EP1672088B2 - Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage à froid, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue - Google Patents

Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage à froid, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue Download PDF

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Publication number
EP1672088B2
EP1672088B2 EP06002618.4A EP06002618A EP1672088B2 EP 1672088 B2 EP1672088 B2 EP 1672088B2 EP 06002618 A EP06002618 A EP 06002618A EP 1672088 B2 EP1672088 B2 EP 1672088B2
Authority
EP
European Patent Office
Prior art keywords
zinc
steel
rolled
sheet
coating
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
EP06002618.4A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1672088A1 (fr
EP1672088B1 (fr
Inventor
Ronald Kefferstein
Xavier Jartoux
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
Original Assignee
ArcelorMittal 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
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Application filed by ArcelorMittal France SA filed Critical ArcelorMittal France SA
Priority to EP10006299.1A priority Critical patent/EP2224034B1/fr
Publication of EP1672088A1 publication Critical patent/EP1672088A1/fr
Publication of EP1672088B1 publication Critical patent/EP1672088B1/fr
Application granted granted Critical
Publication of EP1672088B2 publication Critical patent/EP1672088B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C21D8/0278Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21DWORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20Deep-drawing
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • C23C2/28Thermal after-treatment, e.g. treatment in oil bath
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • C23C2/28Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29Cooling or quenching
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62Quenching devices
    • C21D1/673Quenching devices for die quenching

Definitions

  • the invention relates to a method for producing a part with very high mechanical characteristics, shaped by stamping, from a strip of rolled steel sheet and in particular hot rolled and coated with a metal or metal. a metal alloy providing protection of the surface and steel.
  • the steel sheets to be subjected to high temperature forming and / or a heat treatment are not delivered coated for reasons of resistance of the coating during the heat treatment, the heat treatment of the steels generally being carried out at relatively high temperatures well above 700 ° C. Indeed, a coating of zinc deposited on a metal surface has been considered until now as being able to melt, flow, foul the hot forming tools, during heating, at temperatures above the melting temperature of zinc , and degrade during rapid cooling. The coating is therefore performed on finished part which requires a careful cleaning of surfaces and hollow parts. This cleaning requires the use of acids and / or bases whose recycling and storage are a significant financial burden and present risks for operators and the environment.
  • the heat treatment must be carried out under a controlled atmosphere in order to avoid decarburization and oxidation of the steel. Then, in the case of hot forming, calamine, by its abrasive power, damages the forming tools, which reduces the quality of the parts obtained from the dimensional and aesthetic point of view or requires frequent and expensive repairs tools. Finally, to increase their resistance to corrosion, the parts thus obtained must receive an expensive post-processing whose application is difficult or impossible, especially in the case of parts with depressions.
  • the post-coatings of steels with very high mechanical characteristics also have the disadvantage of creating hydrogen embrittlement risks in electro-galvanizing techniques or modifying the mechanical properties of these steels in dip galvanizing techniques. previously formed parts.
  • the object of the invention is to propose to the users, steel sheets rolled from 0.2 mm to about 4 mm thick, coated in particular after hot rolling, and to undergo a shaping, cold followed by a heat treatment, as well as a process for making part by forming, from these coated steel sheets, the temperature rise being ensured without decarburization of the steel of the sheet, without oxidation of the surface of the sheet; said sheet, before, during and after the heat treatment.
  • the invention also relates to the use of a strip of rolled and in particular hot-rolled steel sheet coated with zinc or a zinc-based alloy providing protection of the surface and steel of the sheet metal.
  • the parts having high mechanical properties in hardness and high surface hardness characteristics and a very good resistance to abrasion.
  • the process presented in the diagram of the figure 1 consists, from a sheet of a steel for heat treatment and hot forming, in particular hot rolled and coated with zinc or a zinc-based alloy, in the production of a hot-formed part in the form of tool means such as a stamping press.
  • the zinc or zinc alloy coating is selected so as to provide corrosion protection for the base sheet in a coil.
  • the coating forms a layer which combines with the steel of the strip and present at this moment a mechanical strength avoiding the melting of coating metal.
  • the formed compound has high resistance to corrosion, abrasion, wear and fatigue.
  • the coating does not alter the formability properties of the steel and thus allows a wide variety of cold and hot forming.
  • the strip After hot rolling, the strip can be pickled and cold rolled before being coated. In the case where the sheet is cold rolled, it can be annealed before being coated.
  • the rolled sheet can be coated, for example, with zinc, or zinc aluminum alloys.
  • the sheet is cold stamped to obtain the piece.
  • the resulting part is then subjected to a heat treatment to give it high mechanical characteristics.
  • a base steel having a breaking strength Rm of about 500 MPa will make it possible to obtain heat-treated parts having a steel with a resistance Rm greater than 1500 MPa.
  • the sheet is subjected to a temperature rise preferably between 700 ° C and 1200 ° C in a furnace with an atmosphere no longer requiring control, because of the barrier to oxidation formed by the coating.
  • a temperature rise preferably between 700 ° C and 1200 ° C in a furnace with an atmosphere no longer requiring control, because of the barrier to oxidation formed by the coating.
  • the zinc-based coating is transformed into an alloyed surface layer having different phases depending on the temperature treatment and having a high hardness of more than 600 HV 100g.
  • sheets having a thickness of between 0.2 mm and 4 mm may be used, having good shaping properties as well as good corrosion resistance.
  • the sheets delivered coated have a significant resistance to corrosion during temperature rises, shaping, heat treatments, and during the use of finished formed parts.
  • the presence of the coating during heat treatments makes it possible to avoid, in addition to corrosion, the decarburization of the base steel.
  • the effect of protection against decarburization of the intermetallic alloy allows the use of high temperature furnace exceeding 900 ° C having an uncontrolled atmosphere, and this, even for heating times of several minutes.
  • the parts obtained Due to the characteristics of the coating after temperature rise, the parts obtained have an increased resistance to fatigue, wear, abrasion and corrosion, including on the wafer because of the galvanic behavior of the zinc with the steel.
  • the coating is weldable before and after temperature rise.
  • the steel of the sheet ensures, by cooling quenching effect, high mechanical characteristics of the part obtained after shaping.
  • Example 1 zinc coating on steel.
  • One piece is made from the cold-rolled steel sheet 1 mm thick and continuously galvanized double-sided, with a coating thickness of approximately 10 ⁇ m.
  • the sheet is austenitized at 950 ° C. before forming and quenching in the tool, the coating acting as a lubricant during shaping, in addition to its protective functions against cold corrosion, hot and against decarburization.
  • the alloy coating does not interfere with the extraction of heat by the tool and can promote it. After forming and quenching, it is no longer necessary to strip the part or to protect it, the base coating providing protection throughout the process.
  • the part produced is of a matte gray appearance without sag or bubble, without flaking or cracks, and not having calamine on the wafer, in section.
  • Scanning electron microscopic observations show on the surface and in section that the coating retains a homogeneous structure and texture and that Fe-Zn alliation occurs in less than 5 minutes at 950 ° C.
  • the coating comprises as shown in comparative manner on the Figures 3a and 3b respectively representing, in section, the coating before and after heat treatment, a Zn diffusion interface, with a thickness of between 5 and 10 ⁇ m, is a layer formed by nodules of Zn-Fe alloy in a zinc matrix layer with a thickness of between 10 and 15 ⁇ m.
  • Table 1 below shows the loss of corrosion mass after 500 and 1000 hours of salt spray, for an uncoated reference steel, for a galvanized reference steel without heat treatment, and a steel according to two forms of the invention.
  • Table 1 Loss of mass in g / m 2 Loss of mass in g / m 2 After 500 hours After 1000 hours
  • the coating after heat treatment is resistant to salt spray.
  • this surface composed of zinc and iron, can be phosphated in conventional surface treatment baths of the phosphating type.
  • the corrosion tests carried out after phosphating and cataphoresis painting show excellent results.
  • the zinc iron alloy layer also provides galvanic protection for cathodic protection type slices.
  • Example 2 Coating of zinc aluminum on steel (not forming part of the invention).
  • a 10 ⁇ m coating is applied to a sheet of about 1 mm.
  • This coating is composed of 50 to 55% aluminum and 45 to 50% zinc with possibly a small amount of silicon.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Forging (AREA)
  • Heat Treatment Of Articles (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
EP06002618.4A 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage à froid, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue Expired - Lifetime EP1672088B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10006299.1A EP2224034B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0004427A FR2807447B1 (fr) 2000-04-07 2000-04-07 Procede de realisation d'une piece a tres hautes caracteristiques mecaniques, mise en forme par emboutissage, a partir d'une bande de tole d'acier laminee et notamment laminee a chaud et revetue
EP01400861A EP1143029B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécanique, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP01400861A Division EP1143029B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécanique, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue
EP01400861.9 Division 2001-04-04

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP10006299.1A Division-Into EP2224034B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue
EP10006299.1 Division-Into 2010-06-17

Publications (3)

Publication Number Publication Date
EP1672088A1 EP1672088A1 (fr) 2006-06-21
EP1672088B1 EP1672088B1 (fr) 2010-08-18
EP1672088B2 true EP1672088B2 (fr) 2015-01-28

Family

ID=8848960

Family Applications (3)

Application Number Title Priority Date Filing Date
EP06002618.4A Expired - Lifetime EP1672088B2 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage à froid, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue
EP01400861A Revoked EP1143029B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécanique, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue
EP10006299.1A Revoked EP2224034B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue

Family Applications After (2)

Application Number Title Priority Date Filing Date
EP01400861A Revoked EP1143029B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécanique, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue
EP10006299.1A Revoked EP2224034B1 (fr) 2000-04-07 2001-04-04 Procédé de réalisation d'une pièce à très hautes caractéristiques mécaniques, mise en forme par emboutissage, à partir d'une bande de tôle d'acier laminée et notamment laminée à chaud et revêtue

Country Status (12)

Country Link
US (1) US6564604B2 (da)
EP (3) EP1672088B2 (da)
JP (2) JP3663145B2 (da)
AR (1) AR028319A1 (da)
AT (2) ATE478167T1 (da)
BR (2) BRPI0102747B1 (da)
CA (1) CA2343340C (da)
DE (5) DE60119826T2 (da)
DK (1) DK1143029T3 (da)
ES (3) ES2350399T5 (da)
FR (1) FR2807447B1 (da)
PT (2) PT1143029E (da)

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EP1403388A1 (de) 2002-09-26 2004-03-31 ThyssenKrupp Stahl AG Verfahren zum Herstellen von Produkten durch Umformen bei erhöhten Temperaturen
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EP1143029A1 (fr) 2001-10-10
DE01400861T1 (de) 2005-05-04
ATE478167T1 (de) 2010-09-15
EP1672088A1 (fr) 2006-06-21
CA2343340C (fr) 2008-07-08
EP1143029B1 (fr) 2006-05-24
JP2005047001A (ja) 2005-02-24
ES2350399T5 (es) 2015-11-10
AR028319A1 (es) 2003-05-07
ATE327353T1 (de) 2006-06-15
ES2350399T3 (es) 2011-01-21
FR2807447A1 (fr) 2001-10-12
DE60142859D1 (de) 2010-09-30
ES2428638T3 (es) 2013-11-08
EP1672088B1 (fr) 2010-08-18
EP2224034A1 (fr) 2010-09-01
JP3663145B2 (ja) 2005-06-22
JP3825456B2 (ja) 2006-09-27
JP2001353548A (ja) 2001-12-25
BR0102747A (pt) 2001-12-04
PT1143029E (pt) 2006-09-29
DE10006299T1 (de) 2012-01-26
DK1143029T3 (da) 2006-09-18
DE60119826T2 (de) 2006-12-14
FR2807447B1 (fr) 2002-10-11
BRPI0117371B1 (pt) 2016-06-14
EP2224034B1 (fr) 2013-07-17
US20010042393A1 (en) 2001-11-22
BRPI0102747B1 (pt) 2016-08-30
DE20122563U1 (de) 2006-05-11
US6564604B2 (en) 2003-05-20
PT1672088E (pt) 2010-11-04
CA2343340A1 (fr) 2001-10-07
ES2263567T3 (es) 2006-12-16
DE60119826D1 (de) 2006-06-29

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