KR100478725B1 - Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process - Google Patents

Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process Download PDF

Info

Publication number
KR100478725B1
KR100478725B1 KR1019970062028A KR19970062028A KR100478725B1 KR 100478725 B1 KR100478725 B1 KR 100478725B1 KR 1019970062028 A KR1019970062028 A KR 1019970062028A KR 19970062028 A KR19970062028 A KR 19970062028A KR 100478725 B1 KR100478725 B1 KR 100478725B1
Authority
KR
South Korea
Prior art keywords
steel sheet
plating
dip galvanized
alloying
galvanized steel
Prior art date
Application number
KR1019970062028A
Other languages
Korean (ko)
Other versions
KR19990041443A (en
Inventor
김종상
남태현
Original Assignee
주식회사 포스코
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to KR1019970062028A priority Critical patent/KR100478725B1/en
Publication of KR19990041443A publication Critical patent/KR19990041443A/en
Application granted granted Critical
Publication of KR100478725B1 publication Critical patent/KR100478725B1/en

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)

Abstract

본 발명은 자동차용 강판으로 사용되며 도금부착성 및 합금화처리성이 우수한 고강도 합금화 용융아연 도금강판의 제조방법에 관한 것으로 보다 상세하게는 0.10∼0.14 wt.%의 알루미늄을 포함한 용융아연 도금욕을 이용하여 실리콘이 0.1∼1.0 wt.% 함유된 고강도 합금화 용융아연 도금강판을 제조하는 방법에 있어서, 상기 도금욕에 주석을 0.05∼0.10wt..% 첨가하여 고강도 합금화 용융아연 도금강판을 제조하는 것을 특징으로 하는 도금부착성 및 합금화 처리성이 우수한 고강도 합금화 용융아연 도금강판의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a high strength alloyed hot-dip galvanized steel sheet which is used as a steel sheet for automobiles and has excellent plating adhesion and alloying treatment properties, and more specifically, using a hot-dip zinc plating bath containing 0.10 to 0.14 wt.% Aluminum. In the method for producing a high strength alloyed hot-dip galvanized steel sheet containing 0.1 to 1.0 wt.% Of silicon, by adding 0.05 to 0.10wt ..% of tin to the plating bath to produce a high strength alloyed hot-dip galvanized steel sheet It is related with the manufacturing method of the high strength alloying hot-dip galvanized steel sheet excellent in the plating adhesiveness and alloying treatment property.

상기와 같은 본 발명에 의하여 통상의 합금화 용융아연 도금욕에 0.05∼0.10 wt.%의 주석을 첨가하여 미도금발생 억제 및 도금부착성이 향상된 합금화 용융아연 도금강판의 제조가 가능하므로 생산성을 향상시키고 표면품질 불량을 크게 감소시킬 수 있다.According to the present invention as described above it is possible to manufacture the alloyed hot-dip galvanized steel sheet with the addition of 0.05 ~ 0.10 wt. Surface quality defects can be greatly reduced.

Description

도금부착성 및 합금화 처리성이 우수한 고강도 합금화 용융아연 도금강판의 제조방법Manufacturing method of high strength alloyed hot dip galvanized steel sheet excellent in plating adhesion and alloying treatment

본 발명은 자동차용 강판으로 사용되며 도금부착성 및 합금화처리성이 우수한 고강도 합금화 용융아연 도금강판의 제조방법에 관한 것으로 보다 상세히는 강중 실리콘함량이 0.1∼1.0 wt.% 함유한 냉연강판을 대상으로 0.10∼0.14 wt.%의 알루미늄이 포함된 통상의 합금화 용융아연 도금욕에 주석을 0.05∼0.10 wt.% 첨가하여 일반 저탄소강과 동등한 도금부착성 및 합금화 처리성을 갖는 고강도 합금화 용융아연 도금강판을 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a high strength alloyed hot-dip galvanized steel sheet which is used as a steel sheet for automobiles and has excellent plating adhesion and alloying treatment, and more specifically, to a cold rolled steel sheet containing 0.1 to 1.0 wt.% Silicon in steel. Tin was added 0.05 to 0.10 wt.% To a conventional alloyed hot dip galvanizing bath containing 0.10 to 0.14 wt.% Of aluminum to prepare a high strength alloyed hot dip galvanized steel sheet having plating adhesion and alloying treatment properties equivalent to that of general low carbon steel. It is about how to.

현재 자동차 배기가스의 환경오염의 방지를 위해 연비규제가 강화됨에따라 자동차의 연비개선책으로서 자동차의 경량화가 도모되고 있는데 이와같은 대책의 하나로서 강판의 고장력화에 의한 자동차 소재의 무게를 감소시키기 위하여 자동차 차체용 고장력 용융아연 도금강판의 수요가 증가하고 있는 현실이다.As fuel economy regulations are strengthened to prevent environmental pollution of automobile exhaust gas, automobiles are being designed to be lightweight as an improvement of fuel efficiency.As one of such measures, automobiles are required to reduce the weight of automobile materials due to high tensile strength of steel sheets. The demand for high-strength hot-dip galvanized steel for automobiles is increasing.

그러나 통상의 P, Mn 등의 고용강화 원소를 이용하는 고강도강 제조방법은 가공성 증가에 한계가 있어 강의 강도를 크게 감소시키지 않고 연성을 유지시킬 수 있는 실리콘과 같은 원소를 이용하여 최근에 개발된 초심가공용 고장력강을 사용하고 있다.However, the conventional method for manufacturing high strength steel using solid solution strengthening elements such as P and Mn has a limitation in increasing workability, and has recently been developed for super-machining using elements such as silicon, which can maintain ductility without significantly reducing the strength of steel. High tensile steel is used.

그러나 상기의 초심가공용 고장력강은 Si, Mn, P 등의 난도금성 원소를 모두 함유하는데 특히, 강성분에 Si 농도가 0.1wt.%이상 함유시에는 통상의 용융아연 열연강판의 제조공정에서 열간압연과정 및 연속소둔 열처리공정중에서 실리콘이 강판 표면으로 확산되어 이들 원소의 농도가 모재보다 10∼100배정도 높게 되는데 이와 같이 결정입계나 입내에 농화된 실리콘은 로내 분위기중의 극미량 수분이나 불순물과 반응하여 SiO2 산화물 피막을 형성하므로써 용융아연 도금공정에서 용융아연과의 도금부착성(Wettability)을 크게 저하시키다.However, the high-strength steel for super-core processing contains all of the non-plating elements such as Si, Mn, and P. In particular, when the Si content of 0.1wt.% Or more is contained in the steel component, hot rolling process in the manufacturing process of the hot-dip galvanized steel sheet In the continuous annealing heat treatment process, the silicon diffuses to the surface of the steel sheet, and the concentration of these elements is about 10 to 100 times higher than that of the base material. Thus, the silicon concentrated in the grain boundary or in the mouth reacts with the trace amount of moisture or impurities in the furnace atmosphere to form SiO 2. By forming the oxide film, the plating adhesion with the molten zinc in the molten zinc plating process is greatly reduced.

그 결과 젖음성 확보가 곤란하게 되어 미도금현상이 다발하게 되거나, 용융도금이 되더라도 도금밀착성을 열화시켜 가공시 도금박리가 발생하며 합금화열처리시 합금화가 크게 지연되는 문제점이 있다.As a result, it is difficult to secure the wettability, which leads to unplated phenomena, or even hot-dip plating, which causes deterioration of the plating adhesion and causes plating peeling during processing and greatly delays alloying during alloying heat treatment.

상기와 같은 Si 함유강의 도금부착성 문제를 해결하기 위하여 종래에는 용융아연 도금욕의 Al첨가량을 0.10∼0.20 wt.%에서 0.21∼0.25 wt.%로 증가시켜서 소지철과 도금층 계면에 Zn-Fe-Al-Si계 및 Fe-Al-Si계의 합금중 생성량을 증가시켜 0합금원소의 산화층을 환원시키는 효과에 의해 계면에서 합금원소의 산화피막으로 인한 용융도금 젖음성저하를 방지하는 방법을 이용하였다.In order to solve the plating adhesion problem of the Si-containing steel as described above, the Al addition amount of the hot dip galvanizing bath is increased from 0.10 to 0.20 wt.% To 0.21 to 0.25 wt.%, So that Zn-Fe— By reducing the oxide layer of the alloying element 0 by increasing the amount of Al-Si and Fe-Al-Si-based alloys, the method of preventing melt plating wettability due to the oxide film of the alloying element at the interface was used.

그러나 상기와 같은 방법으로 도금욕내 증가된 알루미늄은 미니스팡글 강판 제조시 도금욕에 불가피하게 불순물로 첨가되는 Pb와 공존시 입계부식이 발생하기 용이하기 때문에 경시 도금박리가 발생할 가능성이 높다.However, the increased aluminum in the plating bath in the above manner is likely to cause delamination over time because the grain boundary corrosion occurs easily when co-existing with Pb, which is inevitably added as an impurity to the plating bath in the manufacture of the mini-spangle steel sheet.

또한, 도금욕내 알루미늄 농도의 증가는 도금욕내 상부드로스 발생량을 증가시키고 합금화반응을 크게 지연시키는 문제점이 있다.In addition, an increase in the aluminum concentration in the plating bath has a problem of increasing the amount of upper dross in the plating bath and greatly delaying the alloying reaction.

또 하나의 Si함유강의 도금부착성 문제를 해결하기 위한 방법으로 용융도금전에 Fe, Ni, Fe-O, Fe-C 계 및 기타 다양한 합금원소계의 무전해 또는 전기도금에 의한 예비도금을 실시하는 방법이다.In order to solve the plating adhesion problem of another Si-containing steel, pre-plating is performed by electroless or electroplating of Fe, Ni, Fe-O, Fe-C and various alloy elements before hot dip plating. Way.

이는 고온소둔에 의해서 소지철계면에 합금원소가 농화되어도 예비도금층 하부에 노화됨으로써 소둔과정 또는 가열과정시 분위기중 수분과의 반응을 차단하기 때문에 실리콘의 산화가 방지되므로 도금부착성 및 합금화처리성이 크게 향상된다.This prevents oxidation of silicon because it prevents the oxidation of silicon during the annealing process or heating process by aging under the preplating layer even when alloying elements are concentrated on the base iron surface by high temperature annealing. Greatly improved.

그러나 강판표면에 예비도금하는 방법을 통상 전기도금방식으로 실시하기 때문에 소지철의 요철이 큰 열연산세강판을 도금소재로 하는 경우, 짧은 도금공정으로 인해 요철부에 도금부착량 편차가 발생한다.However, since the method of pre-plating the surface of the steel sheet is usually performed by the electroplating method, when the thermally calcined fine steel sheet having large unevenness of base steel is used as the plating material, a short plating process causes variation in the amount of plating deposition.

즉 요철부는 평활한 도금층 표면보다 양극과의 간격차이가 있기 때문으로 볼록부는 평활한 표면보다 도금부착량이 많게 되나 오목부분은 도금부착량이 적게되거나 전혀 도금이 되지 않는 문제점이 발생할 가능성이 있다.That is, since the uneven portion has a gap difference from the anode than the smooth plating layer surface, the convex portion has a larger amount of plating adhesion than the smooth surface, but the concave portion may have a small amount of plating adhesion or no plating at all.

따라서 이를 방지하기 위하여 전기도금공정을 길게 하거나 감속작업을 행하는 방법이 있으나, 볼록부에서의 과도금이 발생하므로 바람직하지 않다.Therefore, in order to prevent this, there is a method of lengthening the electroplating process or performing a deceleration operation, but it is not preferable because overplating occurs in the convex portion.

특히 이와같이 예비도금하는 원소는 경도가 크고 연성이 부족한 원소로서 도금부착량이 큰 경우 가공시 도금박리가 발생하는 문제가 있다. In particular, the element to be pre-plated in this way has a problem that the plating peeling occurs during processing when the plating adhesion amount is large as a high hardness and insufficient ductility.

또한, 전처리 공정에서 예비도금을 전기도금방식으로 실시할 경우, 설비가 복잡하기 때문에 경제적으로도 바람직하지 않다.In addition, when pre-plating is carried out by electroplating in the pretreatment process, it is not economically preferable because of the complicated equipment.

한편 최근 실리콘 첨가강의 도금성을 향상시키기 위해 직화로(Direct Dired Furnace)에서 과잉의 공기를 투입하여 산화피막을 형성한 후 10% H2 - 90% H2 환원 분위기의 가열로(RTS)에서 환원처리를 함으로써 도금성을 크게 향상시킬 수 있어 이에 대한 연구가 진행되고 있다. 즉 직화로에서 공기비를 통상의 0.9에서 1.05로 증가시켜 철산화물 두께를 증가시킨 후 환원열처리하면 순수한 Fe층이 강판표면에 형성될 수 있다.In recent years silicone added to the flame to enhance the river plating property (Direct Dired Furnace) 10% H 2 and then charged into the air to form an oxide film of over-in-reduction in heating in (RTS) of 90% H 2 reducing atmosphere The treatment can greatly improve the plating property, and research on this has been conducted. That is, in the direct furnace, the air ratio may be increased from 0.9 to 1.05 to increase the iron oxide thickness, and then reduced heat treatment may form a pure Fe layer on the surface of the steel sheet.

그러나 만일 산화피막이 두껍게 잔존하면 도금박리가 발생하고 실리콘이 강판표면에 농화되면 아연도금층은 강판표면에 강하게 밀착되지 못하거나 미도금이 발생한다.However, if the oxide film remains thick, the plating peeling occurs and if the silicon is concentrated on the surface of the steel sheet, the galvanized layer may not be strongly adhered to the surface of the steel sheet or unplated.

그러므로 직화로에서 철산화물의 두께를 적절하게 조절하는 것이 매우 중요하며 따라서 현장적용이 곤란한 문제점이 있다.Therefore, it is very important to properly control the thickness of the iron oxide in the oven, and therefore there is a problem that it is difficult to apply the site.

본 발명은 상기와 같은 문제점을 해결하기 위하여 강중 실리콘을 0.1∼1.0 wt.% 함유한 고강도 냉연강판을 대상으로 0.10∼0.14 wt.%의 알루미늄을 포함한 통상의 합금화 용융아연 도금욕에서 일반 저탄소강과 동등한 도금부착성을 갖는 고강도 용융아연 도금강판을 제조하는 방법을 제공하는 것을 그 목적으로 한다.In order to solve the above problems, the present invention is a high-strength cold-rolled steel sheet containing 0.1-1.0 wt.% Silicon in steel, which is equivalent to that of general low carbon steel in a conventional alloyed hot dip galvanizing bath containing 0.10 to 0.14 wt.% Aluminum. Its object is to provide a method for producing a high strength hot dip galvanized steel sheet having plating adhesion.

본 발명은 상기와 같은 목적을 달성하기 위하여 실리콘이 0.1∼1.0 wt.% 함유한 고강도 냉연강판을 0.10∼0.14 wt.%의 알루미늄을 포함한 통상의 합금화 용융아연 도금욕에 주석 0.05∼0.10 wt.%을 첨가하여 일반 저탄소강과 동등한 도금부착성 및 합금화처리성을 갖는 고강도 합금화 용융아연 도금강판 제조방법을 제공한다.In order to achieve the above object, the present invention provides a high strength cold rolled steel sheet containing 0.1 to 1.0 wt.% Of silicon and 0.05 to 0.10 wt.% Of tin in a conventional alloyed hot dip galvanizing bath containing 0.10 to 0.14 wt.% Of aluminum. It provides a high strength alloyed hot-dip galvanized steel sheet manufacturing method having the plating adhesion and alloying treatment properties equivalent to the general low carbon steel.

이하, 본 발명의 수치한정에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, numerical limitation of this invention is demonstrated.

먼저 강의 강도를 증가시키기 위하여 강중의 실리콘농도를 0.1∼1.0wt.%로 한정하는 이유는 실리콘 함량이 0.1 wt.% 미만에서는 강의 강도증가가 뚜렷하지 않으며 1.0 wt.% 를 초과하면 과도한 실리콘 산화물의 편석으로 도금욕에 주석을 첨가하더라도 미도금이 발생하고 합금화처리성이 크게 떨어지기 때문이다.First, in order to increase the strength of the steel, the silicon concentration in the steel is limited to 0.1 to 1.0 wt.% Because the strength increase of the steel is not significant when the silicon content is less than 0.1 wt.%, And when the silicon content exceeds 1.0 wt.%, This is because even though tin is added to the plating bath as segregation, unplating occurs and alloying treatment properties are greatly degraded.

상기와 같이 실리콘함유강의 합금화속도가 지연되는 이유는 도금전 열처리과정시 결정입계에 편석된 실리콘이 철의 확산경로를 차단하기 때문인 것으로 알려져 있다.The reason why the alloying speed of the silicon-containing steel is delayed as described above is that the silicon segregated at the grain boundaries during the heat treatment process before the plating blocks the diffusion path of iron.

합금화 용융아연 도금강판 제조시 용융아연 도금욕의 알루미늄 성분을 0.10∼0.14 wt.% 로 관리하는 이유는 도금욕중의 알루미늄 함량이 0.10 wt.% 미만에서는 취약한 케피탈 감마(Γ)상이 두껍게 발달하여 파우더링성이 현저히 열화되고 알루미늄 함량이 0.14 wt.% 이상으로 높을 경우 소지철과 도금층사이의 계면에 생성되는 철-알루미늄-아연의 치밀한 3원계 화합물이 두껍게 발달하여 합금화 열처리시 소지철로부터 철원자가 아연도금층내로 확산하는 것을 방해하기 때문이다.The reason why the aluminum component of the hot dip galvanizing bath is controlled to 0.10 to 0.14 wt.% In the production of alloyed hot dip galvanized steel sheet is that the weak powder of Gamma (Γ), which is fragile, develops when the aluminum content of the plating bath is less than 0.10 wt.%. When the ringability is markedly deteriorated and the aluminum content is higher than 0.14 wt.%, A dense ternary compound of iron-aluminum-zinc formed at the interface between the base iron and the plating layer is thickly developed. This is because it prevents it from spreading inside.

따라서, 통상의 합금화 용융아연 도금강판 제조시에는 신속하고 균일한 합금화 열처리를 위해 알루미늄 함량을 0.10∼0.14 wt.%로 낮게 관리하는 것이다.Therefore, in the manufacture of a conventional alloyed hot-dip galvanized steel sheet, the aluminum content is controlled as low as 0.10 to 0.14 wt.% For quick and uniform alloying heat treatment.

한편 도금욕내 주석첨가농도를 0.05∼0.1 wt..%로 한정한 이유는 0.05 wt.% 미만으로 첨가시 표면장력감소가 적어서 도금부착성의 개선이 뚜렷하지 않으며 도금층과 소지철의 계면에서 다공성의 철-아연-알루미늄 3원계 합금층을 형성하므로 합금화반응이 억제되기 때문이고 0.10 wt.% 를 초과하면 합금화반응은 촉진되나, 도금욕 상부의 주석에 기인한 드로스 발생량이 많게 되어 표면품질이 열화되고 도금층을 장기 보관시 검게 변색되는 문제점이 발생하기 때문이다.On the other hand, the reason of limiting the tin addition concentration in the plating bath to 0.05 to 0.1 wt ..% is that the surface tension decreases when added to less than 0.05 wt.%, So that the improvement of plating adhesion is not obvious, and the porous iron at the interface between the plating layer and the base iron is not apparent. Because the zinc-aluminum tertiary alloy layer is formed, the alloying reaction is suppressed. If it exceeds 0.10 wt.%, The alloying reaction is promoted, but the dross generation amount due to tin on the upper part of the plating bath is increased, resulting in deterioration of the surface quality. This is because a problem of discoloration occurs when the plating layer is stored for a long time.

상기와 같이 본 발명에서는 주석을 0.05∼0.10 wt..%를 첨가함으로써 소지강판에 생성되어 합금화 반응을 저해하는 치밀한 철-아연-알루미늄 3원계 합금층 대신에 합금화반응을 저해하지 않는 철-아연-알루미늄-주석의 4원계 합금층을 형성하여 도금욕의 표면장력을 크게 감소시켜 일반 저탄소강과 동등한 합금화 반응을 가능하게 함으로써 표면품질 및 생산성을 향상하게 한다.As described above, in the present invention, iron-zinc- does not inhibit the alloying reaction instead of the dense iron-zinc-aluminum tertiary alloy layer which is produced in the base steel sheet by adding 0.05 to 0.10 wt ..% of tin to inhibit the alloying reaction. By forming a quaternary alloy layer of aluminum-tin, the surface tension of the plating bath is greatly reduced to enable alloying reaction equivalent to that of general low carbon steel, thereby improving surface quality and productivity.

실례로서 0.14wt.% 알루미늄 - 0.10wt.% 주석도금욕에서 용융도금시 얻어진 도금층내부의 주석의 분포위치를 알기 위해서 도금층의 깊이방향으로 GDS(Glow Discharge Spectrometer)로 분석한 결과 도금층과 소지철의 계면에 알루미늄 농도가 저하되면서 동시에 주석이 농화되어 있음을 볼 수 있다.For example, in order to know the distribution position of tin in the plating layer obtained by hot-dip plating in 0.14wt.% Aluminum-0.10wt.% Tin plating bath, GDS (Glow Discharge Spectrometer) analysis was conducted in the depth direction of the plating layer. It can be seen that tin is concentrated at the same time as the aluminum concentration decreases at the interface.

이는 초기 합금층이 통상의 철-아연-알루미늄의 3원 합금층이 아닌 철-아연-알루미늄-주석의 4원 합금층이 생성된 것을 시사하고 있다.This suggests that the initial alloy layer produced a ternary alloy layer of iron-zinc-aluminum-tin, rather than a ternary alloy layer of ordinary iron-zinc-aluminum.

따라서 0.10wt.% 주석-0.14wt.% 알루미늄 도금욕에서 주석첨가시 도금층이 응고할 때 도금층과 소지철의 계면에서 철-아연 확산 반응의 장벽으로 작용하는 철-아연-알루미늄 3원계의 치밀한 합금층 대신에 합금화반응을 저해하지 않는 다공성의 철-아연-알루미늄-주석의 4원계 합금층을 형성하여 합금화속도가 증가된 것으로 판단된다.Therefore, the dense alloy of the iron-zinc-aluminum ternary system, which acts as a barrier of the iron-zinc diffusion reaction at the interface between the plating layer and the ferrous iron when the plating layer solidifies in 0.10wt.% Tin-0.14wt.% Aluminum plating bath. It is believed that the alloying rate was increased by forming a porous alloy layer of porous iron-zinc-aluminum-tin that does not inhibit the alloying reaction instead of the layer.

이하 실시예를 들어 본 발명을 보다 상세히 설명한다.The present invention will be described in more detail with reference to the following Examples.

<실시예><Example>

표 1은 본 발명에 의한 실시예를 나타낸 것으로 실리콘이 각각 0.01, 0.5, 1.5 wt.% 함유된 0.8mm 두께의 냉연강판을 사용하여 연속용융 도금공정에서 도금욕내 알루미늄 함량 및 주석함량을 변화시킨 도금욕에 3초간 침적하고 도금부착량을 단면기준으로 45g/㎡으로 하였다.Table 1 shows an embodiment according to the present invention using a 0.8mm thick cold-rolled steel sheet containing 0.01, 0.5 and 1.5 wt.% Of silicon, respectively, to change the aluminum content and the tin content in the plating bath in a continuous hot dip plating process. It was immersed in the bath for 3 seconds, and the plating deposition amount was 45 g / m <2> on a cross-sectional basis.

도금부착성은 180°굽힘시험하여 육안으로 도금박리상태를 관찰하여 평가하였다.Plating adhesion was evaluated by visually observing the plating peeling state by 180 ° bending test.

합금화 열처리 조건은 520℃에서 15초간 동일하게 열처리한 후 파우더링지수 및 합금층내 철함량을 측정하여 하기 표 1에 나타내었다.Alloying heat treatment conditions are shown in Table 1 by measuring the powdering index and the iron content in the alloy layer after the same heat treatment for 15 seconds at 520 ℃.

여기서 파우더링 지수(P/I)는 1에 가까울수록 양호하고 5에 가까울수록 불량을 의미한다.Here, the powdering index (P / I) is closer to 1 is good, and closer to 5 means poor.

표 1.Table 1.

Figure pat00001
Figure pat00001

상기 표 1에서 알 수 있는 바와 같이 본 발명의 조건을 만족하는 발명예(1∼4)는 일반 저탄소강(5)과 동등한 도금부착성, 도금층의 파우더링 지수 및 합금화 처리성을 나타내었으나, 비교예(6)와 같이 알루미늄, 주석함량이 본 발명의 범위를 만족하더라도 강중 실리콘 함량이 0.01wt.%로 낮으면 과도한 합금화로 인한 파우더링성이 저하되므로 합금화 처리조건을 변경하여야 한다.As can be seen from Table 1, Inventive Examples (1 to 4) satisfying the conditions of the present invention showed plating adhesion, powdering index of the plating layer, and alloying treatment properties equivalent to those of general low carbon steel (5). As in Example (6), even if the aluminum and tin content satisfies the scope of the present invention, if the silicon content in the steel is low as 0.01wt.%, The powdering property due to excessive alloying is lowered, so the alloying treatment conditions should be changed.

강중 실리콘 함량이 1.0wt.%를 초과한 비교예(8∼9)에서는 주석을 첨가하더라도 미도금발생으로 인한 도금부착성 열화 및 미합금화가 다량 발생하였다.In Comparative Examples (8-9) in which the silicon content in the steel exceeded 1.0 wt.%, Even when tin was added, the plating adhesion deterioration and the unalloyation occurred due to the unplating.

또한 실리콘 함량이 0.1∼1.0 wt.% 인 조건에서 주석첨가량이 0.05 wt.% 미만인 경우(비교예 9,11)에는 도금부착성이 불량하고 미합금화가 발생한 반면 주석 함량이 1.0 wt.%를 초과하면(비교예 10,12) 과도한 철-아연 확산반응으로 도금부착성이 파우더링성이 저하되었다.In addition, when the amount of tin added was less than 0.05 wt.% Under the conditions of silicon content of 0.1 to 1.0 wt.% (Comparative Examples 9 and 11), the plating adhesion was poor and unalloyed, while the tin content exceeded 1.0 wt.%. Lower surface (Comparative Examples 10, 12) Excessive iron-zinc diffusion reaction reduced the plating adhesion powdering property.

따라서 본 발명의 아연도금욕내 주석을 0.05∼0.10 wt.% 로 첨가하여 사용하면, 강중 실리콘이 0.1∼1.0 wt.% 함유된 고강도 강에서도 일반 저탄소강과 동등한 도금부착성 및 합금화처리가 가능하였으며 내파우더링성이 우수한 합금화 용융아연 도금강판을 얻을 수 있었다.Therefore, when the tin in the galvanizing bath of the present invention is added at 0.05 to 0.10 wt.%, Even in high strength steel containing 0.1 to 1.0 wt.% Of silicon in steel, plating adhesion and alloying treatment equivalent to those of general low carbon steel were possible. An alloyed hot dip galvanized steel sheet having excellent powdering properties was obtained.

상기와 같은 본 발명에 의하여 통상의 합금화 용융아연 도금욕에 0.05∼0.10 wt.%의 주석을 첨가하여 미도금발생 억제 및 도금부착성이 향상된 합금화 용융아연 도금강판의 제조가 가능하므로 생산성을 향상시키고 표면품질 불량을 크게 감소시킬 수 있다.According to the present invention as described above it is possible to manufacture the alloyed hot-dip galvanized steel sheet with the addition of 0.05 ~ 0.10 wt. Surface quality defects can be greatly reduced.

Claims (1)

0.10∼0.14 wt.%의 알루미늄과 0.05∼0.10wt.%의 주석을 포함한 용융아연도금욕을 이용하여 고강도합금화용융아연도금강판을 제조하는 방법에 있어서, 상기 강판은 실리콘이 0.1∼0.10wt.% 함유된 것을 특징으로 하는 도금부착성 및 합금화 처리성이 우수한 고강도 합금화 용융아연 도금강판의 제조방법.A method of producing a high strength alloyed hot dip galvanized steel sheet using a hot dip galvanizing bath containing 0.10 to 0.14 wt.% Aluminum and 0.05 to 0.10 wt.% Tin, wherein the steel sheet is 0.1 to 0.10 wt.% Silicon. A method for producing a high strength alloyed hot dip galvanized steel sheet having excellent plating adhesion and alloying treatment, characterized in that it contains.
KR1019970062028A 1997-11-21 1997-11-21 Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process KR100478725B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019970062028A KR100478725B1 (en) 1997-11-21 1997-11-21 Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019970062028A KR100478725B1 (en) 1997-11-21 1997-11-21 Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process

Publications (2)

Publication Number Publication Date
KR19990041443A KR19990041443A (en) 1999-06-15
KR100478725B1 true KR100478725B1 (en) 2005-08-29

Family

ID=37304263

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019970062028A KR100478725B1 (en) 1997-11-21 1997-11-21 Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process

Country Status (1)

Country Link
KR (1) KR100478725B1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100530048B1 (en) * 2001-03-07 2005-11-22 주식회사 포스코 A method for manufacturing hot galvanizing steel sheet with good surface appearance
CN113881911A (en) * 2021-09-10 2022-01-04 湖南株冶有色金属有限公司 Silicon-tin alloy contained in hot galvanizing bath

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59182958A (en) * 1983-03-31 1984-10-17 Sumitomo Metal Ind Ltd Alloyed and galvanized steel sheet and its production
JPH02166261A (en) * 1988-12-20 1990-06-26 Nkk Corp Manufacture of alloyed hot dip galvanized steel sheet excellent in workability and coating suitability
JPH02166265A (en) * 1988-12-20 1990-06-26 Nkk Corp Manufacture of alloyed hot dip galvanized steel sheet having excellent workability and coating characteristics
JPH02175853A (en) * 1988-09-02 1990-07-09 Verdun H Farnsworth Composition for galvanizing bath
JPH03253550A (en) * 1990-01-16 1991-11-12 Nippon Steel Corp Production of alloyed hot dip galvanized steel sheet having superior spot weldability and hot dip galvanizing bath

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59182958A (en) * 1983-03-31 1984-10-17 Sumitomo Metal Ind Ltd Alloyed and galvanized steel sheet and its production
JPH02175853A (en) * 1988-09-02 1990-07-09 Verdun H Farnsworth Composition for galvanizing bath
JPH02166261A (en) * 1988-12-20 1990-06-26 Nkk Corp Manufacture of alloyed hot dip galvanized steel sheet excellent in workability and coating suitability
JPH02166265A (en) * 1988-12-20 1990-06-26 Nkk Corp Manufacture of alloyed hot dip galvanized steel sheet having excellent workability and coating characteristics
JPH03253550A (en) * 1990-01-16 1991-11-12 Nippon Steel Corp Production of alloyed hot dip galvanized steel sheet having superior spot weldability and hot dip galvanizing bath

Also Published As

Publication number Publication date
KR19990041443A (en) 1999-06-15

Similar Documents

Publication Publication Date Title
JP4990345B2 (en) Manufacturing method of high manganese steel hot dip galvanized steel sheet with excellent plating surface quality
JP2016084543A (en) Hot-dip plating steel sheet excellent in plating adhesion and method for manufacturing the same
JP5830541B2 (en) Hot-dip galvanized steel sheet excellent in plating property, plating adhesion and spot weldability, and its production method
US4584211A (en) Continuous hot dip aluminum coating method
JP4264373B2 (en) Method for producing molten Al-based plated steel sheet with few plating defects
JP2007107050A (en) HOT DIP Al BASED PLATED STEEL SHEET HAVING EXCELLENT WORKABILITY AND METHOD FOR PRODUCING THE SAME
KR101115741B1 (en) Method for manufacturing high manganese hot dip galvanized steel sheet with superior weldability
KR100478725B1 (en) Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process
KR102305753B1 (en) Zn-Al-Mg BASED HOT DIP ALLOY COATED STEEL MATERIAL HAVING EXCELLENT CORROSION RESISTANCE OF PROCESSED PARTS AND METHOD OF MANUFACTURING THE SAME
JP2705386B2 (en) Hot-dip galvanizing method for Si-containing steel sheet
JPH0688251A (en) Si containing high strength galvannealed steel sheet
JP2001295017A (en) High strength hot-dip zincing steel sheet having good corrosion resistance and press-workability
KR100685034B1 (en) Method for manufacturing high strength galvannealed steel sheet
JP2976845B2 (en) Galvannealed steel sheet
JP2841898B2 (en) Alloyed hot-dip galvanized steel sheet with excellent surface smoothness
JP3838277B2 (en) Alloyed hot-dip galvanized steel sheet with excellent powdering resistance
JPS61190056A (en) Production of aluminum hot dipped ti-containing steel sheet having excellent heat resistance and high-temperature strength
JPH0971851A (en) Production of zinc-tin alloy plated steel sheet
JP2765078B2 (en) Alloyed hot-dip coated steel sheet and method for producing the same
JP2654588B2 (en) P-containing high-strength galvannealed steel sheet
KR19990053135A (en) Manufacturing method of high strength hot dip galvanized steel sheet
JP2700516B2 (en) Method for producing high Si content strength galvannealed steel sheet with good plating adhesion
KR910000915B1 (en) Alloyed-zinc- plated steel sheet and process for preparing the same
JPH04314848A (en) Manufacture of high tensile strength galvannealed steel sheet excellent in workability
JPH04218655A (en) Manufacture of galvannealed steel sheet excellent in workability

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20130315

Year of fee payment: 9

FPAY Annual fee payment

Payment date: 20140317

Year of fee payment: 10

FPAY Annual fee payment

Payment date: 20150311

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20160314

Year of fee payment: 12

LAPS Lapse due to unpaid annual fee