WO2006089854A1 - Beschichtetes stahlblech oder -band - Google Patents

Beschichtetes stahlblech oder -band Download PDF

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Publication number
WO2006089854A1
WO2006089854A1 PCT/EP2006/050955 EP2006050955W WO2006089854A1 WO 2006089854 A1 WO2006089854 A1 WO 2006089854A1 EP 2006050955 W EP2006050955 W EP 2006050955W WO 2006089854 A1 WO2006089854 A1 WO 2006089854A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
steel
steel sheet
sup
case
Prior art date
Application number
PCT/EP2006/050955
Other languages
German (de)
English (en)
French (fr)
Inventor
Manfred Meurer
Sabine Zeizinger
Rudolf Schönenberg
Wilhelm Warnecke
Original Assignee
Thyssenkrupp Steel Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thyssenkrupp Steel Ag filed Critical Thyssenkrupp Steel Ag
Priority to ES06724846.8T priority Critical patent/ES2650741T3/es
Priority to JP2007556589A priority patent/JP5270172B2/ja
Priority to CA2596825A priority patent/CA2596825C/en
Priority to CN2006800056157A priority patent/CN101128614B/zh
Priority to AU2006218005A priority patent/AU2006218005B2/en
Priority to US11/816,799 priority patent/US20080142125A1/en
Priority to EP06724846.8A priority patent/EP1851352B8/de
Publication of WO2006089854A1 publication Critical patent/WO2006089854A1/de

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0222Pretreatment 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
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18Removing excess of molten coatings from elongated material
    • C23C2/20Strips; Plates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30Fluxes or coverings on molten baths
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-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
    • C23C2/36Elongated material
    • C23C2/38Wires; Tubes
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-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
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips

Definitions

  • the invention relates to a coated steel sheet or strip with a base layer consisting of steel, on whose at least one upper side by hot dip coating a zinc coating is applied.
  • the zinc coating ensures high corrosion resistance. This is the larger, the thicker the coating is.
  • the red test carried out on a bare, unpainted sample in accordance with DIN 50021 results in red rust already after 24 hours at a coat run of 25 g / m 2 , whereas with a coating overlay of 70 g / m 2 red rust only after 120 hours arises.
  • the thickness of the coating required in the prior art for sufficient corrosion resistance involves problems in weldability. This is especially true if by laser welding at high welding speeds through-welding in the lap joint is to be generated without minimum gap, as in particular in the field of construction of
  • the seam produced by such a weld should be free of through holes, have a substantial crater freedom and have no open pores.
  • hot dip coating on a steel substrate comprises 0.2 wt% Al and 0.5 wt% Mg
  • Zinc coating has been applied.
  • the resulting hot dip coated steel strip at a coating weight of 44 g / m 2 per side in the painted state in a salt spray test in which the respective sample sprayed with a NaCl solution under the conditions specified in Japanese Industrial Standard JIS Z 2371 has been, after a spraying time of more than 2,000 h, a first rust formation on. This long period until the formation of rust was achieved by the combined anti-corrosive effect of zinc coating and painting.
  • the object of the invention was therefore to provide a flat steel product which has an optimum combination of high corrosion resistance and optimized weldability and which is particularly suitable for use as a material for automotive body construction or for the construction of household appliances.
  • a coated steel sheet or strip which has a base layer made of steel, on the at least one upper side of which a hot dip coating is applied, which consists of a layer of 0.05-0.30% by weight of Al and 0.2-2.0% by weight of Mg, balance zinc and unavoidable impurities existing melt is formed and each side with a coating thickness of at most 3.5 microns and a maximum coating weight of 25 g / m 2 ensures that the steel sheet shows the first formation of red rust at the earliest after 250 hours in the salt spray test carried out according to DIN 50021-SS.
  • a hot-dip-coated flat steel product according to the invention has surprisingly good corrosion resistance at a maximum coating weight of 25 g / m 2 per side, minimized in comparison with the prior art.
  • the low coating weight and the associated low thickness of the coating of a maximum of 3.5 microns each side in combination with the high corrosion resistance makes inventive sheet or strip particularly suitable for the production of components that are produced by welding of individual sheet metal elements.
  • elements for automobile bodies or home appliance technology can be produced with sheet steel produced according to the invention by the individual sheet metal parts formed from sheet metal or strip according to the invention by laser beam welding at high temperatures
  • the corrosion resistance of the invention is based on a salt spray test according to DIN 50021-SS in a
  • the magnesium content contained in the melt intended for the coating is found essentially unchanged in the coating.
  • the Al content of the coating in the finished steel strip according to the invention is generally 1.8 to 3.2, in particular 2 to 3 times, higher than in the melt.
  • Optimum corrosion protection is achieved if the coating has a Mg content of 0.4-1.0% by weight, in particular at least 0.5% by weight.
  • the melt preferably contains less than 0.15% by weight of aluminum. Practical Al contents of the melt in this case are in the range of 0.12-0.14% by weight.
  • the Al content of the melt is preferably at least 0.15% by weight.
  • SI / nm 050215WO The use in body construction, shows up when such a metal sheet or tape is painted. So one carried out in accordance with DIN EN ISO 6860 Mandrel bending test for inventive sheets or strips at room temperature and -20 0 C gives a good Lackanhaftungshack. In particular, even at a temperature of -20 0 C show no Lackabplatzept and spalling of the coating from the base material.
  • a full-scale coating comprising a 20 ⁇ m thick cathodic dip coating, a 32 ⁇ m thick surfacer coat layer applied thereto and a 40 ⁇ m thick basecoat film was applied to a steel sheet sample after alkaline cleaning and phosphating.
  • the bending over the conical mandrel performed neither at room temperature nor at -20 0 C to a detachment of the paint layer.
  • sheets or tapes according to the invention have excellent resistance to stone chipping.
  • DIN 65996-1B it was possible to demonstrate that, in the case of steel sheets according to the invention, no flaking of the coating from the base layer is caused by rockfall.
  • a steel fine strip in a galvanizing plant which is traversed at a strip speed of typically 60 to 150 m / min, is subjected to a continuously running strip hot-dip galvanizing process.
  • the sheet or strip to be galvanized is first placed in an oven,
  • SI / nm 050215WO for example, a DFF furnace (Direct Fired Furnace) or, preferably, a RTF furnace (Radiant Type Furnace) annealed. Following the oven, the sheet or strip passes through the reduction furnace section, where it is maintained under a protective gas atmosphere of 3.5-75% hydrogen. The temperatures achieved in the course of the annealing are in the range of 720 - 850 0 C.
  • the thus annealed strip or sheet is then passed through a so-called proboscis under exclusion of air in the zinc bath, by a 0.05 to 0.30 wt .-% Al and 0.2 to 2.0 wt .-% Mg, in particular 0.4 to 1.0 wt .-% or 0.5 to 1.0 wt .-%, remainder zinc and unavoidable impurities containing melt is formed.
  • the thickness of the coating is limited in a conventional manner by means of stripping nozzles to a value of 3.5 microns maximum page, so that the resulting flat product according to the invention, the maximum coating weight of 25 g / m 2 per side is limited.
  • an inert gas stream may originate from the wiping nozzles used to adjust the coating thickness, or may be discharged from separate nozzles which disperse the inert gas over the bath surface.
  • the entire melt bath may be surrounded by an enclosure in which an inert atmosphere is maintained. Nitrogen is particularly suitable as inert gas for this purpose.
  • the slag can also be reduced in that the bath temperature to a range of 380-450 0 C is set.
  • the strip temperature can when dipping to 360 to 500 0 C are limited to minimize the oxidation tendency especially in the immersion area.
  • the coated strip After exiting the melt bath, the coated strip is cooled at a cooling rate of at least 10 K / s.
  • the melts used to produce such a layer preferably have an Al content of less than 0.15% by weight, in particular 0.12-0.14% by weight.
  • a thin-film coating can finally be applied to the coating in a manner known per se.
  • the thus annealed steel strip was then cooled so that it is immersed with a melt bath immersion temperature of 465 0 C held in the housing in a housing under a maximum of 10 ppm oxygen-containing inert gas bath melt.
  • the molten bath consisted of a Zn melt containing, in addition to unavoidable impurities (eg, Fe contents being dragged through the belt into the molten bath), 0.2 wt% Al, 0.8 wt% Mg.
  • the dive time was two seconds.
  • the layer thickness of the coating applied on both sides of the steel strip has been adjusted within the Schmelzenbadeinhausung by means also arranged in the housing Abstreifdüsen to a coating thickness of 3 microns per side (corresponding to a weight of 21 g / m 2 each side) ,
  • the stripping was also done by means of nitrogen gas.
  • the steel band has been trained.
  • the resulting hot dip coated steel strip had Ra values of 1.8 ⁇ m at Pc values of 46 cm -1 determined according to SEP 1940 Steel Iron Test Sheet.
  • the salt spray test carried out on a unpainted blank in the manner described in accordance with DIN 50021 SS gave a first formation of red rust only after a spraying time of 312 hours.
  • a conventional Zn coating with a coating weight of 25 g / m 2 per side provided sheets showed after 24 hours, a red rust formation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/EP2006/050955 2005-02-22 2006-02-15 Beschichtetes stahlblech oder -band WO2006089854A1 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES06724846.8T ES2650741T3 (es) 2005-02-22 2006-02-15 Chapa o banda de acero recubiertas
JP2007556589A JP5270172B2 (ja) 2005-02-22 2006-02-15 コーティングされた鋼板又はストリップ
CA2596825A CA2596825C (en) 2005-02-22 2006-02-15 Coated steel sheet or strip
CN2006800056157A CN101128614B (zh) 2005-02-22 2006-02-15 镀层钢板或钢带
AU2006218005A AU2006218005B2 (en) 2005-02-22 2006-02-15 Coated steel sheet or coil
US11/816,799 US20080142125A1 (en) 2005-02-22 2006-02-15 Coated Steel Sheet or Strip
EP06724846.8A EP1851352B8 (de) 2005-02-22 2006-02-15 Beschichtetes stahlblech oder -band

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05003762A EP1693477A1 (de) 2005-02-22 2005-02-22 Beschichtetes Stahlblech oder -band
EP05003762.1 2005-02-22

Publications (1)

Publication Number Publication Date
WO2006089854A1 true WO2006089854A1 (de) 2006-08-31

Family

ID=34933875

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/050955 WO2006089854A1 (de) 2005-02-22 2006-02-15 Beschichtetes stahlblech oder -band

Country Status (9)

Country Link
US (1) US20080142125A1 (ko)
EP (2) EP1693477A1 (ko)
JP (1) JP5270172B2 (ko)
KR (1) KR101268570B1 (ko)
CN (1) CN101128614B (ko)
AU (1) AU2006218005B2 (ko)
CA (1) CA2596825C (ko)
ES (1) ES2650741T3 (ko)
WO (1) WO2006089854A1 (ko)

Cited By (1)

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US8481172B2 (en) * 2006-05-15 2013-07-09 Thyssenkrupp Steel Ag Steel sheet product provided with an anticorrosion coating and process for producing it

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PL1857567T3 (pl) * 2006-05-15 2017-09-29 Thyssenkrupp Steel Europe Ag Sposób wytwarzania płaskiego produktu stalowego powleczonego ochronnym systemem przeciwkorozyjnym
DE102007048504B4 (de) * 2007-10-10 2013-11-07 Voestalpine Stahl Gmbh Korrosionsschutzbeschichtung für Stahlbleche und Verfahren zum Konditionieren einer Korrosionsschutzbeschichtung
EP2055799A1 (de) * 2007-11-05 2009-05-06 ThyssenKrupp Steel AG Stahlflachprodukt mit einem vor Korrosion schützenden metallischen Überzug und Verfahren zum Erzeugen eines vor Korrosion schützenden metallischen Zn-Mg Überzugs auf einem Stahlflachprodukt
EP2141255B1 (en) * 2008-07-04 2020-03-18 Volvo Car Corporation Improved corrosion inhibiting structure
WO2010130883A1 (fr) 2009-05-14 2010-11-18 Arcelormittal Investigacion Y Desarrollo Sl Procede de fabrication d'une bande metallique revetue presentant un aspect ameliore
DE102010037254B4 (de) 2010-08-31 2012-05-24 Thyssenkrupp Steel Europe Ag Verfahren zum Schmelztauchbeschichten eines Stahlflachprodukts
DE102011051731B4 (de) 2011-07-11 2013-01-24 Thyssenkrupp Steel Europe Ag Verfahren zur Herstellung eines durch Schmelztauchbeschichten mit einer metallischen Schutzschicht versehenen Stahlflachprodukts
DE102012101018B3 (de) 2012-02-08 2013-03-14 Thyssenkrupp Nirosta Gmbh Verfahren zum Schmelztauchbeschichten eines Stahlflachprodukts
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
US9863029B2 (en) * 2012-08-01 2018-01-09 Dongkuk Steel Mill Co., Ltd. Apparatus for forming nitrogen cloud to produce hot dip coated steel sheet
RU2015111349A (ru) * 2012-10-24 2016-12-20 Магна Интернэшнл Инк. Лазерное плакирование сварных швов в автомобильных деталях
KR101439694B1 (ko) 2012-12-26 2014-09-12 주식회사 포스코 Zn-Mg 합금도금강판 및 그의 제조방법
ES2851199T3 (es) 2013-07-03 2021-09-03 Outokumpu Nirosta Gmbh Procedimiento para recubrir productos planos de acero con una capa protectora metálica
GB2521363A (en) * 2013-12-17 2015-06-24 Eaton Ind Netherlands Bv Method for producing a housing for medium voltage switchgear and such a housing
EP3239347B1 (en) 2014-12-24 2019-08-07 Posco Zinc alloy plated steel material having excellent weldability and processed-part corrosion resistance and method of manufacturing same
US20190003027A1 (en) * 2015-08-06 2019-01-03 Thyssenkrupp Steel Europe Ag Method for producing a zinc-magnesium-galvannealed hot-dip coating and flat steel product provided with such a coating
CN108018513A (zh) * 2016-10-28 2018-05-11 宝山钢铁股份有限公司 一种热浸镀锌铝镁镀层钢板及其制造方法
KR102031466B1 (ko) 2017-12-26 2019-10-11 주식회사 포스코 표면품질 및 내식성이 우수한 아연합금도금강재 및 그 제조방법
DE102018212540A1 (de) * 2018-07-27 2020-01-30 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Beschichten eines Kraftfahrzeugrohbauteils sowie Kraftfahrzeugrohbauteil
DE102019215050B4 (de) * 2019-09-30 2023-09-07 Thyssenkrupp Steel Europe Ag Verfahren zum Herstellen einer Laserlötverbindung zwischen beschichteten Stahlblechbauteilen
DE102019217912A1 (de) * 2019-11-20 2021-05-20 Volkswagen Aktiengesellschaft Verfahren zum Laserstrahllöten

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GB2110248A (en) * 1981-11-18 1983-06-15 Nisshin Steel Co Ltd Process for preparing hot-dip zinc-plated steel sheets
JPH09143658A (ja) * 1995-11-15 1997-06-03 Nippon Steel Corp 耐黒変性の優れた溶融Zn−Mg−Al−Coめっき鋼板
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Publication number Priority date Publication date Assignee Title
US8481172B2 (en) * 2006-05-15 2013-07-09 Thyssenkrupp Steel Ag Steel sheet product provided with an anticorrosion coating and process for producing it

Also Published As

Publication number Publication date
US20080142125A1 (en) 2008-06-19
CA2596825C (en) 2013-03-19
AU2006218005B2 (en) 2011-11-17
AU2006218005A1 (en) 2006-08-31
EP1693477A1 (de) 2006-08-23
EP1851352A1 (de) 2007-11-07
CN101128614B (zh) 2012-07-18
CN101128614A (zh) 2008-02-20
JP5270172B2 (ja) 2013-08-21
CA2596825A1 (en) 2006-08-31
EP1851352B8 (de) 2017-10-18
JP2008531844A (ja) 2008-08-14
KR20070105371A (ko) 2007-10-30
KR101268570B1 (ko) 2013-05-28
EP1851352B1 (de) 2017-09-06
ES2650741T3 (es) 2018-01-22

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