A composite coating and a preparation method thereof

Abstract

The present application discloses a composite coating and a preparation method thereof. The composite coating is deposited on a substrate, and successively includes the substrate, a ytterbium zirconium silver alloy layer, and a carbon nitride zirconium silver alloy layer. In order to overcome the disadvantages such as great difficulty in process control, poor bonding force with the substrate, uncontrollable coating color, rough surface, and poor antiviral effect, this paper proposes a method for preparing an environmentally friendly composite antiviral coating with scratch resistance, high antiviral rate, and color controllability by using a composite target and through multi-arc ion plating. The composite coating provided by the present application significantly improves the antiviral rate compared with depositing only one of the ytterbium zirconium silver alloy layer or the carbon nitride zirconium silver alloy layer alone.

Description

Technical Field

[0001] This article relates to, but is not limited to, the field of metal materials, and particularly relates to, but is not limited to, an environmentally friendly composite antiviral coating and a preparation method thereof. Background Art

[0002] The public has put forward higher requirements for the hygiene and safety of furniture and equipment. At present, a large number of surface technologies and materials with antibacterial functions have emerged on the market. Due to the differences in the structures, growth environments, and transmission methods of viruses and bacteria, some antibacterial surface materials and related technologies cannot play a good inhibitory role on viruses.

[0003] In the existing research materials on antiviral surface materials at present:

[0004] The method of preparing a polymer antiviral coating by chemical vapor deposition technology is difficult to control the conditions for the free radical chain polymerization reaction of monomers, and the thickness of the coating also needs to be monitored simultaneously. Therefore, the process control of this technology is difficult, the cost is high, and it is not suitable for large-scale production. At the same time, the bonding force between the polymer coating and the substrate is poor, and it is very easy to fall off during daily use and is not scratch-resistant.

[0005] The method of forming an antiviral film layer through anodization - coating - drying treatment requires controlling the temperature of the modifier liquid and the number of coating times, and the operation process is relatively cumbersome and the cost is high. The gloss of the film layer surface is relatively low and it is very easy to change the color of the original oxide film.

[0006] The antiviral coating prepared by the cold spraying method has a rough surface and poor decorative effect.

[0007] When preparing a silver / stainless steel layer / antioxidant layer by physical vapor deposition technology, it is difficult for viruses to directly contact silver ions, and the actual antiviral effect is poor. Summary of the Invention

[0008] The following is an overview of the subject matter described in detail in this article. This overview is not intended to limit the scope of protection of the claims.

[0009] In order to overcome the disadvantages such as large process control difficulty, poor bonding force with the substrate, uncontrollable coating color, rough surface, and poor antiviral effect, this article proposes an environmentally friendly composite antiviral coating with scratch resistance, high antiviral rate, and color controllability, which is prepared by using a composite target and through multi-arc ion plating.

[0010] This article provides a composite coating, characterized in that the composite coating is deposited on a substrate, and in sequence is the substrate, a ytterbium zirconium silver alloy layer, and a carbon nitrogen zirconium silver alloy layer.

[0011] In an embodiment provided by the present application, in the ytterbium zirconium silver alloy layer, the atomic ratio of zirconium, silver and ytterbium is (75 to 90):(6 to 15):(4 to 10).

[0012] In an embodiment provided by the present application, in the carbonitride zirconium silver alloy layer, the atomic ratio of zirconium and silver is (85 to 90):(10 to 15).

[0013] In an embodiment provided by the present application, the substrate is selected from any one or more of copper alloy, nickel alloy and chromium alloy.

[0014] In an embodiment provided by the present application, the thickness of the composite coating is 550 nm to 1000 nm.

[0015] In an embodiment provided by the present application, the thickness of the ytterbium zirconium silver alloy layer is 300 nm to 800 nm;

[0016] Optionally, the thickness of the carbonitride zirconium silver alloy layer is 100 nm to 600 nm.

[0017] In another aspect, the present application provides a method for preparing the above composite coating, and the preparation method is to prepare the ytterbium zirconium silver alloy layer and the carbonitride zirconium silver alloy layer by arc ion plating;

[0018] During the preparation of the ytterbium zirconium silver alloy layer, only inert gas is used in the arc ion plating;

[0019] During the preparation of the carbonitride zirconium silver alloy layer, the inert gas and reaction gas are used in the arc ion plating;

[0020] The inert gas is selected from any one or more of helium, neon and argon;

[0021] The reaction gas includes nitrogen and acetylene.

[0022] In an embodiment provided by the present application, the inert gas has a purity greater than 99.99%, and the reaction gas is nitrogen with a purity greater than 99.99% and acetylene with a purity greater than 98%;

[0023] The base vacuum of the arc ion plating is greater than 2×10 -3 Pa.

[0024] In an embodiment provided by the present application, during the preparation of the carbonitride zirconium silver alloy layer, the flow ratio of the inert gas, the acetylene and the nitrogen is (100 to 500):(40 to 100):(300 to 500).

[0025] In another aspect, the present application provides a kitchen and bathroom hardware product, including a substrate and the above coating.

[0026] In an implementation provided by the present application, the kitchen and bathroom hardware product is an antiviral kitchen and bathroom hardware product for use in the kitchen or bathroom.

[0027] Other features and advantages of this document will be elaborated in the subsequent specification, and partly become apparent from the specification, or are understood by implementing this document. Other advantages of this document can be achieved and obtained through the solutions described in the specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The drawings are used to provide an understanding of the technical solutions in this document, and constitute a part of the specification. Together with the embodiments of this document, they are used to explain the technical solutions in this document, and do not constitute a limitation to the technical solutions in this document.

[0029] Figure 1 It is a cross-sectional scanning electron microscope image of Example 1.

[0030] Figure 2 It is a cross-sectional scanning electron microscope image of Example 2.

[0031] Figure 3 It is a cross-sectional scanning electron microscope image of Example 3.

[0032] Figure 4 It is a cross-sectional scanning electron microscope image of Example 4.

[0033] Figure 5 It is a cross-sectional scanning electron microscope image of Example 5.

[0034] Figure 6 It is a cross-sectional scanning electron microscope image of Comparative Example 1.

[0035] Figure 7 It is a cross-sectional scanning electron microscope image of Comparative Example 2.

[0036] Figure 8 It is a cross-sectional scanning electron microscope image of Comparative Example 3.

[0037] Figure 9 It is a schematic diagram of the sample after the scratch resistance test of Example 2. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0038] To make the objectives, technical solutions, and advantages of this document clearer, the embodiments of this document are described in detail below. It should be noted that, without conflict, the embodiments in this document and the features in the embodiments can be combined arbitrarily with each other.

[0039] The base material (Cu / Ni / Cr) is electroplated with Ni and Cr on the copper alloy by electroplating in sequence, which is a common base material and process in the sanitary ware industry. Specifically, the thickness of the Ni layer is 12 to 20 micrometers, and the thickness of the Cr layer is 3 to 5 micrometers. The manufacturer is Changtai Kemei Kitchen and Bathroom Technology Co., Ltd.

[0040] Example 1:

[0041] Install 5 AgZrYb alloy targets with an atomic ratio of Ag:Zr:Yb of 6:84:10 in one column for the arc source, and install 10 AgZr alloy targets with an atomic ratio of Ag:Zr of 10:90 in two columns for the arc source. Load the substrate (Cu / Ni / Cr) and evacuate for coating. The coating process includes ion bombardment, depositing a bottom layer, and reactive coating. The base vacuum for coating is 0.002 pa, the coating vacuum is 0.4 pa, the bias voltage is 120 V, and the current is 200 A. Other process parameters are shown in Table 1 below:

[0042] Table 1: Process Parameter Table for Example 1

[0043] Sputtering target Argon flow rate Acetylene flow rate Nitrogen flow rate Coating time The first layer AgZrYb 450 sccm 0 0 240s×5 The second layer AgZr 450 sccm 45 sccm 300 sccm 120s×3

[0044] The thickness of the ytterbium zirconium silver alloy coating obtained in Example 1 is 506.9 nm; the thickness of the carbon nitrogen zirconium silver alloy coating obtained is 241.2 nm.

[0045] Example 2:

[0046] The difference between Example 2 and Example 1 is only that the coating time of the ytterbium zirconium silver alloy coating in Example 2 is 160 s × 10, and the coating time of the carbon nitrogen zirconium silver alloy coating in Example 2 is 80 s × 2.

[0047] The thickness of the ytterbium zirconium silver alloy coating obtained in Example 2 is 761.5 nm; the thickness of the carbon nitrogen zirconium silver alloy coating obtained is 116.1 nm.

[0048] Example 3:

[0049] The difference between Example 3 and Example 1 is only that the coating time of the ytterbium zirconium silver alloy coating in Example 3 is 200 s × 4, and the coating time of the carbon nitrogen zirconium silver alloy coating in Example 3 is 100 s × 3.

[0050] The thickness of the ytterbium zirconium silver alloy coating obtained in Example 3 is 339.4 nm; the thickness of the carbon nitrogen zirconium silver alloy coating obtained is 227.8 nm.

[0051] Example 4:

[0052] The difference between Example 4 and Example 1 is only that the atomic ratio of Ag:Zr:Yb in the AgZrYb alloy target in Example 4 is 9:81:10, and the atomic ratio of Ag:Zr in the AgZr alloy target is 13:87.

[0053] The thickness of the ytterbium zirconium silver alloy coating obtained in Example 4 is 505.7 nm; the thickness of the carbon nitrogen zirconium silver alloy coating obtained is 243.4 nm.

[0054] Example 5:

[0055] Example 5 is only different from Example 1 in that the substrate of Example 5 is a copper alloy (copper alloy model: H59 - 76.4*76*1, purchased from Xiamen Jingyicheng Metal Products Co., Ltd.). The coating time of the ytterbium-zirconium-silver alloy coating in Example 5 is 240s×6, and the coating time of the carbonitride-zirconium-silver alloy coating in Example 5 is 120s×2.

[0056] The thickness of the ytterbium-zirconium-silver alloy coating obtained in Example 5 is 568.5nm; the thickness of the carbonitride-zirconium-silver alloy coating obtained is 148.3nm.

[0057] Comparative Example 1:

[0058] Comparative Example 1 is only different from Example 1 in that there is no coating in this comparative example, that is, the substrate (Cu / Ni / Cr).

[0059] Comparative Example 2:

[0060] Comparative Example 2 is only different from Example 1 in that the coating time of the ytterbium-zirconium-silver alloy coating in Comparative Example 2 is 240s×7, and the coating time of the carbonitride-zirconium-silver alloy coating in Comparative Example 2 is 0.

[0061] The thickness of the ytterbium-zirconium-silver alloy coating obtained in Comparative Example 2 is 750.2nm; the thickness of the carbonitride-zirconium-silver alloy coating obtained is 0.

[0062] Comparative Example 3:

[0063] Comparative Example 3 is only different from Example 1 in that the coating time of the ytterbium-zirconium-silver alloy coating in Comparative Example 3 is 0, and the coating time of the carbonitride-zirconium-silver alloy coating in Comparative Example 3 is 240s×7.

[0064] The thickness of the ytterbium-zirconium-silver alloy coating obtained in Comparative Example 3 is 0; the thickness of the carbonitride-zirconium-silver alloy coating obtained is 751.6nm.

[0065] The antiviral rate, scratch resistance, and appearance color of the above examples and comparative examples are shown in Table 2 below:

[0066] Table 2: Performance Statistics Table of Examples and Comparative Examples

[0067]

[0068]

[0069] It can be seen from Table 2 and the cross-sectional SEM images of each example and comparative example that:

[0070] 1. Samples obtained by electroplating Ni and Cr on copper alloys commonly used in the sanitary ware industry (i.e., the substrates described in this article) have a low antiviral rate against the H1N1 influenza virus (as shown in Comparative Example 1);

[0071] 2. Using the cathodic arc ion plating technique to deposit only one layer of the composite film layer, its antiviral rate is lower than that of the sample with two layers of the composite film layer;

[0072] 3. During the film deposition process, when the gas flow ratio of nitrogen and acetylene is fixed, different factors such as the film deposition time and target composition will affect the appearance color (Lab value) of the sample, and the preparation process can be adjusted according to the required color of the film. In Examples 1 to 5, the content of acetylene and nitrogen introduced is fixed, and the color of the coating surface is golden yellow.

[0073] 4. The values of Ra and Rq indicate that the surface roughness of the sample coating prepared in the examples of this application is small, that is, the surface is relatively smooth.

Claims

1. A composite coating, characterized in that, the composite coating is deposited on a substrate, successively being the substrate, a ytterbium zirconium silver alloy layer and a carbonitride zirconium silver alloy layer; in the ytterbium zirconium silver alloy layer, the atomic ratio of zirconium, silver and ytterbium is (75 to 90):(6 to 15):(4 to 10); in the carbonitride zirconium silver alloy layer, the atomic ratio of zirconium and silver is (85 to 90):(10 to 15); the preparation method of the composite coating is to prepare the ytterbium zirconium silver alloy layer and the carbonitride zirconium silver alloy layer by arc ion plating; during the process of preparing the ytterbium zirconium silver alloy layer, only inert gas is used in arc ion plating; during the process of preparing the carbonitride zirconium silver alloy layer, inert gas and reactive gas are used in arc ion plating; the reactive gas includes nitrogen and acetylene; during the process of preparing the carbonitride zirconium silver alloy layer, the flow rate ratio of the inert gas, the acetylene and the nitrogen is (100 to 500):(40 to 100):(300 to 500).

2. The composite coating according to claim 1, characterized in that, the substrate is selected from any one or more of copper alloy, nickel alloy and chromium alloy.

3. The composite coating according to claim 1 or 2, characterized in that, the thickness of the composite coating is 550 nm to 1000 nm.

4. The composite coating according to claim 1 or 2, characterized in that, the thickness of the ytterbium zirconium silver alloy layer is 300 nm to 800 nm.

5. The composite coating according to claim 1 or 2, characterized in that, the thickness of the carbonitride zirconium silver alloy layer is 100 nm to 600 nm.

6. The composite coating according to claim 1 or 2, characterized in that, the Ag:Zr:Yb atomic ratio of the ytterbium zirconium silver alloy layer is 6:84:10, and the Ag:Zr atomic ratio of the carbonitride zirconium silver alloy layer is 10:90; or the Ag:Zr:Yb atomic ratio of the ytterbium zirconium silver alloy layer is 9:81:10, and the Ag:Zr atomic ratio of the carbonitride zirconium silver alloy layer is 13:

87.

7. The composite coating according to claim 1 or 2, characterized in that, the inert gas is selected from any one or more of helium, neon and argon.

8. A kitchen and bathroom hardware product, comprising a substrate and the coating according to any one of claims 1 to 7.

9. The kitchen and bathroom hardware product according to claim 8, characterized in that, the kitchen and bathroom hardware product is an antiviral kitchen and bathroom hardware product for kitchen or bathroom use.

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