EP4234750A1 - Ultrahochfestes stahlblech mit hervorragender duktilität und verfahren zur herstellung davon - Google Patents

Ultrahochfestes stahlblech mit hervorragender duktilität und verfahren zur herstellung davon Download PDF

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Publication number
EP4234750A1
EP4234750A1 EP21883121.2A EP21883121A EP4234750A1 EP 4234750 A1 EP4234750 A1 EP 4234750A1 EP 21883121 A EP21883121 A EP 21883121A EP 4234750 A1 EP4234750 A1 EP 4234750A1
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Prior art keywords
steel sheet
less
temperature
cold
high strength
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EP21883121.2A
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English (en)
French (fr)
Inventor
Joo-Hyun Ryu
Yeon-Sang Ahn
Kang-Hyun Choi
Eul-Yong Choi
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Posco Holdings Inc
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Posco Co Ltd
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Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Publication of EP4234750A1 publication Critical patent/EP4234750A1/de
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    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
    • C21D1/22—Martempering
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
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    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
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    • 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
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    • 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
    • C21D8/0226—Hot rolling
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    • 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
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • 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
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • 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
    • C21D8/0273—Final recrystallisation annealing
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    • 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
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • 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
    • C22C38/04—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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—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
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    • 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
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    • 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
    • C21D2211/002—Bainite
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    • 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
    • C21D2211/005—Ferrite
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
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    • 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
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    • C23C2/06—Zinc or cadmium or alloys based thereon
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    • 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

Definitions

  • the present disclosure relates to a steel sheet suitable as a vehicle material, and more particularly, to an ultra-high strength steel sheet having excellent ductility.
  • the phase-transformation steel is classified into ferrite-martensite dual phase (DP) steel in which a hard martensite phase is formed in a ferrite matrix, transformation induced plasticity (TRIP) steel using transformation induced plasticity of retained-austenite, and complexed phase (CP) steel composed of ferrite and a hard bainite or martensite structure.
  • DP ferrite-martensite dual phase
  • TRIP transformation induced plasticity
  • CP complexed phase
  • Each type of steel has different mechanical properties, that is, a tensile strength and an elongation, according to a type and fraction of a mother phase and a second phase.
  • TRIP steel containing a large amount of a retained-austenite phase has the highest tensile strength and elongation balance (TS ⁇ EI) value.
  • Patent Document 1 discloses steel that contains about 10% of a retained-austenite phase, in addition to ferrite and martensite, has a product of a tensile strength and an elongation of 21,000 MPa% or more, and may secure a tensile strength of 780 MPa or more.
  • carbon (C) and silicon (Si) are added to the steel in high contents of about 0.2% and about 1.5% or more, respectively, spot weldability and hot-dip galvanizing properties may be deteriorated.
  • annealing is performed twice in order to realize high physical properties, there is a problem in that the manufacturing cost of the steel sheet is increased.
  • Patent Document 2 discloses a technique capable of lowering a content of Si to a level of 1% in order to secure excellent plating properties and spot weldability and securing a tensile strength of 980 MPa or more and an elongation of 15% or more by being composed of martensite, bainite, and ferrite without containing a retained-austenite phase as a microstructure.
  • high-strength steel having an excellent yield strength has been adopted for structural members such as a member, a seat rail, and a pillar, but the steel has a yield strength of 700 MPa or less, and thus has limitations in its applications.
  • An aspect of the present disclosure is to provide a steel sheet, a steel sheet suitable for a vehicle structural member and the like, having an excellent tensile strength and yield strength and improved ductility, and a method for manufacturing the same.
  • an ultra-high strength steel sheet having excellent ductility contains, by wt%, 0.1 to 0.2% of carbon (C), 0.1 to 1.0% of silicon (Si), 2.0 to 3.0% of manganese (Mn), 1.0% or less (excluding 0%) of aluminum (Al), 1.0% or less of chromium (Cr), 0.5% or less of molybdenum (Mo), 0.1% or less of titanium (Ti), 0.1% or less of niobium (Nb), 0.1% or less (excluding 0%) of antimony (Sb), 0.05% or less of phosphorus (P), 0.02% or less of sulfur (S), 0.02% or less of nitrogen (N), and a balance of Fe and unavoidable impurities, wherein the ultra-high strength steel sheet satisfies the following Relational Expressions 1 to 3.
  • each element represents a weight content
  • a method for manufacturing an ultra-high strength steel sheet having excellent ductility includes: preparing a steel slab satisfying the alloy composition and Relational Expressions 1 to 3; heating the steel slab to a temperature within a range of 1,050 to 1,300°C; hot rolling the heated steel slab at a temperature within a range of 800 to 1,000°C to manufacture a hot-rolled steel sheet; coiling the hot-rolled steel sheet at a temperature within a range of 400 to 700°C; cold rolling the coiled hot-rolled steel sheet at a total reduction ratio of 20 to 70% to manufacture a cold-rolled steel sheet; annealing the cold-rolled steel sheet at a temperature within a range of 800 to 900°C; cooling the continuously annealed cold-rolled steel sheet to a temperature range of 250 to 400°C; and reheating and maintaining the cooled cold-rolled steel sheet, wherein the reheating and maintaining are performed at a temperature within a range of the cooled temperature + 50°C or higher to the cooled temperature + 200°
  • a steel sheet having an excellent tensile strength and yield strength and improved ductility may be provided, and the steel sheet of the present disclosure has an advantage of guaranteeing formability and crashworthiness required for a steel sheet for cold forming.
  • the inventors of the present disclosure have intensively conducted studies to provide a steel sheet as a vehicle material that guarantees formability and crashworthiness because it has an excellent tensile strength and ductility and has an excellent yield strength, and thus is applicable to a structural member required to be processed into a complex shape, and the like.
  • a steel sheet having a structure advantageous for securing desired physical properties may be provided by optimizing an alloy composition system and manufacturing conditions, thereby completing the present disclosure.
  • the present disclosure is characterized by providing a steel sheet having a composite structure in which a soft phase and a hard phase are properly dispersed by controlling a content relationship between specific elements among alloy components and optimizing process conditions of a steel sheet manufactured through a series of processes.
  • An ultra-high strength steel sheet having excellent ductility may contain, by wt%, 0.1 to 0.2% of carbon (C), 0.1 to 1.0% of silicon (Si), 2.0 to 3.0% of manganese (Mn), 1.0% or less (excluding 0%) of aluminum (Al), 1.0% or less of chromium (Cr), 0.5% or less of molybdenum (Mo), 0.1% or less of titanium (Ti), 0.1% or less of niobium (Nb), 0.1% or less (excluding 0%) of antimony (Sb), 0.05% or less of phosphorus (P), 0.02% or less of sulfur (S), and 0.02% or less of nitrogen (N).
  • C carbon
  • Si silicon
  • Mn manganese
  • Al aluminum
  • Cr chromium
  • Mo molybdenum
  • Ti titanium
  • Nb niobium
  • P antimony
  • S 0.05% or less of phosphorus
  • S sulfur
  • N nitrogen
  • a content of each element is based on weight, and a ratio of a structure is based on area, unless specifically stated otherwise.
  • Carbon (C) is an element that significantly contributes to enhancing the strength of the steel sheet. C precipitates in grains of the steel sheet to induce solid solution strengthening and promotes formation of martensite in the steel to strengthen the steel.
  • C is an austenite stabilizing element and plays an important role in forming retained-austenite. Specifically, as the amount of carbon (C) solid-dissolved in austenite is increased, austenite stability is increased, such that a fraction of austenite in the steel is increased. This induces an increase in fraction of martensite formed due to transformation of austenite, such that an effect of improving the strength of the steel sheet may be obtained, and some austenite remains at room temperature to remain as retained-austenite.
  • C may be added in an amount of 0.1% or more.
  • the content thereof exceeds 0.2%, the fraction of the martensite phase is excessively increased, and a fraction of a ferrite phase having an excellent elongation and impact absorption energy is relatively decreased. This causes a reduction in ductility of the steel sheet and an increase in possibility of occurrence of brittleness.
  • C may be contained in an amount of 0.1 to 0.2%, and more preferably 0.12% or more and 0.18% or less.
  • Silicon (Si) is an element contributing to stabilization of retained-austenite by suppressing precipitation of carbides in ferrite and inducing diffusion of carbon in ferrite to austenite.
  • Si in an amount of 0.1% or more.
  • Si oxide is formed on a steel surface, which may cause deterioration of the effects of hot-dip plating and chemical conversion coating.
  • Si may be contained in an amount of 0.1 to 1.0%, and more preferably 0.2% or more, and still more preferably 0.40 or more. Meanwhile, still more preferably, Si may be contained in an amount of 0.9% or less.
  • Manganese (Mn) may act as an austenite stabilizing element similar to C. Specifically, Mn may contribute to increasing the fraction of martensite in the steel by reducing a critical cooling rate at which martensite is formed in the composite structure steel.
  • Mn is contained in an amount of 2.0% or more.
  • weldability of the steel sheet is deteriorated, which may cause deterioration of hot rolling properties.
  • Mn forms a striped band called a Mn-Band, which inhibits formability and increases a risk of processing cracks.
  • Mn may be contained in an amount of 2.0 to 3.0%, and more preferably 2.2% or more and 2.8% or less.
  • Aluminum (Al) is an element added for deoxidation of the steel, and is a ferrite stabilizing element similar to Si. Al is effective to improve hardenability of martensite by distributing carbon in ferrite into austenite, and is an element useful for improving the ductility of the steel sheet by effectively suppressing precipitation of carbides in bainite when held in a bainite region.
  • Al may be contained in an amount of 1.0% or less, and 0% is excluded. More preferably, Al may be contained in an amount of 0.01% or more.
  • Al refers to acid-soluble aluminum (Sol.Al).
  • Chromium is an element added to improve the hardenability of steel and secure high strength, and plays an important role in the formation of martensite.
  • Cr is advantageous in manufacturing a composite structural steel having high ductility by minimizing a decrease in elongation compared to an increase in strength.
  • Cr may be contained in an amount of 1.0% or less, and there is no difficulty in securing intended physical properties even when Cr is not intentionally added.
  • Molybdenum (Mo) is an element that forms carbides in the steel, and may contribute to improving a yield strength and a tensile strength by forming fine carbides in steel through combination with Ti, Nb, and the like, in the steel. When a content of Mo exceeds 0.5%, the elongation of the steel is decreased, and the manufacturing cost is increased.
  • Mo may be contained in an amount of 0.5% or less, and there is no difficulty in securing intended physical properties even when Mo is not intentionally added.
  • Titanium (Ti) may contribute to securing the yield strength and the tensile strength of the steel by forming fine carbides in the steel similar to Mo.
  • Ti forms nitride to precipitate N contained in the steel as TiN, such that it is possible to prevent N from being combined with Al to be precipitated as AlN, which may have an effect of reducing a risk of cracks occurring in a casting process.
  • Ti may be contained in an amount of 0.1% or less, and there is no difficulty in securing intended physical properties even when Ti is not intentionally added.
  • Niobium (Nb) is segregated at austenite grain boundaries to suppress coarsening of austenite grains during an annealing heat treatment and to precipitate fine carbides on the grains, thereby contributing to increasing the strength of the steel sheet.
  • Nb may be contained in an amount of 0.1% or less, and there is no difficulty in securing intended physical properties even when Nb is not intentionally added.
  • Antimony (Sb) is distributed on grain boundaries to delay diffusion of oxidizing elements such as Mn, Si, and Al in the steel through grain boundaries, such that Sb has an advantageous effect in suppressing a surface concentration of oxides and suppressing coarsening of the surface concentrate depending on a temperature rise and a hot rolling process change.
  • Sb may be contained in an amount of 0.1% or less, and 0% is excluded. More preferably, Sb may be contained in an amount of 0.01% or more.
  • Phosphorus (P) is segregated at grain boundaries and becomes a major cause of temper brittleness, causing deterioration of the weldability and toughness. Therefore, it is advantageous to control a content of P to be as close to 0% as possible.
  • P is inevitably contained in the steel manufacturing process, a process for decreasing the content of P is difficult, and the manufacturing cost is increased due to an additional process, therefore it is effective to manage an upper limit thereof.
  • the content of P may be limited to 0.05% or less and more preferably may be limited to 0.03% or less. However, it should be noted that 0% may be excluded in consideration of a level that is unavoidably added.
  • S Sulfur
  • S is an impurity that is unavoidably contained in the steel together with P, and has a problem of inhibiting the ductility and weldability of the steel sheet. Therefore, it is also advantageous to control a content of S as low as possible to be as close to 0% as possible, but in consideration of the cost and time consumed in a process for decreasing the content of S, it is effective to manage an upper limit thereof.
  • the content of S may be limited to 0.02% or less and more preferably may be limited to 0.01% or less. However, it should be noted that 0% may be excluded in consideration of a level that is unavoidably added.
  • Nitrogen (N) may be combined with Al in the steel to form an alumina-based non-metallic inclusion of AlN.
  • AlN deteriorates the casting quality and increases the brittleness of the steel sheet, causing an increase in risk of fracture defects.
  • a content of N may be limited to 0.02% or less and more preferably may be limited to 0.01% or less. However, 0% may be excluded in consideration of a level that is unavoidably added.
  • the remaining component of the present disclosure is iron (Fe).
  • Fe iron
  • unintended impurities may be inevitably mixed from raw materials or surrounding environments in a general manufacturing process. Therefore, it is difficult to exclude these impurities. Since these impurities may be recognized in the general manufacturing process by those skilled in the art, all the contents thereof are not particularly described in the present specification.
  • each element represents a weight content.
  • Relational Expressions 1 and 2 are component relational expressions derived by quantifying a degree of contribution to reinforcing the yield strength and the tensile strength of the steel sheet through control of the fraction of the microstructural phase constituting the steel sheet and improvement of the solid solution strengthening effect.
  • C has a relatively larger coefficient than Si and Mn, and this is because C is solid-dissolved in the grains of the steel sheet and significantly contributes to the improvement of the strength.
  • Si has a relatively smaller coefficient than C, which is due to a smaller effect contributing to solid solution strengthening than C.
  • Al has a negative coefficient value, which contributes to solid solution strengthening, but causes retaining of ferrite in a dual phase region during annealing or promotion of ferrite transformation during subsequent cooling, resulting in a further decrease in strength.
  • Cr and Mo are representative hardenable elements, and suppress ferrite transformation during cooling after annealing, such that they have an effect of improving strength and are represented by positive values.
  • Ti and Nb are elements that form fine carbides and contribute to improvement of the strength
  • Ti and Nb may have a positive coefficient value in the strength relational expression according to the component elements.
  • fine carbides are formed and the amount of solid-dissolved carbon is reduced at the same time, and thus, the solid solution strengthening effect of carbon is decreased.
  • Ti and Nb have a positive coefficient value when the precipitation strengthening effect is dominant due to addition thereof, whereas Ti and Nb may have a negative coefficient value when the solid solution strengthening effect of carbon due to precipitation of carbides is dominant.
  • Relational Expression 3 is a component relational expression derived by quantifying a degree of contribution to improving the elongation of the steel sheet as well as the improvement of the solid solution strengthening effect by specific elements.
  • C and Mn are advantageous for the improvement of strength by the solid solution strengthening effect, but since the elongation tends to be decreased due to the improvement of strength, C and Mn have a negative coefficient value.
  • Al has a positive coefficient value because it is effective in increasing the elongation.
  • Si also has a positive coefficient value in Relational Expression 3 because it contributes to the improvement of strength by the solid solution strengthening and securing retained-austenite.
  • the steel sheet having the alloy composition system of the present disclosure contains a soft phase and a hard phase that are properly dispersed as a microstructure, and in particular, contains, in terms of an area fraction, 3 to 20% of ferrite, 1 to 10% of retained-austenite, 1 to 30% of bainite, 30 to 70% of tempered martensite, and a balance of fresh martensite.
  • the ferrite is an allotrope of iron (Fe) having a body centered cubic (BCC) structure, and is a soft structure unlike martensite and bainite. Therefore, an elongation thereof is higher than those of the bainite and martensite phases, and has excellent impact absorption energy.
  • the ferrite may be contained in an area fraction of 3 to 20% and more preferably 5 to 15%.
  • the retained-austenite refers to an austenite structure remaining in the steel without being transformed into martensite or bainite in a series of heat treatment processes during the manufacturing process of the steel sheet (in the present disclosure, corresponding to [annealing - cooling - reheating and maintaining] processes), and serves to adjust a balance between the strength and the elongation of the steel sheet.
  • the retained-austenite phase is useful for improving the balance between strength and elongation because it increases the tensile strength (TS) ⁇ elongation (EI) value of the steel sheet.
  • the retained-austenite phase may be contained in an area fraction of 1% or more, but when the fraction thereof exceeds 10%, sensitivity of liquid metal embrittlement is increased, causing deterioration of spot weldability.
  • the retained-austenite may be contained in an area fraction of 1 to 10% and more preferably 3 to 9%.
  • the bainite may contribute to improving workability by reducing a difference in strength between the structures in the steel. That is, the bainite serves to prevent cracks, defects, and fractures in the steel sheet due to a difference in hardness between ferrite and retained-austenite phases having relatively low hardness and tempered martensite and fresh martensite having relatively high hardness.
  • the bainite may be contained in an area fraction of 1% or more and more preferably 5% or more.
  • the fraction exceeds 30%, the fraction of fresh martensite is decreased, and thus, it is difficult to secure a desired level of strength.
  • the bainite may be contained in an area fraction of 1 to 30%.
  • the tempered martensite refers to a structure obtained by tempering a martensite phase obtained by quenching austenite at a temperature of about 500°C to soften the martensite phase.
  • a tempered martensite phase has higher strength than the structures described above, and thus significantly contributes to improving the yield strength and the tensile strength of the steel sheet.
  • carbon in the martensite obtained by quenching is distributed to the surrounding austenite during the tempering process to increase thermal stability of the austenite, which may allow the austenite to remain at room temperature. Therefore, the tempered martensite has an effect of improving the elongation of the steel sheet.
  • the tempered martensite phase is preferably contained in an area fraction of 30% or more. However, when the fraction exceeds 70%, a fraction of the retained-austenite phase may be relatively decreased.
  • the tempered martensite may be contained in an area fraction of 30 to 70%.
  • a fresh martensite phase may be contained.
  • the fresh martensite phase is a structure obtained in a process of final cooling to room temperature and has the highest strength, the fresh martensite phase significantly contributes to improving the yield strength and the tensile strength of the steel sheet.
  • a fraction of the fresh martensite phase is not particularly limited, but as an example, it should be noted that the fresh martensite phase may be contained in an area fraction of 3% or more.
  • the steel sheet of the present disclosure has an excellent tensile strength, yield strength, and elongation due to appropriate formation of a soft phase and a hard phase, and specifically, may have a yield strength of 700 MPa or more, a tensile strength of 980 MPa or more, and an elongation of 13% or more.
  • the steel sheet of the present disclosure may be a cold-rolled steel sheet, and may be a hot-dip galvanized steel sheet including a zinc-based plating layer formed on at least one surface of the cold-rolled steel sheet or an alloyed hot-dip galvanized steel sheet obtained by subjecting the hot-dip galvanized steel sheet to an alloying treatment.
  • the zinc-based plating layer may be a zinc plating layer mainly containing zinc or a zinc alloy plating layer containing aluminum and/or magnesium in addition to zinc.
  • a desired steel sheet may be manufactured through processes of [steel slab reheating - hot rolling - coiling - cold rolling - continuous annealing - cooling - reheating and maintaining], and then, processes of [hot-dip galvanizing - alloying heat treatment] may be further performed.
  • a steel slab satisfying all the alloy composition systems described above may be prepared and then heated. This process is performed to smoothly perform a subsequent hot rolling process and to obtain sufficient physical properties of a desired steel sheet.
  • the heating process may be performed to a temperature within a range of 1,050 to 1,300°C.
  • the heating temperature is lower than 1,050°C, friction between the steel sheet and the rolling mill is increased, and a load applied to the roller during the hot rolling is rapidly increased.
  • the temperature exceeds 1,300°C, the energy cost required for temperature rise is increased, and the amount of surface scale is also increased, which may lead to a loss of the material.
  • the heating process may be performed to a temperature within a range of 1,050 to 1,300°C, and more preferably may be performed to a temperature within a range of 1,090 to 1,250°C.
  • the steel slab heated according to the above may be hot-rolled to manufacture a hot-rolled steel sheet, and in this case, finish hot rolling may be performed at a temperature within a range of 800 to 1,000°C.
  • the finish hot rolling process in the hot rolling may be performed at a temperature within a range of 800 to 1,000°C, and more preferably may be performed at a temperature within a range of 850 to 950°C.
  • the hot-rolled steel sheet manufactured according to the above may be coiled, and in this case, the coiling may be performed at a temperature within a range of 400 to 700°C.
  • the strength of the hot-rolled steel sheet is excessively increased, which may cause a rolling load during subsequent cold rolling.
  • an excessive cost and time are required to cool the hot-rolled steel sheet to the coiling temperature, causing an increase in process cost.
  • the temperature exceeds 700°C a scale is excessively generated on the surface of the hot-rolled steel sheet, which is highly likely to cause surface defects and deteriorates plating properties.
  • the coiling process may be performed at a temperature within a range of 400 to 700°C, and more preferably may be performed at a temperature within a range of 500 to 700°C.
  • the coiled hot-rolled steel sheet may be cooled to room temperature.
  • a cooling rate is not particularly limited, but the cooling may be performed by air cooling.
  • the hot-rolled steel sheet may be cold-rolled to manufacture a cold-rolled steel sheet, and in this case, the cold rolling may be performed at a cold reduction ratio of 20 to 70%.
  • the cold reduction ratio during the cold rolling is less than 20%, it is difficult to obtain a steel sheet having a desired thickness, and it is difficult to correct a shape of the steel sheet.
  • the cold reduction ratio exceeds 70%, cracks are likely to occur at an edge portion of the steel sheet, and a cold rolling load is caused.
  • coarse ferrite may be formed during subsequent continuous annealing.
  • the cold rolling may be performed at a cold reduction ratio of 20 to 70%, and more preferably may be performed at a cold reduction ratio of 30 to 60%.
  • the hot-rolled steel sheet may be subjected to a pickling treatment.
  • the pickling treatment is a process of removing the scale formed on the surface of the hot-rolled steel sheet using hydrochloric acid (HCl) or the like, and may be performed under common conditions, and therefore, the conditions thereof are not particularly limited.
  • the cold-rolled steel sheet manufactured according to the above may be subjected to an annealing treatment, as an example, a continuous annealing process may be performed, but is not limited thereto. Any of known annealing methods may be used.
  • ferrite formed in the cold-rolled steel sheet may be recrystallized through the annealing process, and the fractions of ferrite and austenite in the steel may be adjusted.
  • the strength of the steel sheet manufactured after the final heat treatment (referred to a reheating process described below) is determined by the fraction of each phase formed.
  • the fraction of the austenite is increased, the fraction of martensite or bainite transformed from austenite is increased, and thus the strength of the steel sheet tends to be improved.
  • the strength may be additionally controlled by a series of heat treatment conditions described below.
  • carbon (C) in the steel may be distributed through the annealing process, and as a result, the amount of carbon (C) contained in austenite is increased, such that the steel sheet may have up to 10 area% of an austenite phase even at room temperature.
  • the annealing process may be performed at a temperature within a range of 800 to 900°C.
  • the fraction of austenite formed through the annealing process is decreased, such that fractions of tempered martensite, bainite, and fresh martensite formed during a heat treatment described below may not be sufficient. This may cause decreases in yield strength and tensile strength of a final steel sheet.
  • the temperature exceeds 900°C the fraction of austenite in the steel sheet is excessively high, such that some austenite is transformed into ferrite during a heat treatment process described below.
  • a carbon concentration in retained-austenite is decreased and mechanical stability is reduced, causing a decrease in elongation of the steel sheet.
  • moisture generated as Fe in the steel is oxidized reacts with Si, Mn, and Al in the steel to increase the possibility of forming an oxide coating film on the steel sheet.
  • the oxide coating film inhibits wettability of Zn during hot-dip galvanizing, which may cause deterioration of the surface quality of the steel sheet.
  • the annealing process may be performed at a temperature within a range of 800 to 900°C, and more preferably may be performed at a temperature within a range of 820 to 870°C.
  • the cold-rolled steel sheet after completing the annealing process according to the above may be cooled.
  • quenched martensite may be formed by performing cooling on the annealed cold-rolled steel sheet, and to this end, the cooling is preferably performed at a temperature equal to or lower than a martensite transformation initiation temperature (Ms). More preferably, the cooling may be performed to a temperature range of 250 to 400°C.
  • Ms martensite transformation initiation temperature
  • a fraction of quenched martensite is increased as the temperature during the cooling is lower, which may induce improvement of the strength of the steel sheet.
  • supersaturated carbon in martensite is distributed to surrounding austenite in a subsequent heat treatment process to increase the stability of retained-austenite, and as a result, an increase in elongation may be achieved.
  • the cooling may be performed at an average cooling rate of 2 to 50°C/s.
  • the cooling rate is less than 2°C/s, ferrite is further transformed during the cooling, resulting in a decrease in strength.
  • rapid cooling is performed at a cooling rate of more than 50°C/s, a cooling deviation between positions of the steel sheet occurs, causing deterioration of the shape of the steel sheet.
  • a cooling method is not particularly limited.
  • the cooling may be performed by a single cooling method in which cooing is performed to a cooling end temperature at an initial set cooling rate as it is, and as another example, the cooling may be performed by a step-by-step cooling method in which slow cooling is performed up to a certain section and then strong cooling is performed to a cooling end temperature, but the cooling method is not limited thereto.
  • a process of maintaining the steel sheet at the cooled temperature for a certain period of time may be performed, and in this process, an isothermal transformation phase may be additionally introduced to obtain an effect of accelerating the transformation of bainite in a subsequent process.
  • the maintaining process may be performed for 0.1 to 60 minutes.
  • the cooled cold-rolled steel sheet, and furthermore, the cooled and maintained cold-rolled steel sheet may be tempered by reheating the cooled cold-rolled steel sheet to a temperature range higher than the cooling temperature by about 50 to 200°C, and then maintaining the cooled cold-rolled steel sheet for a predetermined time.
  • the quenched martensite phase formed in the cooling process is tempered and transformed into tempered martensite, and the tempered martensite has an advantage of a high yield strength because carbon is fixed to dislocations.
  • supersaturated carbon (C) in quenched martensite is redistributed into the surrounding austenite, or bainite transformation is induced to improve the stability of retained-austenite, such that an effect of improving an elongation may be obtained.
  • the reheating may be limited to be performed at the cooled temperature + 200°C or lower.
  • the steel sheet After completing the process of reheating and maintaining the cooled cold-rolled steel sheet as described above, the steel sheet may be cooled to room temperature under common conditions, and finally, a steel sheet having a structure in which certain fractions of a soft phase and a hard phase are properly distributed may be obtained.
  • a steel sheet having a microstructure composed of, in terms of an area fraction, 3 to 20% of ferrite, 1 to 10% of retained-austenite, 1 to 30% of bainite, 30 to 70% of tempered martensite, and a balance of fresh martensite may be obtained, and such a steel sheet of the present disclosure may have an excellent yield strength and tensile strength and improved ductility.
  • the process of cooling to room temperature is not particularly limited, but may be performed by air cooling as an example. However, it is obvious that the process may be replaced with known cooling methods such as water cooling, oil cooling, and furnace cooling.
  • a plated steel sheet including a plating layer formed on at least one surface thereof may be manufactured by plating the cold-rolled steel sheet after completing the series of heat treatment processes according to the above as described below.
  • a hot-dip galvanized steel sheet may be manufactured by immersing the steel sheet manufactured through the series of processes described above in a hot-dip zinc-based plating bath.
  • the hot-dip galvanizing may be performed under common conditions, and as an example, the hot-dip galvanizing may be performed to a temperature within a range of 430 to 490°C.
  • the composition of the hot-dip zinc-based plating bath in the hot-dip galvanizing is not particularly limited, and the hot-dip zinc-based plating bath may be a pure zinc plating bath or a zinc-based alloy plating bath containing Si, Al, Mg, and the like.
  • An hot-dip galva-annealed steel sheet may be obtained by subjecting the hot-dip galvanized steel sheet to an alloying heat treatment, if necessary.
  • the process conditions of the alloying heat treatment process are not particularly limited as long as they are common conditions.
  • the alloying heat treatment process may be performed to a temperature within a range of 480 to 600°C.
  • Each cold-rolled steel sheet manufactured according to the above was subjected to a continuous annealing treatment at the temperature T1 (°C) shown in Table 2 for 1 minute, the continuous annealed steel sheet was cooled to the temperature T2 (°C) and then maintained for 10 seconds, the steel sheet was reheated to the temperature T3 (°C) and then maintained for 1 minute, and then the reheated steel sheet was cooled (air-cooled) to room temperature, thereby manufacturing a final steel sheet.
  • the cooling to the temperature T2 after the annealing treatment was uniformly performed at a cooling rate of 15°C/s.
  • the yield strength (YS), the tensile strength (TS), and the elongation (El) were measured, and the mechanical properties were measured by a universal tensile tester using ASTM tensile test pieces.
  • Relational Expression 1 characterized in the present disclosure, contributes to enhancing the yield strength by the microstructure fraction and solid solution strengthening effect of the steel sheet
  • Relational Expression 2 contributes to improving the tensile strength of the steel sheet
  • Relational Expression 3 contributes to improving the ductility of the steel sheet.
  • FIG. 1 is a photograph of the structure of Inventive Example 1, and it may be confirmed that ferrite, retained-austenite, tempered martensite, and bainite are formed within the desired fraction ranges, and the fresh martensite phase is formed as a residual structure.
  • FIG. 2 is a photograph of the structure of Comparative Example 6, and it may be confirmed that the tempered martensite phase is not formed in a desired fraction, the retained-austenite phase is not sufficiently secured, and the fresh martensite phase is formed in a relatively high fraction.

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CN116507753A (zh) 2023-07-28
US20230357881A1 (en) 2023-11-09

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