KR20070105371A - Plated steel plate or coil - Google Patents
Plated steel plate or coil Download PDFInfo
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- KR20070105371A KR20070105371A KR1020077021513A KR20077021513A KR20070105371A KR 20070105371 A KR20070105371 A KR 20070105371A KR 1020077021513 A KR1020077021513 A KR 1020077021513A KR 20077021513 A KR20077021513 A KR 20077021513A KR 20070105371 A KR20070105371 A KR 20070105371A
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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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
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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
- C23C2/30—Fluxes or coverings on molten baths
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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
- C23C2/34—Hot-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
- C23C2/36—Elongated material
- C23C2/38—Wires; Tubes
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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
- C23C2/34—Hot-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
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Mechanical Engineering (AREA)
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- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
본 발명은 강재와, 강재의 적어도 하나의 상부 표면에 용융 아연 도금법에 의해 아연 도금층이 형성되어 있는 기본 층을 구비하고 있는 도금 강판 또는 코일에 관한 것이다. 상기 도금 강판 또는 코일에 있어서, 아연 도금층은 높은 레벨의 내식성을 보장한다. 도금층의 두께가 두꺼울수록 내식성은 커진다. 따라서, 종래의 합금화된 아연 도금층에 있어서, DIN 50021에 따라 밝고 미도장된 샘플에 분무 시험을 한 결과 25 g/㎡의 도금층이 부착된 경우에 24 시간이 경과한 후에 적녹이 발생하였고, 반면에 70 g/㎡의 도금층이 부착된 경우에는 120 시간이 경과한 후에 적녹이 발생하였다. 종래의 기술에서 충분한 내식성을 위해 필요로 하는 도금층의 두께는 용접성과 관련하여 문제점을 야기한다. 특히 차제 제조 분야 또는 가전 분야에서 요구하는 것과 같이 최소한의 용접 갭도 없는 중첩 접합부에 침투 용접을 하기 위해 사용되는 레이저 용접을 높은 용접 속도로 하는 경우에 그러하다. 상기 용접에 의해 제조되는 이음매에는 관통 구멍이 없어야 하고, 실질적으로 크레이터와 미세 기공이 없어야 한다.The present invention relates to a plated steel sheet or coil having a steel material and a base layer on which at least one upper surface of the steel material is formed by a hot dip galvanizing method. In the plated steel sheet or coil, the galvanized layer ensures a high level of corrosion resistance. The thicker the plating layer, the greater the corrosion resistance. Therefore, in the conventional alloyed galvanized layer, red rust occurred after 24 hours in the case of spray test on a bright and uncoated sample according to DIN 50021, when a plated layer of 25 g / m 2 was attached, whereas When the plating layer of 70 g / m <2> adhered, red rust generate | occur | produced after 120 hours passed. The thickness of the plating layer required for sufficient corrosion resistance in the prior art causes problems with respect to weldability. This is especially the case when high welding speeds are used for laser welding used for penetration welding at overlapping joints where there is no minimum welding gap as required in automotive manufacturing or consumer electronics. The joints produced by welding should be free of through holes and substantially free of craters and micropores.
Description
본 발명은 하지 코팅된 강에 용융 아연 도금에 의해 적어도 한 층의 아연 도금층이 도포되어 피복된 강판 또는 스트립에 관한 것이다.The present invention relates to a steel sheet or strip coated with at least one layer of galvanized layer by hot dip galvanizing on a base coated steel.
이러한 종류의 강판 또는 강 스트립 위의 아연 도금층은 내식성을 향상시킨다. 도금층의 두께가 두꺼울수록 내식성은 더욱 증가한다. 따라서 종래의 합금화된 아연 도금층을 가지고서 독일공업규격 50021(DIN 50021)에 따른 스프레이 시험을 밝고, 도장되지 않은 시편에 대해 수행할 때에, 25 g/㎡의 도금층의 경우에는 24 시간 경과 후에 적녹(red rust)이 발생한 반면에, 70 g/㎡의 도금층의 경우에는 120 시간이 경과할 때까지 적녹이 발생하지 않았다.Galvanized layers on steel strips or steel strips of this kind improve corrosion resistance. The thicker the plating layer is, the higher the corrosion resistance is. Therefore, when a spray test according to German Industrial Standard 50021 (DIN 50021) with a conventional alloyed galvanized layer is carried out on bright, unpainted specimens, a red rust after 24 hours for a 25 g / m2 plated layer On the other hand, in the case of a 70 g / m 2 plated layer, red rust did not occur until 120 hours had elapsed.
그러나, 종래의 기술에서 적절한 내식성을 위해 필요로 하는 도금층의 두께는 용접성에 있어서 문제를 초래한다. 특히, 자동차 샤시 제조 분야 또는 가전(domestic engineering) 분야에서와 같이, 중첩 접합부에 접합 갭을 생성하지 않으면서 레이저 용접에 의해 생성되는 전체적 용접(through-welding)을 높은 용접 속도로 하고자 하는 경우에는 더욱 그러하다. 상기 용접에 의해 형성되는 이음매(seam)에는 관통된 구멍이 없어야 하고, 큰 크레이터(crater)가 없어야 하며, 어떠한 미세 기공(open pore)도 없어야 한다.However, the thickness of the plating layer required for proper corrosion resistance in the prior art causes problems in weldability. This is especially true when high welding speeds are required for the overall welding produced by laser welding without creating a bonding gap in the overlapping joints, such as in automotive chassis manufacturing or domestic engineering. It is true. The seam formed by the welding should be free of perforated holes, free of large craters, and free of any open pores.
도금 부착량을 감소시키는 동시에 내식성이 향상된 용융 아연 도금 강판의 제조를 위한 하나의 가능례가 유럽특허공보 EP 0 038 904 B1호에 개시되어 있다. 상기 종래 기술에 따르면, Al: 0.2 질량%와 Mg: 0.5 질량%를 함유하는 아연 도금층이 용융 아연 도금에 의해 강 기판 위에 피복되어 있다. 각 측면에 44 g/㎡의 도금 부착량으로 피복된 이러한 방식에 의해 획득된 용융 아연 도금 강 스트립은 마그네슘 성분이 첨가된 결과로 도장된 상태에서, 일본 산업 규격 JIS Z 2371에 기재되어 있는 조건 하에서 NaCl 용액으로 분무된 각 시편을 염 분무 시험한 결과 2,000 시간이 더 경과한 후에야 최초의 녹이 형성되었다. 녹이 발생하기까지의 이러한 긴 시간은 아연 도금층과 도장이 조합된 내식성에 의해 달성된 것이다.One possibility for producing a hot dip galvanized steel sheet with reduced plating adhesion and improved corrosion resistance is disclosed in EP 0 038 904 B1. According to the above prior art, a zinc plating layer containing Al: 0.2% by mass and Mg: 0.5% by mass is coated on the steel substrate by hot dip galvanizing. The hot dip galvanized steel strip obtained by this method coated with a plating adhesion amount of 44 g / m 2 on each side was coated with NaCl under the conditions described in Japanese Industrial Standard JIS Z 2371, with the magnesium component added thereto. Salt spray tests of each specimen sprayed with solution resulted in the formation of the first rust after 2,000 hours. This long time until rust occurs is achieved by the corrosion resistance combined with the galvanized layer and the coating.
유럽특허공보 EP 0 038 904 B1호에 의해 도금 부착량이 감소되고 동시에 우수한 내식성이 달성됨에도 불구하고, 이러한 방식에 의해 제조된 용융 아연 도금 강판은 여전히 용접성이 중요시되는 자동차 제조 분야에서 부과하는 사양을 만족시키지는 못한다.Although the plating adhesion is reduced and at the same time excellent corrosion resistance is achieved by EP 0 038 904 B1, the hot-dip galvanized steel sheet produced by this method still meets the specifications imposed in the field of automobile manufacturing where weldability is important. I can't let you.
따라서, 본 발명의 목적은, 특히 자동차 샤시 제작 또는 가전제품용 재료로 사용되기에 적합한 강으로서, 높은 내식성과 최적의 용접성이 최적으로 조합된 평판형 강 제품을 생산하는 것이다.It is therefore an object of the present invention to produce flat steel products which are optimally combined with high corrosion resistance and optimum weldability, particularly as steels suitable for use in automobile chassis fabrication or for home appliance materials.
상기 목적은, DIN 50021-SS에 따라 수행되는 염 분사 연무 시험(salt spray mist test)에서 250 시간이 경과한 후에 최초 적녹이 발생하는 것을 보증하는 강판으로, 하지 도금(ground coating)된 강재에 Al: 0.05-0.30 질량%와 Mg: 0.2-2.0 질량%와 잔부는 아연 및 불가피한 불순물을 함유하는 용융 금속으로 제조된 도금층을 각 측면위에 도금층 두께가 최대 3.5 ㎛ 및 도금 부착량이 최대 25 g/㎡인 적어도 하나의 도금층이 도금되어 있는 본 발명에 따르는 도금 강판 또는 스트립에 의해 달성된다.The purpose is a steel sheet which ensures that the first red rust occurs after 250 hours in the salt spray mist test performed in accordance with DIN 50021-SS. : 0.05-0.30% by mass and Mg: 0.2-2.0% by mass and the balance of the coating layer made of molten metal containing zinc and unavoidable impurities, the plating layer thickness on each side up to 3.5 ㎛ and the coating adhesion amount up to 25 g / ㎡ This is achieved by a plated steel sheet or strip according to the invention in which at least one plating layer is plated.
본 발명에 따른 용융 아연 도금 평판형 강 제품은, 각 측면에 도금 부착량이 최대 25 g/㎡인 종래 기술에 비해 도금 부착량이 감소되면서도 매우 우수한 내식성을 가지고 있다. 낮은 도금 부착량과 각 측면에의 최대 3.5 ㎛의 작은 도금층 두께와 고내식성의 조합은 본 발명에 따른 강판 또는 스트립이 특히 각 강판 부재를 용접하여 제조되는 구성요소의 생산에 적합하게 한다. 따라서, 본 발명에 따라 제조된 강판을 가지고서 자동차 샤시 또는 가전용품 분야의 부재들을 제조할 수 있는데, 특히 본 발명에 따른 강판 또는 스트립으로부터 제조된 각 강판 부재들이 높은 용접 속도로 레이저 빔 용접되어 경제적으로 용접될 수 있고 최적의 결과를 낳게된다.Hot-dip galvanized flat steel products according to the present invention have very good corrosion resistance while reducing the amount of plating adhesion compared to the prior art, where the plating adhesion amount on each side is at most 25 g / m 2. The combination of low plating adhesion and a small plating layer thickness of up to 3.5 μm on each side and high corrosion resistance make the steel sheet or strip according to the invention particularly suitable for the production of components produced by welding each steel sheet member. Thus, it is possible to produce members in the field of automotive chassis or household appliances with the steel sheet produced according to the invention, in particular each steel sheet member made from the steel sheet or strip according to the invention is laser beam welded at high welding speed and economically It can be welded and produces optimal results.
본 발명에 따른 내식성은, 밝은 미도장된 강판 위에 부식제로서 중성 5% NaCl 용액이 챔버 내에서 35 ± 2 ℃의 온도에서 연속적으로 분무되는 부식 단기 시험 프로세스인 DIN 50021-SS에 따르는 염 분무 연무 시험에 기초하여 결정된다. 챔버 내에서 강판 샘플들은 수평 방향으로 65 내지 75° 기울어져서 위치하고 있다. 이러한 방식으로 수행된 실제 시험에서, 본 발명에 따라 도금된 강판과 스트립에는 시험 지속 시간이 300 시간 경과된 후에도 어떠한 적녹도 발생하지 않았다.The corrosion resistance according to the invention is a salt spray mist test according to DIN 50021-SS, a corrosion short-term test process in which a neutral 5% NaCl solution as a caustic is continuously sprayed in a chamber at a temperature of 35 ± 2 ° C. on a bright uncoated steel sheet. Is determined on the basis of In the chamber the steel plate samples are placed at an angle of 65 to 75 ° in the horizontal direction. In the actual test performed in this way, no red rust occurred on the steel sheets and strips plated according to the present invention even after 300 hours of test duration.
도금층을 위한 용융 금속 내의 마그네슘 성분은 본질적으로 변하지 않고 도금층 내에 잔류한다. 이와는 대조적으로, 본 발명에 따르는 완성된 강 스트립 내 도금층의 Al 성분 함량은 통상적으로 용융 금속 내의 함량보다 1.8 내지 3.2, 특히 2 내지 3배 높다. 최적의 방식(corrosion protection)은 도금층 내의 Mg 함량이 0.4-1.0 질량%, 특히 적어도 0.5 질량%일 때에 얻어진다.The magnesium component in the molten metal for the plating layer remains essentially unchanged in the plating layer. In contrast, the Al component content of the plating layer in the finished steel strip according to the invention is typically 1.8 to 3.2, in particular 2 to 3 times higher than the content in the molten metal. Optimal corrosion protection is obtained when the Mg content in the plating layer is 0.4-1.0 mass%, in particular at least 0.5 mass%.
강 기재에의 도금을 합금화 용융 아연 도금으로 하고자 하는 경우에는, 용융 금속은 Al을 0.15 질량% 미만 함유하는 것이 바람직하다. 이 경우에 표준에 적합한 용융 금속의 Al 함량은 0.12-0.14 질량% 범위이다.In the case where the plating on the steel substrate is intended to be alloyed hot dip galvanizing, the molten metal preferably contains less than 0.15 mass% of Al. In this case the Al content of the molten metal suitable for the standard is in the range of 0.12-0.14 mass%.
이와 대조적으로, 본 발명에 따라 통상적인 용융 아연 도금 강판의 경우에는, 용융 금속의 Al 함량은 적어도 0.15 질량%인 것이 바람직하다.In contrast, in the case of a conventional hot dip galvanized steel sheet according to the present invention, the Al content of the molten metal is preferably at least 0.15 mass%.
본 발명에 따른 평판형 제품이 특히 샤시 제조에 적합하게 하는 추가적인 놀라운 물성은 이러한 강판 또는 스트립에 도장을 할 때 더욱 명확해진다. 이에 따라서, 본 발명에 따르는 강판 또는 스트립에 DIN EN ISO 6860에 기초한 상온과 -20℃에서의 맨드럴 굽힘 시험은 우수한 도장 부착능을 보여준다. 특히 -20℃에서 기지 재료로부터의 도장 박리(flaking) 또는 도금층 박리의 징후가 전혀 없다.The additional surprising properties that make the flat product according to the invention particularly suitable for the manufacture of the chassis become clearer when painting such steel sheets or strips. Accordingly, the mandrel bending test at room temperature and -20 ° C based on DIN EN ISO 6860 on the steel sheet or strip according to the present invention shows excellent paint adhesion. There is no sign of paint flaking or plating layer peeling from the known material, especially at -20 ° C.
도장 부착능을 결정하기 위해 실시된 시험에서, 알칼리 세정 및 인산염 피막 처리(phosphating) 후에 강판 시편 위에 완전한 도장 구조가 도포되었고, 상기 구조는 20 ㎛ 두께의 음극 용융 도장 도막, 그 위에 32 ㎛ 두께의 필러 도장 도막 및 40 ㎛ 두께의 기본 도금층을 포함한다. 원추형 맨드럴 위에서 수행된 굽힘은 상온 및 -20℃에서 도장 도막의 어떠한 분리(detachment)도 일으키지 않았다.In tests conducted to determine paint adhesion, a complete coating structure was applied on steel sheet specimens after alkali cleaning and phosphating, which structure was a 20 μm thick melt coating film, 32 μm thick thereon. Filler coating film and 40 micrometers thick base plating layer are included. The bending performed on the conical mandrel did not cause any detachment of the coating film at room temperature and -20 ° C.
고내식성 및 우수한 도장 부착능 외에, 본 발명에 따른 강판 또는 스트립은 돌 충격(stone impact)에 대해 탁월하게 우수한 저항성을 구비하고 있다. 예를 들면, DIN 65996-1B에 따라 수행된 돌 충격 시험에서, 본 발명에 따른 강판 또는 스트립에 돌 충격을 가했을 때에 기본 도금층으로부터 어떠한 도금층의 박리도 야기되지 않았다.In addition to high corrosion resistance and good paint adhesion, the steel sheets or strips according to the invention have excellent resistance to stone impact. For example, in the stone impact test performed according to DIN 65996-1B, no peeling of the plating layer from the base plating layer was caused when the stone impact was applied to the steel sheet or the strip according to the present invention.
본 발명에 따르는 강판을 제조하기 위해, 청정한 강 스트립이 전형적인 스트립 속도인 60 내지 150 m/min으로 작동하는 용융 아연 도금 설비에서 연속 용융 아연 도금된다. 이를 위해, 용융 아연 도금될 강판 또는 스트립은 우선 DFF로(Direct Fired Furnace) 또는 바람직하게는 RTF로(Radiant Type Furnace) 같은 로 내에서 어닐링된다. 로에서 나온 후에, 상기 강판 또는 스트립은 수소 3.5-75%의 보호성 가스 분위기로 유지되고 있는 환원로 설비로 들어간다. 어닐링을 거치는 동안에 온도는 720-850℃ 범위에 있게 된다.To produce the steel sheet according to the invention, a clean steel strip is continuously hot dip galvanized in a hot dip galvanizing plant operating at a typical strip speed of 60 to 150 m / min. For this purpose, the steel sheet or strip to be hot dip galvanized is first annealed in a furnace such as a direct fire furnace (FFF) or preferably a radiant type furnace (RTF). After exiting the furnace, the steel sheet or strip enters a reduction furnace installation which is maintained in a protective gas atmosphere of 3.5-75% hydrogen. During the annealing the temperature is in the range 720-850 ° C.
상기 방식에 따라 어닐링된 강판 또는 스트립은 공기가 배제된 상태에서 노즐을 통해 Al: 0.05-0.30 질량%와 Mg: 0.2-2.0 질량%, 특히 각각을 0.4-1.0 질량%와 0.5-1.0 질량%와 잔부는 아연 및 불가피한 불순물을 함유하는 용융 금속으로 제조된 아연욕(zinc bath)으로 전달된다.The steel sheet or strip annealed according to the above method is characterized in that Al: 0.05-0.30 mass% and Mg: 0.2-2.0 mass%, especially 0.4-1.0 mass% and 0.5-1.0 mass% The balance is transferred to a zinc bath made of molten metal containing zinc and unavoidable impurities.
강판 또는 스트립이 용융 욕으로부터 나온 후에, 도금층의 두께는 스트리퍼 노즐을 사용하여 본래 알려져 있는 방식에 따라 각 측면 위에 최대 두께 3.5 ㎛로 제한되고, 그 결과로 본 발명에 따라 얻어지는 평판형 제품의 도금층 부착량은 각 측면에 최대 25 g/㎡로 제한된다.After the steel sheet or strip emerges from the molten bath, the thickness of the plated layer is limited to a maximum thickness of 3.5 μm on each side in a manner known per se using a stripper nozzle, and consequently the amount of plated layer adhesion of the flat product obtained according to the present invention. Is limited to a maximum of 25 g / m 2 on each side.
용융 욕 위에 슬래그와 금속간화합물 상이 지나치게 생성되는 것을 방지하기 위해, 욕 표면 전체에 걸쳐 불활성 가스를 불어 넣을 수도 있다. 상기 불활성 가스 유동은 도금층의 두께를 조절하기 위해 사용되는 스트리퍼 노즐로부터 나올 수도 있고, 또는 불활성 가스를 연무 형태로 욕 표면에 분산시키는 별도의 노즐로부터 공급될 수도 있다. 선택적으로는, 용융 욕 전체는 불활성 분위기로 유지되는 하우징 인클로저에 의해 둘러싸일 수도 있다. 이러한 목적을 위한 불활성 가스로는 질소가 특히 적합하다.In order to prevent excessive generation of slag and intermetallic phases on the molten bath, an inert gas may be blown over the bath surface. The inert gas flow may come from a stripper nozzle used to adjust the thickness of the plating layer, or may be supplied from a separate nozzle which disperses the inert gas in the form of a mist on the bath surface. Optionally, the entire melt bath may be surrounded by a housing enclosure maintained in an inert atmosphere. Nitrogen is particularly suitable as an inert gas for this purpose.
욕 온도를 380-450℃로 조절하면 슬래그 생성이 또한 감소될 수 있다. 이와 동일한 목적을 위해, 특히 스트립의 침지 영역에서의 산화 경향을 감소시키기 위해 침지되는 스트립의 온도는 360-500℃로 제한될 수 있다.Adjusting the bath temperature to 380-450 ° C. may also reduce slag production. For this same purpose, the temperature of the strip to be immersed can be limited to 360-500 ° C., in particular to reduce the tendency of oxidation in the immersion region of the strip.
용융 욕으로부터 나온 후에, 도금 스트립은 적어도 10 K/s의 냉각 속도로 냉각된다.After exiting the molten bath, the plating strip is cooled at a cooling rate of at least 10 K / s.
필요하다면, 0.3-1.5%의 압하율로 인-라인 압연 장치에 의해 압연되어, 표면 위에 원하는 집합조직(texture)을 얻을 수도 있다.If necessary, it may be rolled by an in-line rolling apparatus at a reduction ratio of 0.3-1.5% to obtain a desired texture on the surface.
도금 강판이 인-라인으로 300-600℃ 범위의 온도에서 가열되기 때문에, ZnMg 도금층 내에서 재분배(redistribution)가 일어나거나 ZnFeMg 도금층으로의 전반적인 합금화가 일어난다. 상기의 도금층을 제조하는 데에 사용되는 용융 금속은 Al을 0.15 질량 % 미만, 특히 0.12-0.14 질량% 함유하는 것이 바람직하다.Since the plated steel sheet is heated in-line at a temperature in the range of 300-600 ° C., redistribution occurs in the ZnMg plating layer or overall alloying to the ZnFeMg plating layer occurs. The molten metal used to produce the plating layer preferably contains less than 0.15% by mass of Al, in particular 0.12-0.14% by mass.
응용 범위를 확장하기 위해, 본래 알려져 있는 방식에 의해 도금층 위에 박막 층을 부착시키는 것도 가능하다.In order to extend the scope of application, it is also possible to deposit a thin film layer on the plating layer by means known in the art.
본 발명에 의해 달성되는 효과들은 실험을 통해 확인이 되었는데, 먼저 통상적인 IF 강으로부터 심하게 압연된 두께 0.82 ㎜의 강 스트립이 알칼리 분무 세정, 브러쉬 세척 및 전해 세척되었다.The effects achieved by the present invention have been confirmed by experiments, first of which a steel strip of 0.82 mm thick, heavily rolled from a conventional IF steel, was alkali spray cleaned, brush cleaned and electrolytic washed.
그리고 나서 상기 세척된 강을 보호성 가스(5% H2, 잔부 N2) 분위기에서 800℃로 어닐링하였다. 어닐링 시간은 60초이다.The washed steel was then annealed to 800 ° C. in a protective gas (5% H 2 , balance N 2 ) atmosphere. Annealing time is 60 seconds.
상기 방식에 따라 어닐링된 강 스트립을, 최대로 산소를 10 ppm 함유하는 보호성 가스 분위기 하에서 하우징 인클로저 내에 수용되어 있는 용융 욕 내로 침지 온도 465℃로 침지되도록 냉각하였다. 상기 용융 욕은 불가피한 불순물(예를 들면, 스트립에 의해 용융 욕 내에 도입되는 철 성분)외에도 Al: 0.2 질량%와 Mg: 0.8 질량%를 함유하는 Zn 용융 금속으로 구성되어 있다. 침지 시간은 2초이다.The annealed steel strip was cooled in this manner to be immersed at a immersion temperature of 465 ° C. into a molten bath housed in a housing enclosure under a protective gas atmosphere containing up to 10 ppm of oxygen. The molten bath is composed of a Zn molten metal containing 0.2% by mass of Al and 0.8% by mass of Mg in addition to unavoidable impurities (for example, an iron component introduced into the molten bath by a strip). Immersion time is 2 seconds.
용융 욕에서 꺼내진 후에, 여전히 용융 욕 하우징 인클로저 내에 유지되면서 하우징 인클로저 내에 설치되어 있는 스트리퍼 노즐을 사용하여 각 측면 위에 3 ㎛의 도금층 두께(각 측면 당 도금 부착량 21 g/㎡에 상당)로 강 스트립의 양쪽 측면 위에 부착된 도금층의 두께가 조절된다. 스트리핑도 질소 가스에 의해 수행될 수도 있다.After being removed from the molten bath, the steel strip remains on the molten bath housing enclosure while using a stripper nozzle installed in the housing enclosure with a thickness of 3 μm on each side (equivalent to 21 g / m2 plating deposit per side) on each side. The thickness of the plating layer attached on both sides of is adjusted. Stripping may also be performed with nitrogen gas.
마지막으로 강 스트립을 드레스한다. 얻어진 용융 욕-도금 강 스트립은 스탈아이젠 시험 데이터시트 에스이피 1940(StahlEisen Test Datasheet SEP 1940)에 따라 측정된 Pc 값이 46 ㎝-1, Ra 값이 1.8 ㎛이다.Finally dress the river strip. The resulting molten bath-plated steel strip had a Pc value of 46 cm −1 and a Ra value of 1.8 μm, measured according to the StahlEisen Test Datasheet SEP 1940.
도금층의 부착과 그 성형성을 측정하기 위해, 완성된 도금 강 스트립으로부 터 채취한 시편을 가지고서 스탈아이젠 시험 데이터시트 에스이피 1931(StahlEisen Test Datasheet SEP 1931)에 따라 볼 충격 경도 시험을 하였다. 상기 결과는 우수한 부착과 우수한 성형능에 해당하는 스테이지 1(stage 1)로 분류될 수 있다.To measure the adhesion of the plated layer and its formability, the ball impact hardness test was performed according to the StahlEisen Test Datasheet SEP 1931 with specimens taken from the finished plated steel strip. The results can be classified into stage 1, which corresponds to good adhesion and good moldability.
적당한 몰드 내에서 원형 강판 블랭크로부터 모자-형상의 부재를 드로잉하는 딥 드로잉 시험에서, 최대 0.45 g/㎡의 매우 낮은 마찰값(friction value)를 얻었다.In the deep drawing test, which draws a hat-shaped member from a circular steel sheet blank in a suitable mold, a very low friction value of up to 0.45 g / m 2 was obtained.
레이저-빔 용접된 이음매에 있어서, 모든 경우에서 매우 우수한 용접성을 얻을 수 있었다. 예를 들면, 최대 용접 속도 5 m/min으로 접합부 갭 "0"인 레이저 빔 용접한 경우에 에러가 없는(error-free) 결과가 달성되었다.In laser-beam welded joints, very good weldability was obtained in all cases. For example, an error-free result was achieved when laser beam welding with junction gap "0" at a maximum welding speed of 5 m / min.
전술한 방법으로 도금된 미도장의 밝은 시편에 대해 DIN 50021 SS에 따라 실시된 염 분무 시험에서, 분무 후 312 시간이 경과한 후에도 적녹이 생성되지 않았다. 각 측면에 도금 부착량 25 g/㎡으로 아연 도금된 통상의 강판의 경우에는 24 시간이 경과한 후에 이미 적녹이 생성되었다.In the salt spray test conducted according to DIN 50021 SS on unpainted bright specimens plated in the manner described above, no red rust was produced even after 312 hours after spraying. In the case of a normal steel plate galvanized with a plating deposition amount of 25 g / m 2 on each side, red rust was already formed after 24 hours had elapsed.
DIN EN ISO 6860에 기초한 원추형 맨드럴 굽힘 시험에서, 본 발명에 따라 도금된 샘플에의 도장 부착성은 상온과 -20℃ 모두에서 우수하였다. DIN 55996-1B에 따른 돌 충격 시험에서도 강 기본 층으로부터 도금층이 전혀 박리되지 않았다.In conical mandrel bending tests based on DIN EN ISO 6860, paint adhesion to samples plated according to the present invention was excellent at both room temperature and -20 ° C. In the stone impact test according to DIN 55996-1B, the plating layer did not peel off from the steel base layer at all.
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| US11332816B2 (en) | 2017-12-26 | 2022-05-17 | Posco | Zinc alloy plated steel material having excellent surface quality and corrosion resistance |
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| PL1857567T3 (en) * | 2006-05-15 | 2017-09-29 | Thyssenkrupp Steel Europe Ag | Method of manufacturing a flat steel product coated with a corrosion protection system |
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| DE102007048504B4 (en) * | 2007-10-10 | 2013-11-07 | Voestalpine Stahl Gmbh | Anti-corrosion coating for steel sheets and method of conditioning a corrosion protection coating |
| EP2055799A1 (en) * | 2007-11-05 | 2009-05-06 | ThyssenKrupp Steel AG | Flat steel product with an anti-corrosion metal coating and method for creating an anti-corrosion metal coating on a flat steel product |
| EP2141255B1 (en) * | 2008-07-04 | 2020-03-18 | Volvo Car Corporation | Improved corrosion inhibiting structure |
| WO2010130883A1 (en) | 2009-05-14 | 2010-11-18 | Arcelormittal Investigacion Y Desarrollo Sl | Method for producing a coated metal band having an improved appearance |
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| AU2013209303B2 (en) * | 2012-08-01 | 2015-05-07 | Dongkuk Coated Metal Co., Ltd. | Method and apparatus for producing zinc-aluminum alloy-coated steel sheet with superior workability and corrosion resistance |
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| ES2851199T3 (en) | 2013-07-03 | 2021-09-03 | Outokumpu Nirosta Gmbh | Procedure for coating flat steel products with a metallic protective layer |
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| CN108018513A (en) * | 2016-10-28 | 2018-05-11 | 宝山钢铁股份有限公司 | A kind of dip galvanized aluminum magnesium clad steel sheet and its manufacture method |
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| FR1446872A (en) | 1964-09-15 | 1966-07-22 | Inland Steel Co | Protective coating made of zinc-based alloys |
| IT1036986B (en) * | 1975-06-13 | 1979-10-30 | Centro Speriment Metallurg | STEEL ALLOY AND COATED ALLOY PRODUCTS |
| AU525668B2 (en) * | 1980-04-25 | 1982-11-18 | Nippon Steel Corporation | Hot dip galvanizing steel strip with zinc based alloys |
| JPS5891162A (en) * | 1981-11-18 | 1983-05-31 | Nisshin Steel Co Ltd | Manufacture of galvanized steel plate |
| JPS6362835A (en) * | 1986-09-02 | 1988-03-19 | Nikko Aen Kk | Zinc alloy for hot dip galvanizing and method for using same |
| WO1993011271A1 (en) * | 1991-12-06 | 1993-06-10 | Kawasaki Steel Corporation | Method of manufacturing molten zinc plated steel plates having few unplated portions |
| JP3357471B2 (en) * | 1994-08-22 | 2002-12-16 | 川崎製鉄株式会社 | Zn-Mg-Al-based hot-dip galvanized steel excellent in corrosion resistance and method for producing the same |
| JP3113189B2 (en) * | 1995-11-15 | 2000-11-27 | 新日本製鐵株式会社 | Hot-dip Zn-Mg-Al-Co plated steel sheet with excellent blackening resistance |
| JP3201469B2 (en) * | 1997-11-04 | 2001-08-20 | 日新製鋼株式会社 | Mg-containing hot-dip Zn-base plated steel sheet |
| JPH11140665A (en) * | 1997-11-11 | 1999-05-25 | Nippon Steel Corp | Painted steel sheet excellent in end face corrosion resistance and method for producing the same |
| JPH11140614A (en) * | 1997-11-13 | 1999-05-25 | Nippon Steel Corp | Weldable painted steel sheet with excellent corrosion resistance |
| JP2000160315A (en) * | 1998-11-27 | 2000-06-13 | Nippon Steel Corp | Hot dip galvannealed steel |
| JP2002322527A (en) * | 2001-04-25 | 2002-11-08 | Nippon Steel Corp | Al-Zn-Mg alloy plated steel products |
| JP2004244650A (en) * | 2003-02-10 | 2004-09-02 | Nippon Steel Corp | Method for producing Zn-Al-Mg based alloy plated steel material |
-
2005
- 2005-02-22 EP EP05003762A patent/EP1693477A1/en not_active Withdrawn
-
2006
- 2006-02-15 CA CA2596825A patent/CA2596825C/en not_active Expired - Fee Related
- 2006-02-15 US US11/816,799 patent/US20080142125A1/en not_active Abandoned
- 2006-02-15 KR KR1020077021513A patent/KR101268570B1/en not_active Expired - Fee Related
- 2006-02-15 ES ES06724846.8T patent/ES2650741T3/en active Active
- 2006-02-15 AU AU2006218005A patent/AU2006218005B2/en not_active Ceased
- 2006-02-15 JP JP2007556589A patent/JP5270172B2/en not_active Expired - Fee Related
- 2006-02-15 EP EP06724846.8A patent/EP1851352B8/en not_active Not-in-force
- 2006-02-15 CN CN2006800056157A patent/CN101128614B/en active Active
- 2006-02-15 WO PCT/EP2006/050955 patent/WO2006089854A1/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11332816B2 (en) | 2017-12-26 | 2022-05-17 | Posco | Zinc alloy plated steel material having excellent surface quality and corrosion resistance |
| US11643714B2 (en) | 2017-12-26 | 2023-05-09 | Posco Co., Ltd | Method for manufacturing zinc alloy plated steel material having excellent surface quality and corrosion resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006218005A1 (en) | 2006-08-31 |
| KR101268570B1 (en) | 2013-05-28 |
| EP1851352B8 (en) | 2017-10-18 |
| JP5270172B2 (en) | 2013-08-21 |
| EP1693477A1 (en) | 2006-08-23 |
| CN101128614B (en) | 2012-07-18 |
| WO2006089854A1 (en) | 2006-08-31 |
| CA2596825C (en) | 2013-03-19 |
| EP1851352B1 (en) | 2017-09-06 |
| AU2006218005B2 (en) | 2011-11-17 |
| CN101128614A (en) | 2008-02-20 |
| US20080142125A1 (en) | 2008-06-19 |
| CA2596825A1 (en) | 2006-08-31 |
| EP1851352A1 (en) | 2007-11-07 |
| JP2008531844A (en) | 2008-08-14 |
| ES2650741T3 (en) | 2018-01-22 |
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