KR19990041443A - A method of producing a high strength alloyed hot-dip galvanized steel sheet excellent in plating adhesion and alloying treatment property - Google Patents
A method of producing a high strength alloyed hot-dip galvanized steel sheet excellent in plating adhesion and alloying treatment property Download PDFInfo
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- KR19990041443A KR19990041443A KR1019970062028A KR19970062028A KR19990041443A KR 19990041443 A KR19990041443 A KR 19990041443A KR 1019970062028 A KR1019970062028 A KR 1019970062028A KR 19970062028 A KR19970062028 A KR 19970062028A KR 19990041443 A KR19990041443 A KR 19990041443A
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- 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
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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 producing a high strength alloyed galvanized steel sheet which is used as a steel sheet for automobiles and which is excellent in plating adhesion and alloying treatment property, and more particularly to a method for producing a galvanized steel sheet using a hot dip galvanizing bath containing 0.10 to 0.14 wt.% Aluminum Characterized in that a high strength alloyed hot-dip galvanized steel sheet is produced by adding 0.05 to 0.10 wt% of tin to the plating bath in the production of a high strength alloyed hot-dip galvanized steel sheet containing 0.1 to 1.0 wt% of silicon To a process for producing a high-strength alloyed hot-dip galvanized steel sheet excellent in galvanization resistance and plating adhesion.
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, it is possible to produce an alloyed hot-dip galvanized steel sheet in which the tin generation is suppressed and the adhesion of plating is improved by adding 0.05 to 0.10 wt.% Of tin to a conventional galvannealing hot dip galvanizing bath. It is possible to greatly reduce the defective surface quality.
Description
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 producing a high strength alloyed hot dip galvanized steel sheet which is used as a steel sheet for automobiles and which is excellent in plating adhesion and alloying treatment property and more specifically to a cold rolled steel sheet containing 0.1-1.0 wt. A high-strength alloyed hot-dip galvanized steel sheet with plating adhesion and galvannealing property equivalent to general low-carbon steel was prepared by adding 0.05 to 0.10 wt.% Tin to a conventional alloyed hot-dip galvanizing bath containing 0.10 to 0.14 wt. .
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.In order to prevent environmental pollution of automobile exhaust gas, regulation of fuel economy has been strengthened. As a measure to improve fuel efficiency of automobiles, weight reduction of automobiles is being promoted. As one of such countermeasures, automobile materials There is a growing demand for high tensile strength hot-dip galvanized steel sheets for automobiles.
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 of producing high strength steel using solid solution strengthening elements such as P and Mn has limitations in the workability, so that it is possible to use a silicon-like element capable of maintaining ductility without significantly reducing the steel strength, High tensile strength 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 강판표면으로 확산되어 이들 원소의 농도가 모재보다 10∼100배정도 높게 되는데 이와 같이 결정입계나 입내에 농화된 실리콘은 로내 분위기중의 극미량 수분이나 불순물과 반응하여 SiO2산화물 피막을 형성하므로써 용융아연 도금공정에서 용융아연과의 도금부착성(Wettability)을 크게 저하시키다.However, the above-mentioned high tensile strength steel for machining includes all of the elements of iridescent elements such as Si, Mn and P. Especially when the Si concentration is 0.1 wt.% Or more in the steel component, the hot rolling process in the manufacturing process of a normal hot- The concentration of these elements is 10 to 100 times higher than that of the base material. In this way, the silicon grains concentrated in the grain boundaries or in the mouth react with trace moisture or impurities in the furnace atmosphere to form SiO 2 By forming an oxide film, the plating adhesion with molten zinc in the hot dip galvanizing 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 becomes difficult to secure wettability, so that plating plating becomes complicated, and even when hot dip coating is performed, plating adhesion is deteriorated, plating peeling occurs during processing, and alloying is greatly delayed 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 합금원소의 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, conventionally, the amount of Al in the hot-dip galvanizing bath was increased from 0.10 to 0.20 wt.% To 0.21 to 0.25 wt.%, A method of preventing the lowering of the wettability of the molten plating due to the oxidation film of the alloy element at the interface is utilized by the effect of reducing the oxidation layer of the alloy element by increasing the amount of the Al-Si and Fe-Al-Si alloy.
그러나 상기와 같은 방법으로 도금욕내 증가된 알루미늄은 미니스팡글 강판제조시 도금욕에 불가피하게 불순물로 첨가되는 Pb와 공존시 입계부식이 발생하기 용이하기 때문에 경시 도금박리가 발생할 가능성이 높다.However, aluminum increased in the plating bath by the above-mentioned method is likely to cause plating detachment over time because it is easy to generate a grain boundary condition when coexisting with Pb which is inevitably added as an impurity in a plating bath in manufacturing a minispangel steel sheet.
또한, 도금욕내 알루미늄 농도의 증가는 도금욕내 상부드로스 발생량을 증가시키고 합금화반응을 크게 지연시키는 문제점이 있다.Also, an increase in the aluminum concentration in the plating bath has a problem of increasing the amount of the upper dross generated in the plating bath and significantly 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.As a method for solving the plating adhesion problem of another Si-containing steel, pre-plating is performed by electroless plating or electroplating of Fe, Ni, Fe-O, Fe-C and various other alloying elements before hot dip coating Method.
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 is because even if the alloying elements are concentrated on the ferrous iron interface due to the high temperature annealing, it is aged under the preliminary plating layer to block the reaction with moisture in the atmosphere during the annealing process or heating process, so that oxidation of the silicon is prevented, 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 preliminary plating on the surface of the steel sheet is usually carried out by electroplating, when the hot-rolled steel sheet having a large unevenness of the base steel is used as the plating material, a variation in the deposition amount of the plating occurs in the concave-
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 concave and convex portions have a gap with respect to the positive electrode than the smooth plating layer surface, there is a possibility that the convex portion has a larger plating amount than a smooth surface, but the concave portion has a smaller plating amount or no plating.
따라서 이를 방지하기 위하여 전기도금공정을 길게 하거나 감속작업을 행하는 방법이 있으나, 볼록부에서의 과도금이 발생하므로 바람직하지 않다.Therefore, there is a method of lengthening the electroplating process or performing a decelerating operation in order to prevent this, but it is undesirable because over-plating occurs at the convex portion.
특히 이와같이 예비도금하는 원소는 경도가 크고 연성이 부족한 원소로서 도금부착량이 큰 경우 가공시 도금박리가 발생하는 문제가 있다.Particularly, the preplating element has a large hardness and is insufficient in ductility. When the plating adhesion amount is large, there is a problem that plating peeling occurs during processing.
또한, 전처리 공정에서 예비도금을 전기도금방식으로 실시할 경우, 설비가 복잡하기 때문에 경제적으로도 바람직하지 않다.In addition, when the pre-plating is performed by the electroplating method in the pretreatment step, the equipment is complicated and is not economically advantageous.
한편 최근 실리콘 첨가강의 도금성을 향상시키기 위해 직화로(Direct Dired Furnace)에서 과잉의 공기를 투입하여 산화피막을 형성한 후 10% H2- 90% H2환원분위기의 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 plating ability can be greatly improved, and research on this is proceeding. That is, when the air ratio is increased from 0.9 to 1.05 in the direct furnace to increase the iron oxide thickness, a pure Fe layer can be formed on the surface of the steel sheet by reducing heat treatment.
그러나 만일 산화피막이 두껍게 잔존하면 도금박리가 발생하고 실리콘이 강판표면에 농화되면 아연도금층은 강판표면에 강하게 밀착되지 못하거나 미도금이 발생한다.However, if the oxide film remains thick, plating detachment occurs, and if the silicon is concentrated on the surface of the steel sheet, the galvanized layer is not firmly 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 control the thickness of iron oxide properly in the direct fire furnace, and thus it is difficult to apply it to the field.
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 provides a high-strength cold-rolled steel sheet containing 0.1 to 1.0 wt.% Of silicon in steel, which is equivalent to a general low-carbon steel in a conventional galvannealed zinc plating bath containing 0.10 to 0.14 wt. It is an object of the present invention to provide a method of manufacturing 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 in an amount of 0.05 to 0.10 wt.% Tin in a conventional alloyed hot-dip galvanizing bath containing 0.10 to 0.14 wt.% Aluminum, The present invention provides a method of manufacturing a high strength alloyed hot dip galvanized steel sheet having plating adhesion and alloying treatment equivalent to that of general low carbon steel.
이하, 본 발명의 수치한정에 대하여 설명한다.Hereinafter, the numerical limitations of the present invention will be described.
먼저 강의 강도를 증가시키기 위하여 강중의 실리콘농도를 0.1∼1.0wt.%fh 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.The reason for limiting the silicon concentration of the steel to 0.1 ~ 1.0 wt%.% Fh in order to increase the steel strength first is that the strength increase of the steel is not clear when the silicon content is less than 0.1 wt.%. When the silicon content exceeds 1.0 wt.%, This is because even if tin is added to the plating bath due to segregation, unplating occurs and the alloying treatment property is greatly deteriorated.
상기와 같이 실리콘함유강의 합금화속도가 지연되는 이유는 도금전 열처리과정시 결정입계에 편석된 실리콘이 철의 확산경로를 차단하기 때문인 것으로 알려져있다.The reason why the alloying speed of the silicon-containing steel is delayed as described above is believed to be that silicon segregated at grain boundaries during the pre-plating heat treatment process 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.When the aluminum content in the plating bath is less than 0.10 wt.%, The weak capillary gamma (?) Phase develops thickly, and the powder of the powdered zinc- When the aluminum content is remarkably deteriorated and the aluminum content is as high as 0.14 wt.% Or more, a dense ternary compound of iron-aluminum-zinc generated at the interface between the base iron and the plating layer is developed thickly, To prevent it from diffusing into it.
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 production of ordinary galvannealed galvanized steel sheet, the aluminum content is controlled to be 0.10-0.14 wt.% For rapid 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 why the concentration of tin added in the plating bath is limited to 0.05 to 0.1 wt ..% is that when the amount is less than 0.05 wt.%, The decrease in surface tension is small and the improvement in the plating adhesion is not clear. In the interface between the plating layer and the substrate iron, - Alloying reaction is promoted when the content exceeds 0.10 wt.%, But the amount of dross generated due to tin in the upper part of the plating bath is increased and the surface quality is deteriorated And the black layer is discolored 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, by adding 0.05 to 0.10 wt.% Of tin, iron-zinc-tin alloy alloys which do not inhibit the alloying reaction are produced instead of the dense iron-zinc- A quaternary alloy layer of aluminum-tin is formed so that the surface tension of the plating bath is greatly reduced to enable an alloying reaction equivalent to a 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.As an example, in order to know the distribution of tin in the plating layer obtained in 0.14 wt.% Aluminum-0.10 wt.% Tin plating bath, the concentration of tin in the plating layer was analyzed by GDS (Glow Discharge Spectrometer) It can be seen that the aluminum concentration is lowered at the interface and the tin is concentrated at the same time.
이는 초기 합금층이 통사의 철-아연-알루미늄의 3원 합금층이 아닌 철-아연-알루미늄-주석의 4원 합금층이 생성된 것을 시사하고 있다.This suggests that the initial alloy layer was a quaternary alloy layer of iron-zinc-aluminum-tin, not a synthetic ternary alloy layer of 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, when a tin is added in a 0.10 wt.% Tin-0.14 wt.% Aluminum plating bath, a dense alloy of iron-zinc-aluminum ternary system which acts as a barrier for the iron-zinc diffusion reaction at the interface between the plated layer and the iron- It is judged that the alloying speed is increased by forming a porous iron-zinc-aluminum-tin quaternary alloy layer which does not inhibit the alloying reaction.
이하 실시예를 들어 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to examples.
<실시예><Examples>
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 example according to the present invention. It shows a case where a cold-rolled steel sheet having a thickness of 0.8 mm containing silicon of 0.01, 0.5 and 1.5 wt.%, Respectively, The substrate was immersed in a bath for 3 seconds, and the amount of plating adhered was 45 g / m < 2 >
도금부착성은 180°굽힘시험하여 육안으로 도금박리상태를 관찰하여 평가하였다.The plating adhesion was evaluated by observing the state of plating peeling with the naked eye by 180 ° bending test.
합금화 열처리 조건은 520℃에서 15초간 동일하게 열처리한 후 파우더링지수 및 합금층내 철함량을 측정하여 하기 표 1에 나타내었다.The alloying heat treatment conditions were the same heat treatment at 520 ° C for 15 seconds and then the powdering index and the iron content in the alloy layer were measured and are shown in Table 1 below.
여기서 파우더링 지수(P/I)는 1에 가까울수록 양호하고 5에 가까울수록 불량을 의미한다.Here, the powdering index (P / I) is better as it approaches 1, and the closer to 5, the better.
표 1.Table 1.
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 the above Table 1, the inventive examples (1 to 4) satisfying the conditions of the present invention exhibited the plating adhesion equivalent to the general low carbon steel (5), the powdering index of the plated layer and the alloying treatment property, Even if the content of aluminum and tin satisfy the range of the present invention as in Example (6), if the content of silicon in steel is as low as 0.01 wt.%, The powdering property due to excessive alloying is lowered.
강중 실리콘 함량이 1.0wt.%를 초과한 비교예(8∼9)에서는 주석을 첨가하더라도 미도금발생으로 인한 도금부착성 열화 및 미합금화가 다량 발생하였다.In the comparative examples (8 to 9) in which the silicon content in the steel exceeded 1.0 wt.%, Deterioration of plating adhesion and unalloying due to unplated occurrences occurred even when tin was added.
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 주석함량이 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.% (Comparative Examples 9 and 11) under conditions of silicon content of 0.1 to 1.0 wt.%, The adhesion of the plating was poor and unalloying occurred, while the tin content exceeded 1.0 wt.% (Comparative Examples 10 and 12), the plating adhesion was deteriorated due to excessive iron-zinc diffusion reaction, and the powdering property was deteriorated.
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 zinc plating bath of the present invention is added in an amount of 0.05 to 0.10 wt.%, Plating adhesion and alloying treatment equivalent to general low carbon steel can be achieved even in high strength steel containing 0.1 to 1.0 wt. An alloyed hot-dip galvanized steel sheet excellent in powdering property 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, it is possible to produce an alloyed hot-dip galvanized steel sheet in which the tin generation is suppressed and the adhesion of plating is improved by adding 0.05 to 0.10 wt.% Of tin to a conventional galvannealing hot dip galvanizing bath. It is possible to greatly reduce the defective surface quality.
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| 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 |
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| CA1335867C (en) * | 1988-09-02 | 1995-06-13 | Verdun Hildreth Farnsworth | Rare earth and aluminium containing galvanising 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 |
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| 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 |
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