WO2022124609A1 - 연성 및 성형성이 우수한 고강도 용융아연도금강판 및 그 제조방법 - Google Patents
연성 및 성형성이 우수한 고강도 용융아연도금강판 및 그 제조방법 Download PDFInfo
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- WO2022124609A1 WO2022124609A1 PCT/KR2021/016592 KR2021016592W WO2022124609A1 WO 2022124609 A1 WO2022124609 A1 WO 2022124609A1 KR 2021016592 W KR2021016592 W KR 2021016592W WO 2022124609 A1 WO2022124609 A1 WO 2022124609A1
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- steel sheet
- hot
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 33
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 33
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- 239000010959 steel Substances 0.000 claims abstract description 116
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 54
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- 239000011572 manganese Substances 0.000 claims abstract description 30
- 239000011651 chromium Substances 0.000 claims abstract description 29
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
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- 229910000794 TRIP steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to the production of high-strength hot-dip galvanized steel sheet with a tensile strength of 980 MPa or higher, which is mainly used for structural members of automobiles.
- the present invention relates to a hot-dip galvanized steel sheet having a ratio (YS/TS) of 0.65 or more and excellent in ductility and formability, and a method for manufacturing the same.
- precipitation-reinforced high-strength steel is a technology that secures strength by adding carbon and nitride forming elements such as Nb, Ti, V, etc. to precipitate carbon and nitride, and refining crystal grains through suppression of grain growth by fine precipitates.
- the above technique has the advantage of being easy to secure high strength compared to the low manufacturing cost, but since the recrystallization temperature is rapidly increased due to fine precipitates, there is a disadvantage that high-temperature annealing must be performed to cause sufficient recrystallization to secure ductility.
- precipitation-reinforced steel which is strengthened by precipitating carbon and nitride on a ferrite matrix, has a problem in that it is difficult to obtain high-strength steel of 600 MPa or more.
- transformation-reinforced high-strength steel is DP (Dual Phase) steel composed of a soft ferrite matrix and two hard martensite phases, and TRIP (Transformation Induced Plasticity) steel with high ductility by using transformation-induced plasticity of retained austenite.
- CP Complexed Phase steel composed of a complex structure of ferrite and hard bainite or martensite has been developed.
- high-strength steel sheets are required to improve fuel efficiency and durability, and demand for high-strength steel sheets with a tensile strength of 780-980 MPa or more is increasing for vehicle body structures or reinforcement materials in terms of collision safety and passenger protection.
- DP steel has excellent ductility and is the most widely used automotive steel sheet, but has a low yield ratio (YR) and poor formability and workability. Moreover, in the trend of the steel sheet gradually increasing in strength, cracks or wrinkles occur during press forming of automobile parts, making it difficult to manufacture complex parts. In the case of TRIP steel, the yield ratio is superior to that of DP steel, so the workability is good.
- high-strength steel can be applied to more complex parts by manufacturing steel that satisfies a certain level of yield ratio while securing high ductility of existing DP steel through careful heat treatment. This can be achieved by utilizing the latest heat treatment technology, Quenching and Partitioning (Q&P) heat treatment to secure retained austenite.
- Q&P Quenching and Partitioning
- Patent Document 1 As a prior art for simultaneously securing the ductility and workability of the high-tensile steel sheet, the invention disclosed in Patent Document 1 is exemplified.
- austenite that cannot be stabilized depending on the Q&P temperature, so fresh martensite (FM) is formed in the final cooling step.
- FM fresh martensite
- the invention disclosed in patent document 2 is mentioned.
- the above technology utilizes tempered martensite generated through quenching heat treatment to obtain high strength and high ductility at the same time, and provides a method of manufacturing a cold rolled steel sheet excellent in plate shape after continuous annealing.
- the carbon content is high at 0.2% or more, so the weldability is inferior, and the Si addition amount is also high at 1.0% or more, so there is a problem that dents may occur in the furnace during annealing.
- Patent Document 3 which is a prior art, provides a method for manufacturing a high-strength cold-rolled steel sheet with excellent hole expandability through quenching and reheating.
- Patent Document 1 Japanese Patent Laid-Open No. JP2002-177278
- Patent Document 2 Japanese Patent Application Laid-Open No. JP2010-090432
- Patent Document 3 Korean Patent Publication No. KR2016-0173006
- the present invention relates to a hot-dip galvanized steel sheet having a yield strength (YS) and elongation (EL) relational expression YS ⁇ EL of 9000 or more and a yield ratio (YS/TS) of 0.65 or more, excellent in ductility and formability, used for automotive structural members, and
- An object of the present invention is to provide a method for manufacturing the same.
- the subject of this invention is not limited to the above-mentioned content.
- the subject of the present invention will be understood from the overall content of the present specification, and those of ordinary skill in the art to which the present invention pertains will have no difficulty in understanding the additional subject of the present invention.
- One aspect of the present invention is
- the microstructure of the base steel sheet in area%, is the sum of bainite and tempered martensite: 70% or more, ferrite: 10% or less, and the remainder consists of fresh martensite and retained austenite, and the retained austenite fraction is the area It relates to a hot-dip galvanized steel sheet excellent in ductility and formability of 5% or less in %.
- the continuously annealed steel sheet is first cooled at an average cooling rate of 10 °C or less to a temperature range of 630 to 680 °C, and secondary cooled at an average cooling rate of 5 °C or higher to a temperature of 300 to 350 °C using hydrogen gas. After, after reheating to a temperature of 400 ⁇ 480 °C, the process of holding for 60 seconds or more; and
- Hot-dip galvanized steel sheet with excellent ductility and formability including a step of cooling at an average cooling rate of 5°C or higher to a temperature of Ms-100°C or lower after hot-dip galvanizing treatment at the maintained temperature of 400 to 450°C; it's about how
- the microstructure of the hot-dip galvanized steel sheet is composed of, in area%, the sum of bainite and tempered martensite: 70% or more, ferrite: 10% or less, the remainder fresh martensite and retained austenite, and the retained austenite fraction This area % may be 5% or less.
- It may further include a process of alloying heat treatment on the manufactured hot-dip galvanized steel sheet.
- the present invention has a useful effect in manufacturing high-strength hot-dip galvanized steel sheet having an excellent yield ratio (YS/TS) compared to conventional DP steel while satisfying high ductility, which is a characteristic of DP steel, by optimizing the components and manufacturing process.
- YS/TS yield ratio
- high ductility which is a characteristic of DP steel
- FIG. 1 is a diagram showing the change in the yield strength (YS) and the elongation (EL) relational expression YS ⁇ EL according to the yield ratio (YS / TS) in an embodiment of the present invention.
- FIG. 2 is a diagram showing changes in the yield strength (YS) and elongation (EL) relational expression YS ⁇ EL according to Relation 1 in an embodiment of the present invention.
- FIG 3 is a diagram showing a change in the hole expandability value according to Relation 1 in an embodiment of the present invention.
- the present inventors confirmed that the workability can be improved by increasing the yield ratio compared to the conventional DP steel when the retained austenite, ferrite, bainite, and fresh martensite are introduced into the final microstructure by optimizing the steel composition and manufacturing process. did In addition, this microstructure change has the effect of improving ductility by relieving the concentration of local stress and strain after necking and delaying the generation, growth, and coalescence of voids that cause ductile failure, and furthermore, the residual amount of less than 5% during final cooling It was confirmed through an experiment that austenite was formed to further improve ductility, and the present invention was completed based on the experimental results.
- the present invention reduces the fraction of ferrite and martensite compared to the conventional DP steel and introduces retained austenite and bainite, thereby increasing the yield ratio compared to the conventional DP steel, thereby securing workability.
- it helps to improve ductility by forming a large amount of movable dislocations around retained austenite during plastic deformation.
- This precisely controlled composite structure steel can secure ductility while maintaining a higher yield ratio compared to existing DP steel. Through this, it is possible to manufacture a high-tensile hot-dip galvanized steel sheet having excellent ductility and workability.
- the hot-dip galvanized steel sheet having excellent ductility and formability of the present invention is, by weight, carbon (C): 0.06 to 0.16%, silicon (Si): 0.8% or less (excluding 0%), manganese (Mn): 2.1 ⁇ 2.7%, Molybdenum (Mo): 0.4% or less (excluding 0%), Chromium (Cr): 1% or less (excluding 0%), Phosphorus (P): 0.1% or less (excluding 0%), Sulfur (S) : 0.02% or less, aluminum (sol.Al): 1% or less (excluding 0%), titanium (Ti): 0.001 to 0.04%, niobium (Nb): 0.001 to 0.04%, nitrogen (N): 0.01% or less (excluding 0%), boron (B): 0.01% or less, antimony (Sb): 0.05% or less, the remainder including Fe and other unavoidable impurities, C, The components of Si, Al, Mn, Cr, Mo
- Carbon (C) is a very important element added to strengthen the metamorphic structure. Carbon promotes the formation of hard martensite in composite steel to improve strength. As the carbon content increases, the amount of martensite increases. However, if the content exceeds 0.16%, the strength of martensite increases, but the difference in strength with ferrite with a low carbon concentration becomes large. Due to this difference in strength, fracture easily occurs at the interphase interface during plastic deformation, thereby reducing ductility and work hardening rate. In addition, due to poor weldability, welding defects occur when processing customer parts. On the other hand, when the carbon content is lowered to less than 0.06%, it is difficult to secure the desired strength.
- the carbon content it is preferable to limit the carbon content to a range of 0.06 to 0.16%, and more preferably, to control it to a range of 0.07 to 0.15%.
- Silicon (Si) is a ferrite stabilizing element and contributes to the formation of retained austenite by promoting ferrite transformation and promoting carbon concentration in untransformed austenite during the Q&P process. In addition, it is effective in reducing the interphase hardness difference by increasing the strength of ferrite through solid solution strengthening, and is a useful element that can secure strength without reducing the ductility of the steel sheet. However, when it exceeds 0.8%, it causes surface scale defects to adversely affect the plating surface quality, and also lowers weldability and chemical conversion treatment property, so that the upper limit of the addition amount is limited to 0.8%. More preferably, it is controlled to 0.7% or less.
- Manganese (Mn) is an element for reinforcing steel while preventing hot brittleness due to the generation of FeS by refining particles without reducing ductility and completely precipitating sulfur (S) in the steel as MnS. At the same time, in composite steel, it serves to lower the critical cooling rate at which the martensite phase is obtained, thereby facilitating the formation of martensite.
- the content is less than 2.1%, it is difficult to secure the strength targeted in the present invention, whereas if it exceeds 2.7%, problems such as weldability and hot-rollability are highly likely to occur, and martensite is formed excessively to the material This is unstable, and there is a problem in that Mn-Bands (bands of Mn oxide) are formed in the tissue, which increases the risk of processing cracks and plate breakage. In addition, there is a problem that Mn oxide is eluted on the surface during annealing, greatly impairing plating properties. Therefore, in the present invention, it is preferable to limit the content of Mn to 2.1 to 2.7%, and more preferably, to control it in the range of 2.3 to 2.5%.
- Molybdenum is an element that delays the transformation of austenite into pearlite and improves the refinement and strength of ferrite. Such Mo improves the hardenability of steel and has the advantage that the yield ratio can be controlled by finely forming martensite at grain boundaries.
- the higher the content the higher the manufacturing cost increases, which is disadvantageous in terms of cost. Therefore, it is preferable to appropriately control the content.
- the content of Mo is limited to 0.4% or less, and 0% is excluded in consideration of the amount unavoidably added for manufacturing. More preferably, the Mo content is controlled to 0.3% or less.
- Chromium (Cr) is a component added to improve hardenability of steel and secure high strength. And as an element that plays a very important role in the formation of martensite, it is advantageous in manufacturing a composite steel having high ductility by minimizing a decrease in elongation compared to an increase in strength.
- Cr-based carbides such as Cr 23 C 6 are formed. Some of these carbides are dissolved in the annealing process, and some remain undissolved. After cooling, the amount of solid solution C in martensite is lowered to an appropriate level It is an element advantageous for manufacturing composite structure steel with a low yield ratio by suppressing the occurrence of elongation at the yield point because it can be controlled.
- the content of Cr when the content exceeds 1%, the effect is not only saturated, but there is a problem in cold rolling performance due to excessive hot-rolling strength increase. There is a problem in that the elongation decreases due to coarsening. Therefore, in the present invention, it is preferable to limit the content of Cr to 1% or less, and 0% is excluded in consideration of the amount unavoidably added in manufacturing. More preferably, the Cr content is controlled to 0.6% or less.
- ⁇ P 0.1% or less (excluding 0%)
- Phosphorus (P) is a substitution element having the greatest solid solution strengthening effect, and is the most advantageous element for improving in-plane anisotropy and securing strength without increasing formability.
- Phosphorus (P) is a substitution element having the greatest solid solution strengthening effect, and is the most advantageous element for improving in-plane anisotropy and securing strength without increasing formability.
- Phosphorus (P) is a substitution element having the greatest solid solution strengthening effect, and is the most advantageous element for improving in-plane anisotropy and securing strength without increasing formability.
- the possibility of brittle fracture increases significantly, and there is a problem in that the possibility of plate breakage of the slab during hot rolling and acting as an element impairing the plating surface properties. 0% is excluded in consideration of the added level.
- S is an impurity element that is unavoidably added to steel, and it is an element that reduces ductility and weldability, so it is important to manage it as low as possible.
- S Sulfur
- 0% is excluded in consideration of the level that is unavoidably added during the manufacturing process.
- Aluminum for acid value (sol.Al) is an element added for grain size refinement and deoxidation of steel, and is a ferrite stabilizing element similar to Si. And it is an effective component for improving martensite hardenability and forming retained austenite by distributing carbon in ferrite to austenite.
- it is a useful element that can improve the ductility of the steel sheet by effectively suppressing the precipitation of carbides in the bainite when maintained in the bainite region during annealing.
- the content exceeds 1.0%, it is advantageous to increase the strength due to the effect of grain refinement, but there is a problem that not only increases the possibility of surface defects of the plated steel sheet due to excessive formation of inclusions during the steel making operation, but also increases the manufacturing cost. . Therefore, in the present invention, it is preferable to control the content of sol.Al to 1.0% or less.
- Titanium (Ti) and niobium (Nb) are effective elements for increasing the strength of a steel sheet and refining grains by forming nano-precipitates. When these elements are added, they combine with carbon to form very fine nano-precipitates. These nano-precipitates serve to reduce the hardness difference between the phases by strengthening the matrix.
- the content of Ti and Nb is less than 0.001%, respectively, it is difficult to secure such an effect, and when the content exceeds 0.04%, respectively, the manufacturing cost increases and ductility may be greatly reduced due to excessive precipitates. Therefore, it is preferable to limit the Ti and Nb contents to 0.001 to 0.04%, respectively, and more preferably, to control them in the range of 0.005 to 0.02%, respectively.
- ⁇ N 0.01% or less (excluding 0%)
- Nitrogen (N) is a component that has an effective action to stabilize austenite, but when it exceeds 0.01%, there is a problem in that the refining cost of steel rises rapidly, and the risk of cracking during casting due to formation of AlN is greatly increased, so its upper limit It is preferable to limit it to 0.01%. However, 0% is excluded in consideration of the unavoidably added level.
- Boron (B) is a component that delays the transformation of austenite into pearlite during the cooling process during annealing, and is a hardenable element that suppresses ferrite formation and promotes martensite formation. However, if the content exceeds 0.003%, excessive B is concentrated on the surface, which may lead to deterioration of plating adhesion, so the content is controlled to 0.003% or less. More preferably, the B content is controlled to 0.002% or less.
- Antimony (Sb) is distributed at grain boundaries and delays diffusion of oxidizing elements such as Mn, Si, and Al through grain boundaries to suppress surface thickening of oxides, and also suppresses surface thickening due to temperature rise and changes in hot rolling process. It has an excellent effect on However, when the content exceeds 0.05%, the effect is not only saturated, but also the manufacturing cost and processability are inferior, so the content is limited to 0.05% or less. More preferably, the Sb content is controlled to 0.03% or less.
- the hot-dip galvanized steel sheet of the present invention can secure ductility while improving workability by increasing the yield ratio compared to the existing DP steel.
- the microstructure and phase fraction control conditions as follows.
- the microstructure fraction, distribution and concentration of components in the microstructure will be described.
- the hot-dip galvanized steel sheet of the present invention in terms of area%, has a microstructure, the sum of bainite and tempered martensite: 70% or more, ferrite: 10% or less, and the balance consists of fresh martensite and retained austenite, The residual austenite fraction is 5% or less in terms of area%. If the sum of bainite and tempered martensite is less than 70% or ferrite exceeds 10%, there is a problem in that a desired yield ratio cannot be secured. In addition, there is a problem in that the content of Si and Al must be increased in order for the retained austenite to exceed 5%.
- the present invention can manufacture a hot-dip galvanized steel sheet having a yield strength (YS) and elongation (EL) relational formula YS ⁇ EL of 9000 or more and a yield ratio (YS/TS) of 0.65 or more.
- YS yield strength
- EL elongation
- YS/TS yield ratio
- Si and Al are ferrite stabilizing elements that contribute to the formation of retained austenite and martensite by promoting ferrite transformation and promoting C concentration into untransformed austenite.
- C is also an element contributing to martensite formation and fraction adjustment by promoting C concentration in untransformed austenite.
- Mn, Cr, Mo, and B are elements contributing to the improvement of hardenability, their contribution to the concentration of C in austenite is relatively low compared to C, Si, and Al. Therefore, it is very important to adjust the ratio of C, Si, Al and other hardenable elements Mn, Cr, Mo, and B well.
- the yield strength (YS), elongation (EL) relational expression YS ⁇ EL according to the yield ratio (YS / TS) can be secured to 9000 or more, , furthermore, it is possible to secure a hole expandability value of 30% or more by securing the fraction of bainite and tempered martensite to 70% or more and at the same time reducing the interphase hardness difference.
- the value defined by Relation 1 exceeds 0.35, the above-described effect disappears.
- the composite structure in which ferrite, bainite, martensite, and retained austenite are simultaneously formed disperses each phase finely and uniformly and at the same time reduces the difference in hardness between phases. can improve
- this microstructure change has the effect of improving ductility by relieving the concentration of local stress and strain after necking and delaying the generation, growth, and coalescence of voids that cause ductile failure.
- HER hole expansion ratio
- YS yield strength
- EL elongation
- YS/TS yield ratio
- bainite has the effect of reducing the difference in hardness between the phases of ferrite and martensite.
- the process of partially forming ferrite is also important.
- the fraction of ferrite can be controlled to 10% or less through single-phase station annealing or single-phase station direct annealing, and a small amount of additional ferrite can be formed in the slow cooling section. Through this, further improvement of ductility is promoted.
- by precipitating fine nano-precipitates in ferrite it is possible to further reduce the difference in hardness between phases to improve workability.
- the desired strength can be secured by introducing a small amount of fresh martensite during final cooling.
- the method for manufacturing a hot-dip galvanized steel sheet of the present invention includes a step of preparing a steel slab satisfying the compositional components and Relational Equation 1, and then reheating it; a process of hot rolling the reheated slab so that the temperature at the exit side of the finish rolling becomes Ar3 ⁇ Ar3 + 50 °C, and then winding it at 400 ⁇ 650 °C and cooling it to room temperature at an average cooling rate of 0.1 °C or less; manufacturing a cold rolled steel sheet by cold rolling the cooled hot rolled steel sheet at a reduction ratio of 40 to 70%; continuous annealing of the cold-rolled steel sheet at a temperature of 820 to 860°C; The continuously annealed steel sheet is first cooled at an average cooling rate of 10 °C or less to a temperature range of 630 to 680 °C, and secondary cooled at an average cooling rate of 5 °C or higher to a temperature of 300 to 350 °C using hydrogen gas.
- the slab reheating process is a process of heating a steel slab in order to smoothly perform a subsequent rolling process and obtain sufficient properties of a target steel sheet.
- the present invention is not particularly limited to such reheating conditions, and normal reheating conditions are sufficient.
- One example is to reheat in the temperature range of 1100 ⁇ 1300 °C.
- the reheated steel slab is finish hot rolled so that the temperature at the exit side of the finish rolling is Ar3 ⁇ Ar3 + 50 °C.
- the present invention is not limited to a specific hot rolling condition at this time, and a normal hot rolling temperature may be used.
- the cold rolled steel sheet is manufactured by cold rolling the cooled hot rolled steel sheet at a reduction ratio of 40 to 70%.
- cold rolling is performed at a reduction ratio of 40 to 70%. If the cold rolling reduction ratio is less than 40%, it is difficult to secure the target thickness as well as difficult to correct the shape of the steel sheet. There is a problem that brings Therefore, in the present invention, it is preferable to limit the cold rolling reduction to 40 to 70%.
- continuous annealing is performed on the cold-rolled steel sheet in a temperature range of 820 to 860°C.
- This continuous annealing process is to form ferrite and austenite at the same time as recrystallization, and to distribute carbon.
- the continuous annealing temperature is less than 820° C., it is difficult to secure a sufficient austenite fraction, so that the desired martensite, bainite and retained austenite fractions cannot be obtained after annealing.
- productivity declines and excessive austenite is formed, and the bainite and martensite fractions after cooling significantly increase, which increases yield strength and decreases ductility, making it difficult to secure high ductility properties.
- the surface thickening caused by elements such as Si, Mn, and B that reduce the wettability of hot-dip galvanizing may deteriorate, resulting in deterioration of the plating surface quality.
- the continuously annealed steel sheet is first cooled at an average cooling rate of 10° C. or less to a temperature range of 630 to 680° C., and an average cooling rate of 5° C. or more to a temperature of 300 to 350° C. using hydrogen gas. After secondary cooling, reheat to a temperature of 400 to 480 °C, and hold for 60 seconds or more.
- the continuously annealed steel sheet is first cooled at an average cooling rate of 10°C or less to a temperature range of 630-680°C, and 5°C/s or more up to a temperature range of 300-360°C using a hydrogen quenching facility using hydrogen gas. Secondary cooling at an average cooling rate introduces some fresh martensite. Then, it is immediately reheated to a temperature of 400 ⁇ 480°C and maintained for more than 60 seconds to form bainite, and carbon is concentrated in the surrounding untransformed austenite.
- the quenching temperature it is very important to control the quenching temperature to 300 ⁇ 360°C below Ms, which is the martensite formation temperature during secondary cooling. If the quenching temperature exceeds 360° C., the initially formed fraction of martensite is very small or it is difficult to form martensite, so carbon partitioning does not occur smoothly, so that it is difficult to form a desired fraction of retained austenite during final cooling. On the other hand, if it is less than 300°C, the plate shape may deteriorate and equipment load may occur.
- the reheating temperature it is important to control the reheating temperature to 400 ⁇ 480 °C higher than the Ms temperature. If the reheating temperature is less than 400 °C, the formation of bainite does not occur quickly and the carbon partitioning is not made smoothly. That is, it is very important to carefully control the secondary quenching temperature and reheating temperature during Q&P annealing to form a desired microstructure.
- fresh martensite adjacent to bainite is adjacent to bainite by hot-dip galvanizing treatment of the maintained steel sheet at a temperature of 400 to 450° C.
- a final product in which is formed can be manufactured.
- the temper rolling may be performed at a reduction ratio of less than 1%.
- the present invention may further include a step of alloying heat treatment on the manufactured hot-dip galvanized steel sheet.
- Steel slabs having the composition shown in Table 1 were prepared. And after reheating the steel slab to a temperature range of 1050 to 1250 °C, finish hot rolling was performed at a temperature of 950 °C within the range of Ar3 to Ar3 + 50 °C.
- the hot-rolled steel sheets in this way were wound at 400 to 650° C. and then cooled at a cooling rate of 0.1° C. or less per second to prepare a hot-rolled steel sheet. After pickling the hot-rolled steel sheet, it was cold-rolled at a reduction ratio of 40 to 70%. Thereafter, the cold-rolled steel sheet was subjected to continuous annealing at the temperature shown in Table 2 below, and then Q&P heat treatment was performed under the conditions shown in Table 2 below.
- the QP heat-treated cold-rolled steel sheet is then subjected to hot-dip galvanizing treatment, alloying heat treatment, and final cooling to introduce fresh martensite and retained austenite, followed by temper rolling of less than 1% to obtain a hot-dip galvanized steel sheet. prepared.
- microstructure and mechanical properties were evaluated for each of the steel sheets prepared as described above, and the results are shown in Table 3 below.
- a tensile test for each test piece was performed in the L direction using ASTM standards to evaluate tensile properties (tensile strength (TS), yield strength (YS), and elongation (El)).
- TS tensile strength
- El elongation
- the microstructure fraction was used by analyzing the matrix structure at the plate thickness of 1/4t of the annealed steel sheet. Specifically, ferrite, bainite, fresh martensite, and austenite fractions were measured using FE-SEM and image analyzer after nital corrosion. In addition, hole expandability was measured using a hole expandability tester.
- N was contained as an impurity element within the range of 30-50 ppm.
- F stands for ferrite
- B stands for bainite
- TM stands for tempered martensite
- FM stands for fresh martensite
- RA retained austenite
- the yield strength (YS) and the elongation relation YS ⁇ EL are 9000 or more, and the yield When the ratio (YS/TS) is 0.65 or more, it can be seen that the material and workability of the steel sheet targeted in the present invention can be secured.
- Comparative Example 1 the steel composition was within the range of the present invention, but the secondary cooling temperature was too low, so that the fraction of retained austenite exceeded 5%, and a load was generated on the equipment due to the excessive cooling rate.
- the steel composition component was within the range of the present invention, but the secondary cooling temperature was too high, so that tempered martensite was not sufficiently formed and carbon partitioning did not occur, so that the target yield ratio could not be obtained.
- Comparative Example 3 the steel composition was within the range of the present invention, but the reheating temperature was too low to obtain the desired strength because tempered martensite was excessively formed. The target yield ratio cannot be obtained because the martensite fraction is high.
- Comparative Examples 5-10 is a case where both the steel composition component and the manufacturing process conditions are outside the scope of the present invention. Specifically, in Comparative Examples 5-6, the steel composition component is outside the scope of the present invention, and the continuous annealing temperature and reheating temperature are within the scope of the invention. , ferrite was formed excessively, and the desired yield ratio could not be obtained. In addition, in Comparative Examples 7-8, the steel composition was outside the scope of the present invention, the secondary cooling temperature and the reheating temperature were too high, and the target yield ratio could not be obtained, and in Comparative Examples 9-10, the reheating temperature was too high, the target I could't get the surrender fee.
- Figure 1 shows the change of the relationship formula YS ⁇ EL in the yield strength (YS) and the elongation (EL) according to the yield ratio (YS / TS) in Examples of the present invention (invention steel 1-6 and comparative steel 5-10)
- Figure 2 is a figure showing the change in yield strength (YS) and elongation (EL) relational expression YS ⁇ EL according to Relational Equation 1 in an embodiment of the present invention (invention steel 1-6 and comparative steel 5-10)
- Figure 3 is a figure showing the change of the hole expandability value according to the relation 1 in the embodiment of the present invention (invention steel 1-6 and comparative steel 5-10).
- invention steel 1-6 in FIGS. 1-3 shows the invention steel corresponding to invention example 1-6,
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Abstract
Description
Claims (6)
- 중량%로, 탄소(C): 0.06~0.16%, 실리콘(Si): 0.8% 이하(0% 제외), 망간(Mn): 2.1~2.7%, 몰리브덴(Mo): 0.4% 이하(0% 제외), 크로뮴(Cr): 1% 이하(0% 제외), 인(P): 0.1% 이하(0% 제외), 황(S): 0.02% 이하, 알루미늄(sol.Al): 1% 이하(0% 제외), 타이타늄(Ti): 0.001~0.04%, 나이오븀(Nb): 0.001~0.04%, 질소(N): 0.01% 이하(0% 제외), 붕소(B): 0.01% 이하, 안티몬(Sb): 0.05% 이하, 잔부 Fe 및 기타 불가피한 불순물을 포함하고,소지강판 두께 1/4t 지점의 기지조직 내 소강 성분 중 C, Si, Al, Mn, Cr, Mo 및 B의 성분이 하기 관계식 1을 만족하고,소지강판의 미세조직이, 면적%로, 베이나이트 및 템퍼드 마르텐사이트의 합: 70% 이상, 페라이트: 10% 이하, 잔부 프레시 마르텐사이트와 잔류 오스테나이트로 구성되며, 상기 잔류오스테나이트 분율이 면적%로 5% 이하인 연성 및 성형성이 우수한 용융아연도금강판.[관계식 1](4×C + Si + Al)/(Mn + Cr + 5×Mo + 200×B)≤0.35
- 제 1항에 있어서, 상기 용융아연 도금강판은, 구멍확장성(Hole Expansion Ratio, HER)이 30% 이상이며, 항복강도(YS) 및 연신율(EL) 관계식 YS×EL이 9000 이상이면서, 항복비(YS/TS)가 0.65 이상인 것을 특징으로 하는 연성 및 성형성이 우수한 용융아연도금강판.
- 중량%로, 탄소(C): 0.06~0.16%, 실리콘(Si): 0.8% 이하(0% 제외), 망간(Mn): 2.1~2.7%, 몰리브덴(Mo): 0.4% 이하(0% 제외), 크로뮴(Cr): 1% 이하(0% 제외), 인(P): 0.1% 이하(0% 제외), 황(S): 0.02% 이하, 알루미늄(sol.Al): 1% 이하(0% 제외), 타이타늄(Ti): 0.001~0.04%, 나이오븀(Nb): 0.001~0.04%, 질소(N): 0.01% 이하(0% 제외), 붕소(B): 0.01% 이하, 안티몬(Sb): 0.05% 이하, 잔부 Fe 및 기타 불가피한 불순물을 포함하고, 하기 관계식 1을 만족하는 강 슬라브를 마련한 후, 이를 재가열하는 공정;상기 재가열된 슬라브를 마무리압연 출구측 온도가 Ar3~Ar3+50℃가 되도록 열간압연하고, 이어, 400~650℃에서 권취한 후 0.1℃이하의 평균냉각속도로 상온까지 냉각시키는 공정;상기 냉각된 열연강판을 40~70%의 압하율로 냉간압연하여 냉연강판을 제조하는 공정;상기 냉연강판을 820~860℃의 온도에서 연속 소둔하는 공정;상기 연속소둔된 강판을 630~680℃의 온도범위까지 10℃이하의 평균냉각속도로 1차 냉각하고, 수소가스를 이용하여 300~350℃의 온도까지 5℃이상의 평균 냉각속도로 2차 냉각한 후, 400~480℃의 온도까지 재가열한 후, 60초 이상 유지하는 공정; 및상기 유지된 400~450℃의 온도에서 용융아연도금 처리한 후, Ms~100℃이하의 온도까지 5℃이상의 평균냉각속도로 냉각하는 공정;을 포함하는 연성 및 성형성이 우수한 용융아연도금강판 제조방법.[관계식 1](4×C + Si + Al)/(Mn + Cr + 5×Mo + 200×B)≤0.35
- 제 3항에 있어서, 상기 용융아연도금강판의 미세조직이, 면적%로, 베이나이트 및 템퍼드 마르텐사이트의 합: 70% 이상, 페라이트: 10% 이하, 잔부 프레시 마르텐사이트, 잔류 오스테나이트로 구성되며, 잔류오스테나이트 분율이 면적%로 5% 이하인 것을 특징으로 하는 연성 및 성형성이 우수한 용융아연도금강판 제조방법.
- 제 3항에 있어서, 상기 제조된 용융아연도금강판에 합금화 열처리하는 공정을 추가로 포함하는 연성 및 성형성이 우수한 용융아연도금강판 제조방법.
- 제 3항에 있어서, 상기 제조된 용융아연도금강판에 1% 미만의 압하율로 조질압연을 실시하는 것을 특징으로 하는 연성 및 성형성이 우수한 용융아연도금강판 제조방법.
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