CN110835770A - Iron plating solution for pretreatment bottom plating for manufacturing galvanized steel sheet - Google Patents
Iron plating solution for pretreatment bottom plating for manufacturing galvanized steel sheet Download PDFInfo
- Publication number
- CN110835770A CN110835770A CN201910766074.9A CN201910766074A CN110835770A CN 110835770 A CN110835770 A CN 110835770A CN 201910766074 A CN201910766074 A CN 201910766074A CN 110835770 A CN110835770 A CN 110835770A
- Authority
- CN
- China
- Prior art keywords
- iron
- plating solution
- steel sheet
- plating
- iron plating
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/34—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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Abstract
The present invention relates to an iron plating solution for pretreatment bottom plating for manufacturing a galvanized steel sheet. The iron plating solution for pretreating bottom plating according to the present invention comprises: a salt containing iron; an alkaline salt for adjusting the pH of the iron plating solution; an antioxidant and a complexing agent for inhibiting the formation of iron oxide and inhibiting the formation of precipitates in the iron plating solution; a surface modifier for smoothing an iron-plated coating film covering the matrix iron; a co-precipitating agent; and a stress reducer. According to the above configuration, it is possible to produce a hot-dip galvanized steel sheet having a good surface appearance by completely suppressing the occurrence of non-plating defects on the plated surface after hot-dip galvanizing the cold-rolled steel sheet while suppressing the release of Mn, Si, and the like from the cold-rolled steel sheet or the high-tensile steel sheet for automobiles due to external physical impact, thermal shock, or chemical impact.
Description
Technical Field
The present invention relates to an iron plating solution for pretreatment bottom plating for manufacturing a galvanized steel sheet.
Background
Steel sheets are widely used as structural materials for automobiles, home electric appliances, building materials, and the like because of their excellent mechanical strength, good workability, and abundant resources, but since steel sheets themselves are very poor in corrosion resistance, they are usually galvanized on the surface to prolong the life thereof.
The steel plate for household appliances mainly uses an electro-galvanized steel plate as a main material, and is coated or added with patterns in order to improve the aesthetic property or visual effect of the surface, and the high-grade appearance is preferably considered in the design, and manufacturers are required to meet the requirements. However, in order to achieve beauty, defects of materials must be removed, and an under plating technique or a painting technique capable of hiding the defects which cannot be removed is required.
Therefore, in order to hide defects such as umbrella-shaped, spilt-shaped marking of the base layer, a process of plating nickel and a corresponding electrolyte in a pretreatment process of electrogalvanized steel sheet production equipment to be 50mg/m2～150mg/m2The plating amount of (2) hides the defects of the base layer, resulting in an effect of improving the ability of the pretreatment process. This, in turn, brings about the derivatization effect of using the Ni flash plating technique in the pretreatment of all surface treatment processes.
Although the amount of nickel plated on steel sheets for home appliances is very small, it is considered that nickel plating is harmful to the environment according to public opinion, and development of other techniques is required.
That is, nickel is classified as a heavy metal, and the investment cost for wastewater treatment of wastewater containing nickel electrolyte is increased due to strict wastewater discharge conditions (in korea, the content of discharged water is required to be 20mg to 40 mg/liter depending on regions, and in china, the content of discharged water is required to be 0.2 to 0.4ppm depending on regions), so that it is difficult to use the above-mentioned technology.
In addition, in the case of steel sheets for automobiles, the pretreatment capability of hot-dip galvanized steel sheets or the defects of the base layer in the original market environment do not have as great an influence on the aesthetic appearance of the plated surface layer.
However, as the types of automobile steel sheets become various, the cases of the automobile steel sheets also change.
That is, the advent of electric vehicles, hydrogen fuel cell vehicles, and vehicles that consume less fuel than conventional fossil fuel vehicles and eliminate sources of air pollution has led to the need for re-evaluation of fuel consumption of fossil fuel vehicles fueled by light oil or unleaded gasoline.
In order to reduce fuel consumption, the weight of automobiles must be reduced, and alternative materials must be developed, and moreover, the weight reduction of automobiles is not limited to fossil fuel automobiles, electric automobiles, hydrogen fuel cell vehicles, but also must be driven over long distances with less fuel, so that the development of alternative materials for automobile steel plates for weight reduction of automobiles is a hot tide all over the world.
Aluminum steel plates are light and strong in tensile force, and therefore can be used as an alternative material, but aluminum welding is difficult and requires a special connecting device or a steel plate joining technique. Therefore, the cost per car is increased by 200 to 300 ten thousand won.
With the development of steel sheets having light weight and high tensile strength steel sheets for automobiles using iron as a material, a new steel market is on the spot, but steel cannot be directly used as a material. That is, only by imparting corrosion resistance to the surface of the iron and steel plate material through other metal or chemical conversion treatment can durability and aesthetic property be imparted to the product to improve the value of the product.
In order to improve tensile strength, newly developed high tensile strength automobile steel sheets are composed of a plurality of metal elements or metal-like elements, and typically have increased Mn and Si components, but Mn and Si are elements that are easily oxidized and cause non-plating defects when hot dip galvanizing is performed.
[ Prior art documents ]
[ patent document ]
Patent document 1: korean granted patent No. 10-0428561 (granted on 12.04.2004)
Patent document 2: korean patent No. 10-0971555 (granted on 14 months in 2010)
Patent document 3: korean granted patent No. 10-0360098 (granted on 10/25/2002)
Disclosure of Invention
The invention provides an iron plating solution for pre-treatment bottom plating for manufacturing a galvanized steel sheet with beautiful surface.
The present invention also provides an iron plating solution for pre-treatment bottom plating for manufacturing a hot-dip galvanized steel sheet having a beautiful surface.
The invention also provides an iron plating solution for pre-treatment bottom plating for manufacturing the electro-galvanized steel sheet with beautiful surface.
The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
The iron plating solution for pretreatment bottom plating for manufacturing a galvanized steel sheet according to the present invention includes: a salt containing iron; an alkaline salt for adjusting the pH of the iron plating solution; an antioxidant and a complexing agent for inhibiting the formation of iron oxide and inhibiting the formation of precipitates in the iron plating solution; a surface modifier (leveling agent) for smoothing an iron-plated coating film covering the matrix iron; a co-precipitating agent (precipitation assisting agent); and a stress reducer.
The iron plating solution may be prepared by dissolving ferrous sulfate powder or ferrous chloride powder, or may be prepared by dissolving iron powder in an aqueous sulfuric acid solution.
The iron plating solution can be prepared by dissolving ferrous sulfate in an electrolyte at a ratio of 10-900 g/L or ferrous chloride in a ratio of 10-800 g/L, or dissolving iron powder in a sulfuric acid aqueous solution at a ratio of 1g of iron powder to 0.5-10 g of concentrated sulfuric acid, wherein the purity of the iron powder is above 90%, the size of the iron powder is 10-500 μm, and the concentration of the concentrated sulfuric acid is above 90%. When the amount of the iron powder is 100g, 50-1000 g of concentrated sulfuric acid with a concentration of 90% or more is dissolved in the iron powder at a corresponding ratio.
The iron plating solution may be prepared by adding 1 to 500 g/l of ammonia water to the aqueous solution of ferrous sulfate or ferrous chloride or the iron plating solution prepared by dissolving iron in concentrated sulfuric acid to prepare an alkaline salt, so that the pH of the iron plating solution (stock solution: solution in a state where pure water or diluted water is not added for plating) is in the range of 5 to 14 at room temperature.
Fe metal ions (including Fe) in the iron plating solution2+、Fe3+The total of all the Fe ions contained in the solution) may be 20 to 120 g/liter in the stock solution.
The iron plating solution may be diluted to 35 to 55 g/liter, and then the plating operation may be performed in a state where the temperature of the electrolyte is 25 to 85 ℃ within a range of pH 0.8 to 2.5.
The plating operation can be performed by using the iron plating solution at a current density of 10 to 150 ASD.
The iron plating solution may include any one or more selected from the group consisting of disodium ethylenediaminetetraacetate (EDTA-2Na), monoethanolamine Sulfamic Acid (monoethanolamine Amine sulfonic Acid), Ammonium hydroxide (Ammonium hydroxide), ethylene-chlorohydrine (ethylene-chlorohydrine), Hydrogen Oxide (Hydrogen Oxide), and polyethylene glycol (polyethylene glycol).
The alkaline salt may be used to increase the pH of the iron plating solution.
The galvanized steel sheet may be a high-tensile automotive steel sheet.
The high tensile automotive steel sheet may be Giga steel (Giga steel).
In the manufacturing process of the hot-dip galvanized steel sheet, the pretreatment bottom plating iron plating solution is used as a bottom plating electrolyte for the base iron and is used in an apparatus located between the pretreatment process and the base heat treatment process. The pretreatment process is used for cleaning the surface of the steel plate to maintain the cleanness of the matrix iron, and the matrix heat treatment is positioned before the non-oxidation annealing furnace process used for the annealing treatment.
Specific matters of other embodiments are included in the following detailed description.
According to the iron plating solution for pretreatment bottom plating of the present invention, it is possible to form an unoxidized pure iron plating layer by performing iron plating after performing a pretreatment process (degreasing, pickling) on a base layer of a cold-rolled steel sheet (a general cold-rolled steel sheet and a high-tensile steel sheet for an automobile), and further it is possible to suppress a phenomenon that metal particles or element particles (Mn, Si, etc.) of similar metals are released from the base layer of the cold-rolled steel sheet or the high-tensile steel sheet for an automobile due to external physical impact, thermal impact, or chemical impact, and to completely suppress unplated defects occurring on a plating surface after hot-dip galvanizing the base layer of the cold-rolled steel sheet, thereby producing a hot-dip galvanized steel sheet having a good surface appearance.
Further, according to the iron plating solution for pretreating bottom plating of the present invention, it is possible to completely suppress defects after the electrogalvanizing process, which are originally invisible to the naked eye on the surface of the cold-rolled steel sheet due to metal thickening on the surface of the cold-rolled steel sheet.
Those skilled in the art will be able to fully understand that the embodiments of the technical idea of the present invention can provide various effects not specifically mentioned.
Drawings
Fig. 1 is a photograph showing a plating surface and a plating amount according to pH.
Fig. 2 is a graph showing plating efficiency (% current efficiency of the electrolyte) according to pH.
Fig. 3 is a photograph showing the electrolyte complexing agent without generating sludge (precipitate).
Fig. 4 is a photograph showing the results of the adhesion test of iron plating.
FIGS. 5a to 5c are photographs of the surface of test pieces showing the results of the reproducibility test of the splay defect for the electrogalvanized steel sheet having the splay defect of the company D.
Detailed Description
The advantages, features and methods of accomplishing the same of the present invention will become more apparent with reference to the embodiments described in detail hereinafter. However, the present invention is not limited to the embodiments described herein, and may be embodied in other forms. The embodiments described herein are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include the plural expressions unless the context clearly dictates otherwise.
Unless defined differently, all terms used herein including technical or scientific terms have the same meaning as commonly understood by one having ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Hereinafter, the iron plating solution for pretreatment of bottom plating according to the present invention will be described in detail.
The iron plating solution for pretreatment undercoating for manufacturing a galvanized steel sheet according to the present invention includes a salt containing iron, an alkaline salt for adjusting (e.g., raising) the pH of the iron plating solution, an antioxidant and a complexing agent for suppressing the formation of iron oxide and the formation of precipitates in the iron plating solution, a surface modifier (leveling agent) for smoothing an iron plating film covering a matrix iron, a co-precipitation agent (precipitation assistant), and a stress reducer.
The galvanized steel sheet may be a high-tensile automotive steel sheet. The high tensile automotive steel sheet may be giga steel (Gigasteel). In the manufacturing process of the hot-dip galvanized steel sheet, the pretreatment bottom plating iron plating solution is used as a bottom plating electrolyte for the base iron and is used in an apparatus located between the pretreatment process and the base heat treatment process. The pretreatment process is used for cleaning the surface of the steel plate to maintain the cleanness of the matrix iron, and the matrix heat treatment is positioned before the non-oxidation annealing furnace process used for the annealing treatment.
Also, the iron plating solution may be prepared by dissolving ferrous sulfate powder or dissolving iron powder in an aqueous sulfuric acid solution.
The iron plating solution may be prepared by dissolving ferrous sulfate in an electrolyte at a concentration of 10 to 900 g/liter, or by dissolving iron powder in an aqueous sulfuric acid solution at a ratio of 1g of iron powder to 0.5 to 10g of concentrated sulfuric acid, wherein the purity of the iron powder is 90% or more, the size of the iron powder is 10 to 500 μm, and the concentration of the concentrated sulfuric acid is 90% or more. When the amount of the iron powder is 100g, 50-1000 g of concentrated sulfuric acid with a concentration of 90% or more is dissolved in the iron powder at a corresponding ratio.
In order to prevent the reduction of current efficiency due to the reduction of pH by gases (e.g., oxygen and hydrogen) generated during the iron electroplating operation, ammonia water may be added to the ferrous sulfate aqueous solution or the iron plating solution prepared by dissolving iron in concentrated sulfuric acid at a concentration of 1 to 500 g/l to prepare an alkaline salt, so that the pH of the iron plating solution (stock solution: solution without adding pure water or diluted water for the plating operation) may be in a range of 5 to 14 at room temperature.
And, Fe metal ions (including Fe) in the iron plating solution2+、Fe3+The total of all the Fe ions contained in the solution) may be 20 to 120 g/liter in the stock solution.
The iron plating solution may be diluted to 35 to 55 g/liter, and the plating operation may be performed at a pH of 0.8 to 2.5 and at an electrolyte temperature of 25 to 85 ℃.
Further, the plating operation can be performed by using the iron plating solution at a current density of 10 to 150 ASD.
In order to improve the plating surface and the plating characteristics, the iron plating solution may use organic or inorganic additives having functions of a complexing agent, a leveling agent, a co-precipitating agent, an antioxidant, and the like, and may include one or more substances selected from the group consisting of EDTA-2Na (disodium ethylenediaminetetraacetate), (monoethanolamine sulfonic Acid), Ammonium hydroxide (Ammonium hydroxide), ethylene-chlorohydrine (chlorohydrin), Hydrogen Oxide (Hydrogen Oxide), and Polyethylene Glycol (Polyethylene Glycol).
The antioxidant is used for preventing ferrous ions in the iron plating solution from being oxidized into ferric ions, and ethylenediamine + citric acid series, glycine, benzene sulfonate, 4-oxo-valeric acid or a mixture of the two can play the function.
The stress reducer may use tridecyloxy poly (ethyleneoxy) ethanol (III), N- (3-hydroxybutylidene) p-aminobenzenesulfonic acid (N- (3-Hydroxy butylidene) -p-sulfonicic acid), diisodecyl phthalate, or a mixture thereof.
As the co-precipitating agent of the precipitation auxiliary agent, ethyleneimine may be used, and the co-precipitating agent may perform an action of causing a trace amount of metal components present in the plating solution to be precipitated together with electrodeposition of iron components.
The surface modifier (leveling agent) densifies the structure of the electrodeposited iron plating while suppressing gas generation at the anode and supplying uniform electrons when the cathode performs an electrodeposition reaction, thereby making the electrodeposition process smoothly performed. The surface modifier can use 2-methoxy-1-naphthaldehyde, glycol, polyethylene glycol, monolauryl ether, polyimine, ethylenediamine and other anionic surfactants, and preferably uses nonionic surfactants. Alternatively, a mixture of these and the like may be used.
The complexing agent enables an iron metal component and a conductive salt to react well in the iron plating solution, and can improve the stability of iron ions in the plating solution, thereby bringing the effect that the iron ions are not easy to oxidize. The complexing agent may be gluconic acid, ethylenediamine + citric acid series, glycine, benzenesulfonate, 4-oxo-pentanoic acid, or a mixture thereof.
In addition, the reducing agent is oxidized to supply electrons to the metal ions to precipitate the metal ions as a metal. In order to improve the reduction efficiency, the reducing agent should be stable against self-decomposition after the plating solution is prepared, and should not cause precipitation in the resultant after the reduction is performed.
Further, it is necessary to be able to control the precipitation rate.
The reducing agent used is sodium hypophosphite (NaH)2PO2H2O), Dimethylaminobenzaldehyde (DMAB), Diethylaminobenzaldehyde (DEAB), sodium borohydride (SHB: sodium borohydrate, NaBH)4) For example, sodium hypophosphite has a property of precipitating together with phosphorus (P) as a strong reducing agent.
When electrolytic plating and chemical metal electrodeposition occur, stress occurs inside the plating layer. Such stress naturally generates tension (tensile) and compression (compressive) because expansion (extended) or contraction (contact) occurs between the substance of the plated layer and the plated layer. Residual stress in the plating layer affects the characteristics of the plating layer. When a large stress is applied, peeling, cracking, bulging, and the like of the plating layer due to insufficient adsorption are observed, and various phenomena such as corrosion of the plating layer, reduction in fatigue strength due to high tensile force, and non-plating of the plating layer occur.
The stress remover may use tridecyloxy poly (ethyleneoxy) ethanol, N- (3-hydroxybutylidene) sulfanilic acid, diisodecyl phthalate, or a mixture thereof.
As a result of observing the experiment of the solution containing no ammonia, the thickness of the plating layer was very thin, and it was found that the electrodeposition rate was very slow. However, the higher the concentration of ammonia, the thicker the thickness of the plating layer. Namely, it was confirmed that the plating speed was affected. Further, it was confirmed that the higher the concentration of ammonia, the more stable the plating surface shape. It is known that this has a very close correlation with the pH of the electrolyte.
The effect of the complexing agent in the plating is very important. The component proportion of the plating layer or whether plating is carried out or not is determined according to the type and concentration of the complexing agent. The complexing agent stabilizes the pH of the solution and reduces the difference in the reduction potentials of the two metals during alloy plating, thereby acting to facilitate good alloy formation.
Therefore, with the present patent, studies were made on how the complexing agent for Fe plating affects the plating layer and the secondary plating. In order to investigate the influence of the plating layer, the change of the surface of the plating layer and the plating speed were observed.
The hydrocarbon-based complexing agent is a representative complexing agent in Fe plating, and may include at least any one of carboxylic acids, α -hydroxy acids (AHAs), and amino acids, for example, the complexing agent may include at least any one of carboxylic acids having a carboxyl group (COOH) and derivatives thereof, the complexing agent may include at least any one of α -hydroxy acids (AHAs) and derivatives thereof in which a part of the carboxyl group (COOH) is substituted with a hydroxyl group (OH), and the complexing agent may include a group having both a carboxyl group (COOH) and an amino group (NH) and a hydroxyl group (COOH), and the complexing agent may include a group having a carboxyl group (COOH) and an amino group2) At least any one of the amino acids and derivatives thereof of (1).
The α -hydroxy acid does not significantly affect the stability of the plating solution or the rate of formation of the plating layer when mixed as a single component in an Fe plating electrolyte, but rather acts to increase the rate of formation of the plating layer when added with two or more complexing agents.
Hereinafter, examples of the iron plating solution for preliminary plating according to the present invention and comparative examples will be described in more detail with reference to the accompanying drawings.
Fig. 1 is a photograph showing a plating surface and a plating amount according to pH.
Referring to fig. 1, it was confirmed that the plating amount has a close relationship with pH.
Also, the plated surface becomes black due to the influence of hydroxide generated in the plating, which becomes an oxidized surface, so that the iron plating layer may also be dissolved by the sulfur zinc electrolyte in the electro-galvanizing process.
Fig. 2 is a graph showing plating efficiency (% current efficiency of the electrolyte) according to pH.
Referring to fig. 2, it can be known that plating efficiency is approximately proportional to pH in a certain pH range.
Fig. 3 is a photograph showing the electrolyte complexing agent without generating sludge (precipitate).
Referring to fig. 3, the precipitates in the iron plating solution do not generate oxides due to oxygen or hydrogen generated over time or at the time of plating.
Fig. 4 is a photograph showing the results of the adhesion test of iron plating.
The adhesion test of the iron plating was performed in the following manner.
2 Sn/Cu plates
Plating adhesion test
Measurement equipment: cross Hatch Cutters (ERICHSEN/295)
The determination method comprises the following steps: relevant Standard-ASTM D3359
Number of cuts x distance (mm): 11X 1
-thickness of the layer: 50 to 125 μm
-adhesive Tape (Tape): TESA #7475
Adhesion to steel: 12.5N/cm (original)
Referring to fig. 4, it can be confirmed that the adhesion test result is no peeling of the plating layer between the cells.
FIGS. 5a to 5c are photographs showing the surface of test pieces subjected to the reproducibility test of the shot defects with respect to the electrogalvanized steel sheet having shot defects of the company D.
The steel sheet in which the shot or umbrella-shaped defect occurs after the electrogalvanizing is performed has a property in which the defect occurs again when the zinc plating layer is immersed in a normal-temperature 5% hydrochloric acid aqueous solution and the electrogalvanizing is performed again.
FIGS. 5b and 5c show the surface of a steel sheet after electrogalvanizing a steel sheet having a serious umbrella-shaped or spikelet-shaped defect of the company D by cutting the steel sheet into test pieces of 70mm × 150mm, immersing the steel sheet in an aqueous solution at room temperature containing 5% hydrochloric acid for several minutes, and then performing electrogalvanizing at 50A/4 minutes, and FIG. 5A shows the surface of the steel sheet after electrogalvanizing the test pieces for 35A/10 seconds and then for 50A/4 minutes.
Referring to fig. 5a to 5c described above, it was confirmed that the umbrella-shaped or spikelet-shaped defects occurring in the base layer were completely hidden after the iron plating using the iron plating solution for bottom plating according to the present invention.
Although the preferred embodiments of the present invention have been illustrated and described, it will be understood by those having ordinary knowledge in the art to which the present invention pertains that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. The embodiments described above are therefore to be considered in all respects as illustrative and not restrictive.
Claims (10)
1. An iron plating solution for pre-treatment bottom plating for manufacturing a galvanized steel sheet, comprising:
a salt containing iron;
an alkaline salt for adjusting the pH of the iron plating solution;
an antioxidant and a complexing agent for inhibiting the formation of iron oxide and inhibiting the formation of precipitates in the iron plating solution;
a surface modifier for smoothing an iron-plated coating film covering the matrix iron;
a co-precipitating agent; and
a stress reducing agent.
2. The iron plating solution for pretreatment undercoating according to claim 1,
the iron plating solution is prepared by dissolving ferrous sulfate powder or ferrous chloride powder, or by dissolving iron powder in an aqueous sulfuric acid solution.
3. The iron plating solution for pretreatment undercoating according to claim 2,
the iron plating solution is prepared by dissolving ferrous sulfate in an electrolyte in an amount of 10-900 g/L or ferrous chloride in an amount of 10-800 g/L, or dissolving iron powder in a sulfuric acid aqueous solution in an amount of 0.5-10 g of concentrated sulfuric acid per 1g of iron powder, wherein the purity of the iron powder is above 90%, the size of the iron powder is 10-500 μm, and the concentration of the concentrated sulfuric acid is above 90%.
4. The iron plating solution for pretreatment undercoating according to claim 3,
the iron plating solution is prepared by adding 1-500 g/L ammonia water to the aqueous solution of ferrous sulfate or ferrous chloride or an iron plating solution prepared by dissolving iron in concentrated sulfuric acid to prepare an alkaline salt, so that the pH of the iron plating solution is in the range of 5-14 at normal temperature, wherein the iron plating solution is a stock solution without adding pure water or diluted water for plating operation.
5. The iron plating solution for pretreatment undercoating according to claim 4,
the amount of Fe metal ions in the iron plating solution is 20-120 g/L in the stock solution, wherein the Fe metal ions comprise Fe2+、Fe3+The sum of all the Fe ions contained.
6. The iron plating solution for pretreatment undercoating according to claim 5,
diluting the iron plating solution to 35-55 g/L, and further performing plating operation in a state that the pH value is within a range of 0.8-2.5 and the temperature of the electrolyte is within a range of 25-85 ℃.
7. The iron plating solution for pretreatment undercoating according to claim 6,
performing a plating operation using the iron plating solution at a current density of 10 to 150 ASD.
8. The iron plating solution for pretreatment undercoating according to claim 7,
the iron plating solution includes any one or more selected from the group consisting of disodium ethylenediaminetetraacetate, monoethanolamine sulfamic acid, ammonium hydroxide, chlorohydrin, hydrogen oxide, and polyethylene glycol.
9. The iron plating solution for pretreatment undercoating according to claim 1,
in a manufacturing process of a hot-dip galvanized steel sheet, the pre-treatment bottom plating iron plating solution is used as an electrolyte for bottom plating of base iron, and is used in an apparatus located between a pre-treatment process for cleaning the surface of the steel sheet to maintain the cleanliness of the base iron and a base heat treatment process located before a non-oxidation annealing furnace process for annealing treatment,
the galvanized steel sheet is a high-tension automobile steel sheet;
the high-tension automobile steel plate is gigabit steel.
10. The iron plating solution for pretreatment undercoating according to claim 1,
the alkaline salt is used to increase the pH of the iron plating solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0096021 | 2018-08-17 | ||
| KR1020180096021A KR101974066B1 (en) | 2018-08-17 | 2018-08-17 | iron plating solution for pretreament underplating to make giga steel at steel sheet surface for high-tension automobile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110835770A true CN110835770A (en) | 2020-02-25 |
Family
ID=67763781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910766074.9A Pending CN110835770A (en) | 2018-08-17 | 2019-08-19 | Iron plating solution for pretreatment bottom plating for manufacturing galvanized steel sheet |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101974066B1 (en) |
| CN (1) | CN110835770A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881991A (en) * | 2021-11-19 | 2022-01-04 | 山东省路桥集团有限公司 | Coating pretreatment method for steel structure bridge |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023553487A (en) * | 2020-12-14 | 2023-12-21 | ポスコ カンパニー リミテッド | Iron electroplating solution and electroplated steel sheets manufactured using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020160221A1 (en) * | 2001-04-25 | 2002-10-31 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hot-dip galvanized steel sheet |
| KR20090112919A (en) * | 2008-04-25 | 2009-10-29 | 남동화학(주) | Zinc plated steel having iron flash plating film thereon and composition of bath of iron flash plating and method for manufacturing the zinc plated steel |
| CN104981346A (en) * | 2013-02-12 | 2015-10-14 | 塔塔钢铁艾默伊登有限责任公司 | Coated steel suitable for hot-dip galvanising |
| CN107385497A (en) * | 2016-06-10 | 2017-11-24 | 株式会社Ttm | Possess and constructed for carrying out the vertical-type plating coating groove of the soluble electrode of flash iron or plating iron |
| CN107805830A (en) * | 2017-10-11 | 2018-03-16 | 武汉钢铁有限公司 | Flash iron plating solution and flash method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100360098B1 (en) | 1998-12-04 | 2002-12-18 | 주식회사 포스코 | Chromate pretreatment solution for galvanized steel sheet |
| KR100428561B1 (en) | 2001-12-21 | 2004-04-29 | 주식회사 포스코 | Pretreatment Composition for Painted Steel Sheets |
| KR100971555B1 (en) | 2010-02-25 | 2010-07-21 | 주식회사 유니테크 | High concentration ni-flash plating composition for pre-treatment of cold-rolled steel sheet in electrolytic galvanized iron plating process |
-
2018
- 2018-08-17 KR KR1020180096021A patent/KR101974066B1/en active
-
2019
- 2019-08-19 CN CN201910766074.9A patent/CN110835770A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020160221A1 (en) * | 2001-04-25 | 2002-10-31 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hot-dip galvanized steel sheet |
| KR20090112919A (en) * | 2008-04-25 | 2009-10-29 | 남동화학(주) | Zinc plated steel having iron flash plating film thereon and composition of bath of iron flash plating and method for manufacturing the zinc plated steel |
| CN104981346A (en) * | 2013-02-12 | 2015-10-14 | 塔塔钢铁艾默伊登有限责任公司 | Coated steel suitable for hot-dip galvanising |
| CN107385497A (en) * | 2016-06-10 | 2017-11-24 | 株式会社Ttm | Possess and constructed for carrying out the vertical-type plating coating groove of the soluble electrode of flash iron or plating iron |
| CN107805830A (en) * | 2017-10-11 | 2018-03-16 | 武汉钢铁有限公司 | Flash iron plating solution and flash method |
Non-Patent Citations (1)
| Title |
|---|
| 张允诚等: "《电镀手册第3版》", 31 January 2007, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881991A (en) * | 2021-11-19 | 2022-01-04 | 山东省路桥集团有限公司 | Coating pretreatment method for steel structure bridge |
| CN113881991B (en) * | 2021-11-19 | 2023-08-11 | 山东省路桥集团有限公司 | Pretreatment method for coating steel structure bridge |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101974066B1 (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102260891B (en) | Method for electrodepositing nanocrystalline nickel-cobalt alloy by double-pulse | |
| CN102433577B (en) | Rare earth-nickel-cobalt-boron multi-element alloy anticorrosion and wear-resistant plating, electroplating liquid and preparation method of electroplating liquid | |
| CN109957822B (en) | Copper alloy electroplating process | |
| TWI630284B (en) | Passivation of micro-discontinuous chromium deposited from a trivalent electrolyte | |
| CN113463072B (en) | Method for chemically plating nickel or nickel alloy coating in eutectic solvent | |
| CN110835770A (en) | Iron plating solution for pretreatment bottom plating for manufacturing galvanized steel sheet | |
| CN102605393B (en) | Ni-W-Fe-Co alloy electroplating liquid and electroplating process thereof | |
| CN102492968A (en) | Copper plating method on brass base material | |
| CN107923056B (en) | Electrogalvanized steel sheet produced using flash galvanizing solution and method for producing same | |
| CN100487168C (en) | Electrolyte media for the deposition of tin alloys and methods for depositing tin alloys | |
| CN102703763B (en) | Multielement zinc-aluminum alloy wire and manufacturing method thereof | |
| CN110117783A (en) | A kind of method of Electroless Nickel Plating of Aluminum Alloy mixed metal activation | |
| CN109518237A (en) | Zinc-nickel phosphorus electroplate liquid, preparation method and electro-plating method | |
| Das et al. | Effect of bath stabilizers on electroless nickel deposition on ferrous substrates | |
| CN102171386A (en) | Zinc alloy electroplating baths and processes | |
| CN105543912A (en) | Method for preparing compound surfactant/La-Ni-Mo-W codeposited coating on copper matrix | |
| CN110129779B (en) | Method for chemically dipping iron on surface of aluminum alloy | |
| CN111270276A (en) | Flash galvanizing plating solution and preparation method thereof and flash galvanizing method | |
| KR20200092882A (en) | Indium electroplating compositions and methods for electroplating indium on nickel | |
| CN110129842A (en) | A kind of compound cyanide-free gold electroplating plating solution preparation and gold process is electroplated using its | |
| CN108411343A (en) | A kind of plating cobalt tungsten manganese high-strength steel and its preparation method and application | |
| CN216074060U (en) | Coating structure for zinc alloy die casting plated with pearl nickel and electrophoretic painting | |
| Thangaraj | Electrodeposition and corrosion behaviour of some Zn–Fe group metal alloys by pulsed current | |
| CN108559915B (en) | A kind of dilval and preparation method thereof | |
| CN117248257A (en) | Ternary alloy electrodeposition method |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200225 |