KR100940651B1 - Electrically Galvanized Steel Sheet Having Excellent Corrosion Resistance and Surface Appearance and Manufacturing Method Thereof - Google Patents

Abstract

The present invention includes a zinc nickel lead plating layer 1-9 g / m ² including 8-12 wt% Ni formed on the surface of a steel sheet and a zinc plating layer of 8 g / m ² or more formed on the zinc nickel lead plating layer, wherein the zinc plating layer The present invention relates to a multilayer galvanized steel sheet and a method of manufacturing such a steel sheet, characterized in that the current density at the time of forming the zinc nickel lead gold layer is 1.1 to 1.5 times the current density.

The multi-layer galvanized steel sheet according to the present invention includes an appropriate zinc-nickel alloy lead plating layer and a zinc plating layer by zinc electroplating, and by determining an optimal current density ratio when forming a plating layer, excellent corrosion resistance, adhesion and surface whiteness and linearity It has a surface appearance where no mark is generated.

Zinc Nickel Leading Gold Layer, Multi-Layer Galvanized Steel Sheet, Current Density, Ballistic Plating, Surface Whiteness

Description

Electrically Galvanized Steel Sheet Having Excellent Corrosion Resistance and Surface Appearance and Manufacturing Method Thereof}

The present invention relates to a galvanized steel sheet and a method for manufacturing the same, which are capable of ensuring excellent corrosion resistance and surface appearance in the case of galvanizing a steel sheet, and more particularly, improve the corrosion resistance of a galvanized steel sheet and appear on the plating layer. The present invention relates to a galvanized steel sheet and a method for manufacturing the same, which improve surface appearance by removing streaks or linear marks.

Galvanized steel sheet has many advantages in terms of ease of plating, economics, corrosion resistance, etc. among the surface-treated products is a steel sheet widely used as a member for home appliances, construction members, automotive members and the like.

In general, galvanized steel sheet is generally protected by the sacrificial method of the plating layer formed on the surface. That is, since corrosion or damage of the plating layer is made first and then the steel sheet is damaged, it is very important to secure corrosion resistance of the plating layer itself in the plated steel sheet. In addition, such a galvanized steel sheet is often used as a coating steel sheet, so the surface appearance of the plating layer also needs to be excellent.

In order to improve the corrosion resistance of the plating layer, it is important to slow down the corrosion of the zinc component in the zinc plating layer.In order to reduce the corrosion rate of the zinc component, alloy plating (zinc-nickel, zinc-cobalt, zinc-iron, etc.) has been developed and used. have.

However, if only the zinc alloy plated layer is used to secure corrosion resistance, the manufacturing cost of the plated steel sheet increases, and if the plated layer becomes thick due to brittleness of the alloyed metal, cracks may occur during processing and the adhesion to the steel sheet is deteriorated. May appear.

Plating of the galvanized steel sheet is mainly performed by a zinc electroplating method, and zinc electroplating baths, which are frequently used, include chloride baths, sulfate baths, cyan baths and neutral salt baths. Among them, the sulfate bath is a plating bath that is used because it uses less insoluble electrode than other plating baths due to the use of insoluble electrode. Appears, and has the problem that the adhesiveness of a plating layer becomes bad.

In order to suppress the occurrence of such linear mark or other streaks on the surface of the galvanized layer, it may be the most preferable method to prevent abnormal structure from recrystallization of the hot rolled steel sheet, which is the base iron of the cold rolled steel sheet. However, it is difficult to control the abnormal structure that may occur between the local particles and particles in a large number of continuous processes, so conventionally, a method for managing the surface appearance through various separate post-treatment processes such as using an additive is Although used, there is a limit to improving the surface appearance only by conventional methods such as using such additives.

The present invention is to provide a multilayer galvanized steel sheet having a superior surface appearance and further excellent corrosion resistance by solving the above problems and a method for making such a multilayer galvanizing.

The present invention includes Ni: 8 to 12% by weight formed on the surface of the steel sheet, characterized in that it comprises a zinc nickel lead gold layer of 1 ~ 9g / m ² and 8g / m ² or more galvanized layer formed on the zinc nickel lead gold layer A double layer galvanized steel sheet having excellent corrosion resistance and improved surface appearance.

Furthermore, the present invention is Ni on the surface of the steel sheet: the current density during the formation of 8% to 12% zinc nickel wire coating layer of 1 ~ 9g / m ² steps leading gold to form and the zinc-nickel plating The zinc-nickel wire coating layer during the formation that contains the weight It relates to a method for manufacturing a multi-layer galvanized steel sheet comprising a zinc plating step of forming a zinc plating layer of 8g / m ² or more at a current density of 1.1 ~ 1.5 times.

Furthermore, the present invention is Ni formed on the surface of the steel sheet: duplex galvanized containing 8 to 12 zinc nickel wire coating layer containing by weight% 1 ~ 9g / m ² and 8g / m ² or more of the zinc coating layer formed on the zinc-nickel wire coating layer It relates to a multi-layer galvanized steel sheet characterized in that the steel sheet is subjected to one or two or more post treatments selected from the group consisting of phosphate treatment, anti-fingerprint treatment, chromium treatment and coating treatment.

Furthermore, the present invention is Ni on the surface of the steel sheet: the current density during the formation of 8% to 12% zinc nickel wire coating layer of 1 ~ 9g / m ² steps leading gold to form and the zinc-nickel plating The zinc-nickel wire coating layer during the formation that contains the weight Phosphate treatment, anti-fingerprint, chromium treatment of the multilayer galvanized steel sheet manufactured by the method of manufacturing a multilayer galvanized steel sheet, comprising a galvanizing step of forming a galvanized layer of 8 g / m ² or more at a current density of 1.1 to 1.5 times. The present invention relates to a method for producing a multi-layer galvanized steel sheet, characterized in that one or two or more post-treatments selected from the group consisting of treatment and coating treatment.

The multi-layer galvanized steel sheet according to the present invention includes an appropriate zinc-nickel alloy lead plating layer and a zinc plating layer by zinc electroplating, and by determining an optimal current density ratio between the plating layers, it has excellent corrosion resistance, adhesion and surface whiteness, and linear marks. Has a surface appearance that does not occur.

Hereinafter, the zinc-nickel lead metal layer and plating conditions of the present invention will be described in detail.

As a lead, zinc-nickel plating is used to limit the nickel content of the plating layer to a range of 8 to 12% by weight, preferably 10 to 12% by weight, for corrosion resistance and adhesion. When the nickel content of the plating layer is less than 8% by weight, phase transformation (phase transformation between the gamma phase and the delta phase) of the plating layer may occur, which may cause corrosion resistance. On the other hand, although the corrosion resistance is increased up to about 17% by weight of the nickel content of the plating layer, when the nickel content exceeds 12% by weight, the adhesiveness of the plating layer is reduced by hardening, and defects easily occur when the chipping is impacted. Appears. Therefore, the nickel content of the zinc nickel plating layer is limited to 8 to 12% by weight.

The plating amount of the zinc-nickel plating layer is 1 to 9 g / m ² , and preferably 3 to 7 g / m ² . If less than 1g / m ² , the effect of improving the corrosion resistance is small and the effect of suppressing the linear mark on the surface is insignificant. On the other hand, if it exceeds 9g / m ² , the plating layer is hardened to reduce the surface adhesion during processing and the manufacturing cost is high. This can be high.

The zinc-nickel lead gold layer of the present invention may be formed using a hydrochloric acid bath or a sulfuric acid bath after a general degreasing and pickling process.

When the plating bath is formed with a hydrochloric acid bath, under the conditions of Zn: 70 to 110 g / L, Ni: 8 to 14 g / L, Cl: 200 to 310 g / L, temperature: 50 to 65 ° C, and pH: 3 to 5 Can be done.

In hydrochloric acid bath, Zn is added by 70 ~ 110g / L to secure proper Ni content in the lead gold layer. If it is less than 70g / L, the conductivity and plating efficiency are lowered. The gloss may be degraded, resulting in poor appearance.

Ni is added in the amount of 8 ~ 14g / L, less than 8g / L can not ensure the appropriate content of Ni to be included in the lead gold layer, while if it exceeds 14g / L, the plating layer may be hardened and workability may be reduced.

Cl may be added as much as 200 ~ 310g / L as an element for securing the plating efficiency and adhesion by adjusting the ion balance. If the content of Cl is less than 200g / L, the conductivity of the plating solution is lowered, the plating efficiency is lowered, while if it exceeds 310g / L, the ion balance is not matched, the plating adhesion is lowered.

The plating bath temperature of the hydrochloric acid bath can be 50 ~ 65 ℃ bar temperature is less than 50 ℃ because the ion activation of the plating layer is not achieved takes a long time to form the plating layer, while the plating solution is evaporated above 65 ℃ Can be difficult to control.

The pH of the hydrochloric acid bath is adjusted to 3-5. If the pH is less than 3, the surface appearance may deteriorate, whereas if the pH is greater than 5, the balance of plating ions may be broken and plating adhesion may be degraded.

When the plating bath is set as a sulfate bath to form a zinc-nickel lead gold layer, sulfuric acid bath conditions of Zn: 25 to 60 g / L, Ni: 40 to 80 g / L, temperature: 50 to 65 ° C, and pH: 1 to 3 Plating is performed at.

In the sulfuric acid bath, Zn is in the range of 25 to 60 g / L, but below 25 g / L, the conductivity and plating efficiency may be reduced, whereas when it exceeds 60 g / L, the gloss of the surface may be degraded, resulting in poor appearance.

In addition, Ni is added to 40 ~ 80g / L, less than 40g / L can not secure the appropriate content of Ni to be included in the lead gold layer, while if it exceeds 80g / L, the plating layer is cured, the workability may be reduced. .

The plating bath temperature of the sulfuric acid bath can be 50 ~ 65 ℃ like hydrochloric acid bath, if it is less than 50 ℃ thermal efficiency is low, it takes a long time to form the plating layer because the ion activation of the plating layer is not achieved, whereas if it exceeds 65 ℃ The plating liquid can evaporate, making control difficult.

And the pH of the sulfuric acid bath is adjusted to 1-3. If the pH is less than 1, the surface appearance may be deteriorated, whereas if the pH is greater than 3, the balance of plating ions may be broken and plating adhesion may be reduced.

Hereinafter, the zinc plating layer and plating conditions of the present invention will be described in detail.

If the plated layer of the plated steel sheet is formed only of an alloy plated layer, in particular a zinc-nickel plated layer, the manufacturing cost of the plated steel sheet is rapidly increased, and the physical properties of the plated steel sheet during post-treatment such as phosphate treatment are not sufficiently improved. In addition, such a plated steel sheet may have low adhesiveness after processing and whiteness of the plated layer may be reduced.

Therefore, in the present invention, after performing the zinc-nickel lead metal, the plating is performed on the zinc-nickel lead metal layer in an amount of 8 g / m ² or more in a zinc plating bath. At a plating amount of less than 8 g / m ² , the surface of the zinc-nickel lead gold layer is reflected, so that the whiteness of the surface may be reduced, and the thickness of the plating layer may be reduced, thereby reducing the corrosion resistance.

The current density at the time of forming the zinc plating layer of the present invention is controlled to 1.1 to 1.5 times the current density at the time of forming the zinc nickel lead gold layer, which is the lower plating layer. If the current density is less than 1.1 times, if the plating line speed is low, the initial impact voltage may be low, resulting in poor surface appearance due to grain coarsening.On the other hand, if it exceeds 1.5 times, edge ballistic plating may occur at high speed. It is limited to 1.5 times.

The ratio of the current density can be controlled by adjusting the voltage during the plating process. That is, if a specific voltage is applied to the resistance value of the plating layer, a desired current density can be obtained. A current density range is formed between the plating layers by applying a voltage such that the current density ratio is 1.1 to 1.5 times by using a voltage meter during plating. .

The zinc plated layer of the present invention is formed of a sulfuric acid bath for the surface appearance, unlike when forming a zinc-nickel lead metal layer, in which both a sulfuric acid bath and a hydrochloric acid bath were available. In the sulfuric acid bath, zinc sulfate (ZnSO ₄ ) is supplied so that zinc ions are 60 to 120 g / L, and electroplating under conditions of pH: 0.5 to 2.5, temperature: 50 to 65 ° C., and flow rate: 1.0 to 2.5 m / sec. This is done. In this case, preferably, the current density of the sulfuric acid bath may be performed by adjusting the plating at 30 to 200 A / dm ² .

Zinc ions in sulfuric acid baths are limited to 60 to 120 g / L, but if they are less than 60 g / L, they can lead to ballistics and lower productivity, while above 120 g / L, they often precipitate when the temperature of the plating solution is lowered. This may be a problem and the unnecessary cost may be increased because a large amount of metal ions are contained.

In addition, the pH in the sulfuric acid bath is maintained at 0.5 to 2.5, the plating is carried out, if the pH is less than 0.5, the surface appearance is poor, if it exceeds 2.5 may cause the plating layer peeling.

Since the flow rate in the plating bath is necessary for smooth ion supply, it maintains a flow rate of 1.0 to 2.5 m / sec. If the flow rate is less than 1.0m / sec, the ion supply may not be smooth, and ballistic plating may occur. On the other hand, at flow rates exceeding 2.5m / sec, cavitation may occur, resulting in poor surface appearance.

The current density of the sulfuric acid bath can be limited to the range of 30 ~ 120A / dm ² . If the current density is less than 30A / dm ² , productivity may be reduced, and surface appearance may be poor due to the coarsening of particles. On the other hand, if the current density is higher than 200A / dm ² , the flow of the solution may not be good to supply ions. In this case, ballistic plating may occur.

In the galvanizing step, an additive, preferably a conduction aid, may be additionally added to improve conductivity during plating. Conductive aids that can be used in the present invention are 6 ~ 60g / L Na ₂ SO ₄ , 4 ~ 40g / L K ₂ SO ₄ , 2 ~ 30g / L CaSO _{4 It} is possible or a mixture thereof. The addition of these additives improves the conductivity, allowing the plating to be carried out more efficiently.

The galvanized steel sheet thus produced may undergo a certain post-treatment process. Such post-treatment may be phosphate treatment, anti-fingerprint treatment, chromium treatment, coating treatment or a combination thereof.

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is a zinc-nickel plating bath using a hydrochloric acid bath (zinc concentration 80g / L, nickel concentration 12g / L, temperature 60 ℃, pH 4.0, current density 100A / dm ² ) the plated layer using a cold-rolled steel sheet as a metal Zinc-nickel electroplating was conducted while changing the nickel content and plating amount. Subsequently, plating was performed while changing the plating amount and current density (30-200 A / dm ² ) in the zinc plating bath in a sulfate bath under conditions of a zinc concentration of 75 g / L, pH 1.2, and a flow rate of 2.0 m / sec. Leading amount + zinc plating amount) were plated in 2 kinds of 15g / m ² and 20g / m ² respectively.

(1) Plating layer corrosion resistance evaluation

Corrosion resistance of the plated layer was evaluated by the salt spray test (SST) of the KS standard to evaluate the occurrence time of 5% red rust.

(2) Evaluation of adhesion of plating layer

Plating adhesiveness was determined to be defective when the plating layer was buried on the tape by bending the tape after bending to 2T, and was judged to be good when it was not buried.

(3) Surface appearance of plating layer (linear mark evaluation)

The presence or absence of a linear mark was judged visually, and when the mark was observed with the naked eye, it was judged as bad, and when it was not observed, it was judged as good.

(4) Whiteness Evaluation of Plating Layer

Whiteness was measured with the color difference meter Juki JP7200C, and 83 or more was good and the following was judged as bad.

After performing the experiment for each condition, the results regarding the total plating amount 15g / m ² is shown in Table 1, and the results regarding the total plating amount 20g / m ² are shown in Table 2, respectively.

Plating Material No Zinc-Nickel Alloy Plating Material Galvanized material Current density ratio (Zn-Ni / Zn) Corrosion Resistance (Hrs) Surface whiteness Adhesion Surface linear mark Plating layer nickel content (%) Plating amount (g / m2) Plating amount (g / m2) One 7 4 11 1: 1.2 14 Good Good Good 2 8 4 11 1: 1.2 21 Good Good Good 3 12 4 11 1: 1.2 29 Good Good Good 4 13 4 11 1: 1.2 29 Good Bad Good 5 11 0.5 14.5 1: 1.2 11 Good Good Good 6 11 One 14 1: 1.2 19 Good Good Good 7 11 7 8 1: 1.2 34 Good Good Good 8 11 8 7 1: 1.2 35 Bad Bad Bad 9 11 4 11 1: 1 27 Bad Good Good 10 11 4 11 1: 1.1 28 Good Good Good 11 11 4 11 1: 1.5 27 Good Good Good 12 11 4 11 1: 1.6 27 Bad Bad Good

Plating Material No Zinc-Nickel Alloy Plating Material Galvanized material Current density ratio (Zn-Ni: Zn) Corrosion Resistance (Hrs) Surface whiteness Adhesion Surface linear mark Plating layer nickel content (%) Plating amount (g / m2) Plating amount (g / m2) 13 7 6 14 1: 1.2 31 Good Good Good 14 8 6 14 1: 1.2 40 Good Good Good 15 12 6 14 1: 1.2 43 Good Good Good 16 13 6 14 1: 1.2 43 Good Bad Good 17 11 0.5 19.5 1: 1.2 18 Good Good Good 18 11 One 19 1: 1.2 33 Good Good Good 19 11 9 13 1: 1.2 53 Good Good Good 20 11 10 12 1: 1.2 54 Bad Bad Good 21 11 6 14 1: 1 41 Bad Good Good 22 11 6 14 1: 1.1 42 Good Good Good 23 11 6 14 1: 1.5 41 Good Good Good 24 11 6 14 1: 1.6 41 Bad Bad Good

As shown in Table 1 and Table 2, the multilayer galvanized steel sheet having a plating amount and nickel content corresponding to the numerical range of the present invention is excellent in corrosion resistance, surface whiteness and adhesion, and does not show a linear mark on the surface. It can be seen that the manufacture of a multi-layer galvanized steel sheet.

Claims (8)

A lead gold step of forming a zinc nickel lead gold layer containing 1 to 9 g / m ² of Ni: 8 to 12 wt% on the surface of the steel sheet using a Ni-containing plating bath; And A zinc plating step of forming a zinc plating layer of 8g / m ² or more using a Zn-containing plating bath on the zinc nickel plating layer, The zinc plating step is supplied in a sulfuric acid bath Zn ions: 60 ~ 120g / L, pH: 0.5 ~ 2.5, temperature: 50 ~ 60 ℃, flow rate: 1.0 ~ 2.5m / sec and current density: 30 ~ 200A / dm ² , wherein the current density is 1.1 to 1.5 times the current density at the time of forming the zinc nickel lead gold layer. According to claim 1, The Ni-containing plating bath is Zn: 70 ~ 110g / L, Ni: 8 ~ 14g / L, Cl: 200 ~ 310g / L, temperature: 50 ~ 65 ℃ and pH: hydrochloric acid of 3 ~ 5 Method for producing a multi-layer galvanized steel sheet characterized in that the bath. The multi-layer galvanizing of claim 1, wherein the Ni-containing plating bath is a sulfuric acid bath of Zn: 25 to 60 g / L, Ni: 40 to 80 g / L, temperature: 50 to 65 ° C, and pH: 1-3. Method of manufacturing steel sheet. delete The method according to claim 1, wherein the Zn-containing plating bath is selected from the group consisting of 6 to 60 g / L Na ₂ SO ₄ , 4 to 40 g / L K ₂ SO ₄ and 2 to 30 g / L CaSO ₄ ; A method for producing a multilayer galvanized steel sheet, characterized in that it further adds two or more conduction aids. One or two selected from the group consisting of phosphate treatment, anti-fingerprint treatment, chromium treatment and coating treatment of the multilayer galvanized steel sheet produced by the method of any one of claims 1, 2, 3 and 5. A post-treatment method for producing a multilayer galvanized steel sheet. delete delete