Cr-zr-n alloy material and alloy coating, alloy film product, use in high-brightness surface coating, and preparation method

Abstract

The present application relates to a Cr-Zr-N alloy material and alloy coating, an alloy film product, the use in a high-brightness surface coating, and a preparation method. The chemical formula of the Cr-Zr-N alloy material is (CrxZryNz)Ma, wherein M is a doping element, x, y, z and a are each independently atomic ratios, 47.1≤x≤81.6, 12.1≤y≤33.2, 4.7≤z≤35.9, and 0≤a / (x+y+z+a)≤0.05.

Description

Cr-Zr-N alloy materials, alloy coatings, alloy film products, applications and preparation methods in high-gloss surface coatings

[0001] Related applications

[0002] This application claims priority to Chinese Patent Application No. CN2023107494675, filed on June 21, 2023, entitled "Cr-Zr-N Alloy Materials and Alloy Coatings, Alloy Film Articles, Applications and Preparation Methods in High-Gloss Surface Coatings", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of alloy coating technology, and in particular to Cr-Zr-N alloy materials and alloy coatings, alloy film products, their application in high-brightness surface coatings, and preparation methods. Background Technology

[0004] With the development of technology and the improvement of living standards, people are not only focusing on the practical performance of products in various fields such as automobiles, wearable products, 3C products, and sports products, but also placing higher demands on the aesthetics of product appearance, such as a significant increase in attention to high-gloss surfaces. Among these products, the representative "3C products" are a collective term for computer, communication, and consumer electronics products, also known as "information appliances," such as computers, tablets, mobile phones, or digital audio players. Because 3C products are generally small in size, they are often collectively referred to as "3C small appliances."

[0005] One traditional method to improve the surface gloss of products is to use an alloy coating with a high chromium (Cr) content. However, such coatings usually have poor corrosion resistance and are prone to corrosion during use.

[0006] Therefore, it is necessary to develop new alloy coating materials in order to prepare alloy coatings with high brightness and good corrosion resistance.

[0007] Summary of the Invention

[0008] According to various embodiments and examples of this application, one aspect of this application provides a Cr-Zr-N alloy material; in addition, other aspects of this application also provide Cr-Zr-N alloy coatings and alloy film articles, as well as the application of the aforementioned Cr-Zr-N alloy material or Cr-Zr-N alloy coating in high-brightness surface coatings and the preparation method of the aforementioned Cr-Zr-N alloy coating.

[0009] In a first aspect of this application, a Cr-Zr-N alloy material is provided, wherein the chemical formula of the Cr-Zr-N alloy material is (Cr x Zry N z M a M is a dopant element, where x, y, z and a are each an atomic ratio, 47.1≤x≤81.6, 12.1≤y≤33.2, 4.7≤z≤35.9, and 0≤a / (x+y+z+a)≤0.05.

[0010] In some implementations, the sum of x, y, and z is 100.

[0011] In some implementations, y is greater than z.

[0012] In some implementations, 63.19-0.925y≤x≤95.79-y and 31.4+0.9y≤x≤18.5y-171.85.

[0013] In some embodiments, the doping element is a non-metallic element, a metallic element, or a combination thereof;

[0014] The non-metallic elements include one or more of O, C, B, Si, and Ar;

[0015] The metallic elements include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0016] In some implementations, 0 ≤ a / (x+y+z+a) ≤ 0.02.

[0017] In a second aspect of this application, a Cr-Zr-N alloy coating is provided, the Cr-Zr-N alloy coating comprising a film layer formed from the Cr-Zr-N alloy material described in the first aspect of this application.

[0018] In some embodiments, the Cr-Zr-N alloy coating satisfies the following two characteristics:

[0019] The X-ray diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2°.

[0020] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating, the characteristic atomic spacing is used as the abscissa and the diffraction intensity is used as the ordinate. It has diffraction peaks within the range, and The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies

[0021] In some embodiments, the Cr-Zr-N alloy coating satisfies one or more of the following characteristics:

[0022] The X-ray diffraction pattern of the Cr-Zr-N alloy coating was obtained by Kα radiation from a Cu target;

[0023] The selected area electron diffraction pattern of the Cr-Zr-N alloy coating was obtained using TEM characterization technology, with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0024] In some embodiments, the thickness of the Cr-Zr-N alloy coating is d. min ~6μm, where d min Selected from 10nm to 50nm;

[0025] Optionally, d min The process involves using 10nm, 20nm, 25nm, 30nm, 40nm, or 50nm.

[0026] Optionally, the thickness of the Cr-Zr-N alloy coating is 1 μm to 2.5 μm.

[0027] In a third aspect of this application, an alloy film article is provided, comprising a substrate and the Cr-Zr-N alloy coating described in the second aspect of this application; wherein the Cr-Zr-N alloy coating is located on at least one side of the substrate.

[0028] In some embodiments, the surface material of the substrate is one of alloy, elemental metal, and inorganic non-metallic material;

[0029] Optionally, the alloy material type 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 materials;

[0030] Optionally, the elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium;

[0031] Optionally, the inorganic non-metallic material includes one or more of ceramics and glass.

[0032] In some embodiments, the surface material of the substrate is one of light alloys or one of stainless steel alloys;

[0033] Optionally, the light alloy includes one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0034] In some embodiments, the alloy film article satisfies one or more of the following characteristics:

[0035] The Cr-Zr-N alloy coating is in direct contact with the substrate or has a transition layer;

[0036] The Cr-Zr-N alloy coating is located on the surface of the alloy film product, or the Cr-Zr-N alloy coating is further provided with a surface layer on the side away from the substrate, and the surface layer is a single-layer structure or a multi-layer structure.

[0037] In some embodiments, the alloy film product is one of the following: 3C digital products, automotive products, aerospace products, wearable products, and sports products.

[0038] In a fourth aspect of this application, the application of the Cr-Zr-N alloy material described in the first aspect of this application in the preparation of a high-brightness surface coating or the application of the Cr-Zr-N alloy coating described in the second aspect of this application as a high-brightness surface coating is provided, wherein, by Lab method testing, the brightness value L of the high-brightness surface coating is ≥70; wherein, the high-brightness surface coating is also a corrosion-resistant protective coating.

[0039] In a fifth aspect of this application, a method for preparing an alloy coating is provided, comprising the following steps: using vapor deposition technology to deposit the constituent elements of the Cr-Zr-N alloy coating at a preset atomic ratio on at least a portion of the surface of a substrate to form the Cr-Zr-N alloy coating described in the second aspect of this application.

[0040] In some embodiments, the method for preparing the Cr-Zr-N alloy coating includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using one or more targets including chromium and zirconium, sputtering depositing the constituent elements of the Cr-Zr-N alloy coating on at least a portion of the surface of the substrate to form the Cr-Zr-N alloy coating.

[0041] In some embodiments, the preparation method satisfies one or more of the following characteristics:

[0042] The sputtering deposition temperature is 30℃~330℃;

[0043] The total pressure of the mixed gas containing argon and nitrogen is 0.3 Pa to 1.2 Pa.

[0044] The target material includes a chromium target and a zirconium target, and the power density of the chromium target is 3.5 W / cm². 2 ~6.7W / cm 2 The power density of the zirconium target is 0.5 W / cm². 2 ~3.0W / cm 2 ;

[0045] The target material includes an alloy target comprising at least two metallic elements found in the Cr-Zr-N alloy coating; optionally, the target material includes a chromium-zirconium-based alloy target with a power density of 4 W / cm³. 2 ~6W / cm 2 ;

[0046] The substrate is biased from -150V to -20V;

[0047] The sputtering deposition time is 10 min to 150 min;

[0048] The nitrogen-containing gas is nitrogen, and the flow rate of the nitrogen gas is 5 sccm to 52 sccm;

[0049] The nitrogen-containing gas is nitrogen, and the ratio of argon to nitrogen in the mixed gas is (2-6):1.

[0050] Details of one or more embodiments of the present invention are set forth in the following drawings and description. Other features, objects, and advantages of the invention will become apparent from the specification, drawings, and claims. Attached Figure Description

[0051] To more clearly illustrate the technical solutions in the embodiments or examples of this application, and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments or examples will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of this application. Those skilled in the art can obtain other drawings based on these drawings without creative effort. 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 illustrating this application. The various dimensions of each component shown in the drawings are arbitrarily shown; they may be precise or not drawn to scale. For example, to make the illustration clearer, the dimensions of some components are appropriately exaggerated in the drawings. Unless otherwise specified, the components in the drawings are not drawn to scale. This application does not limit each dimension of each component.

[0052] In the following description, the same reference numerals indicate the same parts.

[0053] Figure 1 is a schematic diagram of the structure of an exemplary alloy film article containing the Cr-Zr-N alloy material of this application in one embodiment of the present application, including a substrate and an exemplary Cr-Zr-N alloy coating of this application;

[0054] Figure 2 is a schematic diagram of the structure of the alloy film product in several embodiments of this application; (A) includes a substrate, a transition layer and an exemplary Cr-Zr-N alloy coating of this application; (B) includes a substrate, a transition layer, an exemplary Cr-Zr-N alloy coating of this application and a surface layer; (C) includes a substrate, an exemplary Cr-Zr-N alloy coating of this application and a surface layer.

[0055] Figure 3 is a schematic diagram of an apparatus for preparing the Cr-Zr-N alloy coating of this application in one embodiment of the present application;

[0056] Figure 4 shows the Cr prepared in Example 1 of this application. 81.6 Zr 13.7 N 4.7 SEM cross-sectional view of the alloy coating;

[0057] Figure 5 shows the Cr prepared in Example 1 of this application. 81.6 Zr 13.7 N 4.7 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;

[0058] Figure 6 shows the Cr prepared in Example 2 of this application. 61.4 Zr 33 .2N 5.4 SEM cross-sectional view of the alloy coating;

[0059] Figure 7 shows the Cr prepared in Example 2 of this application. 61.4 Zr 33 .2N 5.4 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;

[0060] Figure 8 shows the Cr prepared in Example 3 of this application. 47.1 Zr 17.4 N 35.5 SEM cross-sectional view of the alloy coating;

[0061] Figure 9 shows the Cr prepared in Example 3 of this application. 47.1 Zr 17.4 N 35.5 XRD diffraction pattern of the alloy coating;

[0062] Figure 10 shows the Cr prepared in Example 4 of this application. 52.0 Zr 12.1 N 35.9 SEM cross-sectional view of the alloy coating;

[0063] Figure 11 shows the Cr prepared in Example 4 of this application. 52.0Zr 12.1 N 35.9 XRD diffraction pattern of the alloy coating;

[0064] Figure 12 shows the Cr prepared in Example 5 of this application. 60.9 Zr 26.1 N 13 SEM cross-sectional view of the alloy coating;

[0065] Figure 13 shows the Cr prepared in Example 5 of this application. 60.9 Zr 26.1 N 13 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;

[0066] Figure 14 shows the Cr prepared in Example 6 of this application. 60.9 Zr 26.1 N 13 SEM cross-sectional image of the alloy coating, which is the lower layer of a double-layer structured coating, with a titanium nitride coating (as a surface layer) above it.

[0067] Figure 15 shows the Cr prepared in Example 7 of this application. 60.9 Zr 26.1 N 13 The SEM cross-sectional image of the alloy coating shows that a Cr layer (as a transition layer) is disposed between the substrate and the Cr-Zr-N alloy coating, and a titanium nitride coating (as a surface layer) is also present above the Cr-Zr-N alloy coating; the alloy film product has a sandwich structure protective structure, and the Cr-Zr-N alloy coating serves as the middle structural layer of the three-layer coating structure.

[0068] Figure 16 shows the Cr prepared in Example 13 of this application. 49.5 Zr 18.0 N 32.5 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0069] Figure 17 shows the Cr prepared in Comparative Example 1 of this application. 88.9 Zr 11.1 SEM cross-sectional view of the alloy coating;

[0070] Figure 18 shows the Cr prepared in Comparative Example 2 of this application. 37.8 Zr 16.2 N 46 SEM cross-sectional view of the alloy coating;

[0071] Figure 19 shows 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 (C) corresponding to the SEAD pattern of the alloy coating;

[0072] Figure 20 shows 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.

[0073] In the XRD diffraction pattern, the horizontal axis represents 2θ (in degrees), and the vertical axis represents the X-ray diffraction intensity (in au). Based on the selected area electron diffraction (SAED) pattern of the alloy coating, its corresponding radial intensity profile is obtained, expressed as characteristic interatomic spacing (d) - diffraction intensity, with d as the horizontal axis and units of angstroms. The vertical axis represents electron diffraction intensity, measured in au.

[0074] In the radial intensity profiles corresponding to XRD diffraction patterns and SAED patterns, au has a well-known meaning in the art.

[0075] In some SEM images, some cross-sectional delamination occurs when the silicon wafer fractures during the preparation of the test sample, but this does not affect the observation and analysis of the cross-sectional morphology. The positions of different structural layers in the substrate and protective coating can be determined based on the thickness of the corresponding structural layer. Refer to the structural layer position markings in Figures 14 and 15.

[0076] Explanation of reference numerals in the attached figures: 1 is the vacuum chamber, 2 is the sample stage, 3 is the DC anode, 4 is the chromium target (also referred to as the Cr target), and 5 is the zirconium target (also referred to as the Zr target).

[0077] 100 is the substrate, 200 is the transition layer (also called the transition film), 300 is the Cr-Zr-N alloy coating, and 400 is the surface layer (also called the surface film). In this application, unless otherwise specified, the chromium target 4 is a Cr target with radio frequency assisted DC cathode charging, and the zirconium target 5 is a Zr target with radio frequency assisted DC cathode charging. Detailed Implementation

[0078] The present application will be further described in detail below with reference to the accompanying drawings, embodiments, and examples. It should be understood that these embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. 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 modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0079] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.

[0080] the term

[0081] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0082] The terms “and / or,” “or / and,” and “and / or” as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. “Any and all combinations” includes any two related listed items, any more related listed items, or a combination of all related listed items. For example, “A and / or B” includes three parallel options: A, B, and “a combination of A and B.”

[0083] In this application, the terms "multiple", "various", "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.

[0084] 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 instances of "one or more" shall be understood in the same way unless otherwise specified.

[0085] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0086] In this document, the term "suitable" in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0087] In this document, terms such as "preferred," "better," "more suitable," and "ideal" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0088] In this application, terms such as "further," "even more," "particularly," "for example," "like," "example," and "exemplary" are used for descriptive purposes to indicate that different technical solutions preceding and following each other are related in terms of their coverage, but should not be construed as limiting the preceding technical solution or restricting the scope of protection of this application. In this application, unless otherwise specified, A (e.g., B) indicates that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0089] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "present" or "absent." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. In this application, descriptions such as "optionally contains" and "optionally includes" indicate "contains or does not contain." "Optional component X" indicates whether component X exists or does not exist.

[0090] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0091] The terms “containing,” “comprising,” and “including” as used in this application are synonyms and are inclusive or open-ended, and do not exclude additional, uncited members, elements, or method steps.

[0092] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0093] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, 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, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0094] In this article, unless otherwise specified, "approximately" means within a certain range above and below the given number. The range of fluctuation may vary depending on the type and value of the given number. For example, fluctuations within ±2%, ±1%, ±0.5%, etc., are allowed. For example, approximately 2° can be expressed as 2° ± 0.02°, etc.

[0095] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that constant-temperature treatment allows temperature fluctuations within the precision range controlled by the instrument. Fluctuations are permitted within ranges such as ±5℃, ±4℃, ±3℃, ±2℃, and ±1℃. The temperature unit ℃ refers to "degrees Celsius".

[0096] In this application, the term "room temperature" generally refers to 4℃ to 35℃, for example, 20℃ ± 5℃. In some embodiments of this application, "room temperature" refers to 10℃ to 30℃. In some embodiments of this application, "room temperature" refers to 20℃ to 30℃.

[0097] In this application, the term "room temperature" generally refers to 20℃ to 35℃, for example, 20℃ to 35℃. In some embodiments of this application, "room temperature" refers to 30℃ to 35℃. In some embodiments of this application, "room temperature" refers to 30℃.

[0098] In this application, if the unit for a data range is only followed by the right endpoint, it indicates that the units for the left and right endpoints are the same. For example, 3~5h means that the units for the left endpoint "3" and the right endpoint "5" are both h (hours), and both have the same meaning as 3h~5h. Furthermore, similar descriptions involving other parameters such as temperature and size also apply to the above understanding.

[0099] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0100] The mass or weight of the relevant components mentioned in the embodiments or examples of this application can refer not only to the detailed content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments or examples of this application is within the scope disclosed in the embodiments or examples of this application. The mass or weight in the embodiments or examples of this application can be units known in the chemical industry, such as micrograms (μg), milligrams (mg), grams (g), and kilograms (kg).

[0101] In this application, where the method flow involves multiple steps, unless otherwise explicitly stated herein, there is no strict order restriction on the execution of these steps; they can be executed in any order other than those described. Moreover, any step may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be performed alternately or simultaneously with other steps or parts of the sub-steps or stages of other steps.

[0102] When describing positional relationships, unless otherwise specified, when an element such as a layer, film, or substrate is referred to as being "on" another film layer, it may be directly on the other film layer or there may be intermediate film layers. Furthermore, when a layer is referred to as being "below" another layer, it may be directly below it or there may be one or more intermediate layers. It is also understood that when a layer is referred to as being "between" two layers, it may be the only layer between the two layers, or there may be one or more intermediate layers.

[0103] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0104] Unless otherwise stated, a singular term may include a plural term and should not be understood as having a quantity of one.

[0105] In this application, the exemplary descriptions such as "in some implementations (or embodiments)" and "in one implementation (or embodiment)" may cover, 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.

[0106] Traditional Cr-Zr-N alloy coatings are typically nanocrystalline with a high content of columnar crystals. On the one hand, these alloy coatings often struggle to achieve high L values, typically around 55–65. On the other hand, the high content of columnar crystals in these coatings promotes the formation of a highly ordered, oriented structure. The presence of numerous crystals within this highly ordered structure leads to intercrystalline gap defects, primarily manifested as penetrating columnar gaps. Correspondingly, shadows are observed between the columnar crystals in the scanning electron microscope (SEM) cross-sectional images. These penetrating columnar gaps may be a significant factor contributing to the poor corrosion resistance of the alloy coating. The inventors of this application hypothesize that the traditionally oriented, ordered structure tends to result in insufficient coating density. Under corrosive conditions, corrosive media can rapidly penetrate the coating through these gaps and react with the substrate, thereby leading to poor corrosion resistance of the alloy coating.

[0107] Furthermore, the surface protection of alloy materials currently on the market mainly employs methods such as anodizing and magnetron sputtering. For example, aluminum alloys are primarily protected by anodizing, which works by immersing the aluminum alloy material in a strong acid or alkali solution to form an oxide and metal alloy coating on the surface, thus creating surface protection. However, because the solution is a strong acid or alkali, the resulting product lacks sufficient gloss and has low hardness. In addition, the production process generates a large amount of wastewater, waste liquid, and waste gas, which is detrimental to the environment.

[0108] According to various embodiments and examples of this application, one aspect of this application provides a Cr-Zr-N alloy material capable of forming a Cr-Zr-N alloy coating that simultaneously possesses high brightness and high corrosion resistance. When the Cr-Zr-N alloy coating is located on the surface of an alloy film product, it can simultaneously impart high brightness and high corrosion resistance to the alloy film product. Furthermore, other aspects of this application also provide a Cr-Zr-N alloy coating and an alloy film product, as well as the application of the aforementioned Cr-Zr-N alloy material or Cr-Zr-N alloy coating in high-brightness surface coatings and a method for preparing the aforementioned Cr-Zr-N alloy coating.

[0109] The Cr-Zr-N alloy material provided in this application mainly contains three elements: Cr, Zr, and N, and these three elements have a specific relative atomic ratio (Cr...). x Zr y N zThe properties of 47.1 ≤ x ≤ 81.6, 12.1 ≤ y ≤ 33.2, and 4.7 ≤ z ≤ 35.9 give this Cr-Zr-N alloy material the ability to form a highly disordered distribution and a sufficiently dense packing of atoms, resulting in a dense Cr-Zr-N alloy coating. When the Cr-Zr-N alloy coating is located on the surface of a product, it not only imparts a high-gloss and aesthetically pleasing surface but also provides excellent corrosion resistance. The Cr-Zr-N alloy coating containing the Cr-Zr-N alloy material of this application exhibits a significantly longer protection time in salt spray corrosion tests than traditional Cr-Zr-N alloy coatings.

[0110] Furthermore, the Cr-Zr-N alloy coating provided in this application offers excellent corrosion resistance while also possessing high hardness, thereby better reducing scratch formation or mitigating scratch damage. Moreover, the Cr-Zr-N alloy coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0111] The Cr-Zr-N alloy coating provided in this application can be used as a surface layer for alloy film products, combining aesthetic decoration with the aforementioned protective functions. The Cr-Zr-N alloy coating provided in this application can also be located between the substrate and the surface layers of other structures, providing excellent protection and superior corrosion resistance and scratch resistance.

[0112] The Cr-Zr-N alloy coating provided in this application can be applied to a wide variety of substrates, including but not limited to alloys, elemental metals, and inorganic non-metallic materials.

[0113] When the Cr-Zr-N alloy coating provided in this application appears in the protective coating of an alloy film product, the position of the Cr-Zr-N alloy coating can be flexibly set. For example, the Cr-Zr-N alloy coating can be used for surface protection, in which case the Cr-Zr-N alloy coating is located on the surface of the alloy film product, providing a high-gloss surface. The Cr-Zr-N alloy coating can also be used as an intermediate protective layer, in which case other structural layers are provided on the outside of the Cr-Zr-N alloy coating, that is, the Cr-Zr-N alloy coating is not used as a surface layer. Cr-Zr-N alloy coatings in different positions can achieve good scratch resistance and good corrosion resistance.

[0114] The method for preparing Cr-Zr-N alloy coating provided in this application is simple, easy to operate, environmentally friendly, and has the advantages of being quantifiable, efficient, and reproducible, making it suitable for industrial applications.

[0115] In a first aspect of this application, a Cr-Zr-N alloy material is provided, the chemical formula of which is (Cr x Zr y N z M a M is a dopant element, where x, y, z, and a are each an independent atomic ratio, 47.1≤x≤81.6, 12.1≤y≤33.2, 4.7≤z≤35.9, and 0≤a / (x+y+z+a)≤0.05. This Cr-Zr-N alloy material can simultaneously provide a Cr-Zr-N alloy coating with a high-brightness surface and excellent corrosion resistance, and can be used to prepare alloy film products with the Cr-Zr-N alloy coating of this application.

[0116] The Cr-Zr-N alloy material provided in one aspect of this application may also be referred to as "Cr-Zr-N alloy material of this application," "Cr-Zr-N alloy material of this application," "Exemplary Cr-Zr-N alloy material of this application," or "Cr-Zr-N alloy material provided in this application," and includes, but is not limited to, the Cr-Zr-N alloy material provided in the first aspect. All the foregoing references should be interpreted non-limitingly and are not intended to limit the scope of this application. For example, the scope of this application is not limited to "Cr-Zr-N alloy material of this application." Descriptions such as "Cr-Zr-N alloy material of this application" in this application are non-limitingly understood to refer to an exemplary Cr-Zr-N alloy material provided in one aspect of this application and do not limit the scope of the Cr-Zr-N alloy material provided in this application.

[0117] The Cr-Zr-N alloy coating provided in one aspect of this application may also be referred to as "Cr-Zr-N alloy coating of this application," "Cr-Zr-N alloy coating of this application," "Exemplary Cr-Zr-N alloy coating of this application," or "Cr-Zr-N alloy coating provided in this application," and includes, but is not limited to, the Cr-Zr-N alloy coating provided in the first aspect. All the foregoing references should be interpreted non-limitingly and are not intended to limit the scope of this application. For example, the scope of this application is not limited to "Cr-Zr-N alloy coating of this application." Descriptions such as "Cr-Zr-N alloy coating of this application" in this application are non-limitingly understood to refer to an exemplary Cr-Zr-N alloy coating provided in one aspect of this application and do not limit the scope of the Cr-Zr-N alloy coating provided in this application.

[0118] In this application, unless otherwise specified, "Cr-Zr-N alloy" and "CrZrN alloy" both refer to alloys containing chromium (Cr), zirconium (Zr) and nitrogen (N), and may also contain other alloying elements, and the two terms are used interchangeably.

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

[0120] In this application, unless otherwise specified, the “atomic ratio” of two or more elements refers to the ratio of the number of atoms.

[0121] In this application, unless otherwise specified, "Cr-Zr-N ternary alloy" and "CrZrN ternary alloy" both refer to alloys composed of three elements: Cr, Zr, and N.

[0122] The Cr-Zr-N alloy material provided in this application mainly contains three elements: Cr, Zr, and N, and these three elements have a specific relative atomic ratio (Cr...). x Zr y N z The properties 47.1≤x≤81.6, 12.1≤y≤33.2, and 4.7≤z≤35.9 give this Cr-Zr-N alloy material the ability to form a highly disordered distribution and a fully densely packed arrangement of atoms, resulting in a dense Cr-Zr-N alloy coating. When this Cr-Zr-N alloy coating is applied to the surface of a product, it not only imparts a high-gloss, aesthetically pleasing surface but also provides excellent corrosion resistance. The Cr-Zr-N alloy coating containing this Cr-Zr-N alloy material exhibits a significantly longer protection time in salt spray corrosion tests than traditional Cr-Zr-N alloy coatings.

[0123] Traditional Cr-Zr-N alloy coatings are typically nanocrystalline with a high content of columnar crystals, and their structure usually contains numerous through-pores. This results in poor surface reflectivity and low brightness, as well as poor corrosion resistance. The Cr-Zr-N alloy material provided in this application, however, can form a dense coating with a highly disordered and well-packed structure, containing only a very small number of through-pores or non-through-pores. The Cr, Zr, and N atoms, with their distinct radii, have a specific atomic ratio that facilitates aggregation into a highly disordered state during deposition. This highly disordered state allows for close packing, forming a dense, high-brightness surface with excellent reflectivity. It also promotes dense growth of the alloy coating and inhibits the formation of continuous, numerous through-pores, thus creating an effective barrier between the substrate and the corrosive environment. Furthermore, the presence of chromium and zirconium in the Cr-Zr-N alloy coating provided in this application gives it sufficient chemical inertness in corrosive environments. Based on the Cr-Zr-N alloy material of this application, a Cr-Zr-N alloy coating can be formed that not only has a highly disordered atomic distribution, but also has sufficient packing at the atomic scale. This can avoid or reduce the through gaps formed due to the highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "sufficient packing" of atoms in the alloy coating make the alloy coating have a highly dense structure, which can provide a high-brightness surface and also has excellent corrosion resistance.

[0124] In the Cr-Zr-N alloy material and Cr-Zr-N alloy coating of this application, based on the special atomic ratio of Cr, Zr, and N, a high Cr content and the introduction of Zr and N make it easier for Cr and Zr to form strong bond energies. This facilitates the rapid growth of the Cr-Zr alloy with a suitable atomic ratio during the deposition process. Furthermore, the addition of an appropriate amount of nitrogen further promotes the re-nucleation of the Cr-Zr alloy, thus forming the Cr-Zr-N alloy of this application. By improving the density of the coating nucleation, the coating brightness and corrosion resistance can be improved, as well as the coating hardness. Specifically, in terms of atomic size, the atomic radius of Cr is [missing information]. The atomic radius of Zr is The atomic radius of N is Cr and Zr have similar atomic sizes, while N atoms are smaller. During nucleation, an appropriate amount of small-sized N atoms can penetrate into the pores of large-sized Cr and Zr metal grains with suitable atomic ratios, achieving a better pore-filling effect and making the atomic arrangement more compact. At the same time, it can suppress the growth defects of the columnar crystal structure of the thin film, thereby improving the brightness and corrosion resistance of the coating, and also helping to improve the hardness of the coating.

[0125] Cr is a high-brightness metallic raw material in coating materials. A higher Cr content can effectively improve the brightness of the alloy coating. Simultaneously, the Cr-Zr-N alloy material of this application can be used to create a highly dense Cr-Zr-N alloy coating, further improving the surface reflectivity of the coating. The combination of these two characteristics results in a higher brightness and a higher brightness value (i.e., L value) during colorimetric measurements. The L value of the Cr-Zr-N alloy coating of this application can reach ≥70, and in some cases as high as 81, exhibiting a high-brightness silvery-white color, far exceeding the L value of traditional alloy coatings (traditional L values ​​are approximately 55-65). High-brightness coatings possess aesthetic appeal and excellent decorative properties. When applied to substrates (such as pure metals and alloys), they achieve a high-brightness and aesthetic effect, making the coating color closer to the substrate color, resulting in a surface with virtually no color difference. This characteristic gives the Cr-Zr-N alloy coating provided in this application an excellent decorative effect, making it particularly suitable for (but not limited to) 3C digital products, such as mobile phone components, achieving a high-gloss metallic effect. It can also be applied to wearable products, automotive products, sports products and other fields.

[0126] When testing the chromaticity value of alloy coatings, the sample used should be made of a substrate material suitable for practical applications. A Konica CM-3700A-U benchtop spectrophotometer (Japan) can be used to test the L, a, and b values ​​of the sample. An F2 light source is selected for the light receiving system. Six matrix points are tested for each sample, and the average value is taken. Here, the L value represents the luminance value, the a value represents the red and green chromaticity values, and the b value represents the yellow and blue chromaticity values. A larger L value indicates higher luminance and a denser coating surface. The mechanism is as follows: the spectrophotometer receives incident light on the surface of the sample, causing reflection, and obtains a reflectance curve. The amplitude of this curve reflects the density of the material, which can be characterized by the L value. For the same material, the higher its density, the larger the displayed L value.

[0127] The Cr-Zr-N alloy material provided in this application possesses both highly disordered atomic distribution and high atomic density, enabling dense atomic packing even under highly disordered atomic arrangement. This results in a Cr-Zr-N alloy coating with a unique atomic arrangement of "highly disordered yet sufficiently dense," thereby avoiding or reducing the formation of through-grain gaps caused by highly ordered arrangement. This results in a highly dense structure, exhibiting a high-brightness surface with excellent reflective properties and providing superior corrosion resistance. Using Cr-Zr-N alloy material to prepare Cr-Zr-N alloy coatings effectively reduces common defects in traditional crystalline coatings, such as significantly reducing or eliminating through-grain gaps in columnar crystal structure coatings. This makes the Cr-Zr-N alloy coating more conducive to dense growth, achieving a smooth, high-brightness surface and endowing the alloy coating with excellent corrosion resistance.

[0128] Furthermore, the Cr-Zr-N alloy coating prepared using the Cr-Zr-N alloy material of this application has a dense structure, providing excellent corrosion resistance while also exhibiting high hardness, thus better reducing scratch formation or mitigating scratch damage. Moreover, the Cr-Zr-N alloy coating provided by this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0129] The Cr-Zr-N alloy coating prepared using the Cr-Zr-N alloy material of this application can be used as the surface layer of alloy film products, providing both aesthetic decoration and protective functions. The Cr-Zr-N alloy coating provided by this application can also be located between the substrate and the surface layer, providing excellent protection and exhibiting superior corrosion resistance and scratch resistance.

[0130] In some implementations, when the proportional relationship of 47.1≤x≤81.6, 12.1≤y≤33.2 and 4.7≤z≤35.9 is satisfied and x+y+z=100 is met, x can be any of the following values ​​or an interval selected from any two of the following values: 47.1, 52.0, 53.8, 54.8, 60.9, 61.4, 81.6, etc.

[0131] In some implementations, when the proportional relationship of 47.1≤x≤81.6, 12.1≤y≤33.2 and 4.7≤z≤35.9 is satisfied and x+y+z=100 is met, y can be any of the following values ​​or an interval selected from any two of the following values: 12.1, 13.0, 13.7, 17.4, 26.1, 30.0, 33.2, etc.

[0132] In some implementations, when the proportional relationship of 47.1≤x≤81.6, 12.1≤y≤33.2 and 4.7≤z≤35.9 is satisfied and x+y+z=100 is met, z can be any of the following values ​​or an interval selected from any two of the following values: 4.7, 5.4, 6.2, 10.1, 13.0, 20.2, 25.5, 35.5, 35.9, etc.

[0133] In some implementations, the sum of x, y, and z is 100. In this case, x, y, and z correspond to the atomic percentages of Cr, Zr, and N, respectively. This constraint on the atomic ratios of Cr, Zr, and N within a more suitable range allows for a denser structure in the resulting Cr-Zr-N alloy coating, leading to higher brightness and better corrosion resistance. Furthermore, it can also improve the coating's hardness.

[0134] The Cr-Zr-N alloy materials and Cr-Zr-N alloy coatings provided in this application may or may not contain doping elements, and can be flexibly selected according to the additional functional requirements of the alloy materials and / or alloy coatings. It is understood that in this application, when doping elements are present, the type and amount of doping elements are limited to not affecting the high brightness and corrosion resistance of the Cr-Zr-N alloy coating.

[0135] In this application, the chemical formula of the Cr-Zr-N alloy material can be written as (Cr x Zr y N z M a In this equation, x, y, and z are each independently represented by positive atomic ratios, M is the dopant element, and a is the atomic ratio of element M, which is either 0 or positive. During nucleation, N atoms can penetrate into the pores of large-sized Cr and Zr metal grains, achieving a better pore-filling effect. This results in a denser atomic stack in the coating and can also suppress growth defects in the columnar crystal structure of the thin film, thereby improving the corrosion resistance of the coating.

[0136] When a is 0, the Cr-Zr-N alloy material does not contain any doping elements, corresponding to a Cr-Zr-N ternary alloy material. When a > 0, the Cr-Zr-N alloy material contains doping elements, where 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.

[0137] Unless otherwise specified, the Cr-Zr-N alloy material provided in this 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 even further such as the Cr-Zr-N ternary alloy material (in which case, a=0). By limiting the content of doping elements, the influence of doping elements on the highly disordered and sufficiently densely packed atoms in the Cr-Zr-N alloy coating of this application can be minimized. This is beneficial for reducing the components required for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Zr and N to form a denser coating, which is beneficial for achieving better corrosion resistance and also for obtaining higher hardness.

[0138] In some embodiments, a / (x+y+z)=0. In this case, the composition of the Cr-Zr-N ternary alloy material is simple, making it easier to prepare and control. The Cr-Zr-N ternary alloy coating formed in this way can achieve a dense structure, resulting in high brightness and high corrosion resistance; furthermore, it can also achieve high coating hardness.

[0139] In some implementations, 0

[0140] In some implementations, 0

[0141] ​​In some preferred embodiments, 0

[0142] In some embodiments, based on any of the aforementioned suitable embodiments, y is greater than z. In this case, the Cr-Zr-N alloy material provided in this application has a high Cr content, followed by a low Zr content and a low nitrogen content. This special atomic ratio design can better improve the density of coating nucleation, thereby further improving the coating's brightness and corrosion resistance. During nucleation, N atoms can penetrate into the pores of large-sized Cr and Zr metal grains, achieving a better pore-filling effect, resulting in a denser atomic stack in the coating. This also better suppresses growth defects in the columnar crystal structure of the thin film, better improves the surface reflectivity of the coating, thereby increasing the brightness, and significantly enhances corrosion resistance. Furthermore, it can promote better coating hardness.

[0143] In some embodiments, based on any of the aforementioned suitable embodiments, 63.19-0.925y≤x≤95.79-y and 31.4+0.9y≤x≤18.5y-171.85. In this case, the atomic ratios of Cr, Zr, and N can be more precisely controlled within an optimal range, resulting in a Cr-Zr-N alloy coating that is more likely to achieve a denser structure, higher brightness, and better corrosion resistance. Furthermore, it can also facilitate the achievement of better coating hardness.

[0144] In some implementations, the doping element is a non-metallic element, a metallic element, or a combination thereof, which can be flexibly selected according to the additional functional requirements of the Cr-Zr-N alloy coating.

[0145] ​Non-limitingly, the non-metallic element may include one or more of O, C, B, Si, and Ar. Non-limitingly, the metallic element may include one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0146] It should be noted that, in any embodiment within the context of this application, the Cr-Zr-N alloy material and Cr-Zr-N alloy coating provided by this application are permitted to contain unavoidable impurities introduced during the preparation process. "Unavoidable impurities" are not intentionally added impurities; their presence is primarily due to unintentional introduction during the preparation process. Non-limiting examples of "unavoidable impurities" include elements such as C and O present in the air, and components from raw materials or equipment. The atomic content of "unavoidable impurities" in the alloy material or alloy coating is typically trace or minute, generally negligible, for example, less than 0.01% atomic content. Taking the technical solution of "Cr-Zr-N alloy coating being a Cr-Zr-N ternary alloy material composed of Cr, Zr, and N elements" as an example, theoretically, the Cr-Zr-N alloy coating is composed of Cr, Zr, and N elements. However, trace or minute amounts of other elements besides Cr, Zr, and N, such as C and O, may be introduced during the preparation process.

[0147] In a second aspect of this application, a Cr-Zr-N alloy coating is provided, comprising a film layer formed from the Cr-Zr-N alloy material described in the first aspect of this application. As previously explained, based on the specific atomic ratio of Cr, Zr, and N, this Cr-Zr-N alloy coating forms a highly disordered atomic distribution and a sufficiently dense atomic arrangement, possessing a "highly disordered and sufficiently dense" dense coating structure. This improves surface reflectivity and increases brightness, while also suppressing the formation of continuous, numerous penetrating fissures, significantly enhancing the coating's corrosion resistance.

[0148] Furthermore, the increased density of the coating structure allows for higher coating hardness. The dense Cr-Zr-N alloy coating provided in this application offers excellent corrosion resistance while also possessing high hardness, thus better reducing scratch formation or mitigating scratch damage. Moreover, the Cr-Zr-N alloy coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs. The Cr-Zr-N alloy coating provided in this application can be used as a surface layer for alloy film products, providing both aesthetic decoration and protective functions. The Cr-Zr-N alloy coating provided in this application can also be positioned between the substrate and the surface layer, providing excellent protection and superior corrosion resistance and scratch resistance.

[0149] In some embodiments, the Cr-Zr-N alloy coating satisfies the following two characteristics:

[0150] The X-ray diffraction pattern of the Cr-Zr-N alloy coating has peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2°.

[0151] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in... It has diffraction peaks within the range, and The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies unit It means "E".

[0152] The method used in this application to characterize the structure of the Cr-Zr-N alloy coating can also be used to characterize the Cr-Zr-N alloy material in the first aspect of this application. The Cr-Zr-N alloy material is not limited to the coating form and can be an independent raw material, such as alloy sheet or alloy plate.

[0153] For example, in some embodiments, Cr-Zr-N alloy materials satisfy the following two characteristics:

[0154] The X-ray diffraction pattern of Cr-Zr-N alloy material has peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2°.

[0155] In the radial intensity profile corresponding to the selected area electron diffraction pattern of Cr-Zr-N alloy, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in... It has diffraction peaks within the range, and The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies

[0156] Furthermore, the XRD test results and radial intensity profiles corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy material can also be found in the description of the X-ray diffraction pattern and radial intensity profiles corresponding to the selected area electron diffraction pattern in the Cr-Zr-N alloy coating in this paper. The corresponding optional and preferred methods can also be applied to this Cr-Zr-N alloy material.

[0157] The Cr-Zr-N alloy coating provided in this application is not clearly defined by the traditional perfect single crystal or fully amorphous state, but focuses on the degree of close packing of atoms. Based on a specific atomic ratio of Cr, Zr, and N, this degree of close packing is closely related to the disorder of atomic arrangement and the appropriate mismatch of atomic size. The highly dense Cr-Zr-N alloy coating provided in this application has both high brightness and excellent corrosion resistance. In addition, it can also achieve high hardness. Structurally, it simultaneously satisfies the following requirements: at least one broad peak (furthermore, there can be no sharp peaks, i.e., all are broad peaks) in the diffraction angle range of 30° to 50° in the XRD pattern, and the radial intensity profile of the selected area electron diffraction pattern is... The range has at least one broad peak (furthermore, there may be no sharp peaks, that is, all are broad peaks).

[0158] Unlike traditional Cr-Zr-N alloy coatings that are nanocrystalline with a high columnar crystal content (containing numerous through-holes), the Cr-Zr-N alloy coating provided in this application can form a dense coating with a highly disordered and sufficiently densely packed structure, containing very few or no through-holes. In the Cr-Zr-N alloy coating of this application, the three atoms with vastly different radii—Cr, Zr, and N—aggregate into a highly disordered state during deposition and form a dense packing, resulting in a high-brightness surface with excellent reflectivity. This facilitates dense growth of the alloy coating and inhibits the formation of continuous, numerous through-holes, thereby creating an effective barrier between the substrate and the corrosive environment. Furthermore, because the Cr-Zr-N alloy coating provided in this application contains chromium and zirconium, the coating possesses sufficient self-chemical inertness in corrosive environments. The Cr-Zr-N alloy material in the Cr-Zr-N alloy coating provided in this application not only has a highly disordered atomic distribution, but also has sufficient packing at the atomic scale, thereby avoiding or reducing through gaps caused by highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "sufficient packing" of atoms in the alloy coating make the alloy coating have a highly dense structure, which can simultaneously provide a high-gloss surface and excellent corrosion resistance.

[0159] In this application, whether the constituent atoms of the alloy coating possess a "highly disordered" state is evaluated using XRD technology. More specifically, the XRD pattern of the Cr-Zr-N alloy coating shows broad and gentle ridges, which are referred to as "broad peaks" of the 2θ (°) diffraction peak. The length of the ordered atomic arrangement can be obtained from the half-maximum width at half-maximum (FWHM) of this broad peak using the Scherrer formula. The calculation method is: D = Kλ / (β·cosθ), where D is the length of the ordered atomic arrangement (representing grain size in crystalline materials), K is the Scherrer constant, λ is the X-ray wavelength, β is the FWHM of the diffraction peak (the width at half-maximum of the diffraction peak height), and θ is the diffraction angle. It can be seen that the FWHM is inversely proportional to the length D of the ordered atomic arrangement, and the shorter the length D, the higher the disorder of the atomic distribution. Therefore, the full width at half maximum (FWHM) of diffraction peaks within a specific range in an XRD pattern can be used to reflect the degree of disordered atomic distribution: the wider the FWHM, the shorter the length of the ordered arrangement of atoms, and the more disordered the overall atomic distribution; the aforementioned broad and gently bulging "broad peaks" can reflect the highly disordered atomic distribution in the material as a whole.

[0160] Generally speaking, the higher the ordered arrangement of atoms, the stronger the crystallinity, and the easier it is to form large-sized grains over a long distance. The narrower the diffraction peaks in the XRD pattern, and high crystallinity is often accompanied by sharp peaks. However, in the alloy coating of this application, the three atoms Cr, Zr, and N can be arranged in a highly disordered manner as a whole in the Cr-Zr-N alloy coating, which is manifested as a broad and gentle bulge (broad peak) in the XRD pattern of the Cr-Zr-N alloy coating. This is manifested as at least one "broad peak" in the diffraction angle range of 30° to 50° 2θ (°).

[0161] In this application, unless otherwise specified, a “broad peak” in an XRD pattern can be defined as having a half-width at half-maximum (WHM) of ≥2°. The WHM of a broad peak can further be ≥2.19°, even further ≥2.2°, even further ≥2.3°, even further ≥3°, even further ≥3.5°, even further ≥4°, and even further ≥5°. The full width at half maximum (FWHM) of any "broad peak" in an XRD chart can be any of the following values ​​independently: greater than or equal to any of the following values; greater than or equal to any of the following values ​​(except 10°) and less than or equal to 10°; or selected from any two of the following value ranges: 2°, 2.19°, 2.2°, 2.5°, 3°, 3.5°, 4°, 4.04°, 4.42°, 4.5°, 5°, 5.5°, 6°, 6.5°, 7°, 7.5°, 8.42°, 8.5°, 8.85°, 9°, 9.11°, 9.33°, 9.5°, 10°, etc. As a non-limiting example, the range may be selected from any of the following ranges: 2°~10°, 2°~9.5°, 2°~9.4°, 2.1°~9.5°, 2.1°~9.4°, 2.15°~9.35°, 2.19°~9.33°, etc.

[0162] In this application, unless otherwise specified, "peak" in an X-ray diffraction (XRD) pattern refers to a diffraction peak with a full width at half maximum (FWHM) of <2°.

[0163] More specifically, in the Cr-Zr-N alloy coating provided in this application, the XRD pattern shows peaks within a diffraction angle range of 30° to 50° (2θ°), and at least one diffraction peak in the XRD pattern is a broad peak. This special microstructure state of having at least one "broad peak" can be represented by the criteria of "having at least one 2θ° diffraction peak with a half-width at half-maximum (HWHM) ≥ 2° within the range of 30° to 50°" or "having at least one 2θ° diffraction peak with a HWHM ≥ 2° within the range of 30° to 50°". The following method can be used to determine whether the criteria of "having at least one 2θ° diffraction peak with a HWHM ≥ 2° within the range of 30° to 50°" are met: in the XRD pattern, if the HWHM value of the 2θ° diffraction peak is ≥ 2°, it is judged as a "broad peak"; if the HWHM value of the 2θ° diffraction peak is < 2°, it is judged as a sharp peak. For a given 2θ (°) position, it can be any of three states: no peak, broad peak, or sharp peak. In the X-ray diffraction (XRD) pattern, the characteristic broad peak characteristics of the Cr-Zr-N alloy coating provided in this application are quite obvious.

[0164] In traditional Cr-Zr-N alloy coatings with high columnar crystal content, the diffraction peaks in the diffraction angle range of 30° to 50° 2θ (°) often appear as sharp peaks with a full width at half maximum (FWHM) of <2°, without any broad peaks.

[0165] In this application, XRD patterns of the alloy coating can be obtained using conventional instruments and methods in the art. For example, a Bruker D8 Advance XRD diffractometer (Germany) can be used.

[0166] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and at least one 2θ (°) diffraction peak in the range of 30° to 50° is a broad peak. The full width at half maximum (FWHM) of the broad peak can be referred to the examples in the context; for example, if the FWHM of the broad peak is ≥2.19°, then at least one 2θ (°) diffraction peak in the range of 30° to 50° satisfies ≥2.19°.

[0167] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has a broad peak in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) of this broad peak can be seen in the examples in the context.

[0168] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has two or more broad peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) values ​​of these broad peaks can be independently referred to in the examples in the context.

[0169] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has all 2θ (°) diffraction peaks as broad peaks in the diffraction angle range of 30° to 50°, that is, there are no sharp peaks. The full width at half maximum (FWHM) values ​​of these broad peaks can be independently referred to in the examples in the context.

[0170] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has peaks in the diffraction angle range of 2θ (°) from 30° to 50°, and the full width at half maximum (FWHM) of each of the 2θ (°) diffraction peaks in the range of 30° to 50° independently satisfies ≥2°, further satisfies ≥2.19°, even further satisfies ≥2.2°, even further satisfies ≥2.3°, even further satisfies ≥3°, even further satisfies ≥3.5°, even further satisfies ≥4°, and even further satisfies ≥5°.

[0171] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating of this application has one and only one diffraction peak in the diffraction angle range of 2θ (°) from 30° to 50°, and the peak is broad.

[0172] In some embodiments, the X-ray diffraction pattern of the Cr-Zr-N alloy coating is obtained by using Cu target Kα rays.

[0173] In this application, the XRD pattern of the alloy coating can be obtained using the following instruments and methods: a Bruker D8 Advance XRD diffractometer from Germany is used in θ-2θ mode with Cu target Kα rays at a wavelength λ of 0.15406 nm. The X-ray tube is controlled at 40 kV and 40 mA, and the scanning range is 20° to 80° with precise scanning measurements in steps of 0.01°.

[0174] Conventional analytical methods in this field (including but not limited to analytical software provided by the instrument supplier) can be used to obtain the full width at half maximum (FWHM) value. For example, the steps to obtain the FWHM value may include: first, correcting the diffraction peak, which may include: smoothing, background subtraction, removal of Kα2 lines, and subtraction of instrument broadening, etc.; and then fitting the diffraction peak with the Pseudo-Voigt function to obtain the FWHM value of the diffraction peak.

[0175] There are no specific limitations on the analysis software. 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 spectral data. For example, the following method can be used: First, perform scale correction, then determine the center of the transmission spot of the diffraction ring, and then convert it into an XRD pattern (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm); the diffraction peaks are stripped of a straight background, and then fitted using the Voigt function to obtain the full width at half maximum (FWHM) values ​​of the corresponding diffraction peaks.

[0176] Traditional XRD patterns cannot adequately characterize the atomic packing density in alloy coatings because: when inspecting physical vapor deposition (PVD) films or coatings at the atomic scale (e.g., 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 (e.g., grains or amorphous materials with diameter <3nm).

[0177] In this application, whether the atoms constituting the coating are "sufficiently densely packed" is evaluated using selected area electron diffraction (SAED). Electron waves are chosen because their wavelengths are significantly smaller (<0.01 nm), resulting in higher resolution. More specifically, if only continuous diffraction rings of uniform brightness exist on the SEED pattern, and these rings are relatively wide, it indicates that the atoms in the coating are densely packed in a highly randomized manner. For quantitative characterization, the SAED pattern can be converted into a characteristic interatomic spacing (d)-radial intensity profile, where the characteristic interatomic spacing (d) is on the x-axis and the diffraction intensity is on the y-axis. If the diffraction rings in the SEED are relatively wide, the corresponding half-maximum width at half-maximum (FWHM) of the radial intensity profile is also wide, reflecting a strong density of atomic arrangement in the alloy coating.

[0178] In this application, the atomic radius of Cr is [missing information]. The atomic radius of Zr is The atomic radius of N is Three types of atoms with significantly different diameters possess a suitable atomic size mismatch, and under conditions of high random mixing, they can form a sufficiently densely packed structure. During the growth of PVD thin films or alloy coatings, the sufficiently dense atomic packing in Cr-Zr-N alloy coatings facilitates dense growth, suppressing the formation and growth of columnar crystals that would otherwise result from localized ordering, thus making it difficult for continuous through-hole pores to form in large quantities. Therefore, the half-width at half-maximum (HWHM) of the radial intensity profile can be used as a characteristic parameter of the sufficiently densely packed structure of the alloy coating to reflect the atomic packing density; the larger the HWHM value, the better the atomic packing density. In short, this application's use of the HWHM of the SAED radial intensity profile as a characteristic parameter of sufficiently dense atomic packing is scientifically sound and consistent with established principles.

[0179] When the half-width at half-maximum (WHM) of the radial intensity profile exceeds a certain threshold, the atoms in the coating can achieve sufficient close packing. Based on extensive experimental exploration by the inventors, in this application, unless otherwise specified, the threshold for determining whether sufficient close packing of atoms has been achieved in the SAED-radial intensity profile is defined as follows: That is, the half-width value is considered to be This allows for a fully dense packing of atoms.

[0180] In this application, transmission electron microscopy (TEM) technology can be used to obtain radial intensity profiles of the characteristic interatomic spacing (d) of the alloy coating sample.

[0181] In this application, the radial intensity profile corresponding to the selected area electron diffraction (SAED) pattern of the alloy coating can be denoted as a SAED-radial intensity profile, or as a characteristic interatomic spacing-intensity quantitative spectrum of the selected area electron diffraction (SAED) pattern. The selected area electron diffraction pattern obtained using transmission electron microscopy (TEM) can be denoted as a TEM-SAED pattern, or as a TEM-SAED pattern. Similarly, the SAED-radial intensity profile obtained using TEM can also be denoted as a TEM-SAED-radial intensity profile.

[0182] In this application, alloy coatings (including the Cr-Zr-N alloy coating of this application) can be obtained using conventional instruments and methods in the art. Based on the selected area electron diffraction (SAED) pattern of the alloy coating, its corresponding radial intensity profile is obtained. The intensity profile is expressed as characteristic interatomic spacing (d) versus diffraction intensity, with d as the abscissa and units in angstroms. The vertical axis represents electron diffraction intensity.

[0183] In this application, unless otherwise specified, the full width at half maximum (FWHM) of the diffraction peaks in the radial intensity profile of the SAED plot are... It is then judged as a broad peak; the full width at half maximum (FWHM) of the diffraction peak. These are identified as sharp peaks. For a specific characteristic atomic spacing, they can be in any of three states: no peaks, sharp peaks, or broad peaks. In the radial intensity profile, the characteristic diffraction peaks of the Cr-Zr-N alloy coating provided in this application exhibit a relatively obvious broad peak characteristic. Unless otherwise specified, "broad peak" in the radial intensity profile of a selected area electron diffraction pattern (SAED) refers to the full width at half maximum (FWHM). The diffraction peak, the "sharp peak" refers to the full width at half maximum (FWHM). The diffraction peaks.

[0184] In this application, radial strength profiles or SAED-radial strength profiles are involved, which can be obtained using TEM techniques unless otherwise specified.

[0185] In this application, unless otherwise specified, the "broad peak" in the radial intensity profile corresponding to the SAED diagram can be defined as having a half-width at half-maximum (WHM) that satisfies... The full width at half maximum (FWHM) of the broad peak can be further... Going further Going further Going further Going further

[0186] In this application, the full width at half maximum (FWHM) data of the radial intensity profile corresponding to the selected area electron diffraction pattern can be obtained using (but not limited to) the following transmission electron microscopy (TEM) methods:

[0187] TEM test sample preparation: The sample was thinned using a Helios 5 CX focused ion beam (FIB) from ThemoFisher Ltd. to obtain an electronically transparent, TEM-observable planar sample.

[0188] SAED Image Acquisition: A ThemoFisher Talos F200x transmission electron microscope (TEM) was used with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm to acquire the selected area electron diffraction (SAED) pattern of the sample. Based on the SAED pattern, a radial intensity profile was obtained, and the full width at half maximum (FWHM) value of the diffraction peak was obtained by integral assignment.

[0189] Based on the principle that the half-width at half-maximum (WHM) of the diffraction peaks in the radial intensity profile corresponds to the width of the diffraction rings in the selected area electron diffraction (SAED) pattern, the selected area electron diffraction (SAED) pattern of the alloy coating can be converted into the corresponding radial intensity profile.

[0190] Those skilled in the art will understand that the wider the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing of atoms, and the more sufficient the atomic packing in the Cr-Zr-N alloy coating of this application; the half-width at half-maximum (WHM) of the diffraction peak in the radial intensity profile is a quantitative indicator of the diffraction ring width, and the larger the WHM value, the more sufficient the atomic packing.

[0191] In some embodiments, the selected area electron diffraction (SAED) pattern of the Cr-Zr-N alloy coating is obtained using transmission electron microscopy (TEM) with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0192] In some embodiments, the radial intensity profile of the selected area electron diffraction pattern of the Cr-Zr-N alloy coating of this application, in Within the range, there is at least one half-width. The diffraction peaks.

[0193] The radial strength profile of the Cr-Zr-N alloy coating provided in this application, The full width at half maximum (FWHM) of diffraction peaks within the range has an upper limit due to the atomic close-packing limit. An unrestricted example of this upper limit is as follows:

[0194] In this application, the half-width at half-maximum (WHM) of the "broad peak" in the radial intensity profile corresponding to the SAED diagram can independently be any of the following values, can be greater than or equal to any of the following values, or can be greater than or equal to any of the following values ​​and less than or equal to the aforementioned upper limit value (e.g., Each of the following can be independently selected from any two of the following intervals: Etc. As a non-limiting example, the full width at half maximum (FWHM) of the "broad peak" in the radial intensity profile corresponding to the SAED plot can be selected from any of the following ranges: etc.

[0195] In some embodiments, the radial strength profile of the Cr-Zr-N alloy coating of this application is shown. full width at half maximum (FWHM) of diffraction peaks within the range

[0196] In some embodiments, the radial strength profile of the Cr-Zr-N alloy coating of this application is shown. The full width at half maximum (FWHM) of the diffraction peaks within the range can each independently be any of the following values, can each independently be greater than or equal to any of the following values, and can each independently be selected from an interval consisting of any two of the following values: Etc. As a non-limiting example, it may be selected from any of the following ranges: wait.

[0197] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating of this application is in The range contains one broad peak; its full width at half maximum (FWHM) value can be found in the examples within the context. (The full WHM value of the broad peak is used as an example.) For example, the radial intensity profile corresponding to the selected area electron diffraction pattern is in At least one diffraction peak within the range satisfies

[0198] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating of this application is in The range contains two or more broad peaks, and their half-width values ​​can be independently referenced in the examples in the context.

[0199] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Zr-N alloy coating of this application is in All diffraction peaks within the range are broad peaks, and the full width at half maximum (FWHM) of all diffraction peaks satisfy the following conditions: See also the context definition.

[0200] In some embodiments, the characteristic atomic spacing of the Cr-Zr-N alloy coating of this application is obtained using TEM diffraction data; wherein, an electron accelerating voltage of 200kV and a selected area aperture diameter of 900nm are used to perform TEM diffraction tests on the alloy coating.

[0201] In some implementations, TEM testing uses an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm to obtain the selected area electron diffraction (SAED) pattern of the Cr-Zr-N alloy coating.

[0202] In some embodiments, based on any of the foregoing suitable embodiments, the thickness of the Cr-Zr-N alloy coating is d. min ~6μm, where d min It can be selected from 10nm to 50nm, d min It can also be any of the following thicknesses, or a range selected from any two of the following thicknesses: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, etc.; for example, the thickness of the Cr-Zr-N alloy coating can be 25nm~6μm, 30nm~6μm, 40nm~6μm, 50nm~6μm, 1.0μm~2.5μm, 1.0μm~2.0μm, etc. The size unit μm represents "micrometer" and "nm" represents "nanometer".

[0203] By controlling the thickness of the Cr-Zr-N alloy coating to a suitable level, the corrosion resistance and / or high hardness of the alloy coating can be better utilized. The thicker the Cr-Zr-N alloy coating, the better it is for improving the corrosion resistance and / or hardness of the alloy coating.

[0204] The Cr-Zr-N alloy coating provided in this application offers excellent corrosion resistance while also possessing high hardness, thus better reducing scratch formation or mitigating scratch damage. Furthermore, the Cr-Zr-N alloy coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs. Compared to traditional alloy coatings, the Cr-Zr-N alloy coating of this application provides a denser structure, achieving better corrosion resistance, high hardness, and other properties at the same thickness. This allows for a reduction in coating thickness while maintaining superior protective properties, thereby saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0205] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 10 nm to 6 μm.

[0206] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 25 nm to 6 μm.

[0207] In some embodiments, the thickness of the Cr-Zr-N alloy coating is 1 μm to 2.5 μm.

[0208] Furthermore, when a relatively thin Cr-Zr-N alloy coating of this application is formed on the substrate, the resulting alloy film product can exhibit a silvery-white metallic luster, which is close to the metallic color of the substrate, thus achieving a beautiful decorative effect without altering the substrate color.

[0209] In a third aspect of this application, an alloy film article is provided, comprising a substrate 100 and a Cr-Zr-N alloy coating as described in the second aspect of this application (Cr-Zr-N alloy coating 300 as shown in FIG. 1); wherein the Cr-Zr-N alloy coating is located on at least one side of the substrate.

[0210] The alloy film products provided in this application include the film layer formed by the Cr-Zr-N alloy coating of this application, and are therefore referred to as alloy film products.

[0211] The Cr-Zr-N alloy coating provided in this application can be used as a surface layer for alloy film products, serving both aesthetic and protective functions. Furthermore, the Cr-Zr-N alloy coating provided in this application can also be positioned between the substrate and the surface layer, providing excellent protection and superior corrosion resistance and scratch resistance.

[0212] The Cr-Zr-N alloy coating provided in this application can be located on one or both sides of the substrate.

[0213] In some embodiments, the surface material of the substrate is one of alloys, elemental metals, and inorganic non-metallic materials. Non-limitingly, the alloy material type 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 materials. Non-limitingly, the elemental metal may be any of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium. Non-limitingly, the inorganic non-metallic material may include one or more of ceramics and glass. Non-limitingly, the inorganic non-metallic material may include silicon wafers.

[0214] The Cr-Zr-N alloy coating provided in this application can be applied to a variety of substrates, including but not limited to alloys, elemental metals, and inorganic non-metallic materials (such as silicon wafers, ceramics, and glass).

[0215] In some embodiments, the surface material of the substrate is one of the light alloys or one of the stainless steel alloys; optionally, the light alloy may include one or more of the titanium alloy, aluminum alloy and magnesium alloy.

[0216] In some embodiments, the surface material of the substrate is one of the light alloys; further, the light alloy may include one or more of titanium alloys, aluminum alloys and magnesium alloys.

[0217] In some embodiments, the surface material of the substrate is one of the stainless steel alloys. Further, the stainless steel alloy can be any one of austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, etc.

[0218] In some embodiments, the alloy film article satisfies one or more of the following characteristics:

[0219] The Cr-Zr-N alloy coating is in direct contact with the substrate (without a transition layer) or a transition layer is provided. Furthermore, the transition layer can be a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed between the Cr-Zr-N alloy coating provided in this application and the substrate).

[0220] The Cr-Zr-N alloy coating is located on the surface of the alloy film product, or the Cr-Zr-N alloy coating on the side away from the substrate is provided with a surface layer. Furthermore, the surface layer can be a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed on the Cr-Zr-N alloy coating provided in this application).

[0221] In this application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably. Both refer to the structural layer with transitional properties located between the substrate and the Cr-Zr-N alloy coating of this application in the alloy film product. It can be a single-layer structure or a multi-layer structure.

[0222] 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 Cr-Zr-N alloy coating of this application located on the surface of the product away from the substrate, and can be a single-layer structure or a multi-layer structure.

[0223] In some embodiments, the Cr-Zr-N alloy coating 300 is in direct contact with the substrate 100 (in which case there is no transition layer).

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

[0225] In some embodiments, the Cr-Zr-N alloy coating 300 is located on the surface of the alloy film article.

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

[0227] Figure 1 provides a schematic diagram of the structure of an exemplary alloy film article containing the Cr-Zr-N alloy coating of this application in one embodiment of the present application, including a substrate 100 and a Cr-Zr-N alloy coating 300.

[0228] Figure 2 provides a schematic diagram of the structure of the alloy film product in several embodiments of this application: (A) includes a substrate 100, a transition layer 200 and a Cr-Zr-N alloy coating 300; (B) includes a substrate 100, a transition layer 200, a Cr-Zr-N alloy coating 300 and a surface layer 400; (C) includes a substrate 100, a Cr-Zr-N alloy coating 300 and a surface layer 400.

[0229] When the Cr-Zr-N alloy coating provided in this application appears in the protective coating of an alloy film product, the position of the Cr-Zr-N alloy coating can be flexibly set. It can be used as a single structural layer of the protective coating, or as one layer in a multi-layer protective coating. For example, the Cr-Zr-N alloy coating can be used for surface protection, in which case the Cr-Zr-N alloy coating is located on the surface of the alloy film product, providing a high-gloss surface. The Cr-Zr-N alloy coating can also be used as an intermediate protective layer, in which case other structural layers are provided on the outside of the Cr-Zr-N alloy coating, that is, the Cr-Zr-N alloy coating is not used as a surface layer. Different coating position settings can achieve good scratch resistance and good corrosion resistance.

[0230] In some embodiments, the alloy film product is one of the following: 3C digital products, automotive products, aerospace products, wearable products, and sports products.

[0231] Without limitation, 3C digital products may include, but are not limited to, mobile device components, wearable components, and automotive components.

[0232] Depending on the main components of the substrate, alloy film products can be any of the following: light alloy products, stainless steel products, elemental metals, and inorganic non-metallic substrate products (such as ceramic-based products, silicon-based products, and glass-based products), indicating that the main components of the substrate are light alloys, stainless steel, elemental metals, etc. Non-limitingly, light alloy products may include, but are not limited to, aluminum alloy products, titanium alloy products, and magnesium alloy products. Non-limitingly, stainless steel products may include, but are not limited to, austenitic stainless steel, ferritic stainless steel, and martensitic stainless steel. Non-limitingly, elemental metal products may include, but are not limited to, zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium, and further, copper, aluminum, iron, silver, and chromium.

[0233] In one embodiment, the alloy film product is an aluminum alloy product.

[0234] In one embodiment, the alloy film product is a stainless steel product.

[0235] In one embodiment, the alloy film product is an inorganic non-metallic base product, and may further be a silicon-based product, a ceramic-based product, or a glass-based product.

[0236] In one embodiment, the alloy film product is a copper product.

[0237] Alloy film products can be intermediate or final products. Final products can be used or sold directly. Intermediate products can be further processed or assembled with other components into new products.

[0238] In a fourth aspect of this application, the application of the Cr-Zr-N alloy material described in the first aspect of this application or the Cr-Zr-N alloy coating described in the second aspect of this application is provided.

[0239] As previously stated, the Cr-Zr-N alloy coating of this application can be used as a surface layer or located between the substrate and the surface layer.

[0240] In some embodiments, the application of the Cr-Zr-N alloy material described in the first aspect of this application in the preparation of a high-brightness surface coating or the application of the Cr-Zr-N alloy coating described in the second aspect of this application as a high-brightness surface coating is provided; further, the brightness value L of the high-brightness surface coating is ≥70 as tested by the Lab method. In some embodiments, the high-brightness surface coating also serves as a corrosion-resistant protective coating.

[0241] In this application, unless otherwise specified, "surface coating" refers to a coating located on the surface of the article, which may be the Cr-Zr-N alloy coating of this application, or may include an additional surface layer on top of the Cr-Zr-N alloy coating of this application.

[0242] When the Cr-Zr-N alloy coating of this application is applied to the surface of an article, it can not only give the article a high-gloss surface, but also provide excellent corrosion resistance.

[0243] The L value of the Cr-Zr-N alloy coating of this application can reach ≥70, and in some cases up to 81, and exhibits a high-brightness silver-white color, which is much higher than the L value of traditional alloy coatings (traditional L value is about 55-65).

[0244] In some implementations, the luminance value L is tested using the Lab method and is ≥70, further ≥75, and even further ≥80.

[0245] In some embodiments, taking an aluminum alloy substrate as an example, a corrosion-resistant protective coating comprising the Cr-Zr-N alloy coating of this application is formed on the surface of the aluminum alloy substrate. This corrosion-resistant protective coating provides protection for ≥24 hours in a salt spray corrosion resistance test, meaning it can pass the 24-hour test. In most embodiments, it can also pass the 48-hour test using the ASTM B117 salt spray test method. Furthermore, more detailed test methods described above or below can be used. Taking an aluminum alloy substrate as an example, traditional alloy coatings, under the same test conditions, generally cannot achieve a protection time of 8 hours in a salt spray corrosion resistance test.

[0246] The Cr-Zr-N alloy coating provided in this application can combine excellent corrosion resistance and high hardness at a relatively low thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs. When the alloy coating is thin, the resulting alloy film product can exhibit a silvery-white metallic luster, closely resembling the metallic color of the substrate, which is more conducive to achieving an aesthetically pleasing decorative effect without altering the base material's color.

[0247] In a fifth aspect of this application, a method for preparing an alloy coating is provided, comprising the following steps: depositing the constituent elements of a Cr-Zr-N alloy coating onto at least a portion of the surface of a substrate according to a preset atomic ratio using vapor deposition technology, thereby forming the Cr-Zr-N alloy coating described in the second aspect of this application.

[0248] The method for preparing Cr-Zr-N alloy coating provided in this application is simple, easy to operate, environmentally friendly, and has the advantages of being quantifiable, efficient, and reproducible, making it suitable for industrial applications.

[0249] The definition of the matrix may be included in the third aspect of this application.

[0250] In some embodiments, the vapor deposition technique is physical vapor deposition. Further, physical vapor deposition can be achieved through one or more of the following methods: vacuum evaporation, sputtering deposition, arc plasma deposition, ion deposition, and molecular beam epitaxy.

[0251] In one embodiment, the physical vapor deposition method is magnetron sputtering deposition.

[0252] In some embodiments, sputtering deposition (such as magnetron sputtering) technology is used to deposit the constituent elements of the Cr-Zr-N alloy coating onto at least a portion of the substrate surface according to a preset atomic ratio.

[0253] In some embodiments, the apparatus shown in Figure 3 can be referred to. The apparatus 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 charging, and the zirconium target 5 is a zirconium target with radio frequency assisted DC cathode charging. This figure is not drawn to a 1:1 scale, and the relative dimensions of the components are shown in the figure only as examples to facilitate understanding of this application, but are not necessarily drawn to actual scale. The scale in the figure does not constitute a limitation of this application. The Cr-Zr-N alloy coating of this application can be formed by reactive sputtering with N2-containing gas (such as an Ar / N2 mixture) in the vacuum chamber 1.

[0254] In some embodiments, the preparation method of the Cr-Zr-N alloy coating includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using one or more targets including chromium and zirconium, the constituent elements of the Cr-Zr-N alloy coating are sputtered and deposited on at least a portion of the surface of the substrate to form the Cr-Zr-N alloy coating. The nitrogen-containing gas can be, but is not limited to, nitrogen. In this case, the gas ratio of argon to nitrogen in the mixed gas can be (2-6):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, etc. By selecting nitrogen as the nitrogen-containing gas and controlling the nitrogen content to a certain level, the performance of the Cr-Zr-N alloy coating of this application can be further adjusted.

[0255] The target material may include one or more of chromium targets, zirconium targets, and alloy targets. The alloy target includes at least two metallic elements from the Cr-Zr-N alloy coating. The atomic ratio of the metallic elements in the alloy target may be the same as or close to the atomic ratio of the corresponding metallic elements in the Cr-Zr-N 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, etc. In some embodiments, the atomic ratio of Cr to Zr in the chromium-zirconium-based alloy target is 65%:35%. In some embodiments, the alloy target includes all metallic elements from the Cr-Zr-N alloy coating. Examples of alloy targets can be found in Example 2 below.

[0256] 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 predetermined chemical formula (Cr...). x Zr y N z M a Within the range. For example, a chromium-zirconium based alloy target can be a chromium-zirconium-nitrogen alloy target composed of chromium, zirconium, and nitrogen (i.e., a CrZrN alloy target).

[0257] In some embodiments, a chromium-zirconium alloy target is used to replace the chromium target 4 in Figure 3 and is installed in the position where the original chromium target 4 in Figure 3 is located.

[0258] In some embodiments, the method for preparing a Cr-Zr-N alloy coating, taking sputtering deposition (such as magnetron sputtering deposition) as an example, includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using a chromium target and a zirconium target or a chromium-zirconium alloy target (i.e., a CrZr alloy target), the constituent elements of the Cr-Zr-N alloy coating are sputtered and deposited on at least a portion of the surface of the substrate to form a Cr-Zr-N alloy coating.

[0259] In some embodiments, the step of "sputtering and depositing the constituent elements of the Cr-Zr-N alloy coating on at least a portion of the surface of the substrate" further includes the following step: cleaning the substrate. The method for cleaning the substrate can employ conventional cleaning methods in this technical field (including but not limited to the decorative plating field).

[0260] 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 it on the sample stage of a sputtering deposition apparatus (such as magnetron sputtering deposition). The sample stage can be a rotatable sample stage.

[0261] In one embodiment, cleaning the substrate includes the following steps: ultrasonically cleaning the substrate in deionized water (DI water) for 10 to 15 minutes, baking the cleaned substrate in a vacuum oven for 15 to 20 minutes, and then placing it on a rotatable sample stage in a vacuum chamber.

[0262] In some embodiments, after the step of "cleaning the substrate" and before the step of "sputtering and depositing the constituent elements of the Cr-Zr-N alloy coating on at least a portion of the surface of the substrate", the following step is included: forming a transition layer (which may serve as a buffer film) on at least a portion of the surface of the cleaned substrate. For example, the constituent elements of the transition layer may be deposited onto at least a portion of the surface of the cleaned substrate.

[0263] In some embodiments, after the Cr-Zr-N alloy coating of this application is formed on one side of the substrate, a surface layer may be deposited to form, which may be a single-layer structure or a multi-layer structure.

[0264] In some embodiments, the sputtering deposition temperature is 30°C to 330°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 150°C, 200°C, 250°C, 300°C, 330°C, etc.

[0265] In some embodiments, the total pressure of the mixture containing argon and nitrogen is 0.3 Pa to 1.2 Pa; for example, 0.3 Pa, 0.5 Pa, 0.8 Pa, 1 Pa, 1.2 Pa, etc. The pressure unit Pa refers to "Pascal".

[0266] In some embodiments, sputtering is performed using radio frequency assisted DC sputtering. Compared to other preparation methods, this can further improve the performance of the alloy coating formed by sputtering deposition.

[0267] In some embodiments, the target material includes a chromium target with a power density of 3.5 W / cm². 2 ~6.7W / cm 2 Unit: W / cm² 2 It refers to "tiles per square centimeter".

[0268] In some embodiments, the target material includes a zirconium target with a power density of 0.5 W / cm². 2 ~3.0W / cm 2 .

[0269] In some embodiments, the target material includes a chromium target and a zirconium target, wherein the power density of the chromium target is 3.5 W / cm². 2 ~6.7W / cm 2 Furthermore, the power density of the zirconium target is 0.5 W / cm². 2 ~3.0W / cm 2 .

[0270] In some embodiments, the target material includes an alloy target comprising at least two metallic elements in a Cr-Zr-N alloy coating; optionally, the target material includes a chromium-zirconium-based alloy target with a power density of 4 W / cm². 2 ~6W / cm 2 .

[0271] In some embodiments, the target material includes a chromium-zirconium alloy target with a power density of 5 W / cm². 2 .

[0272] In some embodiments, a chromium-zirconium alloy target with a power density of 4 W / cm² is used. 2 ~6W / cm 2 5W / cm can be selected. 2 .

[0273] In some implementations, the substrate bias voltage is -150V to -20V; for example, -150V, -120V, -100V, -90V, -80V, -60V, -50V, -40V, -30V, -20V, etc. The unit V refers to "volt".

[0274] In some embodiments, the flow rate of the nitrogen-containing gas can be from 5 sccm to 52 sccm; for example, 5 sccm, 10 sccm, 20 sccm, 25 sccm, 30 sccm, 40 sccm, 50 sccm, 52 sccm, etc. Further, the nitrogen-containing gas is nitrogen. The unit sccm (standard cubic centimeter per minute) is a flow rate unit used to characterize gas flow rate.

[0275] 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 Cr-Zr-N alloy coating of this application can be controlled by adjusting the deposition time; the longer the deposition time, the greater the thickness of the Cr-Zr-N alloy coating.

[0276] In some implementations, the background vacuum of the vacuum chamber used is ≤5.0×10⁻⁶. -4 Pa. This pressure setting ensures the collision between sputtered particles and gas molecules, while also reducing the entry of impurities into the gas molecules during the deposition process, thereby improving the corrosion resistance, purity, and adhesion of the Cr-Zr-N alloy coating of this application.

[0277] Understandably, argon and nitrogen-containing gases can be introduced into the vacuum chamber through a single path or mixed in a mixing cylinder before entering the chamber, thereby reducing the impurity content of the Cr-Zr-N alloy coating of this application and improving its performance.

[0278] In some embodiments, "using sputtering deposition (such as magnetron sputtering deposition) technology to load the constituent elements of the Cr-Zr-N alloy coating onto at least a portion of the substrate surface according to a preset atomic ratio" includes the following steps: introducing a mixed gas containing argon and nitrogen into the vacuum chamber 1, maintaining the pressure inside the vacuum chamber 1 at 0.5 Pa to 0.8 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 / cm². 2 ~6.7W / cm 2 The power density of zirconium target 5 was set to 0.5 W / cm². 2 ~3.0W / cm 2 A Cr-Zr-N alloy coating is deposited on at least a portion of the surface of the cleaned substrate; furthermore, Cr-Zr-N alloy coatings of different thicknesses can be obtained by controlling the film formation time.

[0279] The following are some examples.

[0280] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where conditions are not specified, reference should be made to the guidelines given in this application, or to experimental manuals or conventional conditions in the art, or to the conditions recommended by the manufacturer, or to experimental methods known in the art.

[0281] In the following examples, the measurement parameters of the raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are subject to acceptable deviations due to instrument testing accuracy or operational precision.

[0282] Test method:

[0283] 1. Colorimetric value test of alloy coating

[0284] When testing the colorimetric value of an alloy coating, the sample is placed on a substrate suitable for practical applications, and the degree to which the alloy coating improves the substrate's properties, such as density, is assessed. The surface material of a "substrate suitable for practical applications" can include, but is not limited to, aluminum alloys and stainless steel.

[0285] The L, a, and b values ​​of the samples were tested using a Konica CM-3700A-U benchtop spectrophotometer manufactured in Japan. An F2 light source was selected for the light receiving system. The average value was taken after testing 6 matrix points for each sample.

[0286] Wherein, L value represents the brightness value, a value represents the red or green chromaticity value, and 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.

[0287] A larger L value indicates higher brightness and a denser coating surface. The mechanism is as follows: When incident light is incident on the surface of the sample, a reflectance curve is obtained. The amplitude of this curve reflects the density of the material, which can be characterized by the L value. For the same material, the higher its density, the larger the displayed L value.

[0288] 2. Morphology and composition analysis of alloy coatings

[0289] All samples tested used silicon wafers as the substrate.

[0290] Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used for testing.

[0291] Morphological analysis: A Hitachi Regulus 8230 scanning electron microscope was used.

[0292] Compositional analysis: X-ray energy dispersive spectroscopy (EDX) was performed using a Hitachi Regulus 8230 scanning electron microscope. The relative intensities of all elements were corrected using the ZAF method.

[0293] Test parameters: electron accelerating voltage is 15 kV, beam current is 10 μA, sample magnification is 200x, and 10 points are tested for each sample and the average value is taken.

[0294] 3. X-ray diffraction (XRD) test of alloy coating

[0295] When performing XRD tests on alloy coatings, silicon wafers are used as the substrate.

[0296] 3.1. Calculate the full width at half maximum (FWHM) of the diffraction peaks in the XRD pattern.

[0297] The Bruker D8 Advance XRD diffractometer from Germany was used in θ-2θ mode with Cu target Kα rays at a wavelength of 0.15406 nm. The X-ray tube was controlled at 40 kV and 40 mA, and the scanning range was 20° to 80° with precise scanning measurements in steps of 0.01°.

[0298] The steps to obtain the full width at half maximum (FWHM) value are as follows: First, the diffraction peak is corrected, including smoothing, background subtraction, removal of Kα2 lines, and subtraction of instrument broadening. Then, the diffraction peak is fitted with the Pseudo-Voigt function to obtain the FWHM value of the diffraction peak.

[0299] 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): First, scale correction was performed, then the center of the transmission spot of the diffraction ring was determined, and then it was converted into an XRD pattern (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm); the diffraction peaks were stripped of the straight background, and then fitted with the Voigt function to obtain the full width at half maximum (FWHM) values ​​of the corresponding diffraction peaks.

[0300] 3.2. Determine whether the XRD pattern of the alloy coating shows broad peaks.

[0301] The method for determining whether there are broad peaks in the diffraction angle range of 2θ (°) between 30° and 50° in the XRD diffraction pattern is as follows: If the full width at half maximum (FWHM) of the 2θ (°) diffraction peak is ≥2°, it is judged as a broad peak; if the FWHM of the 2θ (°) diffraction peak is <2°, it is judged as a sharp peak.

[0302] For a given 2θ (°) position, it can be any of the three states: no peak, sharp peak, or broad peak.

[0303] 4. TEM test

[0304] When performing TEM testing on alloy coatings, silicon wafers are used as the substrate.

[0305] 4.1. The following method was used to obtain the full width at half maximum (FWHM) data of the diffraction rings in the TEM diffraction pattern:

[0306] TEM test sample preparation: The sample was thinned using a Helios 5 CX focused ion beam (FIB) from ThemoFisher Ltd. to obtain an electronically transparent, TEM-observable planar sample.

[0307] SAED Image Acquisition: A Talos F200x transmission electron microscope (TEM) from ThemoFisher, Inc. was used with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm to acquire the selected area electron diffraction (SAED) pattern of the sample.

[0308] Radial intensity profile acquisition: The SAED spectrum data obtained above was processed using EDP2XRD software (version 1.0.0, copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney). First, scale correction was performed, then the center of the transmission spot of the diffraction ring was determined, and finally it was 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 interatomic spacing as the abscissa and the diffraction intensity as the ordinate.

[0309] The steps to obtain the full width at half maximum (FWHM) value are as follows: subtract the straight background from the diffraction peak, and then fit it with the Voigt function to obtain the FWHM value of the corresponding diffraction peak.

[0310] 4.2. Determining the radial intensity profile of a TEM selected area electron diffraction pattern. Methods for determining whether there are broad peaks within a given range: the full width at half maximum (FWHM) of the diffraction peaks corresponding to the characteristic atomic spacing. It is then judged as a broad peak; the full width at half maximum (FWHM) of the diffraction peak corresponding to the characteristic atomic spacing. It is identified as a sharp peak. For a specific characteristic atomic spacing, it can be any of three states: no peak, sharp peak, or broad peak.

[0311] 5. Salt spray corrosion resistance test of alloy coating

[0312] During the salt spray corrosion resistance test of the alloy coating, the sample to be tested uses a substrate suitable for practical applications, and the degree to which the alloy coating improves the corrosion resistance of the substrate is detected. The surface material of the "substrate suitable for practical applications" can include, but is not limited to: aluminum alloy and stainless steel.

[0313] The ASTM B117 salt spray test standard was adopted, the solution pH value was 6.5 to 7.2, and the chemical composition of the solution was: sodium chloride (NaCl), deionized water and sodium hydroxide (NaOH).

[0314] A 12-hour period can be used as a sub-cycle of the salt spray corrosion resistance test.

[0315] The testing cycles for alloy coatings prepared on substrates of different materials can vary, for example:

[0316] The testing cycle for aluminum alloy matrix samples is 48 hours or 24 hours.

[0317] The testing cycle for stainless steel substrate samples is 144 hours or 96 hours.

[0318] The testing cycle for the copper substrate sample is 12 hours.

[0319] The standard for "passing (OK)" salt spray corrosion resistance test is: after the sample is tested, there is no corrosion, discoloration, or rust on the appearance.

[0320] The standard for "Not Passed (NG)" salt spray corrosion resistance test is: after the sample is tested, there is corrosion, discoloration or rust on the appearance.

[0321] 6. Hardness test of alloy coating

[0322] When testing the hardness of alloy coatings, the sample to be tested should use a substrate suitable for practical applications.

[0323] The surface material of the "substrate suitable for practical application" may include, but is not limited to: aluminum alloy, stainless steel, and copper sheet.

[0324] In the following examples, unless otherwise specified, aluminum alloys and stainless steel are used as substrates to test the hardness of alloy coatings. The alloy coating is deposited on the aluminum alloy or stainless steel using preset preparation parameters to obtain the test sample, which is then used to test the hardness of the alloy coating. This is mainly because: during nanoindentation testing, the probe penetrates the test sample, generating strong pressure. This requires the substrate to have a certain degree of toughness. If a brittle silicon wafer is used, cracking may occur during the test, leading to inaccurate test results. Alloy materials, due to their excellent toughness, are more suitable as the test substrate for nanoindentation testing. Furthermore, using alloy materials as the substrate to measure nanohardness is more universally applicable in the characterization of nanohardness parameters in the coating field.

[0325] The hardness of each film or coating was tested using an NHT3 nanoindenter manufactured by Anton-Paar in Austria. It was equipped with a tetrahedral Berkvich indenter, and the indentation depth was set to 100 nm. The load changed with the indentation depth. Five matrix points were tested for each sample and the average value was taken.

[0326] In the following examples, DI water refers to deionized water.

[0327] The stainless steel sheets, aluminum alloy sheets, and silicon wafers in the following embodiments and comparative examples are all made of the same material.

[0328] In the following examples, the target material is sputtered using radio frequency assisted DC sputtering.

[0329] In the following examples, the XRD patterns and SAED-radial intensity profiles refer to "there is one and only one broad peak". Unless otherwise specified, this means that there is one and only one characteristic peak, and that peak is a broad peak.

[0330] Example 1.

[0331] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 81.6 Zr 13.7 N 4.7 .

[0332] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, hold at that temperature for 15 minutes. The unit of measurement mm refers to "millimeters".

[0333] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0334] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 5 sccm, maintain the Ar:N2 gas flow ratio at 6:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 6 W / cm³. 2 The power density of the Zr target was set to 1.5 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and the film thickness was 1300 nm by controlling the film formation time.

[0335] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0336] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 81.6 Zr 13.7 N 4.7 .

[0337] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.31, a: 0.26, b: 2.88, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.30, a: 0.20, b: 2.45, exhibiting a silvery-white color.

[0338] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0339] The hardness value of the aluminum alloy substrate sample was 13.7 GPa, and the hardness value of the stainless steel substrate sample was 14.6 GPa.

[0340] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 4. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 5. SEM results show that the Cr-Zr-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 30°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 30°–50° is ≥2°, with only one broad peak in the range of 30°–50° having a FWHM of 9.11°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0341] Example 2.

[0342] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 61.4 Zr 33.2 N 5.4 The preparation method is as follows:

[0343] In this embodiment, a chromium-zirconium alloy target is selected as the target material. The original Cr target at position 4 in Figure 3 is replaced with a CrZr alloy target with an atomic percentage of 65%:35% for Cr and Zr.

[0344] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, keep at room temperature (about 30°C) for 15 minutes.

[0345] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0346] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the CrZr alloy target using an RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 7 sccm, maintain the Ar:N2 gas flow ratio at 6:1, maintain the pressure inside the furnace at 0.7 Pa, turn on the bias voltage and set it to -100V, and set the power density of the CrZr alloy target to 5 W / cm³. 2 A Cr-Zr-N alloy coating was deposited, and the film thickness was 2500 nm by controlling the film formation time.

[0347] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0348] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 61.4 Zr 33.2 N 5.4 .

[0349] The colorimetric values ​​of the aluminum alloy substrate sample were L: 79.05, a: 0.43, b: 3.54, and the colorimetric values ​​of the stainless steel substrate sample were L: 81.74, a: 0.33, b: 3.04, exhibiting a silvery-white color.

[0350] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0351] The hardness value of the aluminum alloy substrate sample was 15.1 GPa, and the hardness value of the stainless steel substrate sample was 16.3 GPa.

[0352] The test sample underwent SEM cross-sectional testing; the cross-sectional morphology is shown in Figure 6. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 7. SEM results show that the Cr-Zr-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 30°–50° is ≥2°, with exactly one broad peak of 8.85° within the 30°–50° range. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0353] Example 3.

[0354] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 47.1 Zr 17.4 N 35.5 The preparation method is as follows:

[0355] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0356] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0357] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 42 sccm, maintain an Ar:N2 gas ratio of 2:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 3.9 W / cm³. 2 The power density of the Zr target was set to 1.9 W / cm². 2A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1600 nm was obtained.

[0358] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0359] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 47.1 Zr 17.4 N 35.5 .

[0360] The colorimetric values ​​of the aluminum alloy substrate sample were L: 73.92, a: 0.43, b: 4.78, and the colorimetric values ​​of the stainless steel substrate sample were L: 75.50, a: 0.36, b: 4.69, exhibiting a bright silver-white color.

[0361] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0362] The hardness value of the aluminum alloy substrate sample was 18.2 GPa, and the hardness value of the stainless steel substrate sample was 20.4 GPa.

[0363] The SEM cross-sectional analysis of the test sample is shown in Figure 8, and the XRD diffraction pattern is shown in Figure 9. The SEM results show that the Cr-Zr-N alloy coating has a dense structure, and no through-column seams were observed. The XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has broad peaks in the range of 30°–50°, and the full width at half maximum (FWHM) of all 2θ (°) peaks in this range is ≥2°, with only one broad peak in the range of 30°–50° having a FWHM of 4.42°. The radial intensity profile of the TEM selected area electron diffraction pattern is shown in... There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0364] Example 4.

[0365] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 52.0 Zr 12.1 N 35.9 The preparation method is as follows:

[0366] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4Pa, heat to 150℃, and hold at that temperature for 15 minutes;

[0367] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0368] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 42 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.1 W / cm². 2 The power density of the Zr target was set to 1.5 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1700 nm was obtained.

[0369] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0370] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 52.0 Zr 12.1 N 35.9 .

[0371] The colorimetric values ​​of the aluminum alloy substrate sample were L: 74.16, a: 0.47, b: 4.00, and the colorimetric values ​​of the stainless steel substrate sample were L: 75.70, a: 0.41, b: 3.95, exhibiting a silvery-white color.

[0372] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0373] The hardness value of the aluminum alloy substrate sample was 16.7 GPa, and the hardness value of the stainless steel substrate sample was 19.2 GPa.

[0374] The test sample underwent SEM cross-sectional testing, and the cross-sectional morphology is shown in Figure 10. The XRD diffraction pattern is shown in Figure 11. SEM results show that the Cr-Zr-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has broad peaks in the range of 30°–50°, and the full width at half maximum (FWHM) of all 2θ (°) peaks in this range is ≥2°. Among these, there is only one broad peak with a FWHM of 4.04° in the 30°–50° range. The radial intensity profile of the TEM selected area electron diffraction pattern is shown in... There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0375] Example 5.

[0376] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 60.9 Zr 26.1 N 13.0 The preparation method is as follows:

[0377] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0378] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0379] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 14 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.7 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 5 W / cm³. 2 The power density of the Zr target was set to 2.7 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0380] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0381] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 60.9 Zr 26.1 N 13.0 .

[0382] The colorimetric values ​​of the aluminum alloy substrate sample were L: 79.21, a: 0.41, b: 3.91, and the colorimetric values ​​of the stainless steel substrate sample were L: 79.95, a: 0.33, b: 3.73, exhibiting a bright silvery-white color.

[0383] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0384] The hardness value of the aluminum alloy substrate sample was 11.8 GPa, and the hardness value of the stainless steel substrate sample was 13.7 GPa.

[0385] The SEM cross-sectional analysis of the test sample is shown in Figure 12, and the XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 13. The SEM results show that the Cr-Zr-N alloy coating has a dense structure, and no through-column seams were observed. The XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has broad peaks in the range of 30°–50°, and the full width at half maximum (FWHM) of all 2θ (°) peaks in the 30°–50° range is ≥2°, with only one broad peak in the 30°–50° range having a FWHM of 9.33°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0386] Example 6.

[0387] In this example, the substrate surface has a double-layer thin film structure, including a film with the chemical composition Cr. 60.9 Zr 26.1 N 13 The material comprises a Cr-Zr-N alloy coating and a second coating with a chemical composition of TiN, forming a bilayer thin film structure denoted as Cr-Zr-N / TiN. In this case, a multilayer thin film structure is attached to the substrate surface, wherein the Cr-Zr-N alloy coating provided in this application serves as the intermediate layer, located between the substrate and the surface layer. The preparation method is as follows:

[0388] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0389] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0390] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 14 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.7 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 5 W / cm³. 2 The power density of the Zr target was set to 2.7 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0391] Deposition of the surface layer (second coating): Replace the Zr target in the furnace with a Ti target, turn on the sample stage rotation rack, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use DC power to power the Ti target, and introduce Ar and N2 gas. Set the N2 gas flow rate to 10 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5 W / cm³. 2 A TiN coating was deposited, and by controlling the film deposition time, a film thickness of 100 nm was obtained.

[0392] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0393] Component analysis revealed that the component was Cr. 60.9 Zr 26.1 N 13 The alloy coating surface is coated with a TiN coating.

[0394] The colorimetric values ​​tested for the aluminum alloy substrate sample were L: 58.85, a: 6.65, b: 12.85, and for the stainless steel substrate sample were L: 59.83, a: 6.82, b: 13.61, exhibiting a golden-yellow hue. The test results here represent the colorimetric values ​​of the surface TiN layer.

[0395] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0396] The hardness value of the aluminum alloy substrate sample was 11.7 GPa, and the hardness value of the stainless steel substrate sample was 14.2 GPa.

[0397] The cross-sectional morphology of the test sample was measured by SEM, and the results are shown in Figure 14. The SEM results show that the Cr-Zr-N alloy coating has a dense structure.

[0398] It should be noted that the vertical cracks in the SEM morphology image of Figure 14 correspond to the cracks generated during the process of breaking the silicon wafer, and are not columnar cracks caused by the growth of Cr-Zr-N thin films.

[0399] Example 7.

[0400] In this example, a three-layer thin film structure is attached to the substrate surface, consisting sequentially of a transition layer (as the bottom coating), an alloy coating containing Cr-Zr-N alloy material, and a second coating on the surface. This three-layer thin film structure is denoted as Cr / Cr-Zr-N / TiN, where the transition layer is a Cr layer, and the chemical composition of the Cr-Zr-N alloy coating is Cr. 60.9 Zr 26.1 N 13 The second coating has the chemical composition of TiN. The preparation method is as follows:

[0401] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0402] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0403] Deposition of the underlayer coating (transition layer): Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use RF-assisted DC power supply to power the Cr target, introduce Ar gas, set the Ar gas flow rate to 42 sccm, maintain the pressure inside the furnace at 0.5 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 5 W / cm³. 2 A Cr coating was deposited, and by controlling the film formation time, a film thickness of 300 nm was obtained.

[0404] Deposition of the Cr-Zr-N alloy coating of this application: The sample stage rotation was turned on, the rotation speed was set to 6 revolutions per minute, and the distance between the sample stage and the target surface was adjusted to 8 cm. The Cr and Zr targets were powered by an RF-assisted DC power supply. Ar and N2 gases were introduced, with the N2 gas flow rate set to 14 sccm. The gas volume was set to maintain an Ar:N2 gas ratio of 3:1, and the furnace pressure was maintained at 0.7 Pa. The bias voltage was turned on and set to -100V. The power density of the Cr target was set to 5 W / cm³. 2 The power density of the Zr target was set to 2.7 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0405] Deposition of the surface layer (second coating): Replace the Zr target in the furnace with a Ti target, turn on the sample stage rotation rack, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use DC power to power the Ti target, and introduce Ar and N2 gas. Set the N2 gas flow rate to 10 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5 W / cm³. 2 A TiN coating was deposited, and by controlling the film deposition time, a film thickness of 100 nm was obtained.

[0406] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0407] Compositional analysis revealed that the substrate surface has a three-layer thin film structure, with the chemical composition being Cr (transition layer), Cr2, Cr3, Cr4, Cr5, Cr6, Cr7, Cr8, Cr9, Cr10, Cr11, Cr21, Cr22, Cr22, Cr3 ... 60.9 Zr 26.1 N 13 (A Cr-Zr-N alloy coating of this application) and TiN (a second coating), the three-layer thin film structure being Cr / Cr-Zr-N / TiN.

[0408] The colorimetric values ​​for the aluminum alloy substrate sample were L: 56.64, a: 7.07, b: 14.11, and for the stainless steel substrate sample were L: 58.73, a: 7.35, b: 14.35, exhibiting a golden-yellow hue. The test results here represent the colorimetric values ​​of the surface TiN layer.

[0409] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0410] The hardness value of the aluminum alloy substrate sample was 13.2 GPa, and the hardness value of the stainless steel substrate sample was 15.1 GPa.

[0411] The test sample underwent SEM cross-sectional testing, and the cross-sectional morphology is shown in Figure 15. The SEM test results show that the alloy coating has a dense structure.

[0412] It should be noted that the vertical cracks in the SEM morphology image of Figure 15 correspond to the cracks generated during the process of breaking the silicon wafer, and are not columnar cracks caused by the growth of Cr-Zr-N thin films.

[0413] Example 8.

[0414] In this example, the chemical composition of the Cr-Zr-N alloy coating is Cr. 60.9 Zr 26.1 N 13 The preparation method is as follows:

[0415] Substrate pretreatment: Copper and silicon wafer samples with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0416] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0417] Deposition of Cr-Zr-N alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 14 sccm, maintain the Ar:N2 gas flow rate ratio at 3:1, maintain the furnace pressure at 0.7 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 5 W / cm³. 2 The power density of the Zr target was set to 2.7 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0418] Samples using copper sheets as the substrate were subjected to salt spray corrosion resistance testing, hardness testing, and colorimetric value testing. Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0419] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 60.9 Zr 26.1 N13 .

[0420] The colorimetric values ​​of the copper substrate sample were L: 80.15, a: 0.53, b: 4.63, exhibiting a bright silvery-white color.

[0421] In the salt spray corrosion resistance test, the copper substrate sample can pass the 12-hour test, demonstrating certain protective properties.

[0422] The hardness value of the copper substrate sample was 7.9 GPa.

[0423] SEM results showed that the Cr-Zr-N alloy coating had a dense structure and no through-column seams were observed. XRD results showed that the XRD diffraction pattern contained broad peaks, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the range of 30° to 50° was ≥2°, with only one broad peak in the range of 30° to 50° having a FWHM of 9.33°. The radial intensity profile of the TEM selected area electron diffraction pattern showed... There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0424] Example 9. The thickness of the Cr-Zr-N alloy coating is approximately 50 nm.

[0425] Using essentially the same method as in Example 5, the chemical composition of the Cr-Zr-N alloy coating is Cr 60.9 Zr 26.1 N 13.0 The only difference is that the thickness of the Cr-Zr-N alloy coating is adjusted to 50nm.

[0426] The colorimetric values ​​of the aluminum alloy substrate sample were L: 80.11, a: 0.41, b: 3.61, and the colorimetric values ​​of the stainless steel substrate sample were L: 80.95, a: 0.34, b: 3.43, exhibiting a bright silver-white color.

[0427] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0428] The hardness value of the aluminum alloy substrate sample was 8.2 GPa, and the hardness value of the stainless steel substrate sample was 9.7 GPa.

[0429] Example 10. The thickness of the Cr-Zr-N alloy coating is approximately 6 μm.

[0430] Using essentially the same method as in Example 5, the chemical composition of the Cr-Zr-N alloy coating is Cr 60.9 Zr 26.1 N 13.0The only difference is that the thickness of the Cr-Zr-N alloy coating is adjusted to 6000nm.

[0431] The colorimetric values ​​of the aluminum alloy substrate sample were L: 77.31, a: 0.45, b: 3.81, and the colorimetric values ​​of the stainless steel substrate sample were L: 76.94, a: 0.34, b: 3.83, exhibiting a bright silver-white color.

[0432] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0433] The hardness value of the aluminum alloy substrate sample was 22.8 GPa, and the hardness value of the stainless steel substrate sample was 24.7 GPa.

[0434] Example 11. Containing doped elements

[0435] In this embodiment, the chemical composition of the Cr-Zr-N alloy coating containing doped elements is Cr. 47.1 Zr 17.4 N 30.5 C5, at this point, normalized with the sum of the atomic ratios of Cr, Zr, and N set to 100, yields an atomic ratio of approximately 49.579:18.316:32.105. The atomic percentage of dopant element C in the Cr-Zr-N alloy coating is 5%. The preparation method is as follows:

[0436] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0437] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0438] Deposition of the Cr-Zr-N alloy coating of this application: The sample stage rotation was turned on, the rotation speed was set to 6 revolutions per minute, and the distance between the sample stage and the target surface was adjusted to 8 cm. The Cr and Zr targets were powered by an RF-assisted DC power supply. Ar, C2H2, and N2 gases were introduced, with the N2 gas flow rate set to 35 sccm and the C2H2 gas flow rate set to 6 sccm. The gas flow rate was set to maintain an Ar:(C2H2+N2) gas flow rate ratio of 2:1. The furnace pressure was maintained at 0.8 Pa. The bias voltage was turned on and set to -100V. The power density of the Cr target was set to 3.9 W / cm³. 2The power density of the Zr target was set to 1.9 W / cm². 2 The Cr-Zr-N alloy coating of this application (which is a carbon-doped Cr-Zr-N alloy coating) was deposited, and the film thickness was 1600 nm by controlling the film formation time.

[0439] Samples using stainless steel sheets and aluminum alloy sheets as substrates underwent salt spray corrosion resistance testing, hardness testing, and colorimetric value testing. Samples using silicon wafers as substrates underwent SEM and component analysis, XRD analysis, and TEM testing.

[0440] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 47.1 Zr 17.4 N 30.5 C5.

[0441] The colorimetric values ​​of the aluminum alloy substrate sample were L: 72.72, a: 0.41, b: 4.58, and the colorimetric values ​​of the stainless steel substrate sample were L: 73.81, a: 0.38, b: 4.27, exhibiting a bright silvery-white hue. The XRD diffraction pattern showed at least one broad peak at a diffraction angle 2θ (°) within the range of 30°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern showed… It has at least one broad peak within the range.

[0442] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0443] The hardness value of the aluminum alloy substrate sample was 18.9 GPa, and the hardness value of the stainless steel substrate sample was 20.4 GPa.

[0444] According to the inventors' experimental findings, when using other non-metallic doping elements (such as Si, B, O, etc.) or metallic doping elements (such as Al), high brightness and excellent corrosion resistance can still be provided when the atomic ratio of the doping elements is appropriate (such as 4 at%) or 2 at%). In some embodiments, in the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, and stainless steel substrate samples can pass the test for 144 hours. Furthermore, at least one broad peak can be observed in the XRD diffraction pattern within the diffraction angle range of 2θ (°) from 30° to 50°, and the radial intensity profile of the TEM selected area electron diffraction pattern... It has at least one broad peak within the range. In addition, it also has high hardness.

[0445] "at%" indicates the percentage of atoms.

[0446] Example 12.

[0447] In this embodiment, the chemical composition of the alloy coating is Cr. 50 Zr 30 N 20 The element composition does not conform to the following combination formula: 63.19-0.925y≤x≤95.79-y and 31.4+0.9y≤x≤18.5y-171.85.

[0448] In this example, the chemical composition of the alloy coating is Cr. 50 Zr 30 N 20 The preparation method is as follows:

[0449] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0450] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0451] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 18 sccm, maintain an Ar:N2 gas ratio of 3:1, maintain the furnace pressure at 0.7 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.5 W / cm³. 2 The power density of the Zr target was set to 3.0 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0452] Samples using stainless steel sheets and aluminum alloy sheets as substrates underwent salt spray corrosion resistance testing, hardness testing, and colorimetric value testing. Samples using silicon wafers as substrates underwent SEM and component analysis, XRD analysis, and TEM testing.

[0453] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 50 Zr 30 N 20 .

[0454] The colorimetric values ​​for the aluminum alloy substrate sample were L: 77.01, a: 0.92, b: 4.52, and for the stainless steel substrate sample were L: 79.06, a: 0.54, b: 3.98, both exhibiting a silvery-white hue. In the salt spray corrosion resistance test, the aluminum alloy substrate sample passed the 24-hour test (failed the 48-hour test), and the stainless steel substrate sample passed the 96-hour test (failed the 144-hour test), demonstrating excellent protective properties. The hardness value for the aluminum alloy substrate sample was 11.6 GPa, and for the stainless steel substrate sample was 12.7 GPa.

[0455] The XRD diffraction pattern shows at least one broad peak at a diffraction angle 2θ (°) in the range of 30°–50°, and the radial intensity profile of the TEM selected area electron diffraction pattern is... It has at least one broad peak within the range.

[0456] Example 13.

[0457] In this embodiment, the chemical composition of the alloy coating is Cr. 49.5 Zr 18.0 N 32.5 The preparation method is as follows:

[0458] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0459] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0460] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 42 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.7 W / cm³. 2 The power density of the Zr target was set to 1.8 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1600 nm was obtained.

[0461] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to XRD analysis and TEM tests.

[0462] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 49.5 Zr 18.0 N 32.5 .

[0463] The colorimetric values ​​of the aluminum alloy substrate sample were L: 74.52, a: 0.41, b: 4.48, and the colorimetric values ​​of the stainless steel substrate sample were L: 75.70, a: 0.32, b: 4.39, exhibiting a bright silvery-white color.

[0464] In the salt spray corrosion resistance test, aluminum alloy substrate samples can pass the test for 48 hours, while stainless steel substrate samples can pass the test for 144 hours, demonstrating excellent protective properties.

[0465] The hardness value of the aluminum alloy substrate sample was 18.5 GPa, and the hardness value of the stainless steel substrate sample was 19.4 GPa.

[0466] The XRD test results (see Figure 16(A)) show that the diffraction angle 2θ (°) in the XRD diffraction pattern has broad peaks in the range of 30° to 50°, and the full width at half maximum (FWHM) of all 2θ (°) peaks in the range of 30° to 50° is ≥2°, with exactly one broad peak in the range of 30° to 50° having a FWHM of 2.19°; the TEM-SAED test results (see Figure 16(B) and (C)) show that the radial intensity profile (C) corresponding to the TEM selected area electron diffraction pattern (B) is... There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0467] Regarding the intrinsic mechanism analysis of the high hardness and excellent corrosion resistance of the Cr-Zr-N alloy coating provided in this application, the inventors of this application have discovered through extensive experimental exploration that for the Cr-Zr-N alloy coating of this application, the following two conditions must be met simultaneously: (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 within the range of 30° to 50°. When at least one broad peak is present within the specified range, the prepared Cr-Zr-N alloy coating exhibits excellent corrosion resistance and high hardness. However, if only one broad peak is present in the XRD diffraction pattern within the range of 30°–50°, and the radial intensity profile of the TEM-SAED image shows… If no broad peaks are found within the specified 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 24-hour salt spray corrosion resistance test. If the radial intensity profile of the TEM-SAED image is not within this range... The presence of at least one broad peak within the range, while the absence of a broad peak at the diffraction angle 2θ (°) in the XRD diffraction pattern within the range of 30° to 50°, may also lead to poor corrosion resistance of the Cr-Zr-N alloy coating. See Comparative Example 4 below for reference.

[0468] Comparative Example 1.

[0469] In this comparative example, the chemical composition of the alloy coating is Cr. 88.9 Zr 11.1 The preparation method is as follows:

[0470] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0471] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0472] Deposition of Cr-Zr alloy coating: Turn on the sample stage rotation rack, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using an RF-assisted DC power supply, introduce Ar gas, maintain the pressure inside 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 / cm². 2 The power density of the Zr target was set to 0.8 W / cm². 2 A Cr-Zr alloy coating was deposited, and by controlling the film formation time, a film thickness of 1900 nm was obtained.

[0473] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis tests.

[0474] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 88.9 Zr 11.1 .

[0475] The colorimetric values ​​of the aluminum alloy substrate sample were L: 83.21, a: -0.21, b: 0.88, and the colorimetric values ​​of the stainless steel substrate sample were L: 85.05, a: -0.25, b: 0.79, exhibiting a silvery-white color.

[0476] The test sample underwent SEM cross-sectional testing, and the cross-sectional morphology is shown in Figure 17. The SEM results show that the alloy coating film has crystallization defects, a non-dense structure, and obvious gaps.

[0477] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <24h) and the stainless steel substrate sample failed the 144h test (NG, protection time <48h), indicating poor protective performance.

[0478] The hardness value of the aluminum alloy substrate sample was 18.5 GPa, and the hardness value of the stainless steel substrate sample was 19.6 GPa.

[0479] Comparative Example 2.

[0480] In this comparative example, the chemical composition of the alloy coating is Cr. 37.8 Zr 16.2 N 46 The preparation method is as follows:

[0481] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0482] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0483] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 52 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.9 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 3.5 W / cm³. 2 The power density of the Zr target was set to 1.8 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, a film thickness of 1000 nm was obtained.

[0484] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0485] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 37.8 Zr 16.2 N 46 .

[0486] The colorimetric values ​​of the aluminum alloy substrate sample were L: 61.87, a: 0.57, b: 4.45, and the colorimetric values ​​of the stainless steel substrate sample were L: 67.38, a: 0.49, b: 4.29. The colors were dull and lacked metallic luster.

[0487] The SEM cross-sectional analysis of the test sample is shown in Figure 18. The XRD diffraction pattern, TEM selected area electron diffraction pattern, and radial intensity profile are shown in Figure 19. The SEM results show that the alloy coating film has a loose structure with obvious through-beam gaps. The XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has two peaks in the range of 30°–50°, both of which are sharp peaks (2θ peaks with a half-width at half-maximum (FWHM) < 2°). The FWHMs of the two sharp peaks in the 30°–50° range are 0.66° and 1.24°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern is shown in Figure 19. There are two peaks within the range, with half-widths of 100 and 250 respectively. That is, there are two peaks.

[0488] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <24h) and the stainless steel substrate sample failed the 144h test (NG, protection time <48h), indicating poor protective properties.

[0489] The hardness value of the aluminum alloy substrate sample was 16.6 GPa, and the hardness value of the stainless steel substrate sample was 18.1 GPa.

[0490] Comparative Example 3.

[0491] In this comparative example, the thin film structure is TiN, and the chemical composition of the alloy coating is TiN.

[0492] To prepare this comparative coating, the Zr target inside the furnace was replaced with a Ti target. The preparation method is as follows:

[0493] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶.-4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0494] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0495] Deposition of TiN coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use DC power to power the Ti target, and introduce Ar and N2 gas. Set the N2 gas flow rate to 10 sccm, maintain the Ar:N2 gas flow rate ratio at 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5 W / cm³. 2 A TiN coating was deposited, and by controlling the film deposition time, a film thickness of 200 nm was obtained.

[0496] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric value tests.

[0497] Composition analysis revealed that the alloy coating on the substrate surface is composed of TiN.

[0498] The colorimetric values ​​of the aluminum alloy substrate sample were L: 57.95, a: 6.45, b: 13.95, and the colorimetric values ​​of the stainless steel substrate sample were L: 59.33, a: 6.92, b: 13.91, exhibiting a golden yellow color.

[0499] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection time < 24h).

[0500] The hardness value of the aluminum alloy substrate sample was 3.8 GPa, and the hardness value of the stainless steel substrate sample was 4.3 GPa.

[0501] Comparative Example 4.

[0502] 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:

[0503] Substrate pretreatment: Stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0504] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0505] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Zr targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 45 sccm, maintain an Ar:N2 gas ratio of 2:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.6 W / cm². 2 The power density of the Zr target was set to 2.2 W / cm². 2 A Cr-Zr-N alloy coating was deposited, and by controlling the film formation time, the thickness of the resulting alloy coating film was 1400 nm.

[0506] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric tests. Samples using silicon wafers as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM tests.

[0507] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 39.6 Zr 19.4 N 41 .

[0508] The colorimetric values ​​of the aluminum alloy substrate sample were L: 64.71, a: 0.58, b: 4.15, and the colorimetric values ​​of the stainless steel substrate sample were L: 66.38, a: 0.49, b: 4.27, exhibiting a silvery-white color.

[0509] SEM results showed that the alloy coating film had crystallization defects, a non-dense structure, and obvious through-column seams. The XRD diffraction pattern, TEM selected area electron diffraction pattern, and radial intensity profile results are shown in Figure 20. The XRD results showed that the diffraction angle 2θ (°) in the XRD diffraction pattern had two peaks in the range of 30°–50°, both of which were sharp peaks (2θ peaks with a half-width at half-maximum (FWHM) < 2°). The FWHMs of the two sharp peaks in the 30°–50° range were 1.87° and 1.02°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern... There are two peaks within the range, with half-widths of 100 and 250 respectively. That is, there is one peak.

[0510] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h) and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating that it does not have the protective properties for the substrate.

[0511] The hardness value of the aluminum alloy substrate sample was 15.4 GPa, and the hardness value of the stainless steel substrate sample was 17.2 GPa.

[0512] Comparative Example 5. Alloy coating thickness 50nm

[0513] Using essentially the same method as Comparative Example 4, the chemical composition of the alloy coating was Cr. 39.6 Zr 19.4 N 41 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 50nm.

[0514] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h), and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating a lack of protective properties against the substrate. The hardness value of the aluminum alloy substrate sample was 9.1 GPa, and the hardness value of the stainless steel substrate sample was 9.8 GPa.

[0515] Comparative Example 6. Alloy coating thickness 1000nm

[0516] Using essentially the same method as Comparative Example 4, the chemical composition of the alloy coating was Cr. 39.6 Zr 19.4 N 41 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 1000nm.

[0517] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h), and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating a lack of protective properties against the substrate. The hardness value of the aluminum alloy substrate sample was 16.5 GPa, and the hardness value of the stainless steel substrate sample was 17.9 GPa.

[0518] Comparative Example 7. Alloy coating thickness 2500 nm

[0519] Using essentially the same method as Comparative Example 4, the chemical composition of the alloy coating was Cr. 39.6 Zr 19.4 N 41 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 2500nm.

[0520] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h), and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating a lack of protective properties against the substrate. The hardness value of the aluminum alloy substrate sample was 20.5 GPa, and the hardness value of the stainless steel substrate sample was 21.1 GPa.

[0521] Comparative Example 8. Alloy coating thickness 6000nm

[0522] Using essentially the same method as Comparative Example 4, the chemical composition of the alloy coating was Cr. 39.6 Zr 19.4 N 41 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 6000nm.

[0523] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h), and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating a lack of protective properties against the substrate. The hardness value of the aluminum alloy substrate sample was 22.1 GPa, and the hardness value of the stainless steel substrate sample was 23.7 GPa.

[0524] Comparative Examples 9-11. No protective coating

[0525] Salt spray corrosion resistance tests were conducted using bare aluminum alloy sheets, bare stainless steel sheets, and bare copper sheets, respectively. The results showed that significant corrosion occurred within 12 hours.

[0526] Results analysis:

[0527] The Cr-Zr-N alloy coating provided in this application has a certain atomic ratio of Cr, Zr, and N elements, and has a high Cr content.

[0528] The protective coatings in Examples 1-5 and 8-13 are single-layer thin film structures. The Cr-Zr-N alloy coating provided in this application directly provides surface protection to the substrate. At this time, the surface of the alloy film product has a high brightness value. Moreover, according to the salt spray corrosion resistance test results, the Cr-Zr-N alloy coating provided in Examples 1-13 can be used as the protective coating itself or as part of the protective coating, both of which can bring excellent corrosion protection to the substrate.

[0529] According to the salt spray corrosion resistance test results, the Cr-Zr-N alloy coatings provided in this application (Examples 1-13) all provide excellent corrosion protection to the substrate. Example 6 is a double-layer thin film structure, with the Cr-Zr-N alloy coating provided in this application serving as the lower protective layer. A surface layer (TiN) is also attached to the surface of the Cr-Zr-N alloy coating away from the substrate, which serves as a surface protective coating (located in the upper layer). The Cr-Zr-N alloy coating in Example 7 is a three-layer thin film structure, consisting of a transition layer (as the bottom coating), the Cr-Zr-N alloy coating, and the TiN coating on the surface, sequentially from the substrate surface. The Cr-Zr-N alloy coating in Example 11 contains doping elements with a certain atomic percentage (≤5 at%).

[0530] Examples 1-7, 9-11, and 13 all used aluminum alloy and stainless steel substrates. The aluminum alloy surface passed the 48-hour salt spray corrosion resistance test, and the stainless steel surface passed the 144-hour salt spray corrosion resistance test. Example 8 used a copper substrate, and the copper substrate (copper is a relatively reactive alloy) passed the 12-hour salt spray corrosion resistance test.

[0531] In Example 12, the elemental composition of the Cr-Zr-N alloy coating does not conform to the following combination formula: 63.19-0.925y≤x≤95.79-y and 31.4+0.9y≤x≤18.5y-171.85. It 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).

[0532] The alloy coating provided in this application can be used independently as a single-layer film or in a multi-layer composite film. For example, it can be used as one of the layers, as a surface layer (exposed), as a bottom coating (in contact with the substrate), or as an intermediate layer (located between the bottom coating and the surface layer).

[0533] Based on XRD and TEM selected area electron diffraction (SED) results, the Cr-Zr-N alloy coatings provided in this application (Examples 1-13) exhibit at least one broad peak (furthermore, all are broad peaks with a full width at half maximum (FWHM) ≥ 2°) in the XRD diffraction pattern within the range of 30°–50°. The radial intensity profile of the TEM SED pattern also shows… The range has at least one broad peak (furthermore, all are broad peaks, with a half-width of 1 / 250). The Cr-Zr-N alloy coatings in each embodiment all possess a “highly disordered and fully densely packed” atomic arrangement, which is consistent with the highly compact structure in the SEM morphology characterization results.

[0534] In addition, the Cr-Zr-N alloy coatings provided in this application (Examples 1-13) all have high hardness, and possess both excellent corrosion resistance and high hardness characteristics.

[0535] The bare substrates of Comparative Examples 9-11, without a protective coating, were not resistant to salt spray corrosion and showed obvious corrosion within 12 hours.

[0536] The alloy coating film in Comparative Example 1 lacked nitrogen (N), while the alloy coating films in Comparative Examples 2 and 4 had higher N content. Comparative Example 3 did not have a Cr-Zr-N alloy coating (Comparative Example 3 had a TiN coating). The results showed that Comparative Examples 1-4 all exhibited no corrosion resistance (NG) failure. The inventors speculate that the reason might be that the film structure is not dense, containing gaps, such as through-holes, allowing corrosive solutions to quickly pass through these gaps and contact the substrate, thus leading to the coating's corrosion resistance failure.

[0537] For the alloy coatings of different thicknesses in Comparative Examples 5-8, their hardness and corrosion resistance were significantly inferior to the Cr-Zr-N alloy coating of the same thickness in this application. Even with a thickness as high as 6000 nm (6 micrometers), Comparative Example 8 still exhibited poor corrosion resistance. The presumed reasons may be that the film structure is not dense, containing gaps, such as through-cracks, allowing corrosive solutions to quickly pass through and contact the substrate, leading to coating corrosion failure. While increasing the coating thickness can increase its hardness, structural defects still exist. In contrast, the Cr-Zr-N alloy coating provided in this application can achieve both excellent corrosion resistance and high hardness at a relatively low thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs. With a thinner alloy coating, the resulting alloy film product can exhibit a silvery-white metallic luster, closely resembling the metallic color of the substrate, which is more conducive to achieving an aesthetically pleasing decorative effect without altering the substrate color.

[0538] The technical features of the above embodiments and examples can be combined in any suitable manner. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0539] The above embodiments and examples are merely illustrative of several implementations of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. Furthermore, it should be understood that after reading the above teachings, those skilled in the art can make various alterations or modifications to this application, and the equivalent forms obtained also fall within the scope of protection of this application. It should also be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A Cr-Zr-N alloy material, wherein, The Cr-Zr-N alloy material has a chemical formula of (Cr x Zr y N z )M a , M is a doping element, wherein x, y, z and a are each independently an atomic ratio, 47.1≤x≤81.6, 12.1≤y≤33.2, 4.7≤z≤35.9, and 0≤a / (x+y+z+a)≤0.

05.

2. The Cr-Zr-N alloy material according to claim 1, wherein x, y and z are 100 in total.

3. The Cr-Zr-N alloy material according to claim 1 or 2, wherein y is greater than z.

4. The Cr-Zr-N alloy material according to any one of claims 1 to 3, wherein 63.19-0.925y≤x≤95.79-y and 31.4+0.9y≤x≤18.5y-171.

85.

5. The Cr-Zr-N alloy material according to any one of claims 1 to 4, wherein The doping element is a non-metallic element, a metallic element or a combination thereof; The non-metallic element comprises one or more of O, C, B, Si and Ar; The metallic element comprises one or more of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

6. The Cr-Zr-N alloy material according to any one of claims 1 to 5, wherein 0≤a / (x+y+z+a)≤0.

02.

7. A Cr-Zr-N alloy coating, wherein The Cr-Zr-N alloy coating comprises a film layer formed by the Cr-Zr-N alloy material according to any one of claims 1-6.

8. The Cr-Zr-N alloy coating according to claim 7, wherein The Cr-Zr-N alloy material or the Cr-Zr-N alloy coating satisfies the following two characteristics: The X-ray diffraction pattern of the Cr-Zr-N alloy material or the Cr-Zr-N alloy coating has a peak in the range of diffraction angle 2θ (°) of 30°-50°, and the half-height width of at least one 2θ (°) diffraction peak in the range of 30°-50° satisfies ≥2°; The selected area electron diffraction pattern of the Cr-Zr-N alloy coating corresponds to a radial intensity profile with the characteristic interatomic distance as the abscissa and the diffraction intensity as the ordinate, in which have diffraction peaks within a range, and the half-height width of at least one diffraction peak in the range satisfies 9. The Cr-Zr-N alloy coating according to claim 7 or 8, wherein The Cr-Zr-N alloy coating satisfies one or more of the following characteristics: The X-ray diffraction pattern of the Cr-Zr-N alloy coating is obtained by Cu target Kα ray; The selected area electron diffraction pattern of the Cr-Zr-N alloy coating is obtained by TEM characterization technology with an electron accelerating voltage of 200kV and a selected area aperture diameter of 900nm.

10. The Cr-Zr-N alloy coating according to any one of claims 7 to 9, wherein The thickness of the Cr-Zr-N alloy coating is d min ~ 6 μm, wherein d min is selected from 10 nm ~ 50 nm; Optionally, d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, or 50 nm; Optionally, the thickness of the Cr-Zr-N alloy coating is 1μm-2.5μm.

11. An alloy film article comprising a substrate and a Cr-Zr-N alloy coating according to any one of claims 7 to 10; wherein, The Cr-Zr-N alloy coating is located on at least one side of the substrate.

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

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

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

15. The alloy film article of claim 11, wherein, The alloy film product is one of a 3C digital product, an automotive product, an aerospace product, a wearable product and a sports product.

16. Use of a Cr-Zr-N alloy material according to any one of claims 1 to 6 for the production of a high-brightness surface coating or use of a Cr-Zr-N alloy coating according to any one of claims 7 to 10 as a high-brightness surface coating, wherein The brightness value L of the high-brightness surface coating is ≥70 tested by Lab method; and the high-brightness surface coating is also a corrosion-resistant protective coating.

17. A method for preparing a Cr-Zr-N alloy coating, comprising the step of: depositing constituent elements of the Cr-Zr-N alloy coating on at least a part of a surface of a substrate in a preset atomic ratio by a vapor deposition technique to form the Cr-Zr-N alloy coating according to any one of claims 7 to 10.

18. The production method according to claim 17, wherein The method for preparing the Cr-Zr-N alloy coating comprises the step of: sputter depositing constituent elements of the Cr-Zr-N alloy coating on at least a part of a surface of a substrate using one or more targets comprising chromium and zirconium under the condition of supplying a mixed gas comprising argon and a nitrogen-containing gas to form the Cr-Zr-N alloy coating.

19. The production method according to claim 18, wherein One or more of the following characteristics are satisfied: The temperature for sputter deposition is 30°C to 330°C; The total gas pressure of the mixed gas comprising argon and the nitrogen-containing gas is 0.3 Pa to 1.2 Pa; The target material includes a chromium target having a power density of 3.5 W / cm 2 ~ 6.7 W / cm 2 and a zirconium target having a power density of 0.5 W / cm 2 ~ 3.0 W / cm 2 ; The target material includes an alloy target including at least two metal elements in the Cr-Zr-N alloy coating; optionally, the target material includes a chromium-zirconium-based alloy target with a power density of 4 W / cm 2 ~ 6 W / cm 2 ; The bias voltage for the substrate is -150 V to -20 V; The time for sputter deposition is 10 min to 150 min; The nitrogen-containing gas is nitrogen gas, and the gas flow rate of the nitrogen gas is 5 seem to 52 seem; The nitrogen-containing gas is nitrogen gas, and the gas amount ratio of argon to nitrogen in the mixed gas is (2-6): 1.

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