EP1637618B1 - Procede de preparation de tole mince en acier a resistance elevee presentant une resistance excellente a la rupture differee apres formation - Google Patents

Procede de preparation de tole mince en acier a resistance elevee presentant une resistance excellente a la rupture differee apres formation Download PDF

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Publication number
EP1637618B1
EP1637618B1 EP03817075A EP03817075A EP1637618B1 EP 1637618 B1 EP1637618 B1 EP 1637618B1 EP 03817075 A EP03817075 A EP 03817075A EP 03817075 A EP03817075 A EP 03817075A EP 1637618 B1 EP1637618 B1 EP 1637618B1
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Prior art keywords
mass
delayed
steel
steel sheets
strength
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EP1637618A4 (fr
EP1637618A1 (fr
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Toshiki Nonaka
Nobuhiro Fujita
Hirokazu Taniguchi
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Nippon Steel Corp
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Nippon Steel Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/004Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/14Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/004Dispersions; Precipitations

Definitions

  • the present invention relates to a method of manufacturing high-strength steel sheets, which inhibit delayed failures and delayed fractures that lead to problems, particularly with high-strength steel sheets.
  • This technology changes the morphology of delayed fracture from intergranular to transgranular by precipitating alloy carbides and using the precipitated alloy carbides as hydrogen trap sites.
  • JP-A-11-293383 discloses that oxides consisting primarily of Ti and Mg are effective in preventing the occurrence of hydrogen defects.
  • this paper concerns the high-strength steel sheets having certain specific structures, but does not concern any fundamental measures for improving delayed-fracture resistance.
  • JP-A-2001-288531 discloses a steel for machine structures, especially steel wire rods or steel wire, suppressed coarse crystal grain after heat treatment at 900°C and 1200°C in austenite region, which is used after QT treatment, carburization hardening treatment, high frequency hardening treatment.
  • JP-A-11-71629 discloses a thick steel plate for structural purpose combining high strength and high toughness.
  • delayed-fracture resistance after forming of high-strength steel sheets can be improved without deteriorating the formability thereof by forming compounds or composite compounds of Mg and controlling the shape of such compounds.
  • the inventors discovered effective manufacturing methods for high-strength steel sheets using existing manufacturing equipment (such as hot-rolling, continuous annealing, hot-dip galvanizing and electrolytic equipment).
  • delayed fracture in tempered martensite steel starts from the voids and other defects resulting from the accumulation of hydrogen in prior austenite grain boundaries or other regions.
  • JP-A-11-293383 it is known that resistance to hydrogen-induced delayed fracture is improved by controlling the dispersion pattern of oxides in steel plates to which Mg and Ti are added in combination.
  • the inventors studied the influences of various crystallized products and precipitates, and the strength and structure of steel sheets, in order to secure or improve the delayed-fracture resistance thereof after forming in the service environment thereof.
  • equation (A) was defined as the condition to satisfy the above compatibility (Equation (A) will be discussed in detail later.).
  • the parameters described in (i), (ii) and (iii) can be effectively controlled by limiting the manufacturing conditions so that the shape of the crystallized or precipitated products, such as oxides, nitrides and sulfides, of various elements, is controlled so as to form the trap sites of hydrogen.
  • Quantity of residual austenite The upper limit of residual austenite is limited to 7 vol.% because residual austenite increases the susceptibility to delayed fracture when it changes to martensite by working induced transformation.
  • Mean particle diameter The mean particle diameter is limited to between 0.01 ⁇ m and 5.0 ⁇ m.
  • the particles to form the hydrogen trap sites must have substantial sizes. Besides, the presence of fine particles in large quantities is unfavorable for securing the ductility of steel sheets and makes difficult the manufacture thereof.
  • the lower limit of the mean particle diameter was set at 0.01 ⁇ m, and the upper limit was set at 5.0 ⁇ m because coarse particles do not form trap sites and can sometimes become the starting point of fracture.
  • Particle density The particle density was limited to between 100 and 100000/mm 2 . Lower particle densities mean few trap sites, which, in turn, means that adequate post-forming delayed-fracture property cannot be secured. Therefore, the lower limit was set at 100/mm 2 .
  • the upper limit was set at 100000/mm 2 because higher particle densities deteriorate ductility and formability and saturate the delayed-fracture resistance improving effect.
  • Particle distribution The particle distribution was defined so that the ratio between the standard deviation ⁇ from the mean particle diameter and the mean particle diameter d satisfies ⁇ /d ⁇ 1.0. If ⁇ /d > 1.0, particles are widespread, which, in turn, reduces the delayed fracture improving effect and thereby deteriorates ductility and increases the number of fracture starting points. Therefore, the upper limit of ⁇ /d was set at 1.0.
  • Particles are measured by observing membranes or sampled replicas through a scanning or transmission electron microscope, with a magnification of 5000 to 100000, in at least 30 visual fields.
  • the particle diameter is evaluated by the circle equivalent diameter obtained by image analysis. In determining density, each composite precipitated or crystallized compound is counted as one.
  • composition analysis is done by using energy dispersive x-ray (EDX) analysis and electron energy loss spectroscopy (EELS), structural analysis is done by analyzing diffraction patterns.
  • EDX energy dispersive x-ray
  • EELS electron energy loss spectroscopy
  • the composite compounds are compounds (such as carbides, nitrides, oxides and sulfides) of Mg and other alloying additives (such as Ti, Nb, V, Cr, Mo, REM, and Ca).
  • the present invention relates to high-strength steel sheets and primarily to steel sheets having a tensile strength of not lower than 780 MPa and a thickness in the range of 0.5 to 4.0 mm.
  • Equation (A) was derived from Fig. 1 as described below, based on the understanding that the volume percentage, mean particle diameter, density, Mg content and tensile strength of residual austenite are the factors involved in delayed-fracture resistance.
  • Figs. 2 to 4 show the effects of the individual variables on delayed-fracture resistance.
  • shows good delayed-fracture resistance and ⁇ shows poor delayed-fracture resistance.
  • Fig. 2 shows the relationship between f(V ⁇ ) and volume percentage of residual austenite V ⁇ . It is assumed that Mg content is 300 ppm, mean particle diameter is 0.4 ⁇ m, density is 1500 particle/mm 2 , and tensile strength is 1480 MPa.
  • Fig. 3 shows the relationship between f(Mg) and the quantity of Mg added. It is assumed that the volume percentage of residual austenite is 3.0%, mean particle diameter is 0.4 ⁇ m, density is 1500 particle/mm 2 , and tensile strength is 1480 MPa.
  • Fig. 4 shows the relationship between f(p) and the density of crystallized and precipitated compounds. It is assumed that the volume percentage of residual austenite is 3.0%, Mg content is 30 ppm and tensile strength is 1380 MPa. If density is low, delayed-fracture resistance is poor.
  • % means mass%.
  • C is an element that increases the strength of steel sheets. C is particularly necessary for increasing strength as it forms hard phases such as martensite and austenite. In order to obtain 780 MPa or greater strength, C of not less than 0.05% is necessary. If, however, the C content is too high, the amount of cementite, which becomes the starting point of brittle fracture, increases, thereby causing hydrogen brittleness. Therefore, the upper limit is set at 0.3%.
  • Si is a substitutional solid solution strengthening element that greatly hardens steel. Si effectively increases the strength of steel sheets and inhibits the precipitation of cementite. If the Si content exceeds 3.0%, scale removal in the hot-rolling process becomes costly and prone to economic disadvantage. Therefore, the upper limit is set at 3.0%.
  • Si content should preferably be not more than 0.6% because too much Si addition deteriorates coatability.
  • Mn is an element that is effective for increasing the strength of steel sheets. As this effect is unobtainable if Mn content is less than 0.01%, the lower limit is set at 0.01%. On the other hand, too much Mn addition not only promotes joint segregation with P and S but also deteriorates workability. Therefore, the upper limit is set at 3.0%
  • P is an element that promotes intergranular fracture by intergranular segregation. While a lower P content is preferable, too low an addition is unfavorable from the viewpoint of production cost. As P deteriorates corrosion resistance, the upper limit is set at 0.02%
  • S is an element that promotes hydrogen absorption in corrosive environments. While a lower content is preferable, it is unpreferable from the viewpoint of production cost to reduce S content too much.
  • the upper limit is set at 0.02% because a lower content is preferable, particularly for enhancing workability.
  • Al at not less than 0.01%, is added for deoxidation. However, too much addition increases alumina and other inclusions, thereby deteriorating workability and weldability. Therefore, the upper limit is set at 3.0%. Addition of not less than 0.2% Al is preferable for inhibiting the formation of residual austenite.
  • N contributes to deterioration of workability and formation of blowholes during welding. Therefore, a lower N content is preferable.
  • the upper limit is set at 0.01% because an addition in excess thereof deteriorates workability.
  • Mg is a necessary element because compounds of Mg effectively improve delayed-fracture resistance. Mg is also necessary for producing composite crystallized or precipitated compounds with other elements and controlling the shape thereof in such a manner as to contribute to improvement of delayed-fracture resistance. Thus, not less than 0.0002% Mg is added.
  • the upper limit is set at 0.01%.
  • V, Ti, Nb and Zr are strong-carbide-forming elements that improve strength and delayed-fracture resistance by forming precipitates and inclusions.
  • V is effective for increasing steel strength and refining particle size.
  • the lower limit is set at 0.005%.
  • the upper limit is set at 1%
  • Ti is an element that effectively increases steel strength and refines particle size.
  • the lower limit is set at 0.002% because the number of precipitates decreases therebelow.
  • the upper limit is set at 1% because coarse precipitated or crystallized compounds are formed thereabove, which, in turn, lower workability and the delayed-fracture resistance.
  • Nb also effectively increases steel strength and refines particle size.
  • the lower limit is set at 0.002% as said effect is unobtainable therebelow.
  • the upper limit is set at 1% because carbonitride precipitation increases and, as a result, workability and delayed-fracture resistance drop thereabove.
  • Zn is an element that effectively increases steel strength and refines particle size.
  • the lower limit is set at 0.002% because the number of precipitates decreases therebelow.
  • the upper limit is set at 1% because coarse precipitated or crystallized compounds are formed thereabove, which, in turn, lowers workability and delayed-fracture resistance.
  • Cr, Mo and W are elements that form carbides and exhibit resistance to temper softening and are necessary for the improvement of strength and delayed-fracture resistance.
  • the Cr is effective for increasing steel strength.
  • the lower limit is set at 0.005% because said effect is unobtainable therebelow.
  • the upper limit is set at 5% because workability drops thereabove.
  • Mo not only increases hardenability and stably forms martensite in continuous annealing lines but also strengthens grain boundaries and inhibits the occurrence of hydrogen brittleness.
  • the lower limit is set at 0.005% because said effects are unobtainable therebelow.
  • the upper limit is set at 5% because said effects saturate thereabove.
  • W is an element that increases steel strength.
  • the lower limit is set at 0.005% because said effect is unobtainable therebelow.
  • the upper limit is set at 5% because workability drops thereabove.
  • Cu is effective for strengthening and fine precipitation thereof contributes to the improvement of delayed-fracture resistance.
  • the upper limit is set at 2.0% because excessive addition brings about deterioration of workability.
  • Ni and Co are strengthening elements that increase hardenability.
  • Ni has effects to improve delayed-fracture property by forming Ni sulfides and, thereby, inhibiting hydrogen penetration and increases the strength of steel sheets by enhancing the hardenability thereof.
  • the lower limit is set at 0.005% because said effects are unobtainable therebelow, whereas the upper limit is set at 2% because workability drops thereabove.
  • the upper limit is set at 2.0% because excessive addition brings about deterioration of workability.
  • B is an element effective for increasing the strength of steel sheets.
  • the lower limit is set at 0.0002% because said effect is unobtainable therebelow, whereas the upper limit is set at 0.1% because hot workability deteriorates thereabove.
  • REM rare-earth metals
  • Ca and Y are effective for the shape control of inclusions and conducive to delayed-fracture resistance. While the lower limit is set at 0.0005%, the upper limit is set at 0.01% because excessive addition deteriorates hot workability.
  • slabs having specified compositions are hot-rolled.
  • finish rolling is carried out at a temperature not lower than the Ar 3 point in order to prevent the excessive straining of ferrite particles and the lowering of workability.
  • the finish rolling temperature should preferably be not higher than 940°C.
  • Coiling at higher temperatures promotes recrystallization and particle growth and improves workability. At the same time, however, coiling at higher temperatures promotes the growth of scale formed during hot rolling and, thereby, lowers pickling efficiency. Therefore, the coiling temperature is set at not higher than 800°C.
  • the coiling temperature is set at not lower than 500°C.
  • the lower limit of the draft is set at 30%. If the draft exceeds 80%, sheet edge cracks and profile shape irregularities tend to occur. Therefore, the upper limit is set at 80%.
  • the continuous annealing temperature is set at not lower than 600°C and not higher than 950°C. Annealing is done by using continuous annealing equipment or box annealing equipment.
  • annealed steel sheets may be held in a temperature range between 200°C and 700°C for 1 minute to 10 hours and, then, cooled. This heat treatment causes precipitation of alloy carbides or nitrides (such as carbonitrides containing V, Cr, Mo and W).
  • the precipitates thus formed serve as new hydrogen trap sites and further improve delayed-fracture resistance. If the temperature is low and the time is short, adequate precipitation does not occur. If the temperature is high and the time is long, precipitated compounds become coarse. As the precipitates fail to serve as trap sites in both cases, the temperature and time are limited to the ranges described above.
  • the slab casting speed is between 1.0 m/minute and 3.0 m/minute for stable use of the delayed fracture improving effect of Mg compounds.
  • the steel sheets according to the present invention are cold-rolled or metal-coated.
  • Metal coating may be ordinary zinc-coating, etc. Coating may be provided by either hot-dip process or electrolytic process. Post-coating alloying heat treatment or multi-layer coating may be applied, too.
  • Film-laminated uncoated or coated steel sheets are also within the scope of the present invention.
  • High-strength automotive parts such as bumpers, door impact beams and other reinforcing members manufactured of high-strength steel sheets according to the present invention (such as steel sheets with strength of not lower than 780 MPa) also maintain excellent properties (such as strength and rigidity) and exhibit good shock absorption and delayed-fracture resistance.
  • the steels were heated in the heating furnace at temperatures between 1160C° and 1250°C, hot-rolled with finishing temperatures between 870°C and 900°C, and coiled at temperatures between 650°C and 750°C.
  • the steels were then made into steel sheets by applying cold rolling after pickling, recrystallization annealing and 0.4% temper-rolling.
  • the steels marked with H and K were alloyed galvanized steel sheets with a coating weight of 50 g/m 2 on each side.
  • the steel marked with I was further subjected to film laminating treatment.
  • Table 2 shows the manufacturing methods and properties of the steel sheets.
  • Table 3 shows evaluations of the delayed-fracture resistance of the steel sheets. Evaluations were made by bending 80 mm by 30 mm rectangular specimens, fitting a waterproof strain gage on the surface thereof, dipping the specimens in a 0.5 mol/l sulfuric acid, electrolyzing the solution, and causing hydrogen penetration.
  • the high-strength steel sheets produced by according the present invention effectively disperse Mg compounds or composite crystallized or precipitated compounds, which function as hydrogen trap sites, and thereby make ductility compatible with delayed-fracture resistance after forming.
  • the high-strength automotive members prepared by forming the high-strength steel sheets produced by the present invention also maintained excellent properties and exhibited good shock absorption and delayed-fracture resistance.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Claims (2)

  1. Procédé de fabrication d'une tôle d'acier laminée à froid très résistante ou d'une tôle d'acier galvanisée présentant une excellente résistance à la rupture différée en post-formage, caractérisé en ce qu'il comprend les étapes consistant à :
    préparer une brame contenant, en % en masse,
    C : 0,05 à 0,3 %,
    Si : pas plus de 3,0 %,
    Mn : 0,01 à 3,0 %,
    P : pas plus de 0,02 %,
    S : pas plus de 0,02 %,
    Al : 0,01 à 3,0 %,
    N : pas plus de 0,01 % et
    Mg : 0,0002 à 0,01 %, éventuellement un ou plus des éléments qui suivent :
    V : 0,005 à 1 % en masse,
    Ti : 0,002 à 1 % en masse,
    Nb : 0,002 à 1 % en masse,
    Zr : 0,002 à 1 % en masse,
    Cr : 0,005 à 5 % en masse,
    Mo : 0,005 à 5 % en masse,
    W : 0,005 à 5 % en masse,
    Cu : 0,005 à 2,0 % en masse,
    Ni : 0,005 à 2,0 % en masse,
    Co : 0,005 à 2,0 % en masse,
    B : 0,0002 à 0,1 % en masse,
    REM : 0,0005 à 0,01 % en masse,
    Ca : 0,0005 à 0,01 % en masse et
    Y : 0,0005 à 0,01 % en masse
    le restant comprenant du fer et des impuretés inévitables par coulée en continu avec une vitesse de coulée de 1,0 à 3,0 m/min, laminer à chaud ladite brame à une température de finition qui n'est pas inférieure au point Ar3,
    enrouler la bande laminée à chaud à une température de 500 °C à 800 °C,
    laminer à froid avec un étirage de 30 à 80 % après application d'un décapage, appliquer un recuit de recristallisation par immersion à une température qui n'est pas inférieure à 600° C et n'est pas supérieure à 950 °C, et
    appliquer un dressage par laminage à froid, et appliquer éventuellement une galvanisation.
  2. Procédé de fabrication d'une tôle en acier laminée à froid très résistante ou d'une tôle en acier galvanisée présentant une excellente résistance à la rupture différée en post-formage décrite dans la revendication 1, caractérisé en ce qu'il comprend en-outre l'étape consistant à :
    maintenir la bande dans la plage de températures de 200 à 700 °C pendant 1 minute à 10 heures après le recuit.
EP03817075A 2003-05-27 2003-05-27 Procede de preparation de tole mince en acier a resistance elevee presentant une resistance excellente a la rupture differee apres formation Expired - Lifetime EP1637618B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/006617 WO2004106571A1 (fr) 2003-05-27 2003-05-27 Tole mince en acier a resistance elevee presentant une resistance excellente a la rupture differee apres formation et procede de preparation associe, et parties automobiles necessitant une certaine resistance fabriquees a partie de tole mince en acier a resistance elevee

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EP1637618A1 EP1637618A1 (fr) 2006-03-22
EP1637618A4 EP1637618A4 (fr) 2006-10-18
EP1637618B1 true EP1637618B1 (fr) 2010-07-14

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US (2) US20070006948A1 (fr)
EP (1) EP1637618B1 (fr)
AU (1) AU2003235443A1 (fr)
DE (1) DE60333400D1 (fr)
WO (1) WO2004106571A1 (fr)

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JP4510488B2 (ja) * 2004-03-11 2010-07-21 新日本製鐵株式会社 成形性および穴拡げ性に優れた溶融亜鉛めっき複合高強度鋼板およびその製造方法
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JP5214905B2 (ja) * 2007-04-17 2013-06-19 株式会社中山製鋼所 高強度熱延鋼板およびその製造方法
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KR101975136B1 (ko) * 2015-03-13 2019-05-03 제이에프이 스틸 가부시키가이샤 고강도 냉연 강판 및 그 제조 방법
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DE60333400D1 (de) 2010-08-26
AU2003235443A1 (en) 2005-01-21
WO2004106571A1 (fr) 2004-12-09
US20110120598A1 (en) 2011-05-26
US20070006948A1 (en) 2007-01-11
EP1637618A1 (fr) 2006-03-22

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