EP3186401A1 - Procédé pour la fabrication d'un acier d'emballage azoté - Google Patents

Procédé pour la fabrication d'un acier d'emballage azoté

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Publication number
EP3186401A1
EP3186401A1 EP15732735.4A EP15732735A EP3186401A1 EP 3186401 A1 EP3186401 A1 EP 3186401A1 EP 15732735 A EP15732735 A EP 15732735A EP 3186401 A1 EP3186401 A1 EP 3186401A1
Authority
EP
European Patent Office
Prior art keywords
steel
nitrogen
ppm
annealing furnace
gas
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
EP15732735.4A
Other languages
German (de)
English (en)
Other versions
EP3186401B1 (fr
Inventor
Burkhard KAUP
Blaise Massicot
Dirk Matusch
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 AG
ThyssenKrupp Rasselstein GmbH
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Rasselstein GmbH
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 AG, ThyssenKrupp Rasselstein GmbH filed Critical ThyssenKrupp AG
Priority to RSP20191157 priority Critical patent/RS59266B1/sr
Publication of EP3186401A1 publication Critical patent/EP3186401A1/fr
Application granted granted Critical
Publication of EP3186401B1 publication Critical patent/EP3186401B1/fr
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Classifications

    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0257—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0405—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing of ferrous alloys
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
    • C21D8/0436—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
    • C21D8/0457—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
    • C21D8/0473—Final recrystallisation annealing
    • 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
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25

Definitions

  • the invention relates to a method for producing an embroidered packaging steel having the features of claim 1 and an embroidered packaging steel in the form of a flat steel product having the features of claim 12.
  • packaging steel flat steel products such as steel sheets or steel strips, which are intended for the production of packaging (hereinafter referred to as packaging steel), is known from the prior art.
  • a steel sheet for packaging purposes and a method for its production is described, which was prepared from an aluminum-killed, continuously cast carbon-manganese steel and received by embroidering a lot of unbound, dissolved nitrogen, wherein the Minimum amount of unbound nitrogen is defined as a function of a desired hardness category of the steel sheet and (for example for the hardness category T61 of the European standard 145-78) has an amount of unbound nitrogen of at least 5 ppm.
  • the chemical composition of the steel sheet disclosed therein corresponds to the usual soft steels in terms of carbon and manganese content and has, for example, a carbon content in the range of 0.03 to 0.1 wt .-% and a manganese content of 0.15 to 0.5 wt. -% on.
  • the steel sheet is characterized by a high yield strength in the range of 350-550 N / mm 2 .
  • a maximum value of 100 ppm is given, stating that the steel sheet at a higher content of unbound nitrogen due to the associated increase in strength no longer cold-rollable and thus not for the intended use as cold-rolled packaging steel suitable is.
  • a steel is first cast continuously, then hot rolled, cold rolled, recrystallized annealed and finally rolled.
  • Post-rolling is followed by a thermal aftertreatment in which free dislocations formed in the steel by re-rolling are fixed by the unbound nitrogen introduced by the seepage to increase the hardness and yield strength over the post-temper values.
  • the thermal aftertreatment can advantageously be combined with another thermal treatment of the post-rolled steel, which is to be carried out anyway in the context of the production of a packaging steel, such as, for example, melting a tin layer applied electrolytically to the surface of the steel sheet or baking a lacquer layer applied to the steel sheet surface ,
  • EP 0 216 399 B1 Because of the proposed upper limit in EP 0 216 399 B1 for the amount of unbound and dissolved in steel nitrogen of 100 ppm, the strengths of this known packaging steel are limited. It seems possible in principle to produce steel sheets with an even higher content of unbound nitrogen in the steel in order to achieve tensile strengths above 600 MPa. Thus, for example, EP 1 342 798 B1 and DE 1 433 690 A1 describe embroidered steels having a nitrogen content of up to 250 ppm or up to 400 ppm. However, such high levels of unbound nitrogen in the steel have not been realized in practice.
  • the embroidering of a steel can be introduced in the manufacturing process of the steel by introducing nitrogen into the molten steel, for example by blowing nitrogen gas N 2 .
  • a process for embroidering steel melts in steel production in the oxygen inflation process is described, for example, in DE 2 237 498.
  • Flat steel products in particular steel strips, can be embroidered by surface conditioning, for example by diffusion of nitrogen into the steel sheet surface, which can be done for example by gas nitriding in an ammonia atmosphere with slight overpressure, by bath nitriding in nitrogen-containing salt baths or by plasma nitriding.
  • surface conditioning for example by diffusion of nitrogen into the steel sheet surface, which can be done for example by gas nitriding in an ammonia atmosphere with slight overpressure, by bath nitriding in nitrogen-containing salt baths or by plasma nitriding.
  • the object of the invention is to show a flat steel product (sheet steel or steel strip) for the production of packaging, which has the highest possible strength at the same time has good elongation at break and good forming properties.
  • a packaging steel with strengths of at least 600 MPa with an elongation at break of at least 5% should be made available.
  • the higher-strength packaging steel must simultaneously have sufficient formability for the intended use as packaging steel, for example in deep-drawing or ironing, so that from the flat steel product intended packaging, such as cans or cans can be produced.
  • the present as flat steel product packaging steel should have the usual thicknesses in the fine and Feinstblech Scheme, which are regularly produced by cold rolling.
  • the process of the present invention can produce an embroidered packaging steel having a carbon content of 10 to 1000 ppm and an amount of unbound steel dissolved nitrogen of greater than 100 ppm and preferably greater than 150 ppm, with the steel being upset in two stages ,
  • a molten steel is nitrided to a maximum nitrogen content of 160 ppm by feeding nitrogen to the molten steel, for example in the form of a nitrogen-containing gas and / or a nitrogen-containing solid.
  • a slab is poured and hot rolled into a hot strip.
  • the hot strip is subsequently pickled (after cooling to ambient temperature), if necessary, and cold rolled to a flat steel product (steel sheet or steel strip).
  • the cold-rolled steel flat product is then recrystallized in an annealing furnace.
  • the second step of the nitrogenizing step is carried out by introducing a nitrogen-containing gas into the annealing furnace and directing it to the flat steel product to increase the amount of unbound nitrogen in the steel beyond the amount of nitrogen introduced into the molten steel in the first stage of the nitrogenizing step continue to increase.
  • the two-stage embroidering of the packaging steel ensures that the hot-rolled strip with the cold rolling devices (rolling mills) usually used for the production of packaging steels can be easily converted into a flat steel product, in particular to a steel strip, cold rolled.
  • This is made possible by the fact that in the first stage of the Aufstickens a content of unbound nitrogen of at most 160 ppm is introduced into the molten steel.
  • the hot strip produced from the embroidered molten steel by hot rolling remains cold-rolled at these nitrogen contents, so that a fine or very fine sheet can be produced in the standard thickness for packaging purposes from the hot strip by cold rolling. Higher nitrogen contents in the molten steel also lead to undesirable defects in the slab cast from the molten steel.
  • the desired strength of the packaging steel preferably greater than 600 MPa, is achieved during cold rolling and in the second stage of the nitrogen blanketing of the flat steel product during its recrystallizing annealing.
  • flat steel products, in particular steel strips, with thicknesses in the fine and Feinstblech Scheme for use as packaging steel with very high tensile strengths at the same time high elongation at break of preferably at least 5% can be produced without suffering a restriction in the forming properties.
  • the steel melt is embossed in the first stage by introducing nitrogen gas (N 2 ) and / or lime nitrogen (CaCN 2 ) and / or manganese nitrogen (MnN) into the molten steel.
  • the embroidering of the flat steel product in the second stage is preferably carried out by introducing ammonia gas (NH 3 ) into the annealing furnace, in which the steel flat product is annealed in a recrystallizing manner.
  • the ammonia gas is thereby gassed by means of spray nozzles on the surface of the flat steel product.
  • the amount of ammonia gas introduced into the annealing furnace is preferably adjusted so that an ammonia equilibrium with an ammonia concentration in the range of 0.05 to 1.5% is established in the annealing furnace.
  • the ammonia concentration in the annealing furnace is preferably detected by means of an ammonia sensor, and the detected measured value of the ammonia equilibrium concentration is used for controlling the amount of ammonia gas introduced into the annealing furnace per unit time.
  • an inert gas is preferably introduced into the annealing furnace during the recrystallizing annealing in the annealing furnace in the second stage of the addition of nitrogen, for example nitrogen gas and / or hydrogen gas or a mixture thereof, for example in a composition of 95% by weight. Nitrogen gas and 5% by weight of hydrogen gas.
  • the total amounts of unbound nitrogen introduced by the two-stage embroidering of the packaging steel are between 100 and 500 ppm, preferably above 150 ppm and more preferably in the range between 200 and 350 ppm.
  • a maximum nitrogen content of 160 ppm is introduced into the molten steel. Maintaining an upper limit of about 160 ppm for the content of unbound nitrogen in the molten steel ensures that no defects occur on the slab produced from the molten steel, for example in the form of pores and cracks, which can oxidise by ambient oxygen.
  • the hot strip produced from the slab remains cold-rolled at a nitrogen content of at most 160 ppm.
  • the amount of unbound nitrogen which can additionally be introduced in the second stage when the steel flat product is being embroidered is preferably in the range from 180 to 350 ppm.
  • a total amount of unbound nitrogen in the packaging steel according to the invention of up to 500 ppm can be introduced by the two stages of the embroidering.
  • tensile strengths of more than 650 MPa and up to 1000 Mpa can be achieved, whereby a linear relationship has been established between the content of unbound nitrogen and the tensile strength and, for example for tensile strengths of about 650 MPa, a content of unbound nitrogen of approx 200 ppm is required.
  • the cold-rolled steel flat product For recrystallizing annealing of the cold-rolled steel flat product, it is preferably heated in the annealing furnace to temperatures of more than 600 ° C. and in particular of more than 620 ° C.
  • the recrystallizing annealing restores the formability of the cold-rolled steel flat product.
  • heating of the flat steel product to a temperature of 620 ° C. to 660 ° C. and more preferably of approximately 640 ° C. has proven to be preferred.
  • a plurality of spray nozzles are preferably used, with which a nitrogen-containing gas, such as ammonia gas, can be uniformly applied to the surface of the flat steel product.
  • the plurality of spray nozzles are preferably arranged equidistant from each other.
  • a homogeneous nitriding of the flat steel product over the entire surface is possible.
  • FIG. 1 a schematic representation of an annealing furnace in which the second stage of the method according to the invention is carried out;
  • an embroidered molten steel is initially produced in a converter and / or in a subsequent ladle treatment, which has a content of free, unbound (ie dissolved in steel) nitrogen of up to 160 ppm.
  • the carbon content of the steel produced is preferably in the range from 10 to 1000 ppm and more preferably between 100 and 900 ppm and usually between 400 and 900 ppm.
  • the converter is filled with scrap and pig iron and the melt is blown with oxygen gas and nitrogen gas, wherein the oxygen gas (02) from above and nitrogen gas (N2) is injected from below into the converter by means of bottom nozzles.
  • oxygen gas (02) from above and nitrogen gas (N2) is injected from below into the converter by means of bottom nozzles.
  • N2 nitrogen gas
  • a nitrogen content in the molten steel of 70 to 120 ppm sets, whereby it comes to a saturation.
  • the composition and esp. The nitrogen content of the melt is detected. If the given analysis has not been made (for example, if the level of phosphorus is too high) oxygen gas is bubbled through an oxygen lance and argon gas (Ar) through the bottom nozzles. Since hardly any more carbon (C) is present in the steel, no overpressure arises and the nitrogen of the air is pulled in with, whereby it can come to an additional nitriding.
  • manganese nitride for example in the form of a wire of MnN powder in a steel shell, may be added in the third argon sink.
  • the amount of possibly missing nitrogen is converted into a required amount of MnN (for example, into a required length of the MnN wire), which is added to the melt.
  • the MnN is added until the predetermined nitrogen target level or Mn upper limit of the steel is reached.
  • the melt is placed in a distributor trough to pour a slab from the molten steel. Due to leaks and diffusion of atmospheric nitrogen, the nitrogen content may rise by about 10 ppm. An upper limit of the amount of dissolved nitrogen in the cast steel slab of about 160 ppm should not be exceeded, because at higher nitrogen contents, defects may form on the slab such as cracks or pores, which lead to undesired oxidation.
  • the slab cast from the molten steel is then hot rolled and cooled to room temperature.
  • the hot strip produced has thicknesses in the range of 1 to 4 mm and is possibly wound up into a roll (coil).
  • the hot strip must be cold rolled, with a reduction in thickness ranging from 50 to more than 90%.
  • Thin sheet is understood to mean a sheet with a thickness of less than 3 mm and a fine sheet has a thickness of less than 0.5 mm.
  • the hot strip which may have been wound up as a roll, is unwound from the roll, pickled and introduced into a cold rolling device, for example a cold rolling mill.
  • the cold-rolled steel strip In order to restore the crystal structure of the steel, which has been destroyed during cold rolling, the cold-rolled steel strip must be recrystallized. This is done by passing the cold-rolled steel strip through a continuous annealing furnace in which the steel strip is heated to temperatures above the recrystallization point of the steel and in particular to temperatures above 600 ° C. In the process according to the invention, a further embroidering of the steel strip in a second stage takes place simultaneously with the recrystallization annealing. This is carried out in the annealing furnace by introducing into the annealing furnace a nitrogen-containing gas, preferably ammonia (NH 3 ).
  • FIG. 1 schematically shows a continuous annealing furnace for carrying out the recrystallization and the second stage of the nitrogenizing step.
  • various zones are formed, which are arranged one after the other in the direction of passage (strip running direction V, in FIG. 1 from right to left) of the steel strip guided through the continuous annealing furnace.
  • a heating zone 1 arranged on the input side of the continuous annealing furnace, the steel strip S is heated to temperatures in the range from 600 ° C. to 750 ° C.
  • the heating zone 1 is followed by a holding zone 2, in which the temperature of the steel strip S is maintained in the above-mentioned temperature range.
  • a plurality of cascades 3a, 3b, 3c of spray nozzles in the strip running direction are arranged one behind the other.
  • Each cascade 3a, 3b, 3c comprises a plurality of nozzles 3, which are arranged transversely to the strip running direction at a distance from each other.
  • the nozzles 3 are coupled to a gas supply line via which they are charged with a nitrogen-containing gas.
  • a nitrogen-containing gas As the gas particularly suitable for the second stage of the gasification, ammonia gas has been found.
  • a nozzle device for treating a flat steel product wherein the nozzle device comprises an outer tube and an inner tube disposed therein with a primary opening for feeding a gas flowing through the nozzle device in the outer tube and the outer tube is provided with a secondary opening through which the gas escape can.
  • the primary opening of the inner tube and the secondary opening of the outer tube are offset from each other. This allows a very homogeneous flow of gas to the surface of the flat steel product.
  • a homogeneous fumigation of the surface of the steel strip in the holding zone 2 of the continuous annealing furnace with the nitrogen-containing gas (ammonia) can be achieved, whereby over the surface of the steel strip, in particular across its width, a homogeneous diffusion of nitrogen and thereby the formation of a homogeneous, nitrogen-enriched and cured surface layer can be achieved.
  • the nitrogen-containing gas ammonia
  • the method of direct loading of the steel strip (gassing) with a nitrogen-containing gas by means of nozzles has two major advantages: Firstly, only a low concentration of nitrogen (NH 3 concentration) in the protective gas is required, resulting in a low consumption of nitrogen-containing gas (eg NH 3 consumption). On the other hand, there is no formation of a nitride layer due to a very short reaction time. Following gassing with a nitrogen-containing gas (eg NH 3 treatment), the steel strip is annealed even further (expediently more than 5 seconds) at unchanged temperatures, before it is cooled. This results in a homogenization of the nitrogen distribution over the cross section of the steel strip and consequently to improved forming properties.
  • NH 3 concentration nitrogen
  • NH 3 consumption nitrogen-containing gas
  • this can be used to avoid expansion loss due to paint aging (see page 6, lines 14 - 20).
  • a nitrogen-containing atmosphere with a nitrogen equilibrium concentration which is as constant as possible must be maintained during the passage of the steel strip S through the holding zone 2 of the continuous annealing furnace.
  • is in the range of cascades 3a, 3b, 3c with the Nozzles 3 detects the nitrogen concentration formed.
  • ammonia is used as the nitrogen-containing gas
  • the ammonia concentration formed in the holding zone 2 by gassing with ammonia is measured for this purpose.
  • a concentration sensor arranged outside the continuous annealing furnace is provided, which may, for example, be a laser spectroscopy sensor.
  • This is fed to a gas sample taken from the holding zone 2 in order to detect the ammonia concentration and from this the nitrogen concentration of the gas atmosphere in the holding zone 2.
  • the gas sample is, for example, taken at the point indicated by reference numeral 4 in FIG.
  • the concentration of the nitrogen in the gas atmosphere of the holding zone 2 detected by the concentration sensor is supplied to and used by a controller to keep the amount of nitrogen-containing gas (ammonia) sprayed into the holding zone 2 via the nozzles 3 constant at a predetermined target value.
  • Target values for the equilibrium concentration of the ammonia in the range of 0.05 to 1.5%, and preferably of less than 1%, in particular less than 0.2%, have proven particularly expedient when ammonia is used as the nitrogen-containing gas.
  • the equilibrium concentration of the ammonia is in the range of 0.1 to 1.0%, and more preferably between 0.1 and 0.2%.
  • an inert gas is expediently introduced into the annealing furnace in the holding zone 2 in addition to the nitrogen-containing gas (ammonia).
  • This may, for example, be nitrogen gas and / or hydrogen gas.
  • a mixture of about 95% nitrogen and about 5% hydrogen gas is used.
  • a plurality of cooling zones 5, 6 adjoin the holding zone 2 in the strip running direction V, with a faster cooling of the steel strip S in a first cooling zone 5 and a slower cooling in a subsequent second cooling zone 6.
  • the steel strip S leaves the continuous annealing furnace and is dry-rolled (dressed) in order to give the strip the forming properties required for the production of packaging.
  • the degree of rolling varies between 0.4 and 2%, depending on the intended use of the packaging steel.
  • the steel strip can also be wet rolled to another Thickness reduction by up to 43% (double reduced steel strip, "double reduced DR") .
  • the steel strip S is then optionally fed to a coating plant in which the surface of the steel strip to increase the corrosion resistance, for example, electrolytically with a tin or a It has been found that packaging steels produced by the process according to the invention also have better properties in terms of their corrosion resistance than the known flat steel products.
  • embroidered steel strips can be produced, which are characterized by a very high strength of more than 600 MPa with simultaneously good elongation at break of more than 5% and good forming properties.
  • the increased through the two-stage Aufsticken strength and elongation at break are very homogeneous over the cross section of the steel strip both in and across the rolling direction of the cold-rolled steel strip. This results from the very homogeneous introduction of unbound nitrogen into the steel, especially in the second stage of the stitching.
  • the recrystallizing annealing and the second step of the embossing can be carried out in a continuous annealing furnace instead of in a continuous annealing furnace.
  • the cold rolled and wound as a roll steel strip S is placed in a crucible annealing furnace and annealed there under a protective gas atmosphere at the required for a recrystallizing annealing annealing temperatures of more than 520 ° C.
  • the annealing process takes place in an "open-coü" process in which spacers are inserted between the layers of the rolled steel strip to form the surface of the steel strip to keep the diffusion of nitrogen accessible.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé pour la fabrication d'un acier d'emballage azoté présentant une teneur en carbone de 10 à 1000 ppm et une quantité d'azote non lié, dissous dans l'acier, supérieure à 100 ppm, l'azotage ayant lieu en deux étapes, à savoir une première étape, dans laquelle une masse fondue d'acier est azotée à une teneur en azote de maximum 160 ppm par introduction d'un gaz contenant de l'azote et/ou d'un solide contenant de l'azote dans la masse fondue d'acier, et une deuxième étape, dans laquelle un produit en acier plat obtenu par laminage à froid à partir de la masse fondue d'acier azoté est traité par un gaz contenant de l'azote pour augmenter davantage l'azote non lié dans le produit en acier plat. La deuxième étape de l'azotage a lieu dans un four de recuit, dans lequel le produit en acier plat est simultanément recuit avec recristallisation. Les aciers d'emballage fabriqués par ce procédé se caractérisent par une solidité élevée supérieure à 600 MPa et par un bon allongement à la rupture qui est régulièrement supérieur à 5 % ainsi que par de bonnes propriétés de déformation. L'invention concerne en outre un acier d'emballage azoté sous forme d'un produit en acier plat.
EP15732735.4A 2014-08-27 2015-07-02 Procédé de fabrication d'un acier d'emballage nitruré Active EP3186401B1 (fr)

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RSP20191157 RS59266B1 (sr) 2014-08-27 2015-07-02 Postupak za proizvodnju nitriranog čelika za ambalažu

Applications Claiming Priority (2)

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DE102014112286.0A DE102014112286A1 (de) 2014-08-27 2014-08-27 Verfahren zur Herstellung eines aufgestickten Verpackungsstahls
PCT/EP2015/065055 WO2016030056A1 (fr) 2014-08-27 2015-07-02 Procédé pour la fabrication d'un acier d'emballage azoté

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EP3186401B1 EP3186401B1 (fr) 2019-06-12

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EP (1) EP3186401B1 (fr)
JP (1) JP6357274B2 (fr)
KR (1) KR102439567B1 (fr)
CN (1) CN106661655B (fr)
AU (1) AU2015309232B2 (fr)
BR (1) BR112017002172B1 (fr)
CA (1) CA2954713C (fr)
DE (1) DE102014112286A1 (fr)
ES (1) ES2734402T3 (fr)
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DE102020112485B3 (de) 2020-05-08 2021-08-12 Thyssenkrupp Rasselstein Gmbh Stahlblech und Verfahren zur Herstellung eines Stahlblechs für Verpackungen
EP3875611A1 (fr) * 2020-03-06 2021-09-08 ThyssenKrupp Rasselstein GmbH Produit en acier laminé à froid pour emballages

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3221477B1 (fr) 2014-11-19 2020-06-03 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'un acier d'emballage nitré
EP3736348B1 (fr) * 2014-11-19 2023-06-07 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'un acier d'emballage brodé
EP3875611A1 (fr) * 2020-03-06 2021-09-08 ThyssenKrupp Rasselstein GmbH Produit en acier laminé à froid pour emballages
DE102020112485B3 (de) 2020-05-08 2021-08-12 Thyssenkrupp Rasselstein Gmbh Stahlblech und Verfahren zur Herstellung eines Stahlblechs für Verpackungen
WO2021224026A1 (fr) 2020-05-08 2021-11-11 Thyssenkrupp Rasselstein Gmbh Tôle d'acier et procédé de production d'une tôle d'acier pour emballage

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BR112017002172A2 (pt) 2017-11-21
KR102439567B1 (ko) 2022-09-02
US10920309B2 (en) 2021-02-16
BR112017002172B1 (pt) 2021-09-08
AU2015309232A1 (en) 2017-02-02
WO2016030056A1 (fr) 2016-03-03
ES2734402T3 (es) 2019-12-05
CN106661655A (zh) 2017-05-10
US20170253957A1 (en) 2017-09-07
KR20170046642A (ko) 2017-05-02
RS59266B1 (sr) 2019-10-31
EP3186401B1 (fr) 2019-06-12
CA2954713A1 (fr) 2016-03-03
CN106661655B (zh) 2018-09-28
AU2015309232B2 (en) 2018-06-14
JP6357274B2 (ja) 2018-07-11
DE102014112286A1 (de) 2016-03-03
JP2017534748A (ja) 2017-11-24
CA2954713C (fr) 2020-05-12

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