Cr-ti-n alloy material, cr-ti-n alloy film, cr-ti-n alloy coating, alloy film product and use

Abstract

The present application relates to a Cr-Ti-N alloy material, a Cr-Ti-N alloy film, a Cr-Ti-N alloy coating, an alloy film product and the use. The Cr-Ti-N alloy material comprises Cr element, Ti element, and N element. In the Cr-Ti-N alloy material, the atomic ratio of Cr element to Ti element to N element is x: y: z, where 5.0≤x≤90.0, 5.0≤y≤79.0, and 2.4≤z≤26.5.

Description

Cr-Ti-N alloy materials, Cr-Ti-N alloy films, Cr-Ti-N alloy coatings, alloy film products and applications

[0001] Related applications

[0002] This application claims priority to Chinese Patent Application No. CN2024108012138, filed on June 20, 2024, entitled "Cr-Ti-N alloy materials, Cr-Ti-N alloy films and preparation methods thereof, Cr-Ti-N alloy coatings, alloy film products and applications", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of alloy coating technology, and particularly to Cr-Ti-N alloy materials, Cr-Ti-N alloy films, Cr-Ti-N alloy coatings, alloy film products and applications, and also to methods for preparing Cr-Ti-N alloy films. Background Technology

[0004] With technological advancements and development, wearable devices, 3C products, automobiles, and sports products are increasingly widely used, leading to higher demands on their mechanical properties, such as corrosion resistance and hardness. Common alloy materials (such as stainless steel, aluminum alloys, and titanium alloys) or pure metals (such as Cu and Ag) often exhibit weak corrosion resistance, low surface hardness, and susceptibility to corrosion and scratches during use, limiting their widespread application. While theoretically, alloy coatings can improve one or more mechanical properties such as corrosion resistance and hardness, these properties are not ideal in many products on the market. Summary of the Invention

[0005] According to various embodiments and examples of this application, this application provides at least one Cr-Ti-N alloy material, a Cr-Ti-N alloy film and its preparation method, a Cr-Ti-N alloy coating, an alloy film product, and its application. The Cr-Ti-N alloy material possesses excellent corrosion resistance and can form Cr-Ti-N alloy films, alloy coatings including Cr-Ti-N alloy films, or related alloy film products. The related Cr-Ti-N alloy films or Cr-Ti-N alloy coatings can be used as protective coatings for products, improving the protective capabilities of the products.

[0006] In a first aspect of this application, a Cr-Ti-N alloy material is provided, comprising Cr, Ti and N elements, wherein the atomic ratio of Cr, Ti and N elements in the Cr-Ti-N alloy material is x:y:z, 5.0≤x≤90.0, 5.0≤y≤79.0, and 2.4≤z≤26.5.

[0007] In some embodiments, a Cr-Ti-N alloy material is provided, comprising the chemical formula Cr x Ti y N z M a The composition of the CrTiN-based alloy is as follows: M is a doping element, x, y, z and a are the atomic ratios of Cr, Ti, N and M, respectively, 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, and 0≤a / (x+y+z+a)≤0.05.

[0008] In some implementations, 0 ≤ a / (x+y+z+a) ≤ 0.02.

[0009] In some embodiments, x, y, and z satisfy the following characteristics: 54.4 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 25.6, and 5.0 ≤ z ≤ 20.0. This is beneficial for imparting higher brightness to the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating.

[0010] In some embodiments, x, y, and z satisfy the following characteristics: 21.0 ≤ x ≤ 60.6, 37.0 ≤ y ≤ 60.0, and 2.4 ≤ z ≤ 19.0. The corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating can exhibit a stainless steel-like metallic color.

[0011] In some embodiments, x, y, and z satisfy the following characteristics: 5.0 ≤ x ≤ 27.0, 66.0 ≤ y ≤ 79.0, 5.0 ≤ z ≤ 16.0, x ≤ 4.5y - 279, and 84 - y ≤ x ≤ 125.2 - 1.4y. The corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating can exhibit a titanium alloy-like metallic color.

[0012] In some embodiments, x, y, and z satisfy the following characteristics: 43.0 ≤ x ≤ 60.6, 25.6 ≤ y ≤ 37.0, and 13.8 ≤ z ≤ 20.0. This is beneficial for imparting higher hardness to the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating.

[0013] In some implementations, the sum of x, y, and z is a value selected from 95 to 100;

[0014] Optionally, the Cr-Ti-N alloy material is made of Cr x Ti y N z The composition of the CrTiN-based alloy is such that the sum of x, y, and z is 100.

[0015] In some embodiments, the mass percentage of Cr, Ti, and N in the Cr-Ti-N alloy material is greater than or equal to 80%, optionally greater than or equal to 90%, further optionally greater than or equal to 95%, and even more optionally 100%.

[0016] In some embodiments, the doping element is a non-metallic element, a metallic element, or a combination thereof;

[0017] The non-metallic elements include one or more of O, C, B, Si, H, and Ar;

[0018] The metallic elements include one or more of Zr, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0019] In some embodiments, the Cr-Ti-N alloy material is a component of the Cr-Ti-N alloy film.

[0020] In some embodiments, the Cr-Ti-N alloy film satisfies the following two characteristics:

[0021] The X-ray diffraction pattern of the Cr-Ti-N alloy film 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°.

[0022] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in... It has diffraction peaks within the range, and in The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies ≥

[0023] In some embodiments, in the X-ray diffraction pattern of the Cr-Ti-N alloy film, at least one 2θ(°) diffraction peak in the range of 34° to 50° has a full width at half maximum (FWHM) of ≥1.69°.

[0024] In some embodiments, the Cr-Ti-N alloy film satisfies one or more of the following characteristics:

[0025] The X-ray diffraction pattern of the Cr-Ti-N alloy film was obtained by using Cu target Kα rays;

[0026] The selected area electron diffraction pattern of the Cr-Ti-N alloy film was obtained by using TEM characterization, which was performed in a mode with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0027] In a second aspect of this application, a Cr-Ti-N alloy film is provided, wherein at least a portion of the Cr-Ti-N alloy film is composed of the Cr-Ti-N alloy material described in the first aspect of this application.

[0028] In some embodiments, the thickness of the Cr-Ti-N alloy film is d. min ~6μm, where d min Selected from 10nm~0.9μm;

[0029] Optionally, d min The available sizes are 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 0.3μm, 0.5μm, 0.8μm, or 0.9μm.

[0030] Optionally, the thickness of the Cr-Ti-N alloy film is 0.3 μm to 2.0 μm.

[0031] In a third aspect of this application, a Cr-Ti-N alloy coating is provided, which includes the Cr-Ti-N alloy film described in the second aspect of this application.

[0032] In a fourth aspect of this application, an alloy film article is provided, comprising a substrate and at least one of the Cr-Ti-N alloy film described in the second aspect of this application and the Cr-Ti-N alloy coating described in the third aspect of this application; wherein the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is located on at least one side of the substrate.

[0033] In some embodiments, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is bonded to a surface of a material near the substrate, namely, any one of alloys, elemental metals, and inorganic non-metallic materials.

[0034] The alloy material types include one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based, and zinc-based.

[0035] The elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium;

[0036] The inorganic non-metallic materials include one or more of ceramics and glass.

[0037] In some embodiments, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is bonded to a surface of a material near the substrate: a light alloy or a stainless steel alloy; wherein the light alloy includes one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0038] In some embodiments, the alloy film article satisfies one or more of the following characteristics:

[0039] The Cr-Ti-N alloy film is in direct contact with the substrate or has a transition layer.

[0040] The Cr-Ti-N alloy film is located on the surface of the alloy film product or the Cr-Ti-N alloy film is further provided with a surface layer on the side away from the substrate. The surface layer is a single-layer structure or a multi-layer structure.

[0041] The Cr-Ti-N alloy coating is in direct contact with the substrate or has a transition layer;

[0042] The Cr-Ti-N alloy coating is located on the surface of the alloy film product, or the Cr-Ti-N alloy coating on the side away from the substrate is further provided with a surface layer, which is a single-layer structure or a multi-layer structure.

[0043] In some embodiments, the alloy film product is one of the following: 3C digital products, automotive products, aerospace products, wearable products, and sports products.

[0044] In a fifth aspect of this application, the application of the Cr-Ti-N alloy material described in the first aspect of this application in the preparation of a corrosion-resistant protective coating is provided, or the application of the Cr-Ti-N alloy film described in the second aspect of this application or the Cr-Ti-N alloy coating described in the third aspect of this application as a corrosion-resistant protective coating is provided.

[0045] In some embodiments, the corrosion-resistant protective 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 is composed of sodium chloride, water and sodium hydroxide, with a pH of 6.5 to 7.2.

[0046] When the corrosion-resistant protective coating is bonded to an aluminum alloy substrate, the corrosion-resistant protective coating can pass a corrosion test of at least 48 hours;

[0047] When the corrosion-resistant protective coating is applied to a stainless steel substrate, the corrosion-resistant protective coating is able to pass a corrosion test of at least 72 hours.

[0048] In some embodiments, the thickness of the corrosion-resistant protective coating is ≥50 nm;

[0049] Optionally, the corrosion-resistant protective coating is a hard corrosion-resistant protective coating, and the thickness of the corrosion-resistant protective coating is ≥0.9μm;

[0050] When the corrosion-resistant protective coating is bonded to an aluminum alloy substrate, the hardness value of the hard corrosion-resistant protective coating is ≥10GPa;

[0051] When the corrosion-resistant protective coating is bonded to a stainless steel substrate, the hardness value of the hard corrosion-resistant protective coating is ≥12GPa.

[0052] In some implementations, x, y, and z satisfy the first or second set of characteristics as follows:

[0053] Group 1: 43.0≤x≤60.6, 25.6≤y≤37.0 and 13.8≤z≤20.0;

[0054] The second group: 54.4≤x≤90.0, 5.0≤y≤25.6, and 5.0≤z≤20.0;

[0055] Furthermore, the corrosion-resistant protective coating is also a high-brightness surface coating; wherein, tested by the Lab method, the brightness value L of the high-brightness surface coating is ≥80.

[0056] In a sixth aspect of this application, a method for preparing a Cr-Ti-N alloy film is provided, comprising the following steps: depositing the constituent elements of the Cr-Ti-N alloy film on at least a portion of the surface of a substrate according to a preset atomic ratio using a vapor deposition technique to form the Cr-Ti-N alloy film described in the second aspect of this application.

[0057] In some embodiments, the method for preparing the Cr-Ti-N alloy film includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using one or more targets including chromium and titanium, the constituent elements of the Cr-Ti-N alloy film are sputtered and deposited on at least a portion of the surface of the substrate to form the Cr-Ti-N alloy film.

[0058] In some embodiments, the method for preparing the Cr-Ti-N alloy film satisfies one or more of the following characteristics:

[0059] The sputtering deposition temperature is 30℃~330℃;

[0060] The total pressure of the mixed gas containing argon and nitrogen is 0.4 Pa to 1.8 Pa;

[0061] The target material includes a chromium target and a titanium target, and the power density of the chromium target is 0.5 W / cm². 2 ~9.1W / cm 2 The power density of the titanium target is 0.5 W / cm². 2 ~8.1W / cm 2 ;

[0062] The target material includes an alloy target, which comprises at least two metallic elements from the Cr-Ti-N alloy film; optionally, the target material includes a chromium-titanium-based alloy target, wherein the power density of the chromium-titanium-based alloy target is 4 W / cm². 2 ~6W / cm 2 ;

[0063] The substrate is biased from -150V to -20V;

[0064] The sputtering deposition time is 10 min to 150 min;

[0065] The nitrogen-containing gas is nitrogen, and the flow rate of the nitrogen gas is 3 sccm to 53 sccm;

[0066] The nitrogen-containing gas is nitrogen, and the ratio of argon to nitrogen in the mixed gas is (0.5-6):1.

[0067] The Cr-Ti-N alloy material provided in this application includes three elements: Cr, Ti, and N, and these three elements have a specific relative atomic ratio (Cr... x Ti y N z The properties of x, y, and z, ≤ 90.0, 5.0 ≤ x ≤ 79.0, and 2.4 ≤ z ≤ 26.5, give this Cr-Ti-N alloy material the ability to form a highly disordered distribution and a sufficiently dense packing of atoms, resulting in a dense Cr-Ti-N alloy coating. When the Cr-Ti-N alloy film or coating provided in this application is located on the surface of a product, it provides excellent corrosion resistance. The Cr-Ti-N alloy film and coating containing the Cr-Ti-N alloy material provided in this application exhibit a significantly longer protection time in salt spray corrosion tests than traditional Cr-Ti-N alloy coatings.

[0068] Furthermore, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application not only offer excellent corrosion resistance but also possess high hardness, thereby better reducing scratch formation or mitigating scratch damage. Moreover, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0069] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application is located on the surface of the product, it can also give the product a beautiful surface with high gloss.

[0070] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can be applied to a variety of substrates, including but not limited to alloys, elemental metals, inorganic non-metallic materials, and other substrates.

[0071] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can be used as a surface layer of alloy film products, combining aesthetic decoration with the aforementioned protective functions. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can also be located between the substrate and the surface layers of other structures, providing excellent protection and superior corrosion resistance and scratch resistance.

[0072] When Cr-Ti-N alloy films or coatings are bonded to the surface of light alloy substrates (such as titanium alloys), they not only enhance the corrosion resistance and hardness of the titanium alloy surface, thus improving its protective capabilities, but also, due to the presence of a certain amount of Ti in the Cr-Ti-N alloy films and coatings, their coefficients of thermal expansion relative to the light alloy substrate (such as titanium alloys) are similar. This results in excellent adhesion between the Cr-Ti-N alloy films or coatings and the light alloy substrate (such as titanium alloys). Furthermore, titanium is abundant in nature and has a relatively low manufacturing cost.

[0073] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application appears in the protective coating of an alloy film product, the position of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be flexibly set. For example, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be used for surface protection. In this case, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is located on the surface of the alloy film product, which can provide a high-gloss surface for the alloy film product. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating can also be used as an intermediate protective layer. In this case, other structural layers are provided on the outside of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating, that is, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is not used as a surface layer. Cr-Ti-N alloy films or Cr-Ti-N alloy coatings in different positions can achieve good corrosion resistance and good scratch resistance.

[0074] The preparation methods of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings provided in this application are simple, easy to operate, environmentally friendly, and have the advantages of being quantifiable, efficient, and reproducible, making them suitable for industrial applications.

[0075] Details of one or more embodiments of the present invention are set forth in the following drawings and description. Other features, objects, and advantages of the invention will become apparent from the specification, drawings, and claims. Attached Figure Description

[0076] 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.

[0077] In the following description, the same reference numerals indicate the same parts.

[0078] Figure 1 is a schematic diagram of the structure of an alloy film product containing Cr-Ti-N alloy material according to an embodiment of this application. The alloy film product includes a substrate and a Cr-Ti-N alloy film.

[0079] Figure 2 is a schematic diagram of the structure of the alloy film product in several embodiments of this application; (A) includes a substrate, a transition layer and a Cr-Ti-N alloy film; (B) includes a substrate, a transition layer, a Cr-Ti-N alloy film and a surface layer; (C) includes a substrate, a Cr-Ti-N alloy film and a surface layer.

[0080] Figure 3 is a schematic diagram of an apparatus for preparing Cr-Ti-N alloy film or Cr-Ti-N alloy coating according to an embodiment of this application;

[0081] Figure 4 shows the Cr prepared in Example 1 of this application. 5.0 Ti 79.0 N 16.0 SEM cross-sectional view of the alloy coating;

[0082] Figure 5 shows the Cr prepared in Example 1 of this application. 5.0 Ti 79.0 N 16.0 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;

[0083] Figure 6 shows the Cr prepared in Example 2 of this application. 12.7 Ti 77.9 N 9.4 SEM cross-sectional view of the alloy coating;

[0084] Figure 7 shows the Cr prepared in Example 2 of this application. 12.7 Ti 77.9 N 9.4 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0085] Figure 8 shows the Cr prepared in Example 3 of this application. 5.0 Ti 68.6 N 26.4 SEM cross-sectional view of the alloy coating;

[0086] Figure 9 shows the Cr prepared in Example 3 of this application. 5.0 Ti 68.6 N 26.4 XRD diffraction pattern of the alloy coating;

[0087] Figure 10 shows the Cr prepared in Example 4 of this application. 14.8 Ti 70.0 N 15.2 SEM cross-sectional view of the alloy coating;

[0088] Figure 11 shows the Cr prepared in Example 4 of this application. 14.8 Ti 70.0 N 15.2 XRD diffraction pattern of the alloy coating;

[0089] Figure 12 shows the Cr prepared in Example 5 of this application. 18.0 Ti 66.0 N 16.0 SEM cross-sectional view of the alloy coating;

[0090] Figure 13 shows the Cr prepared in Example 5 of this application. 18.0 Ti 66.0 N 16.0 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;

[0091] Figure 14 shows the Cr prepared in Example 6 of this application. 21.0 Ti 60.0 N 19.0 SEM cross-sectional view of the alloy coating;

[0092] Figure 15 shows the Cr prepared in Example 6 of this application. 21.0 Ti 60.0 N19.0 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;

[0093] Figure 16 shows the Cr prepared in Example 7 of this application. 27.0 Ti 68.0 N 5.0 SEM cross-sectional view of the alloy coating;

[0094] Figure 17 shows the Cr prepared in Example 7 of this application. 27.0 Ti 68.0 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;

[0095] Figure 18 shows the Cr prepared in Example 8 of this application. 36.6 Ti 49.2 N 14.2 SEM cross-sectional view of the alloy coating;

[0096] Figure 19 shows the Cr prepared in Example 8 of this application. 36.6 Ti 49.2 N 14.2 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;

[0097] Figure 20 shows the Cr prepared in Example 9 of this application. 37.6 Ti 60.0 N 2.4 SEM cross-sectional view of the alloy coating;

[0098] Figure 21 shows the Cr prepared in Example 9 of this application. 37.6 Ti 60.0 N 2.4 XRD diffraction pattern of the alloy coating;

[0099] Figure 22 shows the Cr prepared in Example 10 of this application. 38.3 Ti 35.2 N 26.5 SEM cross-sectional view of the alloy coating;

[0100] Figure 23 shows the Cr prepared in Example 10 of this application. 38.3 Ti 35.2 N 26.5 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0101] Figure 24 shows the Cr prepared in Example 11 of this application. 43.0 Ti 37.0 N 20.0 SEM cross-sectional view of the alloy coating;

[0102] Figure 25 shows the Cr prepared in Example 11 of this application. 43.0 Ti 37.0 N 20.0 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;

[0103] Figure 26 shows the Cr prepared in Example 12 of this application. 44.0 Ti 37.0 N 19.0 SEM cross-sectional view of the alloy coating;

[0104] Figure 27 shows the Cr prepared in Example 12 of this application. 44.0 Ti 37.0 N 19.0 XRD diffraction pattern of the alloy coating;

[0105] Figure 28 shows the Cr prepared in Example 13 of this application. 49.2 Ti 37.0 N 13.8 SEM cross-sectional view of the alloy coating;

[0106] Figure 29 shows the Cr prepared in Example 13 of this application. 49.2 Ti 37.0 N 13.8 XRD diffraction pattern of the alloy coating;

[0107] Figure 30 shows the Cr prepared in Example 14 of this application. 53.0 Ti 30.0 N 17.0 SEM cross-sectional view of the alloy coating;

[0108] Figure 31 shows the Cr prepared in Example 14 of this application. 53.0 Ti 30.0 N 17.0 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;

[0109] Figure 32 shows the Cr prepared in Example 15 of this application. 54.4 Ti 25.6 N 20.0 SEM cross-sectional view of the alloy coating;

[0110] Figure 33 shows the Cr prepared in Example 15 of this application. 54.4 Ti25.6 N 20.0 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;

[0111] Figure 34 shows the Cr prepared in Example 16 of this application. 60.6 Ti 37.0 N 2.4 SEM cross-sectional view of the alloy coating;

[0112] Figure 35 shows the Cr prepared in Example 16 of this application. 60.6 Ti 37.0 N 2.4 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0113] Figure 36 shows the Cr prepared in Example 17 of this application. 60.6 Ti 25.6 N 13.8 SEM cross-sectional view of the alloy coating;

[0114] Figure 37 shows the Cr prepared in Example 17 of this application. 60.6 Ti 25.6 N 13.8 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;

[0115] Figure 38 shows the Cr prepared in Example 18 of this application. 62.9 Ti 18.9 N 18.2 SEM cross-sectional view of the alloy coating;

[0116] Figure 39 shows the Cr prepared in Example 18 of this application. 62.9 Ti 18.9 N 18.2 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;

[0117] Figure 40 shows the Cr prepared in Example 19 of this application. 69.4 Ti 25.6 N 5.0 SEM cross-sectional view of the alloy coating;

[0118] Figure 41 shows the Cr prepared in Example 19 of this application. 69.4 Ti 25.6 N 5.0 XRD diffraction pattern of the alloy coating;

[0119] Figure 42 shows the Cr prepared in Example 20 of this application. 72.2 Ti 5.0 N 22.8 SEM cross-sectional view of the alloy coating;

[0120] Figure 43 shows the Cr prepared in Example 20 of this application. 72.2 Ti 5.0 N 22.8 XRD diffraction pattern of the alloy coating;

[0121] Figure 44 shows the Cr prepared in Example 21 of this application. 75.0 Ti 5.0 N 20.0 SEM cross-sectional view of the alloy coating;

[0122] Figure 45 shows the Cr prepared in Example 21 of this application. 75.0 Ti 5.0 N 20.0 XRD diffraction pattern of the alloy coating;

[0123] Figure 46 shows the Cr prepared in Example 22 of this application. 90.0 Ti 5.0 N 5.0 SEM cross-sectional view of the alloy coating;

[0124] Figure 47 shows the Cr prepared in Example 22 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;

[0125] Figure 48 shows the Cr prepared in Example 23 of this application. 62.9 Ti 18.9 N 18.2 The SEM cross-sectional image of the alloy coating shows that a CrN layer (as a transition layer) is disposed between the substrate and the Cr-Ti-N alloy coating, which is in contact with the Cr-Ti-N alloy coating. The Cr-Ti-N alloy coating serves as the surface layer of the double-layer structure coating.

[0126] Figure 49 shows the Cr prepared in Example 24 of this application. 62.9 Ti 18.9 N 18.2The SEM cross-sectional image of the alloy coating shows that a Ti layer (as a transition layer) is disposed between the substrate and the Cr-Ti-N alloy coating, and a chromium nitride coating (as a surface layer) is also present above the Cr-Ti-N alloy coating; the alloy film product has a sandwich structure protective structure, and the Cr-Ti-N alloy coating serves as the middle structural layer of the three-layer coating structure.

[0127] Figure 50 shows the Cr prepared in Comparative Example 1 of this application. 20.9 Ti 79.1 SEM cross-sectional view of the alloy coating;

[0128] Figure 51 shows the Cr prepared in Comparative Example 2 of this application. 44.4 Ti 16.1 N 39.5 SEM cross-sectional view of the alloy coating;

[0129] Figure 52 shows the Cr prepared in Comparative Example 2 of this application. 44.4 Ti 16.1 N 39.5 XRD diffraction pattern (A), selected area electron diffraction (SAED) pattern (B), and radial intensity profile (C) corresponding to the SEAD pattern of the alloy coating;

[0130] Figure 53 shows the Cr prepared in Comparative Example 3 of this application. 35.4 Ti 25.8 N 38.8 SEM cross-sectional view of the alloy coating;

[0131] Figure 54 shows the Cr prepared in Comparative Example 3 of this application. 35.4 Ti 25.8 N 38.8 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;

[0132] Figure 55 is a SEM cross-sectional view of the CrN alloy coating prepared in Comparative Example 4 of this application.

[0133] In the aforementioned XRD diffraction pattern, the horizontal axis represents 2θ (in degrees), and the vertical axis represents X-ray diffraction intensity (in au). Based on the selected area electron diffraction (SAED) pattern of the alloy coating, its corresponding radial intensity profile is obtained, expressed as characteristic interatomic spacing (d) - diffraction intensity, with d as the horizontal axis and units of angstroms. The vertical axis represents electron diffraction intensity, measured in au.

[0134] In the radial intensity profiles corresponding to XRD diffraction patterns and SAED patterns, au has a well-known meaning in the art.

[0135] In some SEM images, some cross-sectional delamination occurs when the silicon wafer is brittle and fractured during the preparation of the test sample, but this does not affect the observation and analysis of the cross-sectional morphology. The positions of different structural layers in the substrate and protective coating can be determined based on the thickness of the corresponding structural layer.

[0136] Explanation of reference numerals in the attached figures: 1 is the vacuum chamber, 2 is the sample stage, 3 is the DC anode, 4 is the chromium target (also referred to as the Cr target, which can be a Cr target with radio frequency assisted DC cathode power supply), and 5 is the titanium target (also referred to as the Ti target, which can be a Ti target with radio frequency assisted DC cathode power supply).

[0137] 100 is the substrate, 200 is the transition layer (also known as the transition film), 300 is the Cr-Ti-N alloy film, and 400 is the surface layer (also known as the surface film). Detailed Implementation

[0138] The present application will be further described in detail below with reference to the accompanying drawings, embodiments, and examples. It should be understood that these embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0139] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.

[0140] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0141] The terms “and / or,” “or / and,” and “and / or” as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. “Any and all combinations” includes any two related listed items, any more related listed items, or a combination of all related listed items. For example, “A and / or B” includes three parallel options: A, B, and “a combination of A and B.”

[0142] In this application, the terms "multiple", "various", "multiple times", "several", "several", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0143] In this application, unless otherwise specified, "one or more" means any one of the listed items or any combination of the listed items. Similarly, "one or more" and other instances that otherwise indicate "one or more" shall be understood in the same way unless otherwise specified.

[0144] The terms “combinations thereof,” “any combination thereof,” and “any combination thereof” as used in this application include all suitable combinations of any two or more of the listed items.

[0145] In this application, the word "suitable" in "suitable combination", "suitable method", "any suitable method" etc., shall be defined as being able to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0146] In this application, terms such as "preferred," "better," "more suitable," "more preferable," and "more advantageous" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0147] In this application, terms such as "further," "even more," "particularly," "for example," "like," "example," and "exemplary" are used for descriptive purposes to indicate that different technical solutions preceding and following each other are related in terms of their coverage, but should not be construed as limiting the preceding technical solution or restricting the scope of protection of this application. In this application, unless otherwise specified, A (e.g., B) indicates that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0148] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "present" or "absent." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. Unless otherwise specified, the descriptions such as "optionally include" and "optionally contain" in this application, taking "optionally include" as an example, mean "may include or not include." "Optional component X" indicates whether component X exists or does not exist.

[0149] The terms “containing,” “comprising,” and “including” as used in this application are synonyms and are inclusive or open-ended, not excluding additional, uncited members or features. Members or features include, for example, materials or components, structures, elements, instruments, etc.; non-limiting examples of members or features include actions, conditions under which actions occur, timing, states, etc.

[0150] In this application, the technical features or solutions described in open-ended language include both closed-ended technical features or solutions consisting of the listed contents and open-ended technical features or solutions that include the listed contents.

[0151] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0152] In this article, unless otherwise specified, "approximately" indicates a range within a certain degree above and below the given number. The range of fluctuation may vary depending on the type and value of the given number. For example, fluctuations within ±2%, ±1%, ±0.5%, etc., are permitted. For instance, "approximately 2°" could be expressed as 2° ± 0.02°, etc.

[0153] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0154] In this application, the term "room temperature" generally refers to 4℃ to 35℃, for example, 20℃ ± 5℃. In some embodiments of this application, "room temperature" refers to 10℃ to 30℃. In some embodiments of this application, "room temperature" refers to 20℃ to 30℃.

[0155] In this application, if the unit for a data range is only followed by the right endpoint, it indicates that the units for the left and right endpoints are the same. For example, 3~5h means that the units for the left endpoint "3" and the right endpoint "5" are both h (hours), and both have the same meaning as 3h~5h. Furthermore, similar descriptions involving other parameters such as temperature and size also apply to the above understanding.

[0156] In this application, the temperature unit ℃ refers to "degrees Celsius". The unit "angstrom" indicates the angle of view. The size unit μm represents the micrometer, and "nm" represents the nanometer. The pressure unit Pa refers to the Pascal. The power density unit of the target material is W / cm². 2 "Watts per square centimeter" refers to watts per square centimeter. The bias unit V stands for "volt." sccm (standard cubic centimeter per minute) is a unit of flow rate used to characterize gas flow.

[0157] The mass or weight of the relevant components mentioned in the embodiments of this application can refer not only to the content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Without limitation, the mass mentioned in the embodiments of this application can be a unit known in the chemical industry, such as microgram (μg), milligram (mg), gram (g), or kilogram (kg).

[0158] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0159] In this application, where the method flow involves multiple steps, unless otherwise explicitly stated herein, there is no strict order restriction on the execution of these steps; they can be executed in any order other than those described. Moreover, any step may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be performed alternately or simultaneously with other steps or parts of the sub-steps or stages of other steps.

[0160] When describing positional relationships, unless otherwise specified, when an element such as a layer, film, or substrate is referred to as being "on" another film layer, it may be directly on the other film layer or there may be intermediate film layers. Furthermore, when a layer is referred to as being "below" another layer, it may be directly below it or there may be one or more intermediate layers. It is also understood that when a layer is referred to as being "between" two layers, it may be the only layer between the two layers, or there may be one or more intermediate layers.

[0161] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0162] Unless otherwise stated, a singular term may include a plural term and should not be understood as having a quantity of one.

[0163] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0164] In this application, the exemplary descriptions such as "in some implementations (or embodiments)," "in one implementation (or embodiment)," "based on any suitable implementation in this application, in some implementations," or similar exemplary descriptions may cover, but are not limited to, the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0165] Traditional Cr-Ti-N alloy coatings are typically nanocrystalline with a high content of columnar crystals. This high content of columnar crystals promotes the formation of a highly ordered, oriented structure. The presence of numerous crystals within this highly ordered structure leads to intercrystalline gap defects, primarily manifested as through-crystal gaps. Correspondingly, shadows are observed between the columnar crystals in the cross-sectional images obtained using scanning electron microscopy (SEM). These through-crystal gaps may be a significant factor contributing to the poor corrosion resistance of the alloy coating. The inventors of this application hypothesize that the traditional ordered structure with its oriented orientation tends to result in insufficient coating density. Under corrosive conditions, corrosive media can rapidly penetrate the coating through these gaps and react with the substrate, thereby leading to poor corrosion resistance of the alloy coating.

[0166] In addition, traditional Cr-Ti-N alloy coatings often struggle to achieve high L values ​​in terms of brightness; for example, the L value is typically around 55 to 65.

[0167] Currently, alloy materials on the market mainly employ surface protection methods such as anodizing and magnetron sputtering. For example, aluminum alloys are primarily protected by anodizing. The working principle involves immersing the aluminum alloy material in a strong acid or alkali solution, forming an oxide and metal / alloy coating on the surface to create surface protection. However, because the solution is a strong acid or alkali, the resulting product has poor corrosion resistance, low hardness, and poor brightness. Furthermore, the production process generates large amounts of wastewater, waste liquid, and waste gas, which is detrimental to the environment.

[0168] According to various embodiments and examples of this application, this application provides at least one Cr-Ti-N alloy material, a Cr-Ti-N alloy film and its preparation method, a Cr-Ti-N alloy coating, an alloy film product, and its application. The Cr-Ti-N alloy material possesses excellent corrosion resistance and can form Cr-Ti-N alloy films, alloy coatings including Cr-Ti-N alloy films, or related alloy film products. The related Cr-Ti-N alloy films and Cr-Ti-N alloy coatings can be used as protective coatings for products, improving the protective capabilities of the products.

[0169] The Cr-Ti-N alloy material provided in this application may also be referred to as "Cr-Ti-N alloy material of this application", "Cr-Ti-N alloy material of this application", "Cr-Ti-N alloy material described in this application", "Cr-Ti-N alloy material of this application", "Cr-Ti-N alloy material of this application", "Cr-Ti-N alloy material of this application", "Cr-Ti-N alloy material provided in this application", "Cr-Ti-N alloy material described in this application", etc., and may include, but is not limited to, the Cr-Ti-N alloy material provided in the first aspect.

[0170] In this application, unless otherwise specified, "Cr-Ti-N alloy" and "CrTiN alloy" both refer to alloys containing Cr, Ti and N elements, and may also contain other alloying elements, and the two can be used interchangeably.

[0171] In this application, unless otherwise specified, "Cr-Ti-N alloy material" refers to an alloy material containing Cr, Ti, and N elements. Specifically, in the Cr-Ti-N alloy material provided in this application, the three elements Cr, Ti, and N have a specific atomic ratio x:y:z. In this application, the morphology of the Cr-Ti-N alloy material is not particularly limited and may be, but is not limited to, an alloy coating.

[0172] In this application, unless otherwise specified, "Cr-Ti-N ternary alloy" and "CrTiN ternary alloy" both refer to alloys composed of three elements: Cr, Ti and N.

[0173] In a first aspect of this application, a Cr-Ti-N alloy material is provided, comprising Cr, Ti and N elements, wherein the atomic ratio of Cr, Ti and N elements in the Cr-Ti-N alloy material is x:y:z, 5.0≤x≤90.0, 5.0≤y≤79.0, and 2.4≤z≤26.5.

[0174] In this application, unless otherwise specified, the “atomic ratio” of two or more elements refers to the ratio of the number of atoms, which can be calculated using the atomic molar ratio.

[0175] The Cr-Ti-N alloy material provided in this application includes three elements: Cr, Ti, and N, and these three elements have a specific relative atomic ratio (Cr... x Ti y N zThe properties of x, y, and z, ≤ 90.0, 5.0 ≤ x ≤ 79.0, and 2.4 ≤ z ≤ 26.5, give this Cr-Ti-N alloy material the ability to form a highly disordered distribution and a sufficiently dense packing of atoms, enabling the formation of a dense Cr-Ti-N alloy film or coating. When the Cr-Ti-N alloy film or coating provided in this application is located on the surface of a product, it provides excellent corrosion resistance. The Cr-Ti-N alloy film and coating containing the Cr-Ti-N alloy material of this application exhibit a significantly longer protection time in salt spray corrosion resistance tests than traditional Cr-Ti-N alloy coatings.

[0176] Traditional Cr-Ti-N alloy coatings are typically nanocrystalline with a high content of columnar crystals, and their structure usually contains numerous through-pores, resulting in poor corrosion resistance. However, the Cr-Ti-N alloy material provided in this application can form a dense coating with a highly disordered and sufficiently densely packed structure, containing very few through-pores or non-through-pores. The Cr, Ti, and N atoms, with their distinct radii, have a specific atomic ratio that facilitates aggregation into a highly disordered state during deposition. This highly disordered state allows for close packing, promoting dense growth of the alloy coating and inhibiting the formation of continuous, numerous through-pores, thus creating an effective barrier between the substrate and the corrosive environment. Furthermore, the presence of chromium and titanium in the Cr-Ti-N alloy coating provided in this application gives it sufficient chemical inertness in corrosive environments. Based on the Cr-Ti-N alloy material of this application, a Cr-Ti-N alloy coating can be formed that not only has a highly disordered atomic distribution, but also has sufficient packing at the atomic scale. This can avoid or reduce the through gaps formed due to the highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "sufficient packing" of atoms in the alloy coating make the alloy coating have a highly dense structure, which can provide excellent corrosion resistance.

[0177] Furthermore, the Cr-Ti-N alloy coating prepared using the Cr-Ti-N alloy material provided in this application has a dense structure, which provides excellent corrosion resistance while also having high hardness, thereby better reducing the occurrence of scratches or weakening scratch damage.

[0178] In the Cr-Ti-N alloy material, Cr-Ti-N alloy film, and Cr-Ti-N alloy coating provided in this application, based on the specific atomic ratio of Cr, Ti, and N, a certain amount of Cr, a certain amount of Ti, and a small amount of N are used. This makes it easier for Cr and Ti to form strong bond energies, which is beneficial for promoting the rapid growth of Cr-Ti alloy with a suitable atomic ratio during the deposition process. Furthermore, the addition of a small amount of nitrogen can further promote the re-nucleation of the Cr-Ti alloy to form a CrTiN-based alloy composition. By improving the density of the coating nucleation, the corrosion resistance and hardness of the coating can be improved. Specifically, in terms of atomic size, the atomic radius of Cr is... The atomic radius of Ti is The atomic radius of N is Cr and Ti have similar atomic sizes, while N atoms are smaller. During nucleation, an appropriate amount of small N atoms can penetrate into the pores of large Cr and Ti metal grains with suitable atomic ratios, achieving a better pore-filling effect and making the atomic arrangement more compact. At the same time, it can suppress the growth defects of the columnar crystal structure of the thin film, thereby improving the corrosion resistance of the coating and also helping to improve the hardness of the coating.

[0179] The numerous through-pores in traditional Cr-Ti-N alloy coatings result in poor surface reflectivity and low brightness. However, when the Cr-Ti-N alloy film or coating provided in this application is applied to the surface of a product, it can impart a high-brightness, aesthetically pleasing surface. Cr is a high-brightness metallic raw material in coating materials; a higher Cr content effectively enhances the brightness of the alloy coating. Simultaneously, the Cr-Ti-N alloy material provided in this application can be formulated into a highly dense Cr-Ti-N alloy coating, further improving the surface reflectivity of the coating. The combination of these two characteristics results in higher brightness and a higher brightness value (i.e., L value) during colorimetric measurements. The L value of the Cr-Ti-N alloy coating provided in this application can reach ≥75, and in some cases, ≥80, exhibiting a high-brightness silvery-white color, far exceeding the L value of traditional alloy coatings (traditional L values ​​are approximately 55-65). High-gloss coatings offer aesthetic appeal and excellent decorative properties. When applied to substrates (such as pure metals and alloys), they achieve a high-gloss, aesthetically pleasing effect, making the coating color more closely match the substrate and creating a near-colorless surface. This characteristic gives the Cr-Ti-N alloy coating provided in this application excellent surface decoration effects, making it suitable for (but not limited to) 3C digital products, such as mobile phone components, achieving a high-gloss metallic effect. It can also be applied to wearable products, automotive products, and sporting goods.

[0180] In this application, unless otherwise specified, the Lab method may be used to represent the test and analysis luminance value L.

[0181] In this application, when testing the chromaticity value of the alloy coating, the sample used is made of a substrate material suitable for practical applications. A Konica CM-3700A-U benchtop spectrophotometer (Japan) can be used to test the L, a, and b values ​​of the sample. An F2 light source is selected as the light receiving system. At least six (e.g., 6) matrix points are tested for each sample, and the average value is taken. Here, the L value represents the luminance value, the a value represents the red 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; a positive value represents the red chromaticity value, and a negative value represents the green chromaticity value. The b value represents the yellow-blue color of the object; a positive value represents the yellow chromaticity value, and a negative value represents the blue chromaticity value. A larger L value indicates higher luminance, indicating a denser coating surface. The mechanism is as follows: When incident light is incident on the surface of the sample, a reflectance curve is obtained. The amplitude of the curve can reflect the density of the material, which can be characterized by the L value. For the same material, the higher its density, the larger the L value it displays.

[0182] In this application, unless otherwise specified, the colorimetric value Lab is tested as follows: an F2 light source is selected for the light receiving system, and multiple (e.g., 6) matrix points are tested for each sample, and the average value is taken. Furthermore, a spectrophotometer is used for testing. Even further, the testing instrument is a Konica CM-3700A-U benchtop spectrophotometer manufactured in Japan. The testing temperature can be room temperature, or more specifically, 25°C.

[0183] The Cr-Ti-N alloy material provided in this application possesses a highly disordered atomic distribution and a high degree of atomic density. It can achieve dense atomic packing even with a highly disordered atomic arrangement, resulting in a unique atomic arrangement of "highly disordered and sufficiently densely packed" in the formed Cr-Ti-N alloy film and coating. This avoids or reduces the formation of through-grain gaps caused by highly ordered arrangement, resulting in a highly dense structure in the Cr-Ti-N alloy film and coating. This provides excellent corrosion resistance, as well as high hardness and high gloss. Using the Cr-Ti-N alloy material provided in this application to prepare Cr-Ti-N alloy coatings can effectively reduce common defects in traditional crystalline coatings. For example, through-grain gaps in columnar crystal structure coatings are significantly reduced or eliminated, making the Cr-Ti-N alloy coating more conducive to dense growth. This imparts excellent corrosion resistance to the alloy coating and also helps to improve coating hardness and obtain a smooth, high-gloss surface.

[0184] In some implementations, x can be any of the following values ​​or an interval selected from 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, 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.

[0185] In some implementations, y can be any of the following values ​​or an interval selected from any two of the following values: 5.0, 6.0, 7.0, 8.0, 10, 15, 18.3, 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, etc.

[0186] In some implementations, z can be any of the following values, or an interval selected from 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.

[0187] In the context of this application, x, y, and z can be combined in any suitable way, such as in the form x+y+z=100.

[0188] The Cr-Ti-N alloy materials, Cr-Ti-N alloy films, and Cr-Ti-N alloy coatings provided in this application may or may not contain doping elements, and can be flexibly selected according to one or more additional functional requirements of the alloy materials, alloy films, and alloy coatings. It is understood that in this application, when doping elements are present, the type and amount of doping elements are limited to at least not affecting the corrosion resistance of the Cr-Ti-N alloy coating; more preferably, at least one of high coating hardness and high surface gloss can also be achieved.

[0189] In some implementations, z / (x+y+z) ≤ 26.5%, and optionally, 2.4% ≤ z / (x+y+z) ≤ 26.5%. Non-limitingly, (x+y) / (x+y+z) can also be any of the following percentages or a range selected from any two of the following percentages: 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.

[0190] In some embodiments, a Cr-Ti-N alloy material is provided, comprising Cr, Ti, and N elements. In this Cr-Ti-N alloy material, the atomic ratio of Cr, Ti, and N elements is x:y:z, where 5.0 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 79.0, and 2.4 ≤ z ≤ 26.5. The Cr-Ti-N alloy material also includes doping elements. During the nucleation process, N atoms can penetrate into the pores of large-sized Cr and Ti metal grains, achieving a better pore-filling effect. This results in a denser atomic stack in the coating and can also suppress growth defects in the columnar crystal structure of the thin film, thereby improving the corrosion resistance of the coating.

[0191] In this application, the doping element in the Cr-Ti-N alloy material may be referred to as "M element". Unless otherwise specified, the doping element in the Cr-Ti-N alloy material refers to any element other than Cr, Ti and N in the Cr-Ti-N alloy material.

[0192] As a non-limiting example, in some embodiments, the doping element in the Cr-Ti-N alloy material may include carbon, and more specifically, may be carbon.

[0193] In some embodiments, the mass percentage of Cr, Ti, and N in the Cr-Ti-N alloy material (which can be denoted as f) wt It can be greater than or equal to 80%, optionally greater than or equal to 90%, and further optionally, f wt Greater than or equal to 95%, and further optionally, f wt It is 100%. Without limitation, f wt It can also be any of the following values, greater than or equal to any of the following values, or an interval selected from any two of the following values: 80%, 85%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc. wt It can also be greater than or equal to any of the aforementioned values ​​and less than or equal to 100%, for example, f. wtIt can be 80%–100%, 90%–100%, 95%–100%, 99%–100%, etc.

[0194] In other embodiments, the Cr-Ti-N alloy material mainly comprises three elements: Cr, Ti, and N. Furthermore, the sum of the atomic ratios of these three elements accounts for a proportion (which can be denoted as f) of the sum of the atomic ratios of all elements in the Cr-Ti-N alloy material. N ≥95%, further as f N ≥98%, and even higher, such as f N =100% (at this point, the Cr-Ti-N alloy material is a Cr-Ti-N ternary alloy material). Non-limitingly, f N It can also be any of the following values, greater than or equal to any of the aforementioned values, or an interval selected from any two of the following values: 95%, 96%, 97%, 98%, 99%, etc. N It can also be greater than or equal to any of the following values ​​and less than or equal to 100%, for example, f N It can be 95% to 100%.

[0195] By limiting the content of dopant elements in Cr-Ti-N alloy materials to a suitable range, the influence of dopant elements on the highly disordered and densely packed atoms in Cr-Ti-N alloy films and coatings can be minimized. This helps to reduce the number of components required for doping or reduce the difficulty of doping, simplify the preparation process, promote the synergistic deposition of Cr, Ti and N to form a denser coating, and achieve better corrosion resistance. In addition, it also helps to obtain higher hardness.

[0196] In some embodiments of this application, the Cr-Ti-N alloy material comprises Cr x Ti y N z M a The composition of the CrTiN-based alloy is given, where x, y, and z are each independently represented by positive atomic ratios, M is a dopant element, and a is the atomic ratio of element M, which is either 0 or positive.

[0197] In this application, unless otherwise specified, "CrTiN-based alloy composition" refers to an alloy composition that includes at least Cr, Ti, and N elements. Typically, Cr, Ti, and N constitute the main elements in a CrTiN-based alloy composition.

[0198] In this application, unless otherwise specified, "Cr-Ti-N ternary alloy composition" and "CrTiN ternary alloy composition" both refer to alloy compositions consisting of three elements: Cr, Ti, and N.

[0199] When a is 0, the CrTiN-based alloy composition does not contain dopants, corresponding to the Cr-Ti-N ternary alloy composition. When a > 0, the CrTiN-based alloy composition contains dopants, where a / (x+y+z) is numerically equal to the "relative atomic percentage of the dopant element relative to Cr, Ti, and N," and a / (x+y+z+a) is numerically equal to the atomic percentage of the dopant element in the CrTiN-based alloy composition. The "relative atomic percentage of the dopant element M relative to Cr, Ti, and N" refers to the ratio of the number of atoms of the dopant element M in the material to the sum of the number of atoms of Cr, Ti, and N, expressed as a percentage.

[0200] By limiting the content of dopant elements in the CrTiN-based alloy composition to a suitable range, the influence of dopant elements on the highly disordered and densely packed atoms in the CrTiN-based alloy composition can be minimized. This is beneficial for reducing the components required for doping or lowering the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Ti and N to form a denser Cr-Ti-N alloy material, which is conducive to achieving better corrosion resistance. In addition, it is also beneficial to obtain higher hardness.

[0201] 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 Greater than or equal to 90%, and optionally, f w0 Greater than or equal to 95%, and further optionally, f w0 It is 100%. Without limitation, f w0 It can also be any of the following values, greater than or equal to any of the following values, or an interval selected from any two of the following values: 80%, 85%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc. w0 It can also be greater than or equal to any of the aforementioned values ​​and less than or equal to 100%, for example, f. w0 It can be 80%–100%, 90%–100%, or 95%–100%.

[0202] In some embodiments, the total atomic number of Cr, Ti, and N is the percentage of the total atomic number of all elements in the CrTiN-based alloy composition (which can be denoted as f). N0 It can be greater than or equal to 95%, further f N0 It can be greater than or equal to 98%, and further can be 100%. Without limitation, f N0It can also be any of the following values, greater than or equal to any of the following values, or an interval selected from any two of the following values: 95%, 96%, 97%, 98%, 99%, etc. N0 It can also be greater than or equal to any of the aforementioned values ​​and less than or equal to 100%, for example, f. N0 It can be 95% to 100%.

[0203] In some embodiments, the CrTiN-based alloy component constitutes a percentage by mass of the Cr-Ti-N alloy material (which can be denoted as f). w1 ) can be greater than or equal to 80%, optionally, f w1 Greater than or equal to 90%, and optionally, f w1 Greater than or equal to 95%, and further optionally, f w1 It is 100%. Without limitation, f w1 It can also be any of the following values, greater than or equal to any of the following values, or an interval selected from any two of the following values: 80%, 85%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc. w1 It can also be greater than or equal to any of the aforementioned values ​​and less than or equal to 100%, for example, f. w1 It can be 80%–100%, 90%–100%, or 95%–100%. In some embodiments, f w1 The content is 100%. At this point, the Cr-Ti-N alloy material is a Cr-Ti-N ternary alloy material, with a simple composition, making it easier to prepare and control. The Cr-Ti-N ternary alloy coating formed at this time can obtain a dense structure, achieving high corrosion resistance; in addition, it can also obtain high coating hardness.

[0204] In some embodiments, a Cr-Ti-N alloy material is provided, comprising the chemical formula Cr x Ti y N z M aThe CrTiN-based alloy composition, in which M is a doping element, and x, y, z, and a are the atomic ratios of Cr element, Ti element, N element, and M element respectively, with 5.0 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 79.0, 2.4 ≤ z ≤ 26.5, and 0 ≤ a / (x + y + z + a) ≤ 0.05. By adjusting a / (x + y + z + a), the content of the doping element in the CrTiN-based alloy composition can be adjusted, and those skilled in the art can select a suitable value of a / (x + y + z + a) according to 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 intervals 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.

[0205] Numerically, a / (x + y + z + a) is equal to 1 - f N0 . For example, in some embodiments, a = 0, and f N0 is 100%. In some embodiments, a / (x + y + z + a) is 0.05, and f N0 is 95%.

[0206] In some embodiments, 0 ≤ a / (x + y + z + a) ≤ 0.05, and optionally, 0 ≤ a / (x + y + z) ≤ 0.05.

[0207] In some embodiments, 0 < a / (x + y + z + a) ≤ 0.05, and optionally, 0 < a / (x + y + z) ≤ 0.05.

[0208] 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 some 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 at a relatively low level, and the influence of the doping element on the highly disordered and fully dense-packed atoms in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating can be minimized, which is beneficial to reducing the required elements for doping or reducing the doping difficulty, simplifying the preparation process, promoting the co-deposition of Cr-Ti-N to form a denser coating, and is beneficial to achieving better corrosion resistance. In addition, it is also beneficial to obtain higher hardness and higher brightness.

[0209] In some implementations, 0 ≤ a / (x+y+z+a) ≤ 0.02. The value of a / (x+y+z+a) can also be found in the definition in the context.

[0210] In some embodiments, a / (x+y+z)=0. In this case, the composition corresponding to the Cr-Ti-N ternary alloy is simple, making it easier to prepare and control. The Cr-Ti-N ternary alloy coating formed in this way can achieve a dense structure, resulting in high corrosion resistance; furthermore, it can also achieve high coating hardness.

[0211] In the context of this application, x, y, z, and a can be combined in any suitable way, for example, in the form of x+y+z+a=100.

[0212] In some embodiments of this application, the chemical formula of the Cr-Ti-N alloy material is Cr x Ti y N z M a At this point, the mass percentage f of the CrTiN-based alloy component in the Cr-Ti-N alloy material is... w1 The value is 100%, where the definitions of x, y, z, and a can be found in the context of this application.

[0213] In some embodiments, x, y, and z satisfy the following characteristics: 54.4 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 25.6, and 5.0 ≤ z ≤ 20.0. This is beneficial for imparting higher brightness to the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating. Further optionally, x + y + z = 100.

[0214] In some embodiments, x, y, and z satisfy the following characteristics: 21.0 ≤ x ≤ 60.6, 37.0 ≤ y ≤ 60.0, and 2.4 ≤ z ≤ 19.0. The corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating may exhibit a stainless steel-like metallic color. Further optionally, x + y + z = 100.

[0215] In some embodiments, x, y, and z satisfy the following characteristics: 5.0 ≤ x ≤ 27.0, 66.0 ≤ y ≤ 79.0, 5.0 ≤ z ≤ 16.0, x ≤ 4.5y - 279, and 84 - y ≤ x ≤ 125.2 - 1.4y. The corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating can exhibit a titanium-like metallic color. Further optionally, x + y + z = 100.

[0216] In some embodiments, x, y, and z satisfy the following characteristics: 43.0 ≤ x ≤ 60.6, 25.6 ≤ y ≤ 37.0, and 13.8 ≤ z ≤ 20.0. This is beneficial for imparting higher hardness to the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating. Further optionally, x + y + z = 100.

[0217] Based on any suitable characteristics mentioned above (e.g., 5.0 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 79.0, 2.4 ≤ z ≤ 26.5, or any suitable combination of x, y, and z mentioned above), the sum of x, y, and z can be a value selected from 95 to 100. Without limitation, the sum of x, y, and z can be any of the following values, or can be selected from any interval consisting of any two of the following values: 95, 96, 97, 98, 99, 100, etc.

[0218] Based on any suitable characteristics mentioned above (e.g., 5.0 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 79.0, 2.4 ≤ z ≤ 26.5, or any suitable combination of x, y, and z), in some embodiments, the sum of x, y, and z is 100. In this case, the ratio of Cr, Ti, and N atoms is constrained within a more suitable range, making the resulting Cr-Ti-N alloy coating more likely to achieve a denser structure and better corrosion resistance. Furthermore, it can also improve coating hardness and further facilitate the achievement of higher gloss.

[0219] In some embodiments, the mass percentage f of the CrTiN-based alloy component in the Cr-Ti-N alloy material w1 It can be greater than or equal to 80%, further greater than or equal to 90%, even further greater than or equal to 95%, and can also be equal to 100%. See the definition above for further details.

[0220] In some embodiments, the Cr-Ti-N alloy material accounts for 100% of the mass percentage of the Cr-Ti-N alloy film.

[0221] In some embodiments, the Cr-Ti-N alloy material accounts for 100% by mass in the Cr-Ti-N alloy coating.

[0222] In some embodiments, based on any of the aforementioned suitable embodiments, x is greater than y. In this case, the Cr content in the Cr-Ti-N alloy material is high, exceeding the sum of the Ti and N contents. This specific atomic ratio design can better improve the nucleation density of the Cr-Ti-N alloy film and coating, thereby further improving their corrosion resistance. Furthermore, it can further improve hardness and brightness characteristics. During nucleation, N atoms can penetrate into the pores of large-sized Cr and Ti metal grains, achieving better pore-filling effects and resulting in denser atomic stacking in the coating. This significantly enhances corrosion resistance, promotes better hardness in the Cr-Ti-N alloy film and coating, better suppresses growth defects in the columnar crystal structure of the film, and further improves the surface reflectivity of the Cr-Ti-N alloy film and coating, thereby increasing brightness.

[0223] In some embodiments, the doping elements in the Cr-Ti-N alloy material are non-metallic elements, metallic elements, or combinations thereof, and can be flexibly selected according to the additional functional requirements of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating.

[0224] Non-limitingly, the non-metallic element may include, but is not limited to, one or more of O, C, B, Si, H, and Ar. Non-limitingly, the metallic element may include, but is not limited to, one or more of Zr, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

[0225] In some embodiments, the Cr-Ti-N alloy material is a constituent material of the Cr-Ti-N alloy film. In this case, the Cr-Ti-N alloy material constitutes the Cr-Ti-N alloy film. Further reference can be made to the context of this application regarding the Cr-Ti-N alloy film.

[0226] In some embodiments, the Cr-Ti-N alloy material is a constituent material of the Cr-Ti-N coating. In this case, the Cr-Ti-N alloy material constitutes the Cr-Ti-N alloy coating. Further reference can be made to the context of this application regarding the Cr-Ti-N alloy coating.

[0227] It should be noted that, in any embodiment within the context of this application, the Cr-Ti-N alloy material, Cr-Ti-N alloy film, and Cr-Ti-N alloy coating provided by this application are permitted to contain unavoidable impurities introduced during the preparation process. "Unavoidable impurities" are not intentionally added impurities; their presence is primarily due to unintentional introduction during the preparation process. Non-limiting examples of "unavoidable impurities" include elements such as C and O present in the air, and components from raw materials or equipment. The atomic content of "unavoidable impurities" in the alloy material, alloy film, or alloy coating is typically trace or minute, generally negligible, for example, less than 0.01% atomic content. Taking the technical solution of "Cr-Ti-N alloy coating being a Cr-Ti-N ternary alloy material composed of Cr, Ti, and N elements" as an example, theoretically, the Cr-Ti-N alloy coating is composed of Cr, Ti, and N elements. However, trace or minute amounts of other elements besides Cr, Ti, and N, such as C, O, and H, may be introduced during the preparation process.

[0228] In a second aspect of this application, a Cr-Ti-N alloy film is provided, at least a portion of which is composed of the Cr-Ti-N alloy material described in the first aspect of this application.

[0229] The Cr-Ti-N alloy film provided in this application may also be referred to as "Cr-Ti-N alloy film of this application", "Cr-Ti-N alloy film of this application", "Cr-Ti-N alloy film described in this application", "Cr-Ti-N alloy film of this application", "Cr-Ti-N alloy film of this application", "Cr-Ti-N alloy film of this application", "Cr-Ti-N alloy film provided in this application", "Cr-Ti-N alloy film described in this application", etc., and may include, but is not limited to, the Cr-Ti-N alloy film provided in the second aspect.

[0230] In a third aspect of this application, a Cr-Ti-N alloy coating is provided, comprising the Cr-Ti-N alloy film described in the second aspect of this application.

[0231] The Cr-Ti-N alloy coating provided in this application may also be referred to as "Cr-Ti-N alloy coating of this application", "Cr-Ti-N alloy coating of this application", "Cr-Ti-N alloy coating described in this application", "Cr-Ti-N alloy coating of this application", "Cr-Ti-N alloy coating of this application", "Cr-Ti-N alloy coating of this application", "Cr-Ti-N alloy coating provided in this application", "Cr-Ti-N alloy coating described in this application", etc., and may include, but is not limited to, the Cr-Ti-N alloy coating provided by a third party.

[0232] As mentioned earlier, based on the special atomic ratio of Cr, Ti, and N, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating form a highly disordered atomic distribution and a fully dense atomic arrangement, which has a "highly disordered and fully dense" dense structure. It can also suppress the formation of continuous and numerous penetrating gaps, significantly improving the corrosion resistance of the Cr-Ti-N alloy film and Cr-Ti-N coating.

[0233] The increased density of the Cr-Ti-N alloy film and coating structure allows for the achievement of higher hardness. The dense structure of the Cr-Ti-N alloy film and coating provided in this application offers excellent corrosion resistance while also possessing high hardness, thus better reducing scratch formation or mitigating scratch damage. Furthermore, the Cr-Ti-N alloy film and coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0234] The Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application can be used as the surface layer of alloy film products, providing both aesthetic decoration and protective functions. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can also be located between the substrate and the surface layer, providing excellent protection and superior corrosion resistance and scratch resistance.

[0235] The improved density of the Cr-Ti-N alloy film and Cr-Ti-N coating structure can also enhance surface reflectivity and thus increase brightness.

[0236] In some embodiments, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can each independently satisfy the following two characteristics:

[0237] The X-ray diffraction pattern of the Cr-Ti-N alloy film 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°.

[0238] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in... It has diffraction peaks within the range, and in The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies ≥

[0239] In some embodiments, the Cr-Ti-N alloy coating satisfies the following two characteristics:

[0240] 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°.

[0241] 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. The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies ≥

[0242] In some embodiments, the full width at half maximum (FWHM) of at least one 2θ(°) diffraction peak in the range of 34° to 50° in the X-ray diffraction pattern of the Cr-Ti-N alloy film satisfies ≥1.69°.

[0243] In some embodiments, the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 34° to 50° in the X-ray diffraction pattern of the Cr-Ti-N alloy coating satisfies ≥1.69°.

[0244] In some embodiments, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can each independently satisfy one or more of the following characteristics:

[0245] X-ray diffraction patterns of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings were obtained using Cu target Kα radiation.

[0246] Selected area electron diffraction (SEED) patterns of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings were obtained by TEM characterization, which was performed in a mode with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0247] The methods used in this application to characterize the structure of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings can also be used to characterize the Cr-Ti-N alloy material of the first aspect of this application. Furthermore, the Cr-Ti-N alloy material may not be limited to the coating form and may be an independent raw material, such as alloy sheets or alloy plates.

[0248] For example, in some embodiments, Cr-Ti-N alloy materials satisfy the following two characteristics:

[0249] The X-ray diffraction pattern of the Cr-Ti-N alloy material 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°.

[0250] In the radial intensity profile corresponding to the selected area electron diffraction pattern of Cr-Ti-N alloy, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in... It has diffraction peaks within the range, and The full width at half maximum (FWHM) of at least one diffraction peak within the range satisfies ≥

[0251] Furthermore, the XRD test results and radial intensity profiles corresponding to the selected area electron diffraction patterns of the Cr-Ti-N alloy material can also be found in the description of the X-ray diffraction patterns and radial intensity profiles corresponding to the selected area electron diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating in this paper. The corresponding optional and preferred methods can also be applied to this Cr-Ti-N alloy material.

[0252] The Cr-Ti-N alloy films and coatings provided in this application are not clearly categorized as either perfectly single crystals or fully amorphous states, but rather focus on the degree of close packing of atoms. Based on a specific atomic ratio of Cr, Ti, and N, this close packing degree is closely related to the disorder of atomic arrangement and the appropriate mismatch in atomic size. The highly dense Cr-Ti-N alloy films and coatings provided in this application exhibit excellent corrosion resistance. Furthermore, they also achieve high hardness and high brightness values. Structurally, they simultaneously satisfy the following requirements: at least one broad peak (furthermore, there can be no sharp peaks, i.e., all are broad peaks) within the diffraction angle range of 34°–50° in the XRD pattern, and the radial intensity profile of the selected area electron diffraction pattern... The range has at least one broad peak (furthermore, there may be no sharp peaks, that is, all are broad peaks).

[0253] Unlike traditional Cr-Ti-N alloy coatings that are nanocrystalline with a high columnar crystal content (containing numerous through-holes), the Cr-Ti-N alloy film and coating provided in this application can form a dense coating with a highly disordered and sufficiently densely packed structure, containing very few or no through-holes. In the Cr-Ti-N alloy film and coating provided in this application, the three atoms of Cr, Ti, and N with vastly different radii condense into a highly disordered state during deposition and form a dense packing, making the alloy coating easy to grow densely and suppressing the formation of continuous, numerous through-holes, thereby forming an effective isolation between the substrate and the corrosive environment. In addition, it can also form a dense, high-brightness surface with excellent reflective properties. Furthermore, since the Cr-Ti-N alloy film and coating provided in this application contain chromium and titanium, the coating has sufficient self-chemical inertness in the corrosive environment. The Cr-Ti-N alloy material in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application not only has a highly disordered atomic distribution, but also has sufficient packing at the atomic scale, thereby avoiding or reducing through-holes caused by highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "sufficient packing" of atoms in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating give the Cr-Ti-N alloy film and Cr-Ti-N alloy coating a highly dense structure, which can provide excellent corrosion resistance, as well as high hardness and high gloss surface.

[0254] Unless otherwise specified in this application, whether the constituent atoms of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating possess a "highly disordered" state is evaluated by XRD technology. Specifically, the XRD patterns of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating show broad and gentle ridges, which are referred to as "broad peaks" of the 2θ (°) diffraction peak. The length of the ordered atomic arrangement can be obtained from the half-maximum width at half-maximum (FWHM) of this broad peak using the Scherrer formula. The calculation method is: D = Kλ / (β·cosθ), where D is the length of the ordered atomic arrangement (representing the grain size in crystalline materials), K is the Scherrer constant, λ is the X-ray wavelength, β is the FWHM of the diffraction peak (the width at half-maximum of the 2θ (°) diffraction peak height), and θ is the diffraction angle. It is evident that the full width at half maximum (FWHM) is inversely proportional to the length D of the ordered atomic arrangement. The shorter the length D of the ordered atomic arrangement, the higher the disorder of the atomic distribution. Therefore, the FWHM of the diffraction peaks within a specific range in the XRD pattern can be used to reflect the degree of atomic disorder: the wider the FWHM, the shorter the length of the ordered atomic arrangement, and the more disordered the overall atomic distribution. The aforementioned broad and gently sloping "broad peaks" can reflect the highly disordered atomic distribution throughout the material.

[0255] Unless otherwise specified, this application refers to XRD diffraction patterns and diffraction peaks in the patterns, with the horizontal axis being 2θ and the unit being °.

[0256] In this application, unless otherwise specified, the "half-width at half maximum" (FWHM) of an XRD diffraction pattern refers to the diffraction peak with the horizontal axis at 2θ. As a non-limiting example, "FWHM" satisfying ≥1.6° means that the FWHM corresponding to the "2θ (°) diffraction peak" is ≥1.6°.

[0257] Generally speaking, the higher the atomic order, the stronger the crystallinity, and the easier it is to form large-sized grains over a longer distance. The narrower the diffraction peaks in the XRD pattern, and high crystallinity is often accompanied by sharp peaks. However, in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application, the Cr, Ti, and N atoms can be arranged in a highly disordered manner as a whole in the Cr-Ti-N alloy coating, which is manifested as a broad and gentle bulge (broad peak) in the XRD pattern of the Cr-Ti-N alloy coating. This is manifested as at least one "broad peak" in the diffraction angle range of 34° to 50° 2θ (°).

[0258] In this application, unless otherwise specified, a "broad peak" in an XRD pattern can be defined as a diffraction peak with a full width at half maximum (FWHM) of ≥1.6° (2θ(°)). The FWHM of a broad peak can further be ≥2°, even further ≥2.2°, even further ≥2.3°, even further ≥3°, even further ≥3.32°, even further ≥3.5°, even further ≥4°, even further ≥4.21°, and even further ≥5°. The full width at half maximum (FWHM) of any "broad peak" in an XRD pattern (in 2θ (°)) can independently be any of the following values: greater than or equal to any of the following values; greater than or equal to any of the following values ​​(except 10°) and less than or equal to 10°; or selected from an interval consisting of 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°, 3.32°, 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°, 7°, 7.5°, 8°, 8.00°, 8.5°, 9°, 9.5°, 9.50°, 10°, 10.00°, etc. As a non-limiting example, the half-width at half-maximum (in 2θ (°)) of the "broad peak" can be selected from any of the following ranges: 1.6°–10°, 1.8°–10°, 2°–10°, 3.32°–10°, 4.21°–10°, 1.6°–9.5°, 1.69°–5.40°, 1.8°–9.5°, 2°–9.5°, 3.32°–9.5°, 4.21°–9.5°, 2°–9.4°. 3.32°~9.4°, 1.6°~8°, 1.8°~8°, 2°~8°, 3.32°~8°, 4.21°~8°, 1.6°~6.0°, 1.8°~6.0°, 2°~6.0°, 3.32°~6.0°, 4.21°~6.0°, 1.6°~5.5°, 1.8°~5.5°, 2°~5.5°, 3.32°~5.5°, 4.21°~5.5°, etc.

[0259] In this application, unless otherwise specified, "peak" in an X-ray diffraction (XRD) pattern refers to a diffraction peak with a full width at half maximum (FWHM) of < 1.6° (in terms of 2θ (°)).

[0260] More specifically, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application have peaks in the XRD pattern within the diffraction angle range of 2θ (°) from 34° to 50°, and at least one diffraction peak in the XRD pattern is a broad peak. This special microstructure state of having at least one "broad peak" can be represented by the criteria of "having at least one 2θ (°) diffraction peak with a half-width at half-maximum (HWHM) ≥ 1.6° within the range of 34° to 50°" or "having at least one 2θ (°) diffraction peak with a HWHM ≥ 1.6° within the range of 34° to 50°". The following method can be used to determine whether the criteria of "having at least one 2θ (°) diffraction peak with a HWHM ≥ 1.6° within the range of 34° to 50°" are met: in the XRD pattern, if the HWHM value of the 2θ (°) diffraction peak is ≥ 1.6°, it is judged as a "broad peak"; if the HWHM value of the 2θ (°) diffraction peak is < 1.6°, it is judged as a sharp peak. For a given 2θ (°) position, it can be any of three states: no peak, broad peak, or sharp peak. In the X-ray diffraction (XRD) pattern, the characteristic broad peak characteristics of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application are quite obvious.

[0261] In traditional Cr-Ti-N alloy coatings with high columnar crystal content, the diffraction peaks in the diffraction angle range of 34° to 50° 2θ (°) often appear as sharp peaks with a half-width of less than 1.6°, without any broad peaks.

[0262] In this application, XRD patterns of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings can be obtained using conventional instruments and methods in the art. For example, a Bruker D8 Advance XRD diffractometer (Germany) can be used.

[0263] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application each independently have peaks in the diffraction angle range of 2θ (°) from 34° to 50°, and at least one 2θ (°) diffraction peak in the range of 34° to 50° is a broad peak. The full width at half maximum (FWHM) of the broad peak can be referred to the examples in the context. For example, if the FWHM of the broad peak is ≥3.32°, then at least one 2θ (°) diffraction peak in the range of 34° to 50° satisfies ≥3.32°.

[0264] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application each independently have a broad peak in the diffraction angle range of 2θ (°) from 34° to 50°, and the full width at half maximum (FWHM) of the broad peak can be seen in the examples in the context.

[0265] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application each independently have two or more broad peaks in the diffraction angle range of 2θ (°) from 34° to 50°, and the full width at half maximum (FWHM) values ​​of these broad peaks can be independently referred to in the examples in the context.

[0266] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application are all broad peaks in the diffraction angle range of 34° to 50°, i.e. there are no sharp peaks. The full width at half maximum (FWHM) values ​​of these broad peaks can be independently referred to in the examples in the context.

[0267] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application each independently have peaks in the diffraction angle range of 2θ (°) from 34° to 50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction peaks in the range of 34° to 50° each independently satisfies ≥1.6°, further can each independently satisfy ≥2°, even further can each independently satisfy ≥3.32°, even further can each independently satisfy ≥4.21°, and even further can each independently satisfy ≥5°.

[0268] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in this application each independently have one and only one diffraction peak in the diffraction angle range of 2θ (°) from 34° to 50°, and the peak is broad.

[0269] In some embodiments, the X-ray diffraction patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating are obtained by using Cu target Kα rays, and further by Kα1 rays.

[0270] In this application, the XRD patterns of Cr-Ti-N alloy films and alloy coatings can be obtained using the following instruments and methods: A Bruker D8 Advance XRD diffractometer from Germany is used in θ-2θ mode with Cu target Kα rays at a wavelength λ of 0.15406 nm. The X-ray tube is controlled at 40 kV and 40 mA, and the scanning range is 20° to 80° with precise scanning measurements in steps of 0.01°.

[0271] Conventional analytical methods in this field (including but not limited to analytical software provided by the instrument supplier) can be used to obtain the full width at half maximum (FWHM) value. For example, the steps to obtain the FWHM value may include: first, correcting the diffraction peak, which may include: smoothing, background subtraction, removal of Kα2 lines, and subtraction of instrument broadening, etc.; and then fitting the diffraction peak with the Pseudo-Voigt function to obtain the FWHM value of the diffraction peak.

[0272] There are no specific limitations on the analysis software. EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) can be used to process the spectral data. For example, the following method can be used: First, perform scale correction, then determine the center of the transmission spot of the diffraction ring, and then convert it into an XRD pattern (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm); after subtracting the straight background from the diffraction peaks, the Voigt function is used for fitting to obtain the full width at half maximum (FWHM) values ​​of the corresponding diffraction peaks.

[0273] Traditional XRD patterns cannot adequately characterize the atomic packing density in Cr-Ti-N alloy films and coatings. This is because XRD methods often suffer from insufficient resolution when inspecting physical vapor deposition (PVD) films or coatings at the atomic scale (e.g., diameter <3nm), due to the relatively large wavelength of X-rays (>0.1nm). Therefore, they are not suitable for PVD films or coatings with low order (e.g., grains with diameter <3nm or amorphous materials).

[0274] In this application, whether the atoms in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating achieve "sufficiently close packing" can be evaluated by selected area electron diffraction (SAED). Electron waves are chosen because their wavelengths are significantly smaller (<0.01 nm), resulting in higher resolution. Specifically, if only continuous diffraction rings of uniform brightness exist on the SEAD pattern, and these rings are relatively wide, it indicates that the atoms in the coating are arranged in a highly random and densely packed manner. For quantitative characterization, the SAED pattern can be converted into a characteristic interatomic spacing (d)-radial intensity profile, where the characteristic interatomic spacing (d) is on the x-axis and the diffraction intensity is on the y-axis. If the diffraction rings in the SEED are relatively wide, the corresponding half-width at half-maximum (FWHM) of the radial intensity profile is also relatively wide, reflecting a strong atomic packing in the alloy coating.

[0275] In this application, the atomic radius of Cr is [missing information]. The atomic radius of Ti is The atomic radius of N is Three types of atoms with significantly different diameters possess a suitable atomic size mismatch, and under conditions of high random mixing, they can form a sufficiently densely packed structure. During the growth of PVD thin films or alloy coatings, the sufficiently dense atomic packing in Cr-Ti-N alloy films and coatings facilitates dense growth, suppressing the formation and growth of columnar crystals that would otherwise result from localized ordering, thus making it difficult for continuous through-hole pores to form in large quantities. Therefore, the half-width at half-maximum (HWHM) of the radial intensity profile can be used as a characteristic parameter of the sufficiently densely packed structure of Cr-Ti-N alloy films and coatings to reflect the atomic packing density. The larger the HWHM value, the better the atomic packing density of the Cr-Ti-N alloy films and coatings. In short, this application's use of the HWHM of the SAED radial intensity profile as a characteristic parameter of sufficiently dense atomic packing is scientifically sound and consistent with established principles.

[0276] When the half-width at half-maximum (WHM) of the radial intensity profile exceeds a certain threshold, the atoms in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating can achieve sufficient close packing. Based on extensive experimental exploration by the inventors, in this application, unless otherwise specified, the threshold for determining whether sufficient close packing of atoms has been achieved in the SAED-radial intensity profile is defined as follows: That is, the half-width value is considered to be ≥ This allows for a fully dense packing of atoms.

[0277] In this application, transmission electron microscopy (TEM) technology can be used to obtain radial intensity profiles of characteristic interatomic spacing (d) of Cr-Ti-N alloy films and Cr-Ti-N alloy coating samples.

[0278] In this application, the radial intensity profile corresponding to the selected area electron diffraction (SAED) pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can be denoted as a SAED-radial intensity profile, or as a characteristic interatomic spacing-intensity quantitative spectrum of the selected area electron diffraction (SAED) pattern. The selected area electron diffraction pattern obtained using transmission electron microscopy (TEM) can be denoted as a TEM-SAED pattern, or as a TEM-SAED pattern. Similarly, the SAED-radial intensity profile obtained using TEM can also be denoted as a TEM-SAED-radial intensity profile.

[0279] In this application, alloy coatings (including the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application) can be obtained using conventional instruments and methods in the art. Based on the selected area electron diffraction (SAED) patterns of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating, their corresponding radial intensity profiles are obtained. These are expressed as characteristic interatomic spacing (d) versus diffraction intensity, with d as the abscissa and units in angstroms. The vertical axis represents electron diffraction intensity.

[0280] In this application, unless otherwise stated, in the radial intensity profile of the SAED plot, the full width at half maximum (FWHM) of the diffraction peaks is ≥ Then it is judged as a broad peak; the full width at half maximum (FWHM) of the diffraction peak is < These are identified as sharp peaks. For a specific characteristic atomic spacing, they can be any of three states: no peaks, sharp peaks, or broad peaks. In the radial intensity profile, the characteristic diffraction peaks of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application exhibit a relatively obvious broad peak characteristic. Unless otherwise specified, "broad peak" in the radial intensity profile of a selected area electron diffraction pattern (SAED) refers to a full width at half maximum (FWHM) ≥ 1 / 2. The diffraction peak, the "sharp peak" refers to the full width at half maximum (FWHM). The diffraction peaks.

[0281] In this application, radial strength profiles or SAED-radial strength profiles are involved, which can be obtained using TEM techniques unless otherwise specified.

[0282] In this application, unless otherwise specified, the "broad peak" in the radial intensity profile corresponding to the SAED diagram can be defined as having a half-width at half-maximum (WHM) of ≥ 1 / 2. The full width at half maximum (FWHM) of a broad peak can be further increased to ≥ Going further can be ≥ Going further can be ≥ Going further can be ≥ Going further can be ≥

[0283] In this application, the full width at half maximum (FWHM) data of the radial intensity profile corresponding to the selected area electron diffraction pattern can be obtained using (but not limited to) the following transmission electron microscopy (TEM) methods:

[0284] TEM test sample preparation: The sample was thinned using a Helios 5CX focused ion beam (FIB) from ThemoFisher Ltd. to obtain an electronically transparent, TEM-observable planar sample.

[0285] SAED Image Acquisition: A ThemoFisher Talos F200x transmission electron microscope (TEM) was used with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm to acquire the selected area electron diffraction (SAED) pattern of the sample. Based on the SAED pattern, a radial intensity profile was obtained, and the full width at half maximum (FWHM) value of the diffraction peak was obtained by integral assignment.

[0286] Based on the principle that the half-width at half-maximum (WHM) of diffraction peaks in the radial intensity profile corresponds to the width of diffraction rings in the selected area electron diffraction (SAED) pattern, the selected area electron diffraction (SAED) patterns of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings can be converted into corresponding radial intensity profiles.

[0287] Those skilled in the art will understand that the wider the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing of atoms, and the more sufficient the atomic packing in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application; the half-width at half-maximum (WHM) of the diffraction peak in the radial intensity profile is a quantitative indicator of the diffraction ring width, and the larger the WHM value, the more sufficient the atomic packing.

[0288] In some embodiments, the selected area electron diffraction (SAED) patterns of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating are obtained using transmission electron microscopy (TEM) with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0289] In some embodiments, the radial intensity profile of the selected area electron diffraction pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application shows that... Within the range, there is at least one half-width ≥ The diffraction peaks.

[0290] The radial strength profile of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application, The full width at half maximum (FWHM) of diffraction peaks within the range has an upper limit due to the atomic close-packing limit. An unrestricted example of this upper limit is as follows:

[0291] In this application, the half-width at half-maximum (WHM) of the "broad peak" in the radial intensity profile corresponding to the SAED diagram can independently be any of the following values, can be greater than or equal to any of the following values, and can be greater than or equal to any of the following values ​​but less than or equal to the aforementioned upper limit value (e.g., Each of the following can be independently selected from any two of the following intervals: Etc. As a non-limiting example, the full width at half maximum (FWHM) of the "broad peak" in the radial intensity profile corresponding to the SAED plot can be selected from any of the following ranges: etc.

[0292] In some embodiments, the radial strength profiles of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application show... The full width at half maximum (FWHM) of the diffraction peaks within the range is ≤

[0293] In some embodiments, the radial strength profiles of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application show... The full width at half maximum (FWHM) of each diffraction peak within the range can independently be any of the following values, can independently be greater than or equal to any of the following values, and can independently be selected from any two of the following value ranges: Etc. As a non-limiting example, it may be selected from any of the following ranges: wait.

[0294] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application is in The range contains one wide peak, whose full width at half maximum (FWHM) value can be found in the examples in the context. The wide peak's FWHM is ≥ 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 ≥

[0295] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application is in The range contains two or more broad peaks, and their half-width values ​​can be independently referenced in the examples in the context.

[0296] In some embodiments, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application is in All diffraction peaks within the range are broad peaks, and the full width at half maximum (FWHM) of all diffraction peaks satisfies ≥ See also the context definition.

[0297] In some embodiments, the characteristic atomic spacing of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application is obtained by TEM diffraction data; wherein, an electron accelerating voltage of 200kV and a selected area aperture diameter of 900nm are used to perform TEM diffraction tests on the alloy coating.

[0298] In some implementations, TEM testing uses an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm to obtain the selected area electron diffraction (SAED) pattern of the Cr-Ti-N alloy coating.

[0299] In some embodiments of this application, the thickness of the Cr-Ti-N alloy film (which can be denoted as d) M1 ) is d min ~6μm, where d min It can be selected from 10nm to 3μm; d min It can also be any of the following thicknesses, or a range selected from any two of the following thicknesses: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 100nm, 0.1μm, 0.2μm, 300nm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.8μm, 0.9μm, etc. Non-limitingly, d M1 It can also be any of the following thicknesses, or selected from any two of the following thickness ranges: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 100nm, 0.1μm, 0.2μm, 300nm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.8μm, 0.9μm, 1μm, 1.1μm, 1.2μm, 1.3μm, 1.4μm, 1.46μm, 1.5μm, 1.52μm, 1.6μm, 1.8μm, 1.87μm, 2μm, 2.0μm, 2.2μm, 2.5μm, 2.7μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, etc.; for example, the thickness d of the Cr-Ti-N alloy film. M1 It can be 25nm~6μm, 30nm~6μm, 40nm~6μm, 50nm~6μm, 0.3μm~6.0μm, 0.3μm~3.0μm, 0.3μm~2.5μm, 0.3μm~2.0μm, 0.5μm~6.0μm, 0.5μm~3.0μm , 0.5μm~2.5μm, 0.8μm~6.0μm, 0.8μm~3.0μm, 0.8μm~2.5μm, 0.9μm~6.0μm, 0.9μm~3.0μm, 0.9μm~2.5μm, 1.0μm~2.5μm, 1.0μm~2.0μm, etc.

[0300] In some implementations, d min The available sizes are 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 0.3μm, 0.5μm, 0.8μm, or 0.9μm.

[0301] In some embodiments, the thickness of the Cr-Ti-N alloy film is 0.3 μm to 2.5 μm, and optionally 0.3 μm to 2.0 μm.

[0302] In some embodiments of this application, the thickness of the Cr-Ti-N alloy coating (which can be denoted as d) M2 ) is d min ~6μm, where d min The definition of is given in the context. Without limitation, d M2 It can also be any of the following thicknesses, or a range selected from any two of the following thicknesses: 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 100nm, 0.1μm, 0.2μm, 300nm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.8μm, 0.9μm, 1μm, 1.1μm, 1.2μm, 1.3μm, 1.4μm, 1.46μm, 1.5μm, 1.52μm, 1.6μm, 1.8μm, 1.87μm, 2μm, 2.0μm, 2.2μm, 2.5μm, 2.7μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, etc.; for example, d M2 It can be 25nm~6μm, 30nm~6μm, 40nm~6μm, 50nm~6μm, 0.3μm~6.0μm, 0.3μm~3.0μm, 0.3μm~2.5μm, 0.3μm~2.0μm, 0.5μm~6.0μm, 0.5μm~3.0μm , 0.5μm~2.5μm, 0.8μm~6.0μm, 0.8μm~3.0μm, 0.8μm~2.5μm, 0.9μm~6.0μm, 0.9μm~3.0μm, 0.9μm~2.5μm, 1.0μm~2.5μm, 1.0μm~2.0μm, etc.

[0303] In some embodiments, the thickness of the Cr-Ti-N alloy coating is 0.3 μm to 2.5 μm, and optionally 0.3 μm to 2.0 μm.

[0304] By controlling the thickness of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating to a suitable level, the corrosion resistance and / or high hardness of the alloy film and coating can be better utilized. The thicker the Cr-Ti-N alloy film and Cr-Ti-N alloy coating, the more beneficial it is to improving the corrosion resistance and / or hardness of the alloy coating.

[0305] The Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application offer excellent corrosion resistance while also possessing high hardness, thus better reducing scratch formation or mitigating scratch damage. Furthermore, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application can achieve both high corrosion resistance and high hardness at a relatively low thickness, saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs. Compared to traditional alloy coatings, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application offer a denser structure, achieving at least one of better corrosion resistance and higher hardness at the same thickness. This allows for a reduction in the thickness of the alloy film or coating while maintaining superior protective properties, thereby saving raw materials, simplifying processes, shortening production cycles, and significantly reducing costs.

[0306] In some embodiments, the thickness of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is 10 nm to 6 μm.

[0307] In some embodiments, the thickness of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is 25 nm to 6 μm.

[0308] In some embodiments, the thickness of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is 1 μm to 2.5 μm.

[0309] Furthermore, when a relatively thin Cr-Ti-N alloy film or Cr-Ti-N alloy coating of this application is formed on the substrate, the resulting alloy film product can exhibit a silvery-white metallic luster, which is close to the metallic color of the substrate, thus achieving a beautiful decorative effect without altering the substrate color.

[0310] In a fourth aspect of this application, an alloy film article is provided, comprising a substrate and at least one of the Cr-Ti-N alloy film described in the second aspect of this application and the Cr-Ti-N alloy coating described in the third aspect of this application; wherein the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is located on at least one side of the substrate.

[0311] The alloy film product provided in this application includes a film layer composed of at least one of Cr-Ti-N alloy film and Cr-Ti-N alloy coating, and is therefore referred to as an alloy film product.

[0312] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can be used as a surface layer for alloy film products, serving both aesthetic and protective functions. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can also be located between the substrate and the surface layer, providing excellent protection and superior corrosion resistance and scratch resistance.

[0313] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can be located on one or both sides of the substrate.

[0314] In one embodiment shown in Figure 1, the alloy film article includes a substrate 100 and a Cr-Ti-N alloy film 300 located on one side of the substrate. It is understood that the Cr-Ti-N alloy film 300 may also be located on both sides of the substrate 100.

[0315] In some embodiments, the alloy film article includes a substrate and a Cr-Ti-N alloy coating located on one side of the substrate. It is understood that the Cr-Ti-N alloy coating may also be located on both sides of the substrate.

[0316] In some embodiments, a Cr-Ti-N alloy film or coating is bonded to a surface of a material near the substrate, comprising any one of the following: alloys, elemental metals, and inorganic non-metallic materials. Non-limitingly, the alloy material type may include one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based, and zinc-based materials. Non-limitingly, the elemental metal may be any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium. Non-limitingly, the inorganic non-metallic material may include one or more of ceramics and glass. Non-limitingly, the inorganic non-metallic material may include silicon wafers.

[0317] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can be applied to a variety of substrates. The substrate material can include, but is not limited to, alloys (such as aluminum alloys), elemental metals, inorganic non-metallic materials (such as silicon wafers, ceramics, and glass).

[0318] In some embodiments, the Cr-Ti-N alloy coating is bonded to a surface of a material near the substrate, consisting of a light alloy, a stainless steel alloy, or a silicon-based material. Non-limitingly, the light alloy may include one or more of titanium alloys, aluminum alloys, and magnesium alloys. Non-limitingly, the silicon-based material may be a silicon wafer or a silicon-containing compound; further, the silicon-containing compound may include, but is not limited to, one or more of silicon oxides, silicon-carbon composites, and silicon-nitrogen composites.

[0319] In some embodiments, a Cr-Ti-N alloy film or Cr-Ti-N alloy coating is bonded to a surface of a material near the substrate: a light alloy or a stainless steel alloy. Without limitation, the light alloy may include one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0320] In some embodiments, a Cr-Ti-N alloy film or Cr-Ti-N alloy coating is bonded to the surface of a light alloy substrate on the side closest to the substrate. Without limitation, the light alloy may include one or more of titanium alloys, aluminum alloys, and magnesium alloys.

[0321] In some embodiments, a Cr-Ti-N alloy film or Cr-Ti-N alloy coating is bonded to the surface of an aluminum alloy substrate on the side closest to the substrate.

[0322] When Cr-Ti-N alloy films or coatings are bonded to the surface of light alloy substrates (such as titanium alloys), they not only enhance the corrosion resistance and hardness of the titanium alloy surface, thus improving its protective capabilities, but also, due to the presence of a certain amount of Ti in the Cr-Ti-N alloy films and coatings, their coefficients of thermal expansion relative to the light alloy substrate (such as titanium alloys) are similar. This results in excellent adhesion between the Cr-Ti-N alloy films or coatings and the light alloy substrate (such as titanium alloys). Furthermore, titanium is abundant in nature and has a relatively low manufacturing cost.

[0323] In some embodiments, a Cr-Ti-N alloy film or Cr-Ti-N alloy coating is bonded to the surface of the stainless steel alloy on the side closest to the substrate. Without limitation, the stainless steel alloy can be any of austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, etc.

[0324] In some embodiments, the alloy film article satisfies one or more of the following characteristics:

[0325] The Cr-Ti-N alloy film is in direct contact with the substrate (without a transition layer) or a transition layer is provided; furthermore, the transition layer can be a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed between the Cr-Ti-N alloy film and the substrate);

[0326] The Cr-Ti-N alloy film is located on the surface of the alloy film product or on the side of the Cr-Ti-N alloy film away from the substrate, and the surface layer is a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed on the Cr-Ti-N alloy film provided in this application).

[0327] The Cr-Ti-N alloy coating is in direct contact with the substrate (without a transition layer) or has a transition layer (that is, one or more structural layers can be formed between the Cr-Ti-N alloy coating and the substrate);

[0328] The Cr-Ti-N alloy coating is located on the surface of the alloy film product, or the Cr-Ti-N alloy coating on the side away from the substrate is further provided with a surface layer, which is a single-layer structure or a multi-layer structure (that is, one or more structural layers can be formed on the Cr-Ti-N alloy coating provided in this application).

[0329] In this application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably. Both refer to a structural layer with transitional properties located between the substrate and the Cr-Ti-N alloy film or Cr-Ti-N alloy coating in an alloy film product. It can be a single-layer structure or a multi-layer structure.

[0330] In this application, unless otherwise specified, "surface layer" and "surface film layer" have the same meaning and can be used interchangeably. Both refer to the structural layer in alloy film products located on the side of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating away from the substrate and located on the surface of the product. It can be a single-layer structure or a multi-layer structure.

[0331] In some embodiments, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is in direct contact with the substrate (in which case there is no transition layer).

[0332] In some embodiments, a transition layer is provided between the Cr-Ti-N alloy film or Cr-Ti-N alloy coating and the substrate.

[0333] In some embodiments, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is located on the surface of the alloy film article.

[0334] In some embodiments, a surface layer is also provided on the side of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating away from the substrate.

[0335] Figure 2 provides a schematic diagram of the structure of the alloy film product in several embodiments of this application; (A) includes a substrate 100, a transition layer 200 and a Cr-Ti-N alloy film 300; (B) includes a substrate 100, a transition layer 200, a Cr-Ti-N alloy film 300 and a surface layer 400; (C) includes a substrate 100, a Cr-Ti-N alloy film 300 and a surface layer 400.

[0336] In some embodiments, the alloy film article includes a substrate, a transition layer, and a Cr-Ti-N alloy coating.

[0337] In some embodiments, the alloy film article includes a substrate, a transition layer, a Cr-Ti-N alloy coating, and a surface layer 400.

[0338] In some embodiments, the alloy film article includes a substrate, a Cr-Ti-N alloy coating, and a surface layer 400.

[0339] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application appears in the protective coating of an alloy film product, the position of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be flexibly set. It can be used as a single structural layer of the protective coating, or as a layer in a multi-layered protective coating. For example, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be used for surface protection. In this case, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is located on the surface of the alloy film product, providing a high-gloss surface. Alternatively, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can also be used as an intermediate protective layer. In this case, other structural layers are provided on the outside of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating, meaning the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is not used as a surface layer. Different alloy film positions and different coating positions can achieve better corrosion resistance and scratch resistance.

[0340] In this application, unless otherwise specified, "protective coating" refers to a coating located on a substrate that protects the substrate. The protective function may include, but is not limited to, at least one of corrosion resistance, hardness protection (such as scratch resistance).

[0341] In some embodiments, the alloy film product can be one of the following: 3C digital products, automotive products, aerospace products, wearable products, and sports products.

[0342] Without limitation, 3C digital products may include, but are not limited to, mobile device components, wearable components, and automotive components.

[0343] Depending on the main components of the substrate, alloy film products can be any of the following: light alloy products, stainless steel products, elemental metals, and inorganic non-metallic substrate products (such as ceramic-based products, silicon-based products, and glass-based products), indicating that the main components of the substrate are light alloys, stainless steel, elemental metals, etc. Non-limitingly, light alloy products can include, but are not limited to, aluminum alloy products, titanium alloy products, and magnesium alloy products. Non-limitingly, stainless steel products can include, but are not limited to, austenitic stainless steel, ferritic stainless steel, and martensitic stainless steel. Non-limitingly, elemental metal products can be, but are not limited to, any of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver, and chromium, further including any of copper, aluminum, iron, silver, and chromium.

[0344] In one embodiment, the alloy film product is an aluminum alloy product.

[0345] In one embodiment, the alloy film product is a stainless steel product.

[0346] In one embodiment, the alloy film product is an inorganic non-metallic base product, and may further be a silicon-based product, a ceramic-based product, or a glass-based product.

[0347] In one embodiment, the alloy film product is a copper product.

[0348] Alloy film products can be intermediate or final products. Final products can be used or sold directly. Intermediate products can be further processed or assembled with other components into new products.

[0349] In a fifth aspect of this application, the application of the Cr-Ti-N alloy material described in the first aspect of this application in the preparation of a corrosion-resistant protective coating is provided, or the application of the Cr-Ti-N alloy film described in the second aspect of this application or the Cr-Ti-N alloy coating described in the third aspect of this application as a corrosion-resistant protective coating is provided.

[0350] Cr-Ti-N alloy films or Cr-Ti-N alloy coatings can be used as surface layers or located between the substrate and the surface layer.

[0351] In some implementations, the corrosion-resistant protective coating can pass a corrosion test for at least 48 hours according to the ASTM B117 salt spray test standard; wherein the composition of the corrosive solution used for the corrosion test is: sodium chloride, water and sodium hydroxide, with a pH of 6.5 to 7.2;

[0352] When a corrosion-resistant protective coating is bonded to an aluminum alloy substrate, the coating can pass a test cycle of T. m1 (e.g. T) m1 Corrosion test (48 hours);

[0353] When a corrosion-resistant protective coating is bonded to a stainless steel substrate, the coating can pass a test cycle of T. m2 (e.g. T) m2 Corrosion test (72 hours).

[0354] 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 protective coating bonded to aluminum alloy substrate" means that the corrosion-resistant protective coating is formed on the surface of the aluminum alloy substrate.

[0355] Without limitation, T m1 The duration can be 48 hours, 60 hours, 72 hours, 84 hours, 96 hours, 120 hours or longer.

[0356] Without limitation, T m2 The duration can be 72 hours, 84 hours, 96 hours, 120 hours, 144 hours or longer.

[0357] In some embodiments, taking an aluminum alloy substrate as an example, a corrosion-resistant protective coating, including the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application, is formed on the surface of the aluminum alloy substrate. This corrosion-resistant protective coating provides protection for ≥48 hours in a salt spray corrosion resistance test, meaning it can pass the 48-hour test. Most embodiments also pass the 72-hour test using the ASTM B117 salt spray test method. Further, more detailed test methods described above or below can be used. Taking an aluminum alloy substrate as an example, traditional alloy coatings, under the same test conditions, generally cannot achieve a protection time of 8 hours in a salt spray corrosion resistance test.

[0358] The Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application can combine excellent corrosion resistance and high hardness at a relatively low thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs. When the alloy coating is thin, the resulting alloy film product can exhibit a silvery-white metallic luster, closely resembling the metallic color of the substrate, which is more conducive to achieving an aesthetically pleasing decorative effect without altering the base material's color.

[0359] In some embodiments, the thickness of the corrosion-resistant protective coating is ≥50nm, and may also be greater than or equal to any of the following thicknesses, or may be selected from any two of the following thickness ranges: 50nm, 100nm, 0.1μm, 0.2μm, 300nm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.8μm, 0.9μm, 1μm, 1.1μm, 1.2μm, 1.3μm, 1.4μm, 1.46μm, 1.5μm, 1.52μm, 1.6μm, 1.8μm, 1.87μm, 2μm, 2.0μm, 2.2μm, 2.5μm, 2.7μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, etc.

[0360] In some embodiments, the corrosion-resistant protective coating is a hard corrosion-resistant protective coating; when the substrate of the corrosion-resistant protective coating is an aluminum alloy, the hardness value of the hard corrosion-resistant protective coating is ≥7.2GPa; when the substrate of the corrosion-resistant protective coating is stainless steel, the hardness value of the hard corrosion-resistant protective coating is ≥8.1GPa.

[0361] In some embodiments, the corrosion-resistant protective coating is a hard corrosion-resistant protective coating with a thickness ≥0.9μm; when the substrate of the corrosion-resistant protective coating is aluminum alloy, the hardness value of the hard corrosion-resistant protective coating is ≥10GPa; when the substrate of the corrosion-resistant protective coating is stainless steel, the hardness value of the hard corrosion-resistant protective coating is ≥12GPa.

[0362] In some embodiments, the corrosion-resistant protective coating is a hard corrosion-resistant protective coating with a thickness ≥0.9μm; when the substrate of the corrosion-resistant protective coating is aluminum alloy, the hardness value of the hard corrosion-resistant protective coating is ≥13GPa; when the substrate of the corrosion-resistant protective coating is stainless steel, the hardness value of the hard corrosion-resistant protective coating is ≥16GPa.

[0363] In some embodiments, the corrosion-resistant protective coating is a hard corrosion-resistant protective coating with a thickness ≥1.0μm; when the substrate of the corrosion-resistant protective coating is aluminum alloy, the hardness value of the hard corrosion-resistant protective coating is ≥14GPa; when the substrate of the corrosion-resistant protective coating is stainless steel, the hardness value of the hard corrosion-resistant protective coating is ≥16GPa.

[0364] In some embodiments, the application of the Cr-Ti-N alloy material described in the first aspect of this application in the preparation of a high-brightness surface coating, or the application of the Cr-Ti-N alloy film described in the second aspect of this application, or the Cr-Ti-N alloy coating described in the third aspect of this application, as a high-brightness surface coating; further, the brightness value L of the high-brightness surface coating is tested by the Lab method to be ≥75, and even further, L≥80. In some embodiments, the high-brightness surface coating also serves as a corrosion-resistant protective coating.

[0365] In this application, unless otherwise specified, "surface coating" refers to a coating located on the surface of the article, which may be the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application, or may include an additional surface layer on top of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application.

[0366] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application is located on the surface of the product, it can not only give the product a high-gloss surface, but also provide excellent corrosion resistance.

[0367] The L value of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided in this application can reach ≥75, some can reach ≥80, and some can reach ≥81, and exhibit a high-brightness silver-white color, which is much higher than the L value of traditional alloy coatings (traditional L value is about 55-65).

[0368] In some implementations, the luminance value L is tested using the Lab method and is ≥75, further L is ≥80, even further L is ≥81, and even further L is ≥82.

[0369] In some implementations, x, y, and z satisfy the first or second set of characteristics as follows:

[0370] Group 1: 43.0≤x≤60.6, 25.6≤y≤37.0 and 13.8≤z≤20.0;

[0371] The second group: 54.4≤x≤90.0, 5.0≤y≤25.6, and 5.0≤z≤20.0;

[0372] Furthermore, the corrosion-resistant protective coating is also a high-gloss surface coating; wherein, tested by the Lab method, the gloss value L of the high-gloss surface coating is ≥80.

[0373] In a sixth aspect of this application, a method for preparing a Cr-Ti-N alloy film is provided, comprising the following steps: depositing the constituent elements of the Cr-Ti-N alloy film at a predetermined atomic ratio on at least a portion of the surface of a substrate using vapor deposition technology, thereby forming the Cr-Ti-N alloy film described in the second aspect of this application. It is understood that the constituent elements of the Cr-Ti-N alloy film include at least Cr, Ti, and N elements.

[0374] In a sixth aspect of this application, a method for preparing a Cr-Ti-N alloy coating is also provided, comprising the following steps: depositing the constituent elements of the Cr-Ti-N alloy coating onto at least a portion of the surface of a substrate using vapor deposition technology according to a preset atomic ratio, thereby forming the Cr-Ti-N alloy coating described in the third aspect of this application. It is understood that the constituent elements of the Cr-Ti-N alloy coating include at least Cr, Ti, and N elements.

[0375] In this application, the phrase "depositing component X on at least a portion of the surface of the substrate" can mean that component X can be deposited directly on at least a portion of the surface of the substrate, or component X can be deposited after a transition layer is formed on at least a portion of the surface of the substrate.

[0376] The preparation methods of Cr-Ti-N alloy films and Cr-Ti-N alloy coatings provided in this application are simple, easy to operate, environmentally friendly, and have the advantages of being quantifiable, efficient, and reproducible, making them suitable for industrial applications.

[0377] The definition of the matrix may be incorporated into the context of this application, including but not limited to the second and third aspects of this application.

[0378] In some embodiments, the vapor deposition technique is physical vapor deposition. Further, physical vapor deposition can be achieved through one or more of the following methods: vacuum evaporation, sputtering deposition, arc plasma deposition, ion deposition, and molecular beam epitaxy.

[0379] In one embodiment, the physical vapor deposition method is magnetron sputtering deposition.

[0380] In some embodiments, sputtering deposition (such as magnetron sputtering deposition) technology is used to deposit the constituent elements of a Cr-Ti-N alloy film or Cr-Ti-N alloy coating onto at least a portion of the surface of the substrate according to a preset atomic ratio.

[0381] In some embodiments, the apparatus shown in FIG3 can be referred to. The apparatus shown in FIG3 includes a vacuum chamber 1, a sample stage 2, a DC anode 3, a chromium target 4, and a titanium target 5; wherein, the chromium target 4 is a chromium target with radio frequency assisted DC cathode charging, and the titanium target 5 is a titanium target with radio frequency assisted DC cathode charging. This figure is not drawn to a 1:1 scale, and the relative dimensions of the components are shown in the figure only as examples to facilitate understanding of this application, but are not necessarily drawn to actual scale, and the scale in the figure does not constitute a limitation of this application. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating described in this application can be formed by reactive sputtering with N2-containing gas (such as an Ar / N2 mixture) in the vacuum chamber 1.

[0382] In some embodiments, the method for preparing a Cr-Ti-N alloy film includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using one or more targets including chromium and titanium, the constituent elements of the Cr-Ti-N alloy film are sputtered and deposited on at least a portion of the surface of a substrate to form a Cr-Ti-N alloy film.

[0383] In some embodiments, the method for preparing a Cr-Ti-N alloy coating includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using one or more targets including chromium and titanium, the constituent elements of the Cr-Ti-N alloy coating are sputtered and deposited on at least a portion of the surface of the substrate to form a Cr-Ti-N alloy coating.

[0384] The nitrogen-containing gas can be, but is not limited to, nitrogen. In this case, the ratio of argon to nitrogen in the mixed gas can be (0.5–6):1, or (1–6):1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, etc., or any range of the two ratios mentioned above. By selecting nitrogen as the nitrogen-containing gas and controlling the nitrogen content to a certain level, the performance of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be further adjusted.

[0385] The target material may include one or more of chromium targets, titanium targets, and alloy targets. The alloy target includes at least two metallic elements in a Cr-Ti-N alloy film or Cr-Ti-N alloy coating. The atomic ratio of the metallic elements in the alloy target may be the same as or close to the atomic ratio of the corresponding metallic elements in the Cr-Ti-N alloy film or 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 embodiments, the atomic ratio of Cr to Ti in the chromium-titanium-based alloy target is (20%–25%):(80%–75%), for example, 18:66, 25:75, etc. In some embodiments, the alloy target includes all metallic elements in a Cr-Ti-N alloy film or Cr-Ti-N alloy coating. Examples of alloy targets can be found in Example 5 below.

[0386] In this application, unless otherwise specified, a "chromium-titanium based alloy target" includes at least chromium and titanium, and may include or exclude other elements. When other elements are included, it is understood that the chemical composition of the target material should generally be within the range of the predetermined chemical formula Cr. x Ti y N z M a Within the range. For example, a chromium-titanium based alloy target can be a chromium-titanium-nitrogen alloy target composed of chromium, titanium, and nitrogen (i.e., a CrTiN alloy target).

[0387] In some embodiments, a chromium-titanium alloy target is used to replace the chromium target 4 in Figure 3 and is installed in the position where the original chromium target 4 in Figure 3 was located.

[0388] In some embodiments, the method for preparing a Cr-Ti-N alloy film or Cr-Ti-N alloy coating, taking sputtering deposition (such as magnetron sputtering deposition) as an example, includes the following steps: under the condition of introducing a mixed gas containing argon and nitrogen, using a chromium target and a titanium target or a chromium-titanium alloy target (i.e., a CrTi alloy target), the constituent elements of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating are sputtered and deposited on at least a portion of the surface of the substrate, thereby forming a Cr-Ti-N alloy film or Cr-Ti-N alloy coating accordingly.

[0389] In some embodiments, the step of "sputtering and depositing the constituent elements of a Cr-Ti-N alloy film or Cr-Ti-N alloy coating on at least a portion of the surface of the substrate" further includes the following step: cleaning the substrate. The method for cleaning the substrate can employ conventional cleaning methods in this technical field (including but not limited to the decorative plating field).

[0390] In some embodiments, cleaning the substrate includes the following steps: ultrasonically cleaning the substrate in water for 10 to 15 minutes, vacuum drying the cleaned substrate for 15 to 20 minutes, and then placing it on the sample stage of a sputtering deposition apparatus (such as magnetron sputtering deposition). The sample stage can be a rotatable sample stage.

[0391] In one embodiment, cleaning the substrate includes the following steps: ultrasonically cleaning the substrate in deionized water (DI water) for 10 to 15 minutes, baking the cleaned substrate in a vacuum oven for 15 to 20 minutes, and then placing it on a rotatable sample stage in a vacuum chamber.

[0392] In some embodiments, after the step of "cleaning the substrate" and before the step of "sputtering and depositing the constituent elements of a Cr-Ti-N alloy film or Cr-Ti-N alloy coating on at least a portion of the surface of the substrate", the following step is further included: forming a transition layer (which may serve as a buffer film) on at least a portion of the surface of the cleaned substrate. For example, the constituent elements of the transition layer may be deposited onto at least a portion of the surface of the cleaned substrate.

[0393] In some embodiments, after forming a Cr-Ti-N alloy film or Cr-Ti-N alloy coating on one side of the substrate, a surface layer can be deposited, which can be a single-layer structure or a multi-layer structure.

[0394] In some embodiments, the method for preparing the Cr-Ti-N alloy film or Cr-Ti-N alloy coating satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0395] The sputtering deposition temperature is 30℃~330℃;

[0396] The total pressure of the mixed gas containing argon and nitrogen is 0.4 Pa to 1.8 Pa;

[0397] The target materials include chromium targets and titanium targets, with the chromium target having a power density of 0.5 W / cm². 2 ~9.1W / cm 2 Furthermore, the power density of the titanium target is 0.5 W / cm². 2 ~8.1W / cm 2 ;

[0398] The target material includes an alloy target, which comprises at least two metallic elements found in a Cr-Ti-N alloy film; optionally, the target material includes a chromium-titanium-based alloy target with a power density of 4 W / cm². 2 ~6W / cm 2 ;

[0399] The substrate bias voltage is -150V to -20V;

[0400] The sputtering deposition time is 10 min to 150 min;

[0401] The nitrogen-containing gas is nitrogen, and the flow rate of nitrogen is 3 sccm to 53 sccm;

[0402] The nitrogen-containing gas is nitrogen, and the ratio of argon to nitrogen in the mixed gas is (0.5-6):1, which can be (1-6):1.

[0403] 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.

[0404] In some embodiments, the total pressure of the mixed gas containing argon and nitrogen is 0.4 Pa to 1.8 Pa, and can be selected as 0.4 Pa to 1.0 Pa; for example, 0.4 Pa, 0.5 Pa, 0.8 Pa, 1 Pa, 1.2 Pa, 1.4 Pa, 1.6 Pa, 1.8 Pa, etc., or can be a range consisting of any two of the aforementioned pressures.

[0405] 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 Cr-Ti-N alloy film or Cr-Ti-N alloy coating formed by sputtering deposition.

[0406] In some embodiments, the target material includes a chromium target, and the power density of the chromium target can be 0.5 W / cm². 2 ~9.1W / 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 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 7W / cm2 8W / cm 2 9W / cm 2 9.1W / cm 2 ,wait.

[0407] In some embodiments, the target material includes a titanium target, and the power density of the titanium target can be 0.5 W / cm². 2 ~8.1W / cm 2 0.5W / 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 2 2.0W / cm 2 2.5W / cm 2 2.8W / cm 2 3W / cm 2 3.5W / cm 2 3.8W / cm 2 4W / cm 2 4.5W / cm 2 5W / cm 2 6W / cm 2 7W / cm 2 8W / cm 2 8.0W / cm 2 wait.

[0408] In some embodiments, the target material includes a chromium target and a titanium target, wherein the power density of the chromium target can be 0.5 W / cm². 2 ~9.1W / cm 2 Furthermore, the power density of the titanium target can reach 0.5 W / cm². 2 ~8.1W / cm 2 .

[0409] In some embodiments, the target material includes an alloy target comprising at least two metallic elements in a Cr-Ti-N alloy film or a Cr-Ti-N alloy coating; optionally, the target material includes a chromium-titanium-based alloy target, wherein the power density of the chromium-titanium-based alloy target can be 4 W / cm². 2 ~6W / cm 2 .

[0410] In some embodiments, the target material includes a chromium-titanium alloy target, and the power density of the chromium-titanium alloy target can be 6 W / cm². 2 .

[0411] In some implementations, a chromium-titanium alloy target is used, with a power density of up to 4 W / cm². 2 ~6W / cm 2 6W / cm can be selected. 2 .

[0412] In some implementations, the bias voltage of the substrate can be from -150V to -20V; for example, -150V, -120V, -100V, -90V, -80V, -60V, -50V, -40V, -30V, -20V, etc., or it can be a range consisting of any two of the aforementioned bias voltages.

[0413] In some embodiments, the flow rate of the nitrogen-containing gas can be 3 sccm to 53 sccm; for example, 3 sccm, 5 sccm, 10 sccm, 20 sccm, 25 sccm, 30 sccm, 40 sccm, 50 sccm, 53 sccm, etc., or it can be a range consisting of any two of the aforementioned gas flow rates. Furthermore, the nitrogen-containing gas can be nitrogen gas.

[0414] In some embodiments, the sputtering deposition time can be from 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 film and the target Cr-Ti-N alloy coating can be controlled by adjusting the deposition time; as the deposition time increases, the corresponding thickness of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating increases accordingly.

[0415] 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 film and Cr-Ti-N alloy coating provided in this application.

[0416] Understandably, argon and nitrogen-containing gases can be introduced into the vacuum chamber through a single path or mixed in a mixing cylinder before entering the chamber, thereby reducing the impurity content of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in this application and improving the performance of the alloy film and alloy coating.

[0417] In some embodiments, "depositing the constituent elements of a Cr-Ti-N alloy film or Cr-Ti-N alloy coating onto at least a portion of the substrate surface using sputtering deposition (such as magnetron sputtering) technology according to a preset atomic ratio" includes the following steps: introducing a mixed gas containing argon and nitrogen into a vacuum chamber 1, maintaining the pressure inside the vacuum chamber 1 at 0.3 Pa to 0.9 Pa, turning on the bias voltage and setting it to -150 V to -20 V, and setting the power density of the chromium target 4 to 0.5 W / cm². 2 ~9.1W / cm 2 The power density of titanium target 5 was set to 0.5 W / cm². 2 ~8.1W / cm 2 A Cr-Ti-N alloy film or Cr-Ti-N alloy coating is deposited on at least a portion of the surface of the cleaned substrate; furthermore, Cr-Ti-N alloy films or Cr-Ti-N alloy coatings of different thicknesses can be obtained by controlling the film formation time.

[0418] The following are some examples.

[0419] The embodiments of this application will be described in detail below with reference to some examples. It should be understood that these embodiments are only for illustrating this application and are not intended to limit the scope of this application. For experimental methods in the following embodiments where conditions are not specified, please refer to the guidelines given in this application first, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0420] In the following examples, the measurement parameters of the raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are subject to acceptable deviations due to instrument testing accuracy or operational precision.

[0421] In the following embodiments, some Cr-Ti-N alloy coatings are Cr-Ti-N alloy films.

[0422] Test method:

[0423] 1. Colorimetric value test of alloy film or alloy coating

[0424] When testing the colorimetric value of an alloy film or coating, the sample to be tested uses a substrate suitable for practical applications. The degree to which the alloy film or coating improves the properties of the substrate, such as its density, is detected. The surface material of the "substrate suitable for practical applications" can include, but is not limited to, aluminum alloys and stainless steel.

[0425] The L, a, and b values ​​of the samples were tested using a Konica CM-3700A-U benchtop spectrophotometer manufactured in Japan. An F2 light source was selected for the light receiving system. The average value was taken after testing 6 matrix points for each sample.

[0426] Wherein, L value represents the brightness value, a value represents the red or green chromaticity value, and b value represents the yellow or blue chromaticity value. The a value represents the red and green color of the object, with positive values ​​representing red chromaticity values ​​and negative values ​​representing green chromaticity values. The b value represents the yellow and blue color of the object, with positive values ​​representing yellow chromaticity values ​​and negative values ​​representing blue chromaticity values.

[0427] A larger L value indicates higher brightness and a denser coating surface. The mechanism is as follows: When incident light is incident on the surface of the sample, a reflectance curve is obtained. The amplitude of this curve reflects the density of the material, which can be characterized by the L value. For the same material, the higher its density, the larger the displayed L value.

[0428] 2. Morphology and composition analysis of alloy coatings

[0429] All samples tested used silicon wafers as the substrate.

[0430] Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used for testing.

[0431] Morphological analysis: A Hitachi Regulus 8230 scanning electron microscope was used.

[0432] Compositional analysis: X-ray energy dispersive spectroscopy (EDX) was performed using a Hitachi Regulus 8230 scanning electron microscope. The relative intensities of all elements were corrected using the ZAF method.

[0433] Test parameters: the accelerating voltage of electrons is 15 kV, the beam current is 10 μA, the magnification of the sample is 200x, and the average value of 10 points is taken for each sample.

[0434] 3. X-ray diffraction (XRD) test of alloy films or alloy coatings

[0435] When performing XRD tests on alloy films or alloy coatings, silicon wafers are used as the substrate.

[0436] 3.1. Calculate the full width at half maximum (FWHM) of the diffraction peaks in the XRD pattern.

[0437] The German Bruker D8 Advance XRD diffractometer was used in θ-2θ mode with Cu target Kα rays at a wavelength of 0.15406 nm. The X-ray tube was controlled at 40 kV and 40 mA, and the scanning range was 20° to 80° with precise scanning measurements in steps of 0.01°.

[0438] The steps to obtain the full width at half maximum (FWHM) value are as follows: First, the diffraction peak is corrected, including smoothing, background subtraction, removal of Kα2 lines, and subtraction of instrument broadening. Then, the diffraction peak is fitted with the Pseudo-Voigt function to obtain the FWHM value of the diffraction peak.

[0439] The spectral data were processed using EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney): First, scale correction was performed, then the center of the transmission spot of the diffraction ring was determined, and then it was converted into an XRD pattern (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm); the diffraction peaks were stripped of the straight background, and then fitted with the Voigt function to obtain the full width at half maximum (FWHM) values ​​of the corresponding diffraction peaks.

[0440] 3.2. Determine whether the XRD pattern of the alloy film or alloy coating shows broad peaks.

[0441] The method for determining whether there are broad peaks in the XRD diffraction pattern within the diffraction angle range of 34° to 50° is as follows: In the XRD pattern, if the full width at half maximum (FWHM) of the 2θ diffraction peak is ≥1.6°, it is judged as a broad peak; if the FWHM of the 2θ diffraction peak is <1.6°, it is judged as a sharp peak.

[0442] For a given 2θ (°) position, it can be any of the three states: no peak, sharp peak, or broad peak.

[0443] 4. Transmission electron microscopy (TEM) testing

[0444] When performing TEM tests on alloy films or alloy coatings, silicon wafers are used as the substrate.

[0445] 4.1. The following method was used to obtain the full width at half maximum (FWHM) data of the diffraction rings in the TEM diffraction pattern:

[0446] TEM test sample preparation: The sample was thinned using a Helios 5CX focused ion beam (FIB) from ThemoFisher Ltd. to obtain an electronically transparent, TEM-observable planar sample.

[0447] SAED Image Acquisition: A Talos F200x transmission electron microscope (TEM) from ThemoFisher, Inc. was used with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm to acquire the selected area electron diffraction (SAED) pattern of the sample.

[0448] Radial intensity profile acquisition: The SAED spectrum data obtained above was processed using EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney). First, scale correction was performed, then the center of the transmission spot of the diffraction ring was determined, and finally it was converted into a radial intensity profile (where the electron wavelength is 0.00251 nm and the X-ray wavelength is 0.154 nm), with the characteristic interatomic spacing as the abscissa and the diffraction intensity as the ordinate.

[0449] The steps to obtain the full width at half maximum (FWHM) value are as follows: subtract the straight background from the diffraction peak, and then fit it with the Voigt function to obtain the FWHM value of the corresponding diffraction peak.

[0450] 4.2. Determining the radial intensity profile of a TEM selected area electron diffraction pattern. Method for determining whether there are broad peaks within the range: The full width at half maximum (FWHM) of the diffraction peak corresponding to the characteristic atomic spacing is ≥ Then it is judged as a broad peak; the full width at half maximum (FWHM) of the diffraction peak corresponding to the characteristic atomic spacing is < It is identified as a sharp peak. For a specific characteristic atomic spacing, it can be any of three states: no peak, sharp peak, or broad peak.

[0451] 5. Salt spray corrosion resistance test of alloy film or alloy coating

[0452] When conducting salt spray corrosion resistance tests on alloy films or alloy coatings, the test sample uses a substrate suitable for practical applications to detect the degree to which the alloy film or alloy coating improves the corrosion resistance of the substrate. The surface material of the "substrate suitable for practical applications" can include, but is not limited to, aluminum alloys, titanium alloys, and stainless steel.

[0453] The ASTM B117 salt spray test standard was adopted, the solution pH value was 6.5 to 7.2, and the chemical composition of the solution was: sodium chloride (NaCl), deionized water and sodium hydroxide (NaOH).

[0454] A 12-hour period can be used as a sub-cycle of the salt spray corrosion resistance test.

[0455] The testing cycles for alloy coatings prepared on substrates of different materials can vary, for example:

[0456] The testing cycle for aluminum alloy matrix samples is 48 hours or 24 hours.

[0457] The testing cycle for stainless steel substrate samples is 144 hours or 96 hours.

[0458] The testing cycle for the copper substrate sample is 8 hours.

[0459] The standard for "Pass (OK)" in salt spray corrosion resistance testing is: after the test, the sample shows no corrosion, discoloration, or rust. For example, "Pass 48H" indicates a 48-hour salt spray corrosion resistance test. "Pass 72H" indicates a 72-hour salt spray corrosion resistance test. "Pass 144H" indicates a 144-hour salt spray corrosion resistance test. "Pass 8H" indicates an 8-hour salt spray corrosion resistance test.

[0460] The standard for "NG" (Not Passed) salt spray corrosion resistance test is: after the test, the sample shows signs of corrosion, discoloration, or rust. For example, "NG" indicates an 8-hour salt spray corrosion resistance test. "NG" indicates a 12-hour salt spray corrosion resistance test. "NG" indicates a 24-hour salt spray corrosion resistance test. "Protection Duration < 8h" indicates corrosion occurred within 8 hours of the test. "Protection Duration < 12h" indicates corrosion occurred within 12 hours of the test.

[0461] 6. Hardness test of alloy film or alloy coating

[0462] When testing the hardness of alloy films or alloy coatings, the sample to be tested should be a substrate suitable for practical applications.

[0463] The surface material of the "substrate suitable for practical application" may include, but is not limited to: aluminum alloy, titanium alloy, stainless steel, and copper sheet.

[0464] In the following examples, unless otherwise specified, aluminum alloy or stainless steel is used as the substrate when testing the hardness of alloy films or coatings. The alloy film or coating is deposited on the aluminum alloy or stainless steel using preset preparation parameters to obtain the test sample, which is then used to test the hardness of the alloy film or coating. This is mainly because: during nanoindentation testing, the probe penetrates the test sample, generating strong pressure. This requires the substrate to have a certain degree of toughness. If a brittle silicon wafer is used, cracking may occur during the test, leading to inaccurate test results. Alloy materials, due to their excellent toughness, are more suitable as the test substrate for nanoindentation testing. Furthermore, using alloy materials as the substrate for measuring nanohardness is more universally applicable in the fields of coatings and nanohardness parameter characterization.

[0465] The hardness of each film or coating was tested using an NHT3 nanoindenter manufactured by Anton-Paar in Austria. It was equipped with a tetrahedral Berkvich indenter, and the indentation depth was set to 100 nm. The load changed with the indentation depth. Five matrix points were tested for each sample and the average value was taken.

[0466] 7. Bonding Force Test Method

[0467] The adhesion strength is characterized by a cross-cut adhesion test, which can be performed according to or with reference to the provisions of GB / T 9286-2021 standard. The detailed steps are as follows: Use a manual single-edged cutting knife to cut 10×10 1mm×1mm grids on the coated area of ​​the sample surface. Apply 3M 610 adhesive tape to the grid area. Within 5 minutes of applying the tape, hold one end of the tape suspended in the air and peel it off smoothly at an angle of approximately 60° within 0.5s to 1.0s. Determine the grade according to the provisions of GB / T 9286-2021 standard, where grade 0 (marked as "OK") is passed, indicating that the alloy film or alloy coating has excellent adhesion, and grades 1-5 (marked as "NG") are failures.

[0468] The test results are described below and in Table 2.

[0469] In the following examples, DI water refers to deionized water.

[0470] The stainless steel sheets, titanium alloy sheets, aluminum alloy sheets, and silicon wafers in the following embodiments and comparative examples are all made of the same material.

[0471] In the following examples, the target material is sputtered using radio frequency assisted DC sputtering.

[0472] In the following examples, the XRD patterns and SAED-radial intensity profiles refer to "there is one and only one broad peak". Unless otherwise specified, this means that there is one and only one characteristic peak, and that peak is a broad peak.

[0473] The preparation parameters and some structural characterization parameters of the following embodiments and comparative examples can be found in Table 1.

[0474] In the following examples, the Cr-Ti-N alloy coating is a Cr-Ti-N alloy film.

[0475] Example 1.

[0476] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 5.0 Ti 79.0 N 16.0 At this point, the Cr-Ti-N alloy coating is a Cr-Ti-N alloy film.

[0477] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0478] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0479] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 22 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.5 Pa, turn on the bias voltage, and set it to -100 V. Set the power density of the Cr target to 0.5 W / cm³. 2 The power density of the Ti target was set to 8.0 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 2200 nm by controlling the film formation time.

[0480] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0481] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0482] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0483] The bonding strength was tested using titanium alloy sheets.

[0484] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 5.0 Ti 79.0 N 16.0 ;

[0485] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 4. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 5. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°. Among these, there is only one broad peak with a FWHM of 5.05° within the range of 34°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0486] Colorimetric test results: The colorimetric values ​​for the aluminum alloy substrate sample were L: 76.44, a: 0.58, b: 5.51; the colorimetric values ​​for the stainless steel substrate sample were L: 77.51, a: 0.55, b: 4.45.

[0487] Hardness test results: The hardness value of the aluminum alloy substrate sample was 19.6 GPa, and the hardness value of the stainless steel substrate sample was 16.2 GPa.

[0488] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0489] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0-level (“OK”) judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0490] Example 2.

[0491] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 12.7 Ti 77.9 N 9.4 .

[0492] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0493] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0494] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 15 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.4 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 1.3 W / cm². 2 The power density of the Ti target was set to 7.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 2200 nm by controlling the film formation time.

[0495] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0496] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0497] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0498] The bonding strength was tested using titanium alloy sheets.

[0499] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 12.7 Ti 77.9 N 9.4 ;

[0500] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 6. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 7. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°. Among these, there is only one broad peak with a FWHM of 4.87° within the range of 34°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0501] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 76.55, a: 0.59, b: 5.31, and the colorimetric values ​​of the stainless steel substrate sample are L: 77.09, a: 0.57, b: 4.59.

[0502] Hardness test results: The hardness value of the aluminum alloy substrate sample was 17.4 GPa, and the hardness value of the stainless steel substrate sample was 15.1 GPa.

[0503] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0504] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0505] Example 3.

[0506] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 5.0 Ti 68.6 N 26.4 .

[0507] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0508] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0509] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 32 sccm, maintain an Ar:N2 gas ratio of 1:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 0.6 W / cm³. 2 The power density of the Ti target was set to 7.0 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1800 nm by controlling the film formation time.

[0510] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0511] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0512] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0513] The bonding strength was tested using titanium alloy sheets.

[0514] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 5.0 Ti 68.6 N 26.4 ;

[0515] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 8. The XRD diffraction pattern can be seen in Figure 9. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 3.32° in the range of 34° to 50°.

[0516] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 77.21, a: 0.57, b: 3.37, and the colorimetric values ​​of the stainless steel substrate sample are L: 77.92, a: 0.54, b: 3.22.

[0517] Hardness test results: The hardness value of the aluminum alloy substrate sample was 15.3 GPa, and the hardness value of the stainless steel substrate sample was 17.3 GPa.

[0518] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0519] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0520] Example 4.

[0521] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 14.8 Ti 70.0 N 15.2 .

[0522] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0523] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0524] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 21 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure 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 / cm³. 2 The power density of the Ti target was set to 7.1 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1460 nm by controlling the film formation time.

[0525] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0526] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0527] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0528] The bonding strength was tested using titanium alloy sheets.

[0529] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 14.8 Ti 70.0 N 15.2 .

[0530] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 10. The XRD diffraction pattern can be seen in Figure 11. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 2.03° in the range of 34° to 50°.

[0531] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 77.21, a: 0.45, b: 4.55, and the colorimetric values ​​of the stainless steel substrate sample are L: 78.25, a: 0.43, b: 4.04.

[0532] Hardness test results: The hardness value of the aluminum alloy substrate sample was 17.7 GPa, and the hardness value of the stainless steel substrate sample was 17.4 GPa.

[0533] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0534] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0535] Example 5. Preparation using an alloy target.

[0536] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 18.0 Ti 66.0 N 16.0 .

[0537] In this embodiment, a chromium-titanium alloy target is selected as the target material. The original Cr target at the position of chromium target 4 in Figure 3 is replaced with a CrTi alloy target with an atomic percentage of 25%:75% for Cr and Ti.

[0538] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0539] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0540] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 22 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the CrTi target to 6 W / cm³. 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1100 nm by controlling the film formation time.

[0541] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0542] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0543] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0544] The bonding strength was tested using titanium alloy sheets.

[0545] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 18.0 Ti 66.0 N 16.0 .

[0546] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 12. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 13. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 3.00°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0547] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 79.14, a: 0.45, b: 2.48, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.07, a: 0.46, b: 2.53.

[0548] Hardness test results: The hardness value of the aluminum alloy substrate sample was 16.1 GPa, and the hardness value of the stainless steel substrate sample was 19.2 GPa.

[0549] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0550] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0551] Example 6.

[0552] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 21.0 Ti 60.0 N 19.0 .

[0553] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0554] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0555] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 25 sccm, maintain the Ar:N2 gas ratio at 2:1, maintain the furnace pressure at 0.7 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 2.1 W / cm². 2 The power density of the Ti target was set to 6.1 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1600 nm by controlling the film formation time.

[0556] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0557] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0558] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0559] The bonding strength was tested using titanium alloy sheets.

[0560] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 21.0 Ti 60.0 N 19.0 .

[0561] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 14. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 15. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 2.68°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0562] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 79.63, a: 0.42, b: 2.47, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.37, a: 0.44, b: 2.54.

[0563] Hardness test results: The hardness value of the aluminum alloy substrate sample was 15.8 GPa, and the hardness value of the stainless steel substrate sample was 17.3 GPa.

[0564] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0565] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0566] Example 7.

[0567] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 27.0 Ti 68.0 N 5.0 .

[0568] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0569] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0570] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 7 sccm, maintain an Ar:N2 gas ratio of 6:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 2.7 W / cm². 2 The power density of the Ti target was set to 6.6 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1300 nm by controlling the film formation time.

[0571] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0572] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0573] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0574] The bonding strength was tested using titanium alloy sheets.

[0575] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 27.0 Ti 68.0 N 5.0 .

[0576] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 16. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 17. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°. Among these, there is only one broad peak with a FWHM of 4.94° within the range of 34°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0577] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 79.01, a: 0.54, b: 2.75, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.29, a: 0.54, b: 2.68.

[0578] Hardness test results: The hardness value of the aluminum alloy substrate sample was 10.6 GPa, and the hardness value of the stainless steel substrate sample was 13.2 GPa.

[0579] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0580] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0581] Example 8.

[0582] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 36.6 Ti 49.2 N 14.2 .

[0583] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0584] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0585] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 20 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.5 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 3.7 W / cm². 2 The power density of the Ti target was set to 4.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1870 nm by controlling the film formation time.

[0586] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0587] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0588] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0589] The bonding strength was tested using titanium alloy sheets.

[0590] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 36.6 Ti 49.2 N 14.2 .

[0591] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 18. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 19. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 5.09°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0592] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 78.64, a: 0.46, b: 3.43, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.76, a: 0.43, b: 3.29.

[0593] Hardness test results: The hardness value of the aluminum alloy substrate sample was 14.0 GPa, and the hardness value of the stainless steel substrate sample was 14.8 GPa.

[0594] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0595] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0596] Example 9.

[0597] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 37.6 Ti 60.0 N 2.4 .

[0598] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0599] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0600] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 3 sccm, maintain the Ar:N2 gas flow ratio at 6:1, maintain the furnace pressure at 0.4 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 3.8 W / cm³. 2 The power density of the Ti target was set to 6.1 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1400 nm by controlling the film formation time.

[0601] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0602] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0603] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0604] The bonding strength was tested using titanium alloy sheets.

[0605] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 37.6 Ti 60.0 N 2.4 .

[0606] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 20. The XRD diffraction pattern can be seen in Figure 21. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 5.40° in the range of 34° to 50°.

[0607] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 79.64, a: 0.53, b: 2.68, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.68, a: 0.52, b: 2.62.

[0608] Hardness test results: The hardness value of the aluminum alloy substrate sample was 11.5 GPa, and the hardness value of the stainless steel substrate sample was 12.4 GPa.

[0609] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0610] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0611] Example 10.

[0612] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 38.3 Ti 35.2 N 26.5 .

[0613] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0614] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0615] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 32 sccm, maintain the Ar:N2 gas flow ratio at 1:1, maintain the furnace pressure at 0.8 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 3.9 W / cm³. 2 The power density of the Ti target was set to 3.6 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1200 nm by controlling the film formation time.

[0616] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0617] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0618] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0619] The bonding strength was tested using titanium alloy sheets.

[0620] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 38.3 Ti 35.2 N 26.5 .

[0621] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 22. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 23. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 2.91°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0622] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 80.64, a: 0.25, b: 3.24, and the colorimetric values ​​of the stainless steel substrate sample are L: 80.43, a: 0.26, b: 3.27.

[0623] Hardness 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.

[0624] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0625] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0626] Example 11.

[0627] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 43.0 Ti 37.0 N 20.0 .

[0628] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0629] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0630] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 26 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.4 W / cm². 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 2700 nm by controlling the film formation time.

[0631] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0632] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0633] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0634] The bonding strength was tested using titanium alloy sheets.

[0635] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 43.0 Ti 37.0 N 20.0 .

[0636] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 24. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 25. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°. Among these, there is only one broad peak with a FWHM of 2.48° within the range of 34°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0637] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.37, a: 0.27, b: 2.56, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.58, a: 0.24, b: 2.18.

[0638] Hardness test results: The hardness value of the aluminum alloy substrate sample was 21.2 GPa, and the hardness value of the stainless steel substrate sample was 14.9 GPa.

[0639] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0640] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0641] Example 12.

[0642] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 44.0 Ti 37.0 N 19.0 .

[0643] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0644] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0645] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 25 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.7 Pa, turn on the bias voltage, set it to -100V, and set the power density of the Cr target to 4.5 W / cm². 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1400 nm by controlling the film formation time.

[0646] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0647] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0648] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0649] The bonding strength was tested using titanium alloy sheets.

[0650] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 44.0 Ti 37.0 N 19.0 .

[0651] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 26. The XRD diffraction pattern can be seen in Figure 27. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 2.63° in the range of 34° to 50°.

[0652] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.50, a: 0.24, b: 2.52, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.23, a: 0.23, b: 2.65.

[0653] Hardness test results: The hardness value of the aluminum alloy substrate sample was 22.0 GPa, and the hardness value of the stainless steel substrate sample was 21.6 GPa.

[0654] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0655] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0656] Example 13.

[0657] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 49.2 Ti 37.0 N 13.8 .

[0658] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0659] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0660] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, introduce Ar and N2 gas, set the N2 gas flow rate to 20 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, set the power density of the Cr target to 5.0 W / cm³. 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1800 nm by controlling the film formation time.

[0661] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0662] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0663] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0664] The bonding strength was tested using titanium alloy sheets.

[0665] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 49.2 Ti 37.0 N 13.8 .

[0666] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 28. The XRD diffraction pattern can be seen in Figure 29. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 2.29° in the range of 34° to 50°.

[0667] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.94, a: 0.21, b: 2.02, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.94, a: 0.23, b: 2.37.

[0668] Hardness test results: The hardness value of the aluminum alloy substrate sample was 19.3 GPa, and the hardness value of the stainless steel substrate sample was 21.9 GPa.

[0669] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0670] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0671] Example 14.

[0672] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 53.0 Ti 30.0 N 17.0 .

[0673] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0674] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0675] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 23 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 5.4 W / cm². 2 The power density of the Ti target was set to 3.1 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1300 nm by controlling the film formation time.

[0676] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0677] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0678] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0679] The bonding strength was tested using titanium alloy sheets.

[0680] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 53.0 Ti 30.0 N 17.0 .

[0681] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 30. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 31. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 2.68°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0682] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.63, a: 0.20, b: 2.32, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.21, a: 0.18, b: 2.16.

[0683] Hardness test results: The hardness value of the aluminum alloy substrate sample was 23.3 GPa, and the hardness value of the stainless steel substrate sample was 26.5 GPa.

[0684] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0685] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0686] Example 15.

[0687] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 54.4 Ti 25.6 N 20.0 .

[0688] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0689] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0690] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 26 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 5.5 W / cm². 2 The power density of the Ti target was set to 2.6 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1200 nm by controlling the film formation time.

[0691] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0692] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0693] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0694] The bonding strength was tested using titanium alloy sheets.

[0695] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 54.4 Ti 25.6 N 20.0 .

[0696] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 32. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 33. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 4.21°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0697] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.80, a: 0.19, b: 2.21, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.93, a: 0.19, b: 2.14.

[0698] Hardness test results: The hardness value of the aluminum alloy substrate sample was 20.0 GPa, and the hardness value of the stainless steel substrate sample was 23.6 GPa.

[0699] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0700] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0701] Example 16.

[0702] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 60.6 Ti 37.0 N 2.4 .

[0703] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0704] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0705] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 3 sccm, maintain an Ar:N2 gas ratio of 6:1, maintain the furnace pressure at 0.4 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 6.1 W / cm². 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1700 nm by controlling the film formation time.

[0706] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0707] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0708] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0709] The bonding strength was tested using titanium alloy sheets.

[0710] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 60.6 Ti 37.0 N 2.4 .

[0711] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 34. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 35. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 1.85°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0712] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 82.70, a: 0.19, b: 2.09, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.65, a: 0.17, b: 2.15.

[0713] Hardness test results: The hardness value of the aluminum alloy substrate sample was 21.9 GPa, and the hardness value of the stainless steel substrate sample was 22.4 GPa.

[0714] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0715] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0716] Example 17.

[0717] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 60.6 Ti 25.6 N 13.8 .

[0718] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0719] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0720] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 20 sccm, maintain an Ar:N2 gas ratio of 2:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 6.1 W / cm². 2 The power density of the Ti target was set to 2.6 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1520 nm by controlling the film formation time.

[0721] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0722] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0723] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0724] The bonding strength was tested using titanium alloy sheets.

[0725] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 60.6 Ti 25.6 N 13.8 .

[0726] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 36. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 37. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 1.69°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0727] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 80.01, a: 0.28, b: 2.95, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.16, a: 0.23, b: 2.62.

[0728] Hardness test results: The hardness value of the aluminum alloy substrate sample was 18.4 GPa, and the hardness value of the stainless steel substrate sample was 20.4 GPa.

[0729] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0730] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0731] Example 18.

[0732] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 62.9 Ti 18.9 N 18.2 .

[0733] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0734] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0735] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 24 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 6.3 W / cm². 2 The power density of the Ti target was set to 1.9 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 2000 nm by controlling the film formation time.

[0736] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0737] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0738] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0739] The bonding strength was tested using titanium alloy sheets.

[0740] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 62.9 Ti 18.9 N 18.2 .

[0741] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 38. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 39. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 2.60°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0742] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 83.07, a: 0.09, b: 1.54, and the colorimetric values ​​of the stainless steel substrate sample are L: 83.31, a: 0.05, b: 1.45.

[0743] Hardness test results: The hardness value of the aluminum alloy substrate sample was 20.1 GPa, and the hardness value of the stainless steel substrate sample was 22.4 GPa.

[0744] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0745] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0746] Example 19.

[0747] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 69.4 Ti 25.6 N 5.0 .

[0748] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0749] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0750] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 7 sccm, maintain an Ar:N2 gas ratio of 6:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 7.1 W / cm². 2 The power density of the Ti target was set to 2.6 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1600 nm by controlling the film formation time.

[0751] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0752] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0753] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0754] The bonding strength was tested using titanium alloy sheets.

[0755] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 69.4 Ti 25.6 N 5.0 .

[0756] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 40. The XRD diffraction pattern can be seen in Figure 41. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 4.29° in the range of 34° to 50°.

[0757] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 82.95, a: 0.10, b: 1.81, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.91, a: 0.04, b: 1.66.

[0758] Hardness test results: The hardness value of the aluminum alloy substrate sample was 20.5 GPa, and the hardness value of the stainless steel substrate sample was 22.2 GPa.

[0759] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0760] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0761] Example 20.

[0762] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 72.2 Ti 5.0 N 22.8 .

[0763] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0764] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0765] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 29 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.8 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 7.3 W / cm². 2 The power density of the Ti target was set to 0.5 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 900 nm by controlling the film formation time.

[0766] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0767] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0768] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0769] The bonding strength was tested using titanium alloy sheets.

[0770] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 72.2 Ti 5.0 N 22.8 .

[0771] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 42. The XRD diffraction pattern can be seen in Figure 43. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 4.61° in the range of 34° to 50°.

[0772] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 83.04, a: 0.11, b: 1.17, and the colorimetric values ​​of the stainless steel substrate sample are L: 83.29, a: 0.06, b: 0.88.

[0773] Hardness test results: The hardness value of the aluminum alloy substrate sample was 13.5 GPa, and the hardness value of the stainless steel substrate sample was 14.2 GPa.

[0774] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0775] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0776] Example 21.

[0777] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 75.0 Ti 5.0 N 20.0 .

[0778] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0779] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0780] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 26 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 7.6 W / cm². 2 The power density of the Ti target was set to 0.5 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1100 nm by controlling the film formation time.

[0781] Samples using silicon wafers as the substrate were subjected to SEM and component analysis, as well as XRD analysis.

[0782] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0783] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0784] The bonding strength was tested using titanium alloy sheets.

[0785] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 75.0 Ti 5.0 N 20.0 .

[0786] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 44. The XRD diffraction pattern can be seen in Figure 45. The SEM test results show that the Cr-Ti-N alloy coating has a dense structure and no through-column seams were observed. The XRD test results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34° to 50°, and the half-width at half-maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern in the range of 34° to 50° is ≥1.6°. Among them, there is only one broad peak with a FWHM of 2.91° in the range of 34° to 50°.

[0787] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 81.82, a: 0.35, b: 1.87, and the colorimetric values ​​of the stainless steel substrate sample are L: 81.97, a: 0.31, b: 1.80.

[0788] Hardness test results: The hardness value of the aluminum alloy substrate sample was 14.6 GPa, and the hardness value of the stainless steel substrate sample was 16.4 GPa.

[0789] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0790] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0791] Example 22.

[0792] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 90.0 Ti 5.0 N 5.0 .

[0793] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0794] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0795] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 7 sccm, maintain an Ar:N2 gas ratio of 6:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 9.1 W / cm². 2 The power density of the Ti target was set to 0.5 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 900 nm by controlling the film formation time.

[0796] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0797] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0798] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0799] The bonding strength was tested using titanium alloy sheets.

[0800] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 90.0 Ti 5.0 N 5.0 .

[0801] The test sample was characterized by SEM cross-section, and the cross-sectional morphology is shown in Figure 46. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 47. SEM results show that the Cr-Ti-N alloy coating has a dense structure, and no through-column seams were observed. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has a broad peak in the range of 34°–50°, and the full width at half maximum (FWHM) of the 2θ (°) diffraction angle in the XRD diffraction pattern within the range of 34°–50° is ≥1.6°, with only one broad peak in the range of 34°–50° having a FWHM of 2.99°. The radial intensity profile of the TEM selected area electron diffraction pattern shows… There is one and only one broad peak within the range, and the full width at half maximum (FWHM) is [value missing].

[0802] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 83.47, a: 0.05, b: 0.99, and the colorimetric values ​​of the stainless steel substrate sample are L: 83.40, a: 0.05, b: 0.95.

[0803] Hardness test results: The hardness value of the aluminum alloy substrate sample was 13.6 GPa, and the hardness value of the stainless steel substrate sample was 14.5 GPa.

[0804] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0805] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0806] Example 23. A transition layer CrN is provided.

[0807] In this example, the alloy coating on the substrate has a two-layer structure, and its chemical composition is CrN / Cr. 62.9 Ti 18.9 N 18.2 These correspond to the transition layer and the Cr-Ti-N alloy film, respectively. In other words, a CrN transition layer is provided, and the thicknesses of the transition layer and the Cr-Ti-N alloy film are 300 nm and 1000 nm, respectively.

[0808] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0809] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0810] First, deposit the CrN coating (transition layer): Turn on the sample stage rotating stand, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr target using an RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 13 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the Cr target power density to 5.0 W / cm². 2A Cr-N alloy coating was deposited, and the thickness of the resulting Cr-N film was 300 nm by controlling the film formation time.

[0811] Next, depositing the Cr-Ti-N alloy film: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using an RF-assisted DC power supply, and introduce Ar and N2 gas. The N2 gas flow rate is set to 24 sccm, and the gas volume is set to maintain an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, set it to -100V, and set the power density of the Cr target to 6.3 W / cm². 2 The power density of the Ti target was set to 1.9 W / cm². 2 A Cr-Ti-N alloy film was deposited, and the thickness of the resulting Cr-Ti-N film was 1000 nm by controlling the film formation time.

[0812] SEM and composition analysis were performed on samples using silicon wafers as the substrate.

[0813] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0814] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0815] The bonding strength was tested using titanium alloy sheets.

[0816] Compositional analysis revealed that the compositions of the two structural layers of the alloy coating on the substrate surface were CrN / Cr, respectively. 62.9 Ti 18.9 N 18.2 .

[0817] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 48.

[0818] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 82.59, a: 0.14, b: 1.71, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.45, a: 0.14, b: 1.85.

[0819] Hardness test results: The hardness value of the aluminum alloy substrate sample was 14.4 GPa, and the hardness value of the stainless steel substrate sample was 16.1 GPa.

[0820] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0821] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0822] Example 24.

[0823] In this example, the coating on the substrate has a three-layer structure, with the chemical composition being Ti / Cr in sequence. 62.9 Ti 18.9 N 18.2 / CrN, corresponding to the transition layer, Cr-Ti-N alloy film and surface layer, respectively, with thicknesses of 300nm, 1000nm and 200nm.

[0824] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0825] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0826] First, deposit the Ti coating (transition layer): Turn on the sample stage rotating stand, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Ti target using an RF-assisted DC power supply, introduce Ar2 gas, set the Ar gas flow rate to 60 sccm, maintain the pressure inside the furnace at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5.0 W / cm². 2 A Ti coating was deposited, and the thickness of the resulting Ti film was 300 nm by controlling the film formation time.

[0827] Next, deposit the Cr-Ti-N alloy film (intermediate layer): Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using an RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 24 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 6.3 W / cm². 2 The power density of the Ti target was set to 1.9 W / cm². 2A Cr-Ti-N alloy film was deposited, and the thickness of the resulting Cr-Ti-N film was 1000 nm by controlling the film formation time.

[0828] Finally, deposit the CrN coating (surface layer): Turn on the sample stage rotating stand, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr target using an RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 13 sccm, maintain the Ar:N2 gas flow ratio at 3:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the Cr target power density to 5.0 W / cm². 2 A Cr-N alloy coating was deposited, and the thickness of the resulting Cr-N film was 200 nm by controlling the film formation time.

[0829] SEM and composition analysis were performed on samples using silicon wafers as the substrate.

[0830] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0831] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0832] The bonding strength was tested using titanium alloy sheets.

[0833] Compositional analysis revealed that the coating on the substrate surface has a three-layer structure, with the chemical composition of each layer being Ti / Cr, in descending order. 62.9 Ti 18.9 N 18.2 / CrN.

[0834] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 49.

[0835] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 82.60, a: -0.13, b: 1.71, and the colorimetric values ​​of the stainless steel substrate sample are L: 82.11, a: -0.14, b: 1.15.

[0836] Hardness test results: The hardness value of the aluminum alloy substrate sample was 16.1 GPa, and the hardness value of the stainless steel substrate sample was 18.2 GPa.

[0837] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0838] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0839] As an example, based on Example 24, the Ti transition layer can be replaced with a Cr transition layer.

[0840] The inventors also experimented with replacing the three-layer coating structure in Example 24 with Cr / Cr 53.0 Ti 30.0 N 17.0 / CrN, corresponding to the transition layer, Cr-Ti-N alloy film and surface layer respectively, with thicknesses of 300nm, 1000nm and 200nm respectively. In the salt spray corrosion resistance test, the aluminum alloy substrate sample can pass the test for 48h, and the stainless steel substrate sample can pass the test for 144h.

[0841] Example 25. Contains doped elements

[0842] 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 It can also be referred to as Cr-Ti-NC alloy coating.

[0843] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0844] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0845] Deposition of Cr-Ti-NC alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar, C2H2, and N2 gases, setting the Ar flow rate to 60 sccm, the N2 flow rate to 14 sccm, and the C2H2 flow rate to 6 sccm. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 7.0 W / cm². 2 The power density of the Ti target was set to 2.0 W / cm². 2A Cr-Ti-NC alloy coating was deposited, and the thickness of the resulting Cr-Ti-NC film was 900 nm by controlling the film formation time.

[0846] Compositional analysis was performed on samples using silicon wafers as the substrate.

[0847] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0848] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0849] The bonding strength was tested using titanium alloy sheets.

[0850] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 66.9 Ti 18.3 N 10.1 C 4.7 .

[0851] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 83.05, a: 0.10, b: 1.50, and the colorimetric values ​​of the stainless steel substrate sample are L: 83.21, a: 0.07, b: 1.48.

[0852] Hardness test results: The hardness value of the aluminum alloy substrate sample was 13.6 GPa, and the hardness value of the stainless steel substrate sample was 14.7 GPa.

[0853] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0854] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0855] Based on the inventors' experimental findings, when using other non-metallic doping elements (such as Si, B, O, H, etc.) or metallic doping elements (such as Al), excellent corrosion resistance and high hardness can still be provided when the atomic ratio of the doping elements is appropriate (such as 4 at% or 2 at%). In some embodiments, such as Cr... 66.9 Ti 18.3 N 10.1 C 4.7 Alloy coating, Cr 36.6 Ti 49.2 N 9.2 C5 alloy coating, Cr 53.0 Ti30.0 N 12.0 In the C5 alloy coating salt spray corrosion resistance test, aluminum alloy substrate samples passed the test for 48 hours, while stainless steel substrate samples passed the test for 144 hours. Furthermore, it exhibits at least one broad peak in the XRD diffraction pattern within the diffraction angle range of 2θ (°) 34°–50°, and the radial intensity profile of the TEM selected area electron diffraction pattern... It has at least one broad peak within the range.

[0856] "at%" indicates the atomic percentage, expressed in terms of quantity.

[0857] Example 26. The thickness of the Cr-Ti-N alloy coating is approximately 50 nm.

[0858] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 43.0 Ti 37.0 N 20.0 .

[0859] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0860] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0861] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 26 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.4 W / cm². 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 50 nm by controlling the film formation time.

[0862] Compositional analysis was performed on samples using silicon wafers as the substrate.

[0863] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0864] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0865] The bonding strength was tested using titanium alloy sheets.

[0866] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 43.0 Ti 37.0 N 20.0 .

[0867] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 79.32, a: 0.17, b: 1.26, and the colorimetric values ​​of the stainless steel substrate sample are L: 79.58, a: 0.14, b: 1.18.

[0868] Hardness test results: The hardness value of the aluminum alloy substrate sample was 7.2 GPa, and the hardness value of the stainless steel substrate sample was 8.1 GPa.

[0869] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0870] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0871] Example 27. The thickness of the Cr-Ti-N alloy coating is approximately 6 μm.

[0872] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr. 43.0 Ti 37.0 N 20.0 .

[0873] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0874] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0875] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 26 sccm, maintain the Ar:N2 gas flow ratio at 2:1, maintain the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.4 W / cm². 2 The power density of the Ti target was set to 3.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 6000 nm by controlling the film formation time.

[0876] Compositional analysis was performed on samples using silicon wafers as the substrate.

[0877] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0878] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0879] The bonding strength was tested using titanium alloy sheets.

[0880] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 43.0 Ti 37.0 N 20.0 .

[0881] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 80.72, a: 0.37, b: 2.16, and the colorimetric values ​​of the stainless steel substrate sample are L: 80.58, a: 0.24, b: 2.28.

[0882] Hardness 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.

[0883] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy samples passed the 48-hour test, while stainless steel samples passed the 144-hour test, demonstrating excellent protective properties.

[0884] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer peeling off. It reached the 0th grade judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0885] Example 28. (Substrate is copper sheet)

[0886] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr.62.9 Ti 18.9 N 18.2 .

[0887] Substrate pretreatment: Copper and silicon wafer samples with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0888] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0889] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, and power the Cr and Ti targets using an RF-assisted DC power supply. Introduce Ar and N2 gas, setting the N2 gas flow rate to 24 sccm and maintaining an Ar:N2 gas ratio of 2:1. Maintain the furnace pressure at 0.6 Pa, turn on the bias voltage, and set it to -100V. Set the power density of the Cr target to 6.3 W / cm². 2 The power density of the Ti target was set to 1.9 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 2000 nm by controlling the film formation time.

[0890] Compositional analysis was performed on samples using silicon wafers as the substrate.

[0891] A copper sheet was used to conduct a salt spray corrosion resistance test;

[0892] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 62.9 Ti 18.9 N 18.2 .

[0893] Salt spray corrosion resistance results: The copper sheet substrate sample passed the 8-hour test and has certain protective properties.

[0894] Furthermore, the inventors of this application use Cr 62.9 Ti 18.9 N 18.2 Cr-Ti-N alloy coatings with thicknesses of 50 nm and 6000 nm were prepared using atomic ratios of Cr, respectively. 36.6 Ti 49.2 N 14.2 Cr-Ti-N alloy coatings with thicknesses of 50 nm and 6000 nm were prepared using atomic ratios of Cr, respectively. 53.0 Ti 30.0 N17.0 Cr-Ti-N alloy coatings with thicknesses of 50 nm and 6000 nm were prepared using different atomic ratios. In the salt spray corrosion resistance test, the aluminum alloy substrate samples could pass the test for 48 hours, and the stainless steel substrate samples could pass the test for 144 hours.

[0895] Cr was also prepared based on copper sheets. 62.9 Ti 18.9 N 18.2 Alloy coating and Cr 36.6 Ti 49.2 N 14.2 Alloy coatings can pass 8-hour salt spray corrosion resistance tests.

[0896] Comparative Example 1.

[0897] In this comparative example, the chemical composition of the alloy coating is Cr. 20.9 Ti 79.1 The preparation method is as follows:

[0898] Substrate pretreatment: Copper and silicon wafer samples with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0899] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0900] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using an RF-assisted DC power supply, introduce Ar gas, set the Ar gas flow rate to 80 sccm, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 2.2 W / cm². 2 The power density of the Ti target was set to 8.1 W / cm². 2 A Cr-Ti alloy coating was deposited, and the film thickness was 1400 nm by controlling the film formation time.

[0901] SEM and composition analysis were performed on samples using silicon wafers as the substrate.

[0902] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0903] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0904] The bonding strength was tested using titanium alloy sheets.

[0905] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 20.9 Ti 79.1 .

[0906] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 50.

[0907] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 77.56, a: 0.57, b: 2.05, and the colorimetric values ​​of the stainless steel substrate sample are L: 78.07, a: 0.57, b: 2.31.

[0908] Hardness test results: The hardness value of the aluminum alloy substrate sample was 7.6 GPa, and the hardness value of the stainless steel substrate sample was 8.0 GPa.

[0909] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy substrate samples failed the 48h test (NG, protection time < 12h), and stainless steel substrate samples failed the 144h test (NG, protection time < 48h), indicating a lack of protective properties against the substrate.

[0910] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0911] Comparative Example 2.

[0912] In this comparative example, the chemical composition of the Cr-Ti-N alloy coating is Cr 44.4 Ti 16.1 N 39.5 .

[0913] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0914] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0915] Deposition of alloy coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supply, and introduce Ar and N2 gas. Set the N2 gas flow rate to 53 sccm, maintain the Ar:N2 gas flow ratio at 5:4, maintain the furnace pressure at 0.9 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 4.6 W / cm³. 2 The power density of the Ti target was set to 1.8 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1630 nm by controlling the film formation time.

[0916] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0917] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0918] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0919] The bonding strength was tested using titanium alloy sheets.

[0920] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 44.4 Ti 16.1 N 39.5 .

[0921] The test sample was characterized by SEM cross-section; the cross-sectional morphology is shown in Figure 51. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 52. SEM results show that the alloy coating film has a loose structure with obvious through-column seams. XRD results show that the diffraction angle 2θ (°) in the XRD diffraction pattern has two peaks in the range of 34°–50°, both of which are sharp peaks (2θ peaks with a half-width at half-maximum (FWHM) < 1.6°). The FWHMs of the two sharp peaks in the 34°–50° range are 0.34° and 1.58°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern is shown in Figure 52. There are two peaks within the range, with half-widths of 100 and 250 respectively. That is, there are two peaks.

[0922] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 58.04, a: 1.80, b: 7.83, and the colorimetric values ​​of the stainless steel substrate sample are L: 60.89, a: 1.26, b: 8.54.

[0923] Hardness test results: The hardness value of the aluminum alloy substrate sample was 13.4 GPa, and the hardness value of the stainless steel substrate sample was 14.8 GPa.

[0924] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy substrate samples failed the 48h test (NG, protection time < 12h), and stainless steel substrate samples failed the 144h test (NG, protection time < 48h), indicating a lack of protective properties against the substrate.

[0925] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0926] Comparative Example 3.

[0927] In this comparative example, the chemical composition of the Cr-Ti-N alloy coating is Cr 35.4 Ti 25.8 N 38.8 .

[0928] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in deionized water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0929] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0930] Depositing alloy coatings: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr and Ti targets using RF-assisted DC power supplies, and introduce Ar and N2 gases. Set the N2 gas flow rate to 52 sccm, maintain an Ar:N2 gas ratio of 5:4, maintain the furnace pressure at 0.9 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Cr target to 3.6 W / cm². 2 The power density of the Ti target was set to 2.7 W / cm². 2 A Cr-Ti-N alloy coating was deposited, and the film thickness was 1400 nm by controlling the film formation time.

[0931] Samples using silicon wafers as the substrate were subjected to SEM and composition analysis, XRD analysis, and TEM testing.

[0932] Hardness and color values ​​were tested using stainless steel and aluminum alloy sheets.

[0933] Samples using titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests.

[0934] The bonding strength was tested using titanium alloy sheets.

[0935] Compositional analysis revealed that the alloy coating on the substrate surface consisted of Cr. 35.4 Ti 25.8 N 38.8 .

[0936] The test sample was characterized by SEM cross-section; the cross-sectional morphology is shown in Figure 53. The XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile are shown in Figure 54. SEM results show that the alloy coating film has a loose structure with obvious through-column seams. XRD results show that the XRD diffraction pattern has two peaks in the diffraction angle 2θ (°) range of 34°–50°, both of which are sharp peaks (2θ peaks with a half-width at half-maximum (FWHM) < 1.6°). The FWHMs of the two sharp peaks in the 34°–50° range are 0.52° and 1.26°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern is shown in Figure 54. There are two peaks within the range, with half-widths of 100 and 250 respectively. That is, there are two peaks.

[0937] Colorimetric test results: The colorimetric values ​​of the aluminum alloy substrate sample are L: 60.57, a: 0.83, b: 7.07, and the colorimetric values ​​of the stainless steel substrate sample are L: 60.22, a: 1.18, b: 8.51.

[0938] Hardness test results: The hardness value of the aluminum alloy substrate sample was 12.3 GPa, and the hardness value of the stainless steel substrate sample was 13.3 GPa.

[0939] Salt spray corrosion resistance results: Titanium alloy and aluminum alloy substrate samples failed the 48h test (NG, protection time < 12h), and stainless steel substrate samples failed the 144h test (NG, protection time < 48h), indicating a lack of protective properties against the substrate.

[0940] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0941] Comparative Example 4.

[0942] In this comparative example, the thin film structure is CrN, and the chemical composition of the alloy coating is CrN.

[0943] The preparation method for this comparative coating is as follows:

[0944] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0945] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0946] Depositing CrN coating: Turn on the sample stage rotating rack, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, power the Cr target with DC power, and introduce Ar and N2 gas. Set the N2 gas flow rate to 15 sccm, maintain the Ar:N2 gas flow rate ratio at 3:1, maintain the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the Cr target power density to 5 W / cm³. 2 A CrN coating was deposited, and by controlling the film formation time, a film thickness of 1800 nm was obtained.

[0947] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric value tests.

[0948] Composition analysis revealed that the alloy coating on the substrate surface was composed of CrN.

[0949] The test sample was characterized by SEM cross-section, and the cross-sectional morphology can be seen in Figure 55.

[0950] The colorimetric values ​​of the aluminum alloy substrate sample were L: 74.92, a: 0.68, b: 4.89, and the colorimetric values ​​of the stainless steel substrate sample were L: 75.07, a: 0.69, b: 5.17, exhibiting a silvery-white color.

[0951] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection time < 24h).

[0952] The hardness value of the aluminum alloy substrate sample was 12.8 GPa, and the hardness value of the stainless steel substrate sample was 13.3 GPa.

[0953] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0954] Comparative Example 5.

[0955] In this comparative example, the thin film structure is TiN, and the chemical composition of the alloy coating is TiN.

[0956] The preparation method for this comparative coating is as follows:

[0957] Substrate pretreatment: Titanium alloy sheets, stainless steel sheets, aluminum alloy sheets, and silicon wafers with an aspect ratio of 50mm×50mm were ultrasonically cleaned in DI water for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a coating machine. The vacuum chamber was evacuated to 5×10⁻⁶. -4 Pa, heat to 150℃, and hold at that temperature for 15 minutes.

[0958] Plasma cleaning: Ar gas is introduced, the furnace pressure is maintained at 2.0 Pa, the bias voltage is turned on and set to -800 V, and plasma cleaning is performed for 20 minutes. The purpose is to use plasma etching to remove tiny impurities from the sample surface.

[0959] Deposition of TiN coating: Turn on the sample stage rotating frame, set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use DC power to power the Ti target, and introduce Ar and N2 gas. Set the N2 gas flow rate to 10 sccm, maintain the Ar:N2 gas flow rate ratio at 3:1, maintain the pressure inside the furnace at 0.5 Pa, turn on the bias voltage and set it to -100V, and set the power density of the Ti target to 5 W / cm³. 2 A TiN coating was deposited, and by controlling the film deposition time, a film thickness of 600 nm was obtained.

[0960] Samples using stainless steel sheets and aluminum alloy sheets as substrates were subjected to salt spray corrosion resistance tests, hardness tests, and colorimetric value tests.

[0961] Composition analysis revealed that the alloy coating on the substrate surface is composed of TiN.

[0962] The colorimetric values ​​of the aluminum alloy substrate sample were L: 57.95, a: 6.45, b: 13.95, and the colorimetric values ​​of the stainless steel substrate sample were L: 59.33, a: 6.92, b: 13.91, exhibiting a golden yellow color.

[0963] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time < 12h) and the stainless steel substrate sample failed the 144h test (NG, protection time < 24h).

[0964] The hardness value of the aluminum alloy substrate sample was 4.1 GPa, and the hardness value of the stainless steel substrate sample was 4.4 GPa.

[0965] Adhesion test results: A cross-cut adhesion test was performed on the film layer on the titanium alloy substrate. Small pieces peeled off at the intersection of the cuts. The actual damage within the cross-cut area did not exceed 5%. According to the GB / T 9286-2021 standard, it was judged to be Grade 1 and the test failed.

[0966] Comparative Example 6. Alloy coating thickness 50nm

[0967] Using essentially the same method as Comparative Example 3, the chemical composition of the alloy coating was Cr. 35.4 Ti 25.8 N 38.8 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 50nm.

[0968] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h) and the stainless steel substrate sample failed the 144h test (NG, protection time <24h).

[0969] Adhesion test results: A cross-cut adhesion test was performed on the film layer on the titanium alloy substrate. Small pieces peeled off at the intersection of the cuts. The actual damage within the cross-cut area did not exceed 5%. According to the GB / T 9286-2021 standard, it was judged to be Grade 1 and the test failed.

[0970] Comparative Example 7. Alloy coating thickness 1000 nm

[0971] Using essentially the same method as Comparative Example 3, the chemical composition of the alloy coating was Cr. 35.4 Ti 25.8 N 38.8 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 1000nm.

[0972] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h) and the stainless steel substrate sample failed the 144h test (NG, protection time <24h).

[0973] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0974] Comparative Example 8. Alloy coating thickness 2500nm

[0975] Using essentially the same method as Comparative Example 3, the chemical composition of the alloy coating was Cr. 35.4 Ti 25.8 N 38.8 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 2500nm.

[0976] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h) and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating that it does not have the protective properties for the substrate.

[0977] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0978] Comparative Example 9. Alloy coating thickness 6000 nm

[0979] Using essentially the same method as Comparative Example 3, the chemical composition of the alloy coating was Cr. 35.4 Ti 25.8 N 38.8 The difference lies in the thickness of the alloy coating, which has been changed from 1400nm to 6000nm.

[0980] In the salt spray corrosion resistance test, the aluminum alloy substrate sample failed the 48h test (NG, protection time <12h) and the stainless steel substrate sample failed the 144h test (NG, protection time <24h), indicating that it does not have the protective properties for the substrate.

[0981] Adhesion test results: The film layer on the titanium alloy substrate was subjected to a cross-cut adhesion test. There was peeling at the edge of the cut, and the area was greater than 5% but less than 15%. According to GB / T 9286-2021 standard, it was judged to be level 2 and the test failed.

[0982] Comparative Examples 10-12. No protective coating.

[0983] Salt spray corrosion resistance tests were conducted using bare aluminum alloy sheets, bare stainless steel sheets, and bare copper sheets, respectively. The results showed that significant corrosion occurred within 12 hours.

[0984] Table 1.

[0985] In Table 1, spaces and "\" indicate items not specified in the table. In Example 23, Cr 62.9 Ti 18.9 N 18.2The thicknesses of the Ti / CrN were 1 μm and 0.3 μm, respectively. In Example 24, the Ti / Cr... 62.9 Ti 18.9 N 18.2 The thicknesses of / CrN are 0.3 μm, 1 μm and 0.2 μm, respectively.

[0986] In Table 1, " / " indicates that it is not set.

[0987] Results analysis:

[0988] According to the salt spray corrosion resistance test results, the Cr-Ti-N alloy coatings provided in this application (such as Examples 1-28) can all provide excellent corrosion protection to the substrate, and are excellent corrosion-resistant protective coatings. Among them, Examples 1-22 and 25-28 are single-layer thin film structures, in which the Cr-Ti-N alloy coating directly contacts the substrate, serving as a surface film layer to provide surface protection to the substrate. Example 23 is a double-layer thin film structure, in which the Cr-Ti-N alloy coating provided in this application serves as the lower protective layer, and a surface layer (TiN) is also provided on the side of the Cr-Ti-N alloy coating away from the substrate. The surface layer serves as a surface protective coating (located on the top layer); the coating in Example 24 has a three-layer thin film structure, consisting of a transition layer, a Cr-Ti-N alloy coating, and a surface alloy coating sequentially from the substrate surface; the alloy coating in Example 25 contains doping elements with a certain atomic percentage (≤5 at%); Examples 1-27 all used aluminum alloy and stainless steel substrates, while Example 28 used a copper substrate. The aluminum alloy surface can pass a 48-hour salt spray corrosion resistance test, the stainless steel surface can pass a 144-hour salt spray corrosion resistance test, and the copper substrate (copper is a relatively reactive alloy) can pass an 8-hour salt spray corrosion resistance test. The Cr-Ti-N alloy coating provided in this application can be used independently as a single-layer thin film or in a multi-layer composite thin film. For example, it can be used as one layer, as a surface layer (exposed), as a bottom coating (in contact with the substrate), or as an intermediate layer (located between the bottom coating and the surface layer).

[0989] The bare substrates of Comparative Examples 10-12, without a protective coating, were not resistant to salt spray corrosion and showed obvious corrosion within 12 hours.

[0990] Based on XRD and TEM selected area electron diffraction results, the Cr-Ti-N alloy coating provided in this application (as in Examples 1-28) exhibits at least one broad peak (furthermore, all are broad peaks with a full width at half maximum (FWHM) ≥ 1.6°) in the XRD diffraction pattern with a diffraction angle 2θ (°) in the range of 34°–50°. The radial intensity profile of the TEM selected area electron diffraction pattern also shows… It has at least one broad peak within the range (furthermore, all are broad peaks, with a half-width of ≥ 1 / 2). The Cr-Ti-N alloy coatings provided in this application all have highly disordered atomic distribution and fully close-packed atomic arrangement, which is consistent with the highly dense structure in the SEM morphology characterization results.

[0991] According to the surface hardness test results of the alloy film product, the Cr-Ti-N alloy coating provided in this application can also provide a high surface hardness.

[0992] The Cr-Ti-N alloy coatings in Examples 1-22, 25, etc., also serve as hard corrosion-resistant protective coatings with a coating thickness ≥0.9μm; when aluminum alloy is used as the substrate, the hardness value is ≥10GPa; when stainless steel is used as the substrate, the hardness value is ≥12GPa.

[0993] As can be seen, the Cr-Ti-N alloy coating provided in this application can be used as the protective coating itself or as part of the protective coating. It provides excellent corrosion resistance, can inhibit corrosion, and can also provide high hardness to resist scratches and abrasions. ...

Claims

1. A Cr-Ti-N alloy material comprising Cr, Ti and N elements, wherein the atomic ratio of Cr, Ti and N elements in the Cr-Ti-N alloy material is x:y:z, 5.0≤x≤90.0, 5.0≤y≤79.0, and 2.4≤z≤26.

5.

2. The Cr-Ti-N alloy material according to claim 1, wherein 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 as follows: M is a doping element, x, y, z and a are the atomic ratios of Cr, Ti, N and M, respectively, 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, and 0≤a / (x+y+z+a)≤0.

05.

3. The Cr-Ti-N alloy material according to claim 2, wherein 0≤a / (x+y+z+a)≤0.

02.

4. The Cr-Ti-N alloy material according to any one of claims 1 to 3, wherein x, y, and z satisfy the following characteristics: 54.4≤x≤90.0, 5.0≤y≤25.6, and 5.0≤z≤20.

0.

5. The Cr-Ti-N alloy material according to any one of claims 1 to 3, wherein x, y, and z satisfy the following characteristics: 21.0≤x≤60.6, 37.0≤y≤60.0, and 2.4≤z≤19.

0.

6. The Cr-Ti-N alloy material according to any one of claims 1 to 3, wherein x, y, and z satisfy the following characteristics: 5.0≤x≤27.0, 66.0≤y≤79.0, 5.0≤z≤16.0, x≤4.5y-279, and 84-y≤x≤125.2-1.4y.

7. The Cr-Ti-N alloy material according to any one of claims 1 to 3, wherein x, y, and z satisfy the following characteristics: 43.0≤x≤60.6, 25.6≤y≤37.0, and 13.8≤z≤20.

0.

8. The Cr-Ti-N alloy material according to any one of claims 1 to 7, wherein The sum of x, y, and z is a value selected from 95 to 100; Optionally, the Cr-Ti-N alloy material is composed of a CrTiN-based alloy component with a chemical formula of Cr x Ti y N z x, y, and z sum to 100.

9. The Cr-Ti-N alloy material according to any one of claims 1 to 8, wherein The mass percentage of Cr, Ti, and N in the Cr-Ti-N alloy material is greater than or equal to 80%, and optionally greater than or equal to 90%.

10. The Cr-Ti-N alloy material according to claim 9, wherein The mass percentage of Cr, Ti, and N in the Cr-Ti-N alloy material is greater than or equal to 95%, and can be selected as 100%.

11. The Cr-Ti-N alloy material according to any one of claims 1 to 10, wherein The doping element is a non-metallic element, a metallic element, or a combination thereof; The non-metallic elements include one or more of O, C, B, Si, H, and Ar; The metallic elements include one or more of Zr, V, Nb, Mo, Hf, Ta, W, Ni, Mo, Fe, Ag, Au, Cu, and Al.

12. The Cr-Ti-N alloy material according to any one of claims 1 to 11, wherein The Cr-Ti-N alloy material is a component of the Cr-Ti-N alloy film; The Cr-Ti-N alloy film satisfies the following two characteristics: The X-ray diffraction pattern of the Cr-Ti-N alloy film 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 of the selected area electron diffraction pattern of the Cr-Ti-N alloy film, with the characteristic atomic spacing as the abscissa and the diffraction intensity as the ordinate, in have diffraction peaks within a range, and in the half-height width of at least one diffraction peak in the range of 2θ = 5° to 10° satisfies Optionally, the Cr-Ti-N alloy film satisfies one or more of the following characteristics: The X-ray diffraction pattern of the Cr-Ti-N alloy film was obtained by using Cu target Kα rays; The selected area electron diffraction pattern of the Cr-Ti-N alloy film was obtained by using TEM characterization, which was performed in a mode with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

13. The Cr-Ti-N alloy material of claim 12, wherein In the X-ray diffraction pattern of the Cr-Ti-N alloy film, the full width at half maximum (FWHM) of at least one 2θ (°) diffraction peak in the range of 34° to 50° satisfies ≥1.69°.

14. A Cr-Ti-N alloy film or Cr-Ti-N alloy coating, wherein, At least a portion of the Cr-Ti-N alloy film is composed of the Cr-Ti-N alloy material as described in any one of claims 1 to 13; the Cr-Ti-N alloy coating includes the Cr-Ti-N alloy film.

15. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating according to claim 14, wherein The thickness of the Cr-Ti-N alloy film is d min ~ 6 μm, wherein d min is selected from the range of 10 nm to 0.9 μm; Optionally, d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 0.3 pm, 0.5 pm, 0.8 pm, or 0.9 pm; Optionally, the thickness of the Cr-Ti-N alloy film is 0.3 μm to 2.0 μm.

16. An alloy film article, wherein, It includes a substrate and the Cr-Ti-N alloy film or Cr-Ti-N alloy coating as described in claim 14 or 15; wherein the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is located on at least one side of the substrate.

17. The alloy film article of claim 16, wherein, The Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is bonded to the surface of the following material on the side close to the substrate: any one of alloys, elemental metals and inorganic non-metallic materials; The alloy material types include one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based, and zinc-based. 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 materials include one or more of ceramics and glass; Optionally, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is bonded to a surface of a material near the substrate: one of a light alloy or one of a stainless steel alloy; wherein the light alloy includes one or more of titanium alloy, aluminum alloy and magnesium alloy.

18. The alloy film article according to claim 16 or 17, wherein it satisfies one or more of the following characteristics: The Cr-Ti-N alloy film is in direct contact with the substrate or has a transition layer. The Cr-Ti-N alloy film is located on the surface of the alloy film product or the Cr-Ti-N alloy coating is further provided with a surface layer on the side away from the substrate. The surface layer is a single-layer structure or a multi-layer structure. The Cr-Ti-N alloy coating is in direct contact with the substrate or has a transition layer; The Cr-Ti-N alloy coating is located on the surface of the alloy film product, or the Cr-Ti-N alloy coating on the side away from the substrate is further provided with a surface layer, which is a single-layer structure or a multi-layer structure.

19. The use of the Cr-Ti-N alloy material according to any one of claims 1 to 13 in the preparation of a corrosion-resistant protective coating, or the use of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating according to claim 14 or 15 as a corrosion-resistant protective coating.

20. The use according to claim 19, wherein, x, y, and z satisfy either the first or second set of characteristics as follows: Group 1: 43.0≤x≤60.6, 25.6≤y≤37.0 and 13.8≤z≤20.0; The second group: 54.4≤x≤90.0, 5.0≤y≤25.6, and 5.0≤z≤20.0; Furthermore, the corrosion-resistant protective coating is also a high-brightness surface coating; wherein, tested by the Lab method, the brightness value L of the high-brightness surface coating is ≥80.

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