EP2649214A2 - Process for manufacturing high manganese content steel with high mechanical resistance and formability, and steel so obtainable - Google Patents

Process for manufacturing high manganese content steel with high mechanical resistance and formability, and steel so obtainable

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Publication number
EP2649214A2
EP2649214A2 EP11820814.9A EP11820814A EP2649214A2 EP 2649214 A2 EP2649214 A2 EP 2649214A2 EP 11820814 A EP11820814 A EP 11820814A EP 2649214 A2 EP2649214 A2 EP 2649214A2
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EP
European Patent Office
Prior art keywords
steel
optionally
annealing
twip
content
Prior art date
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Granted
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EP11820814.9A
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German (de)
French (fr)
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EP2649214B1 (en
Inventor
Alessandro Ferraiuolo
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Rina Consulting Centro Sviluppo Materiali SpA
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Centro Sviluppo Materiali SpA
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Classifications

    • 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
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for drawing, e.g. 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
    • C21D6/00—Heat treatment 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for drawing, e.g. for deep-drawing
    • C21D8/0447—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for drawing, e.g. 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
    • C21D9/52—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
    • 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
    • C22C38/02—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
    • C22C38/06—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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • 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

Definitions

  • the present invention refers to the field of products made of high manganese content austenitic steel and with high mechanical resistance and high formabil- ity (steels named as TWIP, Twinning Induced Plasticity) .
  • TWIP type steels constitute within high resistance steel field a unique family being characterized in that the same display peculiar mechanical properties.
  • TWIP steels have austenitic structure with face-centered cubic lattice (FCC) along with a low stacking fault energy (SFE) promoting the activation of twinning deformation mechanisms (mechanically induced twinning) .
  • FCC face-centered cubic lattice
  • SFE stacking fault energy
  • the atoms of solute interact with dislocations through two mechanisms:
  • this TWIP steel type in particular in strip form, is particularly appreciated in the automotive field.
  • the TWIP steel strips allow the manufacturing of complexly shaped automotive components in a relatively simple way and use thereof under conditions requiring high mechanical performances, in particular for parts involved in energy absorption and structure reinforcing.
  • compositions for single alloy elements or combinations of alloy elements, independently from each other are:
  • the proposed process comprises also the further operating step to produce a metallic coating on the hot obtained strip using a zinc based alloy containing magnesium and aluminium.
  • the steel according to the invention can be used for the manufacturing of complexly shaped components to be employed for energy absorption, structure reinforcing and in general terms for automotive applications .
  • Austenitic TWIP steel according to the invention optionally coated with zinc alloy, can be used in form of strip, sheet, bar, billet, pipe.
  • SFE stacking fault energy
  • manganese plays a determining role in the stabilization of the austenitic phase. Compositionally the range thereof is 16-18% according to the present inven ⁇ tion. In correspondence of this interval of Mn percentages the maximum stabilization of austenite is observed.
  • the silicon exerts the function to increase the mechanical resistance and ductility of the steel.
  • Si content is comprised between 0.05 and 2.0%. When the percentage thereof is lower than 0.05, often a thick iron and manganese oxide layer is formed resulting in increased pickling duration, and in decreased corrosion resistance of the annealed steel and surface quality of the cold rolled sheet. When the percentage thereof is higher than 2.0%, stability properties of the steel are decreased.
  • the aluminium presence is finalized to the increment of the ductility of the steel.
  • the content thereof in the austenitic steel according to the invention is comprised between 0.01 and 2.0%.
  • the content of Al is lower than 0.01%, the mechanical resistance is increased but a quick degradation of the ductility occurs.
  • it is present in percentage higher than 2.0%, the steel exhibits decreased ductility along with lower castability during the continuous casting and corrosion susceptibility during hot rolling with consequent worsening of the surface quality of the resulting product.
  • Nitrogen promotes the gemination generation, by means of reaction with aluminium and precipitation of fine nitrides (during the solidification) within the austenitic grains, the presence thereof improves both mechanical resistance and suitability to be elongated during the steel working. Nitrogen is present in the steel used according to the invention in percentage lower than 0.1%. In fact when the content of N is higher than 0.1%, excess nitride precipitation takes place resulting in cold machinability and formability degradation.
  • Nb+Co and Re+W promote the formation of geminations, and improve both the mechanical resistance and the suitability to be elongated during steel working.
  • Figure 1 shows the microstructure of a non- deformed TWIP steel, according to example 2 of the present invention.
  • Figure 2 shows the microstructure, of a TWIP steel according to example 2 of the present invention after deformation, wherein the presence of geminates is observed.
  • a steel containing C 0.6; Mn 18; Ni 0.5; 0.3; Al 1.0; P+Sn+Sb+As 0.1; S+Se+Te 0.01; N 0.05; Nb+Co 0.1,- apart from iron and unavoidable impurities, is subjected to the process according to the present invention.
  • a 1.0 mm thick strip of claimed steel is obtained using a continuous casting plant and it is hot rolled, cold rolled and subjected to recrystallization annealing according to the invention as reported hereinafter.
  • Continuous recrystallization annealing occurs at 1000°C for 90s in non-decarburizing atmosphere, carbon activity within annealing atmosphere is 0.15, nitrogen content is 100% and dew point -25°C.
  • the final product exhibits the following mechanical features: Rp0.2 290 MPa,. Rm 1000 MPa and A80 90%, and has austenitic microstructure.
  • This product is used for the manufacturing of auto- motive components requiring high mechanical resistance and high formability, as for example car structural elements .
  • a steel containing C 0.6; Mn 17; Si 0.3; Al 0.04; P+Sn+Sb+As ⁇ 0.1; S+Se+Te 0.01; N 0.05; Re+W 0.2, apart from iron and unavoidable impurities, is subjected to the process according to the present invention.
  • a 2.0 mm thick tube made of this steel obtained using a continuous casting plant is hot rolled, cold rolled and subjected to recrystallization annealing according to the invention as reported hereinafter.
  • the recrystallization annealing is carried out in batch at 750°C for 180 minutes.
  • the carbon ⁇ activity within annealing atmosphere is 0.15
  • the nitrogen percentage within the furnace is 95%
  • the dew point is - 30°C
  • hydrogen is 5%.
  • the final strip exhibits the following mechanical features Rp0.2 310 MPa, Rm 950 MPa and A80 80% and has austenitic microstructure.
  • This product is used for the preparation of automotive components requiring high mechanical resistance and high ductility, as for example structure reinforcing bars of cars.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The subject of the present invention is a process for the production of an austenitic steel with high mechanical resistance and formability. The proposed steel has the following chemical composition in percentage by weight: C 0.2-1.5; Mn 10-25; optionally Ni<2; 0.05-2.00; A1 0.01-2.0; N<0.1; P+Sn+Sb+As<0.2; S+Se+Te<0.5; and optionally Nb+Co<1 and/or Re+W<1, the balance being Fe apart from unavoidable impurities, and is subjected to a specific recrystallization annealing treatment. Another subject of the present invention is the so ob- tainable austenitic steel product and the use thereof in the automotive industry. Figure 2 shows the microstructure - of a TWIP steel according to the invention after deformation - wherein the geminates presence is observed.

Description

PROCESS FOR MANUFACTURING HIGH MANGANESE CONTENT STEEL WITH HIGH MECHANICAL RESISTANCE AND FORMABILITY, AND
STEEL SO OBTAINABLE
- · *****
The present invention refers to the field of products made of high manganese content austenitic steel and with high mechanical resistance and high formabil- ity (steels named as TWIP, Twinning Induced Plasticity) .
High manganese content TWIP type steels constitute within high resistance steel field a unique family being characterized in that the same display peculiar mechanical properties. TWIP steels have austenitic structure with face-centered cubic lattice (FCC) along with a low stacking fault energy (SFE) promoting the activation of twinning deformation mechanisms (mechanically induced twinning) .
In the metals the two fundamental and competitive mechanisms -by means of which the plastic deformation occurs are dislocation slip and geminate formation (gemination) .
In order to obtain a steel which is deformed preferentially by means of gemination it is necessary to set up the metallurgical design of the steel in such way that the content of solute is suitable to simultaneously increase shear stress for dislocation slip and reduce the stacking fault energy (SFE) .
The atoms of solute interact with dislocations through two mechanisms:
1) Interaction among solute and dislocation produced reticular distortions. This interaction is related in some degree to dimensional difference of solute and solvent atoms. Substitutive atoms reduce stress conditions in proximity of the dislocation line: it results therefrom that a greater tension is necessary in order the dislocation to be moved.
2) In face-centered cubic lattice (FCC) the ordinary dislocations under determined conditions (low stacking fault energy) become unstable and tend to separate in two partial dislocations (Shockley dislocations) . The lattice region between the two partial dislocations is characterized by a structure defect named stacking defect, that is the normal sequence of highly stacked crystalline sheets, is altered passing from typical sequence of a face-centered cubic lattice (FCC) to that of compact hexagonal lattice (HCP) . The concentration of solute in the zone of stacking defect, at equilibrium, tends to be greater than the average value. This heterogeneous solute atom distribution exerts a further resistance to dislocation slip (Suzuki effect) .
In a typical curve true stress-true strain of a TWIP steel three steps can be distinguished:
1° step: at the beginning of plastic deformation phase wherein the deformation occurs predominantly by means of dislocation slip.
2° step: as the deformation and relative shear stress increase as a result of material hardening, the gemination demanding a greater activation energy, compared to dislocation slip, but constant one (independent of the deformation), progressively starts. Therefore a thresh- old deformation value, above which further material deformation occurs predominantly by germination, exists. This threshold value can be controlled by means of an opportune steel metallurgical design. For still increasing deformations the deformation proceeds by gemination and this results in the characteristic high ductility TWIP effect. The non-dependence of the gemination tension on deformation results in the fact that the deformation proceeds homogenously in the material and without necking (high uniform elongation) .
3° step: when the deformation reaches high values also the gemination is hindered and from this point on the deformation occurs non-homogenously and the failure occurs by localized necking.
As it is known, this TWIP steel type, in particular in strip form, is particularly appreciated in the automotive field. In fact the TWIP steel strips allow the manufacturing of complexly shaped automotive components in a relatively simple way and use thereof under conditions requiring high mechanical performances, in particular for parts involved in energy absorption and structure reinforcing.
According to the state of the art there are some proposals aiming to obtain TWIP steels exhibiting high mechanical properties and suitable for providing the above reported performances in the automotive field.
In US 2010 258212 a process for the production of high-tensile TWIP type steel involving the control of the starting steel composition and in particular of titanium content (4.0-5.0%) as an essential alloy element is proposed.
However, it does not exist a process, according to known art, completely satisfactory from the point of view of the best compromise between formability and mechanical resistance, as well as the stability of aus- tenitic phase and the surface quality of the obtained product .
Therefore there is a need in the specific field to provide a production process of a TWIP steel, in order ah optimal compromise between mechanical resistance and formability and high superficial quality to be reached.
This requirement is satisfied by the process according to the present invention wherein conditions in order the stability of the austenitic phase using the control of the chemical composition and heat treatment steps to be obtained are developed.
It is therefore the subject of the present invention a process for. the production high Mn content steel of TWIP (Twinning Induced Plasticity) type, with high mechanical resistance and formability, that has the following chemical composition, in percentage by weight :
C 0.2-1.5; Mn 10-25; optionally Ni<2; Si 0.05-2.00; Al 0.01-2.0; N<0.1; P+Sn+Sb+As<0.2 ; S+Se+Te<0.5; and optionally Nb+Co<l and/or Re+W<l, the balance being Fe apart from unavoidable impurities, and that, after having been subjected to cold rolling, is subjected to re- crystallization annealing carried out continuously at a temperature within the range of 900°C-1100°C for a time comprised between 60 seconds and 120 seconds or carried out at batches at a temperature within the range of 700°C-800°C for a time comprised between 30 minutes and 400 minutes, annealing atmosphere being such that carbon activity ac is between 0.1 and 1.0, nitrogen N2 content is between 90% and 100% for continuous annealing and between 0% and 100% for batch annealing, hydrogen content is between 0% and 10% for continuous annealing and between 0% and 100% for batch annealing, dew point is lower than 0°C and preferably between - 10°C and -50°C.
The preferred ranges of composition for single alloy elements or combinations of alloy elements, independently from each other, are:
C 0.4-0.8; Mn 16-19; optionally Ni<1.0; Si 0.2-0.4; Al 0.1-1.5; N 0.01-0.05; and optionally Nb+Co 0,1-0.4 and/or Re+W 0.3-0.7.
According to an embodiment thereof the proposed process comprises also the further operating step to produce a metallic coating on the hot obtained strip using a zinc based alloy containing magnesium and aluminium.
It is also a subject of the present invention a free coating austenitic TWIP steel, obtainable as above indicated, with the following mechanical features:
Rp0.2 between 250 and 350 MPa
Rm between 850 and 1100 MPa
A80 between 60 -and 100 %.
It is also a subject of the invention the above said austenitic steel coated with a zinc based magnesium and aluminium containing alloy obtainable using the further above reported operating step .
The steel according to the invention, optionally- coated with zinc alloy, can be used for the manufacturing of complexly shaped components to be employed for energy absorption, structure reinforcing and in general terms for automotive applications .
Austenitic TWIP steel according to the invention, optionally coated with zinc alloy, can be used in form of strip, sheet, bar, billet, pipe.
Finally it is also another subject of the invention Mn high content steel used as starting material for the above described process .
The metallurgical role exerted by the various alloy elements of TWIP steels according to the invention can be distinguished in at least four different effects:
1) Stabilization of austenitic phase with face-centered cubic lattice (FCC) . Relatively to this effect Mn and C as alloy elements exert the main role.
2) Control of the stacking fault energy (SFE) . The energy optimal range of the stacking fault energy in order the best properties of the steel in terms of ductility to be obtained is 20-40mJ/m2. Relatively to this effect the alloy elements Mn and C, together with Al and Si, exert the main role.
3) Optimization of TWIP behaviour by means of the control of plastic deformation threshold, starting therefrom the deformation occurs almost exclusively by gemination. This effect can be controlled in fine way with typically limited percents of large sized atoms like Nb, Co, Re and W. 4) Some elements, among which Al, when added at appropriate amounts, in addition to the effect on SFE, tend to act against the HCP martensite formation during the deformation of the alloy.
The function of the single alloy elements, as well as the reason for the specific selection of upper and lower range limits of the relative weight percentages, are explained hereinafter.
Carbon contributes to the stabilization of austen- ite. Compositionally the range thereof is 0.2-1.5%.
When C is lower than 0.2% crack formation is observed during the steel working. When C is higher than 1.5% a lower formability is observed.
Also manganese plays a determining role in the stabilization of the austenitic phase. Compositionally the range thereof is 16-18% according to the present inven^ tion. In correspondence of this interval of Mn percentages the maximum stabilization of austenite is observed.
The silicon exerts the function to increase the mechanical resistance and ductility of the steel. Si content is comprised between 0.05 and 2.0%. When the percentage thereof is lower than 0.05, often a thick iron and manganese oxide layer is formed resulting in increased pickling duration, and in decreased corrosion resistance of the annealed steel and surface quality of the cold rolled sheet. When the percentage thereof is higher than 2.0%, stability properties of the steel are decreased.
The aluminium presence is finalized to the increment of the ductility of the steel. The content thereof in the austenitic steel according to the invention is comprised between 0.01 and 2.0%. When the content of Al is lower than 0.01%, the mechanical resistance is increased but a quick degradation of the ductility occurs. When, on the contrary, it is present in percentage higher than 2.0%, the steel exhibits decreased ductility along with lower castability during the continuous casting and corrosion susceptibility during hot rolling with consequent worsening of the surface quality of the resulting product.
Nitrogen promotes the gemination generation, by means of reaction with aluminium and precipitation of fine nitrides (during the solidification) within the austenitic grains, the presence thereof improves both mechanical resistance and suitability to be elongated during the steel working. Nitrogen is present in the steel used according to the invention in percentage lower than 0.1%. In fact when the content of N is higher than 0.1%, excess nitride precipitation takes place resulting in cold machinability and formability degradation.
Nb+Co and Re+W promote the formation of geminations, and improve both the mechanical resistance and the suitability to be elongated during steel working.
Through the experimental activity the present invention in based on, it has been found that it is fundamental to control the activity of carbon in the atmosphere of annealing furnace in order a control of non- decarburizing or re-carburizing to be carried out. Up to now a general description has been offered for the present invention. With the aid of the following figures and examples it will be now supplied a more detailed description of embodiments thereof, in order to better understand its objects, features and advantages.
Figure 1 shows the microstructure of a non- deformed TWIP steel, according to example 2 of the present invention.
Figure 2 shows the microstructure, of a TWIP steel according to example 2 of the present invention after deformation, wherein the presence of geminates is observed.
Example 1
A steel, containing C 0.6; Mn 18; Ni 0.5; 0.3; Al 1.0; P+Sn+Sb+As 0.1; S+Se+Te 0.01; N 0.05; Nb+Co 0.1,- apart from iron and unavoidable impurities, is subjected to the process according to the present invention.
A 1.0 mm thick strip of claimed steel is obtained using a continuous casting plant and it is hot rolled, cold rolled and subjected to recrystallization annealing according to the invention as reported hereinafter.
Continuous recrystallization annealing occurs at 1000°C for 90s in non-decarburizing atmosphere, carbon activity within annealing atmosphere is 0.15, nitrogen content is 100% and dew point -25°C.
The final product exhibits the following mechanical features: Rp0.2 290 MPa,. Rm 1000 MPa and A80 90%, and has austenitic microstructure.
This product is used for the manufacturing of auto- motive components requiring high mechanical resistance and high formability, as for example car structural elements .
Example 2
A steel, containing C 0.6; Mn 17; Si 0.3; Al 0.04; P+Sn+Sb+As<0.1; S+Se+Te 0.01; N 0.05; Re+W 0.2, apart from iron and unavoidable impurities, is subjected to the process according to the present invention.
A 2.0 mm thick tube made of this steel obtained using a continuous casting plant is hot rolled, cold rolled and subjected to recrystallization annealing according to the invention as reported hereinafter.
The recrystallization annealing is carried out in batch at 750°C for 180 minutes. The carbon · activity within annealing atmosphere is 0.15, the nitrogen percentage within the furnace is 95%, the dew point is - 30°C, and hydrogen is 5%.
The final strip exhibits the following mechanical features Rp0.2 310 MPa, Rm 950 MPa and A80 80% and has austenitic microstructure.
. This product is used for the preparation of automotive components requiring high mechanical resistance and high ductility, as for example structure reinforcing bars of cars.
Example 3
In this comparative example TWIP steels from examples 1 and 2, obtained according to the process of the present invention, and comparative steels TRIP 800, HSLA S700MC and DP 980 are compared in terms of mechanical properties, microstructure and supply condi- tions .
The comparison results are reported in the following table :
RpO .2 Rm A80 Microstructure Supply con¬
(MPa) (MPa) (%) ditions
Exam le 290 1000 90 Austenite Hot and 1 cold rolled
Exam le 310 950 80 Austenite Hot and 2 cold rolled
TRIP 800 500 850 30 Ferrite + Baini- Hot and te/Martensite + cold rolled residual Austenite
HSLA 700 850 15 Ferrite + Bainite Hot rolled (S700MC)
DP 980 650 1000 14 Ferrite + Marten- Cold rolled site

Claims

1. Process for manufacturing high Mn content austenitic steel of the TWIP (Twinning Induced Plasticity) type, with high mechanical resistance and formability, characterized in that the steel has the following chemical composition, in percentage by weight:
C 0.2-1.5; Mn 10-25; optionally Ni<2; Si 0.05-2.00; Al 0.01-2.0; N<0.1; P+Sn+Sb+As<0.2 ; S+Se+Te<0.5 ; and optionally Nb+Co<l and/or Re+W<l, the balance being Fe apart from unavoidable impurities, and in that, after having been subjected to cold rolling, it is subjected to recrystallxzation annealing carried out continuously at a temperature within the range of 900°C-1100°C for a time interval between 60 seconds and 120 seconds or carried out at batches at a temperature within the range of 700°C-800°C for a time interval between 30 minutes and 400 minutes, annealing atmosphere being such that Carbon activity ac is between 0.1 and 1.0, nitrogen N2 content is between 90% and 100% for continuous annealing and between 0% and 100% for batch annealing, hydrogen content is between 0% and 10% for continuous annealing and between 0% and 100% for batch annealing, dew point is lower than 0°C and preferably between - 10°C and -50°C.
2. Process according to claim 1, wherein preferred composition ranges for single alloy elements or for combination of alloy elements, independently from each other, are :
C 0.4-0.8; Mn 16-19; optionally Ni<1.0; Si 0.2-0.4; Al 0.1-1.5; N 0.01-0.05; and optionally Nb+Co 0.1-0.4 and/or Re+W 0.3-0.7.
3. Process according to claim 1 or 2, comprising the further operation of making a metallic coating obtained under hot conditions by a zinc based alloy containing magnesium and aluminum.
4. Austenitic steel with twinning induced plasticity (TWIP) , characterized in that it is obtainable by the process according to claim 1 or 2, with the following mechanical features :
Rp0.2 between 250 and 350 MPa
Rm between 850 and 1100 MPa
A80 between 60 and 100 %.
5. Austenitic steel coated by a zinc based alloy containing magnesium and aluminum, characterized in that it is obtainable by the process according to claim 3.
6. Use of austenitic steel according to claim 4 or 5 for manufacturing complex geometry components, for absorption of energy, structural reinforces and automotive applications.
7. High manganese content steel, characterized in that it has the following chemical composition, in percentage by weight: C 0.2-1.5; Mn 10-25; optionally Ni<2; Si 0.05-2.00; Al 0.01-2.0; N<0.1; P+Sn+Sb+As<0.2 ; S+Se+Te<0.5; and optionally Nb+Co<l and/or Re+W<l, the balance being Fe apart from unavoidable impurities.
8. Steel according to claim 7, wherein preferred composition ranges for single alloy elements or for combination of alloy elements are: C 0.4-0.8; Mn 16-19; optionally Ni<1.0; Si 0.2-0.4; Al 0.1-1.5; N 0.01-0.05; and optionally Nb+Co 0.1-0.4 and/or Re+W 0.3-0.7.
EP11820814.9A 2010-12-07 2011-12-07 Process for manufacturing high manganese content steel with high mechanical resistance and formability, and steel so obtainable Active EP2649214B1 (en)

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ITRM2010A000641A IT1403129B1 (en) 2010-12-07 2010-12-07 PROCEDURE FOR THE PRODUCTION OF HIGH MANGANESE STEEL WITH MECHANICAL RESISTANCE AND HIGH FORMABILITY, AND STEEL SO OBTAINABLE.
PCT/IT2011/000401 WO2012077150A2 (en) 2010-12-07 2011-12-07 Process for manufacturing high manganese content steel with high mechanical resistance and formability, and steel so obtainable

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3095889A1 (en) 2015-05-22 2016-11-23 Outokumpu Oyj Method for manufacturing a component made of austenitic steel
WO2017081072A1 (en) 2015-11-09 2017-05-18 Outokumpu Oyj Method for manufacturing an austenitic steel component and use of the component

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013003516A1 (en) 2013-03-04 2014-09-04 Outokumpu Nirosta Gmbh Process for the production of an ultra-high-strength material with high elongation
KR101657808B1 (en) * 2014-12-22 2016-09-20 주식회사 포스코 Austenitic steel with excellent resistance for adiabatic shear band formability and method for manufacturing thereof
TWI504756B (en) 2015-01-30 2015-10-21 中國鋼鐵股份有限公司 Manufacture method of high strength and high ductility steel
SI3117922T1 (en) 2015-07-16 2018-07-31 Outokumpu Oyj Method for manufacturing a component of austenitic twip or trip/twip steel
US11420419B2 (en) 2015-12-24 2022-08-23 Posco Austenite-based molten aluminum-plated steel sheet having excellent properties of plating and weldability
CN105755388B (en) * 2016-04-18 2018-04-24 和县隆盛精密机械有限公司 A kind of casting method of mechanical arm high-strength abrasion-proof casting
DE102016117494A1 (en) 2016-09-16 2018-03-22 Salzgitter Flachstahl Gmbh Process for producing a formed component from a medium manganese steel flat product and such a component
KR101903174B1 (en) 2016-12-13 2018-10-01 주식회사 포스코 Low alloy steel sheet with excellent strength and ductility
WO2018188766A1 (en) 2017-04-11 2018-10-18 Thyssenkrupp Steel Europe Ag Cold-rolled flat steel product annealed in a bell-type furnace, and method for the production of said product
CN107574377B (en) * 2017-09-07 2019-05-03 北京科技大学 A kind of high energy absorption type high manganese TWIP steel based on nanostructure and preparation method thereof
KR101952818B1 (en) 2017-09-25 2019-02-28 주식회사포스코 Low alloy steel sheet with high strength and ductility and method of manufacturing same
EP3735479A4 (en) * 2018-01-05 2021-07-28 The University of Hong Kong STEEL FOR AUTOMOTIVE AND ITS PRODUCTION PROCESS
CN117265419B (en) * 2022-06-15 2025-10-17 宝山钢铁股份有限公司 High-formability, easy-phosphating and high-manganese cold-rolled steel sheet with strength of 1000-1600MPa and manufacturing method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2796083B1 (en) * 1999-07-07 2001-08-31 Usinor PROCESS FOR MANUFACTURING IRON-CARBON-MANGANESE ALLOY STRIPS, AND STRIPS THUS PRODUCED
DE10259230B4 (en) * 2002-12-17 2005-04-14 Thyssenkrupp Stahl Ag Method for producing a steel product
FR2876708B1 (en) * 2004-10-20 2006-12-08 Usinor Sa PROCESS FOR MANUFACTURING COLD-ROLLED CARBON-MANGANESE AUSTENITIC STEEL TILES WITH HIGH CORROSION RESISTANT MECHANICAL CHARACTERISTICS AND SHEETS THUS PRODUCED
FR2876711B1 (en) * 2004-10-20 2006-12-08 Usinor Sa HOT-TEMPERATURE COATING PROCESS IN ZINC BATH OF CARBON-MANGANESE STEEL BANDS
FR2878257B1 (en) * 2004-11-24 2007-01-12 Usinor Sa PROCESS FOR MANUFACTURING AUSTENITIC STEEL SHEET, FER-CARBON-MANGANIZED WITH VERY HIGH RESISTANCE AND ELONGATION CHARACTERISTICS, AND EXCELLENT HOMOGENEITY
WO2006082104A1 (en) * 2005-02-02 2006-08-10 Corus Staal Bv Austenitic steel having high strength and formability, method of producing said steel and use thereof
EP1878811A1 (en) * 2006-07-11 2008-01-16 ARCELOR France Process for manufacturing iron-carbon-manganese austenitic steel sheet with excellent resistance to delayed cracking, and sheet thus produced
KR100985286B1 (en) * 2007-12-28 2010-10-04 주식회사 포스코 High strength and high manganese steel excellent in delayed fracture resistance and manufacturing method
US8528379B2 (en) 2009-04-08 2013-09-10 Kirk Ernest Williamson Method and apparatus for applying tension to flexible items

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012077150A2 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3095889A1 (en) 2015-05-22 2016-11-23 Outokumpu Oyj Method for manufacturing a component made of austenitic steel
WO2016188948A1 (en) 2015-05-22 2016-12-01 Outokumpu Oyj Method for manufacturing a component made of austenitic steel
WO2017081072A1 (en) 2015-11-09 2017-05-18 Outokumpu Oyj Method for manufacturing an austenitic steel component and use of the component
EP3173504A1 (en) 2015-11-09 2017-05-31 Outokumpu Oyj Method for manufacturing an austenitic steel component and use of the component
US12241139B2 (en) 2015-11-09 2025-03-04 Outokumpu Oyj Method for manufacturing an austenitic steel component and use of the component

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IT1403129B1 (en) 2013-10-04
CN103339279B (en) 2016-09-28
WO2012077150A3 (en) 2012-11-22
CN103339279A (en) 2013-10-02
ITRM20100641A1 (en) 2012-06-08
KR20140025324A (en) 2014-03-04
EP2649214B1 (en) 2016-12-07

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