EP1472026B1 - Method for the production of moulded metal pieces - Google Patents
Method for the production of moulded metal pieces Download PDFInfo
- Publication number
- EP1472026B1 EP1472026B1 EP02742936A EP02742936A EP1472026B1 EP 1472026 B1 EP1472026 B1 EP 1472026B1 EP 02742936 A EP02742936 A EP 02742936A EP 02742936 A EP02742936 A EP 02742936A EP 1472026 B1 EP1472026 B1 EP 1472026B1
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- Prior art keywords
- metal
- casting
- die
- metal body
- process according
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/007—Semi-solid pressure die casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/14—Machines with evacuated die cavity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/20—Accessories: Details
- B22D17/22—Dies; Die plates; Die supports; Cooling equipment for dies; Accessories for loosening and ejecting castings from dies
- B22D17/24—Accessories for locating and holding cores or inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
Definitions
- the invention relates to a method for producing metal moldings, in particular weight-reduced moldings made of light metal.
- GB 892934 relates to the production of complex structures with foamed metal core and closed non-porous surface.
- DE 198 32 794 C1 describes a method for producing a hollow profile filled with metal foam. This method comprises the steps of pressing the hollow profile from a cladding material with an extruder having an extrusion die with a die and a mandrel, feeding the metal foam from a foam material through a supply channel to the hollow profile formed in the mandrel.
- a wheel for a motor vehicle which comprises at least one metallic foam core, which is arranged exposed to the inside of the wheel and has a casting wall towards the outside of the wheel.
- the foamed aluminum foam core is placed in a mold to cast the wheel and positioned so that the outer casting skin is formed between the mold and the foam core during casting.
- DE 195 02 307 A1 describes a deformation element, in whose housing a filling of an aluminum foam is provided as an energy absorber.
- the housing may be made of metal or plastic.
- the filler is a mere insert without material connection to the housing.
- So z. B. in the DE 195 01 508 C1 claimed a component for the chassis of a motor vehicle and a method for producing such a component.
- a core of aluminum foam is introduced into a die, which remains after the pressing of the aluminum in the mold in the component of die-cast aluminum (principle of the lost core).
- the aluminum foam used is produced from a mixture of aluminum powder with a blowing agent and is produced in a manner known per se in a multistage process (such a process is described, for example, in the article "Economic Production Techniques for the Production of Aluminum Foams, Aluminum, Volume 76 2000, page 491 ff) DE 195 01 508 C1
- the invention is therefore a process for the production of metal moldings according to the preamble of claim 1, which is characterized in that one inserts metal body according to the characterizing part of claim 1 with all sides closed surface and a hollow structure in the interior in a mold and the remaining mold cavity with a metal or a metal alloy is filled.
- the surface area of the metal body preferably has a higher average density than the interior of the metal body by a factor of 1.5 to 20, preferably 3 to 15, particularly preferably 5 to 10.
- the molded article produced therefrom is correspondingly reduced in weight.
- the metallic structure surrounding the metal body core
- the molded article produced therefrom is correspondingly reduced in weight.
- no weight reduction is associated with it, but an optionally more expensive material can be produced more cheaply by embedding a cheaper shaped article.
- a metal foam core is suitable, which has an integral foam structure.
- the metal body is encapsulated with a liquid molten metal, which can be done for example in a die casting machine.
- Light metals in particular aluminum or aluminum alloys, are particularly suitable for the process according to the invention, it being possible for the metals or alloys used to produce the moldings to be different from those of the molded articles.
- the metal body used is a metal integral molded foam which, in contrast to the foam bodies conventionally described in the literature, does not have a uniform foam morphology along its cross section.
- a metal body is a molded foam body that can be produced in the outer zones contour-faithful and whose outer shell is close to the density of the metal or the metal alloy used.
- This metallic integral foam thus represents a true gradient material. Inside the molded body, however, the density is reduced by the occurrence of gas bubbles, so that the average density of the entire molded body is below the theoretical density of the metal or metal alloy used (FIG.).
- the average density per cubic millimeter of the outer millimeter layer of the molding is by a factor of 1.5 to 20, preferably 3 to 15, particularly preferably 5 to 10, higher than the average density in the interior of the molding.
- Such moldings are produced by a die-casting directly from the melt with the addition of a blowing agent.
- the thickness of the outer skin of the molded body and thus the temperature and pressure stability can be adjusted according to the particular use, while the contour accuracy of the resulting molded body allows exact positioning during further processing.
- the metal body to be used according to the invention be used to reduce a complicated metal casting in the weight that they are used as remaining in the final product cores.
- the virtually closed outer skin of the integral molded foam body to be used in accordance with the invention also makes it suitable for use in vacuum casting processes, since the quality of the resulting surface makes it possible to evacuate the casting mold in the final body production method according to the invention, without any continuously disturbing gas leakage from the interior of the core body and thus accompanying decrease in the vacuum observed.
- the introduction of the Integralformschaumkernes in the mold used can either manually or by conventional industrial methods, eg. B. by robots done.
- the subsequent encapsulation and thus the formation of the weight-reduced target workpiece can be done due to the temperature and pressure stability of the core body outer skin quite well with metals or metal alloys of a higher melting point or at a higher processing temperature than the melting point of the core material.
- Such a procedure the use higher even provides the advantage that the outer surface of the core body is partially melted and thus forms during the subsequent solidification process of the end body an intimate metallic bond between the core material and the enveloping shell material of the Endwerk unanimouses.
- a vehicle part should be made of an aluminum material as an integrally foamed metal body.
- a casting chamber of a die casting machine was filled with a corresponding amount of molten metal.
- magnesium hydride in powder form was added to the liquid metal as foam-producing blowing agent.
- the mold cavity was underfilled volume defined. Due to the resulting turbulence is a good mixing in the mold cavity and the foaming of the cavity.
- the metal solidified on the mold walls and formed a dense and homogeneous wall of the metal body, wherein both the wall thicknesses and the porosity and its gradient could be adjusted by varying process parameters.
- the component had a mass of only about 40% compared to conventional die castings made of the same material.
- the metal body produced according to the example was then used as the core in a larger mold inserted and closed the mold. Then, according to the usual die casting method, a molten metal was pressed from the casting chamber of the die casting machine into the mold cavity. In this filling the mold cavity was completely filled, excess metal was removed after cooling of the molding from the Anschusskanal and the end of the casting chamber. The result of this process was a weight-reduced molded part, which had cavities in the region of the inserted core body, but in the area of the non-core-filled structures corresponded to a solid casting.
- the molded article produced according to the example had a lower density and a better vibration absorption behavior than the corresponding solid material comparison body.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Metallformteilen, insbesondere von gewichtsreduzierten Formteilen aus Leichtmetall.The invention relates to a method for producing metal moldings, in particular weight-reduced moldings made of light metal.
Im Zuge gestiegener ökologischer Anforderungen, aber auch für den Einsatz in Hochtechnologieanwendungen wie Flugzeugbau, Automobilbau oder in statisch anspruchsvollen Teilen ist eine Gewichtsreduzierung bei Metallformteilen von eminenter Bedeutung. In diesem Kontext sind besonders Leichtmetalle Werkstoffe, die ein immer weiteres Verbreitungsgebiet sichern. Eine weitere Möglichkeit zur Gewichtsreduktion ist der Einsatz von geschäumten metallischen Werkstoffen. Die dabei verwendeten Schäume zeichnen sich durch leichte Bauweise, Steifigkeit, Druckfestigkeit, verbesserte mechanische und akustische Dämpfung u. a. aus. Auch die Herstellung von Bauteilen aus geschäumten metallischen Werkstoffen ist bekannt.In the course of increased ecological requirements, but also for use in high-tech applications such as aircraft construction, automotive engineering or in statically demanding parts, a weight reduction in metal moldings is of eminent importance. In this context, especially light metals are materials that secure an ever wider circulation area. Another possibility for weight reduction is the use of foamed metallic materials. The foams used are characterized by their lightweight construction, rigidity, compressive strength, improved mechanical and acoustic damping and the like. a. out. The production of components made of foamed metallic materials is known.
Von besonderem Interesse ist jedoch die Verwendung von Gießkernen aus Metallschaum zur Herstellung von innen geschäumten metallischen Formteilen.However, of particular interest is the use of casting cores made of metal foam for the production of internally foamed metallic moldings.
So wird z. B. in der
Gegenstand der Erfindung ist demnach ein Verfahren zur Herstellung von Metallformteilen nach dem Oberbegriff des Anspruchs 1, welches dadurch gekennzeichnet ist, dass man Metallkörper gemäss Kennzeichen des Anspruchs 1 mit allseitig geschlossener Oberfläche und einer Hohlstruktur im Innern in eine Form einlegt und der verbleibende Formhohlraum anschließend mit einem Metall oder einer Metalllegierung gefüllt wird.The invention is therefore a process for the production of metal moldings according to the preamble of claim 1, which is characterized in that one inserts metal body according to the characterizing part of claim 1 with all sides closed surface and a hollow structure in the interior in a mold and the remaining mold cavity with a metal or a metal alloy is filled.
Dabei hat der Oberflächenbereich des Metallkörpers vorzugsweise eine um den Faktor 1,5 bis 20, bevorzugt 3 bis 15, besonders bevorzugt 5 bis 10 höhere durchschnittliche Dichte als das Innere des Metallkörpers.In this case, the surface area of the metal body preferably has a higher average density than the interior of the metal body by a factor of 1.5 to 20, preferably 3 to 15, particularly preferably 5 to 10.
Im Falle dass die den Metallkörper (Kern) umhüllende Metallstruktur eine höhere Dichte hat als die mittlere Dichte des verwendeten Metallkörpers, wird das daraus hergestellte Formteil entsprechend gewichtsreduziert. Falls es eine im wesentlichen gleiche Dichte hat, ist damit natürlich keine Gewichtsreduzierung verbunden, jedoch lässt sich ein gegebenenfalls teureres Material durch Einbettung eines billigeren Formkörpers preisgünstiger herstellen.In the case where the metallic structure surrounding the metal body (core) has a higher density than the average density of the metal body used, the molded article produced therefrom is correspondingly reduced in weight. Of course, if it has a substantially equal density, no weight reduction is associated with it, but an optionally more expensive material can be produced more cheaply by embedding a cheaper shaped article.
Als Metallkörper ist ein Metallschaumkern geeignet, der eine Integralschaumstruktur aufweist. Gewöhnlich wird der Metallkörper mit einer flüssigen Metallschmelze umgossen, was beispielsweise in einer Druckgießmaschine erfolgen kann.As a metal body, a metal foam core is suitable, which has an integral foam structure. Usually, the metal body is encapsulated with a liquid molten metal, which can be done for example in a die casting machine.
Es ist auch möglich, den Metallkörper mit Metall in teilerstarrtem Zustand entsprechend dem Semi Solid Casting-Process zu umgießen.It is also possible to encase the metal body with partially solidified metal according to the semi-solid casting process.
Je nach Geometrie und gewünschter oder angestrebter mechanischer Eigenschaft der Metallformteile ist es natürlich auch möglich, mehrere gleichartige oder unterschiedliche Metallkörper zu umgießen.Of course, depending on the geometry and the desired or desired mechanical properties of the metal moldings, too possible to encase several identical or different metal bodies.
Besonders geeignet für das erfindungsgemäße Verfahren sind Leichtmetalle, insbesondere Aluminium oder Aluminiumlegierungen, wobei die zur Herstellung der Formteile verwendeten Metalle oder Legierungen andere sein können als die der Formkörper.Light metals, in particular aluminum or aluminum alloys, are particularly suitable for the process according to the invention, it being possible for the metals or alloys used to produce the moldings to be different from those of the molded articles.
Wie oben angeführt, wird als Metallkörper ein Metallintegralformschaum eingesetzt, der im Gegensatz zu den in der Literatur üblicherweise beschriebenen Schaumkörpern entlang seines Querschnittes keine gleichmäßige Schaummorphologie aufweist. (Die Herstellung eines solchen Metallkörpers wird in
Die praktisch geschlossene Außenhaut der erfindungsgemäß zu verwendenden Integralformschaumkörper ermöglicht auch ihre Anwendung in Vakuumgießprozessen, da bei der Qualität der entstehenden Oberfläche ein Evakuieren der Gießform bei dem erfindungsgemäßen Verfahren der Endkörperherstellung möglich ist, ohne kontinuierlich in störendem Maße Gasleckagen aus dem Inneren des Kernkörpers und eine damit einhergehende Verminderung des Vakuums zu beobachten.The virtually closed outer skin of the integral molded foam body to be used in accordance with the invention also makes it suitable for use in vacuum casting processes, since the quality of the resulting surface makes it possible to evacuate the casting mold in the final body production method according to the invention, without any continuously disturbing gas leakage from the interior of the core body and thus accompanying decrease in the vacuum observed.
Das Einbringen des Integralformschaumkernes in die verwendete Gießform kann entweder manuell oder nach sonst üblichen Industrieverfahren, z. B. durch Roboter, erfolgen. Das nachfolgende Umgießen und damit die Ausbildung des gewichtsreduzierten Zielwerkstückes kann aufgrund der Temperatur- und Druckstabilität der Kernkörperaußenhaut durchaus auch mit Metallen bzw. Metalllegierungen eines höheren Schmelzpunktes bzw. bei einer höheren Verarbeitungstemperatur als dem Schmelzpunkt des Kernmateriales erfolgen. Ein solches Verfahren, das den Einsatz höher schmelzender Umhüllungsmaterialien vorsieht, hat sogar den Vorteil, dass die Außenfläche des Kernkörpers partiell angeschmolzen wird und somit sich beim nachfolgenden Erstarrungsprozess des Endkörpers ein inniger metallischer Verbund zwischen dem Kernmaterial und dem umhüllenden Schalenmaterial des Endwerkstückes bildet. Wie bei den industriellen Gießverfahren üblich, ist unter anderem durch die ausgezeichnete Druckstabilität der verwendeten Kernkörper eine Nachbehandlung des endgültigen Werkstückes in der Regel nicht nötig. Die Erfindung wird nachfolgend in einem Ausführungsbeispiel näher beschrieben. Die einzige Figur zeigt einen Ausschnitt eines als Kern geeigneten Integralformschaums.The introduction of the Integralformschaumkernes in the mold used can either manually or by conventional industrial methods, eg. B. by robots done. The subsequent encapsulation and thus the formation of the weight-reduced target workpiece can be done due to the temperature and pressure stability of the core body outer skin quite well with metals or metal alloys of a higher melting point or at a higher processing temperature than the melting point of the core material. Such a procedure, the use higher even provides the advantage that the outer surface of the core body is partially melted and thus forms during the subsequent solidification process of the end body an intimate metallic bond between the core material and the enveloping shell material of the Endwerkstückes. As usual in the industrial casting, among other things by the excellent pressure stability of the core used a post-treatment of the final workpiece is usually not necessary. The invention will be described in more detail in an embodiment. The single figure shows a section of a suitable as a core Integralformschaums.
In einer handelsüblichen Druckgießmaschine sollte ein Fahrzeugteil aus einem Aluminiumwerkstoff als integral geschäumter Metallkörper hergestellt werden. Hierzu wurde in einem ersten Schritt eine Gießkammer einer Druckgießmaschine mit einer entsprechenden Menge an Metallschmelze gefüllt. In die geschlossene Gießkammer wurde als schaumerzeugendes Treibmittel Magnesiumhydrid in Pulverform dem flüssigen Metall zugegeben. Nahezu gleichzeitig begann ein schnelles Einschieben des Gemisches aus Treibmittel und Metallschmelze in den Formhohlraum. Der Formhohlraum wurde volumendefiniert unterfüllt. Durch die entstehenden Turbulenzen erfolgt eine gute Durchmischung in dem Formhohlraum und das Ausschäumen des Hohlraumes. Durch die Sprühfüllung erstarrte das Metall an den Formwänden und bildete eine dichte und homogene Wandung des Metallkörpers aus, wobei sowohl die Wandstärken als auch die Porosität und deren Gradient durch Variation von Verfahrensparametern einstellbar waren.In a commercial die casting machine, a vehicle part should be made of an aluminum material as an integrally foamed metal body. For this purpose, in a first step, a casting chamber of a die casting machine was filled with a corresponding amount of molten metal. In the closed casting chamber, magnesium hydride in powder form was added to the liquid metal as foam-producing blowing agent. Almost simultaneously, a rapid insertion of the blowing agent / molten metal mixture into the mold cavity began. The mold cavity was underfilled volume defined. Due to the resulting turbulence is a good mixing in the mold cavity and the foaming of the cavity. As a result of the spray filling, the metal solidified on the mold walls and formed a dense and homogeneous wall of the metal body, wherein both the wall thicknesses and the porosity and its gradient could be adjusted by varying process parameters.
Der "Schuss" erfolgte vor der Schaumbildung, der Schäumungsprozess lief "in situ" in dem Formhohlraum ab. Es wurde schnell in die kalte Form geschäumt. Das Bauteil wies eine Masse von nur ca. 40 % gegenüber konventionellen Druckgießteilen aus gleichem Material auf. Der gemäß dem Beispiel hergestellte Metallkörper wurde dann als Kern in eine größere Gießform eingelegt und die Gießform geschlossen. Dann wurde entsprechend dem üblichen Druckgussverfahren eine Metallschmelze aus der Gießkammer der Druckgussmaschine in den Formhohlraum gepresst. Bei diesem Füllgang wurde der Formhohlraum vollständig gefüllt, überschüssiges Metall wurde nach dem Erkalten des Formkörpers aus dem Anschusskanal und dem Ende der Gießkammer entfernt. Das Ergebnis dieses Prozesses war ein gewichtsreduziertes Formteil, das im Bereich des eingelegten Kernkörpers Hohlräume aufwies, im Bereich der nicht vom Kern gefüllten Strukturen aber einem Vollgussteil entsprach.The "shot" occurred before foaming, the foaming process was "in situ" in the mold cavity. It was quickly foamed into the cold form. The component had a mass of only about 40% compared to conventional die castings made of the same material. The metal body produced according to the example was then used as the core in a larger mold inserted and closed the mold. Then, according to the usual die casting method, a molten metal was pressed from the casting chamber of the die casting machine into the mold cavity. In this filling the mold cavity was completely filled, excess metal was removed after cooling of the molding from the Anschusskanal and the end of the casting chamber. The result of this process was a weight-reduced molded part, which had cavities in the region of the inserted core body, but in the area of the non-core-filled structures corresponded to a solid casting.
Am Schnitt des beispielhaften Metallkörpers (Fig.) ist die Konturentreue entsprechend der verwendeten Form deutlich erkennbar, ebenso die unterschiedliche' Morphologie am Rande und im Innern des Formkörpers sowie die Druckstabilität des Kernes an Hand der flachen Eindruckspur des Auswerfers.At the intersection of the exemplary metal body (Fig.) The contour fidelity is clearly recognizable according to the shape used, as well as the different 'morphology at the edge and inside the molding and the pressure stability of the core on the basis of the flat impression track of the ejector.
Der gemäß dem Beispiel hergestellte Formkörper wies eine geringere Dichte und ein besseres Schwingungsabsorbtionsverhalten als der entsprechende Vollmaterial-Vergleichskörper auf.The molded article produced according to the example had a lower density and a better vibration absorption behavior than the corresponding solid material comparison body.
Claims (9)
- Process for producing shaped metal parts, wherein metal bodies are placed into a casting mould and the remaining mould cavity is then filled with a metal or a metal alloy by pressure die-casting, characterized in that the metal body is formed in a pressure die-casting machine by rapid introduction of a mixture of a foam-producing blowing agent and a metal melt and then foaming so as to fill the mould cavity, wherein the foaming process takes place "in situ" in the mould cavity, and a dense and homogeneous wall of the metal body is produced by the spray-filling of the metal and its solidification on the mould walls, resulting in an integral foam structure with a surface which is closed on all sides.
- Process according to Claim 1, characterized in that the surface region of the metal body has a mean density which is higher than the interior of the metal body by a factor of 1.5 to 20, preferably 3 to 15, particularly preferably 5 to 10.
- Process according to Claims 1 and 2, characterized in that the metal structure which surrounds the metal body (core) has a higher density than the mean density of the metal body used.
- Process according to Claims 1 to 3, characterized in that the metal body is surrounded with a liquid metal melt by casting.
- Process according to Claims 1 to 3, characterized in that the surrounding of the metal body by casting is carried out using metal in the partially solidified state, in accordance with the semi-solid metal casting process.
- Process according to Claims 1 to 5, characterized in that, after the metal body has been placed into the die and before the metal enters the die, a vacuum is applied to the die and only then is the die filled.
- Process according to Claims 1 to 6, characterized in that a plurality of similar or different metal bodies are placed into a die and are then surrounded by casting.
- Process according to one of Claims 1 to 7, characterized in that a metal melt comprising light metal, in particular aluminium or an aluminium alloy, is used to fill the die.
- Process according to one of Claims 1 to 8, characterized in that a metal body made from light metal is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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SI200230612T SI1472026T1 (en) | 2001-05-16 | 2002-05-03 | Method for the production of moulded metal pieces |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10123899 | 2001-05-16 | ||
DE10123899A DE10123899A1 (en) | 2001-05-16 | 2001-05-16 | Production of metal molded parts comprises placing a metal body with closed surfaces on all sides and a hollow structure inside into a mold, and filling the remaining mold hollow space with a metal or metal alloy |
PCT/EP2002/004866 WO2002092261A2 (en) | 2001-05-16 | 2002-05-03 | Method for the production of moulded metal pieces |
Publications (2)
Publication Number | Publication Date |
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EP1472026A2 EP1472026A2 (en) | 2004-11-03 |
EP1472026B1 true EP1472026B1 (en) | 2007-07-11 |
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EP02742936A Expired - Lifetime EP1472026B1 (en) | 2001-05-16 | 2002-05-03 | Method for the production of moulded metal pieces |
Country Status (9)
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US (1) | US6854506B2 (en) |
EP (1) | EP1472026B1 (en) |
JP (2) | JP2005500162A (en) |
AT (1) | ATE366630T1 (en) |
AU (1) | AU2002342227A1 (en) |
CA (1) | CA2443828C (en) |
DE (2) | DE10123899A1 (en) |
ES (1) | ES2290316T3 (en) |
WO (1) | WO2002092261A2 (en) |
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DE102004046466B4 (en) * | 2004-09-24 | 2013-02-21 | Robotec Engineering Gmbh | Plant and method for inserting core supports into a casting mold |
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DE102022106525A1 (en) | 2022-03-21 | 2023-09-21 | Bayerische Motoren Werke Aktiengesellschaft | Method for producing a foam element and component |
DE102022106524A1 (en) | 2022-03-21 | 2023-09-21 | Bayerische Motoren Werke Aktiengesellschaft | Method for producing a foam element, component and tool |
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2001
- 2001-05-16 DE DE10123899A patent/DE10123899A1/en not_active Withdrawn
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2002
- 2002-05-03 AT AT02742936T patent/ATE366630T1/en active
- 2002-05-03 AU AU2002342227A patent/AU2002342227A1/en not_active Abandoned
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- 2002-05-03 DE DE50210474T patent/DE50210474D1/en not_active Expired - Lifetime
- 2002-05-03 EP EP02742936A patent/EP1472026B1/en not_active Expired - Lifetime
- 2002-05-03 CA CA002443828A patent/CA2443828C/en not_active Expired - Fee Related
- 2002-05-03 ES ES02742936T patent/ES2290316T3/en not_active Expired - Lifetime
- 2002-05-03 JP JP2002589184A patent/JP2005500162A/en active Pending
- 2002-05-14 US US10/146,701 patent/US6854506B2/en not_active Expired - Fee Related
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2009
- 2009-03-16 JP JP2009062550A patent/JP2009166130A/en active Pending
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WO2002092261A2 (en) | 2002-11-21 |
WO2002092261A3 (en) | 2004-05-27 |
DE50210474D1 (en) | 2007-08-23 |
DE10123899A1 (en) | 2002-11-21 |
AU2002342227A1 (en) | 2002-11-25 |
US20020189779A1 (en) | 2002-12-19 |
EP1472026A2 (en) | 2004-11-03 |
CA2443828A1 (en) | 2002-11-21 |
JP2005500162A (en) | 2005-01-06 |
CA2443828C (en) | 2009-06-23 |
ES2290316T3 (en) | 2008-02-16 |
JP2009166130A (en) | 2009-07-30 |
US6854506B2 (en) | 2005-02-15 |
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