EP1534869B1 - Ultrahochfester stahl und verfahren zur herstellung eines mit zink oder zinklegierung platierten stahlbleches - Google Patents

Ultrahochfester stahl und verfahren zur herstellung eines mit zink oder zinklegierung platierten stahlbleches Download PDF

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Publication number
EP1534869B1
EP1534869B1 EP03769565A EP03769565A EP1534869B1 EP 1534869 B1 EP1534869 B1 EP 1534869B1 EP 03769565 A EP03769565 A EP 03769565A EP 03769565 A EP03769565 A EP 03769565A EP 1534869 B1 EP1534869 B1 EP 1534869B1
Authority
EP
European Patent Office
Prior art keywords
zinc
sheet
zinc alloy
coated
steel
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.)
Expired - Lifetime
Application number
EP03769565A
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English (en)
French (fr)
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EP1534869A2 (de
Inventor
Antoine Moulin
Jean-Luc Lapointe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArcelorMittal France SA
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Arcelor France SA
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
Application filed by Arcelor France SA filed Critical Arcelor France SA
Publication of EP1534869A2 publication Critical patent/EP1534869A2/de
Application granted granted Critical
Publication of EP1534869B1 publication Critical patent/EP1534869B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment 
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to a steel with very high mechanical strength, and a method of manufacturing a sheet of this steel coated with zinc or zinc alloy.
  • dual phase steels have a microstructure composed of ferrite and martensite, which enables them to reach tensile strengths ranging from 400 MPa to more than 1200 MPa.
  • the surface of the sheets has a very poor wettability vis-à-vis zinc or zinc alloys.
  • the sheets then comprise uncoated portions, which constitute privileged areas for the initiation of corrosion.
  • the present invention therefore aims to provide a steel composition does not have the disadvantages of the compositions of the prior art, and having in particular a good coating ability with zinc or zinc alloys, while maintaining high mechanical characteristics.
  • a first object of the invention is constituted by a steel with very high mechanical strength, the chemical composition of which comprises, in% by weight: 0.080% ⁇ C ⁇ 0.120% 0.800% ⁇ Mn ⁇ 0.950% If ⁇ 0.300% Cr ⁇ 0.300% 0.150% ⁇ Mo ⁇ 0.350% 0.020% ⁇ Al ⁇ 0.100% P ⁇ 0.100% B ⁇ 0.010% Ti ⁇ 0.050% the remainder being iron and impurities resulting from the preparation, its microstructure consisting of ferrite and martensite.
  • This embodiment makes it possible to obtain a steel sheet having a tensile strength of the order of 500 MPa.
  • the steel comprises: 0.100% ⁇ C ⁇ 0.140% 0.800% ⁇ Mn ⁇ 0.950% If ⁇ 0.300% Cr ⁇ 0.300% 0.200% ⁇ Mo ⁇ 0.400% 0.020% ⁇ Al ⁇ 0.100% P ⁇ 0.100% B ⁇ 0.010% Ti ⁇ 0.050% the rest being iron and impurities resulting from the elaboration.
  • This embodiment makes it possible to obtain a steel sheet having a tensile strength of the order of 600 MPa.
  • a second object of the invention is constituted by a sheet of steel with very high mechanical strength according to the invention, and coated with zinc or zinc alloy.
  • the sheet is maintained at the holding temperature for 10 to 1000 seconds.
  • the zinc-containing bath or molten zinc alloy is maintained at a temperature of between 450 and 480 ° C, and the immersion time of the sheet is between 2 and 400 seconds.
  • the bath contains mainly zinc.
  • a fourth object of the invention is the use of a very high-strength steel sheet coated with zinc or zinc alloy, for the manufacture of auto parts.
  • the present invention is based on the new observation that by limiting the manganese, silicon and chromium contents to the maximum values claimed, excellent heatability of the shades thus produced can be obtained. Depending on the level of mechanical characteristics sought, the contents of quenching elements such as carbon and molybdenum, which have been found to be not detrimental to this coating, will be adjusted.
  • the steel composition according to the invention contains between 0.080 and 0.120%, by weight of carbon, since it has been observed that for a carbon content of less than 0.060%, the grade was no longer hardenable, and no longer allowed obtain the desired high mechanical characteristics. Beyond 0.250% by weight, the carbon greatly deteriorates the weldability of the grade.
  • the composition also contains between 0.800 and 0.950% by weight of manganese.
  • the lower limit is required to obtain a hardenable steel grade, while the upper limit must be respected in order to ensure a good coating of the grade.
  • the composition also contains up to 0.300% by weight of silicon.
  • the upper limit must be respected in order to ensure a good coating of the grade.
  • composition further contains up to 0.300% by weight of chromium.
  • the upper limit must be respected in order to ensure a good coating of the grade.
  • composition according to the invention must contain between 0.150 and 0.0350% by weight of molybdenum since it has been observed that for a content of less than 0.100%, the grade no longer makes it possible to obtain the desired high mechanical characteristics. Beyond 0.500% by weight, molybdenum greatly deteriorates the weldability of the grade.
  • composition may also optionally contain up to 0.010% by weight of boron which will then be protected if necessary by a content of 0.050% by weight maximum of titanium. This latter element has a greater affinity for nitrogen than boron, the trap by formation of titanium nitrides.
  • the steel composition may also contain various unavoidable residual elements, among which may be mentioned N, Nb, Cu, Ni, W, V.
  • the steel according to the invention finds particular applications in the field of the manufacture of parts for the automobile, and more particularly for the manufacture of visible parts such as bodywork elements, which will present a good appearance after painting, unlike those manufactured so far with the steels of the prior art.
  • compositions were produced in the form of 15 kg ingots.
  • the ingots were then reheated at 1250 ° C for 45 minutes, then hot rolled in 7 passes, the end of rolling temperature being 900 ° C.
  • the sheets thus obtained were cooled by quenching with water with a retarder at a cooling rate of the order of 25 ° C./s, and then wound at 550 ° C. before being cooled.
  • the sheets are then subjected to galvanization by dipping in a zinc bath, with a residence time in the bath depending on the selected line speed (between 80 and 150 m / min), then cooled at a speed of 5 ° C. / s to room temperature.
  • Test 1 Influence of the molybdenum content and the presence of boron
  • the sheets of shades A, B, C and F are hot dip galvanized and the dew point is adjusted to -40 ° C.
  • the sheets made in shades A and B have gaps in their coatings, unlike shades C and F which have continuous coatings.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Coating With Molten Metal (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (7)

  1. Stahl von sehr hoher mechanischer Festigkeit, dadurch gekennzeichnet, dass seine chemische Zusammensetzung, in Gewichts%, folgendes umfasst: 0,080 % ≤ C ≤ 0,120 % 0,800 % ≤ Mn ≤ 0,950 % Si ≤ 0,300 % Cr ≤ 0,300.% 0,150 % ≤ Mo ≤ 0,350 % 0,020 % ≤ Al ≤ 0,100 % P ≤ 0,100 % B ≤ 0,010 % Ti ≤ 0,050 %
    wobei Eisen und Verunreinigungen, die sich durch die Verarbeitung ergeben, den Rest ausmachen und seine Mikrostruktur aus Ferrit und Martensit besteht.
  2. Folie von sehr hoher mechanischer Festigkeit aus Stahl gemäß Anspruch 1, dadurch gekennzeichnet, dass sie mit Zink oder Zinklegierung beschichtet ist.
  3. Verfahren zur Herstellung einer Stahlfolie gemäß Anspruch 2, dadurch gekennzeichnet, dass es diejenigen Schritte umfasst, welche darin bestehen:
    - eine Bramme herzustellen, deren Zusammensetzung dem Anspruch,1 entspricht; die Bramme zunächst warm und dann kalt zu walzen, um eine Folie zu erhalten,
    - die Folie mit einer Geschwindigkeit, die zwischen 2 und 100 °C/s liegt, zu erhitzen bis eine Haltetemperatur erreicht wird, die zwischen 700 und 900 °C liegt.
    - die Folie mit einer Geschwindigkeit, die zwischen 2 und 100 °C/s liegt, abzukühlen bis eine Temperatur erreicht wird, die derjenigen eines Bades nahekommt, welches Zink oder eine geschmolzene Zinklegierung enthält, und dann
    - die Folie durch Eintauchen in das Bad mit Zink oder mit einer Zinklegierung zu beschichten und sie bis auf Raumtemperatur abzukühlen, und zwar mit einer Abkühlgeschwindigkeit, die zwischen 2 und 100 °C/s liegt.
  4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass die Folie für einen Zeitraum von 10 bis 1000 Sekunden bei der Haltetemperatur gehalten wird.
  5. Verfahren gemäß entweder dem Anspruch 3 oder dem Anspruch 4, dadurch gekennzeichnet, dass das Bad, welches Zink oder eine geschmolzene Zinklegierung enthält, bei einer Temperatur, die zwischen 450 und 480 °C liegt, gehalten wird und dass die Eintauchzeit der Folie zwischen 2 und 400 Sekunden liegt.
  6. Verfahren gemäß einem beliebigen der Ansprüche 3 bis 5, dadurch gekennzeichnet, dass das Bad hauptsächlich Zink enthält.
  7. Verwendung einer Folie von sehr hoher mechanischer Festigkeit aus Stahl, welche mit Zink oder Zinklegierung beschichtet ist und dem Anspruch 2 entspricht, zur Herstellung von Automobilteilen.
EP03769565A 2002-09-06 2003-09-04 Ultrahochfester stahl und verfahren zur herstellung eines mit zink oder zinklegierung platierten stahlbleches Expired - Lifetime EP1534869B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0211040 2002-09-06
FR0211040A FR2844281B1 (fr) 2002-09-06 2002-09-06 Acier a tres haute resistance mecanique et procede de fabrication d'une feuille de cet acier revetue de zinc ou d'alliage de zinc
PCT/FR2003/002641 WO2004022793A2 (fr) 2002-09-06 2003-09-04 Acier a tres haute resistance mecanique et procede de fabrication d'une feuille de cet acier revetue de zinc ou d'alliage de zinc

Publications (2)

Publication Number Publication Date
EP1534869A2 EP1534869A2 (de) 2005-06-01
EP1534869B1 true EP1534869B1 (de) 2007-11-14

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EP03769565A Expired - Lifetime EP1534869B1 (de) 2002-09-06 2003-09-04 Ultrahochfester stahl und verfahren zur herstellung eines mit zink oder zinklegierung platierten stahlbleches

Country Status (15)

Country Link
US (2) US7976647B2 (de)
EP (1) EP1534869B1 (de)
JP (1) JP2005538248A (de)
KR (2) KR101072961B1 (de)
CN (1) CN100422352C (de)
AT (1) ATE378431T1 (de)
AU (1) AU2003278256A1 (de)
BR (1) BR0314470B1 (de)
CA (1) CA2497870C (de)
DE (1) DE60317520T2 (de)
ES (1) ES2294334T3 (de)
FR (1) FR2844281B1 (de)
MX (1) MXPA05002509A (de)
RU (1) RU2321667C2 (de)
WO (1) WO2004022793A2 (de)

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EP2123786A1 (de) 2008-05-21 2009-11-25 ArcelorMittal France Verfahren zur Herstellung von kalt gewalzten Zweiphasen-Stahlblechen mit sehr hoher Festigkeit und so hergestellte Bleche
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CN102796852B (zh) * 2012-07-16 2014-07-02 鑫光热处理工业(昆山)有限公司 一种渗碳强化的等温淬火工件及加工方法
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WO2016001708A1 (en) 2014-07-03 2016-01-07 Arcelormittal Method for producing a high strength coated steel sheet having improved strength, formability and obtained sheet
WO2016020714A1 (en) * 2014-08-07 2016-02-11 Arcelormittal Method for producing a coated steel sheet having improved strength, ductility and formability
WO2017109539A1 (en) 2015-12-21 2017-06-29 Arcelormittal Method for producing a high strength steel sheet having improved strength and formability, and obtained high strength steel sheet
WO2017109542A1 (en) 2015-12-21 2017-06-29 Arcelormittal Method for producing a high strength steel sheet having improved ductility and formability, and obtained steel sheet
CN115216589A (zh) * 2022-07-28 2022-10-21 湖南华菱湘潭钢铁有限公司 一种改善大厚度高强海洋工程用钢心部韧性的热处理方法

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CN1145709C (zh) * 2000-02-29 2004-04-14 川崎制铁株式会社 应变时效硬化特性优良的高强度冷轧钢板及其制造方法
JP4304812B2 (ja) * 2000-03-09 2009-07-29 Ｊｆｅスチール株式会社 溶融亜鉛メッキ鋼板およびその製造方法
AU780588B2 (en) * 2000-04-07 2005-04-07 Jfe Steel Corporation Hot rolled steel plate, cold rolled steel plate and hot dip galvanized steel plate being excellent in strain aging hardening characteristics, and method for their production
ES2690275T3 (es) * 2000-10-31 2018-11-20 Jfe Steel Corporation Chapa de acero laminado en caliente de alta resistencia y método para la fabricación de la misma
BR0210265B1 (pt) * 2001-06-06 2013-04-09 folha de aÇo galvanizado ou galvanelado com imersço a quente.
AU2002361112A1 (en) * 2002-12-26 2004-07-29 Nippon Steel Corporation Alloyed-molten-zinc-plated steel sheet with excellent processability and high strength and process for producing the same
JP4443910B2 (ja) * 2003-12-12 2010-03-31 Ｊｆｅスチール株式会社 自動車構造部材用鋼材およびその製造方法

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EP1534869A2 (de) 2005-06-01
ES2294334T3 (es) 2008-04-01
DE60317520D1 (de) 2007-12-27
US7976647B2 (en) 2011-07-12
AU2003278256A1 (en) 2004-03-29
KR101072961B1 (ko) 2011-10-12
KR20110102498A (ko) 2011-09-16
FR2844281B1 (fr) 2005-04-29
CN100422352C (zh) 2008-10-01
ATE378431T1 (de) 2007-11-15
BR0314470B1 (pt) 2013-02-19
US20060102256A1 (en) 2006-05-18
CN1688724A (zh) 2005-10-26
CA2497870A1 (fr) 2004-03-18
AU2003278256A8 (en) 2004-03-29
JP2005538248A (ja) 2005-12-15
FR2844281A1 (fr) 2004-03-12
KR20050036990A (ko) 2005-04-20
DE60317520T2 (de) 2008-10-16
RU2005109922A (ru) 2005-09-10
CA2497870C (fr) 2012-01-31
WO2004022793A2 (fr) 2004-03-18
BR0314470A (pt) 2005-07-26
WO2004022793A3 (fr) 2004-05-06
US20110223441A1 (en) 2011-09-15
RU2321667C2 (ru) 2008-04-10
MXPA05002509A (es) 2005-06-03

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