CN114540894B - Sterilizing wear-resistant corrosion-resistant composite coating, preparation method thereof and sterilizing wear-resistant corrosion-resistant product - Google Patents

Abstract

A sterilization wear-resistant corrosion-resistant composite coating, a preparation method thereof and a sterilization wear-resistant corrosion-resistant product, wherein the sterilization wear-resistant corrosion-resistant composite coating comprises: the full gloss nickel layer, the microporous nickel layer and the decorative chromium composite sterilization layer are sequentially arranged on the base material; the decorative chromium composite sterilization layer and the microporous nickel layer are respectively provided with a nano needle structure, and are respectively formed by a first composite raw material containing a first bactericidal ammonium salt and a second composite raw material containing a second bactericidal ammonium salt, and the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-The concentration of the second bactericidal ammonium salt in the second composite raw material is 100g/L and 50-100g/L. The sterilizing, wear-resisting and corrosion-resisting composite plating can be obtained only by a single electroplating method, has a good sterilizing effect, and does not need to be sprayed with nano Ag ⁺ 、Cu ²⁺ And can realize the effects of wear resistance and high corrosion resistance.

Description

Sterilizing, wear-resistant and corrosion-resistant composite coating and its preparation method and sterilizing, wear-resistant and corrosion-resistant products

Technical field

This application relates to, but is not limited to, the field of sterilization and anti-corrosion materials, and particularly refers to a sterilization, wear-resistant and corrosion-resistant composite coating and its preparation method and sterilization, wear-resistant and corrosion-resistant products.

Background technique

Bacteria are microorganisms that are widespread in nature and are found almost everywhere. Some pathogenic bacteria among bacteria can cause various diseases in the human body, thereby threatening human health. With the outbreak of the COVID-19 epidemic, countries around the world attach great importance to the development of the health industry, especially healthy kitchen and bathroom home products that can be sterilized and anti-viral. At present, the surface material of large hardware products in kitchens and bathrooms (such as showers, faucets, etc.) can use microporous nickel composite plating formed by electroplated full-gloss nickel layer + microporous nickel layer + decorative chromium layer. Among them, the formation of microporous nickel layer can increase the corrosion protection of the coating.

Microporous nickel refers to adding some fine particles with poor conductivity to the bright nickel solution. During the electroplating process, nickel is continuously deposited on the parts. At the same time, these particles are also brought into the plating layer, and finally form a hole that penetrates to the nickel layer. Discontinuous small holes (commonly known as micropores). When parts are corroded, the existence of these micropores increases the exposed area of the nickel layer, disperses the corrosion current well, greatly reduces the corrosion current per unit area on the surface of the part, and therefore reduces the corrosion rate, thereby avoiding It prevents concentrated deep corrosion and plays an anti-corrosion effect.

However, products with microporous nickel plating prepared by electroplating technology alone cannot achieve sterilization and antibacterial functions for the time being. It is usually necessary to spray a layer of sterilization material containing nanometer Ag ⁺ and Cu ²⁺ on the surface, or prepare it through PVD technology. Composite materials containing Ag ⁺ /Cu ²⁺ , but Ag ⁺ and Cu ²⁺ are easily absorbed by the pores of human skin, which is not good for human health. The cost of PVD coating is high. In addition, most of the sterilization and antibacterial effects of kitchen and bathroom products currently on the market are explained through test reports from third-party institutions, which cannot be visualized.

Contents of the invention

The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the application.

This application provides a sterilizing, wear-resistant and corrosion-resistant composite plating and its preparation method and sterilizing, wear-resistant and corrosion-resistant products. The sterilizing, wear-resistant and corrosion-resistant composite plating can be obtained only through a separate electroplating method and also has a good sterilization effect. , there is no need to spray antibacterial materials containing nanometer Ag ⁺ and Cu ²⁺ , and it can achieve wear resistance and high corrosion resistance.

This application provides a sterilization, wear-resistant and corrosion-resistant composite coating, including: an all-gloss nickel layer, a microporous nickel layer, and a decorative chromium composite sterilization layer; the all-gloss nickel layer is set to a location where sterilization, anti-wear or anti-corrosion requirements are required On the base material, the microporous nickel layer is disposed on the surface of the full-gloss nickel layer away from the base material, and the decorative chromium composite sterilization layer is disposed on the side of the microporous nickel layer away from the base material. On the surface of , and the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-100g/L, and the concentration of the second bactericidal ammonium salt in the second composite raw material is 50-100g/L.

In the embodiments of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt can each be independently selected from any one of alkyl quaternary ammonium iodide salts and alkyl aromatic hydrocarbon quaternary ammonium iodide salts, or Various.

In the embodiments of the present application, the carbon chain length of the alkyl group in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbon quaternary ammonium iodide salt may be 12-18.

In the embodiments of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt can each be independently selected from dodecyldimethylbenzylammonium iodide and dodecyltrimethyliodide. Ammonium iodide, tetradecyldimethylbenzylammonium iodide, tetradecyltrimethylammonium iodide, cetyldimethylbenzylammonium iodide, cetyltrimethylammonium iodide , any one or more of octadecyldimethylbenzylammonium iodide and octadecyltrimethylammonium iodide.

In the embodiment of the present application, the raw materials of the decorative chromium composite sterilization layer may include: first quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystals with a concentration of 10-20g/L, It is 1-5mL/L sulfuric acid, solid chromic acid with a concentration of 200-450g/L, and decorative chromium additive CR 842 with a concentration of 5-15mL/L.

In the embodiment of the present application, the raw materials of the microporous nickel layer may include: second quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystal with a concentration of 10-20g/L, and 150-400g/L nickel sulfate, 60-120g/L nickel chloride, 30-80g/L boric acid, 0.1-0.5mL/L bright nickel ZD-220, 5- Liquid additive MPS 800 at 80mL/L and liquid additive Mark 904 at a concentration of 0.1-2mL/L.

In the embodiment of the present application, the raw materials of the all-gloss nickel layer may include: nickel sulfate with a concentration of 300-500g/L, nickel chloride with a concentration of 30-80g/L, nickel chloride with a concentration of 30-80g/L. Boric acid, cylinder opening agent NIB-90 with a concentration of 5-10mL/L, main gloss agent NIB-90 with a concentration of 1-3mL/L, and wetting agent Ni-66B with a concentration of 1-5mL/L.

In the embodiment of the present application, the sterilizing, wear-resistant and corrosion-resistant composite coating may be silver-white.

In embodiments of the present application, the thickness of the full-gloss nickel layer may be 20-50 μm, the thickness of the microporous nickel layer may be 20-50 μm, and the thickness of the decorative chromium composite sterilization layer may be >0.5 μm.

This application also provides a method for preparing the sterilization, wear-resistant and corrosion-resistant composite coating as described above, including:

(1) Pre-treatment of the substrate: including polishing and cleaning;

(2) Electroplating the full-gloss nickel layer on the surface of the pre-treated base material;

(3) electroplating the microporous nickel layer on the surface of the full-gloss nickel layer;

(4) Electroplating the decorative chromium composite germicidal layer on the surface of the microporous nickel layer.

In the embodiment of the present application, the conditions for electroplating the all-gloss nickel layer in step (2) may include: temperature is 40-60°C, cathode current density is 3.5-10A/dm ² , and electroplating time is 600-2400s.

In the embodiment of the present application, the conditions for electroplating the microporous nickel layer in step (3) may include: temperature is 40-60°C, cathode current density is 3-8A/dm ² , and electroplating time is 600-1800s.

In the embodiment of the present application, the conditions for electroplating the decorative chromium composite sterilization layer in step (4) may include: the temperature is 40-60°C, the cathode current density is 5-20A/dm ² , and the electroplating time is 300-900s. .

This application also provides a sterilizing, wear-resistant and corrosion-resistant product, including a base material and the sterilizing, wear-resistant and corrosion-resistant composite coating as mentioned above.

In embodiments of the present application, the substrate may be a metal substrate or a plastic substrate.

In the embodiment of the present application, the sterilization, wear-resistant and corrosion-resistant product is a sterilization product for kitchen or bathroom.

The sterilization, wear-resistant and corrosion-resistant composite coating in the embodiment of the present application includes a full-gloss nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer. The raw materials forming the decorative chromium composite sterilization layer include bactericidal ammonium salts, so that the decorative chromium composite sterilization layer It has a bactericidal effect, and the decorative chromium composite bactericidal layer forms a nano-needle structure, which further enhances the bactericidal effect of the wear-resistant and corrosion-resistant composite coating; in addition, the raw materials for forming the microporous nickel layer can also include bactericidal ammonium salts and microporous nickel. The layer can also form a nano-needle structure, which can not only further enhance the sterilization effect of the sterilization, wear-resistant and corrosion-resistant composite coating, but also when the surface decorative chromium composite sterilization layer is worn, the inner microporous nickel layer also has a sterilization effect, and the entire product The sterilization effect is better and longer-lasting.

In addition, the sterilization, wear-resistant and corrosion-resistant composite coatings of the embodiments of the present application can obtain better sterilization effects only through a single electroplating method, without the need to spray composite materials containing Ag ⁺ and Cu ²⁺ or prepare Ag ⁺ / Cu ²⁺ composite material; in short, the sterilization, wear-resistant and corrosion-resistant composite coating of the embodiment of the present application is low in cost, simple to prepare, has rapid and broad-spectrum sterilization effect, and the sterilization effect can be directly displayed through high-definition display technology. In addition, the sterilizing, wear-resistant and corrosion-resistant composite coating in the embodiment of the present application also has the advantage of high corrosion resistance.

Additional features and advantages of the application will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the application. Other advantages of the application can be realized and obtained by the solutions described in the specification and drawings.

Description of drawings

The drawings are used to provide an understanding of the technical solution of the present application and constitute a part of the specification. They are used to explain the technical solution of the present application together with the embodiments of the present application and do not constitute a limitation of the technical solution of the present application.

Figure 1 is a schematic front structural view of the sterilization, wear-resistant and corrosion-resistant composite coating according to the embodiment of the present application;

Figure 2 is a scanning electron microscope image of the microporous nickel layer of the sterilization, wear-resistant and corrosion-resistant composite coating in Example 1 of the present application;

Figure 3 is an atomic force microscope (AFM) image of the surface morphology of the sterilization, wear-resistant and corrosion-resistant composite coating of the sterilization, wear-resistant and corrosion-resistant product in Example 1 of the present application;

Figure 4 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 1 of the present application;

Figure 5 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 2 of the present application;

Figure 6 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 3 of the present application;

Figure 7 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 4 of the present application;

Figure 8 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 5 of the present application;

Figure 9 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 6 of the present application;

Figure 10 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 7 of the present application;

Figure 11 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 8 of the present application;

Figure 12 is an atomic force microscope (AFM) image of the surface morphology of the semi-finished product obtained in step (3) of Example 1 of the present application;

Figure 13 is an experimental operation diagram of the product according to the embodiment of the present application being rubbed 20,000 times;

Figure 14 is a real-time visual microscope image of the sterilization, wear-resistant and corrosion-resistant product in Example 1 of the present application after being rubbed 20,000 times. The left image is a visual microscope image of the bacteria after they were left standing on the sample surface for 2 minutes and the timing started (1s). The right image is the bacteria. The visual microscope picture at the 2nd second after the sample surface was left standing for 2 minutes;

Figure 15 is a real-time visual microscope image of the highly corrosion-resistant product in Comparative Example 5 of the present application after being rubbed 20,000 times. The upper image is a visual microscope image of the timing (1s) after the bacteria rested on the sample surface for 2 minutes. The lower image shows the time since the bacteria rested on the sample surface. The visual microscope picture at the 2nd second after placing the sample on the surface for 2 minutes.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present application more clear, the embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

The embodiment of the present application provides a sterilization, wear-resistant, and corrosion-resistant composite coating. As shown in Figure 1, the sterilization, wear-resistant, and corrosion-resistant composite coating includes: a full-gloss nickel layer 10, a microporous nickel layer 20, and a decorative chromium composite sterilization layer. 30; The all-gloss nickel layer 10 is disposed on the base material 100 that requires sterilization, anti-wear or corrosion resistance, and the microporous nickel layer 20 is disposed on the side of the all-gloss nickel layer 10 away from the base material 100 On the surface, the microporous nickel layer 20 has micropores 21, and the decorative chromium composite sterilization layer 30 is provided on the surface of the microporous nickel layer 20 on the side away from the substrate 100;

The decorative chromium composite bactericidal layer 30 and the microporous nickel layer 20 have nanoneedle structures 31 and 22 respectively, and are respectively composed of a first composite raw material containing a first bactericidal ammonium salt and a second composite raw material containing a second bactericidal ammonium salt. Formed, and the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-100g/L, and the concentration of the second bactericidal ammonium salt in the second composite raw material is 50-100g/L .

The sterilization, wear-resistant and corrosion-resistant composite coating in the embodiment of the present application includes a full-gloss nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer. The raw materials forming the decorative chromium composite sterilization layer include bactericidal ammonium salts, so that the decorative chromium composite sterilization layer It has a bactericidal effect, and the decorative chromium composite bactericidal layer forms a nano-needle structure, which further enhances the bactericidal effect of the wear-resistant and corrosion-resistant composite coating; in addition, the raw materials for forming the microporous nickel layer can also include bactericidal ammonium salts and microporous nickel. The layer can also form a nano-needle structure, which can not only further enhance the sterilization effect of the sterilization, wear-resistant and corrosion-resistant composite coating, but also when the surface decorative chromium composite sterilization layer is worn, the inner microporous nickel layer also has a sterilization effect, and the entire product The sterilization effect is better and longer-lasting.

In addition, the sterilization, wear-resistant and corrosion-resistant composite coatings of the embodiments of the present application can obtain better sterilization effects only through a single electroplating method, without the need to spray composite materials containing Ag ⁺ and Cu ²⁺ or prepare Ag ⁺ / Cu ²⁺ composite material; in short, the sterilization, wear-resistant and corrosion-resistant composite coating of the embodiment of the present application is low in cost, simple to prepare, has rapid and broad-spectrum sterilization effect, and the sterilization effect can be directly displayed through high-definition display technology. In addition, the sterilizing, wear-resistant and corrosion-resistant composite coating in the embodiment of the present application also has the advantage of high corrosion resistance.

In the sterilization, wear-resistant and corrosion-resistant composite coating in the embodiment of the present application, a potential difference can be formed between the full-gloss nickel layer and the microporous nickel layer, thereby achieving high corrosion resistance.

In the embodiments of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt can each be independently selected from any one of alkyl quaternary ammonium iodide salts and alkyl aromatic hydrocarbon quaternary ammonium iodide salts, or Various.

In the embodiments of the present application, the carbon chain length of the alkyl group in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbon quaternary ammonium iodide salt may be 12-18.

In the embodiments of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt can each be independently selected from dodecyldimethylbenzylammonium iodide and dodecyltrimethyliodide. Ammonium iodide, tetradecyldimethylbenzylammonium iodide, tetradecyltrimethylammonium iodide, cetyldimethylbenzylammonium iodide, cetyltrimethylammonium iodide , any one or more of octadecyldimethylbenzylammonium iodide and octadecyltrimethylammonium iodide.

In the embodiment of the present application, the raw materials of the decorative chromium composite sterilization layer may include: first quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystals with a concentration of 10-20g/L, It is 1-5mL/L sulfuric acid, solid chromic acid with a concentration of 200-450g/L, and decorative chromium additive CR 842 with a concentration of 5-15mL/L.

In the embodiment of the present application, the raw materials of the microporous nickel layer may include: second quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystal with a concentration of 10-20g/L, and 150-400g/L nickel sulfate, 60-120g/L nickel chloride, 30-80g/L boric acid, 0.1-0.5mL/L bright nickel ZD-220, 5- Liquid additive MPS 800 at 80mL/L and liquid additive Mark 904 at a concentration of 0.1-2mL/L.

In the embodiment of the present application, the raw materials of the all-gloss nickel layer may include: nickel sulfate with a concentration of 300-500g/L, nickel chloride with a concentration of 30-80g/L, nickel chloride with a concentration of 30-80g/L. Boric acid, cylinder opening agent NIB-90 with a concentration of 5-10mL/L, main gloss agent NIB-90 with a concentration of 1-3mL/L, and wetting agent Ni-66B with a concentration of 1-5mL/L.

In the description of this application, the concentration (g/L, mL/L) of a certain raw material of the all-gloss nickel layer, the microporous nickel layer or the decorative chromium composite sterilization layer refers to the concentration of the raw material in the all-gloss nickel layer, the microporous nickel layer, and the microporous nickel composite sterilization layer. The concentration in the mixture composed of all raw materials of the porous nickel layer or the decorative chromium composite sterilization layer. Among them, the concentration of sulfuric acid is 1-5mL/L. It means that in the electroplating raw material of 1L decorative chromium composite sterilization layer, the amount of sulfuric acid equivalent to 98 mass% is 1-5mL. Of course, other mass fractions of sulfuric acid can also be used as raw materials. , just need to convert the dosage according to the dosage of pure sulfuric acid.

In the embodiment of the present application, the decorative chromium composite sterilization layer may be silver-white, so the sterilization high-corrosion-resistant composite coating may be silver-white.

In embodiments of the present application, the thickness of the full-gloss nickel layer may be 20-50 μm, the thickness of the microporous nickel layer may be 20-50 μm, and the thickness of the decorative chromium composite sterilization layer may be >0.5 μm.

The embodiments of the present application also provide a method for preparing the sterilization, wear-resistant and corrosion-resistant composite coating as described above, including:

(1) Pre-treatment of the substrate: including polishing and cleaning;

(2) Electroplating the full-gloss nickel layer on the surface of the pre-treated base material;

(3) Electroplating the microporous nickel layer on the surface of the full-gloss nickel layer;

(4) Electroplating the decorative chromium composite germicidal layer on the surface of the microporous nickel layer.

In the embodiment of the present application, the cleaning process in the pretreatment described in step (1) may include fine cleaning processes such as wax removal, oil removal, electrolysis, and pure water cleaning.

In the embodiment of the present application, the conditions for electroplating the all-gloss nickel layer in step (2) may include: temperature is 40-60°C, cathode current density is 3.5-10A/dm ² , and electroplating time is 600-2400s.

In the embodiment of the present application, the conditions for electroplating the microporous nickel layer in step (3) may include: temperature is 40-60°C, cathode current density is 3-8A/dm ² , and electroplating time is 600-1800s.

In the embodiment of the present application, the conditions for electroplating the decorative chromium composite sterilization layer in step (4) may include: the temperature is 40-60°C, the cathode current density is 5-20A/dm ² , and the electroplating time is 300-900s. .

The embodiment of the present application also provides a sterilizing, wear-resistant and corrosion-resistant product, including a substrate and the sterilizing, wear-resistant and corrosion-resistant composite coating as described above.

In embodiments of the present application, the substrate may be a metal substrate or a plastic substrate. The metal substrate may be aluminum alloy, copper alloy, zinc alloy, magnesium alloy, stainless steel, alloy steel, etc., and the plastic substrate Materials such as ABS, etc.

In the embodiment of the present application, the sterilization wear-resistant and corrosion-resistant products can be sterilization products for kitchens or bathrooms, such as sinks, knives, faucets, wash basins, pendants, showers, shower room handles, and shower room frames. wait.

The cylinder opening agent NIB-90, main gloss agent NIB-90, and wetting agent Ni-66B used in the following examples and comparative examples were purchased from Xiamen Huahui New Material Technology Co., Ltd., bright nickel ZD-220, and liquid additives MPS 800, liquid additive Mark 904, and decorative chromium additive CR 842 were purchased from Atotech (China) Chemical Co., Ltd. (ATOTECH), and cetyltrimethylammonium iodide was purchased from Jinjinle Chemical Co., Ltd.

Example 1

(1) Pre-treatment of electroplating

Perform polishing treatment, fine cleaning (including wax removal, oil removal, electrolysis, pure water cleaning), zinc immersion, copper pre-plating and other pre-processing on the magnesium alloy substrate;

(2) Electroplating a full-gloss nickel layer on the surface of the pre-treated substrate

The electroplating solution to form the all-gloss nickel layer includes: nickel sulfate with a concentration of 350g/L, nickel chloride with a concentration of 40g/L, boric acid with a concentration of 45g/L, cylinder opening agent NIB-90 with a concentration of 9mL/L, Main gloss agent NIB-90 with a concentration of 1.8mL/L, wetting agent Ni-66B with a concentration of 2.5mL/L;

The electroplating process conditions include: temperature of 55°C, cathode current density of 6A/dm ² , and electroplating time of 1200s;

(3) Electroplating a microporous nickel layer on the surface of the all-gloss nickel layer

The electroplating solution to form the microporous nickel layer includes: cetyltrimethylammonium iodide with a concentration of 50g/L, anhydrous citric acid crystals with a concentration of 10g/L, nickel sulfate with a concentration of 300g/L, and nickel sulfate with a concentration of 10g/L. 80g/L nickel chloride, 45g/L boric acid, 0.2mL/L bright nickel ZD-220, 45mL/L liquid additive MPS 800, 0.4mL/L liquid additive Mark 904;

The electroplating process conditions include: temperature of 55°C, cathode current density of 7A/dm ² , and electroplating time of 1200s;

(4) Electroplating a decorative chromium composite bactericidal layer on the surface of the microporous nickel layer

The electroplating solution to form the decorative chromium composite sterilization layer includes: cetyltrimethylammonium iodide with a concentration of 50g/L, anhydrous citric acid crystals with a concentration of 10g/L, sulfuric acid with a concentration of 2.5mL/L, and It is 350g/L solid chromic acid and decorative chromium additive CR 842 with a concentration of 12mL/L;

The electroplating process conditions include: the temperature is 55°C, the cathode current density is 12A/dm ² , and the electroplating time is 900s.

Example 2

The preparation method is basically the same as in Example 1, except that in the electroplating solution used for electroplating the microporous nickel layer in step (3) and in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4), sixteen The concentration of alkyltrimethylammonium iodide is 100g/L.

Comparative example 1

The preparation method is basically the same as in Example 1, except that in the electroplating solution used for electroplating the microporous nickel layer in step (3) and in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4), sixteen The concentration of alkyltrimethylammonium iodide is 150g/L.

Comparative example 2

The preparation method is basically the same as in Example 1, except that in the electroplating solution used for electroplating the microporous nickel layer in step (3) and in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4), sixteen The concentration of alkyltrimethylammonium iodide is 0g/L.

Comparative example 3

The preparation method is basically the same as that in Example 1, except that in the electroplating solution used to electroplat the microporous nickel layer in step (3), the concentration of anhydrous crystalline organic citric acid is 0g/L.

Comparative example 4

The preparation method is basically the same as that in Example 1, except that in the electroplating solution used for electroplating the microporous nickel layer in step (3), the concentration of cetyltrimethylammonium iodide is 0 g/L.

Comparative example 5

The preparation method is basically the same as in Example 1, except that in the electroplating solution used for electroplating the microporous nickel layer in step (3), the concentration of anhydrous crystalline organic citric acid is 0g/L, and the concentration of cetyltrimethyl The concentration of ammonium iodide is 0g/L.

Comparative example 6

The preparation method is basically the same as in Example 1, except that the concentration of anhydrous crystalline organic citric acid in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4) is 0g/L.

Comparative example 7

The preparation method is basically the same as that in Example 1, except that the concentration of cetyltrimethylammonium iodide in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4) is 0 g/L.

Comparative example 8

The preparation method is basically the same as that in Example 1, except that in the electroplating solution used for electroplating the decorative chromium composite sterilization layer in step (4), the concentration of anhydrous crystalline organic citric acid is 0g/L, and the concentration of cetyl triacetyl The concentration of methylammonium iodide is 0g/L.

The Phenom field emission scanning electron microscope Pharos G2 (resolution 1.8nm@15Kv) was used to observe the formation of the microporous nickel layer in step (3) of the embodiment of the present application. Figure 2 is a scanning electron microscope image of the microporous nickel layer of the sterilization, wear-resistant and corrosion-resistant composite coating in Example 1 of the present application (the morphology of the microporous nickel layer in Example 2 and Comparative Examples 1-8 is similar to Figure 2). It can be seen that a microporous nickel layer with micropores is formed on the surface of the coating in Example 1.

Figure 3 is an atomic force microscope (AFM) picture of the surface morphology of the sterilization, wear-resistant and corrosion-resistant composite coating of the sterilization, wear-resistant and corrosion-resistant product in Example 1 of the present application; Figure 4 is the surface morphology of the composite coating of the product in Comparative Example 1 of the present application. Figure 5 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 2 of the present application; Figure 6 is the surface morphology of the composite coating of the product of Comparative Example 3 of the present application. Microscope (AFM) picture; Figure 7 is an atomic force microscope (AFM) picture of the surface morphology of the composite coating of the product of Comparative Example 4 of the present application. Figure 8 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 5 of the present application. Figure 9 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 6 of the present application. Figure 10 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 7 of the present application. Figure 11 is an atomic force microscope (AFM) image of the surface morphology of the composite coating of the product of Comparative Example 8 of the present application. The surface morphology atomic force microscope (AFM) pictures here are all based on the surface on the side away from the substrate as the test surface, that is, the decorative chromium composite layer formed in step (4).

It can be seen from Figures 3 to 11 that the decorative chromium composite layer of the sterilization, wear-resistant and corrosion-resistant composite coatings of the products of Example 1 and Comparative Examples 3-5 of the present application does form a nanoneedle structure, in which the decorative chromium of Example 1 The height of the nano-needles of the composite sterilization layer is 20-50nm, the nano-needles appear to be agglomerated, and there is a certain distance between each agglomerated nano-needles; in addition, the decorative chromium composite sterilization of the sterilization, wear-resistant and corrosion-resistant composite coating in Example 2 of the present application The layers also form nanoneedle structures. However, the decorative chromium composite layer of the composite coatings of Comparative Examples 1-2 and 6-8 did not form a nanoneedle structure, indicating that the formation of the nanoneedle structure requires an appropriate concentration of quaternary ammonium salts such as cetyltrimethylammonium iodide. and the participation of anhydrous citric acid crystallization.

Figure 12 is an atomic force microscope (AFM) image of the surface morphology of the semi-finished product obtained in step (3) of Example 1 of the present application. The surface morphology atomic force microscope (AFM) picture here uses the microporous nickel layer as the test surface. It can be seen that the microporous nickel layer in Example 1 of the present application indeed forms a nanoneedle structure.

According to Chinese national standard GB/T 6461-2002, the corrosion resistance of the products of the examples and comparative examples was tested through the CASS salt spray test method. The test results are shown in Table 1.

According to the Chinese national standard GB/T21510-2008, the antibacterial properties of the products of the Examples and Comparative Examples were tested (using E. coli test). The results are shown in Table 1.

The products of the examples and comparative examples were rubbed 20,000 times in accordance with the Chinese national standard GB/T 9266-2009 (Figure 13 is an experimental operation diagram of the example product being rubbed 20,000 times), and in accordance with the Chinese national standard GB/T 21510-2008 Appendix C, place E. coli on the surface away from the base material of the products of Examples and Comparative Examples before and after rubbing (for the products of Examples, placed on the surface of the decorative chromium composite sterilization layer), let it stand for 2 minutes, and then use Double transmission biological microscope was used to observe the status of bacteria on its surface.

It was observed that before rubbing 20,000 times, the bacteria on the surface of the sterilization products of the examples were stationary; however, the bacteria on the surfaces of the products of Comparative Examples 1-2 and 6-8 were always flowing, and the number of flowing bacteria was almost unchanged. After rubbing 20,000 times, the bacteria on the surface of the sterilization product of Example 1-2 are still stationary; but the bacteria on the surface of the products of Comparative Examples 1-2 and 6-8 have been flowing, and the number of flowing bacteria is almost unchanged. Bacteria on the surface of products with proportions 3-5 also began to flow. This is because the decorative chromium composite sterilization layer on the surface of the product has been worn away, affecting the sterilization effect. Among them, Figure 14 is a real-time visual microscope image of the sterilization, wear-resistant and corrosion-resistant product in Example 1 of the present application after being rubbed 20,000 times. The left image is a visual microscope image of bacteria starting to time (1st s) after standing on the sample surface for 2 minutes. The right image is Visual microscopy of the bacteria after they were left on the sample surface for 2 minutes and started timing at 2 s. The observed microscopic picture 2 s after starting to time is the same as the state at the beginning of timing. The bacteria are stationary, indicating that the bacteria have been killed. Figure 15 is a real-time visual microscopy image of the sterilization product in Comparative Example 5 of the present application after being rubbed 20,000 times. The upper image is a visual microscopy image of the bacteria on the surface of the sample after 2 minutes and the timing starts (1s). The lower image is the bacteria on the surface of the sample. The visual microscope picture at the 2nd second after starting the timing after 2 minutes. In both the upper and lower pictures, there are more bacteria flowing (it can be seen that the position of the bacteria in the circle has changed), and the number of flowing bacteria is almost unchanged.

Table 1

It can be seen from the examples and comparative examples that the products containing the microporous nickel layer in the examples and comparative examples of the present application have high corrosion resistance, and the CASS salt spray effect of the product can reach the 48h level 9 level.

Comparing Example 1-2 with Comparative Example 1-2, it can be seen that when the concentration of cetyltrimethylammonium iodide is 50-100g/L, the sterilizing composite coating of the product can form a nanoneedle structure, and the product has Better sterilization effect. When the concentration of cetyltrimethylammonium iodide increased to 150g/L, the product's bactericidal composite coating did not form a nanoneedle structure, and the product's sterilization of E. coli was reduced to 84.2%.

Comparing Examples 1-2 and 3-5, it can be seen that compared with the double-plated layer (microporous nickel layer and decorative chromium composite sterilization layer), both of which have a nano-needle structure, the sterilization wear-resistant and corrosion-resistant composite coating, the single plating layer ( Decorative chromium composite bactericidal layer) The bactericidal, wear-resistant and corrosion-resistant composite coating with nano-needle structure has a significantly reduced antibacterial rate after 20,000 times of friction, indicating that the bactericidal, wear-resistant and corrosion-resistant composite coating with nano-needle structure in both coatings has more durable sterilization Effect.

In short, the sterilizing effect of the sterilizing, wear-resistant, and corrosion-resistant composite coatings in the embodiments of the present application can be directly displayed using dual-transmission high-definition display technology, and the sterilizing effect of the sterilizing, wear-resistant, and corrosion-resistant composite coatings both having nanoneedle structures is significantly better than The single coating has a sterilizing, wear-resistant and corrosion-resistant composite coating with a nano-needle structure.

Although the embodiments disclosed in the present application are as above, the described contents are only used to facilitate the understanding of the present application and are not intended to limit the present application. Anyone skilled in the field to which this application belongs can make any modifications and changes in the form and details of the implementation without departing from the spirit and scope disclosed in this application. However, the scope of patent protection of this application still must The scope is defined by the appended claims.

Claims (10)

1. A sterilizing, wear-resistant and corrosion-resistant composite coating, characterized in that it includes: an all-gloss nickel layer, a microporous nickel layer, and a decorative chromium composite sterilization layer; the all-gloss nickel layer is located on a sterilizing, wear-resistant or corrosion-resistant surface. On the required substrate, the microporous nickel layer is arranged on the surface of the full-gloss nickel layer away from the substrate, and the decorative chromium composite sterilization layer is arranged on the surface of the microporous nickel layer away from the substrate. On the surface of the side; the decorative chromium composite sterilization layer and the microporous nickel layer both have a nanoneedle structure; Wherein, the raw materials of the decorative chromium composite sterilization layer include: cetyltrimethylammonium iodide with a concentration of 50-100g/L, anhydrous citric acid crystal with a concentration of 10-20g/L, and anhydrous citric acid crystal with a concentration of 1-100g/L. 5mL/L sulfuric acid, solid chromic acid with a concentration of 200-450g/L, decorative chromium additive CR 842 with a concentration of 5-15mL/L; The raw materials of the microporous nickel layer include: cetyltrimethylammonium iodide with a concentration of 50-100g/L, anhydrous citric acid crystal with a concentration of 10-20g/L, and anhydrous citric acid crystal with a concentration of 150-400g/L. Nickel sulfate, nickel chloride with a concentration of 60-120g/L, boric acid with a concentration of 30-80g/L, bright nickel ZD-220 with a concentration of 0.1-0.5mL/L, and liquid with a concentration of 5-80mL/L Additive MPS800, liquid additive Mark 904 with a concentration of 0.1-2mL/L; The thickness of the all-gloss nickel layer is 20-50 μm, the thickness of the microporous nickel layer is 20-50 μm, and the thickness of the decorative chromium composite sterilization layer is >0.5 μm. 2. The sterilizing, wear-resistant and corrosion-resistant composite coating according to claim 1, wherein the raw materials of the all-gloss nickel layer include: nickel sulfate with a concentration of 300-500g/L, and chloride with a concentration of 30-80g/L. Nickel, boric acid with a concentration of 30-80g/L, cylinder opening agent NIB-90 with a concentration of 5-10mL/L, main gloss agent NIB-90 with a concentration of 1-3mL/L, NIB-90 with a concentration of 1-5mL/L Wetting agent Ni-66B. 3. The sterilizing, wear-resistant and corrosion-resistant composite coating according to claim 1, wherein the sterilizing, wear-resistant and corrosion-resistant composite coating is silvery white. 4. A method for preparing a sterilizing, wear-resistant and corrosion-resistant composite coating according to any one of claims 1 to 3, characterized in that it includes: (1) Pre-treatment of the substrate: including polishing and cleaning; (2) Electroplating the full-gloss nickel layer on the surface of the pre-treated base material; (3) Electroplating the microporous nickel layer on the surface of the full-gloss nickel layer; (4) Electroplating the decorative chromium composite germicidal layer on the surface of the microporous nickel layer. 5. The preparation method according to claim 4, wherein the conditions for electroplating the all-optical nickel layer in step (2) include: temperature is 40-60°C, cathode current density is 3.5-10A/dm ² , electroplating time for 600-2400s. 6. The preparation method according to claim 4, wherein the conditions for electroplating the microporous nickel layer in step (3) include: a temperature of 40-60°C, a cathode current density of 3-8A/ ^dm2 , and an electroplating time of for 600-1800s. 7. The preparation method according to claim 4, wherein the conditions for electroplating the decorative chromium composite sterilization layer in step (4) include: a temperature of 40-60°C, a cathode current density of 5-20A/ ^dm2 , and electroplating The time is 300-900s. 8. A sterilizing, wear-resistant and corrosion-resistant product, characterized by comprising a base material and the sterilizing, wear-resistant and corrosion-resistant composite coating according to any one of claims 1 to 3. 9. The sterilization, wear-resistant and corrosion-resistant product according to claim 8, wherein the base material is a metal base material or a plastic base material. 10. The sterilizing wear-resistant and corrosion-resistant product according to claim 8 or 9, wherein the sterilizing wear-resistant and corrosion-resistant product is a sterilizing product for kitchen or bathroom use.