WO2017155263A1 - Tôle d'acier galvanisée par immersion à chaud ayant une aptitude au durcissement par cuisson et une résistance au vieillissement supérieures, et procédé permettant de la fabriquer - Google Patents

Tôle d'acier galvanisée par immersion à chaud ayant une aptitude au durcissement par cuisson et une résistance au vieillissement supérieures, et procédé permettant de la fabriquer Download PDF

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WO2017155263A1
WO2017155263A1 PCT/KR2017/002417 KR2017002417W WO2017155263A1 WO 2017155263 A1 WO2017155263 A1 WO 2017155263A1 KR 2017002417 W KR2017002417 W KR 2017002417W WO 2017155263 A1 WO2017155263 A1 WO 2017155263A1
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steel sheet
hot
less
dip galvanized
hardening
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PCT/KR2017/002417
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English (en)
Korean (ko)
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한상호
안연상
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주식회사 포스코
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Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to US16/079,641 priority Critical patent/US20190071746A1/en
Priority to CN201780016428.7A priority patent/CN108779537A/zh
Priority to EP17763524.0A priority patent/EP3428302A4/fr
Priority to JP2018546894A priority patent/JP2019512600A/ja
Publication of WO2017155263A1 publication Critical patent/WO2017155263A1/fr

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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
    • 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
    • C21D8/0273—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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/0426—Hot 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
    • C21D8/0421—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
    • C21D8/0473—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
    • C22C38/02—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
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • 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
    • C21D2211/005—Ferrite
    • 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
    • C21D2211/008—Martensite
    • 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
    • C21D8/0226—Hot 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
    • C21D8/0221—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
    • 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

Definitions

  • the present invention relates to a hot-dip galvanized steel sheet having excellent baking hardening and age resistance and a method of manufacturing the same, and more particularly, hot-dip galvanizing coating having excellent baking hardening and anti-aging properties which can be preferably applied as a material for panel panels for automobiles. It relates to a steel sheet and a method of manufacturing the same.
  • high-strength steels are being actively used to satisfy both the weight reduction and the high strength of the automobile body.
  • the hardening hardening phenomenon is the phenomenon that the yield strength increases due to the solid solution of activated carbon and nitrogen attached to the dislocation generated in the fret, which increases the strength of the hardening. Due to its improved properties, it is ideal for automotive exterior paneling materials. In addition, it is required to have a certain level of aging resistance to guarantee the aging for a certain period or more in order to apply the material for the automotive exterior panel.
  • Japanese Patent Laid-Open Publication No. 2005-264176 discloses a steel sheet having a composite structure mainly composed of martensite, and has a fine Cu precipitate having a particle diameter of 1 to 100 nm in the structure for improving workability.
  • distributed was disclosed.
  • this technique needs to add an excess of 2 to 5% of Cu in order to precipitate fine Cu particles, which may cause red brittleness resulting from Cu and excessively increase manufacturing costs.
  • Japanese Laid-Open Patent Publication No. 2004-292891 discloses a composite steel sheet comprising a ferrite as a main phase, a residual austenite as a two phase, and a veriniite and martensite as a low temperature transformation phase, and a method for improving the ductility and extension flange of the steel sheet. have.
  • this technique has a problem in that it is difficult to secure the plating quality by adding a large amount of Si and Al to secure the retained austenite phase, and it is difficult to secure the surface quality during steelmaking and performance.
  • due to the metamorphic organic plasticity has a high yield ratio high initial YS value.
  • Korean Patent Laid-Open Publication No. 10-2012-0073564 is a technique for providing a high-strength hot-dip galvanized steel sheet with good workability, comprising a steel sheet including a composite of soft ferrite and hard martensite as a microstructure, and its elongation and r value.
  • a manufacturing method for improving the Lankford value is disclosed.
  • this technique not only ensures excellent plating quality as a large amount of Si is added, but also causes a problem in that the manufacturing cost increases due to the addition of a large amount of Ti and Mo.
  • One of the objects of the present invention is to provide a hot-dip galvanized steel sheet excellent in hardening hardening and aging resistance and a method of manufacturing the same.
  • One aspect of the present invention includes a cold rolled steel sheet and a hot dip galvanized layer formed on the surface of the cold rolled steel sheet, wherein the cold rolled steel sheet is weight percent, C: 0.02 to 0.08%, Mn: 1.3 to 2.1%, and Si: 0.3 % Or less (except 0%), Cr: 1.0% or less (except 0%), P: 0.1% or less (except 0%), S: 0.01% or less (except 0%), N: 0.01% or less (Excluding 0%) and sol.Al: 0.01% to 0.06%, Mo: 0.2% or less (excluding 0%) and B: 0.003% or less (excluding 0%) Containing a remainder Fe and unavoidable impurities, comprising 90-99 area% ferrite and 1-10 area% martensite as a microstructure, at a point of 1 / 4t of the sheet thickness of the cold rolled steel sheet, The ratio (a / b) of the average carbon concentration a in the ferrite located in the imaginary
  • the ratio (d / c) of the average manganese concentration c in martensite and the average manganese concentration d in ferrite located in an imaginary circle having the long axis of the martensite is 0.9 or less is excellent in hardening hardening and aging resistance It provides a galvanized steel sheet.
  • C 0.02 ⁇ 0.08%, Mn: 1.3 ⁇ 2.1%, Si: 0.3% or less (excluding 0%), Cr: 1.0% or less (excluding 0%) ), P: 0.1% or less (excluding 0%), S: 0.01% or less (excluding 0%), N: 0.01% or less (excluding 0%), and sol.Al: 0.01 to 0.06%, Reheating a steel slab comprising at least one selected from the group consisting of Mo: 0.2% or less (excluding 0%) and B: 0.003% or less (excluding 0%), the balance Fe and inevitable impurities; Hot rolling a reheated steel slab in an austenitic single phase region to obtain a hot rolled steel sheet, winding the hot rolled steel sheet, cold rolling the wound hot rolled steel sheet to obtain a cold rolled steel sheet, and the cold rolled steel sheet at 760 to 850 ° C.
  • Continuous annealing at step the first step of cooling the continuous annealing cold rolled steel sheet at an average cooling rate of 2 ⁇ 14 °C / sec to 630 ⁇ 670 °C, the first cooled cold rolled steel sheet (Ms + 20) ⁇ ( Ms + 50) Secondary cooling at an average cooling rate of 3 to 12 ° C./sec until the third cooling of the secondary cooled cold rolled steel sheet at a rate of 4 to 8 ° C./sec to 440 to 480 ° C., the third cooling Immersing the cold rolled steel sheet into a hot dip galvanizing bath to obtain a hot dip galvanized steel sheet, and finally cooling the hot dip galvanized steel sheet at an average cooling rate of 3 ° C./sec or more to (Ms-100) ° C. or lower. It provides a method for producing a hot-dip galvanized steel sheet having excellent baking hardening and aging resistance comprising a.
  • the hot-dip galvanized steel sheet according to an embodiment of the present invention is very excellent in hardening hardening and aging resistance, it can be preferably applied as a material for automotive exterior panels.
  • the inventors of the present invention as a result of in-depth study to provide a hot-dip galvanized steel sheet not only excellent in formability by securing strength and ductility at the same time to be suitable as a material for the exterior panel of the automobile, but also excellent hardening and aging resistance, cold rolled steel sheet
  • a hot-dip galvanized steel sheet satisfying the intended physical properties was provided, and thus the present invention was completed.
  • the hot dip galvanized steel sheet of the present invention includes a cold rolled steel sheet and a hot dip galvanized layer formed on one or both sides of the cold rolled steel sheet.
  • the composition of the hot dip galvanized layer is not particularly limited, and may be a pure galvanized layer or a zinc-based alloy plated layer containing Si, Al, Mg, or the like.
  • the hot dip galvanized layer may be an alloyed hot dip galvanized layer.
  • alloy component and the preferred content range of the cold rolled steel sheet is described in detail. It is noted that the content of each component described below is based on weight unless otherwise specified.
  • Carbon is an essential element added to secure the composite structure desired in the present invention, and in general, as the content of carbon increases, martensite is more easily formed, which is advantageous for producing a composite tissue steel, but the intended strength and yield ratio (yield) In order to secure strength / tensile strength), it is required to manage the proper content. If the carbon content is less than 0.02%, it may be difficult to secure the strength targeted in the present invention, and it may be difficult to form an appropriate level of martensite. On the other hand, when the content exceeds 0.08%, grain boundary bainite is promoted during cooling after annealing, so that the yield ratio of steel is increased, and bending and surface defects are easily generated during processing into automotive parts. Therefore, in the present invention, the carbon content is controlled to 0.02 to 0.08%, more preferably 0.03 to 0.06%.
  • Manganese is an element that improves the hardenability in composite steel, especially an important role in the formation of martensite. If the content of manganese is less than 1.3%, it is difficult to form a composite tissue steel because martensite is impossible to form. On the other hand, if it exceeds 2.1%, martensite is excessively formed and the material becomes unstable. And there is a problem that greatly increases the risk of plate breaking. In addition, there is a problem in that the manganese oxide is eluted to the surface during annealing greatly inhibit the plating property. Therefore, in the present invention, the content of manganese is controlled to 1.3 to 2.1%, more preferably, 1.4 to 1.8%.
  • Silicon contributes to the increase in strength of the steel sheet by solid solution strengthening, but is not intentionally added in the present invention, even if silicon is not added, there is no significant problem in terms of securing physical properties. However, 0% is excluded in consideration of the amount inevitably added during manufacture. On the other hand, when the silicon content exceeds 0.3% there is a problem that the plating surface properties are inferior, in the present invention, the silicon content is controlled to 0.3% or less.
  • Chromium is a component having properties similar to manganese and is an element added to improve the hardenability of steel and the strength of steel.
  • chromium helps to form martensite and forms coarse Cr-based carbides such as Cr23C6 during hot rolling to precipitate the amount of dissolved carbon in steel below an appropriate level, thereby suppressing the yield point yield (YP-El). It is an advantageous element for the production of composite steel with low yield ratio.
  • chromium is an advantageous element for producing high-strength composite tissue steel having high ductility by minimizing ductility drop relative to strength increase. However, when the content exceeds 1.0%, the martensite tissue fraction is excessively increased to cause a decrease in strength and elongation. In the present invention, the chromium content is controlled to 1.0% or less.
  • Phosphorus is the most advantageous element to secure the strength without significantly deteriorating the formability, but when excessively added, the possibility of brittle fracture is greatly increased, which greatly increases the possibility of plate breakage of the slab during hot rolling. Bar, in the present invention, the phosphorus content is controlled to 0.1%.
  • Sulfur is an inevitable impurity contained in steel, and it is desirable to keep the content as low as possible.
  • sulfur in steel increases the possibility of generating red brittle, and the content is controlled to 0.01% or less.
  • Nitrogen is an inevitable impurity contained in steel, and it is important to keep the content as low as possible, but for this purpose, the refining cost of the steel is rapidly increased, so the operating conditions are controlled at 0.01% or less, which is possible.
  • Acid soluble aluminum is an element added for the refinement of particle size and deoxidation, and when the content is less than 0.01%, the aluminum-killed steel cannot be produced in a normal stable state, whereas the content is greater than 0.06%. In this case, it is advantageous to increase the strength due to the grain refinement effect, while the inclusions are excessively formed during steelmaking operation, thereby increasing the possibility of surface defects of the plated steel sheet, and also causing a sharp increase in manufacturing cost. Therefore, in the present invention, the content of acid soluble aluminum is controlled to 0.01 to 0.06%.
  • Molybdenum is an element added to delay the transformation of austenite into pearlite and at the same time to refine the ferrite and improve the strength of the steel. Molybdenum also helps to improve the hardenability of the steel. However, when the content of molybdenum exceeds 0.1%, there is a problem that the production cost is drastically increased and not only economic efficiency is reduced, but also the ductility of the steel is reduced. In the present invention, the content of molybdenum is controlled to 0.1% or less. .
  • boron is an element added to prevent secondary work brittleness due to phosphorus in steel, but even if boron is not added, there is no major problem in terms of securing physical properties.
  • the content of boron exceeds 0.003%, there is a problem that causes a decrease in ductility of the steel, in the present invention, the content of boron is controlled to 0.003% or less.
  • the cold rolled steel sheet of the present invention includes 90 to 99 area% of ferrite and 1 to 10 area% of martensite as its microstructure.
  • the area ratio of martensite is less than 1%, it is difficult to obtain a steel sheet having a low yield ratio because it is difficult to form a composite structure. On the other hand, if it exceeds 10%, it is difficult to secure the desired workability due to excessive increase in strength. Therefore, it is preferable that it is 1-10 area%, and, as for the area ratio of martensite, it is more preferable that it is 2-5%.
  • the ratio of the average carbon concentration a in martensite and the average carbon concentration b in ferrite located in an imaginary circle having the major axis of the martensite at a diameter of 1 / 4t (a / b) ) Has a value less than or equal to 1.4.
  • a normal baking treatment (approximately 170 ° C., about 20) is performed by appropriately distributing fine martensite in the ferrite matrix and appropriately controlling the ratio of the carbon concentration present in the martensite and inside the ferrite around the martensite. It is designed so that carbon strongly concentrated in martensite can easily diffuse into surrounding ferrite. If the ratio (a / b) of the average carbon concentration exceeds 1.4, the content of solid solution carbon present in the ferrite may be too small to secure the desired baking hardenability. On the other hand, the lower the ratio (a / b) of the above average carbon concentration is, the more favorable it is to secure the bake hardenability. Therefore, the lower limit thereof is not particularly limited in the present invention.
  • the cold rolled steel sheet of the present invention has a ratio of the average manganese concentration c in martensite and the average manganese concentration d in ferrite located in an imaginary circle having the long axis of martensite as the diameter d at a point of 1 / 4t of sheet thickness d.
  • / c) has a value of 0.9 or less, and more preferably 0.8 or less. If the ratio (d / c) of the average manganese concentration exceeds 0.9, the amount of manganese present in the ferrite is too high to facilitate the formation of manganese bands in the tissue, resulting in processing cracks during molding due to the decrease in ductility of steel. The chances are high.
  • the lower the ratio (d / c) of the average manganese concentration is, the more advantageous for securing ductility, and therefore, the lower limit thereof is not particularly limited in the present invention.
  • the share (M) of martensite having an average circular equivalent diameter of 5 ⁇ m or less (excluding 0 ⁇ m) present in a ferrite grain boundary (including grain boundary triple points) defined by Equation 1 may be 90% or more.
  • M gb is the number of martensites having an average circular equivalent diameter of 5 ⁇ m or less (excluding 0 ⁇ m) present in the ferrite grain boundary
  • M in is a martensite having an average circular equivalent diameter of 5 ⁇ m or less (excluding 0 ⁇ m) present in the ferrite grain boundary. Number of sites
  • the fine martensite having an average circular equivalent diameter of 5 ⁇ m or less mainly exists in grain boundaries rather than in ferrite grains, which is advantageous for maintaining a low yield ratio and improving ductility.
  • the share (M) of martensite is less than 90%, the martensite formed in the crystal grains increases the yield strength upon tensile deformation, thereby increasing the yield ratio, thereby making it difficult to control the yield ratio through temper rolling.
  • martensite present in the crystal grains significantly impedes the progression of dislocations during processing, thereby weakening the ferrite ductility, thereby causing lowering of the elongation.
  • the cold rolled steel sheet of the present invention may include a part of bainite in addition to the ferrite and martensite.
  • the yield ratio of the steel is significantly increased. It is preferable to suppress.
  • the area ratio B of bainite defined by Equation 2 may be 3 or less. If the area ratio (B) of bainite is greater than 3, the carbon concentration around bainite increases, thereby deteriorating the ductility of the steel, and the yield ratio may increase rapidly.
  • Equation 2 B ⁇ A B / (A F + A M + A B ) ⁇ ⁇ 100
  • a F means the area ratio of ferrite
  • a M means the area ratio of martensite
  • a B means the area ratio of bainite
  • a plated layer may be formed on the surface of the cold rolled steel sheet of the present invention, the plated layer may be either a hot dip galvanized layer or an alloyed hot dip galvanized layer.
  • the plating layer is formed on the surface of the cold rolled steel sheet, there is an advantage that the corrosion resistance is significantly improved.
  • Hot-dip galvanized steel sheet of the present invention described above can be produced by various methods, the production method is not particularly limited. However, as a preferred example, it may be prepared by the following method.
  • the steel slab having the above-described component system is reheated.
  • This process is performed in order to perform the following hot rolling process smoothly, and to fully acquire the physical property of the target steel plate.
  • the process conditions of such a reheating step are not particularly limited and may be ordinary conditions.
  • the reheating process may be performed in a temperature range of 1100 to 1300 ° C.
  • the reheated steel slab is hot rolled in an austenitic single phase station to obtain a hot rolled steel sheet.
  • the reason why the hot rolling is performed in the austenitic single phase is to increase the uniformity of the tissue.
  • the finish rolling temperature may be (Ar3 + 50) to 950 ° C. If the finish rolling temperature is lower than (Ar3 + 50) ° C., the ferrite and austenite two-phase rolling is highly likely to cause material unevenness. On the other hand, if the finish rolling temperature is higher than 950 ° C., the material is formed by abnormal coarse grain formation by high temperature rolling Non-uniformity may be caused, and thus coil distortion may occur when the hot-rolled steel sheet is cooled.
  • the theoretical temperature of Ar3 can be calculated
  • Ar 3 (° C.) 910-310 [C] -80 [Mn] -20 [Cu] -15 [Cr] -55 [Ni] -80 [Mo]
  • the coiling temperature may be 450 ⁇ 700 °C. If the winding temperature is less than 450 ° C., excessive martensite or bainite formation may cause excessive increase in strength of the hot rolled steel sheet, which may cause problems such as poor shape due to subsequent cold rolling. On the other hand, when the coiling temperature exceeds 700 °C, the surface thickening of the elements, such as Si, Mn and B in the steel to reduce the wettability of the hot-dip galvanized may be severe.
  • the wound hot rolled steel sheet is cold rolled to obtain a cold rolled steel sheet.
  • the cold reduction rate may be 40 to 80%. If the cold reduction rate is less than 40%, securing a target thickness may be difficult, and shape correction of the steel sheet may be difficult. On the other hand, when the cold rolling reduction exceeds 80%, cracks may occur at the edge of the steel sheet, and cold rolling load may be caused.
  • the cold rolled steel sheet is continuously annealed. This process is performed to form ferrite and austenite at the same time as recrystallization and to distribute carbon.
  • annealing temperature is 760-850 degreeC. If the annealing temperature is less than 760 ° C, not only sufficient recrystallization is achieved, but sufficient austenite is difficult to form, which makes it difficult to secure the target strength in the present invention. On the other hand, if it exceeds 850 °C, productivity is lowered, austenite is excessively formed, bainite is formed in a subsequent cooling process, there is a problem that the ductility of the steel is reduced.
  • the annealing temperature range is all equivalent to the two-phase (ferrite + austenite) temperature range, it is more preferable to perform annealing at a temperature containing as much of the ferrite region as possible. This is because the more the initial ferrite at the two-phase annealing temperature, the easier the grain growth after annealing and the better the ductility.
  • Ms martensite transformation start temperature
  • the annealing temperature is more preferably 770 ⁇ 810 °C.
  • the continuous annealing cold rolled steel sheet is first cooled to an average cooling rate of 2 to 14 ° C / sec to 630 to 670 ° C.
  • the higher the primary cooling end temperature or the slower the primary cooling rate the higher the tendency of uniformity and coarsening of the ferrite, which is advantageous for securing ductility of steel.
  • the present invention is characterized by giving a sufficient time for the carbon to diffuse into austenite during the primary cooling, which is very significant in the present invention.
  • carbon diffuses and moves to austenite where carbon concentration is high, and as the temperature increases, the diffusion degree increases as the time increases.
  • the primary cooling end temperature is less than 630 ° C.
  • the diffusion activity of carbon is low due to too low temperature, so that the carbon concentration in the ferrite is increased, the yield ratio is increased, and the cracking tendency is increased during processing.
  • the primary cooling end temperature exceeds 670 °C is advantageous in terms of diffusion of carbon, there is a disadvantage that requires a too high cooling rate in the subsequent cooling, the secondary process.
  • the primary cooling rate is less than 2 °C / sec is disadvantageous in terms of productivity, on the other hand, if it exceeds 14 °C / sec is not preferable because the carbon diffusion can not occur sufficiently.
  • the first cold-rolled cold rolled steel sheet is secondarily cooled to an average cooling rate of 3 to 12 ° C / sec to (Ms + 20) to (Ms + 50) ° C.
  • an average cooling rate 3 to 12 ° C / sec to (Ms + 20) to (Ms + 50) ° C.
  • the secondary cooling end temperature is higher than (Ms + 50) ° C.
  • the tertiary cooling rate can not only be controlled relatively high, but also the possibility that martensite is formed before the plating bath is immersed is increased.
  • the secondary cooling rate is less than 3 ° C / sec martensite is not formed, but is disadvantageous in terms of productivity, on the other hand, if it exceeds 12 ° C / sec as a whole, the flow rate of the plate is faster and may cause problems such as plate distortion .
  • the theoretical temperature of Ms can be obtained by the following equation.
  • the secondary cold-rolled cold rolled steel sheet is thirdly cooled at a rate of 4 to 8 ° C / sec to 440 to 480 ° C.
  • the temperature range is a temperature range of a conventional zinc-based plating bath, this step is performed to prevent the martensite structure is formed before the cold-rolled steel sheet is immersed in the zinc-based plating bath. If the tertiary cooling rate is less than 4 ° C./sec, martensite is not formed, but it is disadvantageous in terms of productivity. On the other hand, if it exceeds 8 ° C./sec, some martensite is formed in the mouth and some bainite is formed. Ductility may deteriorate with increasing yield strength.
  • the cold-rolled cold rolled steel sheet is immersed in a hot dip galvanized bath to obtain a hot dip galvanized steel sheet.
  • the composition of the hot dip galvanizing bath is not particularly limited, and may be a pure galvanizing bath or a zinc alloy plating bath containing Si, Al, Mg, or the like.
  • the hot-dip galvanized steel sheet is finally cooled to an average cooling rate of 3 ° C / sec or more to (Ms-100) ° C or less. If the final cooling end temperature is less than (Ms-100) ° C., fine martensite may not be obtained, and a problem of plate shape defect may be caused.
  • the average cooling rate is less than 3 ° C / sec martensite is not only irregularly formed in the grain boundary or in the mouth due to the too slow cooling rate, the formation ratio of the grain boundary martensite to the mouth can not be produced low resistance steel.
  • an alloying hot dip galvanized steel sheet can be obtained by carrying out alloying heat treatment of a hot dip galvanized steel sheet before final cooling as needed.
  • the alloying heat treatment process conditions are not particularly limited and may be normal conditions.
  • the alloying heat treatment process may be performed in a temperature range of 480 ⁇ 600 °C.
  • the reduction ratio is preferably 0.3 to 1.6%, more preferably 0.5 to 1.4%. If the reduction ratio is less than 0.3%, sufficient dislocations are not formed and are disadvantageous in terms of plate shape, and in particular, there is a fear that plating platen defects may occur. On the other hand, when the reduction ratio exceeds 1.6%, it is advantageous in terms of dislocation formation, but side effects such as plate breakage may occur due to the limitation of facility capacity.
  • Inventive Steels 1, 2, 4, and 5 and Comparative Examples 1 and 2 correspond to alloyed hot dip galvanized steel sheets in Table 1
  • Inventive Steels 3 and 6 correspond to hot dip galvanized steel sheets.
  • the primary cooling end temperature was 650 ° C
  • the secondary cooling end temperature was 560 ° C
  • the tertiary cooling end temperature was 460 ° C
  • the plating bath temperature was constant at 480 ° C.
  • the microstructure fraction and the C and Mn concentration ratios are the results of analyzing the structure at the plate thickness of 1 / 4t, and the microstructure fraction was first analyzed by martensite and bainite through Lepelar corrosion using an optical microscope. Observations were made again using SEM (3,000 times), and then the size and distribution of martensite were measured as the average value three times through Count Point operation.
  • the concentration ratio of C and Mn preferentially measures the concentration of C and Mn present in each phase in a line and point method using an EDS (Energy Dispersive Spectropy) method using a TEM in a CPS (Count Per Sec) method. This was measured quantitatively.
  • the standard for measuring the concentrations of C and Mn in Aesop, ferrite and martensite was the average carbon concentration in martensite as the concentration of C and Mn measured at positions adjacent to the imaginary circle whose diameter is the minor axis of martensite.
  • the concentrations of C and Mn measured in the ferrite in contact with the imaginary circle having the minor axis of martensite were taken as the average carbon concentration in the ferrite.
  • Inventive Examples 1 to 7 satisfying the alloy composition and manufacturing conditions proposed by the present invention have a tensile strength of 450 to 650 MPa and excellent strength, and a yield ratio of 0.57 or less. It has a low elongation of 33% or more, excellent in ductility, and has a baking hardening amount (BH) of 35 MPa or more, which is excellent in quench hardening, and has a YP-El value of 0%, indicating excellent aging resistance.
  • BH baking hardening amount
  • Comparative Example 1 the annealing temperature was lower than the range proposed by the present invention, and austenite was not sufficiently formed during annealing, so that martensite was not sufficiently formed in the final structure.
  • Comparative Example 2 the annealing temperature exceeds the range proposed by the present invention, but the hardening hardening property is secured by martensite structure formation, but an aging problem is caused.
  • Comparative Examples 3 and 4 the secondary or tertiary cooling rate exceeds the range proposed by the present invention, thereby preventing the desired baking hardening property or causing an aging problem.
  • Comparative Example 5 the primary cooling rate exceeded the range proposed by the present invention, so that the diffusion of carbon during cooling did not sufficiently occur, so that the desired hardening hardening property of the present invention could not be secured.
  • Comparative Examples 6 to 8 have a high content of C and Cr in the steel, so that a large amount of bainite was formed, resulting in low elongation.

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Abstract

L'invention concerne une tôle d'acier laminée à froid ayant une aptitude au durcissement par cuisson et une résistance au vieillissement excellentes, et un procédé permettant de la fabriquer. La tôle d'acier laminée à froid comprend, en pourcentage massique : de 0,02 à 0,08 % de C; de 1,3 à 2,1 % de Mn; de 0,3 % ou moins (à l'exclusion de 0 %) de Si; de 1,0 % ou moins (à l'exclusion de 0 %) de Cr; de 0,1 % ou moins (à l'exclusion de 0 %) de P; de 0,01 % ou moins (à l'exclusion de 0 %) de S; de 0,01 % ou moins (à l'exclusion de 0 %) de N; et de 0,01 à 0,06 % d'Al sol.; au moins un élément choisi dans le groupe constitué de 0,2 % ou moins (à l'exclusion de 0 %) de Mo et 0,003 % ou moins (à l'exclusion de 0 %) de B; le reste étant constitué de Fe et d'autres impuretés inévitables, la tôle d'acier contenant, comme microstructure, de 90 à 99 % de ferrite et de 1 à 10 % de martensite en fraction surfacique. Un rapport (a/b) d'une concentration moyenne en carbone a dans la martensite et d'une concentration moyenne en carbone b dans la ferrite à l'intérieur d'un cercle imaginaire ayant comme diamètre un axe majeur de la martensite, à un endroit où l'épaisseur de la tôle est égale à 1/4 x t, est inférieur ou égal à 1,4, et un rapport (d/c) d'une concentration moyenne en manganèse c dans la martensite et d'une concentration moyenne en manganèse d dans la ferrite à l'intérieur d'un cercle imaginaire ayant comme diamètre un axe majeur de la martensite, à un endroit où l'épaisseur de la tôle est égale à 1/4 t, est inférieur ou égal à 0,9.
PCT/KR2017/002417 2016-03-08 2017-03-07 Tôle d'acier galvanisée par immersion à chaud ayant une aptitude au durcissement par cuisson et une résistance au vieillissement supérieures, et procédé permettant de la fabriquer WO2017155263A1 (fr)

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US16/079,641 US20190071746A1 (en) 2016-03-08 2017-03-07 Steel sheet hot-dip plated with zinc based layer with superior bake hardenability and aging resistance, and manufacturing method thereof
CN201780016428.7A CN108779537A (zh) 2016-03-08 2017-03-07 具有优异的烘烤硬化性和耐时效性的热浸镀锌钢板及其制造方法
EP17763524.0A EP3428302A4 (fr) 2016-03-08 2017-03-07 Tôle d'acier galvanisée par immersion à chaud ayant une aptitude au durcissement par cuisson et une résistance au vieillissement supérieures, et procédé permettant de la fabriquer
JP2018546894A JP2019512600A (ja) 2016-03-08 2017-03-07 焼付硬化性及び耐時効性に優れた溶融亜鉛系めっき鋼板及びその製造方法

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EP3730635A4 (fr) * 2017-12-22 2020-10-28 Posco Feuille d'acier à haute résistance présentant de propriétés de résistance aux chocs et une aptitude au formage excellentes, et son procédé de fabrication
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KR102031452B1 (ko) * 2017-12-24 2019-10-11 주식회사 포스코 소부경화성 및 도금밀착성이 우수한 냉연강판, 용융 아연계 도금강판 및 그 제조방법
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EP3730636A4 (fr) * 2017-12-22 2020-10-28 Posco Tôle d'acier à haute résistance présentant une excellente aptitude au façonnage, et procédé de fabrication de celle-ci
EP3730635A4 (fr) * 2017-12-22 2020-10-28 Posco Feuille d'acier à haute résistance présentant de propriétés de résistance aux chocs et une aptitude au formage excellentes, et son procédé de fabrication
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US20190071746A1 (en) 2019-03-07
KR101767818B1 (ko) 2017-08-11

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