the art (including but not limited to analytical software provided by the instrument supplier). For example, the steps for obtaining the FWHM value may include: first, performing correction processing on the diffraction peak, which may include smoothing, background subtraction, removal of Kα2 lines, subtraction of instrumental broadening, etc., and then fitting the diffraction peak with a Pseudo-Voigt function to obtain the FWHM value of the diffraction peak.

[0155] The analysis software is not particularly limited. Without limitation, 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, scale calibration is performed, then the center of the diffraction ring transmission spot is determined, and then converted into an XRD spectrum (wherein the electron wavelength is 0.00251 nanometers (nm) and the X-ray wavelength is 0.154 nm); the diffraction peak is subtracted from the straight line background, and then fitted with a Voigt function to obtain the half-height width of the corresponding diffraction peak.

[0156] Regarding the characterization of the degree of atomic density in alloy coatings, traditional XRD patterns cannot provide a good representation. This is because: when detecting physical vapor deposition (PVD) films or coatings at the atomic scale (such as diameter <3nm), the XRD method often has insufficient resolution due to the large wavelength of X-rays (>0.1nm), and is not suitable for PVD films or coatings with low order (such as grains or amorphous particles with a diameter <3nm).

[0157] In the present application, whether the atoms constituting the alloy coating reach "sufficiently densely packed" is evaluated by selected area electron diffraction pattern (SAED). The electron wave is selected because its wavelength is significantly smaller (<0.01nm), so that the resolution is higher. In more detail, if there are only continuous diffraction rings with consistent brightness on the SEAD diagram, the diffraction rings are relatively wide, indicating that the atoms in the coating are densely packed in a highly random mixed manner. In order to quantitatively characterize, the SAED spectrum can be converted into a characteristic atomic spacing (d)-radial intensity profile, wherein the characteristic atomic spacing (d) is the horizontal coordinate and the diffraction intensity is the vertical coordinate. If the diffraction rings are wider in SEAD, then accordingly, the half-height width of the radial intensity profile is wider, reflecting that the atomic arrangement densely packed in the alloy coating is stronger.

[0158] In this application, in terms of atomic size, the Cr atomic radius is The atomic radius of Zr is The atomic radius of N is The three kinds of atoms with very different diameters have a suitable atomic size mismatch, and under conditions where random mixing is high, a fully densely packed structure can be formed. In the process of PVD film or alloy coating growth, the fully densely packed atoms in the alloy coating make the coating easy to dense growth, which can suppress the formation and growth of columnar crystals originally caused by local ordering, and thus make it difficult for continuous through-type pores to form in large quantities. Thus, the half-height width of the radial intensity profile can be used as the characteristic parameter of the fully densely packed structure of the alloy coating to reflect the atomic dense packing in the alloy coating. The larger the value of the half-height width is, the better the atomic dense packing in the alloy coating is reflected. In short, the present application adopts the half-height width of the radial intensity profile of SAED as the characteristic parameter of the fully densely packed atoms, which is in line with scientific principles and scientific.

[0159] When the half-height width of the radial intensity profile is greater than a certain threshold, the atoms in the coating are able to achieve sufficient dense packing. Based on a large number of experimental explorations by the inventors, in this application, unless otherwise specified, the half-height width threshold for judging whether the atoms are sufficiently densely packed in the SAED-radial intensity profile is determined as That is, the half-height width ≥ When the atoms are fully packed together,

[0160] In the present application, a transmission electron microscope (TEM) technique may be used to obtain a radial intensity profile of characteristic atomic spacing (d) of the alloy coating sample.

[0161] In this application, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating can be recorded as a SAED-radial intensity profile, or as a characteristic atomic spacing-intensity quantitative spectrum of the selected area electron diffraction pattern (SAED pattern). A selected area electron diffraction pattern obtained using transmission electron microscopy can be recorded as a TEM selected area electron diffraction pattern or as a TEM-SAED pattern. A SAED-radial intensity profile obtained using transmission electron microscopy can also be recorded as a TEM-SAED-radial intensity profile.

[0162] In this application, the alloy coating (including the alloy coating of this application) can be obtained by conventional instruments and methods in the art, and the corresponding radial intensity profile is obtained based on the selected area electron diffraction pattern (SAED) of the alloy coating. It is expressed in the form of characteristic atomic spacing (d)-diffraction intensity, with d as the horizontal axis and the unit being angstroms. The vertical axis represents the electron diffraction intensity.

[0163] In this application, unless otherwise specified, the half-height width of the diffraction peak in the radial intensity profile of the SAED pattern is ≥ It is judged as a broad peak; the half-height width of the diffraction peak is < It is judged to be sharp peaks. For a specific characteristic interatomic distance, it can be any of the three states: no peak, sharp peak or broad peak. In the radial intensity profile, the broad peak characteristics of the characteristic diffraction peak of the alloy coating provided by the present application are more obvious. Unless otherwise specified, the "broad peak" in the radial intensity profile of the selected area electron diffraction pattern (SAED pattern) refers to a half-height width ≥ The diffraction peak of “peak” refers to the half-height width < diffraction peaks.

[0164] In the present application, radial intensity profiles or SAED-radial intensity profiles, unless otherwise specified, can be obtained using TEM technology.

[0165] In this application, unless otherwise specified, a “broad peak” in the radial intensity profile corresponding to the SAED pattern can be defined as a peak whose half-height width satisfies ≥ The half-height width of the broad peak can be further ≥ Further can ≥ Further can ≥ Further can ≥ Further can ≥ Further can ≥

[0166] In the present application, the following transmission electron microscopy (TEM) method may be used (but not limited to) to obtain the half-maximum width data in the radial intensity profile corresponding to the selected area electron diffraction pattern:

[0167] TEM sample preparation: The sample was thinned using a Helios 5CX focused ion beam (FIB) from Thermo Fisher Scientific Inc., USA, to obtain an electron-transparent, TEM-observable planar sample.

[0168] SAED image acquisition: A Talos F200x transmission electron microscope (TEM) from Thermo Fisher Scientific Inc. (USA) was used with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm to obtain the selected area electron diffraction pattern (SAED) of the sample. Based on the selected area electron diffraction pattern (SAED) diagram, a radial intensity profile was obtained, and the half-maximum width of the diffraction peak was obtained by assigning the integrated half-maximum width.

[0169] According to the principle that the half-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.

[0170] Those skilled in the art know that the larger the width of the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing of the atoms, and the more densely packed the atoms are in the 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 diffraction ring width, and the larger the half-height width value, the more densely packed the atoms are.

[0171] In some embodiments, the selected area electron diffraction pattern (SAED) of the alloy coating of the present application is obtained using a transmission electron microscope (TEM) characterization technique, with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0172] In some embodiments, in the radial intensity profile of the selected area electron diffraction pattern of the alloy coating of the present application, There is at least one half-height width ≥ diffraction peaks.

[0173] In the radial strength cross-sectional diagram of the alloy coating provided in this application, The half-height width of the diffraction peak in the range has an upper limit due to the atomic close packing limit, and a non-limiting example of the upper limit is as follows:

[0174] In the present application, the half-height width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be independently 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 the aforementioned upper limit (such as ), and can also be independently selected from the interval consisting of any two of the following values: As a non-limiting example, the half-height width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any of the following ranges: etc.

[0175] In some embodiments, the radial strength profile of the alloy coating of the present application is: The half-height width of the diffraction peak within the range ≤

[0176] In some embodiments, the radial strength profile of the alloy coating of the present application is: The half-height width of the diffraction peak within the range can be independently any of the following values, can be independently greater than or equal to any of the following values, and can also be independently selected from the interval consisting of any two of the following values: As non-limiting examples, any of the following ranges may be selected: wait.

[0177] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating of the present application is There is a broad peak within the range. The half-height width of the broad peak can be found in the examples in the context. For example, the radial intensity profile corresponding to the selected area electron diffraction pattern is At least one diffraction peak within the range satisfies ≥

[0178] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating of the present application is There are two or more broad peaks in the range, and their half-height width values ​​can be independently referred to in the examples above.

[0179] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating of the present application is All diffraction peaks within the range are broad peaks, and the half-height width of all diffraction peaks meets ≥ See also context definition.

[0180] In some embodiments, the characteristic atomic spacing of the alloy coating of the present application is obtained using TEM diffraction data; wherein, the TEM diffraction test of the alloy coating is performed using an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0181] In some embodiments, the TEM test uses a mode with 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 alloy coating.

[0182] In some embodiments, the X-ray diffraction pattern of the alloy coating has a half-width at least one 2θ (°) diffraction peak within the range of 30° to 50° that satisfies ≥3.5°.

[0183] In some embodiments, in the radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating, The half-height width of at least one diffraction peak within the range satisfies ≥

[0184] In some embodiments, the alloy coating provided by the present application satisfies the following conditions: the half-maximum width of the diffraction peak in the diffraction angle 2θ (°) range of 30° to 50° in the XRD pattern satisfies ≥ 2°, and the radial intensity profile of the selected area electron diffraction pattern satisfies The half-height width of the diffraction peaks within the range satisfies ≥

[0185] In some embodiments, based on any of the above suitable embodiments, the thickness of the alloy coating is d min ~6μm, where d min Can be selected from 10nm to 50nm, d minIt can also be any of the following thicknesses, or an interval consisting of any two of the following thicknesses: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, etc.; for example, the thickness of the alloy coating can be 25nm~6μm, 30nm~6μm, 40nm~6μm, 50nm~6μm, 1.0μm~2.5μm, 1.0μm~2.0μm, etc. By controlling the alloy coating of the present application to have a more appropriate thickness, the high hardness characteristics and / or corrosion resistance of the alloy coating can be better utilized. The thicker the alloy coating, the more conducive it is to improving its hardness and / or corrosion resistance. The alloy coating provided by the present application can have both 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 nitrogen-rich alloy coatings, the alloy coating of the present application can provide a denser structure at the same thickness, achieving better comprehensive performance of high hardness characteristics and corrosion resistance.

[0186] In some embodiments, the thickness of the alloy coating is 10 nm to 6 μm.

[0187] In some embodiments, the thickness of the alloy coating is 25 nm to 6 μm.

[0188] In some embodiments, the thickness of the alloy coating is 1 μm to 2.5 μm.

[0189] The size unit μm stands for “micrometer” and “nm” stands for “nanometer”.

[0190] In addition, when the alloy of the present application is thin, the formed coated product can also present a silvery white metallic color, which is close to the metallic color of the substrate, which is conducive to achieving a beautiful decorative effect without changing the color of the substrate.

[0191] The alloy coatings provided in various embodiments of the present application may or may not be doped with other elements, and can be flexibly selected based on the additional functional requirements of the alloy material and / or the alloy coating. It is understood that in the present application, when doping elements are included, the type and amount of the doping elements are limited to not affecting the high hardness and corrosion resistance of the alloy coating of the present application.

[0192] In this application, the chemical formula of the Cr-Zr-N alloy material can be expressed as (Cr x Zr y N z )M a, where x, y, and z are each independently a positive atomic ratio, M is the doping element, and a is the atomic ratio of the M element and is either 0 or a positive number. During the nucleation process, nitrogen atoms can penetrate into the pores of large Cr and Zr metal grains, achieving a good pore-filling effect. This results in denser atomic stacking in the coating, suppresses growth defects in the film's columnar crystal structure, and improves the coating's corrosion resistance.

[0193] When a is 0, the Cr-Zr-N alloy material does not contain doping elements, corresponding to a Cr-Zr-N ternary alloy material. When a>0, the Cr-Zr-N alloy material contains doping elements, wherein a / (x+y+z) is numerically equal to the "relative atomic percentage of the doping element relative to Cr, Zr, and N", and a / (x+y+z+a) is numerically equal to the "atomic percentage of the doping element in the Cr-Zr-N alloy material". The "relative atomic percentage of the doping element M relative to Cr, Zr, and N" refers to the ratio of the number of atoms of the doping element M in the material to the sum of the number of atoms of Cr, Zr, and N, expressed as a percentage.

[0194] Unless otherwise specified, the Cr-Zr-N alloy material provided in each embodiment of the present application mainly contains three elements: Cr, Zr and N. 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, further such as 0≤a / (x+y+z)≤0.05), further such as ≥98% (corresponding to 0≤a / (x+y+z+a)≤0.02, further such as 0≤a / (x+y+z)≤0.02), and further such as Cr-Zr-N ternary alloy material (at this time, a=0). By limiting the content of doping elements, the influence of doping elements on the highly disordered and fully densely packed arrangement of atoms in the alloy coating of the present application can be minimized, which is beneficial to reducing the elements required for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the coordinated deposition of Cr, Zr and N to form a denser coating, and beneficial to achieving higher hardness and better corrosion resistance.

[0195] In some embodiments, a / (x+y+z)=0. In this case, the Cr-Zr-N ternary alloy material has a simple composition and is easier to prepare and manipulate. The Cr-Zr-N ternary alloy coating formed in this case can achieve a dense structure, high hardness, and high corrosion resistance.

[0196] In some embodiments, 0

[0197] In some embodiments, 0

[0198] In some preferred embodiments, 0

[0199] In some embodiments, the doping element is a non-metallic element, a metallic element, or a combination thereof, and can be flexibly selected based on the additional functional requirements of the alloy coating. It is understood that in the present application, when a doping element is included, the type and amount of the doping element are limited to form the alloy coating structure of the present application without affecting the simultaneous achievement of high hardness and excellent corrosion resistance.

[0200] Without limitation, the non-metallic element may include one or more of O, C, B, Si, and Ar. Without limitation, the metal element may include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0201] ​​​It should be noted that in any embodiment of the present application, the alloy coating of the present application is allowed to contain inevitable impurities introduced during the preparation process. "Inevitable impurities" are not intentionally added impurities, and their main reason for existence is that they are unintentionally introduced during the preparation process; non-limiting examples of "inevitable impurities" include, for example, elements such as C and O present in the air, and they may also come from components in raw materials or equipment. The atomic content of "inevitable impurities" in the alloy coating is usually trace or minute, and can generally be ignored, such as less than 0.01% atomic content. Taking the technical solution of "the alloy coating is a Cr-Zr-N ternary alloy material composed of Cr, Zr and N elements" as an example, in this case, theoretically, the alloy coating is composed of three elements: Cr, Zr and N. However, trace or minute amounts of other elements other than Cr, Zr and N, such as C, O, etc., may be introduced during the preparation process.

[0202] In a second aspect of the present application, a Cr—Zr—N alloy material is provided, which is as defined in the first aspect of the present application, and may also be a Cr—Zr—N alloy material in any embodiment in the above and below.

[0203] In some embodiments, the chemical formula of the Cr-Zr-N alloy material is (Cr x Zr y N z )M a , wherein x, y and z are each independently an atomic ratio, 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5, M is a doping element, a is the atomic ratio of the M element, and 0≤a / (x+y+z)≤0.05.

[0204] In some embodiments, 1.8y-19.7≤x≤-1.1y+98.5.

[0205] In some embodiments, the sum of x, y, and z is 100.

[0206] The Cr-Zr-N alloy material provided in the present application may or may not be doped with other elements. The definition of the doping elements may refer to the first aspect of the present application.

[0207] The Cr-Zr-N alloy material has the ability to form a highly disordered distribution of atoms and a sufficiently dense arrangement. On the one hand, the atoms are highly disordered. Based on the highly disordered atomic distribution, the atoms contained in the alloy coating can form a sufficiently dense arrangement, so that the alloy coating has a dense structure and reduces or avoids the penetrating column cracks in traditional high-hardness alloy coatings. Therefore, the formed alloy coating has high hardness characteristics, can reduce the occurrence of surface scratches, and also has excellent corrosion resistance.

[0208] In addition, the Cr—Zr—N alloy material is not limited to the use of preparing alloy coatings.

[0209] In some embodiments, the Cr-Zr-N alloy material satisfies the following two characteristics:

[0210] The X-ray diffraction pattern of the Cr-Zr-N alloy material has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and the half-maximum width of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2°;

[0211] In the radial intensity profile corresponding to the selected area electron diffraction pattern of Cr-Zr-N alloy material, the characteristic atomic distance is taken as the horizontal axis and the diffraction intensity is taken as the vertical axis. There is a diffraction peak in the range of The half-height width of at least one diffraction peak within the range satisfies ≥

[0212] Furthermore, the XRD test results of the Cr-Zr-N alloy material and the radial intensity profile corresponding to the selected area electron diffraction pattern can also refer to the description of the radial intensity profile corresponding to the X-ray diffraction pattern and the selected area electron diffraction pattern in the Cr-Zr-N alloy coating in this article, and the corresponding optional and preferred methods can also be applied to the Cr-Zr-N alloy material.

[0213] In a third aspect of the present application, a coated article is provided, comprising a substrate and an alloy coating. The alloy coating may be the alloy coating described in the first aspect of the present application; the alloy coating is located on at least one side of the substrate. The alloy coating may be present in a protective coating of the coated article, imparting high hardness and excellent corrosion resistance to the protective coating.

[0214] The alloy coating provided in this application can be located on one side or both sides of the substrate.

[0215] In some embodiments, the surface material of the substrate is one of an alloy, a simple metal and an inorganic non-metallic material. Without limitation, the material type of the alloy may 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. Without limitation, the simple metal may be any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium. Without limitation, the inorganic non-metallic material may include one or more of ceramics and glass. Without limitation, the inorganic non-metallic material may include a silicon wafer.

[0216] Furthermore, the alloy coating provided in this application can be applied to a variety of substrates, the materials of which include but are not limited to alloys, elemental metals, etc., and can also be used for other types of substrates such as inorganic non-metallic materials (such as silicon wafers, ceramics, glass).

[0217] In some embodiments, the surface material of the substrate is one of light alloys or one of stainless steel alloys; optionally, the light alloy may include one or more of titanium alloy, aluminum alloy and magnesium alloy.

[0218] In some embodiments, the surface material of the substrate is one of light alloys; further, the light alloy may include one or more of titanium alloy, aluminum alloy and magnesium alloy.

[0219] In some embodiments, the surface material of the substrate is a stainless steel alloy. Further, the stainless steel alloy can be any one of austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, etc.

[0220] In some embodiments, the coated article satisfies one or more of the following characteristics:

[0221] The alloy coating and the substrate are in direct contact (in this case, there is no transition film layer) or a transition film layer is provided. Furthermore, the transition film layer can be a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed between the alloy coating provided in the present application and the substrate);

[0222] The alloy coating is located on the surface of the coated product or a surface film layer is provided on the side of the alloy coating away from the substrate. Furthermore, the surface film layer can be a single-layer structure or a multi-layer structure (that is, one or more structural layers can continue to be formed on the alloy coating provided in this application).

[0223] In some embodiments, the alloy coating 300 is in direct contact with the substrate 100 (in this case, there is no transition film layer).

[0224] In some embodiments, a transition film layer 200 is provided between the alloy coating 300 and the substrate 100 .

[0225] In some embodiments, the alloy coating 300 is located on the surface of the coated article.

[0226] In some embodiments, a surface film layer 400 is further provided on a side of the alloy coating 300 away from the substrate 100 .

[0227] In this application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably. Both refer to a structural layer with transitional properties located between the substrate and the alloy coating of this application in a coated product, which can be a single-layer structure or a multi-layer structure.

[0228] In this application, unless otherwise specified, "surface layer" and "surface film layer" have the same meaning and can be used interchangeably. Both refer to the structural layer of the alloy coating of the present application in the coated product that is away from the substrate and located on the surface of the product. It can be a single-layer structure or a multi-layer structure.

[0229] In some embodiments, the alloy coating 300 is in direct contact with the substrate 100 (in this case, there is no transition film layer).

[0230] In some embodiments, a transition film layer 200 is provided between the alloy coating 300 and the substrate 100 .

[0231] In some embodiments, the alloy coating 300 is located on the surface of the coated article.

[0232] In some embodiments, a surface film layer 400 is further provided on a side of the alloy coating 300 away from the substrate 100 .

[0233] FIG1 is a schematic structural diagram of a coated product including an exemplary alloy coating of the present application in one embodiment of the present application, including a substrate 100 and an alloy coating 300 .

[0234] Figure 2 is a schematic structural diagram of the coated product in several embodiments of the present application: (A) includes a substrate 100, a transition film layer 200 and an alloy coating 300; (B) includes a substrate 100, a transition film layer 200, an alloy coating 300 and a surface film layer 400; (C) includes a substrate 100, an alloy coating 300 and a surface film layer 400.

[0235] In the coated product, the position of the alloy coating provided by the present application can be flexibly set. It can directly contact the substrate or not directly contact the substrate. It can serve as a surface film layer or be located between the surface film layers of the substrate and other structures and serve as an intermediate film layer. When serving as an intermediate film layer, other film layers are also provided on the outside of the alloy coating, so that the alloy coating of the present application does not need to serve as a surface film layer. The alloy coating of the present application in different positions can effectively resist scratches and scrapes while also providing excellent corrosion resistance. When the alloy coating provided by the present application is used on the surface of a coated product, it can provide a high-brightness surface, so that the coating has both beautiful decoration and protective functions.

[0236] When the alloy coating of the present application is applied to the surface of a coated article, the highly dense structure of the alloy coating can also achieve better coating reflective properties, thereby providing the coated article with a high-brightness surface. When testing the chromaticity of the alloy coating, the sample to be tested is made of a substrate material suitable for actual application, and the degree to which the alloy coating improves the substrate's compactness and other properties is examined. A CM-3700A-U desktop spectrophotometer manufactured by Konica (Japan) can be used to test the sample's L value, a value, and b value. The light receiving system uses an F2 light source. Six matrix points are tested for each sample and the average value is taken. The L value represents the brightness value, the a value represents the red and green chromaticity values, and the b value represents the yellow and blue chromaticity values. A higher L value indicates a higher brightness, indicating a denser coating surface. The mechanism is as follows: A spectrophotometer reflects incident light from the surface of the sample to be tested, generating a reflectance curve. The amplitude of this curve reflects the material's density, which can be represented by the L value. For the same material, the higher the density, the larger the L value displayed.

[0237] According to the difference in the main components of the substrate, the coated product can be any one of a light alloy product, a stainless steel product, a single substance metal, an inorganic non-metallic based product (such as a ceramic based product, a silicon based product, a glass based product), etc., indicating that the main components of the substrate are light alloy, stainless steel, single substance metal, etc., respectively. Without limitation, light alloy products may include but are not limited to aluminum alloy products, titanium alloy products, magnesium alloy products, etc. Without limitation, stainless steel products may include but are not limited to austenitic stainless steel, ferritic stainless steel, martensitic stainless steel. Without limitation, single substance metal products may include but are 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.

[0238] In a fourth aspect of the present application, a use of the alloy coating described in the first aspect of the present application is provided.

[0239] The application fields of the alloy coating described in the first aspect of this application include but are not limited to the application fields of traditional hard coatings, such as but not limited to 3C digital products, automotive parts or accessories, mechanical processing, mold manufacturing, geological drilling, textile industry and aerospace and other product or technical fields.

[0240] Examples of the hard corrosion-resistant coating in the first aspect of this application and its applicable fields can also refer to the relevant application fields of the hard coating in the first aspect mentioned above.

[0241] In some embodiments, there is provided an application of the Cr-Zr-N alloy material described in the second aspect of the present application in preparing a hard corrosion-resistant coating, or an application of the alloy coating described in the first aspect of the present application as at least a portion of a hard corrosion-resistant coating, or an application of the coated product described in the third aspect of the present application in preparing a product having a hard corrosion-resistant coating. As a non-limiting example, the product having a hard corrosion-resistant coating may be a structural part having high requirements for both hardness and corrosion resistance in the fields of 3C digital products, machining, mold manufacturing, geological drilling, textile industry, aerospace, tool surfaces, etc.

[0242] The prepared hard corrosion-resistant coating can also have excellent durability.

[0243] The alloy coating provided herein can be used as at least a portion of a hard, corrosion-resistant coating, either as a single-layer protective coating or as a layer of a multi-layer protective coating, and as a surface, intermediate, or bottom layer of a hard, corrosion-resistant coating. The aforementioned coated product can be an intermediate or final product, and can be further manufactured into various products having a hard, corrosion-resistant coating. This hard, corrosion-resistant coating not only exhibits high hardness but also provides excellent corrosion resistance.

[0244] The final product can be used or sold directly, while the intermediate product can be further processed or assembled with other components into new products.

[0245] In some embodiments, using an aluminum alloy substrate as an example, a hard coating comprising the alloy coating of the present invention is formed on the surface of the aluminum alloy substrate, and the protection duration in a salt spray corrosion test can be ≥ 24 hours, that is, it can pass the 24-hour test, and most embodiments can also pass the 48-hour test; the ASTM B117 salt spray test method can be used, and reference can also be made to the Examples section below. Conventional alloy nitride coatings generally struggle to achieve a protection duration of 8 hours in a salt spray corrosion test under the same test conditions.

[0246] When the alloy coating of the present application is used for protection, it can also provide better hardness and corrosion resistance than traditional protective layers at the same thickness. Therefore, it can meet the dual requirements of high hardness and high corrosion resistance at a thinner thickness, which is beneficial to saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0247] In the fifth aspect of the present application, a method for preparing an alloy coating is provided, which includes the following steps: using vapor deposition technology to deposit the constituent elements of the alloy coating on at least a portion of the surface of the substrate according to a preset atomic ratio to form the alloy coating described in the first aspect of the present application.

[0248] The preparation method of the alloy coating provided in the present application is simple, easy to operate, green and environmentally friendly, and also has the advantages of being quantifiable, highly efficient and reproducible, and is suitable for industrial applications.

[0249] The definition of the substrate may be referred to in the second aspect of the present application.

[0250] In some embodiments, the method for preparing the alloy coating includes the following steps: under the condition of introducing a mixed gas comprising argon and nitrogen-containing gas, using one or more target materials comprising chromium and zirconium, sputtering and depositing the constituent elements of the alloy coating on at least a portion of the surface of the substrate to form the alloy coating.

[0251] In some embodiments, sputtering coating (eg, magnetron sputtering coating) is used to deposit the constituent elements of the alloy coating on at least a portion of the surface of the substrate according to a preset atomic ratio.

[0252] Please refer to the device shown in Figure 3. The device shown in Figure 3 includes a vacuum chamber 1, a sample stage 2, a DC anode 3, a chromium target 4 and a zirconium target 5; wherein the chromium target 4 is a chromium target with radio frequency assisted DC cathode power, and the zirconium target 5 is a zirconium target with radio frequency assisted DC cathode power. The figure is not drawn in a 1:1 ratio, and the relative sizes of the various elements in the figure are only drawn as examples to facilitate the understanding of the present application, but are not necessarily drawn in true proportion. The proportions in the figure do not constitute a limitation to the present application. The alloy coating of the present application can be formed by reactive sputtering with an N2-containing gas (such as an Ar / N2 mixed gas) in the vacuum chamber 1.

[0253] In some embodiments, a method for preparing an alloy coating comprises the following steps: sputtering and depositing the constituent elements of the alloy coating on at least a portion of the surface of a substrate using one or more targets including chromium and zirconium while introducing a mixed gas comprising argon and a nitrogen-containing gas to form the alloy coating. The nitrogen-containing gas may be, but is not limited to, nitrogen. In this case, the gas ratio of argon to nitrogen in the mixed gas may be (2-6):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, etc. Selecting nitrogen as the nitrogen-containing gas and controlling the nitrogen content to a certain level can further adjust the performance of the alloy coating of the present application.

[0254] The target material may 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 alloy coating. The atomic ratio of the metal elements in the alloy target may be the same as or close to the atomic ratio of the corresponding metal elements in the alloy coating. In some embodiments, the alloy target is a chromium-zirconium-based alloy target, wherein the chromium-zirconium-based alloy target includes at least chromium and zirconium, such as a CrZr alloy target, a CrZrN alloy target, and the like. In some embodiments, the atomic ratio of Cr and Zr in the chromium-zirconium-based alloy target (such as a CrZr alloy target) is 65%:35%. In some embodiments, the alloy target includes all the metal elements in the alloy coating. Examples of alloy targets can be found in Example 1 below.

[0255] In this application, unless otherwise specified, a "chromium-zirconium-based alloy target" includes at least chromium and zirconium, and may include or exclude other elements. When other elements are included, it is understood that the chemical composition of the target material should generally be within the preset chemical formula (Cr x Zr y N z )M a For example, the chromium-zirconium-based alloy target may be a chromium-zirconium-nitrogen alloy target (ie, a CrZrN alloy target) composed of three elements: chromium, zirconium, and nitrogen.

[0256] In some embodiments, a chromium-zirconium alloy target is used to replace the chromium target 4 in FIG. 3 and is installed at the location of the original chromium target 4 in FIG. 3 .

[0257] In some embodiments, the preparation method of the alloy coating, taking the sputtering coating method (such as magnetron sputtering coating) as an example, includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen-containing gas, using a chromium target and a zirconium target or a chromium-zirconium alloy target (i.e., a CrZr alloy target), sputtering and depositing the constituent elements of the alloy coating on at least a portion of the surface of the substrate to form the alloy coating.

[0258] In some embodiments, the step of "sputter-depositing the constituent elements of the alloy coating on at least a portion of the surface of the substrate" further includes the step of cleaning the substrate. The substrate cleaning method can be conventional cleaning methods in the art (including but not limited to the field of decorative plating).

[0259] In some embodiments, cleaning the substrate includes the following steps: ultrasonically cleaning the substrate in water for 10 to 15 minutes, vacuum drying the cleaned substrate for 15 to 20 minutes, and then placing the dried substrate on a sample stage of a sputtering coating device (e.g., magnetron sputtering coating). The sample stage may be a rotatable sample stage.

[0260] In one embodiment, the cleaning treatment of the substrate includes the following steps: placing the substrate in deionized water (DI water) for ultrasonic cleaning for 10 to 15 minutes, placing the cleaned substrate in a vacuum baking oven for 15 to 20 minutes, and placing it on a rotatable sample stage in a vacuum chamber after drying.

[0261] In some embodiments, after the step of "cleaning the substrate", and before the step of "sputtering and depositing constituent elements of the alloy coating on at least a portion of the surface of the substrate", the following step is also included: forming a transition film layer on at least a portion of the surface of the cleaned substrate. For example, the constituent elements of the transition film layer can be deposited on at least a portion of the surface of the cleaned substrate.

[0262] In some embodiments, after the alloy coating of the present application is formed on one side of the substrate, deposition may continue to form a surface film layer, which may be a single-layer structure or a multi-layer structure.

[0263] In some embodiments, the temperature of sputtering deposition 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.

[0264] In some embodiments, the total gas pressure of the mixed gas comprising argon gas and nitrogen-containing gas is 0.5 Pa to 0.9 Pa, for example, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, etc. The pressure unit Pa refers to "Pascal".

[0265] In some embodiments, the target material is sputtered by radio frequency assisted direct current sputtering, which can further improve the performance of the alloy coating formed by sputtering deposition compared to other preparation methods.

[0266] In some embodiments, the target material includes a chromium target, and the power density of the chromium target is 3.5 W / cm 2 ~6.7W / cm 2 Unit: W / cm 2 Refers to "watts per square centimeter".

[0267] In some embodiments, the target material comprises a zirconium target, and the power density of the zirconium target is 0.8 W / cm 2 ~3.5W / cm 2 .

[0268] In some embodiments, 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 ~6W / cm 2 .

[0269] In some embodiments, the substrate is biased at a voltage between -150 V and -20 V; for example, -150 V, -120 V, -100 V, -90 V, -80 V, -60 V, -50 V, -40 V, -30 V, -20 V, etc. The unit V refers to "volts."

[0270] In some embodiments, the nitrogen-containing gas has a flow rate of 5 sccm to 52 sccm, such as 5 sccm, 6 sccm, 8 sccm, 10 sccm, 20 sccm, 25 sccm, 30 sccm, 40 sccm, 50 sccm, or 52 sccm. Furthermore, the nitrogen-containing gas is nitrogen gas. The unit sccm (standard cubic centimeter per minute) is a flow unit used to represent the gas flow rate.

[0271] In some embodiments, the sputtering deposition time is 10 min to 150 min, for example, 10 min, 15 min, 30 min, 45 min, 60 min, 90 min, 100 min, 120 min, etc. The thickness of the alloy coating of the present application can be controlled by adjusting the deposition time. As the deposition time increases, the thickness of the alloy coating increases.

[0272] In some embodiments, the background vacuum degree of the vacuum chamber used is ≤5.0×10 -4 Pa. This pressure setting can ensure the collision between sputtered particles and gas molecules, and can also reduce the entry of impurities into gas molecules during the deposition process, thereby improving the corrosion resistance, purity and bonding strength of the alloy coating of the present application.

[0273] It can be understood that argon and nitrogen-containing gas can be introduced into the vacuum chamber through a single path or mixed through a mixing cylinder and then enter the chamber, thereby reducing the impurity content of the alloy coating of the present application and improving its performance.

[0274] In some embodiments, the preparation method satisfies one or more of the following characteristics:

[0275] The temperature of sputtering deposition is 30℃~330℃;

[0276] The total gas pressure of the mixed gas containing argon and nitrogen is 0.5Pa to 0.9Pa;

[0277] The target material includes a chromium target, and the power density of the chromium target is 3.5W / cm 2 ~6.7W / cm 2 ;

[0278] The target material includes a zirconium target with a power density of 0.8W / cm 2 ~3.5W / cm 2 ;

[0279] The target material includes a chromium-zirconium-based alloy target with a power density of 4W / cm 2 ~6W / cm 2 ;

[0280] The substrate bias voltage is -150V to -20V;

[0281] The gas flow rate of nitrogen is 5 sccm to 52 sccm;

[0282] The sputtering deposition time is 10 min to 150 min;

[0283] The nitrogen-containing gas is nitrogen, and the gas ratio of argon and nitrogen in the mixed gas is (2-6):1;

[0284] The background vacuum degree of the vacuum chamber used is ≤3.0×10 -4 Pa.

[0285] In some embodiments, "using sputtering coating (such as magnetron sputtering coating) technology to deposit the constituent elements of the alloy coating on at least a portion of the surface of the substrate according to a preset atomic ratio" includes the following steps: introducing a mixed gas containing argon and nitrogen-containing gas into the vacuum chamber 1, maintaining the pressure in the vacuum chamber 1 at 0.5 Pa to 0.9 Pa, turning on the bias voltage and setting it to -150 V to -20 V, and setting the power density of the chromium target 4 to 3.5 W / cm 2 ~6.7W / cm 2 , the power density of the zirconium target 5 is set to 0.8W / cm 2 ~3.5W / cm 2 , depositing an alloy coating on at least a portion of the surface of the cleaned substrate; further, alloy coatings with different film thicknesses can be obtained by controlling the film formation time.

[0286] Some examples are provided below.

[0287] 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 intended to illustrate the present application only and are not intended to limit the scope of the present application. The experimental methods for which the conditions are not specified in the following examples are preferably referred to the guidance provided in the present application, and may also be based on the experimental manuals or conventional conditions in this area, or on the conditions recommended by the manufacturer, or with reference to experimental methods known in the art.

[0288] In the following examples, the measured parameters of raw material components may have slight deviations within the range of weighing accuracy unless otherwise specified. For temperature and time parameters, acceptable deviations caused by instrument testing accuracy or operating accuracy are allowed.

[0289] Test method:

[0290] 1. Hardness test of alloy coating

[0291] When testing the hardness of alloy coatings, the sample to be tested uses a substrate that is suitable for actual application.

[0292] The surface material of the "substrate suitable for practical application" may include, but is not limited to: aluminum alloy, stainless steel, and copper sheet.

[0293] In the following examples, unless otherwise specified, aluminum alloy and stainless steel are used as substrates for testing the hardness of alloy coatings. Pre-set preparation parameters are used to deposit alloy coatings on these substrates to obtain test samples for testing the hardness of the alloy coatings. This is primarily due to the fact that during nanoindentation testing, strong pressure is generated when the probe penetrates the test sample, requiring the substrate to possess a certain degree of toughness. Using brittle silicon wafers may cause cracking during testing, leading to inaccurate test results. Alloy materials, due to their superior toughness, are more suitable as test substrates for nanoindentation testing. Furthermore, using alloy materials as substrates to measure nanohardness is more universally applicable in the field of characterizing nanohardness parameters in the coating field.

[0294] The hardness of each film or coating was tested using an NHT3 nanoindenter produced by Anton-Paar, Austria. It was equipped with a tetrahedral Berkvich indenter and the indentation depth was set to 100 nm. The load varied with the indentation depth. Five matrix points were tested for each sample and the average value was taken.

[0295] 2. Salt spray corrosion resistance test of alloy coating

[0296] When testing the salt spray corrosion resistance of alloy coatings, the sample to be tested is a substrate suitable for practical application. The degree to which the alloy coating improves the corrosion resistance of the substrate is determined. The surface material of the "substrate suitable for practical application" can include, but is not limited to, aluminum alloy and stainless steel.

[0297] Adopt ASTM B117 salt spray test standard.

[0298] 12 hours can be used as a sub-cycle of the salt spray corrosion resistance test.

[0299] The test cycle of alloy coatings prepared on substrates of different materials can be different, for example:

[0300] The test cycle for samples containing aluminum alloy matrix is ​​48h or 24h;

[0301] The test cycle for stainless steel substrate samples is 144h or 96h;

[0302] The test period of the copper substrate sample is 12h.

[0303] The standard for "pass (OK)" salt spray corrosion resistance test is: after the sample is tested, there is no corrosion, discoloration, or rust on the surface.

[0304] The standard for "fail (NG)" in the salt spray corrosion resistance test is: after the sample is tested, corrosion, discoloration or rust is found on the surface.

[0305] 3. Morphology and composition test analysis of alloy coating

[0306] All samples to be tested use silicon wafers as substrates.

[0307] Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) testing methods

[0308] Morphology analysis: A scanning electron microscope (SEM) with the model Regulus 8230 produced by Hitachi was used.

[0309] Composition analysis: An energy dispersive X-ray spectrometer (EDX) attached to a Regulus 8230 scanning electron microscope (Hitachi) was used, and the relative intensities of all elements were corrected using the ZAF method.

[0310] Test parameters: electron acceleration voltage is 15 kilovolts (kV), beam current is 10 microamperes (μA), sample magnification is 200 times, and 10 points are tested for each sample and the average is taken.

[0311] 4. X-ray diffraction (XRD) test of alloy coating

[0312] When conducting XRD testing of alloy coatings, silicon wafers were used as substrates.

[0313] 4.1. Calculation of the half-height width of the diffraction peak in the XRD pattern

[0314] A German Bruker D8Advance XRD diffractometer was used in the θ-2θ mode with a Cu target Kα ray and a wavelength λ of 0.15406 nanometers (nm). The X-ray tube was controlled at 40 kilovolts (kV) and 40 milliamperes (mA). The scanning range was 20° to 80°, and precise scanning measurements were performed with a step size of 0.01°.

[0315] The steps for obtaining the half-height width value are as follows: first, the diffraction peak is corrected, including: smoothing, background subtraction, removal of Kα2 line, subtraction of instrument broadening, etc., and the diffraction peak is fitted with the Pseudo-Voigt function to obtain the half-height width value of the diffraction peak.

[0316] The spectral data were processed using EDP2XRD software (version 1.0.0, copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney). The following steps were performed: first, the scale was calibrated, then the center of the diffraction ring transmission spot was determined, and then the data were converted into an XRD pattern (where the electron wavelength was 0.00251 nm and the X-ray wavelength was 0.154 nm). The diffraction peaks were subjected to a straight line background subtraction and then fitted with a Voigt function to obtain the half-height width of the corresponding diffraction peak.

[0317] 4.2. Determine whether the XRD pattern of the alloy coating forms a broad peak

[0318] Method for determining whether there are broad peaks in the diffraction angle 2θ (°) range of 30° to 50° in the XRD diffraction pattern: In the XRD spectrum, if the half-height width of the 2θ (°) diffraction peak is ≥2°, it is judged as a broad peak; if the half-height width of the 2θ (°) diffraction peak is <2°, it is judged as a sharp peak.

[0319] For a given 2θ(°) position, it can be in any of the three states: no peak, sharp peak or broad peak.

[0320] 5. TEM test

[0321] When conducting TEM tests on alloy coatings, silicon wafers were used as substrates.

[0322] 5.1. Obtain the half-width at half maximum of the diffraction rings in the TEM diffraction pattern using the following method:

[0323] TEM test sample preparation: The sample was thinned using a Helios 5CX model focused ion beam (FIB) from Thermo Fisher Scientific Inc., USA, to obtain an electron-transparent, TEM-observable planar sample.

[0324] SAED image acquisition: A Talos F200x transmission electron microscope (TEM) manufactured by Thermo Fisher Scientific Inc. (USA) was used with an electron accelerating voltage of 200 kV and a selected area aperture of 900 nm to obtain selected area electron diffraction (SAED) patterns of the samples.

[0325] Acquisition of radial intensity profile: The SAED spectrum data obtained above were 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 calibrated, then the center of the diffraction ring transmission spot was determined, and finally, the data were converted into a radial intensity profile (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm) with the characteristic atomic spacing as the horizontal axis and the diffraction intensity as the vertical axis.

[0326] The steps for obtaining the half-height width value are as follows: subtract the diffraction peak from the straight line background, and then fit it with the Voigt function to obtain the half-height width value of the corresponding diffraction peak.

[0327] 5.2. Determine the radial intensity profile of the TEM selected area electron diffraction pattern Method to determine whether there is a broad peak within the range: the half-height width of the diffraction peak corresponding to the characteristic atomic spacing is ≥ It is judged as a broad peak; the half-height width of the diffraction peak corresponding to the characteristic atomic spacing is < For a specific characteristic interatomic distance, it can be any of the three states: no peak, sharp peak or broad peak.

[0328] 6. Chromaticity value test of alloy coating

[0329] When testing the chromaticity of an alloy coating, the sample to be tested is a substrate suitable for practical application. The degree to which the alloy coating improves the substrate's properties, such as density, is examined. The surface material of a "substrate suitable for practical application" may include, but is not limited to, aluminum alloy and stainless steel.

[0330] The L value, a value, and b value of the samples were tested using a CM-3700A-U desktop spectrophotometer produced by Konica Japan. The F2 light source was selected as the light receiving system. Six matrix points were tested for each sample and the average value was taken.

[0331] The L value represents the brightness value, the a value represents the red or green chromaticity value, and the b value represents the yellow or blue chromaticity value. The a value represents the red and green color of the object, with positive values ​​representing red chromaticity values ​​and negative values ​​representing green chromaticity values. The b value represents the yellow and blue color of the object, with positive values ​​representing yellow chromaticity values ​​and negative values ​​representing blue chromaticity values.

[0332] A larger L value indicates higher brightness and a denser coating surface. The mechanism is as follows: a spectrophotometer generates a reflectance curve when incident light strikes the surface of the sample being measured, causing reflection. The amplitude of this curve reflects the material's density, which can be represented by the L value. For the same material, the denser it is, the larger the L value it displays.

[0333] 7. Temperature and humidity durability cycle test:

[0334] When testing the alloy coating's temperature and humidity durability cycle, the sample is a substrate suitable for practical application. The degree to which the alloy coating improves the substrate's properties, such as density, is examined. The surface material of the "substrate suitable for practical application" may include, but is not limited to, aluminum alloy and stainless steel.

[0335] Environmental test chamber requirements: can meet the humidity of 90% RH at 65℃, and no humidity requirements at -20℃.

[0336] Test cycle: 72 hours (6 cycles, 12 hours each)

[0337] ℃: degrees Celsius

[0338] RH: relative humidity

[0339] Test steps: perform a single cycle according to the steps in Table 1:

[0340] Table 1.

[0341] Continue for 6 cycles to complete the test.

[0342] Judgment standard: After the test, the sample has no discoloration or corrosion, which means it has passed; after the test, the sample has discoloration or corrosion, which means it has failed.

[0343] In the following examples, DI water refers to deionized water.

[0344] The stainless steel sheets, aluminum alloy sheets and silicon sheets in the following embodiments and comparative examples are made of the same material.

[0345] In the following examples, the target material was sputtered by RF-assisted DC sputtering.

[0346] In the following examples, when the phrase “there is only one broad peak” is used in XRD patterns and SAED-radial intensity profiles, unless otherwise specified, it means there is only one characteristic peak, and that peak is a broad peak.

[0347] Example 1.

[0348] In this example, the chemical composition of the alloy coating is Cr 61.4 Zr 33.2 N 5.4 .

[0349] In this embodiment, the target material is a chromium-zirconium alloy target, and the 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 65%:35%.

[0350] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in deionized water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150°C and keep at this temperature for 15 minutes. Dimensions in mm refer to millimeters and cm to centimeters.

[0351] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0352] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use a radio frequency assisted DC power supply to energize the CrZr alloy target. Pass Ar and N2 gas. Set the N2 gas flow rate to 7 sccm. Set the gas volume to maintain the Ar:N2 gas ratio of 6:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the CrZr alloy target to 5 W / cm 2 , depositing a Cr-Zr-N alloy coating, and controlling the film forming time to obtain a film thickness of 2500nm.

[0353] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0354] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 61.4 Zr 33.2 N 5.4 .

[0355] The aluminum alloy substrate sample tested had a hardness of 15.1 GPa, and the stainless steel substrate sample tested had a hardness of 16.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, and the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0356] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0357] The test sample was characterized by SEM cross section. The cross-sectional morphology can be seen in Figure 4. The XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 5. The SEM test results show that the alloy coating has a dense structure and no penetrating columnar cracks are observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 30° to 50°, and the half-maximum width of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 30° to 50° is ≥2°, among which there is only one broad peak with a half-maximum width of 8.85° in the range of 30° to 50°. The radial intensity profile of the TEM selected area electron diffraction pattern is There is only one broad peak in the range, and the half-height width is

[0358] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample test is L: 79.05, a: 0.43, b: 3.54; the chromaticity value of the stainless steel substrate sample test is L: 81.74, a: 0.33, b: 3.04, and is silvery white in color.

[0359] Example 2.

[0360] In this embodiment, the chemical composition of the alloy coating is Cr 53.8 Zr 40.0 N 6.2 , the preparation method is as follows:

[0361] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0362] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0363] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 8 sccm. Set the gas volume to maintain the Ar:N2 gas ratio of 6:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.2 W / cm 2The power density of the Zr target was set to 3.5W / cm2, and the Cr-Zr-N alloy coating was deposited. By controlling the film formation time, the resulting film thickness was made 2500nm.

[0364] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0365] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 53.8 Zr 40.0 N 6.2 .

[0366] The aluminum alloy substrate sample tested had a hardness of 16.1 GPa, and the stainless steel substrate sample tested had a hardness of 18.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, and the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0367] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0368] The test sample was characterized by SEM cross section. The cross-sectional morphology can be seen in Figure 6. The XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 7. The SEM test results show that the alloy coating has a dense structure and no penetrating columnar cracks are observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 30° to 50°, and the half-maximum width of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 30° to 50° is ≥2°, among which there is only one broad peak with a half-maximum width of 8.42° in the range of 30° to 50°. The radial intensity profile of the TEM selected area electron diffraction pattern is There is only one broad peak in the range, and the half-height width is

[0369] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 77.02, a: 0.52, b: 4.99; the chromaticity value of the stainless steel substrate sample tested is L: 79.36, a: 0.40, b: 4.49, which is silvery white in color.

[0370] Example 3.

[0371] In this embodiment, the chemical composition of the alloy coating is Cr 41.3 Zr 33.2 N25.5 , the preparation method is as follows:

[0372] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0373] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0374] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 33 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 2:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 3.8 W / cm 2 , the power density of the Zr target was set to 3W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 2500nm.

[0375] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0376] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 41.3 Zr 33.2 N 25.5 .

[0377] The aluminum alloy substrate sample tested had a hardness of 17.2 GPa, and the stainless steel substrate sample tested had a hardness of 18.8 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, and the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0378] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0379] The SEM test results show that the alloy coating has a dense structure and no penetrating columnar cracks are observed. The XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be found in Figure 8. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 30° to 50°, and the half-maximum width of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 30° to 50° is ≥2°, of which there are two broad peaks in the range of 30° to 50°, with half-maximum widths of 6.05° and 5.54° respectively; the radial intensity profile of the TEM selected area electron diffraction pattern is There is only one broad peak in the range, and the half-height width is

[0380] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 75.01, a: 0.82, b: 5.52; the chromaticity value of the stainless steel substrate sample tested is L: 77.16, a: 0.64, b: 4.99, which is silvery white in color.

[0381] Example 4.

[0382] In this embodiment, the chemical composition of the alloy coating is Cr 54.8 Zr 35.1 N 10.1 , the preparation method is as follows:

[0383] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, keep at room temperature (about 30℃) for 15 minutes.

[0384] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0385] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 12 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 3:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.3 W / cm 2 , the power density of the Zr target was set to 3.1 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 2200nm.

[0386] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0387] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 54.8 Zr 35.1 N 10.1 .

[0388] The aluminum alloy substrate sample tested had a hardness of 15.9 GPa, and the stainless steel substrate sample tested had a hardness of 17.8 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, and the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0389] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0390] The SEM test results show that the alloy coating has a dense structure and no through-holes are observed. The XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be found in Figure 9. In the XRD diffraction pattern, the diffraction angle 2θ (°) is within the range of 30° to 50° and there is only one broad peak with a half-height width of 9.25°; the radial intensity profile of the TEM selected area electron diffraction pattern is There is only one broad peak in the range, and the half-height width is

[0391] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 76.82, a: 0.54, b: 5.99, and the chromaticity value of the stainless steel substrate sample tested is L: 78.16, a: 0.45, b: 5.49, showing bright silver-white color.

[0392] Example 5.

[0393] In this example, a double-layer film structure is attached to the substrate surface, including a chemical composition of Cr 53.8 Zr 40.0 N 6.2 The alloy coating and the surface film layer with the chemical composition of TiN are recorded as a double-layer film structure as Cr-Zr-N / TiN. In this case, the substrate surface is attached with a multi-layer film structure, in which the alloy coating provided by this application serves as an intermediate film layer, located between the substrate and the surface film layer. The preparation method is as follows:

[0394] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0395] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0396] Deposition of alloy coating (as an intermediate film layer): Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use a radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 8 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 6:1. Maintain the furnace pressure at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.2 W / cm 2 , the power density of the Zr target was set to 3.5 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1000nm.

[0397] Deposition of surface film: Replace the Zr target in the furnace with a Ti target, turn on the sample stage turret, set the speed to 6 revolutions per minute, adjust the distance from the sample stage to the target surface to 8 cm, use a DC power supply to energize the Ti target, introduce Ar and N2 gas, set the N2 gas flow rate to 10 sccm, set the gas volume to maintain the Ar: N2 gas ratio of 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage, set it to -100 V, and set the power density of the Ti target to 5 W / cm 2 , TiN coating is deposited, and by controlling the film formation time, the obtained film thickness is 100nm.

[0398] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples subjected to salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and color value tests. Silicon wafers were used as substrates for samples subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0399] After component analysis, the composition is Cr 53.8 Zr 40.0 N 6.2 The alloy coating surface is covered with a TiN coating.

[0400] The aluminum alloy substrate tested had a hardness of 11.8 GPa, while the stainless steel substrate tested had a hardness of 14.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate passed the test for 48 hours, while the stainless steel substrate passed the test for 144 hours, demonstrating excellent protection.

[0401] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0402] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 56.85, a: 6.65, b: 12.95; the chromaticity value of the stainless steel substrate sample tested is L: 58.83, a: 6.82, b: 13.61, showing a golden color.

[0403] Example 6.

[0404] In this example, a three-layer film structure is attached to the substrate surface, which includes a transition film layer (as a base coating), an alloy coating containing a Cr-Zr-N alloy material, and a surface film layer located on the surface. The three-layer film structure is recorded as Cr / Cr-Zr-N / TiN, where the transition film layer is a Cr layer and the chemical composition of the alloy coating is Cr. 53.8 Zr 40.0 N 6.2 The chemical composition of the surface film is TiN. The preparation method is as follows:

[0405] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0406] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0407] Deposition of bottom coating (transition film): Turn on the sample stage turret, set the speed to 6 revolutions per minute, adjust the distance from the sample stage to the target surface to 8 cm, use a radio frequency assisted DC power supply to energize the Cr target, introduce Ar, set the Ar gas volume to 42 sccm, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100 V, and set the power density of the Cr target to 5 W / cm 2 , depositing a Cr base coating, and by controlling the film forming time, the resulting film thickness is 300nm.

[0408] Deposition of alloy coating (intermediate coating): Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 8 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 6:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.2 W / cm 2 , the power density of the Zr target was set to 3.5 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1000nm.

[0409] Deposition of surface film: Replace the Zr target in the furnace with a Ti target, turn on the sample stage turret, set the speed to 6 revolutions per minute, adjust the distance from the sample stage to the target surface to 8 cm, use a DC power supply to energize the Ti target, introduce Ar and N2 gas, set the N2 gas flow rate to 10 sccm, set the gas volume to maintain the Ar: N2 gas ratio of 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage, set it to -100 V, and set the power density of the Ti target to 5 W / cm 2 , TiN coating is deposited, and by controlling the film formation time, the obtained film thickness is 100nm.

[0410] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0411] The composition analysis shows that there are three layers of thin film structure on the surface of the substrate, and the chemical composition is Cr (transition film layer), Cr 53.8 Zr 40.0 N 6.2 (an alloy coating of the present application) and TiN (surface film layer), the three-layer thin film structure is Cr / Cr-Zr-N / TiN.

[0412] The aluminum alloy substrate tested had a hardness of 13.1 GPa, while the stainless steel substrate tested had a hardness of 13.9 GPa. In the salt spray corrosion test, the aluminum alloy substrate passed the test for 48 hours, while the stainless steel substrate passed the test for 144 hours, demonstrating excellent protection.

[0413] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0414] Chromaticity test results: The aluminum alloy substrate sample tested had a chromaticity of L: 54.69, a: 7.07, b: 14.01, and the stainless steel substrate sample tested had a chromaticity of L: 57.53, a: 7.35, b: 14.50, showing a golden yellow hue. The test results here are the chromaticity values ​​of the TiN surface layer.

[0415] Example 7.

[0416] In this example, the chemical composition of the alloy coating is Cr 53.8 Zr 40.0 N 6.2 , the preparation method is as follows:

[0417] Pretreatment: Copper and silicon wafer samples with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0418] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0419] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use RF-assisted DC power supply to energize the Cr and Zr targets. Pass Ar and N2 gases. Set the N2 gas flow rate to 8 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 6:1. Maintain the furnace pressure at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.2 W / cm 2 , the power density of the Zr target was set to 3.5 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1000nm.

[0420] Samples using copper sheets as the substrate were subjected to salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0421] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 53.8 Zr 40.0 N 6.2 .

[0422] The copper substrate sample tested had a hardness of 8.3 GPa. In the salt spray corrosion test, the copper substrate sample passed the 12-hour test, demonstrating its protective properties.

[0423] In the temperature and humidity durability cycle test, the copper substrate sample can pass the temperature and humidity durability cycle test and has excellent durability performance.

[0424] The SEM test results show that the alloy coating has a dense structure and no through-holes are observed. The diffraction angle 2θ (°) in the XRD diffraction pattern has at least one broad peak in the range of 30° to 50°, and the radial intensity profile of the TEM selected area electron diffraction pattern is There is at least one broad peak in the range.

[0425] The chromaticity values ​​of the copper substrate sample tested are L: 77.81, a: 0.54, b: 5.23, and are bright silver-white in color.

[0426] Example 8. The thickness of the alloy coating is about 50 nm

[0427] The same method as in Example 7 was used, and the chemical composition of the alloy coating was Cr 53.8 Zr 40.0 N 6.2 The only difference is that stainless steel sheet, aluminum alloy sheet and silicon wafer samples are used as substrates to deposit Cr-Zr-N alloy coating, and the thickness of the alloy coating is adjusted to 50nm.

[0428] The aluminum alloy substrate sample tested had a hardness of 8.1 GPa, while the stainless steel substrate sample tested had a hardness of 9.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, while the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protective properties.

[0429] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0430] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 78.12, a: 0.54, b: 4.79; the chromaticity value of the stainless steel substrate sample tested is L: 79.86, a: 0.41, b: 4.69, showing bright silver-white color.

[0431] Example 9. The thickness of the alloy coating is about 6 μm

[0432] The same method as in Example 7 was used, and the chemical composition of the alloy coating was Cr 53.8 Zr 40.0 N 6.2 The only difference is that stainless steel sheet, aluminum alloy sheet and silicon wafer samples are used as substrates to deposit Cr-Zr-N alloy coating, and the thickness of the alloy coating is adjusted to 6000nm.

[0433] The aluminum alloy substrate sample tested had a hardness of 19.1 GPa, while the stainless steel substrate sample tested had a hardness of 20.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, while the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protective properties.

[0434] In the temperature and humidity durability cycle test, aluminum alloy and stainless steel substrate samples can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0435] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 75.22, a: 0.58, b: 5.29; the chromaticity value of the stainless steel substrate sample tested is L: 76.76, a: 0.48, b: 5.42, showing a bright silver-white color.

[0436] Example 10. Containing doping elements

[0437] In this embodiment, the chemical composition of the alloy coating containing doping elements is Cr 41.3 Zr 33.2 N 20.5 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 approximately 43.47:34.95:21.58. The atomic percentage of the doping element C in the alloy coating is 5%. The preparation method is as follows:

[0438] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0439] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0440] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar, C2H2 and N2 gases. Set the N2 gas flow rate to 33 sccm and the C2H2 gas flow rate to 6 sccm. Set the gas volume to maintain the Ar: (C2H2 + N2) gas ratio at 2:1. Maintain the pressure in the furnace at 0.7 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 3.8 W / cm 2 , the power density of the Zr target was set to 3.0 W / cm 2, depositing Cr-Zr-NC alloy coating, by controlling the film forming time, the obtained film thickness is 1600nm.

[0441] Stainless steel sheets and aluminum alloy sheets were used as substrate samples to conduct salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and color value tests.

[0442] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 41.3 Zr 33.2 N 20.5 C5.

[0443] The aluminum alloy substrate sample tested had a hardness of 12.1 GPa, and the stainless steel substrate sample tested had a hardness of 13.3 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 48-hour test, and the stainless steel substrate sample passed the 144-hour test, demonstrating excellent protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0444] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 74.71, a: 0.81, b: 5.22; the chromaticity value of the stainless steel substrate sample tested is L: 76.26, a: 0.62, b: 4.69, showing bright silver-white color.

[0445] The SEM cross-section test was performed on the test sample, and the SEM test results showed that the Cr-Zr-N alloy coating had a dense structure.

[0446] The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has at least one broad peak in the range of 30° to 50°; the TEM test results show that the radial intensity profile of the TEM selected area electron diffraction pattern is There is at least one broad peak in the range.

[0447] According to the experimental exploration results of the inventors, when other non-metallic doping elements (such as Si, B, O, etc.) or metal doping elements (such as Al) are used, when the atomic ratio of the doping elements is appropriate (such as 4at%, 2at%), it can also provide higher hardness and excellent corrosion resistance. In some embodiments, in the salt spray corrosion resistance test experiment, the aluminum alloy substrate sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test. It can also have excellent durability. It can also have at least one broad peak in the diffraction angle 2θ (°) range of 30° to 50° in the XRD diffraction pattern, and the radial intensity profile of the TEM selected area electron diffraction pattern is There is at least one broad peak in the range.

[0448] "at%" means atomic percent, by number.

[0449] Example 11.

[0450] In this embodiment, the chemical composition of the alloy coating is Cr 55.5 Zr 39.1 N 5.4 The elemental composition does not conform to the aforementioned formula 1.8y-19.7≤x≤-1.1y+98.5.

[0451] The preparation method is as follows:

[0452] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0453] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0454] Deposition of the alloy coating of the present application: Turn on the sample stage turret, set the speed to 6 revolutions per minute, adjust the distance from the sample stage to the target surface to 8 cm, use a radio frequency assisted DC power supply to energize the Cr target and the Zr target, introduce Ar and N2 gas, set the N2 gas flow rate to 7 sccm, set the gas volume to maintain the Ar: N2 gas ratio of 6:1, maintain the pressure in the furnace at 0.7 Pa, turn on the bias voltage and set it to -100 V, and set the power density of the Cr target to 4.5 W / cm 2 , the power density of the Zr target was set to 2.9 W / cm 2 , depositing Cr-Zr-N alloy coating, and by controlling the film forming time, the obtained film thickness is 60nm.

[0455] Stainless steel sheets and aluminum alloy sheets were used as substrate samples to conduct salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and color value tests.

[0456] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 55.5 Zr 39.1 N 5.4 .

[0457] The aluminum alloy substrate sample tested had a hardness of 8.2 GPa, and the stainless steel substrate sample had a hardness of 9.1 GPa. In the salt spray corrosion test, the aluminum alloy substrate sample passed the 24-hour test (but failed the 48-hour test), and the stainless steel substrate sample passed the 96-hour test (but failed the 144-hour test), demonstrating good protection. The aluminum alloy and stainless steel substrate samples also passed the temperature and humidity durability cycle test, demonstrating excellent durability.

[0458] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 77.25, a: 0.52, b: 4.96; the chromaticity value of the stainless steel substrate sample tested is L: 79.58, a: 0.42, b: 4.67, which is silvery white in color.

[0459] In addition, the inventors of the present application have found through a large number of experimental explorations that for the alloy coating of the present application, when the following two conditions are met at the same time: (1) the diffraction angle 2θ (°) in the XRD diffraction pattern has at least one broad peak in the range of 30° to 50°, and (2) the radial intensity profile of the TEM selected area electron diffraction pattern is The prepared Cr-Zr-N alloy coating has high hardness and excellent corrosion resistance. If only the XRD diffraction pattern has at least one broad peak in the range of 30° to 50° in the diffraction angle 2θ (°) and the radial intensity profile of TEM-SAED is If there is no broad peak in the range, 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 test. There is at least one broad peak in the range of 0.044° to 0.063°, while there is no broad peak in the diffraction angle 2θ (°) in the XRD diffraction pattern in the range of 30° to 50°, which may also lead to poor corrosion resistance of the Cr-Zr-N alloy coating. Please refer to Comparative Example 4 below.

[0460] Comparative Example 1.

[0461] In this comparative example, the chemical composition of the alloy coating is Cr 88.9 Zr 11.1 The preparation method is as follows:

[0462] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0463] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0464] Deposition of Cr-Zr alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance between the sample stage and the target surface to 8 cm. Use RF-assisted DC power supply to energize the Cr and Zr targets. Introduce Ar gas and maintain the pressure in the furnace at 0.6 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 6.7 W / cm 2 , the power density of the Zr target was set to 0.8 W / cm 2 , depositing Cr-Zr alloy coating, by controlling the film forming time, the obtained film thickness is 1900nm.

[0465] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and color value tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis tests.

[0466] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 88.9 Zr 11.1 .

[0467] The hardness of the aluminum alloy substrate sample tested was 18.5GPa, and the hardness of the stainless steel substrate sample tested was 19.6GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <24 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <48 hours), indicating poor protection properties.

[0468] After the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration and failed, and did not have durable performance.

[0469] The test sample was subjected to SEM cross-sectional testing, and the cross-sectional morphology is shown in Figure 10. The SEM test results show that the alloy coating film has crystal defects, a loose structure, and obvious gaps.

[0470] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 83.21, a: -0.21, b: 0.88; the chromaticity value of the stainless steel substrate sample tested is L: 85.05, a: -0.25, b: 0.79, which is silvery white in color.

[0471] Comparative Example 2.

[0472] In this comparative example, the chemical composition of the alloy coating is Cr 37.8 Zr 16.2 N46 , the preparation method is as follows:

[0473] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0474] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0475] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 52 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 2:1. Maintain the pressure in the furnace at 0.9 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 3.5 W / cm 2 , the power density of the Zr target was set to 1.8 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1000nm.

[0476] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0477] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 37.8 Zr 16.2 N 46 .

[0478] The hardness of the aluminum alloy substrate sample tested was 16.6GPa, and the hardness of the stainless steel substrate sample tested was 18.1GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <24 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <48 hours), indicating poor protection properties.

[0479] After the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration and failed, and did not have durable performance.

[0480] The test sample was subjected to SEM cross-section test, and the cross-sectional morphology can be found in Figure 11. The test results of XRD diffraction pattern, TEM selected area electron diffraction pattern and radial intensity profile can be found in Figure 12. The SEM test results show that the alloy coating film has a loose structure and has obvious penetrating columnar cracks. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has two peaks in the range of 30° to 50°, and both are sharp peaks (2θ peaks with half-height width values ​​of <2°), among which the half-height widths of the two peaks in the range of 30° to 50° are 0.66° and 1.24° respectively. The radial intensity profile of the TEM selected area electron diffraction pattern is There are two peaks in the range, with full width at half maximum of That is, there are two peaks.

[0481] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 61.87, a: 0.57, b: 4.45; the chromaticity value of the stainless steel substrate sample tested is L: 67.38, a: 0.49, b: 4.29. The color is dull and does not have a metallic color.

[0482] Comparative Example 3.

[0483] In this comparative example, the thin film structure is TiN, and the chemical composition of the alloy coating is TiN.

[0484] To prepare the coating of this comparative example, the Zr target in the furnace was replaced with a Ti target. The preparation method is as follows:

[0485] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0486] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0487] Deposition of TiN coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use a DC power supply to energize the Ti target. Pass Ar and N2 gas. Set the N2 gas flow rate to 10 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 3:1. Maintain the pressure in the furnace at 0.5 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Ti target to 5 W / cm 2 , TiN coating is deposited, and by controlling the film formation time, the obtained film thickness is 200nm.

[0488] Stainless steel sheets and aluminum alloy sheets were used as substrate samples to conduct salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and color value tests.

[0489] The composition analysis showed that the alloy coating on the substrate surface was composed of TiN.

[0490] The hardness of the aluminum alloy substrate sample tested was 3.8GPa, and the hardness of the stainless steel substrate sample tested was 4.3GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours).

[0491] After the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration and failed, and did not have durable performance.

[0492] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 57.95, a: 6.45, b: 13.95; the chromaticity value of the stainless steel substrate sample tested is L: 59.33, a: 6.92, b: 13.91, which is golden in color.

[0493] Comparative Example 4.

[0494] In this comparative example, the chemical composition of the alloy coating is Cr 39.6 Zr 19.4 N 41 , the preparation method is as follows:

[0495] Pretreatment: Stainless steel sheets, aluminum alloy sheets and silicon wafers with an aspect ratio of 50 mm × 50 mm were ultrasonically cleaned in DI water for 15 minutes, dried in a baking oven and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5 × 10 -4 Pa, heat to 150℃ and keep constant temperature for 15 minutes.

[0496] Plasma cleaning: Ar gas was introduced, the furnace pressure 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 use plasma etching to remove tiny impurities on the sample surface.

[0497] Deposition of alloy coating: Turn on the sample stage turret and set the speed to 6 revolutions per minute. Adjust the distance from the sample stage to the target surface to 8 cm. Use radio frequency assisted DC power supply to energize the Cr target and Zr target. Pass Ar and N2 gas. Set the N2 gas flow rate to 45 sccm. Set the gas volume to maintain the Ar:N2 gas ratio at 2:1. Maintain the pressure in the furnace at 0.8 Pa. Turn on the bias voltage and set it to -100 V. Set the power density of the Cr target to 4.6 W / cm 2, the power density of the Zr target was set to 2.2 W / cm 2 , depositing Cr-Zr-N alloy coating, by controlling the film forming time, the obtained film thickness is 1400nm.

[0498] Stainless steel sheets and aluminum alloy sheets were used as substrates for samples to undergo salt spray corrosion resistance tests, temperature and humidity durability cycle tests, hardness tests, and colorimetry tests. Silicon wafers were used as substrates for samples to undergo SEM and composition analysis, XRD analysis, and TEM testing.

[0499] According to the composition analysis, the alloy coating on the substrate surface is composed of Cr 39.6 Zr 19.4 N 41 .

[0500] The hardness of the aluminum alloy substrate sample tested was 15.4GPa, and the hardness of the stainless steel substrate sample tested was 17.2GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours), indicating that it does not have the protective properties of the substrate.

[0501] After the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration and failed, and did not have durable performance.

[0502] The SEM test results show that the alloy coating film has crystal defects, a loose structure, and obvious penetrating columnar cracks. The XRD diffraction pattern, TEM selected area electron diffraction pattern, and radial intensity profile of the alloy coating can be found in (A), (B), and (C) of Figure 13. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has two peaks in the range of 30° to 50°, and both are sharp peaks (2θ peaks with a half-height width value of <2°). Among them, the half-height widths of the two peaks in the range of 30° to 50° are 1.87° and 1.02°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern is There are two peaks in the range, with full width at half maximum of That is, there is one peak.

[0503] Chromaticity test results: The chromaticity value of the aluminum alloy substrate sample tested is L: 64.71, a: 0.58, b: 4.15; the chromaticity value of the stainless steel substrate sample tested is L: 66.38, a: 0.49, b: 4.27, which is silvery white in color.

[0504] Comparative Example 5. Alloy coating thickness 50nm

[0505] The same method as in Comparative Example 4 was used, and the chemical composition of the alloy coating was Cr 39.6 Zr19.4 N 41 The difference is that the thickness of the alloy coating is different, changing from 1400nm to 50nm.

[0506] The hardness of the aluminum alloy substrate sample tested was 9.1GPa, and the hardness of the stainless steel substrate sample tested was 9.8GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours), indicating that it does not have the protective properties of the substrate.

[0507] In the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration after the temperature and humidity durability cycle test, failed, and did not have durable performance.

[0508] Comparative Example 6: Alloy coating thickness 1000 nm

[0509] The same method as in Comparative Example 4 was used, and the chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 The difference is that the thickness of the alloy coating is different, changing from 1400nm to 1000nm.

[0510] The hardness of the aluminum alloy substrate sample tested was 16.5GPa, and the hardness of the stainless steel substrate sample tested was 17.9GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours), indicating that it does not have the protective properties of the substrate.

[0511] In the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration after the temperature and humidity durability cycle test, failed, and did not have durable performance.

[0512] Comparative Example 7: Alloy coating thickness 2500 nm

[0513] The same method as in Comparative Example 4 was used, and the chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 The difference is that the thickness of the alloy coating is different, changing from 1400nm to 2500nm.

[0514] The hardness of the aluminum alloy substrate sample tested was 20.5GPa, and the hardness of the stainless steel substrate sample tested was 21.1GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours), indicating that it does not have the protective properties of the substrate.

[0515] In the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration after the temperature and humidity durability cycle test, failed, and did not have durable performance.

[0516] Comparative Example 8: Alloy coating thickness 6000 nm

[0517] The same method as in Comparative Example 4 was used, and the chemical composition of the alloy coating was Cr 39.6 Zr 19.4 N 41 The difference is that the thickness of the alloy coating is different, changing from 1400nm to 6000nm.

[0518] The hardness of the aluminum alloy substrate sample tested was 22.1GPa, and the hardness of the stainless steel substrate sample tested was 23.7GPa. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48-hour test (NG, protection duration <12 hours), and the stainless steel substrate sample failed the 144-hour test (NG, protection duration <24 hours), indicating that it does not have the protective properties of the substrate.

[0519] In the temperature and humidity durability cycle test, the aluminum alloy and stainless steel substrate samples had discoloration after the temperature and humidity durability cycle test, failed, and did not have durable performance.

[0520] Comparative Examples 9-11. No protective coating

[0521] Salt spray corrosion resistance tests were conducted on aluminum alloy chips, stainless steel chips, and copper chips. The results showed that obvious corrosion occurred within 12 hours.

[0522] Result analysis:

[0523] The alloy coatings provided in this application all have certain relative contents of Cr, Zr, and N elements, and the nitrogen content is lower than that of traditional nitrogen-containing alloy coatings.

[0524] The alloy coatings (Examples 1-11) provided in this application can be used as the protective coating itself or as part of the protective coating, and can provide high hardness and excellent corrosion resistance. In addition, they also have excellent durability.

[0525] According to the salt spray corrosion resistance test results, the alloy coatings provided in the present application (Examples 1-11) can all bring excellent corrosion resistance to the substrate; among them, Examples 1-4 and 7-11 are single-layer thin film structures, and the alloy coatings provided in the present application directly provide surface protection for the substrate; Example 5 is a double-layer thin film structure, and the alloy coating provided in the present application serves as the lower protective layer, and a surface film layer (TiN) is also attached to the surface of the alloy coating away from the substrate, and the TiN coating serves as a surface decorative coating (located on the upper layer); the alloy coating of Example 6 is a three-layer thin film structure, which includes a transition film layer (as a bottom coating), an alloy coating, and a TiN coating located on the surface in sequence from the substrate surface; the alloy coating in Example 10 contains a certain atomic percentage of doping elements (≤5at%).

[0526] Examples 1-6, 8-10 all used aluminum alloy and stainless steel substrates. The aluminum alloy surface passed the 48-hour salt spray corrosion test, and the stainless steel surface passed the 144-hour salt spray corrosion test. Example 7 used a copper substrate, and the copper substrate (compared to aluminum alloy, copper is a more active alloy) passed the 12-hour salt spray corrosion test.

[0527] The elemental composition of the alloy coating in Example 11 does not conform to the aforementioned formula 1.8y-19.7≤x≤-1.1y+98.5, and can pass the 24h salt spray corrosion resistance test on the aluminum alloy surface (but fails the 48h test), and can pass the 96h salt spray corrosion resistance test on the stainless steel surface (but fails the 144h test).

[0528] The protective coatings of Examples 1-11 (including the exemplary alloy coatings of the present application) can pass the temperature and humidity durability cycle test and have excellent durability performance.

[0529] The alloy coating provided in this application can be independently used as a single-layer film, or it can be located in a multi-layer composite film. For example, it can be used as one of the layers, that is, as a surface film layer (exposed), as a bottom coating (contacting the substrate), or as an intermediate layer (located between the bottom coating and the surface film layer).

[0530] According to the XRD test and TEM test results, the alloy coating provided by the present application (Examples 1-11) has at least one broad peak in the diffraction angle 2θ (°) in the XRD diffraction pattern within the range of 30° to 50°. Furthermore, the half-height width satisfies ≥2° (and also satisfies ≥3.5°), and the radial intensity profile of the TEM selected area electron diffraction pattern is ≥1. There is at least one broad peak within the range, and further, the half-height width is ≥ (Also meet the requirements of ≥ ), the alloy coatings of each embodiment have a "highly disordered and fully densely packed" atomic arrangement, which is consistent with the highly dense structure in the SEM morphology characterization results.

[0531] The bare substrate chips of Comparative Examples 9-11, without a protective coating, were not resistant to salt spray corrosion and exhibited significant corrosion within 12 hours.

[0532] The alloy coating film of Comparative Example 1 lacked nitrogen, while the alloy coating films of Comparative Examples 2 and 4 had a high nitrogen content. Comparative Example 3 did not have the alloy coating of the present application (Comparative Example 3 was a TiN coating). The results showed that all of Comparative Examples 1-4 failed the corrosion resistance test (NG). The inventors speculate that this may be due to the film structure being loose and having gaps, such as penetrating column gaps, which caused the corrosive solution to quickly pass through the gaps and contact the substrate, thereby causing the coating to fail in corrosion resistance.

[0533] For the alloy coatings of different thicknesses in Comparative Examples 5-8, their hardness and corrosion resistance are significantly inferior to those of the alloy coatings of the present application with the same thickness. Among them, even though Comparative Example 8 adopts a thickness of up to 6000 nm (6 microns), its hardness is relatively high, but its corrosion resistance is still relatively poor. The reasons may be speculated to be: the film structure is not dense, and there are gaps, such as the presence of penetrating column gaps, which causes the corrosive solution to quickly pass through the gaps and contact the substrate, thereby causing the corrosion resistance of the coating to fail; although increasing the thickness of the coating can increase the hardness of the coating, structural defects still exist. The alloy coating provided by the present application can have both high hardness characteristics and excellent corrosion resistance at a relatively low thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs.

[0534] When the alloy coating is thin, the formed coated product can also present a silvery white metallic color, which is close to the color of the base metal, which is conducive to achieving a beautiful decorative effect without changing the color of the base.

[0535] In the temperature and humidity durability cycle test of Comparative Examples 1-8, the aluminum alloy and stainless steel substrate samples had discoloration after the temperature and humidity durability cycle test, failed, and did not have durability.

[0536] The technical features of the above-mentioned embodiments and examples can be combined in any appropriate manner. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments and examples are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0537] The above embodiments and examples only express several embodiments of the present application, which are convenient for understanding the technical solutions of the present application in detail, but they cannot be understood as limiting the scope of protection of the present application. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several variations and improvements can be made, which all fall within the scope of protection of the present application. In addition, it should be understood that after reading the above teaching content of the present application, those skilled in the art can make various changes or modifications to the present application, and the equivalent forms obtained also fall within the scope of protection of the present application. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description and drawings can be used to interpret the content of the claims.

Claims

1. A low-nitrogen alloy coating, wherein: The alloy coating contains a Cr-Zr-N alloy material, and 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, 41.3≤x≤61.4, 33.2≤y≤40.0, 5.4≤z≤25.5, and 0≤a / (x+y+z+a)≤0.

05.

2. The alloy coating according to claim 1, wherein: The sum of x, y, and z is 100.

3. The alloy coating according to claim 1 or 2, wherein: 1.8y-19.7≤x≤-1.1y+98.

5.

4. The alloy coating according to any one of claims 1 to 3, wherein The alloy coating meets the following two characteristics: The X-ray diffraction pattern of the Cr-Zr-N alloy material or the alloy coating has a peak in the diffraction angle 2θ (°) range of 30° to 50°, and the half-height width of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥ 2°; In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material or the alloy coating, the characteristic atomic spacing is taken as the abscissa and the diffraction intensity is taken as the ordinate. There are diffraction peaks in the range of The half-width of at least one diffraction peak in the range satisfies 5. The alloy coating according to claim 4, wherein: The X-ray diffraction pattern of the alloy coating has a half-width of at least one 2θ(°) diffraction peak within the range of 30° to 50° that satisfies ≥3.5°.

6. The alloy coating according to claim 4 or 5, wherein: The radial intensity profile corresponding to the selected area electron diffraction pattern of the alloy coating is The half-width of at least one diffraction peak in the range satisfies 7. The alloy coating according to any one of claims 1 to 6, wherein The thickness of the alloy coating is d min ~6μm, where d min Selected from 10nm to 50nm.

8. The alloy coating according to claim 7, wherein: d min It is 10nm, 20nm, 25nm, 30nm, 40nm or 50nm.

9. The alloy coating according to any one of claims 1 to 8, wherein a=0 or 0, the doping element is a non-metallic element, a metallic element or a combination thereof; 10. The alloy coating according to any one of claims 1 to 9, wherein: The non-metallic elements include one or more of O, C, B, Si and Ar; The metal elements include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

11. A Cr-Zr-N alloy material as defined in any one of claims 1-6, 9-10. The alloy coating is located on at least one side of the substrate.

12. A coated product comprising a substrate and an alloy coating according to any one of claims 1 to 10; wherein: The surface material of the substrate is one of alloy, elemental metal and inorganic non-metallic material; 13. The coated product according to claim 12, wherein: 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 elemental 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 ceramics and glass. The surface material of the substrate is one of the light alloys or one of the stainless steel alloys; 14. The coated product according to claim 12 or 13, wherein: Optionally, the light alloy includes one or more of a titanium alloy, an aluminum alloy and a magnesium alloy. The coated product meets one or more of the following characteristics:

15. The plated product according to any one of claims 12 to 14, wherein: The alloy coating is in direct contact with the substrate or is provided with a transition film layer; The alloy coating is located on the surface of the film-coated product or a surface film layer is provided on the side of the alloy coating away from the substrate, and the surface film layer is a single-layer structure or a multi-layer structure.

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

17. A method for preparing an alloy coating, comprising the following steps: using vapor deposition technology to deposit the constituent elements of the alloy coating on at least a portion of the surface of a substrate according to a preset atomic ratio to form the alloy coating according to any one of claims 1 to 11. The preparation method of the alloy coating comprises the following steps: under the condition of introducing a mixed gas comprising argon and nitrogen-containing gas, using one or more target materials comprising chromium and zirconium, sputtering and depositing the constituent elements of the alloy coating on at least a portion of the surface of the substrate to form the alloy coating.

18. The preparation method according to claim 17, wherein: ​ 19. The preparation method according to claim 18, wherein: The preparation method meets one or more of the following characteristics: The temperature of sputtering deposition is 30℃~330℃; The total gas pressure of the mixed gas containing argon gas and nitrogen-containing gas is 0.5Pa to 0.9Pa; The target material includes a chromium target, and the power density of the chromium target is 3.5 W / cm 2 ~6.7W / cm 2 ; The target material includes a zirconium target, and the power density of the zirconium target is 0.8 W / cm 2 ~3.5W / cm 2 ; The target material includes an alloy target, and the alloy target includes at least two metal elements in the alloy coating; optionally, the target material includes a chromium-zirconium-based alloy target, and the power density of the chromium-zirconium-based alloy target is 4W / cm 2 ~6W / cm 2 ; The bias voltage of the substrate is -150V to -20V; The sputtering deposition time is 10min to 150min; The nitrogen-containing gas is nitrogen gas, and the gas flow rate of the nitrogen gas is 5 sccm to 52 sccm; The nitrogen-containing gas is nitrogen, and the gas volume ratio of argon and nitrogen in the mixed gas is (2-6):1.

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