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 material, Cr-Ti-N alloy film, Cr-Ti-N alloy coating, alloy film product and application

[0001] Related applications

[0002] The present application claims priority to the Chinese patent application No. CN2024108012138, filed on June 20, 2024, entitled “Cr-Ti-N alloy material, Cr-Ti-N alloy film and preparation method thereof, Cr-Ti-N alloy coating, alloy film product and application”, the contents of which are hereby incorporated by reference in its entirety. TECHNICAL FIELD

[0003] The present application relates to the technical field of alloy coating, in particular to a Cr-Ti-N alloy material, a Cr-Ti-N alloy film, a Cr-Ti-N alloy coating, an alloy film product and application, and a preparation method of the Cr-Ti-N alloy film. BACKGROUND

[0004] With the progress and development of science and technology, the application range of products in the fields of wearable products, 3C products, automobiles, sports products, etc. is becoming more and more extensive, and the requirements for the mechanical properties such as corrosion resistance and hardness of the products are becoming higher and higher. The surfaces of some common alloy materials (such as stainless steel, aluminum alloy, titanium alloy) or pure metals (such as Cu, Ag) are prone to have weak corrosion resistance, low surface hardness, and easy to produce corrosion, scratches and other problems during use, which limits the popularization and application. Although theoretically, the corrosion resistance, hardness and other mechanical properties can be improved by setting an alloy coating, however, the performance of many products on the market is not ideal. SUMMARY

[0005] According to various embodiments and various examples of the present application, the present application at least provides a Cr-Ti-N alloy material, a Cr-Ti-N alloy film and a preparation method thereof, a Cr-Ti-N alloy coating, an alloy film product and application. The Cr-Ti-N alloy material has excellent corrosion resistance, and can form a Cr-Ti-N alloy film, an alloy coating including the Cr-Ti-N alloy film, or a related alloy film product. The related Cr-Ti-N alloy film or Cr-Ti-N alloy coating can be used as a product protective coating to improve the protection ability of the product.

[0006] In a first aspect of the present application, a Cr-Ti-N alloy material is provided, which includes Cr elements, Ti elements and N elements, and in the Cr-Ti-N alloy material, the atomic ratio of the Cr elements, Ti elements and N elements 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, which comprises a CrTiN-based alloy component of a chemical formula of Cr x Ti y N z M a , wherein M is a doping element, x, y, z and a are atomic ratios of Cr element, Ti element, N element and M element respectively, 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, and 0≤a / (x+y+z+a)≤0.05.

[0008] In some embodiments, 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. It is advantageous to endow the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating with higher brightness.

[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 present 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 present 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. It is advantageous to endow the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating with higher hardness.

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

[0014] Optionally, the Cr-Ti-N alloy material consists of a CrTiN-based alloy component of a chemical formula of Cr x Ti y N z , wherein the sum of x, y and z is 100.

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

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

[0017] The non-metallic element includes one or more of O, C, B, Si, H and Ar.

[0018] The metallic element includes 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 constituent material of a 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 a peak in the diffraction angle 2θ(°) range of 34°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥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 interatomic distance as the abscissa and the diffraction intensity as the ordinate, there is a diffraction peak in the range of and the half-height width of at least one diffraction peak in the range of satisfies ≥

[0023] In some embodiments, the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° in the X-ray diffraction pattern of the Cr-Ti-N alloy film satisfies ≥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 is obtained by Cu target Kα ray;

[0026] The selected area electron diffraction pattern of the Cr-Ti-N alloy film is obtained by using a TEM characterization method, which is 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 the present application, a Cr-Ti-N alloy film is provided, at least a portion of which is composed of the Cr-Ti-N alloy material according to the first aspect of the present application.

[0028] In some embodiments, the Cr-Ti-N alloy film has a thickness of d min ~ 6 μm, wherein d min is selected from 10 nm ~ 0.9 μm;

[0029] Optionally, d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 0.3 μm, 0.5 μm, 0.8 μm or 0.9 μm;

[0030] Optionally, the Cr-Ti-N alloy film has a thickness of 0.3 μm ~ 2.0 μm.

[0031] In a third aspect of the present application, a Cr-Ti-N alloy coating is provided, which comprises the Cr-Ti-N alloy film according to the second aspect of the present application.

[0032] In a fourth aspect of the present application, an alloy film product is provided, which comprises a substrate and at least one of the Cr-Ti-N alloy film according to the second aspect of the present application and the Cr-Ti-N alloy coating according to the third aspect of the present 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 on the surface of any one of the following materials on the side close to the substrate: alloys, elemental metals and inorganic non-metallic materials;

[0034] The material type of the alloy includes one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based;

[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 material includes one or more of ceramic and glass.

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

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

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

[0040] The Cr-Ti-N alloy film is on the surface of the alloy film product or the side of the Cr-Ti-N alloy film away from the substrate is further provided with a surface layer, and 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 is provided with a transition layer;

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

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

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

[0045] In some embodiments, the corrosion-resistant protective coating can pass the corrosion test for at least 48 hours according to the ASTM B117 salt spray test standard; wherein the composition of the corrosion solution used for the corrosion test is: sodium chloride, water and sodium hydroxide, and the pH is 6.5-7.2;

[0046] When the corrosion-resistant protective coating is combined with an aluminum alloy substrate, the corrosion-resistant protective coating can pass the corrosion test for at least 48 hours;

[0047] When the corrosion-resistant protective coating is combined with a stainless steel substrate, the corrosion-resistant protective coating can pass the corrosion test for 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 ≥0.9 μm;

[0050] When the corrosion protection coating is combined with an aluminum alloy substrate, the hardness value of the hard corrosion protection coating is ≥10 GPa;

[0051] When the corrosion protection coating is combined with a stainless steel substrate, the hardness value of the hard corrosion protection coating is ≥12 GPa.

[0052] In some embodiments, x, y and z satisfy the following first group or second group characteristics:

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

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

[0055] Further, the corrosion protection coating is also a high-brightness surface coating; wherein the brightness value L of the high-brightness surface coating is ≥80 according to Lab method.

[0056] In the sixth aspect of the present application, a preparation method of the Cr-Ti-N alloy film is provided, which comprises the following steps: depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of a substrate according to a preset atomic ratio by using a gas deposition technology to form the Cr-Ti-N alloy film according to the second aspect of the present application.

[0057] In some embodiments, the preparation method of the Cr-Ti-N alloy film comprises the following steps: sputter depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of the substrate by using one or more targets comprising chromium element and titanium element under the condition of introducing a mixed gas comprising argon and nitrogen-containing gas to form the Cr-Ti-N alloy film.

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

[0059] The temperature of sputter deposition is 30℃-330℃;

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

[0061] The target comprises a chromium target and a titanium target, the power density of the chromium target is 0.5 W / cm 2 -9.1 W / cm 2 , and the power density of the titanium target is 0.5 W / cm 2 -8.1 W / cm 2 ;

[0062] The target material includes an alloy target including at least two metal elements in the Cr-Ti-N alloy film; optionally, the target material includes a chromium-titanium-based alloy target, and the power density of the chromium-titanium-based alloy target is 4 W / cm 2 ~ 6 W / cm 2

[0063] The bias voltage of the substrate is -150 V to -20 V.

[0064] The sputter deposition time is 10 min to 150 min.

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

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

[0067] The Cr-Ti-N alloy material provided in the present application includes Cr, Ti and N three elements, and the three elements have a specific relative atomic ratio (Cr x Ti y N z ), 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, so that the Cr-Ti-N alloy material has the ability to form a highly disordered distribution of atoms and a sufficient close-packed arrangement, and can form a structurally dense Cr-Ti-N alloy coating. When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application is located on the surface of an article, it can provide excellent corrosion resistance. The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating containing the Cr-Ti-N alloy material provided in the present application have a much longer protection time in salt spray corrosion resistance test than traditional Cr-Ti-N alloy coatings.

[0068] In addition, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application can have high hardness characteristics while providing excellent corrosion resistance, thereby better reducing scratch generation or weakening scratch damage. Further, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application can have high corrosion resistance and high hardness characteristics at a lower thickness, can save raw materials, simplify processes, shorten production cycles, and significantly reduce costs.

[0069] When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application is located on the surface of an article, it can also impart the article with a high-brightness aesthetic surface.

[0070] ​The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided by the present application can be applied to a variety of substrates, and the material of the substrate can include but is not limited to alloys, elemental metals, inorganic non-metallic materials and the like.

[0071] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided by the present application can be used as a surface layer of an alloy film product, and has both aesthetic decoration and the aforementioned protective effect. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided by the present application can also be located between the surface layer of the substrate and other structures, and has excellent protective effect, can preferably resist corrosion and scratches.

[0072] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is combined with the surface of a light alloy substrate (such as a titanium alloy), the corrosion resistance and hardness of the surface of the titanium alloy can be enhanced, thereby improving the protective ability. In addition, since the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating contain a certain amount of Ti element, the coefficient of thermal expansion of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating relative to the light alloy substrate (such as a titanium alloy) is close, thereby forming excellent bonding force between the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating and the light alloy substrate (such as a titanium alloy). In addition, titanium exists in nature in large quantities, and the manufacturing cost is low.

[0073] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided by the present application appears in the protective coating of the 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, at this time, the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is located on the surface of the alloy film product, and can provide a high-brightness 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, at this time, other structural layers are also 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. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating in different positions can all achieve good corrosion resistance and good scratch resistance.

[0074] The preparation method of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application is simple, easy to operate, green and environmentally friendly, and has the advantages of quantification, high efficiency and good repeatability, and is suitable for industrial application.

[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 diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0093] Figure 16 is a CrTiN alloy coating prepared in Example 7 of the present application; 27.0 Ti 68.0 N 5.0 SEM cross-section of the alloy coating;

[0094] Figure 17 is a CrTiN alloy coating prepared in Example 7 of the present application; 27.0 Ti 68.0 N 5.0 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0095] Figure 18 is a CrTiN alloy coating prepared in Example 8 of the present application; 36.6 Ti 49.2 N 14.2 SEM cross-section of the alloy coating;

[0096] Figure 19 is a CrTiN alloy coating prepared in Example 8 of the present application; 36.6 Ti 49.2 N 14.2 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0097] Figure 20 is a CrTiN alloy coating prepared in Example 9 of the present application; 37.6 Ti 60.0 N 2.4 SEM cross-section of the alloy coating;

[0098] Figure 21 is a CrTiN alloy coating prepared in Example 9 of the present application; 37.6 Ti 60.0 N 2.4 XRD diffractogram of the alloy coating;

[0099] Figure 22 is a CrTiN alloy coating prepared in Example 10 of the present application; 38.3 Ti 35.2 N 26.5 SEM cross-section of the alloy coating;

[0100] Figure 23 is a CrTiN alloy coating prepared in Example 10 of the present application; 38.3 Ti 35.2 N 26.5 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) 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 diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0111] Figure 34 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 16 of the present application; 60.6 Ti 37.0 N 2.4 SEM cross-sectional view of the alloy coating;

[0112] Figure 35 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 16 of the present application; 60.6 Ti 37.0 N 2.4 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0113] Figure 36 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 17 of the present application; 60.6 Ti 25.6 N 13.8 SEM cross-sectional view of the alloy coating;

[0114] Figure 37 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 17 of the present application; 60.6 Ti 25.6 N 13.8 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0115] Figure 38 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 18 of the present application; 62.9 Ti 18.9 N 18.2 SEM cross-sectional view of the alloy coating;

[0116] Figure 39 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 18 of the present application; 62.9 Ti 18.9 N 18.2 XRD diffractogram (A), selected area electron diffraction pattern (SAED) (B) and radial intensity profile of SEAD pattern (C) of the alloy coating;

[0117] Figure 40 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 19 of the present application; 69.4 Ti 25.6 N 5.0 SEM cross-sectional view of the alloy coating;

[0118] Figure 41 is a SEM cross-sectional view of the CrTiN alloy coating prepared in Example 19 of the present application; 69.4 Ti 25.6 N 5.0 XRD diffractogram 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 XRD diffraction pattern and the corresponding radial intensity profile of the SAED pattern, a.u. has the meaning known in the art.

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

[0136] Reference signs: 1 is a vacuum cavity, 2 is a sample table, 3 is a direct current anode, 4 is a chromium target (also referred to as a Cr target, which can be a Cr target for RF-assisted direct current cathode current), 5 is a titanium target (also referred to as a Ti target, which can be a Ti target for RF-assisted direct current cathode current);

[0137] 100 is a substrate, 200 is a transition layer (also referred to as a transition film layer), 300 is a Cr-Ti-N alloy film, and 400 is a surface layer (also referred to as a surface film layer). DETAILED DESCRIPTION

[0138] The present application will be further described below in conjunction with the drawings, embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and are not used to limit the scope of the present application, and the purpose of providing these embodiments and examples is to make the understanding of the disclosed content of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms, and is not limited to the embodiments and examples described herein, and those skilled in the art can make various modifications or changes without departing from the spirit of the present application, and the equivalent forms obtained thereby also fall within the protection scope of the present application. For example, the features described or illustrated as part of an embodiment can be combined in another embodiment in a suitable manner to produce a new embodiment. In addition, in the following description, a large number of details are given in order to provide a more complete understanding of the present application, and it should be understood that the present application can be implemented without one or more of these details.

[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 the present application belongs. The terminology used in the specification of the present application herein is only for the purpose of describing the embodiments and examples and is not intended to limit the present application.

[0140] Unless otherwise stated or contradictory, the terms or phrases used herein have the following meanings:

[0141] The selection scope of the terms "and / or", "or / and", "and / or" used in the present application includes any one of two or more relevant listed items, and also includes any and all combinations of the relevant listed items. For example, "A and / or B" includes three parallel schemes of A, B, and "combination of A and B".

[0142] In the present application, "multiple", "various", "multiple times", "multiple items", "several" and the like, if not specifically limited, refer to more than two or equal to two in number. For example, "one or more" means one or more than two.

[0143] In the present application, "one or more" means any one of the listed items or any combination of the listed items, unless otherwise specified. Similarly, "one or more" and the like otherwise represent "one or more", and the same understanding is made unless otherwise specified.

[0144] In the present application, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0145] In the present application, "suitable combination", "suitable manner", "any suitable manner" and the like, "suitable" is subject to the implementation of the technical solutions of the present application, the solution of the technical problems of the present application, and the realization of the expected technical effects of the present application.

[0146] In the present application, "preferably", "better", "better", "preferably", "better", "better" are only to describe the better effect of the implementation mode or embodiment, and it should be understood that it does not constitute a limitation on the protection scope of the present application. If there are multiple "preferred" in a technical solution, if there is no special description, and there is no contradictory relationship or mutual restriction, each "preferred" is independent.

[0147] In the present application, "further", "further", "particularly", "for example", "such as", "example", "for example" and the like are used for description purposes, indicating that the different technical solutions before and after are related in terms of coverage, but should not be understood as a limitation on the previous technical solution, nor should it be understood as a limitation on the protection scope of the present application. In the present application, if not otherwise specified, A (such as B) means that B is one non-limiting example of A, and it can be understood that A is not limited to B.

[0148] In the present application, "optionally", "optional", "option" means optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "options" in a technical solution, unless otherwise specified, and there is no contradiction or mutual restriction, each "option" is independent. If there is no other description, "optionally includes", "optionally contains" and the like are described in the present application, for example, "optionally includes" means "may include or not include". "Optional component X" means that component X exists or does not exist.

[0149] The terms "containing", "including" and "comprising" used in the present application are synonymous terms, which are inclusive or open, and do not exclude additional, unmentioned members or features. Members or features, such as materials or components, structures, elements, instruments, etc.; non-limiting examples of members or features also include actions, conditions, timing, states, etc.

[0150] In the present application, the technical features or technical solutions described in open language include closed technical features or technical solutions composed of listed contents, and also include open technical features or technical solutions containing listed contents.

[0151] In the present application, with respect to the numerical interval (i.e. numerical range), if not otherwise specified, the distribution of optional values in the numerical interval is considered to be continuous, and includes both numerical endpoints (i.e. minimum value and maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. If not otherwise specified, when the numerical interval only points to the integer in the numerical interval, including the two endpoint integers of the numerical range and each integer between the two endpoints, it is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe characteristics or properties, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows a broad interpretation of the numerical interval type, such as percentage interval, ratio interval, ratio interval, etc.

[0152] In the present application, unless otherwise specified, "about" means within a certain range of the number, and the fluctuation range can vary depending on the type and value of the number. For example, it is allowed to fluctuate within a range of ±2%, ±1%, ±0.5% and the like of the number. For example, about 2° can mean selected from 2°±0.02° and the like.

[0153] The temperature parameters in the present application, if not particularly limited, allow for both constant temperature treatment and for variations within a certain temperature range. It is to be understood that constant temperature treatment allows for fluctuations within the accuracy of the instrument control. Fluctuations within a range of, for example, ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed.

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

[0155] In the present application, units relating to data ranges, if only the right end point is followed by a unit, it means that the units of the left end point and the right end point are the same. For example, 3-5h means that the units of the left end point "3" and the right end point "5" are both h (hour), which has the same meaning as 3h-5h. In addition, similar descriptions related to other parameters such as temperature, size, etc. are also applicable to the above understanding.

[0156] In the present application, the temperature unit °C refers to "degrees Celsius". The unit "Angstrom" is indicated. The size unit μm refers to "micrometer", and "nm" refers to "nanometer". The pressure unit Pa refers to "Pascal". The power density unit W / cm 2 "2" refers to "watts per square centimeter". The bias voltage unit V refers to "volt". sccm (standard cubic centimeter per minute) is a flow rate unit used to represent the flow rate of a gas.

[0157] The mass or weight of the related components mentioned in the embodiments of the present application can not only refer to the content of each component, but also represent the proportional relationship between the mass or weight of each component. Therefore, as long as the content of the related components in the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the embodiments of the present application. Non-limitingly, the mass mentioned in the embodiments of the present application can be micrograms (μg), milligrams (mg), grams (g), kilograms (kg) and other units commonly known in the chemical field.

[0158] All documents mentioned in this application are incorporated herein by reference as if each individual document were specifically and individually indicated to be incorporated by reference. Citation of any reference is not an admission that it is prior art with respect to the present application. To the extent that any meaning or definition of a term in this document conflicts with the meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall control.

[0159] In this application, unless otherwise stated, steps involved in a method flow can not have a strict order limit, and can be executed in other orders than described. Also, any step can include multiple sub-steps or stages, which can not necessarily be executed at the same time, and can be executed at different times, and can not necessarily be executed in sequence, but can be executed in rotation or alternation or simultaneously with other steps or sub-steps or stages of other steps.

[0160] In describing a position relationship, unless otherwise stated, when a component such as a layer, film or substrate is referred to as "on" another film layer, it can be directly on the other film layer or there can be an intervening film layer. Further, when a layer is referred to as "under" another layer, it can be directly under the other layer or there can be one or more intervening layers. It is also understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or there can be one or more intervening layers.

[0161] In the case of using "include", "have", and "contain" described in this document, it is intended to cover non-exclusive inclusion, and unless an explicit limiting term such as "only", "consisting of", etc. is used, another component can also be added.

[0162] Unless otherwise mentioned, the singular form of a term can include the plural form and should not be construed as having a quantity of one.

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

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

[0165] The conventional Cr-Ti-N alloy coating is generally in a nanocrystalline state and has a high content of columnar crystals. The high content of columnar crystals in these alloy coatings promotes the formation of a highly ordered structure arranged in a direction, and a large number of crystals in the highly ordered structure cause intercrystalline gap defects, mainly in the form of penetrating columnar gaps, and there are shadows between the columnar crystals in the corresponding scanning electron microscope (SEM) cross-sections. These penetrating columnar gaps can be one of the important factors leading to poor corrosion resistance of the alloy coating. The inventors of the present application speculate that the conventional ordered structure arranged in a direction is prone to cause the coating to be less dense, and under corrosion conditions, the corrosion medium can quickly penetrate the coating through the penetrating gaps and react with the substrate, thereby resulting in poor corrosion resistance of the alloy coating.

[0166] In addition, the conventional Cr-Ti-N alloy coating often has difficulty in achieving a high L value in terms of brightness effect, for example, the L value is generally about 55-65.

[0167] The alloy materials on the market at present mainly use anodic oxidation, magnetron sputtering and other means for surface protection. For example, aluminum alloy mainly uses anodic oxidation for surface protection, and the working principle is as follows: the aluminum alloy material is placed in a strong acid or strong alkali solution to form an oxide and a metal or alloy coating on the surface to form surface protection. Since the solution is a strong acid or strong alkali, the corrosion resistance of the product formed by this method is not ideal, the hardness is low, the brightness effect is poor, and in addition, a large amount of wastewater, waste liquid and waste gas are generated in the production process, which is not conducive to the environment.

[0168] According to various embodiments and various examples of the present application, the present application at least provides a Cr-Ti-N alloy material, a Cr-Ti-N alloy film and a preparation method thereof, a Cr-Ti-N alloy coating, an alloy film product and application. The Cr-Ti-N alloy material has excellent corrosion resistance, and can form a Cr-Ti-N alloy film, an alloy coating comprising the Cr-Ti-N alloy film or a related alloy film product. The related Cr-Ti-N alloy film and Cr-Ti-N alloy coating can be used as a product protective coating to improve the protection ability of the product.

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

[0170] In the present application, "Cr-Ti-N alloy" and "CrTiN alloy" both represent an alloy containing Cr element, Ti element and N element, allowing to further contain other alloying elements, and both can be used interchangeably, unless otherwise specified.

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

[0172] In the present application, "Cr-Ti-N ternary alloy" and "CrTiN ternary alloy" both represent an alloy composed of Cr element, Ti element and N element.

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

[0174] In the present application, "atomic ratio" of two or more elements represents the ratio of the number of atoms, which can be calculated by atomic molar ratio, unless otherwise specified.

[0175] The Cr-Ti-N alloy material provided in the present application includes three elements of Cr, Ti and N, and the three elements have a specific relative atomic ratio (Cr x Ti y N z), 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, such that the Cr-Ti-N alloy material has the ability to form a highly disordered atomic distribution and a sufficient close-packed arrangement, and can form a Cr-Ti-N alloy film or a Cr-Ti-N alloy coating with a dense structure. When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided by the present application is located on the surface of an article, excellent corrosion resistance can be provided. The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating comprising the Cr-Ti-N alloy material of the present application have a much longer protection time in salt spray corrosion resistance tests than conventional Cr-Ti-N alloy coatings.

[0176] Traditional Cr-Ti-N alloy coatings are usually in a nanocrystalline state and have a high content of columnar crystals, and usually have a large number of through pores in the coating structure, resulting in poor corrosion resistance. The Cr-Ti-N alloy material provided by the present application can form a dense coating with a "highly disordered and close-packed" characteristic structure, containing a small amount of through pores or no through pores; wherein the three atoms of Cr, Ti and N with greatly different radii have a special atomic ratio, which is beneficial to condense into a highly disordered state during deposition, and then can be tightly packed in a highly disordered state, so as to facilitate the dense growth of the alloy coating, and can inhibit the formation of continuous and large through gaps, thereby forming an effective isolation between the substrate and the corrosion environment. In addition, since the Cr-Ti-N alloy coating provided by the present application contains chromium and titanium elements, the coating has sufficient chemical inertness in the corrosion environment. Based on the Cr-Ti-N alloy material of the present application, a Cr-Ti-N alloy coating not only has a highly disordered atomic distribution, but also has a sufficient close-packed structure at the atomic scale, so as to avoid or reduce the through gaps formed due to the highly ordered arrangement. The dual characteristics of "highly disordered atomic distribution" and "sufficient close-packed" of the atoms in the alloy coating make the alloy coating have a highly dense structure, and can provide excellent corrosion resistance.

[0177] In addition, the Cr-Ti-N alloy coating prepared by using the Cr-Ti-N alloy material provided by the present application has a dense structure, and can not only provide excellent corrosion resistance, but also have high hardness characteristics, thereby better reducing the generation of scratches or weakening the scratch damage.

[0178] In the Cr-Ti-N alloy material, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application, based on the special 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, so that Cr and Ti are easy to form strong bond energy, which is conducive to the rapid growth of Cr-Ti alloy with a suitable atomic ratio in the deposition process, and the addition of a small amount of nitrogen can further promote the re-nucleation of Cr-Ti alloy to form a CrTiN-based alloy composition. By improving the compactness of the coating nucleation, the corrosion resistance of the coating can be improved, and the hardness of the coating can also be improved. Among them, in terms of atomic size, the atomic radius of Cr is the atomic radius of Ti is the atomic radius of N is The atomic sizes of Cr and Ti are close, and the atomic size of N is small. In the nucleation process, a proper amount of small-size N atoms can penetrate into the pores of large-size Cr and Ti metal grains with a suitable atomic ratio, achieving a better pore-filling effect, making the atomic arrangement more compact, and at the same time, the growth defects of the thin film columnar crystal structure can be inhibited, thereby better improving the corrosion resistance of the coating, and also being conducive to better improving the hardness of the coating.

[0179] The large amount of penetrating pores in the traditional Cr-Ti-N alloy coating also leads to poor surface reflection characteristics and low brightness. When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application is located on the surface of an article, it can also give the article a high-brightness and beautiful surface. Cr is a high-brightness metal raw material in the coating material, and a higher Cr content can effectively improve the brightness of the alloy coating. At the same time, the Cr-Ti-N alloy material provided in the present application can be made into a Cr-Ti-N alloy coating with high compactness, so that the surface reflection characteristics of the coating are further improved. The two characteristics are superimposed, so that the brightness of the coating surface is higher during the colorimetric measurement process, and the brightness value (i.e. L value) is higher. The L value of the Cr-Ti-N alloy coating provided in the present application can be ≥75, and part of it can be as high as ≥80, which can present a high-brightness silver-white color, which is much higher than the L value of the traditional alloy coating (the traditional L value is about 55-65). The high-brightness coating has a beautiful effect and excellent decorative characteristics. When applied to the surface of a substrate (such as pure metal, alloy and other materials), it can achieve a high-brightness and beautiful effect, so that the color of the coating and the substrate is closer, and an approximately colorless and different surface can be achieved. This characteristic makes the Cr-Ti-N alloy coating provided in the present application have excellent surface decoration effect, which can be applied to (but not limited to) 3C digital products, such as mobile phone parts, which can achieve a high-brightness metal effect, and can also be applied to wearable products, automotive products, sports products and other fields.

[0180] In the present application, the brightness value L can be expressed by Lab method unless otherwise specified.

[0181] In the present application, when testing the chroma value of the alloy coating, the sample to be tested adopts a substrate material suitable for practical application. The L value, a value and b value of the sample can be tested by using a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan, the light receiving system selects F2 light source, and the average value is obtained after testing at least 6 (for example, 6) matrix points of each sample. Among them, the L value represents the brightness value, the a value represents the red or green chroma value, and the b value represents the yellow or blue chroma value. The a value represents the red-green color of the object, the positive value represents the red chroma value, and the negative value represents the green chroma value. The b value represents the yellow-blue color of the object, the positive value represents the yellow chroma value, and the negative value represents the blue chroma value. The larger the L value, the higher the brightness, indicating that the coating surface is more dense. The mechanism is as follows: the spectrophotometer is incident light on the surface of the sample to be tested, forming a reflection, and a reflectivity curve can be obtained. The amplitude of the curve can reflect the density of the material, which can be characterized by the L value, and the higher the density of the same material, the larger the L value displayed.

[0182] In the present application, unless otherwise specified, the chroma value Lab is tested as follows: the light receiving system selects F2 light source, and the average value is obtained after testing at multiple (for example, 6) matrix points of each sample. Further, a spectrophotometer is used for testing. Further, the testing instrument is a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan. The testing temperature can be room temperature, and further can be 25°C.

[0183] The Cr-Ti-N alloy material provided in the present application has a highly disordered atomic distribution and a highly dense atomic arrangement, which can achieve dense packing of atoms under a highly disordered atomic arrangement, so that the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating formed have a special atomic arrangement of "highly disordered and fully dense", thereby avoiding or reducing the through connection of intergranular gaps caused by highly ordered arrangement to form through gaps, so that the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating have a highly dense structure, which can provide excellent corrosion resistance. In addition, it can also provide high hardness and high brightness characteristics. The Cr-Ti-N alloy coating prepared by using the Cr-Ti-N alloy material provided in the present application can effectively reduce the defects commonly found in traditional crystalline coatings, such as the large reduction or disappearance of the through gaps between the grains in the columnar crystal structure coating, so that the Cr-Ti-N alloy coating is more conducive to dense growth, which can endow the alloy coating with excellent corrosion resistance. In addition, it is also beneficial to improve the hardness of the coating and to obtain a smooth and high-brightness surface.

[0184] In some embodiments, x can be any of the following values or a range 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 embodiments, y can be any of the following values or a range 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 embodiments, z can be any of the following values or a range 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 present application, x, y, z are combined in any suitable manner, for example, in the manner of x+y+z=100.

[0188] The Cr-Ti-N alloy material, Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided by the present application can contain or not contain a doping element, which can be selected flexibly according to the additional functional requirements of one or more of the alloy material, alloy film and alloy coating. It can be understood that in the present application, when the doping element is contained, the type and doping amount of the doping element are limited at least not to affect the corrosion resistance of the Cr-Ti-N alloy coating; further preferably, at least one of higher coating hardness and higher surface brightness can also be achieved.

[0189] In some embodiments, z / (x+y+z)≤26.5%, optionally, 2.4%≤z / (x+y+z)≤26.5%. Without limitation, (x+y) / (x+y+z) can also be any one 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, which includes Cr element, Ti element and N element, in the Cr-Ti-N alloy material, the atomic ratio of the Cr element, the Ti element and the N element is x:y:z, 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5; the Cr-Ti-N alloy material further includes a doping element. In the nucleation process, N atoms can penetrate into the pores of large-size Cr, Ti metal grains, achieve a better pore-filling effect, make the atomic stacking of the coating more dense, and also can inhibit the growth defects of the thin film columnar crystal structure, thereby improving the corrosion resistance of the coating.

[0191] In the present application, the doping element in the Cr-Ti-N alloy material can be recorded as "M element". Without other indications, the doping element in the Cr-Ti-N alloy material refers to other elements in the Cr-Ti-N alloy material different from any one of Cr, Ti and N.

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

[0193] In some embodiments, the mass percentage (which can be recorded as f wt ) of the three elements of Cr, Ti and N in the Cr-Ti-N alloy material can be greater than or equal to 80%, optionally, greater than or equal to 90%, further optionally, f wt is greater than or equal to 95%, and still further optionally, f wt is 100%. Without limitation, f wt may also be any one of the following values, greater than or equal to any one of the following values, or a range selected from any two of the following values: 80%, 85%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc. wt may also be greater than or equal to any one of the foregoing values and less than or equal to 100%, for example, f wtmay be 80% to 100%, 90% to 100%, 95% to 100%, 99% to 100%, etc.

[0194] In some embodiments, the Cr-Ti-N alloy material mainly contains Cr, Ti and N, and further, the sum of the atomic ratios of the three elements accounts for a proportion (denoted as f N ) of the sum of the atomic ratios of all elements in the Cr-Ti-N alloy material of ≥95%, further like f N ≥98%, and more further like f N =100% (at this time, the Cr-Ti-N alloy material is a Cr-Ti-N ternary alloy material). Without limitation, f N may also be any of the following values, greater than or equal to any of the foregoing values, or selected from the interval consisting of any two of the following values: 95%, 96%, 97%, 98%, 99%, etc., f N may also be greater than or equal to any of the following values and less than or equal to 100%, for example, f N may be 95% to 100%.

[0195] By limiting the content of the doping element in the Cr-Ti-N alloy material within a more appropriate range, the influence of the doping element on the atomic highly disordered and fully dense Cr-Ti-N alloy film and Cr-Ti-N alloy coating can be minimized, which is conducive to reducing the required elements for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the collaborative deposition of Cr, Ti and N to form a more dense coating, which is conducive to achieving better corrosion resistance, in addition, it is also conducive to obtaining higher hardness.

[0196] In some embodiments of the present application, the Cr-Ti-N alloy material includes a CrTiN-based alloy component with a chemical formula of Cr x Ti y N z M a , wherein x, y and z are each independently an atomic ratio and a positive number, M is a doping element, and a is an atomic ratio of the M element and is 0 or a positive number.

[0197] In the present application, unless otherwise specified, the "CrTiN-based alloy component" refers to an alloy component that at least includes Cr element, Ti element and N element. Generally, in the CrTiN-based alloy component, the Cr element, Ti element and N element constitute the main elements.

[0198] In the present application, unless otherwise specified, the "Cr-Ti-N ternary alloy component" and "CrTiN ternary alloy component" both refer to an alloy component composed of Cr element, Ti element and N element.

[0199] When a is 0, the CrTiN-based alloying component does not contain the doping element, corresponding to a Cr-Ti-N ternary alloying component. When a > 0, the CrTiN-based alloying component contains the doping element, wherein a / (x+y+z) is equal in value to the relative atomic percentage of the doping element with respect to Cr, Ti and N, and a / (x+y+z+a) is equal in value to the atomic percentage of the doping element in the CrTiN-based alloying component. The relative atomic percentage of the doping element M with respect to Cr, Ti and N refers to the ratio of the number of atoms of the doping element M to the sum of the number of atoms of Cr, Ti and N in the material, expressed in percentage.

[0200] By limiting the content of the doping element in the CrTiN-based alloying component within a more appropriate range, the influence of the doping element on the atomic highly disordered and fully dense CrTiN-based alloying component can be minimized, which is conducive to reducing the required doping element or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr, Ti and N to form a more dense Cr-Ti-N alloy material, which is conducive to achieving better corrosion resistance. In addition, it is also conducive to obtaining higher hardness.

[0201] In some embodiments, the mass percentage of Cr, Ti and N in the CrTiN-based alloying component (which can be denoted as f w0 ) can be greater than or equal to 80%, optionally, f w0 is greater than or equal to 90%, further optionally, f w0 is greater than or equal to 95%, and still further optionally, f w0 is 100%. Without limitation, f w0 may also be any of the following values, greater than or equal to any of the following values, or selected from the interval consisting of any two of the following values: 80%, 85%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc. f w0 may also be greater than or equal to any of the foregoing values and less than or equal to 100%, for example, f w0 may be 80% to 100%, 90% to 100%, or 95% to 100%.

[0202] In some embodiments, the total number of atoms of Cr, Ti and N with respect to the number of atoms of all elements in the CrTiN-based alloying component (which can be denoted as f N0 ) can be greater than or equal to 95%, further f N0 may 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 aCrTiN-based alloy composition, where M is a doping element, x, y, z and a are atomic ratios of Cr element, Ti element, N element and M element respectively, 5.0≤x≤90.0, 5.0≤y≤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 a person skilled in the art can select a suitable value of a / (x+y+z+a) according to the needs. In some embodiments, a / (x+y+z+a) can be any of the following values, greater than 0 and less than or equal to any of the following values, or selected from the interval consisting of any two of the following values: 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, etc.

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

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

[0207] In some embodiments, 0<a / (x+y+z+a)≤0.05, 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 other embodiments, 0<a / (x+y+z+a)≤0.02, further for example 0<a / (x+y+z+a)≤0.02, 0<a / (x+y+z+a)≤0.01, 0<a / (x+y+z+a)≤0.01, 0<a / (x+y+z+a)<0.01, etc. At this time, the content of the doping element can be controlled to be relatively low, the impact of the doping element on the atomic highly disordered and fully dense Cr-Ti-N alloy film and Cr-Ti-N alloy coating can be minimized, which is conducive to reducing the number of elements required for doping or reducing the difficulty of doping, simplifying the preparation process, promoting the synergistic deposition of Cr-Ti-N to form a more dense coating, and facilitating better corrosion resistance. In addition, it is also conducive to obtaining higher hardness and higher brightness.

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

[0210] In some embodiments, a / (x+y+z) = 0. In this case, the composition corresponds to a Cr-Ti-N ternary alloy composition, which is simple and easy to prepare and manipulate. The Cr-Ti-N ternary alloy coating formed in this case can have a dense structure and can achieve high corrosion resistance. In addition, a higher coating hardness can also be obtained.

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

[0212] In some embodiments of the present application, the chemical formula of the Cr-Ti-N alloy material is Cr x Ti y N z M a In this case, the mass percentage f of the CrTiN-based alloy composition in the Cr-Ti-N alloy material is 100%, wherein the definitions of x, y, z and a can be referred to the context of the present application. w1

[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 advantageous to impart a 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 can 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 alloy-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 advantageous to endow the corresponding Cr-Ti-N alloy film or Cr-Ti-N alloy coating with higher hardness. Further optionally, x+y+z=100.

[0217] Based on any suitable characteristics as aforementioned (e.g. 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, also as any suitable combination of x, y and z as aforementioned), the sum of x, y and z can be a value selected from 95-100. Non- limitingly, the sum of x, y and z can be any of the following values, also can be selected from an interval consisting of any two of the following values: 95, 96, 97, 98, 99, 100, etc.

[0218] Based on any suitable characteristics as aforementioned (e.g. 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.5, also as any suitable combination of x, y and z as aforementioned), 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 in a more suitable range, so that the Cr-Ti-N alloy coating formed is advantageous to obtain a more compact structure, and is advantageous to achieve better corrosion resistance. In addition, it can also be advantageous to improve the hardness of the coating, and can be more advantageous to achieve higher brightness.

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

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

[0221] In some embodiments, the mass percentage of Cr-Ti-N alloy material in the Cr-Ti-N alloy coating is 100%.

[0222] In some embodiments, x is greater than y based on any suitable embodiment described above. In this case, the Cr content in the Cr-Ti-N alloy material is higher than the sum of the Ti and N contents, and this special atomic ratio design can better improve the nucleation density of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, thereby further improving the corrosion resistance of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, and further improving the hardness and brightness characteristics. In this case, during the nucleation process, N atoms can penetrate into the pores of large-size Cr and Ti metal grains, achieving better pore filling effect, making the atomic stacking of the coating more dense, which can significantly improve the corrosion resistance, and further promote the hardness of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, and better inhibit the growth defects of the columnar crystal structure of the thin film, and better improve the surface reflection characteristics of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, thereby improving the brightness value.

[0223] In some embodiments, the doping element in the Cr-Ti-N alloy material is a non-metallic element, a metallic element, or a combination thereof, which can be flexibly selected according to the additional functional requirements of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating.

[0224] Non-limitingly, the non-metallic element can include but is not limited to one or more of O, C, B, Si, H, and Ar. Non-limitingly, the metallic element can 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. The Cr-Ti-N alloy film can also refer to the context of the present application.

[0226] In some embodiments, the Cr-Ti-N alloy material is a constituent material of the Cr-Ti-N alloy coating. In this case, the Cr-Ti-N alloy material constitutes the Cr-Ti-N alloy coating. The Cr-Ti-N alloy coating can also refer to the context of the present application.

[0227] It should be noted that in any of the embodiments of the context of the present application, the Cr-Ti-N alloy material, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application can contain inevitable impurities introduced during the preparation process. The "inevitable impurities" are not intentionally added impurities, and the main reason for their existence is that they are unintentionally brought in during the preparation process. Non-limiting examples of "inevitable impurities" include C, O and other elements present in the air, which can also come from the composition of raw materials or equipment. The atomic content of "inevitable impurities" in the alloy material, alloy film or alloy coating is usually trace or micro, which can be generally ignored, such as less than 0.01% atomic content. Taking the technical solution of "Cr-Ti-N alloy coating composed of Cr-Ti-N ternary alloy material of Cr element, Ti element and N element" as an example, in theory, the Cr-Ti-N alloy coating is composed of Cr, Ti and N elements, but trace or micro amounts of other elements such as C, O and H may be introduced during the preparation process in addition to Cr, Ti and N elements.

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

[0229] The Cr-Ti-N alloy film provided by the present application can also be described as "the Cr-Ti-N alloy film of the present application", "the Cr-Ti-N alloy film of the present application", "the Cr-Ti-N alloy film described in the present application", "the Cr-Ti-N alloy film of the present application", "the Cr-Ti-N alloy film of the present application", "the Cr-Ti-N alloy film provided by the present application", "the Cr-Ti-N alloy film described in the present application", etc. Moreover, it can include but is not limited to the Cr-Ti-N alloy film provided in the second aspect.

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

[0231] The Cr-Ti-N alloy coating provided by the present application can also be described as "the Cr-Ti-N alloy coating of the present application", "the Cr-Ti-N alloy coating of the present application", "the Cr-Ti-N alloy coating described in the present application", "the Cr-Ti-N alloy coating of the present application", "the Cr-Ti-N alloy coating of the present application", "the Cr-Ti-N alloy coating provided by the present application", "the Cr-Ti-N alloy coating described in the present application", etc. Moreover, it can include but is not limited to the Cr-Ti-N alloy coating provided in the third aspect.

[0232] As mentioned above, based on the special atomic proportion of Cr, Ti and N, the highly disordered atomic distribution and the fully dense atomic arrangement are formed in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, which has the dense structure of "highly disordered and fully dense", and can inhibit the formation of continuous and large amount of penetrating cracks, thereby significantly improving the corrosion resistance of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating.

[0233] Based on the improvement of the structural density of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, higher hardness can also be obtained. The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application have a dense structure, which can not only provide excellent corrosion resistance, but also have high hardness characteristics, thereby better reducing the generation of scratches or weakening the scratch damage. Further, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application can have high corrosion resistance and high hardness characteristics at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing the cost.

[0234] The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application can be used as a surface layer of an alloy film product, which has both aesthetic and decorative effects and protective effects. The Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application can also be located between the substrate and the surface layer, thereby providing excellent protection, better corrosion resistance and scratch resistance.

[0235] Based on the improvement of the structural density of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, the surface reflection characteristics can also be improved to increase the 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 a peak in the range of diffraction angle 2θ(°) of 34°-50°, and the half-height width of at least one 2θ(°) diffraction peak in the range of 34°-50° satisfies ≥1.6°;

[0238] In the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film, with the characteristic interatomic distance as the abscissa and the diffraction intensity as the ordinate, there is a diffraction peak in the range of , and the half-height width of at least one diffraction peak in the range of satisfies ≥

[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. The Cr-Ti-N alloy material is not limited to the coating form and can be an independent raw material, such as alloy sheet or alloy plate.

[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 the Cr-Ti-N alloy material, with the characteristic interatomic distance as the abscissa and the diffraction intensity as the ordinate, there are diffraction peaks in the range of and The half-height width of at least one diffraction peak in the range of satisfies ≥

[0251] Further, the XRD test results and the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy material can also refer to the description of the X-ray diffraction pattern, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating in this article, and the corresponding optional and preferred modes can also be applicable to the Cr-Ti-N alloy material.

[0252] The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application are not strictly divided by traditional perfect single crystals or sufficient amorphous states, but focus on the close packing degree of atomic arrangement, which is closely related to the disorder of atomic arrangement and the suitable mismatch degree of atomic size on the basis of the specific atomic ratio of Cr, Ti and N. The highly dense Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application have excellent corrosion resistance in performance, in addition, high hardness characteristics and high brightness values can also be obtained, and in structure, at least one wide peak (further, there can be no sharp peak, that is, all wide peaks) in the diffraction angle 2θ(°) range of 34°-50° in the XRD pattern and at least one wide peak (further, there can be no sharp peak, that is, all wide peaks) in the radial intensity profile of the selected area electron diffraction pattern in the range of are simultaneously satisfied.

[0253] Different from the conventional Cr-Ti-N alloy coating in nanocrystalline state and high columnar crystal content (with a large number of through holes), the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the application can form a dense coating with "highly disordered and fully dense" characteristic structure, containing a small amount of through pores or no through pores. In the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the application, Cr, Ti and N, three atoms with different radii, are condensed into a highly disordered state during deposition and form a tight packing, so that the alloy coating is easy to grow densely, and the formation of continuous and large through gaps can be inhibited, thereby forming an effective isolation between the substrate and the corrosion environment, and in addition, a dense and high-brightness surface with better reflective properties can be formed. In addition, due to the presence of chromium and titanium elements in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the application, the coating has sufficient chemical inertness in the corrosion environment. The Cr-Ti-N alloy material in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the application not only has a highly disordered atomic distribution, but also has a fully dense packing at the atomic scale, thereby avoiding or reducing the through gaps caused by highly ordered arrangement. The dual characteristics of "highly disordered distribution" and "fully dense packing" of atoms in the Cr-Ti-N alloy film and Cr-Ti-N alloy coating make the Cr-Ti-N alloy film and Cr-Ti-N alloy coating have a highly dense structure, which can provide excellent corrosion resistance, and in addition, can also provide a high-hardness and high-brightness surface.

[0254] In the present application, unless otherwise specified, whether the constituent atoms of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating have a "highly disordered" state is evaluated by XRD technology. In detail, the XRD pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating shows a wide and slow ridge, which is referred to as a "broad peak" of the 2θ(°) diffraction peak. By the half-height width value of the broad peak, the length of atomic ordering can be obtained by using the Scherrer formula. The calculation method is: D = Kλ / (β·cosθ), wherein D is the length of atomic ordering (representing the grain size in crystalline materials), K is the Scherrer constant, λ is the X-ray wavelength; β is the half-height width value (Full Width at Half Maximum, FWHM) of the 2θ(°) diffraction peak at half the height, and θ is the diffraction angle. It can be seen that the half-height width FWHM is inversely proportional to the length D of atomic ordering, and the shorter the length D of atomic ordering, the higher the disorder of atomic distribution. Therefore, the degree of disorder of atomic distribution can be reflected by the half-height width FWHM of the diffraction peak in a specific range of the XRD pattern: the wider the half-height width FWHM, the shorter the length of atomic ordering, and the more disordered the overall atomic distribution; the "broad peak" of the wide and slow ridge can reflect the highly disordered distribution of atoms in the whole material.

[0255] In the present application, unless otherwise specified, the XRD diffraction pattern and the diffraction peak in the pattern are related to the horizontal axis of 2θ with the unit of °.

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

[0257] Generally speaking, the higher the atomic ordering, the stronger the crystallinity, the easier it is to form large-size grains in a longer distance, and the narrower the diffraction peak in the XRD pattern, and high crystallinity is often accompanied by sharp peaks. However, in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application, the three atoms of Cr, Ti and N can be arranged in a highly disordered manner in the Cr-Ti-N alloy coating, so that the XRD pattern of the Cr-Ti-N alloy coating shows a wide and slow ridge (broad peak), and at least one peak in the range of 34°-50° of the diffraction angle 2θ(°) is a "broad peak".

[0258] In the present application, a "broad peak" in an XRD pattern can be defined as a diffraction peak having a half-height width (in 2-theta (°)) of > 1.6°, unless otherwise specified. The half-height width of a broad peak can further be > 2°, can further be > 2.2°, can further be > 2.3°, can further be > 3°, can further be > 3.32°, can further be > 3.5°, can further be > 4°, can further be > 4.21°, can further be > 5°. The half-height width (in 2-theta (°)) of any "broad peak" in an XRD pattern can independently be any of the following values, can be greater than or equal to any of the following values, can be greater than or equal to any of the following values (except for 10°) and less than or equal to 10°, can be selected from the interval defined by any two of the following values: 1.6°, 1.60°, 1.65°, 1.69°, 1.8°, 1.85°, 2°, 2.00°, 2.03°, 2.2°, 2.29°, 2.48°, 2.5°, 2.63°, 2.60°, 2.68°, 2.91°, 2.99°, 3°, 3.00°, 3.32°, 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 non-limiting examples, the half-height width (in 2-theta (°)) of a "broad peak" can be selected from any of the following ranges: 1.6° to 10°, 1.8° to 10°, 2° to 10°, 3.32° to 10°, 4.21° to 10°, 1.6° to 9.5°, 1.69° to 5.40°, 1.8° to 9.5°, 2° to 9.5°, 3.32° to 9.5°, 4.21° to 9.5°, 2° to 9.4°, 3.32° to 9.4°, 1.6° to 8°, 1.8° to 8°, 2° to 8°, 3.32° to 8°, 4.21° to 8°, 1.6° to 6.0°, 1.8° to 6.0°, 2° to 6.0°, 3.32° to 6.0°, 4.21° to 6.0°, 1.6° to 5.5°, 1.8° to 5.5°, 2° to 5.5°, 3.32° to 5.5°, 4.21° to 5.5°, etc.

[0259] In the present application, a "sharp peak" in an X-ray diffraction (XRD) pattern refers to a diffraction peak having a half-height width (in 2-theta (°)) of < 1.6°, unless otherwise specified.

[0260] In more detail, the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the present application have XRD patterns with peaks in the diffraction angle 2θ(°) range of 34°-50°, and at least one peak in the XRD pattern is a broad peak. The special microstructure state of "at least one peak being a broad peak" can be expressed as "having at least one 2θ(°) diffraction peak in the range of 34°-50° with a half-height width ≥1.6°" or "at least one 2θ(°) diffraction peak in the range of 34°-50° having a half-height width satisfying ≥1.6°". The method for determining whether "having at least one 2θ(°) diffraction peak in the range of 34°-50° with a half-height width ≥1.6°" is satisfied is as follows: if the half-height width of a 2θ(°) diffraction peak in the XRD pattern is ≥1.6°, it is determined to be a "broad peak"; if the half-height width of a 2θ(°) diffraction peak is <1.6°, it is determined to be a sharp peak. For a specified 2θ(°) position, it can be any one of the three states of no peak, broad peak or sharp peak. The broad peak characteristic of the characteristic diffraction peaks of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the present application is more obvious in the X-ray diffraction (XRD) pattern.

[0261] In the conventional Cr-Ti-N alloy coating with a high content of columnar crystals, the diffraction peak in the diffraction angle 2θ(°) range of 34°-50° is often a sharp peak with a half-height width <1.6°, and no broad peak appears.

[0262] In the present application, the XRD pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating can be obtained by using conventional instruments and methods in the art. For example, a German Bruker D8 Advance XRD diffractometer can be used.

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

[0264] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy film and Cr-Ti-N alloy coating provided in the present application each independently has one broad peak in the diffraction angle 2θ(°) range of 34°-50°, and the half-height width of the broad peak can be referred to the examples in the context.

[0265] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application each independently has 2 or more broad peaks in the range of diffraction angle 2θ (°) of 34°-50°, and the full width at half maximum of the broad peaks can each independently refer to the examples in the context.

[0266] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application each independently has all the 2θ (°) diffraction peaks in the range of diffraction angle 2θ (°) of 34°-50° as broad peaks, i.e. there is no sharp peak, and the full width at half maximum of the 2θ (°) diffraction peaks in the range of 34°-50° can each independently satisfy ≥1.6°, further can each independently satisfy ≥2°, further can each independently satisfy ≥3.32°, further can each independently satisfy ≥4.21°, further can each independently satisfy ≥5°.

[0267] In some embodiments, the X-ray diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application each independently has a peak in the range of diffraction angle 2θ (°) of 34°-50°, and the full width at half maximum of the 2θ (°) diffraction peaks in the range of 34°-50° can each independently satisfy ≥1.6°, further can each independently satisfy ≥2°, further can each independently satisfy ≥3.32°, further can each independently satisfy ≥4.21°, further can each independently satisfy ≥5°.

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

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

[0270] In the present application, the XRD pattern of the Cr-Ti-N alloy film and the alloy coating can be obtained by using the following instrument and method: using a German Bruker D8 Advance XRD diffractometer, in θ-2θ mode, using Cu target Kα ray, wavelength λ of 0.15406 nm, X-ray tube controlled at 40 kV and 40 mA, scanning range of 20°-80°, and precise scanning measurement with a step of 0.01°.

[0271] The full width at half maximum value can be obtained by using the conventional analysis method in the art (including but not limited to the analysis software provided by the instrument supplier). For example, the step of obtaining the full width at half maximum value can include: first correcting the diffraction peak, which can include: smoothing, background subtraction, removal of Kα2 line, removal of instrument broadening, etc., and then fitting the diffraction peak with a Pseudo-Voigt function to obtain the full width at half maximum value of the diffraction peak.

[0272] The analysis software is not particularly limited, and non-limitingly, EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) can be used to process the spectrum data, for example, the following method can be used: first, a ruler correction is performed, then the center of the diffraction ring transmission spot is determined, and then an XRD spectrum is converted (wherein the electron wavelength is 0.00251 nanometers (nm), and the X-ray wavelength is 0.154 nm; after the diffraction peak is subtracted from a straight line background and then fitted by a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0273] Regarding the characterization of the atomic close-packed degree in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating, the traditional XRD pattern cannot well characterize it, because when detecting a physical vapor deposition (PVD) film or coating at an atomic scale (such as a diameter < 3 nm), the XRD method often has insufficient resolution due to the relatively large wavelength (> 0.1 nm) of X-rays, and is not suitable for PVD films or coatings with low order (such as grains or amorphous with a diameter < 3 nm).

[0274] In the present application, whether the atoms in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating reach “sufficient close packing” can be evaluated by a selected area electron diffraction pattern (Selected Area Electron Diffraction, SAED). The electron wave is selected because its wavelength is significantly smaller (< 0.01 nm), thereby having higher resolution. In detail, if only a continuous diffraction ring with uniform brightness exists on the SEAD pattern, and the diffraction ring is relatively wide, it indicates that the atoms in the coating are arranged in a highly random mixed manner. In order to quantitatively characterize, the SAED pattern can be converted into a characteristic atomic spacing (d)-radial intensity profile, wherein the characteristic atomic spacing (d) is taken as the horizontal coordinate, and the diffraction intensity is taken as the vertical coordinate. If the diffraction ring in the SEAD is relatively wide, then correspondingly, the half-height width of the radial intensity profile is relatively wide, reflecting that the atomic arrangement in the alloy coating is relatively strong.

[0275] In the present application, at the atomic size, the Cr atomic radius is The Ti atomic radius is The N atomic radius is Three kinds of atoms with different diameters can form a full dense packing structure under the condition of high random mixing degree. In the growth process of PVD thin film or alloy coating, the full dense packing of atoms in Cr-Ti-N alloy film and Cr-Ti-N alloy coating makes the Cr-Ti-N alloy film and Cr-Ti-N alloy coating easy to grow densely, which can inhibit the formation and growth of columnar crystals caused by local ordering, and thus makes it difficult to form a large number of continuous through-type pores. Therefore, the half width of the radial intensity profile can be used as a characteristic parameter of the full dense packing structure of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating to reflect the atomic packing property in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating. The larger the value of the half width, the better the atomic packing property in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating. In short, the half width of the radial intensity profile of the SAED is used as a characteristic parameter of the full dense packing of atoms, which is in line with scientific principles and has scientific nature.

[0276] When the half width of the radial intensity profile is greater than a certain threshold value, the atoms in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can achieve full dense packing. According to a large number of experimental explorations by the inventors, in the present application, the threshold value of the half width of the SAED-radial intensity profile for judging whether the atomic full dense packing is achieved is determined as that is, it is considered that the full dense packing of atoms can be achieved when the half width value is greater than or equal to .

[0277] In the present application, the characteristic interatomic distance (d) radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating sample can be obtained by using the transmission electron microscope (TEM) technology.

[0278] In the present application, the radial intensity profile corresponding to the selected area electron diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can be recorded as SAED-radial intensity profile, and also can be recorded as a characteristic interatomic distance-intensity quantitative atlas of the selected area electron diffraction pattern (SAED pattern). The selected area electron diffraction pattern obtained by using the transmission electron microscope technology can be recorded as TEM selected area electron diffraction pattern, and also can be recorded as TEM-SAED pattern. The SAED-radial intensity profile obtained by using the transmission electron microscope technology can also be recorded as 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: using a Talos F200x model transmission electron microscope (TEM) of Themo Fisher Co., Ltd., USA, with an electron acceleration voltage of 200 kV, a selected area aperture diameter of 900 nm, and obtaining a selected area electron diffraction pattern (SAED) of the sample. Based on the selected area electron diffraction pattern (SAED), a radial intensity profile is obtained, and the half-height width value of the diffraction peak is obtained by using the integral half-height width assignment.

[0286] According to the principle that the half-height width of the diffraction peak in the radial intensity profile corresponds to the width of the diffraction ring in the selected area electron diffraction pattern (SAED), the selected area electron diffraction pattern (SAED) of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating can be converted into the corresponding radial intensity profile.

[0287] As known by those skilled in the art, the larger the width of the diffraction ring in the selected area electron diffraction pattern, the stronger the random mixing degree of atoms, and the more sufficient the atomic close packing in the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application. The half-height width of the diffraction peak in the radial intensity profile is a quantitative indicator of the width of the diffraction ring, and the larger the half-height width value, the more sufficient the atomic close packing.

[0288] In some embodiments, the selected area electron diffraction pattern (SAED) of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating is obtained using a transmission electron microscope (TEM) characterization technique with an electron acceleration voltage of 200 kV and a selected area aperture diameter of 900 nm.

[0289] In some embodiments, the radial intensity profile of the selected area electron diffraction pattern of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application has at least one diffraction peak with a half-height width ≥ in the range of .

[0290] In the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided in the present application, the half-height width of the diffraction peak in the range of has an upper limit value due to the atomic close packing limit. Non-limiting examples of the upper limit value are

[0291] In the present application, the half-height width of the "wide peak" in the radial intensity profile corresponding to the SAED pattern can be any of the following values independently, can be greater than or equal to any of the following values, can be greater than or equal to any of the following values and less than or equal to the aforementioned upper limit value (such as ), and can also be independently selected from the interval formed by any two of the following values: etc. As non-limiting examples, the half-width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any of the following ranges: etc.

[0292] In some embodiments, the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application has a half-width of the diffraction peak in the range of ≤

[0293] In some embodiments, the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application has a half-width of the diffraction peak in the range of ≤ etc. As non-limiting examples, the half-width of the "broad peak" in the radial intensity profile corresponding to the SAED pattern can be selected from any of the following ranges: etc.

[0294] In some embodiments, the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application has one broad peak in the range of ≥ , for example, the radial intensity profile corresponding to the SAED pattern has at least one diffraction peak in the range of ≥

[0295] In some embodiments, the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application has two or more broad peaks in the range of ≥

[0296] In some embodiments, the radial intensity profile of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application has all diffraction peaks are broad peaks in the range of ≥ and can also be defined in the context.

[0297] In some embodiments, the characteristic atomic spacing of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application is obtained by TEM diffraction data; wherein the TEM diffraction test is performed with an electron accelerating voltage of 200 kV and a selected area aperture diameter of 900 nm.

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

[0299] In some embodiments of the present application, the thickness (denoted as d M1 ) of the Cr-Ti-N alloy film is d min ~ 6 μm, wherein d min may be selected from the range of 10 nm ~ 3 μm; d min may also be any one of the following thicknesses, or selected from the range consisting of any two of the following thicknesses: 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 100 nm, 0.1 μm, 0.2 μm, 300 nm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 0.9 μm, etc. Without limitation, d M1 may also be any one of the following thicknesses, or selected from the range consisting of any two of the following thicknesses: 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 100 nm, 0.1 μm, 0.2 μm, 300 nm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.46 μm, 1.5 μm, 1.52 μm, 1.6 μm, 1.8 μm, 1.87 μm, 2 μm, 2.0 μm, 2.2 μm, 2.5 μm, 2.7 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, etc.; for example, the thickness d M1 may be 25 nm ~ 6 μm, 30 nm ~ 6 μm, 40 nm ~ 6 μm, 50 nm ~ 6 μm, 0.3 μm ~ 6.0 μm, 0.3 μm ~ 3.0 μm, 0.3 μm ~ 2.5 μm, 0.3 μm ~ 2.0 μm, 0.5 μm ~ 6.0 μm, 0.5 μm ~ 3.0 μm, 0.5 μm ~ 2.5 μm, 0.8 μm ~ 6.0 μm, 0.8 μm ~ 3.0 μm, 0.8 μm ~ 2.5 μm, 0.9 μm ~ 6.0 μm, 0.9 μm ~ 3.0 μm, 0.9 μm ~ 2.5 μm, 1.0 μm ~ 2.5 μm, 1.0 μm ~ 2.0 μm, etc.

[0300] In some embodiments, d min is 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 0.3 μm, 0.5 μm, 0.8 μm, or 0.9 μm.

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

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

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

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

[0305] The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application can provide excellent corrosion resistance while also having high hardness characteristics, and can better reduce the occurrence of scratches or weaken scratch damage. Further, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application can have high corrosion resistance and high hardness characteristics at a lower thickness, which can save raw materials, simplify the process, shorten the production cycle, and significantly reduce costs. Compared with traditional alloy coatings, the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application can provide a denser structure, and can achieve at least one of better corrosion resistance and better high hardness characteristics at the same thickness, thereby reducing the thickness of the alloy film or coating while maintaining good protective properties, thus saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing costs.

[0306] In some embodiments, the thickness of the Cr-Ti-N alloy film or the 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 the 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 the Cr-Ti-N alloy coating is 1 μm to 2.5 μm.

[0309] In addition, when forming the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating of the present application on a substrate with a relatively thin thickness, the alloy film product formed can exhibit a silver-white metallic color close to the color of the substrate metal, achieving an aesthetic and decorative effect without changing the color of the substrate.

[0310] In the fourth aspect of the present application, an alloy film product is provided, which includes a substrate and at least one of the Cr-Ti-N alloy film described in the second aspect of the present application and the Cr-Ti-N alloy coating described in the third aspect of the present 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 by the present application includes a film layer composed of at least one of the Cr-Ti-N alloy film and the 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 herein can be used as a surface layer of an alloy film product, and has both decorative and protective effects. The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided herein can also be located between a substrate and a surface layer, and has excellent protective effects, and can be resistant to corrosion and scratches.

[0313] The Cr-Ti-N alloy film or Cr-Ti-N alloy coating provided herein can be located on one side or both sides of a substrate.

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

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

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

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

[0318] In some embodiments, the Cr-Ti-N alloy coating is bonded on the surface of the following materials on the side close to the substrate: light alloys, stainless steel alloys, or silicon-based materials. Non-limitingly, the light alloy can include one or more of titanium alloy, aluminum alloy, and magnesium alloy. Non-limitingly, the silicon-based material can be a silicon wafer or a silicon-containing compound, and further, the silicon-containing compound can include but is not limited to one or more of silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and the like.

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

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

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

[0322] When the Cr-Ti-N alloy film or Cr-Ti-N alloy coating is bonded on the surface of a light alloy substrate (such as titanium alloy), not only can the corrosion resistance and hardness of the surface of the titanium alloy be enhanced, thereby improving the protection ability. In addition, because the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating contain a certain amount of Ti element, the coefficient of thermal expansion of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating relative to the light alloy substrate (such as titanium alloy) is close, thereby excellent bonding force can be formed between the Cr-Ti-N alloy film or Cr-Ti-N alloy coating and the light alloy substrate (such as titanium alloy). In addition, titanium exists in nature in large quantities, and the manufacturing cost is low.

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

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

[0325] The Cr-Ti-N alloy film is in direct contact with the substrate (at this time there is no transition layer) or is provided with a transition layer; further, the transition layer can be a single-layer structure or a multi-layer structure (that is, one or more structure 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 the Cr-Ti-N alloy film is further provided with a surface layer on the side away from the substrate, and the surface layer is a single-layer structure or a multi-layer structure (that is, one or more structure layers can be further formed on the Cr-Ti-N alloy film provided in the present application);

[0327] The Cr-Ti-N alloy coating layer is in direct contact with the substrate (in which case there is no transition layer) or is provided with a transition layer (i.e. one or more layers of structural layer can be formed between the Cr-Ti-N alloy coating layer and the substrate).

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

[0329] In the present application, unless otherwise specified, "transition layer" and "transition film layer" have the same meaning and can be used interchangeably, both referring to a structural layer with transition properties between the substrate and the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer in the alloy film product, which can be a single-layer structure or a multi-layer structure.

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

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

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

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

[0334] In some embodiments, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer is on the surface of the alloy film product.

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

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

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

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

[0339] When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer provided in the present application appears in the protective coating layer of the alloy film product, the position of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer can be flexibly set. The Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer can be used as a single structural layer of the protective coating layer, or as a layer in a multi-layer structure of the protective coating layer. For example, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer can be used for surface protection, in which case the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer is located on the surface of the alloy film product, and can provide a high-brightness surface for the alloy film product. For another example, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer can also be used as an intermediate protective layer, in which case other structural layers are provided on the outside of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer, i.e., the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating layer is not used as a surface layer. Different positions of the alloy film and different positions of the coating layer can achieve good corrosion resistance and good scratch resistance.

[0340] In the present application, unless otherwise specified, the "protective coating layer" refers to a coating layer on the substrate that protects the substrate. The protective effect can include at least one of, but is not limited to, corrosion resistance, hardness protection (such as resistance to scratches), and the like.

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

[0342] Non-limitingly, the 3C digital product can include, but is not limited to, mobile device parts, wearable parts, vehicle-mounted parts, and the like.

[0343] According to the difference of the main component of the substrate, the alloy film product can be any one of light alloy product, stainless steel product, single-element metal, inorganic non-metallic substrate product (such as ceramic substrate product, silicon substrate product, glass substrate product) and the like, which represents the main component of the substrate is light alloy, stainless steel, single-element metal and the like respectively. Non-limitingly, the light alloy product can include but is not limited to aluminum alloy product, titanium alloy product, magnesium alloy product and the like. Non-limitingly, the stainless steel product can include but is not limited to austenitic stainless steel, ferritic stainless steel, martensitic stainless steel. Non-limitingly, the single-element metal product can be but is not limited to any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium, further such as any one of copper, aluminum, iron, silver and chromium.

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

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

[0346] In one of the embodiments, the alloy film product is an inorganic non-metallic substrate product, which can further be a silicon substrate product, a ceramic substrate product or a glass substrate product.

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

[0348] The alloy film product can be an intermediate product or a final product. The final product can be directly used or sold. The intermediate product can be further processed or assembled with other elements into a new product.

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

[0350] The Cr-Ti-N alloy film or the Cr-Ti-N alloy coating can be used as a surface layer or located between the substrate and the surface layer.

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

[0352] When the corrosion-resistant protective coating is combined with the aluminum alloy substrate, the corrosion-resistant protective coating can pass the corrosion test with a test period of T m1 (such as T m1 48 hours);

[0353] When the corrosion protection coating is combined on a stainless steel substrate, the corrosion protection coating can pass the corrosion test with a test period of T m2 (As T m2 is 72 hours).

[0354] In the present application, unless otherwise specified, "the coating is combined on X substrate" means that the forming substrate of the coating is X, that is, the coating is formed on the surface of the substrate X. For example, "the corrosion protection coating is combined on the aluminum alloy substrate" means that the corrosion protection coating is formed on the surface of the aluminum alloy substrate.

[0355] Non-limitingly, T m1 may be 48 hours, 60 hours, 72 hours, 84 hours, 96 hours, 120 hours, or longer.

[0356] Non-limitingly, T m2 may be 72 hours, 84 hours, 96 hours, 120 hours, 144 hours, or longer.

[0357] In some embodiments, taking the aluminum alloy substrate as an example, the corrosion protection coating including the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided by the present application is formed on the surface of the aluminum alloy substrate, and the corrosion protection coating can pass the salt spray corrosion test for ≥48 hours, that is, it can pass the 48-hour test, and most embodiments can also pass the 72-hour test, using the ASTM B117 salt spray test method; further, the more detailed test method described above or below can be used. Taking the aluminum alloy substrate as an example, the protection time of the conventional alloy coating in the salt spray corrosion test under the same test conditions is generally difficult to reach 8 hours.

[0358] The Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application can have excellent corrosion resistance and high hardness characteristics at a lower thickness, thereby saving raw materials, simplifying the process, shortening the production cycle, and significantly reducing the cost. In the case of a thin alloy coating, the alloy film product formed can present a silver-white metal color close to the color of the substrate metal, which is more conducive to achieving an aesthetic, non-changing substrate color decorative effect.

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

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

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

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

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

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

[0365] In the present application, unless otherwise specified, the "surface coating" refers to the coating on the surface of an article, which can be the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application, or can be an additional surface layer provided on the basis of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application.

[0366] When the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application is located on the surface of an article, it not only imparts the article with a high-brightness surface, but also provides excellent corrosion resistance.

[0367] The L value of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating provided in the present application can be ≥75, some can be ≥80, some can be as high as ≥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 embodiments, the brightness value L is ≥75, further can be L≥80, and more further can be ≥81, and more further can be ≥82, as tested by Lab method.

[0369] In some embodiments, x, y and z satisfy the following first group or second group characteristics:

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

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

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

[0373] In the sixth aspect of the present application, a method for preparing the Cr-Ti-N alloy film is provided, which comprises the following steps: depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of the substrate according to a preset atomic ratio by using a vapor deposition technique to form the Cr-Ti-N alloy film described in the second aspect of the present application. It can be understood that the constituent elements of the Cr-Ti-N alloy film at least include Cr element, Ti element and N element.

[0374] In the sixth aspect of the present application, a method for preparing the Cr-Ti-N alloy film is provided, which comprises the following steps: depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of the substrate according to a preset atomic ratio by using a vapor deposition technique to form the Cr-Ti-N alloy film described in the second aspect of the present application. It can be understood that the constituent elements of the Cr-Ti-N alloy film at least include Cr element, Ti element and N element.

[0375] In the present application, the "surface" in "depositing the component X on at least a part of the surface of the substrate" can directly deposit the component X on at least a part of the surface of the substrate, or form a transition layer on at least a part of the surface of the substrate before depositing the component X.

[0376] The method for preparing the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application is simple, easy to operate, green and environmentally friendly, and has the advantages of quantification, high efficiency and good repeatability, and is suitable for industrial application.

[0377] The definition of the substrate can be involved in the context of the present application, including but not limited to the second aspect and the third aspect of the present application.

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

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

[0380] In some embodiments, the constituent elements of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating are deposited on at least a part of the surface of the substrate according to a preset atomic ratio by using a sputtering technique (such as magnetron sputtering).

[0381] In some embodiments, the device shown in FIG. 3 can be referred to. The device shown in FIG. 3 includes a vacuum chamber 1, a sample stage 2, a direct current anode 3, a chromium target 4, and a titanium target 5. The chromium target 4 is a chromium target for radio frequency assisted direct current cathode electric conduction, and the titanium target 5 is a titanium target for radio frequency assisted direct current cathode electric conduction. The drawing is not drawn in a 1:1 ratio, and the relative sizes of the elements are only drawn in the drawing by way of example to facilitate understanding of the present application, but are not necessarily drawn in true scale, and the scale in the drawing does not constitute a limitation on the present application. The Cr-Ti-N alloy film or the Cr-Ti-N alloy coating described in the present application can be formed by forming reactive sputtering with N2-containing gas (such as Ar / N2 mixed gas) in the vacuum chamber 1.

[0382] 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-containing gas, using one or more targets including chromium and titanium elements, sputtering and depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of the substrate to form the Cr-Ti-N alloy film.

[0383] 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-containing gas, using one or more targets including chromium and titanium elements, sputtering and depositing the constituent elements of the Cr-Ti-N alloy film on at least a part of the surface of the substrate to form the Cr-Ti-N alloy film.

[0384] The nitrogen-containing gas can be, but is not limited to, nitrogen. In this case, the gas volume ratio of argon to nitrogen in the mixed gas can be (0.5-6):1, optionally (1-6):1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, etc., and can also be an interval formed by any two of the aforementioned ratios. When nitrogen is selected as the nitrogen-containing gas and the content of nitrogen is controlled, the performance of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating can be further adjusted.

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

[0386] In this application, unless otherwise specified, the "chromium-titanium-based alloy target" includes at least chromium and titanium, and can or can not include other elements. When including other elements, it is understood that the chemical composition in the target material should generally be within the preset chemical formula Cr x Ti y N z M a For example, the chromium-titanium-based alloy target can be a chromium-titanium-nitrogen alloy target (i.e., a CrTiN alloy target) including chromium, titanium, and nitrogen.

[0387] In some embodiments, the chromium-titanium alloy target can replace the chromium target 4 in FIG. 3 and be installed at the position of the original chromium target 4 in FIG. 3.

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

[0389] In some embodiments, the method for preparing the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating further includes the following step before the step of "sputtering and depositing the constituent elements of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating on at least a part of the surface of a substrate": cleaning the substrate. The method for cleaning the substrate can use a conventional cleaning method in the 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 bias voltage of the substrate is -150V to -20V;

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

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

[0402] The nitrogen-containing gas is nitrogen, and the gas flow 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℃ to 330℃, such as 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 150℃, 200℃, 250℃, 300℃, 330℃, etc., and can also be an interval formed by any two of the foregoing temperatures.

[0404] In some embodiments, the total gas pressure of the mixed gas containing argon and the nitrogen-containing gas is 0.4Pa to 1.8Pa, which can be 0.4Pa to 1.0Pa; for example, 0.4Pa, 0.5Pa, 0.8Pa, 1Pa, 1.2Pa, 1.4Pa, 1.6Pa, 1.8Pa, etc., and can also be an interval formed by any two of the foregoing pressures.

[0405] In some embodiments, the sputtering is performed by a radio frequency assisted direct current sputtering method. Compared with other preparation methods, the performance of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating formed by sputtering deposition can be further improved.

[0406] In some embodiments, the target material includes a chromium target, and the power density of the chromium target can be 0.5W / cm 2 to 9.1W / cm 2 , and can also be any of the following values or an interval formed by 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 8 W / cm 2 9 W / cm 2 9.1 W / cm 2 , etc.

[0407] In some embodiments, the target material includes a titanium target, and the power density of the titanium target can be 0.5 W / cm 2 8.1 W / cm 2 , optionally 0.5 W / cm 2 8.0 W / cm 2 , or any of the following values or a range selected from any two of the following values: 0.5 W / cm 2 1 W / cm 2 1.5 W / cm 2 1.8 W / cm 2 2.0 W / cm 2 2.5 W / cm 2 2.8 W / cm 2 3 W / cm 2 3.5 W / cm 2 3.8 W / cm 2 4 W / cm 2 4.5 W / cm 2 5 W / cm 2 6 W / cm 2 7 W / cm 2 8 W / cm 2 8.0 W / cm 2 , etc.

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

[0409] In some embodiments, the target material includes an alloy target, the alloy target includes at least two metal 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, and the power density of the chromium-titanium-based alloy target can be 4 W / cm 2 6 W / 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 / cm 2 .

[0411] In some embodiments, the target material uses a Cr-Ti alloy target, and the power density can be 4 W / cm 2 ~ 6 W / cm 2 , and optionally 6 W / cm 2 .

[0412] In some embodiments, the bias voltage of the substrate can be -150 V to -20 V; for example, -150 V, -120 V, -100 V, -90 V, -80 V, -60 V, -50 V, -40 V, -30 V, -20 V, and the like, and can also be an interval formed by any two of the foregoing bias voltages.

[0413] In some embodiments, the gas 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, and the like, and can also be an interval formed by any two of the foregoing gas flow rates. Further, the nitrogen-containing gas can be nitrogen.

[0414] In some embodiments, the sputter deposition time can be 10 min to 150 min, for example, 10 min, 15 min, 30 min, 45 min, 60 min, 90 min, 100 min, 120 min, and the like, and can also be an interval formed by any two of the foregoing time lengths. 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, and the corresponding thickness of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating increases as the deposition time increases.

[0415] In some embodiments, the base vacuum degree of the vacuum chamber used is ≤ 5.0 x 10 -4 Pa. This pressure setting can ensure the collision of sputtering particles and gas molecules, while also reducing the entry of impurities in the gas molecules during deposition, to improve the corrosion resistance, purity, and bonding force of the Cr-Ti-N alloy film and the Cr-Ti-N alloy coating provided by the present application.

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

[0417] In some embodiments, "depositing the constituent elements of the Cr-Ti-N alloy film or Cr-Ti-N alloy coating on at least a portion of the surface of the substrate in a preset atomic ratio by sputtering deposition (e.g., magnetron sputtering deposition)" comprises the following steps: introducing a mixed gas comprising argon and a nitrogen-containing gas into the vacuum chamber 1, maintaining the pressure in the vacuum chamber 1 at 0.3 Pa to 0.9 Pa, turning on the bias voltage, setting the bias voltage to -150 V to -20 V, setting the power density of the chromium target 4 to 0.5 W / cm 2 ~ 9.1 W / cm 2 , and setting the power density of the titanium target 5 to 0.5 W / cm 2 ~ 8.1 W / cm 2 , and setting the power density of the titanium target 5 to 0.5 W / cm

[0418] Some embodiments are provided below.

[0419] The embodiments of the present application will be described in detail below with some embodiments. It should be understood that these embodiments are only used to illustrate the present application and are not used to limit the scope of the present application. The experimental methods not specified in the following examples are preferably referred to the guidance given in the present application, and can also be carried out according to the experimental manual or conventional conditions in the art, or according to the conditions suggested by the manufacturer, or according to the experimental methods known in the art.

[0420] In the following examples, the measurement parameters of the raw material components may, without specific instructions, have slight deviations within the weighing accuracy range. The temperature and time parameters allow for acceptable deviations caused by instrument testing accuracy or operation accuracy.

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

[0422] Test methods:

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

[0424] When testing the colorimetric value of the alloy film or alloy coating, the sample to be tested uses a substrate suitable for practical application to detect the improvement degree of the compactness and other properties of the alloy film or alloy coating on the substrate. The surface material of the "substrate suitable for practical application" can include but is not limited to aluminum alloy, stainless steel.

[0425] The L value, a value and b value of the sample are tested by a CM-3700A-U benchtop spectrophotometer produced by Konica, Japan, the light receiving system selects F2 light source, and the average value is taken after testing 6 matrix points of each sample.

[0426] Wherein, L value represents the brightness value, a value represents the red or green chroma value, b value represents the yellow or blue chroma value. The a value represents the red-green color of the object, the positive value represents the red chroma value, and the negative value represents the green chroma value. The b value represents the yellow-blue color of the object, the positive value represents the yellow chroma value, and the negative value represents the blue chroma value.

[0427] The larger the L value, the higher the brightness, indicating that the coating surface is more dense. The mechanism is as follows: the spectrophotometer is incident light on the surface of the measured sample, forming a reflectivity curve, and the amplitude of the curve can reflect the density of the material, which can be characterized by the L value. The higher the density of the same material, the larger the L value displayed.

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

[0429] The sample to be measured is a silicon wafer as a substrate.

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

[0431] Morphology analysis: scanning electron microscope model Regulus 8230 produced by Hitachi Company.

[0432] Composition analysis: X-ray energy dispersive spectrometer (EDX) attached to scanning electron microscope model Regulus 8230 produced by Hitachi Company. The relative intensity of all elements is corrected by ZAF method.

[0433] Test parameters: acceleration voltage of electron is 15 kilovolts (kV), beam current is 10 microamperes (μA), magnification of sample is 200 times, and 10 points of each sample are tested to obtain average value.

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

[0435] When performing XRD test of alloy film or alloy coating, silicon wafer is used as substrate.

[0436] 3.1. Calculate the half-height width value of diffraction peak in XRD spectrum

[0437] German Bruker D8 Advance XRD diffractometer is used in θ-2θ mode, Cu target Kα ray is used, wavelength λ is 0.15406 nm, X-ray tube is controlled at 40 kV and 40 mA, scanning range is 20°-80°, and precise scanning measurement is performed with step 0.01°.

[0438] The step of obtaining the half-height width value is: first, the diffraction peak is corrected, including: smoothing, removing background, removing Kα2 line, removing instrument broadening, etc. After fitting the diffraction peak with a Pseudo-Voigt function, the half-height width value of the diffraction peak is obtained.

[0439] The EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) is used to process the spectrum data: first, the ruler is corrected, then the center of the diffraction ring transmission spot is determined, and then it is converted into an XRD spectrum (where the electron wavelength is 0.00251 nanometers, and the X-ray wavelength is 0.154 nanometers; after removing the straight background of the diffraction peak and fitting it with a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0440] 3.2. Determine whether the XRD pattern of the alloy film or alloy coating forms a broad peak

[0441] The method for determining whether there is a broad peak in the XRD diffraction pattern in the range of diffraction angle 2θ(°) of 34°-50° is: in the XRD spectrum, if the half-height width value of the 2θ(°) diffraction peak is ≥1.6°, it is determined to be a broad peak; if the half-height width value of the 2θ(°) diffraction peak is <1.6°, it is determined to be a sharp peak.

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

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

[0444] When performing the TEM test of the alloy film or alloy coating, a silicon wafer is used as the substrate.

[0445] 4.1. The half-height width data of the diffraction ring of the TEM diffraction pattern are obtained by the following method:

[0446] TEM test sample preparation: a Helios 5CX model focused ion beam (FIB) of Thermo Fisher Limited is used to thin the sample to obtain an electron-transparent, TEM-observable planar sample.

[0447] SAED image acquisition: Talos F200x transmission electron microscope (TEM) from Thermo Fisher Scientific was used to acquire the selected area electron diffraction (SAED) pattern of the sample, with an electron accelerating voltage of 200 kV and a selected area aperture of 900 nm in diameter.

[0448] Radial intensity profile acquisition: The SAED pattern data obtained above was processed using EDP2XRD software (Version 1.0.0, Copyright by Hongwei Liu, The Australian Center for Microscopy and Microanalysis, The University of Sydney) by first performing a scale correction, then determining the center of the diffraction ring transmission spot, and finally converting to a radial intensity profile (with an electron wavelength of 0.00251 nm and an X-ray wavelength of 0.154 nm), with the characteristic atomic spacing as the horizontal coordinate and the diffraction intensity as the vertical coordinate.

[0449] The step of obtaining the half-height width value is as follows: after subtracting the linear background from the diffraction peak and fitting with a Voigt function, the half-height width value of the corresponding diffraction peak is obtained.

[0450] 4.2. Method for determining whether the radial intensity profile of the TEM selected area electron diffraction pattern is a broad peak within the range of If the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is ≥ , it is determined to be a broad peak; if the half-height width value of the diffraction peak corresponding to the characteristic atomic spacing is < , it is determined to be a sharp peak. For a specific characteristic atomic spacing, it can be any one of the three states of no peak, sharp peak or broad peak.

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

[0452] When performing the salt spray corrosion resistance test of the alloy film or alloy coating, the sample to be tested uses a substrate suitable for actual application, and the improvement degree of the corrosion resistance of the alloy film or alloy coating to the substrate is detected. The surface material of the "substrate suitable for actual application" can include but is not limited to: aluminum alloy, titanium alloy, stainless steel.

[0453] ASTM B117 salt spray test standard is used, with a solution pH value of 6.5-7.2, and a solution chemical composition of sodium chloride (NaCl), deionized water and sodium hydroxide (NaOH).

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

[0455] The test period of the alloy coating prepared on different substrates can be different, for example:

[0456] The test period of the sample of the aluminum alloy substrate is 48h or 24h;

[0457] The test period of the sample of the stainless steel substrate is 144h or 96h;

[0458] The test period of the sample of the copper sheet substrate is 8h.

[0459] The standard for passing (OK) the salt spray corrosion resistance test is that after the sample is tested, there is no corrosion, no color difference, and no rust on the appearance. For example, “pass 48H” means that the test period is 48h of salt spray corrosion resistance test. “Pass 72H” means that the test period is 72h of salt spray corrosion resistance test. “Pass 144H” means that the test period is 144h of salt spray corrosion resistance test. “Pass 8H” means that the test period is 8h of salt spray corrosion resistance test.

[0460] The standard for failing (NG) the salt spray corrosion resistance test is that after the sample is tested, there is corrosion, color difference, or rust on the appearance. For example, “fail 8H” means that the test period is 8h of salt spray corrosion resistance test. “Fail 2H” means that the test period is 12h of salt spray corrosion resistance test. “Fail 24H” means that the test period is 24h of salt spray corrosion resistance test. “Protection time <8h” means that corrosion occurs when the test time is less than 8h. “Protection time <12h” means that corrosion occurs when the test time is less than 12h.

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

[0462] When testing the hardness of the alloy film or alloy coating, the sample to be tested uses a substrate that can be suitable for actual application,

[0463] The surface material of the “substrate that can be suitable for actual application” can include but is not limited to: aluminum alloy, titanium alloy, stainless steel, copper sheet.

[0464] In the following examples, unless otherwise specified, when testing the hardness of the alloy film or alloy coating, an aluminum alloy or stainless steel is used as the substrate, and an alloy film or alloy coating is deposited on the aluminum alloy or stainless steel using predetermined preparation parameters to obtain a sample to be tested for testing the hardness of the alloy film or alloy coating. This is mainly because during the nanoindentation test, the probe pierces the sample to be tested, forming a strong pressure. At this time, the substrate is required to have a certain toughness. If a silicon wafer with high brittleness is used, cracking may occur during the test, resulting in inaccurate test results. Alloy materials have excellent toughness and are more suitable as the measured substrate for nanoindentation tests. At the same time, using alloy materials as the substrate for measuring nano-hardness is more universal in the field of coating and nano-hardness parameter characterization.

[0465] The hardness of each film or each coating was tested by using a nanoindenter NHT3 produced by Anton-Paar, Austria, which was configured with a tetrahedral Berkvich indenter, and the indentation depth was set to 100 nm, and the load changed with the indentation depth. The average value of 5 matrix points of each sample was taken after testing.

[0466] 7. Bonding force test method

[0467] The bonding force was characterized by cross-hatch test, which can be performed according to or with reference to the provisions in GB / T 9286-2021 standard. The detailed steps are as follows: 10x10 1mmx1mm small squares were drawn on the plating film area of the sample surface with a manual single-edge cutting knife, and 3M610 adhesive tape was pasted on the drawn square area. Within 5 minutes after pasting the adhesive tape, the free end of the adhesive tape was held and torn off at an angle of about 60° within 0.5s to 1.0s, and the grade was determined according to the provisions in GB / T 9286-2021 standard, wherein 0 grade (marked as "OK") is passed, indicating that the alloy film or alloy coating has excellent bonding force, and 1-5 grades (marked as "NG") are failed.

[0468] The above test results can be referred to in the following description and Table 2.

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

[0470] The stainless steel sheet, titanium alloy sheet, aluminum alloy sheet and silicon sheet in each of the following examples and comparative examples have the same material, respectively.

[0471] In the following examples, the target material is sputtered by radio frequency assisted direct current sputtering.

[0472] In the XRD pattern and SAED-radial intensity profile in the following examples, "only one wide peak" refers to "only one characteristic peak, and the peak is a wide peak" unless otherwise specified.

[0473] The preparation parameters and part of the structure characterization parameters of each of the following examples and comparative examples can be referred to in Table 1.

[0474] In the following examples, Cr-Ti-N alloy coating is taken as an example, which is 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 time, the Cr-Ti-N alloy coating is a Cr-Ti-N alloy film.

[0477] Substrate pretreatment: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length to width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0478] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0479] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gas was introduced, the N2 gas flow was set to 22 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 0.5 W / cm 2 , the power density of the Ti target was set to 8.0 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 2200 nm.

[0480] Silicon wafers were used as the substrate samples for SEM and composition analysis, XRD analysis and TEM testing;

[0481] Stainless steel sheets and aluminum alloy sheets were used for hardness testing and colorimetric value testing;

[0482] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance testing;

[0483] Titanium alloy sheets were used for adhesion testing.

[0484] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 5.0 Ti 79.0 N 16.0 ;

[0485] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 4, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 5. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 5.05° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0486] Chromatic value test results: the test chromatic value of the aluminum alloy substrate sample is L: 76.44, a: 0.58, b: 5.51, and the test chromatic value of the stainless steel substrate sample is L: 77.51, a: 0.55, b: 4.45

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

[0488] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection properties.

[0489] Adhesion test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching 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 9.4 .

[0492] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with an aspect ratio of 50mmx50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a plating machine vacuum chamber, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0493] ​Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0494] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 15 sccm, the gas flow ratio of Ar:N2 was kept at 3:1, the pressure in the furnace was kept at 0.4 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 1.3 W / cm 2 , the power density of the Ti target was set at 7.8 W / cm 2 , and a Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 2200 nm.

[0495] Silicon wafers were used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM testing were performed;

[0496] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and colorimetric value testing;

[0497] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as the substrate of the sample, and salt spray corrosion resistance testing was performed;

[0498] Titanium alloy sheets were used for adhesion testing.

[0499] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 12.7 Ti 77.9 N 9.4 ;

[0500] The test sample was subjected to SEM cross-section characterization, the cross-section morphology can be seen from FIG. 6, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 7. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 4.87° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0503] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protective properties.

[0504] The bonding force test results: the film layer on the titanium alloy substrate is tested by the grid test, and the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, which reaches the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

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

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

[0509] Deposition of alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Ti target are powered by radio frequency assisted direct current power supply, Ar and N2 gas are introduced, the N2 gas flow is set to 32 sccm, the gas flow ratio of Ar:N2 is kept at 1:1, the furnace pressure is kept at 0.8 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 0.6 W / cm 2 , the power density of the Ti target is set to 7.0 W / cm 2 , and the Cr-Ti-N alloy coating is deposited. The film thickness is controlled to be 1800 nm by controlling the film forming time.

[0510] The sample with a silicon wafer as the substrate was subjected to SEM and composition analysis and XRD analysis;

[0511] The stainless steel sheet and the aluminum alloy sheet were used to test the hardness value and the color value;

[0512] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate of the sample to perform the salt spray corrosion resistance test;

[0513] The titanium alloy sheet was used to perform the adhesion test.

[0514] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 5.0 Ti 68.6 N 26.4 ;

[0515] The SEM cross-section characterization of the test sample was performed, the cross-section morphology can be seen in FIG. 8, and the XRD diffraction pattern can be seen in FIG. 9. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 3.32° in the range of 34°-50°;

[0516] The color value test results: the color value of the aluminum alloy substrate sample tested was L: 77.21, a: 0.57, b: 3.37, and the color value of the stainless steel substrate sample tested was L: 77.92, a: 0.54, b: 3.22;

[0517] The hardness value 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] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection properties;

[0519] The adhesion test results: the film layer on the titanium alloy substrate was tested by the grid test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent adhesion.

[0520] Example 4.

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

[0522] Pre-treatment of the substrate: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at 150°C for 15 minutes.

[0523] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0524] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 21 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 1.5 W / cm 2 , the power density of the Ti target was set to 7.1 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1460 nm.

[0525] Silicon wafers were used as the substrate samples for SEM and composition analysis, and XRD analysis.

[0526] Stainless steel sheets and aluminum alloy sheets were used for hardness and colorimetric value tests.

[0527] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance tests.

[0528] Titanium alloy sheets were used for adhesion tests.

[0529] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 14.8 Ti 70.0 N 15.2 .

[0530] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 10, and the XRD diffraction pattern can be seen in Figure 11. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through-column joint is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 2.03° in the range of 34°-50°.

[0531] Chromaticity value test results: the chromaticity value of the aluminum alloy substrate sample is L: 77.21, a: 0.45, b: 4.55, and the chromaticity value of the stainless steel substrate sample is L: 78.25, a: 0.43, b: 4.04.

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

[0533] Salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, with excellent protection properties;

[0534] Bonding force test results: the film layer on the titanium alloy substrate was tested by cross-hatch, and the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

[0535] Example 5. Preparation using 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, the target material is selected as a chromium-titanium alloy target, and the original Cr target at the position of the chromium target 4 in Figure 3 is replaced with a CrTi alloy target with an atomic percentage of Cr and Ti of 25%:75%.

[0538] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with an aspect ratio of 50mmx50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0539] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0540] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set at 22 sccm, the gas flow was set to keep the Ar:N2 gas flow ratio at 2:1, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set at -100 V, and the power density of the CrTi target was set at 6 W / cm 2 , a Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 1100 nm.

[0541] Silicon wafers were used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM testing were performed;

[0542] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and color value testing;

[0543] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as the substrate of the sample, and salt spray corrosion resistance testing was performed;

[0544] Titanium alloy sheets were used for adhesion testing.

[0545] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 18.0 Ti 66.0 N 16.0 .

[0546] The test sample was subjected to SEM cross-section characterization, the cross-section morphology can be seen from FIG. 12, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 13. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating columnar joint is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 3.00° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0549] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protective properties.

[0550] The adhesion test results: the film layer on the titanium alloy substrate is tested by the grid test, and the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, which reaches the 0 level 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 pieces, stainless steel pieces, aluminum alloy pieces and silicon piece samples with a length-width ratio of 50 mm x 50 mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5 x 10 -4 Pa, and heated to 150°C 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 remove small impurities on the surface of the sample by plasma etching.

[0555] Deposition of alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Ti target are powered by radio frequency assisted direct current power supply, Ar and N2 gas are introduced, the N2 gas flow is set to 25 sccm, the gas flow ratio of Ar:N2 is maintained at 2:1, the furnace pressure is maintained at 0.7 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 2.1 W / cm 2 , the power density of the Ti target is set to 6.1 W / cm 2 , and the Cr-Ti-N alloy coating is deposited. The film thickness is controlled to be 1600 nm.

[0556] The sample with a silicon wafer as the substrate was subjected to SEM and composition analysis, XRD analysis and TEM testing;

[0557] The stainless steel sheet and the aluminum alloy sheet were used for hardness value testing and color value testing;

[0558] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample for salt spray corrosion resistance testing;

[0559] The titanium alloy sheet was used for adhesion testing.

[0560] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 21.0 Ti 60.0 N 19.0 .

[0561] The SEM cross-section characterization of the test sample was performed, the cross-section morphology can be seen from FIG. 14, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 15. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 2.68° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0562] The color value test results: the color value of the aluminum alloy substrate sample is L: 79.63, a: 0.42, b: 2.47, and the color value of the stainless steel substrate sample is L: 79.37, a: 0.44, b: 2.54.

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

[0564] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass 48h testing, and the stainless steel substrate sample can pass 144h testing, which has excellent protection properties.

[0565] The adhesion test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had 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] Pre-treatment of the substrate: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0569] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0570] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 7 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 2.7 W / cm 2 , the power density of the Ti target was set to 6.6 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled by the deposition time to be 1300 nm.

[0571] Silicon sheets were used as the substrate samples for SEM and composition analysis, XRD analysis and TEM testing;

[0572] Stainless steel sheets and aluminum alloy sheets were used for hardness testing and colorimetric value testing;

[0573] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance testing;

[0574] Titanium alloy sheets were used for adhesion testing.

[0575] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 27.0 Ti 68.0 N 5.0 .

[0576] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 16, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 17. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 4.94° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0577] Chroma value test results: the test chroma value of the aluminum alloy substrate sample is L: 79.01, a: 0.54, b: 2.75, and the test chroma value of the stainless steel substrate sample is L: 79.29, a: 0.54, b: 2.68.

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

[0579] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0580] Adhesion test results: the film layer on the titanium alloy substrate was tested by cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment grade 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 pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with an aspect ratio of 50mmx50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0584] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min, so as to remove small impurities on the surface of the sample by plasma etching.

[0585] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 20 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.5 Pa, the bias voltage was turned on and set at -100 V, and the power density of the Cr target was set at 3.7 W / cm 2 , the power density of the Ti target was set at 4.8 W / cm 2 , and the Cr-Ti-N alloy coating was deposited by controlling the film forming time to make the thickness of the obtained film 1870 nm.

[0586] The silicon wafer was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed;

[0587] The stainless steel sheet and the aluminum alloy sheet were used for hardness value test and colorimetric value test;

[0588] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance test was performed;

[0589] The titanium alloy sheet was used for adhesion test.

[0590] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 36.6 Ti 49.2 N 14.2 .

[0591] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen from FIG. 18, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 19. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 5.09° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0594] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protective properties.

[0595] The adhesion test results: the film layer on the titanium alloy substrate is tested by the grid test, and the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, which reaches the 0 level 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 pieces, stainless steel pieces, aluminum alloy pieces, and silicon piece samples with a length-width ratio of 50 mm x 50 mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5 x 10 -4 Pa, and heated to 150°C 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 remove small impurities on the surface of the sample by plasma etching.

[0600] Deposition of alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Ti target are powered by radio frequency assisted direct current power supply, Ar and N2 gas are introduced, the N2 gas flow is set to 3 sccm, the gas flow ratio of Ar:N2 is maintained at 6:1, the furnace pressure is maintained at 0.4 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 3.8 W / cm 2 , and the power density of the Ti target is set to 6.1 W / cm 2 , and the Cr-Ti-N alloy coating is deposited. The film thickness is controlled to be 1400 nm.

[0601] The sample with a silicon wafer as the substrate was subjected to SEM and composition analysis and XRD analysis.

[0602] The stainless steel sheet and the aluminum alloy sheet were used to test the hardness value and the color value.

[0603] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample to perform the salt spray corrosion resistance test.

[0604] The titanium alloy sheet was used to perform the adhesion test.

[0605] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 37.6 Ti 60.0 N 2.4 .

[0606] The SEM cross-section characterization of the test sample was performed, the cross-section morphology can be seen in FIG. 20, and the XRD diffraction pattern can be seen in FIG. 21. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) of 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 5.40° in the range of 34°-50°.

[0607] The color value test results: the color value of the aluminum alloy substrate sample tested was L: 79.64, a: 0.53, b: 2.68, and the color value of the stainless steel substrate sample tested was L: 79.68, a: 0.52, b: 2.62.

[0608] The hardness value 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] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection properties.

[0610] The adhesion test results: the film layer on the titanium alloy substrate was tested by the cross-hatch method, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent adhesion.

[0611] Example 10.

[0612] In this example, the chemical composition of the Cr-Ti-N alloy coating was 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] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 22, and the XRD diffraction pattern, TEM- SAED pattern and radial intensity profile can be seen in Figure 23. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 2.91° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of 34°-50°, and the half-height width value is .

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

[0623] Hardness value test results: the hardness value of the aluminum alloy substrate sample is 20.8 GPa, and the hardness value of the stainless steel substrate sample is 22.4 GPa.

[0624] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0625] Adhesion test results: the film layer on the titanium alloy substrate was tested by cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment grade 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 pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0629] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min, so as to remove small impurities on the surface of the sample by plasma etching.

[0630] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 26 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.6 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 4.4 W / cm 2 , the power density of the Ti target was set at 3.8 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 2700 nm.

[0631] The silicon wafer was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed.

[0632] The stainless steel sheet and the aluminum alloy sheet were used to test the hardness value and the color value.

[0633] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and the salt spray corrosion resistance test was performed.

[0634] The titanium alloy sheet was used to test the adhesion.

[0635] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 43.0 Ti 37.0 N 20.0 .

[0636] The cross-sectional SEM characterization of the test sample was performed, the cross-sectional morphology can be seen from FIG. 24, and the XRD diffraction pattern, the TEM-SAED pattern and the radial intensity profile can be seen from FIG. 25. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of the diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 2.48° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0639] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protective properties.

[0640] The bonding force test results: the film layer on the titanium alloy substrate is tested by the grid test, and the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, which reaches the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

[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 pieces, stainless steel pieces, aluminum alloy pieces, and silicon piece samples with a length-width ratio of 50 mm x 50 mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber is vacuumed to 5 x 10 -4 Pa, and heated to 150°C 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 small impurities on the surface of the sample.

[0645] Deposition of alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Ti target are powered by radio frequency assisted direct current power supply, Ar and N2 gas are introduced, the N2 gas flow is set to 25 sccm, the gas flow ratio of Ar:N2 is maintained at 2:1, the furnace pressure is maintained at 0.7 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 4.5 W / cm 2 , the power density of the Ti target is set to 3.8 W / cm 2 , and the Cr-Ti-N alloy coating is deposited. The film thickness is controlled to be 1400 nm by controlling the film forming time.

[0646] The sample with a silicon wafer as the substrate was subjected to SEM and composition analysis and XRD analysis.

[0647] The stainless steel sheet and the aluminum alloy sheet were used to test the hardness value and the color value.

[0648] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate of the sample to perform the salt spray corrosion resistance test.

[0649] The titanium alloy sheet was used to perform the adhesion test.

[0650] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 44.0 Ti 37.0 N 19.0 .

[0651] The SEM cross-section characterization of the test sample was performed, the cross-section morphology can be seen in FIG. 26, and the XRD diffraction pattern can be seen in FIG. 27. The SEM test results showed that the Cr-Ti-N alloy coating structure was dense, and no penetrating column seam was observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern was all ≥1.6°, and there was only one wide peak with a half-height width of 2.63° in the range of 34°-50°.

[0652] The color value test results: the color value of the aluminum alloy substrate sample was L: 81.50, a: 0.24, b: 2.52, and the color value of the stainless steel substrate sample was L: 81.23, a: 0.23, b: 2.65.

[0653] The hardness value 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] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample could pass the 48h test, and the stainless steel substrate sample could pass the 144h test, which had excellent protection properties.

[0655] The adhesion test results: the film layer on the titanium alloy substrate was subjected to the cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent adhesion.

[0656] Example 13.

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

[0658] Pre-treatment of the substrate: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in the vacuum chamber of a plating machine. The vacuum chamber was evacuated to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0659] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0660] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 20 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 5.0 W / cm 2 , the power density of the Ti target was set to 3.8 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1800 nm by controlling the film deposition time.

[0661] Silicon wafers were used as the substrate samples for SEM and composition analysis, and XRD analysis.

[0662] Stainless steel sheets and aluminum alloy sheets were used for hardness and colorimetric value tests.

[0663] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance tests.

[0664] Titanium alloy sheets were used for adhesion tests.

[0665] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 49.2 Ti 37.0 N 13.8 .

[0666] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 28, and the XRD diffraction pattern can be seen in Figure 29. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 2.29° in the range of 34°-50°.

[0667] Chromatic value test results: the chromatic value of the aluminum alloy substrate sample tested was L: 81.94, a: 0.21, b: 2.02, and the chromatic value of the stainless steel substrate sample tested was L: 81.94, a: 0.23, b: 2.37.

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

[0669] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0670] Bonding force test results: the film layer on the titanium alloy substrate was tested by cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

[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 sheet samples with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0674] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0Pa, the bias voltage was turned on and set to-800V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0675] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the sample stage to the target surface distance to 8 cm, use radio frequency assisted direct current power supply to introduce electricity for the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 23 sccm, set the gas flow ratio to keep Ar:N2 at 2:1, keep the pressure in the furnace body at 0.6 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 5.4 W / cm 2 , set the power density of the Ti target to 3.1 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 1300 nm.

[0676] Use silicon wafers as the substrate of the sample to perform SEM and composition analysis, XRD analysis and TEM testing;

[0677] Use stainless steel sheets and aluminum alloy sheets to perform hardness value testing and colorimetric value testing;

[0678] Use titanium alloy sheets, stainless steel sheets and aluminum alloy sheets as the substrate of the sample to perform salt spray corrosion resistance testing;

[0679] Use titanium alloy sheets to perform adhesion testing.

[0680] According to the composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 53.0 Ti 30.0 N 17.0 .

[0681] SEM cross-section characterization of the test sample shows that the cross-sectional morphology can be seen in FIG. 30, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in FIG. 31. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 2.68° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

[0683] Hardness value 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: the titanium alloy substrate, aluminum alloy sample can pass 48h test, stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0685] Bonding force test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment grade in GB / T 9286-2021, which showed that the Cr-Ti-N alloy coating had excellent bonding force.

[0686] Example 15.

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

[0688] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with a length-width ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0689] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0690] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 26sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the furnace pressure was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 5.5 W / cm 2 , the power density of the Ti target was set to 2.6 W / cm 2 , and the Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1200 nm by controlling the film forming time.

[0691] Silicon wafers were used as substrate samples for SEM and composition analysis, XRD analysis and TEM testing;

[0692] Stainless steel sheets and aluminum alloy sheets were used for hardness value test and color value test;

[0693] The salt spray corrosion resistance test was performed on samples with titanium alloy sheet, stainless steel sheet, and aluminum alloy sheet as the substrate.

[0694] The binding force test was performed on the titanium alloy sheet.

[0695] According to the component analysis, the component of the alloy coating on the surface of the substrate was Cr 54.4 Ti 25.6 N 20.0 .

[0696] The SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen from FIG. 32, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 33. The SEM test result shows that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test result shows that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 4.21° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0697] The colorimetric value test result: the colorimetric value of the aluminum alloy substrate sample is L: 81.80, a: 0.19, b: 2.21, and the colorimetric value of the stainless steel substrate sample is L: 81.93, a: 0.19, b: 2.14.

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

[0699] The salt spray corrosion resistance result: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection characteristics.

[0700] The binding force test result: the grid test was performed on the film layer on the titanium alloy substrate, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent binding force.

[0701] Example 16.

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

[0703] Pre-treatment of the substrate: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, which was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0704] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0705] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 3 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the pressure in the furnace body was kept at 0.4 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 6.1 W / cm 2 , the power density of the Ti target was set to 3.8 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1700 nm by controlling the film deposition time.

[0706] Silicon wafers were used as the substrate samples for SEM and composition analysis, XRD analysis and TEM testing;

[0707] Stainless steel sheets and aluminum alloy sheets were used for hardness testing and colorimetric value testing;

[0708] Titanium alloy sheets, stainless steel sheets and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance testing;

[0709] Titanium alloy sheets were used for adhesion testing.

[0710] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 60.6 Ti 37.0 N 2.4 .

[0711] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 34, and the XRD diffraction pattern, TEM- SAED pattern and radial intensity profile can be seen in Figure 35. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 1.85° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0714] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection properties.

[0715] Adhesion test results: the film layer on the titanium alloy substrate was tested by cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0716] Example 17.

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

[0718] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0719] ​Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min, so as to remove small impurities on the surface of the sample by plasma etching.

[0720] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 20 sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the pressure in the furnace was kept at 0.5 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 6.1 W / cm 2 , the power density of the Ti target was set at 2.6 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1520 nm.

[0721] The silicon wafer was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed;

[0722] The stainless steel sheet and the aluminum alloy sheet were used for hardness value test and color value test;

[0723] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and the salt spray corrosion resistance test was performed;

[0724] The titanium alloy sheet was used for adhesion test.

[0725] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 60.6 Ti 25.6 N 13.8 .

[0726] The cross-section of the test sample was characterized by SEM, the cross-sectional morphology can be seen from FIG. 36, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen from FIG. 37. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of diffraction angle 2θ(°), and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 1.69° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

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

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

[0729] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test, which has excellent protective properties.

[0730] The bonding force test results: the film layer on the titanium alloy substrate is tested by the grid test, and the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, which reaches the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

[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 pieces, stainless steel pieces, aluminum alloy pieces, and silicon piece samples with a length-width ratio of 50 mm x 50 mm are placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, and the vacuum chamber is vacuumed to 5 x 10 -4 Pa, and heated to 150°C 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 remove small impurities on the surface of the sample by plasma etching.

[0735] Deposition of alloy coating: the sample stage turntable is turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface is adjusted to 8 cm, the Cr target and the Ti target are powered by a radio frequency assisted direct current power supply, Ar and N2 gases are introduced, the N2 gas flow is set to 24 sccm, the gas flow ratio of Ar:N2 is maintained at 2:1, the furnace pressure is maintained at 0.6 Pa, the bias voltage is turned on and set to -100 V, the power density of the Cr target is set to 6.3 W / cm 2 , the power density of the Ti target is set to 1.9 W / cm 2 , and the Cr-Ti-N alloy coating is deposited. The film thickness is controlled to be 2000 nm by controlling the film forming time.

[0736] The sample with a silicon wafer as the substrate was subjected to SEM and composition analysis, XRD analysis, and TEM testing;

[0737] The stainless steel sheet and the aluminum alloy sheet were used to test the hardness value and the color value;

[0738] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate of the sample to perform the salt spray corrosion resistance test;

[0739] The titanium alloy sheet was used to perform the adhesion test.

[0740] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 62.9 Ti 18.9 N 18.2 .

[0741] The SEM cross-section characterization of the test sample was performed, the cross-section morphology can be seen in FIG. 38, and the XRD diffraction pattern, TEM-SAED pattern, and radial intensity profile can be seen in FIG. 39. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of the diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, wherein there is only one wide peak with a half-height width of 2.60° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0742] The color value test results: the color value of the aluminum alloy substrate sample tested was L: 83.07, a: 0.09, b: 1.54, and the color value of the stainless steel substrate sample tested was L: 83.31, a: 0.05, b: 1.45.

[0743] The hardness value 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] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, which has excellent protection properties.

[0745] The adhesion test results: the film layer on the titanium alloy substrate was tested by the grid test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had 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] Pre-treatment of the substrate: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0749] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0750] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power source, Ar and N2 gases were introduced, the N2 gas flow was set to 7 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 7.1 W / cm 2 , the power density of the Ti target was set to 2.6 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled by the deposition time to be 1600 nm.

[0751] Silicon wafers were used as the substrate samples for SEM and composition analysis, XRD analysis;

[0752] Stainless steel sheets and aluminum alloy sheets were used for hardness and colorimetric value tests;

[0753] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as the substrate samples for salt spray corrosion resistance tests;

[0754] Titanium alloy sheets were used for adhesion tests.

[0755] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 69.4 Ti 25.6 N 5.0 .

[0756] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 40, and the XRD diffraction pattern can be seen in Figure 41. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no through-column joint is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 4.29° in the range of 34°-50°.

[0757] Chromatic value test results: the chromatic value of the aluminum alloy substrate sample tested was L: 82.95, a: 0.10, b: 1.81, and the chromatic value of the stainless steel substrate sample tested was L: 82.91, a: 0.04, b: 1.66.

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

[0759] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0760] Bonding force test results: the film layer on the titanium alloy substrate was tested by cross-hatch test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

[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 sheet samples with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0764] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0Pa, the bias voltage was turned on and set to-800V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0765] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the sample stage to the target surface distance to 8 cm, use radio frequency assisted direct current power supply to introduce electricity for the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 29 sccm, set the gas flow ratio to keep Ar:N2 at 2:1, keep the pressure in the furnace body at 0.8 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 7.3 W / cm 2 , set the power density of the Ti target to 0.5 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 900 nm.

[0766] Use silicon wafers as the substrate of the sample to perform SEM and composition analysis, and XRD analysis;

[0767] Use stainless steel sheets and aluminum alloy sheets to perform hardness value testing and color value testing;

[0768] Use titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as the substrate of the sample to perform salt spray corrosion resistance testing;

[0769] Use titanium alloy sheets to perform adhesion testing.

[0770] According to the composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 72.2 Ti 5.0 N 22.8 .

[0771] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in FIG. 42, and the XRD diffraction pattern can be seen in FIG. 43. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the 2θ(°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 4.61° in the range of 34°-50°.

[0772] The color value test results: the color value of the aluminum alloy substrate sample is L: 83.04, a: 0.11, b: 1.17, and the color value of the stainless steel substrate sample is L: 83.29, a: 0.06, b: 0.88.

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

[0774] Salt spray corrosion resistance results: titanium alloy substrates, aluminum alloy samples can pass 48h test, stainless steel substrate samples can pass 144h test, with excellent protective properties;

[0775] Bonding force test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent bonding force.

[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 pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with a length-width ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a plating machine vacuum chamber, which was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at this temperature for 15 minutes.

[0779] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0Pa, the bias voltage was turned on and set to -800V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0780] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 26sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the furnace pressure was kept at 0.6Pa, the bias voltage was turned on and set to -100V, the power density of the Cr target was set to 7.6W / cm 2 , the power density of the Ti target was set to 0.5W / cm 2 , and the Cr-Ti-N alloy coating was deposited. The film thickness was controlled by the deposition time to be 1100nm.

[0781] Silicon wafers were used as the substrate of the sample for SEM and composition analysis, XRD analysis;

[0782] Stainless steel pieces and aluminum alloy pieces were used for hardness value test and color value test;

[0783] Titanium alloy pieces, stainless steel pieces and aluminum alloy pieces were used as the substrate of the sample for salt spray corrosion resistance test;

[0784] Titanium alloy sheet was used for adhesion testing.

[0785] Composition analysis showed that the composition of the alloy coating on the surface of the substrate was Cr 75.0 Ti 5.0 N 20.0 .

[0786] SEM cross-section characterization was performed on the test sample, the cross-section morphology can be seen in Figure 44, and the XRD diffraction pattern can be seen in Figure 45. The SEM test results showed that the Cr-Ti-N alloy coating structure was dense, and no through column seam was observed; the XRD test results showed that the XRD diffraction pattern had a wide peak in the range of diffraction angle 2θ(°) 34°-50°, and the half-height width value of the diffraction angle 2θ(°) in the range of 34°-50° of the XRD diffraction pattern was all ≥1.6°, and there was only one wide peak with a half-height width of 2.91° in the range of 34°-50°.

[0787] Chroma value test results: the test chroma value of the aluminum alloy substrate sample was L: 81.82, a: 0.35, b: 1.87, and the test chroma value of the stainless steel substrate sample was L: 81.97, a: 0.31, b: 1.80.

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

[0789] Salt spray corrosion resistance results: the titanium alloy substrate, aluminum alloy sample can pass 48h test, and the stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0790] Adhesion test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and no plated film layer fell off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0791] Example 22.

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

[0793] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheet samples with an aspect ratio of 50mm×50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5×10 -4 Pa, heated to 150℃, and kept at 150℃ for 15 minutes.

[0794] Plasma cleaning: Ar gas was introduced, the pressure in the furnace was kept at 2.0 Pa, the bias voltage was turned on and set at -800 V, and plasma cleaning was performed for 20 min, so as to remove small impurities on the surface of the sample by plasma etching.

[0795] Deposition of alloy coating: the sample stage turntable was turned on and set at 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set at 7 sccm, the gas flow ratio of Ar:N2 was kept at 6:1, the pressure in the furnace was kept at 0.5 Pa, the bias voltage was turned on and set at -100 V, the power density of the Cr target was set at 9.1 W / cm 2 , the power density of the Ti target was set at 0.5 W / cm 2 , and a Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 900 nm.

[0796] The silicon wafer was used as the substrate of the sample, and SEM and composition analysis, XRD analysis and TEM test were performed;

[0797] The stainless steel sheet and the aluminum alloy sheet were used for hardness value test and colorimetric value test;

[0798] The titanium alloy sheet, the stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and the salt spray corrosion resistance test was performed;

[0799] The titanium alloy sheet was used for adhesion test.

[0800] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 90.0 Ti 5.0 N 5.0 .

[0801] The cross-section of the test sample was characterized by SEM, the cross-sectional morphology can be seen from FIG. 46, and the XRD diffraction pattern, the TEM-SAED pattern and the radial intensity profile can be seen from FIG. 47. The SEM test results show that the Cr-Ti-N alloy coating structure is dense, and no penetrating column seam is observed; the XRD test results show that the XRD diffraction pattern has a wide peak in the range of 34°-50° of the diffraction angle 2θ (°), and the half-height width value of the 2θ (°) diffraction angle in the range of 34°-50° of the XRD diffraction pattern is all ≥1.6°, and there is only one wide peak with a half-height width of 2.99° in the range of 34°-50°; the radial intensity profile of the TEM selected area electron diffraction pattern has only one wide peak in the range of , and the half-height width value is

[0802] Chromaticity value test results: the chromaticity value of the aluminum alloy substrate sample was L: 83.47, a: 0.05, b: 0.99, and the chromaticity value of the stainless steel substrate sample was L: 83.40, a: 0.05, b: 0.95.

[0803] Hardness value 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: the titanium alloy substrate, aluminum alloy sample can pass 48h test, stainless steel substrate sample can pass 144h test, with excellent protection characteristics.

[0805] Bonding force test results: the film layer on the titanium alloy substrate was tested by grid test, the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent bonding force.

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

[0807] In this example, the alloy coating on the substrate is a double-layer structure, and the chemical composition is CrN / Cr 62.9 Ti 18.9 N 18.2 , respectively, corresponding to the transition layer and the Cr-Ti-N alloy film, that is, a CrN transition layer is provided, and the thickness of the transition layer and the Cr-Ti-N alloy film is 300 nm and 1000 nm, respectively.

[0808] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon piece samples with a length-width ratio of 50mmx50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at a constant temperature for 15 minutes.

[0809] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0810] First, deposit a CrN coating (transition layer): turn on the sample table turntable and set the rotation speed to 6 revolutions per minute, adjust the distance between the sample table and the target surface to 8 cm, use radio frequency assisted direct current power to introduce electricity to the Cr target, introduce Ar and N2 gas, set the N2 gas flow to 13 sccm, set the gas flow ratio to keep Ar:N2 at 3:1, keep the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 5.0 W / cm 2, and a Cr-N alloy coating was deposited. The thickness of the obtained Cr-N film was controlled to be 300 nm by controlling the film forming time.

[0811] Secondly, a Cr-Ti-N alloy film was deposited. The sample stage was turned on, the rotation speed was set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 24 sccm, the gas flow ratio of Ar:N2 was set to 2:1, the pressure in the furnace body was maintained at 0.6 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Cr target was set to 6.3 W / cm 2 , the power density of the Ti target was set to 1.9 W / cm 2 , and a Cr-Ti-N alloy film was deposited. The thickness of the obtained Cr-Ti-N film was controlled to be 1000 nm by controlling the film forming time.

[0812] Silicon wafers were used as the substrate of the sample for SEM and composition analysis;

[0813] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and color value testing;

[0814] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as the substrate of the sample for salt spray corrosion resistance testing;

[0815] Titanium alloy sheets were used for adhesion testing.

[0816] According to the composition analysis, the compositions of the two structural layers of the alloy coating on the surface of the substrate were CrN / Cr 62.9 Ti 18.9 N 18.2 .

[0817] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in FIG. 48.

[0818] The color value test results were as follows: the color value of the aluminum alloy substrate sample was L: 82.59, a: 0.14, and b: 1.71, and the color value of the stainless steel substrate sample was L: 82.45, a: 0.14, and b: 1.85.

[0819] The hardness value test results were as follows: 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] The salt spray corrosion resistance results were as follows: the titanium alloy substrate sample and the aluminum alloy substrate sample passed the 48h test, and the stainless steel substrate sample passed the 144h test, which had excellent protective properties.

[0821] Bonding force test results: The film layer on the titanium alloy substrate was tested by grid test, and the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, which showed that the Cr-Ti-N alloy coating had excellent bonding force.

[0822] Example 24.

[0823] In this example, the coating on the substrate is a three-layer structure, and the chemical composition components are Ti / Cr 62.9 Ti 18.9 N 18.2 / CrN, corresponding to the transition layer, Cr-Ti-N alloy film and surface layer respectively, and the thickness is 300 nm, 1000 nm and 200 nm respectively.

[0824] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon piece samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

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

[0826] First, deposit Ti coating (transition layer): turn on the sample stage turntable and set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use radio frequency assisted direct current power to electrify the Ti target, introduce Ar 2 gas, set the Ar gas flow to 60 sccm, keep the furnace pressure at 0.5 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Ti target to 5.0 W / cm 2 , deposit Ti coating, and control the film forming time to make the obtained Ti film thickness 300 nm.

[0827] Second, deposit Cr-Ti-N alloy film (intermediate layer): turn on the sample stage turntable and set the rotation speed to 6 revolutions per minute, adjust the distance between the sample stage and the target surface to 8 cm, use radio frequency assisted direct current power to electrify the Cr target and Ti target, introduce Ar and N2 gas, set the N2 gas flow to 24 sccm, set the gas flow to keep the Ar:N2 gas flow ratio at 2:1, keep the furnace pressure at 0.6 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 6.3 W / cm 2 , and set the power density of the Ti target to 1.9 W / cm 2The Cr-Ti-N alloy film was deposited, and the thickness of the obtained Cr-Ti-N film was controlled to be 1000 nm by controlling the film forming time.

[0828] Finally, the CrN coating (surface layer) was deposited: the sample stage turntable was turned on, the rotation speed was set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target was powered by a radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 13 sccm, the gas flow ratio of Ar:N2 was set to 3:1, the pressure in the furnace body was maintained at 0.6 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Cr target was set to 5.0 W / cm 2 The Cr-N alloy coating was deposited, and the thickness of the obtained Cr-N film was controlled to be 200 nm by controlling the film forming time.

[0829] The silicon wafer was used as the substrate of the sample, and SEM and composition analysis were performed;

[0830] The stainless steel sheet and the aluminum alloy sheet were used for hardness value testing and color value testing;

[0831] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance testing was performed;

[0832] The titanium alloy sheet was used for adhesion testing.

[0833] According to the composition analysis, the coating on the surface of the substrate was a three-layer structure, and the chemical composition of each structure layer was Ti / Cr 62.9 Ti 18.9 N 18.2 / CrN.

[0834] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in FIG. 49.

[0835] The color value test results were as follows: the color value of the aluminum alloy substrate sample was L: 82.60, a: -0.13, and b: 1.71, and the color value of the stainless steel substrate sample was L: 82.11, a: -0.14, and b: 1.15.

[0836] The hardness value test results were as follows: 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] The salt spray corrosion resistance results were as follows: the titanium alloy substrate sample and the aluminum alloy substrate sample could pass the 48 h test, and the stainless steel substrate sample could pass the 144 h test, which had excellent protection properties.

[0838] Bonding force test results: The film layer on the titanium alloy substrate was tested by grid test, and the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, which showed that the Cr-Ti-N alloy coating had excellent bonding force.

[0839] As an example, on the basis of embodiment 24, the Ti transition layer can be replaced by a Cr transition layer.

[0840] The inventors also tried to replace the three-layer coating structure in embodiment 24 with a 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, and the thicknesses are 300 nm, 1000 nm and 200 nm respectively. In the salt spray corrosion test, the aluminum alloy substrate sample can pass the 48 h test, and the stainless steel substrate sample can pass the 144 h test.

[0841] Embodiment 25. Containing a doping element

[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 , which can also be referred to as a Cr-Ti-N-C alloy coating.

[0843] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon pieces with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a coating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0844] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0845] Deposition of Cr-Ti-N-C alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar, C2H2 and N2 gases were introduced, the Ar gas flow was set to 60 sccm, the N2 gas flow was set to 14 sccm, the C2H2 gas flow was set to 6 sccm, the pressure in the furnace body was kept at 0.6 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 7.0 W / cm 2 , and the power density of the Ti target was set to 2.0 W / cm 2, a Cr-Ti-N-C alloy coating was deposited, and the thickness of the obtained Cr-Ti-N-C film was 900 nm by controlling the film forming time.

[0846] The silicon wafer was used as the substrate of the sample for composition analysis.

[0847] The stainless steel sheet and the aluminum alloy sheet were used for hardness value testing and color value testing.

[0848] The titanium alloy sheet, the stainless steel sheet, and the aluminum alloy sheet were used as the substrate of the sample for salt spray corrosion resistance testing.

[0849] The titanium alloy sheet was used for adhesion testing.

[0850] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was Cr 66.9 Ti 18.3 N 10.1 C 4.7 .

[0851] The color value testing results were as follows: the color value of the aluminum alloy substrate sample was L: 83.05, a: 0.10, and b: 1.50, and the color value of the stainless steel substrate sample was L: 83.21, a: 0.07, and b: 1.48.

[0852] The hardness value testing results were as follows: 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] The salt spray corrosion resistance results were as follows: the titanium alloy substrate sample and the aluminum alloy substrate sample could pass the 48h test, and the stainless steel substrate sample could pass the 144h test, which had excellent protective properties.

[0854] The adhesion testing results were as follows: the cross-hatch test was performed on the film layer on the titanium alloy substrate, and the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, which reached the 0-level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent adhesion.

[0855] According to the experimental exploration results of the inventor, when other non-metallic doping elements (such as Si, B, O, H, etc.) or metal doping elements (such as Al) are used, excellent corrosion resistance and high hardness can also be provided when the atomic ratio of the doping element is appropriate (such as 4at%, 2at%). In some embodiments, for example, 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 C5 alloy coating, in salt spray corrosion resistance test experiment, the aluminum alloy substrate sample can pass 48h test, the stainless steel substrate sample can pass 144h test. There can also be at least one broad peak in the XRD diffraction pattern in the diffraction angle 2θ(°) 34°~50° range, and the radial intensity profile of the TEM selected area electron diffraction pattern in the range of 34°~50° has at least one broad peak.

[0856] "at%" means atomic percentage, in quantity.

[0857] Example 26. The Cr-Ti-N alloy coating has a thickness of about 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 sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with an aspect ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0860] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0861] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gas was introduced, the N2 gas flow was set to 26sccm, the gas flow ratio of Ar:N2 was kept at 2:1, the furnace pressure was kept at 0.6 Pa, the bias voltage was turned on and set to -100V, the power density of the Cr target was set to 4.4 W / cm 2 , the power density of the Ti target was set to 3.8 W / cm 2 , the Cr-Ti-N alloy coating was deposited, and the film thickness was controlled to be 50 nm by controlling the film forming time.

[0862] The silicon sheet was used as the substrate sample for composition analysis;

[0863] The stainless steel sheet and the aluminum alloy sheet were used for hardness value test and color value test;

[0864] The titanium alloy sheet, stainless steel sheet and aluminum alloy sheet were used as the substrate of the sample for salt spray corrosion resistance test.

[0865] The titanium alloy sheet was used for binding force test.

[0866] The composition of the alloy coating on the surface of the substrate was Cr 43.0 Ti 37.0 N 20.0 .

[0867] The colorimetric value test results showed that the colorimetric value of the aluminum alloy substrate sample was L: 79.32, a: 0.17, and b: 1.26, and the colorimetric value of the stainless steel substrate sample was L: 79.58, a: 0.14, and b: 1.18.

[0868] The hardness value test results showed that 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] The salt spray corrosion resistance results showed that the titanium alloy substrate sample and the aluminum alloy substrate sample could pass the 48 h test, and the stainless steel substrate sample could pass the 144 h test, which had excellent protection properties.

[0870] The binding force test results showed that the film layer on the titanium alloy substrate was tested by grid test, and the surface appearance was normal, the cutting edge was smooth and complete, and there was no film layer falling off, which reached the 0 level judgment grade in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating had excellent binding force.

[0871] In example 27, the thickness of the Cr-Ti-N alloy coating was about 6 μm

[0872] In this example, the chemical composition of the Cr-Ti-N alloy coating was Cr 43.0 Ti 37.0 N 20.0 .

[0873] Substrate pretreatment: the titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, and heated to 150℃, and kept at this temperature for 15 minutes.

[0874] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, the purpose of which was to remove small impurities on the surface of the sample by plasma etching.

[0875] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 revolutions per minute, adjust the sample stage to the target surface distance to 8 cm, use radio frequency assisted direct current power supply to introduce electricity for the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 26 sccm, set the gas flow ratio to keep Ar:N2 at 2:1, keep the pressure in the furnace body at 0.6 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 4.4 W / cm 2 , set the power density of the Ti target to 3.8 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 6000 nm.

[0876] Use silicon wafers as the substrate of the sample for composition analysis;

[0877] Use stainless steel sheets and aluminum alloy sheets for hardness value testing and color value testing;

[0878] Use titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets as the substrate of the sample for salt spray corrosion resistance testing;

[0879] Use titanium alloy sheets for adhesion testing.

[0880] According to the composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 43.0 Ti 37.0 N 20.0 .

[0881] The color value test results: the color value of the aluminum alloy substrate sample tested is L: 80.72, a: 0.37, b: 2.16, and the color value of the stainless steel substrate sample tested is L: 80.58, a: 0.24, b: 2.28.

[0882] The hardness value test results: the hardness value of the aluminum alloy substrate sample is 26.5 GPa, and the hardness value of the stainless steel substrate sample is 28.3 GPa.

[0883] The salt spray corrosion resistance results: the titanium alloy substrate and the aluminum alloy sample can pass the 48h test, and the stainless steel substrate sample can pass the 144h test, showing excellent protective properties.

[0884] The adhesion test results: the film layer on the titanium alloy substrate is tested by the crosshatch method, the surface appearance is normal, the cutting edge is smooth and complete, and there is no film layer falling off, reaching the 0 level judgment level in GB / T 9286-2021, indicating that the Cr-Ti-N alloy coating has excellent adhesion.

[0885] Example 28. (The substrate is a copper sheet)

[0886] In this example, the chemical composition of the Cr-Ti-N alloy coating is Cr62.9 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 The Cr-Ti-N alloy coating with a thickness of 50 nm and 6000 nm was prepared respectively according to the atomic ratio, and the aluminum alloy substrate sample can pass the 48 h test and the stainless steel substrate sample can pass the 144 h test in the salt spray corrosion resistance test experiment.

[0895] The Cr-Ti-N alloy coating and Cr-Ti-N alloy coating were also prepared respectively based on the copper sheet, and the salt spray corrosion resistance test can pass the 8 hour test. 62.9 Ti 18.9 N 18.2 The alloy coating and Cr-Ti-N alloy coating were also prepared respectively based on the copper sheet, and the salt spray corrosion resistance test can pass the 8 hour test. 36.6 Ti 49.2 N 14.2 The alloy coating and Cr-Ti-N alloy coating were also prepared respectively based on the copper sheet, and the salt spray corrosion resistance test can pass the 8 hour test.

[0896] Comparative Example 1.

[0897] In this comparative example, the chemical composition of the alloy coating is Cr 20.9 Ti 79.1 , and the preparation method is as follows:

[0898] Substrate pretreatment: the copper sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, and heated to 150°C for 15 minutes.

[0899] Plasma cleaning: Ar gas was introduced, the furnace pressure was maintained at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0900] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and Ti target were powered by radio frequency assisted direct current power supply, Ar gas was introduced, the gas flow was set to 80 sccm, the furnace pressure was maintained at 0.5 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 2.2 W / cm 2 , the power density of the Ti target was set to 8.1 W / cm 2 , and the Cr-Ti alloy coating was deposited. The film thickness was controlled by the deposition time to be 1400 nm.

[0901] Silicon wafers were used as substrate samples for SEM and composition analysis.

[0902] Stainless steel sheets and aluminum alloy sheets were used for hardness value testing and color value testing.

[0903] Titanium alloy sheets, stainless steel sheets, and aluminum alloy sheets were used as substrate samples for salt spray corrosion resistance testing.

[0904] Adhesion test was performed on the titanium alloy sheet.

[0905] The composition of the alloy coating on the surface of the substrate was Cr 20.9 Ti 79.1 .

[0906] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen in FIG. 50.

[0907] Chroma value test results: the chroma value of the aluminum alloy substrate sample was L: 77.56, a: 0.57, b: 2.05, and the chroma value of the stainless steel substrate sample was L: 78.07, a: 0.57, b: 2.31.

[0908] Hardness value 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: the titanium alloy substrate and the aluminum alloy sample cannot pass the 48h test (NG, protection time <12h), and the stainless steel substrate sample cannot pass the 144h test (NG, protection time <48h), and does not have the protection characteristics of the substrate.

[0910] Adhesion test results: the film layer on the titanium alloy substrate was tested by grid test, and the edge of the notch had peeling phenomenon, the area was greater than 5% but less than 15%, according to the standard GB / T 9286-2021, it was determined as level 2 grade, and the test was failed.

[0911] Comparative Example 2.

[0912] In this comparative example, the chemical composition of the Cr-Ti-N alloy coating was Cr 44.4 Ti 16.1 N 39.5 .

[0913] Substrate pretreatment: titanium alloy sheets, stainless steel sheets, aluminum alloy sheets and silicon sheets with a length-width ratio of 50mm x 50mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5x10 -4 Pa, heated to 150℃, and kept at this temperature for 15 minutes.

[0914] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0915] Deposition of alloy coating: Turn on the sample stage turret, set the rotation speed to 6 rounds per minute, adjust the distance between the sample stage and the target surface to 8 cm, use a radio frequency assisted direct current power supply to introduce electricity to the Cr target and the Ti target, introduce Ar and N2 gas, set the N2 gas flow to 53 sccm, set the gas flow ratio to keep the Ar:N2 gas flow ratio at 5:4, keep the pressure in the furnace body at 0.9 Pa, turn on the bias voltage and set it to -100 V, set the power density of the Cr target to 4.6 W / cm 2 , set the power density of the Ti target to 1.8 W / cm 2 , deposit a Cr-Ti-N alloy coating, and control the film formation time to make the obtained film thickness 1630 nm.

[0916] Use silicon wafers as the substrate of the sample to perform SEM and composition analysis, XRD analysis and TEM testing;

[0917] Use stainless steel sheets and aluminum alloy sheets to perform hardness value testing and colorimetric value testing;

[0918] Use titanium alloy sheets, stainless steel sheets and aluminum alloy sheets as the substrate of the sample to perform salt spray corrosion resistance testing;

[0919] Use titanium alloy sheets to perform adhesion testing.

[0920] According to the composition analysis, the composition of the alloy coating on the surface of the substrate is Cr 44.4 Ti 16.1 N 39.5 .

[0921] SEM cross-section characterization of the test sample shows that the cross-sectional morphology can be seen in FIG. 51, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in FIG. 52. The SEM test results show that the alloy coating film structure is loose and there are obvious penetrating column seams. The XRD test results show that there are two peaks in the XRD diffraction pattern in the range of 34°-50°, and both are sharp peaks (half-height width value <1.6° 2θ peak), wherein the half-height widths of the two sharp peaks in the range of 34°-50° are 0.34° and 1.58°, respectively. The radial intensity profile of the TEM selected area electron diffraction pattern has two peaks in the range of , and the half-height widths are , that is, there are two sharp peaks.

[0922] The colorimetric value test results are as follows: the colorimetric value of the aluminum alloy substrate sample is L: 58.04, a: 1.80, b: 7.83, and the colorimetric value of the stainless steel substrate sample is L: 60.89, a: 1.26, b: 8.54.

[0923] Hardness value 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: the titanium alloy substrate and the aluminum alloy sample could not pass the 48 h test (NG, protection time < 12 h), and the stainless steel substrate sample could not pass the 144 h test (NG, protection time < 48 h), and did not have protection characteristics for the substrate.

[0925] Bonding force test results: the film layer on the titanium alloy substrate was tested by grid test, and there was peeling phenomenon at the edge of the notch, the area was greater than 5% but less than 15%, according to the GB / T 9286-2021 standard, it was determined as level 2 grade, and the test was failed.

[0926] Comparative Example 3.

[0927] In this comparative example, the chemical composition of the Cr-Ti-N alloy coating was Cr 35.4 Ti 25.8 N 38.8 .

[0928] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon piece samples with a length-width ratio of 50 mm x 50 mm were placed in deionized water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a coating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at a constant temperature for 15 minutes.

[0929] Plasma cleaning: Ar gas was introduced, the furnace pressure was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0930] Deposition of alloy coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target and the Ti target were powered by radio frequency assisted direct current power supply, Ar and N2 gases were introduced, the N2 gas flow was set to 52 sccm, the gas flow ratio of Ar:N2 was kept at 5:4, the pressure in the furnace was kept at 0.9 Pa, the bias voltage was turned on and set to -100 V, the power density of the Cr target was set to 3.6 W / cm 2 , the power density of the Ti target was set to 2.7 W / cm 2 , and a Cr-Ti-N alloy coating was deposited. The film thickness was controlled to be 1400 nm.

[0931] Silicon pieces were used as the substrate sample for SEM and composition analysis, XRD analysis and TEM testing.

[0932] Stainless steel sheet, aluminum alloy sheet are used for hardness value test and color value test;

[0933] Titanium alloy sheet, stainless steel sheet, aluminum alloy sheet are used as the sample of the base body for salt spray corrosion resistance test;

[0934] Titanium alloy sheet is used for bonding force test.

[0935] After component analysis, the component of the alloy coating on the surface of the base body is Cr 35.4 Ti 25.8 N 38.8 .

[0936] SEM cross-section characterization is performed on the test sample, the cross-section morphology can be seen in Figure 53, and the XRD diffraction pattern, TEM-SAED pattern and radial intensity profile can be seen in Figure 54. The SEM test result shows that the alloy coating film structure is loose, and there is obvious penetrating column seam. The XRD test result shows that there are two peaks in the XRD diffraction pattern in the range of 34°-50°, and both are sharp peaks (half-width value <1.6° of 2θ peak), among them, the half-width of the two sharp peaks in the range of 34°-50° is 0.52°, 1.26° respectively. The radial intensity profile of the TEM selected area electron diffraction pattern has two peaks in the range of , and the half-width is , that is, there are two sharp peaks.

[0937] The color value test result: the color value of the aluminum alloy base material sample is L: 60.57, a: 0.83, b: 7.07, and the color value of the stainless steel base material sample is L: 60.22, a: 1.18, b: 8.51.

[0938] The hardness value test result: the hardness value of the aluminum alloy base material sample is 12.3GPa, and the hardness value of the stainless steel base material sample is 13.3GPa.

[0939] The salt spray corrosion resistance result: the titanium alloy base material and the aluminum alloy base sample cannot pass the 48h test (NG, protection time <12h), the stainless steel base material sample cannot pass the 144h test (NG, protection time <48h), and it does not have the protection characteristics for the base body.

[0940] The bonding force test result: the film layer on the titanium alloy base material is tested by grid test, and there is peeling phenomenon at the edge of the notch, the area is greater than 5% but less than 15%, according to the standard of GB / T 9286-2021, it is judged as level 2 grade, and the test is 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] To make the coating of the present comparative example, the preparation method is as follows:

[0944] Pre-treatment of the substrate: titanium alloy sheet, stainless steel sheet, aluminum alloy sheet and silicon sheet samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a coating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150°C, and kept at this temperature for 15 minutes.

[0945] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes, so as to remove small impurities on the surface of the sample by plasma etching.

[0946] Deposition of CrN coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Cr target was powered by a direct current source, Ar and N2 gases were introduced, the N2 gas flow was set to 15 sccm, the gas flow ratio of Ar:N2 was kept at 3:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Cr target was set to 5 W / cm 2 , the CrN coating was deposited, and the film thickness was controlled to be 1800 nm.

[0947] The stainless steel sheet and the aluminum alloy sheet were used as the substrate of the sample, and salt spray corrosion resistance test, hardness test and color value test were performed.

[0948] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was CrN.

[0949] SEM cross-section characterization was performed on the test sample, and the cross-section morphology can be seen from FIG. 55.

[0950] The color value of the aluminum alloy substrate sample was tested as L: 74.92, a: 0.68, and b: 4.89, and the color value of the stainless steel substrate sample was tested as L: 75.07, a: 0.69, and b: 5.17, which was silver white in 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 tested as 12.8 GPa, and the hardness value of the stainless steel substrate sample was tested as 13.3 GPa.

[0953] Bonding force test results: The film layer on the titanium alloy substrate was tested by grid test, and the edge of the notch had peeling phenomenon, the area was greater than 5% but less than 15%, according to the GB / T 9286-2021 standard, it was determined as level 2 grade, and the test was failed.

[0954] Comparative Example 5.

[0955] In the present comparative example, the film structure was TiN, and the chemical composition of the alloy coating was TiN.

[0956] To make the coating of the present comparative example, the preparation method was as follows:

[0957] Substrate pretreatment: titanium alloy pieces, stainless steel pieces, aluminum alloy pieces and silicon piece samples with a length-width ratio of 50 mm x 50 mm were placed in DI water for ultrasonic cleaning for 15 minutes, dried in an oven, and then placed in a vacuum chamber of a plating machine, the vacuum chamber was vacuumed to 5 x 10 -4 Pa, heated to 150℃, and kept at 150℃ for 15 minutes.

[0958] Plasma cleaning: Ar gas was introduced, the pressure in the furnace body was kept at 2.0 Pa, the bias voltage was turned on and set to -800 V, and plasma cleaning was performed for 20 minutes. The purpose was to remove small impurities on the surface of the sample by plasma etching.

[0959] Deposition of TiN coating: the sample stage turntable was turned on and set to 6 revolutions per minute, the distance between the sample stage and the target surface was adjusted to 8 cm, the Ti target was powered by a direct current source, Ar and N2 gases were introduced, the N2 gas flow was set to 10 sccm, the gas flow ratio of Ar:N2 was kept at 3:1, the pressure in the furnace body was kept at 0.5 Pa, the bias voltage was turned on and set to -100 V, and the power density of the Ti target was set to 5 W / cm 2 , and a TiN coating was deposited. By controlling the film formation time, the obtained film thickness was 600 nm.

[0960] Stainless steel pieces and aluminum alloy pieces were used as the substrate samples for salt spray corrosion resistance test, hardness test and color value test.

[0961] According to the composition analysis, the composition of the alloy coating on the surface of the substrate was TiN.

[0962] The color value of the aluminum alloy substrate sample was tested as L: 57.95, a: 6.45, and b: 13.95, and the color value of the stainless steel substrate sample was tested as L: 59.33, a: 6.92, and b: 13.91, which showed 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 tested to be 4.1 GPa, and the hardness value of the stainless steel substrate sample was tested to be 4.4 GPa.

[0965] The bonding force test result: The film layer on the titanium alloy substrate was tested by cross-hatch test, and small pieces were peeled off at the intersection of the notch. The actual damage in the grid area was not more than 5%, according to the GB / T 9286-2021 standard, it was determined to be grade 1, and the test was failed.

[0966] Comparative Example 6. Alloy coating thickness 50 nm

[0967] The same method as Comparative Example 3 was used, and the chemical composition of the alloy coating was Cr 35.4 Ti 25.8 N 38.8 , the difference is that the thickness of the alloy coating is changed from 1400 nm to 50 nm.

[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] The bonding force test result: The film layer on the titanium alloy substrate was tested by cross-hatch test, and small pieces were peeled off at the intersection of the notch. The actual damage in the grid area was not more than 5%, according to the GB / T 9286-2021 standard, it was determined to be grade 1, and the test was failed.

[0970] Comparative Example 7. Alloy coating thickness 1000 nm

[0971] The same method as Comparative Example 3 was used, and the chemical composition of the alloy coating was Cr 35.4 Ti 25.8 N 38.8 , the difference is that the thickness of the alloy coating is changed from 1400 nm to 1000 nm.

[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] The bonding force test result: The film layer on the titanium alloy substrate was tested by cross-hatch test, ...

Claims

1. A Cr-Ti-N alloy material comprising Cr element, Ti element and N element, wherein the atomic ratio of the Cr element, the Ti element and the N element is x:y:z, 5.0≤x≤90.0, 5.0≤y≤79.0, 2.4≤z≤26.

5.

2. The Cr-Ti-N alloy material according to claim 1, wherein The Cr-Ti-N alloy material includes a CrTiN-based alloy component of a chemical formula of Cr x Ti y N z M a , wherein M is a doping element, x, y, z, and a are 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%, or 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%, or optionally, 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 element comprises one or more of O, C, B, Si, H and Ar; The metallic element comprises 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 constituent material of a 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 a peak in the range of diffraction angle 2θ (°) of 34° to 50°, and the half-height width of at least one 2θ (°) diffraction peak in the range of 34° to 50° satisfies ≥1.6°; 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 is obtained by Cu target Kα ray; The selected area electron diffraction pattern of the Cr-Ti-N alloy film is obtained by using TEM characterization method under the mode of electron acceleration voltage of 200 kV and selected area diaphragm diameter of 900 nm.

13. The Cr-Ti-N alloy material of claim 12, wherein The half-height width 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°.

14. A Cr-Ti-N alloy film or Cr-Ti-N alloy coating, wherein, The Cr-Ti-N alloy film is composed of the Cr-Ti-N alloy material according to any one of claims 1 to 13; and the Cr-Ti-N alloy coating comprises 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 Cr-Ti-N alloy film has a thickness of 0.3 μm to 2.0 μm.

16. An alloy film article, wherein, The alloy film product comprises a substrate and the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating as claimed 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 on the surface of any one of the following materials on the side close to the substrate: alloys, elemental metals and inorganic non-metallic materials; The alloy material type comprises one or more of nickel-based, iron-based, tungsten-based, titanium-based, silicon-based, aluminum-based, copper-based, cobalt-based, zirconium-based and zinc-based; The elemental metal is any one of zinc, gold, platinum, zirconium, hafnium, niobium, tantalum, nickel, copper, aluminum, iron, silver and chromium; The inorganic non-metallic material comprises one or more of ceramic and glass; Optionally, the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating is bonded on the surface of one of light alloys or one of stainless steel alloys on the side close to the substrate; wherein the light alloys comprise one or more of titanium alloy, aluminum alloy and magnesium alloy.

18. The alloy film product of claim 16 or 17, which satisfies one or more of the following characteristics: The Cr-Ti-N alloy film is in direct contact with the substrate or is provided with 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, and 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 is provided with 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 is further provided with a surface layer on the side away from the substrate, and the surface layer is a single-layer structure or a multi-layer structure.

19. Use of the Cr-Ti-N alloy material of any one of claims 1 to 13 in the preparation of a corrosion-resistant protective coating, or use of the Cr-Ti-N alloy film or the Cr-Ti-N alloy coating as claimed in claim 14 or 15 as a corrosion-resistant protective coating.

20. The use according to claim 19, wherein, x, y and z satisfy the following first group or second group characteristics: First group: 43.0 ≤ x ≤ 60.6, 25.6 ≤ y ≤ 37.0 and 13.8 ≤ z ≤ 20.0; Second group: 54.4 ≤ x ≤ 90.0, 5.0 ≤ y ≤ 25.6 and 5.0 ≤ z ≤ 20.0; Further, the corrosion-resistant protective coating is also a high-brightness surface coating; wherein the high-brightness surface coating has a brightness value L ≥ 80 as tested by Lab method.

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