WO2020111775A1 - Galvanized steel sheet having excellent plating adhesion and corrosion resistance, and manufacturing method therefor - Google Patents

Galvanized steel sheet having excellent plating adhesion and corrosion resistance, and manufacturing method therefor Download PDF

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Publication number
WO2020111775A1
WO2020111775A1 PCT/KR2019/016475 KR2019016475W WO2020111775A1 WO 2020111775 A1 WO2020111775 A1 WO 2020111775A1 KR 2019016475 W KR2019016475 W KR 2019016475W WO 2020111775 A1 WO2020111775 A1 WO 2020111775A1
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Prior art keywords
steel sheet
plating
zinc
corrosion resistance
layer
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PCT/KR2019/016475
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French (fr)
Korean (ko)
Inventor
한도경
김흥윤
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주식회사 포스코
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Priority claimed from KR1020190150456A external-priority patent/KR102276742B1/en
Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to CN201980078052.1A priority Critical patent/CN113195777B/en
Priority to JP2021529848A priority patent/JP7244728B2/en
Priority to EP19888373.8A priority patent/EP3889309A4/en
Priority to US17/296,787 priority patent/US11618939B2/en
Publication of WO2020111775A1 publication Critical patent/WO2020111775A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates

Definitions

  • the present invention relates to a galvanized steel sheet, and more particularly, to a galvanized steel sheet excellent in plating adhesion and corrosion resistance and a method for manufacturing the same.
  • the suppression layer When the suppression layer is not continuously formed at the interface between the base material and the plating layer, Fe in the base material elutes into the plating layer, and there is a problem that the plating layer is peeled off as the plating adhesion decreases. Therefore, in order to secure a plating adhesion of a certain level or higher, the suppression layer must be continuously generated.
  • Patent Document 1 Korean Patent Publication No. 10-2015-0074882
  • One aspect of the present invention is to provide a galvanized steel sheet having excellent adhesion to plating as well as excellent frictional properties and excellent corrosion resistance by plating with a certain level of Fe elution.
  • One aspect of the present invention includes a steel plate and a galvanized layer formed on at least one surface of the steel plate, wherein the zinc plated layer is weight% in aluminum (Al): 5.1-35.0%, magnesium (Mg): 4.0-25.0%. It provides a zinc-plated steel sheet having excellent plating adhesion and corrosion resistance, including the remaining zinc (Zn) and other unavoidable impurities, and an Al-Fe suppression layer having a thickness of 0.01 to 15 ⁇ m at the interface between the substrate and the zinc plating layer.
  • It provides a method for producing a zinc plated steel sheet having excellent plating adhesion and corrosion resistance, characterized in that the temperature of the zinc plating bath is greater than 555°C to less than 600°C, and the inlet temperature of the steel sheet is greater than 565°C to less than 600°C. .
  • the galvanized steel sheet of the present invention not only has excellent corrosion resistance, but also has an effect of inducing an improvement in workability as the frictional properties of the plated layer are improved.
  • FIG. 1 is a view showing a cross-sectional view of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
  • Figure 2 shows the results of the sear-bending test (sealer-bending test) of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention (where, the scale bar (scale bar) is 2mm).
  • Figure 3 shows a photograph of the shape of the crack in the outer region after the bending test of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
  • Figure 4 shows the results of 3D roughness scan of the surfaces of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
  • Figure 5 shows a photograph taken the surface after the salt spray test of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
  • the present inventors have studied in depth how to improve the friction characteristics and corrosion resistance of the plating layer while maintaining the plating adhesion of the galvanized steel sheet.
  • a galvanized steel sheet excellent in plating adhesion and corrosion resistance may include a steel sheet and a zinc plated layer formed on at least one surface of the steel sheet.
  • the type of the steel sheet is not particularly limited, and may be, for example, a Fe-based steel sheet used as a substrate of a conventional galvanized steel sheet, that is, a hot rolled steel sheet or a cold rolled steel sheet.
  • a hot-rolled steel sheet it has a large amount of oxidation scale on its surface, and this oxidation scale has a problem of degrading plating adhesion and deteriorating plating quality. It is more preferable.
  • carbon steel, ultra-low carbon steel, and high manganese steel used as materials for automobiles may be mentioned.
  • the zinc plated layer may be formed on one side or both sides of the steel sheet.
  • the zinc plating layer may include aluminum (Al): 5.1 to 35.0%, magnesium (Mg): 4.0 to 25.0%, residual zinc (Zn) and other unavoidable impurities in weight percent, which may include Al, Mg, It can be formed from a plating bath containing the balance Zn and other inevitable impurities.
  • Mg in the galvanized layer is an element that plays a very important role in improving the corrosion resistance of the plating layer, and Mg contained in the plating layer suppresses the growth of zinc oxide-based corrosion products with little effect of improving corrosion resistance in harsh corrosion environments, and is dense and improves corrosion resistance.
  • the highly effective zinc hydroxide-based corrosion product is stabilized on the surface of the plating layer.
  • the content of Mg is less than 4.0%, the effect of improving corrosion resistance due to the production of a Zn-Mg-based compound cannot be sufficiently obtained, whereas when the content exceeds 25.0%, the effect of improving corrosion resistance is saturated, while the Mg oxidative dross is a plating bath. There is a problem that is excessively generated in the bath.
  • Mg is contained in the zinc plating layer at 4.0 to 25.0%.
  • the Mg may be more advantageously contained at 5.1% or more, and the Mg may be more advantageously contained at 9.0% or less.
  • Al in the galvanized layer is added for the purpose of reducing the dross generated by the Mg oxidation reaction in the molten zinc alloy plating bath to which Mg is added, and Al is combined with Zn and Mg to improve the corrosion resistance of the plated steel sheet. It is also advantageous.
  • the Al content is less than 5.1%, the effect of preventing oxidation of the surface layer portion of the plating bath by adding Mg is insufficient, and an effect of improving corrosion resistance cannot be sufficiently obtained.
  • the content exceeds 35.0%, the Fe dissolution amount of the steel sheet immersed in the plating bath increases rapidly to form a Fe alloy-based dross, and furthermore, a Zn/Al binary vacancy phase in the plating layer is formed to form the cross-section and the coating section It lowers the effect of improving the corrosion resistance of Mg.
  • Al in the galvanized layer at 5.1 to 35.0%, and more advantageously it may be included at 11 to 15%.
  • the zinc plating layer may be referred to as a Zn-Al-Mg-based alloy plating layer by containing a certain amount of Al, Mg and Zn and inevitable impurities, and a thickness of 20 to 40 ⁇ m, preferably It may have a thickness of 20 to 35 ⁇ m.
  • the galvanized steel sheet of the present invention may include an Al-Fe suppression layer having a thickness of 0.01 to 15 ⁇ m at the interface between the base steel sheet and the zinc plating layer, and the Al-Fe suppression layer is preferably a FeAl 3 alloy phase.
  • the Al-Fe-based suppression layer is interposed between the base iron and the plating layer, and may serve to impart adhesion between the base iron and the alloy plating layer. Particularly, when the galvanized steel sheet is processed, the Al-Fe-based suppression layer prevents peeling of the plating layer, thereby improving the workability.
  • the Al-Fe suppression layer preferably has a thickness variation of 0.01 to 3 ⁇ m.
  • the thickness variation of the Al-Fe suppressing layer exceeds 3 ⁇ m, the suppressing layer is formed discontinuously, so that the effect of plating adhesion by the suppressing layer cannot be sufficiently obtained.
  • the Al-Fe suppression layer has a thickness variation of 0, but the present invention limits the lower limit of the thickness variation to 0.01 ⁇ m in consideration of this, as Fe is diffused from the base iron into the plating layer as described later. Can be.
  • the zinc plated layer of the present invention includes a first region having a Fe content of 40 to 95% and a second region having a Fe content of 0.01% or more and less than 40%, and the Fe is diffused (eluted) from the iron into the plating layer. It mainly includes.
  • the first region and the second region are formed on the Al-Fe suppression layer, of which the first region is mainly adjacent to the iron in the zinc plating layer, and the second region is mainly the zinc plating layer. It exists adjacent to the surface. Accordingly, the second region may be formed in an area fraction of 0.01 to 40% in the surface layer portion of the zinc plated layer.
  • a portion that is continuously darkened at the interface between the base iron and the plating layer is the first region, and the remaining region up to the surface layer of the plating layer except for this is the second region.
  • the first region and the second region in the galvanized layer may be formed over the entire thickness of the plating layer, but the size, shape, and fraction (the fraction occupied by the cross-section or surface of the plating layer) are not particularly limited. According to the plating conditions suggested in the invention, it is revealed that the regions according to the Fe content will be formed as described above.
  • the zinc-plated layer of the present invention despite the diffusion of Fe from the base iron into the plating layer, the Al-Fe suppression layer is continuously formed at the interface between the base iron and the plating layer, as well as excellent plating adhesion, Fe diffusion By (elution), the surface properties of the plated layer are improved to have a surface roughness (Ra) of 3 to 4 ⁇ m.
  • the zinc-plated steel sheet of the present invention comprises the steps of preparing a zinc plating bath together with the steel sheet; Preparing a galvanized steel sheet by immersing the steel sheet in the zinc plating bath and performing plating; And cooling the galvanized steel sheet.
  • the zinc plated layer may be formed on one or both sides of the steel sheet.
  • the zinc plating bath is aluminum (Al): 5.1 to 35.0%, magnesium (Mg): 4.0 to 25.0%, the balance by weight to obtain the zinc plating layer intended in the present invention. It is preferred to include zinc (Zn) and other unavoidable impurities. More advantageously, the Al may be included in an amount of 11 to 15%. In addition, more advantageously, Mg may be included at 5.1% or more, and may be included at 9.0% or less.
  • plating is performed by immersing the steel sheet in a zinc plating bath having the above-described alloy composition, the temperature of the zinc plating bath is greater than 555°C to less than 600°C, and the inlet temperature of the steel sheet is greater than 565°C ⁇ It is characterized by being less than 600°C.
  • the temperature of the plating bath is controlled to a temperature not higher than the melting point and not more than 500°C, whereas in the present invention, the intended plating layer can be formed by controlling the temperature of the galvanizing bath relatively high. It is.
  • the present invention provides sufficient thermal energy to form the Al-Fe suppression layer at the interface between the base iron and the plating layer while dipping the steel plate in the zinc plating bath while simultaneously allowing the Fe in the iron to diffuse into the plating layer. It is necessary to do this, and this cannot be achieved when the temperature of the galvanizing bath is controlled to 555°C or less, or when the inlet temperature of the steel sheet is controlled to 565°C or less. That is, the Al-Fe suppressing layer is discontinuously formed, or the diffusion of Fe into the plating layer does not sufficiently occur, so that a zinc plated layer having the intended properties cannot be obtained.
  • the temperature of the zinc plating bath is 600°C or higher, the possibility that the inside of the steel sheet and the plating bath is eroded will lead to a reduction in the life of the equipment.
  • the temperature of the zinc plating bath is too high, or if the inlet temperature of the steel sheet is 600° C. or more, there is a problem in that the surface of the plating material becomes defective due to an increase in Fe alloy dross.
  • the inlet temperature of the steel sheet can be controlled to 5 to 20°C higher than the zinc plating bath temperature.
  • the present invention can be carried out with a plating adhesion amount of 130 to 180 g/m 2 in plating according to the above, from which a galvanized layer having a thickness of 20 to 40 ⁇ m can be obtained.
  • the plating material obtained after completing the plating in the zinc plating bath may be cooled, and in the present invention, cooling may be performed stepwise in order to obtain a zinc plated layer having the above-described first and second regions.
  • the cooling may include a first cooling step of cooling at a cooling rate of 0.01 to 5°C/s to 230 to 270°C and a second cooling step at a cooling rate of 0.05 to 20°C/s to room temperature.
  • the solid-liquid phase is properly formed while sufficiently solidifying the single phase through the first cooling process, and then the cooling rate during the second cooling is relatively increased compared to the first cooling to completely solidify.
  • a method of cooling including moisture during cooling is excluded, and gas can be preferably injected.
  • gas is sprayed on both the front and back surfaces of the plating material, and a desired cooling rate can be secured through pressure control of the gas.
  • an inert gas such as nitrogen or argon may be used as the gas.
  • prior to performing the cooling may further include the step of gas wiping the plating material is formed a plating layer.
  • the gas wiping is a process for adjusting the plating adhesion amount, and the method is not particularly limited.
  • air or nitrogen may be used as a gas to be used, and nitrogen is more preferable. This is because when using air, Mg oxidation occurs preferentially on the surface of the plating layer, which may cause surface defects in the plating layer.
  • a zinc plating layer including the above-described first and second regions in the plating layer is formed on one aspect of the present invention.
  • the galvanized steel sheet can be obtained.
  • the galvanized steel sheet of the present invention not only has excellent plating adhesion and corrosion resistance, but also has an effect of improving workability during subsequent processing as the frictional properties of the surface of the plating layer are improved.
  • a cold rolled steel sheet (0.0016%C-0.081%Mn-0.002%Si-0.0091%P-0.0043%S-0.036%Sol.Al) having a thickness of 1.0mm, a width of 110mm, and a length of 200mm as a test piece for plating.
  • Each galvanized steel sheet was manufactured by plating under the conditions of Table 1 below. At this time, the cooling after plating was performed by spraying nitrogen on the front and back surfaces of the steel sheet, the first cooling was terminated at 250°C, and the second cooling was performed to room temperature.
  • the composition of the plating bath is within the scope of the present invention
  • the manufacturing process conditions of the plated steel sheet are out of the scope of the present invention.
  • -It was difficult to form an Al suppression layer. Therefore, the friction/lubricating properties of the plating layer decreased as the roughness decreased, resulting in cracks of branches in the plating layer after processing, and the corrosion resistance was low due to the dropping of the plating layer.
  • Comparative Example 3-4 had a low Mg content compared to the Inventive Example, so that the corrosion resistance of the surface and the cross section was poor.
  • Comparative Example 6 in which the composition components of the plating bath as well as the manufacturing process conditions were outside the scope of the present invention, it was difficult to form a continuous Fe-Al suppression layer due to low thermal energy required for Fe diffusion of the steel sheet. Therefore, the friction/lubricating properties of the plating layer decreased as the roughness decreased, resulting in cracks of branches in the plating layer after processing, and the corrosion resistance was low due to the dropping of the plating layer. Furthermore, the amount of Mg-Zn vacancy phase formation was small, and the corrosion resistance of the surface of the plating layer and the cross-section was reduced.
  • FIG. 1 is a view showing a cross-sectional view of the plating layer of the invention example 1 and comparative example 5 in the embodiment of the present invention.
  • the cut surface is FIB-processed, and the plate is coated with platinum, gold, or carbon to protect the processed section. 1 is a part of the area coated on the flat plate is observed together.
  • FIG. 2 shows the results of the sear-bending test (sealer-bending test) of Example 1 and Comparative Example 5 in the Examples of the present invention (here, scale bar (scale bar) is 2mm).
  • the sealer bending experiment was evaluated to the extent that the plated layer was exposed to the mastic sealer portion of the bent portion by bending the plate portion 90 degrees after applying adhesive to the plated layer of the mastic sealer (purple) and the plate. At this time, a picture of the mastic sealer portion taken with an optical microscope is shown in FIG. 2.
  • Figure 3 shows a photograph of the shape of the crack of the outer region after the bending test of the invention example 1 and comparative example 5 in the embodiment of the present invention. At this time, the bending test is shown in FIG. 3 a picture taken by an electron scanning microscope after bending the plating material itself 180 degrees.
  • inventive example 1 As shown in Fig. 3, inventive example 1, the shape of the crack is formed in parallel in one direction, while in comparison 5, the fracture is changed to a branch-type in the behavior formed in parallel in one direction, and Crack propagation behavior can be observed. It is expected that these results will affect the corrosion resistance of the processed area.
  • FIG. 4 shows the results of 3D roughness scan of the surfaces of Inventive Example 1 and Comparative Example 5 in the Examples of the present invention.
  • FIG. 5 shows a photograph of the surface of the plated steel sheet of Inventive Example 1 and Comparative Example 5 in 1200 hours after the salt spray test for 1200 hours.
  • 5 vol.% of NaCl brine 35° C. was placed in the chamber, and the brine was sprayed at 1.55 ml per hour on each plating material (150 ⁇ 70 (mm 2 ) sized specimen) to generate red rust.
  • the corrosion resistance was evaluated.
  • Example 1 As shown in FIG. 5, while the corrosion resistance of Example 1 was maintained for 1200 hours in a corrosive environment, it was confirmed that corrosion occurred significantly in Comparative Example 5.

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Abstract

The objective of one aspect of the present invention is to provide: a galvanized steel sheet having excellent plating adhesion, having a plated layer with improved friction characteristics by means of a predetermined level of Fe elution, and having excellent corrosion resistance; and a manufacturing method therefor.

Description

도금 밀착성 및 내부식성이 우수한 아연도금강판 및 이의 제조방법 Galvanized steel sheet with excellent plating adhesion and corrosion resistance and method for manufacturing the same
본 발명은 아연도금강판에 관한 것으로서, 보다 상세하게는 도금밀착성 및 내부식성이 우수한 아연도금강판 및 이의 제조방법에 관한 것이다.The present invention relates to a galvanized steel sheet, and more particularly, to a galvanized steel sheet excellent in plating adhesion and corrosion resistance and a method for manufacturing the same.
기존의 용융아연도금강판은 모재 강판과 도금층 사이(계면)에 형성된 Fe-Al 억제층(inhibition layer)이 존재하고, 이러한 억제층은 모재 강판과 도금층의 계면에서 도금 밀착력을 확보하는 동시에, 모재에서 도금층 내로 농도 구배에 의한 Fe 확산을 억제하는 것으로 알려져 있다. In the existing hot-dip galvanized steel sheet, there is an Fe-Al inhibition layer formed between the base steel sheet and the plating layer (interface), and the suppressing layer secures plating adhesion at the interface between the base steel sheet and the plating layer, and at the same time It is known to suppress the diffusion of Fe due to a concentration gradient into the plating layer.
모재와 도금층의 계면에서 억제층이 연속적으로 생성되지 못하는 경우 모재 내 Fe가 도금층 내로 용출되고, 도금 밀착력이 저하됨에 따라 도금층이 박리되는 문제가 있다. 따라서, 일정 수준 이상의 도금 밀착력을 확보하기 위해서는 억제층이 연속적으로 생성되어야만 한다.When the suppression layer is not continuously formed at the interface between the base material and the plating layer, Fe in the base material elutes into the plating layer, and there is a problem that the plating layer is peeled off as the plating adhesion decreases. Therefore, in order to secure a plating adhesion of a certain level or higher, the suppression layer must be continuously generated.
한편, 모재 내 Fe가 도금층으로 확산하는 경우 도금층의 조도 및 표면 거칠기의 향상과 같은 마찰특성에 대한 효과를 얻을 수 있다.On the other hand, when Fe in the base material diffuses into the plating layer, it is possible to obtain an effect on friction characteristics such as improvement in roughness and surface roughness of the plating layer.
하지만, 모재와 도금층 계면에 억제층이 연속적으로 형성되는 경우에는 Fe의 확산이 억제되어 상기 마찰특성에 대한 효과를 이용하기에 많은 제약이 따른다.However, when the suppression layer is continuously formed at the interface between the base material and the plating layer, diffusion of Fe is suppressed, and there are many limitations in using the effect on the friction characteristics.
이에, 도금 밀착력을 유지한 채로 Fe 확산에 따른 효과를 동시에 얻을 수 있는 방안에 대한 기술의 개발이 요구되고 있는 실정이다.Accordingly, there is a need to develop a technique for a method to simultaneously obtain the effect of Fe diffusion while maintaining the adhesion to plating.
[선행기술문헌][Advanced technical literature]
[특허문헌][Patent Document]
(특허문헌 1) 한국 공개특허공보 제10-2015-0074882호(Patent Document 1) Korean Patent Publication No. 10-2015-0074882
본 발명의 일 측면은, 도금 밀착성이 우수할 뿐만 아니라 일정 수준의 Fe 용출에 의해 도금층의 마찰특성이 향상되고 우수한 내부식성을 가지는 아연도금강판 및 이의 제조방법을 제공하고자 하는 것이다.One aspect of the present invention is to provide a galvanized steel sheet having excellent adhesion to plating as well as excellent frictional properties and excellent corrosion resistance by plating with a certain level of Fe elution.
본 발명의 과제는 상술한 내용에 한정하지 아니한다. 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 누구라도 본 발명 명세서 전반에 걸친 내용으로부터 본 발명의 추가적인 과제를 이해하는데 어려움이 없을 것이다.The subject of this invention is not limited to the above-mentioned content. Anyone having ordinary knowledge in the technical field to which the present invention pertains will have no difficulty in understanding additional problems of the present invention from the contents throughout the present specification.
본 발명의 일 측면은, 소지강판 및 상기 소지강판의 적어도 일면에 형성된 아연도금층을 포함하고, 상기 아연도금층은 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하며, 상기 소지강판과 아연도금층 계면에 두께 0.01~15㎛의 Al-Fe 억제층을 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판을 제공한다.One aspect of the present invention includes a steel plate and a galvanized layer formed on at least one surface of the steel plate, wherein the zinc plated layer is weight% in aluminum (Al): 5.1-35.0%, magnesium (Mg): 4.0-25.0%. It provides a zinc-plated steel sheet having excellent plating adhesion and corrosion resistance, including the remaining zinc (Zn) and other unavoidable impurities, and an Al-Fe suppression layer having a thickness of 0.01 to 15 µm at the interface between the substrate and the zinc plating layer.
본 발명의 다른 일 측면은, 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하는 아연도금욕을 준비하는 단계; 상기 아연도금욕에 소지강판을 침지하고, 도금을 행하여 아연도금강판을 제조하는 단계; 및 상기 아연도금강판을 냉각하는 단계를 포함하고,In another aspect of the present invention, preparing a zinc plating bath containing aluminum (Al): 5.1-35.0%, magnesium (Mg): 4.0-25.0%, residual zinc (Zn) and other unavoidable impurities by weight%. ; Preparing a galvanized steel sheet by immersing the steel sheet in the zinc plating bath and performing plating; And cooling the galvanized steel sheet,
상기 아연도금욕의 온도는 555℃ 초과~600℃ 미만이고, 상기 소지강판의 인입온도는 565℃ 초과~600℃ 미만인 것을 특징으로 하는 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법을 제공한다.It provides a method for producing a zinc plated steel sheet having excellent plating adhesion and corrosion resistance, characterized in that the temperature of the zinc plating bath is greater than 555°C to less than 600°C, and the inlet temperature of the steel sheet is greater than 565°C to less than 600°C. .
본 발명에 의하면, 소지철로부터 도금층 내로 Fe 용출이 발생하더라도 도금 밀착성이 우수한 아연도금강판을 제공할 수 있다.Advantageous Effects of Invention According to the present invention, it is possible to provide a galvanized steel sheet having excellent plating adhesion even when Fe elution occurs from the base iron into the plating layer.
또한, 본 발명의 아연도금강판은 내부식성이 우수할 뿐만 아니라, 도금층의 마찰특성이 향상됨에 따라 가공성의 향상을 유도하는 효과가 있다 할 것이다.In addition, the galvanized steel sheet of the present invention not only has excellent corrosion resistance, but also has an effect of inducing an improvement in workability as the frictional properties of the plated layer are improved.
도 1은 본 발명의 일 실시예에 따른 발명예 1과 비교예 5의 단면을 관찰한 사진을 나타낸 것이다.1 is a view showing a cross-sectional view of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 발명예 1과 비교예 5의 실러벤딩 실험(sealer-bending test) 결과를 나타낸 것이다 (여기서, 스케일 바(scale bar)는 2mm 이다). Figure 2 shows the results of the sear-bending test (sealer-bending test) of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention (where, the scale bar (scale bar) is 2mm).
도 3은 본 발명의 일 실시예에 따른 발명예 1과 비교예 5의 굽힘시험 후 외권부 크랙의 형상을 관찰한 사진을 나타낸 것이다.Figure 3 shows a photograph of the shape of the crack in the outer region after the bending test of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 발명예 1과 비교예 5의 표면을 3D 조도 스캔한 결과를 나타낸 것이다.Figure 4 shows the results of 3D roughness scan of the surfaces of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 발명예1과 비교예 5의 염수분무시험 후 표면을 촬영한 사진을 나타낸 것이다.Figure 5 shows a photograph taken the surface after the salt spray test of Inventive Example 1 and Comparative Example 5 according to an embodiment of the present invention.
본 발명자들은 아연도금강판의 도금 밀착성은 유지한 채 도금층의 마찰특성과 내부식성을 향상시킬 수 있는 방안에 대하여 깊이 연구하였다.The present inventors have studied in depth how to improve the friction characteristics and corrosion resistance of the plating layer while maintaining the plating adhesion of the galvanized steel sheet.
그 결과, 도금욕 내 합금조성과 도금조건을 최적화하는 것으로부터, (기존 Fe-Al 합금층을 소지강판(소지철)과 도금층의 계면에 형성하는 것과는 다르게) 도금층 내에서 소지철로부터 확산된 Fe이 농도 구배를 가지도록 도금층을 구성함으로써 의도하는 물성을 가지는 아연도금강판을 제공할 수 있음을 확인하고, 본 발명을 완성하기에 이르렀다.As a result, from optimizing the alloy composition and plating conditions in the plating bath, Fe diffused from the iron in the plating layer (unlike the existing Fe-Al alloy layer is formed at the interface between the steel plate (base iron) and the plating layer) It has been confirmed that a galvanized steel sheet having desired properties can be provided by constructing a plating layer to have this concentration gradient, and the present invention has been completed.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 일 측면에 따른 도금 밀착성 및 내부식성이 우수한 아연도금강판은 소지강판 및 상기 소지강판의 적어도 일면에 형성된 아연도금층을 포함할 수 있다.A galvanized steel sheet excellent in plating adhesion and corrosion resistance according to an aspect of the present invention may include a steel sheet and a zinc plated layer formed on at least one surface of the steel sheet.
본 발명에서는 상기 소지강판의 종류에 대해서는 특별히 한정하지 않으며, 예를 들면, 통상의 아연도금강판의 소지로 사용되는 Fe계 소지강판 즉, 열연강판 또는 냉연강판일 수 있다. 다만, 열연강판의 경우 그 표면에 다량의 산화 스케일을 가지며, 이러한 산화 스케일은 도금 밀착성을 저하시켜 도금 품질을 열위하게 하는 문제가 있으므로, 산 용액에 의해 미리 산화 스케일을 제거한 열연강판을 소지로 함이 보다 바람직하다. 일 예로, 자동차용 소재로 사용되는 탄소강, 극저탄소강, 고망간강 등을 들 수 있다.In the present invention, the type of the steel sheet is not particularly limited, and may be, for example, a Fe-based steel sheet used as a substrate of a conventional galvanized steel sheet, that is, a hot rolled steel sheet or a cold rolled steel sheet. However, in the case of a hot-rolled steel sheet, it has a large amount of oxidation scale on its surface, and this oxidation scale has a problem of degrading plating adhesion and deteriorating plating quality. It is more preferable. For example, carbon steel, ultra-low carbon steel, and high manganese steel used as materials for automobiles may be mentioned.
한편, 상기 아연도금층은 상기 소지강판의 일면 또는 양면에 형성될 수 있다.Meanwhile, the zinc plated layer may be formed on one side or both sides of the steel sheet.
상기 아연도금층은 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함할 수 있으며, 이는 상기 함량으로 Al, Mg, 잔부 Zn 및 기타 불가피한 불순물을 포함하는 도금욕으로부터 형성할 수 있다.The zinc plating layer may include aluminum (Al): 5.1 to 35.0%, magnesium (Mg): 4.0 to 25.0%, residual zinc (Zn) and other unavoidable impurities in weight percent, which may include Al, Mg, It can be formed from a plating bath containing the balance Zn and other inevitable impurities.
상기 아연도금층 내 Mg은 도금층의 내식성 향상에 매우 주요한 역할을 하는 원소로서, 도금층 내부에 함유된 Mg은 가혹한 부식 환경에서 내식성 향상 효과가 적은 아연산화물계 부식생성물의 성장을 억제하고, 치밀하며 내식성 향상 효과가 큰 아연수산화물계 부식생성물을 도금층 표면에서 안정화시킨다.Mg in the galvanized layer is an element that plays a very important role in improving the corrosion resistance of the plating layer, and Mg contained in the plating layer suppresses the growth of zinc oxide-based corrosion products with little effect of improving corrosion resistance in harsh corrosion environments, and is dense and improves corrosion resistance. The highly effective zinc hydroxide-based corrosion product is stabilized on the surface of the plating layer.
이러한 Mg의 함량이 4.0% 미만이면 Zn-Mg계 화합물 생성에 의한 내식성 향상 효과를 충분히 얻을 수 없고, 반면 그 함량이 25.0%를 초과하게 되면 내식성 향상 효과가 포화되는 한편, Mg 산화성 드로스가 도금욕 욕면에 과도하게 생성되는 문제가 있다.If the content of Mg is less than 4.0%, the effect of improving corrosion resistance due to the production of a Zn-Mg-based compound cannot be sufficiently obtained, whereas when the content exceeds 25.0%, the effect of improving corrosion resistance is saturated, while the Mg oxidative dross is a plating bath. There is a problem that is excessively generated in the bath.
따라서, 본 발명에서는 상기 아연도금층 내에 Mg은 4.0~25.0%로 함유됨이 바람직하다. 상기 Mg은 보다 유리하게는 5.1% 이상으로 함유할 수 있으며, 상기 Mg 은 보다 더 유리하게는 9.0% 이하로 함유할 수 있다. Therefore, in the present invention, it is preferable that Mg is contained in the zinc plating layer at 4.0 to 25.0%. The Mg may be more advantageously contained at 5.1% or more, and the Mg may be more advantageously contained at 9.0% or less.
상기 아연도금층 내 Al은 Mg을 첨가한 용융아연합금 도금욕 내에서 Mg 산화반응에 의해 발생하는 드로스를 감소시키기 위한 목적으로 첨가하며, Al은 Zn 및 Mg와 조합하여 도금강판의 내식성을 향상시키는데에도 유리하다.Al in the galvanized layer is added for the purpose of reducing the dross generated by the Mg oxidation reaction in the molten zinc alloy plating bath to which Mg is added, and Al is combined with Zn and Mg to improve the corrosion resistance of the plated steel sheet. It is also advantageous.
이러한 Al의 함량이 5.1% 미만이면 Mg 첨가에 의한 도금욕 표층부 산화를 방지하는 효과가 미흡하고, 내식성 향상 효과를 충분히 얻을 수 없다. 반면, 그 함량이 35.0%를 초과할 경우에는 도금욕에 침지된 강판의 Fe 용출량이 급증하여 Fe 합금계 드로스가 형성되고, 더욱이 도금층 내 Zn/Al 2원 공석상이 형성되어 단면부 및 도장부에 대한 Mg의 내식성 향상 효과를 저하시킨다.When the Al content is less than 5.1%, the effect of preventing oxidation of the surface layer portion of the plating bath by adding Mg is insufficient, and an effect of improving corrosion resistance cannot be sufficiently obtained. On the other hand, when the content exceeds 35.0%, the Fe dissolution amount of the steel sheet immersed in the plating bath increases rapidly to form a Fe alloy-based dross, and furthermore, a Zn/Al binary vacancy phase in the plating layer is formed to form the cross-section and the coating section It lowers the effect of improving the corrosion resistance of Mg.
따라서, 본 발명에서는 상기 아연도금층 내에 Al을 5.1~35.0%로 포함함이 바람직하며, 보다 유리하게는 11~15%로 포함할 수 있다.Therefore, in the present invention, it is preferable to include Al in the galvanized layer at 5.1 to 35.0%, and more advantageously it may be included at 11 to 15%.
상술한 바와 같이, 본 발명에서 아연도금층은 일정량의 Al, Mg과 잔부로 Zn 및 불가피한 불순물을 포함하는 것으로 Zn-Al-Mg계 합금도금층이라 칭할 수 있으며, 20~40㎛의 두께, 바람직하게는 20~35㎛의 두께를 가질 수 있다.As described above, in the present invention, the zinc plating layer may be referred to as a Zn-Al-Mg-based alloy plating layer by containing a certain amount of Al, Mg and Zn and inevitable impurities, and a thickness of 20 to 40 μm, preferably It may have a thickness of 20 to 35㎛.
본 발명의 아연도금강판은 상기 소지강판과 아연도금층 계면에 두께 0.01~15㎛의 Al-Fe 억제층을 포함할 수 있으며, 상기 상기 Al-Fe계 억제층은 FeAl 3 합금상인 것이 바람직하다.The galvanized steel sheet of the present invention may include an Al-Fe suppression layer having a thickness of 0.01 to 15 µm at the interface between the base steel sheet and the zinc plating layer, and the Al-Fe suppression layer is preferably a FeAl 3 alloy phase.
구체적으로, 상기 Al-Fe계 억제층은 소지철과 도금층의 사이에 개재되어, 소지철과 합금 도금층 간 밀착력을 부여하는 역할을 할 수 있다. 특히, 아연도금강판의 가공시 상기 Al-Fe계 억제층이 도금층의 박리를 예방함으로써 가공성을 보다 향상시키는 효과도 얻을 수 있다.Specifically, the Al-Fe-based suppression layer is interposed between the base iron and the plating layer, and may serve to impart adhesion between the base iron and the alloy plating layer. Particularly, when the galvanized steel sheet is processed, the Al-Fe-based suppression layer prevents peeling of the plating layer, thereby improving the workability.
한편, 상기 Al-Fe 억제층은 두께 편차가 0.01~3㎛를 만족하는 것이 바람직하다. Al-Fe 억제층의 두께 편차가 3㎛를 초과하게 되면 억제층이 불연속성으로 형성되어 억제층에 의한 도금 밀착성 효과를 충분히 얻을 수 없다. 상기 Al-Fe 억제층의 두께 편차가 0인 것이 가장 바람직할 것이나, 본 발명은 후술하는 바와 같이 소지철로부터 도금층 내로 Fe이 확산 되는 바, 이를 고려하여 상기 두께 편차의 하한을 0.01㎛로 제한할 수 있다.Meanwhile, the Al-Fe suppression layer preferably has a thickness variation of 0.01 to 3 μm. When the thickness variation of the Al-Fe suppressing layer exceeds 3 µm, the suppressing layer is formed discontinuously, so that the effect of plating adhesion by the suppressing layer cannot be sufficiently obtained. It is most preferable that the Al-Fe suppression layer has a thickness variation of 0, but the present invention limits the lower limit of the thickness variation to 0.01 µm in consideration of this, as Fe is diffused from the base iron into the plating layer as described later. Can be.
본 발명의 아연도금층은 내부에 Fe 함량이 40~95%인 제1 영역 및 Fe 함량이 0.01% 이상~40% 미만인 제2 영역을 포함하며, 상기 Fe은 소지철로부터 도금층 내로 확산(용출)된 것을 주로 포함한다.The zinc plated layer of the present invention includes a first region having a Fe content of 40 to 95% and a second region having a Fe content of 0.01% or more and less than 40%, and the Fe is diffused (eluted) from the iron into the plating layer. It mainly includes.
상기 제1 영역과 제2 영역은 상기 Al-Fe 억제층 상부에 형성된 것으로, 이 중 상기 제1 영역은 상기 아연도금층 내에서 주로 소지철과 인접하여 존재하고, 상기 제2 영역은 주로 상기 아연도금층의 표면과 인접하여 존재한다. 이에 따라, 상기 제2 영역은 상기 아연도금층의 표층부에 면적분율 0.01~40%로 형성될 수 있다.The first region and the second region are formed on the Al-Fe suppression layer, of which the first region is mainly adjacent to the iron in the zinc plating layer, and the second region is mainly the zinc plating layer. It exists adjacent to the surface. Accordingly, the second region may be formed in an area fraction of 0.01 to 40% in the surface layer portion of the zinc plated layer.
도 1을 참조하여 설명하면, 발명예를 나타내는 도면에서 소지철과 도금층의 계면에서 연속적으로 어둡게 보여지는 부분이 제1 영역이고, 이를 제외한 도금층 표층까지의 나머지 영역이 제2 영역인 것이다.Referring to FIG. 1, in the drawing showing an example of the invention, a portion that is continuously darkened at the interface between the base iron and the plating layer is the first region, and the remaining region up to the surface layer of the plating layer except for this is the second region.
본 발명은 상기 아연도금층 내에서 상기 제1 영역과 제2 영역은 도금층 전 두께에 걸쳐 형성될 수 있으나, 그 크기, 형상, 분율(도금층 단면 또는 표면에서 차지하는 분율) 등에 대해서는 특별히 한정하지 아니하며, 본 발명에서 제안하는 도금조건에 의할 경우 상기와 같이 Fe 함량에 따른 영역이 구분되어 형성될 것임을 밝혀둔다.In the present invention, the first region and the second region in the galvanized layer may be formed over the entire thickness of the plating layer, but the size, shape, and fraction (the fraction occupied by the cross-section or surface of the plating layer) are not particularly limited. According to the plating conditions suggested in the invention, it is revealed that the regions according to the Fe content will be formed as described above.
상술한 바와 같이, 본 발명의 아연도금층은 소지철로부터 도금층 내로 Fe 확산이 일어남에도 불구하고, 소지철과 도금층 계면에 Al-Fe 억제층이 연속적으로 형성되어 도금 밀착성이 우수할 뿐만 아니라, Fe 확산(용출)에 의해 도금층의 표면 특성이 개선되어 3~4㎛의 표면조도(Ra)를 가질 수 있다.As described above, the zinc-plated layer of the present invention, despite the diffusion of Fe from the base iron into the plating layer, the Al-Fe suppression layer is continuously formed at the interface between the base iron and the plating layer, as well as excellent plating adhesion, Fe diffusion By (elution), the surface properties of the plated layer are improved to have a surface roughness (Ra) of 3 to 4 μm.
즉, 기존 아연도금재 대비 높은 표면조도(Ra)를 가짐으로써 마찰 및 윤활 특성이 향상되어 이후 가공시 가공성 향상에 유리한 효과가 있는 것이다.That is, by having a high surface roughness (Ra) compared to the existing zinc plated material, the friction and lubrication properties are improved, which is advantageous in improving the workability during subsequent processing.
이하, 본 발명의 다른 일 측면에 따른 도금 밀착성 및 내부식성이 우수한 아연도금강판을 제조하는 방법에 대하여 상세히 설명한다.Hereinafter, a method of manufacturing a galvanized steel sheet having excellent plating adhesion and corrosion resistance according to another aspect of the present invention will be described in detail.
본 발명의 아연도금강판은, 소지강판과 함께 아연도금욕을 준비하는 단계; 상기 아연도금욕에 상기 소지강판을 침지하고, 도금을 행하여 아연도금강판을 제조하는 단계; 및 상기 아연도금강판을 냉각하는 단계를 포함하여 제조할 수 있다.The zinc-plated steel sheet of the present invention comprises the steps of preparing a zinc plating bath together with the steel sheet; Preparing a galvanized steel sheet by immersing the steel sheet in the zinc plating bath and performing plating; And cooling the galvanized steel sheet.
이때, 상기 아연도금층은 상기 소지강판의 단면 또는 양면에 형성할 수 있다.At this time, the zinc plated layer may be formed on one or both sides of the steel sheet.
상기 소지강판은 앞서 언급한 바와 같으며, 상기 아연도금욕은 본 발명에서 의도하는 아연도금층을 얻기 위하여 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하는 것이 바람직하다. 보다 유리하게는 상기 Al을 11~15%로 포함할 수 있다. 또한 보다 유리하게는, Mg을 5.1% 이상으로 포함할 수 있으며, 9.0% 이하로 포함할 수 있다. The steel sheet is as mentioned above, the zinc plating bath is aluminum (Al): 5.1 to 35.0%, magnesium (Mg): 4.0 to 25.0%, the balance by weight to obtain the zinc plating layer intended in the present invention. It is preferred to include zinc (Zn) and other unavoidable impurities. More advantageously, the Al may be included in an amount of 11 to 15%. In addition, more advantageously, Mg may be included at 5.1% or more, and may be included at 9.0% or less.
본 발명은 상술한 합금조성을 가지는 아연도금욕에 소지강판을 침지하여 도금을 행함에 있어서, 상기 아연도금욕의 온도는 555℃ 초과~600℃ 미만이고, 상기 소지강판의 인입 온도는 565℃ 초과~600℃ 미만인 것을 특징으로 한다.In the present invention, plating is performed by immersing the steel sheet in a zinc plating bath having the above-described alloy composition, the temperature of the zinc plating bath is greater than 555°C to less than 600°C, and the inlet temperature of the steel sheet is greater than 565°C~ It is characterized by being less than 600°C.
통상, 아연도금강판을 제조하는 경우 도금욕의 온도를 융점 이상, 최대 500℃를 넘지 않는 온도로 제어하는 반면, 본 발명에서는 아연도금욕의 온도를 상대적으로 높게 제어함으로써 의도하는 도금층을 형성할 수 있는 것이다.In general, in the case of manufacturing a galvanized steel sheet, the temperature of the plating bath is controlled to a temperature not higher than the melting point and not more than 500°C, whereas in the present invention, the intended plating layer can be formed by controlling the temperature of the galvanizing bath relatively high. It is.
구체적으로, 본 발명은 소지강판을 아연도금욕 내에 침지하여 도금을 행할시 소지철과 도금층 계면에 Al-Fe 억제층을 형성하는 동시에 소지철 내 Fe가 도금층 내로 확산이 가능하도록 열적 에너지를 충분히 제공할 필요가 있으며, 이는 상기 아연도금욕의 온도를 555℃ 이하로 제어하거나, 소지강판의 인입 온도를 565℃ 이하로 제어하는 경우에는 달성할 수 없다. 즉, Al-Fe 억제층이 불연속적으로 형성되거나, 도금층 내로 Fe 확산이 충분히 일어나지 못하게 되어 의도하는 물성을 가지는 아연도금층을 얻을 수 없게 된다.Specifically, the present invention provides sufficient thermal energy to form the Al-Fe suppression layer at the interface between the base iron and the plating layer while dipping the steel plate in the zinc plating bath while simultaneously allowing the Fe in the iron to diffuse into the plating layer. It is necessary to do this, and this cannot be achieved when the temperature of the galvanizing bath is controlled to 555°C or less, or when the inlet temperature of the steel sheet is controlled to 565°C or less. That is, the Al-Fe suppressing layer is discontinuously formed, or the diffusion of Fe into the plating layer does not sufficiently occur, so that a zinc plated layer having the intended properties cannot be obtained.
반면, 상기 아연도금욕의 온도가 600℃ 이상이면 소지강판 및 도금욕 내부 설비가 침식되어 장비의 수명 단축을 초래할 가능성이 높아진다. 또한, 상기 아연도금욕의 온도가 너무 높거나, 상기 소지강판의 인입 온도가 600℃ 이상이면 Fe 합금 드로스가 증가하여 도금재의 표면이 불량해지는 문제가 있다.On the other hand, if the temperature of the zinc plating bath is 600°C or higher, the possibility that the inside of the steel sheet and the plating bath is eroded will lead to a reduction in the life of the equipment. In addition, if the temperature of the zinc plating bath is too high, or if the inlet temperature of the steel sheet is 600° C. or more, there is a problem in that the surface of the plating material becomes defective due to an increase in Fe alloy dross.
보다 바람직하게, 상기 소지강판의 인입 온도는 상기 아연도금욕 온도 대비 5~20℃ 높게 제어할 수 있다.More preferably, the inlet temperature of the steel sheet can be controlled to 5 to 20°C higher than the zinc plating bath temperature.
본 발명은 상술한 바에 따라 도금을 행함에 있어서 130~180g/m 2의 도금 부착량으로 행할 수 있으며, 이로부터 두께 20~40㎛의 아연도금층을 얻을 수 있다.The present invention can be carried out with a plating adhesion amount of 130 to 180 g/m 2 in plating according to the above, from which a galvanized layer having a thickness of 20 to 40 μm can be obtained.
상기에 따라 아연도금욕 내에서 도금을 완료한 후 얻어진 도금재를 냉각할 수 있으며, 본 발명에서는 상술한 제1 영역 및 제2 영역을 가지는 아연도금층을 얻기 위하여 단계적으로 냉각을 수행할 수 있다.According to the above, the plating material obtained after completing the plating in the zinc plating bath may be cooled, and in the present invention, cooling may be performed stepwise in order to obtain a zinc plated layer having the above-described first and second regions.
구체적으로, 상기 냉각은 230~270℃까지 0.01~5℃/s의 냉각속도로 냉각하는 제1 냉각 단계 및 상온까지 0.05~20℃/s의 냉각속도로 제2 냉각 단계를 포함할 수 있다. Specifically, the cooling may include a first cooling step of cooling at a cooling rate of 0.01 to 5°C/s to 230 to 270°C and a second cooling step at a cooling rate of 0.05 to 20°C/s to room temperature.
본 발명에서는 제1 냉각 공정을 통해 단상의 응고를 충분히 진행시키면서 고체-액체상을 적절히 형성시킨 다음, 제2 냉각시 냉각속도를 제1 냉각 대비 상대적으로 높여 행함으로써 완전히 고상화시킬 수 있다.In the present invention, the solid-liquid phase is properly formed while sufficiently solidifying the single phase through the first cooling process, and then the cooling rate during the second cooling is relatively increased compared to the first cooling to completely solidify.
본 발명에서는 상기 냉각시 수분을 포함하여 냉각하는 방법을 제외하며, 바람직하게 가스를 분사하여 행할 수 있다.In the present invention, a method of cooling including moisture during cooling is excluded, and gas can be preferably injected.
이때, 도금재의 전면 및 이면 모두에 가스를 분사하며, 상기 가스의 압력조절을 통해 원하는 냉각속도를 확보할 수 있다. 일 예로, 상기 가스로는 질소, 아르곤 등의 불활성 가스를 사용할 수 있다.At this time, gas is sprayed on both the front and back surfaces of the plating material, and a desired cooling rate can be secured through pressure control of the gas. For example, an inert gas such as nitrogen or argon may be used as the gas.
한편, 상기 냉각을 행하기에 앞서 도금층이 형성된 도금재를 가스 와이핑처리하는 단계를 더 포함할 수 있다. 상기 가스 와이핑은 도금 부착량을 조정하기 위한 공정으로서, 그 방법에 대해서는 특별히 한정되는 것은 아니다.On the other hand, prior to performing the cooling may further include the step of gas wiping the plating material is formed a plating layer. The gas wiping is a process for adjusting the plating adhesion amount, and the method is not particularly limited.
이때, 사용되는 가스로는 공기 또는 질소를 이용할 수 있으며, 이 중 질소를 이용함이 보다 바람직하다. 이는, 공기를 사용할 경우 도금층 표면에서 Mg 산화가 우선적으로 발생함으로써 도금층의 표면결함을 유발할 수 있기 때문이다.At this time, air or nitrogen may be used as a gas to be used, and nitrogen is more preferable. This is because when using air, Mg oxidation occurs preferentially on the surface of the plating layer, which may cause surface defects in the plating layer.
상술한 일련의 공정을 완료함으로써 소지철과 도금층 계면에 연속적으로 형성된 Al-Fe 억제층을 포함하면서, 도금층 내에 상술한 제1 영역과 제2 영역을 포함하는 아연도금층이 형성된 본 발명의 일 측면에 따른 아연도금강판을 얻을 수 있다.By completing the above-described series of processes, while including an Al-Fe suppression layer continuously formed at the interface between the base iron and the plating layer, a zinc plating layer including the above-described first and second regions in the plating layer is formed on one aspect of the present invention. The galvanized steel sheet can be obtained.
이러한 본 발명의 아연도금강판은 도금 밀착성 및 내부식성이 우수할 뿐만 아니라, 도금층 표면의 마찰특성이 개선됨에 따라 이후의 가공시 가공성이 향상되는 효과도 얻을 수 있다.The galvanized steel sheet of the present invention not only has excellent plating adhesion and corrosion resistance, but also has an effect of improving workability during subsequent processing as the frictional properties of the surface of the plating layer are improved.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 한다. 다만, 하기의 실시예는 본 발명을 예시하여 보다 상세하게 설명하기 위한 것일 뿐, 본 발명의 권리범위를 한정하기 위한 것이 아니라는 점에 유의할 필요가 있다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의해 결정되는 것이기 때문이다.Hereinafter, the present invention will be described in more detail through examples. However, it is necessary to note that the following examples are only intended to illustrate the present invention in more detail and are not intended to limit the scope of the present invention. This is because the scope of the present invention is determined by matters described in the claims and reasonably inferred therefrom.
(실시예)(Example)
도금용 시험편으로 두께 1.0mm, 폭 110mm, 길이 200mm인 냉연강판(0.0016%C-0.081%Mn-0.002%Si-0.0091%P-0.0043%S-0.036%Sol.Al)을 소지강판으로 준비한 후, 하기 표 1의 조건으로 도금을 행하여 각각의 아연도금강판을 제조하였다. 이때, 도금 후 냉각은 강판의 전면 및 이면에 질소를 분사하여 행하였으며, 제1 냉각은 250℃에서 종료하고, 제2 냉각은 상온까지 행하였다.Prepare a cold rolled steel sheet (0.0016%C-0.081%Mn-0.002%Si-0.0091%P-0.0043%S-0.036%Sol.Al) having a thickness of 1.0mm, a width of 110mm, and a length of 200mm as a test piece for plating. Each galvanized steel sheet was manufactured by plating under the conditions of Table 1 below. At this time, the cooling after plating was performed by spraying nitrogen on the front and back surfaces of the steel sheet, the first cooling was terminated at 250°C, and the second cooling was performed to room temperature.
구분division 도금욕 조성(중량%)Plating bath composition (% by weight) 도금 조건Plating condition 도금층 두께(㎛)Plating layer thickness (㎛)
AlAl MgMg 도금욕온도(℃)Plating bath temperature (℃) 인입온도(℃)Inlet temperature (℃) 제1 냉각속도(℃/s)1st cooling rate (℃/s) 제2 냉각속도(℃/s)2nd cooling rate (℃/s)
발명예1Inventive Example 1 2424 99 557557 567567 2.92.9 1010 3232
발명예2Inventive Example 2 2424 44 557557 567567 2.92.9 1010 2828
발명예3Inventive Example 3 2424 5.15.1 557557 567567 2.92.9 1010 2929
비교예1Comparative Example 1 2424 4.54.5 545545 560560 2.92.9 1010 3434
비교예2Comparative Example 2 2424 5.55.5 550550 565565 2.92.9 1010 3636
비교예3Comparative Example 3 2424 33 557557 567567 2.92.9 1010 2525
비교예4Comparative Example 4 2424 3.83.8 557557 567567 2.92.9 1010 2727
비교예5Comparative Example 5 2424 33 555555 565565 2.92.9 1010 2929
비교예6Comparative Example 6 2424 3.83.8 555555 565565 2.92.9 1010 2828
(표 1의 도금욕 조성 중 잔부는 Zn과 불가피한 불순물이다.)(The remainder of the plating bath composition in Table 1 is Zn and inevitable impurities.)
상기에 따라 제조된 각각의 아연도금강판에 대해 도금 밀착성, 표면특성 및 내부식성에 대해 평가하였다.For each galvanized steel sheet prepared according to the above, it was evaluated for plating adhesion, surface properties and corrosion resistance.
먼저, 도금욕의 조성 뿐만아니라 도금강판 제조공정 조건이 본 발명의 범위를 만족하는 발명예 1-3의 경우, 모두 소지철과 도금층 계면에 연속적인 Fe-Al 억제층 형성이 가능하고, 조도 상승에 따라 마찰/윤활특성의 유지가 가능하여 가공 시 도금층 탈락을 효과적으로 억제할 수 있어 내부식성이 우수하였다. First, in the case of Inventive Examples 1-3 in which not only the composition of the plating bath but also the conditions of the manufacturing process of the plated steel sheet satisfy the scope of the present invention, it is possible to form a continuous Fe-Al suppression layer at the interface between the base iron and the plating layer, and the illuminance increases According to this, it is possible to maintain the friction/lubricating properties, so it is possible to effectively suppress the plating layer drop-off during processing, thereby providing excellent corrosion resistance.
한편 도금욕 조성은 본 발명범위 이내이나, 도금강판 제조공정 조건이 본 발명의 범위를 벗어난 비교예 1-2는 낮은 도금욕 및 인입온도 때문에 소지강판의 Fe 확산에 필요한 열적에너지가 낮아 연속적인 Fe-Al 억제층을 형성하기 어려웠다. 따라서 조도 감소에 따른 도금층의 마찰/윤활특성이 하락하여 가공후 도금층내 가지 형태의 크랙이 발생하고 도금층 탈락으로 내식성이 저하였다. On the other hand, although the composition of the plating bath is within the scope of the present invention, the manufacturing process conditions of the plated steel sheet are out of the scope of the present invention. -It was difficult to form an Al suppression layer. Therefore, the friction/lubricating properties of the plating layer decreased as the roughness decreased, resulting in cracks of branches in the plating layer after processing, and the corrosion resistance was low due to the dropping of the plating layer.
또한 비교예 3-4는 발명예 대비 Mg 함량이 낮아 표면 및 단면부의 내식성이 좋지 않았다. In addition, Comparative Example 3-4 had a low Mg content compared to the Inventive Example, so that the corrosion resistance of the surface and the cross section was poor.
아울러, 도금욕의 조성성분 뿐만 아니라 제조공정 조건이 본 발명의 범위를 벗어난 비교예 6은, 소지강판의 Fe 확산에 필요한 열적에너지가 낮아 연속적인 Fe-Al 억제층을 형성하기 어려웠다. 따라서 조도 감소에 따른 도금층의 마찰/윤활특성이 하락하여 가공후 도금층내 가지 형태의 크랙이 발생하고 도금층 탈락으로 내식성이 저하였다. 나아가, Mg-Zn 공석상 형성량이 작아 도금층 표면 및 단면부의 내식성이 저하하였다. In addition, in Comparative Example 6, in which the composition components of the plating bath as well as the manufacturing process conditions were outside the scope of the present invention, it was difficult to form a continuous Fe-Al suppression layer due to low thermal energy required for Fe diffusion of the steel sheet. Therefore, the friction/lubricating properties of the plating layer decreased as the roughness decreased, resulting in cracks of branches in the plating layer after processing, and the corrosion resistance was low due to the dropping of the plating layer. Furthermore, the amount of Mg-Zn vacancy phase formation was small, and the corrosion resistance of the surface of the plating layer and the cross-section was reduced.
한편, 아연도금강판의 단면을 관찰하기 위하여, 압연 방향의 수직 방향(두께 방향)으로 절단한 다음, 전자주사현미경(Scanning Electron Microscope, SEM)을 이용하여 관찰하였다. 도 1은 본 발명의 실시예에서 발명예 1과 비교예 5의 도금층 단면을 관찰한 사진을 나타낸 것이다. On the other hand, in order to observe the cross section of the galvanized steel sheet, it was cut in the vertical direction (thickness direction) in the rolling direction, and then observed using a scanning electron microscope (SEM). 1 is a view showing a cross-sectional view of the plating layer of the invention example 1 and comparative example 5 in the embodiment of the present invention.
도 1에 나타낸 바와 같이, 발명예 1과 비교예 5 모두 소지철과 도금층 사이에 Fe-Al 억제층이 존재하고, 도금층 내로 Fe 확산이 일어난 것을 확인할 수 있다. 그런데, 상기 비교예 5의 경우 Fe의 확산이 일어남과 동시에 Fe-Al 억제층이 불연속적으로 형성됨에 따라 도금 밀착력이 저하될 것으로 예측된다.As shown in FIG. 1, it can be confirmed that Fe-Al suppressing layer was present between the base iron and the plating layer in both of Inventive Example 1 and Comparative Example 5, and Fe diffusion occurred into the plating layer. However, in the case of the comparative example 5, it is predicted that the adhesion of plating will decrease as the diffusion of Fe occurs and the Fe-Al suppressing layer is discontinuously formed.
한편, 아연도금강판의 단면을 관찰함에 있어서, 절단면을 FIB 가공하며, 가공부를 보호하기 위하여 평판부에 백금, 금 또는 카본으로 코팅을 행한다. 도 1은 평판부에 코팅된 영역의 일부가 함께 관찰된 것이다.On the other hand, in observing the cross section of the galvanized steel sheet, the cut surface is FIB-processed, and the plate is coated with platinum, gold, or carbon to protect the processed section. 1 is a part of the area coated on the flat plate is observed together.
또한 아연도금강판의 도금 밀착력을 평가하기 위하여, 실러벤딩실험(sealer-bending test)을 행하고, 그 결과를 도 2에 나타내었다. 도 2는 본 발명의 실시예에서 발명예 1과 비교예 5의 실러벤딩 실험(sealer-bending test) 결과를 나타낸 것이다(여기서, 스케일 바(scale bar)는 2mm 이다). 상기 실러벤딩실험은 마스틱 실러(보라색)와 평판의 도금층에 접착제를 발라 서로 붙인 뒤 평판부를 90도로 굽힘(bending)함으로써 그 굽힘 부위의 마스틱 실러 부분에 도금층 묻어나오는 정도로 평가하였다. 이때, 광학현미경으로 상기 마스틱 실러 부분을 촬영한 사진을 도 2에 나타낸 것이다.In addition, in order to evaluate the plating adhesion of the galvanized steel sheet, a sealer-bending test was performed, and the results are shown in FIG. 2. Figure 2 shows the results of the sear-bending test (sealer-bending test) of Example 1 and Comparative Example 5 in the Examples of the present invention (here, scale bar (scale bar) is 2mm). The sealer bending experiment was evaluated to the extent that the plated layer was exposed to the mastic sealer portion of the bent portion by bending the plate portion 90 degrees after applying adhesive to the plated layer of the mastic sealer (purple) and the plate. At this time, a picture of the mastic sealer portion taken with an optical microscope is shown in FIG. 2.
도 2에 나타낸 바와 같이, 발명예 1의 경우 도금층 박리가 발생하지 아니한 반면, 비교예 5에서는 도금층이 박리된 것을 확인할 수 있다.As shown in FIG. 2, in the case of Inventive Example 1, peeling of the plating layer did not occur, whereas in Comparative Example 5, it was confirmed that the plating layer was peeled.
그리고, 아연도금강판의 굽힘 시험 후 외권부의 크랙 발생 여부를 관찰하였으며, 그 결과를 도 3에 나타내었다. 도 3은 본 발명의 실시예에서 발명예 1과 비교예 5의 굽힘시험 후 외권부 크랙의 형상을 관찰한 사진을 나타낸 것이다. 이때, 상기 굽힘 시험은 도금재 자체를 180도 굽힌 뒤 외권부를 전자주사현미경으로 촬영한 사진을 도 3에 나타낸 것이다.And, after the bending test of the galvanized steel sheet was observed whether or not cracks in the outer zone, the results are shown in Figure 3. Figure 3 shows a photograph of the shape of the crack of the outer region after the bending test of the invention example 1 and comparative example 5 in the embodiment of the present invention. At this time, the bending test is shown in FIG. 3 a picture taken by an electron scanning microscope after bending the plating material itself 180 degrees.
도 3에 나타낸 바와 같이, 발명예 1은 크랙의 형상이 한 방향으로 평행하게 형성되어 있는 반면, 비교에 5는 한 방향으로 평행하게 형성되는 거동에서 가지모양(branch-type)으로 변화되는 파괴 및 크랙 전파 거동을 관찰할 수 있다. 이러한 결과는 가공된 부위의 내식성에 영향을 미칠 것이라 예상된다.As shown in Fig. 3, inventive example 1, the shape of the crack is formed in parallel in one direction, while in comparison 5, the fracture is changed to a branch-type in the behavior formed in parallel in one direction, and Crack propagation behavior can be observed. It is expected that these results will affect the corrosion resistance of the processed area.
또한 아연도금강판의 표면특성을 확인하기 위하여, 아연도금강판을 3D 조도 스캔하였으며, 그 결과를 도 4에 나타내었다. 도 4는 본 발명의 실시예에서 발명예 1과 비교예 5의 표면을 3D 조도 스캔한 결과를 나타낸 것이다.In addition, in order to confirm the surface characteristics of the galvanized steel sheet, the galvanized steel sheet was scanned in 3D roughness, and the results are shown in FIG. 4. Figure 4 shows the results of 3D roughness scan of the surfaces of Inventive Example 1 and Comparative Example 5 in the Examples of the present invention.
도 4에 나타낸 바와 같이, 도금층 전체로 Fe 확산이 일어나고, 그러한 도금층 내에서 Fe 농도 구배에 따라 층이 분리된 발명예 1의 경우 비교예 5 대비 조도 및 표면 거칠기가 크게 향상된 것을 확인할 수 있다. As shown in FIG. 4, it can be seen that Fe diffusion occurs throughout the plating layer, and in the case of Inventive Example 1 in which the layers were separated according to the Fe concentration gradient in the plating layer, roughness and surface roughness were significantly improved compared to Comparative Example 5.
나아가, 도 5는 본 발명의 실시예에서 발명예 1과 비교예 5의 도금강판에 대한 1200시간 염수분무시험 후 표면을 촬영한 사진을 나타낸 것이다. 이때, 챔버 내에 5vol.%의 NaCl 염수(35℃)를 적치하고, 상기 염수를 각 도금재(150×70(mm 2) 크기의 시편)에 시간당 1.55ml로 분무하여 적청이 발생하는 시간을 통해 내부식성을 평가하였다.Furthermore, FIG. 5 shows a photograph of the surface of the plated steel sheet of Inventive Example 1 and Comparative Example 5 in 1200 hours after the salt spray test for 1200 hours. At this time, 5 vol.% of NaCl brine (35° C.) was placed in the chamber, and the brine was sprayed at 1.55 ml per hour on each plating material (150×70 (mm 2 ) sized specimen) to generate red rust. The corrosion resistance was evaluated.
도 5에 나타낸 바와 같이, 발명예 1은 부식 환경에서 1200시간 동안 내부식성을 유지하는 반면, 비교예 5의 경우 부식이 크게 일어난 것을 확인할 수 있다.As shown in FIG. 5, while the corrosion resistance of Example 1 was maintained for 1200 hours in a corrosive environment, it was confirmed that corrosion occurred significantly in Comparative Example 5.

Claims (10)

  1. 소지강판 및 상기 소지강판의 적어도 일면에 형성된 아연도금층을 포함하고,A steel plate and a zinc plated layer formed on at least one surface of the steel plate,
    상기 아연도금층은 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하며,The zinc plated layer contains aluminum (Al): 5.1 to 35.0%, magnesium (Mg): 4.0 to 25.0%, residual zinc (Zn) and other unavoidable impurities in weight percent.
    상기 소지강판과 아연도금층 계면에 두께 0.01~15㎛의 Al-Fe 억제층을 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판.A galvanized steel sheet having excellent plating adhesion and corrosion resistance, comprising an Al-Fe suppression layer having a thickness of 0.01 to 15 µm at the interface between the base steel sheet and the zinc plated layer.
  2. 제 1항에 있어서,According to claim 1,
    상기 아연도금층은 Fe 함량이 40~95%인 제1 영역 및 Fe 함량이 0.01% 이상~40% 미만인 제2 영역을 포함하고,The zinc plating layer includes a first region having a Fe content of 40 to 95% and a second region having a Fe content of 0.01% or more and less than 40%,
    상기 제2 영역은 상기 아연도금층의 표층부에 면적분율 0.01~40%로 형성된 것인 도금 밀착성 및 내부식성이 우수한 아연도금강판.The second region is a galvanized steel sheet having excellent plating adhesion and corrosion resistance, which is formed in an area fraction of 0.01 to 40% in the surface layer portion of the galvanized layer.
  3. 제 1항에 있어서,According to claim 1,
    상기 아연도금층은 중량%로 알루미늄(Al): 11~15%, 마그네슘(Mg): 5.1~9.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판.The zinc plated layer is a galvanized steel sheet having excellent adhesion to plating and corrosion resistance, including aluminum (Al): 11-15%, magnesium (Mg): 5.1-9.0%, residual zinc (Zn) and other inevitable impurities in weight percent.
  4. 제 1항에 있어서,According to claim 1,
    상기 아연도금층은 표면조도(Ra)가 3~4㎛인 도금 밀착성 및 내부식성이 우수한 아연도금강판.The zinc plated layer is a galvanized steel sheet having a surface roughness (Ra) of 3 to 4 µm with excellent plating adhesion and corrosion resistance.
  5. 중량%로 알루미늄(Al): 5.1~35.0%, 마그네슘(Mg): 4.0~25.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하는 아연도금욕을 준비하는 단계;Preparing a zinc plating bath containing aluminum (Al): 5.1-35.0%, magnesium (Mg): 4.0-25.0%, residual zinc (Zn) and other inevitable impurities by weight;
    상기 아연도금욕에 소지강판을 침지하고, 도금을 행하여 아연도금강판을 제조하는 단계; 및Preparing a galvanized steel sheet by immersing the steel sheet in the zinc plating bath and performing plating; And
    상기 아연도금강판을 냉각하는 단계를 포함하고,Cooling the galvanized steel sheet,
    상기 아연도금욕의 온도는 555℃ 초과~600℃ 미만이고, 상기 소지강판의 인입온도는 565℃ 초과~600℃ 미만인 것을 특징으로 하는 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.A method of manufacturing a galvanized steel sheet having excellent plating adhesion and corrosion resistance, characterized in that the temperature of the zinc plating bath is greater than 555°C to less than 600°C, and the inlet temperature of the steel sheet is greater than 565°C to less than 600°C.
  6. 제 5항에 있어서,The method of claim 5,
    상기 소지강판의 인입온도는 상기 아연도금욕 온도 대비 5~20℃ 높은 것인 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.A method for manufacturing a zinc plated steel sheet having excellent plating adhesion and corrosion resistance, wherein the temperature of the steel sheet is 5 to 20°C higher than the temperature of the zinc plating bath.
  7. 제 5항에 있어서,The method of claim 5,
    상기 냉각은 230~270℃까지 0.01~5℃/s의 냉각속도로 냉각하는 단계 및 상온까지 0.05~20℃/s의 냉각속도로 냉각하는 단계를 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.The cooling is a galvanized steel sheet having excellent plating adhesion and corrosion resistance, including cooling at a cooling rate of 0.01 to 5°C/s to 230 to 270°C and cooling at a cooling rate of 0.05 to 20°C/s to room temperature. Method of manufacturing.
  8. 제 5항에 있어서,The method of claim 5,
    상기 냉각은 가스를 분사하여 행하는 것인 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.The cooling is performed by spraying a gas, and the method of manufacturing a galvanized steel sheet excellent in plating adhesion and corrosion resistance.
  9. 제 5항에 있어서,The method of claim 5,
    상기 냉각을 행하기 전에 상기 아연도금강판을 가스 와이핑하는 단계를 더 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.Method of manufacturing a galvanized steel sheet excellent in plating adhesion and corrosion resistance further comprising the step of gas-wiping the galvanized steel sheet before the cooling.
  10. 제 5항에 있어서,The method of claim 5,
    상기 아연도금욕은 중량%로 알루미늄(Al): 11~15%, 마그네슘(Mg): 5.1~9.0%, 잔부 아연(Zn) 및 기타 불가피한 불순물을 포함하는 도금 밀착성 및 내부식성이 우수한 아연도금강판의 제조방법.The zinc plating bath is aluminum by weight (11% to 15% by weight), magnesium (Mg): 5.1% to 9.0%, zinc zinc plated steel sheet with excellent adhesion to plating and corrosion resistance, including residual zinc (Zn) and other inevitable impurities. Method of manufacturing.
PCT/KR2019/016475 2018-11-28 2019-11-27 Galvanized steel sheet having excellent plating adhesion and corrosion resistance, and manufacturing method therefor WO2020111775A1 (en)

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