EP1309734A1 - Highly stable, steel and steel strips or steel sheets cold-formed, method for the production of steel strips and uses of said steel - Google Patents
Highly stable, steel and steel strips or steel sheets cold-formed, method for the production of steel strips and uses of said steelInfo
- Publication number
- EP1309734A1 EP1309734A1 EP02732754A EP02732754A EP1309734A1 EP 1309734 A1 EP1309734 A1 EP 1309734A1 EP 02732754 A EP02732754 A EP 02732754A EP 02732754 A EP02732754 A EP 02732754A EP 1309734 A1 EP1309734 A1 EP 1309734A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel
- strip
- cold
- production
- sheet according
- 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 117
- 239000010959 steel Substances 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005098 hot rolling Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22C38/04—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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C21D8/0226—Hot 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
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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.
Landscapes
- 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
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10128544 | 2001-06-13 | ||
DE10128544A DE10128544C2 (en) | 2001-06-13 | 2001-06-13 | High-strength, cold-workable sheet steel, process for its production and use of such a sheet |
PCT/EP2002/006480 WO2002101109A1 (en) | 2001-06-13 | 2002-06-13 | Highly stable, steel and steel strips or steel sheets cold-formed, method for the production of steel strips and uses of said steel |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1309734A1 true EP1309734A1 (en) | 2003-05-14 |
EP1309734B1 EP1309734B1 (en) | 2007-08-15 |
EP1309734B2 EP1309734B2 (en) | 2012-06-20 |
Family
ID=7688074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02732754A Expired - Lifetime EP1309734B2 (en) | 2001-06-13 | 2002-06-13 | Highly stable, steel and steel strips or steel sheets cold-formed, method for the production of steel strips and uses of said steel |
Country Status (12)
Country | Link |
---|---|
US (1) | US20030145911A1 (en) |
EP (1) | EP1309734B2 (en) |
JP (1) | JP4227010B2 (en) |
KR (1) | KR100536645B1 (en) |
CN (1) | CN1215188C (en) |
AT (1) | ATE370258T1 (en) |
CA (1) | CA2414138C (en) |
DE (2) | DE10128544C2 (en) |
DK (1) | DK1309734T3 (en) |
ES (1) | ES2292762T5 (en) |
PT (1) | PT1309734E (en) |
WO (1) | WO2002101109A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3831597A4 (en) * | 2018-07-27 | 2021-09-22 | Posco | Low-density clad steel sheet having excellent formability and fatigue property and manufacturing method therefor |
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DE10259230B4 (en) * | 2002-12-17 | 2005-04-14 | Thyssenkrupp Stahl Ag | Method for producing a steel product |
FR2857980B1 (en) | 2003-07-22 | 2006-01-13 | Usinor | PROCESS FOR MANUFACTURING HIGH-STRENGTH FERRO-CARBON-MANGANESE AUSTENITIC STEEL SHEET, EXCELLENT TENACITY AND COLD SHAPINGABILITY, AND SHEETS THUS PRODUCED |
DE102004028236B3 (en) * | 2004-06-11 | 2005-11-17 | Rolf-Josef Schwartz | Assembly for heating workpieces before shaping in a press, e.g. high tensile steel sheets for automobile bodywork components, has a kiln with a jet field and fans to give the workpieces a convective heating action |
DE102004054444B3 (en) * | 2004-08-10 | 2006-01-19 | Daimlerchrysler Ag | Method for making steel articles with high rigidity and plasticity comprises mechanical shaping of steel in which twinning induce plasticity or shearband induced plasticity is produced, to give increase in rigidity of at least 30 percent |
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DE102005010243A1 (en) * | 2005-03-05 | 2006-09-07 | Sms Demag Ag | Method and plant for producing a lightweight steel with a high manganese content |
DE102005057599A1 (en) * | 2005-12-02 | 2007-06-06 | Volkswagen Ag | lightweight steel |
DE102005062221B3 (en) * | 2005-12-20 | 2007-05-03 | Salzgitter Flachstahl Gmbh | Deformable light alloy steel with TRIP) and TWIP properties useful in production of products having decreased crack liability twinning induced plasticity (TWIP) good ductility and tensile strength without increase in hydrogen embrittlement |
KR100742833B1 (en) | 2005-12-24 | 2007-07-25 | 주식회사 포스코 | High manganese hot-dip galvanized steel sheet with excellent corrosion resistance and manufacturing method |
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EP3831597A4 (en) * | 2018-07-27 | 2021-09-22 | Posco | Low-density clad steel sheet having excellent formability and fatigue property and manufacturing method therefor |
US11752752B2 (en) | 2018-07-27 | 2023-09-12 | Posco Co., Ltd | Low-density clad steel sheet having excellent formability and fatigue property |
US12358274B2 (en) | 2018-07-27 | 2025-07-15 | Posco Co., Ltd | Method of manufacturing clad steel sheet having excellent formability and fatigue property |
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DE10128544C2 (en) | 2003-06-05 |
ES2292762T3 (en) | 2008-03-16 |
KR20030019908A (en) | 2003-03-07 |
EP1309734B1 (en) | 2007-08-15 |
JP4227010B2 (en) | 2009-02-18 |
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DE50210689D1 (en) | 2007-09-27 |
JP2004521192A (en) | 2004-07-15 |
CA2414138A1 (en) | 2002-12-02 |
PT1309734E (en) | 2007-11-28 |
EP1309734B2 (en) | 2012-06-20 |
CA2414138C (en) | 2012-12-11 |
US20030145911A1 (en) | 2003-08-07 |
CN1463297A (en) | 2003-12-24 |
ATE370258T1 (en) | 2007-09-15 |
CN1215188C (en) | 2005-08-17 |
DE10128544A1 (en) | 2003-01-02 |
WO2002101109A1 (en) | 2002-12-19 |
KR100536645B1 (en) | 2005-12-14 |
ES2292762T5 (en) | 2012-10-29 |
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