EP0588182A2 - Foam sound damping or insulating element manufacturing method thereof and its use - Google Patents

Foam sound damping or insulating element manufacturing method thereof and its use Download PDF

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Publication number
EP0588182A2
EP0588182A2 EP93114133A EP93114133A EP0588182A2 EP 0588182 A2 EP0588182 A2 EP 0588182A2 EP 93114133 A EP93114133 A EP 93114133A EP 93114133 A EP93114133 A EP 93114133A EP 0588182 A2 EP0588182 A2 EP 0588182A2
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EP
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Prior art keywords
workpiece
foam body
component
component according
aluminum
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EP93114133A
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German (de)
French (fr)
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EP0588182A3 (en
EP0588182B1 (en
Inventor
Stefan Dr. Lahner
Manfred Roller
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Faist Automotive GmbH and Co KG
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M Faist GmbH and Co KG
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    • GPHYSICS
    • G10MUSICAL INSTRUMENTS; ACOUSTICS
    • G10KSOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K11/00Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/16Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/162Selection of materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • B22F7/004Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
    • B22F7/006Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part the porous part being obtained by foaming
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/105Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B22F2003/1052Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding assisted by energy absorption enhanced by the coating or powder

Definitions

  • the invention relates to a sound wave damping and / or damping, i.e. acoustically active component made of foam of the type mentioned in the preamble of claim 1 and a method for its production and use.
  • Such components are already known (DE-OS 27 35 153), but only as acoustically effective components. They have the task of forming the greatest possible resistance against the penetration of sound waves from one side of the component to the other. This function is known as “soundproofing”. In addition, such components occasionally have the task of already dampening the generation of sound waves on one side of the component; this task, referred to as a "sound-absorbing" function, is achieved, for example, by the component being connected directly to the sound-emitting element, for example a body panel, by means of, for example, Press, glue, clip.
  • the foam components used primarily for sound insulation purposes mostly have plastics such as polyurethane (DE-OS 27 35 153).
  • the cell walls represent more or less flexible cuticles.
  • open-cell foam structures with those foam structures that are closed-celled or that are filled or impregnated with fillers.
  • the manufacturing costs of such double structures are relatively high.
  • open-pore foam fleece (DE-PS 36 24 427).
  • Thermally insulating laminate elements are also known (DE-OS 38 21 468 and G 92 03 734.8). These laminate elements are partly also acoustically effective. These components are each made up of several different layers of one or more materials, that is to say in a complicated manner. Because they are not self-supporting, you need additional stiffening, usually in the form of an aluminum support plate. With the variants, which are made of different materials, there is also the problem of recycling.
  • the invention has for its object to improve the component of the type mentioned in such a way that with good acoustic effectiveness it also has good thermal insulation properties, is easy to manufacture, has lightweight features and offers advantages over other materials in disposal.
  • the foam body is designed in a special way.
  • the foam body is formed from a workpiece which has a compacted mixture of powdered aluminum or a powdered aluminum alloy on the one hand and powdered blowing or blowing agent on the other hand and, if required, powdered aluminum oxide compounds.
  • the workpiece can for example by the method described in DE-PS 40 18 360 and it has been shown that the use of that method, ie the circumvention of the method described in US Pat. No. 4,713,277, is significantly more acoustically effective in the manufacture Leads components.
  • This compacted workpiece is placed, for example, in a mold, the cavity walls of which determine the outer contours of the finished foam body.
  • the shape can be made from such that the top is open.
  • the aluminum powder is melted by heating and the blowing gas or propellant gas is released upon decomposition of the blowing agent or blowing agent, which transforms the aluminum melt into a foam structure with preferably essentially closed cells.
  • the open design With the open design, the possibility of free foaming is given.
  • the normally relatively round to polygonal foam pores are flattened with increasing degree of compression and molded in an ellipsoidal manner or the cell webs fold in perpendicular to the compression direction. This leads to an anisotropic heat conduction behavior, which leads to a reduction in the heat conduction in the workpiece thickness direction and a slightly increased heat conduction in the workpiece plane direction, ie, a higher thermal insulation of the workpiece.
  • such a mat-shaped pressed workpiece made of the aluminum blowing agent powder mixture into cavities between components and to heat the workpiece so that it inflates between the opposite walls of the components and essentially completely fills the intermediate space.
  • such a component also acts as a vibration-damping unit that dampens the adjacent components and also stiffens the overall construction.
  • the invention therefore offers a simple possibility of forming composite bodies with both mechanical and acoustically damping or insulating functions.
  • the component according to the invention favors disposal, since it can be easily separated from other materials of the overall assembly and can be reused without the formation of harmful and environmentally harmful gases and vapors in the usual metal separation and processing method. It is therefore also possible to use recyclable aluminum materials for the production of the compacted workpiece and therefore of the sound wave damping or insulating and heat insulating component.
  • a blackening of the workpiece produced on one side leads to a significant increase in the emission coefficient and thus to an increase in thermal insulation.
  • powdered aluminum in a large excess over the proportions of the blowing agent powder, in a ratio between 10: 1 and 1000: 1.
  • compounds containing aluminum oxide in proportions of 0-30% (based on the total amount of powder).
  • Blowing agents, as well as other constituents are largely homogeneously distributed in the aluminum powder, unless certain areas of the workpiece from the powder mixture are to foam less when heat is applied.
  • the powder mixture is compacted to the workpiece under a pressure of advantageously between 10 and 500 MPa. Temperatures in the range between 400 and 900 ° C should be used for heating and foaming.
  • the component according to the invention can also be cold-formed even after foaming in order to adapt it even better to certain space requirements.
  • the component according to the invention is particularly preferably used in motor vehicles and machine systems, specifically as a sound-absorbing partition and / or sound-absorbing cover for vibrating wall parts and / or sound-absorbing thermal insulation of the entire exhaust line.
  • components with cell walls made of aluminum or aluminum alloys of the foamed cells forming the foam form a multifunctional structural component which not only corresponds to the wishes of an acoustically good effectiveness, but also solves the above-mentioned object and also has other advantages brings:
  • the aluminum structure is dimensionally stable and therefore self-supporting, but also much better thermally insulating compared to compact aluminum .
  • the total weight is relatively low in the extent of the void formation. Disposal can be done together with the other metal components aluminum in particular without separating. The very costly segregation of plastic parts is avoided, particularly when used in automobile construction. The result is a simple recycling process.
  • FIG. 1 schematically shows in cross section part of a type of “front shell” which, with its curved outer side 2, faces the passenger compartment within a motor vehicle.
  • the component consists of an abundance of hollow cells 3, the cell walls 3a of which, as shown in FIG. 3, consist of aluminum. While the surface 2 facing the passenger compartment has an essentially closed, non-porous, thin aluminum skin which extends to the edge part 5, the sound-generating engine compartment can face the open-cell inner side 1, so that the sound enters the cells 3 or in spaces 3c can penetrate between adjacent cells 3.
  • the inherently rigid foam body 8 from the hollow cells absorbs part of the sound waves that pass through the openings 3b in the cell walls 3a and / or into the spaces 3c penetrate neighboring cells 3, which do not, as at the connection point 3c of adjacent cells 3, frit and / or fuse together in the heat used in the foam formation.
  • the aluminum skin 4 and the edge part 5 of the component are formed, for example, by fusing or frying the cell walls 3a.
  • the component according to the exemplary embodiment of FIG. 1 is provided on the inside 1 with recesses 6;
  • the component has a zone B of less thickness at this point than in the other zones A.
  • the minimum thickness of the component should be 2 mm; the layer thickness of the edge part 5 of the component of FIGS. 1 and 2 is approximately 3 mm, while the layer thickness in the zones A is of the order of cm.
  • the distribution of layer thicknesses, cell and cavity sizes and cell wall thicknesses depends on the functions of sound absorption. In many cases, it is advisable to alternate zones of very good sound absorption with zones per se of less good sound absorption, as a result of which very specific overlay functions can be formed.
  • the mixture in a compacting stage under a pressure of, for example, 50 MPa becomes that in FIG. 4 schematically in cross section shown workpiece 7 pressed together.
  • this can have relatively large dimensions and can be designed like a mat or profile.
  • the workpiece 7 can be made like any other workpiece made of normal aluminum or aluminum alloy without additions using known machining methods, such as Bending, milling, cutting, drilling, punching, extrusion, can be brought into any two or three-dimensional shape 7a.
  • the workpiece 7 is foamed in a heating and deformation stage, for example within a hollow mold, to give the foam body 8, shown schematically in cross section in FIG. 4, which has an essentially open-cell foam structure of the cells 3, but can be covered on the outside with a thin skin 4, without significantly affecting the acoustic effectiveness.
  • a temperature of 750 ° C. is sufficient for heating in order to form a foam body 8 with an average porosity of approximately 80% and an average cell size of approximately 0.8 mm.

Abstract

In the case of a sound-damping and/or sound-insulating and heat-insulating element of lightweight construction, in which the cell walls (3a) of foamed pores or cells (3), forming a foam body (8), consist substantially of aluminium or an aluminium alloy, the foam body is formed by a workpiece (7) which is deformed by heating and has a compacted mixture of powdered aluminium (9) or a powdered aluminium alloy and powdered blowing agent (10) and, if need be, powdered aluminium oxides (11). Since the material is, to the greatest extent, a monomaterial, simple metal recycling is possible. <IMAGE>

Description

Die Erfindung bezieht sich auf ein Schallwellen dämpfendes und/oder dämmendes, d.h. akustisch wirksames Bauelement aus Schaumstoff der im Oberbegriff des Anspruchs 1 genannten Art sowie auf ein Verfahren zu dessen Herstellung und dessen Verwendung.The invention relates to a sound wave damping and / or damping, i.e. acoustically active component made of foam of the type mentioned in the preamble of claim 1 and a method for its production and use.

Derartige Bauelemente sind bereits bekannt (DE-OS 27 35 153), jedoch nur als akustisch wirksame Bauteile. Sie haben die Aufgabe, einen möglichst großen Widerstand gegen das Durchdringen von Schallwellen von der einen Seite des Bauelements auf die andere zu bilden. Diese Funktion bzeichnet man als "schalldämmend". Darüber hinaus haben solche Bauelemente gelegentlich auch die Aufgabe, schon die Entstehung von Schallwellen an der einen Seite des Bauelements zu dämpfen; diese als "schalldämpfende" Funktion bezeichnete Aufgabe wird beispielsweise dadurch erreicht, daß das Bauelement unmittelbar mit dem schallabgebenden Element, beispielsweise ein Karosserieblech, verbunden wird durch z.B. Andrücken, Kleben, Clipsen.Such components are already known (DE-OS 27 35 153), but only as acoustically effective components. They have the task of forming the greatest possible resistance against the penetration of sound waves from one side of the component to the other. This function is known as "soundproofing". In addition, such components occasionally have the task of already dampening the generation of sound waves on one side of the component; this task, referred to as a "sound-absorbing" function, is achieved, for example, by the component being connected directly to the sound-emitting element, for example a body panel, by means of, for example, Press, glue, clip.

Darüber hinaus ist es bekannt (DE-PS 32 24 224), für beispielsweise Auspufftöpfe schalldämpfende Scheiben aus geschäumter Keramik zu verwenden, deren untereinander in Verbindung stehende Poren zur Aufnahme von Abgaskondensaten dienen. Keramisches Material ist jedoch verhältnismäßig starr und kann nach der Formgebung und Sinterung in seiner Form nicht mehr ohne weiteres geändert werden.In addition, it is known (DE-PS 32 24 224), for example Exhaust mufflers to use sound-absorbing discs made of foamed ceramic, the interconnected pores of which serve to hold exhaust gas condensates. However, ceramic material is relatively rigid and its shape can no longer be changed easily after shaping and sintering.

Ferner ist es bekannt (US-PS 4 713 277), in eine Aluminiumschmelze ein Verdickungsmittel unter Umrühren einzubringen. Dieses Verdickungsmittel (metallisches Calcium) dient zur Stabilisierung der Schmelzenviskosität. Nach Zugabe von Titanhydridpulver in die verhältnismäßig niedrigviskose Aluminiumschmelze wird unter weiterem Rühren eine innige Mischung erzielt. Nun wird das Rührgerät aus der Form genommen und diese wird mit einem Deckel fest verschlossen. Dann wird durch den Aufschäumprozeß ein Schaumstoffkörper gebildet, welcher im wesentlichen geschlossene Zellen aufweist. Die Hohlraumwände der geschlossenen Form definieren die Außenkonfiguration des Schaumstoffkörpers. Zylinderförmige Schaumstoffkörper dieser Art, die mit Durchgangslöchern versehen sind, werden als schalldämpfende Einsätze in Auspufftöpfen verwendet.Furthermore, it is known (US Pat. No. 4,713,277) to introduce a thickener into an aluminum melt while stirring. This thickener (metallic calcium) serves to stabilize the melt viscosity. After the addition of titanium hydride powder to the relatively low-viscosity aluminum melt, an intimate mixture is achieved with further stirring. Now the mixer is removed from the mold and this is tightly closed with a lid. Then a foam body is formed by the foaming process, which has essentially closed cells. The cavity walls of the closed mold define the outer configuration of the foam body. Cylindrical foam bodies of this type, which are provided with through holes, are used as sound-absorbing inserts in mufflers.

Die bisher für Schalldämmungszwecke primär verwendeten Bauelemente aus Schaumstoff weisen jedoch meistens Kunststoffe, wie Polyurethan, auf (DE-OS 27 35 153). Dabei stellen die Zellwände mehr oder weniger biegeweiche Häutchen dar. Für Spezialaufgaben ist es auch bekannt, offenzellige Schaumstrukturen mit solchen Schaumstrukturen zu verbinden, welche geschlossenzellig sind oder mit Füllstoffen gefüllt bzw. imprägniert werden. Die Herstellungskosten solcher Doppel-Strukturen sind verhältnismäßig hoch. Dies gilt auch für offenporigen Schaumstoffvlies (DE-PS 36 24 427). Darüber hinaus ergeben sich auch Probleme bei der Entsorgung nicht mehr benutzbarer Konstruktionen, welche mit solchen akustisch wirksamen Bauelementen ausgerüstet sind.However, the foam components used primarily for sound insulation purposes mostly have plastics such as polyurethane (DE-OS 27 35 153). The cell walls represent more or less flexible cuticles. For special tasks it is also known to connect open-cell foam structures with those foam structures that are closed-celled or that are filled or impregnated with fillers. The manufacturing costs of such double structures are relatively high. This also applies to open-pore foam fleece (DE-PS 36 24 427). In addition, there are problems with the disposal of unusable constructions, which with such acoustically effective components are equipped.

Ebenfalls bekannt sind thermisch isolierende Schichtstoffelemente (DE-OS 38 21 468 und G 92 03 734.8). Diese Schichtstoffelemente sind z.T. auch akustisch wirksam. Diese Bauelemente sind jeweils aus mehreren verschiedenen Schichten eines oder mehrerer Werkstoffe, also kompliziert, aufgebaut. Sie benötigen, da die nicht selbsttragend sind, zusätzlich eine Versteifung, meist in Form eines Aluminiumträgerblechs. Bei den Varianten, die aus unterschiedlichen Materialien aufgebaut sind, stellt sich zudem das Problem des Recyclings.Thermally insulating laminate elements are also known (DE-OS 38 21 468 and G 92 03 734.8). These laminate elements are partly also acoustically effective. These components are each made up of several different layers of one or more materials, that is to say in a complicated manner. Because they are not self-supporting, you need additional stiffening, usually in the form of an aluminum support plate. With the variants, which are made of different materials, there is also the problem of recycling.

Der Erfindung liegt die Aufgabe zugrunde, das Bauelement der eingangs genannten Gattung dahingehend zu verbessern, daß es bei guter akustischer Wirksamkeit gleichzeitig gute Wärmeisolationseigenschaften aufweist, einfach herstellbar ist, Leichtbaumerkmale besitzt und gegenüber anderen Materialien Vorteile bei der Entsorgung bietet.The invention has for its object to improve the component of the type mentioned in such a way that with good acoustic effectiveness it also has good thermal insulation properties, is easy to manufacture, has lightweight features and offers advantages over other materials in disposal.

Die Erfindung ist im Anspruch 1 gekennzeichnet, und in Unteransprüchen sind weitere Ausbildungen derselben beansprucht.The invention is characterized in claim 1, and further embodiments thereof are claimed in subclaims.

Auch anhand der Figurenbeschreibung werden bevorzugte Ausbildungsformen noch näher erläutert.Preferred forms of training are also explained in more detail with the aid of the description of the figures.

Bei dem erfindungsgemäßen akustisch wirksamen und thermisch isolierenden Bauelement ist der Schaumstoffkörper in besonderer Weise ausgebildet. Aus einem Werkstück, das eine kompaktierte Mischung aus pulverförmigem Aluminium bzw. einer pulverförmigen Aluminiumlegierung einerseits und pulverförmigem Bläh- bzw. Treibmittel andererseits sowie bedarfsweise pulverförmigen Aluminiumoxidverbindungen aufweist, wird durch Verformen und Erwärmen der Schaumstoffkörper gebildet. Das Werkstück kann beispielsweise nach dem in der DE-PS 40 18 360 beschriebenen Verfahren hergestellt werden und es hat sich gezeigt, daß die Anwendung jenes Verfahrens, d.h. die Umgehung des in der US-PS 4 713 277 beschriebenen Verfahrens, zu wesentlichen Vorteilen bei der Herstellung akustisch wirksamer Bauelemente führt. Abgesehen davon, daß das separate Herstellen einer Aluminiumschmelze, welche nur schwierig zu stabilisieren ist, vor dem Zugeben von Blähmittel vermieden wird, wird die einfache Herstellung beliebiger Formteile beim Anwender selbst möglich, sofern ein derartiges aus Aluminiumpulver und Blähmittelpulver und u.U. aluminiumoxidhaltigem Füllstoff gepreßtes Werkstück als Ausgangsmaterial verwendet wird.In the acoustically effective and thermally insulating component according to the invention, the foam body is designed in a special way. The foam body is formed from a workpiece which has a compacted mixture of powdered aluminum or a powdered aluminum alloy on the one hand and powdered blowing or blowing agent on the other hand and, if required, powdered aluminum oxide compounds. The workpiece can for example by the method described in DE-PS 40 18 360 and it has been shown that the use of that method, ie the circumvention of the method described in US Pat. No. 4,713,277, is significantly more acoustically effective in the manufacture Leads components. In addition to the fact that the separate production of an aluminum melt, which is difficult to stabilize, is avoided before the addition of blowing agent, the user is able to easily produce any molded parts, provided that such a workpiece is pressed from aluminum powder and blowing agent powder and possibly aluminum oxide-containing filler Starting material is used.

Dieses kompaktierte Werkstück wird beispielsweise in eine Form eingelegt, deren Hohlraumwände die Außenkonturen des fertigen Schaumstoffkörpers bestimmt. Die Form kann jedoch aus so ausgebildet sein, daß die Oberseite offen ist. Durch Erhitzen wird das Aluminiumpulver aufgeschmolzen und wird für die Abgabe von Bläh- bzw. Treibgas beim Zersetzen des Bläh- bzw. Treibmittels gesorgt, das die Aluminiumschmelze in eine Schaumstoffstruktur mit bevorzugt im wesentlichen geschlossenen Zellen umformt. Bei der offen gestalteten Formvariante wird damit die Möglichkeit zum freien Aufschäumen gegeben. Durch nachträgliches Stauchen frei, ohne Dickenbegrenzung, aufgeschäumter Werkstücke werden die normal relativ runden bis polygonalen Schaumporen mit zunehmendem Stauchungsgrad abgeflacht und ellipsoidartig eingeformt bzw. falten sich die Zellstege senkrecht zur Stauchrichtung ein. Dies führt zu einem anisotropen Wärmeleitungsverhalten, das zu einer Verringerung der Wärmeleitung in Werkstückdickenrichtung und einer leicht erhöhten Wärmeleitung in Werkstückebenenrichtung führt, d.h. eine höhere Wärmedämmung des Werkstücks bewirkt.This compacted workpiece is placed, for example, in a mold, the cavity walls of which determine the outer contours of the finished foam body. However, the shape can be made from such that the top is open. The aluminum powder is melted by heating and the blowing gas or propellant gas is released upon decomposition of the blowing agent or blowing agent, which transforms the aluminum melt into a foam structure with preferably essentially closed cells. With the open design, the possibility of free foaming is given. By subsequent upsetting free, without thickness limitation, foamed workpieces, the normally relatively round to polygonal foam pores are flattened with increasing degree of compression and molded in an ellipsoidal manner or the cell webs fold in perpendicular to the compression direction. This leads to an anisotropic heat conduction behavior, which leads to a reduction in the heat conduction in the workpiece thickness direction and a slightly increased heat conduction in the workpiece plane direction, ie, a higher thermal insulation of the workpiece.

Darüber hinaus ist es auch möglich, ein solches beispielsweise mattenförmiges gepreßtes Werkstück aus der Aluminium-Blähmittelpulver-Mischung in Hohlräume zwischen Bauteilen einzulegen und das Werkstück zu erwärmen, so daß es sich zwischen den gegenüberliegenden Wänden der Bauteile aufbläht und den Zwischenraum im wesentlichen vollständig ausfüllt. Außer der akustisch wirksamen schalldämpfenden Aufgabe wirkt ein solches Bauelement gleichzeitig als Vibrationen der anliegenden Bauteile dämmendes und die Gesamtkonstruktion auch versteifendes Aggregat.In addition, it is also possible to insert such a mat-shaped pressed workpiece made of the aluminum blowing agent powder mixture into cavities between components and to heat the workpiece so that it inflates between the opposite walls of the components and essentially completely fills the intermediate space. In addition to the acoustically effective sound-absorbing task, such a component also acts as a vibration-damping unit that dampens the adjacent components and also stiffens the overall construction.

Die Erfindung bietet daher eine einfache Möglichkeit, Verbundkörper mit sowohl mechanischen als auch akustisch dämpfenden bzw. dämmenden Funktionen zu bilden. Gleichzeitig begünstigt das erfindungsgemäße Bauelement die Entsorgung, da es leicht ohne Bildung schädlicher und die Umwelt verseuchender Gase und Dämpfe im üblichen Metalltrenn- und Aufbereitungsverfahren von anderen Werkstoffen des Gesamtaggregats trennbar und der Wiederverwendung zuführbar ist. Es können daher auch recycelbare Aluminiumwerkstoffe zur Herstellung des kompaktierten Werkstücks und daher des Schallwellen dämpfenden bzw. dämmenden und wärmedämmenden Bauelements verwendet werden.The invention therefore offers a simple possibility of forming composite bodies with both mechanical and acoustically damping or insulating functions. At the same time, the component according to the invention favors disposal, since it can be easily separated from other materials of the overall assembly and can be reused without the formation of harmful and environmentally harmful gases and vapors in the usual metal separation and processing method. It is therefore also possible to use recyclable aluminum materials for the production of the compacted workpiece and therefore of the sound wave damping or insulating and heat insulating component.

Eine Schwärzung des erzeugten Werkstücks auf einer Seite führt zu einer deutlichen Erhöhung des Emissionskoeffizienten und somit zu einer Erhöhung der Wärmedämmung.A blackening of the workpiece produced on one side leads to a significant increase in the emission coefficient and thus to an increase in thermal insulation.

Bei dem erfindungsgemäßen Verfahren nach Anspruch 9 empfiehlt es sich, pulverförmiges Aluminium in großem Überschuß über die Anteile des Blähmittelpulvers anzuwenden und zwar in einem verhältnis zwischen 10:1 und 1000:1. In einer beispielhaften Ausführung der Erfindung ist es zweckmäßig, zusätzlich aluminiumoxydhaltige Verbindungen in Anteilen von 0-30% (bezogen auf die Gesamtpulvermenge) zuzugeben. In allen Fällen sollte das Treibmittel, als auch andere Bestandteile weitgehend homogen im Aluminiumpulver verteilt sein, sofern nicht bestimmte Bereiche des Werkstücks aus der Pulvermischung bei Anwendung von Wärme weniger stark aufschäumen sollen. Die Pulvermischung wird unter einem Druck von zweckmäßigerweise zwischen 10 und 500 MPa zu dem Werkstück kompaktiert. Zum Erwärmen und Aufschäumen sollten Temperaturen im Bereich zwischen 400 und 900 °C angewendet werden.In the method according to the invention according to claim 9, it is advisable to use powdered aluminum in a large excess over the proportions of the blowing agent powder, in a ratio between 10: 1 and 1000: 1. In an exemplary embodiment of the invention, it is expedient to additionally add compounds containing aluminum oxide in proportions of 0-30% (based on the total amount of powder). In all cases, it should Blowing agents, as well as other constituents, are largely homogeneously distributed in the aluminum powder, unless certain areas of the workpiece from the powder mixture are to foam less when heat is applied. The powder mixture is compacted to the workpiece under a pressure of advantageously between 10 and 500 MPa. Temperatures in the range between 400 and 900 ° C should be used for heating and foaming.

Das erfindungsgemäße Bauelement kann auch nach dem Aufschäumen noch zusätzlich kaltverformt werden, um es an bestimmte Raumerfordernisse noch besser anzupassen.The component according to the invention can also be cold-formed even after foaming in order to adapt it even better to certain space requirements.

Besonders bevorzugt verwendet wird das erfindungsgemäße Bauelement bei Kraftfahrzeugen und Maschinenanlagen und zwar als schalldämmende Trennwand und/oder schalldämpfende Abdeckung von vibrierenden Wandteilen und/oder schalldämmende Wärmeisolation des gesamten Abgasstranges.The component according to the invention is particularly preferably used in motor vehicles and machine systems, specifically as a sound-absorbing partition and / or sound-absorbing cover for vibrating wall parts and / or sound-absorbing thermal insulation of the entire exhaust line.

Es hat sich gezeigt, daß Bauelemente mit aus Aluminium oder Aluminiumlegierungen bestehenden Zellwänden der den Schaumstoff bildenden aufgeschäumten Zellen ein Multifunktions-Strukturbauteil bilden, das nicht nur den Wünschen einer akustisch guten Wirksamkeit entspricht, sondern auch die oben genannte Aufgabe löst und darüber hinaus weitere Vorteile mit sich bringt: Abgesehen von der einfachen Herstellbarkeit durch Aufschäumen von insbesondere Aluminiumpulver und einem gasabspaltenden Treibmittelpulver unter ausreichender Erwärmung insbesondere unmittelbar in der Hohlform, welche den äußeren Konturen des Bauelements entspricht, ist die Aluminiumstruktur formstabil und daher selbsttragend, gegenüber Kompaktaluminium aber auch wesentlich besser thermisch isolierend. Das Gesamtgewicht ist im Ausmaß der Hohlraumbildung verhältnismäig niedrig. Die Entsorgung kann zusammen mit den anderen Metallbauteilen aus insbesondere Aluminium ohne Trennen erfolgen. Insbesondere bei der Anwendung im Automobilbau wird das sehr kostspielige Absondern von Kunststoffteilen vermieden. Ein einfaches Recyclingverfahren ist die Folge.It has been shown that components with cell walls made of aluminum or aluminum alloys of the foamed cells forming the foam form a multifunctional structural component which not only corresponds to the wishes of an acoustically good effectiveness, but also solves the above-mentioned object and also has other advantages brings: Apart from the ease of manufacture by foaming in particular aluminum powder and a gas-releasing blowing agent powder with sufficient heating, in particular directly in the hollow form, which corresponds to the outer contours of the component, the aluminum structure is dimensionally stable and therefore self-supporting, but also much better thermally insulating compared to compact aluminum . The total weight is relatively low in the extent of the void formation. Disposal can be done together with the other metal components aluminum in particular without separating. The very costly segregation of plastic parts is avoided, particularly when used in automobile construction. The result is a simple recycling process.

Ein Ausführungsbeispiel der Erfindung wird anhand der Zeichnung erläutert. Dabei zeigen:

Figur 1
einen schematischen Querschnitt durch ein erfindungsgemäßes Bauteil;
Figur 2
einen vergrößerten Ausschnitt aus dem rechten oberen Bereich von Figur 1;
Figur 3
einen noch weiter vergrößerten schematischen Aufriß aus einem Teil des Bauelements und
Figur 4
schematisch die Stufen des Herstellungsverfahrens.
An embodiment of the invention is explained with reference to the drawing. Show:
Figure 1
a schematic cross section through an inventive component;
Figure 2
an enlarged section of the upper right area of Figure 1;
Figure 3
a further enlarged schematic elevation of part of the device and
Figure 4
schematically the stages of the manufacturing process.

In Figur 1 ist schematisch im Querschnitt ein Teil einer Art "Vorsatzschale" dargestellt, welche mit ihrer gewölbten Außenseite 2 innerhalb eines Kraftfahrzeugs dem Fahrgastraum zugewandt ist. Das Bauelement besteht aus einer Fülle von hohlen Zellen 3, deren Zellwände 3a etwa gemäß Figur 3 aus Aluminium bestehen. Während die dem Fahrgastraum zugewandte Oberfläche 2 eine im wesentlichen geschlossene, nicht poröse dünne Aluminiumhaut aufweist, die sich bis zu dem Randteil 5 hinzieht, kann dem schallerzeugenden Motorraum die offenzellige Innenseite 1 zugewandt sein, so daß der Schall in die Zellen 3 bzw. in Zwischenräume 3c zwischen benachbarten Zellen 3 eindringen kann. Der eigensteife Schaumstoffkörper 8 aus den hohlen Zellen absorbiert einen Teil der Schallwellen, die durch die Durchbrechungen 3b in den Zellwänden 3a und/oder in die Zwischenräume 3c zwischen benachbarten Zellen 3 eindringen, welche nicht wie an der Verbindungsstelle 3c von aneinanderliegenden Zellen 3 bei der bei der Schaumbildung angewendeten Hitze zusammenfritten und/oder verschmelzen. Die Aluminiumhaut 4 und der Randteil 5 des Bauelements sind beispielsweise durch Verschmelzen oder Verfritten der Zellwände 3a gebildet.FIG. 1 schematically shows in cross section part of a type of “front shell” which, with its curved outer side 2, faces the passenger compartment within a motor vehicle. The component consists of an abundance of hollow cells 3, the cell walls 3a of which, as shown in FIG. 3, consist of aluminum. While the surface 2 facing the passenger compartment has an essentially closed, non-porous, thin aluminum skin which extends to the edge part 5, the sound-generating engine compartment can face the open-cell inner side 1, so that the sound enters the cells 3 or in spaces 3c can penetrate between adjacent cells 3. The inherently rigid foam body 8 from the hollow cells absorbs part of the sound waves that pass through the openings 3b in the cell walls 3a and / or into the spaces 3c penetrate neighboring cells 3, which do not, as at the connection point 3c of adjacent cells 3, frit and / or fuse together in the heat used in the foam formation. The aluminum skin 4 and the edge part 5 of the component are formed, for example, by fusing or frying the cell walls 3a.

Um ausladenden Konturen auszuweichen bzw. Abstützelemente aufzunehmen, ist das Bauelement nach dem Ausführungsbeipiel von Figur 1 an der Innenseite 1 mit Aussparungen 6 versehen; zu diesem Zweck weist das Bauelement an dieser Stelle eine Zone B geringerer Dicke als in den anderen Zonen A auf.In order to avoid protruding contours or to accommodate support elements, the component according to the exemplary embodiment of FIG. 1 is provided on the inside 1 with recesses 6; For this purpose, the component has a zone B of less thickness at this point than in the other zones A.

Die Mindestdicke des Bauelements sollte 2 mm betragen; so beträgt die Schichtdicke des Randteils 5 des Bauelements von Figuren 1 und 2 etwa 3 mm, während die Schichtdicke in den Zonen A in der Größenordnung von cm liegt. Die Verteilung der Schichtdicken, Zellen- und Hohlraumgrößen und Zellwanddicken hängt von den Funktionen der Schallabsorption ab. Vielfach empfiehlt es sich, Zonen sehr guter Schallabsorption mit Zonen per se weniger guter Schallabsorption abwechseln zu lassen, wodurch ganz bestimmte Überlagungsfunktionen gebildet werden können.The minimum thickness of the component should be 2 mm; the layer thickness of the edge part 5 of the component of FIGS. 1 and 2 is approximately 3 mm, while the layer thickness in the zones A is of the order of cm. The distribution of layer thicknesses, cell and cavity sizes and cell wall thicknesses depends on the functions of sound absorption. In many cases, it is advisable to alternate zones of very good sound absorption with zones per se of less good sound absorption, as a result of which very specific overlay functions can be formed.

Gemäß Figur 4 wird ausgehend von Aluminiumpulver 9 einerseits und Titanhydridpulver 10 andererseits und gegebenenfalls pulverförmigem Aluminiumoxid 11 in einem Mischverfahren eine homogene Mischung dieser beiden bzw. drei Pulver hergestellt. Dabei werden etwa 100 gr Aluiminiumpulver 0,5 gr Titanhydridpulver und 25 gr Aluminiumoxid zugesetzt.According to FIG. 4, starting from aluminum powder 9 on the one hand and titanium hydride powder 10 on the other hand and optionally powdered aluminum oxide 11, a homogeneous mixture of these two or three powders is produced in a mixing process. About 100 grams of aluminum powder, 0.5 grams of titanium hydride powder and 25 grams of aluminum oxide are added.

Nach dem guten Vermischen der Pulver 9, 10 und eventuell 11 wird das Gemisch in einer Kompaktierungsstufe unter einem Druck von beispielsweise 50 MPa zu dem in Figur 4 schematisch im Querschnitt dargestellten Werkstück 7 zusammengepreßt. Dieses kann im Vergleich zur Schichtdicke verhältnismäßig große Abmessungen aufweisen und mattenartig oder profilförmig ausgebildet sein.After the powders 9, 10 and possibly 11 have been mixed well, the mixture in a compacting stage under a pressure of, for example, 50 MPa becomes that in FIG. 4 schematically in cross section shown workpiece 7 pressed together. In comparison to the layer thickness, this can have relatively large dimensions and can be designed like a mat or profile.

Nun kann das Werkstück 7 wie jedes andere Werkstück aus normalem Aluminium bzw. Aluminiumlegierung ohne Zusätze mit bekannten Bearbeitungsmethoden, wie z.B. Biegen, Fräsen, Schneiden, Bohren, Stanzen, Strangpressen, in jede beliebige zwei- bzw. dreidimensionale Form 7a gebracht werden.Now the workpiece 7 can be made like any other workpiece made of normal aluminum or aluminum alloy without additions using known machining methods, such as Bending, milling, cutting, drilling, punching, extrusion, can be brought into any two or three-dimensional shape 7a.

Schließlich wird das Werkstück 7 in einer Erwärmungs- und Verformungsstufe beispielsweise innerhalb einer Hohlform zu dem in Figur 4 schematisch im Querschnitt dargestellten Schaumstoffkörper 8 aufgeschäumt, der eine im wesentlichen offenzellige Schaumstoffstruktur der Zellen 3 aufweist, außen aber mit einer dünnen Haut 4 überzogen sein kann, ohne daß hierdurch die akustische Wirksamkeit wesentlich beeinträchtigt wird. Diese Eigenschaft ist sehr überraschend, da anzunehmen war, daß der Schaumstoffkörper 8 Durchbrechungen aufweisen müßte. Bei diesem Beispiel reicht zum Erwärmen eine Temperatur von 750 C aus, um einen Schaumstoffkörper 8 mit einer durchschnittlichen Porosität von etwa 80% und einer durchschnittlichen Zellengröße von etwa 0,8 mm zu bilden.Finally, the workpiece 7 is foamed in a heating and deformation stage, for example within a hollow mold, to give the foam body 8, shown schematically in cross section in FIG. 4, which has an essentially open-cell foam structure of the cells 3, but can be covered on the outside with a thin skin 4, without significantly affecting the acoustic effectiveness. This property is very surprising since it could be assumed that the foam body would have 8 openings. In this example, a temperature of 750 ° C. is sufficient for heating in order to form a foam body 8 with an average porosity of approximately 80% and an average cell size of approximately 0.8 mm.

Claims (20)

Schallwellen dämpfendes und/oder dämmendes und wärmeisolierendes Bauelement in Leichtbauweise aus Schaumstoff, bei dem die Zellwände der den Schaumstoff bildenden aufgeschäumten Zellen im wesentlichen aus Aluminium oder einer Aluminiumlegierung bestehen,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) aus einem durch Erwärmen verformten Werkstück (7) gebildet ist, der eine kompaktierte Mischung aus pulverförmigem Aluminium bzw. einer pulverförmigen Aluminiumlegierung (9), pulverförmigem Bläh- bzw. Treibmittel (10) und bedarfsweise pulverförmigen Aluminiumoxidverbindungen (11) aufweist.
Sound wave damping and / or insulating and heat insulating component in lightweight construction made of foam, in which the cell walls of the foamed cells forming the foam essentially consist of aluminum or an aluminum alloy,
characterized by
that the foam body (8) is formed from a workpiece (7) deformed by heating, which comprises a compacted mixture of powdered aluminum or a powdered aluminum alloy (9), powdered blowing or blowing agent (10) and, if necessary, powdered aluminum oxide compounds (11) having.
Bauelement nach Anspruch 1,
dadurch gekennzeichnet,
daß eine Vielzahl der Zellen (3) des Schaumstoffkörpers (8) offenzellig ist.
Component according to Claim 1,
characterized by
that a plurality of the cells (3) of the foam body (8) is open-celled.
Bauelement nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß ein Teil der Oberfläche (2) mit einer im wesentlichen geschlossenen, nicht porösen dünnen Aluminiumhaut (4) überzogen ist.
Component according to Claim 1 or 2,
characterized by
that part of the surface (2) is covered with a substantially closed, non-porous thin aluminum skin (4).
Bauelement nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) Zonen (A) größerer Dicke und andere Zonen (B) geringerer Dicke aufweist.
Component according to one of the preceding claims,
characterized by
that the foam body (8) has zones (A) of greater thickness and other zones (B) of reduced thickness.
Bauelement nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) eine durchschnittliche Porosität zwischen 60% und 90% aufweist.
Component according to one of the preceding claims,
characterized by
that the foam body (8) has an average porosity between 60% and 90%.
Bauelement nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) eine durchschnittliche Poren- bzw. Zellgröße zwischen 0,1 und 1,5 mm aufweist.
Component according to one of the preceding claims,
characterized by
that the foam body (8) has an average pore or cell size between 0.1 and 1.5 mm.
Bauelement nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) eine Dichte zwischen 0,3 und 2,0 g/cm³ aufweist.
Component according to one of the preceding claims,
characterized by
that the foam body (8) has a density between 0.3 and 2.0 g / cm³.
Bauelement nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) auf einer Seite geschwärzt ist.
Component according to one of the preceding claims,
characterized by
that the foam body (8) is blackened on one side.
Verfahren zur Herstellung eines Schallwellen dämpfenden und/oder dämmenden und wärmeisolierenden Bauelementes in Leichtbauweise nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß Pulver (9) aus Aluminium oder der Aluminiumlegierung mit einem Pulver (10) des Treibmittels im Verhältnis zwischen 10:1 und 1000:1 (A1-Pulver zu Treibmittelpulver), sowie mit einem Pulver (11) von Aluminiumoxid in Anteilen von 0 - 30% (bezogen auf Gesamtpulvermenge) zu einer im wesentlichen homogen verteilten Mischung gemischt und durch Pressen unter einem Druck zwischen 10 und 500 MPa zu dem Werkstück (7) kompaktiert wird.
Method for producing a sound wave damping and / or insulating and heat insulating component in lightweight construction according to one of the preceding claims,
characterized,
that powder (9) made of aluminum or aluminum alloy with a powder (10) of the blowing agent in a ratio between 10: 1 and 1000: 1 (A1 powder to blowing agent powder), and with a powder (11) of aluminum oxide in proportions of 0 - 30% (based on the total amount of powder) is mixed into an essentially homogeneously distributed mixture and compacted to the workpiece (7) by pressing under a pressure between 10 and 500 MPa.
Verfahren nach Anspruch 9,
dadurch gekennzeichnet,
daß das Werkstück (7) durch mechanische Bearbeitungsverfahren, wie Biegen, Schneiden, Fräsen, Bohren, Stanzen, Sägen und Strangpressen, in eine beliebige zwei- bzw. dreidimensionale Form (7a) gebracht wird.
Method according to claim 9,
characterized,
that the workpiece (7) is brought into any two-dimensional or three-dimensional shape (7a) by mechanical processing methods such as bending, cutting, milling, drilling, punching, sawing and extrusion.
Verfahren nach Anspruch 9 oder 10,
dadurch gekennzeichnet,
daß das Werkstück (7 bzw. 7a) zum Aufschäumen zwischen 400°C und 900°C erwärmt wird.
A method according to claim 9 or 10,
characterized by
that the workpiece (7 or 7a) is heated for foaming between 400 ° C and 900 ° C.
Verfahren nach einem der Ansprüche 9 bis 11,
dadurch gekennzeichnet,
daß das Werkstück (7 oder 7a) in einer im wesentlichen geschlossenen Form so erwärmt wird, daß es diese beim Aufschäumen vollständig ausfüllt und sich in die Form eines Schaumstoffkörpers (8) verformt, wobei es nicht zwingend notwendig ist, daß das Werkstück (7a) in seiner Form der Form des endgültigen Schaumstoffkörpers (8) vor dem Aufschäumen angepaßt werden muß.
Method according to one of claims 9 to 11,
characterized by
that the workpiece (7 or 7a) is heated in a substantially closed form so that it completely fills it up when foaming and deforms into the shape of a foam body (8), it not being absolutely necessary that the workpiece (7a) in its shape the shape of the final foam body (8) must be adjusted before foaming.
Verfahren nach einem der Ansprüche 9 bis 11,
dadurch gekennzeichnet,
daß das Werkstück (7 oder 7a) frei aufgeschäumt und anschließend mehr oder weniger stark gestaucht und somit auf Endstärke gebracht wird.
Method according to one of claims 9 to 11,
characterized,
that the workpiece (7 or 7a) is foamed freely and then more or less compressed and thus brought to its final strength.
Verfahren nach einem der Ansprüche 9 bis 13,
dadurch gekennzeichnet,
daß der Schaumstoffkörper (8) zusätzlich kaltverformt wird.
Method according to one of claims 9 to 13,
characterized by
that the foam body (8) is additionally cold worked.
Verfahren nach einem Ansprüche 9 bis 14,
dadurch gekennzeichnet,
daß das Werkstück einseitig geschwärzt wird, beispielsweise durch Graphitierung.
Method according to one of claims 9 to 14,
characterized,
that the workpiece is blackened on one side, for example by graphitization.
Verwendung eines Bauelementes nach einem der Ansprüche 1-8 als schalldämmendes Bauteil, beispielsweise Trennwand, in Kraftfahrzeugen, Flugzeugen, Schiffen oder Maschinenanlagen.Use of a component according to one of claims 1-8 as a sound-absorbing component, for example a partition, in motor vehicles, aircraft, ships or machine systems. Verwendung eines Bauelementes nach einem der Ansprüche 1-8 als schalldämpfende Abdeckung von vibrierenden Wandteilen in Kraftfahrzeugen, Flugzeugen, Schiffen oder Maschinenanlagen.Use of a component according to one of claims 1-8 as a sound-absorbing cover for vibrating wall parts in motor vehicles, aircraft, ships or machine systems. Verwendung eines Bauelementes nach einem der Ansprüche 1-8 als wärmeisolierendes Bauteil in Kraftfahrzeugen, Flugzeugen, Schiffen oder Maschinenanlagen.Use of a component according to one of claims 1-8 as a heat-insulating component in motor vehicles, aircraft, ships or machine systems. Verwendung eines Bauelementes nach einem der Ansprüche 1-8 als schalldämmendes bzw. schalldämpfendes und wärmeisolierendes Bauteil in Kraftfahrzeugen, Flugzeugen, Schiffen oder Maschinenanlagen.Use of a component according to one of claims 1-8 as a sound-absorbing or sound-absorbing and heat-insulating component in motor vehicles, aircraft, ships or machine systems. Verwendung eines Bauelementes nach einem der Ansprüche 1-8 als ein selbsttragendes Strukturbauteil in Kraftfahrzeugen, Flugzeugen, Schiffen oder Maschinenanlagen.Use of a component according to one of claims 1-8 as a self-supporting structural component in motor vehicles, aircraft, ships or machine systems.
EP93114133A 1992-09-18 1993-09-03 Thermally and acoustically insulating composite element, manufacturing method thereof and its use Revoked EP0588182B1 (en)

Applications Claiming Priority (2)

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DE9212607U DE9212607U1 (en) 1992-09-18 1992-09-18 Sound wave damping and / or insulating component made of foam
DE9212607U 1992-09-18

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EP0588182A3 EP0588182A3 (en) 1995-05-31
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AT (1) ATE152851T1 (en)
CZ (1) CZ282028B6 (en)
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ES (1) ES2102566T3 (en)
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AT406649B (en) * 1996-05-02 2000-07-25 Mepura Metallpulver METHOD FOR PRODUCING POROUS MATRIX MATERIALS, IN PARTICULAR MOLDED BODIES, BASED ON METALS, AND SEMI-FINISHED PRODUCTS THEREFOR
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HU9302579D0 (en) 1994-03-28
ATE152851T1 (en) 1997-05-15
EP0588182A3 (en) 1995-05-31
HUT68467A (en) 1995-06-28
HU215772B (en) 1999-02-01
ES2102566T3 (en) 1997-08-01
EP0588182B1 (en) 1997-05-07
DE59306374D1 (en) 1997-06-12
PL172699B1 (en) 1997-11-28
CZ282028B6 (en) 1997-04-16
PL300380A1 (en) 1994-03-21
DE9212607U1 (en) 1994-02-24
CZ193693A3 (en) 1994-04-13

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