EP2432910B1 - Procédé de revêtement par immersion à chaud d'un produit plat en acier contenant de 2 à 35 % en masse de mn, ainsi que produit plat en acier - Google Patents

Procédé de revêtement par immersion à chaud d'un produit plat en acier contenant de 2 à 35 % en masse de mn, ainsi que produit plat en acier Download PDF

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EP2432910B1
EP2432910B1 EP10717595.2A EP10717595A EP2432910B1 EP 2432910 B1 EP2432910 B1 EP 2432910B1 EP 10717595 A EP10717595 A EP 10717595A EP 2432910 B1 EP2432910 B1 EP 2432910B1
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Prior art keywords
flat steel
steel product
annealing
layer
coating
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EP2432910B2 (fr
EP2432910A1 (fr
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Manfred Meurer
Martin Norden
Wilhelm Warnecke
Marc Blumenau
Matthias Dahlem
Jennifer Schulz
Klaus Josef Peters
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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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
    • 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
    • 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
    • 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
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
    • 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

Definitions

  • the invention relates to a process for the hot dip coating of a zinc flat or a zinc alloy containing 2 to 35% by weight of Mn, and to a flat steel product provided with a zinc or zinc alloy coating.
  • Typical alloying elements are manganese, chromium, silicon, aluminum, and the like, which form stable non-reducible surface oxides upon conventional recrystallizing annealing. These oxides can prevent the reactive wetting with a molten zinc.
  • steels with high manganese contents are, due to their favorable combination of properties consisting of high strengths of up to 1,400 MPa on the one hand and extremely high strains (uniform strains of up to 70% and elongations at break of up to 90%), in principle particularly suitable for use in the field of vehicle construction , especially in the automotive industry.
  • Specially suitable steels with high Mn contents for this application from 6 wt .-% to 30 wt .-%, for example, from DE 102 59 230 A1 , the DE 197 27 759 C2 or the DE 199 00 199 A1 known.
  • Flat products produced from the known steels have an isotropic deformation behavior at high strengths and, moreover, are still ductile even at low temperatures.
  • melt ribbon additionally contains aluminum in an amount sufficient to completely reduce the MnO layer and at least partially reduce the (FeMn) O layer.
  • a method for hot dip coating a high Mn-containing steel substrate is known in which the ratio% H 2 O /% H 2 of the water content% H 2 O to the hydrogen to produce a substantially free of oxidic interlayers metallic protective layer on the steel strip.
  • the content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G such that the ratio% H 2 O /% H 2 is less than or equal to 8 ⁇ 10 -15 ⁇ T G 3.529 , where T denotes the annealing temperature is.
  • This specification is based on the finding that, by means of a suitable setting of the annealing atmosphere, namely its hydrogen content in relation to its dew point, a surface finish of the steel strip to be coated sets during the annealing, which ensures optimum adhesion of the subsequently hot-dip coating guaranteed applied metallic protective coating.
  • the annealing atmosphere set in this way reduces both the iron and the manganese of the steel strip.
  • the aim is to avoid the formation of an adhesion of the melt coating on the high manganese steel substrate impairing oxide layer.
  • the object of the invention to provide a method which allows to provide high levels of Mn-containing flat steel products with a corrosion-protective zinc coating, in which a further improved adhesion of the coating is ensured on the steel substrate.
  • a flat steel product should be created in which as well under high degrees of deformation of each formed of zinc or a zinc alloy Zn coating securely adheres to the steel substrate.
  • this object is achieved in that the hot dip coating of a high Mn contents containing flat steel product, the steps specified in claim 1 are completed.
  • a flat steel product in the form of a steel strip or sheet steel is first provided for hot dip coating a 2 to 35 wt% Mn-containing flat steel product in a continuous process.
  • the coating procedure according to the invention is particularly suitable for steel strips which are highly alloyed in order to ensure high strength and good elongation properties.
  • Steel strips provided with a metallic protective coating by hot-dip coating according to the invention contain (in% by weight) C: ⁇ 1.6%, Mn: 2 - 35%, Al: ⁇ 10%, Ni: ⁇ 10%, Cr: ⁇ 10%, Si: ⁇ 10%, Cu: ⁇ 3%, Nb: ⁇ 0.6%, Ti: ⁇ 0.3%, V: ⁇ 0.3%, P: ⁇ 0.1%, B: ⁇ 0.01%, Mo: ⁇ 0.3%, N: ⁇ 1.0%, balance iron and unavoidable impurities.
  • a steel which (in wt .-%) C: ⁇ 1.00%, Mn: 7.00 - 30.00%, Al: 1.00 - 10.00%, Si :> 2.50 - 8.00% (assuming that the sum of Al content and Si content is> 3.50 - 12.00%), B: ⁇ 0.01%, Ni: ⁇ 8, 00%, Cu: ⁇ 3.00%, N: ⁇ 0.60%, Nb: ⁇ 0.30%, Ti: ⁇ 0.30%, V: ⁇ 0.30%, P: ⁇ 0.01% , Rest contains iron and unavoidable impurities.
  • both hot-rolled and cold-rolled steel strips can be coated in the manner according to the invention as flat steel products, with the method according to the invention being particularly effective in the processing of cold-rolled steel strip.
  • the thus provided flat products are annealed in a working step b).
  • the annealing temperature Tg is 600 - 1100 ° C, while the annealing time, over which the flat steel product is kept at the annealing temperature, 10 - 240 s.
  • the above-mentioned annealing temperature Tg and annealing time under a FeO iron oxide present on the steel flat product be reducing and oxidizing with respect to the manganese contained in the steel substrate.
  • the annealing atmosphere contains 0.01-85 vol .-% H 2 , H 2 O and the balance N 2 and technically unavoidable impurities and has a lying between -70 ° C and +60 ° C dew point, wherein for the H 2 O / H 2 ratio applies: 8x10 -15 * Tg 3.529 ⁇ H 2 O / H 2 ⁇ 0.957
  • the ratio H 2 O / H 2 is set so that it is greater than 8x10 -15 * Tg 3.529 and on the other hand at most equal to 0.957, where Tg the respective annealing temperature is designated.
  • the dew point of the atmosphere is preferably in the range of - 50 ° C to + 60 ° C.
  • the annealing atmosphere in this case typically contains 0.1-85 vol% H 2 .
  • a particularly economical mode of operation of the Annealing continuous furnace used in the invention can be achieved by keeping the dew point of the atmosphere at -20 ° C to +20 ° C.
  • the steel flat product at least partially covering Mn mixed oxide layer is produced by a performed before the hot dip coating annealing on the flat steel product, wherein it is particularly favorable in view of the adhesion of the Zn coating on the steel substrate, if the Mn mixed oxide layer substantially completely covers the surface of the flat steel product after annealing.
  • the Mn mixed oxide layer is defined in the context of the invention as MnO ⁇ Fe metal . That is, metallic iron is present in this Mn mixed oxide layer and not, as in the prior art, oxidized iron.
  • an Mn mixed oxide layer is deliberately set via at least one annealing stage by carrying out the annealing (step b)) under a FeO-reducing and an Mn-oxidizing atmosphere.
  • the layer of Mn mixed oxides produced on the steel substrate according to the invention forms a primer on which the subsequently applied zinc layer surprisingly adheres particularly securely.
  • the Mn mixed oxide layer remains during the Hot dip coating process as far as possible, so that it ensures the permanent cohesion of Zn coating and steel substrate in the finished product.
  • the annealed flat steel product is cooled to a bath inlet temperature with which it enters the Zn melt bath.
  • the bath inlet temperature of the flat steel product is in the range of 310-710 ° C.
  • the melt bath optionally, 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% present to certain properties of the coating in a conventional manner adjust.
  • the Zn coating according to the invention necessarily contains Al contents of 0.05-8% by weight and may additionally have contents of up to 8% by weight Mg, the upper limit of the contents of both elements in practice typically having a maximum of 5% by weight .-% is limited.
  • a flat steel product according to the invention having a Mn content of 2 to 35% by weight and a Zn protective coating which protects against corrosion is accordingly characterized in that the Zn protective coating comprises an Mn mixed oxide layer essentially covering and adhering to the flat steel product, in the metallic one Iron is present, and has a Zn layer which shields the flat steel product and the Mn mixed oxide layer adhering to it against the environment.
  • the Zn protective coating comprises an Fe (Mn) 2 Al 5 layer arranged between the Mn mixed oxide layer and the Zn layer. This arises when in the melt bath, a sufficient amount of aluminum from 0.05 to 5 wt .-% Al is present.
  • the Fe (Mn) 2 Al 5 layer forms a barrier layer, by means of which the reduction of the Mn mixed oxide layer during hot dip is reliably prevented.
  • the barrier layer can convert into FeZn phases, wherein the Mn oxide layer is still preserved.
  • the MnO layer and the Fe (Mn) 2 Al 5 layer of a coating produced and obtained according to the invention thus ensure, even after hot dip coating, that that the outer Zn layer adheres firmly to the steel substrate under high degrees of deformation.
  • the presence of an Mn mixed oxide layer on the surface of the steel substrate according to the invention has a positive effect not only when the Fe (Mn) 2 Al 5 layer is additionally formed, but also when magnesium is used in the molten bath alternatively or in addition to aluminum is present in effective levels.
  • the MnO layer produced according to the invention ensures particularly good and uniform wetting of the flat steel product with at the same time optimal adhesion and minimized risk of cracking or spalling even at high degrees of deformation.
  • a particularly practical embodiment of the invention results in this context when Al and Mg are present in the specified limits simultaneously in the melt bath and for the ratio of the Al content% Al and the Mg content% Mg is:% Al /% Mg ⁇ 1.
  • the Al content of the melt bath is always smaller than its Mg content.
  • Magnesium is characterized by a higher reduction potential on MnO than aluminum. Therefore, in the presence of higher Mg contents in the melt layer, forced dissolution of the MnO skeleton of the mixed oxide layer occurs.
  • the annealing step (step b)) carried out for preparing the hot-dip coating in the context of the method according to the invention can be carried out in one or more stages.
  • different hydrogen contents in the annealing atmosphere are possible depending on the dew point. If the dew point is in the range of -70 ° C to + 20 ° C, the annealing atmosphere may contain at least 0.01% by volume H 2 but less than 3% by volume H 2 . If, on the other hand, a dew point of at least +20 ° C up to and including +60 ° C is set, the hydrogen content should be in the range of 3% to 85%, so that the atmosphere has a reducing effect on iron.
  • the reducing effect with respect to the FeO which may be present and the oxidizing effect with respect to the Mn present in the steel substrate are thus reliably achieved.
  • the annealing step carried out according to the invention can be used for this purpose (Step b) of claim 1) preceded by an additional annealing step, wherein the steel flat product is kept at an annealing temperature of 200 - 1100 ° C for an annealing period of 0.1 - 60 s under an oxidative atmosphere for both Fe and Mn Containing 0.0001 - 5 vol .-% H 2 and optionally 200 - 5500 vol. ppm O 2 and having a dew point lying in the range of -60 ° C to +60 ° C.
  • the annealing step according to the invention is then carried out at a dew point in the range of -70 ° C to +20 ° C in a 0.01 to 85% hydrogen atmosphere taking into account the other parameters to be taken into account during the performance of the annealing step according to the invention, before the flat steel product is passed into the melt bath.
  • Optimal adhesion properties of the Zn coating are achieved in a coating produced according to the invention if the thickness of the Mn mixed oxide layer obtained after annealing (step b)) is 40-400 nm, in particular up to 200 nm.
  • a first sample of the cold-rolled steel strip was then annealed in a one-step annealing process.
  • the steel strip sample is heated at a heating rate of 10 K / s to an annealing temperature Tg of 800 ° C. where the sample was then held for 30 seconds.
  • the annealing was carried out under an annealing atmosphere, which consisted of 5 vol .-% H 2 and 95 vol .-% of N 2 and whose dew point was +25 ° C.
  • the annealed steel strip was cooled at a cooling rate of 20 K / s to a bath inlet temperature of 480 ° C, where it was first subjected to an overaging treatment for 20 seconds. The overaging treatment took place under the unchanged annealing atmosphere.
  • the steel strip was then passed into a 460 ° C, saturated to Fe zinc melt bath, which in addition to Zn, unavoidable impurities and Fe additionally contained 0.23 wt .-% Al. After a dipping time of 2 seconds, the hot-dip-coated steel strip has been led out of the molten bath and cooled to room temperature.
  • the steel strip was first heated to 600 ° C at a heating rate of 10 K / s and held at this annealing temperature for 10 seconds.
  • the annealing atmosphere contained 2000 ppm O 2 and the remainder N 2 . Their dew point was -30 ° C.
  • the steel strip is in a second annealing step to a 800 ° C amount annealing temperature Tg was heated at which it was kept for 30 seconds under a 5 vol .-% H 2 , remainder N 2 containing annealing atmosphere whose dew point was -30 ° C. Thereafter, the steel strip has been cooled under the annealing atmosphere with a cooling temperature of about 20 K / s to 480 ° C and subjected to an overaging treatment for 20 seconds.
  • the steel strip was passed at a bath inlet temperature of 480 ° C in a 460 ° C hot, saturated to Fe melt bath, in turn, 0.23 wt .-% Al and other elements contained in inactive traces of contamination and the remainder zinc. After a dipping time of 2 seconds, the finished hot-dip coated flat steel product is then led out of the melt bath and cooled to room temperature.
  • Fig. 1 schematically shows the structure of the coating Z thus obtained on the steel substrate S.
  • M MnO ⁇ Fe
  • F MnO ⁇ Fe (Mn) 2 Al 5
  • ⁇ phase a FeMnZn layer
  • the thickness of the Mn mixed oxide layer M is 20-400 nm
  • the thickness of the Fe (Mn) 2 Al 5 intermediate layer F is 10-200 nm.
  • the total thickness of the coating layers M and F is accordingly 20-600 nm.
  • the zinc layer Zn is significantly thicker at 3-20 ⁇ m.
  • Fig. 2 an oblique cut of a sample produced in the manner described above is reproduced.
  • the steel substrate S and the Mn y O x manganese mixed oxide layer M with embedded metallic iron lying thereon are clearly visible, the Fe (Mn) 2 Al 5 intermediate layer F lying on the mixed oxide layer M and the Zn layer lying on the intermediate layer F ,
  • the influence of the dew point of the respective annealing atmosphere has been examined for the coating result.
  • the samples were each subjected to an annealing process in which they were also heated at a heating rate of 10 K / s to an annealing temperature Tg of 800 ° C. At this annealing temperature, the sample has then been held for 60 seconds.
  • the annealing was carried out under an annealing atmosphere, each consisting of 5 vol .-% H 2 and 95 vol .-% of N 2 , wherein the respective dew point of the annealing atmosphere between -55 ° C and +45 ° C has been varied.
  • the annealed steel strip was cooled at a cooling rate of 20 K / s to a bath inlet temperature of 480 ° C as in the above-described series of experiments, where it was first subjected to an overaging treatment for 20 seconds.
  • the overaging treatment took place under the unchanged annealing atmosphere.
  • the steel strip was then passed into a 460 ° C, saturated to Fe zinc melt bath, in addition to Zn, unavoidable impurities and Fe additionally in combination 0.4 wt .-% Al and 1.0 Wt .-% Mg or alone 0.14 wt .-%, 0.17 wt .-% or 0.23 wt .-% Al contained.
  • the hot-dip-coated steel strip has been led out of the molten bath and cooled to room temperature.
  • Fig. 3 schematically shows the structure of the thus obtained on the steel substrate S 'ZnMg coating Z' shown.
  • M' MnO ⁇ Fe
  • F MnO ⁇ Fe (Mn) 2 Al 5
  • a FeMnZn layer which in turn is shielded from the environment by a ZnMg layer.
  • the thickness of the Mn mixed oxide layer M ' is 20-400 nm, while the thickness of the Fe (Mn) 2 Al 5 intermediate layer F' is 10-200 nm.
  • the total thickness of the coating layers M 'and F' is accordingly 20-600 nm.
  • the zinc layer ZnMg is significantly thicker at 3-20 ⁇ m.
  • Fig. 4 an oblique cut of a sample produced in the manner described above is reproduced.
  • the steel substrate S 'and the Mn y O x manganese mixed oxide layer M' lying thereon with embedded metallic iron, the Fe (Mn) 2 Al 5 intermediate layer F 'lying on the mixed oxide layer M and the ZnMg lying on the intermediate layer F' are clearly visible Layer to recognize.
  • each of V1-V3 and V4-V6 were obtained from a cold-rolled steel strip consisting of an Al-TRIP steel VS1 and a steel strip consisting of a likewise cold-rolled Si-TRIP steel VS2.
  • the composition of steels VS1 and VS2 are given in Table 5.
  • Table 5 C Mn P Si V al Cr Ti Nb VS1 0.22 1.1 0.02 0.1 0,002 1.7 0.06 0.1 0.001 VS2 0.18 1.8 0.02 1.8 0,002 0 0.06 0.01 0.001
  • the comparative samples V1-V6 were heat-treated in the manner described above for the samples according to the invention before being hot-dip coated in the melt bath.
  • the melt bath contained in each case 0.4% by weight of Al and 1% by weight of Mg.
  • the degree of wetting and the zinc adhesion were likewise examined in each case on the samples V1 - V6 coated in this way.
  • the experimental parameters and results of these experiments are listed in Table 6. It turns out that due to the lower manganese contents of the steels VS1 and VS2 do not form MnO structure in the mixed oxidation layer on the surface of the steel substrate. As a result, no opaque Fe (Mn) 2 layer is formed as a primer.

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Claims (12)

  1. Procédé de revêtement par immersion à chaud d'un produit plat en acier avec du zinc ou un alliage de zinc, ledit produit plat en acier se composant de (en % en poids) C : ≤ 1,6 %, Mn : 2 - 35 %, Al : ≤ 10 %, Ni ≤ 10 %, Cr ≤ 10 %, Si : ≤ 10 %, Cu : ≤ 3 %, Nb : ≤ 0,6 %, Ti : ≤ 0,3 %, V : ≤ 0,3 %, P : ≤ 0,1 %, B : ≤ 0,01 %, Mo : ≤ 0,3 %, N : ≤ 1,0 %, le reste étant du fer et des impuretés inévitables, , ce procédé comportant les étapes de travail suivantes :
    a) mise à disposition du produit plat en acier ;
    b) recuit du produit plat en acier
    - à une température de recuit Tg comprise entre 600 - 1 100 °C,
    - pendant une durée de recuit de 10 - 240 s sous une atmosphère de recuit à effet réducteur par rapport au FeO étant présent sur le produit plat en acier et à effet oxydant par rapport au Mn contenu dans le substrat en acier, cette atmosphère de recuit contenant 0,01 - 85 % en volume de H2, H2O, et le reste étant du N2 ainsi que des impuretés techniquement inévitables, et présentant un point de rosée entre -70 °C et +60 °C, où s'applique pour le rapport H2O/H2 : 8 ⁢ x 10 − 15 * Tg 3,529 < H 2 O / H 2 ≤ 0,957 ,
    Figure imgb0003
    c) refroidissement du produit plat en acier recuit à une température d'entrée en bain ;
    d) passage du produit plat en acier refroidi à la température d'entrée en bain en un temps d'immersion de 0,1 - 10 s à travers un bain de fusion de Zn chaud à 420 - 520 °C et saturé en fer, de telle manière que le produit plat en acier soit revêtu par immersion à chaud d'un revêtement protecteur en Zn anti-corrosion, le bain de fusion de Zn étant composé du constituant principal zinc et d'impuretés inévitables, ainsi que de 0,05 - 8 % en poids de Al et/ou jusqu'à 8 % en poids de Mg ainsi qu'optionnellement de 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 % ;
    e) refroidissement du produit plat en acier pourvu d'un revêtement en Zn sortant du bain de fusion.
  2. Procédé selon la revendication 1, caractérisé en ce que le produit plat en acier est mis à disposition en tant que bande d'acier laminée à froid.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'une étape de recuit précède le recuit (étape de travail b)), lors de laquelle le produit plat en acier est maintenu à une température de recuit de 200 - 1 100 °C pour une durée de recuit de 0,1 - 60 s sous une atmosphère oxydante pour Fe et Mn, laquelle atmosphère contenant 0,0001 - 5 % en volume de H2, ainsi qu'optionnellement 200 à 5 500 ppm en volume de O2 et possédant un point de rosée se situant dans une plage de -60 °C à +60 °C.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le temps d'immersion dans le bain de fusion de Zn est 0,1 - 5 s.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain de fusion en Zn contient respectivement aussi bien Al que Mg.
  6. Procédé selon la revendication 5, caractérisé en ce que la teneur en Al est respectivement inférieure à la teneur en Mg du bain de fusion.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la température du produit plat en acier lors de l'entrée dans le bain de fusion est 360 - 710 °C.
  8. Produit plat en acier avec un substrat en acier qui se compose de (en % en poids) C : ≤ 1,6 %, Mn : 2 - 35 %, Al : ≤ 10 %, Ni ≤ 10 %, Cr ≤ 10 %, Si : ≤ 10 %, Cu : ≤ 3 %, Nb : ≤ 0,6 %, Ti : ≤ 0,3 %, V : ≤ 0,3 %, P : ≤ 0,1 %, B : ≤ 0,01 %, Mo : ≤ 0,3 %, N : ≤ 1,0 %, le reste étant du fer et des impuretés inévitables, et avec un revêtement protecteur en Zn anti-corrosion, formé de zinc ou d'un alliage de zinc, caractérisé en ce que le revêtement protecteur en Zn présente une couche d'oxyde mélangé de Mn, se composant de MnO Femetall, adhérant sur le produit plat en acier et le recouvrant essentiellement, et une couche en Zn protégeant le produit plat en acier et la couche d'oxyde mélangé de Mn y adhérant par rapport à l'environnement.
  9. Produit plat en acier selon la revendication 8, caractérisé en ce que le revêtement protecteur en Zn comporte une couche de Fe (Mn)2Al5 agencée entre la couche en MnO Femetall et la couche de Zn.
  10. Produit plat en acier selon l'une des revendications 8 ou 9, caractérisé en ce que le revêtement protecteur en Zn comporte une couche en FeMnZn se situant entre la couche de MnO Femetall et la couche de Zn.
  11. Produit plat en acier selon l'une des revendications 8 à 10, caractérisé en ce que le revêtement protecteur en Zn est conçu en tant que revêtement d'alliage en ZnMg.
  12. Produit plat en acier selon l'une des revendications 8 à 11, caractérisé en ce qu'il est fabriqué conformément au procédé selon l'une des revendications 1 à 7.
EP10717595.2A 2009-04-23 2010-04-22 Procédé de revêtement par immersion à chaud d'un produit plat en acier contenant de 2 à 35 % en masse de mn, ainsi que produit plat en acier Active EP2432910B2 (fr)

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DE102009018577A DE102009018577B3 (de) 2009-04-23 2009-04-23 Verfahren zum Schmelztauchbeschichten eines 2-35 Gew.-% Mn enthaltenden Stahlflachprodukts und Stahlflachprodukt
PCT/EP2010/055334 WO2010122097A1 (fr) 2009-04-23 2010-04-22 Procédé de revêtement par immersion à chaud d'un produit plat en acier contenant de 2 à 35 % en masse de mn, ainsi que produit plat en acier

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DE102017201697A1 (de) 2017-02-02 2018-08-02 Thyssenkrupp Ag Halbzeug, Verwendung und Verfahren zur Herstellung einer stoffschlüssigen Verbindung
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DE102019108457B4 (de) * 2019-04-01 2021-02-04 Salzgitter Flachstahl Gmbh Verfahren zur Herstellung eines Stahlbandes mit verbesserter Haftung metallischer Schmelztauchüberzüge
US11149327B2 (en) * 2019-05-24 2021-10-19 voestalpine Automotive Components Cartersville Inc. Method and device for heating a steel blank for hardening purposes
EP4092142A1 (fr) * 2019-06-03 2022-11-23 ThyssenKrupp Steel Europe AG Procédé de fabrication d'un composant en tôle à partir d'un produit plat en acier pourvu d'un revêtement anticorrosion
CN113699475A (zh) * 2021-09-01 2021-11-26 四川振鸿钢制品有限公司 一种钢材的热浸镀锌方法
CN115058675A (zh) * 2022-07-15 2022-09-16 攀钢集团攀枝花钢铁研究院有限公司 一种改善热浸镀高强钢镀层质量的方法

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US20120125491A1 (en) 2012-05-24
BRPI1016179B1 (pt) 2020-04-07
JP5834002B2 (ja) 2015-12-16
DE102009018577B3 (de) 2010-07-29
ES2717878T3 (es) 2019-06-26
PL2432910T3 (pl) 2019-07-31
CN102421928A (zh) 2012-04-18
AU2016200172B2 (en) 2017-08-03
CN102421928B (zh) 2015-10-21
AU2010240903A1 (en) 2011-11-10
US9611527B2 (en) 2017-04-04
KR20120025476A (ko) 2012-03-15
JP2012524839A (ja) 2012-10-18
CA2759369C (fr) 2017-02-07
BRPI1016179A2 (pt) 2016-04-19
CA2759369A1 (fr) 2010-10-28
EP2432910B2 (fr) 2022-08-03
EP2432910A1 (fr) 2012-03-28
KR101679006B1 (ko) 2016-11-24
AU2016200172A1 (en) 2016-01-28
WO2010122097A1 (fr) 2010-10-28
TR201906585T4 (tr) 2019-05-21

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