EP1857566B1 - Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication - Google Patents

Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication Download PDF

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Publication number
EP1857566B1
EP1857566B1 EP06113962.2A EP06113962A EP1857566B1 EP 1857566 B1 EP1857566 B1 EP 1857566B1 EP 06113962 A EP06113962 A EP 06113962A EP 1857566 B1 EP1857566 B1 EP 1857566B1
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EP
European Patent Office
Prior art keywords
coating
steel
steel substrate
temperature
layer
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP06113962.2A
Other languages
German (de)
English (en)
Other versions
EP1857566A1 (fr
Inventor
Wilhelm Dr. Warnecke
Manfred Meurer
Rudolf Schönenberg
Michael Keller
Alexander Elsner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel Europe 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
Priority to ES06113962.2T priority Critical patent/ES2636442T3/es
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Priority to EP06113962.2A priority patent/EP1857566B1/fr
Priority to PL06113962T priority patent/PL1857566T3/pl
Priority to CN2007800176280A priority patent/CN101454473B/zh
Priority to PCT/EP2007/054711 priority patent/WO2007132007A1/fr
Priority to CA2650800A priority patent/CA2650800C/fr
Priority to AU2007251550A priority patent/AU2007251550B2/en
Priority to BRPI0711652-7A priority patent/BRPI0711652B1/pt
Priority to US12/300,968 priority patent/US8481172B2/en
Priority to JP2009510444A priority patent/JP5586224B2/ja
Priority to KR1020087027954A priority patent/KR101399085B1/ko
Publication of EP1857566A1 publication Critical patent/EP1857566A1/fr
Application granted granted Critical
Publication of EP1857566B1 publication Critical patent/EP1857566B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • C23C2/0224—Two or more thermal pretreatments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]

Definitions

  • the invention relates to a method for producing a flat steel product formed from a steel substrate, such as steel strip or sheet, and a zinc-based anticorrosive coating applied to at least one of the sides of the steel substrate.
  • metallic coatings are applied, in particular on steel sheets or strips, which are based on zinc or zinc alloys in the majority of applications.
  • Such zinc or zinc alloy coatings protect due to their barrier and cathodic protection effect the corresponding coated steel sheet in practical use against corrosion.
  • the thickness of the coating required in the prior art for sufficient corrosion resistance poses problems in processing, ie in forming and welding. This applies z. B. when in high-wear highly corrosive flanges to be welded by spot welding. This requirement exists in particular in the field of construction of automobile bodies, in general construction applications or in the construction of housings for building services.
  • a metallic protective coating sheet with improved corrosion resistance is from the EP 1 621 645 Al known.
  • the one described there Steel sheet is provided with a protective coating by conventional hot-dip galvanizing, containing (in% by weight) 0.3-2.3% Mg, 0.6-2.3% Al, optionally ⁇ 0.2% other active ingredients and balance Zn and unavoidable impurities.
  • the steel sheet is passed through a melt bath containing 0.3-2.3% by weight of Mg, 0.5-2.3% by weight of Al, optionally less than 0.2% by weight of others Alloy components and passed as rest Zn and unavoidable impurities.
  • a melt bath containing 0.3-2.3% by weight of Mg, 0.5-2.3% by weight of Al, optionally less than 0.2% by weight of others Alloy components and passed as rest Zn and unavoidable impurities.
  • the object of the invention was therefore to provide a method for producing a flat steel product, which has an optimum combination of high corrosion resistance and optimized processability and which is particularly suitable for use as a material for automotive body construction, for general construction or for home appliance.
  • the invention is based on the recognition that general properties such. As adhesion and also weldability of provided with a corrosion-protective Zn-Mg-Al coating steel sheet or strip decisively depends on the distribution of the aluminum in the coating layer. Thus, it has surprisingly been found that when, as predetermined by the invention, in a near-surface intermediate layer of sufficient thickness according to the invention low Al contents are present, compared to conventionally formed sheets improved weldability is given, although the Al content of the coating on the whole a level is guaranteed by the high corrosion protection. The correspondingly produced according to the invention sheets in the boundary layer at the transition to the steel substrate high Al concentration thereby causes the positive effect of aluminum on the corrosion protection is maintained despite the low proportion of Al in the intermediate layer.
  • flat steel products produced according to the invention likewise show a particularly good suitability for phosphating, so that they can be provided with an organic lacquer coating, for example, without any special additional measures.
  • Elements from the group Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn and rare earths can be present up to a total of their contents of 0.8% by weight in the coating produced according to the invention be.
  • Pb, Bi and Cd can be used to form a larger crystal structure (zinc flower), Ti, B, Si to improve the formability, Cu, Ni, Co, Cr, Mn to influence the boundary layer reactions, Sn influencing the surface oxidation and rare earths, especially lanthanum and cerium, to improve the flow behavior of the melt.
  • the impurities which may be present in a corrosion protection coating according to the invention also include the constituents which, as a result of the hot-dip coating, enter the coating from the steel substrate in quantities which do not affect the properties of the coating.
  • the shape of the layer structure desired according to the invention can be directly influenced by a suitable adjustment of the strip inlet and / or bath temperature.
  • the process control according to the invention is achieved in that adjacent to the steel substrate Bound layer high Al and Mg contents accumulate, while in the intermediate layer in particular low Al contents are present.
  • the difference between the temperature of the strip during immersion and the temperature of the melt bath is of particular importance.
  • the inventively minimized presence of Al in the intermediate layer can be set in a safe and targeted manner.
  • an advantageous embodiment of the invention provides that the Al content of the intermediate layer is limited to 0.25 wt .-%.
  • the layer structure used by the invention then has a particularly positive effect on the weldability and the phosphatability with at the same time still good corrosion protection of the coating, if the thickness of the intermediate layer according to the invention is at least 25% of the total thickness of the anticorrosive coating.
  • the information on the structure of the corrosion-coating layer and its individual layers contained herein and in the claims relates to a layer profile determined by a GDOS measurement (glow discharge optical emission spectrometry).
  • a GDOS measurement low discharge optical emission spectrometry
  • the surface layer is in each case not more than 0.2 .mu.m thick, so that with conventional coating thicknesses of 6 .mu.m and more, the fraction of the surface boundary layer in the total thickness of the coating overlay is approximately 3.5% and wide below it lies.
  • the coating has contents of Fe which are more than 0.3% by weight, in particular more than 0.4% by weight or even more than 0.5% by weight.
  • the relatively high Fe contents are present in particular in the region of the boundary layer adjacent to the steel substrate.
  • a flat steel product obtained according to the invention has Performance characteristics, which are superior to the conventional flat steel products, even if they have high Mg and Al contents in their protective coating.
  • the Al content of the anticorrosive coating can be limited to less than 0.6% by weight, in particular less than 0.5% by weight.
  • the total thickness of the anticorrosive coating should be at least 5 ⁇ m , in particular at least 7 ⁇ m .
  • pad weight distribution of the anticorrosive coating of at least 100 g / m 2 prove to be particularly favorable in terms of its protective effect.
  • the weldability is not adversely affected due to the invention prescribed distribution of its Al content.
  • the speed with which the steel substrate passes through the melt bath has only a minor influence on the coating result. Therefore, it can be varied in the range of 50 - 200 m / min, for example, in order to achieve the optimum work result at maximum productivity.
  • the annealing of the steel strip, which precedes the melt bath, should be carried out under a protective gas atmosphere in order to avoid oxidation of the sheet surface.
  • the protective gas atmosphere in a conventional manner contains more than 3.5 vol .-% H 2 and in each case as the radical N 2 .
  • the annealing temperature is also in a known manner in the range of 700 - 900 ° C.
  • the melt bath maintains its optimum temperature evenly despite the entry of the steel substrate.
  • the melt bath itself preferably contains at best traces of iron, since according to the invention the Fe content of the corrosion-coating layer is to be established by alloying in iron originating from the steel substrate. Accordingly, the Fe content of the melt bath is preferably limited to at most 0.1 wt%, more preferably at most 0.07 wt%.
  • a steel atmosphere steel strip under a nitrogen atmosphere containing 5% H 2 and having a dew point of -30 ° C ⁇ 2 ° C is annealed for a holding time of 60 s each Service.
  • the annealing temperature was 800 ° C at a heating rate of 10 ° C / s.
  • the steel strip was quenched at a cooling rate of 5 to 30 ° C / s to a temperature of 470 ° C ⁇ 5 ° C where it was held for 30 seconds. Then the steel strip is with a belt immersion speed of 100 m / min was passed into a melt bath whose bath temperature was 460 ° C ⁇ 5 ° C. The strip inlet temperature of the steel strip was in each case 5 ° C. above the bath temperature of the melt bath.
  • a surface boundary layer has formed on the surface of the respective coating whose Al content is high as a result of oxidation.
  • the thickness of this surface boundary layer is at most 0.2 ⁇ m and is therefore easily broken in the spot or laser welding, without causing a deterioration in the quality of the welding result.
  • the about 2.5 ⁇ m thick intermediate layer to the surface boundary layer includes, whose Al content is below 0.2%, respectively.
  • the thickness of the intermediate layer is therefore approximately 36% of the total overlay thickness of the respective anti-corrosion coating of 7 ⁇ m .
  • the intermediate layer merges into a boundary layer adjacent to the steel substrate, in which the contents of Al, Mg and Fe have increased significantly compared with the corresponding contents of the intermediate layer.
  • the thickness of the superficial oxidation surface boundary layer is max. 0.2 ⁇ m and is based on the determined in a GDOS measurement layer profile in each case in the range of up to 2.7% of the total overlay thicknesses.
  • the amount of Al enrichment on the immediate surface is at most about 1 wt .-%. This is followed up to a thickness of at least 25% of the total overlay of the coating, the intermediate layer with a low Al content of not more than 0.25 wt .-% of. In the boundary layer, the Al content rises to 4.5% at the Border to the steel substrate.
  • the Mg enrichment on the immediate surface of the coating is significantly greater than the Al enrichment. Mg contents of up to 20% are achieved here.
  • the amount of Mg decreases over the intermediate layer and is 0.5 to 2% at a depth of about 25% of the total overlay thickness of the overlay.
  • An increase of the Mg content in the direction of the steel substrate then takes place via the boundary layer. At the border to the steel substrate, the Mg content is up to 3.5%.
  • Table 1 sample According to the invention? melt bath Layer analysis top Shift analysis bottom al Fe mg al Fe mg Editions weight Thickness al Fe mg Editions weight Thickness % *) % *) g / m 2 ⁇ m % *) g / m 2 ⁇ m E1 YES 0.201 0.011 1,589 1.16 1.06 1.52 41.5 7.0 ne ne ne n.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)

Claims (4)

  1. Procédé de fabrication d'un produit plat en acier, dans lequel l'on génère sur un substrat en acier, tel qu'une bande ou une plaque en acier, un revêtement anticorrosif d'une épaisseur totale d'au moins 5 µm, et en ce que le substrat en acier est recuit sous une atmosphère de gaz protecteur contenant plus de 3,5 en pourcentage en volume de H2 et le reste étant du N2 lors d'une température de recuit de 700 - 900 °C et est refroidi à partir d'une température de recuit à une température d'entrée dans le bain, avec laquelle le substrat en acier entre dans un bain de fusion contenant (en pourcentage en poids) 0,1 - 0,4 % de Al, 0,25 - 2,5 % de Mg, jusqu'à 0,2 % de Fe, le reste étant du zinc ainsi que des impuretés inévitables, et est réchauffé à une température de bain de 420 - 500 °C, auquel cas la différence « BET-BT » entre la température d'entrée dans le bain et « BET » et la température du bain « BT » est de -10 °C jusqu'à +70 °C et est modifiée de telle sorte à former sur le substrat en acier un revêtement anticorrosif qui contient (en pourcentage en poids) :
    Mg: 0,25 - 2,5 %,
    Al: 0,2 - 3,0 %,
    Fe: plus de 0,3 - 4,0 %,
    ainsi que, au choix, au total jusqu'à 0,8 % d'un ou plusieurs éléments choisis parmi le groupe se composant de « Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn ainsi que des terres rares »,
    le reste étant du zinc et des impuretés inévitables, et qui présente dans une couche intermédiaire, qui s'étend entre une couche superficielle directement adjacente à la surface du produit plat en acier et une couche limite adjacente au substrat en acier et dont l'épaisseur correspond à au moins 20 % de l'épaisseur totale du revêtement anticorrosif, une teneur en Al étant au maximum de 0,5 % en pourcentage en poids.
  2. Procédé selon la revendication 1, caractérisé en ce que la température du bain est de 440 - 480 °C.
  3. Procédé selon une des revendications précédentes, caractérisé en ce que la température d'entrée dans le bain est de 410 - 510 °C.
  4. Procédé selon une des revendications précédentes, caractérisé en ce que la teneur en Fe du bain de fusion est ≤ à 0,1 en pourcentage en poids.
EP06113962.2A 2006-05-15 2006-05-15 Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication Not-in-force EP1857566B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP06113962.2A EP1857566B1 (fr) 2006-05-15 2006-05-15 Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication
PL06113962T PL1857566T3 (pl) 2006-05-15 2006-05-15 Płaski wyrób stalowy z powłoką chroniącą przed korozją i sposób jego wytwarzania
ES06113962.2T ES2636442T3 (es) 2006-05-15 2006-05-15 Producto de acero plano provisto con un revestimiento anticorrosivo y procedimiento para su fabricación
PCT/EP2007/054711 WO2007132007A1 (fr) 2006-05-15 2007-05-15 Produit plat en acier muni d'un revêtement anti-corrosif et son procédé de fabrication
CA2650800A CA2650800C (fr) 2006-05-15 2007-05-15 Produit plat en acier avec revetement anticorrosion et procede de production
AU2007251550A AU2007251550B2 (en) 2006-05-15 2007-05-15 Sheet steel product provided with an anticorrosion coating and process for producing it
CN2007800176280A CN101454473B (zh) 2006-05-15 2007-05-15 具有防腐蚀覆层的扁钢产品及其制备方法
BRPI0711652-7A BRPI0711652B1 (pt) 2006-05-15 2007-05-15 Produto de aço plano com um revestimento de proteção contra corrosão e método para sua produção
US12/300,968 US8481172B2 (en) 2006-05-15 2007-05-15 Steel sheet product provided with an anticorrosion coating and process for producing it
JP2009510444A JP5586224B2 (ja) 2006-05-15 2007-05-15 防食コーティングを有するフラット鋼生成物並びに防食コーティングを有するフラット鋼生成物の製造方法
KR1020087027954A KR101399085B1 (ko) 2006-05-15 2007-05-15 부식 방지 코팅층을 구비한 평판형 강재 제품 및 그 제조 방법

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06113962.2A EP1857566B1 (fr) 2006-05-15 2006-05-15 Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication

Publications (2)

Publication Number Publication Date
EP1857566A1 EP1857566A1 (fr) 2007-11-21
EP1857566B1 true EP1857566B1 (fr) 2017-05-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06113962.2A Not-in-force EP1857566B1 (fr) 2006-05-15 2006-05-15 Produit d'acier plat revêtu avec une revêtement de protection contre la corrosion et procédé de son fabrication

Country Status (11)

Country Link
US (1) US8481172B2 (fr)
EP (1) EP1857566B1 (fr)
JP (1) JP5586224B2 (fr)
KR (1) KR101399085B1 (fr)
CN (1) CN101454473B (fr)
AU (1) AU2007251550B2 (fr)
BR (1) BRPI0711652B1 (fr)
CA (1) CA2650800C (fr)
ES (1) ES2636442T3 (fr)
PL (1) PL1857566T3 (fr)
WO (1) WO2007132007A1 (fr)

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DE102018132171A1 (de) * 2018-12-13 2020-06-18 Thyssenkrupp Steel Europe Ag Batteriegehäuse und Verwendung
US11920243B2 (en) * 2019-06-03 2024-03-05 Thyssenkrupp Steel Europe Ag Method for manufacturing a sheet metal component from a flat steel product provided with a corrosion protection coating
WO2020259842A1 (fr) * 2019-06-27 2020-12-30 Thyssenkrupp Steel Europe Ag Procédé de fabrication d'un produit plat d'acier revêtu, procédé de fabrication d'un élément en acier et produit plat d'acier revêtu
CN112941417A (zh) * 2021-03-03 2021-06-11 靖江新舟合金材料有限公司 一种合金镀层钢板及其生产方法
CN113430477A (zh) * 2021-05-27 2021-09-24 中电建武汉铁塔有限公司 一种批量热浸镀锌工件用锌液及其制备方法

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AU2007251550B2 (en) 2012-05-03
BRPI0711652A2 (pt) 2011-11-29
ES2636442T3 (es) 2017-10-05
EP1857566A1 (fr) 2007-11-21
CN101454473B (zh) 2013-09-18
CA2650800C (fr) 2013-12-03
AU2007251550A1 (en) 2007-11-22
JP2009537697A (ja) 2009-10-29
US20100024925A1 (en) 2010-02-04
US8481172B2 (en) 2013-07-09
KR101399085B1 (ko) 2014-05-27
BRPI0711652B1 (pt) 2018-03-06
JP5586224B2 (ja) 2014-09-10
CN101454473A (zh) 2009-06-10
PL1857566T3 (pl) 2017-10-31
KR20090007597A (ko) 2009-01-19
WO2007132007A1 (fr) 2007-11-22

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