WO2015055285A1 - Substrat en acier à revêtement en alliage de zinc - Google Patents

Substrat en acier à revêtement en alliage de zinc Download PDF

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Publication number
WO2015055285A1
WO2015055285A1 PCT/EP2014/002705 EP2014002705W WO2015055285A1 WO 2015055285 A1 WO2015055285 A1 WO 2015055285A1 EP 2014002705 W EP2014002705 W EP 2014002705W WO 2015055285 A1 WO2015055285 A1 WO 2015055285A1
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WO
WIPO (PCT)
Prior art keywords
weight
steel substrate
zinc alloy
total
steel
Prior art date
Application number
PCT/EP2014/002705
Other languages
English (en)
Inventor
Nitte Van Landschoot
Hugo Van Schoonevelt
Adrianus Jacobus Wittebrood
Margo Julia VLOT
Original Assignee
Tata Steel Ijmuiden B.V.
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 Tata Steel Ijmuiden B.V. filed Critical Tata Steel Ijmuiden B.V.
Publication of WO2015055285A1 publication Critical patent/WO2015055285A1/fr

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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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • 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
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • the invention relates to a steel substrate with a zinc alloy coating.
  • zinc alloy coatings containing aluminium and magnesium have been developed, most of which contain between 0.5 and 4.0 weight% aluminium and magnesium.
  • Such zinc alloy coatings show a corrosion resistance that is much higher than the traditional galvanised or galvannealed coatings.
  • Most steel companies are now marketing such so called ZnAIMg coatings because they provide an improved corrosion resistance to the customer.
  • Such coatings are also of interest because they can be used with a coating thickness that is thinner than traditionally used while still providing an improved corrosion resistance, thereby saving in the use of zinc.
  • Such ZnAIMg coatings are also frequently used for organic coated steel substrates, both for use inside buildings and for exterior use.
  • the crack pattern after bending of the ZnAIMg coating is changed. Instead of numerous wide cracks, now a pattern with a very high density of fine cracks is formed. These fine cracks result in a higher surface quality of the zinc alloy coated steel substrate.
  • an organic coating is present on top of the ZnAIMg coating, the organic coating can take up the local forces at the fine crack openings and therefore remain intact. Thus, the surface quality of the steel substrate with organic topcoat remains unimpaired.
  • the inventors have now found that by adding more of Bi, Pb, Sn or Sb, or a combination thereof, the crystal structure of the ZnAIMg coating is influenced. Since the zinc alloy coating contains Al and Mg, the zinc alloy coating exhibits a solidification path during its cooling down after galvanisation in a bath with molten zinc alloy. During solidification, nucleation of the zinc takes place at the steel interface. Subsequently, zinc dendrites start to grow from the nuclei into the slightly supercooled liquid layer of zinc alloy. During the growth stage the dendrites grow initially sideways parallel to the interface, and at a later stage thickening of the dendrites occur.
  • a binary phase consisting of zinc and MgZn2 starts to solidify and this binary phase solidifies in between the zinc dendrites.
  • This ternary phase consists of three distinct compounds: a zinc, an aluminium and a MgZn2 phase. Both the binary and the ternary phase have a lamella structure, but the structure of the ternary phase is coarser.
  • the addition of Bi, Pb, Sn or Sb to the coating bath increases the growth velocity of the zinc dendrites.
  • the principle is not yet fully understood, but the inventors are of the opinion that Bi (or Pb, Sn or Sb) segregates in the liquid zinc alloy ahead of the growing dendrites, lowering the surface tension and thereby allowing the growth velocity of the zinc dendrites to increase.
  • the theory is that the growth velocity of the zinc dendrites now is so high, that only the dendrites with a favourable growth direction develop, and the development of dendrites with a non-favourable growth direction is suppressed. On the primary dendrites the secondary and ternary dendrites grow very rapidly, developing a very fine dendritic network.
  • the zinc alloy coating When tension forces are applied to the zinc alloy coating, for instance by bending the steel substrate, the zinc alloy starts to crack. Once nucleated the cracks grow preferentially further through the binary and ternary phases. Due to the fine phase distribution of the binary and ternary phases in the Bi (or Pb, Sn or Sb) containing coating, more cracks per area originate.
  • the zinc alloy layer has a thickness of 2
  • - 30 ⁇ preferably a thickness of 3 - 25 ⁇ , more preferably thickness of 4 - 20 ⁇ , most preferably a thickness of 7 - 15 ⁇ . These are the thicknesses (on each side) that are most commonly used for galvanised steel both without and with a top layer.
  • the zinc alloy coating contains 0.01 - 0.4 weight% in total of Bi and/or Pb and/or Sn and/or Sb, more preferably 0.02 - 0.3 weight% in total of Bi and/or Pb and/or Sn and/or Sb, most preferably 0.04 - 0.2 weight% in total of Bi and/or Pb and/or Sn and/or Sb.
  • the upper limit of 0.5 weight% Bi (or Pb or Sn or Sb) can be used, a lower limit can be used in practice. For instance above 0.3 weight% Bi the solidification sequence is changed, and aluminium is the first phase to solidify. Above 0.3 weight% Bi formation of Mg3Bi2 particle occurs.
  • the zinc alloy coating contains 0.01 - 0.4 weight% Bi, preferably 0.02 - 0.3 weight% Bi, more preferably 0.04 - 0.2 weight% Bi.
  • Bismuth has been found to be an element that can be very well used with out Pb, Sn or Sb. Preferably only small amounts are used, which gives the desired effect.
  • the zinc alloy coating contains 0.1
  • the zinc alloy coating optional contains ⁇ 0.1 weight% in total of Si,
  • Ti, Ca, Mn, La, Ce, Cr, Ni and/or Zr preferably ⁇ 0.04 weight% in total of Si, Ti, Ca, Mn, La, Ce, Cr, Ni and/or Zr, more preferably ⁇ 0.02 weight% in total of Si, Ti, Ca, Mn, La, Ce, Cr, Ni and/or Zr, most preferably ⁇ 0.01 weight% in total of Si, Ti, Ca, Mn, La, Ce, Cr, Ni and/or Zr.
  • These elements are optional, but are usually not added because they make the zinc alloy coating more costly. However, they can be added to prevent dross forming, but then in very mall amounts.
  • the zinc alloy coating contains 1.0 - 2.5 weight% Al and 1.0 - 2.5 weight% Mg, preferably 1.0 - 2.0 weight% Al and 1.0 - 2.0 weight% Mg, most preferably 1.4 - 1.9 weight% Al and 1.4 - 1.9 weight% Mg. It has been found that preferably the amount of Al and Mg is neither too high nor too low, to get a balance between corrosion properties that are good enough and cost of the alloying elements that are not too high.
  • the steel substrate is a steel strip having a length of 100 - 4000 m, a width of 500 - 3000 mm and a thickness of 0.5 - 4.0 mm.
  • This is the type of strip that is usually produced from a slab through hot rolling and cold rolling, which once provided with a zinc alloy coating can be used in a number of industries, such as in the building industry for external and internal building uses, household appliances, and automotive after providing it with a top coating.
  • the steel substrate is a low carbon steel, consisting essentially of iron, preferably with a carbon content from about 0.001 weight% to about 0.15 weight% carbon, and other elements like Mn, P, S, Al, N, Ti, Mo, Nb, to obtain a desired alloying effect
  • Low carbon steel strip is used for most applications, especially in the building industry.
  • the zinc alloy coated steel substrate is provided with a conversion coating either phosphate-based or chrome-based or silicon-based, to promote the adhesion of the single or multiple organic top layers.
  • a conversion coating either phosphate-based or chrome-based or silicon-based, to promote the adhesion of the single or multiple organic top layers.
  • the zinc alloy coated steel substrate can be directly used in the building industry.
  • the steel substrate is a three- dimensional object such as a tube or work piece.
  • a process for producing a steel substrate provided with a zinc alloy coating according to the first aspect of the invention wherein the steel substrate is hot dip galvanised using a bath of molten zinc alloy consisting of (in weight%):
  • the bath of molten zinc alloy having a bath temperature between 340 and 550° C.
  • a zinc alloy coated steel strip having the advantageous effect that only fine cracks are formed during deformation, due to the addition of Bi and/or Pb and/or Sn and/or Sb.
  • the bath temperature is between 370 and 550° C, preferably between 380 and 500° C.
  • the bath temperature varies with the composition. Start of solidification is 335° C for a very rich composition, but 410° C for a lean composition.
  • the composition of the zinc alloy thus determines the temperature of the bath and the strip.
  • the temperature of the steel substrate before entering the bath of molten zinc alloy is at most 30° C above the bath temperature.
  • the temperature of the steel strip should not be lower than the melting point of the zinc alloy to prevent local solidification of the zinc bath. High steel strip temperatures will lead to higher evaporation of the zinc, causing dust forming. High strip temperatures could also heat up the zinc bath, leading to the necessity to cool the zinc bath, which is expensive. Therefore the strip temperature should be just above the temperature of the bath.
  • the steel substrate is a steel strip entering the bath of molten zinc alloy having a speed higher than 15 metres per minute, preferably having a speed higher than 30 metres per minute.
  • a high strip speed reduces or even prevents sagging of the zinc alloy during solidification thereof.
  • the substrate used was a low carbon steel with a sample size of 200 x 120 mm and a thickness of 0.7 mm, having a composition of Interstitial-Free steel (IF steel).
  • the bath temperature was 440 °C.
  • the zinc alloy coating according to the invention was tested as follows.

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

Abstract

La présente invention concerne un substrat en acier revêtu d'un alliage de zinc contenant de l'aluminium et du magnésium. Selon l'invention, le revêtement en alliage de zinc est constitué de (en % en poids) : 0,5 à 3,8 d'Al, 0,5 à 3,0 de Mg, 0,01 à 0,5 au total de Bi et/ou de Pb et/ou de Sn et/ou de Sb, éventuellement < 0,2 au total de Si, Ti, Ca, Mn, La, Ce, Cr, Ni et/ou de Zr, des impuretés inévitables, le reste étant du zinc. L'invention concerne également un procédé de fabrication d'un tel revêtement de substrat en acier pourvu dudit revêtement en alliage de zinc selon l'invention.
PCT/EP2014/002705 2013-10-15 2014-10-06 Substrat en acier à revêtement en alliage de zinc WO2015055285A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13004939.8 2013-10-15
EP13004939 2013-10-15

Publications (1)

Publication Number Publication Date
WO2015055285A1 true WO2015055285A1 (fr) 2015-04-23

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015505A1 (fr) * 2016-07-20 2018-01-25 Tata Steel Ijmuiden B.V. Procédé d'application d'un revêtement zn/al/mg, et revêtement correspondant
CN107641781A (zh) * 2017-09-15 2018-01-30 中国矿业大学 一种清洁的热浸镀锌合金方法
CN108977695A (zh) * 2018-09-30 2018-12-11 济南大学 一种含钛和锑的热浸镀锌铝镁合金及其制备方法
CN110512118A (zh) * 2019-09-12 2019-11-29 河钢股份有限公司 一种汽车用高表面质量锌铝镁镀层钢板及其生产工艺
RU2727391C1 (ru) * 2020-02-03 2020-07-21 Публичное Акционерное Общество "Новолипецкий металлургический комбинат" Способ производства коррозионностойкого окрашенного стального проката с цинк-алюминий-магниевым покрытием

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58189363A (ja) * 1982-04-26 1983-11-05 Nisshin Steel Co Ltd 合金化亜鉛めつき鋼板の製造方法
EP0594520A1 (fr) * 1992-10-21 1994-04-27 Sollac Procédé de galvanisation de produits sidérurgiques et produits sidérurgiques ainsi obtenus
EP1199376A1 (fr) * 1999-05-24 2002-04-24 Nippon Steel Corporation Produit d'acier plaque, feuille d'acier plaquee et feuille d'acier prerevetue possedant une excellente resistance a la corrosion
JP2002371342A (ja) * 2001-06-14 2002-12-26 Sumitomo Metal Ind Ltd 溶融亜鉛めっき鋼板およびその製造方法
EP1621645A1 (fr) * 2004-07-28 2006-02-01 Corus Staal BV Feuille d'acier galvanisé à chaud recouverte de zinc allié.
CN101027421A (zh) * 2004-06-29 2007-08-29 克里斯塔尔公司 具有热浸镀锌合金镀层的钢片及其制备方法
US20110017362A1 (en) * 2007-11-05 2011-01-27 Thyssenkrupp Steel Europe Ag Steel flat product having a metallic coating which protects against corrosion and method for producing a metallic zn-mg coating, which protects against corrosion, on a steel flat product

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58189363A (ja) * 1982-04-26 1983-11-05 Nisshin Steel Co Ltd 合金化亜鉛めつき鋼板の製造方法
EP0594520A1 (fr) * 1992-10-21 1994-04-27 Sollac Procédé de galvanisation de produits sidérurgiques et produits sidérurgiques ainsi obtenus
EP1199376A1 (fr) * 1999-05-24 2002-04-24 Nippon Steel Corporation Produit d'acier plaque, feuille d'acier plaquee et feuille d'acier prerevetue possedant une excellente resistance a la corrosion
JP2002371342A (ja) * 2001-06-14 2002-12-26 Sumitomo Metal Ind Ltd 溶融亜鉛めっき鋼板およびその製造方法
CN101027421A (zh) * 2004-06-29 2007-08-29 克里斯塔尔公司 具有热浸镀锌合金镀层的钢片及其制备方法
EP1621645A1 (fr) * 2004-07-28 2006-02-01 Corus Staal BV Feuille d'acier galvanisé à chaud recouverte de zinc allié.
US20110017362A1 (en) * 2007-11-05 2011-01-27 Thyssenkrupp Steel Europe Ag Steel flat product having a metallic coating which protects against corrosion and method for producing a metallic zn-mg coating, which protects against corrosion, on a steel flat product

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015505A1 (fr) * 2016-07-20 2018-01-25 Tata Steel Ijmuiden B.V. Procédé d'application d'un revêtement zn/al/mg, et revêtement correspondant
CN109563605A (zh) * 2016-07-20 2019-04-02 塔塔钢铁艾默伊登有限责任公司 提供zn-al-mg涂层的方法以及这种涂层
EP3488025B1 (fr) 2016-07-20 2021-01-27 Tata Steel IJmuiden B.V. Procédé d'application d'un revêtement zn/al/mg
CN109563605B (zh) * 2016-07-20 2021-06-11 塔塔钢铁艾默伊登有限责任公司 提供zn-al-mg涂层的方法以及这种涂层
US11306382B2 (en) 2016-07-20 2022-04-19 Tata Steel Ijmuiden B.V. Method for providing a Zn—Al—Mg coating, and such coating
CN107641781A (zh) * 2017-09-15 2018-01-30 中国矿业大学 一种清洁的热浸镀锌合金方法
CN107641781B (zh) * 2017-09-15 2019-04-23 中国矿业大学 一种清洁的热浸镀锌合金方法
CN108977695A (zh) * 2018-09-30 2018-12-11 济南大学 一种含钛和锑的热浸镀锌铝镁合金及其制备方法
CN108977695B (zh) * 2018-09-30 2020-12-01 济南大学 一种含钛和锑的热浸镀锌铝镁合金及其制备方法
CN110512118A (zh) * 2019-09-12 2019-11-29 河钢股份有限公司 一种汽车用高表面质量锌铝镁镀层钢板及其生产工艺
RU2727391C1 (ru) * 2020-02-03 2020-07-21 Публичное Акционерное Общество "Новолипецкий металлургический комбинат" Способ производства коррозионностойкого окрашенного стального проката с цинк-алюминий-магниевым покрытием

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