WO2002101109A1 - Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier - Google Patents

Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier Download PDF

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Publication number
WO2002101109A1
WO2002101109A1 PCT/EP2002/006480 EP0206480W WO02101109A1 WO 2002101109 A1 WO2002101109 A1 WO 2002101109A1 EP 0206480 W EP0206480 W EP 0206480W WO 02101109 A1 WO02101109 A1 WO 02101109A1
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WO
WIPO (PCT)
Prior art keywords
steel
strip
cold
production
sheet according
Prior art date
Application number
PCT/EP2002/006480
Other languages
German (de)
English (en)
Inventor
Harald Hofmann
Bernhard Engl
Manfred Menne
Thomas Heller
Werner Zimmermann
Original Assignee
Thyssenkrupp Stahl Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Thyssenkrupp Stahl Ag filed Critical Thyssenkrupp Stahl Ag
Priority to CA2414138A priority Critical patent/CA2414138C/fr
Priority to KR10-2003-7001684A priority patent/KR100536645B1/ko
Priority to DE50210689T priority patent/DE50210689D1/de
Priority to DK02732754T priority patent/DK1309734T3/da
Priority to JP2003503854A priority patent/JP4227010B2/ja
Priority to EP02732754A priority patent/EP1309734B2/fr
Priority to ES02732754T priority patent/ES2292762T5/es
Publication of WO2002101109A1 publication Critical patent/WO2002101109A1/fr

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Classifications

    • 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
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
    • 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273Final recrystallisation annealing

Definitions

  • the invention relates to an Fe-Mn-Al-Si light steel with carbon and a steel strip or sheet with good cold formability and higher strength.
  • the invention relates to a method for producing strips from such a steel and particularly suitable uses of such a steel.
  • a light steel used for the production of body components and for low-temperature use is known from DE 197 27 759 C2.
  • Fe contains 10% to 30% Mn, 1% to 8% Al and 1 to 6% Si, the sum of the contents of Al and Si not exceeding 12%.
  • carbon is at most contained in the contamination area.
  • carbon is provided as an optional alloy element.
  • the known light steel has> 7% to 27% Mn,> 1% to 10% Al,> 0.7% to 4% Si, ⁇ 0.5% C, ⁇ 10% Cr, ⁇ 10% Ni and ⁇ 0, 3% Cu.
  • the steel can contain N, V, Nb, Ti, P, the sum of these elements not exceeding 2%.
  • the light steel known from EP 1 067 203 AI also contains carbon, namely 0.001 to 1.6%. In addition to Fe 6 - 30% Mn, ⁇ 6% A1, ⁇ 2.5% Si, ⁇ 10% Cr, ⁇ 10% Ni and ⁇ 5% Cu.
  • V, Ti, Nb, B, Zr and rare earths can be contained in the steel, the sum of their contents not exceeding 3%.
  • the known steel may include P, Sn, Sb, and As, the sum of the contents of these elements should not be greater than 0.2%.
  • a method for producing gear parts by pressure rolling is known from DE 197 24 661 C2.
  • a microalloy is made high-strength structural steel, which has a lower yield strength of at least 500 N / mm 2 , is formed from a sheet metal into a blank. This blank is then cold formed into the gear by spinning rolls. In the course of forming the toothing, the sheet metal material is formed to the limit of its forming capacity. Subsequently, a surface of the workpiece provided with the toothing is hardened essentially without heat distortion while maintaining the temperature.
  • the object of the invention is, based on the above-described prior art, to provide a light steel or a steel strip or sheet produced therefrom with good deformability and good strength, which can also be easily produced on an industrial scale.
  • a method for producing a steel strip or sheet and preferred uses for the steel are to be specified.
  • a light steel which has the following composition (in% by weight):
  • the targeted addition of boron leads to a significant improvement in the properties and the manufacturability in the steels according to the invention.
  • the boron content in the steel according to the invention thus brings about a reduction in the yield strength, as a result of which the deformability is significantly improved.
  • the favorable effects of the alloy on the mechanical-technological properties of the steel according to the invention can be further supported by the fact that the carbon content is 0.10-1.00% by weight, if a minimum of 0.10% by weight of carbon is detectable in the steel according to the invention.
  • steel according to the invention or a steel strip or sheet produced from it has a significantly lower ⁇ r value than the sheets known from the prior art and belonging to the type in question here.
  • cold-rolled steel strips and sheets composed according to the invention are distinguished by comparably low yield strengths, improved yield strength with increased hardening exponents (n-value), increased deep-drawing capability (r-value) and lower planar anisotropy ( ⁇ r-value) as well as an increased product of yield strength and elongation out.
  • the tensile strength of steel strips and sheets according to the invention is at least 680 MPa.
  • the product of tensile strength and elongation is at least 41000 MPa.
  • the yield strength of steel sheets and strips according to the invention does not exceed 520 MPa.
  • steels according to the invention or sheets and strips produced therefrom have an extraordinarily high uniform expansion of 20% to more than 45%. N values of up to 0.7 are achieved.
  • a particularly good cold-formable light steel strip or sheet is obtained which, due to its comparatively high strength and low density, is particularly suitable for the production of components for automobile bodies.
  • the excellent ratio of strength and weight makes a steel sheet produced according to the invention for the production of wheels for vehicles, in particular motor vehicles, for the production of components molded by internal high pressure or external high pressure, for the production of high-strength engine parts, such as camshafts or piston rods, for the production of suitable for protection against impulses, such as shelling, certain components, such as armor plates, as well as protective elements intended to protect people, in particular against shelling.
  • the comparatively low weight of the steel sheet according to the invention and the high strength at the same time have a positive effect.
  • Steel sheets according to the invention are also particularly suitable for the production of non-magnetic components with a purely austenitic structure.
  • inventive materials retain their strength even at particularly low temperatures. As such, they are particularly suitable for the production of components used in cryogenics, such as containers or pipes for refrigeration.
  • the positive effects of boron in steel used according to the invention can be achieved particularly safely if the boron content is 0.002% by weight to 0.01% by weight, in particular 0.003 to 0.008% by weight.
  • the C content in the range from 0.1% to 1.0% also ensures improved producibility of steel sheets and strips according to the invention.
  • the formation of intermetallic phases is suppressed due to the presence of carbon. Cracks and instabilities in the band edge area, as they arise in the steel strips produced from the known steels, are thus considerably reduced, the instabilities decreasing to a particular extent with increasing C content.
  • a further improvement in strip edge quality is achieved by adding boron. As a result, the combined Addition of C and B band edge instabilities can be avoided almost completely.
  • the C and B contents provided according to the invention open up a wide range of hot rolling parameters. It has thus been found that the characteristic values of steels according to the invention obtained when high hot rolling temperatures and coiling temperatures are selected are essentially the same as those obtained at low hot rolling temperatures and coiling temperatures. This insensitivity in hot strip production also favors the simple manufacture of steel sheets according to the invention.
  • Si content of steel strips and sheets according to the invention Due to the Si content of steel strips and sheets according to the invention, which are limited to contents above 2.50% by weight, preferably above 2.70% by weight, an improvement over those of light steel strips or sheets having low Si contents was improved Cold rollability.
  • the high addition of Si is expressed in more uniform yield strengths and Tensile strength values as well as higher elongation at break and uniform elongation values.
  • Si in steels according to the invention also leads to higher r and n values and to an isotropic formation of the mechanical properties.
  • the upper limit of the sum formed from AI and Si contents is 12%, since a sum of the AI and Si contents going beyond this limit would entail the risk of embrittlement.
  • a starting material such as slabs, thin slabs or strip
  • the hot-rolling the hot-rolled strip according to the invention at at least 800 ° C., and coiling it at low temperatures, the aforementioned positive effect of carbon and in particular boron is used to the full extent.
  • Boron and carbon for example, produce higher tensile strength and yield strength values with strips that are hot-rolled in this area, while still maintaining acceptable elongation at break values.
  • With increasing hot rolling temperature tensile strength and yield point decrease, while the elongation values increase.
  • the final roll temperatures within the scope specified by the invention, the influence the desired properties of the steel strip obtained in a targeted and simple manner.
  • Hot strip produced according to the invention is characterized by good usage properties. If thinner sheets or strips are to be produced, the hot strip can be cold-rolled into cold strip after coiling, the cold rolling advantageously being carried out with a degree of cold rolling of 30% to 75%.
  • the cold strip obtained is then preferably subjected to annealing, the annealing temperatures being between 600 ° C. and 1100 ° C. Annealing can be carried out in the hood in the temperature range from 600 ° C to 750 ° C or in a continuous process in the annealing furnace at temperatures from 750 ° C to 1100 ° C.
  • annealing can be carried out in the hood in the temperature range from 600 ° C to 750 ° C or in a continuous process in the annealing furnace at temperatures from 750 ° C to 1100 ° C.
  • steel according to the invention or steel strips and sheets produced therefrom consists in the production of cold-formed components by pressure rolling.
  • blanks are produced from the steel, which are then finished by the pressure rolling. Due to its special property profile is suitable Steel according to the invention or sheet metal blanks produced therefrom in a special way for this purpose.
  • a purely austenitic or a structure consisting of a mixture of ferrite and austenite with portions of martensite can be set in the steel according to the invention.
  • the steels according to the invention can therefore be shaped much better. In the course of cold forming, they harden significantly more strongly than the high-strength micro-alloyed or multi-phase steels known to be used for the production by pressure rolling. Depending on the cold deformation, component strengths in the range from 1400 N / mm 2 to 2200 N / mm 2 can be achieved. Additional hardening of the components produced after cold forming can therefore be dispensed with. It also has a favorable effect, in particular in the production of toothed gear components, with regard to the intended use, that the steels used according to the invention for their production are reduced in density due to the high content of light elements such as Si, Al.
  • Table 1 shows the compositions of four steels A, B, C, D, E, of which steels A, B and C correspond to the alloy provided according to the invention, while steels D and E are comparative examples.
  • the steel strips produced from steels A to C according to the invention have excellent cold formability. With high strength and high elongation at break, they each have a pronounced isotropic deformation behavior (r ⁇ 1, ⁇ r ⁇ 0).
  • the steel strips produced from the carbon-free but boron-containing steel C according to the invention also have low yield strengths, increased elongation at break and uniform elongation and isotropic deformation behavior.
  • all variants of steel sheets according to the invention are particularly suitable for the production of Body components, especially for the outer sheets of an automobile body, of wheels for vehicles, in particular motor vehicles, of non-magnetic components, of containers used in cryotechnology, of components molded by internal high pressure or external high pressure, of pipes, in particular for the production of high-strength engine parts such as camshafts or Piston rods are intended for protection against impulses, such as shelling, certain components or protective elements, such as armor plates, or body armor for the human or animal body.
  • Highly resilient gear components can also be produced from steel sheets according to the invention, which are characterized by a low weight and good usage properties, without the need for additional heat treatment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

L'invention concerne un feuillard ou une tôle d'acier présentant une bonne aptitude au formage à froid et une résistance très élevée, constitué(e) d'un acier léger qui comprend (en % en poids) les constituants suivants : C: ≤1,00 %, Mn: 7,00 - 30,00 %, Al: 1,00 - 10,00 %, Si: > 2,50 - 8,00 %, Al + Si: > 3,50 - 12,00 %, B: > 0,00 - < 0,01 %, ainsi qu'éventuellement Ni: < 8,00 %, Cu: < 3,00 %, N: < 0,60 %, Nb: < 0,30 %, Ti: < 0,30 %, V: < 0,30 %, P: < 0,01 %, le reste étant constitué de fer et d'impuretés inévitables.
PCT/EP2002/006480 2001-06-13 2002-06-13 Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier WO2002101109A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA2414138A CA2414138C (fr) 2001-06-13 2002-06-13 Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier
KR10-2003-7001684A KR100536645B1 (ko) 2001-06-13 2002-06-13 고 안정성의 냉간 성형 강 및 강 스트립 또는 강 시트와,강 스트립 제조 방법 및 그 강의 용도
DE50210689T DE50210689D1 (de) 2001-06-13 2002-06-13 Höherfester, kaltumformbarer stahl und stahlband oder -blech, verfahren zur herstellung von stahlband und verwendungen eines solchen stahls
DK02732754T DK1309734T3 (da) 2001-06-13 2002-06-13 Fremgangsmåde til kolddeformering af særligt stabilt stål og stålstrimler eller stålplader til fremstilling af stålstrimler samt anvendelser af dette stål
JP2003503854A JP4227010B2 (ja) 2001-06-13 2002-06-13 冷間成形用高強度鋼および鋼帯もしくは鋼板、鋼帯の製造方法および鋼の製造方法
EP02732754A EP1309734B2 (fr) 2001-06-13 2002-06-13 Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier
ES02732754T ES2292762T5 (es) 2001-06-13 2002-06-13 Acero y banda o chapa de acero de alta resistencia, maleables en frío, procedimiento para la fabricación de bandas de acero y usos de dicho acero

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10128544A DE10128544C2 (de) 2001-06-13 2001-06-13 Höherfestes, kaltumformbares Stahlblech, Verfahren zu seiner Herstellung und Verwendung eines solchen Blechs
DE10128544.2 2001-06-13

Publications (1)

Publication Number Publication Date
WO2002101109A1 true WO2002101109A1 (fr) 2002-12-19

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ID=7688074

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/006480 WO2002101109A1 (fr) 2001-06-13 2002-06-13 Acier et feuillard ou tole d'acier a resistance tres elevee, pouvant etre forme a froid, procede pour produire un feuillard d'acier et utilisations d'un tel acier

Country Status (12)

Country Link
US (1) US20030145911A1 (fr)
EP (1) EP1309734B2 (fr)
JP (1) JP4227010B2 (fr)
KR (1) KR100536645B1 (fr)
CN (1) CN1215188C (fr)
AT (1) ATE370258T1 (fr)
CA (1) CA2414138C (fr)
DE (2) DE10128544C2 (fr)
DK (1) DK1309734T3 (fr)
ES (1) ES2292762T5 (fr)
PT (1) PT1309734E (fr)
WO (1) WO2002101109A1 (fr)

Cited By (23)

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Publication number Priority date Publication date Assignee Title
WO2006048034A1 (fr) * 2004-11-03 2006-05-11 Thyssenkrupp Steel Ag Bande ou tole d'acier extremement resistante a proprietes twip et procede de fabrication de ladite bande a l'aide de la 'coulee directe de bandes'
DE102005057599A1 (de) * 2005-12-02 2007-06-06 Volkswagen Ag Leichtbaustahl
WO2007074994A1 (fr) 2005-12-24 2007-07-05 Posco Tole d'acier a forte teneur en mn, presentant une grande resistance a la corrosion et procede de galvanisation de la tole d'acier
WO2008000347A2 (fr) * 2006-06-30 2008-01-03 Daimler Ag Piston coulé en acier pour moteurs à combustion interne
WO2011081393A3 (fr) * 2009-12-28 2011-11-10 주식회사 포스코 Matériau d'acier austénitique à ductilité supérieure
WO2012033377A2 (fr) * 2010-09-09 2012-03-15 연세대학교 산학협력단 Feuille d'acier à haute résistance mécanique et haute ductilité, et son procédé de production
US8182963B2 (en) 2009-07-10 2012-05-22 GM Global Technology Operations LLC Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates
WO2013032173A2 (fr) 2011-08-26 2013-03-07 주식회사 포스코 Acier à teneur élevée en manganèse présentant une soudabilité supérieure et procédé de fabrication d'une feuille d'acier galvanisée par immersion à chaud à partir de cet acier
WO2013100610A1 (fr) 2011-12-27 2013-07-04 주식회사 포스코 Tôle d'acier galvanisée laminée à chaud à teneur élevée en manganèse et son procédé de fabrication
WO2014098503A1 (fr) 2012-12-21 2014-06-26 주식회사 포스코 Procédé de production d'une feuille en acier galvanisé à chaud à haute teneur en manganèse présentant une excellente aptitude au revêtement et une résistance ultra-élevée et feuille en acier galvanisé à chaud à haute teneur en manganèse produite par ledit procédé
US8926772B2 (en) * 2003-07-22 2015-01-06 Usinor Method of producing austenitic iron/carbon/manganese steel sheets having a high strength and excellent toughness and being suitable for cold forming, and sheets thus produced
WO2015023012A1 (fr) 2013-08-14 2015-02-19 주식회사 포스코 Tôle d'acier à ultra-haute résistance et son procédé de fabrication
US8999085B2 (en) 2005-12-26 2015-04-07 Posco High manganese steel strips with excellent coatability and superior surface property, coated steel strips using steel strips and method for manufacturing the steel strips
KR20160054111A (ko) 2014-11-05 2016-05-16 주식회사 포스코 점용접성 및 도금성이 우수한 고망간강 합금아연도금강판 및 이의 제조방법
KR20160058289A (ko) 2014-11-14 2016-05-25 주식회사 포스코 가공성 및 점용접성이 우수한 합금화 용융아연도금강판 및 그 제조방법
KR20160077558A (ko) 2014-12-23 2016-07-04 주식회사 포스코 도금 품질이 우수한 오스테나이트계 고강도 고망간 용융 알루미늄 도금강판 및 그의 제조방법
KR20160077594A (ko) 2014-12-23 2016-07-04 주식회사 포스코 도금성이 우수한 오스테나이트계 고강도 고망간 용융 알루미늄 도금강판 및 그의 제조방법
KR20160078840A (ko) 2014-12-24 2016-07-05 주식회사 포스코 항복 강도 및 성형성이 우수한 고강도 고망간강 및 그 제조방법
WO2017111491A1 (fr) 2015-12-24 2017-06-29 주식회사 포스코 Tôle d'acier à base d'austénite plaquée d'aluminium à l'état fondu ayant d'excellentes propriétés de plaquage et de soudabilité et son procédé de fabrication
KR101988763B1 (ko) 2017-12-21 2019-06-12 주식회사 포스코 성형성 및 표면품질이 우수한 고강도 강판 및 이의 제조방법
KR20190075588A (ko) 2017-12-21 2019-07-01 주식회사 포스코 항복강도 및 성형성이 우수한 고강도 강판 및 이의 제조방법
KR20190078437A (ko) 2017-12-26 2019-07-04 주식회사 포스코 점 용접성이 우수한 초고강도 고망간 아연도금강판 및 그의 제조방법
KR20190078436A (ko) 2017-12-26 2019-07-04 주식회사 포스코 점용접성이 우수한 고강도 고망간 도금강판 용접 구조물 및 그의 제조방법

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US20030145911A1 (en) 2003-08-07
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ATE370258T1 (de) 2007-09-15
DK1309734T3 (da) 2007-12-27
JP2004521192A (ja) 2004-07-15
KR100536645B1 (ko) 2005-12-14
KR20030019908A (ko) 2003-03-07
EP1309734B1 (fr) 2007-08-15
DE50210689D1 (de) 2007-09-27
CN1215188C (zh) 2005-08-17
DE10128544A1 (de) 2003-01-02
ES2292762T5 (es) 2012-10-29
PT1309734E (pt) 2007-11-28
CA2414138C (fr) 2012-12-11
DE10128544C2 (de) 2003-06-05
JP4227010B2 (ja) 2009-02-18
CA2414138A1 (fr) 2002-12-02
ES2292762T3 (es) 2008-03-16
CN1463297A (zh) 2003-12-24

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