CN114540893A - Bactericidal silvery white composite coating, preparation method thereof and silvery white bactericidal product - Google Patents

Bactericidal silvery white composite coating, preparation method thereof and silvery white bactericidal product Download PDF

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CN114540893A
CN114540893A CN202210194643.9A CN202210194643A CN114540893A CN 114540893 A CN114540893 A CN 114540893A CN 202210194643 A CN202210194643 A CN 202210194643A CN 114540893 A CN114540893 A CN 114540893A
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white
bactericidal
concentration
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composite
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林孝发
林孝山
刘小龙
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Jomoo Kitchen and Bath Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation

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  • Automation & Control Theory (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

A bactericidal silvery-white composite coating, a preparation method thereof and a silvery-white bactericidal product are provided, wherein the bactericidal silvery-white composite coating comprises: a bright nickel layer, a high-sulfur nickel layer and a silver-white chromium composite sterilization layer; the bright nickel layer is arranged on a base material with a sterilization requirement; the high-sulfur nickel layer is arranged on the surface of one side, far away from the base material, of the bright nickel layer; the silver-white-chromium composite sterilization layer is arranged on the surface of the high-sulfur nickel layer, which is far away from one side of the base material; the silver-white-chromium composite sterilization layer has a nano needle structure and is formed by composite raw materials containing bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw materials is 50-100 g/L. The bactericidal silvery-white composite coating and the silvery-white bactericidal product can be directly prepared by an electroplating method without spraying nano Ag+、Cu2+The antibacterial material has good broad-spectrum sterilization effect, and the product has high glossiness.

Description

Bactericidal silvery white composite coating, preparation method thereof and silvery white bactericidal product
Technical Field
The application relates to but is not limited to the technical field of sterilization, in particular to a sterilization silvery white composite coating, a preparation method thereof and a silvery white sterilization product.
Background
The new coronary pneumonia epidemic situation arouses high attention of various countries around the world to large health industries, in particular to healthy kitchen and bathroom household products. The hardware products (such as shower, faucet, etc.) in kitchen and bathroom are essential substances in people's life, and the outermost surface material is usually silver-white chromium with stable electroplating chemical property (high corrosion resistance and good self-repairing capability) and soft color.
However, chromium products prepared by electroplating alone cannot achieve the sterilization function temporarily, and usually a layer containing nano Ag needs to be sprayed on the surface of the chromium products+Or preparing Ag-containing materials by PVD technique+/Cu2+Composite materials of (2), but Ag+/Cu2+Is easy to be absorbed by pores of human skin, can affect and damage organs of human body such as immune system, nervous system, reproductive system and the like, and has higher cost when the spraying method or the PVD method is adopted for coating. Some ammonium salts can be used as antibacterial materials, however, ammonium salt products used in the market are basically liquid, act on the surface of an object in a spraying mode, and after the ammonium salt liquid is dried, the antibacterial effect is ineffective, and the antibacterial service life is short. In addition, most of the sterilization effects of kitchen and bathroom products on the market are described by a detection report of a third-party organization, so that visualization is difficult to realize.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the present application.
The application provides a bactericidal silvery-white composite coating, a preparation method thereof and a silvery-white bactericidal product, wherein the bactericidal silvery-white composite coating can be prepared by an electroplating method independently without spraying nano Ag+、 Cu2+The sterilization material has good broad-spectrum sterilization effect and can realize the visualization of the sterilization effect.
The application provides a silver-white composite coating disinfects includes: a bright nickel layer, a high-sulfur nickel layer and a silver-white chromium composite sterilization layer; the bright nickel layer is arranged on a base material with a sterilization requirement; the high-sulfur nickel layer is arranged on the surface of one side, far away from the base material, of the bright nickel layer; the silver-white-chromium composite sterilization layer is arranged on the surface of the high-sulfur nickel layer, which is far away from one side of the base material; the silver-white-chromium composite sterilization layer has a nano needle structure and is formed by composite raw materials containing bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw materials is 50-100 g/L.
In an embodiment of the present application, the bactericidal ammonium salt may be selected from any one or more of alkyl quaternary ammonium iodide and alkyl aromatic alkyl quaternary ammonium iodide.
In embodiments herein, the alkyl groups in the alkyl quaternary ammonium iodate and the alkyl aromatic hydrocarbyl quaternary ammonium iodate can have a carbon chain length ranging from 12 to 18.
In an embodiment of the present application, the bactericidal ammonium salt may be selected from any one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide.
In an embodiment of the present application, the raw materials of the silver-white-chromium composite bactericidal layer may include: quaternary ammonium iodides with the concentration of 50-100g/L, anhydrous citric acid crystals with the concentration of 10-20g/L, sulfuric acid with the concentration of 0.5-3mL/L, solid chromic acid with the concentration of 250-400g/L and decorative chromium additive CR 842 with the concentration of 5-10 mL/L.
In an embodiment of the present application, the raw material of the high-sulfur nickel layer may include: 450g/L nickel sulfate with the concentration of 350-450g/L, 50-100g/L nickel chloride, 40-60g/L boric acid and 2-4mL/L high-sulfur nickel HAS 90.
In an embodiment of the present application, the raw material of the bright nickel layer may include: the nickel sulfate with the concentration of 350-450g/L, the nickel chloride with the concentration of 60-100g/L, the boric acid with the concentration of 50-70g/L, the bright nickel NF brightening agent with the concentration of 0.5-3mL/L, the nickel 45(4X) softening agent with the concentration of 8-15mL/L, the nickel SA-1 auxiliary agent with the concentration of 5-10mL/L and the nickel Y19 wetting agent with the concentration of 2-5 mL/L.
The application also provides a preparation method of the bactericidal silvery-white composite plating layer, which comprises the following steps:
(1) pretreating a base material: polishing and cleaning;
(2) electroplating the bright nickel layer on the surface of the pretreated substrate;
(3) electroplating the high-sulfur nickel layer on the surface of the bright nickel layer;
(4) and electroplating the silver-white-chromium composite sterilization layer on the surface of the high-sulfur nickel layer.
In an embodiment of the present application, the conditions for electroplating the bright nickel layer in step (2) may include: the temperature is 50-60 ℃, and the cathode current density is 5-10A/dm2The plating time is 900-.
In an embodiment of the present application, the conditions for electroplating the high-sulfur nickel layer in step (3) may include: the temperature is 45-55 deg.C, voltage is 5-10V, and cathode current density is 5-10A/dm2The plating time is 900-.
In an embodiment of the present application, the condition for electroplating the silver-white-chromium composite bactericidal layer in the step (4) may include: the temperature is 50-60 ℃, and the cathode current density is 5-15A/dm2The plating time is 300-900 s.
The application also provides a silvery white sterilizing product, which comprises a base material and the sterilizing silvery white composite coating.
In embodiments of the present application, the substrate may be a metal substrate or a plastic substrate;
in an embodiment of the present application, the silvery white bactericidal product may be a bactericidal product for kitchens or toilets.
The bactericidal silvery-white composite coating provided by the embodiment of the application can be prepared only by a single electroplating method without spraying nano Ag+、Cu2+The composite material or the PVD technology is used for preparing the Ag-containing material+/Cu2+The composite material has a sterilization effect. Moreover, the silver-white chromium composite sterilization layer of the sterilization silver-white composite plating layer is silvery white, so that the sterilization silver-white composite plating layer can show silvery whiteThe color is soft and beautiful; in addition, the silver-white chromium composite sterilization layer is formed by composite raw materials containing bactericidal ammonium salt and has a nanoneedle structure, so that the bactericidal silver-white composite plating layer has good quick and broad-spectrum sterilization effects, and the sterilization effects can be directly displayed through a high-definition display technology. In addition, the bactericidal silvery-white composite plating layer provided by the embodiment of the application also has the advantages of high glossiness and corrosion resistance.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the application. Other advantages of the present application may be realized and attained by the instrumentalities and combinations particularly pointed out in the specification and the drawings.
Drawings
The accompanying drawings are included to provide an understanding of the present disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the examples serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a schematic structural diagram of a bactericidal silvery-white composite coating in an embodiment of the present application;
FIG. 2 is an external view of a silvery white bactericidal product obtained in example 1 of the present application;
FIG. 3 is an Atomic Force Microscope (AFM) image of the surface topography of the silver-white chromium composite bactericidal layer of the silver-white bactericidal product of example 1 of the present application;
FIG. 4 is an Atomic Force Microscope (AFM) image of the surface topography of a silver white chromium composite layer of a silver white product of comparative example 1 of the present application;
FIG. 5 is an Atomic Force Microscope (AFM) image of the surface topography of the Ag-white chromium composite layer of the Ag-white product of comparative example 2 of the present application;
FIG. 6 is an Atomic Force Microscope (AFM) image of the surface topography of a silver white chromium composite layer of a silver white product of comparative example 3 of the present application;
FIG. 7 is an Atomic Force Microscope (AFM) image of the surface topography of a silver white chromium composite layer of a silver white product of comparative example 4 of the present application;
fig. 8 is a real-time visual microscopic image of the silvery white bactericidal product of example 1 of the present application, the left image is a visual microscopic image of the start of timing (1 st s) after the surface of the bacteria-standing sample is set for 2min, and the right image is a visual microscopic image of the start of timing 5 th s after the surface of the bacteria-standing sample is set for 2 min;
fig. 9 is a real-time visual microscopic image of the silver-white product of comparative example 4 of the present application, the upper image is a visual microscopic image of the start of timing (1 st s) after the bacteria have left the surface of the sample for 2min, and the lower image is a visual microscopic image of the start of timing (5 th s) after the bacteria have left the surface of the sample for 2 min.
Detailed Description
To make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The embodiment of the application provides a bactericidal silvery-white composite plating layer, as shown in fig. 1, the bactericidal silvery-white composite plating layer comprises a bright nickel layer 10, a high-sulfur nickel layer 20 and a silvery-white chromium composite bactericidal layer 30; the bright nickel layer 10 is arranged to be positioned on a substrate 100 with sterilization requirements; the high-sulfur nickel layer 20 is arranged on the surface of the bright nickel layer 10 at the side far away from the substrate 100; the silver-white-chromium composite sterilization layer 30 is arranged on the surface of the high-sulfur nickel layer 20 on the side far away from the substrate 100; the silver-white chromium composite bactericidal layer 30 has a nanoneedle structure 31 and is formed by a composite raw material containing bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw material is 50-100 g/L.
In an embodiment of the present application, the bactericidal ammonium salt may be selected from any one or more of alkyl quaternary ammonium iodide and alkyl aromatic alkyl quaternary ammonium iodide.
In embodiments herein, the alkyl groups in the alkyl quaternary ammonium iodate and the alkyl aromatic hydrocarbyl quaternary ammonium iodate can have a carbon chain length ranging from 12 to 18.
In an embodiment of the present application, the bactericidal ammonium salt may be selected from any one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide.
In an embodiment of the present application, the raw materials of the silver-white-chromium composite bactericidal layer may include: quaternary ammonium iodides with the concentration of 50-100g/L, anhydrous citric acid crystals with the concentration of 10-20g/L, sulfuric acid with the concentration of 0.5-3mL/L, solid chromic acid with the concentration of 250-400g/L and decorative chromium additive CR 842 with the concentration of 5-10 mL/L.
In an embodiment of the present application, the raw material of the high-sulfur nickel layer may include: 450g/L nickel sulfate with the concentration of 350-450g/L, 50-100g/L nickel chloride, 40-60g/L boric acid and 2-4mL/L high-sulfur nickel HAS 90.
In an embodiment of the present application, the raw material of the bright nickel layer may include: the nickel sulfate with the concentration of 350-450g/L, the nickel chloride with the concentration of 60-100g/L, the boric acid with the concentration of 50-70g/L, the bright nickel NF brightening agent with the concentration of 0.5-3mL/L, the nickel 45(4X) softening agent with the concentration of 8-15mL/L, the nickel SA-1 auxiliary agent with the concentration of 5-10mL/L and the nickel Y19 wetting agent with the concentration of 2-5 mL/L.
In the description of the present application, the concentration (g/L, mL/L) of a certain raw material of the bright nickel layer, the high-sulfur nickel layer or the silver-white chromium composite bactericidal layer refers to the concentration of the raw material in a mixed solution composed of all the raw materials of the bright nickel layer, the high-sulfur nickel layer or the silver-white chromium composite bactericidal layer. Wherein, the concentration of the sulfuric acid is 0.5-3mL/L, which means that the dosage of the sulfuric acid equivalent to 98 mass percent in the electroplating raw material of the silver white chromium composite sterilization layer is 0.5-3mL, and of course, the sulfuric acid with other mass fractions can be adopted as the raw material, and the dosage can be converted according to the dosage of the pure sulfuric acid.
In the embodiment of the application, the L value of the silver-white-chromium composite sterilization layer is 80 to 90, the a value is-1 to +1, and the b value is-1 to + 1.
In the examples of the present application, the gloss value of the silver-white-chromium composite bactericidal layer is 650 to 660 (high gloss).
The embodiment of the application also provides a preparation method of the bactericidal silvery-white composite plating layer, which comprises the following steps:
(1) pretreating a base material: polishing and cleaning;
(2) electroplating the bright nickel layer on the surface of the pretreated substrate;
(3) electroplating the high-sulfur nickel layer on the surface of the bright nickel layer;
(4) and electroplating the silver-white-chromium composite sterilization layer on the surface of the high-sulfur nickel layer.
In an embodiment of the present application, the cleaning treatment in the pretreatment in step (1) may include a fine cleaning process such as wax removal, oil removal, electrolysis, pure water cleaning, and the like.
In an embodiment of the present application, the conditions for electroplating the bright nickel layer in step (2) may include: the temperature is 50-60 ℃, and the cathode current density is 5-10A/dm2The plating time is 900-.
In an embodiment of the present application, the conditions for electroplating the high-sulfur nickel layer in step (3) may include: the temperature is 45-55 deg.C, the voltage is 5-10V, and the cathode current density is 5-10A/dm2The plating time is 900-.
In an embodiment of the present application, the condition for electroplating the silver-white-chromium composite bactericidal layer in the step (4) may include: the temperature is 50-60 ℃, and the cathode current density is 5-15A/dm2The plating time is 300-900 s.
The bactericidal silvery-white composite coating provided by the embodiment of the application can be prepared only by a single electroplating method without spraying nano Ag+、Cu2+The composite material or the PVD technology is used for preparing the Ag-containing material+/Cu2+The composite material has a sterilization effect. Moreover, the silver-white chromium composite sterilization layer of the sterilization silver-white composite plating layer is silvery white, so that the sterilization silver-white composite plating layer can be silvery white, and is soft in color and luster and attractive in appearance; in addition, the silver-white chromium composite sterilization layer is formed by composite raw materials containing bactericidal ammonium salt and has a nanoneedle structure, so that the bactericidal silver-white composite plating layer has good quick and broad-spectrum sterilization effects, and the sterilization effects can be directly displayed through a high-definition display technology. In addition, the bactericidal silvery white composite plating layer of the embodiment of the applicationAlso has the advantages of high glossiness and corrosion resistance.
The embodiment of the application also provides a silvery white sterilizing product, which comprises a base material and the sterilizing silvery white composite coating.
In embodiments of the present application, the substrate may be a metal substrate, such as an aluminum alloy, a copper alloy, a zinc alloy, a magnesium alloy, stainless steel, alloy steel, or the like, or a plastic substrate, such as ABS plastic, or the like.
In embodiments of the present application, the silvery white bactericidal product may be a bactericidal product for kitchens or toilets, for example, a sink, a cutter, a tap, a wash basin, a shower, a pendant, a shower room handle, a shower room border, etc.
Bright nickel NF brightener, nickel 45(4X) softener, nickel SA-1 adjuvant, nickel Y19 wetting agent, high sulfur nickel HAS 90 solution, decorative chromium additive CR 842, used in the following examples and comparative examples, were purchased from Anmet (China) chemical Co., Ltd. (ATOTECH), and cetyltrimethylammonium iodide was purchased from Kilo-Korea chemical Co., Ltd.
Example 1
(1) Pretreatment before electroplating
Polishing and fine cleaning (including dewaxing, degreasing, electrolyzing and pure water cleaning) the copper alloy substrate;
(2) electroplating bright nickel layer on the surface of the pretreated substrate
The electroplating solution for forming the bright nickel layer comprises: the nickel sulfate solution is prepared from nickel sulfate with the concentration of 400g/L, nickel chloride with the concentration of 80g/L, boric acid with the concentration of 65g/L, bright nickel NF brightener with the concentration of 1mL/L, nickel 45(4X) softener with the concentration of 10mL/L, nickel SA-1 auxiliary agent with the concentration of 8mL/L and nickel Y19 wetting agent with the concentration of 3 mL/L;
the electroplating process conditions comprise: the temperature is 55 ℃, and the cathode current density is 6A/dm2The electroplating time is 1800 s;
(3) electroplating a high-sulfur nickel layer on the surface of the bright nickel layer;
the electroplating solution for forming the high-sulfur nickel layer comprises: 90 of nickel sulfate with the concentration of 380g/L, nickel chloride with the concentration of 70g/L, boric acid with the concentration of 45g/L and high-sulfur nickel HAS with the concentration of 3 mL/L;
the electroplating process conditions comprise: the temperature is 50 ℃, the voltage is 8V, and the cathode current density is 6A/dm2The electroplating time is 1800 s;
(4) electroplating silver, white and chromium composite sterilizing layer on the surface of the high-sulfur nickel layer
The electroplating solution for forming the silver-white-chromium composite sterilization layer comprises: cetyl trimethyl ammonium iodide with the concentration of 50g/L, anhydrous citric acid crystal with the concentration of 10g/L, sulfuric acid with the concentration of 1.5mL/L, solid chromic acid with the concentration of 275g/L and decorative chromium additive CR 842 with the concentration of 8 mL/L;
the electroplating process conditions comprise: the temperature is 55 ℃, and the cathode current density is 15A/dm2The plating time was 600 s.
Example 2
The preparation method is basically the same as that of the example 1, except that: in the electroplating solution adopted by the silver white chromium composite sterilization layer electroplated in the step (4), the concentration of the hexadecyl trimethyl ammonium iodide is 100 g/L.
Comparative example 1
The preparation method is basically the same as that of the example 1, except that: in the electroplating solution adopted by the silver white chromium composite sterilization layer electroplated in the step (4), the concentration of the hexadecyl trimethyl ammonium iodide is 150 g/L.
Comparative example 2
The preparation method is basically the same as that of the example 1, and the difference is only that: in the electroplating solution adopted by the silver white chromium composite sterilization layer electroplated in the step (4), the concentration of anhydrous citric acid crystals is 0 g/L.
Comparative example 3
The preparation method is basically the same as that of the example 1, except that: in the electroplating solution adopted by the silver white chromium composite sterilization layer in the step (4), the concentration of the hexadecyl trimethyl ammonium iodide is 0 g/L.
Comparative example 4
The preparation method is basically the same as that of the example 1, except that: in the electroplating solution adopted by the silver white chromium composite sterilization layer in the step (4), the concentration of the anhydrous crystalline organic citric acid is 0g/L, and the concentration of the hexadecyl trimethyl ammonium iodide is 0 g/L.
Fig. 2 is an appearance diagram of a silvery white sterilizing product obtained in example 1 of the present application (the appearance of the silvery white sterilizing products obtained in example 2 and comparative examples 1 to 4 is substantially identical to that of fig. 2). As can be seen, the silvery white bactericidal product has a silvery white coating with soft color.
FIG. 3 is an Atomic Force Microscope (AFM) image of the surface topography of the silver-white chromium composite bactericidal layer of the silver-white bactericidal product of example 1 of the present application; FIG. 4 is an Atomic Force Microscope (AFM) image of the surface topography of the Ag-white chromium composite layer of the Ag-white product of comparative example 1 of the present application; FIG. 5 is an Atomic Force Microscope (AFM) image of the surface topography of a silver white chromium composite layer of a silver white product of comparative example 2 of the present application; FIG. 6 is an Atomic Force Microscope (AFM) plot of the surface topography of the Ag-white chromium composite layer of the Ag-white product of comparative example 3 of the present application; FIG. 7 is an Atomic Force Microscope (AFM) image of the surface topography of a silver white chromium composite layer of a silver white product of comparative example 4 of the present application.
As can be seen from fig. 3, the silver-white chromium composite bactericidal layer of example 1 of the present application indeed forms a nanoneedle structure, and the height of the nanoneedle is 55-115 nm; in addition, the silver-white chromium composite sterilization layer of the silver-white sterilization product of the embodiment 2 of the application also forms a nano needle structure. However, the silver-white chromium composite layers of comparative examples 1 to 4 did not form a nanoneedle structure, indicating that formation of the nanoneedle structure requires participation of quaternary ammonium salts such as cetyltrimethylammonium iodide and anhydrous citric acid crystals of appropriate concentrations.
The Lab values of the silvery white products of the test examples and comparative examples were measured according to the Chinese national standard GB/T17934.1-1999, in which three different positions were selected for each product to be tested, and the test results are shown in Table 1.
The gloss of the products of the examples and comparative examples was tested according to ISO standard 7668:2010, with three different positions for each product tested, and the results are shown in table 1.
The corrosion resistance of the products of the examples and the comparative examples was tested by the CASS salt spray test method according to the Chinese national standard GB/T6461-2002, and the test results are shown in Table 1.
The antibacterial properties of the products of the examples and comparative examples were tested according to the Chinese national standard GB/T21510-. The results are shown in Table 1.
According to the Chinese national standard GB/T21510-.
The bacteria on the surfaces of the silver white sterilization products of the examples are observed to be still; however, the bacteria on the surface of the silver-white product of the comparative example were always flowing, and the number of flowing bacteria was almost unchanged. Fig. 8 is a real-time visualization microscopic image of the silvery white bactericidal product of example 1 of the present application, the left image is a visualization microscopic image of the bacteria at which timing (1 st s) is started after the surface of the sample is kept still for 2min, the right image is a visualization microscopic image of the bacteria at which timing is started after the surface of the sample is kept still for 2min, and the state observed by the microscopic image after the timing is started for 5s is the same as the state at which timing is started, and the bacteria are all still (only the position observed by the microscope moves), which indicates that the bacteria have been killed. Fig. 9 is a real-time visualization microscopic image of the silver-white product of comparative example 4 of the present application, the upper image is a visualization microscopic image of the start of timing (1 st s) after the surface of the bacteria sample is left for 2min, and the lower image is a visualization microscopic image of the start of timing (5 th s) after the surface of the bacteria sample is left for 2min, wherein the upper image and the lower image both have more bacteria flowing (it can be seen that the bacteria position in the circle at the lower right corner changes under the condition that the observation position of the microscope is unchanged), and the amount of the flowing bacteria hardly changes.
TABLE 1
Figure BDA0003526697670000101
Figure BDA0003526697670000111
Comparing examples 1 and 2 with comparative example 1, it can be seen that when the concentration of cetyltrimethylammonium iodide is 50-100g/L, the silver-white chromium composite bactericidal layer of the silver-white bactericidal product can form a nanoneedle structure, and the silver-white bactericidal product has a good bactericidal effect. When the concentration of the hexadecyl trimethyl ammonium iodide is increased to 150g/L, the silver-white chromium composite layer of the silver-white product does not form a nano needle structure, and the sterilization of the silver-white sterilization product on escherichia coli is reduced to 85.4%.
As can be seen from comparison of examples 1 to 2 with comparative examples 1 to 4, the antibacterial rate of the hexadecyl trimethyl ammonium iodide composite plating layer having a non-nanoneedle structure is significantly reduced compared to the hexadecyl trimethyl ammonium iodide composite plating layer having a nanoneedle structure, which indicates that the nanoneedle structure is very important for the bactericidal effect.
In a word, the bactericidal effect of the bactericidal silvery-white composite coating of the embodiment of the application can be directly displayed by adopting a double-transmission high-definition display technology, and the bactericidal effect of the silvery-white product comprising the silver-white chromium composite bactericidal layer with the nano-needle structure is obviously superior to that of the silver-white product without the nano-needle structure of the comparative example.
Although the embodiments disclosed in the present application are described above, the descriptions are only for the convenience of understanding the present application, and are not intended to limit the present application. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the appended claims.

Claims (10)

1. A bactericidal silvery-white composite coating, comprising: a bright nickel layer, a high-sulfur nickel layer and a silver-white chromium composite sterilization layer; the bright nickel layer is arranged on a base material with a sterilization requirement; the high-sulfur nickel layer is arranged on the surface of one side, far away from the base material, of the bright nickel layer; the silver-white-chromium composite sterilization layer is arranged on the surface of the high-sulfur nickel layer, which is far away from one side of the base material; the silver-white-chromium composite sterilization layer has a nano needle structure and is formed by composite raw materials containing bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw materials is 50-100 g/L.
2. The bactericidal silvery white composite coating of claim 1, wherein the bactericidal ammonium salt is selected from any one or more of alkyl quaternary ammonium iodide and alkyl aromatic alkyl quaternary ammonium iodide;
optionally, the alkyl groups in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbyl quaternary ammonium iodide salt have a carbon chain length of 12 to 18.
3. The biocidal white composite coating of claim 2 wherein said biocidal ammonium salt is selected from any one or more of dodecyl dimethyl benzyl ammonium iodide, dodecyl trimethyl ammonium iodide, tetradecyl dimethyl benzyl ammonium iodide, tetradecyl trimethyl ammonium iodide, hexadecyl dimethyl benzyl ammonium iodide, hexadecyl trimethyl ammonium iodide, octadecyl dimethyl benzyl ammonium iodide and octadecyl trimethyl ammonium iodide.
4. The bactericidal silvery white composite coating of any one of claims 1 to 3, wherein the raw materials of the silvery white chromium composite bactericidal layer comprise: quaternary ammonium iodides with the concentration of 50-100g/L, anhydrous citric acid crystals with the concentration of 10-20g/L, sulfuric acid with the concentration of 0.5-3mL/L, solid chromic acid with the concentration of 250-400g/L and decorative chromium additive CR 842 with the concentration of 5-10 mL/L.
5. The bactericidal silvery-white composite coating of any one of claims 1 to 3, wherein the raw material of the high-sulfur nickel layer comprises: 450g/L nickel sulfate with the concentration of 350-450g/L, 50-100g/L nickel chloride, 40-60g/L boric acid and 2-4mL/L high-sulfur nickel HAS 90.
6. The bactericidal silvery white composite coating of any one of claims 1 to 3, wherein the bright nickel layer comprises the following raw materials: the nickel sulfate with the concentration of 350-450g/L, the nickel chloride with the concentration of 60-100g/L, the boric acid with the concentration of 50-70g/L, the bright nickel NF brightening agent with the concentration of 0.5-3mL/L, the nickel 45(4X) softening agent with the concentration of 8-15mL/L, the nickel SA-1 auxiliary agent with the concentration of 5-10mL/L and the nickel Y19 wetting agent with the concentration of 2-5 mL/L.
7. The method for preparing the bactericidal silvery-white composite coating according to any one of claims 1 to 6, comprising:
(1) pretreating a base material: polishing and cleaning;
(2) electroplating the bright nickel layer on the surface of the pretreated substrate;
(3) electroplating the high-sulfur nickel layer on the surface of the bright nickel layer;
(4) and electroplating the silver-white-chromium composite sterilization layer on the surface of the high-sulfur nickel layer.
8. The production method according to claim 7, wherein the conditions for electroplating the bright nickel layer in step (2) include: the temperature is 50-60 ℃, and the cathode current density is 5-10A/dm2The electroplating time is 900-;
optionally, the conditions for electroplating the high-sulfur nickel layer in step (3) include: the temperature is 45-55 deg.C, voltage is 5-10V, and cathode current density is 5-10A/dm2The plating time is 900-.
9. The production method according to claim 7, wherein the conditions for electroplating the silver white chromium composite bactericidal layer in the step (4) include: the temperature is 50-60 ℃, and the cathode current density is 5-15A/dm2The plating time is 300-900 s.
10. A silvery white bactericidal product comprising a substrate and the bactericidal silvery white composite coating according to any one of claims 1 to 6;
optionally, the substrate is a metal substrate or a plastic substrate;
optionally, the silvery white bactericidal product is a kitchen or toilet bactericidal product.
CN202210194643.9A 2022-03-01 2022-03-01 Bactericidal silvery white composite coating, preparation method thereof and silvery white bactericidal product Pending CN114540893A (en)

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JP2000129492A (en) * 1998-10-22 2000-05-09 Riken Corp Piston ring for internal combustion engine and its production
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