CN109536937B - High-corrosion-resistance galvanized steel sheet and preparation method thereof - Google Patents
High-corrosion-resistance galvanized steel sheet and preparation method thereof Download PDFInfo
- Publication number
- CN109536937B CN109536937B CN201811567578.XA CN201811567578A CN109536937B CN 109536937 B CN109536937 B CN 109536937B CN 201811567578 A CN201811567578 A CN 201811567578A CN 109536937 B CN109536937 B CN 109536937B
- Authority
- CN
- China
- Prior art keywords
- steel sheet
- parts
- galvanized steel
- component
- protective film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention discloses a high-corrosion-resistance galvanized steel sheet and a preparation method thereof. The high corrosion-resistant galvanized steel sheet comprises a cold-rolled steel sheet, a zinc coating on the surface of the cold-rolled steel sheet and a protective film on the surface of the zinc coating, wherein the protective film is formed by solidifying a passivation solution, and the passivation solution comprises a component A and a component B in a mass ratio of 1: 1.2-1.8; the preparation method comprises the following steps: s1, sequentially carrying out alkali washing and water washing on the cold-rolled steel plate; s2, annealing the cleaned cold-rolled steel sheet; s3, hot galvanizing the annealed steel plate to form a galvanized layer; s4, putting the galvanized steel plate into the passivation solution, soaking for 10-15min, taking out, standing for 20-25h, curing to form a protective film, uniformly coating the protective film with the protective solution, and standing for 1-2h to form the high-corrosion-resistance galvanized steel plate. The high corrosion resistance galvanized steel sheet has the advantages of chromium-free passivation and good corrosion resistance.
Description
Technical Field
The invention relates to the technical field of galvanized steel sheets, in particular to a high-corrosion-resistance galvanized steel sheet and a preparation method thereof.
Background
Galvanized steel sheets are low in cost and excellent in performance, and are widely used in the fields of home appliances, aviation and the like, but because galvanized steel sheets contain components such as zinc and aluminum, white rust is easily generated in the galvanized steel sheets in a humid environment, the quality and the appearance of the galvanized steel sheets are affected, and passivation protection of the galvanized steel sheets is very important.
In the prior art, chinese patent application No. CN201611084251.8 discloses a corrosion-resistant galvanized steel sheet product, which comprises a galvanized steel sheet substrate and a surface coating on the surface of the galvanized steel sheet substrate, wherein the surface coating comprises the following components in percentage by mass: zinc chrome yellow: 8-12%, barium sulfate: 4-10%, talc powder: 5-8%, and an organic silicon leveling agent: 0.2-0.8%, silicone resin: 2-4%, acrylic acid defoaming agent: less than or equal to 0.8 percent, and the balance of 919 acrylic resin.
The surface coating of the existing corrosion-resistant galvanized steel plate contains zinc yellow, wherein chromium is hexavalent chromium, which can cause serious harm to the environment and human bodies in the production process, and the treated wastewater contains hexavalent chromium which can not be recycled. Therefore, it is urgently required to prepare a corrosion-resistant galvanized steel sheet without a hexavalent chromium passivation treatment.
Disclosure of Invention
In view of the defects of the prior art, the first object of the invention is to provide a high corrosion-resistant tin-plated steel plate which has the advantages of chromium-free passivation and corrosion resistance.
The second purpose of the invention is to provide a preparation method of a high corrosion-resistant galvanized steel sheet, which has the advantages of simple preparation method and good corrosion resistance of the obtained product by adopting a chromium-free passivation mode.
In order to achieve the first object, the invention provides the following technical scheme: a high corrosion-resistant galvanized steel sheet comprises a cold-rolled steel sheet, a galvanized layer on the surface of the cold-rolled steel sheet and a protective film on the surface of the galvanized layer, wherein the protective film is formed by solidifying a passivation solution; the passivation solution comprises a component A and a component B with the mass ratio of 1:1.2-1.8,
the component A comprises the following components in parts by weight: 1-5 parts of vinyl triethoxysilane, 1-3 parts of sodium trimethylsilanolate and 20-30 parts of distilled water;
the component B comprises the following components in parts by weight: 20-30 parts of acrylic resin, 10-20 parts of hydrogen peroxide, 1-5 parts of lanthanum nitrate, 1-5 parts of zinc phosphate, 10-20 parts of phytic acid, 5-10 parts of silica gel and 15-20 parts of ethanolamine sodium molybdate.
By adopting the technical scheme, the galvanized steel sheet is placed in the passivation solution, so that a layer of compact oxidation film is passivated on the galvanized layer, and the corrosion resistance of the galvanized steel sheet is improved; unreacted silanol groups can also form a cross-linked silane film network structure to prevent the invasion of an aggressive medium and form a stable film layer; the phytic acid in the component B has 12 hydroxyl groups capable of being complexed with metal, 24 oxygen atoms and 6 phosphate groups, can be complexed with metal, a layer of compact monomolecular organic protective film is formed on the surface of the metal, oxygen is effectively prevented from entering the surface of the metal, metal corrosion is inhibited, the phytic acid, silica gel and ethanolamine sodium molybdate are used in a mutual compounding mode, the effect of inhibiting metal corrosion is improved, hydrogen peroxide and lanthanum nitrate are matched and passivated, a rare earth conversion film is formed on the surface of a zinc coating after rare earth salt passivation, the corrosion rate of the metal is effectively reduced, a good corrosion prevention effect is achieved, the phytic acid, the silica gel, vinyltriethoxysilane and other raw materials are green environment-friendly raw materials, and the phytic acid, the silica gel, the vinyltriethoxysilane and other raw materials have good stability, acid resistance.
Further, the preparation method of the passivation solution comprises the following steps: (1) mixing vinyl triethoxysilane, sodium trimethylsilanolate and distilled water, and stirring at 30-40 deg.C to obtain component A;
(2) uniformly stirring phytic acid, silica gel and ethanolamine sodium molybdate at 40-45 ℃, standing for 1-2 hours, sequentially adding acrylic resin, hydrogen peroxide, lanthanum nitrate and zinc phosphate, and stirring at 40-80 ℃ for 30-50min to prepare a component B;
(3) stirring the component A and the component B at 50-80 ℃ for 3-6h to obtain the passivation solution.
According to the technical scheme, firstly, vinyltriethoxysilane and sodium trimethylsilanolate are put into distilled water for hydrolysis, silanol bonds are generated after hydrolysis, phytic acid, silica gel and ethanolamine sodium molybdate in the components are mixed, the corrosion resistance of the phytic acid is improved, then acrylic ester, hydrogen peroxide, lanthanum nitrate, zinc phosphate, phytic acid and the like are mixed, finally the mixture is mixed with the component A, the silanol bonds hydrolyzed from the component A are mixed with acrylic resin, ethanolamine molybdate and the like, the composite passivation film is prepared, and the corrosion resistance of the galvanized steel plate is improved.
Further, the protective film is positioned on the surface of the protective film and is formed by curing a protective liquid, and the protective liquid comprises the following components in parts by weight: 5-10 parts of lotus leaf hydrophobing agent, 1-5 parts of flatting agent, 1-3 parts of dispersing agent, 5-10 parts of polyethylene glycol, 10-15 parts of epoxy resin, 10-20 parts of amino organosilicon, 20-30 parts of water glass and 10-20 parts of polyurethane emulsion.
By adopting the technical scheme, the protective liquid is coated outside the protective film, the polyethylene glycol in the protective liquid plays a role in solvent, the polyethylene glycol has good adhesion and dispersibility, the adhesive force between the protective liquid and the protective film can be improved, the lotus leaf hydrophobing agent can enable the protective liquid to form a layer of protective film such as lotus leaves outside the protective film, moisture and oxygen are prevented from entering, the coating metal and the steel plate are corroded, the epoxy resin, the water glass and the polyurethane emulsion have good adhesion and waterproofness, the adhesive force between the protective film and the protective film can be improved, the waterproofness of the protective film can be improved, moisture or other substances in the air are prevented from entering the protective film, the protection of the galvanized steel plate is further enhanced, and the double protection effect is achieved.
Further, the preparation method of the protective liquid comprises the following steps: mixing water glass, a dispersing agent, epoxy resin and a lotus leaf hydrophobing agent, uniformly stirring at 30-40 ℃, standing for 1-2h, adding amino organic silicon, polyethylene glycol, polyurethane emulsion and a flatting agent, mixing, and stirring at room temperature for 1-2h to obtain the protective liquid.
By adopting the technical scheme, the water glass, the epoxy resin and the lotus leaf hydrophobing agent are dispersed and kept stand to uniformly disperse the water glass, the epoxy resin and the lotus leaf hydrophobing agent, and the amino organic silicon is added to soften the water glass, the epoxy resin and the like and improve the film forming property.
Further, the dispersing agent is a mixture of sodium silicate and sodium polyacrylate in a mass ratio of 1: 0.5-1.2.
By adopting the technical scheme, the sodium silicate can permeate into gaps and pores of each raw material of the protective liquid, the cured silica gel can block capillary channels, the density and the strength of the protective liquid after curing are improved, and the dispersion effect is enhanced when the protective liquid is compounded with sodium polyacrylate.
Further, the leveling agent is one or a composition of more of butyl cellulose, polyacrylic acid and carboxymethyl cellulose.
By adopting the technical scheme, the surface tension of the protective liquid can be reduced by the butyl cellulose, the polyacrylic acid and the carboxymethyl cellulose, the leveling property and the homogeneity of the protective liquid are improved, spots and stains generated in the process of coating are reduced, the coverage is improved, and the formed film is uniform and natural.
In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a high corrosion-resistant galvanized steel sheet comprises the following steps:
s1, sequentially carrying out alkali washing and water washing on the cold-rolled steel plate;
s2, annealing the cleaned cold-rolled steel sheet;
s3, hot galvanizing the annealed steel plate to form a galvanized layer;
s4, putting the galvanized steel plate into the passivation solution, soaking for 10-15min, taking out, standing for 20-25h, curing to form a protective film, uniformly coating the protective film with the protective solution, standing for 1-2h, and curing to form a protective film, thus obtaining the high-corrosion-resistance galvanized steel plate.
By adopting the technical scheme, the cold-rolled steel plate is subjected to alkali washing and water washing, oil stains on the surface of the cold-rolled steel plate can be removed, the viscosity of a zinc coating on the surface of the cold-rolled steel plate is firm, the galvanized steel plate is placed into the passivation solution for soaking, the passivation solution can be uniformly adhered to the whole galvanized steel plate, the passivation is uniform, the thickness of the protective film is the same, the protective solution with the barrier property is coated on the protective film, moisture or other substances can be prevented from entering the protective film, and the galvanized steel plate can be corroded.
Further, the thickness of the zinc plating layer in the step S3 is 25 to 35 μm.
Through adopting above-mentioned technical scheme, the galvanizing coat can protect the cold-rolled steel sheet not receive wearing and tearing, and can improve galvanized steel sheet's corrosion resistance.
Further, the curing temperature of the passivation solution and the protection solution in the step S4 is room temperature.
By adopting the technical scheme, the passivation solution and the protection solution are solidified at room temperature, so that the phenomenon that the surface of the galvanized steel sheet is uneven due to the shrinkage of the passivation solution and the protection solution during high-temperature drying can be avoided.
In conclusion, the invention has the following beneficial effects:
firstly, as the invention adopts the vinyl triethoxysilane and the trimethylsilanol which can be hydrolyzed, one part of the hydrolyzed silanol group reacts with the zinc coating to produce the metal siloxane bond, and the other part reacts with the zinc phosphate, the acrylic resin, the ethanolamine sodium molybdate and the silica gel to carry out composite passivation, a composite passivation film is formed on the metal surface to inhibit the corrosion of the galvanized steel plate, and a cross-linked silane film network structure can be formed by the unreacted third part of the silanol group to prevent aggressive media from entering, the raw materials are green and environment-friendly, and the corrosion resistance effect of the galvanized steel plate is improved by using a chromium-free passivation mode.
Secondly, phytic acid, silica gel and ethanolamine molybdate are preferably adopted to be matched with each other, and the phytic acid can generate a complex reaction with metal to form a layer of compact organic protective film on the technical surface, so that corrosive substances are prevented from entering, the corrosion of the metal is inhibited, and the corrosion resistance effect of the galvanized steel sheet is improved.
Thirdly, the protective effect can be further improved by coating the protective liquid on the outer layer of the protective film, and the lotus leaf hydrophobing agent, the epoxy resin, the water glass, the polyurethane emulsion and the like in the protective liquid have waterproof and waterproof properties, and the epoxy resin and the polyurethane emulsion have film forming properties, so that a hydrophobic protective film can be formed on the outer layer of the protective film, secondary protection is formed on a zinc coating, and the corrosion resistance of the galvanized steel plate is improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation examples 1 to 3 of passivation solutions
In preparation examples 1 to 3, vinyltriethoxysilane was selected from NQ-51 type vinyltriethoxysilane sold by Shandong Wanda New Silicone Material Co., Ltd, sodium trimethylsilanolate, distilled water, hydrogen peroxide, zinc phosphate and lanthanum nitrate were used as analytical reagents, acrylic resin was selected from BR-106 type acrylic resin sold by chemical Co., Ltd, Shanghai, where phytic acid was selected from phytic acid sold under the No. 7531-1 by Zhengzhou Hengxiang chemical products Co., Ltd, and silica gel was selected from RTV906 type silica gel sold by Tachang resin Material Co., Ltd, Toguan.
Preparation example 1: (1) mixing 1kg of vinyltriethoxysilane, 1kg of sodium trimethylsilanolate and 20kg of distilled water according to the ratio in Table 1, and uniformly stirring at 30 ℃ to prepare a component A;
(2) uniformly stirring 10kg of phytic acid, 5kg of silica gel and 15kg of ethanolamine sodium molybdate at 40 ℃, standing for 1 hour, sequentially adding 20kg of acrylic resin, 10kg of hydrogen peroxide, 1kg of lanthanum nitrate and 1kg of zinc phosphate, and stirring for 30min at 40 ℃ to prepare a component B;
(3) and stirring the component A and the component B according to the mass ratio of 1:1.2 at 50 ℃ for 3 hours to obtain the passivation solution.
TABLE 1 raw material ratios of passivation solutions in preparation examples 1-3
Preparation example 2: (1) mixing 3kg of vinyltriethoxysilane, 2kg of sodium trimethylsilanolate and 25kg of distilled water according to the ratio in Table 1, and uniformly stirring at 35 ℃ to prepare a component A;
(2) uniformly stirring 15kg of phytic acid, 8kg of silica gel and 18kg of ethanolamine sodium molybdate at the temperature of 43 ℃, standing for 1.5 hours, sequentially adding 25kg of acrylic resin, 15kg of hydrogen peroxide, 3kg of lanthanum nitrate and 3kg of zinc phosphate, and stirring for 40min at the temperature of 60 ℃ to prepare a component B;
(3) and stirring the component A and the component B according to the mass ratio of 1:1.5 at 65 ℃ for 5 hours to obtain the passivation solution.
Preparation example 3: (1) mixing 5kg of vinyltriethoxysilane, 3kg of sodium trimethylsilanolate and 30kg of distilled water according to the ratio in Table 1, and uniformly stirring at 40 ℃ to prepare a component A;
(2) uniformly stirring 20kg of phytic acid, 10kg of silica gel and 20kg of ethanolamine sodium molybdate at 45 ℃, standing for 2 hours, sequentially adding 320kg of acrylic resin, 20kg of hydrogen peroxide, 5kg of lanthanum nitrate and 5kg of zinc phosphate, and stirring for 50min at 80 ℃ to obtain a component B;
(3) and stirring the component A and the component B according to the mass ratio of 1:1.8 at 80 ℃ for 6 hours to obtain the passivation solution.
Preparation examples 4 to 6 of protecting liquid
The lotus leaf hydrophobizing agent in preparation examples 4-6 is selected from AD3105 type lotus leaf hydrophobizing agent sold by Aoda environmental protection new material Co.Ltd in Dongguan, the epoxy resin is selected from SM593J type epoxy resin sold by Sanzhi chemical engineering Co.Ltd in Jiangsu, the water glass is selected from 1102 type water glass sold by Jinan Van aromatizer chemical engineering Co.Ltd, the polyurethane emulsion is selected from AP119 type polyurethane emulsion sold by the Polymer chemical engineering science Co.Ltd in Jiangmen, the amino silicone is selected from LT-638 type amino silicone sold by Shanghai green copper materials Co.Ltd, the sodium silicate, the sodium polyacrylate and the polyacrylic acid are analytically pure, the hydroxymethyl cellulose is selected from 3446340 type hydroxymethyl cellulose sold by Guangzhou Weibo science Co.Ltd, and the ethyl cellulose is selected from EC50 type ethyl cellulose sold by Guangdong Yue beautifying chemical engineering Co.Ltd.
Preparation example 4: according to the proportion in the table 2, 20kg of water glass, 1kg of dispersing agent, 10kg of epoxy resin and 5kg of lotus leaf hydrophobing agent are mixed, stirred uniformly at 30 ℃, kept stand for 1h, then 10kg of amino organic silicon, 5kg of polyethylene glycol, 10kg of polyurethane emulsion and 1kg of flatting agent are added, mixed and stirred for 1h at room temperature, and then the protective liquid is prepared, wherein the dispersing agent is a mixture of sodium silicate and sodium polyacrylate in a mass ratio of 1:0.5, and the flatting agent is butyl cellulose.
TABLE 2 raw material ratios of the protecting solutions in preparation examples 4 to 6
Preparation example 5: according to the proportion in the table 2, 25kg of water glass, 2kg of dispersing agent, 13kg of epoxy resin and 8kg of lotus leaf hydrophobing agent are mixed, stirred uniformly at 35 ℃, kept stand for 1.5h, then 15kg of amino organic silicon, 8kg of polyethylene glycol, 15kg of polyurethane emulsion and 3kg of flatting agent are added, mixed and stirred at room temperature for 1.5h to obtain the protective liquid, wherein the dispersing agent is a mixture of sodium silicate and sodium polyacrylate in a mass ratio of 1:0.8, and the flatting agent is polyacrylic acid.
Preparation example 6: according to the proportion in the table 2, 30kg of water glass, 3kg of dispersing agent, 15kg of epoxy resin and 10kg of lotus leaf hydrophobing agent are mixed, stirred uniformly at 40 ℃, kept stand for 2 hours, then 20kg of amino organic silicon, 10kg of polyethylene glycol, 20kg of polyurethane emulsion and 5kg of flatting agent are added, mixed and stirred for 2 hours at room temperature, and then the protective liquid is prepared, wherein the dispersing agent is a mixture of sodium silicate and sodium polyacrylate in a mass ratio of 1:1.2, and the flatting agent is hydroxymethyl cellulose.
Examples
Example 1: a high corrosion-resistant galvanized steel sheet comprises a cold-rolled steel sheet, a galvanized layer on the surface of the cold-rolled steel sheet, a protective film on the surface of the galvanized layer and a protective film on the surface of the protective film.
The preparation method of the high corrosion resistance galvanized steel sheet comprises the following steps:
s1, sequentially carrying out alkali washing and water washing on the cold-rolled steel plate;
s2, annealing the cleaned cold-rolled steel sheet;
s3, hot galvanizing the annealed steel plate to form a galvanized layer, wherein the thickness of the galvanized layer is 25 mu m;
and S4, putting the galvanized steel plate into a passivation solution, soaking for 10min, taking out, standing for 20h, curing to form a protective film, uniformly coating the protective film with the protective solution, standing for 1h, and curing to form a protective film, thus obtaining the high-corrosion-resistance galvanized steel plate, wherein the passivation solution is prepared by preparation example 1, and the protective solution is prepared by preparation example 4.
Example 2: a high corrosion-resistant galvanized steel sheet is different from the steel sheet in example 1 in that the thickness of a zinc coating layer in step S3 is 30 μm, the steel sheet after being galvanized is soaked in a passivation solution for 13min and is left for 23h in step S4, the standing time of the steel sheet after being coated on a protective film is 1.5h, the passivation solution is prepared in preparation example 2, and the protection solution is prepared in preparation example 5.
Example 3: a high corrosion-resistant galvanized steel sheet is different from the steel sheet in example 1 in that the thickness of a zinc coating layer in step S3 is 35 μm, the steel sheet after being galvanized is soaked in a passivation solution for 15min and is left for 25h in step S4, the standing time of the steel sheet after being coated on a protective film is 2h, the passivation solution is prepared in preparation example 3, and the protection solution is prepared in preparation example 6.
Comparative example 1: a high corrosion-resistant galvanized steel sheet differs from example 1 in that the mass ratio of component A to component B is 1: 0.9.
Comparative example 2: a high corrosion-resistant galvanized steel sheet differs from example 1 in that the mass ratio of component A to component B is 1: 2.1.
Comparative example 3: a high corrosion-resistant galvanized steel sheet is different from the galvanized steel sheet in example 1 in that the component A of the passivation solution does not contain vinyltriethoxysilane.
Comparative example 4: a high corrosion-resistant galvanized steel sheet is different from the galvanized steel sheet in example 1 in that the component A of the passivation solution does not contain sodium trimethylsilanolate.
Comparative example 5: a high corrosion-resistant galvanized steel sheet is different from example 1 in that the component B of the passivation solution does not contain acrylic resin, zinc phosphate, silica gel and ethanolamine sodium molybdate.
Comparative example 6: a highly corrosion-resistant galvanized steel sheet differs from example 1 in that component B of the passivation solution does not contain phytic acid, silica gel and ethanolamine sodium molybdate.
Comparative example 7: a high corrosion-resistant galvanized steel sheet is different from example 1 in that component B of the passivation solution does not contain hydrogen peroxide and lanthanum nitrate.
Comparative example 8: a high corrosion-resistant galvanized steel sheet is different from the galvanized steel sheet in example 1 in that the protective liquid does not contain a lotus leaf hydrophobizing agent, a polyurethane emulsion, epoxy resin and water glass.
Performance test high corrosion-resistant galvanized steel sheets were prepared according to the methods in examples 1 to 3 and comparative examples 1 to 8, and various performances of the high corrosion-resistant galvanized steel sheets were tested according to the following methods:
1. and (3) corrosion resistance test: each of the galvanized steel sheets obtained in examples 1 to 3 and comparative examples 1 to 8 was cut into a size of 70mm in width × 150mm in length, a cut wound reaching the base of the cold-rolled steel sheet was formed on one side of the galvanized steel sheet, and the cut end faces of four sides were sealed with a tape to prepare samples for corrosion resistance tests; further, a salt water spray test was carried out by the method described in 9.1 of JISK5400-1990 "general test methods for paints", salt water was sprayed on the side where the cut was set, and the test time was set to 240 hours; after the test was completed, the maximum swelling amplitude of the cut was measured on one side.
2. Black stain resistance test: the galvanized steel sheets produced in examples 1 to 3 and comparative examples 1 to 8 were cut into a size of 70mm in width × 150mm in length, and subjected to an exposure test for 6 months outside, and the color tone of the steel sheet before and after the exposure test was measured by a spectrophotometer, and the value L indicating the luminance of the CIE chromaticity diagram (L × a × b chromaticity diagram) was measured to calculate the value Δ L, [ L before test ] - [ L after test ].
3. Fingerprint resistance: after the finger was pressed against one side of the galvanized steel sheet to attach a fingerprint, the evaluation was 0 when the fingerprint was not attached at all, 1 when the fingerprint was attached but the fingerprint disappeared when the finger was wiped off with a cloth, 2 when the fingerprint was attached but the fingerprint remained when the finger was wiped off with a cloth, but the fingerprint remained was difficult to confirm by visual observation, and 3 when the fingerprint was attached and the fingerprint did not disappear completely even when the finger was wiped off with a cloth.
TABLE 3 Property test of high corrosion-resistant galvanized steel sheets obtained in examples 1 to 3 and comparative examples 1 to 8
As can be seen from the data in table 3, the high corrosion-resistant galvanized steel sheets produced according to examples 1 to 3 are excellent in corrosion resistance, the maximum swelling degree on one side of the cut was 1.42mm or less, and it was demonstrated that the galvanized steel sheets produced according to examples 1 to 3 are strong in corrosion resistance, Δ L in blackening resistance detection was 2.65 or less, and no finger mark was attached after being pressed with a finger, and the respective performances were excellent.
Comparative example 1 because the mass ratio of component a to component B was 1:0.9, and the content of component B was relatively small, the maximum swelling degree of the cut flaw on one side was 7.88 in the corrosion resistance test of the produced galvanized steel sheet, the increase was more significant than that in example 1, and the Δ L value was also increased by 5.42 in the blackening resistance test, and the fingerprint was attached by pressing with a finger, indicating that when the mass ratio of component a to component B was 1:1.2-1.8, the corrosion resistance and blackening resistance of the galvanized steel sheet could be improved, and the fingerprint attachment could be prevented.
Comparative example 2 the corrosion resistance, blackening resistance and fingerprint adhesion of the prepared galvanized steel sheet were inferior to those of example 1 because the mass ratio of component a to component B was 1:2.1 and the content of component B was relatively large, which indicates that the corrosion resistance of the galvanized steel sheet was superior when the mass ratio of component a to component B was 1: 1.2-1.8.
Comparative example 3 because no vinyltriethoxysilane was added to component a of the passivation solution, the maximum swelling degree of one side of the cut was 12.82mm, the swelling degree was higher, and the corrosion resistance was poor in the corrosion resistance test of the galvanized steel sheet, indicating that vinyltriethoxysilane can improve the corrosion resistance of the galvanized steel sheet.
Comparative example 4 since sodium trimethylsilanolate was not added to passivation solution component a, the corrosion resistance, blackening resistance and fingerprint adhesion of the galvanized steel sheet were all poor, indicating that sodium trimethylsilanolate can improve the corrosion resistance, blackening resistance of the galvanized steel sheet and can prevent fingerprint adhesion.
Comparative example 5 because no acrylic resin, zinc phosphate, silica gel and sodium ethanolamine molybdate were added to the passivation solution component B, a composite passivation film could not be formed with vinyltriethoxysilane and sodium trimethylsilanolate in the component a, the corrosion resistance of the prepared galvanized steel sheet was poor, the maximum swelling degree of the cut single side was 10.27mm, the blackening resistance was reduced compared with example 1, and the fingerprint adhesion rating was 1, which indicates that acrylic resin, zinc phosphate, silica gel and sodium ethanolamine molybdate could be mutually matched with vinyltriethoxysilane and sodium trimethylsilanolate in the component a to form a composite passivation film, and the corrosion resistance of the galvanized steel sheet was improved.
Comparative example 6 as phytic acid, silica gel and ethanolamine sodium molybdate were not added to the passivation solution component B, the corrosion resistance, blackening resistance and fingerprint adhesion of the galvanized steel sheet were poor, indicating that phytic acid, silica gel and ethanolamine sodium molybdate can improve the corrosion resistance of the galvanized steel sheet.
Comparative example 7 because no hydrogen peroxide and lanthanum nitrate were added to component B in the passivation solution, the maximum swell of the galvanized steel sheet at the cut flaw single side was 10.73mm, which is inferior to that of example 1, indicating that hydrogen peroxide and lanthanum nitrate can improve the corrosion resistance of the galvanized steel sheet.
In the comparative example 8, the lotus leaf hydrophobizing agent, the epoxy resin, the polyurethane emulsion and the water glass are not added into the protective liquid, so that the adhesive force and the waterproof performance of the protective film are poor, the corrosion resistance of the galvanized steel sheet is poor, and the lotus leaf hydrophobizing agent, the epoxy resin, the polyurethane emulsion and the water glass can improve the corrosion resistance of the galvanized steel sheet.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. A high corrosion-resistant galvanized steel sheet is characterized by comprising a cold-rolled steel sheet, a galvanized layer on the surface of the cold-rolled steel sheet, a protective film on the surface of the galvanized layer and a protective film on the surface of the protective film; the protective film is formed by solidifying a passivation solution; the protective film is formed by curing a protective liquid;
the passivation solution comprises a component A and a component B in a mass ratio of 1:1.2-1.8, wherein the component A comprises the following components in parts by weight: 1-5 parts of vinyl triethoxysilane, 1-3 parts of sodium trimethylsilanolate and 20-30 parts of distilled water;
the component B comprises the following components in parts by weight: 20-30 parts of acrylic resin, 10-20 parts of hydrogen peroxide, 1-5 parts of lanthanum nitrate, 1-5 parts of zinc phosphate, 10-20 parts of phytic acid, 5-10 parts of silica gel and 15-20 parts of ethanolamine sodium molybdate;
the protective liquid comprises the following components in parts by weight: 5-10 parts of lotus leaf hydrophobing agent, 1-5 parts of flatting agent, 1-3 parts of dispersing agent, 5-10 parts of polyethylene glycol, 10-15 parts of epoxy resin, 10-20 parts of amino organosilicon, 20-30 parts of water glass and 10-20 parts of polyurethane emulsion.
2. The highly corrosion-resistant galvanized steel sheet according to claim 1, characterized in that the passivating solution is prepared by the following method: (1) mixing vinyl triethoxysilane, sodium trimethylsilanolate and distilled water, and stirring at 30-40 deg.C to obtain component A;
(2) uniformly stirring phytic acid, silica gel and ethanolamine sodium molybdate at 40-45 ℃, standing for 1-2 hours, sequentially adding acrylic resin, hydrogen peroxide, lanthanum nitrate and zinc phosphate, and stirring at 40-80 ℃ for 30-50min to prepare a component B;
(3) stirring the component A and the component B at 50-80 ℃ for 3-6h to obtain the passivation solution.
3. The highly corrosion-resistant galvanized steel sheet according to claim 1, wherein the protective solution is prepared by the following method: mixing water glass, a dispersing agent, epoxy resin and a lotus leaf hydrophobing agent, uniformly stirring at 30-40 ℃, standing for 1-2h, adding amino organic silicon, polyethylene glycol, polyurethane emulsion and a flatting agent, mixing, and stirring at room temperature for 1-2h to obtain the protective liquid.
4. The highly corrosion-resistant galvanized steel sheet according to claim 1, wherein the dispersant is a mixture of sodium silicate and sodium polyacrylate in a mass ratio of 1:0.5 to 1.2.
5. The high corrosion-resistant galvanized steel sheet according to claim 3, wherein the leveling agent is one or a combination of butyl cellulose, polyacrylic acid and carboxymethyl cellulose.
6. A method for manufacturing a high corrosion-resistant galvanized steel sheet according to any one of claims 1 to 5, characterized by comprising the steps of:
s1, sequentially carrying out alkali washing and water washing on the cold-rolled steel plate;
s2, annealing the cleaned cold-rolled steel sheet;
s3, hot galvanizing the annealed steel plate to form a galvanized layer;
s4, putting the galvanized steel plate into the passivation solution, soaking for 10-15min, taking out, standing for 20-25h, curing to form a protective film, uniformly coating the protective film with the protective solution, standing for 1-2h, and curing to form a protective film, thus obtaining the high-corrosion-resistance galvanized steel plate.
7. The method of preparing a highly corrosion-resistant galvanized steel sheet according to claim 6, wherein the thickness of the galvanized layer in the step S3 is 25 to 35 μm.
8. The method for manufacturing a highly corrosion-resistant galvanized steel sheet according to claim 6, wherein the curing temperature of the passivation solution and the shielding solution in step S4 is room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811567578.XA CN109536937B (en) | 2018-12-21 | 2018-12-21 | High-corrosion-resistance galvanized steel sheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811567578.XA CN109536937B (en) | 2018-12-21 | 2018-12-21 | High-corrosion-resistance galvanized steel sheet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109536937A CN109536937A (en) | 2019-03-29 |
| CN109536937B true CN109536937B (en) | 2020-12-15 |
Family
ID=65854067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811567578.XA Active CN109536937B (en) | 2018-12-21 | 2018-12-21 | High-corrosion-resistance galvanized steel sheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109536937B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126880A (en) * | 2020-08-28 | 2020-12-25 | 余姚市永林机械科技有限公司 | High-corrosion-resistance hot-dip galvanized steel plate and preparation method thereof |
| CN112410710A (en) * | 2020-11-11 | 2021-02-26 | 合肥亿昌兴精密机械有限公司 | Corrosion-resistant high-strength galvanized sheet and galvanized sheet preparation process |
| CN112626512B (en) * | 2020-11-28 | 2023-07-21 | 武汉建大威坤钢结构工程股份有限公司 | Processing technology of color steel plate |
| CN114703470A (en) * | 2022-03-10 | 2022-07-05 | 福建宏贯路桥防腐科技股份有限公司 | Environment-friendly passivation solution and passivation process for metal component |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965657A (en) * | 2012-11-22 | 2013-03-13 | 象山华鹰塑料工程有限公司 | Surface treatment fluid for zinc alloy surface anticorrosion film |
| CN103031550A (en) * | 2012-12-18 | 2013-04-10 | 安徽翔艺达机械有限公司 | Metallic workpiece pretreatment silane surface treatment agent and preparation method thereof |
| CN103087629A (en) * | 2012-12-18 | 2013-05-08 | 芜湖恒坤汽车部件有限公司 | Anti-corrosion metal surface silane treatment agent and preparation method thereof |
| CN103668155A (en) * | 2013-12-06 | 2014-03-26 | 长沙艾森设备维护技术有限公司 | Passivating solution and method for passivating ferrous metal surface by employing same |
| CN104328399A (en) * | 2013-07-22 | 2015-02-04 | 无锡永发电镀有限公司 | Aluminium alloy surface passivation solution replacing chromium passivation |
| CN104451641A (en) * | 2014-12-05 | 2015-03-25 | 北京蓝星清洗有限公司 | Water-based composite passivation solution for galvanized steel plate and preparation method of water-based composite passivation solution |
| CN106756959A (en) * | 2016-12-14 | 2017-05-31 | 宁波翔博机械有限公司 | A kind of corrosion resistant galvanized steel plain sheet and preparation method |
| CN107419257A (en) * | 2017-07-04 | 2017-12-01 | 安徽腾龙泵阀制造有限公司 | A kind of surface passivating treatment technique of galvanized steel plain sheet |
-
2018
- 2018-12-21 CN CN201811567578.XA patent/CN109536937B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965657A (en) * | 2012-11-22 | 2013-03-13 | 象山华鹰塑料工程有限公司 | Surface treatment fluid for zinc alloy surface anticorrosion film |
| CN103031550A (en) * | 2012-12-18 | 2013-04-10 | 安徽翔艺达机械有限公司 | Metallic workpiece pretreatment silane surface treatment agent and preparation method thereof |
| CN103087629A (en) * | 2012-12-18 | 2013-05-08 | 芜湖恒坤汽车部件有限公司 | Anti-corrosion metal surface silane treatment agent and preparation method thereof |
| CN104328399A (en) * | 2013-07-22 | 2015-02-04 | 无锡永发电镀有限公司 | Aluminium alloy surface passivation solution replacing chromium passivation |
| CN103668155A (en) * | 2013-12-06 | 2014-03-26 | 长沙艾森设备维护技术有限公司 | Passivating solution and method for passivating ferrous metal surface by employing same |
| CN104451641A (en) * | 2014-12-05 | 2015-03-25 | 北京蓝星清洗有限公司 | Water-based composite passivation solution for galvanized steel plate and preparation method of water-based composite passivation solution |
| CN106756959A (en) * | 2016-12-14 | 2017-05-31 | 宁波翔博机械有限公司 | A kind of corrosion resistant galvanized steel plain sheet and preparation method |
| CN107419257A (en) * | 2017-07-04 | 2017-12-01 | 安徽腾龙泵阀制造有限公司 | A kind of surface passivating treatment technique of galvanized steel plain sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109536937A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109536937B (en) | High-corrosion-resistance galvanized steel sheet and preparation method thereof | |
| EP3006526B1 (en) | Hot-dip aluminum-zinc coated steel sheet with excellent weatherability, corrosion resistance, and alkali resistance, and preparation method and surface treatment agent therefor | |
| Tavandashti et al. | Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor | |
| RU2660490C2 (en) | Anti-corrosive coating composition | |
| DE10320765A1 (en) | Means for coating metals to protect against corrosion | |
| DE10320779A1 (en) | Corrosion protection on metals | |
| KR101715825B1 (en) | Non-solvent high-anticorrosive paint and silane containing high-anticorrosive paint and painting method of double-coated ultraweatheralbility steel structure using the high-anticorrosive paint | |
| EP3075881B1 (en) | Non-combustible color steel sheet for household appliances and building materials and method for manufacturing same | |
| CN104017458A (en) | Solvent-free epoxy antirust coating capable of coating with rust and preparation method thereof | |
| US6749945B2 (en) | Advanced composite ormosil coatings | |
| CA2689947C (en) | Coatings for corrosion susceptible substrates | |
| CN114456683B (en) | Anti-corrosion finish paint and preparation method thereof | |
| CN108329801B (en) | Environment-friendly integrated waterproof coating and preparation method thereof | |
| CN111019465B (en) | Preparation process of organic-inorganic composite water-based acrylic acid anticorrosive paint | |
| CN110735133B (en) | Closed waterborne polyurethane composition and metal surface pretreatment method | |
| KR102064527B1 (en) | A metal panel improved in corrosion, heat shielding and scratching function, and a manufacturing method thereof | |
| CN115637094B (en) | Cast magnesium alloy protective coating system and preparation and use methods thereof | |
| CN113015770A (en) | Organic-inorganic composite coating composition and galvanized steel sheet surface-treated with the same | |
| CN110724414A (en) | Stain-resistant high-temperature-resistant water-based paint and preparation method thereof | |
| CN113789097B (en) | Water-based hardware automatic spraying coating and preparation method thereof | |
| CN115216203A (en) | Water-based chromium-free Dacromet green coating and preparation method thereof | |
| CN112126880A (en) | High-corrosion-resistance hot-dip galvanized steel plate and preparation method thereof | |
| CN111647334A (en) | Laminated scaly heavy-duty anticorrosive paint and preparation method thereof | |
| Zhang et al. | Effect of Sol-Gel Film on the Corrosion Resistance of Low Carbon Steel Plate | |
| CN109810631A (en) | Waterborne organic silicon sol paint and preparation method thereof and product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |