EP0933441A1 - Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen - Google Patents
Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen Download PDFInfo
- Publication number
- EP0933441A1 EP0933441A1 EP98810062A EP98810062A EP0933441A1 EP 0933441 A1 EP0933441 A1 EP 0933441A1 EP 98810062 A EP98810062 A EP 98810062A EP 98810062 A EP98810062 A EP 98810062A EP 0933441 A1 EP0933441 A1 EP 0933441A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- aluminum alloy
- annealing
- temperature range
- heterogenization
- 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
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000004512 die casting Methods 0.000 claims abstract description 9
- 230000005496 eutectics Effects 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 23
- 229910019018 Mg 2 Si Inorganic materials 0.000 claims description 17
- 238000004881 precipitation hardening Methods 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910019752 Mg2Si Inorganic materials 0.000 abstract 2
- 229910000676 Si alloy Inorganic materials 0.000 abstract 1
- 238000007792 addition Methods 0.000 abstract 1
- -1 aluminum-magnesium-silicon Chemical compound 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/05—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
Definitions
- the invention relates to a method for producing a component from an aluminum alloy hardenable by precipitation of Mg 2 Si with Si and / or Mg 2 Si eutectic by die casting.
- An application of the method and the use of a component produced by the method also lie within the scope of the invention.
- Crash behavior is an increasingly important aspect in vehicle construction. This applies to road traffic as well as for rail traffic.
- the die casting process enables high-volume, inexpensive production of thin-walled castings, such as those used as crash-relevant components in automotive engineering.
- Thin-walled parts place high demands on the castability.
- Aluminum alloys that can meet the requirements placed on the flow behavior or mold filling capacity are alloys with a Si and / or Mg 2 Si eutectic.
- the object of the invention is therefore to find a heat treatment with which can achieve a high elongation at break with a sufficient yield strength.
- the component after die casting to increase the ductility to the desired level in a temperature range from 320 to 410 ° C for a period of 320 to 10 min of heterogenization annealing is subjected.
- the preferred temperature range for heterogenization annealing lies between 350 and 380 ° C.
- the heterogenization annealing according to the invention is also an annealing in which the Supersaturation of the rapid solidification is reduced.
- This Si is therefore an annealing in a temperature range between about 350 and 380 ° C particularly advantageous.
- This heterogenization annealing ensures that the Al matrix becomes completely ductile. The crash behavior of the component is improved, because there are larger deformation paths during the ductile fracture.
- An essential aspect of the heat treatment method according to the invention lies in that to a high temperature anneal followed by water quenching dispensed with and the component can be manufactured without warpage.
- the component is cured before the heterogenization annealing to set the desired strength level, preferably in the temperature range of the precipitation hardening of Mg 2 Si in the falling part of the hardness curve. This pre-hardening brings a higher level of strength than in the cast state and thus creates a defined initial state.
- the temperatures and times used for this pre-hardening are in the over-hardening range and aim to produce a pre-segregation of Mg 2 Si precipitates which is as homogeneous as possible. It is thus achieved that the heterogenization annealing can take place with short diffusion paths, ie with shorter times, and consequently a structure which is very homogeneous with respect to the coarsened Mg 2 Si particles.
- Pre-curing in a temperature range of approximately 190 to 210 ° C. is preferred carried out.
- Rapid solidification of thin-walled castings leads to high Si supersaturation, which can be greater than the equilibrium solubility (> 1.60% Si).
- the heat treatment usually carried out according to the prior art at 490 to 530 ° C. with subsequent quenching treatment in water reduces the Si supersaturation to 0.7 to 0.8% Si, while at the same time creating the prerequisite for hardening the workpiece by precipitation hardening of Mg 2 Si to bring higher strength.
- the increase in ductility usually determined as an A5 elongation at break by tensile testing, can be explained by reducing the Si supersaturation and by simultaneously rounding (shaping) the Si or Mg 2 Si eutectic.
- the essential essence of the present invention lies in the over-hardening of the Al matrix to be controlled so that the desired yield point is reached. At the same time the diffusion of the Si, which takes place at a higher temperature, rapidly degrades the high Enable casting supersaturation of Si.
- the coarsening of the hardening phase Mg 2 Si is specifically controlled by placing the aforementioned pre-hardening in the temperature range of the precipitation hardening of Mg 2 Si in the falling part of the hardness curve of the heterogenization annealing, an optimal ratio of yield strength and elongation at break can be achieved.
- the demixing reaction of the Mg 2 Si is controlled in a controlled manner by coarsening the Mg 2 Si particles already present.
- An aluminum alloy used with preference contains essential alloy elements 2.0 to 11.0% by weight of Si and 0.10 to 5.5% by weight of Mg.
- the aluminum alloy can optionally be used still contain 0.1 to 0.5 wt .-% Fe and 0.1 to 1.2 wt .-% Mn.
- the aluminum alloy can add further elements individually max. 0.05 wt%, total Max. 0.2% by weight, as well as aluminum as the remainder along with production-related impurities contain.
- the heterogenization annealing expediently takes place continuously in one Continuous furnace, preferably in the passage through a heating zone with controllable heat transfer.
- the preferred field of application of the method according to the invention is in production thin-walled components with high absorption capacity for kinetic energy through plastic deformation, i.e. crash-relevant components, such as those used as safety parts in the Vehicle construction and in particular used in the automotive industry.
- Fig. 1 shows schematically the conditions for the pre-hardening in the temperature range of the precipitation hardening of Mg 2 Si in the falling part of the hardening curve for three different annealing temperatures.
- alloy Composition (% by weight) Si Fe Mn Mg Ti 1 2.5 0.1 0.68 5.4 0.14 2nd 10.4 0.1 0.57 0.11 0.04
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Of Metal (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Continuous Casting (AREA)
- Heat Treatment Of Articles (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Maintenance And Inspection Apparatuses For Elevators (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Forging (AREA)
Abstract
Description
- Das Werkstoffverhalten zeichnet sich durch einen duktilen Bruch aus und führt zu guten Crasheigenschaften des Bauteiles.
- Der Abbau der Si-Übersättigung erfolgt bei Temperaturen unterhalb von etwa 400° C.
- Es ist keine Abschreckbehandlung erforderlich, so dass Bauteile ohne Verzug hergestellt werden können. Das erfindungsgemässe Verfahren erlaubt auch eine Abkühlung von Bauteilen im Ofen.
- Die gegenläufigen Werkstoffkennwerte wie Rp0.2 und A5 sind gezielt einstellbar, bevorzugt im Bereich tiefer Streckgrenzen (Rp0.2:115 bis 140 MPa).
- Eine infolge kürzerer Diffusionswege mögliche kürzere Glühdauer bei der Heterogenisierungsglühung ermöglicht eine kontinuierliche Glühung in einem Durchlaufofen.
| Legierung | Zusammensetzung (Gew.-%) | ||||
| Si | Fe | Mn | Mg | Ti | |
| 1 | 2.5 | 0.1 | 0.68 | 5.4 | 0.14 |
| 2 | 10.4 | 0.1 | 0.57 | 0.11 | 0.04 |
Claims (10)
- Verfahren zur Herstellung eines Bauteiles aus einer durch Aussscheidung von Mg2Si aushärtbaren Aluminiumlegierung mit Si- und/oder Mg2Si-Eutektikum durch Druckgiessen,
dadurch gekennzeichnet, dass
das Bauteil nach dem Druckgiessen zur Erhöhung der Duktilität auf das gewünschte Mass in einem Temperaturbereich von 320 bis 410°C während einer Zeitdauer von 320 bis 10 min einer Heterogenisierungsglühung unterworfen wird. - Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Heterogenisierungsglühung in einem Temperaturbereich zwischen etwa 350°C und 380°C durchgeführt wird.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Bauteil vor der Heterogenisierungsglühung zur Einstellung des gewünschten Festigkeitsniveaus im Temperaturbereich der Ausscheidungshärtung von Mg2Si im abfallenden Teil der Härtekurve ausgehärtet wird.
- Verfahren nach Anspruch 3 , dadurch gekennzeichnet, dass die Aushärtung in einem Temperaturbereich von etwa 190 bis 210°C durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Aluminiumlegierung als wesentliche Legierungselemente 2.0 bis 11.0 Gew.-% Si und 0.10 bis 5.5 Gew.-% Mg enthält.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Aluminiumlegierung noch 0.1 bis 0.5 Gew.-% Fe und 0.2 bis 1.2 Gew.-% Mn enthält.
- Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass die Aluminiumlegierung weitere Elemente einzeln max. 0.05 Gew.-%, insgesamt max. 0.2 Gew.-%, sowie Aluminium als Rest nebst herstellungsbedingten Verunreinigungen enthält.
- Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Heterogenisierungsglühung kontinuierlich in einem Durchlaufofen durchgeführt wird.
- Anwendung des Verfahrens nach einem der Ansprüche 1 bis 8 zur Herstellung dünnwandiger Bauteile mit hohem Aufnahmevermögen für kinetische Energie durch plastische Verformung.
- Verwendung eines mit dem Verfahren nach einem der Ansprüche 1 bis 8 hergestellten Bauteiles als Sicherheitsteil im Fahrzeugbau.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES98810062T ES2181152T3 (es) | 1998-01-29 | 1998-01-29 | Procedimiento para fabricar una pieza de montaje a partir de una aleacion de aluminio mediante colada a presion. |
| SI9830301T SI0933441T1 (en) | 1998-01-29 | 1998-01-29 | Process for producing an aluminium alloy pressure die cast component |
| EP98810062A EP0933441B1 (de) | 1998-01-29 | 1998-01-29 | Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen |
| DK98810062T DK0933441T3 (da) | 1998-01-29 | 1998-01-29 | Fremgangsmåde til fremstilling af en konstruktionsdel af en aluminiumslegering ved trykstøbning |
| AT98810062T ATE226263T1 (de) | 1998-01-29 | 1998-01-29 | Verfahren zur herstellung eines bauteiles aus einer aluminiumlegierung durch druckgiessen |
| DE59805967T DE59805967D1 (de) | 1998-01-29 | 1998-01-29 | Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen |
| PT98810062T PT933441E (pt) | 1998-01-29 | 1998-01-29 | Processo para a fabricacao de um componente de uma liga de aluminio por moldacao por moldacao por injeccao sob pressao |
| BR9900621-9A BR9900621A (pt) | 1998-01-29 | 1999-01-28 | Processo para produção de um componente de uma liga de alumínio por fundição injetada |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98810062A EP0933441B1 (de) | 1998-01-29 | 1998-01-29 | Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0933441A1 true EP0933441A1 (de) | 1999-08-04 |
| EP0933441B1 EP0933441B1 (de) | 2002-10-16 |
Family
ID=8235907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98810062A Expired - Lifetime EP0933441B1 (de) | 1998-01-29 | 1998-01-29 | Verfahren zur Herstellung eines Bauteiles aus einer Aluminiumlegierung durch Druckgiessen |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0933441B1 (de) |
| AT (1) | ATE226263T1 (de) |
| BR (1) | BR9900621A (de) |
| DE (1) | DE59805967D1 (de) |
| DK (1) | DK0933441T3 (de) |
| ES (1) | ES2181152T3 (de) |
| PT (1) | PT933441E (de) |
| SI (1) | SI0933441T1 (de) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19916037C1 (de) * | 1999-04-09 | 2000-09-14 | Daimler Chrysler Ag | Verfahren zur Herstellung von leistungsführenden Getriebeteilen |
| DE102008056511A1 (de) * | 2008-11-08 | 2010-05-20 | Audi Ag | Verfahren zur Herstellung dünnwandiger Metallbauteile aus einer AI-SiMg-Legierung, insbesondere von Bauteilen eines Kraftfahrzeugs |
| GB2522716A (en) * | 2014-02-04 | 2015-08-05 | Jbm Internat Ltd | Method of manufacture |
| CN110387489A (zh) * | 2018-04-16 | 2019-10-29 | 现代自动车株式会社 | 用于压铸的铝合金及使用其制造铝合金铸件的方法 |
| CN112981190A (zh) * | 2019-12-16 | 2021-06-18 | 现代自动车株式会社 | 用于模铸的铝合金和使用该用于模铸的铝合金制造铸造铝合金的方法 |
| US12344032B2 (en) | 2020-01-14 | 2025-07-01 | Audi Ag | Method for producing a motor vehicle rim made of an aluminum alloy for a wheel of a motor vehicle and corresponding motor vehicle rim |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB390244A (en) * | 1931-11-14 | 1933-04-06 | Horace Campbell Hall | Improvements in the heat treatment of aluminium alloys |
| FR2323771A1 (fr) * | 1975-09-12 | 1977-04-08 | Snecma | Perfectionnements aux pieces moulees en alliage hypoeutectique aluminium-silicium au magnesium et aux traitements thermiques desdites pieces |
| US4419143A (en) * | 1981-11-16 | 1983-12-06 | Nippon Light Metal Company Limited | Method for manufacture of aluminum alloy casting |
| EP0743372A1 (de) * | 1995-05-19 | 1996-11-20 | Tenedora Nemak, S.A. de C.V. | Verfahren und Vorrichtung zur vereinfachten Herstellung einer wärmebehandlungsfähigen Aluminiumlegierung |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB613413A (en) * | 1942-03-21 | 1948-11-29 | Clay Patrick Bedford | Improvements in or relating to methods of shipbuilding |
-
1998
- 1998-01-29 EP EP98810062A patent/EP0933441B1/de not_active Expired - Lifetime
- 1998-01-29 DK DK98810062T patent/DK0933441T3/da active
- 1998-01-29 AT AT98810062T patent/ATE226263T1/de not_active IP Right Cessation
- 1998-01-29 DE DE59805967T patent/DE59805967D1/de not_active Expired - Fee Related
- 1998-01-29 SI SI9830301T patent/SI0933441T1/xx unknown
- 1998-01-29 ES ES98810062T patent/ES2181152T3/es not_active Expired - Lifetime
- 1998-01-29 PT PT98810062T patent/PT933441E/pt unknown
-
1999
- 1999-01-28 BR BR9900621-9A patent/BR9900621A/pt not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB390244A (en) * | 1931-11-14 | 1933-04-06 | Horace Campbell Hall | Improvements in the heat treatment of aluminium alloys |
| FR2323771A1 (fr) * | 1975-09-12 | 1977-04-08 | Snecma | Perfectionnements aux pieces moulees en alliage hypoeutectique aluminium-silicium au magnesium et aux traitements thermiques desdites pieces |
| US4419143A (en) * | 1981-11-16 | 1983-12-06 | Nippon Light Metal Company Limited | Method for manufacture of aluminum alloy casting |
| EP0743372A1 (de) * | 1995-05-19 | 1996-11-20 | Tenedora Nemak, S.A. de C.V. | Verfahren und Vorrichtung zur vereinfachten Herstellung einer wärmebehandlungsfähigen Aluminiumlegierung |
Non-Patent Citations (1)
| Title |
|---|
| SCHNEIDER W ET AL: "WAERMEBEHANDLUNG VON ALUMINIUM-GUSSLEGIERUNGEN FUER DAS VAKUUM- DRUCKGIESSEN", GIESSEREI, vol. 83, no. 1, 8 January 1996 (1996-01-08), pages 20 - 24, XP000581599 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19916037C1 (de) * | 1999-04-09 | 2000-09-14 | Daimler Chrysler Ag | Verfahren zur Herstellung von leistungsführenden Getriebeteilen |
| DE102008056511A1 (de) * | 2008-11-08 | 2010-05-20 | Audi Ag | Verfahren zur Herstellung dünnwandiger Metallbauteile aus einer AI-SiMg-Legierung, insbesondere von Bauteilen eines Kraftfahrzeugs |
| DE102008056511B4 (de) * | 2008-11-08 | 2011-01-20 | Audi Ag | Verfahren zur Herstellung dünnwandiger Metallbauteile aus einer AI-SiMg-Legierung, insbesondere von Bauteilen eines Kraftfahrzeugs |
| GB2522716A (en) * | 2014-02-04 | 2015-08-05 | Jbm Internat Ltd | Method of manufacture |
| GB2522716B (en) * | 2014-02-04 | 2016-09-14 | Jbm Int Ltd | Method of manufacture |
| CN110387489A (zh) * | 2018-04-16 | 2019-10-29 | 现代自动车株式会社 | 用于压铸的铝合金及使用其制造铝合金铸件的方法 |
| US11807918B2 (en) | 2018-04-16 | 2023-11-07 | Hyundai Motor Company | Aluminum alloy for die casting and method for manufacturing aluminum alloy casting using the same |
| DE102018218468B4 (de) | 2018-04-16 | 2025-04-10 | Hyundai Motor Company | Aluminiumlegierung für druckguss und verfahren zur herstellung von aluminiumlegierungsguss unter verwendung derselben |
| DE102018218468B8 (de) | 2018-04-16 | 2025-06-12 | Hyundai Motor Company | Aluminiumlegierung für druckguss und verfahren zur herstellung von aluminiumlegierungsguss unter verwendung derselben |
| CN112981190A (zh) * | 2019-12-16 | 2021-06-18 | 现代自动车株式会社 | 用于模铸的铝合金和使用该用于模铸的铝合金制造铸造铝合金的方法 |
| US12344032B2 (en) | 2020-01-14 | 2025-07-01 | Audi Ag | Method for producing a motor vehicle rim made of an aluminum alloy for a wheel of a motor vehicle and corresponding motor vehicle rim |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2181152T3 (es) | 2003-02-16 |
| PT933441E (pt) | 2003-02-28 |
| SI0933441T1 (en) | 2003-04-30 |
| ATE226263T1 (de) | 2002-11-15 |
| BR9900621A (pt) | 1999-12-14 |
| DE59805967D1 (de) | 2002-11-21 |
| DK0933441T3 (da) | 2003-02-17 |
| EP0933441B1 (de) | 2002-10-16 |
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Legal Events
| Date | Code | Title | Description |
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