EP1434667A1 - Verfahren und vorrichtung zum überlappschweissen zweier überzogener metallplatten mit einem strahl hoher energiedichte - Google Patents
Verfahren und vorrichtung zum überlappschweissen zweier überzogener metallplatten mit einem strahl hoher energiedichteInfo
- Publication number
- EP1434667A1 EP1434667A1 EP02800631A EP02800631A EP1434667A1 EP 1434667 A1 EP1434667 A1 EP 1434667A1 EP 02800631 A EP02800631 A EP 02800631A EP 02800631 A EP02800631 A EP 02800631A EP 1434667 A1 EP1434667 A1 EP 1434667A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molten metal
- sub
- sheets
- coated
- metal bath
- 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.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/0604—Shaping the laser beam, e.g. by masks or multi-focusing by a combination of beams
- B23K26/0608—Shaping the laser beam, e.g. by masks or multi-focusing by a combination of beams in the same heat affected zone [HAZ]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K15/00—Electron-beam welding or cutting
- B23K15/0046—Welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/067—Dividing the beam into multiple beams, e.g. multifocusing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
- B23K26/142—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor for the removal of by-products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
- B23K26/1435—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor involving specially adapted flow control means
- B23K26/1438—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor involving specially adapted flow control means for directional control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
- B23K26/1462—Nozzles; Features related to nozzles
- B23K26/1464—Supply to, or discharge from, nozzles of media, e.g. gas, powder, wire
- B23K26/147—Features outside the nozzle for feeding the fluid stream towards the workpiece
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/21—Bonding by welding
- B23K26/24—Seam welding
- B23K26/244—Overlap seam welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/34—Coated articles, e.g. plated or painted; Surface treated articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
- B23K2103/04—Steel or steel alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
Definitions
- the present invention relates to a method and a device for overlap welding using a high energy density beam of two sheets coated with a material having an evaporation temperature lower than the melting temperature of the constituent material. said sheets.
- coated sheets which comprise a central metal part of thickness, for example between 0.5 and 3 mm and coated on each of its faces with a layer of a protective material, such as for example more or less complex alloys of zinc or aluminum with a thickness of less than 25 ⁇ m.
- the invention applies to sheets coated with any material whose evaporation temperature is lower than the melting temperature of the base material constituting the sheets.
- the metal can reach punctually at the impact spot of the beam with high energy density, a temperature of a few thousand degrees C which is therefore much higher than the vaporization point of the material constituting the coating.
- the coating material located between the two sheets in the overlap zone is quickly in the vapor state and degassed violently. by the only possible path, that is to say by the molten metal bath created in said sheets by the high energy density beam.
- a layer of coating material with a thickness of 10 ⁇ m occupies a volume of a few cubic centimeters once vaporized and the pressure which prevails at the interface in the zone of overlap of the coated sheets can reach a few hundred bars.
- the weld bead has porosities which pose problems for sealing at the level of the overlap area of the coated sheets, or for the mechanical strength of the connections.
- Several solutions have been proposed to eliminate the drawbacks due to the uncontrolled release of vapors from the coating material leading to a poor quality weld bead.
- One of the known solutions consists in producing, before welding, a clearance between the two sheets to be welded to promote the evacuation of the vapors from the coating material.
- a known solution consists in using a beam with a high energy density and a heat source in combination.
- the heat source which precedes the high energy density beam brings about modifications which ensure the welding conditions with conventional parameters.
- the drawback of these hybrid techniques lies in an increase in the significant cost and a reduction in the flexibility of the process.
- microchannels at the interface of the two sheets on one of the coatings in order to facilitate the evacuation of the vaporized coating during welding.
- micro-channels can be formed by corrugations of the sheet or even by micromachining beforehand carried out by means of a laser beam.
- the object of the invention is to avoid the drawbacks mentioned above by proposing a method and a device for overlap welding using a high energy density beam of two coated sheets which make it possible to suppress the expulsions of coating material vapor and the formation of porosities at the weld, while allowing a clearance tolerance before welding to the right of the joint, and without excessive positioning constraint of these coated sheets.
- the subject of the invention is therefore a method of welding by overlapping using a high energy density beam of two sheets coated with a material having an evaporation temperature lower than the melting temperature of the material of the sheets, characterized in that:
- the high energy density beam is separated, on the one hand, into a first sub-beam crossing the two coated sheets in the overlap zone and forming in this zone a first bath of molten metal and, on the other hand , in a second non-traversing sub-beam and forming a second molten metal bath whose depth is less than the thickness of the upper coated sheet and overlapping at least part of the first molten metal bath to promote the evacuation of the coating material vapor,
- a jet of neutral gas at high speed of ejection is directed onto the second molten metal bath to form on the surface of said second molten metal bath a bowl accelerating the evacuation of the vapor from the coating material
- a continuous and sealed weld bead is formed along the overlap zone by displacement of the two sub-beams and the jet of neutral gas or of the two coated sheets.
- the focal point of the first sub-beam is located at a distance of more or less 2mm from the upper face of the upper coated sheet
- the focal point of the first sub-beam is located in the coated sheet greater than a depth between the upper face of this coated sheet and approximately one third of said sheet,
- the focal point of the second sub-beam is located above or below the upper face of the upper sheet
- the surface of the second molten metal bath is greater than the surface of the first molten metal bath
- the surface of the bowl is less than the surface of the second molten metal bath
- the subject of the invention is also a device for overlapping welding using a high energy density beam of two sheets coated with a material having an evaporation temperature lower than the melting temperature of the material of the sheets, characterized in that it comprises - means for separating the beam with a high energy density, on the one hand, into a first sub-beam passing through the two coated sheets in the overlap zone and forming in this zone a first bath of molten metal and, on the other hand, in a second non-traversing sub-beam and forming a second bath of molten metal whose depth is less than the thickness of the upper coated sheet and overlapping at least part of the first molten metal bath to promote the evacuation of vapor from the coating material,
- the means for separating the beam with a high energy density comprise a focusing mirror with two dioptres with different focal lengths, one of said dioptres being movable for adjusting the position of the optical axes of the two sub-beams relative to each other,
- the distance separating the optical axes of the two sub-beams is between 3 and 5mm
- the point of contact of the axis of the neutral gas jet on the upper face of the upper coated sheet corresponds substantially to the point of impact of the optical axis of the second sub-beam on said upper face
- the high energy density beam is a laser beam
- the distance between the free end of the nozzle and the point of contact of the neutral gas jet on the upper face of the upper coated sheet is between 30 and 50mm
- the neutral gas flow is between 12 and 35 l / min, - the nozzle forms with the upper face of the upper coated sheet an angle between 30 and 60 °.
- FIG. 1 is a schematic perspective view of two coated sheets intended to be welded by a welding device according to the invention
- FIG. 2 is a schematic cross-sectional view of the welding device according to the invention
- FIG. 3 is a schematic top view showing the molten metal baths formed on the surface of the sheets coated by the welding device according to the invention.
- the welding device shown diagrammatically in FIGS. 1 and 2 and generally designated by the reference 10 is intended for welding by partial or total covering of two sheets 1 and 2 coated with a material having an evaporation temperature below the melting temperature of the sheet material.
- the sheet 1 has a central metal part 1a and on each of its main faces a layer 1b and 1c of a coating of zinc or aluminum for example.
- the sheet 2 includes a central metal part 2a provided on each of its main faces with a layer 2b and 2c of a coating of more or less complex alloys of zinc or aluminum for example.
- the sheets 1 and 2 may have a coating layer on one side.
- each coated sheet 1 and 2 has a total thickness of between 0.5 and 3mm and each coating layer 1b, 1c and 2b, 2c has a thickness of less than 25pm.
- the sheets 1 and 2 are partially superimposed, as shown in FIG. 1, on an overlap zone A so as to bring into contact at least part of the coating 1 c of the sheet 1 with a part of the coating 2b of the sheet 2 and this over the entire length of said sheets 1 and 2.
- the clearance j between the sheets can be between 0 and 0.3mm.
- this coating material initially present in * the interface of the sheets 1 and 2 is fast in the state of steam during welding of sheets 1 and 2 by a high energy density beam and vapor violently degassed in the molten bath created by the high energy density beam so that the vapor expulsions are numerous which creates porosities in the weld bead and a poor quality bond.
- the welding device of the invention makes it possible to weld coated sheets using a beam with a high energy density 11, such as for example a laser beam of the C02 or YAG type, avoiding ejections from the molten metal bath. .
- the beam with a high energy density 11 which will subsequently be referred to as a laser beam is divided into a first through sub-beam 12 and into a second non-through beam 13, the two sub-beams 12 and 13 having a density of different power at the upper level of the sheet 1.
- the device 10 therefore comprises means for separating the laser beam 11 which consist, for example, of a bifocal head 15 equipped with a focusing mirror with two diopters, respectively 16 and 17, with different focal lengths.
- One of the diopters and in particular the diopter 17 is movable relative to the diopter 16 to position the optical axis X1 of the first sub-beam 12 relative to the optical axis X2 of the second sub-beam 13 on the upper face of the upper sheet 1.
- each sub-beam 12 and 13 is modulated as a function of the thickness of the two coated sheets 1 and 2 in the overlap zone A and also as a function of the thickness of the top coated sheet 1.
- the focal point P1 of the first sub-beam 12 is, in the embodiment shown in FIG. 2, located in the coated sheet 1 greater than a depth p1 substantially equal to one third of the thickness e1 of said sheet 1. According to a variant, the focal point P1 of the first sub-beam 12 can also be located, at a distance more or less 2mm ' from the upper face of the upper coated sheet 1.
- the first sub-beam 12 is intended to connect the coated sheets 1 and 2 by a continuous and watertight weld bead 5 (FIG. 3) and for this purpose, this first sub-beam 12 is a crossing beam which forms over the entire height of the coated sheets 1 and 2 a bath of molten metal 18 having ⁇ . in longitudinal section, the shape of a cone (Fig. 2) and, in cross section, an elliptical shape (Fig. 3).
- the second sub-beam 13 is a non-traversing beam and its focal point P2 is located above or below the upper face of the upper coated sheet 1.
- This second sub-beam 13 is determined to form a bath of molten metal 19 having transversely the shape of an asymmetrical ellipse (Fig. 3) and whose depth p2 is less than the thickness e1 of the upper coated sheet 1 (Fig 2).
- the surface of the second molten metal bath 19 is greater than the surface of the first molten metal bath 18 and this second molten metal bath 19 covers at least part of the first molten metal bath 18.
- the second molten metal bath 19 completely covers the first molten metal bath 18.
- the distance d1 separating the optical axes X1 and X2 from the two sub-beams 12 and 13 is between 3 and 5 mm.
- the device comprises a nozzle 20 for blowing on the second molten metal bath 19 of a hard jet 21 of neutral gas, as for example example of argon, helium, nitrogen or a mixture of these gases.
- neutral gas as for example example of argon, helium, nitrogen or a mixture of these gases.
- This jet 21 of neutral gas has a high ejection speed and forms on the surface of this second molten metal bath 19 a bowl 22 whose surface is less than the surface of the second molten metal bath 19 (Fig. 3).
- the point of contact of the axis X3 of the hard jet 21 of neutral gas on the upper face of the upper coated sheet 1 corresponds substantially to the point of impact of the optical axis X2 of the second sub-beam 13.
- the distance d2 separating the free end of the nozzle 20 and the contact point of the axis X3 of the hard jet 21 of neutral gas on the upper face of the upper coated sheet 1 is between 30 and 50mm.
- the neutral gas flow in the nozzle 20 is between 12 and 35 l / min and this nozzle 20 forms an angle between 30 and 60 °.
- the welding device 10 also comprises means, not shown, of displacement along the arrow f of the means for separating the laser beam 11 as well as the nozzle 20 along the overlap zone A to produce the continuous weld bead 5 and waterproof ensuring the assembly of the two coated sheets 1 and 2.
- the means for separating the laser beam 11 and the nozzle 20 are fixed and the two coated sheets 1 and 2 move according to arrow F.
- the welding speed is between 1 and 5m / min
- the jet 21 of neutral gas makes it possible to act on the geometry of the second molten metal bath 19 to locally reduce its thickness by reducing the depth of degassing, without disturbing the welding of the two coated sheets 1 and 2.
- This jet 21 also has for effect of exerting a back pressure on the molten metal bath.
- a neutral protective or covering gas is blown at the level of the welding zone.
- the method and the device according to the invention allow better degassing of the molten metal bath and suppress the vapor expulsions of the coating material. As a result, the porosities at the weld bead are considerably reduced so that the fatigue resistance of the welded assembly is improved.
- the positioning tolerance of the two coated sheets is very wide and the method can be used on complex trajectories and does not require modifications in terms of the design of the assembled parts, and therefore in the upstream and downstream operations in the operation of welding and adapts to any laser equipment without major modification of the installation.
- the method and the device according to the invention are more tolerant with respect to chemical compositions more loaded with gamma elements. (such as those of high strength steels) which require lower rates of cooling of the molten bath.
- first bath and “second bath” have been used in order to facilitate understanding. In reality, these molten metal baths have no physical separation and they form a single bath.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Laser Beam Processing (AREA)
- Welding Or Cutting Using Electron Beams (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0112990 | 2001-10-09 | ||
FR0112990A FR2830477B1 (fr) | 2001-10-09 | 2001-10-09 | Procede et dispositif de soudage par recouvrement a l'aide d'un faisceau a haute densite d'energie de deux toles revetues |
PCT/FR2002/003380 WO2003031111A1 (fr) | 2001-10-09 | 2002-10-03 | Procede et dispositif de soudage par recouvrement a l'aide d'un faisceau a haute densite d'energie de deux toles revetues |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1434667A1 true EP1434667A1 (de) | 2004-07-07 |
Family
ID=8868089
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02800631A Withdrawn EP1434667A1 (de) | 2001-10-09 | 2002-10-03 | Verfahren und vorrichtung zum überlappschweissen zweier überzogener metallplatten mit einem strahl hoher energiedichte |
Country Status (8)
Country | Link |
---|---|
US (1) | US6914213B2 (de) |
EP (1) | EP1434667A1 (de) |
JP (1) | JP4209326B2 (de) |
BR (1) | BR0213630A (de) |
CA (1) | CA2461994C (de) |
FR (1) | FR2830477B1 (de) |
MX (1) | MXPA04003230A (de) |
WO (1) | WO2003031111A1 (de) |
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DE10262053A1 (de) * | 2002-09-05 | 2004-08-12 | Daimlerchrysler Ag | Verfahren zur Laserbearbeitung beschichteter Bleche |
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JPWO2019189927A1 (ja) * | 2018-03-30 | 2021-04-08 | 古河電気工業株式会社 | 溶接方法および溶接装置 |
JP7081324B2 (ja) * | 2018-06-19 | 2022-06-07 | トヨタ自動車株式会社 | レーザ溶接方法および溶接構造体 |
CN112368104A (zh) * | 2018-06-22 | 2021-02-12 | 古河电气工业株式会社 | 焊接方法以及焊接装置 |
CN111215751B (zh) * | 2019-03-29 | 2022-06-28 | 宝山钢铁股份有限公司 | 一种带铝或者铝合金镀层的钢制差强焊接部件及其制造方法 |
CN113939379A (zh) * | 2019-06-06 | 2022-01-14 | 古河电气工业株式会社 | 焊接方法及焊接装置 |
US20210031297A1 (en) * | 2019-08-01 | 2021-02-04 | GM Global Technology Operations LLC | System and method for multi-task laser welding |
DE102020105505A1 (de) | 2020-03-02 | 2021-09-02 | Trumpf Laser- Und Systemtechnik Gmbh | Verfahren zum Laserschweißen zweier beschichteter Werkstücke |
CN112171059B (zh) * | 2020-09-24 | 2022-08-02 | 长春理工大学 | 一种汽车管件的接头增塑方法及装置 |
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JPH04231190A (ja) * | 1990-12-28 | 1992-08-20 | Fanuc Ltd | 亜鉛メッキ鋼板のレーザ溶接方法と装置 |
JP2836498B2 (ja) * | 1994-09-19 | 1998-12-14 | 住友金属工業株式会社 | レーザ溶接製管方法 |
JPH08108289A (ja) * | 1994-10-07 | 1996-04-30 | Sumitomo Electric Ind Ltd | レーザ加工用光学装置 |
US5603853A (en) * | 1995-02-28 | 1997-02-18 | The Twentyfirst Century Corporation | Method of high energy density radiation beam lap welding |
FR2755048A1 (fr) * | 1996-10-31 | 1998-04-30 | Renault Automation | Dispositif de soudage par faisceau laser |
EP0865863A1 (de) * | 1997-03-19 | 1998-09-23 | Alphatech-Industrie | Bifokussierung-Optik-Kopf |
US6087619A (en) * | 1997-05-13 | 2000-07-11 | Fraunhofer Usa Resource Center | Dual intensity multi-beam welding system |
WO2000066314A1 (en) * | 1999-04-30 | 2000-11-09 | Edison Welding Insitute | Coated material welding with multiple energy beams |
FR2798084B1 (fr) * | 1999-09-03 | 2001-10-19 | Renault | Procede et dispositif de soudage de toles |
JP4356236B2 (ja) * | 2000-12-07 | 2009-11-04 | 住友金属工業株式会社 | 表面コーティングされた金属のレーザ重ね溶接方法 |
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2001
- 2001-10-09 FR FR0112990A patent/FR2830477B1/fr not_active Expired - Fee Related
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2002
- 2002-10-03 CA CA002461994A patent/CA2461994C/fr not_active Expired - Fee Related
- 2002-10-03 EP EP02800631A patent/EP1434667A1/de not_active Withdrawn
- 2002-10-03 JP JP2003534127A patent/JP4209326B2/ja not_active Expired - Fee Related
- 2002-10-03 BR BR0213630-9A patent/BR0213630A/pt active Search and Examination
- 2002-10-03 MX MXPA04003230A patent/MXPA04003230A/es active IP Right Grant
- 2002-10-03 US US10/491,909 patent/US6914213B2/en not_active Expired - Fee Related
- 2002-10-03 WO PCT/FR2002/003380 patent/WO2003031111A1/fr active Application Filing
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CA2461994A1 (fr) | 2003-04-17 |
MXPA04003230A (es) | 2004-07-23 |
CA2461994C (fr) | 2008-12-09 |
FR2830477A1 (fr) | 2003-04-11 |
JP4209326B2 (ja) | 2009-01-14 |
BR0213630A (pt) | 2004-09-14 |
WO2003031111A1 (fr) | 2003-04-17 |
US20040200813A1 (en) | 2004-10-14 |
FR2830477B1 (fr) | 2004-02-06 |
US6914213B2 (en) | 2005-07-05 |
JP2005504641A (ja) | 2005-02-17 |
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