KR20000043696A - Galvanized steel plate alloy-melted and production method thereof - Google Patents
Galvanized steel plate alloy-melted and production method thereof Download PDFInfo
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- KR20000043696A KR20000043696A KR1019980060101A KR19980060101A KR20000043696A KR 20000043696 A KR20000043696 A KR 20000043696A KR 1019980060101 A KR1019980060101 A KR 1019980060101A KR 19980060101 A KR19980060101 A KR 19980060101A KR 20000043696 A KR20000043696 A KR 20000043696A
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- 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
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- 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
- C23C28/021—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 including at least one metal alloy layer
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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
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- 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
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- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- 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
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- 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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- 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
Description
본 발명은 인산염처리성과 전착도장성이 우수한 도금 강판에 관한 것으로서, 보다 상세하게는 그 표면에 Mn을 진공 증착하여 인산염처리성 및 전착도장성과 함께 내식성을 향상시키는 합금화 용융아연도금 강판 및 그 제조방법에 관한 것이다.The present invention relates to a plated steel sheet excellent in phosphate treatment and electrodeposition coating, and more particularly, to an alloyed hot-dip galvanized steel sheet and a method of manufacturing the same, which improves corrosion resistance with phosphate treatment and electrodeposition coating by vacuum depositing Mn on the surface thereof. It is about.
합금화 용융아연도금 강판은 용융아연도금 강판을 아연도금한 직후에 확산 열처리하여 제조한 것으로, 아연도금 강판에 비하여 인산염처리성과 전착도장성이 우수하므로 자동차의 내, 외판용으로 널리 사용된다. 자동차의 내구성에 대한 수요자의 욕구가 강화되고 각국 정부의 규제가 더욱 엄격해지면서, 최근에는 인산염처리성을 개선하여 도장성을 향상시키도록 여러 형태의 이층도금 강판을 개발하여 적용하고 있다.The alloyed hot-dip galvanized steel sheet is produced by diffusion heat treatment immediately after galvanizing the hot-dip galvanized steel sheet, and is widely used for interior and exterior of automobiles because it has better phosphate treatment and electrodeposition coating properties than galvanized steel sheet. As consumers' desire for the durability of automobiles is strengthened and government regulations become more stringent, recently, various types of two-layer plated steel sheets have been developed and applied to improve phosphate treatment properties and improve paintability.
이층도금 강판은 2개의 도금층을 형성한 것으로서, 하층 도금으로 방청성(내식성)을 확보하고, 상층 도금으로 도장성 및 용접성을 향상시킨다. 이 이층도금 강판은 그 제조방법에 따라 이층전기도금 강판과 플래시 도금 강판으로 대별된다.The two-layer plated steel sheet is formed of two plating layers, to secure corrosion resistance (corrosion resistance) by lower layer plating, and to improve paintability and weldability by upper layer plating. This two-layer plated steel sheet is roughly classified into two-layer electroplated steel sheet and flash-plated steel sheet according to the production method thereof.
이층전기도금 강판은 상, 하층 모두를 전기도금법으로 제조하는 것이다. 하층도금으로는 Zn-(10∼20%)Fe, Zn-(10∼15%)Ni 등 소위 Zn-리치 도금계를 적용하여 Zn이 소재 강판에 대하여 갖는 희생방식성을 더욱 강화한다. 상층도금으로는 Zn보다 화성처리성이 월등히 우수한 Fe의 특성을 이용하여 Fe-(15∼50%)Zn, Fe-(0.1∼1%)P, Fe-(15∼20%)Mn 등의 소위 Fe-리치 도금계를 적용한다. 이와 같이 이층도금계를 구성함으로써, 이층전기도금 강판은 전기아연도금 강판이나 용융아연도금 강판, 합금화 용융아연도금 강판 등에 비해서 우수한 방청성과 화성처리성을 동시에 얻을 수 있다. 상층도금의 투착량은 대개 5g/m2이하이다.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 strengthen the sacrificial corrosion resistance of Zn with respect to the 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 treatment than Zn. Fe-rich plating system is applied. By constructing the two-layer plating system as described above, the two-layer electroplating steel sheet can obtain excellent anti-corrosion and chemical conversion treatment property as compared with the electro-galvanized steel sheet, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel sheet and the like. The deposition amount of the upper plating is usually 5 g / m 2 or less.
플래시 도금 강판은 내식성과 용접성이 우수한 합금화 용융아연도금 강판을 소재로 하여 그 표면에 전기도금법으로 화성처리성이 우수한 도금계를 얇게 도금한 제품이다. 상층도금계로는 이층전기도금에서와 마찬가지로 화성처리성이 우수한 Fe-리치계 전기도금이 적용되고 있다. 상층도금계의 예로 Fe-Zn, Fe-Mn 등을 들 수 있다.Flash-coated steel sheet is made of alloyed hot-dip galvanized steel sheet with excellent corrosion resistance and weldability, and is plated with a thin plating system having an excellent chemical conversion treatment on the surface thereof. As the upper layer plating system, Fe-rich electroplating which is excellent in chemical conversion treatment is applied as in the two layer electroplating. Examples of the upper plating system include Fe-Zn, Fe-Mn, and the like.
본 발명의 목적은 플래시 도금 강판의 상층을 전기도금법이 아닌 진공증착법으로 도금하고, 그 상층도금계를 Fe-리치가 아닌 Mn 단 금속을 적용하여, 도금 공정을 단순화하면서 인산염처리성 및 전착도장성과 함께 내식성을 향상시키는 합금화 용융아연도금 강판 및 그 제조방법을 제공하는 데 있다.An object of the present invention is to plate the upper layer of the flash-plated steel sheet by vacuum deposition method, not the electroplating method, and the upper plating system by applying Mn short metal rather than Fe-rich, simplifying the plating process, while phosphate treatment and electrodeposition coating properties In addition, to provide an alloyed hot-dip galvanized steel sheet and a method of manufacturing the same to improve the corrosion resistance.
이를 실현하는 본 발명의 합금화 용융아연도금 강판은 그 표면 위에 진공증착법으로 Mn을 3∼30g/m2의 범위로 부착하여 구성됨을 특징으로 한다.The alloyed hot-dip galvanized steel sheet of the present invention for realizing this is characterized in that it is configured by attaching Mn in the range of 3 to 30 g / m 2 by vacuum deposition on the surface thereof.
본 발명의 합금화 용융아연도금 강판 제조방법은 합금화 용융아연도금 강판의 표면 위에 진공증착법으로 Mn을 3∼30g/m2의 범위로 부착할 때, 소재인 합금화 용융아연도금 강판의 온도를 50∼350℃로 유지함을 특징으로 한다.In the method for producing an alloyed hot-dip galvanized steel sheet of the present invention, when the Mn is deposited on the surface of the alloyed hot-dip galvanized steel sheet by vacuum deposition in the range of 3 to 30 g / m 2 , the temperature of the alloyed hot-dip galvanized steel sheet is 50 to 350. It is characterized by maintaining at ℃.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
상층의 Mn은 인산염 처리시에 인산염 피막으로 치환되므로 이에 필요한 최소한의 부착량이 필요한데 그 부착량이 3g/m2미만인 경우에는 양호한 인산염 피막(5㎛)을 얻을 수 없다. 그렇다고 Mn의 부착량을 높이면 내식성은 향상되지만 경제적 손실을 유발시킨다. 즉, 도장 하지용으로 사용될 경우, Mn의 부착량이 30g/m2이상이면 필요 이상의 내식성을 가지게 되므로 부착량 증가에 따른 생산성 저하 및 소재비용을 증가시킨다. 따라서 Mn의 부착량은 3∼30g/m2이 바람직하다.Since Mn in the upper layer is replaced with a phosphate film at the time of phosphate treatment, a minimum amount of adhesion necessary for this is required. If the adhesion amount is less than 3 g / m 2 , a good phosphate film (5 μm) cannot be obtained. Increasing Mn adhesion increases corrosion resistance but causes economic loss. That is, when used for the coating base material, if the amount of Mn adhesion is more than 30g / m 2 has more than necessary corrosion resistance, increase productivity and material cost increase according to the increase in adhesion amount. Therefore, the deposition amount of Mn is preferably 3 to 30 g / m 2 .
진공증착 공정에서, 소재인 합금화 용융아연도금 강판의 온도가 50℃ 이상에서 밀착성이 양호한 건전한 Mn 도금층이 형성된다. 소재의 온도가 350℃ 초과에서 소재의 표면에서 함금화 용융아연도금층이 증발하기 시작한다. 따라서 소재인 합금화 용융아연도금 강판의 온도는 50∼350℃가 바람직하다.In the vacuum deposition step, a healthy Mn plating layer having good adhesion is formed at a temperature of the alloyed hot-dip galvanized steel sheet as a material at 50 ° C or higher. The alloyed hot dip galvanized layer begins to evaporate from the surface of the material when the temperature of the material exceeds 350 ° C. Therefore, the temperature of the alloyed hot dip galvanized steel sheet which is a raw material is preferably 50 to 350 ° C.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[표 1]본 발명의 실시예 및 비교예의 제조 조건 및 특성 평가 결과[Table 1] Manufacturing conditions and characteristics evaluation results of Examples and Comparative Examples of the present invention
표 1에서 도장성은 도금된 시편에 인산염처리와 전착도장을 실시한 후, 도막 밀착성을 평가하여 판정한다. 이 도막 밀착성은 도막을 크로스 컷 후 테이프의 접착력에 의하여 박리되는 도막의 양을 측정하여 평가한다.In Table 1, the coating property is determined by performing phosphate treatment and electrodeposition coating on the plated specimen, and then evaluating the coating adhesion. This coating film adhesiveness is evaluated by measuring the amount of coating film peeled off by the adhesive force of a tape after a cross cut of a coating film.
여기서 ◎는 박리가 전혀 일어나지 않음을, ○는 박리가 부분적으로 일어나지만 박리부의 면적이 전체의 5% 이내인 것을, △는 박리가 부분적으로 일어나지만 박리부의 면적이 전체의 20% 이내인 것을, 그리고 ×는 전체의 50% 이상의 면적에서 박리가 일어 난 것을 각각 나타낸다.(Circle) means that peeling does not occur at all, o indicates that the peeling occurs partially, but the area of the peeling part is within 5% of the whole, and △ indicates that peeling occurs partially but the area of the peeling part is within 20% of the whole, And x respectively indicate that peeling occurred in an area of 50% or more of the whole.
내식성은 전착도장 시편을 크로스 컷 후 50사이클의 복합부식시험을 실시하여 크로스 컷 분에서 발생하는 블리스터의 최대 폭을 측정하여 평가한다.Corrosion resistance is evaluated by cross-cutting electrodeposition coating specimens after 50 cycles of compound corrosion test and measuring the maximum width of the blisters occurring in the cross-cut powder.
여기서 ◎는 블리스터 발생이 없음, ○는 블리스터가 일부 발생하지만 최대 블리스터의 폭이 2mm이하인 것을, △는 블리스터가 일부 발생하지만 블리스터의 폭이 5mm이하인 것을, 그리고 ×는 5mm이상의 폭을 갖는 블리스터가 다수 발생하는 것을 각각 나타낸다.◎ indicates that there is no blister occurrence, ○ indicates that some blister occurs but the maximum blister width is 2mm or less, △ indicates that some blister occurs but the blister width is 5mm or less, and × is 5mm or more width Each of which shows a large number of blisters having a.
실시예 1∼4에서는 하층도금인 합금화 용융아연도금에 상층도금으로 Mn을 진공증착 도금한다. 이때 Mn의 부착량을 각각 3,7,25,30g/m2으로 하고, 합금화 용융아연도금 강판의 온도를 50, 200,220,220℃로 유지한다. 이러한 실시예 1∼4에서는 박리가 5% 이내로 일어나거나 전혀 일어나지 않고, 블리스터가 2mm이하의 폭으로 발생하거나 발생하지 않는다. 따라서 실시예 1∼4의 도장성 및 내식성은 ○ 또는 ◎와 같이 양호함을 알 수 있다.In Examples 1-4, Mn is vacuum-deposited-plated by upper layer plating on the alloying hot dip galvanizing which is lower plating. At this time, the adhesion amount of Mn is 3,7,25,30g / m 2 , respectively, and the temperature of the alloyed hot-dip galvanized steel sheet is maintained at 50, 200, 220, 220 ° C. In these Examples 1-4, peeling does not occur within 5%, or does not occur at all, and a blister does not generate | occur | produce in the width of 2 mm or less. Therefore, it can be seen that the coating properties and the corrosion resistance of Examples 1 to 4 are good, such as ○ or ◎.
이에 반하여 비교예 1∼3은 실시예 1∼4에서와 같이, 하층도금인 합금화 용융아연도금에 상층도금으로 Mn을 진공증착 도금한다. 그러나 이때, Mn의 부착량을 각각 1,15,15g/m2으로 하고, 합금화 용융아연도금 강판의 온도를 150,25,360℃로 유지한다. 이러한 비교예 1∼3에서는 박리가 20% 이내 또는 50% 이상 일어나고, 블리스터가 5mm이상의 폭으로 발생한다. 따라서 비교예 1∼3의 도장성 및 내식성은 △ 또는 ×와 같이, 실시예 1∼4에 비하여 상당히 불량함을 알 수 있다.On the contrary, in Comparative Examples 1 to 3, as in Examples 1 to 4, Mn was vacuum-deposited-plated on the alloyed hot-dip galvanizing which is the lower plating by upper plating. At this time, however, the deposition amount of Mn is 1,15,15 g / m 2 , respectively, and the temperature of the alloyed hot-dip galvanized steel sheet is maintained at 150,25,360 ° C. In these comparative examples 1 to 3, peeling occurs within 20% or 50% or more, and blisters occur in a width of 5 mm or more. Therefore, it can be seen that the coating properties and the corrosion resistance of Comparative Examples 1 to 3 are considerably poor as compared with Examples 1 to 4, such as Δ or ×.
그리고 비교예 5,6은 한 층, 즉 하층도금이 각각 용융아연도금, 전기아연도금인 것으로, 박리가 20% 이내로 일어나고, 블리스터가 5mm이내 또는 5mm이상의 폭으로 발생한다. 따라서 비교예 5,6의 도장성 및 내식성은 실시예 1∼4에 비하여 상당히 불량함을 알 수 있다.In Comparative Examples 5 and 6, one layer, that is, the lower layer plating, is hot dip galvanizing and electro zinc plating, respectively, and peeling occurs within 20%, and blister occurs within 5 mm or more than 5 mm in width. Therefore, it can be seen that the paintability and corrosion resistance of Comparative Examples 5 and 6 are considerably poor as compared with Examples 1 to 4.
본 발명의 합금화 용융아연도금 강판은 Zn에 비하여 인산염처리성이 우수한 Mn을 사용하기 때문에 인산염처리성 뿐만 아니라 내식성을 향상시킨다. 특히, 본 발명은 Mn을 상층에 피복하여 이층도금 형태를 형성하므로 상층 Mn의 우수한 인산염처리성으로 인하여 전착도장 특성이 향상됨과 동시에 도장 파손부위가 발생할 때 Mn 산화물이 형성되어 1차적으로 소재의 부식을 방지하고, Mn 층이 부식으로 파손될 경우에도 하층의 Zn-Fe 합금층이 2차적으로 소재를 보호하여 소재의 내구성을 더욱 향상시킬 수 있다.Since the alloyed hot-dip galvanized steel sheet of the present invention uses Mn which is superior in phosphate treatment compared to Zn, not only phosphate treatment but also corrosion resistance are improved. In particular, in the present invention, Mn is coated on the upper layer to form a two-layer plating form, so that the electrodeposition coating property is improved due to the excellent phosphate treatment of the upper layer Mn, and at the same time, Mn oxide is formed when the coating breakage occurs, thereby primarily corroding the material. In addition, even when the Mn layer is damaged by corrosion, the underlying Zn-Fe alloy layer may secondarily protect the material to further improve the durability of the material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282488A (en) * | 1989-04-21 | 1990-11-20 | Sumitomo Metal Ind Ltd | Double-ply plated steel sheet |
| JPH06306566A (en) * | 1993-04-19 | 1994-11-01 | Nippon Steel Corp | Production of galvannealed steel sheet excellent in plating adhesion |
| KR950018666A (en) * | 1993-12-30 | 1995-07-22 | 백덕현 | Vacuum deposited manganese / alloyed hot dip galvanized steel sheet and manufacturing method thereof |
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- 1998-12-29 KR KR1019980060101A patent/KR20000043696A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282488A (en) * | 1989-04-21 | 1990-11-20 | Sumitomo Metal Ind Ltd | Double-ply plated steel sheet |
| JPH06306566A (en) * | 1993-04-19 | 1994-11-01 | Nippon Steel Corp | Production of galvannealed steel sheet excellent in plating adhesion |
| KR950018666A (en) * | 1993-12-30 | 1995-07-22 | 백덕현 | Vacuum deposited manganese / alloyed hot dip galvanized steel sheet and manufacturing method thereof |
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