KR101613354B1 - Coated steel plate and mehtod for manufacturing the same - Google Patents

Coated steel plate and mehtod for manufacturing the same Download PDF

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KR101613354B1
KR101613354B1 KR1020140061640A KR20140061640A KR101613354B1 KR 101613354 B1 KR101613354 B1 KR 101613354B1 KR 1020140061640 A KR1020140061640 A KR 1020140061640A KR 20140061640 A KR20140061640 A KR 20140061640A KR 101613354 B1 KR101613354 B1 KR 101613354B1
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plating
steel sheet
less
wiping
amount
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KR20150135605A (en
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이재민
최병욱
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동부제철 주식회사
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18Removing excess of molten coatings from elongated material
    • C23C2/20Strips; Plates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • C23C2/28Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29Cooling or quenching
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-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
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips

Abstract

도금강판이 개시된다. 본 발명에 의한 도금강판은 표면에 도금층이 형성된 도금강판에 있어서, 상기 도금층은 Al: 2.3wt% 초과 4wt% 미만, Mg: 2wt% 미만, 나머지가 Zn 및 기타 불가피 불순물로 이루어지며, Al과 Mg의 비율이 Al/Mg ≥ 1.5 인 것을 특징으로 하는 한다.A coated steel sheet is disclosed. The coated steel sheet according to the present invention is a coated steel sheet having a plated layer formed on its surface, wherein the plated layer is composed of more than 2.3 wt% to less than 4 wt% of Al, less than 2 wt% of Mg and the balance of Zn and other inevitable impurities, Of Al / Mg ≥ 1.5.

Description

도금 강판 및 그 제조방법{COATED STEEL PLATE AND MEHTOD FOR MANUFACTURING THE SAME}BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated steel sheet,

본 발명은 도금강판 및 그 제조방법에 관한 것으로, 보다 상세하게는 도금강판의 표면품질과 내식성이 향상되고 가공성이 우수한 Zn-Mg-Al계 도금강판 및 그 제조 방법에 관한 것이다.The present invention relates to a coated steel sheet and a method of manufacturing the same, and more particularly, to a Zn-Mg-Al-based coated steel sheet having improved surface quality and corrosion resistance of a coated steel sheet and excellent workability and a method of manufacturing the same.

종래기술에 의한 용융아연 도금강판은 자기 희생성이 우수하여 건자재와 가전재 등에 많이 적용되고 있다. 용융아연 도금강판은 부식환경 노출시, 철이 출된 부분에 대하여 아연(Zn)이 희생양극으로 작용하여 도금층에서 아연의 소실이 발생하게 된다. The hot-dip galvanized steel sheet according to the prior art is excellent in self-sacrifice and is widely applied to building materials and household electrical appliances. In case of hot-dip galvanized steel sheet, Zn is lost as a sacrificial anode at the part exposed to corrosive environment, resulting in loss of zinc in the plating layer.

이러한 아연의 희생양극 작용은 부식환경에서 소지철의 녹발생 억제에 탁월한 역할을 하지만 양극효율이 다소 떨어진다. 이러한 문제점을 해결하기 위해, 근래 일본과 유럽에서 Zn에 Mg을 첨가하여 부식환경에서 생성되는 시몬콜라이트(Simonkolleite, Zn5(OH)8Cl2)라는 매우 치밀하고 안정한 산화물을 생성시켜 양극효율을 향상시킨 제품이 생산되고 있다.This sacrificial anodic action of zinc plays an excellent role in suppressing the generation of rust of iron in the corrosive environment, but the anode efficiency is somewhat lower. In order to solve these problems, it has been recently proposed to add Zn to Zn in Japan and Europe to produce very dense and stable oxide called Simonkolleite (Zn 5 (OH) 8 Cl 2 ) Improved products are being produced.

그러나, Zn에 Mg이 첨가된 도금강판에는 아래와 같은 몇 가지 문제점이 있다.However, the coated steel sheet to which Mg is added to Zn has some problems as follows.

Zn에 Mg이 첨가되면서 Mg과 Zn 간에 형성된 취성의 금속간화합물로 인해, 가공시 표면에 과도한 크랙이 발생되거나 도금층 박리가 발생되어, 가공성뿐만 아니라 내식성도 저하되기 때문에 조성과 냉각조건에 따라 생성되는 조직제어가 상당이 중요하다.As Mg is added to Zn, a brittle intermetallic compound formed between Mg and Zn causes excessive cracking on the surface during processing or peeling of the plating layer, resulting in deterioration of corrosion resistance as well as workability. Organizational control is very important.

또한, Zn에 Mg이 첨가되면서 용탕의 Mg성분이 공기중의 산소와 수분이 반응하여 용탕 표면의 산화막이 두껍게 생성된다. 또한 도금두께를 제어하기 위한 공정에서 질소가스를 이용하여 도금 부착량을 제어를 해야만 표면 품질을 얻을 수 있어서 질소가스 사용으로 인한 가공비 상승이 불가피하다.In addition, when Mg is added to Zn, the Mg component of the molten metal reacts with oxygen in the air to form an oxide film on the surface of the molten metal. Also, in the process for controlling the thickness of the plating, the surface quality can be obtained only by controlling the deposition amount of the plating using nitrogen gas, so that the processing cost is inevitably increased due to the use of the nitrogen gas.

또한, 용탕중에 첨가 되어 있는 Mg은 산소와 반응하여 산화물을 다량 형성하게 되어 부원료 손실이 크다. 특히 Mg산화 피막은 다공성 산화물을 형성하기 때문에 산소와 접촉시 지속적으로 산소가 용탕과 반응하여 Mg산화 Dross에 의한 부원료 손실이 크다.In addition, Mg added to the molten metal reacts with oxygen to form a large amount of oxides, which causes a large loss of subsidiary materials. In particular, since the Mg oxide film forms a porous oxide, the oxygen reacts with the molten metal continuously in contact with oxygen, and the loss of the subsidiary material due to Mg oxidation is large.

Mg산화로 인하 부원료 손실을 최소화 시키기 위해서는 Mg이 산화되는 속도보다 먼저 산화되는 원소나 치밀한 산화물을 형성하는 원소가 첨가 되야 한다. 이러한 원소중에 Sr, Ca, Li, Be 등의 미세첨가원소들이 있지만 이러한 미세원소들은 고온상을 생성하거나 산소 친화력이 높아 추가적인 결함원이 되기도 한다.In order to minimize the loss of adhered material by Mg oxidation, elements that are oxidized before the rate at which Mg is oxidized or elements forming dense oxides should be added. Among these elements, there are fine added elements such as Sr, Ca, Li, and Be, but these fine elements generate high temperature images or have high oxygen affinity and become additional defect sources.

Zn-Mg-Al 도금계의 경우에는 희생성으로 작용하는 Zn, Mg와 부식환경에서 생성된 부식생성물에 의해서 내식성이 향상되는 것이 일반적이다. 그러나, 이렇게 생성된 부식생성물은 열충격에 약하여 건조시 크랙이 쉽게 발생되어 산소침투가 용이하게 되며 추가적인 부식이 진행된다.In case of Zn-Mg-Al plating system, corrosion resistance is generally improved by Zn and Mg acting as sacrificial and corrosion products generated in the corrosive environment. However, the corrosion product thus formed is weak to thermal shock, so that cracks are easily generated during drying, so that oxygen penetration is facilitated and further corrosion proceeds.

이러한 현상을 최소화하기 위해서는 Al 수지상이 충분히 발달되어야 한다. 또한 Al은 산소와 반응하여 생성되는 산화물은 Mg보다 치밀한 산화물을 형성하기 때문에 Zn-Mg용탕중에 일정량 첨가되게 되면 Mg이 산화 되는 것을 저지하는 역할을 하게 된다. 또한 Mg은 표준환원 전위값이 낮아 가장 먼저 수분과 반응하여 표면을 염기화시키는데, 표면산화 정도에 따라 표면염기도가 상이한 결과를 보이며, 이러한 표면 산화에 의한 표면 염기도는 후처리 개발에 또한 주요한 요소로 작용하기 때문에 제어의 대상이다. To minimize this phenomenon, the Al resin phase must be fully developed. In addition, Al reacts with oxygen to form oxides that are denser than Mg, so that Mg is prevented from being oxidized if a certain amount is added to the Zn-Mg molten metal. In addition, Mg has a low standard reduction potential and reacts first with moisture to basify the surface. Surface basicity differs depending on the degree of surface oxidation. Surface basicity due to surface oxidation is also a major factor in post-treatment development It is the object of control because it acts.

상기와 같은 문제점을 해결하기 위하여, 본 발명에서는 내식성 향상에 효과적이면서도 우수한 도금 표면성을 확보할 수 있는 도금강판 및 그 제조방법의 제공을 목적으로 한다.In order to solve the above-mentioned problems, the present invention aims to provide a coated steel sheet which is effective for improving corrosion resistance and which has excellent plating surface properties, and a method for producing the same.

본 발명의 바람직한 일 실시예에 의한 도금강판은 표면에 도금층이 형성된 도금강판에 있어서, 상기 도금층은 Al: 2.3wt% 초과 4wt% 미만, Mg: 2wt% 미만, 나머지가 Zn 및 기타 불가피 불순물로 이루어지며, Al과 Mg의 비율이 Al/Mg ≥ 1.5 이다.The coated steel sheet according to a preferred embodiment of the present invention is a coated steel sheet having a plating layer formed on its surface, wherein the plating layer comprises less than 4 wt% of Al, less than 2 wt% of Mg and the balance of Zn and other inevitable impurities And the ratio of Al and Mg is Al / Mg? 1.5.

상기 도금층의 표면의 산소농도는 1wt% 이하일 수 있다.The oxygen concentration on the surface of the plating layer may be 1 wt% or less.

상기 도금층은 Ti: 0.001wt% 이상 0.2wt% 이하, B: 0.0005wt% 이상 0.2wt% 이하, Be: 0.001wt% 이상 0.2wt% 이하, Si: 0.001wt% 이상 0.5wt% 이하, TiB: 0.001wt% 이상 0.2wt% 이하 중 적어도 하나를 더 포함할 수 있다.0.001 wt% to 0.2 wt% of B, 0.001 wt% to 0.2 wt% of B, 0.001 wt% to 0.5 wt% of Si, 0.001 wt% or more and 0.5 wt% or less of Ti, 0.001 wt% or less of Ti, wt% or more and 0.2 wt% or less.

본 발명의 바람직한 다른 실시예에 의한 도금강판의 제조방법은 Al: 2.3wt% 초과 4wt% 미만, Mg: 2wt% 미만, 나머지가 Zn 및 기타 불가피 불순물로 이루어지며, Al과 Mg의 비율이 Al/Mg ≥ 1.5 인 도금 조성물을 430℃~500℃로 가열하여, 용융 도금욕을 제조하는 단계, 상기 용융 도금욕에 강판을 1~3초간 침지하여, 상기 강판의 표면에 도금층을 형성하는 단계, 및 상기 도금층이 형성된 강판을 냉각속도 5℃/sec~30℃/sec로 상온까지 냉각시키는 단계를 포함한다.A method of manufacturing a coated steel sheet according to another preferred embodiment of the present invention is characterized in that Al is contained in an amount of more than 2.3 wt%, less than 4 wt%, Mg: less than 2 wt%, and the balance of Zn and other inevitable impurities, Heating a plating composition having a Mg > = 1.5 to 430 DEG C to 500 DEG C to prepare a hot-dip coating bath; dipping the steel sheet in the hot-dip coating bath for 1 to 3 seconds to form a plating layer on the surface of the steel sheet; And cooling the steel sheet having the plated layer formed thereon to a room temperature at a cooling rate of 5 ° C / sec to 30 ° C / sec.

상기 도금층을 형성하는 단계에서, 도금 부착량은 60g/m2~300g/m2 일 수 있다.In the step of forming the plating layer, the plating adhesion amount may be 60 g / m 2 to 300 g / m 2 .

상기 도금강판의 제조방법은 상기 강판의 표면에 도금층 형성시 도금 부착량 제어를 위해 공기와 질소의 혼합가스를 이용하여 에어 와이핑(air wiping)하는 단계를 더 포함할 수 있다.The method of manufacturing the coated steel sheet may further include air wiping using a mixed gas of air and nitrogen to control the deposition amount of the plating layer on the surface of the steel sheet.

상기 혼합가스중에 공기는 80% 이하일 수 있다.The air in the mixed gas may be 80% or less.

상기 도금강판의 제조방법에서 상기 용융 도금욕은 Ti: 0.001wt% 이상 0.2wt% 이하, B: 0.0005wt% 이상 0.2wt% 이하, Be: 0.001wt% 이상 0.2wt% 이하, Si: 0.001wt% 이상 0.5wt% 이하, TiB: 0.001wt% 이상 0.2wt% 이하 중 적어도 하나를 더 포함할 수 있다. Wherein the molten copper bath contains 0.001 to 0.2 wt% of Ti, 0.001 to 0.2 wt% of B, 0.0005 to 0.2 wt% of B, 0.001 to 0.2 wt% of Be, 0.001 to 1 wt% of Si, Or more and 0.5 wt% or less, and TiB: 0.001 wt% or more and 0.2 wt% or less.

본 발명에 의한 도금강판에 따르면, 도금욕의 조성을 중량%로 Mg첨가 대비 Al을 1.5배 이상 첨가하여 부착량 제어 공정에서 공기(air)와 질소가스를 혼합하여 생성되는 와이핑 마크(wiping mark) 결함을 최소화 할 수 있다.According to the coated steel sheet according to the present invention, when the composition of the plating bath is increased by 1.5 times or more as compared to the Mg addition by the amount of Mg, wiping mark defects produced by mixing air and nitrogen gas in the deposition amount control process Can be minimized.

일반적으로 고내식 도금강판 제조시 도금 부착량 제어를 위한 Mg의 산화를 최소화 하기 위해서 질소를 이용하여 와이핑(wiping)을 실시해야만 우수한 표면 품질을 얻을 수 있다.Generally, in order to minimize the oxidation of Mg for controlling the coating amount during the production of the high corrosion resistant coated steel sheet, it is necessary to perform wiping with nitrogen to obtain excellent surface quality.

본 발명에서는 용융상태에서 Mg보다 치밀한 산화물을 생성하는 첨가원소인 Al을 Mg 대비 일정한 비율이상으로 첨가하여 100% 질소 와이핑(wiping)을 하지 않고도 우수한 표면의 품질을 얻을 수 있다.According to the present invention, excellent surface quality can be obtained without addition of 100% nitrogen wiping by adding Al, which is an additive element that produces denser oxides than Mg, in a molten state at a ratio higher than Mg.

또한, 공기(air)와 질소 혼합비율을 일정량으로 정하여 도금 부착량 제어공정을 거치면 표면 산소농도를 제어되면서 표면에 수분 접촉시 과도한 pH상승으로 인한 후처리 성능 열위 형상을 막을 수 있다. 따라서 추가적인 질소사용에 의한 원가상승요인을 최소화할 수 있다.In addition, if the mixing ratio of air and nitrogen is set to a certain amount and the plating adherence amount control process is performed, the surface oxygen concentration can be controlled and the post-treatment performance disadvantage due to the excessive pH increase upon moisture contact with the surface can be prevented. Therefore, it is possible to minimize the cost increase factor by using additional nitrogen.

따라서, Mg산화에 의한 부원료 소실과 품질 열위 현상을 최소함으로써 고내식 도금강판에 생산 분야에 널리 상용화될 수 있다.Therefore, it can be widely commercialized in the production field of high corrosion resistant coated steel sheet by minimizing the loss of subordinate material and quality dislocation caused by Mg oxidation.

도 1은 Zn-3.2%Al-1.5%Mg 도금욕 조성에 대하여 질소 와이핑(wiping) 후 도금표면 사진이다.
도 2는 Zn-1%Al-1.5%Mg 도금욕 조성에 대하여 공기 와이핑(air wiping) 후 도금표면 사진이다.
도 3는 Zn-3.5%Al-1.5%Mg 도금욕 조성에 대하여 공기 와이핑(air wiping) 후 도금표면 사진이다.
FIG. 1 is a photograph of a plating surface after nitrogen wiping with respect to a Zn-3.2% Al-1.5% Mg plating bath composition.
FIG. 2 is a photograph of a plating surface after air wiping for a Zn-1% Al-1.5% Mg plating bath composition.
3 is a photograph of a plating surface after air wiping for a Zn-3.5% Al-1.5% Mg plating bath composition.

본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하고, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성요소를 지칭한다.BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims. Like reference numerals refer to like elements throughout the specification.

본 발명의 바람직한 일 실시예에 의하면, Al: 1wt% 초과 4wt% 미만, Mg: 2wt% 미만, 나머지가 Zn 및 기타 불가피 불순물로 이루어지는 용융 도금욕이 냉각되어, 도금층의 부착량을 제어하는 공정인 공기 와이핑(air wiping) 공정 중에 도금표면의 산화로 인한 와이핑(wiping) 자국을 최소하기 위해서는 중량%로 Mg첨가 비율대비 Al을 1.5배로 첨가하여 부착량 제어공정에서 생성되는 와이핑 마크(wiping mark) 결함을 최소화 할 수 있다According to a preferred embodiment of the present invention, the hot dip coating bath containing Al in an amount of more than 1 wt% but less than 4 wt%, Mg in an amount of less than 2 wt%, and the balance of Zn and other inevitable impurities is cooled, In order to minimize the wiping mark due to the oxidation of the plating surface during the air wiping process, a wiping mark generated in the deposition amount control process by adding Al 1.5 times by weight to the Mg addition ratio in weight% Minimize defects

그러나 전술한 바와 같이 Al과 Mg을 일정한 비율로 첨가하게 되면 표면외관을 확보할 수 있지만 공기 와이핑(air wiping)으로 인해서 도금 표면의 산소농도가 1% 이상으로 상승하게 되면 수분과 접촉시 표면에 생성된 MgO로 인해서 급격히 표면 pH가 상승하게 된다.However, as described above, when Al and Mg are added at a certain ratio, the surface appearance can be secured. However, when the oxygen concentration on the surface of the plating increases to 1% or more due to air wiping, The surface pH is rapidly increased due to the generated MgO.

표면의 pH가 9이상으로 상승하게 되면 후처리 성능이 급격히 열위해지는 결과를 가져오게 된다. 이러한 현상을 방지하기 위해서는 도금두께 제어를 위한 가스 와이핑 작업시 공기(air)와 질소의 혼합비율이 중요하다. 표면 산소농도를 1%이하로 관리하기 위해서는 공기(air)를 80% 이하로 질소와 혼합하여 사용하게 되면 표면의 산소농도를 1%이하로 관리 가능하다.When the pH of the surface rises to 9 or more, the post-treatment performance is rapidly degraded. To prevent this phenomenon, the mixing ratio of air and nitrogen is important in the gas wiping process for controlling the thickness of the plating. In order to control the surface oxygen concentration to 1% or less, it is possible to control the oxygen concentration on the surface to 1% or less when air is mixed with nitrogen at 80% or less.

또한, Ti: 0.001wt%~0.2wt%, B:0.0005wt%~0.2wt%, Be: 0.001wt%~0.2wt%, Si: 0.001wt%~0.5wt%, TiB: 0.001wt%~0.2wt% 중 적어도 하나 이상이 추가로 상기 도금층의 조성성분으로서 함유될 수 있다. 추가로 첨가되는 상기의 원소들은 조직을 미세화 하는 역할을 함으로써 표면 응고조직의 조도값이 낮게되어 평활도가 향상이 된다.0.001 wt% to 0.2 wt% of B, 0.0005 wt% to 0.2 wt% of B, 0.001 wt% to 0.2 wt% of Be, 0.001 wt% to 0.5 wt% of Si, 0.001 wt% to 0.2 wt% of TiB % May further be contained as a constituent component of the plating layer. The added elements further serve to refine the texture, so that the roughness of the surface solidified structure is lowered and the smoothness is improved.

도 1은 Al/Mg비율이 2.3인 Zn-3.5%Al-1.5%Mg 도금욕 조성으로 공기와 질소를 8:2로 혼합하여 wiping 공정을 거친 도금 표면사진으로 도금표면에 wiping mark가 발생하지 않았다.FIG. 1 is a photograph of a plating surface after wiping with air and nitrogen mixed at a ratio of 8: 2 with a composition of Zn-3.5% Al-1.5% Mg plating bath having an Al / Mg ratio of 2.3 and no wiping mark was formed on the plating surface .

한편, 도2는 도금욕 조성이 Zn-1%Al-1.5%Mg이고 Al/Mg비율이 0.66으로 부착량 제어를 위한 wiping공정을 Air와 질소 혼합비를 8:2로 하였을 경우 도금표면에 wiping mark가 다량 생성되어 외관성이 감소하는 것을 보여주고 있다. FIG. 2 shows a wiping mark on the plating surface when the plating bath composition is Zn-1% Al-1.5% Mg and the Al / Mg ratio is 0.66, And the appearance is reduced.

도 3는 Zn-3.5%Al-1.5%Mg 도금욕 조성에 대하여 질소 와이핑(N2 wiping) 후 도금표면을 관찰한 것으로 Mg산화의 의한 wiping mark 없이 도1과 유사한 표면을 가지고 있어 Al/Mg첨가비율에 따른 발명의 효과를 입증해 준다.FIG. 3 shows the surface of the plating after N 2 wiping with respect to the composition of the Zn-3.5% Al-1.5% Mg plating bath. The plating surface has a surface similar to that of FIG. 1 without wiping mark by Mg oxidation. Demonstrating the effect of the invention on the addition rate.

한편, 본 발명의 일실시예에 따른 합금도금강판은, 전술한 도금 조성물을 가열 용융한 도금욕에 강판을 침지하여 표면에 도금층을 형성함으로써 이루어진다.On the other hand, the alloy-plated steel sheet according to an embodiment of the present invention is formed by immersing a steel sheet in a plating bath in which the above-described plating composition is heated and melted to form a plating layer on its surface.

이때, Al은 응고시 도금층에 초정 형태로 나타나게 되며, 수지상을 형성함으로써 조직을 치밀하게 만드는 역할을 한다. 도금층의 부동태로 작용하는 복잡한 구조의 초정 Al상과 삼원공정상을 생성하기 위해서는, Al이 도금욕의 총중량을 기준으로 1wt% 이상하는 것이 바람직하며 4wt%초가 첨가될 시에는 공정 조성에 가까워지게 되어 도금층 응고시 표면의 응고 수축 조직이 생성되어 외관성을 저해하게 된다.At this time, Al appears in the form of a primer on the plated layer during solidification, and forms a dendritic phase, thereby making the structure dense. It is preferable that Al is added in an amount of 1 wt% or more based on the total weight of the plating bath in order to produce a preliminary Al phase and a three-way process phase of a complex structure acting as passivation of the plating layer. When 4 wt% The coagulation shrinkage structure of the surface is generated during the solidification of the plating layer, thereby deteriorating the appearance.

본 발명의 일실시예에 의하면, Mg은 내식성을 향상시키는 중요한 원소로서, Mg은 내식성에 기여하는 삼원공정상을 생성되기 위해서는 0.1wt% 이상은 첨가되어야 하며 가공성을 저해하는 다각형 형태의 MgZn2이 생성되지 않기 위해서 2%미만으로 첨가되어야 한다. 상기 언급한 Al, Mg의 범위하에서 중량%로 Mg첨가대비 Al을 1.5배 초과하여 합금을 설계시 와이핑(wiping) 공정에서 용융상태의 Al이 치밀한 산화막을 형성하여 외관성을 저해하는 Mg의 산화를 최소화 할 수 있다.According to one embodiment of the present invention, Mg is an important element for improving corrosion resistance. In order to produce a three-way process phase contributing to corrosion resistance, Mg must be added in an amount of 0.1 wt% or more, and a polygonal MgZn 2 In order not to be produced, less than 2% should be added. In the above-mentioned Al and Mg, when the alloy is designed by exceeding 1.5 times of Al relative to Mg addition in weight% by weight, Al in the molten state in the wiping process forms a dense oxide film, Can be minimized.

보통 합금을 설계할 때는 중량%를 기준으로 설계를 하며 합금설계 원소간에 밀도차가 크지 않거나 소량이 첨가될 경우에는 용탕이나 응고 조직에 큰 영향을 미치지 못하지만 본 발명의 합금계는 액체 밀도가 6.57g/cm3인 Zn 가 주요 성분이며 첨가원소가 경량금속으로 액체 밀도가 2.37g/cm3 인 Al과 1.58g/cm3 인 Mg으로 구성되어 있다. 중량%로 설계하게 되면 용탕에 첨가되는 양이 상이하게 된다.In general, alloys are designed on the basis of weight percentage, and when the density difference is not large or a small amount is added between alloying design elements, the alloy system of the present invention has a liquid density of 6.57 g / cm 3 of Zn is the major component and the additive element is a light-weight metal having a liquid density 2.37g / cm 3 And 1.58 g / cm < 3 > Mg. If it is designed as weight%, the amount added to the molten metal becomes different.

밀도를 고려하여 부피% 기준으로 Al과 Mg첨가 비율이 1:1되기 위해서는 중량%로 Al첨가비율이 Mg첨가 대비 약 1.5배가 되야 한다. Al을 1.5배 이상 첨가하게 되면 용탕에 분산되어있는 Mg이 산소와 반응하여 다공성 산화막을 형성하게 되고 Al이 이어 산소와 접촉하여 치밀한 산화막을 형성하면서 Mg에 추가적인 산소 접촉을 최소하게 된다. Considering the density, in order for the ratio of Al and Mg to be added to be 1: 1 by volume, the Al content should be about 1.5 times as high as the Mg content. When Al is added more than 1.5 times, Mg dispersed in the molten metal reacts with oxygen to form a porous oxide film, and Al contacts with oxygen to form a dense oxide film, thereby minimizing additional oxygen contact with Mg.

반면에 중량% 기준으로 Al첨가 비율이 Mg첨가 대비 1.5배 미만 일 경우에는 부피%로 차지하는 비율이 적기 때문에 추가적인 산소 투입으로 인해 Mg산화 방지가 어렵게 된다. 한편, 본 발명의 일실시예는, 전술한 도금 조성물을 강판에 코팅하여 합금도금강판을 제조하는 방법을 제공한다.On the other hand, when the Al addition ratio is less than 1.5 times the Mg addition amount on the basis of the weight percentage, since the ratio of the Al content to the Mg addition amount is small, the oxidation of Mg is difficult due to the addition of oxygen. On the other hand, one embodiment of the present invention provides a method of manufacturing an alloy-coated steel sheet by coating the above-described plating composition on a steel sheet.

도금 조성물을 강판에 코팅하는 방법은, 상술한 조성을 갖는 도금 조성물을 가열하여 420~500℃의 용융 도금욕을 제조하는 단계, 및 도금욕에 강판을 침지하여 그 표면에 도금 조성물을 피복하여 도금층을 형성하는 단계, 및 도금층이 형성된 강판을 5℃/sec~30℃/sec의 냉각속도로 상온까지 냉각하는 단계를 포함한다.A method of coating a plating composition on a steel sheet comprises the steps of heating a plating composition having the above composition to prepare a hot-dip coating bath at 420 to 500 ° C, and dipping a steel sheet in a plating bath to coat the surface of the steel sheet with a plating composition, And cooling the steel sheet having the plated layer formed thereon to a room temperature at a cooling rate of 5 DEG C / sec to 30 DEG C / sec.

여기서, 강판은 냉연강판 또는 열연강판 또는 냉간압연 후 소둔 처리된 강판일 수 있으며, 도금욕에 침지되기 전에 먼저 도금욕의 온도로 조정된 후 도금욕에 침지된다.Here, the steel sheet may be a cold rolled steel sheet or a hot rolled steel sheet or a steel sheet annealed after cold rolling. The steel sheet is first adjusted to the temperature of the plating bath before being dipped in the plating bath, and then immersed in the plating bath.

강판을 도금욕에 침지시킨 후에는 끌어올려 공기(air)와 질소(N2)를 혼합하여 와이핑(wiping)하여 도금 부착량을 조절한다. 필요에 따라 갈바어닐링 노를 통과할 수도 있다. 이때, 도금 부착량은 60g/㎡~300g/㎡로 조정한다.After the steel sheet is immersed in the plating bath, the steel sheet is pulled up and air and nitrogen (N2) are mixed and wiped to adjust the plating adhesion amount. If necessary, it may pass through a galvanic annealing furnace. At this time, the plating adhesion amount is adjusted to 60 g / m 2 to 300 g / m 2.

도금욕 용탕의 온도가 420℃ 미만이면 도금욕의 유동성이 떨어져 도금 피막의 외관이 불량해지고 도금 밀착성이 저하된다. 반면에, 500℃를 초과하면 과도한 산화 피막으로 도금강판의 외관이 불량해지고 도막 밀착성이 저하되며, 도금 후 응고 과정에서 불충분한 냉각을 유발하여 도금층에 흐름 자국과 같은 결함을 발생시킨다.If the temperature of the plating bath molten metal is less than 420 캜, the fluidity of the plating bath deteriorates and the appearance of the plating film becomes poor and the plating adhesion is lowered. On the other hand, when the temperature exceeds 500 캜, the appearance of the coated steel sheet becomes poor due to an excessive oxidation coating, the coating adhesion is deteriorated, and insufficient cooling occurs during the post-plating coagulation process to cause defects such as a flow mark on the plating layer.

냉각속도 5℃/s 미만으로 작업하게 되면 공정조성 부근의 도금조성에서는 표면 요철이 증가하게 되고 검은 반점 형태의 Mg2Zn11상이 다량으로 생성되어 외관성이 급격히 감소하며, 조직이 조대화 되어 내식성 및 가공성이 저하된다. When working at a cooling rate of less than 5 ° C / s, surface irregularities are increased in the plating composition near the process composition, and Mg 2 Zn 11 phase in the form of black spots is formed in a large amount, resulting in a sharp decrease in appearance, And the workability is lowered.

반면, 냉각속도 30℃/s를 초과하면 냉각 공기의 압력으로 인해, 도금층 표면에 주름이 발생하게 되어 외관성이 저하될 뿐만 아니라 과고용에 의한 도금층이 크랙이 발생하게되어 가공성이 열위해진다. 도금 부착량은 60g/㎡ 미만이면 내식성이 불충분하고, 300g/㎡를 초과하면 과도한 부착량에 의해 도금층이 지나치게 두꺼워져, 도금층 자체의 밀착성이 저하되는 동시에, 표면 광택이 저하되어 외관이 나빠진다.On the other hand, if the cooling rate is higher than 30 DEG C / s, wrinkles are generated on the surface of the plating layer due to the pressure of the cooling air, and not only the appearance is deteriorated, but also cracking occurs in the plating layer due to over-coating. If the coating amount is less than 60 g / m 2, the corrosion resistance is insufficient. If the coating amount exceeds 300 g / m 2, the coating layer becomes excessively thick due to the excessive coating amount, and the adhesion of the coating layer itself decreases and the surface gloss decreases to deteriorate the appearance.

침지는 1초~3초 동안 실시한다. 이때, 1초 미만으로 침지하면 도금 부착성이 낮아지고, 3초를 초과하면 합금층이 두꺼워져 외관이 나빠질 수 있다.Immersion is carried out for 1 second to 3 seconds. At this time, when the substrate is immersed for less than 1 second, the adhesion of the plating is lowered, and if it exceeds 3 seconds, the alloy layer becomes thicker and the appearance may be deteriorated.

이하, 비교예와 대비하여 본 발명의 실시예를 상세히 설명하고자 한다. 다만, 이하의 실시예는 본 발명의 실시예를 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, embodiments of the present invention will be described in detail in comparison with Comparative Examples. However, the following examples are illustrative of the present invention, but the present invention is not limited by the following examples.

실시예Example 1 One

두께 0.7mm의 냉연강판을 50℃ 알카리 용액에 30분 동안 침지시킨 후 물로 세척하여 표면의 이물질과 기름을 제거한 시편을 준비하고, 이 시편을 소둔처리 한 후 도금하였다. 이때, 소둔은 수소 10%~30%, 질소 70%~90%로 구성된 환원분위기에서 실시하였으며, 소둔시 열처리 온도는 700℃~750℃이다. A cold-rolled steel sheet having a thickness of 0.7 mm was immersed in an alkali solution at 50 占 폚 for 30 minutes and then washed with water to remove foreign matter and oil from the surface. The specimen was annealed and then plated. At this time, the annealing was performed in a reducing atmosphere composed of 10% to 30% of hydrogen and 70% to 90% of nitrogen, and the annealing temperature in the annealing was 700 ° C to 750 ° C.

도금은 소둔 열처리한 시편을 도금욕 온도로 냉각한 후, 도금욕에 2초간 침적시킨 후 끌어올려 Air와 질소가스를 혼합하여 wiping한 도금 부착량이 60g/㎡~300g/㎡이 되게 조정하고, 5~20℃/sec의 냉각속도로 상온까지 냉각하여 응고시켰다. 이때, 도금욕 온도는 420℃~460℃이다. Coating After annealing the annealed specimen at the plating bath temperature, it was immersed in the plating bath for 2 seconds and then pulled up. Air and nitrogen gas were mixed to adjust the coating amount of wiping to 60g / ㎡ ~ 300g / ㎡. And cooled to room temperature at a cooling rate of ~ 20 ° C / sec to solidify. At this time, the plating bath temperature is 420 ° C to 460 ° C.

이상의 조건으로 합금도금강판을 제조하고, 제조된 합금도금강판의 조성별 표면 외관성 및 도장성, 내식성을 아래와 같이 실시하였다.The alloy-plated steel sheet was produced under the above conditions, and the surface appearance, paintability, and corrosion resistance of the alloy-plated steel sheet were measured as follows.

<외관성> <Appearance>

도금 표면 품질을 Air와 질소 혼합 Wiping시 생성되는 산화 wiping mark 영역으로 평가 하였다.The surface quality of the plating was evaluated as the oxidation wiping mark area produced by air and nitrogen mixed wiping.

◎: 산화 Wiping mark: 5% 미만~ ◎: Oxidation Wiping mark: less than 5%

○: 산화 Wiping mark: 5%이상~ 20%미만○: Oxidation Wiping mark: 5% or more to less than 20%

△: 산화 Wiping mark: 20이상 ~50%미만?: Oxidation Wiping mark: 20 or more to less than 50%

×: 산화 Wiping mark: 50%이상~
×: Oxidation Wiping mark: Greater than 50%

<조업성><Workability>

도금 부착량을 제어하는 공정에서 Air와 질소 혼합 wiping을 하는 과정에서 용탕이 스트립에서 깍여서 나가면서 산화가 되어 Top Dross형태로 생성된다.In the process of controlling the deposition amount of the plating, in the process of wiping with air and nitrogen, the molten metal is oxidized while being cut off from the strip, resulting in a top dross shape.

이러한 Top Dross 발생율은 실제 도금에 사용된 부원료 대비 발생한 Top Dross량에 대하여 분율로 평가를 실시하였다.The incidence of top dross was evaluated with respect to the amount of top dross generated relative to the raw materials used in actual plating.

◎: Top Dross 발생율 10% 이하◎: Top Dross incidence rate 10% or less

○: Top Dross 발생율 10% 초과 ~ 20% 이하○: Top Dross occurrence rate exceeding 10% ~ 20%

△: Top Dross 발생율 10% 초과 ~ 30% 이하△: Top Dross occurrence rate exceeding 10% ~ 30%

×: Top Dross 발생율 30% 초과
×: Top Dross incidence rate exceeded 30%

<평면 내식성><Plane corrosion resistance>

KS D 9502(ASTM B-117)규정에 따라 NaCl 5%, 35℃에서 3,000 시간 염수분무 시험으로 녹 발생을 평가하였다. According to KS D 9502 (ASTM B-117), the occurrence of rust was evaluated by a salt spray test at 5% NaCl and 3,000 hours at 35 ° C.

이때, 시편의 전단면은 4면 모두 피복하고, 3,000시간 경과 후 시편의 표면 부분에서 적청 발생을 육안으로 관찰하였다.At this time, the entire cross section of the specimen was covered on all four sides, and after 3,000 hours, the occurrence of red rust on the surface portion of the specimen was visually observed.

◎: 적청 발생율 5% 이하⊚: Red rust occurrence rate of 5% or less

○: 적청 발생율 5% 초과 ~ 10% 이하○: Red rust occurrence rate exceeding 5% ~ 10%

△: 적청 발생율 10% 초과 ~ 30% 이하?: Red rust occurrence rate exceeding 10% to 30%

×: 적청 발생율 30% 초과×: Red rust occurrence rate exceeding 30%

<도금표면 pH ><Plating surface pH>

도금표면에 증류수 수방울을 떨어트린 후 그 위에 pH 시험지를 접촉시겨 5분 동안 변화하는 PH를 측정하였다.After dropping a drop of distilled water on the surface of the plating, the pH of the pH test paper was changed to 5 minutes.

<후처리 평판 내식성> <Post-treatment plate corrosion resistance>

코팅 조성물(폴리우레탄계)을 바코터(bar coater)를 사용하여 각각 도포하고, PMT가 70~130℃인 조건에서 건조하여 코팅층을 형성하였다. 상기 코팅 조성물의 부착량은 1,000mg/㎡이었다.The coating composition (polyurethane system) was applied using a bar coater, and the PMT was dried at 70 to 130 ° C to form a coating layer. The deposition amount of the coating composition was 1,000 mg / m &lt; 2 &gt;.

이후, 하기 방법으로 코팅 조성물의 건조 도막성능을 ASTM B117에 규정한 방법에 의거하여 평판의 시간 경과에 따른 백청 발생율을 확인하여 평판 내식성을 평가한다.Then, in accordance with the method described in ASTM B117, the dry film performance of the coating composition is evaluated by evaluating the rate of occurrence of white rust over time of the plate by the following method.

◎: 120시간 이상 내식성 만족, ◎: satisfactory corrosion resistance over 120 hours,

○: 120시간 동안 5%이내 백청 발생,○: within 5% for 120 hours,

X: 120시간 동안 5%이상 백청 발생X: Greater than 5% white rust in 120 hours

구분 division 조성 Furtherance 첨가비율Addition ratio Air%/N2%  Air% / N2% 외관성 Appearance 조업성Operability 내식성 SSTCorrosion resistance SST 도금 표면 pHPlating Surface pH 후처리'
내식성
After treatment'
Corrosion resistance
ZnZn Al(%)Al (%) Mg(%)Mg (%) Al/MgAl / Mg wiping markwiping mark Top Dross발생량(%)Top Dross Occurrence (%) 비교예 0Comparative Example 0 bal.honey. 0.20.2 00   100/0100/0 XX 77 비교예 1-1Comparative Example 1-1 bal.honey. 2.32.3 1.71.7 1.35 1.35 70/3070/30 88 비교예 1-2Comparative Example 1-2 bal.honey. 2.52.5 1.91.9 1.32 1.32 70/3070/30 88 비교예 1-3Comparative Example 1-3 bal.honey. 2.82.8 2.32.3 1.22 1.22 70/3070/30 XX XX 88 비교예 1-4Comparative Example 1-4 bal.honey. 3.53.5 2.52.5 1.40 1.40 70/3070/30 XX XX 88 비교예 1-5Comparative Example 1-5 bal.honey. 2.32.3 1.21.2 1.92 1.92 100/0100/0 99 XX 비교예 1-6Comparative Example 1-6 bal.honey. 3.53.5 1.81.8 1.94 1.94 100/0100/0 99 XX 발명예
1-1
Honor
1-1
bal.honey. 2.32.3 1.21.2 1.92 1.92 70/3070/30 88
발명예
1-2
Honor
1-2
bal.honey. 2.52.5 1.61.6 1.56 1.56 70/3070/30 88
발명예
1-3


Honor
1-3


bal.
honey.
2.8
2.8
1.4
1.4
2.00
2.00
70/30
70/30






8
8


발명예
1-7
Honor
1-7
bal.honey. 2.52.5 1.51.5 1.67 1.67 70/3070/30 88
발명예 1-8Examples 1-8 bal.honey. 3.53.5 1.81.8 1.94 1.94 70/3070/30 88

표 1에서 볼 수 있듯이, 본 발명의 일 실시예에 따른 발명예 1-1 내지 1-3 및 1-7 내지 1-8은, Air와 질소 혼합 wiping 조건에서 와이핑 마크 생성을 최소화시켜 외관성을 높이고 조업성을 향상시키는 결과를 보였으며, 또한 표면의 pH를 제어함으로써 우수한 후처리 내식성의 결과를 얻었다. 반면, 비교예 1-1 내지 1-4는 발명예 대비 외관성과 조업성은 열위한 결과를 얻었다. Air를 100%로 사용한 비교예 1-5 내지 1-6은 도금표면의 pH상승으로 후처리 내식성이 열위한 결과를 보였으나 반면에 발명예 1-1 및 1-8은 Air와 질소 혼합으로 우수한 후처리 내식성을 얻었다. As can be seen from Table 1, Inventive Examples 1-1 to 1-3 and 1-7 to 1-8 according to one embodiment of the present invention minimize the occurrence of wiping marks in air and nitrogen mixed wiping conditions, , And the surface pH was controlled to obtain excellent post-treatment corrosion resistance. On the other hand, in Comparative Examples 1-1 to 1-4, the appearance and operability compared to the inventive examples were obtained. Comparative Examples 1-5 to 1-6 in which air was used as 100% showed the result that the pH of the plating surface rose to increase the post-treatment corrosion resistance, whereas Inventive Examples 1-1 and 1-8 were excellent in mixing with air and nitrogen The post-treatment corrosion resistance was obtained.

삭제delete

또한, 발명예 1-1 내지 1-3, 1-7 및 1-8은 Al과 Mg첨가 비율이 1.5 이상인 조성으로, 와이핑 시 80부피% 이하의 Air와 N2를 혼합하여 사용하게 되면 도금표면의 pH상승을 억제하여 우수한 후처리 내식성을 보인 반면, Al과 Mg 첨가 비율이 1.5인 조성이나, 와이핑 시 Air를 80부피% 이상으로 사용한 비교예 1-5,1-6의 경우 열위한 후처리 내식성을 보였다.
The inventive examples 1-1 to 1-3, 1-7 and 1-8 have a composition in which the ratio of Al and Mg is 1.5 or more. When air and N 2 are mixed in an amount of 80% by volume or less when wiping, In the case of Comparative Examples 1-5 and 1-6 in which the Al and Mg addition ratio was 1.5 but the wiping air was used in an amount of 80 vol% or more, Post treatment corrosion resistance.

실시예Example 2 2

두께가 0.7mm인 냉연강판을 50℃ 알카리 용액에 30분 동안 침지시킨 후 물로 세척하여 표면의 이물질과 기름을 제거하여 시편을 준비하였다.A cold-rolled steel sheet having a thickness of 0.7 mm was immersed in an alkali solution at 50 占 폚 for 30 minutes and then washed with water to remove foreign matter and oil from the surface to prepare a specimen.

이 시편을 소둔처리한 후 도금하였는데, 소둔은 수소 10%~30%, 질소 70%~90%로 구성된 환원분위기에서 실시하였으며, 소둔시 열처리 온도는 700℃~750℃이다.The specimens were annealed and plated. The annealing was performed in a reducing atmosphere consisting of 10% to 30% of hydrogen and 70% to 90% of nitrogen, and the annealing temperature was 700 ° C to 750 ° C for annealing.

도금은 소둔 열처리한 시편을 도금욕 온도로 냉각한 후 도금욕에 2초간 침적시킨 후 끌어올려 Air와 질소혼합(1:1) 와이핑(wiping)으로 도금 부착량이 60g/㎡~300g/㎡이 되게 조정하였고, 5~30℃/s의 냉각속도로 상온까지 냉각하여 응고시켰다. 이때, 도금욕 온도는 조성별로 430℃~500℃로 하였다. After annealing, the specimens were cooled to the plating bath temperature, immersed in the plating bath for 2 seconds, then pulled up, and the coating amount of plating was changed from 60 g / ㎡ to 300 g / ㎡ by wiping with air and nitrogen (1: 1) And cooled to room temperature at a cooling rate of 5 to 30 DEG C / s to solidify. At this time, the plating bath temperature was set at 430 ° C to 500 ° C for each composition.

이상의 조건으로 합금도금강판을 제조하고, 제조된 합금도금강판의 조성별 표면조도를 아래의 표 2에 나타냈다.The alloy-plated steel sheet was produced under the above conditions, and the surface roughness of each alloy-plated steel sheet was shown in Table 2 below.

<평활도><Smoothness>

표면조도기를 이용하여 도금표면의 Ra값에 대하여 평가하였다. The Ra value of the surface of the plating was evaluated using a surface roughness tester.

◎: Ra값이 0.5㎛ 이하 ?: Ra value is 0.5 占 퐉 or less

○: Ra값이 0.5㎛ 초과 ~ 0.8㎛이하 ?: Ra value exceeding 0.5 占 퐉 to below 0.8 占 퐉

△: Ra값이 0.8㎛ 초과 ~ 1.2㎛이하 DELTA: Ra value is more than 0.8 mu m to 1.2 mu m or less

X : Ra값이 1.2㎛ 이상
X: Ra value is 1.2 占 퐉 or more

구분division 도금용 조성 (wt%)Composition for plating (wt%) 평활도Smoothness ZnZn AlAl MgMg 첨가원소Additive element 표면조도Surface roughness 비교예 2-1Comparative Example 2-1 Bal.Honey. 2.32.3 0.70.7 XX 비교예 2-2Comparative Example 2-2 Bal.Honey. 2.52.5 1.61.6 비교예 2-3Comparative Example 2-3 Bal.Honey. 2.82.8 1.41.4 비교예 2-4Comparative Example 2-4 Bal.Honey. 3.53.5 0.70.7 XX 발명예 2-1Inventory 2-1 Bal.Honey. 2.32.3 0.70.7 0.01%Ti0.01% Ti 발명예 2-2Example 2-2 Bal.Honey. 2.52.5 1.61.6 0.01%B0.01% B 발명예 2-3Examples 2-3 Bal.Honey. 2.82.8 1.41.4 0.01%Be0.01% Be 발명예 2-4Honorable 2-4 Bal.Honey. 2.82.8 1.41.4 0.01%TiB0.01% TiB 발명예 2-8Honorable 2-8 Bal.Honey. 3.23.2 0.70.7 0.05%Si0.05% Si

위의 표 2에서 확인할 수 있듯이, 미세원소가 첨가되지 않은 발명예 2-1 내지 2-4에 비해, 미세원소가 첨가된 발명예 2-1 내지 2-4의 경우, 표면조도가 감소하면서 평활도가 좋아지는 결과를 얻었다.
As can be seen from the above Table 2, in the case of Examples 2-1 to 2-4 in which the fine elements were added, as compared with Examples 2-1 to 2-4 in which the fine elements were not added, .

실시예Example 3 3

두께와 폭 및 길이가 각각 0.7mm인 냉연강판을 50℃ 알카리 용액에 30분 동안 침지시킨 후 물로 세척하여 표면의 이물질과 기름을 제거하여 시편을 준비하였다.A cold-rolled steel sheet having a thickness, a width and a length of 0.7 mm was immersed in an alkali solution at 50 ° C for 30 minutes and then washed with water to remove foreign substances and oil from the surface.

이 시편을 소둔처리 한 후 도금하였는데, 이때 소둔은 수소 10%~30%, 질소 70%~90%로 구성된 환원분위기에서 실시하였으며, 소둔시 열처리 온도는 700℃~750℃이다.The specimens were annealed and plated. The annealing was performed in a reducing atmosphere composed of 10% to 30% of hydrogen and 70% to 90% of nitrogen, and the annealing temperature was 700 ° C to 750 ° C for annealing.

도금은 소둔 열처리한 시편을 도금욕 온도로 냉각한 후 도금욕에 2초간 침적시킨 후 끌어올려 N2 Wiping으로 도금 부착량이 60g/㎡~300g/㎡이 되게 조정하였고, 냉각속도는 2℃/s~35℃/s 범위로 상온까지 냉각하여 응고시켰다. Plating was performed by cooling the specimens subjected to annealing by the plating bath temperature, immersing them in the plating bath for 2 seconds, pulling them up, adjusting the plating amount from 60 g / m 2 to 300 g / m 2 by N 2 wiping, To 35 [deg.] C / s to coagulate.

도금욕의 온도는 조성별로 작업온도를 달리하여 450℃~550℃범위에서 실시하였다. 이상의 조건으로 합금도금강판을 제조하고, 제조된 도금강판의 조성별 냉각속도와 도금욕 온도에 따른 외관성과 가공성을 평가하여 아래의 표 3에 나타내었다. The temperature of the plating bath was varied within the range of 450 ° C to 550 ° C with different operating temperatures for each composition. The alloy coated steel sheet was manufactured under the above conditions, and the appearance and workability according to the composition cooling rate and plating bath temperature of the produced coated steel sheet were evaluated, and the results are shown in Table 3 below.

<외관성><Appearance>

표면의 외관을 저해하는 요소를 도금표면의 검은 반점, 흐름 무늬로 정의하여, 가장 우수한 외관성을 5점으로 하고, 가장 열위한 외관성을 1점으로 정의하여 아래 같은 기준으로 평가하였다.An element which inhibits the appearance of the surface was defined as a black spots and a flow pattern on the surface of the plating, and the best appearance was rated as 5 points and the appearance for the most heat was defined as 1 point.

도금표면에 외관을 저해하는 요소 없음: 5점There is no element that obstructs appearance on the plating surface: 5 points

도금표면에 검은 반점 생성시: - 2점Black spots on plating surface: - 2 points

도금표면에 요철 생성시: - 1점When unevenness is formed on the plating surface: - 1 point

도금표면에 흐름무늬 생성시: -1점Flow pattern on plating surface: -1 point

도금표면에 주름무늬 생성시: -2점
Crease pattern on plating surface: -2 points

<가공성><Processability>

1T 두께의 시편을 180°로 구부린 후(벤딩시험) 현미경으로 단면을 관찰하여 단위길이당 발생한 크랙 비율을 측정하였다. 이때, 크랙은 도금층 전체를 가로지르는 것으로만 한정하였다.The 1T-thick specimen was bent at 180 ° (bending test), and the cross-section was observed with a microscope to measure the cracking rate per unit length. At this time, the crack was limited to the entire plating layer.

◎: 크랙 발생율 10% 이하◎: Crack occurrence rate 10% or less

○: 크랙 발생율 10% 초과 ~ 20% 이하○: Crack generation rate exceeding 10% to 20% or less

△: 크랙 발생율 20% 초과 ~ 30% 이하?: Crack occurrence rate exceeding 20% to 30% or less

×: 크랙 발생율 30% 초과
X: Cracking rate exceeding 30%

구분division 냉각속도
(℃/sec)
Cooling rate
(° C / sec)
원소element 물성평가Property evaluation
ZnZn AlAl MgMg 외관성Appearance 가공성Processability 비교예 3-1Comparative Example 3-1 22 Bal.Honey. 2.52.5 1.61.6 1One ×× 비교예 3-2Comparative Example 3-2 22 Bal.Honey. 2.82.8 1.41.4 1One ×× 비교예 3-3Comparative Example 3-3 3535 Bal.Honey. 3.53.5 0.70.7 33 발명예 3-1Example 3-1 1010 Bal.Honey. 2.52.5 1.61.6 55 발명예 3-2Example 3-2 1515 Bal.Honey. 2.82.8 1.41.4 55 발명예 3-3Honorable 3-3 2020 Bal.Honey. 3.53.5 0.70.7 55

조성별 냉각속도가 외관성과 가공성에 미치는 영향을 검증한 결과, 표 3과 같은 결과를 얻었다.As a result of examining the effect of cooling rate on the appearance and workability, the results are shown in Table 3.

각각 2℃/sec와 35℃/sec로 설정한 비교예 3-1 내지 3-3에 비해, 냉각속도가 10~15℃/sec인 발명예 3-1 내지 3-3의 경우가 외관성 더 우수한 결과를 보였다. In the case of Examples 3-1 to 3-3 in which the cooling rate is 10 to 15 ° C / sec as compared with Comparative Examples 3-1 to 3-3 set at 2 ° C / sec and 35 ° C / sec, respectively, Showed excellent results.

이는, 냉각속도가 5℃/sec 미만이면(비교예 3-1) 표면에 요철이 발생하게 되고, 냉각속도가 30℃/sec를 초과하면(비교예 3-3) 냉각장비의 고압으로 인해 도금표면에 주름이 생성되어 외관성이 저해된다. This is because if the cooling rate is less than 5 占 폚 / sec (Comparative Example 3-1), unevenness is generated on the surface, and when the cooling rate exceeds 30 占 폚 / sec (Comparative Example 3-3) Wrinkles are generated on the surface to deteriorate the appearance.

또한, 동일 조성에서 냉각속도 2℃/sec로 설정된 비교예 3-1과 냉각속도 35℃/sec로 설정한 비교예 3-3는 냉각속도 10℃/sec인 발명예 3-1와 냉각속도 20℃/sec인 발명예 3-3에 비해 가공성이 저하되는 경향을 보이는데, 이는 냉각속도가 낮을 경우에는 도금층에서 삼원공정상이 과도하게 성장하여 가공성이 열위하게 되며 냉각속도가 과도하게 높을 경우에는 도금층이 과고용상태가 다량의 크랙이 발생하게 된다.Comparative Example 3-1, which was set at a cooling rate of 2 DEG C / sec in the same composition, and Comparative Example 3-3, which was set at a cooling rate of 35 DEG C / sec, 3/3 / ° C / sec, the workability tends to be lowered. When the cooling rate is low, the three-way process phase is excessively grown in the plating layer and the workability is weakened. When the cooling rate is excessively high, And a large amount of cracks are generated in the employment state.

Claims (8)

삭제delete 삭제delete 삭제delete Al: 2.3wt% 초과 4wt% 미만, Mg: 2wt% 미만, 나머지가 Zn 및 기타 불가피 불순물로 이루어지며, Al과 Mg의 비율이 Al/Mg ≥ 1.5 인 도금 조성물을 430℃~500℃로 가열하여, 용융 도금욕을 제조하는 단계;
상기 용융 도금욕에 강판을 1~3초간 침지하여, 상기 강판의 표면에 도금층을 형성하는 단계; 및
상기 도금층이 형성된 강판을 냉각속도 5℃/sec~30℃/sec로 상온까지 냉각시키는 단계를 포함하며,
상기 강판의 표면에 도금층 형성시 도금 부착량 제어를 위해 0 초과 80부피% 이하의 공기와 질소의 혼합가스를 이용하여 에어 와이핑(air wiping)하는 단계를 더 포함하는 도금강판의 제조방법.
The plating composition having Al: more than 2.3 wt%, less than 4 wt%, Mg: less than 2 wt%, and the balance of Zn and other inevitable impurities, and the ratio of Al and Mg being Al / Mg? 1.5 is heated to 430 to 500 캜 , A step of producing a hot-dip coating bath;
Immersing the steel sheet in the hot-dip galvanizing bath for 1 to 3 seconds to form a plating layer on the surface of the steel sheet; And
Cooling the steel sheet having the plated layer formed thereon to a room temperature at a cooling rate of 5 ° C / sec to 30 ° C / sec,
Further comprising the step of air wiping using a mixed gas of air and nitrogen in an amount of more than 0 to 80% by volume in order to control the deposition amount of the plating layer on the surface of the steel sheet.
제 4 항에 있어서,
상기 도금층을 형성하는 단계에서,
도금 부착량은 60g/m2~300g/m2인 것을 특징으로 하는 도금강판의 제조방법.
5. The method of claim 4,
In the step of forming the plating layer,
And the plating adhesion amount is 60 g / m 2 to 300 g / m 2 .
삭제delete 삭제delete 제 4 항에 있어서,
상기 용융 도금욕은 Ti: 0.001wt% 이상 0.2wt% 이하, B: 0.0005wt% 이상 0.2wt% 이하, Be: 0.001wt% 이상 0.2wt% 이하, Si: 0.001wt% 이상 0.5wt% 이하, TiB: 0.001wt% 이상 0.2wt% 이하 중 적어도 하나를 더 포함하는 것을 특징으로 하는 도금강판의 제조방법.
5. The method of claim 4,
Wherein the molten bath comprises at least one selected from the group consisting of Ti: at least 0.001 wt% and at most 0.2 wt%, B: at least 0.005 wt% and not more than 0.2 wt%, B: at least 0.001 wt% : 0.001 wt% or more and 0.2 wt% or less.
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