WO2004108976A2 - Procede de fabrication d'un corps metallique expanse - Google Patents
Procede de fabrication d'un corps metallique expanse Download PDFInfo
- Publication number
- WO2004108976A2 WO2004108976A2 PCT/EP2004/005887 EP2004005887W WO2004108976A2 WO 2004108976 A2 WO2004108976 A2 WO 2004108976A2 EP 2004005887 W EP2004005887 W EP 2004005887W WO 2004108976 A2 WO2004108976 A2 WO 2004108976A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- molten metal
- mold cavity
- mold
- blowing agent
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
- C22C1/083—Foaming process in molten metal other than by powder metallurgy
- C22C1/085—Foaming process in molten metal other than by powder metallurgy with external pressure or pressure buildup to make porous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Definitions
- the invention relates to a method for producing a metal foam body.
- blowing agent for foaming a molten metal is either placed in the mold cavity or brought into contact with the molten metal in a filling or casting chamber. If the blowing agent is placed in the mold cavity, it does not distribute itself homogeneously in the molten metal.
- a metal foam body produced therefrom has an inhomogeneous foam structure.
- the blowing agent is brought into contact with the molten metal in the casting chamber, the decomposition of the blowing agent begins in the casting chamber.
- increased amounts of blowing agent must be introduced into the casting chamber. This causes increased costs.
- the blowing agent is often not homogeneously distributed in the molten metal even when it is added to the casting chamber. In this case too, metal foam bodies have an inhomogeneous foam structure.
- DE 100 09 008 CI discloses a method for producing a composite structure with a metal foam core.
- a metal foam core is inserted into a die and then die-cast with metal.
- the known method is relatively cumbersome. Separate manufacture of a metal foam core and insertion of the same into a mold cavity are required.
- Another disadvantage is that often there is no integral bond between the metal foam core and the overmolded metal shell.
- only minimal component thicknesses of 10 mm can be achieved with the known method.
- a method for producing a metal foam body is known from WO 99/64287.
- the blowing agent is mixed into the molten metal outside a mold cavity.
- the molten metal provided with the blowing agent is then transferred into the mold cavity.
- the molten metal is already foaming.
- the metal foam bodies produced do not have a particularly good surface.
- GB 892,934 describes a method for producing a metal foam body.
- a molten metal is mixed with a blowing agent in a mixing device.
- the mixture consisting of the molten metal and the blowing agent is then transferred into a mold cavity.
- the proposed procedure is difficult to carry out in practice.
- the molten metal sometimes undesirably foams in the mixing device.
- DE 1 164 102 discloses a method for producing a metal foam body, in which a powdery blowing agent is added to a metal melt.
- An extrusion device to which liquid metal is added is used for this.
- the extrusion device has a connection for adding powdered blowing agent.
- the blowing agent is mixed with the liquid metal in the extrusion device. This causes the metal melt to foam.
- the metal foam bodies produced do not have a particularly good surface.
- the object of the invention is to eliminate the disadvantages of the prior art.
- a method is to be specified which enables the production of metal moldings having an improved surface quality with a foam structure present inside in a simple and cost-effective manner.
- the method should enable such metal foam bodies to be mass-produced.
- a blowing agent is added to the molten metal after it leaves the storage container and before it enters the mold cavity. Surprisingly, it succeeds in producing metal foam bodies with an excellent surface quality, which have a foam structure on the inside.
- a particularly homogeneous mixture of the molten metal with the blowing agent is achieved.
- the metal foam bodies made from it have a homogeneous' foam structure on the inside, whereas the upper surface enveloping the core surface consists of a dense metal wall. Metal foam bodies produced in this way have excellent mechanical properties.
- the proposed method even succeeds in producing thin-walled shaped bodies made of metal, the interior of which has a foam structure.
- the blowing agent is only completely decomposed after the metal melt has been injected into the mold cavity.
- the molten metal injected into the mold cavity is quenched on the mold walls and suddenly solidifies there.
- a dense metal wall surrounding the later metal foam body is formed.
- the blowing agent decomposes there.
- a metal core is formed in the interior of the molded body.
- the proposed method is relatively inexpensive. It can be carried out similarly to a conventional die casting process. It is only necessary to supply the propellant in a suitable manner between the storage container and the mold cavity. The amount of blowing agent supplied can be kept relatively low.
- the molten metal and the blowing agent are ' mixed turbulently before entering the mold.
- the blowing agent can be added to the molten metal before the turbulent mixture is produced.
- the blowing agent can be injected into the line before or during the injection of the molten metal or can be fed to a mixing device connected to the line. The effect is advantageously exploited here that the metal melt is passed through the line at an extremely high speed during injection and is mixed turbulently in the process.
- the formation of a turbulent mixture or flow the way from the storage container to the mold cavity causes a particularly uniform distribution of the blowing agent in the molten metal.
- the injection of the molten metal can e.g. B. be carried out by means of a die casting or an extrusion device.
- a die casting or an extrusion device In principle, all known casting processes which allow rapid mold filling can be used to carry out the method according to the invention.
- the following machines have proven to be particularly suitable for injecting the melt into the mold cavity: hot chamber die casting machine, horizontal cold chamber die casting machine, vertical cold chamber die casting machine, mold casting system, in particular a pressure mold casting system or a low pressure casting system, a squeeze casting machine or a machine for Casting semi-solid melts.
- Hot chamber die casting machines can also be used to carry out the method according to the invention.
- the storage or casting container is in the molten metal.
- the mixing device is connected upstream of the mold cavity.
- a squeeze casting machine in which the casting or storage container is designed to be pivotable is also suitable for carrying out the method according to the invention.
- the mixing device is also connected directly upstream of the mold cavity.
- Horizontal cold chamber machines are also suitable for carrying out the method according to the invention.
- the mold cavity is above the casting or storage container. In this case, the mixing device is also connected upstream of the mold cavity in a plane above the storage container.
- the molten metal is made from a vertically arranged storage container or a casting chamber transferred via the line into the mold cavity.
- the mixing device can be switched on in the line.
- the line has a bend upstream of the mixing device. As a result, molten metal metal is already flowing into the mixing device. A particularly homogeneous mixture between blowing agent and molten metal is achieved.
- the mold cavity is completely filled with molten metal.
- a pressure of up to 2000 bar can be exerted on the molten metal in the mold cavity.
- even thin and small mold cavities can be completely filled.
- Complex and thin-walled components with an excellent surface quality can be manufactured. Apart from this, the pressure exerted on the molten metal during the injection and immediately after the injection suppresses foaming thereof.
- the pressure is released no later than 5 seconds after the injection of the molten metal and thus allowing the molten metal to foam.
- the metal melt is foamed in the areas of the core of the component that have not yet solidified.
- the pressure can be relieved with a predefined pressure relief profile.
- the cell size of the foam which forms and its distribution in the volume of the component can thus be controlled.
- the pressure relief is carried out by appropriate control of the die casting and extrusion device. It can be done, for example, by controlled retraction of an injection piston or an extrusion screw.
- the mold cavity can be enlarged after the closure before or during the initial melting of the molten metal. The enlargement of the mold cavity starts at the latest 5 seconds after the
- the mold cavity can be enlarged by 5% to 1000% in relation to its initial volume.
- the mold cavity can be enlarged by opening one or more slides or by pulling out mold cores projecting into the mold cavity. It can also be enlarged by opening the mold or mold shells.
- the mold is completely filled and, after injection, a pressure of up to 2000 bar is applied. No later than 5 seconds after the metal melt is injected, the pressure-applying device is moved in a defined manner so that the pressure is released. Due to the reduction in pressure, gas is released in the molten metal by the blowing agent. The molten metal foams. The excess foamed material is pressed into a free cavity formed in the pressure-applying device, for example a piston space. In this case, the foaming of the molten metal can be realized by controlling the pressure-applying device. In this case, the method can be implemented using conventional molds. According to a further advantageous embodiment, the mold cavity is closed after the metal melt has been transferred.
- the mold cavity can be closed, for example, by targeted cooling of certain areas of the mold. As a result of the cooling, a targeted solidification of the molten metal is achieved in the area of the sprue cross section.
- real-time controlled casting machines Such machines can be controlled so that reprinting does not take place.
- a slide or the like to mold the mold cavity. to close.
- the mold cavity is evacuated before the metal melt is transferred; H.
- the pressure in the mold cavity is lower than the atmospheric pressure.
- a lower gas pressure counteracts the foaming metal melt.
- Particularly homogeneous foam structures form in the core of the metal foam body.
- the amount of blowing agent added can be further reduced with this measure.
- the mold and / or the mixing device can be preheated to a temperature between 50 ° C. and 400 ° C. before the metal melt is transferred. This allows the rate of solidification of the molten metal in the mold and thus also the structure of the metal foam body to be influenced in a targeted manner.
- a metallic permanent shape is expediently used as the shape.
- the mold can face the mold cavity facing the inside, at least in sections, be coated with a ceramic or provided with a ceramic insert.
- the molten metal is expediently formed from a light metal.
- One of the following metals can be used to produce the molten metal: aluminum, aluminum alloy, magnesium, magnesium alloy, zinc, zinc alloy.
- blowing agent is expediently chosen whose decomposition temperature is lower than the solidus temperature of the metal.
- the blowing agent can be oxidized before being added to the molten metal.
- a metal hydride which preferably contains at least one substance selected from the following group can be used as the blowing agent: magnesium hydride, titanium hydride, calcium hydride, zirconium hydride.
- 0.1 to 10% by weight of an additive is added to the molten metal, based on the weight of the metal 'foam body produced therefrom.
- the additive can contain at least one substance selected from the following group: oxide, carbonate, carbide, pure metal, graphite. V 2 0 5 , Fe 3 0 4 , Cr 2 0 3 , Ti0 2 , CuO, Mn 2 0 3 , Sc 2 0 3 , Al 2 0 3 , Si0 2 can in particular be used as the oxide.
- Suitable carbides are e.g. B. VC, SiC.
- Possible carbonates are: MgC0 3 , CaC0 3 .
- Suitable pure metals are: V, Ti, Mn, Fe, Ni.
- Such additives improve the foaming behavior of the molten metal. They can also cause in situ oxidation of the molten metal. Furthermore, they can act as nucleating agents in the formation of gas pores in the act molten. Finally, they can also serve as a catalyst for the decomposition of the blowing agent. You can increase the gas emissions and the rate of decomposition of the blowing agent.
- the additives can generally be used to control the decomposition of the blowing agent.
- pre-oxidized light metal or recycled light metal as the light metal for producing the molten metal.
- the oxides contained in such light metals serve to stabilize the foam structure.
- the molten metal can contain a solid phase between 0 and 70% by volume. In this case, it is a so-called “semi-solid column”.
- the invention furthermore relates to a metal foam body which is produced by the method according to the invention and which advantageously consists of an outer surface which is closed on all sides and an interior which is formed from a metal foam.
- Fig. 1 is a view of a cross section one after the
- FIG. 2 shows a view of a cross section of a metal foam body produced by the method according to the invention
- FIG. 3 shows a three-dimensional reconstruction of the metal foam body according to FIG. 2 carried out by means of a computer tomograph
- FIG. 7 shows a schematic representation of a device for producing metal foam bodies
- FIG. 8b shows the first mold according to FIG. 8a, wherein a mold cavity is enlarged
- 9a shows a second mold for producing a metal foam body
- FIG. 9c shows the second mold according to FIG. 9a, the mold cavity being filled with metal foam
- FIG. 10b shows the third form according to FIG. 10a, with a
- Mold cavity is filled with molten metal
- FIG. 10c shows the third mold according to FIG. 10a, the mold cavity being enlarged.
- In. 1 shows a cross-sectional view of a metal foam body produced according to the prior art.
- the molded body was produced as follows: 1.5 g of magnesium hydride were introduced as a blowing agent into a mold cavity of a metallic permanent mold. Using a conventional extrusion device, 140 g of a commercially available magnesium alloy (type AM 60) are shot into the mold cavity. No reprint has been made.
- the blowing agent is distributed inhomogeneously in the molten metal. The result is a metal foam body with an inhomogeneous pore distribution. In particular, larger pores also form near the surface of the metal foam body.
- a pre Council container 1 of a casting device is connected via a line 2 to a mold cavity 3.
- Line 2 is turned on.
- a from the reservoir 1 incoming line branch opens in the form of a longitudinal slit in the cylinder jacket of the mixing device 4.
- From the mixing device 4 to form hollow 'space 3 leading further duct branches extend from the two cylinder base surfaces to a gate cross-section of the mold cavity 3.
- the reservoir 1 is e.g. B. filled with a melt made of light metal.
- FIG. 3 shows a three-dimensional reconstruction of the metal foam body shown in FIG. 2, produced by means of an X-ray computer tomograph.
- the relative density of the metal foam body on the surface or in a layer located near the surface is 100% in the two-dimensional representation shown in FIG. 3a.
- the relative density decreases towards the inside of the metal foam body. It is 70% in Fig. 3b and 30% in Fig. 3c.
- 4 again shows the density of the distribution of the metal, foam body over its thickness.
- the course of density can be adjusted by changing the process parameters.
- 4 shows the relative density for a total density of the metal foam body of 1.16 g / cm 3 and for a further metal foam body with a total density of 1.63 g / cm 3 .
- 5 shows the pore size for the distribution of metal foam body produced from magnesium as a function of its total density.
- the pore size distribution can also be specifically varied depending on the process parameters selected. 5 shows pore size distributions of magnesium foam bodies with a total density of 1.56 g / cm 3 , 1.44 g / cm 3 , 1.12 g / cm 3 .
- FIG. 6 shows the increase in the bending stiffness in percent of a metal foam body over its density compared to a comparable solid component made of magnesium (density about 1.8 g / cm 3 ).
- the bending stiffness can be increased by up to 65% compared to a solid component.
- the mixing device 4 is here part of a metallic permanent shape.
- the permanent mold is installed in a horizontal cold chamber die casting machine, so that the mixing device 4 lies below the mold cavity 3, but higher than the storage container 1.
- 420 g of molten metal of an AZ 91 alloy are shot into the mold cavity 3 via the mixing device 4 by means of the casting piston. No reprint takes place.
- An examination of the magnesium foam body produced in this way shows that the addition of magnesium carbonate reduces the mean. causes pore size.
- the relative density of the component hardly changes compared to the sole use of propellants, ie without the addition of magnesium carbonate.
- FIG. 8a and 8b show a first mold 4 which surrounds the mold cavity 3.
- the first mold 4 has a first slide 5a and a second slide 5b cooperating therewith.
- the mold cavity 3 has a small volume.
- Retraction of the first slide 5a simultaneously causes a displacement movement of the second slide 5b in the left direction, as a result of which the shape of the mold cavity 3 is changed.
- 9a to c show a second mold 4, in which a mold cavity 3 is connected via the line 2 to the storage container 1 of a piston pressure casting device designated by the reference number 6.
- the mold cavity 3 has a third slide 5c, which can be moved by means of a movement device 7 to enlarge the mold cavity 3.
- metal bodies with a foam structure having a core can be produced as follows:
- Metal melt located in the reservoir 1 is shot into the mold cavity 3, for example, by means of the piston pressure casting device 6.
- blowing agent for example wise titanium hydride injected.
- the mold cavity 3 is completely filled with molten metal. ' Because of the pressure acting on the molten metal, there is initially no foaming.
- the mold cavity 3 can be enlarged by moving the slides 5a, 5b, 5c, in which case a sprue cross section of the mold 4 is closed.
- the mold cavity 3 is initially completely filled with molten metal by means of the piston pressure casting device 6, with blowing agent also being injected into the line 2 during the transfer of the molten metal.
- a piston of the piston pressure casting device 6 is withdrawn with a predetermined speed profile, so that controlled foaming takes place in the mold cavity 3.
- the aforementioned processes it is possible to produce metal foam bodies with a high surface quality.
- the foam structure inside the metal foam body can be checked by the process.
- the parameters of the size of the volume additionally made available for foaming and the speed of the. '' Volume increase through a suitable control of the means for Enlargement of the mold cavity 3, in particular the slide 5a, 5b, 5c or the piston die casting device 6 can be varied.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
Abstract
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE112004000708T DE112004000708B4 (de) | 2003-06-07 | 2004-06-01 | Verfahren zur Herstellung eines Metallschaumkörpers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10325819A DE10325819B4 (de) | 2003-06-07 | 2003-06-07 | Verfahren zur Herstellung eines Metallschaumkörpers |
| DE10325819.1 | 2003-06-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004108976A2 true WO2004108976A2 (fr) | 2004-12-16 |
| WO2004108976A3 WO2004108976A3 (fr) | 2005-06-16 |
Family
ID=33494882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2004/005887 Ceased WO2004108976A2 (fr) | 2003-06-07 | 2004-06-01 | Procede de fabrication d'un corps metallique expanse |
Country Status (2)
| Country | Link |
|---|---|
| DE (2) | DE10325819B4 (fr) |
| WO (1) | WO2004108976A2 (fr) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7699092B2 (en) | 2007-06-18 | 2010-04-20 | Husky Injection Molding Systems Ltd. | Metal-molding system and process for making foamed alloy |
| CN107794394A (zh) * | 2017-10-27 | 2018-03-13 | 合肥紫金钢管股份有限公司 | 一种吸声隔音型双层钢管填充材料及其加工方法 |
| CN120543766A (zh) * | 2025-07-25 | 2025-08-26 | 上海实树汽车工程技术股份有限公司 | 基于图像导入与模型模拟的模具发泡控制系统 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010024669B3 (de) * | 2010-06-18 | 2011-12-08 | Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh | Verfahren zur Herstellung von Metallschäumen und Metallschaum |
| DE102011111614B3 (de) * | 2011-08-25 | 2013-01-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh | Schmelzmetallurgisches Verfahren zur Herstellung eines Metallschaumkörpers und Anordnung zur Durchführung des Verfahrens |
| DE102015220080A1 (de) | 2015-10-15 | 2017-04-20 | Brose Fahrzeugteile Gmbh & Co. Kommanditgesellschaft, Bamberg | Elektronikgehäuse und Herstellungsverfahren |
| DE102022106525A1 (de) | 2022-03-21 | 2023-09-21 | Bayerische Motoren Werke Aktiengesellschaft | Verfahren zum Herstellen eines Schaumelements sowie Bauteil |
| DE102022106524A1 (de) | 2022-03-21 | 2023-09-21 | Bayerische Motoren Werke Aktiengesellschaft | Verfahren zum Herstellen eines Schaumelements, Bauteil sowie Werkzeug |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1164102B (de) * | 1956-03-19 | 1964-02-27 | Lor Corp | Verfahren zur Herstellung von Metallschaumkoerpern |
| GB892934A (en) * | 1959-01-05 | 1962-04-04 | Lor Corp | Casting complex structures with foamed metal core and solid skin |
| JPH0688119B2 (ja) * | 1988-05-25 | 1994-11-09 | 株式会社アーレスティ | ダイカスト鋳造法 |
| AT406027B (de) * | 1996-04-19 | 2000-01-25 | Leichtmetallguss Kokillenbau W | Verfahren zur herstellung von formteilen aus metallschaum |
| AU4604999A (en) * | 1998-06-09 | 1999-12-30 | M.I.M. Huttenwerke Duisburg Gmbh | Method for reinforcing a cavity of a motor vehicle structural member |
| NO311708B1 (no) * | 2000-02-25 | 2002-01-14 | Cymat Corp | Fremgangsmåte og utstyr for tildannelse av stöpte produkter |
| DE10009008C1 (de) * | 2000-02-25 | 2001-09-13 | Bayern Freistaat | Verfahren zur Herstellung einer Verbundstruktur mit einem Metallschaum-Kern |
| DE10045494C2 (de) * | 2000-09-13 | 2002-07-18 | Neue Materialien Fuerth Gmbh | Verfahren zum Herstellen eines Formkörpers aus Metallschaum |
| DE10104339A1 (de) * | 2001-02-01 | 2002-08-08 | Goldschmidt Ag Th | Verfahren zur Herstellung von Metallschaum und danach hergestellter Metallkörper |
| US6915834B2 (en) * | 2001-02-01 | 2005-07-12 | Goldschmidt Ag | Process for producing metal foam and metal body produced using this process |
| AT410104B (de) * | 2001-06-15 | 2003-02-25 | Huette Klein Reichenbach Gmbh | Vorrichtung und verfahren zur herstellung von metallschaum |
| AT410103B (de) * | 2001-06-15 | 2003-02-25 | Huette Klein Reichenbach Gmbh | Verfahren zur herstellung eines leichtgewichtigen formkörpers und formkörper aus metallschaum |
| US7175689B2 (en) * | 2001-06-15 | 2007-02-13 | Huette Klein-Reichenbach Gesellschaft Mbh | Process for producing a lightweight molded part and molded part made of metal foam |
-
2003
- 2003-06-07 DE DE10325819A patent/DE10325819B4/de not_active Expired - Fee Related
-
2004
- 2004-06-01 WO PCT/EP2004/005887 patent/WO2004108976A2/fr not_active Ceased
- 2004-06-01 DE DE112004000708T patent/DE112004000708B4/de not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7699092B2 (en) | 2007-06-18 | 2010-04-20 | Husky Injection Molding Systems Ltd. | Metal-molding system and process for making foamed alloy |
| CN107794394A (zh) * | 2017-10-27 | 2018-03-13 | 合肥紫金钢管股份有限公司 | 一种吸声隔音型双层钢管填充材料及其加工方法 |
| CN120543766A (zh) * | 2025-07-25 | 2025-08-26 | 上海实树汽车工程技术股份有限公司 | 基于图像导入与模型模拟的模具发泡控制系统 |
| CN120543766B (zh) * | 2025-07-25 | 2025-09-26 | 上海实树汽车工程技术股份有限公司 | 基于图像导入与模型模拟的模具发泡控制系统 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10325819A1 (de) | 2005-01-05 |
| DE112004000708D2 (de) | 2006-10-19 |
| DE10325819B4 (de) | 2005-06-23 |
| WO2004108976A3 (fr) | 2005-06-16 |
| DE112004000708B4 (de) | 2007-07-26 |
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