KR19990052846A - Manufacturing method of alloyed hot-dip galvanized steel sheet deposited with manganese / aluminum excellent in corrosion resistance and electrodeposition coating - Google Patents
Manufacturing method of alloyed hot-dip galvanized steel sheet deposited with manganese / aluminum excellent in corrosion resistance and electrodeposition coating Download PDFInfo
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- KR19990052846A KR19990052846A KR1019970072377A KR19970072377A KR19990052846A KR 19990052846 A KR19990052846 A KR 19990052846A KR 1019970072377 A KR1019970072377 A KR 1019970072377A KR 19970072377 A KR19970072377 A KR 19970072377A KR 19990052846 A KR19990052846 A KR 19990052846A
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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Abstract
본 발명은 인산염처리 및 전착도장되어 자동차 등의 소재로 사용되는 이층도금강판의 제조방법에 관한 것이며; 그 목적은 합금화 용융아연 도금강판에 Mn/Al을 이층으로 진공증착함으로써 인산염처리성 및 전착도장성 그리고 특히 내식성이 우수한 Mn/Al 증착 합금화처리 용융아연 도금강판의 제조방법을 제공함에 있다.The present invention relates to a method for producing a two-layer plated steel sheet used in phosphate treatment and electrodeposition coating to be used as a material for automobiles; The purpose of the present invention is to provide a method for manufacturing a Mn / Al deposited alloyed hot-dip galvanized steel sheet having excellent phosphate treatment and electrodeposition coating properties, and particularly corrosion resistance, by vacuum depositing Mn / Al in two layers on an alloyed hot-dip galvanized steel sheet.
상기 목적을 달성하기 위한 본 발명은 이층도금강판의 제조방법에 있어서, 합금화처리 용융아연도금 강판을 일정온도로 가열한 다음, 상기 강판위에 알루미늄을 강판편면당 10g/㎡이하의 부착량으로 진공증착하고, 그위에 망간을 3-10g/㎡의 범위로 진공증착하여 이루어지는 내식성과 전착 도장성이 우수한 망간/알루미늄이 증착된 합금화처리 용융아연 도금강판의 제조방법에 관한 것을 그 요지로 한다.In the present invention for achieving the above object, in the method of manufacturing a two-layer plated steel sheet, the alloyed hot-dip galvanized steel sheet is heated to a constant temperature, and then aluminum is deposited on the steel sheet with an adhesion amount of 10 g / m2 or less per sheet steel sheet. The present invention is directed to a method for producing an alloying hot-dip galvanized steel sheet having excellent manganese / aluminum deposition, which is formed by vacuum evaporation of manganese in a range of 3-10 g / m2.
Description
본 발명은 인산염처리 및 전착도장되어 자동차 등의 소재로 사용되는 도금강판에 관한 것으로, 보다 상세하게는 합금화 용융아연도금강판(Galvannealed steel sheet)의 표면에 Mn/Al을 이층으로 진공증착함으로써 인산염처리성 및 내식성 그리고, 전착도장성이 우수한 도금강판의 제조방법에 관한 것이다.The present invention relates to a plated steel sheet used as a material for automobiles, such as phosphate treatment and electrodeposition coating, and more specifically, phosphate treatment by vacuum deposition of Mn / Al in two layers on the surface of an alloyed galvannealed steel sheet. It relates to a method for producing a plated steel sheet excellent in resistance and corrosion resistance, and electrodeposition coating properties.
용융아연 도금강판을 도금 직후에 확산 열처리하여 제조하는 합금화처리 용융아연Alloyed hot-dip zinc prepared by diffusion heat treatment of hot-dip galvanized steel sheet immediately after plating
도금강판은, 아연도금 강판에 비해서 인산염처리성과 전착도장성이 우수하여 자동차 내외판용으로 널리 사용되고 있다. 같은 용도로 사용되고 있는 도금강판으로는 아연-철 전기도금 강판이 있다.Galvanized steel sheet is widely used for automobile interior and exterior plates because it has superior phosphate treatment and electrodeposition coating properties compared to galvanized steel sheet. A plated steel sheet used for the same purpose is a zinc-iron electroplated steel sheet.
자동차의 내구성에 대한 수요가의 욕구 및 각국 정부의 규제가 더욱 엄격해지면서, 최근에는 이들의 인산염처리성을 개선하여 도장성을 향상시키기 위해서 여러 형태의 이층도금 강판을 개발하여 적용하는 사례가 늘어나고 있다.As the demand for automobile durability and the government's regulations become more stringent, in recent years, there have been increasing cases of developing and applying various types of two-layer plated steel sheets to improve their phosphate treatment properties and improve paintability. have.
이층도금강판은 문자 그대로 2개의 도금층을 형성시키는 기술로서 하층 도금으로 방청성(내식성)을 확보하고 상층 도금으로 도장성 및 용접성을 향상시키는 것을 목표로 한다. 이층도금 강판은 그 제조방법에 따라 이층 전기도금강판과 플래쉬(Flash) 도금강판으로 대별한다.A two-layer plated steel sheet is a technology that literally forms two plating layers, and aims to secure corrosion resistance (corrosion resistance) by lower layer plating and improve paintability and weldability by upper layer plating. Two-layer plated steel sheets are roughly classified into two-layer electroplated steel sheets and flash-plated steel sheets according to the manufacturing method thereof.
이층 전기도금 강판은 상,하층 모두를 전기도금법으로 제조하는 것이다. 하층 도금으로는 Zn-(10-20%)Fe, Zn-(10-15%)Ni 등의 소위 Zn-rich 도금계를 적용하여 Zn가 소지 강판에 대하여 갖는 희생방식성을 더욱 강화한다. 상층 도금으로는 Zn보다 화성처리성이 월등히 우수한 Fe의 특성을 이용하여 Fe-(15-50%)Zn, Fe-(0.1-1%)P, Fe-(15-20%)Mn 등의 소위 Fe-rich 도금계를 적용한다. 이와 같이 이층도금계를 구성함으로써 전기 아연도금 강판이나 용융아연도금강판, 합금화 처리 용융아연도금 강판 등에 비해서 우수한 방청성과 화성처리성을 동시에 얻을 수 있다. 상층 도금의 부착량은 대개 5g/㎡이하이다.In the two-layer electroplating steel sheet, both upper and lower layers are manufactured by the electroplating method. As the lower layer plating, a so-called Zn-rich plating system such as Zn- (10-20%) Fe and Zn- (10-15%) Ni is applied to further enhance the sacrificial corrosion resistance of Zn on the base steel sheet. As the upper layer plating, Fe- (15-50%) Zn, Fe- (0.1-1%) P, Fe- (15-20%) Mn, etc. are used by utilizing the characteristics of Fe, which is much better in chemical conversion than Zn. Fe-rich plating system is applied. By constructing a two-layer plating system as described above, superior anti-corrosion and chemical conversion properties can be obtained at the same time as compared with an electrogalvanized steel sheet, a hot-dip galvanized steel sheet, an alloyed hot-dip galvanized steel sheet, and the like. The deposition amount of the upper layer plating is usually 5 g / m 2 or less.
플래쉬(Flash) 도금강판은 내식성과 용접성이 우수한 합금화 처리 용융아연도금 강판을 소재로 하여 그 표면에 전기도금법으로 화성처리성이 우수한 도금계를 박도금한 제품을 말한다. 상층 도금계로는 이층 전기도금에서와 마찬가지로 화성처리성이 우수한 Fe-rich계 전기도금이 적용되고 있다. 상층도금게의 예로 Fe-Zn, Fe-Mn 등을 들 수 있다.Flash plated steel sheet is made of alloyed hot-dip galvanized steel sheet with excellent corrosion resistance and weldability, and is plated with a plating system having excellent chemical treatment property on the surface by electroplating method. As the upper layer plating system, Fe-rich electroplating, which has excellent chemical conversion treatment, is applied as in the two layer electroplating. Examples of the upper layer plating layer include Fe-Zn, Fe-Mn, and the like.
위에서 언급한 이층도금강판은 모두 전착도장성만을 강조하여 내식성이 다소 떨어진다는 문제가 있다.All of the above-mentioned two-layered steel sheets have a problem in that corrosion resistance is somewhat reduced by emphasizing only electrodeposition coating properties.
본 발명은 합금화처리 용융아연도금강판에 Mn/Al을 이층도금하여 인산염처리성 및 전착도장성과 함께 내식성을 보다 향상시킬 수 있는 합금화 용융아연 도금강판의 제조방법을 제공하는데, 그 목적이 있다.The present invention provides a method for producing an alloyed hot-dip galvanized steel sheet which can further improve corrosion resistance along with phosphate treatment and electrodeposition coating by two-plating Mn / Al on an alloyed hot-dip galvanized steel sheet.
도 1은 합금화 용융아연 도금강판에 Mn/Al이 증착된 소재의 깊이방향1 is a depth direction of a material in which Mn / Al is deposited on an alloyed hot dip galvanized steel sheet
성분분포를 나타내는 그래프이다;A graph showing the component distribution;
도 2는 본 발명에 따라 제조된 소재의 표면형상 및 인산염처리 조직을 나타내는Figure 2 shows the surface shape and phosphate treated tissue of the material produced according to the present invention
사진이다.It is a photograph.
상기 목적을 달성하기 위한 본 발명의 이층도금강판의 제조방법에 있어서, 합금화처리 용융아연도금강판을 일정온도로 가열한 다음, 상기 강판위에 알루미늄을 강판편면당 10g/㎡ 이하의 부착량으로 진공증착하고, 그 위에 망간을 3-10g/㎡의 범위로 진공증착하는 것을 포함하여 구성된다.In the production method of the two-layer plated steel sheet of the present invention for achieving the above object, the alloyed hot-dip galvanized steel sheet is heated to a constant temperature, and then vacuum-deposited aluminum on the steel sheet with an adhesion amount of 10g / ㎡ or less per sheet steel sheet And vacuum depositing manganese thereon in the range of 3-10 g / m 2.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 합금화처리 용융아연도금강판위에 내식성이 우수한 Al을 증착하고, 그위에 인산염처리성 및 전착도장성을 확보할 수 있는 Mn을 도금하는데, 그 특징이 있다.The present invention deposits Al having excellent corrosion resistance on an alloyed hot-dip galvanized steel sheet, and plated Mn on which phosphate treatment property and electrodeposition coating property can be secured.
본 발명에 따라 합금화처리 용융아연도금강판에 Mn/Al 도금하는데, 이때의 도금방법은 진공증착방법을 이용한다. 이는 Mn은 전기도금이 가능하지만, Al은 수용액중의 전기도금이 불가능하여 진공증착방법을 이용하는 것이다.Mn / Al plating on the alloying hot-dip galvanized steel sheet according to the present invention, the plating method at this time uses a vacuum deposition method. This is because Mn is capable of electroplating, but Al is not capable of electroplating in aqueous solution, and thus vacuum deposition is used.
진공증착방법은 통상의 방법대로 소지강판을 탈지처리한 후 표면의 이물질을 제거하여 진공증착장치의 진공조 안에 장입하고 동시에 증착물질을 도가니에 장입한다. 그리고, 진공조의 진공도를 일정수준까지 진공배기 한 후, 증착물질을 용융시킨다.In the vacuum deposition method, after degreasing the base steel sheet as usual, the foreign substances on the surface are removed to be charged into the vacuum chamber of the vacuum deposition apparatus, and the deposition material is charged into the crucible at the same time. Then, the vacuum degree of the vacuum chamber is evacuated to a certain level, and then the deposition material is melted.
이때, 소지강판의 온도는 증착층의 밀착성에 가장 큰 영향을 미친다.At this time, the temperature of the steel sheet has the greatest influence on the adhesion of the deposition layer.
즉, 증착 중 온도가 너무 낮으면 증발된 원자들이 기판에 입사한 후에 충분한 운동에너지를 갖지 못해서 증착조직이 치밀하지 못하게 되고 밀착성도 떨어지게 된다. 본 발명은 이를 고려하여 소지강판을 100℃ 이상으로 가열하나, 350℃ 이상으로 가열하면 소재 표면에 도금되어 있는 합금화 용융아연 도금층이 증발하기 시작하므로 소지강판의 가열은 100-350℃로 한다.In other words, if the temperature is too low during deposition, the evaporated atoms do not have sufficient kinetic energy after entering the substrate, and thus the deposition structure is not dense and the adhesion decreases. In consideration of this, the steel sheet is heated to 100 ° C. or higher, but when heated to 350 ° C. or higher, the alloyed hot dip galvanized layer coated on the surface of the material begins to evaporate, so that the heating of the steel sheet is 100-350 ° C.
이와같이 진공증착하면, Al/Mn이 견고히 밀착될 수 있다.In this way, Al / Mn can be firmly adhered by vacuum deposition.
상기 온도로 유지되는 합금화처리 용융아연 도금강판위에 Al을 증착하는데, 이때 부착량은 강판편면당 10g/㎡이하로 하는 것이 바람직하다. 이는 제조공정 및 제품의 경제성을 고려한 것으로 지나치게 많은 부착량은 경쟁력이 떨어지기 때문이다.Al is deposited on the alloyed hot-dip galvanized steel sheet maintained at the above temperature, wherein the deposition amount is preferably 10 g / m 2 or less per sheet steel sheet. This is because the manufacturing process and the economics of the product is considered, because too much adhesion amount is not competitive.
상기와 같이 Al이 진공증착된 도금층위에 Mn을 증착하는데, 이때의 부착량은 3-10g/㎠ 의 범위가 바람직하다. 그 이유는 상층의 Mn은 인산염처리시에 Mn3(PO4)2로 치환되므로 이에 필요한 최소한의 양이 필요한데, 그 양이 3g/㎡로 부착되는 경우 양호한 인산염 피막을 얻을 수 없기 때문이며, 10g/㎡를 넘어도 도장성이 더 이상 향상되지 않기 때문이다.As described above, Al is deposited on the vacuum-deposited plating layer, and the deposition amount at this time is preferably in the range of 3-10 g / cm 2. The reason is that Mn in the upper layer is replaced by Mn 3 (PO 4 ) 2 during phosphate treatment, so a minimum amount is required. If the amount is attached at 3 g / m 2, a good phosphate coating cannot be obtained. This is because the paintability does not improve any more than m 2.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
[실시예]EXAMPLE
합금화 용융아연 도금강판에 아래 표1과 같이 Mn/Al 를 진공증착 한 다음, 도장성 및 내식성을 평가하고 그 결과를 표 1에 나타내었다. 표 1의 비교예(6)(7)은 종래 용융아연 도금강판과 전기아연도금강판의 특성을 비교 평가한 것이다.Mn / Al was vacuum-deposited on the alloyed hot-dip galvanized steel sheet as shown in Table 1 below, and the paintability and corrosion resistance were evaluated, and the results are shown in Table 1. Comparative Example (6) (7) of Table 1 compares and evaluates the characteristics of the conventional hot-dip galvanized steel sheet and electro-galvanized steel sheet.
그리고, 도금층 특성평가중 1)도장성은 도금된 시편에 인산염처리와 전착도장을 실시한 후 도막밀착성을 평가하여 판정하였으며, 그 평가방법으로는 크로스-컷(Cross-cut)후 테이프 박리시험을 이용하였으며, 판정 기준은 다음과 같이 하였다.In the evaluation of the coating layer characteristics, 1) the coating property was evaluated by performing phosphate treatment and electrodeposition coating on the plated specimens and evaluating the coating adhesion. The evaluation method was a cross-cut tape peel test. , The criterion for evaluation was as follows.
◎: 전혀 박리가 일어나지 않음.(Double-circle): Peeling does not occur at all.
○: 박리가 부분적으로 일어나지만 박리부의 면적이 전체의 5% 이내임.(Circle): Peeling partly occurs but area of a peeling part is less than 5% of the whole.
△: 박리가 부분적으로 일어나지만 박리부의 면적이 전체의 20% 이내임.(Triangle | delta): Although peeling partially occurs, the area of a peeling part is less than 20% of the whole.
X : 전체의 50% 이상의 면적에서 박리가 일어남.X: Peeling occurs in an area of 50% or more of the whole.
2) 내식성은 전착도장 시편을 크로스-컷(Cross-cut)후 50 회(Cycle)의 복합부식시험을 실시하여 크로스-컷(Cross-cut)부에서 발생하는 블리스터(Blister)의 최대폭을 측정하여 평가하였으며, 판정기준은 다음과 같이 하였다.2) Corrosion resistance is measured 50 times after cross-cutting the electrodeposited coating specimens to measure the maximum width of the blister generated in the cross-cut section. The evaluation criteria were as follows.
◎: 블리스터 발생 없음.◎: No blister occurrence.
○: 블리스터가 일부 발생하지만 최대 블리스터 폭이 2mm 이하.○: Some blister occurs, but the maximum blister width is 2 mm or less.
△: 블리스터가 일부 발생하지만 최대 블리스터 폭이 5mm 이하.(Triangle | delta): Although some blister generate | occur | produces, the maximum blister width is 5 mm or less.
X : 5mm 이상의 폭을 갖는 블리스터가 다수 발생.X: A large number of blisters having a width of 5 mm or more occur.
상기 표 1에 나타난 바와같이, 본 발명에 따라 합금화 용융아연 도금강판에 Mn/Al 이 적정조건으로 진공증착된 실시예(1-4)의 경우 종래의 용융아연도금 또는 전기아연도금에 비해 도장성 및 내식성이 향상되었다.As shown in Table 1, in the case of Example (1-4) in which Mn / Al is vacuum-deposited on an alloyed hot-dip galvanized steel sheet according to the present invention under appropriate conditions, paintability is better than conventional hot-dip galvanized or electro-zinc plated. And corrosion resistance was improved.
참고로 도 1에 본 발명재의 깊이 방향성분 분포를 나타내었다. 그리고, 본 발명재의 표면형상 및 인산염처리 조직을 도 2에 나타내었다.For reference, Figure 1 shows the depth direction component distribution of the present invention. In addition, the surface shape and the phosphate treated tissue of the present invention are shown in FIG. 2.
상술한 바와같이, 본 발명에 의하면 인산염처리성 및 전착도장성 그리고 내식성이 동시에 확보되는 이층도금강판을 제공하는 효과가 있다.As described above, according to the present invention, there is an effect of providing a two-layer plated steel sheet having phosphate treatment property, electrodeposition coating property and corrosion resistance at the same time.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019970072377A KR100332914B1 (en) | 1997-12-23 | 1997-12-23 | A method of manufacturing Mn/Al vapor deposited galvannealed steel sheet with high corrosion resistance and good paint ability |
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| KR1019970072377A KR100332914B1 (en) | 1997-12-23 | 1997-12-23 | A method of manufacturing Mn/Al vapor deposited galvannealed steel sheet with high corrosion resistance and good paint ability |
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| KR100332914B1 KR100332914B1 (en) | 2002-08-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100600033B1 (en) * | 1999-12-24 | 2006-07-13 | 재단법인 포항산업과학연구원 | Fabrication method of Mn-vapor deposited galvanized steel sheet |
| KR101271967B1 (en) * | 2011-12-20 | 2013-06-07 | 주식회사 포스코 | A method for manufacturing painted steel sheets blister |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101692929B1 (en) | 2016-08-24 | 2017-01-04 | 서번산업엔지니어링주식회사 | Corrosion resistant coating composition of air conditioning system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR960009192B1 (en) * | 1993-12-30 | 1996-07-16 | 이사장 백덕현 | Mn/al two-layers coated steel sheets with an excellent corrosion resistance and adhesion |
| KR0140834B1 (en) * | 1994-11-09 | 1998-07-15 | 신창식 | Manufacturing method zn-al alloy deposited steel sheet |
| KR0138037B1 (en) * | 1994-12-27 | 1998-07-15 | 신창식 | Manufacturing method for zn-al alloy coated steel sheet |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100600033B1 (en) * | 1999-12-24 | 2006-07-13 | 재단법인 포항산업과학연구원 | Fabrication method of Mn-vapor deposited galvanized steel sheet |
| KR101271967B1 (en) * | 2011-12-20 | 2013-06-07 | 주식회사 포스코 | A method for manufacturing painted steel sheets blister |
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