EP1263540A1 - Procede pour produire des pieces en acier a faible epaisseur de paroi, et pieces ainsi produites - Google Patents

Procede pour produire des pieces en acier a faible epaisseur de paroi, et pieces ainsi produites

Info

Publication number
EP1263540A1
EP1263540A1 EP01900129A EP01900129A EP1263540A1 EP 1263540 A1 EP1263540 A1 EP 1263540A1 EP 01900129 A EP01900129 A EP 01900129A EP 01900129 A EP01900129 A EP 01900129A EP 1263540 A1 EP1263540 A1 EP 1263540A1
Authority
EP
European Patent Office
Prior art keywords
layers
steel
components
tempered
composite material
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
Application number
EP01900129A
Other languages
German (de)
English (en)
Other versions
EP1263540B1 (fr
Inventor
Hans-Toni Junius
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.)
CD Waelzholz Brockhaus GmbH
Original Assignee
Cd Walzholz Produktions-Gesellschaft Mbh
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 Cd Walzholz Produktions-Gesellschaft Mbh filed Critical Cd Walzholz Produktions-Gesellschaft Mbh
Publication of EP1263540A1 publication Critical patent/EP1263540A1/fr
Application granted granted Critical
Publication of EP1263540B1 publication Critical patent/EP1263540B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/008Continuous casting of metals, i.e. casting in indefinite lengths of clad ingots, i.e. the molten metal being cast against a continuous strip forming part of the cast product
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • Y10S428/925Relative dimension specified
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • Y10S428/926Thickness of individual layer specified
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/94Pressure bonding, e.g. explosive
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12458All metal or with adjacent metals having composition, density, or hardness gradient
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12472Microscopic interfacial wave or roughness
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12951Fe-base component
    • Y10T428/12958Next to Fe-base component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12951Fe-base component
    • Y10T428/12958Next to Fe-base component
    • Y10T428/12965Both containing 0.01-1.7% carbon [i.e., steel]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12986Adjacent functionally defined components

Definitions

  • the present invention relates to a method for producing thin-walled components made of steel, which have an inner core layer and outer edge layers, the layers consisting of differently tempered steel alloys and at least partially tempered.
  • the invention further comprises a thin-walled component made of steel with a core layer and martensitic hardened edge layers.
  • the process according to the invention is characterized in that core and surface layers made of steel materials with different tempering properties, namely in particular different martensitic hardenability properties, are combined with one another in such a way that thin-walled components are made available, which combine the respective advantages of case hardening and roll cladding.
  • Composite produces a strength distribution that is comparable to the case hardening curve, which is generally regarded as particularly advantageous.
  • case hardening there is practically no distortion in the method according to the invention, so that a precise, dimensionally and formally accurate component is made available without the need for dimensional corrections.
  • the flat alloy gradients specified according to the invention at the interfaces between the layers prevent the formation of internal material notches, as are inevitable in roll cladding as mentioned at the beginning. Thanks to the thus optimized hardness and strength gradient, there is no longer any risk that the boundary layers will flake off at the joint area, i.e. at the interface, when the load stress is exceeded, when the yield strength is exceeded.
  • the individual layers of steel alloys with different martensitic hardenability properties i.e. different contents of carbon, chromium and manganese are formed, the subsequent remuneration being carried out by martensitic or bainitic quenching, i.e. a heat treatment with the steps of heating-quenching-tempering.
  • the tempered layers consist of higher alloy, i.e. higher carbon steel than the unrefined layers.
  • the flat alloy gradient a correspondingly flat carbon gradient is realized in this case. This transition zone between high-carbon and low-carbon layers extends at one
  • Wall thickness of the components of less than 4 mm over less than 20%, preferably less than 15% of the wall thickness.
  • the coated layers preferably form the
  • Boundary layers of the components which are hard as a surface and have a hardness curve that roughly equates to case hardening.
  • the disadvantage of case hardening that due to the long residence time in the edge zones, a relatively coarse grain structure occurs, which leads to increased sensitivity to microcracks, is avoided by the layer arrangement according to the invention. Due to the relatively short dwell time, a wear-resistant fine grain structure with high toughness in the edge zone also results in the edge layers, which leads to a particularly low sensitivity to microcracks.
  • Components with a wall thickness of less than 4 mm can preferably be produced by the method according to the invention.
  • the tempered layers of the wall thickness i.e.
  • the martensitic hardened layers a cross-sectional proportion of about 10% to 50%.
  • the core layer of the components can also be quenched and tempered, for example hardened, while the edge layers consist of non-hardenable steel alloys or stainless steels.
  • the alloy gradient according to the invention between the surface and core layers can be produced by placing boards made of martensitic hardenable steel parallel to one another at a distance from one another in order to produce the composite material for the surface layers, and the core layer located between them is cast with molten, low-carbon steel.
  • molten, low-carbon steel For example, cold or surface-treated hot strip with predetermined chemical analysis, in particular a high carbon content, is used to form the surface layers. Due to the molten core material cast in between, which has a lower carbon content, the boards melt locally at the material interfaces, which results in a flat alloy or
  • Carbon gradient with a depth of about 0.1-0.3 mm. These properties are made possible by the connection according to the invention by means of a casting process close to the final dimensions.
  • the boards are preferably cooled from the outside by the casting wheels or the casting mold when the molten core material is poured in.
  • the width of the alloy gradient can be controlled so that it is in the range of 0.1 mm and is up to 10% of the total cross section.
  • the band which forms the edge layers is introduced into the casting gap on both sides along the rollers or copper jaws at the edge of the melt sump.
  • the Tapes should be bare, free of scale and oxide and, if necessary, roughened by appropriate surface treatment.
  • melt of the core material comes into contact with the strip surface, it is heated to above 950 ° C., so that a diffusion welding of the melt to the strip surface results in a metallic joining with the flat alloy gradient according to the invention.
  • band forming the outer layers the heat is given off further to the copper rollers or the mold walls, so that the bands do not melt completely, which would not be desirable.
  • the consequence of this casting composite in the wall thickness range close to the final dimensions is an increase in the casting performance, since the heat is dissipated by heating the supplied surface layers, that is to say the casting gap is cooled by the cold material supplied.
  • remuneration By means of partial heat treatment, for example by means of laser or electron radiation, locally limited remuneration, that is to say hardening, can take place.
  • remuneration can be given in the short-term continuous process, preferably in a protective gas furnace.
  • This enables particularly efficient production of functionally optimized strip material and components.
  • Particularly advantageous applications have a thin-walled component made of steel manufactured according to the aforementioned methods, with a soft core layer and martensitic hardened edge layers, which consists of a cold-formed, hardened multi-layer composite material which has carbon-rich, martensitic hardened edge layers and a core layer which is relatively low in carbon. the carbon gradient between the layers being flat.
  • the component can also have non-tempered surface layers, for example made of stainless steel alloys, and a tempered core layer, for example made of spring steel.
  • the wall thickness of the component according to the invention is preferably up to 4.0 mm.
  • the carbon gradient in the transition area extends over approximately 10 to 30% of the wall thickness, in any case more than 0.1 mm.
  • the materials for the outer and core layers are preferably matched to one another such that the hardness of the core layer corresponds to at least 30% to 50% of the hardness of the outer layers.
  • the component can consist of two different materials, for example a low-alloy core layer and high-alloy peripheral layers.
  • the chemical composition of the outer layers can also be different if required, so that a total of at least three layers with different material properties are present. This enables a further improved functional optimization of the components, such as corrosion protection or fusion welding, to be achieved. Furthermore, in the case of those produced according to the invention
  • Fig. 2 is a schematic representation of a casting plant for the production of strip material according to the invention.
  • FIG. 1 shows a section through a cold-formed, martensitic surface layer-hardened component 1. This is preferably formed from strip material with a total thickness S, which is in the range from 0.3 to 4.0 mm.
  • the peculiarity of the component 1 shown is that the layers A, B, A have already been connected to one another before the cold forming to the final dimension S in accordance with the method according to the invention, so that wide transition zones G have been formed at the layer boundaries, which are indicated by hatching and in which a flat carbon gradient has formed between the layer materials due to carbon diffusion and is in the range of several 1/10 mm.
  • the entire component 1 (FIG. 1) after it has been cold formed into a machine component, for example, has been subjected to a martensitic hardening process. As a result, the outer layers A are hardened, while the core B maintains a relatively high toughness.
  • Fig. 2 shows schematically a continuously operating two-roll casting and rolling system. This has two rotating, water-cooled copper rollers 2, which limit a casting gap of 1-5 mm wide.
  • Molten material B is applied to the melt sump 3 from above via an immersion tube 4.
  • Tape material A is fed along the edges of the casting gap from supply coils. With the core material B encapsulated in the casting gap, the connection between the material A supplied as a steel hot band and the melt-supplied material B takes place there. Due to the high surface pressure at temperatures above 950 ° C during hot rolling, there is an optimal metallic joining in any case.
  • the system according to the invention shown can be used to produce steel layer materials with extremely different properties with regard to the tempering of the individual layers.
  • the cold-formable composite material can be processed particularly well and efficiently to its final dimensions.
  • there is no disadvantageous delay in hardness during the subsequent hardening and there is no risk of the edge layers flaking off. This is because they have a fine, tough hard structure, which does not lead to breakage of the component even under high loads or short-term overload.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Continuous Casting (AREA)
  • Heat Treatment Of Steel (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)

Abstract

L'invention concerne un procédé pour produire des pièces en acier à faible épaisseur de paroi, ainsi que des pièces ainsi produites, présentant une couche centrale intérieure (B) et une couche marginale extérieure (A), lesdites couches étant traitées au moins en partie différemment par trempe et revenu. L'invention vise à éviter les inconvénients des procédés connus de plaquage par laminage et de cémentation. A cet effet, le procédé selon l'invention comprend les étapes suivantes : combinaison des couches centrales et marginales, constituées d'alliages d'acier pouvant être traités différemment par trempe et revenu, selon un procédé de coulée, pour former un matériau composite à gradients d'alliage plats au niveau des surfaces limites ; façonnage du matériau composite de sorte qu'il présente les dimensions des pièces à faible épaisseur de paroi ; traitement des pièces par trempe et revenu. Les couches constituées d'alliages d'acier pouvant être traités différemment par trempe et revenu présentent des propriétés différentes.
EP01900129A 2000-03-13 2001-01-05 Procede pour produire des pieces en acier a faible epaisseur de paroi, et pieces ainsi produites Expired - Lifetime EP1263540B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10011758A DE10011758C2 (de) 2000-03-13 2000-03-13 Verfahren zur Herstellung von dünnwandigen Bauteilen aus Stahl und danach hergestellte Bauteile
DE10011758 2000-03-13
PCT/EP2001/000088 WO2001068293A1 (fr) 2000-03-13 2001-01-05 Procede pour produire des pieces en acier a faible epaisseur de paroi, et pieces ainsi produites

Publications (2)

Publication Number Publication Date
EP1263540A1 true EP1263540A1 (fr) 2002-12-11
EP1263540B1 EP1263540B1 (fr) 2004-06-30

Family

ID=7634263

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01900129A Expired - Lifetime EP1263540B1 (fr) 2000-03-13 2001-01-05 Procede pour produire des pieces en acier a faible epaisseur de paroi, et pieces ainsi produites

Country Status (13)

Country Link
US (1) US6953627B2 (fr)
EP (1) EP1263540B1 (fr)
AT (1) ATE270163T1 (fr)
AU (1) AU2372701A (fr)
BR (1) BR0109190B1 (fr)
CA (1) CA2404361C (fr)
CZ (1) CZ303019B6 (fr)
DE (2) DE10011758C2 (fr)
ES (1) ES2223770T3 (fr)
HU (1) HU225711B1 (fr)
MX (1) MXPA02008871A (fr)
SK (1) SK286356B6 (fr)
WO (1) WO2001068293A1 (fr)

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DE10202212B4 (de) * 2002-01-18 2004-02-26 Thyssenkrupp Stahl Ag Verfahren zum Erzeugen von aus metallischem Verbundwerkstoff bestehendem Band oder Blech
DE102005006606B3 (de) 2005-02-11 2006-03-16 Thyssenkrupp Steel Ag Verfahren zum Herstellen von walzplattiertem Warmband zur Weiterverarbeitung zu Kaltband und gewickeltes Coil aus solchem Warmband
DE102006019567B3 (de) * 2006-04-27 2007-11-08 Daimlerchrysler Ag Verfahren zum Herstellen umgeformter Stahlbauteile
DE102007022453B4 (de) * 2007-05-10 2020-02-06 Thyssenkrupp Steel Europe Ag Mehrschichtiges Verbundteil und aus diesem hergestelltes Bauteil
DE102008018204A1 (de) 2008-02-04 2009-08-06 Wickeder Westfalenstahl Gmbh Verbundwerkstoff und Verfahren zur Herstellung eines Verbundwerkstoffs
DE102008008113A1 (de) * 2008-02-08 2009-08-13 Schaeffler Kg Nichtmagnetisierbares Wälzlagerbauteil aus einem austenitischen Werkstoff und Verfahren zur Herstellung eines derartigen Wälzlagerbauteils
DE102008022709A1 (de) 2008-05-07 2009-11-19 Thyssenkrupp Steel Ag Verwendung eines metallischen Verbundwerkstoffs in einer Fahrzeugstruktur
EP2123447B1 (fr) * 2008-05-07 2018-12-26 ThyssenKrupp Steel Europe AG Matière première composite dotée d'un effet de protection balistique
US20100330389A1 (en) * 2009-06-25 2010-12-30 Ford Motor Company Skin pass for cladding thin metal sheets
DE102011106222A1 (de) * 2011-06-07 2012-12-13 Rwe Power Ag Dampferzeugerbauteil sowie Verfahren zur Herstellung eines Dampferzeugerbauteil
DE102013106570A1 (de) * 2013-06-24 2014-12-24 Thyssenkrupp Resource Technologies Gmbh Siebstange, Stangensieb und Verfahren zur Herstellung einer Siebstange
DE102013017798A1 (de) * 2013-10-25 2015-04-30 GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) Verbundstahlblech
DE102014116949A1 (de) * 2014-11-19 2016-05-19 Thyssenkrupp Ag Verfahren zur Herstellung eines Verbundwerkstoffes
EP3541563B1 (fr) 2016-11-18 2020-07-15 SMS Group GmbH Procédé et dispositif de fabrication d'un matériau complexe sous forme de bande continue
EP3914414A4 (fr) * 2019-01-23 2022-11-02 Verd Steel, Inc. Matériaux à gradient interne, outils et procédés

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FR1435936A (fr) * 1965-03-08 1966-04-22 Siderurgie Fse Inst Rech Procédé et dispositif de coulée continue de produits liquides
FR1495365A (fr) * 1965-10-01 1967-12-20
DE3346391C2 (de) * 1983-12-22 1985-11-21 Mannesmann AG, 4000 Düsseldorf Stranggießverfahren und Vorrichtung zum Herstellen von Mehrschichtwerkstoffen
DE4137118A1 (de) * 1991-11-12 1993-05-13 Schaeffler Waelzlager Kg Kaltband zur herstellung praezisions-tiefgezogener, einsatzgehaerteter bauteile, insbesondere waelzlager- und motorenteile
DE19631999A1 (de) * 1996-08-08 1998-02-12 Schloemann Siemag Ag Stranggießverfahren zur Herstellung von Verbundblechen sowie Stranggießanlage
DE19731124C1 (de) 1997-07-19 1999-01-21 Schloemann Siemag Ag Verfahren und Vorrichtung zur Erzeugung von beschichtetem Warm- und Kaltband
DE19850213C2 (de) * 1998-01-23 2001-08-30 Sms Demag Ag Gießverfahren für ein dünnes Metallband und zugehörige Gießvorrichtung
DE19815007C2 (de) * 1998-01-23 2000-07-06 Sms Demag Ag Gießverfahren für einen Metallstrang

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Also Published As

Publication number Publication date
EP1263540B1 (fr) 2004-06-30
DE10011758C2 (de) 2003-10-16
AU2372701A (en) 2001-09-24
ATE270163T1 (de) 2004-07-15
BR0109190B1 (pt) 2011-04-05
SK13272002A3 (sk) 2003-07-01
WO2001068293A1 (fr) 2001-09-20
DE50102738D1 (de) 2004-08-05
HUP0300086A2 (en) 2003-04-28
SK286356B6 (sk) 2008-08-05
CZ303019B6 (cs) 2012-02-29
BR0109190A (pt) 2003-05-27
CZ20023038A3 (cs) 2003-06-18
MXPA02008871A (es) 2004-10-14
DE10011758A1 (de) 2001-09-27
US6953627B2 (en) 2005-10-11
ES2223770T3 (es) 2005-03-01
US20030029530A1 (en) 2003-02-13
HU225711B1 (en) 2007-06-28
CA2404361A1 (fr) 2001-09-20
CA2404361C (fr) 2007-03-06

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