EP3332048A1 - Procédé de production d'un revêtement par immersion à chaud, galvanisé à base de zinc - magnésium et un produit plat en acier doté d'un tel revêtement - Google Patents

Procédé de production d'un revêtement par immersion à chaud, galvanisé à base de zinc - magnésium et un produit plat en acier doté d'un tel revêtement

Info

Publication number
EP3332048A1
EP3332048A1 EP15750686.6A EP15750686A EP3332048A1 EP 3332048 A1 EP3332048 A1 EP 3332048A1 EP 15750686 A EP15750686 A EP 15750686A EP 3332048 A1 EP3332048 A1 EP 3332048A1
Authority
EP
European Patent Office
Prior art keywords
coating
content
steel
zinc
steel substrate
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.)
Granted
Application number
EP15750686.6A
Other languages
German (de)
English (en)
Other versions
EP3332048B1 (fr
Inventor
Georg Parma
Jennifer Schulz
Horst Berndsen
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
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Publication of EP3332048A1 publication Critical patent/EP3332048A1/fr
Application granted granted Critical
Publication of EP3332048B1 publication Critical patent/EP3332048B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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

Definitions

  • the invention relates to a method for producing a zinc-magnesium-galvannealed hot-dip coating on a steel substrate, wherein the steel substrate is typically a flat steel product. As "flat steel product" thereby rolled
  • the invention relates to a
  • the following elements may have a content below the upper limit specified for each of these elements: Si: ⁇ 2%, Pb: ⁇ 0.1%, Ti: ⁇ 0.2%, Ni: ⁇ 1%, Cu: ⁇ 1 %, Co: ⁇ 0.3%, Mn: ⁇ 0.5%, Cr: ⁇ 0.2%, Sr: ⁇ 0.5%, Fe: ⁇ 3%, B: ⁇ 0.1%, Bi: ⁇ 0.1%, Cd: ⁇ 0.1%.
  • the steel flat product thus obtained has a Zn-Mg-Al coating containing, in addition to zinc and unavoidable impurities (in% by weight) Mg: 4-8% and Al 0.5-1.8%, and optionally one or more of contains the following elements with a content below the upper limit specified for each of these elements: Si: ⁇ 2%, Pb: ⁇ 0.1%, Ti: ⁇ 0.2%, Ni: ⁇ 1%, Cu: ⁇ 1% , Co: ⁇ 0.3%, Mn: ⁇ 0.5%, Cr: ⁇ 0.2%, Sr: ⁇ 0.5%, Fe: ⁇ 3%, B: ⁇ 0.1%, Bi: ⁇ 0.1%, Cd: ⁇ 0.1%, REM ⁇ 0.2%, Sn ⁇ 0.5%. That so
  • Coated flat steel product is perfectly protected against corrosion and has good weldability.
  • Galvannealed hot dip coating system due to the increased Fe content in the coating as a result of Galvannealing opposition to an early onset of
  • Coating of steel substrates with a Galvannealed Hot dip coating allows improved corrosion protection.
  • a flat steel product suitably provided with an optimized galvannealed coating should be mentioned.
  • the invention has this
  • the invention provides a process for the production of steel products, in particular flat steel products, which are provided with a hot-dip coating
  • Zinc base are provided and thereby improved
  • the composition of the melt bath chosen so that in the subsequent Galvannealing- treatment a galvannealing coating with optimal
  • the aim of the procedure according to the invention is the
  • Galvannealingtemperatur of 450 - 800 ° C is maintained to produce on the steel substrate a zinc-magnesium galvannealed hot-dip coating, the zinc and unavoidable impurities (in wt .-%) 0.10 - 0.5% AI, 5.0 - 15.0 Fe, 0.10 - 0.8% Mg and optionally one or more of the following elements according to
  • Si ⁇ 2%
  • Pb ⁇ 0.1%
  • Ti ⁇ 0.2%
  • Ni ⁇ 1%
  • Cu ⁇ 1%, Co: ⁇ 0.3%, Mn: ⁇ 0.0001%, Cr: ⁇ 0.2%, Sr: ⁇ 0.5%, B: ⁇ 0.1%, Bi: ⁇ 0 , 1%, Cd: ⁇ 0.1%, REM: ⁇ 0.2%, Sn ⁇ 0.01%.
  • the Al content in the molten bath is 0.10-0.16% by weight to ensure good adhesion of the invention
  • the Fe2A15 inhibition layer causes diffusion of the iron from the base material inhibited in the coating
  • the Fe2A15 layer must not be too weak because otherwise the adhesion between substrate and coating is impaired. But it must not be too pronounced, because otherwise the diffusion of iron into the coating is too much hindered.
  • Mechanism applies both to the limitation of the Al content in the melt bath and to the limitation of the Al content in the coating. Since Al is deposited more strongly in the coating than it is present in the melt bath, the bath and coating have different upper limits.
  • the inventively provided Al contents of the melt bath are adjusted so that there is an optimum for the adhesion of the coating layer structure. If the aluminum content in the melt bath exceeds the upper limit of 0.16% by weight, a covering Fe 2 Al 5 inhibition layer forms between the base material and the coating, which is so thick that no proper galvannealed coating can be formed. If the aluminum content is less than 0.10% by weight, there is insufficient coating adhesion. harmful
  • Influences of the Al content on the formation of an optimal Galvanealed coating can be safely avoided that the Al content of the melt bath is limited to at most 0.15 wt .-%, the positive effect of the presence of Al in the molten bath then particularly safely occurs when the Al content is more than 0.1 wt .-%, so in the expert sense clearly more than 0.1 wt .-% AI in the melt bath is present.
  • Fe content in the melt bath The melt bath should be saturated with Fe, so that the driving force for a diffusion of iron from the
  • Melt bath less than 0.01% can be iron from the
  • the upper limit of the Fe content in the melt bath is determined by the solubility limit of the iron in the melt bath. If this content is exceeded, increased slag formation can occur due to precipitating iron phases.
  • the Mg content in the melt bath is 0.10-0.6 wt%.
  • the upper limit of 0.6 wt .-% applies to a
  • the Mg content of the melt bath is limited to up to 0.4% by weight. At contents of less than 0.1% by weight, however, the effect sought by Mg addition to the melt bath occurs
  • melt bath not taken from the contents of Al, Fe and Mg rest is zinc, wherein in the melt each optionally (in wt .-%) less than 2% Si, less than 0.1% Pb, less than 0 , 2% Ti, less than 1% Ni, less than 1% Cu, less than 0.3% Co, less than 0.0001% Mn, less than 0.2% Cr, less than 0.5% Sr, less than 0.1% B, less than 0.1% Bi, less than 0.1% Cd, less than 0.2% REM, and less than 0.5% Sn.
  • optional elements are present in the form of manufacturing unavoidable, but in view of the behavior of the melt bath and the coating to be generated from it ineffective impurities present or can be used to adjust certain
  • the melt bath temperature TB should be 350-650 ° C. At temperatures below 350 ° C, the melt pool begins to solidify and the steel substrate can no longer be coated. At temperatures greater than 650 ° C it comes increasingly to the evaporation of zinc. This is hazardous to health and leads to
  • melt bath temperatures of at least 430 ° C. have proven to be particularly practical. From one Melt bath temperature of at least 430 ° C, an optimally liquid melt bath can be guaranteed, with which on the respective steel substrate coatings with optimized flow properties and also optimized surface quality and uniformity of the
  • Melt bath temperature is limited to 490 ° C, can also be the loss of zinc by evaporation, the
  • Optimal melt bath temperatures of the inventively provided Zn-Mg-Al-Fe-melt bath are accordingly in the range of 430 - 490 ° C.
  • Galvannealingtemperatur TG is accordingly in the range of 430 - 490 ° C.
  • the Galvannealingtemperatur TG should at
  • the galvannealing temperature must be at least 450 ° C to activate iron diffusion from the steel substrate into the hot dip coating. To be able to use this effect reliably, the
  • the galvannealing time ie the time over which the hot-dip coated steel flat product is kept at the galvannealing temperature, is 10 - 25 s.
  • the Galvannealingzeit must be at least 10 s to the inventively provided
  • Galvannealingzeit be provided by at least 12 s.
  • the galvannealing time should not exceed 25 s in order to achieve a superalloying of the
  • Coating i. to avoid an increase of the Fe contents of the coating to values of more than 15% by weight.
  • Galvannealingzeit is in principle within the limits specified according to the invention variable and can be influenced by the speed with which the respective coated steel substrate by the
  • the galvannealing time can be limited to a maximum of 24 seconds. Coatings with optimal properties can be
  • Galvannealingtemperatur 540 - 720 ° C is.
  • Metallic coating is typically 3 - 20 ⁇ . In the case of layer thicknesses lying in this range, optimal optimum corrosion protection is achieved with optimum performance characteristics and deformation behavior of the steel substrate coated according to the invention.
  • the degree of alloying is defined by the Fe content in the coating.
  • the coating is considered as alloyed when the iron content in the coating is 9% by weight or more, whereas it is considered to be "over-alloyed" when the Fe content in the coating is greater than 15% by weight.
  • the Al content in the coating is 0.10-0.5% by weight.
  • the Fe content in the coating is 5.0-15.0% by weight. To be considered a galvannealed coating, the iron content in the coating must be at least 5.0% by weight during normal production. From a "alloy" can, how
  • the Fe content is at a
  • the Mg content in the coating should be 0.10-0.8% by weight. At this Mg content becomes one compared to a
  • Corrosion protection can be achieved. If the Mg content in the coating is less than 0.10% by weight, then it is none
  • Coating is zinc.
  • the elements in question may be present in the sense of impurities in alloying ineffective levels or targeted at elevated levels for setting certain properties of the coating
  • the invention is particularly well suited for the processing of flat steel products as a steel substrate, since such flat steel products can be processed in accordance with the invention in a manner which is well established in practice with high efficiency.
  • suitable plants for this purpose which are completed by the respective flat steel product in a basically known manner in a continuous pass.
  • the application of the invention is not limited to steel products made of a particular grade of steel, but is suitable for coating all of them
  • steel strips and sheets to which special requirements with regard to corrosion protection are placed.
  • all steel products are suitable, which consist of steels, which can be coated with a Zn-Mg-Al-galvannealed coating of the invention according to the type to be generated.
  • These include in particular IF steels, in particular soft or higher strength IF steels, bake hardening steels, microalloyed steels and
  • a flat steel product according to the invention has a zinc-magnesium-galvannealed hot-dip coating consisting of (in% by weight)
  • Fig. 1 is a schematic representation of one of
  • Fig. 2 is a diagram in which exemplifies the
  • the samples have a degreasing in the continuous
  • melt bath temperature was 460 ° C in each case.
  • Hot-dip coating in a manner also known per se was set to 7 pm.
  • the samples then undergo a Galvannealing treatment, in which they are given over a
  • Galvannealingzeit tG have been kept at a Galvanneatingtemperatur TG.
  • galvannealed hot-dip coatings can be produced as a function of the Mg content
  • Fe contents according to the invention of 8 - have 15 wt .-% at Mg contents of 0.1 to 0.5 wt .-%.
  • Variant 2 passed.
  • the contents Al Ba d and Mg Ba d of Al and Mg of the respectively used melt bath, the Galvanneatingtemperatur TG and the presence of zeta phases ( ⁇ ) are for the existing of the IF steel variant 1 samples in Table 4 and for the IF steel variant 2 existing samples in Table 5

Landscapes

  • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)

Abstract

L'invention concerne un procédé de production d'un revêtement par immersion à chaud, galvanisé à base de Zn - Mg présentant une protection améliorée contre la corrosion sur un substrat en acier et un produit plat en acier ainsi constitué. À cet effet, a) un substrat en acier est mis à disposition, b) le substrat en acier est revêtu par immersion à chaud dans un bain fondu de Fe saturé chauffé à 350 - 650 °C (en % en poids) constitué de 0,1 - 0,16 % d'Al et 0,1 - 0,6 % de Mg et < 2 % de Si, respectivement < 1 % de Ni ou Cu, < 0,3 % de Co, < 0,0001 % de Mn, < 0,5 % de Sr, respectivement < 0,1 % de Pb, B, Bi ou Cd, respectivement < 0,2 % de REM, Ti ou Cr, ou < 0,5 % de Sn, le reste étant constitué de zinc et d'impuretés inévitables et c) un traitement de galvanisation est réalisé, lors duquel le substrat en acier est maintenu pendant 10 - 25 s à 450 - 800 °C pour produire sur le substrat en acier un revêtement par immersion à chaud galvanisé de Zn - Mg, qui comprend, en plus de Zn et d'impuretés inévitables, (en % en poids) 0,10 - 0,5 % d'Al, 5,0 - 15,0 % de Fe, 0,10 - 0,8 % de Mg et < 2 % de Si, respectivement < 1 % de Ni, Cu, < 0,3 % de Co, < 0,0001 % de Mn, < 0,5 % de Sr, respectivement < 0,1 % de B, Bi, Cd, Pb, respectivement < 0,2 % de Cr, Ti, REM, < 0,01 % de Sn.
EP15750686.6A 2015-08-06 2015-08-06 Procédé de production d'un revêtement par immersion à chaud, galvanisé à base de zinc - magnésium et un produit plat en acier doté d'un tel revêtement Active EP3332048B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2015/068177 WO2017020965A1 (fr) 2015-08-06 2015-08-06 Procédé de production d'un revêtement par immersion à chaud, galvanisé à base de zinc - magnésium et un produit plat en acier doté d'un tel revêtement

Publications (2)

Publication Number Publication Date
EP3332048A1 true EP3332048A1 (fr) 2018-06-13
EP3332048B1 EP3332048B1 (fr) 2020-02-19

Family

ID=53872034

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15750686.6A Active EP3332048B1 (fr) 2015-08-06 2015-08-06 Procédé de production d'un revêtement par immersion à chaud, galvanisé à base de zinc - magnésium et un produit plat en acier doté d'un tel revêtement

Country Status (5)

Country Link
US (1) US20190003027A1 (fr)
EP (1) EP3332048B1 (fr)
JP (1) JP6668453B2 (fr)
CN (1) CN107849674A (fr)
WO (1) WO2017020965A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6696274B2 (ja) * 2016-04-11 2020-05-20 日本製鉄株式会社 合金化溶融亜鉛めっき鋼板の製造方法
DE102018132171A1 (de) * 2018-12-13 2020-06-18 Thyssenkrupp Steel Europe Ag Batteriegehäuse und Verwendung
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

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0397840A (ja) * 1989-09-11 1991-04-23 Sumitomo Metal Ind Ltd 合金化溶融亜鉛めっき鋼板
JPH06256925A (ja) * 1993-03-08 1994-09-13 Nippon Steel Corp プレス成形性に優れた亜鉛−鉄合金化溶融亜鉛めっき鋼板
JP2000119832A (ja) * 1998-10-16 2000-04-25 Nippon Steel Corp めっき密着性に優れた溶融亜鉛めっき鋼板
JP2001279412A (ja) * 2000-03-29 2001-10-10 Nippon Steel Corp 耐食性の良好なＳｉ含有高強度合金化溶融亜鉛めっき鋼板とその製造方法
EP1693477A1 (fr) * 2005-02-22 2006-08-23 ThyssenKrupp Steel AG Bande d'acier revêtu
JP4582707B2 (ja) * 2005-04-20 2010-11-17 新日本製鐵株式会社 不メッキ欠陥発生のない溶融亜鉛メッキ方法

Also Published As

Publication number Publication date
JP6668453B2 (ja) 2020-03-18
JP2018529024A (ja) 2018-10-04
WO2017020965A1 (fr) 2017-02-09
CN107849674A (zh) 2018-03-27
EP3332048B1 (fr) 2020-02-19
US20190003027A1 (en) 2019-01-03

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