EP1418247B1 - Magnesium alloy - Google Patents
Magnesium alloy Download PDFInfo
- Publication number
- EP1418247B1 EP1418247B1 EP20030022658 EP03022658A EP1418247B1 EP 1418247 B1 EP1418247 B1 EP 1418247B1 EP 20030022658 EP20030022658 EP 20030022658 EP 03022658 A EP03022658 A EP 03022658A EP 1418247 B1 EP1418247 B1 EP 1418247B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- content
- alloy according
- strontium
- barium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 238000004512 die casting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002591 computed tomography Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007528 sand casting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Definitions
- the invention relates to a magnesium alloy.
- Magnesium alloys containing aluminum are used to cast a wide variety of components.
- calcium, strontium and rare earth elements are added as further alloy constituents.
- the casting properties of the known alloy are still unsatisfactory, i. it has too high a tendency to crack and a high volume deficit. Also, the creep and hot tensile strength of the known alloy leaves much to be desired.
- the object of the invention is to provide a magnesium alloy which has been improved with respect to its creeping, hot-drawing and pouring properties.
- the aluminum content of the alloy according to the invention is preferably 5-8, in particular 5.6-6.4% by weight, the strontium content preferably 1.5-3.5, in particular 2.0-2.6% by weight, and the barium content is preferably 0.1-1.5, especially 0.2-1% by weight.
- Al increases the strength and hardness of Mg. While with an aluminum content of less than 4%, the high viscosity deteriorates the castability of the alloy, with phases containing more than 9% aluminum, which leads to embrittlement.
- the combination of the alloying elements aluminum, strontium and barium in the o.
- Quantities leads to a significant improvement in the creep, hot tensile and casting properties of the alloy. With a strontium content of less than 0.5% and a barium content of less than 0.03%, however, no noticeable increase in these properties is observed. In contrast, a strontium content of more than 4% and a barium content of more than 2.5% leads to a significant deterioration in the castability.
- low Fe, Cu and Ni contents in magnesium alloys are usually included as unavoidable impurities.
- the Fe content is at most 0.004%, the Cu content at a maximum of 0.01% and the Ni content at a maximum of 0.001%.
- the alloy according to the invention may contain 0-0.3% zinc and 0-0.60% manganese. Zinc in combination with A1 increases strength.
- the alloy can contain a maximum of 0.05% silicon.
- the alloy according to the invention thus preferably has the following composition in% by weight: al 4 - 9 Sr 0,5 - 4 Ba 0.03 - 2.5 Zn Max. 0.30 Mn Max. 0.60 Si Max. 0.05 Fe > 0.004 Cu > 0.01 Ni > 0.001 Remaining Mg and production-related impurities.
- the alloy according to the invention has a high creep strength and hot tensile strength. In addition, it has excellent casting properties. For example, computer tomography revealed a very low volume deficit in the cast components. It also has a significantly reduced tendency to crack.
- the alloy of the invention is particularly suitable for die casting. However, it can also be used in other casting processes, in particular also in sand casting or chill casting.
- the alloy according to the invention is suitable above all for motor vehicle components, in particular in the drive train, for example for the cylinder crankcase of a liquid-cooled internal combustion engine or for the transmission housing.
- a commercially available AM60 alloy (4.6-5.4% A1, 0.26-0.50% Mn, 0.20% maximum Zn, 0.05% Si max, 0.008% Cu, max. 0.001% Ni, max 0.004% Fe, balance Mg) were with a Ba / Al master alloy (50% Ba; 50% Al) and with strontium metal (99.99%) alloyed the remaining alloying constituents so as to obtain an alloy having the following composition: al 5.6-6.4% by weight Sr 2.1-2.5% by weight Ba 0.2-1.0% by weight Mn 0.3-0.4% by weight Rest of magnesium
- tensile specimens according to DIN 50125-B6x30 were produced from the alloy.
- the hot tensile strength was determined at the test temperature 100 ° C and 150 ° C, each with three samples. At 100 ° C, the tensile strength is 290 MPa, at 150 ° C 163 MPa, the 0.2% elongation limit is 131 MPa at 100 ° C and 108 Mpa at 150 ° C.
- the commercial magnesium alloy AM60 with 4.6 - 5.4% Al and the other ingredients specified in the specified amounts has a tensile strength of 200 MPa at 100 ° C and 150 MPa at 150 ° C and a 0.2% elongation limit at 100 ° C of 120 MPa and at 150 ° C of 70 MPa.
- the creep strain measurement was carried out according to DIN EN10291 on creep tests without heat treatment with a diameter of 6 mm and a parallel measuring length of 25 mm.
- the stress level is 50 MPa
- the test temperature is 150 ° C.
- a creep strain of 0.14% was measured.
Description
Die Erfindung bezieht sich auf eine Magnesiumlegierung. Magnesiumlegierungen, die Aluminium enthalten, werden zum Gießen unterschiedlichster Bauteile verwendet. Um ihre Kriech- und Warmzugfestigkeit zu erhöhen, werden als weitere Legierungsbestandteile Calcium, Strontium und Selten-Erdelemente zugesetzt.The invention relates to a magnesium alloy. Magnesium alloys containing aluminum are used to cast a wide variety of components. In order to increase their creep and hot tensile strength, calcium, strontium and rare earth elements are added as further alloy constituents.
So ist aus
Allerdings sind die Gusseigenschaften der bekannten Legierung noch nicht zufriedenstellend, d.h. sie besitzt eine zu hohe Warmrissneigung und ein zu hohes Volumendefizit. Auch lässt die Kriech- und Warmzugfestigkeit der bekannten Legierung noch zu wünschen übrig.However, the casting properties of the known alloy are still unsatisfactory, i. it has too high a tendency to crack and a high volume deficit. Also, the creep and hot tensile strength of the known alloy leaves much to be desired.
Aufgabe der Erfindung ist es, eine hinsichtlich ihrer Kriech-, Warmzug- und Gießeigenschaften verbesserte Magnesiumlegierung bereitzustellen.The object of the invention is to provide a magnesium alloy which has been improved with respect to its creeping, hot-drawing and pouring properties.
Dies wird erfindungsgemäß durch die Legierung nach dem Anspruch 1 erreicht. Der Aluminiumgehalt der erfindungsgemäßen Legierung beträgt vorzugsweise 5 - 8, insbesondere 5,6 - 6,4 Gewichts-%, der Strontiumgehalt vorzugsweise 1,5 - 3,5, insbesondere 2,0 - 2,6 Gewichts-%, und der Bariumgehalt vorzugsweise 0,1 - 1,5, insbesondere 0,2 - 1 Gewichts-%.This is inventively achieved by the alloy according to claim 1. The aluminum content of the alloy according to the invention is preferably 5-8, in particular 5.6-6.4% by weight, the strontium content preferably 1.5-3.5, in particular 2.0-2.6% by weight, and the barium content is preferably 0.1-1.5, especially 0.2-1% by weight.
Al erhöht die Festigkeit und Härte von Mg. Während bei einem Aluminiumgehalt von weniger als 4 % sich durch die hohe Viskosität die Gießbarkeit der Legierung verschlechtert, treten bei einem Aluminiumgehalt von über 9 % Phasen auf, die zu einer Versprödung führen.Al increases the strength and hardness of Mg. While with an aluminum content of less than 4%, the high viscosity deteriorates the castability of the alloy, with phases containing more than 9% aluminum, which leads to embrittlement.
Die Kombination der Legierungselemente Aluminium, Strontium und Barium in den o. a. Mengen führt zu einer deutlichen Verbesserung der Kriech-, Warmzug- und Gießeigenschaften der Legierung. Bei einem Strontiumgehalt von weniger als 0,5 % und einem Bariumgehalt von weniger als 0,03 % ist jedoch keine spürbare Erhöhung dieser Eigenschaften mehr festzustellen. Demgegenüber führt ein Strontiumgehalt von mehr als 4 % und ein Bariumgehalt von mehr als 2,5 % zu einer deutlichen Verschlechterung der Gießbarkeit.The combination of the alloying elements aluminum, strontium and barium in the o. A. Quantities leads to a significant improvement in the creep, hot tensile and casting properties of the alloy. With a strontium content of less than 0.5% and a barium content of less than 0.03%, however, no noticeable increase in these properties is observed. In contrast, a strontium content of more than 4% and a barium content of more than 2.5% leads to a significant deterioration in the castability.
Eisen, Kupfer und Nickel führen zu einer deutlichen Herabsetzung der Korrosionsfestigkeit. Andererseits sind geringe Fe-, Cu- und Ni-Gehalte in Magnesiumlegierungen meist als unvermeidbare Verunreinigungen enthalten. Vorzugsweise liegt der Fe-Gehalt jedoch bei maximal 0,004 %, der Cu-Gehalt bei maximal 0,01 % und der Ni-Gehalt bei maximal 0,001 %.Iron, copper and nickel lead to a significant reduction in corrosion resistance. On the other hand, low Fe, Cu and Ni contents in magnesium alloys are usually included as unavoidable impurities. Preferably, however, the Fe content is at most 0.004%, the Cu content at a maximum of 0.01% and the Ni content at a maximum of 0.001%.
Zudem kann die erfindungsgemäße Legierung 0 - 0,3 % Zink und 0 - 0,60 % Mangan enthalten. Zink führt in Kombination mit A1 zur Erhöhung der Festigkeit. Zudem kann die Legierung maximal 0,05 % Silizium enthalten.In addition, the alloy according to the invention may contain 0-0.3% zinc and 0-0.60% manganese. Zinc in combination with A1 increases strength. In addition, the alloy can contain a maximum of 0.05% silicon.
Vorzugsweise weist die erfindungsgemäße Legierung also folgende Zusammensetzung in Gewichts-% auf:
Die erfindungsgemäße Legierung weist eine hohe Kriechfestigkeit und Warmzugfestigkeit auf. Zudem besitzt sie hervorragende Gießeigenschaften. So wurde mit Computertomographie ein sehr geringes Volumendefizit in den gegossenen Bauteilen festgestellt. Auch besitzt sie eine deutliche reduzierte Warmrissneigung.The alloy according to the invention has a high creep strength and hot tensile strength. In addition, it has excellent casting properties. For example, computer tomography revealed a very low volume deficit in the cast components. It also has a significantly reduced tendency to crack.
Die erfindungsgemäße Legierung ist insbesondere für den Druckguss geeignet. Sie kann jedoch auch in anderen Gießverfahren eingesetzt werden, insbesondere auch im Sandguss oder Kokillenguss.The alloy of the invention is particularly suitable for die casting. However, it can also be used in other casting processes, in particular also in sand casting or chill casting.
Die erfindungsgemäße Legierung ist vor allem für Kraftfahrzeugkomponenten geeignet, insbesondere im Antriebsstrang, beispielsweise für das Zylinderkurbelgehäuse einer flüssig gekühlten Brennkraftmaschine oder für das Getriebegehäuse.The alloy according to the invention is suitable above all for motor vehicle components, in particular in the drive train, for example for the cylinder crankcase of a liquid-cooled internal combustion engine or for the transmission housing.
Das nachstehende Beispiel dient der weiteren Erläuterung der Erfindung.The following example serves to further explain the invention.
Einer handelsüblichen AM60-Legierung (4,6 - 5,4 % A1; 0,26 - 0,50 % Mn; max. 0,20 % Zn; max. 0,05 % Si; max. 0,008 % Cu; max. 0,001 % Ni; max. 0,004 % Fe; Rest Mg) wurden mit einer Ba/Al-Vorlegierung (50 % Ba; 50 % Al) und mit Strontium-Metall (99,99 %) die übrigen Legierungsbestandteile so zulegiert, dass eine Legierung mit der nachstehenden Zusammensetzung erhalten wurde:
Zur Durchführung der Warmzugfestigkeitsversuche wurden aus der Legierung Zugproben nach DIN 50125-B6x30 hergestellt. Die Warmzugfestigkeit wurde bei der Prüftemperatur 100°C und 150°C mit jeweils drei Proben bestimmt. Bei 100°C beträgt die Zugfestigkeit 290 MPa, bei 150°C 163 MPa, die 0,2 % Dehn-Grenze beträgt bei 100°C 131 MPa und bei 150°C 108 Mpa.To carry out the hot tensile strength tests, tensile specimens according to DIN 50125-B6x30 were produced from the alloy. The hot tensile strength was determined at the test temperature 100 ° C and 150 ° C, each with three samples. At 100 ° C, the tensile strength is 290 MPa, at 150 ° C 163 MPa, the 0.2% elongation limit is 131 MPa at 100 ° C and 108 Mpa at 150 ° C.
Demgegenüber weist die handelsübliche Magnesiumlegierung AM60 mit 4,6 - 5,4 % Al und den angegebenen weiteren Bestandteilen in den angegebenen Mengen (jedoch ohne Barium und ohne Strontium) eine Zugfestigkeit von 200 MPa bei 100°C und 150 MPa bei 150°C und eine 0,2 % Dehn-Grenze bei 100°C von 120 MPa und bei 150°C von 70 MPa auf.In contrast, the commercial magnesium alloy AM60 with 4.6 - 5.4% Al and the other ingredients specified in the specified amounts (but without barium and without strontium) has a tensile strength of 200 MPa at 100 ° C and 150 MPa at 150 ° C and a 0.2% elongation limit at 100 ° C of 120 MPa and at 150 ° C of 70 MPa.
Die Kriechdehnungsmessung wurde nach DIN EN10291 an Zeitstandproben ohne Wärmebehandlung mit einem Durchmesser von 6 mm und einer parallelen Messlänge von 25 mm durchgeführt. Das Spannungsniveau liegt bei 50 MPa, die Prüftemperatur bei 150°C. Bei einer Prüfdauer von 120 Stunden wurde eine Kriechdehnung von 0,14 % gemessen. Demgegenüber beträgt die Kriechdehnung bei der erwähnten handelsüblichen Magnesiumlegierung ohne Barium und ohne Strontium unter den gleichen Bedingungen nach einer Prüfdauer von 120 Std. 2,2 %.The creep strain measurement was carried out according to DIN EN10291 on creep tests without heat treatment with a diameter of 6 mm and a parallel measuring length of 25 mm. The stress level is 50 MPa, the test temperature is 150 ° C. At a test time of 120 hours, a creep strain of 0.14% was measured. In contrast, the creep in the mentioned commercial magnesium alloy without barium and without Strontium under the same conditions after a test period of 120 hours. 2.2%.
Claims (6)
- A magnesium-based alloy containing the following in percentages by weight:aluminium 4 - 9%strontium 0.5 - 4 %barium 0.03 - 2.5%and optionallyzinc 0 - 0.30%manganese 0 - 0.60%silicon 0 - 0.05%remainder magnesium and impurities due to production.
- An alloy according to claim 1, characterised in that the aluminium content is 5 - 8 wt.%.
- An alloy according to claim 1 or claim 2, characterised in that the strontium content is 1.5 - 3.5 wt.%.
- An alloy according to any of the preceding claims, characterised in that the barium content is 0.2 - 1.5 wt.%.
- An alloy according to any of the preceding claims, characterised in that the impurities are limited to the elements Fe 0.004%, Cu 0.01 % and Ni 0.001 %.
- Use of the alloy according to any of the preceding claims for die-casting the crankcase or gearbox of a motor vehicle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002151663 DE10251663A1 (en) | 2002-11-06 | 2002-11-06 | magnesium alloy |
| DE10251663 | 2002-11-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1418247A1 EP1418247A1 (en) | 2004-05-12 |
| EP1418247B1 true EP1418247B1 (en) | 2007-12-12 |
Family
ID=32103373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20030022658 Expired - Lifetime EP1418247B1 (en) | 2002-11-06 | 2003-10-07 | Magnesium alloy |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP1418247B1 (en) |
| DE (2) | DE10251663A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL181797A (en) | 2007-03-08 | 2011-10-31 | Dead Sea Magnesium Ltd | Creep-resistant magnesium alloy for casting |
| JP5327515B2 (en) * | 2008-11-14 | 2013-10-30 | 株式会社豊田自動織機 | Magnesium alloys for casting and magnesium alloy castings |
| CN102605729B (en) * | 2012-04-16 | 2014-06-11 | 上海应用技术学院 | Lane change barrier shifting device |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1259578B (en) * | 1959-05-01 | 1968-01-25 | Dow Chemical Co | Process for the powder metallurgical production of a dispersion strengthened magnesium alloy |
| US3182390A (en) * | 1959-05-01 | 1965-05-11 | Dow Chemical Co | Method of die-expressing a magnesiumbase alloy |
| US3119725A (en) * | 1961-11-27 | 1964-01-28 | Dow Chemical Co | Die-expressed article of magnesium-base alloy and method of making |
| FR2430458A1 (en) * | 1978-07-07 | 1980-02-01 | Anvar | NEW MAGNESIUM METAL ALLOYS, THEIR PREPARATION AND THEIR APPLICATION, PARTICULARLY TO HYDROGEN STORAGE |
| FR2667328B1 (en) * | 1990-09-28 | 1992-11-06 | Pechiney Electrometallurgie | PROCESS FOR IMPROVING MICRORETASSURE BEHAVIOR OF MAGNESIUM ALLOYS. |
| US5143564A (en) * | 1991-03-28 | 1992-09-01 | Mcgill University | Low porosity, fine grain sized strontium-treated magnesium alloy castings |
| JP3110117B2 (en) * | 1991-12-26 | 2000-11-20 | 健 増本 | High strength magnesium based alloy |
| CA2144421A1 (en) * | 1992-09-11 | 1994-03-31 | Tadayoshi Nakamura | Refined magnesium material and method for producing the same |
| WO1994016114A1 (en) * | 1993-01-15 | 1994-07-21 | United Technologies Automotive, Inc. | Magnesium steering wheel |
| JP3204572B2 (en) * | 1993-06-30 | 2001-09-04 | 株式会社豊田中央研究所 | Heat resistant magnesium alloy |
| US6264763B1 (en) * | 1999-04-30 | 2001-07-24 | General Motors Corporation | Creep-resistant magnesium alloy die castings |
| US6322644B1 (en) * | 1999-12-15 | 2001-11-27 | Norands, Inc. | Magnesium-based casting alloys having improved elevated temperature performance |
-
2002
- 2002-11-06 DE DE2002151663 patent/DE10251663A1/en not_active Withdrawn
-
2003
- 2003-10-07 EP EP20030022658 patent/EP1418247B1/en not_active Expired - Lifetime
- 2003-10-07 DE DE50308775T patent/DE50308775D1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1418247A1 (en) | 2004-05-12 |
| DE10251663A1 (en) | 2004-05-19 |
| DE50308775D1 (en) | 2008-01-24 |
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