WO2015151827A1 - 延性、伸びフランジ性、および溶接性に優れた高強度冷延鋼板、高強度溶融亜鉛めっき鋼板、および高強度合金化溶融亜鉛めっき鋼板 - Google Patents
延性、伸びフランジ性、および溶接性に優れた高強度冷延鋼板、高強度溶融亜鉛めっき鋼板、および高強度合金化溶融亜鉛めっき鋼板 Download PDFInfo
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- WO2015151827A1 WO2015151827A1 PCT/JP2015/058194 JP2015058194W WO2015151827A1 WO 2015151827 A1 WO2015151827 A1 WO 2015151827A1 JP 2015058194 W JP2015058194 W JP 2015058194W WO 2015151827 A1 WO2015151827 A1 WO 2015151827A1
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- Prior art keywords
- steel sheet
- area
- less
- strength
- bainite
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 83
- 239000010959 steel Substances 0.000 title claims abstract description 83
- 239000010960 cold rolled steel Substances 0.000 title claims abstract description 30
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 9
- 239000008397 galvanized steel Substances 0.000 title claims description 9
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 85
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 68
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 64
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002344 surface layer Substances 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- 230000000717 retained effect Effects 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 53
- 238000001816 cooling Methods 0.000 description 39
- 230000000694 effects Effects 0.000 description 23
- 238000005452 bending Methods 0.000 description 22
- 230000001965 increasing effect Effects 0.000 description 22
- 239000002436 steel type Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 238000005098 hot rolling Methods 0.000 description 15
- 238000002791 soaking Methods 0.000 description 14
- 238000005097 cold rolling Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 10
- 230000003247 decreasing effect Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 238000001887 electron backscatter diffraction Methods 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001567 cementite Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- C—CHEMISTRY; METALLURGY
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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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- 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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- 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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- 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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- 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
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- 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
- C21D2211/002—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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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a high-strength cold-rolled steel sheet, high-strength hot-dip galvanized steel sheet, or high-strength alloy having a tensile strength of 980 MPa or more and 0.2% proof stress of 700 MPa or more excellent in ductility, stretch flangeability, and weldability.
- the present invention relates to a galvannealed steel sheet. Below, these steel plates may be collectively called a high-strength steel plate.
- CTS Cross Tension Test
- Patent Document 1 in particular, B is contained, and after appropriately adjusting the ratio of Ti content and N content, the steel structure is mainly tempered martensite, and residual austenite, or further ferrite and martensite is desired.
- the area ratio is As a result, it has been shown that the strength of the steel sheet can be improved and the formability (elongation and stretch flangeability) can be improved. Among them, it is shown that the total elongation (EL) is ensured by containing 5 area% or more of retained austenite.
- Patent Document 1 only high strength and the above formability are studied, and weldability is not considered.
- Patent Document 2 the strength of martensite structure is increased without increasing the volume ratio of martensite, the decrease in ferrite volume contributing to ensuring ductility is minimized, and the volume ratio of ferrite is controlled to 50% or more. Yes.
- a high-strength cold-rolled steel sheet and a high-strength galvanized steel sheet capable of ensuring ductility and delayed fracture resistance and ensuring a high strength with a maximum tensile strength of 900 MPa or more are shown.
- weldability has not been studied.
- Patent Documents 1 and 2 the tensile strength, ductility, and stretch flangeability are studied, but none of the weldability is studied.
- the present invention has been made in view of the above circumstances, and its purpose is to improve weldability in addition to ductility and stretch flangeability in a high strength region having a tensile strength of 980 MPa or more and a 0.2% proof stress of 700 MPa or more.
- the object is to provide an excellent high-strength steel sheet.
- the high-strength cold-rolled steel sheet having a tensile strength of 980 MPa or more and a 0.2% proof stress of 700 MPa or more according to the present invention capable of achieving the above object is C: 0.07 to 0.15% in mass%.
- the area ratio of the following metal structure is tempered martensite: 30 area% or more, bainite: 15 area% or more and 70 area% or less, total of tempered martensite and bainite: 90 area% or more, ferrite: 0 area% or more and 5 areas % Or less, and retained austenite: 0 area It includes the features at satisfying the 4 area% or less.
- the high-strength cold-rolled steel sheet further includes Cu: more than 0% and 0.3% or less, Ni: more than 0% and 0.3% or less, Cr: more than 0% and 0.3% or less.
- One or more selected from the group consisting of Mo: more than 0% and 0.3% or less, V: more than 0% and 0.3% or less, and Nb: more than 0% and 0.03% or less may be contained.
- the high-strength cold-rolled steel sheet may further contain Ca: more than 0% and 0.005% or less.
- the high-strength cold-rolled steel sheet has an area ratio of the following metal structure at a surface layer portion of 20 ⁇ m in the plate thickness direction from the outermost layer portion of the steel sheet: ferrite: 80 area% or more, and martensite And the total area ratio of bainite: 0 area% or more and 20 area% or less may be satisfied.
- the present invention includes a high-strength hot-dip galvanized steel sheet having a galvanized layer on the surface of the high-strength cold-rolled steel sheet, and a high-strength alloyed hot-dip galvanized sheet having an alloyed galvanized layer on the surface of the high-strength cold-rolled steel sheet.
- Steel plates are also included.
- a tensile strength of 980 MPa or more excellent in ductility, stretch flangeability, and weldability and a high strength of 0.2% proof stress of 700 MPa or more are achieved. It is possible to provide a cold-rolled steel sheet, a hot-dip galvanized steel sheet, and an alloyed hot-dip galvanized steel sheet.
- FIG. 1 is a schematic diagram showing heat treatment conditions after hot rolling in the examples.
- FIG. 2 is a schematic diagram illustrating martensite when a gray portion close to black is present in SEM observation after nital corrosion in Examples.
- FIG. 3 is a schematic diagram illustrating bainite when a gray portion close to black is present in SEM observation after nital corrosion in Examples.
- FIG. 4 is a diagram showing a histogram of IQ in the EBSD measurement in the example.
- the present inventors have excellent ductility and stretch flangeability (hereinafter sometimes referred to as workability) even in a high-strength steel sheet having a tensile strength of 980 MPa or more and a 0.2% proof stress of 700 MPa or more.
- workability ductility and stretch flangeability
- intensive studies have been made with a particular focus on the components in the steel and the metal structure. As a result, it has been found that it is effective to appropriately control the C content to be low in order to ensure weldability for the components in steel.
- t / 4 part The area ratio of the following metal structure is tempered martensite: 30 area% or more, bainite: 15 area% or more and 70 area% or less, total of tempered martensite and bainite: 90 area% or more, ferrite: 0 area% or more and 5 areas % Austenite or less, and retained austenite: it has been found that it may be controlled to 0 area% or more and 4 area% or less.
- the present inventors preferably set the area ratio of the following metal structure in the surface layer portion 20 ⁇ m in the plate thickness direction from the outermost layer portion of the steel sheet to ensure good bending workability, and ferrite: 80 area% or more. And the total area ratio of martensite and bainite was found to be controlled to 0 to 20 area%, and the present invention was completed.
- the ratio of tempered martensite is defined in the t / 4 part of the steel sheet, and the ratio of martensite including tempered martensite is defined in the surface layer part. This is because the martensite remains in the surface layer as it is hardened, so it must be specified to include this, but at the t / 4 part, all the martensite as hardened is tempered and becomes tempered martensite. Therefore, it is not necessary to consider martensite as it is quenched.
- high strength means that the tensile strength is 980 MPa or more and the 0.2% proof stress is 700 MPa or more.
- the upper limit of the tensile strength is not particularly limited as long as the requirements of the present invention are satisfied. For example, those having a tensile strength of about 1370 MPa and a 0.2% proof stress of about 980 MPa are also included in the high strength in this specification.
- the area ratio of each metal structure was measured by the point calculation method for ferrite, bainite, and martensite, and the X-ray diffraction method for residual austenite.
- the presence or absence of ferrite was also confirmed by IQ (Image Quality, image quality) based on the sharpness of an EBSD (Electron Back Scatter Diffraction, electron beam backscatter diffraction image) pattern, in addition to the above point calculation method. Details of these measurement methods will be described in the Examples section described later.
- Tempered martensite is an important structure for securing strength. If the tempered martensite is less than 30% by area, the tensile strength or 0.2% proof stress is lowered. In order to exhibit such an effect, the lower limit of the area ratio of tempered martensite is 30 area% or more. Preferably it is 33 area% or more, More preferably, it is 35 area% or more. However, if the area ratio of tempered martensite is too large, the area ratio of bainite is relatively decreased, and ductility and stretch flangeability may be decreased. Therefore, the upper limit of the area ratio of tempered martensite is preferably 85 area% or less, more preferably 75 area% or less.
- Bainite is a structure that is more ductile than tempered martensite, and contributes to the improvement of ductility and stretch flangeability. Ductility falls that a bainite is less than 15 area%. Therefore, the lower limit of the area ratio of bainite is 15 area% or more. Preferably it is 20 area% or more, More preferably, it is 25 area% or more. However, if the area ratio of bainite becomes too large, the area ratio of tempered martensite is relatively reduced, and the tensile strength or 0.2% proof stress is lowered. Therefore, the upper limit of the area ratio of bainite is 70 area% or less. Preferably it is 67 area% or less, More preferably, it is 65 area% or less.
- Total of tempered martensite and bainite 90 area% or more
- the lower limit of the total area ratio of tempered martensite and bainite is 90 area% or more.
- it is 95 area% or more, More preferably, it is 99 area% or more, Most preferably, it is 100 area%.
- Ferrite is a structure that reduces stretch flangeability. Specifically, when the area ratio of ferrite increases, the hardness difference variation portion between the microstructures increases, and microcracks are easily generated during punching, and the stretch flangeability decreases. Therefore, the upper limit of the area ratio of ferrite is set to 5 area% or less. Preferably it is 3 area% or less, More preferably, it is 1 area% or less. Most preferably, it is 0 area%.
- Residual austenite is a structure that reduces stretch flangeability. Specifically, the retained austenite is transformed into hard martensite when punched in the hole expansion test, resulting in an increase in hardness difference between the structures, which tends to cause microcracks and stretch flanges. Sex is reduced. Furthermore, as the area ratio of retained austenite increases, the tensile strength and 0.2% proof stress also decrease. Therefore, the upper limit of the area ratio of retained austenite is 4 area% or less. Preferably it is 2 area% or less, More preferably, it is 1 area% or less. Most preferably, it is 0 area%.
- the metal structure in the t / 4 part of the steel sheet is as described above, and the steel sheet of the present invention may be composed only of the metal structure.
- the remaining structure that may be unavoidably included in the manufacturing method may be included in a range of 3 area% or less, for example. Examples of such a remaining structure include pearlite.
- the steel plate in the surface layer portion of the steel sheet from the outermost layer portion of the steel sheet in the thickness direction of 20 ⁇ m (hereinafter sometimes simply referred to as the surface layer portion).
- the internal metal structure is important for further improving the bending workability in addition to the above characteristics.
- the lower limit of the area ratio of ferrite is preferably 80 area% or more, more preferably 85 area% or more, and further preferably 90 area% or more. Most preferably, it is 100 area%.
- Total area ratio of martensite and bainite preferably 0 to 20 area%
- the upper limit of the total area ratio is preferably 20 area% or less, more preferably 15 area% or less, and still more preferably 10 area% or less. Most preferably, it is 0 area%.
- the metal structure in the surface layer portion of the steel sheet is as described above, and the steel sheet of the present invention may be composed only of the metal structure.
- the remaining structure that may be unavoidably included in the manufacturing method may be included in a range of 3 area% or less, for example. Examples of such a remaining structure include pearlite.
- C 0.07 to 0.15%
- C is an element necessary for ensuring the strength of the steel sheet.
- the lower limit of the C amount is 0.07% or more.
- the lower limit of the C amount is preferably 0.08% or more.
- CTS cross tensile strength
- the upper limit of the C amount is preferably 0.13% or less.
- Si 1.1 to 1.6%
- Si is known as a solid solution strengthening element and is an element that effectively acts to improve the tensile strength while suppressing a decrease in ductility. Further, it is an element that improves bending workability.
- the lower limit of the Si amount is set to 1.1% or more.
- the lower limit of the Si amount is preferably 1.2% or more.
- the upper limit of Si content is set to 1.6% or less.
- the upper limit of the Si amount is preferably 1.55% or less.
- Mn is an element that contributes to increasing the strength of the steel sheet by improving the hardenability.
- the lower limit of the amount of Mn is set to 2.0% or more.
- the lower limit of the amount of Mn is preferably 2.1% or more.
- stretch flangeability ( ⁇ ) can be improved by reducing the amount of Mn. Therefore, the upper limit of the Mn content is 2.8% or less.
- the upper limit of the amount of Mn is preferably 2.6% or less.
- P is an element that is unavoidably contained, and is an element that segregates at the grain boundary and promotes embrittlement of the grain boundary. It is recommended that the amount of P be reduced as much as possible in order to deteriorate hole expandability. Therefore, the upper limit of the P amount is 0.015% or less. The upper limit of the amount of P is preferably 0.013% or less. Note that P is an impurity inevitably contained in the steel, and it is impossible to make the amount 0% in industrial production.
- S more than 0% and 0.005% or less
- S is an element that is inevitably contained, and it is recommended to reduce the amount of S as much as possible in order to generate inclusions and deteriorate workability. Therefore, the upper limit of the amount of S is made 0.005% or less.
- the upper limit of the amount of S is preferably 0.003% or less, more preferably 0.002% or less.
- S is an impurity inevitably contained in the steel, and it is impossible for industrial production to make the amount 0%.
- Al 0.015 to 0.06%
- Al is an element that acts as a deoxidizer.
- the lower limit of the Al content is set to 0.015% or more.
- the lower limit of the Al content is preferably 0.025% or more.
- the upper limit of the Al amount is set to 0.06% or less.
- the upper limit of the amount of Al is preferably 0.050% or less.
- Ti 0.010 to 0.03%
- Ti is an element that improves the strength by forming carbides and nitrides. It is also an element for effectively utilizing the hardenability of B. Specifically, the formation of Ti nitride reduces N in the steel, suppresses the formation of B nitride, B becomes a solid solution state, and can effectively exhibit hardenability. Thus, Ti contributes to increasing the strength of the steel sheet by improving the hardenability.
- the lower limit of the Ti amount is set to 0.010% or more. The lower limit of the Ti amount is preferably 0.015% or more.
- the upper limit of Ti amount is made 0.03% or less.
- the upper limit of the Ti amount is preferably 0.025% or less.
- B is an element that improves hardenability and contributes to increasing the strength of the steel sheet.
- the lower limit of the B amount is set to 0.0010% or more.
- the lower limit of the B amount is preferably 0.0020% or more.
- the upper limit of the amount of B is made 0.004% or less.
- the upper limit of the amount of B is preferably 0.0035% or less.
- the steel sheet of the present invention satisfies the above component composition, and the balance is iron and inevitable impurities.
- Cu more than 0% and less than 0.3%, Ni: more than 0% and less than 0.3%, Cr: more than 0% and less than 0.3%, Mo: more than 0% and less than 0.3%, V: more than 0% 0.3% or less, and Nb: one or more selected from the group consisting of more than 0% and 0.03% or less]
- Cu, Ni, Cr, Mo, V, and Nb are all effective elements for improving the strength. These elements may be contained alone or in appropriate combination.
- Cu is an element effective for further improving the corrosion resistance of the steel sheet, and may be added as necessary.
- the lower limit of the Cu amount is preferably 0.03% or more, more preferably 0.05% or more.
- the upper limit of the amount of Cu is preferably 0.3% or less, and more preferably 0.2% or less.
- Ni is an element that is further effective in improving the corrosion resistance of the steel sheet, and may be added as necessary.
- the lower limit of the Ni amount is preferably 0.03% or more, more preferably 0.05% or more.
- the upper limit of the Ni amount is preferably 0.3% or less, more preferably 0.2% or less.
- Cr more than 0% and 0.3% or less
- Cr is an element that suppresses ferrite generated during cooling from a higher temperature range, and may be added as necessary.
- the lower limit of the Cr amount is preferably 0.03% or more, more preferably 0.05% or more.
- the upper limit of the Cr amount is preferably 0.3% or less, more preferably 0.2% or less.
- Mo more than 0% and 0.3% or less
- Mo is an element that suppresses ferrite generated during cooling from a higher temperature range, and may be added as necessary.
- the lower limit of the Mo amount is preferably 0.03% or more, more preferably 0.05% or more.
- the upper limit of the Mo amount is preferably 0.3% or less, more preferably 0.2% or less.
- V is an element that further refines the structure to improve strength and toughness, and may be added as necessary.
- the lower limit of the V amount is preferably 0.03% or more, more preferably 0.05% or more.
- the upper limit of the V amount is preferably 0.3% or less, more preferably 0.2% or less.
- Nb is an element that further refines the structure to improve strength and toughness, and may be added as necessary.
- the lower limit of the Nb amount is preferably 0.003% or more, more preferably 0.005% or more.
- the upper limit of the Nb amount is preferably 0.03% or less, more preferably 0.02% or less.
- Ca more than 0% and 0.005% or less
- Ca is an element effective for spheroidizing sulfides in steel and enhancing stretch flangeability.
- the lower limit of the Ca content is preferably 0.0005% or more, more preferably 0.001% or more.
- the upper limit of the Ca content is preferably 0.005% or less, more preferably 0.003% or less.
- the steel sheet of the present invention is excellent in all of ductility, stretch flangeability, and weldability in a region where the tensile strength is 980 MPa or more and the 0.2% proof stress is 700 MPa or more.
- the steel sheet of the present invention that satisfies the above requirements is characterized in that it is manufactured by appropriately controlling the annealing process after cold rolling, particularly in the processes of hot rolling, cold rolling, and annealing (soaking and cooling). is there.
- the process characterizing the present invention will be described in the order of hot rolling, cold rolling, and subsequent annealing.
- Preferred conditions for hot rolling are as follows, for example.
- the solid solution of carbides such as TiC in austenite may be lowered, so the lower limit of the heating temperature before hot rolling is preferably 1200 ° C. or more, more preferably Is 1250 ° C. or higher. Since the cost increases when the heating temperature before hot rolling is high, the upper limit of the heating temperature before hot rolling is preferably 1350 ° C. or less, more preferably 1300 ° C. or less.
- the finish rolling temperature of hot rolling is low, rolling in the austenite single phase region cannot be performed and the microstructure may not be homogenized. Therefore, the finish rolling temperature is preferably 850 ° C. or more, more preferably 870 ° C. That's it. When the finish rolling temperature is high, the structure may be coarsened. Therefore, the temperature is preferably 980 ° C. or lower, more preferably 950 ° C. or lower.
- the average cooling rate from finish rolling to winding in hot rolling is preferably 10 ° C./s or more, more preferably 20 ° C./s or more in consideration of productivity.
- the average cooling rate is high, the equipment cost increases, and therefore, it is preferably 100 ° C./s or less, more preferably 50 ° C./s or less.
- Winding temperature CT after hot rolling preferably 660 ° C. or higher
- the coiling temperature CT after hot rolling is less than 660 ° C.
- the surface layer of the hot-rolled sheet is decarburized, or due to the decrease in solid solution Mn and Cr of the surface layer, the element concentration distribution also on the surface layer of the annealed sheet Is formed, the ferrite of the surface layer is increased, and the bending workability is improved.
- the lower limit of CT is preferably 660 ° C. or higher, more preferably 670 ° C. or higher.
- the upper limit of CT is preferably 800 ° C. or lower, more preferably 750 ° C. or lower.
- Cold rolling ratio preferably 20% or more and 60% or less
- the hot-rolled steel sheet is pickled for scale removal and subjected to cold rolling.
- the cold rolling ratio of cold rolling is less than 20%, the plate thickness must be reduced in the hot rolling process in order to obtain a steel plate having a predetermined thickness. Therefore, pickling takes time and productivity is lowered. Therefore, the lower limit of the cold rolling rate is preferably 20% or more, more preferably 25% or more.
- the upper limit of the cold rolling rate is preferably 60% or less, more preferably 55% or less, and still more preferably 50% or less.
- the lower limit of the average heating rate is preferably 1 ° C./s or more, more preferably 3 ° C./s or more, and further preferably 5 ° C./s or more.
- the upper limit of the average heating rate is preferably 20 ° C./s or less, more preferably 18 ° C./s or less, and still more preferably 15 ° C./s or less.
- the Ac3 point temperature is calculated based on the following equation.
- (%) is the content (% by mass) of each element. This equation is described in “Leslie Steel Material Science” (published by Maruzen Co., Ltd., William C. Leslie, p. 273).
- Ac3 910 ⁇ 203 ⁇ (% C) ⁇ 15.2 (% Ni) +44.7 (% Si) +104 (% V) +31.5 (% Mo) +13.1 (% W) ⁇ 30 (% Mn) ⁇ 11 (% Cr) ⁇ 20 (% Cu) +700 (% P) +400 (% Al) +120 (% As) +400 (% Ti)
- the soaking time at the soaking temperature T1 is less than 1 s, the soaking effect cannot be sufficiently exhibited. Therefore, the lower limit of the soaking time is preferably 1 s or more, more preferably 10 s or more. On the other hand, when the soaking time exceeds 100 s, productivity deteriorates. Therefore, the upper limit of the soaking time is preferably 100 s or less, more preferably 80 s or less.
- the lower limit of T2 is set to 460 ° C or higher, preferably 480 ° C or higher.
- the upper limit of T2 is 550 ° C. or lower, preferably 520 ° C. or lower.
- the lower limit of the average cooling rate is preferably 1 ° C./s or more, more preferably 5 ° C./s or more.
- the upper limit of the average cooling rate is preferably 50 ° C./s or less, more preferably 40 ° C./s or less, and further preferably 30 ° C./s or less.
- the secondary cooling step from the cooling stop holding temperature T2 to room temperature [Average cooling rate: preferably 1 ° C / s or more and 20 ° C / s or less]
- the lower limit of the average cooling rate in the secondary cooling step is preferably 1 ° C./s or more, more preferably 3 ° C./s or more.
- the upper limit of the average cooling rate is preferably 20 ° C./s or less, more preferably 15 ° C./s or less, and still more preferably 10 ° C./s or less.
- the present invention also includes a high-strength hot-dip galvanized steel sheet having a galvanized layer on the surface of a high-strength cold-rolled steel sheet, and a high-strength galvannealed steel sheet having an alloyed galvanized layer on the surface of a high-strength cold-rolled steel sheet.
- the high-strength hot-dip galvanized steel sheet of the present invention can be manufactured by performing galvanization by a normal method in the step of the cooling stop holding temperature T2 or the secondary cooling step from the cooling stop holding temperature T2 to room temperature. it can.
- the high-strength galvannealed steel sheet of the present invention can be produced by galvanizing as described above and then performing an alloying treatment by a normal method.
- a steel ingot having the composition shown in Table 1 below was vacuum-melted. Then, it heated to 1250 degreeC and hot-rolled to plate
- the finish rolling temperature was 900 ° C.
- the average cooling rate from finish rolling to winding in hot rolling was 20 ° C./s
- the winding temperature CT was the temperature shown in Table 2 and Table 3 below.
- the obtained hot-rolled steel sheet was pickled and then cold-rolled to a thickness of 2.0 mm. Thereafter, heat treatment was performed under the conditions shown in FIG. 1, Table 2, and Table 3. Furthermore, temper rolling with an elongation of 0.2% was performed.
- Table 1 a blank means 0%.
- the fraction was measured as follows. According to the manufacturing method of this example, the possibility of the presence of tissues other than the above in each region is extremely low. Therefore, the total of martensite, bainite, ferrite, and retained austenite was calculated to be 100 area% at t / 4 part of the steel sheet, and the total of martensite, bainite, and ferrite was calculated to be 100 area% at the surface layer part of the steel sheet.
- martensite As described above, in the present invention, the details of martensite are distinguished by the position of the steel sheet, and those present in the t / 4 part of the steel sheet were determined to be tempered martensite. On the other hand, what exists in the surface layer part of a steel plate was judged to be martensite including both tempered martensite and quenched martensite. In the “organization fraction” column, these are not distinguished and are simply described as “martensite”.
- the retained austenite was cut out from a 2 mm ⁇ 20 mm ⁇ 20 mm test piece from the steel plate, ground to t / 4 part of the plate thickness, then chemically polished, and the amount of retained austenite was measured by X-ray diffraction. (ISIJ Int. Vol. 33. (1933), No. 7, P.776).
- the retained austenite among the above structures that can be included in each region was measured by the X-ray diffraction method, and the other structures such as ferrite were measured by the point counting method after nital corrosion as described later. The reason is that, when performing nital corrosion, both retained austenite and cementite such as cementite are observed as a white or gray structure and cannot be distinguished from each other.
- a test piece of 2 mm ⁇ 20 mm ⁇ 20 mm was cut out from the steel sheet, the cross section parallel to the rolling direction was polished, and the nital corrosion was performed.
- (Scanning Electron Microscope) A photograph (magnification 3000 times) was observed. The observation was performed using a grid with a spacing of 2 ⁇ m for 20 ⁇ m ⁇ 20 ⁇ m per field of view, and each area ratio was measured by distinguishing ferrite, bainite, and martensite based on the color and size of the grains. The measurement was performed for a total of 5 fields of view, and the average value was obtained.
- each structure can be distinguished by the above methods (i) and (ii), but when the structure is gray near black, it may be difficult to distinguish martensite and bainite.
- FIGS. 2 and 3 the inside of a gray tissue close to black is observed, and attention is paid to a white or gray portion (hereinafter, referred to as a white portion) existing in the inside. We decided to distinguish them by their size or number.
- martensite is a material in which a large number of white portions existing inside a gray portion close to black are present. Specifically, when the distance between the center positions of the white portions was measured for adjacent white portions and white portions, the distance having the shortest distance, that is, the closest distance of less than 0.5 ⁇ m was determined as martensite.
- bainite was formed in which a white portion existing in a gray portion close to black was sparse and a small number existed. Specifically, there are three or more white portions, and when the closest distance between adjacent white portions was measured in the same manner as martensite, a portion of 0.5 ⁇ m or more was determined to be bainite.
- each fraction of ferrite, bainite, and martensite measured by the point method is proportional to the value obtained by subtracting the fraction of retained austenite measured by the X-ray diffraction method. After redistribution, the fractions of ferrite, bainite, and martensite were finally determined.
- the steel sheet of the present invention is mainly composed of tempered martensite and bainite and has a reduced ferrite ratio, and it is most preferable that the ferrite is zero, that is, does not exist.
- the fraction of ferrite can be measured by the point calculation method described above, it may be difficult to clearly distinguish ferrite from other structures such as bainite. For this reason, in this embodiment, in addition to the point calculation method, the presence or absence of ferrite is evaluated based on IQ.
- IQ is the definition of the EBSD pattern as described above.
- IQ is known to be affected by the amount of strain in the crystal, and the smaller the IQ, the more strain tends to exist in the crystal. Therefore, the martensite having a high dislocation density includes a disorder of the crystal structure, so that the IQ value decreases, and the ferrite tends to have a high IQ value because of a low dislocation density.
- a method has been proposed in which an absolute value of an IQ value is used as an index, for example, a structure having an IQ value of 4000 or more is determined as ferrite.
- the method based on the absolute value of IQ is easily affected by polishing conditions for structure observation, a detector, and the like, and the absolute value of IQ is likely to fluctuate. It was.
- the present inventors prepared a steel sheet (without ferrite) that satisfies the requirements of the present invention and a steel sheet with a large amount of ferrite, and examined in detail the relationship between IQ and the presence or absence of ferrite.
- IQmin minimum value of all IQ data
- IQmax maximum value of all IQ data
- the IQ value [IQ (F)] of ferrite (F) is calculated based on the following formula (1), and the total number of measurement points where IQ is equal to or greater than the following formula (1) is divided by the total number of measurement points.
- IQ (F) 0.91 ⁇ (IQmax ⁇ IQmin) + IQmin (1)
- IQmin means the minimum value of all IQ data
- IQmax means the maximum value of all IQ data.
- the IQ value was measured as follows. First, a sample was prepared by mechanically polishing a cross section parallel to the rolling direction at a t / 4 site, where t is the thickness of the steel plate. Next, this sample was set in an OIM system manufactured by Texemola Laboratories and tilted by 70 °, and an area of 100 ⁇ m ⁇ 100 ⁇ m was used as a measurement visual field. Next, 180,000 EBSD measurements were performed at an acceleration voltage of 20 kV, 1 step: 0.25 ⁇ m, and an IQ of a body-centered cubic lattice (BCC: Body Centered Cubic) crystal including a body-centered tetragonal lattice (BCT: Body centralized Tetragonal).
- BCC Body Centered Cubic
- BCT Body centralized Tetragonal
- the body-centered tetragonal lattice is one in which the lattice is elongated in one direction by solid solution at a specific interstitial position in the body-centered cubic lattice, and the structure itself is equivalent to the body-centered cubic lattice. , EBSD cannot distinguish these lattices. Therefore, in this embodiment, the measurement of the body-centered cubic lattice includes the body-centered square lattice.
- FIG. 4 shows an example of an IQ histogram obtained by the above method.
- the horizontal axis [(IQ (F) ⁇ IQmin) / (IQmax ⁇ IQmin) ⁇ 100] is the left side of the formula (1A) obtained by modifying the formula (1) as follows, and the vertical axis is the frequency. (Total number of measurement points).
- a region where the value of the horizontal axis in FIG. 4 is 91% or more with respect to the total number of measurement points is indicated by an arrow in the right column of FIG. That is, the region represented by this arrow is a region equal to or greater than the above formula (1).
- a value obtained by dividing the total number of measurement points in the region by the total number of measurement points and multiplying by 100 is 5% or less, which means that there is no ferrite.
- the bending workability (R / t) is obtained by taking a 2 mm ⁇ 40 mm ⁇ 100 mm test piece from the cold-rolled steel sheet so that the rolling direction and the vertical direction are the length of the test piece, and according to the V block method of JIS Z 2248. A test was performed and the minimum bending radius R at which no cracks or cracks occurred was measured. The bending direction is the longitudinal direction of the test piece. A value obtained by dividing R found by a bending test by a nominal plate thickness of 2 mm was defined as R / t.
- test no. Examples 1 to 14 and 17 are examples that satisfy the composition of the present invention and the structure of t / 4 part, and satisfy the preferable structure of the surface layer part.
- test no. 15 and 16 satisfy the composition of the present invention and the structure of t / 4 part, but the CT (° C.) is lowered, so the total area ratio of martensite and bainite in the surface layer part is larger than the preferred range, and further the ferrite This is an example in which the area ratio is smaller than the preferred range.
- Test No. above. 1 to 14, 17 and the above test Nos. 15 and 16 are compared, the test No.
- the test Nos. 1 to 14 and 17 are the test Nos.
- Test No. in Table 4 Nos. 18 to 25 use the steel types 15 to 22 in Table 1 that do not satisfy the composition of the present invention. This is an example manufactured under the heat treatment conditions of 18-25.
- Test No. No. 18 is an example produced by using steel type 15 in Table 1 with a small amount of C and lowering T1 (° C.). . As a result, the tensile strength (TS) and 0.2% yield strength (YS) were lowered. Furthermore, although bainite was not generated, the ductility (El) and stretch flangeability ( ⁇ ) did not decrease because the area ratio of ferrite increased.
- Test No. No. 19 is an example of production using steel type 16 of Table 1 with a large amount of C and increasing T1 (° C.). Since bainite was not produced and only tempered martensite was produced, tensile strength (TS) and 0.2 % Proof stress (YS) was significantly increased. As a result, ductility (El) and stretch flangeability ( ⁇ ) were lowered. Moreover, since the amount of C increased, weldability (CTS) also became low. Furthermore, since the tensile strength (TS) and the 0.2% yield strength (YS) were remarkably increased, the surface layer portion satisfied the preferred structure of the present invention, but the bending workability (R / t) was lowered.
- Test No. 20 is an example using the steel type 17 of Table 1 with a small amount of Si, and the tensile strength (TS) and 0.2% yield strength (YS) were low. Furthermore, since the amount of Si was small, the surface layer portion satisfied the preferred structure of the present invention, but the bending workability (R / t) was lowered.
- Test No. 21 is an example using the steel type 18 of Table 1 with a small amount of Mn, and the tensile strength (TS) and 0.2% yield strength (YS) were low. Although the amount of P was large, the effect of improving stretch flangeability ( ⁇ ) due to the small amount of Mn was great, and the stretch flangeability ( ⁇ ) was not lowered.
- Test No. 22 is an example using the steel type 19 in Table 1 with a large amount of Mn, and bainite was not generated but only tempered martensite was generated, so that the tensile strength (TS) and 0.2% yield strength (YS) were remarkably increased. . As a result, ductility (El) and stretch flangeability ( ⁇ ) were lowered. Furthermore, since the tensile strength (TS) and the 0.2% yield strength (YS) were remarkably increased, the surface layer portion satisfied the preferred structure of the present invention, but the bending workability (R / t) was lowered.
- Test No. No. 23 is an example using the steel type 20 of Table 1 with a small amount of Ti. Although the area ratio of ferrite was increased, the total area ratio of tempered martensite and bainite was decreased, so that the tensile strength (TS), 0 .2% yield strength (YS) and stretch flangeability ( ⁇ ) were lowered.
- TS tensile strength
- YS yield strength
- ⁇ stretch flangeability
- Test No. 24 is an example using the steel type 21 of Table 1 with a large amount of Ti, and the tensile strength (TS) and 0.2% proof stress (YS) became high. As a result, ductility (El) and stretch flangeability ( ⁇ ) were lowered. Furthermore, since the tensile strength (TS) and the 0.2% yield strength (YS) were high, the surface layer portion satisfied the preferred structure of the present invention, but the bending workability (R / t) was lowered.
- Test No. 25 is an example using the steel type 22 in Table 1 with a small amount of B.
- the area ratio of ferrite was increased, but the total area ratio of tempered martensite and bainite was decreased, so that the tensile strength (TS), 0 .2% yield strength (YS) and stretch flangeability ( ⁇ ) were lowered.
- TS tensile strength
- YS yield strength
- ⁇ stretch flangeability
- Test No. in Table 5 Nos. 26 to 46 use the steel types 1 to 7 and 9 to 14 in Table 1 that satisfy the composition of the present invention. This is an example manufactured under the heat treatment conditions of 26-46. Among them, test No. in Table 5 Nos. 26 to 31 use the steel type 1 in Table 1 that satisfies the composition of the present invention, and the test Nos. In Table 3 This is an example manufactured under the heat treatment conditions of 26-31.
- Test No. 26 is an example using the steel type 1 of Table 1 that satisfies the composition of the present invention, T2 (° C.) is low, the area ratio of retained austenite ( ⁇ ) is large, and as a result, the tensile strength (TS), The 0.2% yield strength (YS) and stretch flangeability ( ⁇ ) were lowered.
- Test No. No. 27 is an example using the steel type 1 of Table 1 that satisfies the composition of the present invention, and because T2 (° C.) is high, the area ratio of bainite becomes small. As a result, ductility (El) and stretch flangeability ( ⁇ ) became low.
- Test No. 28 is an example using the steel type 1 of Table 1 that satisfies the composition of the present invention, and because t2 (seconds) is short, the area ratio of bainite is reduced, and as a result, ductility (El) is reduced. .
- Test No. No. 28 is a test no. Since the area ratio of tempered martensite was larger than 27, stretch flangeability ( ⁇ ) was not lowered.
- Test No. 29 is an example using the steel type 1 of Table 1 that satisfies the composition of the present invention, and because t2 (second) is long, the area ratio of tempered martensite is reduced, and the area ratio of bainite is increased. As a result, the tensile strength (TS) and 0.2% yield strength (YS) were lowered.
- Test No. 30 is an example using the steel type 1 of Table 1 which satisfies the composition of the present invention.
- Test No. No. 30 had a low T1 (° C.), no bainite was formed, and the area ratio of ferrite was large, but the total area ratio of tempered martensite and bainite was small, resulting in a tensile strength (TS) of 0. 2% yield strength (YS) and stretch flangeability ( ⁇ ) were lowered.
- T1 ° C.
- TS tensile strength
- YS yield strength
- ⁇ stretch flangeability
- Test No. No. 31 is an example using the steel type 5 of Table 1 that satisfies the composition of the present invention.
- T1 (° C.) is high, and bainite is not generated, and only tempered martensite is generated. Therefore, tensile strength (TS) and 0.2 % Proof stress (YS) was significantly increased. As a result, ductility (El) and stretch flangeability ( ⁇ ) were lowered.
- Test No. Nos. 32 to 35 are examples using the steel types 1 to 4 in Table 1 that satisfy the composition of the present invention. This is an example manufactured under the heat treatment conditions of 32 to 35. Test No. In 32 to 35, the area ratio of bainite increased because T1 (° C.) was low, but the area ratio of tempered martensite decreased, so that the 0.2% proof stress (YS) decreased, and the stretch flange The property ( ⁇ ) decreased.
- Test No. Nos. 36 to 43 use the steel types 6, 7, and 9 to 14 in Table 1 that satisfy the composition of the present invention. This is an example manufactured under the heat treatment conditions of 36-43. Test No. Since 36 to 43 had a low T1 (° C.), the area ratio of bainite was large and the area ratio of tempered martensite was small. As a result, the 0.2% yield strength (YS) was low.
- Test No. Nos. 44 to 46 use the steel type 1 in Table 1 that satisfies the composition of the present invention. This is an example manufactured under the heat treatment conditions of 44 to 46.
- Test No. Nos. 44 to 46 had a low T1 (° C.), so the area ratio of tempered martensite was small, and as a result, the 0.2% yield strength (YS) was low.
- test no. 44 and test no. No. 45 has a low CT (° C.), so that the total area ratio of tempered martensite and bainite in the surface layer portion was increased, the area ratio of ferrite was decreased, and as a result, bending workability was lowered.
- Test No. 46 the area ratio of bainite was large because T1 (° C.) was low, but the area ratio of tempered martensite was small, so the 0.2% proof stress (YS) was low, and stretch flangeability ( ⁇ ) decreased.
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Abstract
Description
本発明の鋼板の板厚をtとしたとき、最表層部から1/4の部位における金属組織は、所望とする強度(引張強度および0.2%耐力)および加工性(延性および伸びフランジ性)を両立するために重要である。
焼戻しマルテンサイトは強度の確保に重要な組織である。焼戻しマルテンサイトが、30面積%未満であると引張強度または0.2%耐力が低下する。このような効果を発揮させるために、焼戻しマルテンサイトの面積率の下限は、30面積%以上とする。好ましくは33面積%以上、より好ましくは35面積%以上である。しかし、焼戻しマルテンサイトの面積率が大きくなりすぎると、相対的にベイナイトの面積率が減少し、延性、伸びフランジ性が低下する場合がある。そのため、焼戻しマルテンサイトの面積率の上限は、好ましくは85面積%以下、より好ましくは75面積%以下である。
ベイナイトは焼戻しマルテンサイトより延性に優れる組織であり、延性、更には伸びフランジ性の向上に寄与する。ベイナイトが、15面積%未満であると延性が低下する。そのために、ベイナイトの面積率の下限を15面積%以上とする。好ましくは20面積%以上、より好ましくは25面積%以上である。しかし、ベイナイトの面積率が大きくなりすぎると、相対的に焼戻しマルテンサイトの面積率が減少し、引張強度または0.2%耐力が低下する。そのため、ベイナイトの面積率の上限は70面積%以下とする。好ましくは67面積%以下、より好ましくは65面積%以下である。
焼戻しマルテンサイトとベイナイトの合計が90面積%未満であると、引張強度、0.2%耐力、および伸びフランジ性が低下する。そのために、焼戻しマルテンサイトとベイナイトの合計面積率の下限を90面積%以上とする。好ましくは95面積%以上、より好ましくは99面積%以上であり、最も好ましくは100面積%である。
フェライトは、伸びフランジ性を低下させる組織である。詳細には、フェライトの面積率が大きくなると、ミクロ組織間の硬度差変動部が大きくなり、打ち抜き加工時のミクロクラックが発生しやすくなり、伸びフランジ性が低下する。そのため、フェライトの面積率の上限を、5面積%以下とする。好ましくは3面積%以下、より好ましくは1面積%以下とする。最も好ましくは0面積%である。
残留オーステナイトは、伸びフランジ性を低下させる組織である。詳細には、残留オーステナイトは、穴広げ試験での打ち抜き加工をした際に、硬質なマルテンサイトに変態して、その結果、組織間の硬度差が増加し、ミクロクラックが発生しやすくなり伸びフランジ性が低下する。更に、残留オーステナイトの面積率が大きくなると、引張強度および0.2%耐力も低下する。そのため、残留オーステナイトの面積率の上限を4面積%以下とする。好ましくは2面積%以下、より好ましくは1面積%以下とする。最も好ましくは0面積%である。
更に、鋼板の最表層部から板厚方向20μmの表層部位(以下では、単に表層部と呼ぶ場合がある。)における鋼板内部の金属組織は、上記特性に加えて更に曲げ加工性を向上させるために重要である。
曲げ変形時の表層の最大引張歪発生部である表層部の組織について、延性の高いフェライトの面積率を多くすることで、表層部の局部伸び、即ちくびれを抑制でき、曲げ加工性を向上することができる。このような効果を有効に発揮させるために、フェライトの面積率の下限は、好ましくは80面積%以上、より好ましくは85面積%以上、更に好ましくは90面積%以上である。最も好ましくは100面積%である。
マルテンサイトとベイナイトの合計面積率が大きくなると、フェライトの面積率が小さくなり、曲げ加工性が低下する。そのため、合計面積率の上限は、好ましくは20面積%以下、より好ましくは15面積%以下、更に好ましくは10面積%以下とする。最も好ましくは0面積%である。
Cは、鋼板の強度を確保するために必要な元素であり、C量が不足すると、引張強度、および0.2%耐力が低下する。そのためにC量の下限を0.07%以上とする。C量の下限は、好ましくは0.08%以上である。しかし、C量が過剰になると溶接性の指標である十字引張強度(CTS)が低下するため、C量の上限を0.15%以下とする。C量の上限は、好ましくは0.13%以下である。
Siは固溶強化元素として知られており、延性の低下を抑えつつ、引張強度を向上させることに有効に作用する元素である。更に、曲げ加工性を向上させる元素でもある。このような効果を有効に発揮させるために、Si量の下限を1.1%以上とする。Si量の下限は、好ましくは1.2%以上である。しかし、過剰に添加しても上記効果が飽和し、無駄であるため、Si量の上限を1.6%以下とする。Si量の上限は、好ましくは1.55%以下である。
Mnは焼入れ性を向上させて鋼板の高強度化に寄与する元素である。このような効果を有効に発揮させるために、Mn量の下限を2.0%以上とする。Mn量の下限は、好ましくは2.1%以上とする。しかしながら、Mn量が過剰になると、加工性が劣化することがある。一方、Mn量を低減させることにより伸びフランジ性(λ)を向上させることができる。そのため、Mn量の上限を2.8%以下とする。Mn量の上限は、好ましくは2.6%以下である。
Pは不可避的に含有する元素であり、粒界に偏析して粒界脆化を助長する元素であり、穴広げ性を劣化させるため、P量はできるだけ低減することが推奨される。そのため、P量の上限は、0.015%以下とする。P量の上限は、好ましくは0.013%以下である。なお、Pは鋼中に不可避的に含まれる不純物であり、その量を0%にすることは工業生産上不可能である。
SもPと同様に不可避的に含有する元素であり、介在物を生成し、加工性を劣化させるため、S量はできるだけ低減することが推奨される。そのため、S量の上限は、0.005%以下とする。S量の上限は、好ましくは0.003%以下、より好ましくは0.002%以下である。なお、Sは鋼中に不可避的に含まれる不純物であり、その量を0%にすることは工業生産上不可能である。
Alは脱酸剤として作用する元素である。こうした作用を有効に発揮させるには、Al量の下限を0.015%以上とする。Al量の下限は、好ましくは0.025%以上である。しかしながら、Al量が過剰になると鋼板中にアルミナなどの介在物が多く生成し、加工性を劣化させることがあるため、Al量の上限を0.06%以下とする。Al量の上限は、好ましくは0.050%以下である。
Tiは、炭化物や窒化物を形成して強度を向上させる元素である。また、Bの焼入れ性を有効に活用するための元素でもある。詳細には、Ti窒化物形成により鋼中Nを低減し、B窒化物の形成を抑制し、Bが固溶状態となり、有効に焼入れ性を発揮できる。このように、Tiは焼入れ性を向上させることにより、鋼板の高強度化に寄与する。このような効果を有効に発揮させるために、Ti量の下限を、0.010%以上とする。Ti量の下限は、好ましくは0.015%以上である。しかしながら、Ti量が過剰になると、Ti炭化物やTi窒化物が過剰となり、延性、伸びフランジ性、および曲げ加工性を劣化させるため、Ti量の上限を0.03%以下とする。Ti量の上限は、好ましくは0.025%以下である。
Bは焼入れ性を向上させて鋼板の高強度化に寄与する元素である。このような効果を有効に発揮させるために、B量の下限を0.0010%以上とする。B量の下限は、好ましくは0.0020%以上である。しかし、B量が過剰になると、その効果が飽和し、コストが増加するだけであるため、B量の上限を0.004%以下とする。B量の上限は、好ましくは0.0035%以下である。
Cu、Ni、Cr、Mo、V、およびNbはいずれも強度向上に有効な元素である。これらの元素は、夫々単独でまたは適宜組み合わせて含有させても良い。
Cuは、更に鋼板の耐食性向上に有効な元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、Cu量の下限を、好ましくは0.03%以上、より好ましくは0.05%以上とする。しかし、Cu量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、Cu量の上限は、好ましくは0.3%以下、より好ましくは0.2%以下である。
Niは、更に鋼板の耐食性向上に有効な元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、Ni量の下限を、好ましくは0.03%以上、より好ましくは0.05%以上とする。しかしながら、Ni量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、Ni量の上限は、好ましくは0.3%以下、より好ましくは0.2%以下である。
Crは、更に高温域からの冷却中に生成するフェライトを抑制する元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、Cr量の下限を、好ましくは0.03%以上、より好ましくは0.05%以上とする。しかしながら、Cr量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、Cr量の上限は、好ましくは0.3%以下、より好ましくは0.2%以下である。
Moは、更に高温域からの冷却中に生成するフェライトを抑制する元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、Mo量の下限を、好ましくは0.03%以上、より好ましくは0.05%以上とする。しかしながら、Mo量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、Mo量の上限は、好ましくは0.3%以下、より好ましくは0.2%以下である。
Vは、更に組織を微細化して強度と靭性を向上させる元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、V量の下限は、好ましくは0.03%以上、より好ましくは0.05%以上である。しかしながら、V量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、V量の上限は、好ましくは0.3%以下、より好ましくは0.2%以下である。
Nbは、更に組織を微細化して強度と靭性を向上させる元素であり、必要に応じて添加しても良い。このような効果を有効に発揮させるために、Nb量の下限を、好ましくは0.003%以上、より好ましくは0.005%以上とする。しかしながら、Nb量が過剰になると、加工性を劣化させる。そのため、Nb量の上限は、好ましくは0.03%以下、より好ましくは0.02%以下である。
Caは、鋼中の硫化物を球状化し、伸びフランジ性を高めることに有効な元素である。このような効果を有効に発揮させるために、Ca量の下限を、好ましくは、0.0005%以上、より好ましくは0.001%以上とする。しかしながら、Ca量が過剰になると、その効果が飽和し、コストが増加するだけである。そのため、Ca量の上限は、好ましくは0.005%以下、より好ましくは0.003%以下である。
熱間圧延後の巻取り温度CTが、660℃未満になると、熱延板の表層が脱炭するか、もしくは、表層の固溶Mn、Crの減少により、焼鈍板の表層にも元素濃度分布が形成され、表層のフェライトが増加し、曲げ加工性が改善する。そのため、CTの下限を、好ましくは660℃以上、より好ましくは670℃以上とする。一方、CTが、高くなりすぎるとスケール除去のための酸洗性が劣化する。そのため、CTの上限は、好ましくは800℃以下、より好ましくは750℃以下である。
熱延鋼板は、スケール除去のために酸洗を施し、冷間圧延に供する。冷間圧延の冷延率が20%未満になると、所定厚さの鋼板を得るために熱間圧延工程で板厚を薄くしなければならず、熱間圧延工程で薄くすると鋼板長さが長くなるため、酸洗に時間がかかり、生産性が低下する。そのため、冷延率の下限を、好ましくは20%以上、より好ましくは25%以上とする。一方、冷延率が60%を超えると、高い冷間圧延機の能力が必要となる。そのため、冷延率の上限は、好ましくは60%以下、より好ましくは55%以下、更に好ましくは50%以下である。
上記冷間圧延後の焼鈍時の平均加熱速度が1℃/s未満となると、生産性が悪化する。そのため、上記平均加熱速度の下限を、好ましくは1℃/s以上、より好ましくは3℃/s以上、更に好ましくは5℃/s以上とする。一方、上記平均加熱速度が20℃/sを超えると、鋼板温度が制御し難くなり、設備コストも増加する。そのため、上記平均加熱速度の上限は、好ましくは20℃/s以下、より好ましくは18℃/s以下、更に好ましくは15℃/s以下である。
上記冷間圧延後の焼鈍時の均熱温度T1がAc3点+25℃未満になると、ベイナイトまたはフェライトが増加し、0.2%耐力の確保が難くなる。そのため、T1の下限は、Ac3点+25℃以上、好ましくはAc3点+35℃以上とする。一方、上記T1がAc3点+70℃を超えると、ベイナイトが減少し、伸びや伸びフランジ性が劣化する。そのため、T1の上限は、Ac3点+70℃以下、好ましくはAc3点+60℃以下である。
Ac3=910-203√(%C)-15.2(%Ni)+44.7(%Si)+104(%V)+31.5(%Mo)+13.1(%W)-30(%Mn)-11(%Cr)-20(%Cu)+700(%P)+400(%Al)+120(%As)+400(%Ti)
上記均熱温度T1での均熱時間が1s未満となると、上記均熱の効果が十分に発揮できない。そのため、上記均熱時間の下限は、好ましくは1s以上、より好ましくは10s以上とする。一方、上記均熱時間が100sを超えると、生産性が悪化する。そのため、上記均熱時間の上限は、好ましくは100s以下、より好ましくは80s以下である。
[冷却停止保持温度T2:460℃以上550℃以下]
まず、均熱温度T1から、冷却停止温度(460℃以上550℃以下)まで冷却した後、当該冷却停止温度にて所定時間(後記するt2)保持する。本明細書では、冷却停止温度にて保持するため、冷却停止温度と保持温度をまとめて冷却停止保持温度T2と呼ぶ場合がある。冷却停止保持温度T2が、460℃未満になると、残留オーステナイトが増加し、伸びフランジ性が劣化する。そのため、T2の下限は、460℃以上、好ましくは480℃以上とする。一方、550℃を超えると、ベイナイトが減少し、加工性が劣化する。そのため、T2の上限は、550℃以下、好ましくは520℃以下である。
上記均熱温度から上記冷却停止保持温度T2までの平均冷却速度が、1℃/s未満になると、生産性が悪化する。そのため、上記平均冷却速度の下限は、好ましくは1℃/s以上、より好ましくは5℃/s以上とする。一方、上記平均冷却速度が50℃/sを超えると、鋼板温度を制御し難くなり、設備コストが増加する。そのため、上記平均冷却速度の上限は、好ましくは50℃/s以下、より好ましくは40℃/s以下、更に好ましくは30℃/s以下である。
冷却停止保持温度T2での保持時間をt2としたとき、上記t2が20s未満になると、ベイナイトが減少し、加工性が劣化する。そのため、t2の下限は、20s以上、好ましくは25s以上とする。一方、上記t2が100sを超えると、焼戻しマルテンサイトが減少し、強度が達成し難くなる。そのため、t2の上限は、100s以下、好ましくは80s以下である。
[平均冷却速度:好ましくは1℃/s以上20℃/s以下]
次に、冷却停止保持温度T2から室温まで冷却する。この2次冷却工程における平均冷却速度が1℃/s未満になると、生産性が劣化する。そのため、2次冷却工程における平均冷却速度の下限は、好ましくは1℃/s以上、より好ましくは3℃/s以上とする。一方、上記平均冷却速度が20℃/sを超えると、設備コストが増加する。そのため、上記平均冷却速度の上限は、好ましくは20℃/s以下、より好ましくは15℃/s以下、更に好ましくは10℃/s以下である。
本実施例では、鋼板のt/4部に存在するマルテンサイト、ベイナイト、フェライト、残留オーステナイトの分率、および鋼板の最表層部から20μm位置(表層部)に存在するマルテンサイト、ベイナイト、フェライトの分率を以下のようにして測定した。本実施例の製造方法によれば、各領域において、上記以外の組織が存在する可能性は極めて低いため、上記以外の組織は測定していない。そこで、鋼板のt/4部ではマルテンサイト、ベイナイト、フェライト、残留オーステナイトの合計が100面積%、鋼板の表層部ではマルテンサイト、ベイナイト、フェライトの合計が100面積%になるように算出した。
IQ(F)=0.91×(IQmax-IQmin)+IQmin・・・(1)
式中、IQminはIQ全データの最小値、IQmaxはIQ全データの最大値をそれぞれ意味する。
(IQ(F)-IQmin)/(IQmax-IQmin)×100≧91・・・(1A)
引張強度(TS)、0.2%耐力(YS)、および延性の指標として伸び(El)については、上記冷延鋼板の圧延方向と垂直方向が試験片の長手となるように、JIS5号試験片(標点距離50mm、平行部幅25mm)を採取し、JIS Z 2241に従って試験した。以下では伸び(El)を延性(El)と記載する。更に、伸びフランジ性(λ)については、上記冷延鋼板から2mm×90mm×90mmの試験片を採取し、JIS Z 2256に従って試験した。
溶接性の評価として、JIS Z 3137に従って、上記冷延鋼板から試験片を採取し、同じ鋼板同士をスポット溶接し、十字引張強度(CTS)を測定した。詳細には、電極として先端径8mmφのドームラジアス型Cu-Cr電極を用い、溶接時間は20サイクル/60Hz、加圧力は400kgfとし、電流値を変化させて溶接径(JIS Z 3137参照)6mmとなる条件のCTSを測定した。
曲げ加工性(R/t)は、圧延方向と垂直方向が試験片の長手となるように、上記冷延鋼板から2mm×40mm×100mmの試験片を採取し、JIS Z 2248のVブロック法に従って試験を行い、割れや亀裂が発生しない最小曲げ半径Rを測定した。なお、曲げ方向は試験片長手方向である。曲げ試験により判明したRを公称板厚2mmで割った値をR/tとした。
(ii)一方、引張強度が1180MPa以上1370MPa以下、且つ、0.2%耐力が700MPa以上の鋼板については、延性(El)は、11%以上、伸びフランジ性(λ)については、20%以上を合格とした。曲げ加工性(R/t)については、2.5以下を良好とした。溶接性は、CTSが20000N以上を合格とした。各領域において、El、λ、CTSは高いほどよく、R/tは小さいほど良い。これらの結果を表4および表5に示す。
Claims (10)
- 質量%で、
C :0.07~0.15%、
Si:1.1~1.6%、
Mn:2.0~2.8%、
P :0%超0.015%以下、
S :0%超0.005%以下、
Al:0.015~0.06%、
Ti:0.010~0.03%、および
B :0.0010~0.004%を含有し、
残部が鉄および不可避不純物であって、
鋼板の板厚の1/4位置において下記金属組織の面積率が、
焼戻しマルテンサイト:30面積%以上、
ベイナイト:15面積%以上70面積%以下、
焼戻しマルテンサイトとベイナイトの合計:90面積%以上、
フェライト:0面積%以上5面積%以下、および
残留オーステナイト:0面積%以上4面積%以下を満足する引張強度が980MPa以上、且つ、0.2%耐力が700MPa以上の高強度冷延鋼板。 - 更に、質量%で、
Cu:0%超0.3%以下、
Ni:0%超0.3%以下、
Cr:0%超0.3%以下、
Mo:0%超0.3%以下、
V :0%超0.3%以下、および
Nb:0%超0.03%以下よりなる群から選ばれる1種以上を含有する請求項1に記載の高強度冷延鋼板。 - 更に、質量%で、Ca:0%超0.005%以下を含有する請求項1に記載の高強度冷延鋼板。
- 更に、質量%で、Ca:0%超0.005%以下を含有する請求項2に記載の高強度冷延鋼板。
- 前記鋼板の最表層部から板厚方向20μmの表層部位において下記金属組織の面積率が、
フェライト:80面積%以上、および
マルテンサイトとベイナイトの合計面積率:0面積%以上20面積%以下を満足する請求項1に記載の高強度冷延鋼板。 - 前記鋼板の最表層部から板厚方向20μmの表層部位において下記金属組織の面積率が、
フェライト:80面積%以上、および
マルテンサイトとベイナイトの合計面積率:0面積%以上20面積%以下を満足する請求項2に記載の高強度冷延鋼板。 - 前記鋼板の最表層部から板厚方向20μmの表層部位において下記金属組織の面積率が、
フェライト:80面積%以上、および
マルテンサイトとベイナイトの合計面積率:0面積%以上20面積%以下を満足する請求項3に記載の高強度冷延鋼板。 - 前記鋼板の最表層部から板厚方向20μmの表層部位において下記金属組織の面積率が、
フェライト:80面積%以上、および
マルテンサイトとベイナイトの合計面積率:0面積%以上20面積%以下を満足する請求項4に記載の高強度冷延鋼板。 - 請求項1~8のいずれかに記載の高強度冷延鋼板の表面に亜鉛めっき層を有する高強度溶融亜鉛めっき鋼板。
- 請求項1~8のいずれかに記載の高強度冷延鋼板の表面に合金化亜鉛めっき層を有する高強度合金化溶融亜鉛めっき鋼板。
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KR20160129038A (ko) | 2016-11-08 |
MX2016012708A (es) | 2016-12-16 |
US10501830B2 (en) | 2019-12-10 |
US20180171442A1 (en) | 2018-06-21 |
KR101926244B1 (ko) | 2018-12-06 |
JP2015200012A (ja) | 2015-11-12 |
CN106103774A (zh) | 2016-11-09 |
CN106103774B (zh) | 2017-10-31 |
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