Coating member and manufacturing method thereof, case and electronic product

Abstract

Provided are a coating member and a manufacturing method thereof, a case, and an electronic product. The coating member includes a substrate, an anodized layer, and a base layer, the anodized layer is formed on a surface of the substrate, the base layer is located on the surface of the anodized layer, and includes a first base layer and a second base layer which are stacked in order along a direction away from the anodized layer, the first base layer and the second base layer being selected from vapor-deposited layers of metal A, the average crystal grain size of the first base layer is smaller than the average crystal grain size of the second base layer, the anodized layer has a microporous structure, and the crystal grains of the first base layer are partially embedded in the micropores of the anodized layer.

Description

[Technical Field]

[0001] (Priority information) This application claims priority to Chinese Patent Application No. 202110484484.1, entitled "Coating Member and Manufacturing Method Thereof, Case and Electronic Product," filed with the State Intellectual Property Administration of the People's Republic of China on April 30, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present application belongs to the technical field of metal surface treatment, and specifically relates to a coating member and a manufacturing method thereof, a case, and an electronic product. [Background technology]

[0003] Due to the need to reduce the weight of electronic products, mainstream models often choose aluminum alloys as the material for the middle frame. Currently, aluminum alloy surfaces are generally treated with anodizing to improve their corrosion resistance, friction resistance, wear resistance, and other properties. PVD (Physical Vapor Deposition) technology can not only significantly improve the wear resistance, corrosion resistance, and hardness of the substrate surface, but also achieve a surface with better color and gloss than anodizing technology. While this technology is widely used for stainless steel materials, PVD coatings are rarely used to protect the surface of aluminum alloy substrates. The main reasons for this are as follows:

[0004] The bonding strength between the aluminum alloy itself and the PVD coating layer is weak, and naturally occurring aluminum oxide is generated on the surface of the aluminum alloy, which affects the bonding between the aluminum alloy and the PVD coating layer. In particular, for conventional aluminum alloys, after anodizing, the surface of the aluminum material exhibits a porous honeycomb structure, making it difficult for the conventional PVD coating layer to bond well with the anodized layer, resulting in problems such as poor surface wear resistance and corrosion resistance. Ultimately, the appearance of the aluminum material lacks a noticeable metallic texture, and the competitive advantage over the mature process solution of anodizing dyeing and sealing is lost. Summary of the Invention [Problem to be solved by the invention]

[0005] In response to the problem that conventional PVD coatings on aluminum alloys after anodizing result in poor wear resistance and corrosion resistance, the present application provides a coated member and a manufacturing method thereof, a case, and an electronic product.

[0006] To solve the above technical problems, the present application uses the following technical solutions. [Means for solving the problem]

[0007] In one aspect, a coating member according to the present application comprises a substrate, an anodized layer, and a base layer, the anodized layer being formed on the surface of the substrate, the base layer being located on the surface of the anodized layer, and comprising a first base layer and a second base layer stacked in order along a direction away from the anodized layer, the first base layer and the second base layer being selected from vapor-deposited layers of metal A, the average crystal grain size of the first base layer being smaller than the average crystal grain size of the second base layer, the anodized layer having a microporous structure, and the crystal grains of the first base layer being partially embedded in the micropores of the anodized layer.

[0008] In an embodiment of the present application, the substrate comprises aluminum or an aluminum alloy.

[0009] In the present embodiment, the metal A comprises Cr and / or Ti.

[0010] In the present embodiment, the thickness of the first base layer is 30 nm to 100 nm, and the thickness of the second base layer is 50 nm to 120 nm.

[0011] In the embodiment of the present application, the average grain size of the crystal grains in the first base layer is 3 nm to 30 nm, and the nano-hardness of the first base layer is 10 GPa to 16 GPa.

[0012] In the embodiment of the present application, the average grain size of the crystal grains in the second base layer is 50 nm to 100 nm, and the nano-hardness of the second base layer is 6 GPa to 9 GPa.

[0013] In an embodiment of the present application, the base layer further includes a third base layer, and the first base layer, the second base layer, and the third base layer are stacked in order along a direction away from the anodized layer, and the third base layer is selected from a vapor-deposited layer of metal A, and has an average crystal grain size smaller than that of the second base layer.

[0014] In the embodiment of the present application, the average grain size of the crystal grains in the third base layer is 30 nm to 60 nm, and the nano-hardness of the third base layer is 8 GPa to 10 GPa.

[0015] In the present embodiment, the thickness of the third base layer is 30 nm to 100 nm.

[0016] In the present embodiment, the thickness of the anodized layer is 4 μm to 16 μm.

[0017] In the present embodiment, the pore diameter of the anodic oxide layer is 10 nm to 100 nm, and the number of pores in the anodic oxide layer is 100 / μm. 2 ~3000 pieces / μm 2 Meet the following.

[0018] In an embodiment of the present application, the coating member further includes a functional layer, which is located on the base layer away from the anodized layer, and includes a color layer, which includes an oxide of metal M, a nitride of metal M, a carbide of metal M, or a combination thereof, and the metal M is one or more selected from Cr, Ti, and W.

[0019] In the present embodiment, the thickness of the color layer is 0.3 μm to 3 μm.

[0020] In an embodiment of the present application, the functional layer further comprises a transition layer located between the color layer and the base layer and comprising metal A and metal M.

[0021] In the present embodiment, the thickness of the transition layer is 0.3 μm to 1 μm.

[0022] In another aspect, the method for producing the coating member according to the present application comprises the steps of: providing a substrate and performing an anodizing treatment on the surface of the substrate to form an anodized layer; Using metal A as a target material, applying a negative bias to the substrate, and forming a first base layer on the surface of the anodized layer by sputtering using a vacuum coating method; and forming a second base layer on the surface of the first base layer by sputtering using metal A as a target material and vacuum coating without applying a bias to the substrate.

[0023] In an embodiment of the present application, the method further includes a step of applying an adhesive to the electrical contact areas on the surface of the substrate before the anodizing treatment, and after the anodizing treatment, removing the adhesive from the surface of the substrate to expose the electrical contact areas, and in a subsequent operation, applying a negative bias to the substrate at the electrical contact areas.

[0024] In the examples of the present application, the anodizing treatment conditions are that the bath solution in the anodizing bath is at least one selected from a sulfuric acid solution, a phosphoric acid solution, and an oxalic acid solution, the molar concentration of the acid in the bath solution is 0.3 mol / L to 0.8 mol / L, and the temperature of the bath solution is 15°C to 25°C.

[0025] In the embodiment of the present application, when the first base layer is manufactured, the vacuum coating conditions are controlled to apply a negative bias to the substrate, with a voltage value of 200V to 400V and a target current of 20A to 30A.

[0026] In an embodiment of the present application, the method further includes, after forming the first base layer and before forming the second base layer, performing ion bombardment on the first base layer for 5 to 10 minutes.

[0027] In the embodiment of the present application, when the second base layer is manufactured, the vacuum coating conditions are controlled to be a direct current mode, no bias, and a target current of 5A to 10A.

[0028] In the examples of the present application, The method further includes applying a negative bias to the substrate using metal A as a target material, and forming a third base layer on the surface of the second base layer by sputtering using a vacuum coating method.

[0029] In the embodiment of the present application, when the third base layer is manufactured, the vacuum coating conditions are controlled to apply a negative bias to the substrate, with a voltage value of 30V to 120V and a target current of 15A to 25A.

[0030] In an embodiment of the present application, the method comprises: The method further includes forming a transition layer on the surface of the base layer by sputtering using metal A and metal M as target materials in a vacuum coating manner, where metal A includes Cr and / or Ti, and metal M includes one or more of Cr, Ti, and W.

[0031] In an embodiment of the present application, the method comprises: The method further includes sputtering a color layer on the surface of the transition layer by vacuum coating using metal M as a target material and introducing at least one of an oxygen source, a nitrogen source, and a carbon source as a reactive gas.

[0032] In another aspect, the case according to the present application includes the above-described coating member.

[0033] In another aspect, an electronic product according to the present application includes the case described above. [Effects of the Invention]

[0034] The coating member according to the present application has an anodized oxide layer formed on the surface of a substrate, and a base layer formed outside the anodized oxide layer, including a first base layer with a smaller average crystal grain size and a second base layer with a larger average crystal grain size. The smaller average crystal grain size of the first base layer allows it to be more easily embedded in the micropores of the anodized oxide layer, increasing the contact area and improving the bonding strength between the base layer and the anodized oxide layer. The larger average crystal grain size of the second base layer reduces internal stress in the base layer to some extent, preventing film delamination caused by excessive stress in the base layer. The base layer formed by bonding the first and second base layers acts as a pore seal for the anodized oxide layer, preventing subsequent dust and other particles from entering the anodized oxide layer. It can also serve as a base for subsequent vacuum coating, effectively improving the bonding strength between the substrate and the subsequent vacuum coating, achieving wear resistance and corrosion resistance.

[0035] Additional aspects and advantages of the disclosure will be set forth in part in the description that follows, and in part will be obvious from the description, or may be learned by practice of the disclosure. [Brief explanation of the drawings]

[0036] [Figure 1] 1 is a schematic diagram of a coating member according to the present application. DETAILED DESCRIPTION OF THE INVENTION

[0037] In order to clarify the technical problems, technical solutions and advantageous effects of the present application, the present application will be described in more detail below with reference to the drawings and examples. It should be understood that the specific examples described herein are only for the purpose of interpreting the present application and are not intended to limit the present application.

[0038] As shown in FIG. 1 , the coating member according to the embodiment of the present application includes a substrate 1, an anodized layer 2, and a base layer 3. The anodized layer 2 is formed on the surface of the substrate 1. The base layer 3 is located on the surface of the anodized layer 2 and includes a first base layer 31 and a second base layer 32 stacked in order along a direction away from the anodized layer 2. The first base layer 31 and the second base layer 32 are selected from vapor-deposited layers of metal A. The average crystal grain size of the first base layer 31 is smaller than the average crystal grain size of the second base layer 32. The anodized layer 2 has a microporous structure, and the crystal grains of the first base layer 31 are partially embedded in the micropores of the anodized layer 2.

[0039] The first base layer 31 has a smaller average crystal grain size, which allows it to be better embedded in the pores of the anodized layer 2, increasing the contact area and further improving the bonding strength between the base layer 3 and the anodized layer 2. The second base layer 32 has a larger average crystal grain size than the first base layer 31, which reduces the internal stress of the base layer 3 to a certain extent and avoids the problem of film delamination caused by excessive stress in the base layer 3. The base layer 3 formed by bonding the first base layer 31 and the second base layer 32 has a sealing effect on the anodized layer 2, preventing subsequent dust and other particles from entering the anodized layer 2. It can also serve as a base for subsequent vacuum coating, which effectively improves the bonding strength between the substrate 1 and the subsequent vacuum coating and achieves wear resistance and corrosion resistance.

[0040] In some embodiments, the substrate 1 comprises aluminum or an aluminum alloy.

[0041] In different embodiments, the substrate 1 may be selected from a single piece of aluminum or aluminum alloy, or a laminated or interlocking structure partially made of aluminum or aluminum alloy.

[0042] In some embodiments, the metal A comprises Cr and / or Ti.

[0043] In some embodiments, the first base layer 31 has a thickness of 30 nm to 100 nm, and the second base layer 32 has a thickness of 50 nm to 120 nm.

[0044] When the thickness of the first base layer 31 is within the above range, it has a strong bonding force with the anodized layer 2, and when the thickness of the second base layer 32 is within the above range, it can better reduce the internal stress of the first base layer 31 and perform transition and buffering functions.

[0045] In some embodiments, the average grain size of the crystal grains in the first base layer 31 is 3 nm to 30 nm, and the nano-hardness of the first base layer 31 is 10 GPa to 16 GPa.

[0046] In some embodiments, the average grain size of the crystal grains in the second base layer 32 is 50 nm to 100 nm, and the nano-hardness of the second base layer 32 is 6 GPa to 9 GPa.

[0047] The first base layer 31 has a fine crystalline structure, is stable and dense, and has high adhesion, but is hard, has high internal stress after molding, and has certain defects (voids, point defects, line defects). The second base layer 32 has a coarse columnar crystalline structure and has a lower relative hardness. The bonding between the second base layer 32 and the first base layer 31 helps reduce internal stress and the number of defects.

[0048] In some embodiments, the base layer 3 further includes a third base layer 33, where the first base layer 31, the second base layer 32 and the third base layer 33 are stacked in order along a direction away from the anodized layer 2, and the third base layer 33 is selected from vapor-deposited layers of metal A and has an average crystal grain size smaller than that of the second base layer 32.

[0049] The second base layer 32 has a coarse columnar crystal structure and is not dense enough, so if another material is directly coated on the second base layer 32, the bonding strength will be insufficient. Therefore, by providing the third base layer 33 on the outside of the second base layer 32, the columnar crystal structure can be converted into a fine crystal structure, forming a denser surface layer, which helps improve the wear resistance and provides a good adhesion base for the subsequent coating layer.

[0050] In some embodiments, the average grain size of the crystal grains in the third base layer 33 is 30 nm to 60 nm, and the nano-hardness of the third base layer 33 is 8 GPa to 10 GPa.

[0051] The average grain size and nano-hardness of the third base layer 33 are between those of the first base layer 31 and the second base layer 32, further improving the overall strength and wear resistance of the base layer 3.

[0052] In some embodiments, the third base layer 33 has a thickness of 30 nm to 100 nm.

[0053] When the thickness of the third base layer 33 is within the above range, it has high coverage and avoids the problem of not covering in place or having too much internal stress.

[0054] In some embodiments, the thickness of the anodized layer 2 is between 4 μm and 16 μm.

[0055] In some embodiments, the pore diameter of the anodic oxide layer 2 is 10 nm to 100 nm, and the number of pores in the anodic oxide layer is 100 / μm 2 ~3000 pieces / μm 2 Meet the following.

[0056] When the pore size and number of the anodized layer 2 are within the above range, it can provide sufficient micropores to bond with the first base layer 31, and the pore size helps the crystal particles of the first base layer 31 to be embedded in the micropores of the anodized layer 2 to improve the bonding strength.

[0057] In some embodiments, the coating member further comprises a functional layer 4 , which is located on the base layer 3 on a side remote from the anodized layer 2 .

[0058] In different embodiments, the functional layer 4 may be a coating film layer realizing different functions, such as an anti-fingerprint layer or a high-hardness layer, or may be a decorative layer, such as a color layer or a glare layer.

[0059] In some embodiments, the functional layer 4 includes a color layer 42 comprising an oxide of a metal M, a nitride of a metal M, or a carbide of a metal M, and combinations thereof, where the metal M is one or more selected from Cr, Ti, and W.

[0060] The color layer 42 may be a single layer or a multi-layer. When the color layer 42 is a multi-layer, different layers may be provided with different oxides of metal M, nitrides of metal M, or carbides of metal M to achieve the purpose of adjusting the color.

[0061] In some embodiments, the thickness of the functional layer 4 is 0.3 μm to 3.7 μm.

[0062] In some embodiments, the thickness of the color layer 42 is between 0.3 μm and 3 μm.

[0063] In some embodiments, the color layer 42 is applied directly to the surface of the base layer 3 .

[0064] In another embodiment, the functional layer 4 further comprises a transition layer 41 located between the color layer 42 and the base layer 3 and comprising a metal A and a metal M.

[0065] The transition layer 41 is used as a transition between the base layer 3 and the color layer 42, the base layer 3 contains metal A, and the color layer 42 is made of an oxide of metal M, a nitride of metal M, or a carbide of metal M. Since the transition layer 41 contains both metal A and metal M, it ensures that the affinity of the transition layer 41 with the base layer 3 and the color layer 42 is high, and that the bonding strength between the transition layer 41 and the base layer 3 and the color layer 42 is high, thereby avoiding stratification caused by excessive material differences.

[0066] In some embodiments, the thickness of the transition layer 41 is between 0.3 μm and 1 μm.

[0067] According to another embodiment of the present application, a method for manufacturing the coating member includes the steps of: a step of preparing a substrate 1 and performing an anodizing treatment on the surface of the substrate 1 to form an anodized layer 2; Using metal A as a target material, applying a negative bias to the substrate 1, and forming a first base layer 31 on the surface of the anodized layer 2 by sputtering using a vacuum coating method; and forming a second base layer 32 on the surface of the first base layer 31 by sputtering using metal A as a target material and vacuum coating without applying a bias to the substrate 1.

[0068] In the manufacturing method described above, during the vacuum coating process of the first base layer 31, a metal A target material is bombarded with high-energy particles to ionize the metal A ions, and a negative bias is applied to the substrate 1 to increase the substrate 1's attraction to the metal A ions and accelerate the metal A ions, providing energy for the metal A ions to deposit and bombard the substrate 1. By applying a negative bias, the formed first base layer 31 transforms from a coarse columnar crystal structure to a fine crystal structure, which is stable and dense, forming an ideal film layer structure with high adhesion performance. During the vacuum coating process of the second base layer 32, a bias-free method is used; the formed metal A ions are deposited on the first base layer 31 and tend to form a coarse columnar crystal structure, which has low hardness and helps reduce the internal stress of the first base layer 31.

[0069] In some embodiments, the method further includes a step of applying an adhesive to the electrical contact areas on the surface of the substrate 1 before the anodizing treatment, and after the anodizing treatment, removing the adhesive from the surface of the substrate 1 to expose the electrical contact areas, and in a subsequent operation, applying a negative bias to the substrate 1 at the electrical contact areas.

[0070] In this manufacturing method, a negative bias must be applied to the substrate 1, and the anodized layer 2 formed by anodization has a non-conductive structure, which is unfavorable for electrical contact between the substrate 1 and the applied power source. In order to ensure the negative bias applied to the substrate 1, the inventors apply an adhesive coating to the electrical contact areas of the substrate 1 before the anodization process, thereby forming protection for the substrate 1, and then remove the adhesive after the anodization process, which effectively ensures the subsequent application of a negative bias to the substrate 1 and improves the quality of the film formation.

[0071] The material used in the adhesive application process is not particularly selected and may be any conventional adhesive material.

[0072] In some embodiments, before the adhesive coating process, the substrate 1 is subjected to a polishing process, which may be chemical polishing, mechanical polishing, or a combination thereof. The polishing process removes the native oxide layer and surface defects (e.g., scratches) on the surface of the substrate 1, thereby improving the surface smoothness of the substrate 1, which helps to ensure direct contact between the adhesive and the surface of the substrate 1 during the adhesive coating process, and also helps to form a denser anodic oxide layer 2 during the anodizing process.

[0073] In some embodiments, after the adhesive coating process, the surface of the substrate 1 is subjected to one or more of the following operations: oil removal, hot water washing, alkaline water washing, cold water washing, and acid washing, thereby forming a smooth surface on the substrate 1, removing oil stains and defects on the surface, and improving the uniformity of the formed film.

[0074] In some embodiments, the anodizing treatment is performed under the following conditions: the bath solution in the anodizing bath is at least one selected from a sulfuric acid solution, a phosphoric acid solution, and an oxalic acid solution; the molar concentration of the acid in the bath solution is 0.3 mol / L to 0.8 mol / L; and the temperature of the bath solution is 15°C to 25°C.

[0075] By the anodization treatment, an anodized layer 2 having uniform pores with a pore size of 10 nm to 100 nm is formed on the surface of the substrate 1, which is useful for embedding the crystal grains of the first base layer 31.

[0076] In some embodiments, before the first base layer 31 is produced, a preliminary vacuum drawing operation is performed on the substrate 1 on which the anodized layer 2 is formed.

[0077] The anodized layer 2 of the substrate 1 has a large number of micropores, which make it very susceptible to dust particles in the air. Furthermore, the micropores also contain debris remaining during processing. The dust and debris remaining in the micropores will become impurities on the surface of the film produced by subsequent vacuum coating, further affecting the performance of the film layer. To solve this problem, the present manufacturing method uses a pre-vacuum method, which changes the air pressure to expel the dust and debris from the micropores of the anodized layer 2, thereby ensuring the quality of the subsequent coating.

[0078] In some embodiments, before manufacturing the first base layer 31, the anodized layer 2 is bombarded with ions to improve the cleanliness of the anodized layer 2 and increase the surface energy of the anodized layer 2.

[0079] In some embodiments, when manufacturing the first base layer 31, the vacuum coating conditions are controlled so that a negative bias is applied to the substrate, the voltage value is 200V to 400V, and the target current is 20A to 30A.

[0080] The bias used in the fabrication of the first base layer 31 is a further improvement of this fabrication method. To further increase the bonding strength between the first base layer 31 and the anodized layer 2, the inventors used a high bias process parameter above the normal range. This bias range encourages metal A ions to enter the micropore structure of the anodized layer 2, increasing the contact area and improving adhesion. However, a negative bias that is too high increases reverse sputtering, reduces the deposition rate, and causes a large number of defects (vacancies, point defects, line defects), damaging the integrity of the film layer and reducing the quality of the film layer and affecting surface performance.

[0081] In some embodiments, after manufacturing the first base layer 31 and before manufacturing the second base layer 32, the method further includes a step of performing ion bombardment on the first base layer 31 for a time period of 5 to 10 minutes to improve the surface energy of the first base layer 31.

[0082] In some embodiments, when manufacturing the second base layer 32, the vacuum coating conditions are controlled to be a direct current mode, no bias, and a target current of 5A-10A.

[0083] To repair the damaged first base layer 31 to some extent, it is necessary to deposit a softer second base layer 32 on top of it to form a transition, reducing the internal stress of the first base layer 31 and decreasing the number of defects.

[0084] In some embodiments, the method further comprises: The method further includes applying a negative bias to the substrate 1 using the metal A as a target material, and forming a third base layer 33 on the surface of the second base layer 32 by sputtering using a vacuum coating method.

[0085] Since the second base layer 32 manufactured without bias has a coarse columnar crystal structure, after the second base layer 32 is deposited to a certain thickness, a third base layer 33 is added to convert the film layer from a columnar structure to a fine crystal structure, finally completing the coating of the base layer 3.

[0086] In some embodiments, when manufacturing the third base layer 33, the vacuum coating conditions are controlled so that a negative bias is applied to the substrate, the voltage value is 30V to 120V, and the target current is 15A to 25A.

[0087] In some embodiments, the method further comprises: The method further includes forming a transition layer 41 on the surface of the base layer 3 by sputtering using metal A and metal M as target materials in a vacuum coating manner, where metal A includes Cr and / or Ti, and metal M includes one or more of Cr, Ti, and W.

[0088] In some embodiments, the method further comprises: The method further includes sputtering a color layer 42 on the surface of the transition layer 41 by vacuum coating using a metal M as a target material and introducing at least one of an oxygen source, a nitrogen source, and a carbon source as a reactive gas.

[0089] The oxygen source is selected from O2, the nitrogen source is selected from N2, and the carbon source is selected from C2H2.

[0090] When multiple types of oxygen, nitrogen, or carbon sources are used as reactive gases, in order to avoid mutual reactions between the reactive gases, it is necessary to introduce each of the oxygen, nitrogen, or carbon sources and cause them to react with the metal M ions sputtered from the target material to form a mixed layer of an oxide of metal M, a nitride of metal M, or a carbide of metal M.

[0091] In some embodiments, when manufacturing the color layer 42, a coating layer of metal M may be obtained without introducing the reactive gas, and the coating layer exhibits metallic luster.

[0092] A case for an electronic product according to another embodiment of the present application includes the coating member.

[0093] Due to the use of the coating material, the case of the electronic product has high surface abrasion resistance and a high aesthetic effect.

[0094] The present invention will now be further described with reference to the following examples. [Example]

[0095] This example illustrates the coating member and method of manufacturing the same disclosed herein, including the following operational steps:

[0096] (1) For the anodizing pretreatment, the aluminum alloy substrate was subjected to the following steps in order: mechanical polishing, adhesive application, oil removal, hot water washing, alkaline washing, cold water washing, acid washing, and cold water washing.

[0097] (2) Anodizing treatment: The pre-treated aluminum alloy substrate is placed in an anodizing tank to perform anodizing. The solution used for anodizing is a sulfuric acid solution with a concentration of 0.5 mol / L, the temperature of the bath solution is 18°C, the thickness of the film layer is 8 mm, the pore size is 20-40 nm, and the number of pores is 2000 / μm. 2 An anodic oxide layer having the following structure was formed.

[0098] (3) Regarding the PVD coating pretreatment, the PVD coating pretreatment includes adhesive removal, cleaning, drying, and preliminary high vacuum evacuation. The adhesive removal is to remove the adhesive in step (1).

[0099] (4) Regarding PVD coating, the aluminum alloy substrate treated as above was placed in a vacuum coating device, and after vacuuming, heating, and ion cleaning, the coating treatment was carried out. Specifically, the procedure is as follows.

[0100] For the manufacture of the first base layer, a Cr target is used, the bias is set to -300V, the Cr target current is set to 25A, the thickness of the coated film layer is set to 50nm, the average crystal grain size of the first base layer is set to 8nm, the nano-hardness of the first base layer is set to 14GPa, and ion bombardment is performed for 10min after coating; For the production of the second base layer, a Cr target is used, and a DC current mode (no bias) is set, and the Cr target current is set to 8A, and the thickness of the coated film layer is set to 80nm, and the average crystal grain size of the second base layer is set to 60nm, and the nano-hardness of the second base layer is set to 8GPa; For the production of the third base layer, a Cr target was used, the bias was set to -80 V, the Cr target current was set to 20 A, the thickness of the coated film layer was set to 60 nm, the average crystal grain size of the third base layer was set to 40 nm, and the nano-hardness of the third base layer was set to 9 GPa, and the coating of the base layer was completed.

[0101] For the preparation of the transition layer, both a Ti target and a Cr target were used for coating, and the direct current mode (no bias) was set, the target current was set to 20 A, and the thickness of the coated film layer was set to 500 nm.

[0102] For the production of the color layer, a Ti target was used, and a reactive gas was introduced during magnetron sputtering. The reactive gas was nitrogen gas, and the DC current mode (no bias) was set. The target current was set to 20 A, and the thickness of the coated film layer was set to 800 nm. [Example]

[0103] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0104] For the manufacture of the first base layer, a Cr target is used, the bias voltage is set to -200V, the Cr target current is set to 20A, the thickness of the coated film layer is set to 100nm, the average crystal grain size of the first base layer is set to 25nm, the nano-hardness of the first base layer is set to 11GPa, and ion bombardment is performed for 10min after coating; For the manufacture of the second base layer, a Cr target is used, a DC current mode (no bias) is set, the Cr target current is set to 10A, the thickness of the coated film layer is set to 50nm, the average crystal grain size of the second base layer is set to 50nm, and the nano-hardness of the second base layer is set to 9GPa; For the production of the third base layer, a Cr target was used, the bias was set to -120 V, the Cr target current was set to 25 A, the thickness of the coated film layer was set to 30 nm, the average crystal grain size of the third base layer was set to 30 nm, and the nano-hardness of the third base layer was set to 10 GPa, and the coating of the base layer was completed. [Example]

[0105] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0106] For the manufacture of the first base layer, a Cr target is used, the bias voltage is set to -400V, the Cr target current is set to 30A, the thickness of the coated film layer is set to 30nm, the average crystal grain size of the first base layer is set to 3nm, the nano-hardness of the first base layer is set to 16GPa, and ion bombardment is performed for 10min after coating; For the production of the second base layer, a Cr target is used, and a DC current mode (no bias) is set, and the Cr target current is set to 5A, and the thickness of the coated film layer is set to 120nm, and the average crystal grain size of the second base layer is set to 100nm, and the nano-hardness of the second base layer is set to 6GPa; For the production of the third base layer, a Cr target was used, the bias was set to -30 V, the Cr target current was set to 15 A, the thickness of the coated film layer was set to 100 nm, the average crystal grain size of the third base layer was set to 60 nm, and the nano-hardness of the third base layer was set to 8 GPa, and the coating of the base layer was completed. [Example]

[0107] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0108] For the production of the first base layer, the thickness of the coated membrane layer was 20 nm. [Example]

[0109] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0110] For the production of the first base layer, the thickness of the coated membrane layer was 150 nm. [Example]

[0111] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0112] For the production of the second base layer, the thickness of the coated membrane layer was 40 nm. [Example]

[0113] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0114] For the production of the second base layer, the thickness of the coated membrane layer was 150 nm. [Example]

[0115] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0116] For the fabrication of the first base layer, the bias was set to -500V. [Example]

[0117] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0118] In step (4), after the second base layer was produced, the transition layer was directly coated without producing the third base layer. [Example]

[0119] This example is intended to illustrate the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0120] In step (3), a preliminary high vacuum is not drawn. <Comparative Example 1>

[0121] This comparative example is intended to compare and explain the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0122] In step (4), when the base layers were manufactured, the first base layer was not manufactured, and the second base layer and the third base layer were manufactured directly. <Comparative Example 2>

[0123] This comparative example is intended to compare and explain the coating member and the manufacturing method thereof according to the present application, and includes most of the operation steps in Example 1, but differs in the following respects.

[0124] In step (4), when the base layer was manufactured, the first base layer and the third base layer were manufactured directly without manufacturing the second base layer. Performance Test

[0125] The coated members produced in Examples 1 to 10 and Comparative Examples 1 and 2 were subjected to the following performance tests.

[0126] 1. Regarding the cross-cut adhesion test, 1) Before testing, inspect the appearance to ensure there are no abnormalities, discoloration, bubbles, cracks, peeling, etc. Wipe the surface of the substrate clean with a dust-free cloth. 2) Hold the cutter knife and cut it so that the knife surface is perpendicular to the test surface, the knife edge does not lift the film layer, the cutting direction is at a 45-degree angle to the sample, and a force is applied evenly to the cutter knife (apply force so that the cutting edge just penetrates the film layer and reaches the substrate) to form a grid of 10 x 10 continuous 1 mm x 1 mm squares. 3) Wipe the debris in the test area clean with a dust-free cloth, pull out a portion of NICHIBAN CT405AP-24 tape evenly, remove the front section, then cut off about 55 mm of tape, place the center point of the tape above the grid, and make sure the direction is parallel to one set of cutting lines, then flatten the tape section above the grid area with a fingernail to ensure good contact between the tape and the film layer (be careful not to damage the tape or film layer with the fingernail), and make sure the length of the tape exceeds the length of the grid by at least 20 mm; 4) Apply the tape and leave it for 90 seconds. Then, hold the floating end of the tape and quickly peel it off within 0.5 to 1.0 seconds at an angle as close to 60 degrees as possible. 5) The peeling condition of the film layer is inspected, and if it exceeds 4B, it is considered to be passed. The specific evaluation criteria are as follows:

[0127] 5B: The cut edge is completely smooth and there is no peeling. 4B: Some coating layer peeling at the intersection of the cut notch, with the affected intersection cut area being 5% or less. 3B: The coating layer is peeled off at the intersection of the cut notch and / or along the edge of the cut notch, with the affected intersection cut area being greater than 5% but not greater than 15%. 2B: The membrane layer is partially or completely peeled off in the form of large pieces along the cut edge and / or partially or completely peeled off in different parts of the lattice, with the cross-cut area affected being greater than 15% but not more than 35%. 1B: The coating layer is peeled off in the form of large pieces along the cut edge and / or partially or completely peeled off in some grids, with the affected cross-cut area being greater than 35% but not greater than 65%. 0B: Peeling degree exceeds 1B.

[0128] 2. Regarding wear resistance, 1) Prepare three parts of RKF 10K (yellow cones) and one part of RKK15P (green cones), totaling 15 L, and place them in the polishing tank of a vibration friction device (ROSLER, model number R180 / 530TE-30, frequency 50±0.5 Hz, amplitude 1.65±0.1 mm). 2) Using a pipette, 10 ml of FC120 is sucked into the polishing tank, and 0.5 L of water is added. 3) Add 0.5L of water to the polishing tank, and add 0.5L of water and 10ml of FC120 every 30 minutes during the test. 4) Prepare a complete machine for testing or a complete machine for use as a counterweight, attach each sample to the complete machine, and place it in the vibration friction test device to conduct the test. Inspect each sample every 0.5 hours and record the longest time that met the criteria (continuous sawtooth wear not exceeding 10 mm (regarding the definition of sawtooth, the linear wear area must have two or more positions with a width between 1 and 1.5 mm, and widths exceeding 1.5 mm are not permitted), point wear not exceeding 1.5 mm x 1.5 mm, and point wear of 1 mm x 1 mm to 1.5 mm x 1.5 mm must not exceed two, and the number of point wear of 1 mm x 1 mm or less is not counted).

[0129] 3. Regarding salt spray testing: In a sealed environment with a temperature of 35°C and humidity of 90%, the surface of the coated component was continuously sprayed with salt water using a 5% by weight NaCl solution with a pH of 6.8. During the test, the appearance of the sample was inspected every 12 hours, and then lightly rinsed with warm water at 38°C, wiped clean with a dust-free cloth, and left at room temperature for 2 hours before inspecting the sample. The appearance of the film layer was normal, and the longest time without any obvious changes in appearance (such as rust, discoloration, or peeling of the surface treatment layer) was recorded.

[0130] The test results obtained are shown in Table 1. [Table 1]

[0131] As can be seen from the test results in Table 1, compared to the comparative example, the coating member of the present application has better film layer adhesion, wear resistance, and corrosion resistance, and it was shown that by controlling the average crystal grain size of different film layers in the base layer, the bonding strength between it and the anodized layer and the outer functional layer can be effectively improved.

[0132] Although the examples of the present application have been described above with reference to the drawings, the present application is not limited to the above specific embodiments, and the above specific embodiments are not restrictive but merely illustrative. A person skilled in the art can implement many forms based on the suggestions of the present application without departing from the spirit of the present application and the scope of protection of the claims, and all of these fall within the scope of protection of the present application. [Explanation of symbols]

[0133] 1 Base material 2. Anodized layer 3 Base Layer 31 First base layer 32 Second base layer 33 Third base layer 4 Functional Layer 41 Transition layer 42 Color Layer

Claims

1. A coating member comprising a substrate, an anodized layer, and a base layer, a first base layer and a second base layer laminated in this order along a direction away from the anodized layer, the first base layer and the second base layer comprising vapor-deposited layers of a metal A, the first base layer comprising a plurality of first crystal particles, the second base layer comprising a plurality of second crystal particles, the first crystal particles having an average crystal grain size smaller than the average crystal grain size of the second crystal particles, the anodized layer having a microporous structure, the first crystal particles being embedded in the micropores of the anodized layer, the first crystal particles having an average crystal grain size of 3 nm to 30 nm, and the second crystal particles having an average crystal grain size of 50 nm to 100 nm.

2. The coating member according to claim 1 , wherein the substrate comprises aluminum or an aluminum alloy.

3. The coated member according to claim 1 , wherein the metal A includes Cr and / or Ti.

4. 2. The coating member according to claim 1, wherein the first base layer has a thickness of 30 nm to 100 nm, and the second base layer has a thickness of 50 nm to 120 nm.

5. The nano-hardness of the first base layer is 10 GPa to 16 GPa; The coating member according to claim 1 , wherein the second base layer has a nano-hardness of 6 GPa to 9 GPa.

6. the base layer further includes a third base layer, the first base layer, the second base layer, and the third base layer being stacked in this order along a direction away from the anodized layer, the third base layer being a vapor-deposited layer of metal A, and the average crystal grain size of the third base layer being smaller than the average crystal grain size of the second crystal grains; 2. The coating member according to claim 1, wherein the average grain size of the crystal grains of the third base layer is 30 nm to 60 nm, and the nano-hardness of the third base layer is 8 GPa to 10 GPa.

7. The thickness of the third base layer is 30 nm to 100 nm. The thickness of the anodized layer is 4 μm to 16 μm. The pore diameter of the anodic oxide layer is 10 nm to 100 nm, and the number of the pores in the anodic oxide layer is 100 / μm ２ ~3000 pieces / μm ２ fulfill, The coated member according to claim 6.

8. The pore diameter of the anodic oxide layer is 10 nm to 100 nm, and the number of the pores in the anodic oxide layer is 100 / μm ２ ~3000 pieces / μm ２ The coating member according to claim 1 , which satisfies the above formula:

9. the functional layer is located on a side of the base layer away from the anodized layer, and the functional layer includes a color layer, the color layer including an oxide of a metal M, a nitride of a metal M, a carbide of a metal M, or a combination thereof, and the metal M is one or more selected from Cr, Ti, and W; The thickness of the color layer is 0.3 μm to 3 μm, The coating member of claim 1 , wherein the functional layer further comprises a transition layer, the transition layer being located between the color layer and the base layer, and the transition layer comprising a metal A and a metal M.

10. providing a substrate and performing an anodizing treatment on the surface of the substrate to form an anodized layer; Using metal A as a target material, applying a negative bias to the substrate, and forming a first base layer on the surface of the anodized layer by sputtering using a vacuum coating method; and forming a second base layer on the surface of the first base layer by sputtering using metal A as a target material in a vacuum coating manner without applying a bias to the substrate.

11. 11. The method of claim 10, further comprising the step of applying an adhesive to electrical contact areas on the surface of the substrate before the anodizing treatment, and removing the adhesive from the surface of the substrate after the anodizing treatment to expose the electrical contact areas.

12. The method according to claim 10, wherein in the anodizing treatment, a bath solution in an anodizing bath is at least one selected from a sulfuric acid solution, a phosphoric acid solution, and an oxalic acid solution, the molar concentration of the acid in the bath solution is 0.3 mol / L to 0.8 mol / L, and the temperature of the bath solution is 15°C to 25°C.

13. The vacuum coating for producing the first base layer includes applying a negative bias to the substrate, with a voltage value of 200V to 400V and a target current of 20A to 30A; The method of claim 10, wherein the vacuum coating for producing the second base layer includes a direct current mode, with a target current of 5 A to 10 A without applying a bias voltage.

14. 11. The method of claim 10, further comprising the step of: after producing the first base layer and before producing the second base layer, subjecting the first base layer to ion bombardment for a time period of 5 minutes to 10 minutes.

15. The method further includes applying a negative bias to the substrate using metal A as a target material, and forming a third base layer on the surface of the second base layer by sputtering using a vacuum coating method; 11. The method of claim 10, wherein the vacuum coating for producing the third base layer comprises applying a negative bias to the substrate, with a voltage value of 30V to 120V and a target current of 15A to 25A.

16. 10. The method of claim 9, further comprising forming a transition layer on the surface of the base layer by sputtering using metal A and metal M as target materials in a vacuum coating manner, wherein the metal A includes Cr and / or Ti, and the metal M includes one or more of Cr, Ti, and W.

17. 10. The method according to claim 9, further comprising the step of: using the metal M as a target material, introducing at least one of an oxygen source, a nitrogen source, and a carbon source as a reactive gas, and forming a color layer on the surface of the transition layer by sputtering in a vacuum coating manner.

18. An electronic product having a case including the coating member according to any one of claims 1 to 9.

Images