EP0971044A1 - Tole d'acier laminée à chaud et à froid revêtue et présentant une très haute résistance après traitement thermique - Google Patents
Tole d'acier laminée à chaud et à froid revêtue et présentant une très haute résistance après traitement thermique Download PDFInfo
- Publication number
- EP0971044A1 EP0971044A1 EP99401690A EP99401690A EP0971044A1 EP 0971044 A1 EP0971044 A1 EP 0971044A1 EP 99401690 A EP99401690 A EP 99401690A EP 99401690 A EP99401690 A EP 99401690A EP 0971044 A1 EP0971044 A1 EP 0971044A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sheet
- composition
- rolled
- aluminum
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/939—Molten or fused coating
-
- 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.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
Definitions
- the invention relates to a hot and cold rolled steel sheet, coated and having a very high resistance after heat treatment.
- the solutions proposed entailing a increased mechanical characteristics are exercised at the expense of formatting properties.
- the characteristics necessary for use are obtained by treatment thermal posterior or concomitant with the shaping.
- the sheets proposed are not delivered coated for problems of dress of the coating during heat treatment.
- the coating is therefore carried out on finished parts which requires careful cleaning of surfaces and parts hollow.
- the heat treatment must be carried out under an atmosphere controlled to avoid decarburization and oxidation of the metal of the sheet.
- the steel sheets for heat treatment have no pre-coating, which requires degreasing, pickling and coating post-treatments.
- pre-annealing and cooling before or after the operation coatings are only used for bring the sheet to a temperature close to that of the bath or to restore the mechanical properties of the sheet degraded during cold rolling.
- These thermal cycles are chosen based on the composition of the steel so that no allotropic transformation takes place during the thermal cycle, the objective being to obtain mechanical characteristics similar to those measured on steel sheets supplied uncoated.
- the object of the invention is to produce a hot-rolled steel sheet or cold of a desired thickness, coated, and with possibilities of extensive shaping and which, after heat treatment carried out on the part finished, allows to obtain a mechanical resistance higher than 1000 MPa, resistance to impact, fatigue, abrasion and significant wear, everything maintaining good corrosion resistance and good suitability to painting and collage. It must also be possible to carry out hot form with quenching in the tool, obtaining the same properties.
- the subject of the invention is a hot-rolled steel sheet, which can optionally be then cold-rolled, coated and heat treated, the steel of the sheet having the following weight composition: 0.15% ⁇ carbon ⁇ 0.5% 0.5% ⁇ manganese ⁇ 3% 0.1% ⁇ silicon ⁇ 0.5% 0.01% ⁇ chromium ⁇ 1%, titanium ⁇ 0.2%, aluminum ⁇ 0.1%, phosphorus ⁇ 0.1%, sulfur ⁇ 0.05%, 0.0005% ⁇ boron ⁇ 0.08%, the balance being iron and impurities inherent in the production.
- the invention also relates to a method of producing a part to from the coated sheet in which after shaping and before treatment thermal, the coating of the part is subjected to an elevation of temperature at a speed greater than 5 ° C / second which may exceed 600 ° C / second.
- the invention also relates to the use of hot-rolled steel sheet and can then be cold rolled and coated, for structural parts and / or anti-intrusion or underbody for land motor vehicle like for example a bumper beam, a door reinforcement, an arm wheel ...
- the sheet according to the invention which results, due to its preparation, from a hot rolling train, can optionally be cold rolled in depending on the desired final thickness. It is then coated with a coating based on aluminum, for example by dipping in a bath further comprising, 8% to 11% silicon, 2% to 4% iron, the sheet having a high mechanical resistance after heat treatment and high resistance to corrosion, as well as good paint and bonding ability.
- the coating has the particular function of protecting the sheet from base against hot and cold corrosion.
- Characteristics mechanical in the delivery state of the sheet according to the invention allow a wide variety of shaping, in particular deep drawing.
- the heat treatment applied during or after a hot forming process the shaping allows to obtain high mechanical characteristics can exceed 1500 MPa for mechanical resistance and 1200 MPa for the elastic limit.
- the final mechanical characteristics are adaptable and depend on the carbon content of the steel and the heat treatment.
- the coating forms a layer having a large resistance to abrasion, wear, fatigue, shock as well as good resistance to corrosion and good paint and bonding ability.
- steel the weight composition of which is as follows: 0.15% ⁇ carbon ⁇ 0.5% 0.5% ⁇ manganese ⁇ 3% 0.1% ⁇ silicon ⁇ 0.5% 0.01% ⁇ chromium ⁇ 1%, titanium ⁇ 0.2%, aluminum ⁇ 0.1%, phosphorus ⁇ 0.1%, sulfur ⁇ 0.05%, 0.0005% ⁇ boron ⁇ 0.08%, the balance being iron and impurities inherent in the preparation is produced in the form of a hot-rolled and possibly cold-rolled sheet to obtain the desired thickness.
- the steel sheet is then coated by dipping, after pickling, in an aluminum bath containing either 8% to 11% of silicon and 2% to 4% of iron, or 2% to 4% of iron without silicon, or alternatively, in an aluminum bath preferably containing from 9% to 10% of silicon and 2% to 3.5% of iron.
- a coating of the sheet metal by dipping in a metal bath containing an aluminum alloy comprising a proportion of approximately 90% aluminum, the coating layer has a first layer of alloy in contact with the steel surface. This layer, directly in contact with the surface of the sheet is strongly alloyed with iron.
- a second coating layer, above the first, contains approximately 90% aluminum and may contain, depending on the composition of the bath, silicon and a little iron.
- the first layer of alloy can crack when the sheet is put in form for the manufacture of parts.
- the coating is subjected to a temperature rise at a speed higher than 5 ° C / second which can exceed 600 ° C / second. This climb in temperature allows a rapid reflow of the aluminum which clogs the cracks caused by the shaping operation of the part.
- Another advantage of the invention lies in the fact that the diffusion iron in the coating will be initiated at high temperature. So we will have a better cohesion between coating and sheet steel.
- the heat treatment can be carried out locally, in heavily deformed areas.
- the steel sheet according to the invention containing 0.21% carbon; 1.14% manganese; 0.020% phosphorus; 0.0038% sulfur; 0.25% silicon; 0.040% aluminum; 0.009% copper; 0.020% nickel; 0.18% chromium; 0.0040% nitrogen; 0.032% titanium; 0.003% boron; 0.0050% calcium is coated with a base layer aluminum about 20 ⁇ m thick.
- the sheet in the state of delivery in reel or in sheets, whose thickness can be between 0.25 mm and 15 mm has good shaping properties as well as good corrosion resistance as well a good aptitude for painting and collage.
- Sheet metal, a coated steel product has significant resistance corrosion at delivery, during shaping and processing as well as during the use of the finished part. After treatment thermal, we obtain a significant mechanical resistance which can exceed 1500 MPa.
- the presence of the coating during the heat treatment of the parts makes it possible to avoid any decarburization of the base metal as well as any oxidation. This is an undeniable advantage, especially in the case of shaping hot. In addition, heating the treated room does not require an oven having a controlled atmosphere to avoid decarburization.
- the heat treatment of the metal of the sheet metal consists of heating a temperature between Ac1, temperature at the start of transformation austenitic, for example, 750 ° C, and 1200 ° C, in an oven, for a time which is a function of the temperature to be reached and the thickness of the sheet of the room.
- the composition is optimized to limit the magnification of the grains during heat treatment. If the target structure is completely martensitic, the holding temperature must be higher than Ac3, for example 840 ° C, temperature at the end of austenitic formation. Maintaining the temperature must be followed by cooling adapted to the final target structure.
- the cooling rate must be higher than the critical speed quench which is 27 ° C / s for austenitization at 900 ° C for 5 min, the sheet having a thickness of approximately 1 mm.
- ferrito-bainitic, or ferrito-martensitics by heating to a temperature between Ac1, for example, 750 ° C and Ac3, for example, 840 ° C followed by suitable cooling.
- a temperature between Ac1 ° C and Ac3 for example, 840 ° C followed by suitable cooling.
- one or more of these phases are present in varying proportions.
- the structure is mainly composed of martensite.
- Chromium, manganese, boron and carbon are added in the composition of the steel according to the invention, for their influence on the hardenability.
- carbon achieves high mechanical characteristics thanks to its effect on the hardness of martensite.
- Aluminum is introduced into the composition in order to trap oxygen and protect the effectiveness of boron.
- Titanium with a ratio of the content to the nitrogen content must be greater than 3.42 is introduced to avoid the combination of boron with nitrogen, nitrogen being combined with titanium.
- Alloy elements, Mn, Cr, B, allow quenchability authorizing quenching in stamping tools or the use of mild harshness limiting deformation of parts during processing thermal.
- the composition according to the invention is optimized from the point of view of weldability.
- the sheet steel can undergo a sulphide globulation treatment made with calcium which has the effect of improving resistance to fatigue sheet metal.
- Steel is particularly suitable for making pieces of structure and anti intrusion.
- the proposed coating avoids different operations of surface preparation as for steel sheets for treatment thermal without coating.
- the modulation of the heat treatment parameters allows achieve, with a given composition, different levels of resistance in hot sheet and cold sheet depending on the thickness targeted.
- the coating based for example of aluminum transforms into a layer alloyed with iron and comprising different phases depending on the heat treatment and presenting a high hardness that can exceed 600HV100g.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Coating With Molten Metal (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
Abstract
Description
0,15% < carbone < 0,5%
0,5% < manganèse < 3%
0,1% < silicium < 0,5%
0,01% < chrome < 1%,
titane < 0,2%,
aluminium < 0,1%,
phosphore < 0,1%,
soufre < 0,05%,
0,0005% < bore < 0,08%, le solde étant du fer et des impuretés inhérentes à l'élaboration.
- la composition pondérale de la tôle est de préférence la suivante:
0,20% < carbone < 0,5%
0,8% < manganèse < 1,5%
0,1% < silicium < 0,35%
0,01% < chrome < 1%,
titane < 0,1%,
aluminium < 0,1%,
phosphore < 0,05%,
soufre < 0,03%,
0,0005% < bore < 0,01%, le solde étant du fer et des impuretés inhérentes à l'élaboration. - dans la composition pondérale de la tôle, la teneur en titane par rapport à la teneur en azote est supérieure à 3,42, le bore ne pouvant plus être combiné à l'azote .
- le bain métallique pour le revêtement comprend dans sa composition pondérale de base, de 9% à 10% de silicium, de 2% à 3,5% de fer, le solde étant de l'aluminium.
- le bain métallique pour le revêtement comprend dans sa composition pondérale de base, de 2% à 4% de fer, le solde étant de l'aluminium.
- le traitement thermique consiste à réchauffer le revêtement et la pièce à une température supérieure à 750°C.
0,15% < carbone < 0,5%
0,5% < manganèse < 3%
0,1% < silicium < 0,5%
0,01% < chrome < 1%,
titane < 0,2%,
aluminium < 0,1%,
phosphore < 0,1%,
soufre < 0,05%,
0,0005% < bore < 0,08%, le solde étant du fer et des impuretés inhérentes à l'élaboration est élaboré sous la forme d'une tôle laminée à chaud et éventuellement laminée à froid pour obtenir l'épaisseur désirée. La tôle d'acier est ensuite revêtue au trempé, après décapage, dans un bain d'aluminium contenant, soit de 8% à 11% de silicium et 2% à 4% de fer, soit de 2% à 4% de fer sans silicium, ou encore, dans un bain d'aluminium contenant de préférence de 9% à 10% de silicium et 2% à 3,5% de fer.
| Traitement thermique | Rm (Mpa) |
| 850°C/5 mn | 1695 |
| 900°C/5 mn | 1675 |
| 950°C/5 mn | 1665 |
Claims (8)
- Tôle d'acier laminée à chaud, pouvant être éventuellement, ensuite, laminée à froid, revêtue, et traitée thermiquement, l'acier de la tôle ayant la composition pondérale suivante :
0,15% < carbone < 0,5%
0,5% < manganèse < 3%
0,1% < silicium < 0,5%
0,01% < chrome < 1%,
titane < 0,2%,
aluminium < 0,1%,
phosphore < 0,1%,
soufre < 0,05%,
0,0005% < bore < 0,08%, le solde étant du fer et des impuretés inhérentes à l'élaboration. - Tôle revêtue selon la revendication 1, caractérisée en ce que la composition pondérale de la tôle est de préférence la suivante:
0,20% < carbone < 0,5%
0,8% < manganèse < 1,5%
0,1% < silicium < 0,35%
0,01% < chrome < 1%,
titane < 0,1%,
aluminium < 0,1%,
phosphore < 0,05%,
soufre < 0,03%,
0,0005% < bore < 0,01%, le solde étant du fer et des impuretés inhérentes à l'élaboration. - Tôle revêtue selon la revendication 1, caractérisée en ce que, dans la composition pondérale de la tôle, la teneur en titane par rapport à la teneur en azote est supérieure à 3,42, le bore ne pouvant plus être combiné à l'azote .
- Tôle revêtue selon la revendication 1, caractérisée en ce que le bain métallique pour le revêtement comprend dans sa composition pondérale de base, de 9% à 10% de silicium, de 2% à 3,5% de fer, le solde étant de l'aluminium.
- Tôle selon la revendication 1, caractérisée en ce que le bain métallique pour le revêtement comprend dans sa composition pondérale de base, de 2% à 4% de fer, le solde étant de l'aluminium.
- Procédé de réalisation d'une pièce à partir de la tôle revêtue selon les revendications 1 à 5, caractérisé en ce que après mise en forme et avant traitement thermique, le revêtement de la pièce est soumis à une élévation de température à une vitesse supérieure à 5°C/ seconde pouvant dépasser 600°C/seconde.
- Procédé selon la revendication 6 caractérisé en ce que le traitement thermique consiste à réchauffer le revêtement et la pièce à une température supérieure à 750°C.
- Utilisation de la tôle d'acier laminée à chaud et pouvant être ensuite laminée à froid et revêtue, selon les revendications 1 à 5, pour des pièces de structure et /ou anti-intrusion ou de soubassement pour véhicule terrestre à moteur.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9808793A FR2780984B1 (fr) | 1998-07-09 | 1998-07-09 | Tole d'acier laminee a chaud et a froid revetue et comportant une tres haute resistance apres traitement thermique |
| FR9808793 | 1998-07-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0971044A1 true EP0971044A1 (fr) | 2000-01-12 |
| EP0971044B1 EP0971044B1 (fr) | 2003-05-14 |
Family
ID=9528455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99401690A Expired - Lifetime EP0971044B1 (fr) | 1998-07-09 | 1999-07-07 | Tole d'acier laminée à chaud et à froid revêtue et présentant une très haute résistance après traitement thermique |
Country Status (11)
| Country | Link |
|---|---|
| US (3) | US6296805B1 (fr) |
| EP (1) | EP0971044B1 (fr) |
| JP (1) | JP3931251B2 (fr) |
| AT (1) | ATE240419T1 (fr) |
| BR (1) | BR9902712A (fr) |
| CA (1) | CA2276911C (fr) |
| DE (1) | DE69907816T2 (fr) |
| DK (1) | DK0971044T3 (fr) |
| ES (1) | ES2196740T3 (fr) |
| FR (1) | FR2780984B1 (fr) |
| PT (1) | PT971044E (fr) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076798A1 (fr) * | 2001-03-21 | 2002-10-03 | Robert Bosch Gmbh | Raclette d'essuie-glace pour le nettoyage de vitres, notamment de vehicules automobiles, et son procede de production |
| WO2007118939A1 (fr) * | 2006-04-19 | 2007-10-25 | Arcelor France | Procede de fabrication d'une piece soudee a tres hautes caracteristiques mecaniques a partir d'une tole laminee et revetue |
| EP1939308A1 (fr) * | 2006-11-14 | 2008-07-02 | ThyssenKrupp Steel AG | Procédé de fabrication d'un composant par trempe de compression thermique et composant haute résistance présentant une amélioration de l'allongement de rupture |
| EP1966404A4 (fr) * | 2005-12-26 | 2009-01-14 | Posco | Feuille d'acier au carbone supérieure en termes d'aptitude au formage et procédé de fabrication de celle-ci |
| DE102007061489A1 (de) | 2007-12-20 | 2009-06-25 | Voestalpine Stahl Gmbh | Verfahren zum Herstellen von gehärteten Bauteilen aus härtbarem Stahl und härtbares Stahlband hierfür |
| WO2009090555A1 (fr) * | 2008-01-15 | 2009-07-23 | Arcelormittal France | Procédé de fabrication de produits estampés et produits estampés préparés à l'aide de celui-ci |
| WO2009135776A1 (fr) * | 2008-05-06 | 2009-11-12 | Thyssenkrupp Steel Ag | Procédé de production d'une pièce moulée en acier à structure à prédominance ferritique-bainitique |
| EP1672088B1 (fr) * | 2000-04-07 | 2010-08-18 | ArcelorMittal France | 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 |
| WO2011101158A1 (fr) | 2010-02-19 | 2011-08-25 | Tata Steel Nederland Technology Bv | Bande, feuille ou ébauche adaptée au thermoformage et procédé de production associé |
| WO2011104443A1 (fr) | 2010-02-24 | 2011-09-01 | Arcelormittal Investigación Y Desarrollo Sl | Procédé de fabrication d'une pièce a partir d'une tôle revêtue d'aluminium ou d'alliage d'aluminium |
| DE202011107125U1 (de) | 2011-04-13 | 2011-11-30 | Tata Steel Ijmuiden Bv | Warmformbares Band, Blech oder Zuschnitt und warmgeformtes Produkt |
| WO2012153008A1 (fr) | 2011-05-12 | 2012-11-15 | Arcelormittal Investigación Y Desarrollo Sl | Procede de fabrication d'acier martensitique a tres haute resistance et tole ou piece ainsi obtenue |
| WO2012167930A1 (fr) | 2011-06-07 | 2012-12-13 | Tata Steel Ijmuiden B.V. | Bande, feuille ou ébauche thermoformable, procédé pour sa production, procédé pour thermoformer un produit et produit thermoformé |
| WO2013014481A1 (fr) | 2011-07-26 | 2013-01-31 | Arcelormittal Investigación Y Desarrollo Sl | Pièce d'acier soudée préalablement mise en forme à chaud à très haute résistance mécanique et procédé de fabrication |
| RU2490133C2 (ru) * | 2009-02-02 | 2013-08-20 | Арселормитталь Инвестигасион И Десаррольо С.Л. | Способ изготовления штампованных деталей с покрытием и детали, полученные таким способом |
| WO2014009004A1 (fr) | 2012-07-10 | 2014-01-16 | Tata Steel Nederland Technology B.V. | Bande, tôle ou flan d'acier thermoformable revêtu(e), et procédé de fabrication de celle/celui-ci |
| WO2015162478A1 (fr) | 2014-04-25 | 2015-10-29 | Arcelormittal | Procede et dispositif de preparation de toles d'acier aluminiees destinees a etre soudees puis durcies sous presse; flan soude correspondant |
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| DE102016222993A1 (de) | 2016-11-22 | 2018-05-24 | Volkswagen Aktiengesellschaft | Verfahren zur Herstellung eines beschichteten Stahlbauteils |
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| KR100646619B1 (ko) | 2001-10-23 | 2006-11-23 | 수미도모 메탈 인더스트리즈, 리미티드 | 열간 프레스 방법, 이를 위한 도금 강철재 및 이의 제조방법 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP3931251B2 (ja) | 2007-06-13 |
| BR9902712A (pt) | 2000-03-08 |
| CA2276911C (fr) | 2009-05-05 |
| DE69907816T2 (de) | 2004-03-11 |
| US6296805B1 (en) | 2001-10-02 |
| ES2196740T3 (es) | 2003-12-16 |
| PT971044E (pt) | 2003-08-29 |
| DK0971044T3 (da) | 2003-08-11 |
| EP0971044B1 (fr) | 2003-05-14 |
| USRE44153E1 (en) | 2013-04-16 |
| ATE240419T1 (de) | 2003-05-15 |
| CA2276911A1 (fr) | 2000-01-09 |
| JP2000038640A (ja) | 2000-02-08 |
| DE69907816D1 (de) | 2003-06-18 |
| USRE44940E1 (en) | 2014-06-10 |
| FR2780984A1 (fr) | 2000-01-14 |
| FR2780984B1 (fr) | 2001-06-22 |
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