EP2054536A2 - Process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of mn with a metallic protective layer - Google Patents

Process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of mn with a metallic protective layer

Info

Publication number
EP2054536A2
EP2054536A2 EP07802701A EP07802701A EP2054536A2 EP 2054536 A2 EP2054536 A2 EP 2054536A2 EP 07802701 A EP07802701 A EP 07802701A EP 07802701 A EP07802701 A EP 07802701A EP 2054536 A2 EP2054536 A2 EP 2054536A2
Authority
EP
European Patent Office
Prior art keywords
coating
steel strip
content
zinc
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07802701A
Other languages
German (de)
French (fr)
Other versions
EP2054536B1 (en
Inventor
Manfred Meurer
Ronny Leuschner
Harald Hofmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by ThyssenKrupp Steel AG filed Critical ThyssenKrupp Steel AG
Priority to PL07802701T priority Critical patent/PL2054536T3/en
Publication of EP2054536A2 publication Critical patent/EP2054536A2/en
Application granted granted Critical
Publication of EP2054536B1 publication Critical patent/EP2054536B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • 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
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • C23C2/04—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
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the invention relates to a method for coating a 6-30 wt .-% Mn-containing hot- or cold-rolled steel strip with a metallic protective layer, in particular a protective layer based on zinc, wherein the steel strip to be coated at a 800-1100 C 0 amount forming annealing temperature under annealed a nitrogen, water and hydrogen-containing annealing atmosphere and then subjected to a hot-dip coating.
  • 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%), particularly suitable for use in the field of vehicle construction , especially in the automotive industry.
  • particularly suitable steels with high Mn contents of 6 wt .-% to 30 wt .-% are known for example from DE 102 59 230 Al, DE 197 27 759 C2 or DE 199 00 199 Al. From the known steels produced flat products have at high strengths isotropic deformation behavior and are still ductile even at low temperatures.
  • Another method for coating a high manganese-containing, from 0.35 to 1.05 wt .-% C, 16 to 25 wt .-% Mn, balance iron and unavoidable impurities containing steel strip is known from WO 2006/042931 Al.
  • the steel strip thus composed is first cold-rolled and then annealed recrystallizing in an atmosphere which is reducing with respect to iron.
  • the annealing parameters are selected such that on both sides of the steel strip an intermediate layer is formed, which consists essentially completely of amorphous oxide (FeMn) O, and additionally adjusts an outer layer consisting of crystalline Mn oxide, wherein the thickness of two layers is at least 0.5 microns.
  • Practical investigations have shown that even such complex precoated steel strips in practice not have the required for a cold deformation adhesion to the steel substrate.
  • JP 07-216524 A discloses a method of hot dipping a hot rolled steel plate having a high tensile strength.
  • the steel plate is first descaled, pickled and cleaned. Then, it is lightly oxidized to produce thereon an iron oxide film having a thickness of 500 - 10,000 ⁇ .
  • This iron oxide film is then reduced by reducing heating to active metallic iron.
  • the reducing heating is carried out in such a way that a selective oxidation of Si and Mn in the steel and a concentration of these elements on the surface are avoided.
  • the reductive heating is carried out under an atmosphere whose hydrogen concentration is controlled in the range of 3 to 25% by volume so as to have a reducing power sufficient for the reduction of iron oxide but to prevent the selective oxidation of Si and Mn ,
  • the object of the invention was to provide a method by which high cost manganese steel sheets can be hot dip coated in a cost effective manner.
  • This object has been achieved in a method of the type specified in that according to the invention for the production of a substantially free of oxidic interlayers metallic protective layer on the steel strip, the ratio% H 2 O /% H 2 of the water content% H 2 O to hydrogen Content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G as follows:
  • the invention is based on the recognition that by a suitable adjustment of the annealing atmosphere, namely its hydrogen content in relation to their water content and their dew point, adjusts a surface finish of the steel strip to be coated during annealing, the optimal adhesion of the subsequently by Ensures hot dip coating applied metallic protective coating.
  • the inventively set annealing atmosphere acts both with respect to the iron and against the manganese of the steel strip reducing.
  • the formation of, according to the inventors, adhesion of the melt coating to the high manganese steel substrate impairing oxide layer thus deliberately avoided.
  • Typical applied in an inventive method calcination temperatures are in the range of 800 - 1100 0 C. Over the entire range of annealing temperatures should according to the invention, the% H 2 O /% H 2 - ratio are each below 4.5 * 10 ⁇ . 4
  • the steel strip processed according to the invention is cold rolled one or more times, then the steel strip can be annealed under the annealing atmosphere set according to the invention during the intermediate annealing carried out between the individual cold rolling steps or during the annealing carried out after the cold rolling to prepare the hot dip coating.
  • the annealing and the hot dip coating can be carried out in a continuous pass.
  • This type of application of the method according to the invention is particularly suitable when the coating is carried out in a conventional coil coating plant, in which an annealing furnace and the hot dip are arranged inline in the usual way and are run continuously in succession in an uninterrupted sequence.
  • the method according to the invention is suitable for hot dip coating of high manganese steel strips with a layer consisting essentially entirely of Zn and unavoidable impurities
  • Z-coating with a zinc-iron layer, which consists of up to 92 wt .-% Zn and up to 12 wt .-% Fe (so-called "ZF coating"), with a Aluminum-zinc layer, whose Al content up to 60 wt .-% and whose Zn content up to 50 wt .-% (so-called "ZF coating"
  • AZ coating is, with an aluminum-silicon layer having an Al content of up to 92% by weight and a Si content of up to 12 wt .-% (see called “AS coating”), with a zinc-aluminum layer having a content of up to 10 wt .-% Al, balance zinc and unavoidable impurities (so-called “ZA coating”) or with a zinc magnesium Layer which has a Zn content of up to 99.5% by weight and an Mg content of up to 5% by weight (so-called “ZnMg coating”) and additionally optionally up to 11% by weight.
  • % Al, up to 4 wt .-% Fe and up to 2 wt .-% Si may contain.
  • 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.
  • the steel strips which are provided with a metallic protective coating by hot-dip coating according to the invention typically contain (in% by weight) C: ⁇ 1.6%, Mn: 6 - 30%, Al: ⁇ 10%, Ni: ⁇ 10%, Cr: ⁇ 10%, Si: ⁇ 8%, Cu: ⁇ 3%, Nb: ⁇ 0.6%, Ti: ⁇ 0.3%, V: ⁇ 0.3%, P: ⁇ 0 , 1%, B: ⁇ 0.01%, N: ⁇ 1.0%, balance iron and unavoidable impurities.
  • Mn 20.0 - 30.0%
  • Al ⁇ 0.5%
  • Si ⁇ 0.5%
  • B ⁇ 0.01%
  • 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 accordance with the invention.
  • Fig. 1 shows the inclusion of a provided according to the invention with a zinc coating steel sheet after a ball impact test
  • Figure 2 shows the inclusion of a comparison with in a deviating from the invention manner with a zinc-coated steel sheet after a ball impact test.
  • Fig. 3 shows the inclusion of a second provided in accordance with the invention with a zinc coating steel sheet after a ball impact test
  • Figure 4 shows the inclusion of a second comparison provided in a deviating from the invention manner with a zinc-coated steel sheet after a ball impact test.
  • Diag. 1 the ratio% H 2 O /% H 2 of the water content% H 2 O to the hydrogen content% H 2 of the annealing atmosphere as a function of the annealing temperature
  • the annealed steel strips were each cooled to a bath inlet temperature of 470 0 C and passed in a continuous pass through a 460 0 C hot zinc molten bath, which consisted of 0.2% Al and the remainder of Zn and unavoidable impurities. After leaving the zinc molten bath, the thickness of the Zn protective coating on the steel strip has been adjusted in a manner known per se by means of a nozzle scraping system.
  • the steel strip provided with the coating can be oiled for transport to the end user and wound up into a coil.
  • test series Vl comprised five experiments Vl .1 - Vl .5 with a steel strip produced from the steel Sl. in the In the course of the test series V2, seven experiments V2.1 - V2.7 were carried out with a steel strip made of steel S2. In test series V3, eleven tests were finally carried out on a steel strip made of steel S3.
  • the ratios% H 2 O /% H 2 maintained in the inventive setting of the annealing atmosphere are separated from the region "N" located above the curve K, in which the ratios% H 2 O /% H 2 of an atmosphere not adjusted according to the invention are arranged.
  • Fig. 1 shows the result of a ball impact test, which was carried out on the obtained from the experiment Vl.4, provided with the Zn protective coating steel is. The perfect adhesion of the coating even in the most deformed area of the molded into the steel sheet dome is clearly visible.
  • Fig. 2 shows the result of a ball impact test, which has been carried out on the steel sheet resulting from experiment Vl .1. The flaking of the coating in the area of the dome formed in the steel sheet are clearly visible.
  • Fig. 3 shows the result of a ball impact test, which was carried out on the steel sheet obtained in experiment Vl .5. Also in this invention coated sample, the coating adheres properly over the entire molded into the sheet dome.
  • FIG. 4 shows the result of a ball impact test, which was carried out on the steel sheet coated in experiment VI.1.
  • the poor adhesion of the coating to the steel substrate is evidenced by the cracks in the most deformed area of the cup formed in the steel sheet.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

The present invention relates to a process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of Mn with a metallic protective layer, in particular a zinc-based protective layer, in which the steel strip to be coated is heat treated at a heat treatment temperature of 800 - 1100°C under a heat treatment atmosphere containing nitrogen, water and hydrogen and is subsequently subjected to melt dip coating. The process of the invention enables steel sheets having high manganese contests to be melt dip coated in an inexpensive way. This is achieved by the ratio %H2O/%H2 of the water content %H20 to the hydrogen content %H2 of the heat treatment atmosphere being set as a function of the respective heat treatment temperature TG as follows: %H2O/%H2 ≤ 8⋅10-15 ⋅TG3,529 to produce a metallic protective layer which is essentially free of oxidic intermediate layers on the steel strip.

Description

VERFAHREN ZUM BESCHICHTEN EINES β - 30 GEW. -% MN PROCESS FOR COATING A β - 30 GEW. -% MN
ENTHALTENDEN WARM- ODER KALTGEWALZTEN STAHLBANDS MITCONTAINING WARM OR COLD ROLLED STEEL STRIPS WITH
EINER METALLISCHEN SCHUTZSCHICHTA METALLIC PROTECTION LAYER
Die Erfindung betrifft ein Verfahren zum Beschichten eines 6 - 30 Gew.-% Mn enthaltenden warm- oder kaltgewalzten Stahlbands mit einer metallischen Schutzschicht, insbesondere einer auf Zink basierenden Schutzschicht, bei dem das zu beschichtende Stahlband bei einer 800 - 1100 C0 betragenden Glühtemperatur unter einer Stickstoff, Wasser und Wasserstoff enthaltenden Glühatmosphäre geglüht und anschließend einer Schmelztauchbeschichtung unterzogen wird.The invention relates to a method for coating a 6-30 wt .-% Mn-containing hot- or cold-rolled steel strip with a metallic protective layer, in particular a protective layer based on zinc, wherein the steel strip to be coated at a 800-1100 C 0 amount forming annealing temperature under annealed a nitrogen, water and hydrogen-containing annealing atmosphere and then subjected to a hot-dip coating.
Stähle mit hohen Mangan-Gehalten eignen sich aufgrund ihrer günstigen Eigenschaftskombination aus hohen Festigkeiten von bis zu 1.400 MPa einerseits und extrem hohen Dehnungen (Gleichmaßdehnungen bis zu 70 % und Bruchdehnungen bis zu 90 %) andererseits grundsätzlich im besonderen Maße für die Verwendung im Bereich des Fahrzeugbaus, insbesondere im Automobilbau. Für diesen Einsatzzweck besonders geeignete Stähle mit hohen Mn- Gehalten von 6 Gew.-% bis 30 Gew.-% sind beispielsweise aus der DE 102 59 230 Al, der DE 197 27 759 C2 oder der DE 199 00 199 Al bekannt. Aus den bekannten Stählen erzeugte Flachprodukte weisen bei hohen Festigkeiten ein isotropes Verformungsverhalten auf und sind darüber hinaus auch bei tiefen Temperaturen noch duktil.On the other hand, 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%), particularly suitable for use in the field of vehicle construction , especially in the automotive industry. For this purpose particularly suitable steels with high Mn contents of 6 wt .-% to 30 wt .-% are known for example from DE 102 59 230 Al, DE 197 27 759 C2 or DE 199 00 199 Al. From the known steels produced flat products have at high strengths isotropic deformation behavior and are still ductile even at low temperatures.
Diesen Vorteilen steht jedoch gegenüber, dass hochmanganhaltige Stähle zu Lochfraß neigen und nur schwer zu passivieren sind. Diese im Vergleich zu niedriger legierten Stählen bei Einwirken erhöhter Chloridionen-Konzentrationen große Neigung zu lokal zwar begrenzter, jedoch intensiver Korrosion macht die Verwendung von zur Werkstoffgruppe der hochlegierten Stahlbleche gehörenden Stählen gerade im Karosseriebau schwierig. Zudem neigen hochmanganhaltige Stähle zu Flächenkorrosion, die das Spektrum ihrer Verwendung ebenfalls einschränkt.These advantages, however, contrast with the fact that high manganese steels tend to pitting and are difficult to passivate. This compared to lower alloyed steels when exposed to elevated chloride ion concentrations great tendency to locally limited, but intense corrosion makes the use of the material group of high-alloy steel sheets belonging steels straight in the body construction difficult. In addition, high manganese steels tend to surface corrosion, which also limits the spectrum of their use.
Daher ist vorgeschlagen worden, auch Stahlflachprodukte, die aus hochmanganhaltigen Stählen erzeugt sind, in an sich bekannter Weise mit einem metallischen Überzug zu versehen, die den Stahl vor korrosivem Angriff schützt. So ist versucht worden, durch elektrolytisches Beschichten auf das Stahlmaterial eine Zinkbeschichtung aufzutragen.It has therefore been proposed to also provide flat steel products, which are produced from high-manganese steels, in a manner known per se with a metallic coating which protects the steel from corrosive attack. Thus, it has been attempted to apply a zinc coating by electrolytic coating on the steel material.
Die auf diese Weise beschichteten, hochmanganlegierten Stahlbänder sind zwar durch die aufgetragene metallische Beschichtung gegen Korrosion geschützt. Allerdings ist das dazu erforderliche elektrolytische Beschichten ein verfahrenstechnisch relativ aufwändiges Verfahren. Dazu kommt die Gefahr einer für den Werkstoff schädlichen Wasserstoffaufnähme . Praktische Versuche, Stahlbänder mit hohen Mangangehalten durch kostengünstiger durchführbares Schmelztauchbeschichten mit einer metallischen Schutzschicht zu versehen, brachten neben grundsätzlichen Problemen bei der Benetzung mit Schmelze insbesondere im Hinblick auf die bei einer Kaltverformung von dem Überzug geforderten Haftung auf dem Stahlsubstrat unbefriedigende Ergebnisse .Although the high-manganese steel strips coated in this way are protected against corrosion by the applied metallic coating. However, the electrolytic coating required for this is a procedurally relatively complicated process. In addition, there is the danger of a harmful hydrogen absorption for the material. Practical attempts to provide steel strips with high manganese contents by means of cost-effective hot-dip coating with a metallic protective layer brought about unsatisfactory results in addition to fundamental problems with wetting with melt, in particular with regard to the adhesion to the steel substrate required for cold deformation of the coating.
Als Grund für diese schlechten Haftungseigenschaften wurde die starke Oxidschicht ermittelt, die sich bei der für das Schmelztauchbeschichten unverzichtbaren Glühung einstellt. Die derart oxidierten Blechoberflächen lassen sich nicht mehr mit der erforderlichen Gleichmäßigkeit und Vollständigkeit mit dem Überzugsmetall benetzen, so dass das Ziel eines flächendeckenden Korrosionsschutzes nicht erreicht wird.The reason for these poor adhesion properties was found to be the thick oxide layer which sets in the annealing required for hot-dip coating. The thus oxidized sheet surfaces can no longer be wetted with the required uniformity and completeness with the coating metal, so that the goal of a nationwide corrosion protection is not achieved.
Die aus dem Bereich von hochlegierten, jedoch niedrigere Mn~Gehalte aufweisenden Stählen bekannten Möglichkeiten der Verbesserung der Benetzbarkeit durch Aufbringen einer Zwischenschicht aus Fe oder Ni führten bei Stahlblechen mit mindestens 6 Gew.-% Mangan nicht zu dem gewünschten Erfolg.The possibilities for improving the wettability known from the field of high-alloy but lower Mn-containing steels by applying an intermediate layer of Fe or Ni did not lead to the desired result in steel sheets containing at least 6% by weight of manganese.
In der DE 10 2005 008 410 B3 ist vorgeschlagen worden, auf ein 6 - 30 Gew.-% Mn enthaltendes Stahlband vor der dem Schmelztauchbeschichten vorangehenden letzten Glühung eine Aluminiumschicht aufzutragen. Das auf dem Stahlband haftende Aluminium verhindert bei der der Schmelzbeschichtung vorgeschalteten Glühung des Stahlbands, dass dessen Oberfläche oxidiert . Anschließend bewirkt die Aluminium-Schicht nach Art eines Haftvermittlers, dass der durch die Schmelzbeschichtung erzeugte Überzug auch dann fest und vollflächig auf dem Stahlband haftet, wenn das Stahlband selbst aufgrund seiner Legierung dazu ungünstige Voraussetzungen bietet. Dazu wird bei dem bekannten Verfahren der Effekt genutzt, dass es bei der der Schmelzbeschichtung notwendig vorgeschalteten Glühbehandlung zu einer Diffusion des Eisens des Stahlbands in die Aluminiumschicht kommt. Im Zuge der Glühung entsteht auf dem Stahlband somit eine metallische, im Wesentlichen aus Al und Fe bestehende Auflage, die Stoffschlüssig mit dem durch das Stahlband gebildeten Untergrund verbunden ist.In DE 10 2005 008 410 B3, it has been proposed to apply an aluminum layer to a steel strip containing 6-30% by weight of Mn prior to the last annealing preceding the hot-dip coating. The aluminum, which adheres to the steel strip, prevents the glowing of the hot melt coating from occurring Steel bands that oxidizes its surface. Subsequently, the aluminum layer in the manner of an adhesion promoter, that the coating produced by the melt coating adheres firmly and fully on the steel strip, even if the steel strip itself offers unfavorable conditions due to its alloy. For this purpose, in the known method, the effect is utilized that diffusion of the iron of the steel strip into the aluminum layer occurs during the annealing treatment necessary upstream of the melt coating. In the course of the annealing, a metallic, essentially consisting of Al and Fe overlay on the steel strip thus formed, which is materially connected to the substrate formed by the steel strip.
Ein anderes Verfahren zum Beschichten eines hochmanganhaltigen, 0,35 - 1,05 Gew.-% C, 16 - 25 Gew.-% Mn, Rest Eisen sowie unvermeidbare Verunreinigungen enthaltendes Stahlband ist aus der WO 2006/042931 Al bekannt. Gemäß diesem bekannten Verfahren wird das derart zusammengesetzte Stahlband zunächst kaltgewalzt und anschließend rekristallisierend in einer Atmosphäre geglüht, die sich in Bezug auf Eisen reduzierend verhält. Dabei sind die Glühparameter so gewählt, dass sich auf dem Stahlband beidseitig eine Zwischenschicht einstellt, die im Wesentlichen vollständig aus amorphem Oxid (FeMn)O besteht, und sich zusätzlich eine äußere Schicht einstellt, die aus kristallinem Mn-Oxid besteht, wobei die Dicke der beiden Schichten mindestens 0,5 μm beträgt. Praktische Untersuchungen haben gezeigt, dass auch derart aufwändig vorbeschichtete Stahlbänder in der Praxis nicht die für eine Kaltverformung geforderte Haftung auf dem Stahlsubstrat aufweisen.Another method for coating a high manganese-containing, from 0.35 to 1.05 wt .-% C, 16 to 25 wt .-% Mn, balance iron and unavoidable impurities containing steel strip is known from WO 2006/042931 Al. According to this known method, the steel strip thus composed is first cold-rolled and then annealed recrystallizing in an atmosphere which is reducing with respect to iron. In this case, the annealing parameters are selected such that on both sides of the steel strip an intermediate layer is formed, which consists essentially completely of amorphous oxide (FeMn) O, and additionally adjusts an outer layer consisting of crystalline Mn oxide, wherein the thickness of two layers is at least 0.5 microns. Practical investigations have shown that even such complex precoated steel strips in practice not have the required for a cold deformation adhesion to the steel substrate.
Neben dem voranstehend erläuterten Stand der Technik ist aus der JP 07-216524 A ein Verfahren zum Heißtauchbeschichten einer warmgewalzten Stahlplatte bekannt, die eine hohe Zugfestigkeit aufweist. Im Zuge dieses bekannten Verfahrens wird die Stahlplatte zunächst entzundert, gebeizt und gereinigt. Dann wird sie schwach oxidiert, um auf ihr einen Eisenoxidfilm zu erzeugen, der eine Dicke von 500 - 10.000 Ä aufweist. Dieser Eisenoxidfilm wird anschließend durch reduzierendes Erhitzen zu aktivem metallischem Eisen reduziert. Die reduzierende Erhitzung wird dabei so durchgeführt, dass eine selektive Oxidation von Si und Mn in dem Stahl und eine Konzentrierung dieser Elemente an der Oberfläche vermieden werden. Zu diesem Zweck wird das reduzierende Erhitzen unter einer Atmosphäre durchgeführt, deren Wasserstoffkonzentration im Bereich von 3 - 25 VoI- % so reguliert wird, dass sie einerseits ein für die Reduzierung des Eisenoxids ausreichendes Reduktionsvermögen aufweist, andererseits jedoch die selektive Oxidation von Si und Mn unterbleibt.Besides the above-mentioned prior art, JP 07-216524 A discloses a method of hot dipping a hot rolled steel plate having a high tensile strength. In the course of this known method, the steel plate is first descaled, pickled and cleaned. Then, it is lightly oxidized to produce thereon an iron oxide film having a thickness of 500 - 10,000 Å. This iron oxide film is then reduced by reducing heating to active metallic iron. The reducing heating is carried out in such a way that a selective oxidation of Si and Mn in the steel and a concentration of these elements on the surface are avoided. For this purpose, the reductive heating is carried out under an atmosphere whose hydrogen concentration is controlled in the range of 3 to 25% by volume so as to have a reducing power sufficient for the reduction of iron oxide but to prevent the selective oxidation of Si and Mn ,
Ausgehend von dem voranstehend erläuterten Stand der Technik bestand die Aufgabe der Erfindung darin, ein Verfahren anzugeben, mit dem sich auf kostengünstige Weise hohe Mangangehalte aufweisende Stahlbleche Schmelztauchbeschichten lassen. Diese Aufgabe ist bei einem Verfahren der eingangs angegebenen Art dadurch gelöst worden, dass erfindungsgemäß zur Herstellung einer im Wesentlichen von oxidischen Zwischenschichten freien metallischen Schutzschicht auf dem Stahlband das Verhältnis %H2O/%H2 des Wasser-Gehaltes %H2O zum Wasserstoff-Gehalt %H2 der Glühatmosphäre in Abhängigkeit von der jeweiligen Glühtemperatur TG wie folgt eingestellt wird:Starting from the above-described prior art, the object of the invention was to provide a method by which high cost manganese steel sheets can be hot dip coated in a cost effective manner. This object has been achieved in a method of the type specified in that according to the invention for the production of a substantially free of oxidic interlayers metallic protective layer on the steel strip, the ratio% H 2 O /% H 2 of the water content% H 2 O to hydrogen Content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G as follows:
- 15 rp 3 , 529- 15 r p 3, 529
%H2O/ %H2 < 8 - 10% H 2 O /% H 2 <8-10
Bei Berücksichtigung dieses %H2O/%H2-Verhältnisses lässt sich über den gesamten Bereich der in Frage kommenden Glühtemperaturen TG ein optimales Arbeitsergebnis gewährleisten .Taking into account this% H 2 O /% H 2 ratio, it is possible to ensure an optimum work result over the entire range of possible annealing temperatures T G.
Die Erfindung geht von der Erkenntnis aus, dass durch eine geeignete Einstellung der Glühatmosphäre, nämlich ihres Wasserstoff-Gehaltes im Verhältnis zu ihrem Wasser- Gehalt sowie ihres Taupunktes, sich beim Glühen eine Oberflächenbeschaffenheit des zu beschichtenden Stahlbands einstellt, die eine optimale Haftung des anschließend durch Schmelztauchbeschichten aufgetragenen metallischen Schutzüberzuges gewährleistet. Die erfindungsgemäß eingestellte Glühatmosphäre wirkt dabei sowohl gegenüber dem Eisen als auch gegenüber dem Mangan des Stahlbands reduzierend. Im Gegensatz zum beispielsweise in der WO 2006/042931 Al beschriebenen Stand der Technik wird gemäß der Erfindung die Entstehung einer nach Feststellung der Erfinder die Haftung des Schmelzüberzugs auf dem hochmanganhaltigen Stahlsubstrat beeinträchtigenden Oxidschicht somit gezielt vermieden. Im Ergebnis wird auf diese Weise ein mit einem metallischen Überzug versehenes, hochfestes und gleichzeitig gut verformbares Stahlband erhalten, bei dem trotz seines hohen Mangangehalts eine überlegene Haftung des Überzugs gewährleistet ist. Diese ermöglicht es, erfindungsgemäß beschichtetes Stahlband problemlos zu Formteilen umzuformen, wie sie im Karosseriebau, insbesondere im Bereich des Automobilkarosseriebaus regelmäßig benötigt werden.The invention is based on the recognition that by a suitable adjustment of the annealing atmosphere, namely its hydrogen content in relation to their water content and their dew point, adjusts a surface finish of the steel strip to be coated during annealing, the optimal adhesion of the subsequently by Ensures hot dip coating applied metallic protective coating. The inventively set annealing atmosphere acts both with respect to the iron and against the manganese of the steel strip reducing. In contrast to the state of the art described, for example, in WO 2006/042931 A1, according to the invention, the formation of, according to the inventors, adhesion of the melt coating to the high manganese steel substrate impairing oxide layer thus deliberately avoided. As a result, obtained in this way provided with a metallic coating, high-strength and at the same time well deformable steel strip, in which despite its high manganese content, a superior adhesion of the coating is ensured. This makes it possible to easily transform coated steel strip according to the invention to form parts, as are regularly required in body construction, in particular in the field of automobile body construction.
Typische, bei einem erfindungsgemäßen Verfahren angewendete Glühtemperaturen liegen im Bereich von 800 - 1100 0C. Über den gesamten Bereich dieser Glühtemperaturen sollte erfindungsgemäß das %H2O/%H2- Verhältnis jeweils unterhalb von 4,5*10~4 liegen.Typical applied in an inventive method calcination temperatures are in the range of 800 - 1100 0 C. Over the entire range of annealing temperatures should according to the invention, the% H 2 O /% H 2 - ratio are each below 4.5 * 10 ~. 4
Indem entsprechend des erfindungsgemäß vorgegebenen Zusammenhangs mit abnehmender Glühtemperatur auch das %H2O/%H2- Verhältnis gesenkt wird, können optimierte Arbeitsergebnisse erreicht werden. Praktische Versuche haben dazu ergeben, dass sich der Erfolg der Erfindung bei einer Glühtemperatur von 850 0C besonders sicher einstellt, wenn das %H2O/%H2-Verhältnis auf bis 2-10~4 beschränkt wird. Bei einer Glühtemperatur von 950 0C ergibt sich eine besonders hohe Betriebssicherheit, wenn das %H2O/%H2-Verhältnis höchstens 2,5-10"4 beträgt. Vermindert werden kann das Verhältnis %H2O/%H2 dadurch, dass der H2-Gehalt angehoben oder der H2O-Gehalt des Atmosphärengases abgesenkt wird. Wird das erfindungsgemäß verarbeitete Stahlband ein oder mehrstufig kaltgewalzt, so kann das Stahlband bei den zwischen den einzelnen Kaltwalzschritten vorgenommenen Zwischenglühungen oder beim im Anschluss an das Kaltwalzen durchgeführte Glühen zur Vorbereitung des Schmelztauchbeschichtens unter der erfindungsgemäß eingestellten Glühatmosphäre geglüht werden.By lowering the% H 2 O /% H 2 ratio in accordance with the context of the present invention with decreasing annealing temperature, optimized work results can be achieved. Practical experiments have shown that the success of the invention at an annealing temperature of 850 0 C sets particularly safe when the% H 2 O /% H 2 ratio is limited to 2-10 ~ 4 . At an annealing temperature of 950 0 C results in a particularly high operational reliability when the% H 2 O /% H 2 ratio is at most 2.5-10 "4. Can be reduced, the ratio% H 2 O /% H 2 characterized in that the H 2 content is raised or the H 2 O content of the atmosphere gas is lowered. If the steel strip processed according to the invention is cold rolled one or more times, then the steel strip can be annealed under the annealing atmosphere set according to the invention during the intermediate annealing carried out between the individual cold rolling steps or during the annealing carried out after the cold rolling to prepare the hot dip coating.
Alternativ oder ergänzend dazu lassen sich das Glühen und das Schmelztauchbeschichten im kontinuierlichen Durchlauf durchführen. Diese Art der Anwendung des erfindungsgemäßen Verfahrens bietet sich insbesondere dann an, wenn das Beschichten in einer konventionellen Bandbeschichtungsanlage ausgeführt wird, bei der in üblicher Weise ein Glühofen und das Schmelztauchbad inline angeordnet sind und in einer unterbrechungsfreien Abfolge kontinuierlich aufeinander folgend durchlaufen werden .Alternatively or additionally, the annealing and the hot dip coating can be carried out in a continuous pass. This type of application of the method according to the invention is particularly suitable when the coating is carried out in a conventional coil coating plant, in which an annealing furnace and the hot dip are arranged inline in the usual way and are run continuously in succession in an uninterrupted sequence.
Das erfindungsgemäße Verfahren eignet sich zum Schmelztauchbeschichten von hochmanganhaltigen Stahlbändern mit einer im Wesentlichen vollständig aus Zn und unvermeidbaren Verunreinigungen bestehenden SchichtThe method according to the invention is suitable for hot dip coating of high manganese steel strips with a layer consisting essentially entirely of Zn and unavoidable impurities
(so genannte "Z-Beschichtung" ) , mit einer Zink-Eisen- Schicht, die aus bis zu 92 Gew.-% Zn und bis zu 12 Gew.-% Fe besteht (so genannte "ZF-Beschichtung" ) , mit einer Aluminium-Zink-Schicht , deren Al-Gehalt bis zu 60 Gew.-% und deren Zn-Gehalt bis zu 50 Gew.-% (so genannte("Z-coating"), with a zinc-iron layer, which consists of up to 92 wt .-% Zn and up to 12 wt .-% Fe (so-called "ZF coating"), with a Aluminum-zinc layer, whose Al content up to 60 wt .-% and whose Zn content up to 50 wt .-% (so-called
"AZ-Beschichtung" ) beträgt, mit einer Aluminium-Silizium- Schicht, die einen Al-Gehalt von bis zu 92 Gew,-% und einen Si -Gehalt von bis zu 12 Gew.-% aufweist (so genannte "AS-Beschichtung" ) , mit einer Zink-Aluminium- Schicht, die einen Gehalt von bis zu 10 Gew.-% Al, Rest Zink und unvermeidbare Verunreinigungen aufweist (so genannte "ZA-Beschichtung" ) oder mit einer Zink- Magnesium-Schicht, die einen Zn-Anteil von bis zu 99,5 Gew.-% und einen Mg-Anteil von bis zu 5 Gew.-% besitzt (so genannte "ZnMg-Beschichtung" ) sowie zusätzlich wahlweise bis zu 11 Gew.-% Al, bis zu 4 Gew.-% Fe und bis zu 2 Gew.-% Si enthalten kann."AZ coating") is, with an aluminum-silicon layer having an Al content of up to 92% by weight and a Si content of up to 12 wt .-% (see called "AS coating"), with a zinc-aluminum layer having a content of up to 10 wt .-% Al, balance zinc and unavoidable impurities (so-called "ZA coating") or with a zinc magnesium Layer which has a Zn content of up to 99.5% by weight and an Mg content of up to 5% by weight (so-called "ZnMg coating") and additionally optionally up to 11% by weight. % Al, up to 4 wt .-% Fe and up to 2 wt .-% Si may contain.
Die erfindungsgemäße Vorgehensweise bei der Beschichtung ist insbesondere für solche Stahlbänder geeignet, die hoch legiert sind, um hohe Festigkeiten und gute Dehnungseigenschaften zu gewährleisten. Die Stahlbänder, die sich in erfindungsgemäßer Weise durch Schmelztauchbeschichten mit einem metallischen Schutzüberzug versehen lassen, enthalten dementsprechend typischerweise (in Gew.-%) C: < 1,6 %, Mn: 6 - 30 %, Al: < 10 %, Ni: < 10 %, Cr: < 10 %, Si: < 8 %, Cu: < 3 %, Nb: < 0,6 %, Ti: < 0,3 %, V: < 0,3 %, P: < 0,1 %, B: < 0,01 %, N: < 1,0 %, Rest Eisen und unvermeidbare Verunreinigungen .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. Accordingly, the steel strips which are provided with a metallic protective coating by hot-dip coating according to the invention typically contain (in% by weight) C: <1.6%, Mn: 6 - 30%, Al: <10%, Ni: <10%, Cr: <10%, Si: <8%, Cu: <3%, Nb: <0.6%, Ti: <0.3%, V: <0.3%, P: <0 , 1%, B: <0.01%, N: <1.0%, balance iron and unavoidable impurities.
Besonders vorteilhaft wirken sich die durch die Erfindung erzielten Effekte bei der Beschichtung von hochlegiertenParticularly advantageous are the effects achieved by the invention in the coating of high-alloy
Stahlbändern aus, die Mangan-Gehalte von mindestensMade of steel strips, the manganese content of at least
6 Gew.-% enthalten. So zeigt sich, dass ein6 wt .-% included. It turns out that one
Stahlgrundmaterial, welches (in Gew.-%) C: < 1,00 %,Steel base material containing (in% by weight) C: <1.00%,
Mn: 20,0 - 30,0 %, Al: < 0,5 %, Si: < 0,5 %, B: < 0,01 %,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 %, Rest Eisen und unvermeidbare Verunreinigungen enthält, sich besonders gut mit einem vor Korrosion schützenden Überzug beschichten lässt.Ni: <3.0%, Cr: <10.0%, Cu: <3.0%, N: <0.6%, Nb: < 0.3%, Ti: <0.3%, V: <0.3%, P: <0.1%, balance iron and unavoidable impurities, can be coated particularly well with a corrosion-protective coating.
Gleiches gilt, wenn ein Stahl als Grundmaterial eingesetzt wird, der (in Gew.-%) C: < 1,00 %, Mn: 7,00 - 30,00 %, Al: 1,00 - 10,00 %, Si: >2,50 - 8,00 % (wobei gilt, dass die Summe aus Al-Gehalt und Si-Gehalt >3,50 - 12,00 % ist), 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 Eisen und unvermeidbare Verunreinigungen enthält .The same applies if a steel is used as the base material, 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.
Mit der Erfindung steht ein kostengünstiger Weg zur Verfügung, hochmanganhaltige Stahlbänder auf wirtschaftliche Weise so gegen Korrosion zu schützen, dass sie für die Produktion von Karosserien für den Fahrzeugbau, insbesondere den Automobilbau, eingesetzt werden können, bei deren praktischem Einsatz sie besonders korrosiven Medien ausgesetzt sind.With the invention, a cost-effective way is available to protect high manganese steel bands in an economical way so against corrosion that they can be used for the production of bodies for vehicle construction, especially automotive, in their practical use they are exposed to particularly corrosive media ,
Wie bei der üblichen Schmelztauchbeschichtung können sowohl warmgewalzte als auch kaltgewalzte Stahlbänder in erfindungsgemäßer Weise beschichtet werden.As with the conventional hot-dip coating, both hot-rolled and cold-rolled steel strips can be coated in accordance with the invention.
Nachfolgend wird die Erfindung anhand einer ein Ausführungsbeispiel darstellenden Zeichnung näher erläutert. Es zeigen jeweils schematisch: Abb. 1 die Aufnahme eines in erfindungsgemäßer Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;The invention will be explained in more detail with reference to a drawing illustrating an exemplary embodiment. Each show schematically: Fig. 1 shows the inclusion of a provided according to the invention with a zinc coating steel sheet after a ball impact test;
Abb. 2 die Aufnahme eines zum Vergleich in einer von der Erfindung abweichenden Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest ;Figure 2 shows the inclusion of a comparison with in a deviating from the invention manner with a zinc-coated steel sheet after a ball impact test.
Abb. 3 die Aufnahme eines zweiten in erfindungsgemäßer Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;Fig. 3 shows the inclusion of a second provided in accordance with the invention with a zinc coating steel sheet after a ball impact test;
Abb. 4 die Aufnahme eines zweiten zum Vergleich in einer von der Erfindung abweichenden Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;Figure 4 shows the inclusion of a second comparison provided in a deviating from the invention manner with a zinc-coated steel sheet after a ball impact test.
Diag. 1 das Verhältnis %H2O/%H2 des Wasser-Gehaltes %H2O zum Wasserstoff-Gehalt %H2 der Glühatmosphäre in Abhängigkeit aufgetragen über die Glühtemperatur Diag. 1 the ratio% H 2 O /% H 2 of the water content% H 2 O to the hydrogen content% H 2 of the annealing atmosphere as a function of the annealing temperature
In drei Versuchsreihen V1,V2,V3 sind drei hochfeste, hochmanganhaltige Stähle S1,S2,S3, deren Zusammensetzung in Tabelle 1 angegeben ist, zu Brammen vergossen und zu Warmband ausgewalzt worden. Das jeweils erhaltene Warmband ist anschließend auf Enddicke kaltgewalzt und in eine konventionelle Schmelztauchbeschichtungsanlage geleitet worden. In der Schmelztauchbeschichtungsanlage sind die Stahlbänder in einer kontinuierlich ablaufenden Arbeitsfolge zunächst gereinigt und danach in einem kontinuierlichen Glühprozess auf die jeweilige Glühtemperatur TG, auf der sie über eine Glühzeit ZG von jeweils 30 Sekunden unter einer in erfindungsgemäßer Weise eingestellten wasserstoffhaltigen Glühatmosphäre gehalten worden sind, gebracht worden.In three test series V1, V2, V3, three high-strength, high-manganese steels S1, S2, S3, the composition of which is given in Table 1, were cast into slabs and rolled into hot-rolled strip. The respective hot strip obtained was then cold rolled to final thickness and passed into a conventional hot dip coating plant. In the hot-dip coating plant, the steel strips are first cleaned in a continuous operating sequence and then held in a continuous annealing process to the respective annealing temperature T G , on which they have been held over an annealing time Z G of 30 seconds under a set according to the invention hydrogen-containing annealing atmosphere, has been brought.
Nach der Glühbehandlung sind die geglühten Stahlbänder jeweils auf eine Badeintrittstemperatur von 470 0C abgekühlt und im kontinuierlichen Durchlauf durch ein 460 0C warmes Zink-Schmelzbad geleitet worden, das aus 0,2 % Al und als Rest aus Zn und unvermeidbaren Verunreinigungen bestand. Nach Austritt aus dem Zink-Schmelzbad ist mittels eines DüsenabstreifSystems in an sich bekannter Weise die Dicke des Zn-Schutzüberzuges auf dem Stahlband eingestellt worden.After the annealing, the annealed steel strips were each cooled to a bath inlet temperature of 470 0 C and passed in a continuous pass through a 460 0 C hot zinc molten bath, which consisted of 0.2% Al and the remainder of Zn and unavoidable impurities. After leaving the zinc molten bath, the thickness of the Zn protective coating on the steel strip has been adjusted in a manner known per se by means of a nozzle scraping system.
In der großtechnischen Anwendung kann auf das Schmelztauchbeschichten des Bandes und die Einstellung der Schichtdicke erforderlichenfalls ein Nachwalzen durchgeführt werden, um die Maßhaltigkeit des erhaltenen Bandes, sein Verformungsverhalten oder seine Oberflächenbeschaffenheit an die jeweiligen Anforderungen anzupassen. Im Anschluss kann das mit dem Überzug versehene Stahlband für den Transport zum Endverbraucher eingeölt und zu einem Coil aufgehaspelt werden.In the industrial application can be carried out on the hot dip coating of the strip and the adjustment of the layer thickness, if necessary, a Nachwalzen to adjust the dimensional accuracy of the obtained strip, its deformation behavior or its surface finish to the respective requirements. Subsequently, the steel strip provided with the coating can be oiled for transport to the end user and wound up into a coil.
Die Versuchsreihe Vl umfasste fünf Versuche Vl .1 - Vl .5 mit einem aus dem Stahl Sl produzierten Stahlband. Im Zuge der Versuchsreihe V2 sind sieben Versuche V2.1 - V2.7 mit einem aus dem Stahl S2 hergestellten Stahlband durchgeführt worden. Bei der Versuchsreihe V3 sind schließlich elf Versuche mit einem aus dem Stahl S3 erzeugten Stahlband gemacht worden.The test series Vl comprised five experiments Vl .1 - Vl .5 with a steel strip produced from the steel Sl. in the In the course of the test series V2, seven experiments V2.1 - V2.7 were carried out with a steel strip made of steel S2. In test series V3, eleven tests were finally carried out on a steel strip made of steel S3.
Die bei den voranstehend genannten Versuchsreihen jeweils angewendete Glühtemperatur TG, der jeweilige H2-Gehalt %H2 der Glühatmosphäre, ihr jeweiliger Taupunkt TP, der jeweilige H2O-Gehalt %H2O, das Verhältnis %H2O/%H2 sowie eine Bewertung des Beschichtungsergebnisses und eine Zuordnung der Versuchsergebnisse als "erfindungsgemäß" bzw. "nicht erfindungsgemäß" sind für die Versuchsreihe Vl in Tabelle 2, für die Versuchsreihe V2 in Tabelle 3 und für die Versuchsreihe V3 in Tabelle 4 angegeben.The annealing temperature T G applied in each case in the above-mentioned test series, the respective H 2 content% H 2 of the annealing atmosphere, their respective dew point TP, the respective H 2 O content% H 2 O, the ratio% H 2 O /% H 2 and an evaluation of the coating result and an assignment of the test results as "according to the invention" or "not according to the invention" are given for the test series VI in Table 2, for the test series V2 in Table 3 and for the test series V3 in Table 4.
In Diag. 1 ist das Verhältnis %H2O/%H2 über die Glühtemperatur TG aufgetragen. Dabei ist durch eine Kurve K der unterhalb dieser Kurve sich befindende Bereich "E", in dem gemäß der BedingungIn Diag. 1, the ratio% H 2 O /% H 2 is plotted against the annealing temperature T G. In this case, by a curve K, the area located below this curve is "E" in which according to the condition
%H2O/%H2 < 8-10 -15 3,529% H 2 O /% H 2 <8-10 -15 3,529
die bei der erfindungsgemäßen Einstellung der Glühatmosphäre eingehaltenen Verhältnisse %H2O/%H2 liegen, von dem oberhalb der Kurve K sich befindenden Bereich "N" abgetrennt, in dem die Verhältnisse %H2O/%H2 einer nicht erfindungsgemäß eingestellten Atmosphäre angeordnet sind.the ratios% H 2 O /% H 2 maintained in the inventive setting of the annealing atmosphere are separated from the region "N" located above the curve K, in which the ratios% H 2 O /% H 2 of an atmosphere not adjusted according to the invention are arranged.
Abb. 1 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus im Versuch Vl.4 gewonnenen, mit dem Zn- Schutzüberzug versehenen Stahlblech durchgeführt worden ist. Die einwandfreie Haftung des Überzugs auch im am stärksten verformten Bereich der in das Stahlblech eingeformten Kalotte ist deutlich zu sehen.Fig. 1 shows the result of a ball impact test, which was carried out on the obtained from the experiment Vl.4, provided with the Zn protective coating steel is. The perfect adhesion of the coating even in the most deformed area of the molded into the steel sheet dome is clearly visible.
Abb. 2 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus Versuch Vl .1 hervorgegangenen Stahlblech durchgeführt worden ist. Die Abplatzungen des Überzugs im Bereich der in das Stahlblech eingeformten Kalotte sind klar zu erkennen.Fig. 2 shows the result of a ball impact test, which has been carried out on the steel sheet resulting from experiment Vl .1. The flaking of the coating in the area of the dome formed in the steel sheet are clearly visible.
Abb. 3 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus im Versuch Vl .5 gewonnenen Stahlblech durchgeführt worden ist. Auch bei dieser erfindungsgemäß beschichteten Probe haftet der Überzug über die gesamte in das Blech eingeformte Kalotte einwandfrei.Fig. 3 shows the result of a ball impact test, which was carried out on the steel sheet obtained in experiment Vl .5. Also in this invention coated sample, the coating adheres properly over the entire molded into the sheet dome.
Abb. 4 zeigt schließlich das Ergebnis eines Kugelschlagtests, der an dem aus dem im Versuch Vl .2 beschichteten Stahlblech durchgeführt worden ist. Die mangelhafte Haftung des Überzugs an dem Stahlsubstrat zeigt sich durch die Risse im am stärksten verformten Bereich der in das Stahlblech eingeformten Kalotte. Finally, FIG. 4 shows the result of a ball impact test, which was carried out on the steel sheet coated in experiment VI.1. The poor adhesion of the coating to the steel substrate is evidenced by the cracks in the most deformed area of the cup formed in the steel sheet.
Stahl C Si Mn P Cr Ni VSteel C Si Mn P Cr Ni V
Sl O ,60 0 ,28 22, 5 o, 021 0 , 003 0 ,077 0 , 006Sl O, 60 0, 28 22, 5 o, 021 0, 003 0, 077 0, 006
S2 O ,63 0 ,20 22, 2 o, 014 0 ,130 0 ,046 0 ,200S2 O, 63 0, 20 22, 2 o, 014 0, 130 0, 046 0, 200
S3 O ,62 0 ,30 22, 5 o, 018 0 , 600 0 , 170 0 ,300S3 O, 62 0, 30 22, 5 o, 018 0, 600 0, 170 0, 300
Angaben in Gew.-%, Rest Fe und unvermeidbare VerunreinigungenData in wt .-%, balance Fe and unavoidable impurities
Tabelle 1Table 1
Tabelle 2Table 2
Tabelle 3Table 3
c \ c \
Tabelle 4 Table 4

Claims

P A T E N T A N S P R Ü C H E PATENT APPLICATIONS
1. Verfahren zum Beschichten eines 6 - 30 Gew.-% Mn enthaltenden warm- oder kaltgewalzten Stahlbands mit einer metallischen Schutzschicht, insbesondere einer auf Zink basierenden Schutzschicht, bei dem das zu beschichtende Stahlband bei einer 800 - 1100 C0 betragenden Glühtemperatur unter einer Stickstoff, Wasser und Wasserstoff enthaltenden Glühatmosphäre geglüht und anschließend einer Schmelztauchbeschichtung unterzogen wird, d a d u r c h g e k e n n z e i c h n e t, d a s s zur Herstellung einer im Wesentlichen von oxidischen Zwischenschichten freien metallischen Schutzschicht auf dem Stahlband das Verhältnis %H2O/%H2 des Wasser-Gehaltes %H2O zum Wasserstoff- Gehalt %H2 der Glühatmosphäre in Abhängigkeit von der jeweiligen Glühtemperatur TG wie folgt eingestellt wird:1. A method for coating a 6-30 wt .-% Mn-containing hot- or cold-rolled steel strip with a metallic protective layer, in particular a protective layer based on zinc, wherein the steel strip to be coated at a 800-1100 C 0 amount forming annealing temperature nitrogen under a , Annealed water atmosphere containing hydrogen and then subjected to a hot-dip coating, characterized in that the ratio of% H 2 O /% H 2 of the water content% H 2 O for producing a substantially free of oxidic interlayers metallic protective layer on the steel strip Hydrogen content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G as follows:
%H2O/%H2 ≤ 8-10~15-TG 3'529 % H 2 O /% H 2 ≤ 8-10 ~15 -T G 3 ' 529
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, d a s s vor dem Schmelztauchbeschichten ein Walzen des Stahlbands durchgeführt wird. 2. The method according to claim 1, characterized in that before the hot dip coating, a rolling of the steel strip is performed.
3. Verfahren nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, d a s s das Walzen in mehreren Walzschritten durchgeführt und das Stahlband zwischen jedem Walzschritt nach Maßgabe von Anspruch 1 geglüht wird.3. The method of claim 2, wherein the rolling is carried out in a plurality of rolling steps and the steel strip is annealed between each rolling step in accordance with claim 1.
4. Verfahren nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s das Glühen und das Schmelztauchbeschichten im kontinuierlichen Durchlauf erfolgt.4. Method according to one of the preceding claims, characterized in that the annealing and the hot dip coating takes place in a continuous pass.
5. Verfahren nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung im Wesentlichen vollständig aus Zn und unvermeidbaren Verunreinigungen besteht.5. Method according to one of the preceding claims, wherein the metallic coating consists essentially completely of Zn and unavoidable impurities.
6. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung eine Zink- Eisen-Beschichtung mit einem Zn-Gehalt von bis zu 92 Gew.-% und einem Fe-Gehalt von bis zu 12 Gew.-% ist.6. The method according to any one of claims 1 to 4, characterized in that the metallic coating is a zinc-iron coating having a Zn content of up to 92 wt .-% and an Fe content of up to 12 wt .-% ,
7. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung eine Aluminium-Zink-Beschichtung mit einem Al-Gehalt von bis zu 60 Gew.-% und einem Zn-Gehalt von bis zu 50 Gew. -% ist.7. The method according to any one of claims 1 to 4, characterized in that the metallic coating is an aluminum-zinc coating having an Al content of up to 60% by weight and a Zn content of up to 50% by weight.
8. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung eine Aluminium-Silizium-Beschichtung mit einem Al-Gehalt von bis zu 92 Gew.-% und einem Si-Gehalt von bis zu 12 Gew. -% ist.8. The method according to any one of claims 1 to 4, characterized in that the metallic coating is an aluminum-silicon coating having an Al content of up to 92 wt .-% and an Si content of up to 12 wt -.% Is ,
9. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung eine Zink- Aluminium-Beschichtung ist, die einen Gehalt an bis zu 10 Gew.-% Al, Rest Zink und unvermeidbare Verunreinigungen aufweist.9. A process according to any one of claims 1 to 4, wherein the metallic coating is a zinc-aluminum coating containing up to 10% by weight of Al, balance zinc and unavoidable impurities.
10. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die metallische Beschichtung eine Zink- Magnesium-Beschichtung ist, die bis zu 99,5 Gew.-% Zn und bis zu 5 Gew. -% Mg enthält.10. A process according to any one of claims 1 to 4, wherein the metallic coating is a zinc magnesium coating containing up to 99.5% Zn by weight and up to 5% Mg by weight.
11. Verfahren nach Anspruch 10, d a d u r c h g e k e n n z e i c h n e t, d a s s die Zink- Magnesium-Beschichtung bis zu 11 Gew.-% Al, bis zu 4 Gew.-% Fe und bis zu 2 Gew.-% Si enthält 11. The method according to claim 10, characterized in that the zinc-magnesium coating contains up to 11 wt .-% Al, up to 4 wt .-% Fe and up to 2 wt .-% Si
12. Verfahren nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s das Stahlband (in Gew.-%) C: < 1,6 %,12. Method according to one of the preceding claims, characterized in that the steel strip (in wt .-%) C: <1.6%, d a d e r c h e c e
Mn: 6 - 30 %, Al: < 10 %, Ni: < 10 %, Cr: < 10 %, Si: < 8 %, Cu: < 3 %, Nb: < 0,6 %, Ti: < 0,3 %, V: < 0,3 %, P: < 0,1 %, B: < 0,01 %, N: < 1,0 %, Rest Eisen und unvermeidbare Verunreinigungen enthält.Mn: 6 - 30%, Al: <10%, Ni: <10%, Cr: <10%, Si: <8%, Cu: <3%, Nb: <0.6%, Ti: <0, 3%, V: <0.3%, P: <0.1%, B: <0.01%, N: <1.0%, balance iron and unavoidable impurities.
13. Verfahren nach Anspruch 12, d a d u r c h g e k e n n z e i c h n e t, d a s s das Stahlband (in Gew.-%) C: < 1,00 %, Mn: 20,0 - 30,0 %,13. The method of claim 12, wherein said steel strip (in weight percent) is 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 %, Rest Eisen und unvermeidbare Verunreinigungen enthält.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%, remainder containing iron and unavoidable impurities.
14. Verfahren nach einem der Ansprüche 1 bis 12, d a d u r c h g e k e n n z e i c h n e t, d a s s das Stahlband (in Gew.-%) : C: < 1,00 %, Mn: 7,00 - 30,00 %, B: < 0,01 %, Ni: < 8,00 %, Cu: < 3,00 %, N: < 0,60 %, Nb: < 0,30 %,14. The method according to any one of claims 1 to 12, characterized in that the steel strip (in wt .-%): C: <1.00%, Mn: 7.00 - 30.00%, B: <0.01% , Ni: <8.00%, Cu: <3.00%, N: <0.60%, Nb: <0.30%,
Ti: < 0,30 %, V: < 0,30 %, P: < 0,01 %, sowie Al: 1,00 - 10,00 % und Si: > 2,50 - 8,00 %, mit der Maßgabe Al-Gehalt + Si-Gehalt > 3,50 - 12,00 %, Rest Eisen und unvermeidbare Verunreinigungen enthält. Ti: <0.30%, V: <0.30%, P: <0.01%, and Al: 1.00 - 10.00% and Si:> 2.50 - 8.00%, with the Measure Al content + Si content> 3.50 - 12.00%, balance iron and unavoidable impurities.
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PL2054536T3 (en) 2011-04-29
WO2008022980A3 (en) 2008-10-30
AU2007287602B2 (en) 2010-11-25
DE102006039307B3 (en) 2008-02-21
ES2353438T3 (en) 2011-03-02
EP2054536B1 (en) 2010-11-03
JP2010501725A (en) 2010-01-21
KR20090040349A (en) 2009-04-23
CN101506403A (en) 2009-08-12
KR101463221B1 (en) 2014-11-19
AU2007287602A1 (en) 2008-02-28
CA2660398A1 (en) 2008-02-28
WO2008022980A2 (en) 2008-02-28
US8394213B2 (en) 2013-03-12
CN101506403B (en) 2011-12-28
CA2660398C (en) 2013-11-05
US20100065160A1 (en) 2010-03-18
DE502007005570D1 (en) 2010-12-16
ATE486974T1 (en) 2010-11-15

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