Application of Cr-Ti-N alloy coating as conductive coating in coated product

Abstract

The invention relates to application of a Cr-Ti-N alloy coating as a conductive coating in a coated product, the coated product comprises a substrate, and the Cr-Ti-N alloy coating is located on at least one part of the surface of the substrate; an X-ray diffraction pattern of the Cr-Ti-N alloy coating has a peak in a diffraction angle 2theta (degree) range of 34-50 degrees, and the full width at half maximum of at least one 2theta (degree) diffraction peak is larger than or equal to 1.6 degrees. A radial intensity profile map corresponding to a selected area electron diffraction pattern of the Cr-Ti-N alloy coating (with the characteristic atom spacing as the abscissa, the characteristic atom spacing as the abscissa, the characteristic atom spacing as the abscissa, the characteristic atom spacing as the abscissa, the characteristic atom spacing as the abscissa and the characteristic atom spacing as the abscissa). With the diffraction intensity as the ordinate), the film has diffraction peaks in the range, and the full width at half maximum of at least one diffraction peak meets the requirement that the square resistance of the surface of the film-coated product is low, for example, the square resistance is smaller than or equal to 12 omega / sq. The Cr-Ti-N alloy coating has metallic luster, good conductivity and excellent corrosion resistance, and can be used as a conductive coating in a coated product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloy coating, in particular to the application of Cr-Ti-N alloy coating as conductive coating in plated products, and further relates to the application of Cr-Ti-N alloy material as conductive coating material in plated products. BACKGROUND

[0002] Products in various fields such as the automotive field, the wearable product field, the 3C product field, the sports product field, etc. are more involved in metal shells, among which the representative "3C products" are collectively referred to as computer, communication and consumer electronics products, also known as "information home appliances", such as computers, tablet computers, mobile phones or digital audio players, etc. Since the volume of 3C products is generally not large, they are often collectively referred to as "3C small household appliances". With the technological innovation in the microelectronics field and the communication field, new demands for the electrical conductivity of the coating attached to the surface of the metal shell have appeared in addition to the traditional requirements for corrosion resistance and / or high hardness, etc.

[0003] Taking aluminum alloy products as an example, aluminum alloy has excellent metal properties, is easy to process and has low cost, so it is the main alloy material choice in existing market alloy parts. However, the existing aluminum alloy protective coating has insulating (i.e. non-conductive) electrical properties, resulting in the entire alloy shell not having conductive properties. In addition, the aluminum alloy materials on the market at present mainly use surface paint spraying, anodic oxidation and other means for surface protection. Surface paint spraying is a traditional aluminum alloy protective material, which uses an epoxy resin-like material, adds a dyeing agent, sprays on the surface of the aluminum alloy, and then solidifies to form a protective coating. The material is a resin material, which is an insulating material coating technology, and does not have a metallic color. Moreover, the adhesion between the coating and the aluminum alloy is weak, and there is a problem of paint peeling during use. Therefore, the resin spraying technology has been gradually replaced by anodic oxidation technology. The working principle of the anodic oxidation of aluminum alloy is to place the aluminum alloy material in a strong acid or strong alkali solution to form an oxide on the surface. The oxide layer on the surface acts as a surface protective layer, and the coating is insulating (i.e. non-conductive). In addition, since the solution is a strong acid or a strong alkali, a large amount of wastewater, waste liquid and waste gas is generated during production, which is not conducive to the environment.

[0004] Therefore, it is necessary to develop a new conductive coating technology. SUMMARY

[0005] Based on this, the present application at least provides the application of Cr-Ti-N alloy coating as conductive coating in plated products. The Cr-Ti-N alloy coating has metallic luster, good conductive properties and excellent corrosion resistance, and can be used as conductive coating in plated products.

[0006] In a first aspect of the present application, there is provided use of a Cr-Ti-N alloy coating as an electrically conductive coating in a coated article.

[0007] In one embodiment, there is provided use of a Cr-Ti-N alloy coating as an electrically conductive coating in a coated article, the coated article comprising a substrate, the Cr-Ti-N alloy coating being located on at least a portion of a surface of the substrate; the Cr-Ti-N alloy coating satisfying both of the following characteristics:

[0008] the X-ray diffraction pattern of the Cr-Ti-N alloy coating has a peak in the range of diffraction angle 2Θ(°) of 34° to 50°, and the half-height width of at least one 2Θ(°) diffraction peak in the range of 34° to 50° satisfies ≥ 1.6°;

[0009] the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has a diffraction peak in the range of characteristic interatomic distance of 0.1 nm to 0.2 nm, and the half-height width of at least one diffraction peak in the range of 0.1 nm to 0.2 nm satisfies ≥ 1.6°; the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has a diffraction peak in the range of characteristic interatomic distance of 0.1 nm to 0.2 nm, and the half-height width of at least one diffraction peak in the range of 0.1 nm to 0.2 nm satisfies ≥ 1.6°;

[0010] the sheet resistance of the surface of the coated article is ≤ 12 Ω / sq.

[0011] In some embodiments, the Cr-Ti-N alloy coating satisfies both of the following characteristics:

[0012] the X-ray diffraction pattern of the Cr-Ti-N alloy coating has a peak in the range of diffraction angle 2Θ(°) of 34° to 50°, and the half-height width of at least one 2Θ(°) diffraction peak in the range of 34° to 50° satisfies ≥ 2°;

[0013] the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has a diffraction peak in the range of characteristic interatomic distance of 0.1 nm to 0.2 nm, and the half-height width of at least one diffraction peak in the range of 0.1 nm to 0.2 nm satisfies ≥ 1.6°; the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has a diffraction peak in the range of characteristic interatomic distance of 0.1 nm to 0.2 nm, and the half-height width of at least one diffraction peak in the range of 0.1 nm to 0.2 nm satisfies ≥ 1.6°; Optionally,

[0014] In one embodiment, there is provided use of a Cr-Ti-N alloy coating as an electrically conductive coating in a coated article, the coated article comprising a substrate, the Cr-Ti-N alloy coating being located on at least a portion of a surface of the substrate;

[0015] ​​The Cr-Ti-N alloy coating includes a Cr-Ti-N alloy material including Cr element, Ti element and N element with atomic ratio of x:y:z, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5.

[0016] The sheet resistance of the surface of the coated article is ≤12Ω / sq.

[0017] In some embodiments, the Cr-Ti-N alloy material includes a CrTiN-based alloy component with chemical formula of Cr x Ti y N z M a , M is a doping element, x, y, z and a are atomic ratios of Cr element, Ti element, N element and M element respectively, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5, and a is 0 or a positive number.

[0018] In some embodiments, the Cr-Ti-N alloy material satisfies one or two of the following characteristics:

[0019] The sum of x, y and z is a number selected from 95-100;

[0020] 0≤a / (x+y+z+a)≤0.05;

[0021] The doping element includes one or more metal elements selected from Ni, Fe, Ag, Au, Cu and Al.

[0022] In some embodiments, a=0 or 0

[0023] In some embodiments, the base surface of the Cr-Ti-N alloy coating is any one of alloy, elemental metal and inorganic non-metallic material; the material type of the alloy includes one or more selected from nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based; the elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium; and the inorganic non-metallic material includes one or more selected from ceramic and glass.

[0024] In some embodiments, the base surface of the Cr-Ti-N alloy coating is one of aluminum alloy, silicon-based material and stainless steel.

[0025] In some embodiments, the sheet resistance test result of the Cr-Ti-N alloy coating satisfies one or two of the following characteristics:

[0026] The Cr-Ti-N alloy coating has a sheet resistance of 0.5 Ω / sq to 12 Ω / sq on a silicon wafer surface.

[0027] The Cr-Ti-N alloy coating has a sheet resistance of 0 Ω / sq on an aluminum alloy surface.

[0028] In some embodiments, the Cr-Ti-N alloy coating has a thickness D2, 50 nm ≤ D2 ≤ 6 μm.

[0029] Optionally, d min ≤ D2 ≤ d max wherein d min is selected from 50 nm to 0.9 μm, d max is selected from 2.7 μm to 6 μm.

[0030] Further optionally, d min is 50 nm, 0.3 μm, 0.5 μm, 0.7 μm, 0.8 μm or 0.9 μm; and d max is 2.7 μm, 3 μm, 4 μm, 5 μm or 6 μm.

[0031] In some embodiments, the Cr-Ti-N alloy coating also functions as a corrosion resistant coating.

[0032] Optionally, the corrosion resistant coating is capable of passing a corrosion test for at least 48 hours according to ASTM B117 salt spray test standard; wherein the corrosion test is performed using a corrosion solution having a composition of sodium chloride, water and sodium hydroxide, and a pH of 6.5 to 7.2.

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

[0034] Optionally, the Cr-Ti-N alloy coating has a thickness greater than or equal to 0.9 μm.

[0035] In some embodiments, the Cr-Ti-N alloy coating provides a surface brightness value L ≥ 70 for the coated article, as tested by the Lab method.

[0036] Optionally, the Cr-Ti-N alloy coating provides a surface brightness value L ≥ 75 for the coated article, as tested by the Lab method.

[0037] In a second aspect of the present application, there is provided the use of a Cr-Ti-N alloy material as defined in the first aspect of the present application as a conductive coating material in a coated article.

[0038] In the application of the Cr-Ti-N alloy coating provided in the application, the Cr, Ti and N elements in the Cr-Ti-N alloy coating are highly disordered and fully close-packed arranged at the atomic level, so that the coating structure is dense, the internal resistance is low, and a Cr-Ti-N alloy coating with good electrical conductivity is formed.

[0039] In the application of the Cr-Ti-N alloy coating provided in the embodiment of the application, the Cr-Ti-N alloy material has a special atomic ratio, which makes the Cr, Ti and N elements highly disordered and fully close-packed arranged at the atomic level, so that the coating structure is dense, the internal resistance is low, and a Cr-Ti-N alloy coating with good electrical conductivity is formed.

[0040] The target Cr-Ti-N alloy coating can be used as an electrically conductive coating on the surface of various commonly used substrates.

[0041] The Cr-Ti-N alloy coating has low nitrogen content, high content of Cr and Ti, low internal stress, good adhesion to the substrate, and is also beneficial to improve the toughness. Further, the Cr-Ti-N alloy material in the Cr-Ti-N alloy coating has high content of Cr and Ti, and the expansion coefficient is close to that of aluminum, so that the coating can be effectively attached to the surface of the aluminum alloy with strong adhesion, and better electrical contact between the coating and the aluminum alloy substrate can be formed, and more effective electrical conductivity can be achieved.

[0042] While providing better electrical conductivity, the dense structure of "highly disordered and fully close-packed" at the atomic level can also reduce or avoid the penetrating columnar joints in the traditional Cr-Ti-N alloy coating, so that the electrically conductive coating can be endowed with excellent corrosion resistance, and therefore, the Cr-Ti-N alloy coating can be used as a corrosion-resistant coating.

[0043] The Cr-Ti-N alloy coating has a dense structure, which can also endow the electrically conductive coating with high hardness, better resistance to scratch and scratch damage; further, the electrically conductive coating can also serve as a hard and corrosion-resistant coating.

[0044] The Cr-Ti-N alloy coating has high content of Cr and Ti, which endows the coating with metallic luster and better appearance.

[0045] Based on the special structural characteristics of "highly disordered and fully close-packed" at the atomic level of the Cr-Ti-N alloy coating, the reflection characteristics of the coating surface can also be improved to provide a higher brightness value.

[0046] The implementation of the Cr-Ti-N alloy coating as an electrically conductive coating in a plated product can adopt a green and environmentally friendly manufacturing technology, which is simple, easy to operate, and has the advantages of quantification, high efficiency and good repeatability, and is suitable for industrial application. Attached Figure Description

[0047] To more clearly illustrate the technical solutions in the embodiments and 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.

[0048] In the following description, the same reference numerals indicate the same parts.

[0049] Figure 1 This is a schematic diagram of the structure of a coated article including a Cr-Ti-N alloy coating according to an embodiment of the present application, including a substrate and a Cr-Ti-N alloy coating;

[0050] Figure 2 The following are schematic diagrams of the structure of the coated product in several embodiments of this application; (A) includes a substrate, a transition film layer and a Cr-Ti-N alloy coating; (B) includes a substrate, a transition film layer, a Cr-Ti-N alloy coating and a surface film layer; (C) includes a substrate, a Cr-Ti-N alloy coating and a surface film layer.

[0051] Figure 3 This is a schematic diagram of an apparatus for preparing a target Cr-Ti-N alloy coating according to one embodiment of this application;

[0052] Figure 4 The Cr prepared in Example 1 of this application 90.0 Ti 5.0 N 5.0 SEM cross-sectional view of the alloy coating;

[0053] Figure 5 The Cr prepared in Example 1 of this application 90.0 Ti 5.0 N 5.0 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;

[0054] Figure 6 The Cr prepared in Example 2 of this application 75.0 Ti5.0 N 20.0 SEM cross-section of the alloy coating;

[0055] Figure 7 CrTiAl alloy coating prepared in Example 1 of the present application 75.0 Ti 5.0 N 20.0 XRD diffractogram of the alloy coating;

[0056] Figure 8 CrTiAl alloy coating prepared in Example 3 of the present application 5.0 Ti 79.0 N 16.0 SEM cross-section of the alloy coating;

[0057] Figure 9 CrTiAl alloy coating prepared in Example 3 of the present application 5.0 Ti 79.0 N 16.0 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating;

[0058] Figure 10 CrTiAl alloy coating prepared in Example 4 of the present application 12.7 Ti 77.9 N 9.4 SEM cross-section of the alloy coating;

[0059] Figure 11 CrTiAl alloy coating prepared in Example 4 of the present application 12.7 Ti 77.9 N 9.4 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating;

[0060] Figure 12 CrTiAl alloy coating prepared in Example 5 of the present application 43.0 Ti 37.0 N 20.0 SEM cross-section of the alloy coating;

[0061] Figure 13 CrTiAl alloy coating prepared in Example 5 of the present application 43.0 Ti 37.0 N 20.0 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SEAD pattern (C) of the alloy coating;

[0062] Figure 14 CrTiAl alloy coating prepared in Example 6 of the present application 62.9 Ti 18.9 N18.2 SEM cross-section of the alloy coating;

[0063] Figure 15 Cr-Ti-N alloy coating prepared in Example 6 of the present application 62.9 Ti 18.9 N 18.2 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SAED pattern (C) of the Cr-Ti-N alloy coating;

[0064] Figure 16 Cr-Ti-N alloy coating prepared in Example 7 of the present application 62.9 Ti 18.9 N 18.2 SEM cross-section of the Cr-Ti-N / CrN coating; a Ti layer (as a transition layer) was arranged between the substrate and the Cr-Ti-N alloy coating, which was in contact with the Cr-Ti-N alloy coating, and a CrN coating (as a surface layer) was further arranged on the Cr-Ti-N alloy coating; the alloy film product had a sandwich structure protective structure, and the Cr-Ti-N alloy coating was used as the middle structural layer of the three-layer structure coating;

[0065] Figure 17 Cr-Ti-N alloy coating prepared in Example 12 of the present application 14.8 Ti 70.0 N 15.2 SEM cross-section of the Cr-Ti-N alloy coating;

[0066] Figure 18 Cr-Ti-N alloy coating prepared in Example 12 of the present application 14.8 Ti 70.0 N 15.2 XRD diffractogram of the Cr-Ti-N alloy coating;

[0067] Figure 19 Cr-Ti-N alloy coating prepared in Example 13 of the present application 38.3 Ti 35.2 N 26.5 SEM cross-section of the Cr-Ti-N alloy coating;

[0068] Figure 20 Cr-Ti-N alloy coating prepared in Example 13 of the present application 38.3 Ti 35.2 N 26.5 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SAED pattern (C) of the Cr-Ti-N alloy coating;

[0069] Figure 21 Cr-Ti-N alloy coating prepared in Comparative Example 3 of the present application 20.9 Ti 79.1 SEM cross-section of the Cr-Ti-N alloy coating;

[0070] Figure 22 Cr-Ti-N alloy coating prepared in Comparative Example 4 of the present application 35.4 Ti 25.8 N 38.8 SEM cross-section of the alloy coating;

[0071] Figure 23 Cr-Ti-N alloy coating prepared in Comparative Example 4 of the present application 35.4 Ti 25.8 N 38.8 XRD diffraction pattern (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of the SAED pattern (C) of the Cr-Ti-N alloy coating.

[0072] In the aforementioned XRD diffraction pattern, the abscissa is 2θ, in °, and the ordinate is X-ray diffraction intensity (Intensity), in a.u.; according to the selected area electron diffraction pattern (SAED) of the alloy coating, the radial intensity profile thereof is obtained, which is expressed in the form of characteristic atomic spacing (d)-diffraction intensity, with d as the abscissa, in angstrom The ordinate is electron diffraction intensity (Intensity), in a.u.

[0073] In the XRD diffraction pattern and the radial intensity profile of the SAED pattern, a.u. has the known meaning in the art.

[0074] In some SEM images, some cross-sectional delamination occurs when the silicon wafer is brittle fractured during preparation of the cross-section of the sample to be tested, but 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 according to the thickness of the corresponding structural layer.

[0075] Legend: 1 is a vacuum chamber, 2 is a sample stage, 3 is a direct current anode, 4 is a chromium target (also referred to as a Cr target, which can be a Cr target for radio frequency assisted direct current cathode current leading), 5 is a titanium target (also referred to as a Ti target, which can be a Ti target for radio frequency assisted direct current cathode current leading);

[0076] 100 is a substrate, 200 is a transition layer (also referred to as a transition film layer), 300 is a Cr-Ti-N alloy coating, and 400 is a surface layer (also referred to as a surface film layer). DETAILED DESCRIPTION

[0077] The present application will be further described in details with reference to the drawings, embodiments and examples. It should be understood that these embodiments and examples are only used to explain the present application and not intended to limit the scope of the present application, and the purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein, and those skilled in the art can make various modifications or changes without departing from the spirit of the present application, and the equivalent forms obtained thereby also fall within the protection scope of the present application. For example, the features described or illustrated as part of an embodiment can be combined in another embodiment in a suitable manner to produce a new embodiment. In addition, in the following description, a large number of details are given in order to provide a more complete understanding of the present application, and it should be understood that the present application can be implemented without one or more of these details.

[0078] 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 in the description of the application herein is for the purpose of describing embodiments and examples only and is not intended to be limiting of the application.

[0079] Unless otherwise indicated or unless contradicted by context, terms or phrases used herein have the following meanings:

[0080] The alternative range of the terms "and / or", "or / and", "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items. For example, "A and / or B" includes three parallel schemes of A, B, and "combination of A and B".

[0081] In the present application, "multiple", "multiple", "multiple", "multiple", "several" and the like, unless otherwise specified, refer to more than two or equal to two in quantity. For example, "one or more" means one or more than two.

[0082] In the present application, unless otherwise specified, "one or more" means any one of the listed items or any combination of the listed items. Similarly, in the case of "one or more" and the like, which otherwise means "one or more", the same understanding is also made unless otherwise specified.

[0083] The "combination thereof", "any combination thereof", "any combination thereof" and the like used in the present application include all suitable combinations of any two or more of the listed items.

[0084] In the present application, "suitable", in "suitable combination", "suitable manner", "any suitable manner" and the like, is subject to the ability to implement the technical solutions of the present application, solve the technical problems of the present application, and achieve the intended technical effects of the present application.

[0085] In the present application, "preferably", "more preferably", "more preferably", "suitable", "better", "better" are only to describe the better effect of the implementation mode or embodiment, and it should be understood that it does not constitute a limitation on the protection scope of the present application. If there are multiple "preferred" in a technical solution, if there is no special description, and there is no contradictory or mutual restrictive relationship, each "preferred" is independent.

[0086] In the present application, "further", "further", "in particular", "for example", "such as", "example", "for example" are used for description purposes, indicating that the different technical solutions before and after are related in terms of coverage, but should not be understood as a limitation on the previous technical solution, nor can it be understood as a limitation on the protection scope of the present application. In the present application, if there is no other description, A (such as B) indicates that B is one non-limiting example of A, and it can be understood that A is not limited to B.

[0087] In the present application, "optionally", "optional", "optional" means optional, that is, optional from two parallel schemes of "yes" or "no". If there are multiple "optional" in a technical solution, if there is no special description, and there is no contradictory or mutually restrictive relationship, each "optional" is independent. If there is no other description, the present application is described as "optionally includes", "optionally contains" and the like. For example, "optionally includes" means "may include or not include". "Optional component X" means that component X exists or does not exist.

[0088] The terms "contain", "include" and "comprise" used in the present application are synonymous terms, which are inclusive or open, and do not exclude additional, unmentioned members or features. Members or features, such as materials or components, structures, elements, instruments, etc.; non-limiting examples of members or features also include actions, conditions, timing, states, etc.

[0089] In the present application, the technical features or technical solutions described in open language include closed technical features or technical solutions composed of listed contents, and also include open technical features or technical solutions containing listed contents.

[0090] In this application, when referring to a numerical interval (i.e., a numerical range), the distribution of the selectable numbers in the numerical interval is considered continuous and includes both numerical endpoints (i.e., the minimum and maximum values) of the numerical interval and every number between the two numerical endpoints, unless otherwise specified. When a numerical interval refers only to integers within the numerical interval, including both endpoints and every integer between the endpoints, it is equivalent to listing each integer directly, unless otherwise specified. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges can be combined. In other words, unless otherwise indicated, numerical ranges disclosed herein are to be understood to include any and all sub-ranges of the numbers within the range. A "number" in a numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. A "numerical interval" is intended to broadly include numerical interval types such as percentage intervals, ratio intervals, and the like.

[0091] In this application, unless otherwise specified, "about" means within a range of 10% of the value, and the fluctuation range can vary depending on the type and value of the number. For example, fluctuations within a range of ±2%, ±1%, ±0.5%, etc. of the number are allowed. For example, about 2° can mean a value selected from 2° ± 0.02°, etc.

[0092] In this application, unless otherwise specified, temperature parameters allow both constant temperature treatment and fluctuations within a certain temperature interval. It should be understood that constant temperature treatment allows fluctuations within the accuracy range controlled by the instrument. Fluctuations within a range of, for example, ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed.

[0093] In this application, the term "room temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of the application, "room temperature" refers to 10°C to 30°C. In some embodiments of the application, "room temperature" refers to 20°C to 30°C.

[0094] In this application, when referring to a data range, if only the unit is indicated after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3-5h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hour), which has the same meaning as 3h-5h. In addition, similar descriptions related to temperature, size, and other parameters are also applicable to the above understanding.

[0095] In this application, the temperature unit °C refers to "degrees Celsius". The unit represents "angstrom". The size unit μm represents "micrometer", and "nm" represents "nanometer". The pressure unit Pa refers to "pascal". The power density unit W / cm 2The term "W / m2" refers to "watts per square centimeter". The term "V" refers to "volt". The term "sccm" (standard cubic centimeter per minute) is a unit of flow used to characterize the flow of a gas.

[0096] The mass or weight of the relevant components mentioned in the embodiments of the present application can refer to the content of each component, and can also represent the mass or weight ratio relationship between each component. Therefore, as long as the content of each component is proportionally enlarged or reduced according to the embodiments of the present application, it is within the scope disclosed by the embodiments of the present application. Non-limitingly, the mass mentioned in the embodiments of the present application can be micrograms (μg), milligrams (mg), grams (g), kilograms (kg) and other units commonly known in the chemical field.

[0097] All the documents mentioned in the present application are cited as references in the present application, as if each document is cited as a reference individually. Unless it conflicts with the purpose and / or technical scheme of the present application, the cited documents are cited in the present application in their entirety and for all purposes. When the present application refers to the cited documents, the definitions of the relevant technical features, terms, nouns, phrases and the like in the cited documents are also cited. When the present application refers to the cited documents, the examples and preferred modes of the cited relevant technical features can also be incorporated into the present application as references, but are limited to the implementation of the present application. It should be understood that when the cited content conflicts with the description in the present application, the present application is used as the reference or is modified according to the description in the present application.

[0098] In the present application, unless there is an explicit different description in the present text, the execution of the steps involved in the method flow does not have strict order restrictions, and they can be executed in other orders than described. Moreover, any step can include multiple sub-steps or multiple stages, which do not necessarily be executed at the same time, but can be executed at different times, and the execution order is not necessarily sequential, but can be executed alternately or simultaneously with other steps or sub-steps or stages of other steps.

[0099] When describing the positional relationship, unless otherwise specified, when a component such as a layer, a film or a substrate is referred to as "on" another film layer, it can be directly on the other film layer or there can be an intermediate film layer. Further, when a layer is referred to as "under" another layer, it can be directly under the other layer, or there can be one or more intermediate layers. It can also be understood that when a layer is referred to as "between" two layers, it can be the only layer between the two layers, or there can be one or more intermediate layers.

[0100] In the case of using "comprising", "having", and "including" in this document, it is intended to cover the non-exclusive inclusion such that additional components not specified can also be present.

[0101] The singular form "a", "an", and "the" can include plural references unless the context clearly indicates otherwise.

[0102] In this application, the terms "first", "second", and the like in the "first aspect", "second aspect", and the like are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or quantity, nor can it be understood as implicitly indicating the importance or quantity of the technical features indicated. Moreover, "first", "second", and the like only serve the purpose of non-exhaustive enumeration description, and it should be understood that they do not constitute a closed limitation on the quantity.

[0103] In this application, the exemplary description or similar exemplary description such as "in some embodiments", "in one embodiment", "based on any suitable embodiment in this application", and the like can cover but is not limited to the following meanings: these schemes can be combined with other schemes in a suitable manner to form new technical schemes.

[0104] Traditional metal coatings pay more attention to hardness characteristics. In order to improve the hardness of the coating, traditional alloy coatings mostly use alloy nitride coatings with a rich nitrogen design. Due to the low content of metal components, the electrical conductivity is often poor. Alloy nitride coatings mainly use different combinations of metal elements to form coatings with different microstructures to achieve different functional characteristics. Traditional alloy coatings mostly use a rich nitrogen design to improve the hardness of the coating. The atomic percentage of nitrogen element is usually higher than 40%. The purpose of the rich nitrogen design is to realize the nitriding of metal elements in the nitride alloy by a large amount or excess of N element ratio, to form a rich nitride system with high content of crystallization to increase the hardness of the coating. However, although the rich nitrogen crystalline coating improves the hardness, it lacks corrosion resistance, especially in the application of light alloy surface protective coating with corrosion resistance requirements. In addition, the high content of nitrogen in the rich nitrogen alloy coating also weakens the metallic properties of the coating, resulting in high internal stress of the coating, poor adhesion to the substrate, and possibly reduced toughness.

[0105] In addition, the inventors of the present application found through a large number of investigations and experimental analyses that the traditional Cr-Ti-N alloy coating is prone to form columnar crystals in the nucleation and crystallization growth process, usually has a columnar crystal structure (more than 90% of the cases form columnar crystals), and a high content of columnar crystals promotes the formation of a highly ordered structure arranged in a direction, and a large number of intercrystalline gap defects caused by crystallization exist in the highly ordered structure, mainly in the form of penetrating columnar gaps, and the columnar crystals between the corresponding scanning electron microscope (SEM) cross-sections have shadows, and it is speculated that these penetrating columnar gaps may cause the alloy coating to be insufficiently dense and hard. The inventors of the present application speculate that the traditional ordered structure arranged in a direction is prone to cause the coating to be insufficiently dense, thereby limiting the improvement of hardness; on the other hand, under corrosion conditions, the corrosion medium can quickly penetrate the coating through the penetrating gaps and react with the substrate, thereby causing the corrosion resistance of the alloy coating to be less than ideal.

[0106] In addition, the alloy materials on the market at present mainly use anodic oxidation, magnetron sputtering and other means for surface protection. For example, aluminum alloys mainly use anodic oxidation for surface protection, and the working principle is as follows: the aluminum alloy material is placed in a strong acid or strong alkali solution to form an oxide and a metal or alloy coating on the surface to form a surface protection layer. Since the surface coating is an oxide, the product formed by this method has poor electrical conductivity, and in addition, a large amount of wastewater, waste liquid and waste gas are generated during production, which is not conducive to environmental protection.

[0107] Based on this, the present application at least provides the application of the Cr-Ti-N alloy coating as a conductive coating in a plated product. The Cr-Ti-N alloy coating has a metallic luster, good electrical conductivity and excellent corrosion resistance, and can be used as a conductive coating in a plated product.

[0108] In the present application, the Cr-Ti-N alloy coating in the plated product can also be described as "the Cr-Ti-N alloy coating of the present application", "the target Cr-Ti-N alloy coating" and the like.

[0109] In the present application, unless otherwise specified, "Cr-Ti-N alloy" and "CrTiN alloy" both represent an alloy containing Cr elements, Ti elements and N elements, and other alloying elements are allowed to be contained, and the two can be used interchangeably.

[0110] In the present application, unless otherwise specified, "Cr-Ti-N alloy material" represents an alloy material containing Cr elements, Ti elements and N elements. Among them, in the Cr-Ti-N alloy material, the three elements of Cr, Ti and N have a specific atomic ratio x:y:z. In the present application, the form of the Cr-Ti-N alloy material is not particularly limited, and can be but is not limited to an alloy coating form.

[0111] In the present application, unless otherwise specified, "Cr-Ti-N ternary alloy" and "CrTiN ternary alloy" both refer to an alloy composed of Cr element, Ti element and N element.

[0112] In the present application, unless otherwise specified, "coated product" refers to a product with an alloy coating on at least a part of the surface of the product substrate. Unless otherwise specified, the coated product has a Cr-Ti-N alloy coating on at least a part of the surface of the product substrate.

[0113] In the present application, unless otherwise specified, "conductive coating" can be located on the surface of the coated product or below the surface of the coated product (in which case it serves as an intermediate structural layer). The Cr-Ti-N alloy coating used in the present application can serve as a conductive coating in a single-layer structure or as one layer in a multi-layer structure. The Cr-Ti-N alloy coating can be located on the surface of the coated product or in a multi-layer structure without specific limitation, as long as it can achieve the desired conductive properties of the product.

[0114] In the first aspect of the present application, the application of Cr-Ti-N alloy coating as a conductive coating in a coated product is provided, the coated product comprising a substrate, the Cr-Ti-N alloy coating being located on at least a part of the surface of the substrate; the sheet resistance of the surface of the coated product is low (e.g. ≤12 Ω / sq). It can be understood that the Cr-Ti-N alloy coating comprises a Cr-Ti-N alloy material.

[0115] In the application of the Cr-Ti-N alloy coating provided in the present application, the three elements of Cr, Ti and N in the Cr-Ti-N alloy coating are highly disordered and fully close-packed at the atomic level, resulting in a dense coating structure, low internal resistance, and thus a Cr-Ti-N alloy coating with good electrical conductivity.

[0116] In the application of the Cr-Ti-N alloy coating provided in an embodiment of the present application, the Cr-Ti-N alloy material has a special atomic ratio, which causes the three elements of Cr, Ti and N to be highly disordered and fully close-packed at the atomic level, resulting in a dense coating structure, low internal resistance, and thus a Cr-Ti-N alloy coating with good electrical conductivity.

[0117] The aforementioned Cr-Ti-N alloy coating has a low nitrogen content, a high content of Cr and Ti, low internal stress, good adhesion to the substrate, and is also beneficial to improving toughness. Further, the Cr-Ti-N alloy material in the aforementioned Cr-Ti-N alloy coating has a high content of Cr and Ti, which is close to the expansion coefficient of aluminum, can effectively adhere to the surface of the aluminum alloy with strong adhesion, can form better electrical contact between the coating and the aluminum alloy substrate, and can achieve more effective electrical conductivity.

[0118] The dense structure of "highly disordered and fully close-packed arrangement" at atomic level can reduce or avoid the through-column gap in the traditional Cr-Ti-N alloy coating, while providing better electrical conductivity, so that the conductive coating can have excellent corrosion resistance, and thus the Cr-Ti-N alloy coating can be used as a corrosion-resistant coating.

[0119] The aforementioned Cr-Ti-N alloy coating structure is dense, and can also give the conductive coating a higher hardness, better resistance to scratch and scratch damage; further, the conductive coating can also serve as a hard and corrosion-resistant coating at the same time.

[0120] The aforementioned Cr-Ti-N alloy coating has high content of Cr and Ti two metal components, which gives the coating a metallic luster and is more beautiful.

[0121] Based on the special structure characteristics of "highly disordered and fully close-packed" at atomic level of the aforementioned Cr-Ti-N alloy coating, the reflection characteristics of the coating surface can also be improved to provide a higher brightness value.

[0122] In some embodiments, the application provides the use of the Cr-Ti-N alloy coating as a conductive coating in a coated article, the coated article comprising a substrate, the Cr-Ti-N alloy coating being located on at least a portion of the surface of the substrate;

[0123] The Cr-Ti-N alloy coating satisfies the following two characteristics:

[0124] The X-ray diffraction pattern of the Cr-Ti-N alloy coating has a peak in the range of diffraction angle 2θ(°) of 34°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥1.6°;

[0125] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating, with the characteristic interatomic distance as the abscissa and the diffraction intensity as the ordinate, there is a diffraction peak in the range of and the half-height width of at least one diffraction peak in the range of satisfies ≥1.6°;

[0126] Optionally, the surface of the coated article has a lower sheet resistance, such as ≤12Ω / sq.

[0127] In some embodiments, the application provides the use of the Cr-Ti-N alloy coating as a conductive coating in a coated article, the coated article comprising a substrate, the Cr-Ti-N alloy coating being located on at least a portion of the surface of the substrate;

[0128] The Cr-Ti-N alloy coating comprises a Cr-Ti-N alloy material, the Cr-Ti-N alloy material comprises Cr elements, Ti elements and N elements with an atomic ratio of x:y:z, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5;

[0129] The surface of the coated product has a low sheet resistance, such as ≤12Ω / sq.

[0130] In the present application, the "atomic ratio" of two or more elements means the ratio of the number of atoms, which can be calculated by the atomic molar ratio, unless otherwise specified.

[0131] In the present application, "Ω / sq" means sheet resistance, unless otherwise specified.

[0132] In the present application, "sheet resistance" has the meaning known in the relevant art, and is also referred to as film resistance, which is generally used to indirectly represent the measurement value of the thermal infrared performance of vacuum coating on a coated sample such as a thin film layer, a glass coated film layer, etc. The value can be directly converted into thermal infrared emissivity. The size of the sheet resistance is independent of the size of the sample, and the unit of measurement is "ohm / sq", which can be translated as "sheet resistance" or "surface resistance".

[0133] In the present application, unless otherwise specified, the sheet resistance tester can be used for testing, and the range of 2000.0Ω / sq can be selected, and further, 5 matrix points of each sample can be tested and the average value is taken. Non-limitingly, a MODEL: ST-21 sheet resistance tester produced by Guangzhou Four-probe Technology can be used.

[0134] In the application provided in the present application, the coated product has a conductive coating comprising a Cr-Ti-N alloy coating, so that the conductive coating not only has good conductivity, but also has excellent corrosion resistance. Taking an aluminum alloy substrate as an example, the protection time in the salt spray corrosion test can be ≥24 hours, i.e. it can pass the 24-hour test, and most embodiments can also pass the 48-hour test; ASTM B117 salt spray test method can be used, and reference can be made to the following example part. The protection time of the traditional hard coating in the salt spray corrosion test under the same test conditions is generally difficult to reach 8 hours. Further, the aforementioned Cr-Ti-N alloy coating can provide good conductivity and excellent corrosion resistance, while also having high hardness characteristics, which can better reduce the generation of scratches or weaken the scratch damage.

[0135] From the electrical performance point of view, Cr and Ti are pure metals with high conductivity. In the Cr-Ti-N alloy coating, the proportion of Cr, Ti and N is selected to make the total content of Cr and Ti high enough and the content of N low, and the proportion of Cr and Ti is much higher than that of N, so that an alloy coating structure with high metal content is formed. The Cr-Ti-N alloy coating with the special atomic ratio has a high metal alloy structure, so that the Cr-Ti-N alloy coating has good electrical conductivity.

[0136] From the protection point of view, the intrinsic characteristics of the corrosion-resistant coating are inertness and sufficient isolation. The "inertness" is specifically expressed as the coating material having sufficient inertness and being not easy to chemically react with the corrosion medium in the service environment. The "sufficient isolation" is specifically expressed as the coating structure being dense enough to fully isolate the substrate from the service environment and prevent or delay the reaction between the substrate and the corrosion medium therein, thereby achieving the purpose of corrosion resistance.

[0137] In the application provided in the present application, the Cr-Ti-N alloy material in the target Cr-Ti-N alloy coating mainly contains Cr, Ti and N, and the three elements have a specific relative atomic ratio, so that the Cr-Ti-N alloy material has the ability to form a highly disordered distribution and a fully dense arrangement of atoms, can form a dense Cr-Ti-N alloy coating, has low internal resistance, excellent corrosion resistance, and can also improve the movement ability of electrons in the transmission process. Combined with the high metal property of the Cr-Ti-N alloy coating, the Cr-Ti-N alloy coating has good electrical conductivity and excellent corrosion resistance, and can be used as a conductive coating in a plated product. The protection time of the target Cr-Ti-N alloy coating in the salt spray corrosion test is much longer than that of the traditional Cr-Ti-N alloy coating.

[0138] On the one hand, in the target Cr-Ti-N alloy coating provided in the application, based on the special atomic ratio of Cr, Ti and N, high content of Cr and Ti can form strong bond energy, promote the rapid growth of Cr-Ti alloy, and the addition of a small amount of nitrogen can promote the re-nucleation of Cr-Ti alloy to form Cr-Ti-N alloy, and improve the density of the coating nucleation.

[0139] On the other hand, in the aforementioned Cr-Ti-N alloy coating with a special atomic ratio, the atoms are highly disordered and fully dense, forming a high-density coating with low internal resistance and improved electron movement ability in the transmission process. In addition, the Cr-Ti-N alloy coating has high metal property, which can further increase the electrical conductivity of the coating.

[0140] In still another aspect, the target Cr-Ti-N alloy coating employs a special element content design, in which the atomic percentage content of Cr and Ti is relatively high, and the nitrogen content is correspondingly low and much lower than the total content of Cr and Ti. The atomic size mismatch degree is good, and the random mixing degree is high. Therefore, the corrosion resistance of the coating can be further improved on the basis of the synergistic effect of Cr, Ti and N, and the hardness can also be improved. In terms of atomic size, the atomic radius of Cr is the atomic radius of Ti is the atomic radius of N is The atomic size of Cr is close to that of Ti, and the atomic size of N is relatively small. In the nucleation process, a small amount of small-size N atoms can penetrate into the pores of large-size Cr and Ti metal grains, achieve the effect of filling pores, and make the atomic arrangement more densely packed. The growth defects of the columnar crystal structure of the film can be inhibited, so that the coating is more dense. The coating is more dense on the basis of having electrical conductivity, so as to achieve the purpose of having good electrical conductivity and good corrosion resistance.

[0141] In still another aspect, the traditional Cr-Ti-N alloy coating with a high content of columnar crystals is in a nanocrystalline state and usually has a large number of through pores. Unlike this, the Cr-Ti-N alloy coating in the present application can form a dense coating with a "highly disordered and fully dense" characteristic structure and contains a small amount of through pores or no through pores. In the Cr-Ti-N alloy coating involved in the present application, the three atoms of Cr, Ti and N with greatly different radii are condensed into a highly disordered state and form a tight packing during deposition, so that the alloy coating is easy to grow densely and can inhibit the formation of continuous and large through gaps, thereby forming an effective isolation between the substrate and the corrosion environment. In addition, the Cr-Ti-N alloy coating contains chromium and titanium elements, so that the coating has sufficient chemical inertness in the corrosion environment. The Cr-Ti-N alloy material in the Cr-Ti-N alloy coating not only has a highly disordered atomic distribution, but also has a fully dense atomic scale, so as to avoid or reduce the through gaps caused by highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "fully dense" of the atoms in the Cr-Ti-N alloy coating make the Cr-Ti-N alloy coating have a highly dense structure, which can not only improve the electrical conductivity by promoting electron transmission, but also provide excellent corrosion resistance, and is also beneficial to improving the hardness. In summary, the Cr-Ti-N alloy coating involved in the present application effectively reduces the defects commonly found in traditional alloy coatings, such as the large number of through gaps between the grains in the columnar crystal structure coating, so that the alloy coating is more conducive to dense growth, thereby endowing the alloy coating with good electrical conductivity and excellent corrosion resistance, and also bringing high hardness characteristics.

[0142] In another aspect, the Cr-Ti-N alloy coating has a relatively high metal content, and has excellent metallic properties, low internal stress, strong adhesion to the substrate, good toughness, and the like, compared to conventional nitrogen-rich alloy coatings. When the Cr-Ti-N alloy coating is applied to a substrate (such as a metal or alloy surface), the Cr-Ti-N alloy coating has low internal stress, high toughness, and the like, and the metallic properties result in a thermal expansion coefficient that is closer to that of the metal or alloy substrate than conventional nitrogen-rich alloy coatings, thereby providing the Cr-Ti-N coating with excellent adhesion and durability, and making it particularly suitable for use in the 3C digital product field, the aerospace field, the automotive field, and the like, to increase the durability of the product or component.

[0143] From the perspective of the substrate material, for an aluminum alloy substrate, aluminum is a relatively active metal that naturally forms an oxide film with a thickness of about 1 nm to 10 nm in the air. The oxide film has the characteristics of thin thickness, porosity, and poor corrosion resistance. How to grow a conductive and corrosion-resistant protective coating on the porous aluminum alloy surface is the key to solving the application of aluminum alloy. Since the coating manufacturing technology mainly uses high-energy sputtering, the surface generates high temperature due to intense atomic motion. Therefore, in the coating manufacturing field, the thermal expansion coefficient of the material is a key parameter for judging the adhesion between materials. The thermal expansion coefficient of aluminum is 2.39 x 10 -5 / ℃, the thermal expansion coefficients of Cr and Ti are 0.62 x 10 -5 / ℃ and 1.3 x 10 -5 / ℃, respectively. The thermal expansion coefficients of Cr and Ti are close to the expansion coefficient of aluminum, which makes the Cr-Ti-N alloy coating with high content of Ti and Cr in the present application have excellent adhesion on the surface of the aluminum alloy. During the preparation of the coating by sputtering, Cr and Ti atoms in the form of high-energy plasma bombard the surface of the aluminum alloy, which can effectively adhere to the surface of the aluminum alloy and form strong adhesion.

[0144] Based on the strong adhesion of the Cr-Ti-N alloy coating on the surface of the aluminum alloy, better electrical contact between the coating and the substrate can be formed, thereby achieving more effective electrical conductivity.

[0145] In some embodiments, the Cr-Ti-N alloy coating in the coated article has a sheet resistance of < 12 Ω / sq, further can be any of the following sheet resistance values, and can be selected from a range of any two of the following sheet resistance values: 0 Ω / sq, 0.5 Ω / sq, 0.6 Ω / sq, 0.7 Ω / sq, 0.8 Ω / sq, 0.9 Ω / sq, 1 Ω / sq, 1.2 Ω / sq, 1.4 Ω / sq, 1.5 Ω / sq, 1.6 Ω / sq, 1.8 Ω / sq, 2 Ω / sq, 2.1 Ω / sq, 2.2 Ω / sq, 2.3 Ω / sq, 2.4 Ω / sq, 2.5 Ω / sq, 2.6 Ω / sq, 2.8 Ω / sq, 3 Ω / sq, 3.4 Ω / sq, 3.5 Ω / sq, 4 Ω / sq, 4.5 Ω / sq, 5 Ω / sq,

[0146] 5.5 Ω / sq, 6 Ω / sq, 6.5 Ω / sq, 7 Ω / sq, 7.5 Ω / sq, 8 Ω / sq, 8.2 Ω / sq, 8.5 Ω / sq, 9 Ω / sq, 10 Ω / sq, etc. Without limitation, the Cr-Ti-N alloy coating in the coated article can have a sheet resistance selected from any of the following ranges: 0-12 Ω / sq, 0-6.6 Ω / sq, 0.5 Ω / sq-6.6 Ω / sq, 0.6 Ω / sq-6.6 Ω / sq, etc.

[0147] In some embodiments, the Cr-Ti-N alloy coating can provide a suitable range of sheet resistance on a silicon wafer surface (e.g., 0.5 Ω / sq-12 Ω / sq).

[0148] In some embodiments, the Cr-Ti-N alloy coating has a sheet resistance that meets one or both of the following characteristics:

[0149] The Cr-Ti-N alloy coating has a sheet resistance on a silicon wafer surface of 0.5 Ω / sq-12 Ω / sq, optionally 0.5 Ω / sq-6.6 Ω / sq, and further optionally 0.6 Ω / sq-6.6 Ω / sq.

[0150] The Cr-Ti-N alloy coating has a sheet resistance on an aluminum alloy surface of 0 Ω / sq.

[0151] Non-limitingly, the sheet resistance of the Cr-Ti-N alloy coating on the silicon wafer surface can also be any of the following values, or can be selected from any two of the following value ranges: 0.5Ω / sq, 1Ω / sq, 1.5Ω / sq, 2Ω / sq, 2.5Ω / sq, 3Ω / sq, 3.5Ω / sq, 4Ω / sq, 4.5Ω / sq, 5Ω / sq, 5.5Ω / sq, 6Ω / sq, 6.5Ω / sq, 7Ω / sq, 7.5Ω / sq, 8Ω / sq, 8.5Ω / sq, 9Ω / sq, 9.5Ω / sq, 12Ω / sq, etc.

[0152] In some embodiments, the Cr-Ti-N alloy coating serves as both a conductive coating and a corrosion-resistant coating in the coated product.

[0153] In some implementations, the corrosion-resistant coating is able to pass a corrosion test for at least 48 hours according to the ASTM B117 salt spray test standard; wherein the corrosion solution used for the corrosion test consists of sodium chloride, water and sodium hydroxide, with a pH of 6.5 to 7.2.

[0154] In some embodiments, when the corrosion-resistant coating is bonded to an aluminum alloy substrate, the corrosion-resistant coating can pass a test cycle of T. m1 (e.g. T) m1 Corrosion test (48 hours);

[0155] In some embodiments, when the corrosion-resistant coating is bonded to a stainless steel substrate, the corrosion-resistant coating can pass a test cycle of T. m2 (e.g. T) m2 Corrosion test (72 hours).

[0156] In this application, unless otherwise specified, "coating bonded to substrate X" means that the substrate on which the coating is formed is X, that is, the coating is formed on the surface of substrate X. For example, "corrosion-resistant coating bonded to aluminum alloy substrate" means that the corrosion-resistant coating is formed on the surface of the aluminum alloy substrate.

[0157] Without limitation, T m1 The duration can be 48 hours, 60 hours, 72 hours, 84 hours, 96 hours, 120 hours or longer.

[0158] Without limitation, T m2 The duration can be 72 hours, 84 hours, 96 hours, 120 hours, 144 hours or longer.

[0159] In some embodiments, the atomic ratio of the Cr-Ti-N alloy material satisfies 5.0≤x≤90, 5.0≤y≤90 and 2.4≤z≤26.5. At this time, the three atomic ratios of Cr, Ti and N can be more accurately controlled in a more optimal range, so that the formed Cr-Ti-N alloy coating is conducive to obtaining a more dense structure, and is conducive to achieving better electrical conductivity and better corrosion resistance.

[0160] In some embodiments, the Cr-Ti-N alloy coating serves as an electrically conductive coating in the coated product, and also simultaneously serves as a hard coating. The aforementioned Cr-Ti-N alloy coating structure is dense, and can also impart a higher hardness to the electrically conductive coating, better resist scratch and scratch damage; further, the electrically conductive coating can also simultaneously serve as a hard and corrosion-resistant coating.

[0161] The high-hardness coating has the effects of high hardness, low friction coefficient and wear resistance, and when applied to a substrate such as a metal substrate or an alloy substrate, the high-hardness effect can be achieved, so that the coating has extremely strong high-hardness and wear-resistant properties, and is particularly suitable for structural parts that have high hardness requirements and are easily worn in the fields of 3C digital products, mechanical processing, mold manufacturing, geological drilling, textile industry, aerospace, tool surface, etc. For example, in the field of portable 3C products, such as the shell parts of mobile phones, which are often rubbed with desktops, pockets, etc., the shell surface needs to be protected by a high-hardness coating to increase the service life of the product. For another example, in the field of molds and cutters, the wear resistance of the mold or cutter can be effectively increased by increasing the high-hardness alloy coating, and the durability of the alloy tool can also be prolonged. For another example, in the field of aerospace, the device shell is easily worn due to overheating friction with air at extremely high speed, and the service life of the shell can be increased by increasing the high-hardness alloy coating on the surface of the shell.

[0162] The application provided in the present application is compatible with but not limited to the application field of traditional hard coatings, such as but not limited to the fields of 3C digital products, automobile parts or accessories, mechanical processing, mold manufacturing, geological drilling, textile industry, aerospace, etc.

[0163] In some embodiments, the corrosion-resistant coating is a hard and corrosion-resistant coating. Further, the thickness of the Cr-Ti-N alloy coating can be greater than or equal to 0.9 μm, and suitable thicknesses of the Cr-Ti-N alloy coating are described in the context.

[0164] In some embodiments, the Cr-Ti-N alloy coating is located on the surface of an aluminum alloy substrate (which can be directly combined or indirectly combined through a transition layer), and the hardness value of the hard and corrosion-resistant coating is ≥13 GPa.

[0165] In some embodiments, the Cr-Ti-N alloy coating is located on the surface of the stainless steel substrate (directly bonded or indirectly bonded through a transition layer), and the hardness value of the hard corrosion-resistant coating is ≥14 GPa.

[0166] In some embodiments, the Cr-Ti-N alloy coating also serves as a high-brightness coating as an electrically conductive coating in the plated product.

[0167] Further, the brightness value L of the high-brightness surface coating is ≥70, optionally ≥75, and further optionally ≥80, as tested by the Lab method. The L value of conventional alloy coatings is often difficult to achieve a high value, and is usually about 55-65.

[0168] In some embodiments, the Cr-Ti-N alloy coating serves as a surface structure layer, and the brightness value L of the surface of the Cr-Ti-N alloy coating is ≥70, optionally ≥75, and further optionally ≥80, as tested by the Lab method.

[0169] In some embodiments, the Cr-Ti-N alloy coating provides a plated product with a surface brightness value L ≥70, optionally ≥75, and further optionally ≥80, as tested by the Lab method.

[0170] The aforementioned Cr-Ti-N alloy coating has high contents of Cr and Ti, two metal components, which gives the coating a metallic luster and a more beautiful appearance.

[0171] Based on the special structural characteristics of the aforementioned Cr-Ti-N alloy coating, which is "highly disordered and fully dense" at the atomic level, the reflection characteristics of the coating surface can also be improved to provide a higher brightness value.

[0172] When the target Cr-Ti-N alloy coating is located on the surface of the coated article, the high compactness structure of the "atomic height disorder and full close packing" of the Cr-Ti-N alloy coating can also obtain better coating reflection characteristics, thereby providing the coated article with a surface having high brightness. Cr is a high-brightness metal raw material in the coating material, and a higher Cr content can effectively improve the brightness of the alloy coating. Meanwhile, the target Cr-Ti-N alloy coating has high compactness, which further improves the surface reflection characteristics of the coating. The two characteristics are superimposed, so that the coating surface has higher brightness and higher brightness value (i.e., L value) during the colorimetric value measurement. The L value of the target Cr-Ti-N alloy coating can be ≥70, and some can be as high as ≥83, and the coating has a high-brightness silver-white color, which is much higher than the L value of the traditional alloy coating (the traditional L value is about 55-65). The high-brightness coating has an aesthetic effect and excellent decorative characteristics. When applied to the surface of a substrate (such as an aluminum alloy), the high-brightness aesthetic effect can be achieved, so that the coating color is closer to the substrate color, and the color difference can be characterized without color difference. This characteristic makes the target Cr-Ti-N alloy coating have excellent decorative effect, and is particularly suitable for 3C digital products, such as mobile phone parts, which can achieve a high-brightness metal effect. It can also be applied to wearable products, automotive products, sports products and other fields.

[0173] In the present application, when testing the colorimetric value of the alloy coating, the sample to be tested uses a substrate material suitable for actual application. The L value, a value and b value of the sample can be tested by a CM-3700A-U table type spectrophotometer produced by Konica, Japan, the light receiving system selects F2 light source, and at least 6 (such as 6) matrix points of each sample are tested and the average value is taken. Among them, the L value represents the brightness value, the a value represents the red or green colorimetric value, and the b value represents the yellow or blue colorimetric value. The a value represents the red-green color of the object, the positive value represents the red colorimetric value, and the negative value represents the green colorimetric value. The b value represents the yellow-blue color of the object, the positive value represents the yellow colorimetric value, and the negative value represents the blue colorimetric value. The larger the L value, the higher the brightness, indicating that the coating surface is more compact. The mechanism is as follows: the spectrophotometer is incident light on the surface of the measured sample, forming a reflection, and a reflectivity curve can be obtained. The amplitude of the curve can reflect the density of the material, which can be characterized by the L value, and the higher the compactness of the same material, the larger the L value displayed.

[0174] In the present application, unless otherwise specified, the colorimetric value Lab is tested as follows: the light receiving system selects F2 light source, and the average value is taken after testing multiple (such as 6) matrix points of each sample. Further, a spectrophotometer is used for testing. Further, the testing instrument is a CM-3700A-U table type spectrophotometer produced by Konica, Japan. The testing temperature can be room temperature, and further can be 25°C.

[0175] The aforementioned coated articles can be intermediate products or end products. Among them, the end products can be directly used or sold. The intermediate products can be further processed or assembled with other elements into new products.

[0176] From the perspective of microstructure, the Cr-Ti-N alloy coating in the application is not strictly divided into traditional perfect single crystal or sufficient amorphous state, but focuses on the close packing degree of atomic arrangement, which is closely related to the disorder of atomic arrangement and the suitable mismatch degree of atomic size on the basis of the specific atomic ratio of Cr, Ti and N; the highly dense Cr-Ti-N alloy coating used in the application has good electrical conductivity and excellent corrosion resistance in performance, and simultaneously satisfies at least one wide peak in the XRD pattern in the diffraction angle 2θ(°) range of 34°-50° (further, there can be no sharp peak, i.e. all wide peaks) and at least one wide peak in the radial intensity profile of the selected area electron diffraction pattern in the range of 34°-50°. (Optionally ) range.

[0177] In some embodiments, the Cr-Ti-N alloy coating satisfies the following two characteristics:

[0178] The X-ray diffraction pattern of the Cr-Ti-N alloy coating has a peak in the diffraction angle 2θ(°) range of 34°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥2°;

[0179] The radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has a diffraction peak in the range of 34°-50°, and the half-height width of at least one diffraction peak in the range of 34°-50° satisfies Optionally,

[0180] The means for structural characterization of the Cr-Ti-N alloy coating in the application can also be used to characterize the Cr-Ti-N alloy material involved in the application, and the Cr-Ti-N alloy material can not be limited to the form of coating, but can be an independent raw material, such as alloy sheet, alloy plate, etc.

[0181] ​​In the present application, whether the constituent atoms of the Cr-Ti-N alloy coating have a "highly disordered" state is evaluated by XRD technology. In detail, the XRD pattern of the Cr-Ti-N alloy coating shows wide and slow ridges, which are referred to as "broad peaks" of the 2θ(°) diffraction peaks. By using the half-height width value of the broad peak, the length of the atomic ordered arrangement can be obtained by using the Scherrer formula. The calculation method is: D = Kλ / (β·cosθ), wherein D is the length of the atomic ordered arrangement (representing the grain size in crystalline materials), K is the Scherrer constant, λ is the X-ray wavelength; β is the half-height width value (Full Width at Half Maximum, FWHM) of the 2θ(°) diffraction peak, and θ is the diffraction angle. It can be seen that the half-height width FWHM is inversely proportional to the length D of the atomic ordered arrangement, and the shorter the length D of the atomic ordered arrangement, the higher the disorder of the atomic distribution. Therefore, the half-height width FWHM of the diffraction peak in a specific range of the XRD pattern can be used to reflect the degree of disorder of the atomic distribution: the wider the half-height width FWHM, the shorter the length of the atomic ordered arrangement, and the more disordered the overall atomic distribution; the aforementioned "broad peak" of the wide and slow ridge can reflect the highly disordered distribution of atoms in the whole material.

[0182] In the present application, unless otherwise specified, the XRD diffraction pattern and the diffraction peak in the pattern have a horizontal coordinate of 2θ with a unit of °.

[0183] In the present application, unless otherwise specified, the "half-height width FWHM" of the XRD diffraction pattern corresponds to the diffraction peak with a horizontal axis of 2θ. As a non-limiting example, "half-height width" satisfying ≥1.6° means that the half-height width of the 2θ(°) diffraction peak is ≥1.6°.

[0184] Generally speaking, the higher the atomic ordered arrangement, the stronger the crystallinity, and the easier it is to form large-size grains in a longer distance, and the narrower the diffraction peak in the XRD pattern, and high crystallinity is often accompanied by sharp peaks. In the application provided in the present application, the three atoms of Cr, Ti and N in the Cr-Ti-N alloy coating can be highly disordered in the whole Cr-Ti-N alloy coating, so as to show wide and slow ridges (broad peaks) in the XRD pattern of the Cr-Ti-N alloy coating, and at least one peak in the range of 34°-50° of the diffraction angle 2θ(°) is a "broad peak".

[0185] In the present application, a "broad peak" in an XRD pattern can be defined as a diffraction peak having a half-height width (in 2 theta (°)) satisfying ≥ 1.6°, unless otherwise specified. The half-height width of a broad peak can further satisfy ≥ 2°, can further satisfy ≥ 2.2°, can further satisfy ≥ 2.5°, can further satisfy ≥ 3°, can further satisfy ≥ 3.5°, can further satisfy ≥ 4°, can further satisfy ≥ 4.5°, can further satisfy ≥ 5°. The half-height width (in 2 theta (°)) of any "broad peak" in an XRD pattern can independently be any of the following values, can be greater than or equal to any of the following values, can be greater than or equal to any of the following values (except for 10°) and less than or equal to 10°, can be selected from the interval defined by any two of the following values: 1.6°, 1.60°, 1.65°, 1.69°, 1.8°, 1.85°, 2°, 2.00°, 2.03°, 2.2°, 2.29°, 2.48°, 2.5°, 2.63°, 2.60°, 2.68°, 2.91°, 2.99°, 3°, 3.00°, 3.09°, 3.32°, 3.5°, 4°, 4.00°, 4.21°, 4.29°, 4.40°, 4.5°, 4.61°, 4.87°, 4.94°, 5°, 5.05°, 5.09°, 5.40°, 5.5°, 5.50°, 6°, 6.00°, 6.5°, 6.59°, 7°, 7.5°, 8°, 8.00°, 8.5°, 9°, 9.5°, 9.50°, 10°, 10.00°, and the like. As non-limiting examples, the half-height width (in 2 theta (°)) of a "broad peak" can be selected from any of the following ranges: 1.6° to 10°, 1.8° to 10°, 2° to 10°, 3.09° to 10°, 4.21° to 10°, 1.6° to 9.5°, 1.8° to 9.5°, 2° to 9.5°, 3.09° to 9.5°, 4.21° to 9.5°, 2° to 9.4°, 3.09° to 9.4°, 1.6° to 8°, 1.8° to 8°, 2° to 8°, 3.09° to 8°, 4.21° to 8°, 1.6° to 6.6°, 1.8° to 6.6°, 2° to 6.6°, 3.09° to 6.6°, 4.21° to 6.6°, 1.69° to 6.59°, 1.8° to 6.59°, 2.29° to 6.59°, 3.09° to 6.59°, 4.21° to 6.59°, 2.03° to 5.05°, 2.03° to 5.40°, and the like.

[0186] In the present application, a "sharp peak" in an X-ray diffraction (XRD) pattern refers to a diffraction peak having a half-height width (in 2 theta (°)) < 1.6°, unless otherwise specified.

[0187] In more detail, in the application provided by the present application, the XRD pattern of the Cr-Ti-N alloy coating has peaks in the diffraction angle 2θ(°) range of 34°-50°, and at least one peak in the XRD pattern is a broad peak. The special microstructure state of "at least one peak being a broad peak" can be represented by "having at least one 2θ(°) diffraction peak in the range of 34°-50° with a half-height width ≥1.6°" or "at least one 2θ(°) diffraction peak in the range of 34°-50° having a half-height width satisfying ≥1.6°". Whether it satisfies "having at least one 2θ(°) diffraction peak in the range of 34°-50° with a half-height width ≥1.6°" can be determined by the following method: if the half-height width value of the 2θ(°) diffraction peak in the XRD pattern is ≥1.6°, it is determined to be a "broad peak"; if the half-height width value of the 2θ(°) diffraction peak is <1.6°, it is determined to be a sharp peak. For a specified 2θ(°) position, it can be any one of the three states of no peak, broad peak or sharp peak. The broad peak characteristic of the characteristic diffraction peak of the Cr-Ti-N alloy coating is more obvious in the X-ray diffraction (XRD) pattern.

[0188] In the traditional Cr-Ti-N alloy coating with a high content of columnar crystals, the diffraction peak in the diffraction angle 2θ(°) range of 34°-50° is often a sharp peak with a half-height width <1.6°, and no broad peak appears.

[0189] In the present application, the XRD pattern of the Cr-Ti-N alloy coating can be obtained by using conventional instruments and methods in the art. For example, a German Bruker D8 Advance XRD diffractometer can be used.

[0190] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has peaks in the diffraction angle 2θ(°) range of 34°-50°, and at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥2.60°.

[0191] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has 1 broad peak in the diffraction angle 2θ(°) range of 34°-50°, and the half-height width value of the broad peak can be referred to the examples in the context.

[0192] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has 2 or more broad peaks in the diffraction angle 2θ(°) range of 34°-50°, and the half-height width values of the broad peaks can be referred to the examples in the context.

[0193] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has all the 2θ(°) diffraction peaks in the range of 34°-50° of diffraction angle 2θ(°) are broad peaks, i.e. there are no sharp peaks, and the half-height width of the broad peaks can refer to the examples in the context.

[0194] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has peaks in the range of 34°-50° of diffraction angle 2θ(°), and the half-height width of the 2θ(°) diffraction peaks in the range of 34°-50° satisfies ≥1.6°, further can satisfy ≥2°, further can satisfy ≥2.2°, further can satisfy ≥2.5°, further can satisfy ≥3°, further can satisfy ≥4.5°, further can satisfy ≥5°.

[0195] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating has only one diffraction peak in the range of 34°-50° of diffraction angle 2θ(°), and the peak is a broad peak.

[0196] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy coating is obtained by Cu target Kα ray, and further is Kα1 ray.

[0197] In the present application, the following instruments and methods can be used to obtain the XRD pattern of the alloy coating: a German Bruker D8 Advance XRD diffractometer, in θ-2θ mode, using Cu target Kα ray, wavelength λ is 0.15406 nm, the X-ray tube is controlled at 40 kV and 40 mA, the scanning range is 20°-80°, and the precise scanning measurement is performed with a step of 0.01°.

[0198] The half-height width value can be obtained by using conventional analysis methods in the art, including but not limited to the analysis software provided by the instrument supplier. For example, the steps of obtaining the half-height width value can include: first, correcting the diffraction peak, which can include: smoothing, background subtraction, removal of Kα2 line, and removal of instrument broadening, etc., and then fitting the diffraction peak with a Pseudo-Voigt function to obtain the half-height width value of the diffraction peak.

[0199] The analysis software is not particularly limited, and the EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) can be used for processing the spectrum data, for example, the following method can be used: first, a ruler correction is performed, then the center of the diffraction ring transmission spot is determined, and then an XRD spectrum is converted (wherein the electron wavelength is 0.00251 nanometers, and the X-ray wavelength is 0.154 nanometers; after the diffraction peak is subtracted from a straight line background and then fitted by a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0200] Regarding the characterization of the atomic close-packed degree in the Cr-Ti-N alloy coating, the traditional XRD spectrum cannot well characterize this, because when detecting a physical vapor deposition (PVD) film or coating at an atomic scale (such as a diameter < 3 nm), the XRD method often has insufficient resolution due to the relatively large wavelength (> 0.1 nm) of X-rays, and is not suitable for PVD films or coatings with low order (such as grains or amorphous with a diameter < 3 nm).

[0201] In the present application, whether the atoms in the Cr-Ti-N alloy coating reach "sufficient close packing" can be evaluated by a selected area electron diffraction pattern (SAED). The electron wave is selected because its wavelength is significantly smaller (< 0.01 nm), thereby having higher resolution. In detail, if only continuous diffraction rings with uniform brightness exist on the SEAD pattern, and the diffraction rings are relatively wide, it indicates that the atoms in the coating are arranged in a highly random mixed manner. In order to quantitatively characterize, the SAED pattern can be converted into a characteristic atomic spacing (d)-radial intensity profile, wherein the characteristic atomic spacing (d) is taken as the horizontal coordinate, and the diffraction intensity is taken as the vertical coordinate. If the diffraction rings in the SEAD are relatively wide, then the half-height width of the radial intensity profile is correspondingly wide, reflecting that the atomic arrangement in the alloy coating is relatively strong.

[0202] In the present application, at the atomic size, the Cr atomic radius is The Ti atomic radius is The N atomic radius is Three kinds of atoms with different diameters have suitable atomic size mismatch, and can form a close-packed structure under the condition of high random mixing degree. In the growth process of PVD thin film or alloy coating, the close packing of atoms in the Cr-Ti-N alloy coating makes the Cr-Ti-N alloy coating easy to grow densely, and can inhibit the formation and growth of columnar crystals caused by local ordering, so that continuous through-type pores are difficult to form in large quantities. Therefore, the half width of the radial intensity profile can be used as a characteristic parameter of the close-packed structure of the Cr-Ti-N alloy coating to reflect the atomic packing of the Cr-Ti-N alloy coating. The larger the value of the half width, the better the atomic packing of the Cr-Ti-N alloy coating. In short, the application uses the half width of the radial intensity profile of SAED as a characteristic parameter of atomic close packing, which is in line with scientific principles and has scientific nature.

[0203] When the half width of the radial intensity profile is greater than a certain threshold value, the atoms in the Cr-Ti-N alloy coating can achieve close packing. According to the inventor's extensive experimental exploration, in the present application, the threshold value of the half width of the SAED-radial intensity profile for judging whether the atomic close packing is achieved is that is, it is considered that the half width value can achieve the close packing of atoms.

[0204] In the present application, the characteristic interatomic distance (d) radial intensity profile of the Cr-Ti-N alloy coating sample can be obtained by transmission electron microscopy (TEM) technology.

[0205] In the present application, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating can be denoted as SAED-radial intensity profile, and can also be denoted as a characteristic interatomic distance-intensity quantitative atlas of the selected area electron diffraction pattern (SAED pattern). The selected area electron diffraction pattern obtained by transmission electron microscopy technology can be denoted as TEM selected area electron diffraction pattern, and can also be denoted as TEM-SAED pattern. The SAED-radial intensity profile obtained by transmission electron microscopy technology can also be denoted as TEM-SAED-radial intensity profile.

[0206] In the present application, the target Cr-Ti-N alloy coating in the plated product can be obtained by using conventional instruments and methods in the art, and the corresponding radial intensity profile can be obtained according to the selected area electron diffraction pattern (SAED) of the Cr-Ti-N alloy coating. It is expressed in the form of characteristic interatomic distance (d)-diffraction intensity, with d as the horizontal coordinate and in angstrom The vertical coordinate is the electron diffraction intensity (Intensity).

[0207] In the present application, the half-height width of a diffraction peak in the radial intensity profile of a SAED pattern is then judged as a wide peak; the half-height width of a diffraction peak in the radial intensity profile of a SAED pattern is judged as a sharp peak. For a specific characteristic atomic spacing, it can be any one of the three states of no peak, sharp peak or wide peak. The wide peak characteristic of the characteristic diffraction peaks of the Cr-Ti-N alloy coating is more obvious in the radial intensity profile. In the radial intensity profile of a SAED pattern, "wide peak" refers to a diffraction peak with a half-height width of "sharp peak" refers to a diffraction peak with a half-height width of .

[0208] In the present application, the radial intensity profile or SAED-radial intensity profile can be obtained by TEM technology, unless otherwise specified.

[0209] In the present application, "wide peak" in the radial intensity profile corresponding to a SAED pattern can be defined as a half-height width satisfying The half-height width of a wide peak can be further further can be further can be further can be further can be further can be further can be

[0210] In the present application, the radial intensity profile corresponding to a SAED pattern can be obtained by (but not limited to) the following transmission electron microscope (TEM) method:

[0211] TEM sample preparation: using the Helios 5CX model focused ion beam (FIB) of Thermo Fisher Limited, the sample is thinned to obtain an electron-transparent, TEM-observable planar sample.

[0212] SAED image acquisition: using the Talos F200x model transmission electron microscope (TEM) of Thermo Fisher Limited, the electron acceleration voltage is 200kV, the selected area aperture diameter is 900nm, the selected area electron diffraction pattern (SAED) of the sample is obtained, based on the selected area electron diffraction pattern (SAED), the radial intensity profile is obtained, the integral half-height width is assigned, and the half-height width value of the diffraction peak is obtained.

[0213] According to the principle that the half-height width of the diffraction peak in the radial intensity profile corresponds to the width of the diffraction ring in the selected area electron diffraction (SAED) pattern, the selected area electron diffraction (SAED) pattern of the Cr-Ti-N alloy coating can be converted into the corresponding radial intensity profile.

[0214] The person skilled in the art knows that the greater the width of the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing degree of atoms, and the more sufficient the atomic close packing in the Cr-Ti-N alloy coating. The half-height width of the diffraction peak in the radial intensity profile is a quantitative indicator of the width of the diffraction ring, and the greater the half-height width value, the more sufficient the atomic close packing.

[0215] In some embodiments, the selected area electron diffraction (SAED) pattern of the Cr-Ti-N alloy coating is obtained using a transmission electron microscope (TEM) characterization technique with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0216] In some embodiments, the radial intensity profile of the selected area electron diffraction pattern of the Cr-Ti-N alloy coating has at least one diffraction peak with a half-height width , optionally at least one diffraction peak with a half-height width , further optionally at least one diffraction peak with a half-height width , and still further optionally at least one diffraction peak with a half-height width . In some of these embodiments, the aforementioned range can be selected

[0217] In the radial intensity profile of the Cr-Ti-N alloy coating, the half-height width of the diffraction peak in the range has an upper limit value due to the limit of atomic close packing, and a non-limiting example of the upper limit value is

[0218] In this application, the half-height width of the "wide peak" in the radial intensity profile corresponding to the SAED pattern can be any of the following values, can be greater than or equal to any of the following values, can be greater than or equal to any of the following values and less than or equal to the aforementioned upper limit value (such as ), can also be selected from the interval consisting of any two of the following values: and so on. As a non-limiting example, the half-height width of the "wide peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any of the following ranges: and so on.​​

[0219] In some embodiments, the radial strength profile of the Cr-Ti-N alloy coating, full width at half maximum (FWHM) of diffraction peaks within the range

[0220] In some embodiments, the radial strength profile of the Cr-Ti-N alloy coating, The full width at half maximum (FWHM) of the diffraction peaks within the range can be any of the following values, can be greater than or equal to any of the following values, or can 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.

[0221] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating 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

[0222] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating is in The range contains two or more broad peaks, and their half-width values ​​can be seen in the examples in the context.

[0223] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating 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.

[0224] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating 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.

[0225] In some embodiments, the characteristic atomic spacing of the Cr-Ti-N alloy coating is obtained by TEM diffraction data; wherein the TEM diffraction test of the alloy coating is performed by using an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0226] In some embodiments, the TEM test is performed by using an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm to obtain a selected area electron diffraction pattern (SAED) of the Cr-Ti-N alloy coating.

[0227] Regarding the internal mechanism analysis of the target Cr-Ti-N alloy coating provided in the application, the inventors of the present application have also found, through a large number of experimental explorations, that for the Cr-Ti-N alloy coating, when the following two conditions are met at the same time, the Cr-Ti-N alloy coating prepared has excellent corrosion resistance: (1) at least one broad peak in the XRD diffraction pattern in the diffraction angle 2θ (°) range of 34°-50°, (2) at least one broad peak in the radial intensity profile of the selected area electron diffraction pattern in the range of 34°-50°.

[0228] The Cr-Ti-N alloy material and the Cr-Ti-N alloy coating involved in the present application can contain a doping element or can not contain a doping element, and can be flexibly selected according to the additional functional requirements of one or more of the alloy material and the alloy coating. It can be understood that in the present application, when the doping element is contained, the type and doping amount of the doping element are limited at least to not affecting the conductivity and corrosion resistance of the Cr-Ti-N alloy coating; further preferably, the high hardness characteristic can also be taken into account at the same time, in addition, a relatively high surface brightness can also be achieved at the same time.

[0229] In some embodiments, in the Cr-Ti-N alloy material, the atomic ratio of Cr element, Ti element and N element is x:y:z, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5; the Cr-Ti-N alloy material further comprises a doping element. In the nucleation process, N atoms can penetrate into the pores of large-size Cr and Ti metal grains, achieve a better pore-filling effect, make the atomic stacking of the coating more dense, also can inhibit the growth defects of the thin film columnar crystal structure, thereby improving the conductivity of the coating, also can improve the corrosion resistance and hardness.

[0230] In the present application, the doping element in the Cr-Ti-N alloy material can be denoted as "M element". Unless otherwise specified, the doping element in the Cr-Ti-N alloy material refers to any other element in the Cr-Ti-N alloy material other than Cr, Ti and N.

[0231] ​As a non-limiting example, in some embodiments, the doping element in the Cr-Ti-N alloy material can include a carbon element, and further can be a carbon element.

[0232] In some embodiments, the mass percentage of Cr, Ti and N in the Cr-Ti-N alloy material (denoted as f wt ) can be greater than or equal to 80%, optionally greater than or equal to 90%, further optionally greater than or equal to 95%, and more further optionally f wt = 100%. Non-limitingly, f wt may be any of the following values, greater than or equal to any of the following values, or selected from the interval consisting of any two of the following values: 80%, 85%, 95%, 96%, 97%, 98%, 99%, etc., f wt may be greater than or equal to any of the foregoing values and less than or equal to 100%, for example f wt may be 95%-100%, 80%-100%, 90%-100%, 99%-100%, etc.

[0233] In other embodiments, the Cr-Ti-N alloy material mainly includes Cr, Ti and N, and further, the sum of the atomic ratios of the three elements accounts for a proportion of the sum of the atomic ratios of all elements in the Cr-Ti-N alloy material (denoted as f N ≥ 95%, further as f N ≥ 98%, and more further as f N = 100% (at this time, the Cr-Ti-N alloy material is a Cr-Ti-N ternary alloy material). Non-limitingly, f N may be any of the following values, greater than or equal to any of the foregoing values, or selected from the interval consisting of any two of the following values: 95%, 96%, 97%, 98%, 99%, etc., f N may be greater than or equal to any of the foregoing values and less than or equal to 100%, for example f N may be 95%-100%.

[0234] By limiting the content of the doping element in the Cr-Ti-N alloy material within a more appropriate range, the influence of the doping element on the atomic highly disordered and fully dense Cr-Ti-N alloy coating can be minimized, which is conducive to reducing the required elements for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Ti and N to form a denser coating, and thus better improving one or more of the aforementioned coating conductivity, corrosion resistance, hardness and coating surface brightness.

[0235] In some embodiments of the present application, the Cr-Ti-N alloy material includes a chemical formula of Cr xTi y N z M a , wherein x, y and z are each independently atomic ratio and positive number, M is a doping element, a is atomic ratio of M element and is 0 or positive number. Further, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5.

[0236] In the present application, unless otherwise specified, "CrTiN-based alloy composition" refers to an alloy composition comprising at least Cr element, Ti element and N element. Generally, in the CrTiN-based alloy composition, Cr element, Ti element and N element constitute main elements.

[0237] In the present application, unless otherwise specified, "Cr-Ti-N ternary alloy composition" and "CrTiN ternary alloy composition" both refer to an alloy composition comprising Cr element, Ti element and N element.

[0238] When a is 0, the CrTiN-based alloy composition does not contain a doping element, corresponding to the Cr-Ti-N ternary alloy composition. When a>0, the CrTiN-based alloy composition contains a doping element, wherein a / (x+y+z) is equal in value to "relative atomic percentage of doping element to Cr, Ti, N", and a / (x+y+z+a) is equal in value to atomic percentage of doping element in the CrTiN-based alloy composition. Wherein, "relative atomic percentage of doping element M to Cr, Ti, N" refers to the ratio of the number of atoms of doping element M to the sum of the number of atoms of Cr, Ti, N in the material, expressed in percentage.

[0239] By limiting the content of the doping element in the CrTiN-based alloy composition within a more appropriate range, the influence of the doping element on the atomic highly disordered and fully dense CrTiN-based alloy composition can be minimized, which is conducive to reducing the required doping elements or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Ti and N to form a more dense Cr-Ti-N alloy material, thereby better improving one or more of the aforementioned coating conductivity, corrosion resistance, hardness and coating surface brightness.

[0240] In some embodiments, the mass percentage of Cr, Ti and N in the CrTiN-based alloy composition (which can be denoted as f w0 ) can be greater than or equal to 80%, optionally, f w0 is greater than or equal to 90%, further optionally, f w0 is greater than or equal to 95%, optionally, f w0 is 100%. Non-limitingly, f w0may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f w0 may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f w0 may be 80% to 100%, 90% to 100%, or 95% to 100%.

[0241] In some embodiments, the total number of atoms of Cr, Ti, and N relative to the number of atoms of all elements in the CrTiN-based alloy composition (which can be denoted as f N0 may be greater than or equal to 95%, further f N0 may be greater than or equal to 98%, and further f N0 may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f N0 may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f N0 may be 95% to 100%.

[0242] In some embodiments, the mass percentage of the CrTiN-based alloy composition in the Cr-Ti-N alloy material (which can be denoted as f w1 may be greater than or equal to 80%, optionally f w1 may be greater than or equal to 90%, further optionally f w1 may be greater than or equal to 95%, further optionally f w1 may be 100%. Non-limitingly, f w1 may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f w1 may be greater than or equal to any of the aforementioned values and less than or equal to 100%, for example, f w1 may be 80%, 85%, or 95% to 100%. In some embodiments, f w1 may be 100%. In this case, the Cr-Ti-N alloy material is a Cr-Ti-N ternary alloy material, which is simple in composition and easy to prepare and manipulate. The Cr-Ti-N ternary alloy coating formed in this case can have a dense structure and can achieve good electrical conductivity. In addition, good corrosion resistance and high coating hardness can also be achieved.

[0243] In some embodiments, the Cr-Ti-N alloy material includes a chemical formula of Cr x Tiy N z M a CrTiN-based alloy component, in which M is a doping element, x, y, z and a are atomic ratios of Cr element, Ti element, N element and M element respectively, 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5, and 0≤a / (x+y+z+a)≤0.05.

[0244] In some embodiments, x can be any of the following values or selected from the interval consisting of any two of the following values: 5.0, 6.0, 7.0, 8.0, 10, 12.5, 12.7, 14.8, 15, 18, 18.0, 18.4, 18.9, 20, 21, 25, 25.6, 27, 27.8, 35, 37, 37.6, 38.3,

[0245] 40, 43, 44, 45, 46.4, 50, 53, 54.4, 55, 60, 60.6, 62.9, 66.9, 69.4, 65, 72.2, 73, 70, 75, 80, 85, 90, etc.

[0246] In some embodiments, y can be any of the following values or selected from the interval consisting of any two of the following values: 5.0, 6.0, 7.0, 8.0, 10, 15, 18.3, 18.4, 18.9, 20, 25.6, 35, 35.2, 37, 37.0, 40, 45, 49.2, 50, 55, 60, 65, 66, 68, 68.6, 70, 75, 76, 77.9, 78, 79, 79.0, 80, 85, 90, etc.

[0247] In some embodiments, z can be any of the following values or selected from the interval consisting of any two of the following values: 2.4, 2.5, 2.6, 2.8, 3.0, 3.3, 3.5, 4.0, 4.5, 5.0, 6, 7, 8, 10, 10.1, 12, 15, 16, 18, 18.2, 20, 22, 24, 25, 26.5, etc.

[0248] In the context of the present application, x, y, z are combined in any suitable manner, for example, in the manner of x+y+z=100.

[0249] In some embodiments, the sum of x, y and z is a value selected from 95-100. Without limitation, the sum of x, y and z can be any of the following values or selected from the interval consisting of any two of the following values: 95, 96, 97, 98, 99, 100, etc.

[0250] The content of the doping element in the CrTiN-based alloy composition can be adjusted by adjusting a / (x+y+z+a). Those skilled in the art can select a suitable value of a / (x+y+z+a) according to the needs. In some embodiments, a / (x+y+z+a) can be any of the following values, greater than 0 and less than or equal to any of the following values, or selected from the interval formed by any two of the following values: 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, etc.

[0251] In numerical terms, a / (x+y+z+a) is equal to 1-f N0 . For example, in some embodiments, a = 0, f N0 is 100%. In some embodiments, a / (x+y+z+a) is 0.05, f N0 is 95%.

[0252] In some embodiments, 0≤a / (x+y+z+a)≤0.05, and optionally, 0≤a / (x+y+z)≤0.05.

[0253] In some embodiments, a = 0 or 0 < a / (x+y+z+a) ≤ 0.05.

[0254] In some embodiments, 0 < a / (x+y+z+a) ≤ 0.05, and optionally, 0 < a / (x+y+z) ≤ 0.05.

[0255] In some embodiments, 0≤a / (x+y+z+a)≤0.02, further for example, 0≤a / (x+y+z)≤0.02, 0≤a / (x+y+z+a)≤0.01, 0≤a / (x+y+z+a)≤0.01, 0≤a / (x+y+z+a)<0.01, etc. In other embodiments, 0 < a / (x+y+z+a) ≤ 0.02, further for example, 0 < a / (x+y+z+a) ≤ 0.02, 0 < a / (x+y+z+a) ≤ 0.01, 0 < a / (x+y+z+a) ≤ 0.01, 0 < a / (x+y+z+a) < 0.01, etc. At this time, the content of the doping element can be controlled to be relatively low, and the influence of the doping element on the high atomic disorder and sufficient close packing in the Cr-Ti-N alloy coating can be minimized, which is conducive to reducing the doping element or reducing the difficulty of doping, simplifying the preparation process, and promoting the synergistic deposition of Cr-Ti-N to form a denser coating.

[0256] In some embodiments, 0≤a / (x+y+z+a)≤0.02. The value of a / (x+y+z+a) can also refer to the definition in the context.

[0257] In some embodiments, a / (x+y+z) = 0. In this case, corresponding to Cr-Ti-N ternary alloy composition, the composition is simple, and it is easier to prepare and manipulate. The Cr-Ti-N ternary alloy coating formed in this case can obtain a dense structure, and can achieve good electrical conductivity, in addition, it can also achieve high corrosion resistance and high hardness.

[0258] In some embodiments, 0≤a / (x+y+z+a)≤0.05 (may also be selected from any suitable range or any suitable value described above), further, the doping elements can include one or more metal elements of Ti, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu and Al.

[0259] x, y, z and a in the context of the present application can be combined in any suitable manner, for example, in the manner of x+y+z+a = 100.

[0260] In some embodiments, a = 0 or 0 < a / (x+y+z+a)≤0.05.

[0261] In some embodiments, the mass percentage f of the CrTiN-based alloy composition in the Cr-Ti-N alloy material is greater than or equal to 80%, and can be greater than or equal to 90%, further can be greater than or equal to 95%, and can be equal to 100%. For reference, please refer to the definition above. w1 may be greater than or equal to 80%, further can be greater than or equal to 90%, further can be greater than or equal to 95%, and can be equal to 100%. For reference, please refer to the definition above.

[0262] In some embodiments, the mass percentage of the Cr-Ti-N alloy material in the Cr-Ti-N alloy coating can be greater than or equal to 80%, optionally, greater than or equal to 90%, further optionally, greater than or equal to 95%, further optionally, 100%, and can be any of the following values, greater than or equal to any of the foregoing values, less than or equal to 100%, or selected from the interval formed by any two of the following values: 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, etc. For example, the mass percentage of the Cr-Ti-N alloy material in the Cr-Ti-N alloy coating can be any of the following ranges: 95%~100%, 80%~100%, 90%~100%, 99%~100%, etc.

[0263] In some embodiments, the Cr-Ti-N alloy coating is composed of the Cr-Ti-N alloy material, and in this case, the mass percentage of the Cr-Ti-N alloy material in the Cr-Ti-N alloy coating is 100%.

[0264] In some embodiments, the coated product satisfies one or more of the following characteristics:

[0265] The Cr-Ti-N alloy material has a mass percentage of 100% in the Cr-Ti-N alloy coating.

[0266] The Cr-Ti-N alloy material has a mass percentage of 100% in the Cr-Ti-N alloy coating.

[0267] The Cr-Ti-N alloy material has a mass percentage of 100% in the Cr-Ti-N alloy coating.

[0268] The Cr-Ti-N alloy material has a mass percentage of 100% in the Cr-Ti-N alloy coating.

[0269] In some embodiments, x, y and z are in the range of 5.0≤x≤90, 5.0≤y≤90 and 2.4≤z≤26.5, with the sum of x, y and z being 100. The atomic ratio of Cr, Ti and N can be more precisely controlled in a better range, which is beneficial to form a more compact Cr-Ti-N alloy coating, thereby better improving one or more of the aforementioned properties of the coating, such as conductivity, corrosion resistance and surface brightness of the coating.

[0270] In some embodiments, the doping element includes one or more metal elements selected from Ni, Fe, Ag, Au, Cu and Al. The doping element can be flexibly selected according to additional functional requirements of the Cr-Ti-N alloy coating. It can be understood that, in the present application, the type and amount of the doping element are limited to those that can form a Cr-Ti-N alloy coating structure and do not affect the realization of good conductivity and excellent corrosion resistance.

[0271] It should be noted that, in any embodiment of the context of the present application, the Cr-Ti-N alloy material and the Cr-Ti-N alloy coating involved in the present application can contain unavoidable impurities introduced during the preparation process. The "unavoidable impurities" are not intentionally added impurities, and the main reason for their existence is that they are unintentionally brought in during the preparation process. Non-limiting examples of "unavoidable impurities" include C, O and other elements present in the air, which can also come from the composition of raw materials or equipment. The atomic content of "unavoidable impurities" in the alloy material or alloy coating is usually trace or micro, which can be generally ignored, such as less than 0.01% atomic content. Taking the technical solution of "the Cr-Ti-N alloy coating is a Cr-Ti-N ternary alloy material composed of Cr element, Ti element and N element" as an example, in theory, the Cr-Ti-N alloy coating is composed of Cr, Ti and N elements, but trace or micro amounts of other elements such as C, O and H can be introduced in addition to Cr, Ti and N elements during the preparation process.

[0272] In the applications provided herein, a Cr-Ti-N alloy coating can be present on a coated article and serve as at least a portion of an electrically conductive coating.

[0273] In some embodiments, a coated article includes a substrate and the aforementioned Cr-Ti-N alloy coating; wherein the Cr-Ti-N alloy coating is present on at least a portion of a surface of the substrate.

[0274] In some embodiments, a coated article includes a substrate and the aforementioned Cr-Ti-N alloy coating; wherein the Cr-Ti-N alloy coating is present on at least one side of the substrate. The Cr-Ti-N alloy coating can be present on a single side or on both sides of the substrate.

[0275] The target Cr-Ti-N alloy coating can be present on a coated article and serve as an electrically conductive coating. The Cr-Ti-N alloy coating can serve as a surface of the coated article (i.e., directly as an electrically conductive coating) or can serve as a surface on which a new electrically conductive coating can be formed (i.e., the Cr-Ti-N alloy coating serves as a formation surface adjacent to the new electrically conductive coating), which facilitates the new electrically conductive coating to grow more densely.

[0276] The target Cr-Ti-N alloy coating can serve as an electrically conductive coating on a variety of commonly used substrates.

[0277] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be any of an alloy, a pure metal, and an inorganic non-metallic material. Without limitation, the alloy can be one or more of a nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based, and zinc-based alloy. Without limitation, the pure metal can be any of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium. Without limitation, the inorganic non-metallic material can include one or more of a ceramic and a glass. Without limitation, the inorganic non-metallic material can include a silicon wafer.

[0278] In the present application, unless otherwise specified, the “substrate in combination with the Cr-Ti-N alloy coating” can serve as a formation surface in direct contact with the Cr-Ti-N alloy coating. The substrate in combination with the Cr-Ti-N alloy coating can be provided by at least a portion of a surface of a substrate of a coated article or by a transition layer between the substrate and the Cr-Ti-N alloy coating.

[0279] The target Cr-Ti-N alloy coating can serve as an electrically conductive coating based on a variety of substrates. The substrate that provides a formation surface for the Cr-Ti-N coating can include, but is not limited to, an alloy (e.g., an aluminum alloy), a pure metal, an inorganic non-metallic material (e.g., a silicon wafer, a ceramic, a glass), and the like.

[0280] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be a light alloy, a stainless steel alloy, or a silicon-based material. Without limitation, the light alloy can include one or more of a titanium alloy, an aluminum alloy, and a magnesium alloy. Without limitation, the silicon-based material can be a silicon wafer or a silicon-containing compound, further, the silicon-containing compound can include, but is not limited to, one or more of a silicon oxide, a silicon-carbon composite, a silicon-nitrogen composite, and the like.

[0281] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be an aluminum alloy, a silicon-based material, or a stainless steel.

[0282] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be a light alloy. Without limitation, the light alloy can include one or more of a titanium alloy, an aluminum alloy, and a magnesium alloy.

[0283] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be an aluminum alloy.

[0284] When the Cr-Ti-N alloy coating is combined with the surface of an aluminum-based substrate (e.g., a titanium alloy), not only can the corrosion resistance and hardness of the surface of the aluminum alloy be enhanced, thereby improving the protection capability. In addition, because the Cr-Ti-N alloy coating contains a certain amount of Ti element, the coefficient of thermal expansion of the Cr-Ti-N alloy coating relative to the aluminum-based substrate (e.g., a titanium alloy) is close, thereby enabling excellent bonding force between the Cr-Ti-N alloy coating and the aluminum-based substrate (e.g., a titanium alloy). In addition, titanium is abundant in nature and has a low manufacturing cost.

[0285] The material of the rest of the substrate, except for the part of the substrate in combination with the Cr-Ti-N alloy coating, can be the same or different. In some embodiments, the substrate can be any one of an alloy, a single-element metal, and an inorganic non-metallic material.

[0286] In some embodiments, the substrate is an aluminum alloy or a silicon wafer.

[0287] To test the performance of the Cr-Ti-N alloy coating, the substrate can also use a material other than aluminum and silicon, for example, a stainless steel can be used to provide a substrate for testing hardness, salt spray corrosion resistance, color value, and the like. At this time, the surface material of the substrate is one of a stainless steel alloy. Further, the stainless steel alloy can be any one of an austenitic stainless steel, a ferritic stainless steel, a martensitic stainless steel, and the like.

[0288] In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be a stainless steel alloy. Without limitation, the stainless steel alloy can be any one of an austenitic stainless steel, a ferritic stainless steel, a martensitic stainless steel, and the like. In some embodiments, the substrate in combination with the Cr-Ti-N alloy coating can be a stainless steel alloy. Without limitation, the stainless steel alloy can be any one of an austenitic stainless steel, a ferritic stainless steel, a martensitic stainless steel, and the like.

[0289] According to the difference of the main component of the substrate, the coated product can be any one of light alloy product, stainless steel product, single-element metal, inorganic non-metallic substrate product (such as ceramic substrate product, silicon substrate product, glass substrate product) and the like, which means that the main component of the substrate is light alloy, stainless steel, single-element metal and the like respectively. Non-limitingly, the light alloy product can include but is not limited to aluminum alloy product, titanium alloy product, magnesium alloy product and the like. Non-limitingly, the stainless steel product can include but is not limited to austenitic stainless steel, ferritic stainless steel, martensitic stainless steel. Non-limitingly, the single-element metal product can be but is not limited to any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium, further such as any one of copper, aluminum, iron, silver and chromium.

[0290] In some embodiments, in the coated product, the Cr-Ti-N alloy coating layer can be in direct contact with the substrate (in which case there is no transition layer) or provided with a transition layer; further, the transition layer can be a single-layer structure or a multi-layer structure (i.e. one or more structural layers can be formed between the Cr-Ti-N alloy coating layer and the substrate).

[0291] In some embodiments, the coated product further comprises a surface layer on the side of the Cr-Ti-N alloy coating layer away from the substrate, in which case the surface layer can be a single-layer structure or a multi-layer structure (i.e. one or more structural layers can be further formed on the Cr-Ti-N alloy coating layer). The target Cr-Ti-N alloy coating layer can be used as the surface film layer of the coated product, having both decorative and protective effects. The target Cr-Ti-N alloy coating layer can also be located between the substrate and the surface layer, having excellent protective effect, and can be better resistant to corrosion and scratches.

[0292] In the present application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably, both referring to the structural layer between the substrate and the Cr-Ti-N alloy coating layer in the coated product, having transition properties, which can be a single-layer structure or a multi-layer structure.

[0293] In the present application, unless otherwise specified, "surface layer" refers to the structural layer on the side of the Cr-Ti-N alloy coating layer away from the substrate and on the surface of the product, which can be a single-layer structure or a multi-layer structure.

[0294] In the application provided in the present application, the target Cr-Ti-N alloy coating layer can be located on one side or both sides of the substrate.

[0295] In Figure 1 In one embodiment shown in the figure, the coated product comprises a substrate 100 and a Cr-Ti-N alloy coating layer 300 located on one side of the substrate. It can be understood that the Cr-Ti-N alloy coating layer 300 can also be located on both sides of the substrate 100.

[0296] In some embodiments, the coated article comprises a substrate and a Cr-Ti-N alloy coating layer on one side of the substrate. It is understood that the Cr-Ti-N alloy coating layer can also be on both sides of the substrate.

[0297] In some embodiments, the Cr-Ti-N alloy coating layer is in direct contact with the substrate (in which case there is no transition layer).

[0298] In some embodiments, a transition layer is provided between the Cr-Ti-N alloy coating layer and the substrate.

[0299] In some embodiments, the Cr-Ti-N alloy coating layer is on the surface of the coated article.

[0300] In some embodiments, the Cr-Ti-N alloy coating layer is on the surface of the coated article.

[0301] Figure 2 Provided are structural diagrams of the coated articles in several embodiments of the present application; (A) includes a substrate 100, a transition layer 200, and a Cr-Ti-N alloy coating layer 300; (B) includes a substrate 100, a transition layer 200, a Cr-Ti-N alloy coating layer 300, and a surface layer 400; (C) includes a substrate 100, a Cr-Ti-N alloy coating layer 300, and a surface layer 400.

[0302] In some embodiments, the coated article comprises a substrate, a transition layer, and a Cr-Ti-N alloy coating layer.

[0303] In some embodiments, the coated article comprises a substrate, a transition layer, a Cr-Ti-N alloy coating layer, and a surface layer.

[0304] In some embodiments, the coated article comprises a substrate, a Cr-Ti-N alloy coating layer, and a surface layer.

[0305] In the coated article, the position of the Cr-Ti-N alloy coating layer can be flexibly set, which can be in direct contact with the substrate or not, can be a surface film layer or an intermediate film layer between the substrate and other surface film layers; when it is an intermediate film layer, other film layers (such as the aforementioned surface layer) can be further provided on the outside of the Cr-Ti-N alloy coating layer, so that the target Cr-Ti-N alloy coating layer is not a surface film layer. Different coating layer position settings can all provide good electrical conductivity, and can also provide excellent corrosion resistance and high hardness characteristics.

[0306] When the target Cr-Ti-N alloy coating layer is on the surface of the coated article, the highly dense structure of the Cr-Ti-N alloy coating layer can provide the coated article with a surface having good electrical conductivity.

[0307] When the target Cr-Ti-N alloy coating is located on the surface of the coated article, the highly dense structure of the Cr-Ti-N alloy coating can also provide better coating reflection characteristics, thereby providing the coated article with a surface having high brightness.

[0308] In the present application, the thickness of the Cr-Ti-N alloy coating can be denoted as D2.

[0309] In some embodiments, 50 nm≤D2≤6 μm.

[0310] In some embodiments, D2 is a value selected from the group consisting of d min and d max , which can be expressed as: d min ≤D2≤d max . In some embodiments, d min may be selected from the group consisting of 50 nm-0.9 μm, and d max may be selected from the group consisting of 2.7 μm-6 μm. In some embodiments, d min is 50 nm, 0.3 μm, 0.5 μm, 0.7 μm, 0.8 μm or 0.9 μm. In some embodiments, d max is 2.7 μm, 3 μm, 4 μm, 5 μm or 6 μm. d min and d max may be combined in any suitable manner.

[0311] Without limitation, d min may also be any one of the following thicknesses, or a thickness selected from the interval consisting of any two of the following thicknesses: 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 100 nm, 0.1 μm, 0.2 μm, 300 nm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, etc. Without limitation, d max may also be any one of the following thicknesses, or a thickness selected from the interval consisting of any two of the following thicknesses: 2.7 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.6 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, etc.

[0312] Without limitation, D2 can also be any one of the following thicknesses, or selected from the interval consisting of any two of the following thicknesses: 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 100 nm, 0.1 μm, 0.2 μm, 300 nm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.46 μm, 1.5 μm, 1.52 μm, 1.6 μm, 1.8 μm, 1.87 μm, 2 μm, 2.0 μm, 2.2 μm, 2.5 μm, 2.7 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, etc. For example, D2 can be 25 nm to 6 μm, 30 nm to 6 μm, 40 nm to 6 μm, 50 nm to 6 μm, 0.3 μm to 6.0 μm, 0.3 μm to 3.0 μm, 0.3 μm to 2.5 μm, 0.3 μm to 2.0 μm, 0.5 μm to 6.0 μm, 0.5 μm to 3.0 μm, 0.5 μm to 2.5 μm, 0.5 μm to 2.0 μm, 0.7 μm to 2.0 μm, 0.8 μm to 6.0 μm, 0.8 μm to 3.0 μm, 0.8 μm to 2.5 μm, 0.9 μm to 6.0 μm, 0.9 μm to 3.0 μm, 0.9 μm to 2.5 μm, 1.0 μm to 2.5 μm, 1.0 μm to 2.0 μm, etc.

[0313] By controlling the Cr-Ti-N alloy coating to have a suitable thickness, it is beneficial to obtain a more suitable electrical conductivity, and also to better take advantage of the corrosion resistance and / or high hardness characteristics of the alloy protective coating. The thicker the Cr-Ti-N alloy coating, the more beneficial it is to improve the corrosion resistance and / or hardness of the alloy coating. The Cr-Ti-N alloy coating can have good electrical conductivity, high corrosion resistance and high hardness characteristics at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle and significantly reducing the cost. Compared with the traditional Ti-containing alloy coating, the aforementioned Cr-Ti-N alloy coating can provide a more compact structure, and can achieve better corrosion resistance and high hardness characteristics at the same thickness.

[0314] In some embodiments, the thickness of the Cr-Ti-N alloy coating is 10 nm to 6 μm.

[0315] In some embodiments, the thickness of the Cr-Ti-N alloy coating is 25 nm to 6 μm.

[0316] In some embodiments, the thickness of the Cr-Ti-N alloy coating is 1 μm to 2.5 μm.

[0317] In some embodiments, the thickness of the Cr-Ti-N alloy coating is 1-2 μm.

[0318] In addition, when forming a Cr-Ti-N alloy coating with a relatively thin thickness on a substrate, the formed plated product can exhibit a silver-white metallic color close to the color of the substrate metal, and can achieve a decorative effect of being beautiful and not changing the color of the substrate.

[0319] In some embodiments, the aforementioned application can be implemented by the following method: using a vapor deposition technique to deposit the constituent elements of the target Cr-Ti-N alloy coating on at least a portion of the surface of the substrate according to a preset atomic ratio to form the target Cr-Ti-N alloy coating. It can be understood that the constituent elements of the target Cr-Ti-N alloy coating at least include Cr elements, Ti elements, and N elements. The implementation of the Cr-Ti-N alloy coating for the conductive coating in the plated product can use green and environmentally friendly manufacturing technology, and has the advantages of simple method, easy operation, quantifiable, high efficiency, and good repeatability, and is suitable for industrial application. The substrate surface combined with the Cr-Ti-N alloy coating can be, but is not limited to, a stainless steel, an aluminum alloy, or a silicon-based material surface.

[0320] In the present application, in "on the surface" in "depositing component X on at least a portion of the surface of the substrate", component X can be directly deposited on at least a portion of the surface of the substrate, or can be deposited after forming a transition layer on at least a portion of the surface of the substrate.

[0321] In some embodiments, the vapor deposition technique is a physical vapor deposition technique. Further, the physical vapor deposition technique can be implemented by one or more of the following ways: vacuum evaporation, sputtering plating, arc plasma plating, ion plating, and molecular beam epitaxy.

[0322] In one embodiment, the physical vapor deposition is realized by magnetron sputtering plating.

[0323] In some embodiments, the constituent elements of the target Cr-Ti-N alloy coating are deposited on at least a portion of the surface of the substrate according to a preset atomic ratio by using a sputtering plating (such as magnetron sputtering plating) technique.

[0324] In some embodiments, reference can be made to the device shown in Figure 3 Figure 3 ​The device shown includes a vacuum chamber 1, a sample stage 2, a direct current anode 3, a chromium target 4, and a titanium target 5; wherein the chromium target 4 is a chromium target for radio frequency assisted direct current cathode electric conduction, and the titanium target 5 is a titanium target for radio frequency assisted direct current cathode electric conduction. The drawing is not drawn in a 1:1 ratio, and the relative sizes of the elements are only drawn in the drawing by way of example for the purpose of understanding the present application, but are not necessarily drawn in true proportion, and the proportion in the drawing does not constitute a limitation on the present application. The Cr-Ti-N alloy coating can be formed by forming a reactive sputtering with N2-containing gas (such as Ar / N2 mixed gas) in the vacuum chamber 1.

[0325] In some embodiments, the implementation method for the foregoing application is exemplified by a sputtering coating method (such as a magnetron sputtering coating method), which includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen-containing gas, using one or more targets including chromium and titanium to sputter deposit the constituent elements of the target Cr-Ti-N alloy coating on at least a part of the surface of the substrate to form the target Cr-Ti-N alloy coating. The nitrogen-containing gas can be, but is not limited to, nitrogen gas, and in this case, the gas amount ratio of argon and nitrogen in the mixed gas can be (2-6):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, etc. When nitrogen gas is selected as the nitrogen-containing gas and the content of nitrogen gas is controlled, the performance of the Cr-Ti-N alloy coating can be further adjusted.

[0326] The target material can include one or more of a chromium target, a titanium target, and an alloy target. The alloy target includes at least two metal elements in the Cr-Ti-N alloy coating. In some preferred examples, the atomic ratio of the metal elements in the alloy target is the same as or close to the atomic ratio of the corresponding metal elements in the target Cr-Ti-N alloy coating. In some embodiments, the alloy target is a chromium-titanium-based alloy target, wherein the chromium-titanium-based alloy target includes at least chromium and titanium, such as a CrTi alloy target, a CrTiN alloy target, etc. In some examples, the atomic ratio of Cr and Ti in the chromium-titanium-based alloy target is (45% to 55%):(55% to 45%), such as 50%:50%. In some embodiments, the alloy target includes all metal elements in the target Cr-Ti-N alloy coating. Examples of the alloy target can be referred to in Example 13A below.

[0327] In the present application, unless otherwise specified, the "chromium-titanium-based alloy target" includes at least chromium and titanium, and can or can not include other elements. When including other elements, it can be understood that the chemical composition in the target material should generally be within the range of a preset chemical formula (such as CrTiN, CrTi, CrTiAl, CrTiAlN, etc.). For example, the chromium-titanium-based alloy target can be a chromium-titanium-nitrogen alloy target (i.e., a CrTiN alloy target) composed of chromium, titanium, and nitrogen. x Ti y N z M a ) of the target material. For example, the chromium-titanium-based alloy target can be a chromium-titanium-nitrogen alloy target (i.e., a CrTiN alloy target) composed of chromium, titanium, and nitrogen.

[0328] In some embodiments, a chromium-titanium alloy target composed essentially of Cr and Ti is used.

[0329] In some embodiments, a chromium-titanium alloy target is used, which is installed Figure 3 at the position of the original chromium target 4, replacing Figure 3 the original chromium target 4.

[0330] In some embodiments, the method for implementing the aforementioned application is exemplified by a sputter coating (e.g., a magnetron sputter coating) method, which comprises the following steps: using a chromium target and a titanium target or using a chromium-titanium alloy target (i.e., a CrTi alloy target), under the condition of introducing a mixed gas containing argon and a nitrogen-containing gas, sputter depositing the constituent elements of the target Cr-Ti-N alloy coating layer on at least a portion of the surface of the substrate, thereby forming the target Cr-Ti-N alloy coating layer.

[0331] In some embodiments, the step of "sputter depositing the constituent elements of the target Cr-Ti-N alloy coating layer on at least a portion of the surface of the substrate" is preceded by the following step: performing a cleaning treatment on the substrate. The method for performing the cleaning treatment on the substrate can use conventional cleaning methods in the technical field (including but not limited to the field of decorative plating).

[0332] In some embodiments, the cleaning treatment on the substrate comprises the following steps: placing the substrate in water for ultrasonic cleaning for 10 to 15 minutes, vacuum drying the cleaned substrate for 15 to 20 minutes, and placing the dried substrate on a sample stage of a sputter coating (e.g., a magnetron sputter coating) device. The sample stage can be a rotatable sample stage.

[0333] In one embodiment, the cleaning treatment on the substrate comprises the following steps: placing the substrate in deionized water (DI water) for ultrasonic cleaning for 10 to 15 minutes, placing the cleaned substrate in a vacuum oven for baking for 15 to 20 minutes, and placing the baked substrate on a rotatable sample stage in a vacuum chamber.

[0334] In some embodiments, after the step of "performing a cleaning treatment on the substrate", the step of "sputter depositing the constituent elements of the target Cr-Ti-N alloy coating layer on at least a portion of the surface of the substrate" is preceded by the following step: forming a transition film layer (which can serve as a buffer film) on at least a portion of the surface of the cleaned substrate, for example, by depositing the constituent elements of the transition film layer on at least a portion of the surface of the cleaned substrate.

[0335] In some embodiments, after forming the target Cr-Ti-N alloy coating layer on one side of the substrate, a surface film layer can also be deposited, which can be a single-layer structure or a multi-layer structure.

[0336] In some embodiments, the sputtering deposition temperature is 30°C to 330°C, such as 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., or it can be a range consisting of any two of the aforementioned temperatures.

[0337] In some embodiments, the total pressure of the mixed gas containing argon and nitrogen is 0.3 Pa to 1.2 Pa, for example, 0.3 Pa, 0.5 Pa, 0.8 Pa, 1.0 Pa, 1.2 Pa, etc., or it can be a range consisting of any two of the aforementioned pressures.

[0338] 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.

[0339] In some embodiments, the target material includes a chromium target with a power density of 1.3 W / cm². 2 ~6.7W / cm 2 1.3W / cm can be selected. 2 ~6.0W / cm 2 It can also be any of the following values ​​or an interval selected from any two of the following values: 1.3W / cm 2 1.5W / cm 2 2.0W / cm 2 2.5W / cm 2 2.8W / cm 2 3W / cm 2 3.5W / cm 2 4W / cm 2 5W / cm 2 5.5W / cm 2 6W / cm 2 6.3W / cm 2 6.5W / cm 2 6.7W / cm 2 wait.

[0340] In some embodiments, the target material includes a titanium target with a power density of 0.5 W / cm². 2 ~8.0W / cm 2 1.5W / cm can be selected. 2 ~8.0W / cm 2 It can also be any of the following values ​​or an interval selected from any two of the following values: 0.5W / cm 2 1W / cm 2 1.5W / cm 2 1.8W / cm 22.0 W / cm 2 2.5 W / cm 2 2.8 W / cm 2 3 W / cm 2 3.5 W / cm 2 3.8 W / cm 2 4 W / cm 2 4.5 W / cm 2 5 W / cm 2 6 W / cm 2 7 W / cm 2 8 W / cm 2 8.0 W / cm 2 and the like.

[0341] In some embodiments, the target material can include a combination of a chromium target and a titanium target.

[0342] In some embodiments, the target material includes an alloy target including at least two metal elements in a target Cr-Ti-N alloy coating; optionally, the target material includes a chromium-titanium-based alloy target having a power density of 4 W / cm 2 ~ 6 W / cm 2 .

[0343] In some embodiments, the target material includes a chromium-titanium alloy target having a power density of 5 W / cm 2 .

[0344] In some embodiments, the target material uses a chromium-titanium alloy target having a power density of 4 W / cm 2 ~ 6 W / cm 2 , optionally 5 W / cm 2 .

[0345] In some embodiments, the bias voltage of the substrate is -150 V to -20 V, for example, -150 V, -120 V, -100 V, -90 V, -80 V, -60 V, -50 V, -40 V, -30 V, -20 V, and the like, and can also be an interval formed by any two of the foregoing bias voltages.

[0346] In some embodiments, the gas flow rate of the nitrogen-containing gas can be 5 sccm to 42 sccm, for example, 5 sccm, 10 sccm, 20 sccm, 25 sccm, 30 sccm, 40 sccm, 42 sccm, and the like, and can also be an interval formed by any two of the foregoing gas flow rates. Further, the nitrogen-containing gas can be nitrogen.

[0347] 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., or it can be a range consisting of any two of the aforementioned time durations. The thickness of the target Cr-Ti-N alloy coating can be controlled by adjusting the deposition time; the longer the deposition time, the greater the thickness of the Cr-Ti-N alloy coating.

[0348] In some embodiments, the deposition time is 120 min and the thickness of the Cr-Ti-N alloy coating is 1.0 μm.

[0349] In some embodiments, the nitrogen-containing gas is nitrogen, and the ratio of argon to nitrogen in the mixed gas is (2-6):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, etc. Selecting nitrogen as the nitrogen-containing gas and controlling its content allows for further adjustment of the performance of the target Cr-Ti-N alloy coating.

[0350] 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-Ti-N alloy coating.

[0351] 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 alloy coating of this application and improving its performance.

[0352] In some embodiments, "depositing the constituent elements of the target Cr-Ti-N alloy coating onto at least a portion of the substrate surface according to a preset atomic ratio using sputtering deposition (such as magnetron sputtering) technology" 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 0.3 Pa to 1.2 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 1.3 W / cm². 2 -6.7W / cm 2 The power density of titanium target 5 was set to 0.5 W / cm². 2 -7.9W / cm 2 A Cr-Ti-N alloy coating is deposited on at least a portion of the surface of the cleaned substrate; furthermore, Cr-Ti-N alloy coatings of different thicknesses can be obtained by controlling the film formation time.

[0353] In a second aspect of the present application, there is provided a use of a Cr-Ti-N alloy material as defined in the first aspect of the present application, and as further described in the embodiments and examples below, as an electrically conductive coating material in a coated article. The Cr-Ti-N alloy material has a suitable atomic size mismatch and a special atomic ratio, and can be "highly disordered and fully dense" with a high degree of random mixing, to form a Cr-Ti-N alloy coating in the coated article as described above.

[0354] In the present application, unless otherwise specified, "an electrically conductive coating material in a coated article" refers to a material contained in an electrically conductive coating in a coated article. In some embodiments, at least a portion of the electrically conductive coating in the coated article is composed of a Cr-Ti-N alloy material.

[0355] In some embodiments, the Cr-Ti-N alloy material satisfies the following two characteristics (the values or value ranges below can also be consistent with the relevant values or value ranges of the Cr-Ti-N alloy coating in the first aspect of the present application):

[0356] The X-ray diffraction pattern of the Cr-Ti-N alloy material has a peak in the range of diffraction angle 2θ(°) of 34°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥2°;

[0357] The selected area electron diffraction pattern of the Cr-Ti-N alloy material has a diffraction peak in the range of (further as ) and (further as ) satisfies Optionally Further optionally Still further optionally

[0358] Further, the XRD test results and the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy material can also refer to the description of the X-ray diffraction pattern and the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy coating in the present application, and the corresponding optional and preferred modes can also be applicable to the Cr-Ti-N alloy material.

[0359] Some embodiments are provided below.

[0360] The embodiments of the present application will be described in detail below with some examples. It should be understood that these examples are only used to illustrate but not to limit the scope of the present application. The experimental methods in the following examples without specified conditions, the priority is given to the guidance in the present application, but also can be in accordance with the experimental manual or conventional conditions in the art, but also in accordance with the manufacturer's recommended conditions, or reference to the known experimental methods in the art.

[0361] In the following examples, the amount of raw material components involved in the parameter, such as no special mention, there may be a slight deviation in the range of weighing accuracy. Involving temperature and time parameters, allow the instrument test accuracy or operation accuracy caused by acceptable deviation.

[0362] In the following examples, some Cr-Ti-N alloy coating is Cr-Ti-N alloy film.

[0363] Test method:

[0364] 1. Square resistance test method

[0365] Sample to be tested: the sample to be tested aluminum alloy or silicon wafer as the substrate.

[0366] Instrument: MODEL: ST-21 square resistance tester produced by Guangzhou Four Probe Technology.

[0367] Test parameters: range selection 2000.0Ω / sq, take the average value after testing 5 matrix points of each sample.

[0368] 2. Salt spray corrosion resistance test of alloy coating

[0369] When the salt spray corrosion resistance test of alloy coating is carried out, the sample to be tested uses the substrate suitable for practical application, and the improvement degree of the corrosion resistance of the alloy coating to the substrate is detected. The surface material of the "substrate suitable for practical application" can include but is not limited to: aluminum alloy, titanium alloy, stainless steel.

[0370] ASTM B117 salt spray test standard is used, the pH value of the solution is 6.5-7.2, and the chemical composition of the solution is: sodium chloride (NaCl), deionized water and sodium hydroxide (NaOH).

[0371] 12 hours can be used as a subcycle of the salt spray corrosion resistance test.

[0372] The test cycle of the alloy coating prepared by the substrate of different materials can be different, for example:

[0373] The test cycle of the aluminum alloy containing substrate sample is 48h or 24h;

[0374] The test cycle of the stainless steel substrate sample is 144h or 96h;

[0375] The test period of the copper sheet substrate sample was 8h.

[0376] The standard for passing (OK) the salt spray corrosion resistance test was that after the sample was tested, there was no corrosion, no color difference, and no rust on the appearance. For example, "pass 48H" indicated a 48h salt spray corrosion resistance test. "Pass 72H" indicated a 72h salt spray corrosion resistance test. "Pass 144H" indicated a 144h salt spray corrosion resistance test. "Pass 8H" indicated an 8h salt spray corrosion resistance test.

[0377] The standard for failing (NG) the salt spray corrosion resistance test was that after the sample was tested, there was corrosion, color difference, or rust on the appearance. For example, "fail 8H" indicated an 8h salt spray corrosion resistance test. "Fail 2H" indicated a 12h salt spray corrosion resistance test. "Fail 24H" indicated a 24h salt spray corrosion resistance test. "Protection duration <8h" indicated that corrosion occurred when the test time was less than 8h. "Protection duration <12h" indicated that corrosion occurred when the test time was less than 12h.

[0378] 3. Hardness test of alloy coating

[0379] When testing the hardness of the alloy coating, the sample to be tested used a substrate that could be suitable for actual application,

[0380] The surface material of the "substrate that can be suitable for actual application" can include but is not limited to: aluminum alloy, titanium alloy, stainless steel, copper sheet.

[0381] When testing the hardness of the alloy coating, aluminum alloy and stainless steel were used as the substrate, and the alloy coating was deposited on the aluminum alloy and stainless steel using preset preparation parameters to obtain the sample to be tested, which was used to test the hardness of the alloy coating. This is mainly because during the nanoindentation test, the probe pierces the sample to be tested, forming a strong pressure. At this time, the substrate is required to have a certain toughness. If a brittle silicon wafer is used, cracking may occur during the test, resulting in inaccurate test results. Alloy materials have excellent toughness and are more suitable as the measured substrate for nanoindentation testing. At the same time, using alloy materials as the substrate to measure nano-hardness is more universal in the field of coating and nano-hardness parameter characterization.

[0382] The hardness of each film or coating was tested using a nanoindenter model NHT3 produced by Anton-Paar of Austria, which was configured with a tetrahedral Berkvich indenter. The indentation depth was set to 100nm, and the load changed with the indentation depth. After testing 5 matrix points for each sample, the average value was taken.

[0383] 4. Colorimetric value test of alloy coating

[0384] When testing the colorimetric value of the alloy coating, the sample to be tested uses a substrate suitable for practical application to detect the improvement degree of the alloy coating on the substrate in terms of compactness and other properties. The surface material of the "substrate suitable for practical application" can include but is not limited to: aluminum alloy, stainless steel.

[0385] The L value, a value and b value of the sample are tested by using a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan, the light receiving system selects F2 light source, and the average value is taken after testing 6 matrix points of each sample.

[0386] Among them, the L value represents the brightness value, the a value represents the red or green chromaticity value, and the b value represents the yellow or blue chromaticity value. The a value represents the red-green color of the object, the positive value represents the red chromaticity value, and the negative value represents the green chromaticity value. The b value represents the yellow-blue color of the object, the positive value represents the yellow chromaticity value, and the negative value represents the blue chromaticity value.

[0387] The larger the L value, the higher the brightness, indicating that the coating surface is more compact. The mechanism is as follows: the spectrophotometer is incident light on the surface of the sample to be tested, forming a reflection, and a reflectivity curve can be obtained. The amplitude of the curve can reflect the density of the material, which can be characterized by the L value, and the higher the compactness of the same material, the larger the L value displayed.

[0388] 5. Morphology and composition test and analysis of alloy coating

[0389] The sample to be tested uses a silicon wafer as the substrate.

[0390] Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) test methods are used.

[0391] Morphology analysis: a scanning electron microscope produced by Hitachi Company with the model Regulus 8230 is used.

[0392] Composition analysis: an X-ray energy dispersive spectrometer (EDX) attached to the scanning electron microscope produced by Hitachi Company with the model Regulus 8230 is used, and the relative intensity of all elements is corrected by ZAF method.

[0393] Test parameters: the acceleration voltage of the electron is 15 kilovolts (kV), the beam current is 10 microamperes (μA), the magnification of the sample is 200 times, and the average value is taken by testing 10 points of each sample.

[0394] 6. X-ray diffraction (XRD) test of alloy coating

[0395] When performing XRD test of the alloy coating, a silicon wafer is used as the substrate.

[0396] 6.1. Calculate the half-height width value of the diffraction peak in the XRD spectrum

[0397] The XRD diffractometer is Bruker D8 Advance XRD diffractometer made in Germany, in θ-2θ mode, Cu target Kα ray, wavelength λ is 0.15406 nm, X-ray tube is controlled at 40 kV and 40 mA, scanning range is 20°-80°, and the step is 0.01° for accurate scanning measurement.

[0398] The step of obtaining the half-height width value is: first, the diffraction peak is corrected, including: smoothing, removing the background, removing Kα2 line, removing instrument broadening, etc., after the diffraction peak is fitted by Pseudo-Voigt function, the half-height width value of the diffraction peak is obtained.

[0399] The EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) is used to process the spectrum data: first, the ruler is corrected, then the center of the diffraction ring transmission spot is determined, and then it is converted into XRD spectrum (wherein the electron wavelength is 0.00251 nm, and the X-ray wavelength is 0.154 nm; after the diffraction peak is deducted from the straight background, and then fitted by Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0400] 6.2. Determine whether the XRD pattern of the alloy coating forms a broad peak

[0401] The method for determining whether there is a broad peak in the XRD diffraction pattern in the diffraction angle 2θ(°) range of 34°-50°: in the XRD spectrum, if the half-height width value of the 2θ(°) diffraction peak is ≥1.6°, it is determined as a broad peak; if the half-height width value of the 2θ(°) diffraction peak is <1.6°, it is determined as a sharp peak.

[0402] For a specified 2θ(°) position, it can be any one of the three states of no peak, sharp peak or broad peak.

[0403] 7. Transmission electron microscopy (TEM) test

[0404] When performing TEM test of the alloy coating, silicon wafer is used as the substrate.

[0405] 7.1. The half-height width data in the diffraction ring of the TEM diffraction pattern is obtained by the following method:

[0406] TEM sample preparation: The sample was thinned by using the Helios 5CX Focused Ion Beam (FIB) from Themo Fisher Limited, and the electron transparent TEM observable planar sample was obtained.

[0407] SAED image acquisition: The selected area electron diffraction (SAED) pattern of the sample was obtained by using the Talos F200x Transmission Electron Microscope (TEM) from Themo Fisher Limited, with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0408] Radial intensity profile acquisition: The SAED pattern data obtained above was processed by using the EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney): first, the ruler correction was performed, then the center of the diffraction ring transmission spot was determined, and finally the radial intensity profile was converted (wherein the electron wavelength was 0.00251 nanometer and the X-ray wavelength was 0.154 nanometer), with the characteristic atomic spacing as the horizontal coordinate and the diffraction intensity as the vertical coordinate.

[0409] The step of obtaining the half-height width value was as follows: after the diffraction peak was subtracted from the straight line background, the Voigt function was used for fitting, and then the half-height width value of the corresponding diffraction peak was obtained.

[0410] 7.2. Method for judging whether the radial intensity profile of the TEM selected area electron diffraction pattern is a wide peak within the range of 0-50 nm-1 If the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is greater than 50 nm-1, it is judged to be a wide peak; if the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is less than 0 nm-1, it is judged to be a sharp peak. For a specific characteristic atomic spacing, it can be any one of the three states of no peak, sharp peak or wide peak.

[0411] 8. Bonding force test method

[0412] ​The bonding force is characterized by the crosshatch test, which can be performed according to or with reference to the provisions in the standard GB / T 9286-2021. The detailed steps are as follows: 10x10 1mmx1mm small squares are drawn on the plating film area of the sample surface with a manual single-edge cutting knife, and 3M610 adhesive tape is attached to the drawn square area. Within 5 minutes after the adhesive tape is attached, the end of the adhesive tape is held in the air, and the adhesive tape is smoothly torn off at an angle of nearly 60° within 0.5s to 1.0s. The grade is determined according to the provisions in the standard GB / T 9286-2021, wherein grade 0 (marked as "OK") is passed, indicating that the alloy coating has excellent bonding force, and grades 1-5 (marked as "NG") are failed.

[0413] The above test results can be referred to in the following description and Table 2.

[0414] In the following examples, DI water refers to deionized water.

[0415] In the following examples 1-13 and comparative examples 1-13, the stainless steel sheet, titanium alloy sheet, aluminum alloy sheet and silicon sheet involved, unless otherwise specified, are of the same material.

[0416] In the following examples, the target material is sputtered by a radio frequency assisted direct current sputtering method.

[0417] In the following examples, in the XRD pattern and the SAED-radial intensity profile, "only one wide peak" refers to only one characteristic peak, and the peak is a wide peak, unless otherwise specified.

[0418] The preparation parameters and part of the structure characterization parameters of the following examples and comparative examples can be referred to in Table 1.

[0419] Example 1.

[0420] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 90.0 Ti 5.0 N 5.0 .

[0421] Pre-treatment of the substrate: the titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with an aspect ratio of 50mmx50mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

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

[0423] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use a radio frequency assisted direct current power supply to introduce electricity to the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 7 sccm, set the gas flow ratio to keep Ar:N2 at 6:1, keep the pressure in the furnace at 0.5 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 9.1 W / cm 2 , set the power density of the Ti target to 0.5 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film have a thickness of 900 nm.

[0424] Aluminum alloy sheets and silicon sheets were used as substrates for the deposition of conductive coatings for the sheet resistance test;

[0425] The samples using silicon sheets as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM testing;

[0426] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and colorimetric value testing;

[0427] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as substrates for the salt spray corrosion resistance test.

[0428] The sheet resistance value of the sample prepared using an aluminum alloy as the substrate was 0 Ω / sq, indicating good conductivity, and the sheet resistance value of the sample prepared using a silicon sheet as the substrate was 6.0 Ω / sq.

[0429] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 90.0 Ti 5.0 N 5.0 .

[0430] SEM cross-sectional characterization of the test sample showed that the cross-sectional morphology could be seen in Figure 4 , and the XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile could be seen in Figure 5 . The SEM test results showed that the Cr-Ti-N alloy coating had a dense structure and no through-column joints were observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° in the XRD diffraction pattern was all ≥2.0°, there was only one wide peak with a half-height width of 2.99° in the range of 34°-50°, and there was only one wide peak in the radial intensity profile of the TEM selected area electron diffraction pattern in the range of , with a half-height width value of

[0431] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 83.47, a: 0.05, and b: 0.99, and the colorimetric value of the stainless steel substrate sample is L: 83.40, a: 0.05, and b: 0.95.

[0432] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 13.6 GPa, and the hardness value of the stainless steel substrate sample is 14.5 GPa.

[0433] The salt spray corrosion resistance results: the titanium alloy substrate sample and the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protection properties.

[0434] Example 2.

[0435] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 75.0 Ti 5.0 N 20.0 .

[0436] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon sheets with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

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

[0438] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 26 sccm, the gas flow ratio of Ar:N2 was maintained at 2:1, the furnace pressure was maintained at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 7.6 W / cm 2 , the power density of the Ti target was set to 0.5 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled by the deposition time to be 1100 nm.

[0439] The sheet resistance test used aluminum alloy sheets and silicon sheets as substrates for depositing conductive coatings.

[0440] The samples using silicon sheets as substrates were subjected to SEM and composition analysis, XRD analysis.

[0441] Stainless steel sheet, aluminum alloy sheet are used for hardness value test and chroma value test.

[0442] Titanium alloy sheet, stainless steel sheet, aluminum alloy sheet are used as the substrate of the sample for salt spray corrosion resistance test.

[0443] The sample prepared with aluminum alloy as the substrate has a square resistance value of 0 Ω / sq, and good conductivity. The sample prepared with silicon sheet as the substrate has a square resistance value of 3.4 Ω / sq.

[0444] Through component analysis, the component of the alloy coating on the surface of the substrate is Cr 75.0 Ti 5.0 N 20.0 .

[0445] SEM cross-section characterization is performed on the test sample. The cross-section morphology can be seen from Figure 6 , and the XRD diffraction pattern can be seen from Figure 7 . The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed. The XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥2.0°, and there is only one wide peak with a half-height width of 2.91° in the range of 34°-50°.

[0446] Chroma value test results: the chroma value of the aluminum alloy substrate sample is L: 81.82, a: 0.35, b: 1.87, and the chroma value of the stainless steel substrate sample is L: 81.97, a: 0.31, b: 1.80.

[0447] Hardness value test results: the hardness value of the aluminum alloy substrate sample is 14.6 GPa, and the hardness value of the stainless steel substrate sample is 16.4 GPa.

[0448] Salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy substrate sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, which has excellent protection characteristics.

[0449] Example 3.

[0450] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 5.0 Ti 79.0 N 16.0 .

[0451] Substrate pretreatment: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with an aspect ratio of 50mm×50mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber is vacuumed to 5×10 -4Pa, heated to 150°C, and kept for 15 minutes.

[0452] Plasma cleaning: Ar gas was introduced to keep the pressure in the furnace at 2.0 Pa, bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 minutes to remove small impurities on the surface of the sample by plasma etching.

[0453] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 22 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.5 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 0.5 W / cm 2 , the power density of the Ti target was set at 8.0 W / cm 2 , and a Cr-Ti-N alloy coating was deposited by controlling the film formation time to make the thickness of the obtained film 2200 nm.

[0454] Aluminum alloy sheets and silicon sheets were used as substrates for the deposition of conductive coatings for sheet resistance testing;

[0455] Silicon sheets were used as substrates for the samples for SEM and composition analysis, XRD analysis and TEM testing;

[0456] Stainless steel sheets and aluminum alloy sheets were used for hardness testing and colorimetric testing;

[0457] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as substrates for the samples for salt spray corrosion resistance testing;

[0458] The sheet resistance value of the sample prepared with aluminum alloy as the substrate was 0 Ω / sq, and the conductivity was good. The sheet resistance value of the sample prepared with a silicon sheet as the substrate was 4.6 Ω / sq.

[0459] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 5.0 Ti 79.0 N 16.0 .

[0460] SEM cross-section characterization was performed on the test sample, and the cross-sectional morphology can be seen in Figure 8 , and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 9The SEM test result shows that the Cr-Ti-N alloy coating structure is dense, and no through column joint is observed; the XRD test result shows that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ(°), and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥2.0°, wherein there is only one wide peak with a half-height width of 5.05° in the range of 34°-50°, the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of 34°-50° of the diffraction angle 2θ(°), and the half-height width value is

[0461] The chroma value test result is that the chroma value of the aluminum alloy substrate sample is L: 76.44, a: 0.58, and b: 5.51, and the chroma value of the stainless steel substrate sample is L: 77.51, a: 0.55, and b: 4.45.

[0462] The hardness value test result is that the hardness value of the aluminum alloy substrate sample is 19.6 GPa, and the hardness value of the stainless steel substrate sample is 16.2 GPa.

[0463] The salt spray corrosion resistance result is that the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection characteristics.

[0464] Example 4.

[0465] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 12.7 Ti 77.9 N 9.4 .

[0466] Substrate pretreatment: the titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50mm×50mm are respectively placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5×10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0467] Plasma cleaning: Ar gas is introduced, the furnace pressure is kept at 2.0Pa, the bias voltage is turned on and set to-800V, and plasma cleaning is performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0468] ​Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use radio frequency assisted direct current power supply to introduce electricity to the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 15 sccm, set the gas flow ratio to keep Ar:N2 at 3:1, keep the pressure in the furnace body at 0.4 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 1.3 W / cm 2 , set the power density of the Ti target to 7.8 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 2200 nm.

[0469] Aluminum alloy sheets and silicon sheets were used as substrates for the deposition of conductive coatings for the sheet resistance test;

[0470] The samples using silicon sheets as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM testing;

[0471] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and colorimetric value testing;

[0472] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as substrates for the salt spray corrosion resistance test;

[0473] The sample prepared using an aluminum alloy as the substrate had a sheet resistance value of 0 Ω / sq, indicating good conductivity, and the sample prepared using a silicon sheet as the substrate had a sheet resistance value of 4.2 Ω / sq.

[0474] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 12.7 Ti 77.9 N 9.4 .

[0475] SEM cross-sectional characterization of the test sample showed that the cross-sectional morphology could be seen in Figure 10 , and the XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile could be seen in Figure 11 . The SEM test results showed that the Cr-Ti-N alloy coating had a dense structure and no through-column joints were observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° in the XRD diffraction pattern was all ≥2.0°, among which there was only one wide peak with a half-height width of 4.87° in the range of 34°-50°, and there was only one wide peak in the radial intensity profile of the TEM selected area electron diffraction pattern in the range of , with a half-height width value of

[0476] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 76.55, a: 0.59, and b: 5.31, and the colorimetric value of the stainless steel substrate sample is L: 77.09, a: 0.57, and b: 4.59.

[0477] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 17.4 GPa, and the hardness value of the stainless steel substrate sample is 15.1 GPa.

[0478] The salt spray corrosion resistance results: the titanium alloy substrate sample and the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protection properties.

[0479] Example 5.

[0480] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 43.0 Ti 37.0 N 20.0 .

[0481] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon sheets with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0482] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0483] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 26 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 4.4 W / cm 2 , and the power density of the Ti target was set to 3.8 W / cm 2 . The Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 2700 nm by controlling the film formation time.

[0484] The sheet resistance test used aluminum alloy sheets and silicon sheets as substrates for depositing conductive coatings.

[0485] The samples using silicon sheets as substrates were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0486] The hardness value test and the chroma value test are carried out by using stainless steel sheet and aluminum alloy sheet.

[0487] The salt spray corrosion resistance test is carried out by using titanium alloy sheet, stainless steel sheet and aluminum alloy sheet as the sample base.

[0488] The sample prepared by using aluminum alloy as the base material has a square resistance value of 0 Ω / sq and good conductivity, and the sample prepared by using silicon sheet as the base material has a square resistance value of 2.6 Ω / sq.

[0489] According to the component analysis, the component of the alloy coating on the surface of the base is Cr 43.0 Ti 37.0 N 20.0 .

[0490] The SEM cross-section characterization of the test sample can be seen from Figure 12 , and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from Figure 13 . The SEM test result shows that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test result shows that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥2.0°, wherein there is only one wide peak with a half-height width of 2.48° in the range of 34°-50°, and there is only one wide peak in the radial intensity profile of the TEM selected area electron diffraction pattern in the range of , and the half-height width value is

[0491] The chroma value test result is that the aluminum alloy base material sample has a test chroma value of L: 81.37, a: 0.27, and b: 2.56, and the stainless steel base material sample has a test chroma value of L: 81.58, a: 0.24, and b: 2.18.

[0492] The hardness value test result is that the aluminum alloy base material sample has a hardness value of 21.2 GPa, and the stainless steel base material sample has a hardness value of 14.9 GPa.

[0493] The salt spray corrosion resistance result is that the titanium alloy base material and the aluminum alloy base sample can pass the 48h test, and the stainless steel base material sample can pass the 144h test, which has excellent protection characteristics.

[0494] Example 6.

[0495] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 62.9 Ti 18.9 N 18.2 .

[0496] Substrate pretreatment: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0497] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0498] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 24 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 6.3 W / cm 2 , the power density of the Ti target was set to 1.9 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 2000 nm by controlling the film deposition time.

[0499] Aluminum alloy sheet and silicon sheet were used as substrates for depositing conductive coatings for sheet resistance testing.

[0500] Silicon sheet was used as the substrate for the sample, and SEM and composition analysis, XRD analysis and TEM testing were performed.

[0501] Stainless steel sheet and aluminum alloy sheet were used for hardness testing and colorimetric value testing.

[0502] Titanium alloy sheet, stainless steel sheet and aluminum alloy sheet were used as the substrate for the sample, and salt spray corrosion resistance testing was performed.

[0503] The sheet resistance value of the sample prepared with aluminum alloy as the substrate was 0 Ω / sq, and the conductivity was good. The sheet resistance value of the sample prepared with silicon sheet as the substrate was 6.6 Ω / sq.

[0504] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 62.9 Ti 18.9 N 18.2 .

[0505] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in Figure 14 , and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 15The SEM test result shows that the Cr-Ti-N alloy coating structure is dense, and no through columnar joint is observed; the XRD test result shows that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥2.0°, wherein there is only one wide peak with a half-height width of 2.60° in the range of 34°-50°, and there is only one wide peak with a half-height width of 2.60° in the range of 34°-50° of the radial intensity profile of the TEM selected area electron diffraction pattern

[0506] The chroma value test result: the tested chroma value of the aluminum alloy substrate sample is L: 83.07, a: 0.09, b: 1.54, and the tested chroma value of the stainless steel substrate sample is L: 83.31, a: 0.05, b: 1.45.

[0507] The hardness value test result: the hardness value of the aluminum alloy substrate sample is 20.1 GPa, and the hardness value of the stainless steel substrate sample is 22.4 GPa.

[0508] The salt spray corrosion resistance result: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection characteristics.

[0509] Example 7.

[0510] In this example, the coating on the substrate is a three-layer structure, and the chemical composition is substrate / Ti / Cr 62.9 Ti 18.9 N 18.2 / CrN, respectively corresponding to the transition layer, the Cr-Ti-N alloy film and the surface layer, and the thicknesses are 300 nm, 1000 nm and 200 nm, respectively.

[0511] Substrate pretreatment: the titanium alloy sheet, the stainless steel sheet, the aluminum alloy sheet and the silicon sheet samples with a length-width ratio of 50mm×50mm are respectively placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5×10 -4 Pa, heated to 150℃, and kept at this temperature for 15 minutes.

[0512] Plasma cleaning: Ar gas is introduced, the furnace pressure is kept at 2.0 Pa, the bias voltage is turned on and set to-800V, and plasma cleaning is performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0513] ​First, depositing Ti coating (transition layer): open the sample stage turntable, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use the radio frequency assisted direct current power supply to electrify the Ti target, input Ar gas, set the Ar gas flow to 60 sccm, maintain the pressure in the furnace body to 0.5 Pa, open the bias voltage, set it to -100 V, and set the power density of the Ti target to 5.0 W / cm 2 , depositing Ti alloy coating, control the film forming time to make the obtained Ti film thickness to be 300 nm.

[0514] Second, depositing Cr-Ti-N alloy coating: open the sample stage turntable, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use the radio frequency assisted direct current power supply to electrify the Cr target and the Ti target, input Ar and N2 gas, set the N2 gas flow to 24 sccm, set the gas flow ratio to maintain the Ar:N2 gas flow ratio to be 2:1, maintain the pressure in the furnace body to 0.6 Pa, open the bias voltage, set it to -100 V, and set the power density of the Cr target to 6.3 W / cm 2 , set the power density of the Ti target to 1.9 W / cm 2 , depositing Cr-Ti-N alloy coating, control the film forming time to make the obtained Cr-Ti-N film thickness to be 1000 nm.

[0515] Finally, depositing CrN coating (surface layer): open the sample stage turntable, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use the radio frequency assisted direct current power supply to electrify the Cr target, input Ar and N2 gas, set the N2 gas flow to 13 sccm, set the gas flow ratio to maintain the Ar:N2 gas flow ratio to be 3:1, maintain the pressure in the furnace body to 0.6 Pa, open the bias voltage, set it to -100 V, and set the power density of the Cr target to 5.0 W / cm 2 , depositing Cr-N alloy coating, control the film forming time to make the obtained Cr-N film thickness to be 200 nm.

[0516] The sheet resistance test uses aluminum alloy sheets and silicon sheets as substrates for depositing conductive coatings;

[0517] The samples using silicon sheets as substrates are subjected to SEM and composition analysis;

[0518] The stainless steel sheets and aluminum alloy sheets are used for hardness value testing and colorimetric value testing;

[0519] The titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets are used as substrates for the salt spray corrosion resistance test;

[0520] The sample prepared with aluminum alloy as the substrate has a sheet resistance value of 0 Ω / sq, which is good in conductivity.

[0521] The coating on the surface of the substrate is a three-layer structure, and the chemical composition of each structural layer is Ti / Cr 62.9 Ti 18.9 N 18.2 / CrN.

[0522] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in Figure 16 .

[0523] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 82.60, a: -0.13, b: 1.71, and the colorimetric value of the stainless steel substrate sample is L: 82.11, a: -0.14, b: 1.15.

[0524] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 16.1 GPa, and the hardness value of the stainless steel substrate sample is 18.2 GPa.

[0525] The salt spray corrosion resistance results: the titanium alloy substrate, the aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0526] Example 8. The thickness of the Cr-Ti-N alloy coating is about 50 nm

[0527] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 43.0 Ti 37.0 N 20.0 .

[0528] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with a length-width ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0529] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose is to remove small impurities on the surface of the sample by plasma etching.

[0530] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 26sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 4.4 W / cm 2The power density of the Ti target was set to 3.8 W / cm 2 A Cr-Ti-N alloy coating was deposited, and the thickness of the resulting film was controlled to be 50 nm by controlling the film formation time.

[0531] Aluminum alloy sheets and silicon sheets were used as substrates for depositing conductive coatings for sheet resistance testing;

[0532] Composition analysis was performed on samples using silicon sheets as substrates;

[0533] Hardness and chroma tests were performed using stainless steel sheets and aluminum alloy sheets;

[0534] Salt spray corrosion tests were performed on samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates;

[0535] The sheet resistance of samples prepared using aluminum alloy as the substrate was 0 Ω / sq, indicating good conductivity, while the sheet resistance of samples prepared using silicon sheets as the substrate was 0.5 Ω / sq.

[0536] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 43.0 Ti 37.0 N 20.0 .

[0537] The chroma test results were basically consistent with those of Example 5.

[0538] Hardness test results: the hardness of the aluminum alloy substrate sample was 7.2 GPa, and the hardness of the stainless steel substrate sample was 8.1 GPa.

[0539] Salt spray corrosion results: titanium alloy substrates and aluminum alloy substrates passed the 48h test, and stainless steel substrates passed the 144h test, demonstrating excellent protective properties.

[0540] In Example 9, the Cr-Ti-N alloy coating had a thickness of about 6 μm

[0541] In this example, the chemical composition of the Cr-Ti-N alloy coating was Cr 43.0 Ti 37.0 N 20.0 .

[0542] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon sheets with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, then dried in an oven and placed in the vacuum chamber of a coating machine, which was evacuated to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

[0543] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0544] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 26 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.6 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 4.4 W / cm 2 , the power density of the Ti target was set at 3.8 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 6000 nm.

[0545] Aluminum alloy sheets and silicon sheets were used as substrates for the deposition of conductive coatings for the sheet resistance test.

[0546] Composition analysis was performed on samples using silicon sheets as substrates.

[0547] Hardness and colorimetric value tests were performed on samples using stainless steel sheets and aluminum alloy sheets.

[0548] Salt spray corrosion resistance tests were performed on samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates.

[0549] The sheet resistance value of samples prepared using aluminum alloy as the substrate was 0 Ω / sq, indicating good conductivity. The sheet resistance value of samples prepared using silicon sheets as the substrate was 12.0 Ω / sq.

[0550] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 43.0 Ti 37.0 N 20.0 .

[0551] The colorimetric value test results were basically consistent with those of Example 5.

[0552] Hardness value test results: the hardness value of the aluminum alloy substrate sample was 26.5 GPa, and the hardness value of the stainless steel substrate sample was 28.3 GPa.

[0553] Salt spray corrosion resistance results: titanium alloy substrates and aluminum alloy samples passed the 48 h test, and stainless steel substrates passed the 144 h test, demonstrating excellent protective properties.

[0554] Example 10. Containing Doped Elements

[0555] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 66.9 Ti 18.3 N 10.1 C 4.7 .

[0556] Pre-treatment of the substrate: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0557] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose of this step was to remove small impurities on the surface of the sample by plasma etching.

[0558] Deposition of Cr-Ti-N-C alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar, C2H2 and N2 gases were introduced, the flow rate of Ar gas was set to 60 sccm, the flow rate of N2 gas was set to 14 sccm, the flow rate of C2H2 gas was set to 6 sccm, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 7.0 W / cm 2 , the power density of the Ti target was set to 2.0 W / cm 2 , and the Cr-Ti-N-C alloy coating was deposited. The film thickness of the obtained Cr-Ti-N-C film was controlled to be 900 nm by controlling the film deposition time.

[0559] Aluminum alloy sheets were used as substrates for the deposition of conductive coatings for the square resistance test.

[0560] Silicon sheets were used as substrates for composition analysis.

[0561] Stainless steel sheets and aluminum alloy sheets were used for hardness and colorimetric value tests.

[0562] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as substrates for salt spray corrosion resistance tests.

[0563] The square resistance value of the sample prepared using aluminum alloy as the substrate was 0 Ω / sq, indicating good electrical conductivity.

[0564] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 66.9 Ti 18.3 N 10.1 C 4.7 .

[0565] The colorimetric value test results: the colorimetric value of the aluminum alloy substrate sample is L: 83.05, a: 0.10, b: 1.50, and the colorimetric value of the stainless steel substrate sample is L: 83.21, a: 0.07, b: 1.48.

[0566] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 13.6 GPa, and the hardness value of the stainless steel substrate sample is 14.7 GPa.

[0567] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protective properties.

[0568] According to the experimental exploration results of the inventor, when other non-metallic doping elements (such as Si, B, O, H, Ar, etc.) or metallic doping elements (such as Al) are used, good electrical conductivity and excellent corrosion resistance can also be provided when the atomic ratio of the doping element is appropriate (such as 4at%, 2at%), the aluminum alloy substrate sample can pass the 48h test. In addition, it also has high hardness. There is at least one wide peak in the XRD diffraction angle 2θ(°) 34°-50° range, and the radial intensity profile of the TEM selected area electron diffraction pattern has at least one wide peak in the range of 34°-50°.

[0569] “at%” represents atomic percentage.

[0570] Example 11. Substrate selection: copper sheet

[0571] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 62.9 Ti 18.9 N 18.2 .

[0572] Substrate pretreatment: place the copper sheet and silicon sheet samples with an aspect ratio of 50mm×50mm in deionized water for ultrasonic cleaning for 15 minutes, dry them in an oven, and then place them in the vacuum chamber of a plating machine, vacuum the vacuum chamber to 5×10 -4 Pa, heat to 150°C, and maintain the temperature for 15 minutes.

[0573] Plasma cleaning: introduce Ar gas, maintain the furnace pressure at 2.0 Pa, turn on the bias voltage and set it to -800V, and perform plasma cleaning for 20 minutes. The purpose is to remove small impurities on the surface of the sample by plasma etching.

[0574] ​Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the sample stage to the target surface distance to 8 cm, Cr target, Ti target using radio frequency auxiliary direct current power supply, Ar and N2 gas, N2 gas flow is set to 24 sccm, set the gas ratio to keep Ar: N2 gas ratio of 2: 1, keep the pressure in the furnace body to 0.6 Pa, open the bias, set to -100 V, the power density of the Cr target is set to 6.3 W / cm 2 , the power density of the Ti target is set to 1.9 W / cm 2 , deposition of Cr-Ti-N alloy coating, by controlling the film forming time to make the film thickness of 2000 nm.

[0575] The copper sheet is used as the base material for the deposition of the conductive coating for the sheet resistance test;

[0576] The silicon wafer is used as the base material for the sample for the composition analysis;

[0577] The copper sheet is used for the salt spray corrosion resistance test;

[0578] The sample prepared with aluminum alloy as the base material has a sheet resistance value of 0 Ω / sq, which has good conductivity.

[0579] According to the composition analysis, the composition of the alloy coating on the surface of the base material is Cr 62.9 Ti 18.9 N 18.2 .

[0580] Salt spray corrosion resistance result: the copper sheet base material sample can pass the 8h test, which has excellent protection properties.

[0581] Example 12.

[0582] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 14.8 Ti 70.0 N 15.2 .

[0583] Pre-treatment of the base material: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon wafer samples with a length-width ratio of 50mm x 50mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0584] Plasma cleaning: Ar gas is introduced, the pressure in the furnace body is kept at 2.0 Pa, the bias 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 small impurities on the surface of the sample.

[0585] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the sample stage to the target surface distance to 8 cm, use the radio frequency auxiliary direct current power supply to introduce electricity for the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 21 sccm, set the gas flow ratio to keep Ar:N2 at 2:1, keep the pressure in the furnace body at 0.5 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 1.5 W / cm 2 , set the power density of the Ti target to 7.1 W / cm 2 , deposit the Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 1460 nm.

[0586] The aluminum alloy sheet was used as the substrate for the deposition of the conductive coating for the sheet resistance test.

[0587] The silicon wafer was used as the substrate for the sample, and SEM and composition analysis and XRD analysis were performed.

[0588] The stainless steel sheet and the aluminum alloy sheet were used for hardness value testing and color value testing.

[0589] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate for the sample for salt spray corrosion resistance testing.

[0590] The sample prepared with the aluminum alloy as the substrate had a sheet resistance value of 0 Ω / sq, and had good conductivity.

[0591] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 14.8 Ti 70.0 N 15.2 .

[0592] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in Figure 17 , and the XRD diffraction pattern can be seen in Figure 18 . The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) of 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥2.0°, and there is only one wide peak with a half-height width of 2.03° in the range of 34°-50°.

[0593] The color value test results: the color value of the aluminum alloy substrate sample was L: 77.21, a: 0.45, b: 4.55, and the color value of the stainless steel substrate sample was L: 78.25, a: 0.43, b: 4.04.

[0594] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 17.7 GPa, and the hardness value of the stainless steel substrate sample is 17.4 GPa.

[0595] The salt spray corrosion resistance results: the titanium alloy substrate, the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection characteristics.

[0596] Example 13.

[0597] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr 38.3 Ti 35.2 N 26.5 .

[0598] Pre-treatment of the substrate: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with a length-width ratio of 50mm*50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a coating machine, the vacuum chamber was vacuumed to 5*10 -4 Pa, heated to 150℃, and kept at this temperature for 15 minutes.

[0599] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0600] Deposition of Cr-Ti-N alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set to 32sccm, the gas flow ratio of Ar:N2 was kept at 1:1, the pressure in the furnace body was kept at 0.8 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 3.9 W / cm 2 , the power density of the Ti target was set to 3.6 W / cm 2 , the Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 1200 nm by controlling the film forming time.

[0601] The silicon wafer was used as the substrate sample for SEM and composition analysis, XRD analysis and TEM test;

[0602] The stainless steel sheet and the aluminum alloy sheet were used for hardness value test and colorimetric value test;

[0603] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate sample for salt spray corrosion resistance test;

[0604] The sample prepared with aluminum alloy as the substrate has a square resistance value of 0Ω / sq, which has good conductivity.

[0605] Adhesion test was performed using titanium alloy sheet.

[0606] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 38.3 Ti 35.2 N 26.5 .

[0607] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in Figure 19 , and the XRD diffraction pattern, TEM SAED pattern and radial intensity profile can be seen in Figure 20 . The SEM test results showed that the Cr-Ti-N alloy coating structure was dense, and no penetrating column seam was observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of 2θ(°) 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern was all ≥1.6°, and there was only one wide peak with a half-height width of 2.91° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern had only one wide peak in the range of , and the half-height width value was

[0608] Chromatic value test results: the test chromatic value of the aluminum alloy substrate sample was L: 80.64, a: 0.25, b: 3.24, and the test chromatic value of the stainless steel substrate sample was L: 80.43, a: 0.26, b: 3.27.

[0609] Hardness value test results: the hardness value of the aluminum alloy substrate sample was 20.8 GPa, and the hardness value of the stainless steel substrate sample was 22.4 GPa.

[0610] Salt spray corrosion resistance results: the titanium alloy substrate, the aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0611] Adhesion test results: the film layer on the titanium alloy substrate was tested by grid test, and the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0612] Example 13A

[0613] This example uses the same method as Example 13, except that the alloy target is used in the step of depositing the Cr-Ti-N alloy coating.

[0614] In this embodiment, in the step of depositing the Cr-Ti-N alloy coating, the target material is selected as a chromium-titanium alloy target, and theFigure 3 The original Cr target at the position of the middle Cr target 4 was replaced by a CrTi alloy target with an atomic percentage of Cr to Ti of 50:50.

[0615] This example is to prepare a Cr-Ti-N alloy coating with the same elemental composition as in Example 13, but using an alloy target in the step of depositing the Cr-Ti-N alloy coating. In this example, the target material is selected to be a chromium-titanium alloy target, and the target power is set to 5 kW. The results show that the test results of each test are basically consistent with those of Example 13, including SEM test, XRD test, TEM test, color value test, salt spray corrosion resistance test, square resistance test and hardness value test. Figure 3 The original Cr target at the position of the middle Cr target 4 was replaced by a CrTi alloy target with an atomic percentage of Cr to Ti of 50:50. During the manufacturing process, the power was set to 5 kW. The results show that the test results of each test are basically consistent with those of Example 13, including SEM test, XRD test, TEM test, color value test, salt spray corrosion resistance test, square resistance test and hardness value test.

[0616] Comparative Example 1. Conventional method: spray coating

[0617] A coating prepared by a common spray coating method in commercially available products was selected. The manufacturing process was as follows: first, a primer was sprayed on the surface of the aluminum alloy, then it was cured, a color layer was sprayed by adding a dyeing agent, and finally a UV paint was sprayed on the surface. It does not have a metallic color, and the total thickness of the coating is 50 μm. After high temperature curing, a protective coating is obtained. The salt spray test can pass 48 hours of salt spray; but the square resistance test shows infinity, indicating that the coating is insulating, i.e. not conductive.

[0618] Comparative Example 2. Conventional method: anodic oxidation

[0619] A coating prepared by a common anodic oxidation method for aluminum alloy in commercially available products was selected. The surface of the aluminum alloy was anodized to form an oxide layer with a thickness of 30 μm. It does not have a metallic color. The salt spray corrosion resistance test can pass 48 hours of salt spray; but the square resistance test shows infinity, indicating that the coating is insulating, i.e. not conductive.

[0620] Comparative Example 3.

[0621] In this comparative example, the chemical composition of the alloy coating is Cr 20.9 Ti 79.1 , and the preparation method is as follows:

[0622] Substrate pretreatment: aluminum alloy and silicon sheet samples with a length to width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine. The vacuum chamber was evacuated to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

[0623] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min, so as to remove small impurities on the surface of the sample by plasma etching.

[0624] Deposition of Cr-Ti alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar gas was introduced, the pressure in the furnace was kept at 0.5 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 2.2 W / cm 2 , the power density of the Ti target was set at 8.1 W / cm 2 , and the Cr-Ti alloy coating was deposited by controlling the film formation time, and the obtained film thickness was 1400 nm.

[0625] The sheet resistance test used aluminum alloy sheets and silicon sheets as substrates for depositing conductive coatings. The samples using aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance testing, hardness testing, and color value testing. The samples using silicon sheets as substrates were also subjected to SEM and composition analysis.

[0626] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 20.9 Ti 79.1 .

[0627] The sheet resistance value of the sample prepared with aluminum alloy as the substrate was 0 Ω / sq, and the sheet resistance value of the sample prepared with silicon sheet as the substrate was 0.3 Ω / sq. The sheet resistance test results showed that the coating of the present application had conductive properties. However, in the salt spray corrosion resistance test, the aluminum alloy substrate sample did not pass the 48 h test (NG, protection time < 12 h), and the corrosion resistance was poor.

[0628] The hardness value of the aluminum alloy substrate sample was tested to be 7.6 GPa. The color value of the aluminum alloy substrate sample was tested to be L: 77.56, a: 0.57, b: 2.05, showing a silver-white metallic color.

[0629] The SEM cross-section test was performed on the test sample, and the cross-section shape can be referred to Figure 21 . The SEM test results showed that the alloy coating film structure had crystallization defects, the structure was loose and not dense, and there were obvious gaps.

[0630] Comparative Example 4.

[0631] In this comparative example, the chemical composition of the Cr-Ti-N alloy coating was Cr 35.4 Ti 25.8 N 38.8 .

[0632] Substrate pretreatment: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0633] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0634] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 52 sccm, the gas flow ratio of Ar:N2 was kept at 5:4, the pressure in the furnace body was kept at 0.9 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 3.6 W / cm 2 , the power density of the Ti target was set to 2.7 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1400 nm by controlling the film deposition time.

[0635] The silicon wafer was used as the substrate for depositing the conductive coating for the sheet resistance test.

[0636] The silicon wafer was used as the substrate for depositing the conductive coating for the sheet resistance test.

[0637] The stainless steel sheet and the aluminum alloy sheet were used as the substrate for hardness testing and colorimetric value testing.

[0638] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate for salt spray corrosion resistance testing.

[0639] The silicon wafer was used as the substrate for depositing the conductive coating for the sheet resistance test.

[0640] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 35.4 Ti 25.8 N 38.8 .

[0641] The cross-sectional SEM characterization of the test sample can be seen in Figure 22 , and the XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile can be seen in Figure 23The SEM test results show that the alloy coating film structure is sparse, and there are obvious through column seams. The XRD test results show that there are two peaks in the XRD diffraction pattern in the range of 34°-50° of diffraction angle 2θ (°), and both are sharp peaks (half-height width value <1.6° of 2θ peak), wherein the half-height widths of the two sharp peaks in the range of 34°-50° are 0.52° and 1.26°, respectively. The radial intensity profile of the selected area electron diffraction pattern of TEM is in the range of 34°-50° , and the half-height widths are , that is, there are two sharp peaks.

[0642] The chroma value test results are as follows: the test chroma value of the aluminum alloy substrate sample is L: 60.57, a: 0.83, and b: 7.07, and the test chroma value of the stainless steel substrate sample is L: 60.22, a: 1.18, and b: 8.51.

[0643] The hardness value test results are as follows: the hardness value of the aluminum alloy substrate sample is 12.3 GPa, and the hardness value of the stainless steel substrate sample is 13.3 GPa.

[0644] The salt spray corrosion resistance results are as follows: the titanium alloy substrate and the aluminum alloy sample cannot pass the 48h test (NG, protection time <12h), and the stainless steel substrate sample cannot pass the 144h test (NG, protection time <48h), and does not have the protection characteristics for the substrate.

[0645] Comparative Example 5.

[0646] In this comparative example, the film structure is CrN, and the chemical composition of the alloy coating is CrN.

[0647] To make the coating of this comparative example, the preparation method is as follows:

[0648] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with an aspect ratio of 50mm×50mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5×10 -4 Pa, heated to 150℃, and kept at this temperature for 15 minutes.

[0649] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to-800V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0650] Deposition of CrN coating: Turn on the sample stage turret, set the rotation speed to 6 rounds per minute, adjust the sample stage to target surface distance to 8 cm, use direct current power supply to electrify the Cr target, introduce Ar and N2 gas, set the N2 gas flow to 15 sccm, set the gas flow ratio to keep Ar:N2 ratio to 3:1, keep the pressure in the furnace to 0.5 Pa, turn on the bias voltage, set it to -100 V, set the power density of the Cr target to 5 W / cm2 2 , deposit the CrN coating, by controlling the film formation time, the obtained film thickness is 1800 nm.

[0651] The sheet resistance test uses aluminum alloy sheets and silicon sheets as substrates for depositing conductive coatings. The samples using aluminum alloy sheets as substrates are subjected to salt spray corrosion resistance tests, hardness tests, and color value tests. The samples using silicon sheets as substrates are also subjected to SEM and composition analysis.

[0652] The sheet resistance value of the sample prepared with aluminum alloy as the substrate is 0 Ω / sq, and the sheet resistance value of the sample prepared with silicon sheet as the substrate is 8.2 Ω / sq. The sheet resistance test results show that the coating of the present application has conductive properties. However, in the salt spray corrosion resistance test, the aluminum alloy substrate sample fails the 48 h test (NG, protection time < 24 h), and has poor corrosion resistance.

[0653] Through composition analysis, the composition of the alloy coating on the surface of the substrate is CrN.

[0654] The color value of the aluminum alloy substrate sample is tested as L: 74.92, a: 0.68, b: 4.89, and the color value of the stainless steel substrate sample is tested as L: 75.07, a: 0.69, b: 5.17, showing a silver-white color.

[0655] In the salt spray corrosion resistance test, the aluminum alloy substrate sample fails the 48 h test (NG, protection time < 12 h), and the stainless steel substrate sample fails the 144 h test (NG, protection time < 24 h).

[0656] The hardness value of the aluminum alloy substrate sample is tested as 12.8 GPa, and the hardness value of the stainless steel substrate sample is tested as 13.3 GPa.

[0657] Comparative Example 6. Alloy coating thickness 50 nm

[0658] Using a method basically the same as Comparative Example 4, the chemical composition of the alloy coating is Cr 35.4 Ti 25.8 N 38.8 , except that the thickness of the alloy coating is changed from 1400 nm to 50 nm.

[0659] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection duration < 24h).

[0660] Comparative Example 7. Alloy coating thickness 1000 nm

[0661] Using essentially the same method as Comparative Example 4, the alloy coating had a chemical composition of Cr 35.4 Ti 25.8 N 38.8 with the difference that the thickness of the alloy coating was changed from 1400 nm to 1000 nm.

[0662] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection duration < 24h).

[0663] Comparative Example 8. Alloy coating thickness 2500 nm

[0664] Using essentially the same method as Comparative Example 4, the alloy coating had a chemical composition of Cr 35.4 Ti 25.8 N 38.8 with the difference that the thickness of the alloy coating was changed from 1400 nm to 2500 nm.

[0665] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection duration < 24h), not having the protection properties of the substrate.

[0666] Comparative Example 9. Alloy coating thickness 6000 nm

[0667] Using essentially the same method as Comparative Example 4, the alloy coating had a chemical composition of Cr 35.4 Ti 25.8 N 38.8 with the difference that the thickness of the alloy coating was changed from 1400 nm to 6000 nm.

[0668] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection duration < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection duration < 24h), not having the protection properties of the substrate.

[0669] Comparative Examples 10-12. No protective coating

[0670] The salt spray corrosion resistance test was performed using aluminum alloy bare chip, stainless steel bare chip and copper bare chip respectively. The results showed that obvious corrosion occurred within 12 hours.

[0671] Comparative Example 13.

[0672] In this comparative example, the thin film structure was TiN, and the chemical structure of the alloy coating was TiN.

[0673] To make the coating of this comparative example, the Ti target in the furnace body was first replaced with a Ti target, and the preparation method was as follows:

[0674] Pre-treatment of the substrate: aluminum alloy pieces and silicon pieces with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, and then dried in an oven and placed in the vacuum chamber of the plating machine. The vacuum chamber was evacuated to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

[0675] Plasma cleaning: Ar gas was introduced to maintain the pressure in the furnace body at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0676] Deposition of TiN coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Ti target was powered by a direct current source, Ar and N2 gases were introduced, the N2 gas flow was set to 20 sccm, the gas flow ratio of Ar:N2 was set to 2:1, the pressure in the furnace body was maintained at 0.7 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Ti target was set to 5 W / cm 2 . The TiN coating was deposited by controlling the film formation time, and the obtained film thickness was 2000 nm.

[0677] The sheet resistance test used aluminum alloy pieces and silicon pieces as substrates for depositing conductive coatings. The samples using aluminum alloy pieces as substrates were subjected to salt spray corrosion resistance test, hardness test and color value test. The samples using silicon pieces as substrates were also subjected to SEM and composition analysis.

[0678] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was TiN.

[0679] The sheet resistance test showed infinity, indicating that the coating was insulating / non-conductive. In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h).

[0680] The hardness value of the aluminum alloy substrate sample was 13.8 GPa. The color value of the aluminum alloy substrate sample was L: 56.96, a: 6.55, b: 30.30, showing a golden yellow color.

[0681] Comparative Example 14.

[0682] The aluminum alloy (6063 series aluminum alloy) was used as the sample to be tested, and the sheet resistance value was 0 Ω / sq. However, the aluminum alloy substrate sample failed the 48 h test (NG, protection time < 24 h).

[0683] Table 1.

[0684]

[0685]

[0686] In Table 1, the space and “\” represent that it is not specified in the table. The thickness of Ti / CrN in Example 7 is 0.3 μm, 1 μm, and 0.2 μm, respectively. 62.9 Ti 18.9 N 18.2 The thickness of Ti / CrN in Example 7 is 0.3 μm, 1 μm, and 0.2 μm, respectively.

[0687] In Table 1, “ / ” represents that it is not set.

[0688] Result analysis:

[0689] The coating surfaces of the target Cr-Ti-N alloy coatings included in Examples 1-13 all have metallic luster.

[0690] The target Cr-Ti-N alloy coatings (such as Examples 1-13) have good electrical conductivity and excellent corrosion resistance on the surface of the aluminum alloy substrate, and have a certain sheet resistance (0.5 Ω / sq-12 Ω / sq) and excellent corrosion resistance on the surface of the silicon wafer. The electrical conductivity of the Cr-Ti-N alloy coating on the surface of the aluminum alloy substrate is very good, while the electrical conductivity on the surface of the silicon wafer is poor or non-conductive. Among them, Examples 1-6, 8-13 are single-layer thin film structures, the Cr-Ti-N alloy coating directly contacts the substrate, and as a surface film layer, it provides surface protection for the substrate; the coating of Example 7 is a three-layer thin film structure, which includes a transition layer, a Cr-Ti-N alloy coating, and a surface layer from the surface of the substrate; the Cr-Ti-N alloy coating in Example 10 contains a certain atomic percentage of doping elements (≤5 at%). The Cr-Ti-N alloy coating can be used as a single-layer thin film (such as Examples 1-6, 8-13) independently, or can be located in a multi-layer composite thin film (such as Example 7), such as one of the layers, that is, as a surface layer (exposed), as a bottom layer coating (contacting the substrate), or as an intermediate layer (between the bottom layer coating and the surface layer).

[0691] The Cr-Ti-N alloy coating can be used as an electrically conductive coating in a plated product, and the implementation can adopt a green and environmentally friendly manufacturing technology. The Cr-Ti-N alloy coating can be formed on the surface of various substrates, such as but not limited to the surface of an aluminum alloy or a silicon wafer.

[0692] According to the salt spray corrosion resistance test results, the target Cr-Ti-N alloy coating (such as Examples 1-13) can bring excellent corrosion resistance protection effect to the substrate, and is an excellent corrosion resistance protective coating; among them, Examples 1-10, 12-13 all use aluminum alloy substrate and stainless steel substrate, and Example 11 uses copper substrate. The aluminum alloy surface can pass the 48h salt spray corrosion resistance test, the stainless steel surface can pass the 144h salt spray corrosion resistance test, and the copper substrate (copper is a relatively active alloy) can pass the 8h salt spray corrosion resistance test.

[0693] In addition, the target Cr-Ti-N alloy coating (such as Examples 1-13) can provide higher hardness based on a certain coating thickness, so that the Cr-Ti-N alloy coating has excellent corrosion resistance and high hardness characteristics.

[0694] According to the coating surface hardness test results, the target Cr-Ti-N alloy coating can also provide higher surface hardness. The coating thickness of the Cr-Ti-N alloy coating in Examples 1-6 and 10 is ≥0.9μm; when the aluminum alloy is used as the substrate, the hardness value is ≥13GPa; when the stainless steel is used as the substrate, the hardness value is ≥14GPa. In some of the examples, the coating thickness is ≥1.0μm; when the aluminum alloy is used as the substrate, the hardness value is ≥14GPa; when the stainless steel is used as the substrate, the hardness value is ≥15GPa.

[0695] It can be seen that the target Cr-Ti-N alloy coating can provide excellent corrosion resistance, can inhibit corrosion, and can also provide high hardness characteristics, and can resist scratches and scratches.

[0696] According to the XRD test and TEM selected area electron diffraction test results, the target Cr-Ti-N alloy coating (such as Examples 1-13) has at least one wide peak (further, all are wide peaks, and the half-height width is all ≥1.6°, and further, all are ≥2°) in the XRD diffraction pattern in the range of diffraction angle 2θ(°) 34°-50°, and has at least one wide peak (further, all are wide peaks, and the half-height width is all ≥1.6°, and further, all are ≥2°) in the radial intensity profile of the TEM selected area electron diffraction pattern in the range of 34°-50°. Further, the half-height width is all ); the target Cr-Ti-N alloy coating all has "highly disordered and fully dense" atomic arrangement, which is consistent with the highly dense structure in the SEM morphology characterization results.

[0697] According to the surface brightness test results, the Cr-Ti-N alloy coating as a surface film layer can also provide higher brightness, and all meet L≥70 (tested by Lab method), which can be referred to Examples 1-6, 8-13. In some examples, L≥75 can be achieved, and in some examples, L≥80 can be achieved.

[0698] According to the results of the crosshatch test, the target Cr-Ti-N alloy coating can also form a higher bonding force on the surface of the titanium alloy.

[0699] The coating prepared by the conventional method in Comparative Example 1 and Comparative Example 2 has certain corrosion resistance, but the coating is insulating (i.e. not conductive).

[0700] The substrates of Comparative Examples 10-12 and 14, without a protective coating, are not resistant to salt spray corrosion. Comparative Examples 10-12 show obvious corrosion within 12 hours, and Comparative Example 14 shows obvious corrosion within 24 hours.

[0701] The coatings in Comparative Examples 3-9 and 11 all have poor corrosion resistance.

[0702] The alloy coating film in Comparative Example 3 lacks N element, the alloy coating film in Comparative Example 5 lacks Ti element, and the alloy coating film in Comparative Example 13 lacks Cr element. It is found that Comparative Examples 1, 5 and 13 all have corrosion resistance test failure (NG). It is speculated that the reason may be that the film structure is not dense, and there are gaps, for example, there are through columnar gaps, which cause the corrosion solution to quickly pass through the gap and contact the substrate, thereby causing the coating corrosion resistance to fail.

[0703] The alloy coating film in Comparative Example 4 has a high content of N element, and also has corrosion resistance test failure (NG).

[0704] Comparative Examples 6-9 have the same Cr, Ti and N atomic ratio as Comparative Example 4, and when the alloy coating is changed to a plurality of different thicknesses, the hardness and corrosion resistance are all significantly worse than the target Cr-Ti-N alloy coating with the same thickness. Even though Comparative Example 9 has a thickness as high as 6000 nm (6 microns), although the hardness is high, the corrosion resistance is still poor. The inventors speculate that the reason may be that the film structure is not dense, and there are gaps, for example, there are through columnar gaps, which cause the corrosion solution to quickly pass through the gap and contact the substrate, thereby causing the coating corrosion resistance to fail; increasing the thickness of the coating can increase the hardness of the coating, but the structural defects still exist.

[0705] The target Cr-Ti-N alloy coating can have excellent corrosion resistance and high hardness characteristics at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs. In the case of a thin alloy coating, the plated product formed can present a silver-white metal color close to the color of the base metal, which is more conducive to achieving an aesthetic, non-altering base color decorative effect.

[0706] Table 2.

[0707]

[0708]

[0709] In Table 2, " / " and space indicate that the values are not mentioned in the table. "n.d." means not detected. "+∞" means that the square resistance is infinite, and it is not conductive.

[0710] The technical features of the above embodiments and examples can be combined in any suitable manner. In order to make the description concise, not all possible combinations of the technical features in the above embodiments and examples are described, but as long as the combinations of the technical features do not contradict, they should be considered to be within the scope of the present disclosure.

[0711] The above embodiments and examples only express several embodiments of the present application, and are convenient for understanding the technical solutions of the present application in detail, but should not be understood as a limitation on the protection scope of the present application. It should be pointed out that, for those skilled in the art, some modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. In addition, it should be understood that, after reading the above teaching content of the present application, those skilled in the art can make various modifications or improvements to the present application, and the equivalent forms obtained are also within the protection scope of the present application. It should also be understood that, based on the technical solutions provided by the present application, those skilled in the art can obtain technical solutions through logical analysis, reasoning or limited experiments, and these are within the protection scope of the appended claims of the present application. Therefore, the protection scope of the present patent should be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. The application of Cr-Ti-N alloy coating as a conductive coating in coated products, characterized in that, The coated article includes a substrate, and the Cr-Ti-N alloy coating is located on at least a portion of the surface of the substrate; the Cr-Ti-N alloy coating satisfies the following two characteristics: The X-ray diffraction pattern of the Cr-Ti-N alloy coating has peaks in the diffraction angle range of 2θ (°) from 34° to 50°, and the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 34° to 50° satisfies ≥1.6°. In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-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 The sheet resistance of the surface of the coated product is ≤12Ω / sq.

2. The application according to claim 1, characterized in that, The Cr-Ti-N alloy coating satisfies the following two characteristics: The X-ray diffraction pattern of the Cr-Ti-N alloy coating has peaks in the diffraction angle range of 2θ (°) from 34° to 50°, and the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 34° to 50° satisfies ≥2°. In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-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 3. The application of Cr-Ti-N alloy coating as a conductive coating in coated products, characterized in that, The coated article includes a substrate, and the Cr-Ti-N alloy coating is located on at least a portion of the surface of the substrate; The Cr-Ti-N alloy coating comprises a Cr-Ti-N alloy material, wherein the Cr-Ti-N alloy material comprises Cr, Ti and N elements in an atomic ratio of x:y:z, 5.0≤x≤90.0, 5.0≤y≤90.0, and 2.4≤z≤26.5; The sheet resistance of the surface of the coated product is ≤12Ω / sq.

4. The application according to claim 3, characterized in that, In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-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 5. The application according to any one of claims 1 to 4, characterized in that, The Cr-Ti-N alloy material includes materials with the chemical formula Cr x Ti y N z M a The composition of the CrTiN-based alloy is given, where M is a doping element, and x, y, z and a are the atomic ratios of Cr, Ti, N and M, respectively, with 5.0≤x≤90.0, 5.0≤y≤90.0, 2.4≤z≤26.5, and a is 0 or a positive number.

6. The application according to claim 5, characterized in that, The Cr-Ti-N alloy material satisfies one or two of the following characteristics: The sum of x, y, and z is a value selected from 95 to 100; 0≤a / (x+y+z+a)≤0.05; The doping elements include one or more metallic elements selected from Ni, Fe, Ag, Au, Cu, and Al.

7. The application according to claim 6, characterized in that, The substrate in which a=0 or 0 is combined with the Cr-Ti-N alloy coating is any one of alloy, elemental metal, and inorganic non-metallic material; 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; the elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium; the inorganic non-metallic material includes one or more of ceramic and glass.

8. The application according to any one of claims 1 to 7, characterized in that, The substrate in combination with the Cr-Ti-N alloy coating is one of aluminum alloy, silicon-based material and stainless steel.

9. The application according to any one of claims 1 to 7, characterized in that, The sheet resistance test results of the Cr-Ti-N alloy coating satisfy one or two of the following characteristics:

10. The application according to any one of claims 1 to 7, characterized in that, The sheet resistance of the Cr-Ti-N alloy coating on the silicon wafer substrate is 0.5Ω / sq to 12Ω / sq; The sheet resistance of the Cr-Ti-N alloy coating on the aluminum alloy substrate is 0 Ω / sq. The thickness of the Cr-Ti-N alloy coating is denoted as D2, where 50nm≤D2≤6μm; 11. The application according to any one of claims 1 to 10, characterized in that, The Cr-Ti-N alloy coating also serves as a corrosion-resistant coating. Optionally, d min ≤D2≤d max , where d min Selected from 50nm~0.9μm, d max Selected from 2.7μm to 6μm; Further, alternatively, d min 50nm, 0.3μm, 0.5μm, 0.7μm, 0.8μm or 0.9μm; d max The sizes are 2.7μm, 3μm, 4μm, 5μm, or 6μm.

12. The application according to any one of claims 1 to 11, characterized in that, Optionally, the corrosion-resistant coating can pass a corrosion test for at least 48 hours according to the ASTM B117 salt spray test standard; wherein the corrosion solution used for the corrosion test is composed of sodium chloride, water and sodium hydroxide, with a pH of 6.5 to 7.

2. ​ 13. The application according to claim 11, characterized in that, The corrosion-resistant coating is a hard corrosion-resistant coating; Optionally, the thickness of the Cr-Ti-N alloy coating is greater than or equal to 0.9 μm.

14. The application according to claim 11, characterized in that, The surface brightness value L of the Cr-Ti-N alloy coating provided by the coated product is ≥70, as tested by the Lab method; Optionally, the Cr-Ti-N alloy coating provides a surface brightness value L≥75 for the coated article, as tested by the Lab method.

15. The application of Cr-Ti-N alloy materials as conductive coating materials in coated products, characterized in that, The Cr-Ti-N alloy material is as defined in any one of claims 1 to 14.

Images