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EP2432910B2 - 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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EP2432910B2
EP2432910B2 EP10717595.2A EP10717595A EP2432910B2 EP 2432910 B2 EP2432910 B2 EP 2432910B2 EP 10717595 A EP10717595 A EP 10717595A EP 2432910 B2 EP2432910 B2 EP 2432910B2
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Prior art keywords
flat steel
steel product
annealing
layer
flat
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English (en)
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EP2432910B1 (fr
EP2432910A1 (fr
Inventor
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 method for hot-dip coating a flat steel product containing 6-35% by weight of Mn with zinc or a zinc alloy, and a flat steel product provided with a zinc or zinc alloy coating.
  • Typical alloying elements are manganese, chromium, silicon, aluminum and others, which form stable, non-reducible oxides on the surface with conventional recrystallizing annealing. These oxides can prevent reactive wetting with a molten zinc.
  • Steels with a high manganese content are particularly suitable for use in vehicle construction due to their favorable combination of properties, consisting of high strengths of up to 1,400 MPa on the one hand and extremely high elongations (uniform elongation up to 70% and elongation at break up to 90%) on the other , especially in the automotive industry.
  • Steels with high Mn contents of 6% by weight to 30% by weight that are particularly suitable for this purpose are, for example, from DE 102 59 230 A1 , the DE 197 27 759 C2 or the DE 199 00 199 A1 known.
  • Flat products made from the known steels exhibit isotropic deformation behavior with high strength and are also still ductile even at low temperatures.
  • the reason for these poor adhesion properties was determined to be the thick oxide layer that develops during the annealing process that is essential for hot-dip coating.
  • the sheet metal surfaces oxidized in this way can no longer be wetted with the coating metal with the required uniformity and completeness, so that the goal of comprehensive corrosion protection is not achieved.
  • WO 2006/042931 A1 Another method for coating a high-manganese steel strip containing 0.35-1.05% by weight C, 16-25% by weight Mn, the remainder iron and unavoidable impurities is known from WO 2006/042931 A1 known.
  • the steel strip composed in this way is first cold-rolled and then recrystallized annealed in an atmosphere which has a reducing effect on iron.
  • the annealing parameters are selected in such a way that an intermediate layer is formed on both sides of the steel strip, which essentially consists entirely of amorphous (FeMn) oxide, and an additional outer layer is formed, which consists of crystalline Mn oxide, with the thickness of the both layers is at least 0.5 ⁇ m. Hot-dip coating then no longer takes place. Rather, the Mn oxide layer in combination with the (FeMn) oxide layer should offer adequate protection against corrosion.
  • This specification is based on the knowledge that by suitably setting the annealing atmosphere, namely its hydrogen content in relation to its dew point, a surface quality of the steel strip to be coated is achieved during annealing that ensures optimal adhesion of the metallic protective coating subsequently applied by hot-dip coating .
  • the annealing atmosphere set in this way has a reducing effect on both the iron and the manganese in the steel strip.
  • the aim is to avoid the formation of an oxide layer that would impair the adhesion of the fused coating to the high-manganese steel substrate.
  • the object of the invention was to provide a method that allows flat steel products containing high levels of Mn to be provided with a zinc coating that protects against corrosion and in which further improved adhesion of the coating on the steel substrate is ensured.
  • a steel flat product was to be created in which the Zn coating formed from zinc or a zinc alloy adheres securely to the steel substrate even under high degrees of deformation.
  • this object is achieved according to the invention in that the work steps specified in claim 1 are carried out during the hot-dip coating of a flat steel product having a high Mn content.
  • a flat steel product in the form of a steel strip or sheet steel is first provided in a continuous process sequence for the hot-dip coating of a flat steel product containing 6-35% by weight of Mn.
  • the coating procedure according to the invention is particularly suitable for steel strips that are highly alloyed in order to ensure high strength and good elongation properties.
  • Steel strips which are provided with a metallic protective coating by hot-dip coating in the manner according to the invention contain (in % by weight) C: ⁇ 1.6%, Mn: 6-35%, 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.
  • the effects achieved by the invention are effective in the coating of high-alloy steel strips which contain manganese contents of at least 6% by weight. It is thus evident that a steel base material which (in % by weight) C: ⁇ 1.00%, Mn: 20.0 - 30.0%, Al: ⁇ 0.5%, Si: ⁇ 0.5% , B: ⁇ 0.01%, Ni: ⁇ 3.0%, Cr: ⁇ 10.0%, Cu: ⁇ 3.0%, N: ⁇ 0.6%, Nb: ⁇ 0.3%, Ti : ⁇ 0.3%, V: ⁇ 0.3%, P: ⁇ 0.1%, the remainder containing iron and unavoidable impurities, can be coated particularly well with a coating that protects against corrosion.
  • a steel is used as the base material which (in % by weight) C: ⁇ 1.00%, Mn: 7.00 - 30.00%, Al: 1.00 - 10.00%, Si : > 2.50 - 8.00% (whereby 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% , balance 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 flat products made available in this way are annealed in a work step b).
  • the glow temperature Tg is 600 - 1100 °C, while the annealing time, over which the steel flat product is kept at the annealing temperature, is 10 - 240 s.
  • the annealing temperature Tg and annealing duration mentioned above has a reducing effect on iron oxide FeO present on the steel flat product and an oxidizing effect on the manganese contained in the steel substrate.
  • the annealing atmosphere contains 0.01 - 85 vol 2 O/H 2 ratio applies: 8th ⁇ 10 ⁇ 15 ⁇ day 3,529 ⁇ H 2 O / H 2 ⁇ 0.957
  • the H 2 O/H 2 ratio is to be set such that it is greater than 8 ⁇ 10 -15 *Tg 3.529 and at most 0.957, with Tg denoting the respective annealing temperature.
  • the dew point of the atmosphere is in the range from -50°C to +60°C.
  • the annealing atmosphere in this case typically contains 0.1-85% by volume of H 2 .
  • a particularly economical mode of operation of the continuous furnace used for annealing according to the invention can be achieved by keeping the dew point of the atmosphere at -20.degree. C. to +20.degree.
  • the Mn mixed oxide layer is defined as MnO ⁇ Fe metal . This means that metallic iron is present in this Mn mixed oxide layer and not oxidized iron, as is the case in the prior art.
  • an Mn mixed oxide layer is set in a targeted manner via at least one annealing stage, in that the annealing (step b)) is carried out under an atmosphere that reduces FeO and an atmosphere that oxidizes Mn.
  • the layer of Mn mixed oxides produced according to the invention on the steel substrate forms an adhesion base to which the subsequently applied zinc layer surprisingly adheres particularly securely.
  • the Mn mixed oxide layer is largely retained during the hot-dip coating process, so that it also ensures the permanent cohesion of the Zn coating and steel substrate in the finished product.
  • the flat steel product which has been cooled to the bath inlet temperature, is then passed through an iron-saturated, 420 - 520 °C hot Zn molten bath within an immersion time of 0.1 - 10 seconds, in particular 0.1 - 5 s, which consists of the main component zinc and zinc unavoidable impurities and 0.05-8% by weight Al and/up to 8% by weight Mg, in particular 0.05-5% by weight Al and up to 5% by weight Mg.
  • the molten 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 in order to determine certain properties of the coating in a manner known per se set.
  • the flat steel product obtained in this way which is hot-dip coated with a Zn protective coating to protect against corrosion, is finally cooled, it being possible for the thickness of the coating to be adjusted in a manner known per se before cooling.
  • the Zn coating according to the invention necessarily contains Al contents of 0.05-8% by weight and additional contents of up to 8% by weight Mg, with the upper limit of the contents of both elements being typically limited to a maximum of 5% by weight in practice. % is limited.
  • a flat steel product according to the invention with an Mn content of 6-35% by weight and a Zn protective coating that protects against corrosion is accordingly characterized in that the Zn protective coating has a Mn mixed oxide layer that essentially covers and adheres to the flat steel product, in which metallic Iron is present, and has a Zn layer that shields the flat steel product and the Mn mixed oxide layer adhering to it from 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 occurs when there is a sufficient quantity of aluminum of 0.05 - 5% by weight Al in the molten bath.
  • the Fe (Mn) 2 Al 5 layer forms a barrier layer through which the reduction of the Mn mixed oxide layer melt dipping is reliably prevented.
  • the barrier layer can transform into FeZn phases, with the Mn oxide layer nevertheless being retained.
  • the MnO layer and the Fe(Mn) 2 Al 5 layer of a coating produced and configured according to the invention thus ensure, even after hot-dip coating, that the outer Zn layer adheres firmly to the steel substrate with high degrees of deformation.
  • the presence of a Mn mixed oxide layer on the surface of the steel substrate according to the invention not only has a positive effect if the Fe(Mn) 2 Al 5 layer is also formed, but also if magnesium is used as an alternative or in addition to aluminum in the molten bath is present in effective levels. Even when a ZnMg coating layer is produced on the steel substrate, the MnO layer produced according to the invention ensures particularly good and uniform wetting of the steel flat product with optimum adhesion and minimized risk of cracking or flaking even with high degrees of deformation.
  • a particularly practical embodiment of the invention results in this connection when the following applies to the ratio of the Al content %Al and the Mg content %Mg: %Al/%Mg ⁇ 1.
  • the Al content is therefore of the melt bath is always smaller than its Mg content.
  • Magnesium is characterized by a higher reduction potential to MnO than aluminum. Therefore, when higher Mg contents are present in the melted layer, there is a forced dissolution of the MnO structure of the mixed oxide layer.
  • the mixed oxide is dissolved to a greater extent, more metallic iron “Fe metal " from the "depth” of the mixed oxide layer is effectively available at the mixed oxide layer/zinc bath reaction front, so that the covering Fe(Mn) 2 Al 5 boundary layer is particularly effective as an adhesion promoter can train. Accordingly, the MnO reduction by dissolved magnesium in situ contributes with a particularly high degree of effectiveness to the boundary layer formation that is aimed at according to the invention and ensures particularly good adhesion of the Zn coating.
  • the annealing step (work step b)) carried out in preparation for the hot-dip coating in the context of the process according to the invention can be carried out in one or more stages. If the annealing is carried out in one stage, different hydrogen contents are possible in the annealing atmosphere depending on the dew point. If the dew point is in the range from -50 °C to +20 °C, the annealing atmosphere can 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. Taking into account the other parameters to be taken into account during the implementation of the annealing step according to the invention, the reducing effect on the FeO that may be present and the oxidizing effect on the Mn present in the steel substrate are thus reliably achieved.
  • an additional annealing step can be carried out before the annealing step (work step b) of claim 1) carried out according to the invention, in which the flat steel product is heated to an annealing temperature of 200 - 1100 °C is maintained for an annealing period of 0.1-60 s under an atmosphere oxidative for both Fe and Mn, containing 0.0001-5 vol.% H 2 and optionally 200-5500 vol.ppm O 2 and a has a dew point 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 from -50 °C to +20 °C in an atmosphere containing 0.01-85% hydrogen, taking into account the other parameters to be taken into account when carrying out the annealing step according to the invention, before the steel flat product into the melt bath.
  • Optimum adhesion properties of the Zn coating are achieved with a coating produced according to the invention when the thickness of the Mn mixed oxide layer obtained after annealing (step b)) is 40-400 nm, in particular up to 200 nm.
  • a cold-rolled steel strip has been produced in a known manner from a high-manganese steel having the composition given in Table 1.
  • Table 1 C Mn P si v Al Cr Ti Nb 0.634 22.2 0.02 0.18 0.2 0.01 0.08 0.001 0.001 Rest iron and unavoidable impurities, data in % by weight
  • a first sample of the cold-rolled steel strip was then annealed in a single-stage annealing process.
  • the steel strip sample was heated at a heating rate of 10 K/s to an annealing temperature Tg of 800° C., at which the sample was then held for 30 seconds.
  • the annealing took place under an annealing atmosphere which consisted of 5% by volume H 2 and 95% by volume N 2 and whose dew point was +25°C.
  • the annealed steel strip was then cooled at a cooling rate of 20 K/s to a bath inlet temperature of 480° C., at which point it was initially subjected to an overaging treatment for 20 seconds.
  • the overaging treatment took place under the unchanged annealing atmosphere.
  • the steel strip was then fed into a 460 °C hot, Fe-saturated molten zinc bath which, in addition to Zn, unavoidable impurities and Fe, also contained 0.23% by weight Al. After an immersion time of 2 seconds, the steel strip, which is now hot-dip coated, was removed from 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 .
  • Her dew point was -30 °C.
  • the steel strip was heated in a second annealing step to an annealing temperature Tg of 800 °C, at which it was held for 30 seconds under an annealing atmosphere containing 5 vol -30 °C.
  • the steel strip was then cooled to 480° C. under the annealing atmosphere at a cooling temperature of approx. 20 K/s and subjected to an overaging treatment for 20 seconds.
  • the steel strip was then fed with a bath inlet temperature of 480 °C into a 460 °C hot melt bath saturated with Fe, which in turn contained 0.23% by weight Al and other elements in ineffective traces of impurities and the remainder zinc.
  • the finished hot-dip coated flat steel product was then removed from the melt bath and cooled to room temperature.
  • Mn mixed oxide layer M 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 Zn is significantly thicker at 3 - 20 ⁇ m.
  • the influence of the dew point of the respective annealing atmosphere on the coating result was examined.
  • the samples were each subjected to an annealing process in which they were also heated to an annealing temperature Tg of 800 °C at a heating rate of 10 K/s.
  • Tg annealing temperature
  • the sample was then held at this annealing temperature for 60 seconds.
  • the annealing took place in each case under an annealing atmosphere that consisted of 5% by volume H 2 and 95% by volume N 2 , the respective dew point of the annealing atmosphere being varied between ⁇ 55° C. and +45° C.
  • 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 test series described above, at which point it was initially subjected to an overaging treatment for 20 seconds.
  • the overaging treatment took place under the unchanged annealing atmosphere.
  • the steel strip was then fed into a 460 °C hot, Fe-saturated molten zinc bath which, in addition to Zn, unavoidable impurities and Fe, also contained a combination of 0.4% by weight Al and 1.0 wt% Mg or alone 0.14 wt%, 0.17 wt% or 0.23 wt% Al.
  • the steel strip, which is now hot-dip coated was removed from the molten bath and cooled to room temperature.
  • 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.
  • the comparative samples C1-C6 were also heat-treated in the manner described above for the samples according to the invention before they were hot-dip coated in the melt bath.
  • the molten bath contained 0.4% by weight Al and 1% by weight Mg in each case.
  • the degree of wetting and the zinc adhesion were also examined on samples C1-C6 coated in this way.
  • the test parameters and results of these tests are listed in Table 6. It turns out that due to the lower manganese content of steels VS1 and VS2, no MnO structure forms in the mixed oxidation layer on the surface of the steel substrate. As a result, no covering Fe(Mn) 2 layer is formed as an adhesion promoter.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Claims (11)

  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 : 6 - 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 0C,
    - 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 -50 0C et +60 0C, où s'applique pour le rapport H2O/H2 : 8 × 10 − 15 * Tg 3,529 < H 2 O / H 2 ≤ 0,957 ,
    Figure imgb0004
    - de sorte qu'une couche d'oxyde mixte de Mn de 20 à 400 nm d'épaisseur, se forme sur le produit plat en acier, recouvrant le produit plat en acier au moins par sections;
    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 0C 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 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 0C 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 0C à +60 0C.
  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 la revendication 1, caractérisé en ce que la teneur en Al est respectivement inférieure à la teneur en Mg du bain de fusion.
  6. 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 0C.
  7. Produit plat en acier avec un substrat en acier qui se compose de (en % en poids) C : ≤ 1,6 %, Mn : 6 - 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.
  8. Produit plat en acier selon la revendication 7, 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.
  9. Produit plat en acier selon l'une des revendications 7 ou 8, 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.
  10. Produit plat en acier selon l'une des revendications 7 à 9, caractérisé en ce que le revêtement protecteur en Zn est conçu en tant que revêtement d'alliage en ZnMg.
  11. Produit plat en acier selon l'une des revendications 7 à 10, caractérisé en ce qu'il est fabriqué conformément au procédé selon l'une des revendications 1 à 6.
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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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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TR201906585T4 (tr) 2019-05-21
CA2759369A1 (fr) 2010-10-28
PL2432910T3 (pl) 2019-07-31
KR101679006B1 (ko) 2016-11-24
JP2012524839A (ja) 2012-10-18
EP2432910B1 (fr) 2019-02-13
BRPI1016179B1 (pt) 2020-04-07
BRPI1016179A2 (pt) 2016-04-19
AU2016200172B2 (en) 2017-08-03
US20120125491A1 (en) 2012-05-24
ES2717878T3 (es) 2019-06-26
EP2432910A1 (fr) 2012-03-28
WO2010122097A1 (fr) 2010-10-28
DE102009018577B3 (de) 2010-07-29
AU2016200172A1 (en) 2016-01-28
JP5834002B2 (ja) 2015-12-16
US9611527B2 (en) 2017-04-04
AU2010240903A1 (en) 2011-11-10
CA2759369C (fr) 2017-02-07
KR20120025476A (ko) 2012-03-15
CN102421928B (zh) 2015-10-21
CN102421928A (zh) 2012-04-18

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