EP1805341B1 - Procédé de revêtement au trempé à chaud dans un bain de zinc des bandes en acier fer-carbone-manganèse - Google Patents

Procédé de revêtement au trempé à chaud dans un bain de zinc des bandes en acier fer-carbone-manganèse Download PDF

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EP1805341B1
EP1805341B1 EP05809221A EP05809221A EP1805341B1 EP 1805341 B1 EP1805341 B1 EP 1805341B1 EP 05809221 A EP05809221 A EP 05809221A EP 05809221 A EP05809221 A EP 05809221A EP 1805341 B1 EP1805341 B1 EP 1805341B1
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Prior art keywords
iron
manganese
zinc
strip
layer
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German (de)
English (en)
French (fr)
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EP1805341A1 (fr
Inventor
Pascal Drillet
Daniel Bouleau
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ArcelorMittal France SA
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ArcelorMittal France SA
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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
    • 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
    • C23C2/34—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/939—Molten or fused coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to a method of hot dip coating in a zinc-based liquid bath comprising aluminum, a strip of austenitic iron-carbon-manganese steel in scrolling.
  • the steel belts conventionally used in the automotive field such as for example the dual-phase steel belts, are coated with a zinc-based coating to protect them against corrosion before they are shaped or delivered.
  • This zinc layer is generally applied continuously either by electrodeposition in an electrolytic bath containing zinc salts, or by vacuum deposition, or by hot quenching of the high speed band in a bath of molten zinc.
  • the steel strips Before being coated with a zinc layer by hot dipping in a zinc bath, the steel strips undergo a recrystallization annealing in a reducing atmosphere in order to give the steel a homogeneous microstructure and to improve its properties. mechanical characteristics. Under industrial conditions, this recrystallization annealing is carried out in an oven in which there is a reducing atmosphere.
  • the strips run in the oven consisting of an enclosure completely isolated from the outside atmosphere, comprising three zones, a first heating zone, a second temperature holding zone, and a third cooling zone, in which there is an atmosphere composed of a reducing gas with respect to iron.
  • This gas may be chosen for example from hydrogen, and mixtures of nitrogen and hydrogen, and has a dew point between -40 ° C and -15 ° C.
  • JP-A-07278772 discloses the manufacture of a manganese-containing galvanized steel strip of hot dipping the steel strip in a zinc-based liquid bath comprising specific Al and min contents.
  • the present invention therefore aims to provide a method for coating by hot dipping in a zinc-based liquid bath, an iron-carbon-manganese steel strip running through a coating based on zinc.
  • the invention also relates to the austenitic iron-carbon-manganese steel strip coated with a zinc-based coating obtainable by this method.
  • the inventors have thus demonstrated that by creating favorable conditions for the bi-layer of mixed oxide (Fe, Mn) O and of manganese oxide forming on the surface of the iron-carbon steel strip.
  • manganese being reduced by the aluminum contained in the zinc-based liquid bath, the surface of the strip became wetting with respect to the zinc, which allowed to coat it with a coating based on zinc.
  • This steel strip is typically between 0.2 and 6 mm, and may be issued from either the hot band or the cold band train.
  • the austenitic iron-carbon-manganese steel used according to the invention comprises, in% by weight: 0.30% ⁇ C ⁇ 1.05%, 16% ⁇ Mn ⁇ 26%, Si ⁇ 1%, Al ⁇ 0.050%, S ⁇ 0.030%, P ⁇ 0.080%, N ⁇ 0.1%, and optionally, one or more elements such as: Cr ⁇ 1%, Mo ⁇ 0.40%, Ni ⁇ 1%, Cu ⁇ 5%, Ti ⁇ 0.50%, Nb ⁇ 0.50%, V ⁇ 0.50%, the remainder of the composition consisting of iron and unavoidable impurities resulting from the preparation.
  • the carbon content is between 0.40 and 0.70% by weight.
  • the carbon content is between 0.40% and 0.70%, the stability of the austenite is increased and the strength is increased.
  • the manganese content in the steel according to the invention is between 20 and 25% by weight.
  • Silicon is an effective element for deoxidizing steel as well as for hardening in the solid phase. However, beyond a content of 1%, Mn 2 SiO 4 and SiO 2 layers are formed on the surface of the steel, which show a reduction ability of the aluminum contained in the water-based bath. zinc significantly lower than the mixed oxide (Fe, Mn) O and manganese oxide MnO layers.
  • the silicon content in the steel is less than 0.5% by weight.
  • Aluminum is also a particularly effective element for the deoxidation of steel. Like carbon, it increases the stacking fault energy. However, its excessive presence in steels with a high manganese content has a disadvantage: In fact, manganese increases the solubility of nitrogen in the liquid iron, and if too much aluminum is present in the steel, Nitrogen combined with aluminum precipitates in the form of aluminum nitrides hindering the migration of grain boundaries during hot processing and greatly increases the risk of crack appearances. An Al content less than or equal to 0.050% makes it possible to avoid a precipitation of AlN. Correlatively, the nitrogen content must be less than or equal to 0.1% in order to prevent this precipitation and the formation of volume defects (blowholes) during solidification.
  • oxides such as MnAl 2 O 4 , MnO.Al 2 O 3, which are more difficult to reduce, are formed during the recrystallization annealing of the steel.
  • aluminum contained in the zinc-based coating bath as oxides (Fe, Mn) O and MnO.
  • oxides (Fe, Mn) O and MnO are much more stable than oxides (Fe, Mn) O and MnO. Therefore, even if it is possible to form on the surface of the steel a zinc-based coating, it will in any case little adherent because of the presence of alumina.
  • it is essential that the aluminum content in the steel is less than 0.050% by weight.
  • Sulfur and phosphorus are impurities that weaken the grain boundaries. Their respective content must be less than or equal to 0.030 and 0.080% in order to maintain sufficient hot ductility.
  • Chromium and nickel can be used as an option to increase the strength of the steel by hardening in solid solution.
  • chromium decreases the stacking fault energy, its content must be less than or equal to 1%.
  • Nickel contributes to a significant elongation rupture, and in particular increases the toughness.
  • the molybdenum may be added in an amount less than or equal to 0.40%.
  • addition of copper to a content of less than or equal to 5% is a means of hardening the steel by precipitation of metallic copper. However, beyond this content, copper is responsible for the appearance of surface defects hot sheet.
  • Titanium, niobium and vanadium are also elements that can optionally be used to obtain precipitation hardening of carbonitrides.
  • Nb or V, or Ti content is greater than 0.50%, excessive precipitation of carbonitrides can cause a reduction in toughness, which should be avoided.
  • the austenitic iron-carbon-manganese steel strip undergoes heat treatment to recrystallize the steel.
  • the recrystallization annealing makes it possible to give the steel a homogeneous microstructure, to improve its mechanical characteristics, and in particular to give it ductility to allow its use in stamping.
  • This heat treatment is performed in an oven inside which there is an atmosphere composed of a reducing gas vis-à-vis the iron, to avoid excessive oxidation of the surface of the strip, and allow good adhesion of zinc.
  • This gas is selected from hydrogen, and nitrogen-hydrogen mixtures.
  • the gaseous mixtures comprising between 20 and 97% by volume of nitrogen and between 3 and 80% by volume of hydrogen, and more preferably between 85 and 95% by volume of nitrogen and between 5 and 15%, are chosen. in volume of hydrogen.
  • hydrogen is an excellent iron reducing agent, it is preferred to limit its concentration because of its high cost relative to nitrogen.
  • calamine is a layer of iron oxide comprising a small proportion of manganese. Gold not only this calamine layer prevents any adhesion of zinc on steel, but also it is a layer that tends to crack easily which makes it all the more undesirable.
  • the atmosphere prevailing in the furnace is certainly reducing with respect to iron, but not for elements such as manganese.
  • the gas constituting the atmosphere in the furnace comprises traces of moisture and / or oxygen that can not be avoided, but it is possible to control by imposing the dew point of said gas.
  • the inventors have observed that, according to the invention, at the end of the recrystallization annealing, the lower the dew point in the oven, or in other words the lower the oxygen partial pressure, the lower the The manganese oxide formed on the surface of the iron-carbon-manganese steel strip is thin. This observation may seem at odds with Wagner's theory that the lower the dew point, the higher the density of oxides formed on the surface of a carbon steel strip. Indeed, when the amount of oxygen decreases on the surface of the carbon steel, the migration of the oxidizable elements contained in the steel to the surface accelerates, which promotes the oxidation of the surface.
  • the inventors believe that in the case of the invention, the amorphous oxide layer (Fe, Mn) O becomes rapidly continuous. It therefore constitutes a barrier for the oxygen of the atmosphere in the furnace, which is no longer in direct contact with the steel. An increase in the oxygen partial pressure in the furnace therefore leads to an increase in the thickness of the manganese oxide and does not cause internal oxidation, ie no layer is observed. additional oxide between the surface of the austenitic iron-carbon-manganese steel and the amorphous oxide layer (Fe, Mn) O.
  • the recrystallization annealing carried out under the conditions of the invention thus makes it possible to form on both sides of the strip a continuous sub-layer of mixed oxide of iron and manganese (Fe, Mn) O amorphous, the thickness of which is preferably between 5 and 10 nm, and a continuous or discontinuous outer layer of crystalline MnO manganese oxide whose thickness is preferably between 5 and 90 nm, preferably between 5 and 50 nm, and more preferably between 10 and 40 nm.
  • the MnO outer layer has a granular appearance, and the size of the MnO crystals increases sharply as the dew point also increases.
  • the inventors have demonstrated that, when the content by weight of aluminum in the zinc-based liquid bath is less than 0.18% and when the manganese oxide layer MnO is greater than 100 nm, the latter It is not reduced by the aluminum contained in the bath, and the zinc-based coating is not obtained due to the non-wetting effect of MnO with respect to the zinc.
  • the dew point according to the invention at least in the zone for maintaining the temperature of the oven, and preferably in the entire enclosure of the oven, is preferably between -80 and 20 ° C, advantageously between - 80 and -40 ° C and more preferably between -60 and -40 ° C.
  • the thickness of the manganese oxide layer becomes too great to be reduced by the aluminum contained in the zinc-based liquid bath under industrial conditions, that is to say during a period of time. time less than 10 seconds.
  • the range -60 to -40 ° C is advantageous because it allows to form a bi-oxide layer of relatively reduced thickness which will be easily reduced by the aluminum contained in the zinc-based bath.
  • the heat treatment comprises a heating phase at a heating rate V1, a holding phase at a temperature T1 and during a holding time M, followed by a cooling phase at a cooling rate V2.
  • the heat treatment is preferably carried out at a heating rate V1 greater than or equal to 6 ° C / s, because below this value the holding time M of the strip in the oven is too long and does not correspond to the industrial requirements. of productivity.
  • the temperature T1 is preferably between 600 and 900 ° C. Indeed, below 600 ° C, the steel will not be completely recrystallized and its mechanical characteristics will be insufficient. Beyond 900 ° C, not only the grain size of the steel increases which is harmful for obtaining good mechanical characteristics, but also the thickness of the manganese oxide layer MnO strongly increases and makes difficult, if not impossible, the subsequent deposition of a coating based on zinc, because the aluminum contained in the bath will not have completely reduced the MnO.
  • T1 is preferably between 600 and 820 ° C., advantageously less than or equal to 750 ° C, and more preferably between 650 and 750 ° C.
  • the holding time M is preferably between 20 s and 60 s, and advantageously between 20 and 40 s.
  • the recrystallization annealing is generally carried out by a radiant tube heater.
  • the strip is cooled to an immersion temperature of the T3 band between (T2 - 10 ° C) and (T2 + 30 ° C), T2 being defined as the temperature of the liquid bath based on zinc.
  • T3 an immersion temperature of the T3 band between (T2 - 10 ° C) and (T2 + 30 ° C)
  • T2 being defined as the temperature of the liquid bath based on zinc.
  • the strip is preferably cooled at a cooling rate V2 of greater than or equal to 3 ° C./s, advantageously greater than 10 ° C./s, so as to avoid the enlargement of the grains and to obtain a steel strip having good mechanical characteristics.
  • V2 a cooling rate of greater than or equal to 3 ° C./s, advantageously greater than 10 ° C./s, so as to avoid the enlargement of the grains and to obtain a steel strip having good mechanical characteristics.
  • the strip is generally cooled by injection of an air flow on both sides.
  • the austenitic iron-carbon-manganese steel strip When, after undergoing recrystallization annealing, the austenitic iron-carbon-manganese steel strip is covered on both sides by the two-layer oxide, it is passed through the zinc-based liquid bath containing 'aluminum.
  • the aluminum contained in the zinc bath contributes not only to the at least partial reduction of the two-layer oxide, but also to obtaining a coating having a homogeneous surface appearance.
  • a homogeneous surface appearance is characterized by a uniform thickness, whereas a heterogeneous appearance is characterized by strong thickness heterogeneities.
  • Fe 2 Al 5 and / or FeAl 3 inter-facial layer is not formed on the surface of iron-carbon-manganese steel, or if it is formed, it is immediately destroyed by the formation of the phases (Fe, Mn) Zn.
  • matts of Fe 2 Al 5 and / or FeAl 3 type are found in the bath.
  • the aluminum content in the bath is adjusted to a value at least equal to the content necessary for the aluminum to completely reduce the crystalline MnO manganese oxide layer and at least partially the oxide (Fe, Mn) O layer. amorphous.
  • the weight content of aluminum in the bath is between 0.15 and 5%. Below 0.15%, the aluminum content will be insufficient to completely reduce the manganese oxide layer MnO and at least partially the layer of (Fe, Mn) O, and the surface of the steel strip will not present sufficient wettability with respect to zinc. Above 5% of aluminum in the bath, a coating of a type different from that obtained by the invention will form on the surface of the steel strip. This coating will include an increasing proportion of aluminum as the aluminum content in the bath increases.
  • the zinc-based bath may also contain iron, preferably at a content such that it is supersaturation with respect to Fe 2 Al 5 and / or FeAl 3 .
  • T2 a temperature preferably greater than or equal to 430 ° C, but to avoid excessive evaporation of zinc, T2 is less than or equal to 480 ° C.
  • the strip is in contact with the bath for a contact time C preferably between 2 and 10 seconds, and more preferably between 3 and 5 seconds.
  • the aluminum does not have enough time to completely reduce the MnO layer of manganese oxide and at least partially the mixed oxide layer (Fe, Mn) O, and thus to make the surface of wetting steel vis-à-vis zinc. Above 10 seconds, the two-layer oxides will certainly be completely reduced, however the line speed may be industrially too low, and the coating too alloyed and then difficult to adjust in thickness.
  • a zinc-based coating comprising, in order from the steel / coating interface, a layer of iron-manganese-zinc alloy composed of two cube and cubic phases. with centered face ⁇ 1, a layer of iron-manganese-zinc alloy ⁇ 1 of hexagonal structure, a layer of iron-manganese-zinc alloy ⁇ of monoclinic structure, and a surface layer of zinc.
  • the inventors have thus verified that according to the invention, and contrary to what happens in the case of a coating of a carbon steel strip in a zinc bath containing aluminum, it is not formed. no Fe 2 Al 5 layer at the steel / coating interface.
  • the aluminum of the bath reduces the bi-oxide layer.
  • the MnO layer is more easily reducible by the aluminum of the bath than the oxide layers based on silicon. This results in a local depletion of aluminum which leads to the formation of a coating comprising FeZn phases instead of the expected Fe 2 Al 5 (Zn) coating, which is formed in the case of carbon steels.
  • a strip coated on both sides by a zinc-based coating comprising in order from the steel / coating interface a layer of iron-manganese-zinc alloy composed of two cubic phase ⁇ and cubic to centered face ⁇ 1, an iron-manganese-zinc alloy layer ⁇ 1 of hexagonal structure, and possibly a layer of iron-manganese-zinc alloy ⁇ of monoclinic structure.
  • the alloying heat treatment is preferably carried out directly at the outlet of the zinc bath, at a temperature of between 490 and 540 ° C., for a duration of between 2 and 10 seconds.
  • Table 2 shows the characteristics of the oxide bi-layer comprising an amorphous continuous lower layer (Fe, Mn) O, and an upper layer MnO, formed on the samples after annealing according to the dew point.
  • Table 2 RT -80 ° C PR -45 ° C PR + 10 ° C Surface color the band yellow green blue Mean diameter of the crystals MnO (nm) 50 discontinuous layer 100 continuous layer 300 continuous layer Thickness of the bilayer (nm) 10 110 1500
  • the samples After being recrystallized, the samples are cooled to a temperature T3 of 480 ° C. and are immersed in a zinc bath comprising, by weight, 0.18% of aluminum and 0.02% of iron, the temperature of which T2 is 460 ° C. The samples remain in contact with the bath for a period of contact C of 3 seconds. After immersion, the samples are examined to see if a zinc-based coating is present on the surface of the sample. Table 3 shows the result obtained as a function of the dew point. Table 3 PR-80 ° C PR -45 ° C PR + 10 ° C Presence of zinc-based coating Yes no no no
  • the inventors have demonstrated that if the oxide bilayer formed on the iron-carbon-manganese austenitic steel strip after recrystallization annealing was greater than 110 nm, the presence in the bath of 0.18% by weight of Aluminum was insufficient to reduce the bi-oxide layer and give the strip sufficient wettability of the zinc to the steel to form a zinc-based coating.
  • Table 5 shows the structures of the various oxide films that formed on the surface of the steel after annealing in function.
  • Table 5 Oxide films Steel A * Steel B Undercoat MnAl 2 O 4 (Fe, Mn) O Upper layer MnO.Al 2 O 3 MnO * according to the invention
  • the samples After having been recrystallized, the samples are cooled to a temperature T3 of 480 ° C. and are immersed in a zinc bath comprising 0.18% of aluminum and 0.02% of iron, whose T2 temperature is 460 ° C. vs. The samples remain in contact with the bath for a contact time C of 3 seconds. After immersion, the samples are coated with a zinc coating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Articles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
EP05809221A 2004-10-20 2005-10-10 Procédé de revêtement au trempé à chaud dans un bain de zinc des bandes en acier fer-carbone-manganèse Active EP1805341B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05809221T PL1805341T3 (pl) 2004-10-20 2005-10-10 Sposób pokrywania przez zanurzenie na gorąco w kąpieli na bazie cynku taśm ze stali żelazo-węgiel-mangan

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0411190A FR2876711B1 (fr) 2004-10-20 2004-10-20 Procede de revetement au trempe a chaud dans un bain de zinc des bandes en acier fer-carbone-manganese
PCT/FR2005/002491 WO2006042930A1 (fr) 2004-10-20 2005-10-10 Procédé de revêtement au trempé à chaud dans un bain de zinc des bandes en acier fer-carbone-manganèse

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EP1805341A1 EP1805341A1 (fr) 2007-07-11
EP1805341B1 true EP1805341B1 (fr) 2008-05-07

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US (1) US7556865B2 (zh)
EP (1) EP1805341B1 (zh)
JP (1) JP4828544B2 (zh)
KR (1) KR100911639B1 (zh)
CN (1) CN100554487C (zh)
AT (1) ATE394517T1 (zh)
BR (1) BRPI0516997A (zh)
CA (1) CA2584449C (zh)
DE (1) DE602005006603D1 (zh)
ES (1) ES2306247T3 (zh)
FR (1) FR2876711B1 (zh)
MX (1) MX2007004728A (zh)
PL (1) PL1805341T3 (zh)
RU (1) RU2363756C2 (zh)
WO (1) WO2006042930A1 (zh)
ZA (1) ZA200703345B (zh)

Cited By (2)

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WO2010122097A1 (de) 2009-04-23 2010-10-28 Thyssenkrupp Steel Europe Ag Verfahren zum schmelztauchbeschichten eines 2-35 gew.-% mn enthaltenden stahlflachprodukts und stahlflachprodukt
DE102018128131A1 (de) * 2018-11-09 2020-05-14 Thyssenkrupp Ag Gehärtetes Bauteil umfassend ein Stahlsubstrat und eine Korrosionsschutzbeschichtung, entsprechendes Bauteil zur Herstellung des gehärteten Bauteils sowie Herstellverfahren und Verwendung

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PL1805341T3 (pl) 2008-10-31
FR2876711A1 (fr) 2006-04-21
KR100911639B1 (ko) 2009-08-12
DE602005006603D1 (de) 2008-06-19
MX2007004728A (es) 2007-06-15
BRPI0516997A (pt) 2008-09-30
US20080083477A1 (en) 2008-04-10
EP1805341A1 (fr) 2007-07-11
CA2584449A1 (fr) 2006-04-27
FR2876711B1 (fr) 2006-12-08
RU2007118637A (ru) 2008-11-27
CN101072892A (zh) 2007-11-14
ES2306247T3 (es) 2008-11-01
ZA200703345B (en) 2008-04-30
CA2584449C (fr) 2010-08-24
US7556865B2 (en) 2009-07-07
ATE394517T1 (de) 2008-05-15
WO2006042930A1 (fr) 2006-04-27
KR20070064373A (ko) 2007-06-20
JP2008517157A (ja) 2008-05-22
CN100554487C (zh) 2009-10-28
JP4828544B2 (ja) 2011-11-30

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