CN115055351A - Preparation method of super-hydrophobic film layer on surface of electrogalvanized steel - Google Patents
Preparation method of super-hydrophobic film layer on surface of electrogalvanized steel Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
The invention belongs to the technical field of galvanized products, and particularly relates to a preparation method of an electro-galvanized surface super-hydrophobic film layer, which comprises the following steps: 1) uniformly coating a layer of base layer reagent on the surface of the electrogalvanizing product, and waiting for natural air drying, wherein a base layer is formed on the surface of the electrogalvanizing product; 2) after air drying, continuously coating a layer of hydrophobic layer solution on the surface of the substrate layer, leveling, repeating coating after natural drying, and forming a super-hydrophobic layer on the surface of the substrate layer; 3) naturally drying to obtain an electro-galvanized product with a super-hydrophobic film layer on the surface; wherein, the super-hydrophobic film layer is composed of a basal layer and a super-hydrophobic layer. The preparation method has the advantages of simple process, low raw material cost, low equipment requirement, nontoxic process and environmental protection, and is beneficial to realizing large-scale industrial production; the prepared super-hydrophobic film layer can effectively improve the corrosion resistance and the hydrophobic property of the surface of the material.
Description
Technical Field
The invention belongs to the technical field of galvanized products, and particularly relates to a preparation method of an electro-galvanized surface super-hydrophobic film layer.
Background
Electrogalvanizing is an effective method for reducing the atmospheric corrosion rate of steel, but in a humid environment, the surface of an electrogalvanized layer is easy to corrode, white loose corrosion products are formed on the surface, a protective layer is damaged, and then the steel matrix begins to corrode. Further post-treatment of the electrogalvanized layer is therefore required. Superhydrophobic surfaces are important for the protection of metals due to their excellent water repellency. The preparation of the super-hydrophobic film layer with high corrosion resistance is one of the new directions of the zinc coating post-treatment technology research. The method can effectively prevent the zinc from contacting with air and improve the corrosion resistance of the zinc layer.
Chinese patent specification with publication No. CN105420735B discloses a super-hydrophobic fluorosilane composite film and a preparation method thereof, the components of the fluorosilane composite film include a substrate layer and a super-hydrophobic layer, the main component of the substrate layer is a composite organic corrosion inhibitor, which plays a role of corrosion inhibition on one hand, and provides active groups for the formation of the super-hydrophobic layer on the other hand, and the main components of the super-hydrophobic layer are fluorosilane (tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane and 4-methyl-tridecafluoroodecyltriethoxysilane). However, the preparation method has complicated steps and high process requirements, so that industrialization is difficult to realize.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of an electro-galvanized surface super-hydrophobic film layer comprises the following steps:
1) uniformly coating a layer of base layer reagent on the surface of the electrogalvanizing product, and waiting for natural air drying, wherein a base layer is formed on the surface of the electrogalvanizing product;
2) after air drying, continuously coating a layer of hydrophobic layer solution on the surface of the substrate layer, leveling, repeatedly coating after natural drying, coating the hydrophobic layer solution for 2-4 times, and forming a super-hydrophobic layer on the surface of the substrate layer;
3) naturally drying to obtain an electrogalvanizing product with a super-hydrophobic film layer on the surface; wherein, the super-hydrophobic film layer is composed of a basal layer and a super-hydrophobic layer.
Further, according to the preparation method of the electro-galvanized surface superhydrophobic film layer, the base layer reagent comprises the following components: the paint comprises an aqueous acrylic emulsion, propylene carbonate, polyoxyethylene polyoxypropylene ether, a polyether siloxane copolymer, cetyl hydroxyethyl cellulose, a polyethyleneimine derivative, a polyacrylate leveling agent, triammonium citrate, nano copper oxide, redox graphene, fumaric acid modified rosin aqueous resin, p-aminobenzoic acid, p-methoxycinnamic acid ethoxyethyl ester and distilled water.
Further, according to the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel, the base layer reagent comprises the following components in parts by mass: 55-65 parts of water-based acrylic emulsion, 2-6 parts of propylene carbonate, 0.5-1.5 parts of polyoxyethylene polyoxypropylene ether, 0.5-0.8 part of polyether siloxane copolymer, 1-2.5 parts of cetyl hydroxyethyl cellulose, 0.5-5 parts of polyethyleneimine derivative, 0.1-1 part of polyacrylate flatting agent, 5-12 parts of triammonium citrate, 0.01-0.1 part of nano copper oxide, 0.1-1 part of redox graphene, 2-8 parts of fumaric acid modified rosin water-based resin, 0.1-0.5 part of p-aminobenzoic acid, 0.01-0.05 part of ethoxy ethyl p-methoxycinnamate and 35-45 parts of distilled water.
Further, the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanizing comprises the following steps:
1) mixing the water-based acrylic emulsion, a polyethyleneimine derivative, redox graphene, cetyl hydroxyethylcellulose and distilled water, stirring at 30 ℃, adjusting the stirring speed to 200-400 rpm, and stirring for 10-20 minutes to obtain a mixture A;
2) adding polyoxyethylene polyoxypropylene ether, polyether siloxane copolymer, fumaric acid modified rosin water-based resin and polyacrylate flatting agent into the mixture A, stirring at 30 ℃, adjusting the stirring speed to be 300-500 rpm, and stirring for 10-20 minutes to obtain a mixture B;
3) and adding para aminobenzoic acid, triammonium citrate, nano copper oxide, ethoxyethyl p-methoxycinnamate and propylene carbonate into the mixture B, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 500-700 rpm, and stirring for 20-30 minutes to obtain the required substrate layer reagent.
Further, according to the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel, the hydrophobic layer solution comprises the following components: absolute ethyl alcohol, distilled water, perfluorodecyl triethoxysilane, and redox graphene.
Further, according to the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel, the hydrophobic layer solution comprises the following components in parts by mass: 80-100 parts of absolute ethyl alcohol, 8-15 parts of distilled water, 1-3 parts of perfluorodecyl triethoxysilane, and 1-3 parts of redox graphene.
Further, according to the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanizing, the preparation method of the hydrophobic layer solution comprises the following steps:
1) mixing absolute ethyl alcohol and distilled water, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 300-500 rpm, and stirring for 5-10 minutes to obtain a mixture C;
2) adding perfluorodecyl triethoxysilane into the mixture C, stirring at the temperature of 30-40 ℃, adjusting the stirring speed to be 500-800 rpm, and stirring for 30-40 minutes to obtain a mixture D;
3) and adding the redox graphene solution into the mixture D, stirring at the temperature of 30-40 ℃, adjusting the stirring speed to 400-500 rpm, and obtaining the required hydrophobic layer solution after 20-40 minutes.
Further, according to the preparation method of the super-hydrophobic membrane layer on the surface of the electrogalvanized product, the electrogalvanized product is subjected to surface cleaning and drying treatment before coating.
Further, according to the preparation method of the electro-galvanized surface super-hydrophobic film layer, the electro-galvanized product is formed by polishing, preprocessing and electroplating a steel substrate sample; wherein the pretreatment comprises ultrasonic ethanol cleaning, distilled water cleaning, oil removing cleaning, absolute ethanol ultrasonic cleaning, distilled water washing and activation, and the pretreatment is carried out after the activation till the surface of a sample becomes grey and gradually becomes fuzzy; during electroplating, the zinc sheet is connected with the anode, the sample is connected with the cathode, and the electroplated sample is soaked in a dilute nitric acid solution for a period of time and then is taken out to be cleaned by distilled water.
Further, according to the preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel, the surface contact angle of the super-hydrophobic film layer is more than or equal to 150 degrees, and the rolling angle is less than or equal to 10 degrees.
The invention has the beneficial effects that:
the invention provides a preparation method of an electro-galvanized surface super-hydrophobic film layer, which has the advantages of simple technical process, no need of high temperature, short preparation period, low raw material cost, low equipment requirement, nontoxic process, environmental friendliness and contribution to realizing large-scale industrial production; the prepared super-hydrophobic film layer can effectively improve the corrosion resistance and the hydrophobic property of the surface of the material.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of the surface of a modified sample in accordance with one embodiment of the present invention;
FIG. 2 is SEM images of a sample before and after etching in accordance with one embodiment of the present invention;
2 (a)5000 times, b)10000 times and c)20000 times before blank sample corrosion
2, (d)5000 times, (e)10000 times and (f)20000 times after the blank sample is corroded in 3% sodium chloride brine;
2 (g)5000 times, (h)10000 times and (i)20000 times before the modified sample is corroded;
2, (j)5000 times, (k)10000 times and (l)20000 times after the modified sample is corroded;
FIG. 3 is a schematic diagram illustrating the wettability of a water droplet on the surface of a sample after modification according to a first embodiment of the present invention;
FIG. 4 is a schematic diagram of the wettability of the surface of the sample after modification by the water droplet in the second embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention mainly relates to experimental medicines
Q235 carbon steel (10mm multiplied by 5mm), absolute ethyl alcohol, perfluorodecyl triethoxysilane, redox graphene solution (2mg/ml), dilute HCl solution (1.0 percent) and dilute HNO 3 Solution (0.6%), degreaser, activator, electroplating liquid, water paint, etc.
Technical scheme
Polishing steel substrate sample
And (3) polishing the sample smoothly by using a metallographic specimen polishing machine, and sequentially polishing by using 220#, 400#, 1000# and 2000# abrasive papers. Water is added during the grinding process to ensure the wetting so as to prevent the excessive heat generated by friction from influencing the tissue structure of the sample. When the sand paper is replaced with thinner sand paper for polishing, the polishing direction needs to be vertically intersected with the last polishing mark so as to ensure that the thicker polishing mark is removed. After polishing, the product must be air-dried and stored by cold wind.
Second, pretreatment
1. Ultrasonic ethanol cleaning is carried out for 3 minutes.
2. After the surface is cleaned by distilled water, the mixture is immediately put into an oil removing agent to remove oil for 30 minutes until a uniform water film appears on the surface.
3. Cleaning with anhydrous alcohol under ultrasonic for about 1 min, washing with distilled water, activating for about 10 min until the surface turns grey and becomes fuzzy, and activating until black speck appears.
Third, preparation of basal layer reagent
55-65 parts of water-based acrylic emulsion, 2-6 parts of propylene carbonate, 0.5-1.5 parts of polyoxyethylene polyoxypropylene ether, 0.5-0.8 part of polyether siloxane copolymer, 1-2.5 parts of cetyl hydroxyethyl cellulose, 0.5-5 parts of polyethyleneimine derivative, 0.1-1 part of polyacrylate flatting agent, 5-12 parts of triammonium citrate, 0.01-0.1 part of nano copper oxide (40nm), 0.1-1 part of redox graphene, 2-8 parts of fumaric acid modified rosin water-based resin, 0.1-0.5 part of p-aminobenzoic acid, 0.01-0.05 part of ethoxy ethyl p-methoxycinnamate and 35-45 parts of distilled water.
(1) Mixing the water-based acrylic emulsion, the polyethyleneimine derivative, the redox graphene, the spermaceti hydroxyethyl cellulose and the distilled water in parts by weight, stirring at the temperature of 30 ℃, adjusting the stirring speed to 200-400 rpm, and stirring for 10-20 minutes;
(2) adding polyoxyethylene polyoxypropylene ether, polyether siloxane copolymer, fumaric acid modified rosin water-based resin and polyacrylate flatting agent, stirring at 30 ℃, adjusting the stirring speed to 300-500 rpm, and stirring for 10-20 minutes;
(3) adding para aminobenzoic acid, triammonium citrate, nano copper oxide, ethoxyethyl p-methoxycinnamate and propylene carbonate into the mixture, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 500-700 rpm, and stirring for 20-30 minutes; and obtaining the basal layer reagent.
Preparation of hydrophobic layer solution
80-100 parts of absolute ethyl alcohol, 8-15 parts of distilled water, 1-3 parts of perfluorodecyl triethoxysilane, and 1-3 parts of redox graphene.
(1) Mixing the anhydrous ethanol and the distilled water in parts by weight, stirring at the temperature of 30 ℃, adjusting the stirring speed to 300-500 rpm, and stirring for 5-10 minutes;
(2) adding perfluorodecyl triethoxysilane, stirring at 30-40 ℃, and adjusting the stirring speed to be 500-800 rpm for 30-40 minutes;
(3) adding a redox graphene solution, stirring at the temperature of 30-40 ℃, and adjusting the stirring speed to 400-500 rpm for 20-40 minutes; thus obtaining hydrophobic layer solution.
Fifth, electroplating
(1) During electroplating, the zinc sheet is connected with the anode, the sample is connected with the cathode, the electroplating current is adjusted to be 30mA, and the front side and the back side of the sample are respectively plated for 5 minutes.
(2) The electroplated sample is soaked in 0.1-0.5% dilute nitric acid solution (about 1 minute) and then is immediately taken out and washed by distilled water.
Sixthly, super-hydrophobic modification
(1) Uniformly coating a layer of basal layer reagent on the surface of the cleaned and dried sample, and waiting for natural air drying (1-3 hours)
(2) And after air drying, coating a layer of hydrophobic layer solution, leveling, waiting for 0.5-1 hour for natural drying, and then repeatedly coating for a total of three times.
The composite film layer prepared by the invention comprises a substrate layer and an ultra-hydrophobic layer, wherein the substrate layer is aqueous acrylic emulsion, propylene carbonate, polyoxyethylene polyoxypropylene ether, triammonium citrate, nano copper oxide, redox graphene, polyether siloxane copolymer, cetyl hydroxyethyl cellulose, polyethyleneimine derivative, polyacrylate leveling agent, fumaric acid modified rosin aqueous resin, p-aminobenzoic acid, p-methoxycinnamate ethoxyethyl, water and the like; the super-hydrophobic layer is absolute ethyl alcohol, perfluorodecyl triethoxysilane, redox graphene solution and the like, and the heptadecafluorodecyl triethoxysilane is used as a main super-hydrophobic treatment agent and graphene oxide is added to further improve the corrosion resistance of the coating. In addition, the whole super-hydrophobic preparation process has simple steps, does not need high temperature, greatly shortens the experimental period and is easy for industrial production.
The following embodiments are relevant to the present invention:
example 1
1. Preparation of basal layer reagent
55 parts of water-based acrylic emulsion, 2 parts of propylene carbonate, 0.5 part of polyoxyethylene polyoxypropylene ether, 0.5 part of polyether siloxane copolymer, 1 part of cetyl hydroxyethyl cellulose, 0.5 part of polyethyleneimine derivative, 0.1 part of polyacrylate flatting agent, 5 parts of triammonium citrate, 0.01 part of nano copper oxide (40nm), 0.1 part of redox graphene, 2 parts of fumaric acid modified rosin water-based resin, 0.1 part of p-aminobenzoic acid, 0.01 part of ethoxy ethyl p-methoxycinnamate and 35 parts of distilled water.
(1) Mixing the above parts by weight of aqueous acrylic emulsion, polyethyleneimine derivative, redox graphene, spermaceti hydroxyethyl cellulose and distilled water, stirring at 30 ℃, adjusting the stirring speed to 200 rpm, and stirring for 10 minutes;
(2) adding polyoxyethylene polyoxypropylene ether, polyether siloxane copolymer, fumaric acid modified rosin water-based resin and polyacrylate flatting agent, stirring at 30 ℃, adjusting the stirring speed to 300 r/min, and stirring for 10 minutes;
(3) adding p-aminobenzoic acid, triammonium citrate, nano copper oxide, ethoxyethyl p-methoxycinnamate and propylene carbonate into the mixture, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 500 revolutions per minute, and stirring for 20 minutes; and obtaining the basal layer reagent.
2. Preparation of hydrophobic layer solution
Adding 10ml of distilled water into 100ml of absolute ethyl alcohol, then adding 2g of perfluorodecyl triethoxysilane into the solution, stirring for 30 minutes by using a magnetic stirrer, and adding 2ml of redox graphene solution during stirring to obtain a hydrophobic layer solution.
100 parts of absolute ethyl alcohol, 10 parts of distilled water, 2 parts of perfluorodecyl triethoxysilane, and 2 parts of redox graphene.
(1) Mixing the anhydrous ethanol and the distilled water in parts by weight, stirring at the temperature of 30 ℃, adjusting the stirring speed to 300 revolutions per minute, and stirring for 5 minutes;
(2) adding perfluorodecyl triethoxysilane, stirring at 30 ℃, and adjusting the stirring speed to 500 rpm for 30 minutes;
(3) adding a redox graphene solution, stirring at 30 ℃, and adjusting the stirring speed to 400 rpm for 20 minutes; thus obtaining hydrophobic layer solution.
3. Superhydrophobic modification
Uniformly coating a layer of basal layer reagent on the surface of the cleaned and dried sample after electroplating, and naturally drying for 2 hours; after air drying, a layer of hydrophobic agent is coated, the mixture is placed flat, and after 0.5 hour of natural drying, the coating is repeated for a total of three times. After air drying, water was dropped to test the hydrophobic property.
The photo of the modified hydrophobicity is shown in 3, the contact angle between the super-hydrophobic surface and water is 161 degrees, and the requirement of the wetting angle of the super-hydrophobic surface is met.
Fig. 1 is an SEM photograph of the sample after surface modification, and fig. 2 is SEM images of the blank sample (unmodified electrogalvanized sample) and the modified sample before and after corrosion, magnified 5000 times, 10000 times, and 20000 times. Observing the (a), (b) and (c) in the graph in fig. 2, it can be found that the surface of the blank sample before corrosion is mainly formed by piling up spherical particles, the surface is flat and compact as a whole, and after corrosion, many holes and irregular branches appear, and a part of the area is desquamated and is rough, as shown in (d), (e) and (f) in the graph in fig. 2, the zinc coating on the surface of the blank sample is eroded, and the compactness of the blank sample is damaged. When the modified samples before etching (FIG. 2 (g), (h), (i)) were observed, it was found that the particles on the surface of the sample were irregular in size and shape and accumulated on the surface of the metal sample in a disordered state. After the modified sample is corroded (fig. 2 (j), (k) and (l)), the number of surface particles is reduced, and the particles are stacked in a ladder-shaped manner on the whole, probably because the surface particles of the modified sample are fused, but the roughness of the surface of the modified sample is not changed greatly after the modified sample is compared with that before and after the corrosion. The surface appearance changes before and after the two groups of samples are corroded are compared, so that the corrosion condition of the modified sample is better than that of a blank sample, and the good corrosion resistance of the modified sample is reflected.
Example 2
1. Preparation of basal layer reagent
65 parts of aqueous acrylic emulsion, 6 parts of propylene carbonate, 1.5 parts of polyoxyethylene polyoxypropylene ether, 0.8 part of polyether siloxane copolymer, 2.5 parts of cetyl hydroxyethyl cellulose, 5 parts of polyethyleneimine derivative, 1 part of polyacrylate flatting agent, 12 parts of triammonium citrate, 0.1 part of nano copper oxide (40nm), 1 part of redox graphene, 8 parts of fumaric acid modified rosin aqueous resin, 0.5 part of p-aminobenzoic acid, 0.05 part of p-methoxycinnamic acid ethoxyethyl ester and 45 parts of distilled water.
(1) Mixing the above parts by weight of aqueous acrylic emulsion, polyethyleneimine derivative, redox graphene, spermaceti hydroxyethyl cellulose and distilled water, stirring at 30 ℃, adjusting the stirring speed to 400 rpm, and stirring for 20 minutes;
(2) adding polyoxyethylene polyoxypropylene ether, polyether siloxane copolymer, fumaric acid modified rosin water-based resin and polyacrylate flatting agent, stirring at 30 ℃, adjusting the stirring speed to 500 revolutions per minute, and stirring for 20 minutes;
(3) adding p-aminobenzoic acid, triammonium citrate, nano copper oxide, ethoxyethyl p-methoxycinnamate and propylene carbonate into the mixture, stirring at the temperature of 30 ℃, adjusting the stirring speed to 700 revolutions per minute, and stirring for 30 minutes; and obtaining the basal layer reagent.
2. Preparation of hydrophobic layer solution
100 parts of absolute ethyl alcohol, 15 parts of distilled water, 3 parts of perfluorodecyl triethoxysilane, and 3 parts of redox graphene.
(4) Mixing the anhydrous ethanol and the distilled water in parts by weight, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 500 rpm, and stirring for 10 minutes;
(5) adding perfluorodecyl triethoxysilane, stirring at 40 ℃, and adjusting the stirring speed to 800 rpm for 40 minutes;
(6) adding a redox graphene solution, stirring at 40 ℃, and adjusting the stirring speed to be 500 rpm for 40 minutes; thus obtaining hydrophobic layer solution.
3. Superhydrophobic modification
Immediately and uniformly coating a layer of basal layer reagent on the surface of the cleaned and dried sample, and waiting for natural air drying (3 hours); after air drying, coating a layer of hydrophobic agent, flatly placing, waiting for 1 hour, naturally drying, and then repeatedly coating for a total of three times. After air drying, water is dripped to test the hydrophobic performance, and the contact angle of the super-hydrophobic surface and water is 159 degrees, as shown in figure 4.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A preparation method of an electro-galvanized surface super-hydrophobic film layer is characterized by comprising the following steps:
1) uniformly coating a layer of base layer reagent on the surface of the electrogalvanizing product, and waiting for natural air drying, wherein a base layer is formed on the surface of the electrogalvanizing product;
2) after air drying, continuously coating a layer of hydrophobic layer solution on the surface of the substrate layer, leveling, repeatedly coating after natural drying, coating the hydrophobic layer solution for 2-4 times, and forming a super-hydrophobic layer on the surface of the substrate layer;
3) naturally drying to obtain an electro-galvanized product with a super-hydrophobic film layer on the surface; wherein, the super-hydrophobic film layer is composed of a basal layer and a super-hydrophobic layer.
2. The preparation method of the electro-galvanized surface superhydrophobic film layer according to claim 1, wherein the base layer reagent comprises the following components: the paint comprises an aqueous acrylic emulsion, propylene carbonate, polyoxyethylene polyoxypropylene ether, a polyether siloxane copolymer, cetyl hydroxyethyl cellulose, a polyethyleneimine derivative, a polyacrylate leveling agent, triammonium citrate, nano copper oxide, redox graphene, fumaric acid modified rosin aqueous resin, p-aminobenzoic acid, p-methoxycinnamic acid ethoxyethyl ester and distilled water.
3. The preparation method of the electro-galvanized surface superhydrophobic film layer according to claim 2, wherein the base layer reagent comprises the following components in parts by mass: 55-65 parts of water-based acrylic emulsion, 2-6 parts of propylene carbonate, 0.5-1.5 parts of polyoxyethylene polyoxypropylene ether, 0.5-0.8 part of polyether siloxane copolymer, 1-2.5 parts of cetyl hydroxyethyl cellulose, 0.5-5 parts of polyethyleneimine derivative, 0.1-1 part of polyacrylate flatting agent, 5-12 parts of triammonium citrate, 0.01-0.1 part of nano copper oxide, 0.1-1 part of redox graphene, 2-8 parts of fumaric acid modified rosin water-based resin, 0.1-0.5 part of p-aminobenzoic acid, 0.01-0.05 part of ethoxy ethyl p-methoxycinnamate and 35-45 parts of distilled water.
4. The preparation method of the electro-galvanized surface superhydrophobic film layer according to claim 3, wherein the preparation method of the base layer reagent comprises the following steps:
1) mixing the water-based acrylic emulsion, a polyethyleneimine derivative, redox graphene, cetyl hydroxyethylcellulose and distilled water, stirring at 30 ℃, adjusting the stirring speed to 200-400 rpm, and stirring for 10-20 minutes to obtain a mixture A;
2) adding polyoxyethylene polyoxypropylene ether, polyether siloxane copolymer, fumaric acid modified rosin water-based resin and polyacrylate flatting agent into the mixture A, stirring at 30 ℃, adjusting the stirring speed to be 300-500 rpm, and stirring for 10-20 minutes to obtain a mixture B;
3) and adding para aminobenzoic acid, triammonium citrate, nano copper oxide, ethoxyethyl p-methoxycinnamate and propylene carbonate into the mixture B, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 500-700 rpm, and stirring for 20-30 minutes to obtain the required substrate layer reagent.
5. The method for preparing the super-hydrophobic film layer on the surface of the electrogalvanized steel sheet according to claim 1, wherein the hydrophobic layer solution comprises the following components: absolute ethyl alcohol, distilled water, perfluorodecyl triethoxysilane and redox graphene.
6. The preparation method of the super-hydrophobic film layer on the surface of the electrogalvanized steel according to claim 5, wherein the hydrophobic layer solution comprises the following components in parts by mass: 80-100 parts of absolute ethyl alcohol, 8-15 parts of distilled water, 1-3 parts of perfluorodecyl triethoxysilane, and 1-3 parts of redox graphene.
7. The method for preparing the super-hydrophobic film layer on the surface of the electrogalvanized steel sheet according to claim 6, wherein the method for preparing the hydrophobic layer solution comprises the following steps:
1) mixing absolute ethyl alcohol and distilled water, stirring at the temperature of 30 ℃, adjusting the stirring speed to be 300-500 rpm, and stirring for 5-10 minutes to obtain a mixture C;
2) adding perfluorodecyl triethoxysilane into the mixture C, stirring at the temperature of 30-40 ℃, adjusting the stirring speed to be 500-800 rpm, and stirring for 30-40 minutes to obtain a mixture D;
3) and adding the redox graphene solution into the mixture D, stirring at the temperature of 30-40 ℃, adjusting the stirring speed to 400-500 rpm, and obtaining the required hydrophobic layer solution after 20-40 minutes.
8. The method for preparing the super-hydrophobic membrane layer on the surface of the electrogalvanized steel sheet according to claim 1, wherein the electrogalvanized steel sheet is subjected to surface cleaning and drying treatment before being coated.
9. The method for preparing the super-hydrophobic film layer on the surface of the electrogalvanized steel according to claim 1, wherein the electrogalvanized steel product is prepared by polishing, pretreating and electroplating a steel substrate sample; wherein the pretreatment comprises ultrasonic ethanol cleaning, distilled water cleaning, oil removing cleaning, absolute ethanol ultrasonic cleaning, distilled water washing and activation, and the pretreatment is carried out after the activation till the surface of a sample becomes grey and gradually becomes fuzzy; during electroplating, the zinc sheet is connected with the anode, the sample is connected with the cathode, and the electroplated sample is soaked in a dilute nitric acid solution for a period of time and then is taken out and washed by distilled water.
10. The method for preparing the super-hydrophobic film layer on the surface of the electrogalvanized zinc according to claim 1, wherein the surface contact angle of the super-hydrophobic film layer is not less than 150 degrees, and the rolling angle is not more than 10 degrees.
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