EP1937853A1 - Bake-hardenable cold rolled steel sheet with superior strength and aging resistance, gal- vannealed steel sheet using the cold rolled steel sheet and method for manufacturing the cold rolled steel sheet - Google Patents
Bake-hardenable cold rolled steel sheet with superior strength and aging resistance, gal- vannealed steel sheet using the cold rolled steel sheet and method for manufacturing the cold rolled steel sheetInfo
- Publication number
- EP1937853A1 EP1937853A1 EP06798860A EP06798860A EP1937853A1 EP 1937853 A1 EP1937853 A1 EP 1937853A1 EP 06798860 A EP06798860 A EP 06798860A EP 06798860 A EP06798860 A EP 06798860A EP 1937853 A1 EP1937853 A1 EP 1937853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel sheet
- steel
- less
- bake
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 249
- 239000010959 steel Substances 0.000 title claims abstract description 249
- 230000032683 aging Effects 0.000 title claims abstract description 70
- 239000010960 cold rolled steel Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 124
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 121
- 239000013078 crystal Substances 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 29
- 230000009467 reduction Effects 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000005098 hot rolling Methods 0.000 claims description 10
- 229910000655 Killed steel Inorganic materials 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- DBIMSKIDWWYXJV-UHFFFAOYSA-L [dibutyl(trifluoromethylsulfonyloxy)stannyl] trifluoromethanesulfonate Chemical compound CCCC[Sn](CCCC)(OS(=O)(=O)C(F)(F)F)OS(=O)(=O)C(F)(F)F DBIMSKIDWWYXJV-UHFFFAOYSA-L 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 62
- 230000000694 effects Effects 0.000 description 34
- 239000010955 niobium Substances 0.000 description 34
- 239000010936 titanium Substances 0.000 description 29
- 238000007792 addition Methods 0.000 description 25
- 239000002244 precipitate Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000006104 solid solution Substances 0.000 description 19
- 238000007670 refining Methods 0.000 description 15
- 230000006866 deterioration Effects 0.000 description 14
- 230000001965 increasing effect Effects 0.000 description 11
- 239000011572 manganese Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000011835 investigation Methods 0.000 description 8
- 230000002542 deteriorative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000005244 galvannealing Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- -1 TiS or Ti C S Chemical compound 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910010968 Ti—V Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
Definitions
- the present invention relates to a cold-rolled steel sheet for outer panels and the like of an automobile body, a galvannealed steel sheet using the cold-rolled steel sheet, and a method for manufacturing the cold-rolled steel sheet. More particularly, the present invention relates to a high strength cold-rolled steel sheet with superior bake hardenability, aging resistance at room temperature and secondary work embrittlement resistance, a galvannealed steel sheet using the cold-rolled steel sheet, and a method for manufacturing the cold-rolled steel sheet.
- a cold-rolled steel sheet As used for the outer panel of the automobile body, a cold-rolled steel sheet is required to have good properties in terms of tensile strength, yield strength, press formability, spot weldability, fatigue resistance, corrosion resistance, etc.
- Steel sheets for improvement of the corrosion resistance can be generally classified into two types, i.e. a electroplated steel sheet and a galvannealed steel sheet.
- the steel sheet exhibits opposite characteristics in terms of strength and formability.
- steel sheets capable of satisfying both characteristics there are multiphase structure cold-rolled steel sheets and bake-hardenable cold-rolled steel sheets.
- the multi-phase structure cold-rolled steel can be easily manufactured, and has a tensile strength in the level of 390 MPa or more. Regardless of its high tensile strength as materials for the automobiles, the multi-phase structure cold-rolled steel has a high elongation as a factor indicating stretchability. However, it has a low average r-value as a factor indicating press formability of the automobiles, and comprises excessive amounts of expensive alloying elements such as Mn, Cr and the like, which results in high manufacturing costs.
- the bake-hardenable cold-rolled steel acts like mild steel in terms of yield strength upon press forming of the steel which has a tensile strength of 390 MPa or less.
- the bake-hardenable cold-rolled steel has excellent ductility, and spontaneously increases in yield strength upon paint baking after press forming.
- This steel is considered ideal in comparison to previous steel, which is generally deteriorated in formability as the strength of the steel increases.
- Bake hardening is a process which employs a kind of strain aging occurring as interstitial elements dissolved in a solid solution state in the steel, such as solute nitrogen or solute carbon, fix dislocations created during deformation.
- a kind of strain aging occurring as interstitial elements dissolved in a solid solution state in the steel such as solute nitrogen or solute carbon
- fix dislocations created during deformation When the steel has high amounts of solute carbon and nitrogen, the bake hardenability value (BH value) advantageously increases, but the natural aging property also increases due to the high amounts of solid solution elements, deteriorating the formability. Thus, it is very important to optimize the amounts of solid solution elements in the steel.
- the bake-hardenable cold-rolled steel sheet is produced by batch annealing a low carbon, P-added, Al-killed steel through coiling of a hot-rolled steel sheet at a lower temperature.
- the hot-rolled steel sheet is coiled at the low temperature of 400 ⁇ 500 0 C, followed by batch annealing to have BH value of about 40 to 50 MPa.
- Japanese Patent Publication No. (Sho) 61-026757 discloses an ultra low carbon cold-rolled steel sheet, which comprises: 0.0005 ⁇ 0.015% of C; 0.05% or less of S+N; and Ti and Nb or a compound thereof.
- Japanese Patent Publication No. (Sho) 57-089437 discloses a method for manufacturing a bake-hardenable cold-rolled steel sheet, which uses Ti-added steel comprising 0.010% or less of C, and has BH value of about 40 MPa or more.
- the methods of the disclosures are to impart the bake hardenability to the steel sheet while preventing deterioration in other properties of the steel sheet by appropriately controlling the amount of solid solution elements in the steel through control of the added amount of Ti and Nb or the cooling rate during annealing.
- the Nb-added steel described above has problems in that workability is degraded due to hot annealing, and in that manufacturing costs are increased due to addition of the specific elements.
- US Patent Nos. 5,556,485 and 5,656,102 (Bethlehem Steel) disclose methods of manufacturing a bake-hardenable cold-rolled steel sheet using a Ti-V based ultra low carbon steel, which comprises 0.0005 ⁇ 0.1% of C; 0 ⁇ 2.5% of Mn; 0 ⁇ 0.5% of Al; 0 ⁇ 0.04% of N; 0 ⁇ 0.5% of Ti; and 0.005 ⁇ 0.6% of V.
- carbide such as VC and the like, created during high temperature annealing can impart the bake hardenability via re-melting even with a lower annealing temperature than that for the Nb-based steel.
- V can create the carbide such as VC, since it does not sufficiently improve the formability due to its significantly low re-melting temperature, Ti is added at an amount of about 0.02% or more in order to enhance the formability, as disclosed in the publications.
- Japanese Patent Laid-open Publication No. (Hei) 5-93502 discloses a method for enhancing the bake hardenability by addition of Sn
- Japanese Patent Laid-open Publication No. (Hei) 9-249936 discloses a method for enhancing the ductility of steel by relieving stress concentration on grain boundaries through addition of V and Nb.
- Japanese Patent Laid-open Publication No. (Hei) 8-49038 discloses a method for enhancing the formability through addition of Zr
- Japanese Patent Laid-open Publication No. (Hei) 7-278654 discloses a method for enhancing the formability by increasing the strength while minimizing deterioration of work hardening index (N- value) through addition of Cr.
- the increase in bake hardenability causes the deterioration in aging resistance at room temperature.
- inventors of the present invention have found that, as the content of P added for high strength of the steel increases, the steel is degraded in the secondary work embrittlement resistance even for the bake hardenable steel which comprises solute carbon dissolved in the solid solution state in the steel, and the more the severe the degradation.
- the ductility-brittleness transition temperature (DBTT) of the steel as a reference to judge the secondary work embrittlement was -20 0 C at a draw ratio of 1.9.
- the DBTT of the steel was 0 - 10 0 C, which can be considered to be a significantly deteriorated value.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a high strength cold-rolled steel sheet with superior bake hardenability, aging resistance at room temperature and secondary work embrittlement resistance, and a galvannealed steel sheet using the cold-rolled steel sheet.
- a bake-hardenable cold-rolled steel sheet with high strength and superior aging resistance comprising, by weight%,: C: 0.0016 ⁇ 0.0025%; Si: 0.02% or less; Mn: 0.2 ⁇ 1.2%; P: 0.05 ⁇ 0.11%; S: 0.01% or less; Sol. Al: 0.08 ⁇ 0.12%; N: 0.0025% or less; Ti: 0-0.003%; Nb: 0.003 ⁇ 0.011%; Mo: 0.01 ⁇ 0.1%; B: 0.0005 ⁇ 0.0015%; and the balance of Fe and other unavoidable impurities, wherein the steel sheet satisfies Equation 1:
- Equation 1 GB-C (that is, the amount of solute carbon in the grain boundaries) is 5 ⁇ 10 ppm, and G-C (that is, the amount of solute carbon in the crystal grains) is 3 ⁇ 7 ppm]
- ASTM No. ASTM grain size
- BH bake hardening degree
- AI aging index
- DBTT DBTT
- AI 44 - (423 x Ti) - (2119 x Nb) - (125 x Mo) — (3).
- a method for manufacturing a bake-hardenable cold-rolled steel sheet with high strength and superior aging resistance comprising: performing homogenization heat treatment for an Al-killed steel slab at 1200 0 C or more, the steel slab comprising, by weight%,: C: 0.0016 ⁇ 0.0025%, Si: 0.02% or less, Mn: 0.2 ⁇ 1.2%, P: 0.05 ⁇ 0.11%, S: 0.01% or less, Sol.
- Fig. 1 is a graph decribing influence of a grain size on bake hardenability and aging index
- Fig. 2 is a graph decribing influence of an amount of solute carbon in steel on the bake hardenability
- Fig. 3 is a graph decribing a result of an internal friction test to Inventive steel No.
- Carbon or nitrogen in steel generally combines with precipitate formation elements such as Al, Ti, Nb, etc. in the steel during hot rolling, forming carbides and nitrides such as TiN, AlN, TiC, Ti C S , NbC, etc. However, when carbon or nitrogen does not
- solute carbon or solute nitrogen combine with the precipitation formation elements in the steel, it exists as solid solutions of carbon or nitride (hereinafter, solute carbon or solute nitrogen) in the steel, and influences the bake hardenability and the aging resistance of the steel.
- carbon is an essential element for the steel, and determines the characteristics of the steel depending on the carbon content in the steel.
- carbon has a very important role, and only a small amount of solute carbon is allowed to remain in the steel as an attempt to improve the bake hardenability and the aging resistance.
- influence of the solute carbon on the bake hardenability and the aging resistance can be changed according to locations of the solute carbon in the steel, that is, whether the solute carbon resides in grain boundaries or in crystal grains.
- solute carbon generally exists in the crystal grains and moves relatively freely.
- solute carbon can combine with movable dislocations, and affect aging properties.
- an aging index (AI) is generally used in the art.
- solute carbon of the grain boundaries rarely affects aging at low temperatures such as AI test, it is activated in a baking condition of high temperatures, and affects the bake hardenability.
- solute carbon in the crystal grains can affect both of the aging properties and the bake hardenability at the same time, whereas the solute carbon the grain boundaries affects only the bake hardenability.
- Fig. 1 shows the BH value and the aging index (AI) in relation to variation in grain size, which is a result of investigation by the inventors of the present invention.
- the inventors of the present invention have found that the grain size is desirably controlled to ASTM No. 9 or more to maximize the aging resistance while minimizing deterioration of the bake hardenability.
- the total amount of carbon is set to 16 - 25 ppm to satisfy the above conditions.
- Nb when added to the steel, it combines with C to precipitate a carbide such as NbC, thereby reducing the amount of solute carbon in the steel.
- Nb-added steel a precipitation ratio of Nb/C is determined depending on the content of Nb and C in the steel. Furthermore, while some of the solute carbon in the steel combines with Nb to precipitate NbC, remaining carbon exist in the solid solution state, and affects the bake hardenability and the aging resistance.
- a total amount of solute carbon is about 8 - 15 ppm, wherein the total amount of solute carbon is obtained by excluding the NbC precipitates in consideration of the added amount of Nb and the carbon content.
- Equation 1 Equation 1:
- Equation 1 the term "C in NbC” means an amount of carbon precipitated in the form of the NbC precipitate.
- Al is also considered as well as the addition of Nb in order to more stably secure the bake hardenability and the aging resistance.
- AlN precipitates have an effect of removing the solute nitrogen in the steel.
- the bake hardenable steel of the present invention since the carbon content of the inventive steel is restricted narrowly in the range of 16 - 25 ppm, the bake hardenable steel of the present invention has the bake hardenability and the aging resistance in a narrow range.
- secondary work embrittlement it can be considered that components of automobiles are generally formed to desired shapes through several repetitions of press forming by automobile manufacturers.
- the secondary work embrittlement means that cracks occur during a process performed after primary press working.
- P is not added to the steel in order to prevent the secondary work embrittlement.
- P has merits in that it serves to increase the strength while suppressing reduction of elongation, and in that it is very low in price.
- Mo has an affinity to the solute carbon in the steel, it suppresses diffusion of the solute carbon into the dislocations when being maintained for a long period of time at room temperature, thereby providing an advantageous effect in terms of aging resistance.
- Equation 3 shows an effect of improving the aging resistance by Mo in a statistical manner.
- the inventors of the present invention deduce an optimal composition for the steel by suitably using the characteristics of Mo without deterioration in properties of the steel possibly caused by excessive addition of Mo.
- the inventors try to maximize the effect of improving the secondary work embrittlement resistance through addition of a suitable amount of B and selection of a suitable coiling temperature at the same time among various methods conventionally used to improve the secondary work embrittlement resistance.
- Carbon (C) is an element used for solid solution strengthening and bake hardening.
- Silicon (Si) is an element for increasing the strength of the steel. However, as the silicon content is increased, the ductility is significantly deteriorated. In addition, since silicon deteriorates galvannealing capability, it is advantageous to minimize the added amount of silicon.
- the added amount of silicon is preferably 0.02% or less.
- Manganese (Mn) is an element used for preventing hot embrittlement caused by formation of FeS by completely precipitating sulfur in the steel into MnS while refining the crystal grains without deteriorating the ductility, and for strengthening the steel. According to the present invention, if the Mn content is less than 0.2%, a suitable tensile strength cannot be obtained, whereas if the Mn content exceeds 1.2%, the formability is deteriorated with a rapid increase in strength due to solid solution strengthening.
- the Mn content is preferably in the range of 0.2 ⁇ 1.2%.
- Phosphorus (P) is a substitutional alloying element which provides the highest solid solution strengthening effect, and serves to enhance the anisotropy while increasing the strength of the steel.
- the P content is less than 0.05%, the secondary work embrittlement resistance can be improved due to such a low content of P in the grain boundaries, but it is difficult to sufficiently obtain the effect of improving the other properties of the steel through the grain refining effect of P.
- the P content is above 0.11%, it occurs a rapid increase of the strength compared with an improved degree of the formability.
- the P content is preferably in the range of 0.05 ⁇ 0.11%.
- [I l l] Sulfur (S) is an element, which precipitates into the sulfide such as MnS and prevents the hot embrittlement caused by FeS. However, if the S content is excessive, some of S remaining after precipitation of MnS makes the grain boundaries brittle, possibly causing the hot embrittlement.
- S is preferably in the range of 0.01% or less.
- Aluminum (Al) is an element which is generally added for deoxidization of the steel. However, according to the present invention, aluminum is used for an effect of improving the grain refining effect and the bake hardenability via precipitation of AlN.
- the grain refining effect is generally obtained using NbC precipitates by addition of Nb
- aluminum serves to further improve the grain refining effect by the AlN precipitates, thereby improving the bake hardenability without deteriorating the aging resistance.
- Al must be added at an amount of at least 0.08% or more in order to achieve advantageous effects of the present invention.
- the Al content is above 0.12%, oxide inclusions are increased during steel making process and causes degradation of surface quality along with deterioration of the formability. Furthermore, the excessive content of Al results in high manufacturing costs.
- the Al content is preferably in the range of 0.08 ⁇ 0.12%.
- Nitrogen (N) exists in the solid solution state before or after annealing, and deteriorates the formability of the steel. Furthermore, since nitrogen has a higher aging ability than other interstitial solid solution elements, it is necessary to fix nitrogen by use of Ti or Al.
- Titanium (Ti) is added to the steel as a carbide and nitride forming element, and forms nitrides such as TiN, sulfides such as TiS or Ti C S , and carbides such as TiC,
- Ti is added at an amount of 0.003% or less so as to fix a small amount of nitrogen.
- the reason of adding such a small amount of Ti is that, generally, when manufacturing the steel in practice, an ultra low amount of Ti is contained with other components to the steel for the purpose of satisfying the properties of the steel, and that, when it is simultaneously added to steel slabs several times for the purpose of continuous casting of the steel, Ti of a previously added steel slab can be transferred into a subsequently added steel slab of the present invention.
- Ti is not necessarily added to the steel, and, if any, Ti is added at an ultra low amount of 0.003% or less under consideration of practical manufacturing conditions irrespective of reduction in bake hardenability thereby.
- Niobium (Nb) is a very important element together with Al and Mo in the present invention.
- Nb is an intensive carbide and nitride former, and serves to control an amount of solute carbon in the steel by pinning carbon of the steel into NbC precipitates.
- NbC precipitates are very fine compared with other precipitates, it acts as an intensive barrier to impede the grain growth during recrys- tallization annealing.
- the grain refining effect of Nb is obtained by use of such effect of the NbC precipitates.
- the present invention is suggested in an attempt to improve the bake hardenability using the solute carbon, which is allowed to remain in the steel.
- the Nb content is preferably in the range of 0.003 ⁇ 0.011% under consideration of the carbon content of 16 ⁇ 25 ppm according to the present invention to obtain both of the bake hardenability and the aging resistance by allowing an amount of solute carbon of about 3 - 7 ppm to remain in the crystal grains of the steel while providing the grain refining effect by the NbC precipitates.
- Molybdenum (Mo) is another very important element of the present invention.
- Mo exists in the solid solution state in the steel, and serves to enhance the strength of the steel or to form an Mo-based carbide.
- Mo serves to increase the bonding force of the grain boundaries while existing as a solid solution element in the steel, so that fracture of the grain boundaries due to phosphorus is prevented, that is, the secondary work embrittlement resistance is improved.
- Mo since Mo has an affinity to carbon, it serves to suppress the diffusion of carbon, improving the aging resistance. Equation 3 represents the effect of improving the aging resistance by Mo in a quantitative manner. For this purpose, it is necessary to add a suitable amount of Mo.
- the Mo content is preferably in the range of 0.01 ⁇ 0.1%.
- Boron (B) is an interstitial element residing in the steel. B is dissolved as a solid solution element in the grain boundaries, or combines with nitrogen to form the nitride such as BN.
- B has a highly significant influence on the properties of the steel compared with an added amount, it is necessary to precisely control the amount added. That is, when even a small amount of B is added, B is segregated in the grain boundaries and improves the secondary work embrittlement resistance.
- the content of B is preferably in the range of 0.0005 ⁇ 0.0015%.
- the steel slab is reheated at a temperature of 1,200 0 C or more, where austenite structure before hot rolling can be sufficiently homogenized.
- the reheated steel slab is then subjected to hot-rolling with finish rolling at a finish rolling temperature of 900 ⁇ 950 0 C, which is just above the Ar temperature, thereby providing a hot rolled steel sheet.
- finish hot rolling temperature is less than 900 0 C, a top portion, a tail portion, and edges of a hot-rolled coil become single-phase regions, thereby increasing the anisotropy while deteriorating the formability of the steel. If the finish hot rolling temperature is above 95O 0 C, crystal grains of the steel become remarkably coarsened, causing defects such as orange peel to be formed on the surface of the steel sheet after machining.
- the steel sheet has refined crystal grains, which improve the aging resistance and the secondary work embrittlement resistance, but it suffers from an excessive increase in yield strength along with deterioration of the formability due to the excessively refined grain size.
- the coiling temperature is preferably controlled to 63O 0 C or less.
- the coiling temperature is controlled to be in the range of 580 ⁇ 630 ? as an exemplary means to make the amount of the solute carbon in the grains, and the amount of the solute carbon in the grain boundaries satisfy Equation 1.
- Such a high reduction rate of 75% or more is set for the purpose of enhancing the formability of the steel sheet, in particular, the r- value, together with the aging resistance through the grain refining effect.
- the steel sheet is subjected to continuous annealing by a typical method at a temperature of 770 ⁇ 830 0 C.
- annealing of the steel sheet is preferably performed at a temperature of 770 0 C or more. That is, when the annealing is performed at a temperature less than 770 0 C, non-recrystallized crystal grains exist in the steel sheet, causing an increase of the yield strength while reducing the elongation and the r-value.
- the cold-rolled steel sheet is subjected to temper rolling at a reduction ratio of 1.2 ⁇ 1.5%, which is more or less higher than a typical temper rolling reduction ratio.
- the reduction ratio of the temper rolling is set to an excessively high value above 1.5%, work hardening occurs and deteriorates the properties of the steel sheet irrespective of improved aging resistance.
- the temper rolling is preferably performed at the reduction ratio of 1.2 ⁇ 1.5%, which is a suitable condition to solve the above problems.
- annealed cold-rolled steel sheets were subjected to hot-dipping at a temperature of 450 ⁇ 470 0 C and galvannealing at a temperature of 500 ⁇ 530 0 C, followed by temper rolling at a temper rolling reduction ratio of about 1.5%.
- BH value, aging index (AI), grain size, and ductility-brittleness transition temperature (DBTT) at a draw ratio of 2.0 for evaluation of secondary work embrittlement were measured with respect to final steel sheets. Results thereof are shown in Table 2.
- Inventive Steel No. 6 of Table 1 an amount of solute carbon in crystal grains was measured, of which result is shown in Fig. 3.
- the inventive steels do not have solute nitrogen in the steel and has an amount of solute carbon of 3.1 ppm or more in the grains.
- the Inventive steels Nos. 1 to 6 have fine crystal grains. That is, since the Inventive steel Nos. 1 to 6 have higher Al contents than a typical Al content, fine AlN precipitates are actively formed in the steel and obstruct the grain growth along with the NbC precipitates upon recrystallization annealing, which results in such fine crystal grains.
- the inventive steels have a bake hardening degree of 38.1 - 47.9 MPa, and an AI of 9.3 - 28.3 MPa, which is used for indicating the aging resistance at room temperature. Accordingly, it can be appreciated that balance between the bake hardenability and the aging resistance is excellent.
- the Inventive steels Nos. 1 to 6 have a relatively low AI in comparison to a relatively high bake hardening degree. It is considered that this phenomenon is based on a retarding effect of the solute carbon in the steel through addition of Mo in addition to the grain refining effect by the AlN precipitates.
- Comparative steel No. 7 has a carbon content of 0.0054%, which is higher than the carbon content of the present invention in the range of 0.0016 - 0.0025%, but satisfies the conditions for the high coiling temperature and the annealing temperature of the present invention.
- the Comparative steel No. 7 has a very fine grain size of ASTM No. 11.7 that satisfies the condition for the grain size of the present invention, and is excellent in view of DBTT and BH value.
- the Comparative steel No. 7 has an AI of 30 MPa or more, which indicates a significantly low aging resistance.
- Comparative steel No. 8 has a significantly low carbon content of 0.0011%, which forms the NbC precipitates without remaining in a solid solution state in the steel. Thus, it can be found that the Comparative steel No. 8 does not exhibit the bake hardenability at all, and has coarsened grains and a low DBTT due to the low carbon content.
- Comparative steel No. 9 has a soluble Al content of 0.023%, which is lower than the Al content of the present invention in the range of 0.08 ⁇ 0.12%, and an Nb content of 0.035%, which is higher than the Nb content of the invention.
- Comparative steel No. 10 does not comprise Mo, and thus cannot be expected to have improved secondary work embrittlement resistance by Mo.
- the Comparative steel No. 10 was coiled at a temperature of 720 0 C, which is higher than the coiling temperature of the present invention, causing a high possibility of activating movement of P.
- Comparative steel No. 11 has a very high Ti content of 0.035%, which causes no solute carbon to remain in the steel. Thus, the BH value and the AI of Comparative steel No. 11 are zero.
- Comparative steel No. 11 does not comprises the solute carbon, which is advantageous to improve the secondary work embrittlement resistance, and cannot be expected to have an increased bonding force of the grain boundaries by addition of B, so that the DBTT of the Comparative steel No. 11 is deteriorated.
- Comparative steel No. 12 sufficiently satisfies the requirement for the composition suggested by the present invention except for a high content of nitrogen.
- Nitrogen is the element which causes a detrimental problem in terms of bake hard- enability and aging resistance.
- the bake-hardenable cold-rolled steel sheet and the galvannealed steel sheet using the same have excellent bake hardenability, aging resistance, and secondary work embrittlement resistance, as well as high strength.
Abstract
Description
Claims
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KR1020050088518A KR100685037B1 (en) | 2005-09-23 | 2005-09-23 | Bake-hardenable cold rolled steel sheet with superior strength and aging resistance, galvannealed steel sheet using the cold rolled steel sheet and method for manufacturing the cold rolled steel sheet |
PCT/KR2006/003777 WO2007035059A1 (en) | 2005-09-23 | 2006-09-22 | Bake-hardenable cold rolled steel sheet with superior strength and aging resistance, gal- vannealed steel sheet using the cold rolled steel sheet and method for manufacturing the cold rolled steel sheet |
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EP1937853A1 true EP1937853A1 (en) | 2008-07-02 |
EP1937853A4 EP1937853A4 (en) | 2011-10-19 |
EP1937853B1 EP1937853B1 (en) | 2013-12-25 |
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EP06798860.0A Active EP1937853B1 (en) | 2005-09-23 | 2006-09-22 | Bake-hardenable cold rolled steel sheet with superior strength and aging resistance method for manufacturing the cold rolled steel sheet |
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US (1) | US20080251168A1 (en) |
EP (1) | EP1937853B1 (en) |
JP (1) | JP4834733B2 (en) |
KR (1) | KR100685037B1 (en) |
CN (1) | CN101310031B (en) |
WO (1) | WO2007035059A1 (en) |
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KR101105040B1 (en) | 2008-06-23 | 2012-01-16 | 주식회사 포스코 | Bake Hardened Steel with Excellent Surface Properties and Secondary Working Embrittlement Resistance and Manufacturing Method Thereof |
WO2009157661A2 (en) * | 2008-06-23 | 2009-12-30 | 주식회사 포스코 | Bake hardening steel with excellent surface properties and resistance to secondary work embrittlement, and preparation method thereof |
US9702031B2 (en) | 2010-11-29 | 2017-07-11 | Nippon Steel & Sumitomo Metal Corporation | Bake-hardenable high-strength cold-rolled steel sheet and method of manufacturing the same |
JP5413539B2 (en) | 2011-09-30 | 2014-02-12 | 新日鐵住金株式会社 | High-strength hot-dip galvanized steel sheet excellent in bake hardenability, high-strength galvannealed steel sheet, and methods for producing them |
JP5310919B2 (en) * | 2011-12-08 | 2013-10-09 | Jfeスチール株式会社 | Method for producing high-strength cold-rolled steel sheets with excellent aging resistance and seizure curability |
CN103014613B (en) * | 2012-12-31 | 2015-07-29 | 上海大学 | The method of thermodiffusion continuous production stalloy and stalloy tandem rolling device thereof |
CN103667649B (en) * | 2013-10-08 | 2015-10-21 | 首钢京唐钢铁联合有限责任公司 | A kind of Nb process pot galvanize ultra-low carbon baking hardening steel plate and manufacture method thereof |
KR101657793B1 (en) * | 2014-12-11 | 2016-09-20 | 주식회사 포스코 | Bake hardening steel sheet having excellent drawability and method for manufacturing thereof |
KR101676194B1 (en) * | 2015-11-13 | 2016-11-15 | 주식회사 포스코 | High Strength Blackplate Having Excellent Flangeability And Method For Manufacturing The Same |
MX2019004458A (en) * | 2016-10-17 | 2019-06-17 | Tata Steel Ijmuiden Bv | Steel substrate for painted parts. |
EP3526360A1 (en) | 2016-10-17 | 2019-08-21 | Tata Steel IJmuiden B.V. | Steel for painted parts |
CN109321839B (en) * | 2018-10-24 | 2021-01-26 | 首钢京唐钢铁联合有限责任公司 | 240 MPa-grade bake-hardening steel and manufacturing method thereof |
EP3906508B1 (en) * | 2018-12-31 | 2024-03-13 | Intel Corporation | Securing systems employing artificial intelligence |
KR20230072728A (en) | 2021-11-18 | 2023-05-25 | 주식회사 포스코 | Bake hardening cold rolled steel sheet, hot dip galvannealed steel sheet having less anisotropy and excellent coated surface quality and method for manufacturing thereof |
CN114959427A (en) * | 2022-05-18 | 2022-08-30 | 包头钢铁(集团)有限责任公司 | Manufacturing method of 180 MPa-grade ultra-low carbon baking hardened steel for automobile |
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- 2005-09-23 KR KR1020050088518A patent/KR100685037B1/en active IP Right Grant
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- 2006-09-22 CN CN2006800428821A patent/CN101310031B/en active Active
- 2006-09-22 US US12/067,617 patent/US20080251168A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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CN101310031A (en) | 2008-11-19 |
US20080251168A1 (en) | 2008-10-16 |
JP4834733B2 (en) | 2011-12-14 |
EP1937853A4 (en) | 2011-10-19 |
EP1937853B1 (en) | 2013-12-25 |
CN101310031B (en) | 2010-12-29 |
JP2009509046A (en) | 2009-03-05 |
KR100685037B1 (en) | 2007-02-20 |
WO2007035059A1 (en) | 2007-03-29 |
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