EP1888807B1 - Porous metal foam body - Google Patents

Porous metal foam body Download PDF

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Publication number
EP1888807B1
EP1888807B1 EP06763358.6A EP06763358A EP1888807B1 EP 1888807 B1 EP1888807 B1 EP 1888807B1 EP 06763358 A EP06763358 A EP 06763358A EP 1888807 B1 EP1888807 B1 EP 1888807B1
Authority
EP
European Patent Office
Prior art keywords
aluminum
alloys
tin
foam body
metal foam
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.)
Not-in-force
Application number
EP06763358.6A
Other languages
German (de)
French (fr)
Other versions
EP1888807A1 (en
Inventor
Markus Kattannek
Frank Prenger
Jochen Spriestersbach
Jürgen Wisniewski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Grillo Werke AG
Original Assignee
Grillo Werke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Grillo Werke AG filed Critical Grillo Werke AG
Priority to EP06763358.6A priority Critical patent/EP1888807B1/en
Priority to PL06763358T priority patent/PL1888807T3/en
Publication of EP1888807A1 publication Critical patent/EP1888807A1/en
Application granted granted Critical
Publication of EP1888807B1 publication Critical patent/EP1888807B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • 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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F3/26—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • C23C4/185—Separation of the coating from the substrate
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component

Definitions

  • the present invention relates to a porous metal foam body, a method for producing the metal foam body and its use.
  • Metal foams and their production are known. Metal foams are made from powder or by melt metallurgy by stirring in nucleating agents and gas.
  • the DE 102 38 284 A1 describes a multi-stage process in which conductive particles are applied to a non-conductive substrate with a foam structure (eg PU foam) as the basis for a subsequent coating by electroplating and then electroplating is carried out.
  • a foam structure eg PU foam
  • Any material that has an open-cell foam structure can be used as the substrate.
  • the substrate serves as a skeleton.
  • the DE-A-35 22 287 discloses an open-pore body for filtering and / or catalytic treatment of gases or liquids and methods for its manufacture, but points like that DE-A-102 38 284 indicate that before the surface is metallized, the pores of the non-metallic substrate must be prepared for electroplating by means of electrically conductive layers.
  • the metal layer according to the cited documents is namely applied by means of electroplating.
  • FR-A-2 679 925 discloses the production of a porous metallic structure by triple metallization of the surface of a porous organic substrate.
  • the metal foams which are known from the prior art, either have closed pores, so that not all surface areas of the Metal foam are accessible or, in the case of open-pore metal foams, are difficult to manufacture and have at least two metal layers.
  • a porous metal foam body obtainable by applying molten zinc, aluminum, tin or their alloys to an open-pore non-metallic substrate and penetration of the molten zinc, aluminum, tin or their alloys into the open pores of the non-metallic substrate, to form a metal foam body, wherein the application of the molten zinc, aluminum, tin, or their alloys by application of drops of molten zinc, aluminum, tin, or their alloys by thermal spraying, by atomization of molten metals or rotational atomization of molten metals in one or more layers takes place and the molten zinc, aluminum, tin, or their alloys precipitate on the surface of at least a partial population of the pores and a metallized surface of the pores is obtained.
  • the metallic component has at least partially penetrated the open-pore non-metallic substrate.
  • the porous metal foam body according to the invention has populations of pores in its lumen which are at least partially provided with a surface with zinc, aluminum, tin, or their alloys.
  • the population can also be formed only partially in the form of a partial population of pores, which has zinc, aluminum, tin, or their alloys on its surface, and in particular is arranged in the outer region of the non-metallic substrate.
  • Such a porous metal foam body therefore has pores on the outside with a surface with zinc, aluminum, tin, or their alloying alloys, whereas in There are no metallized pores inside.
  • the molten zinc, aluminum, tin, or their alloys are applied according to the invention by applying drops of molten zinc, aluminum, tin, or their alloys by thermal spraying, by atomizing molten metal or by rotating atomizing the molten metal.
  • zinc, aluminum, tin or their alloys come into consideration as base metals.
  • Zinc-based materials are suitable as the first layer on the non-metallic substrate, since they ensure good adhesion to this as well as to the overlying metal layers.
  • the metal foam body according to the invention has, for example, a porosity of 5 to 150 pores per 2.54 cm (5 ppi to 150 ppi, pores per inch), but other ranges can also be selected.
  • the pores of the open-pore non-metallic substrate are formed and enclosed by "webs".
  • the surface or the webs of the substrate are coated with a layer, for example by thermal spraying or atomization, for example air atomization.
  • the layer thickness can vary depending on the parameters of the application method of the metal drops can be set.
  • the result is a foam body made of the sprayed material.
  • Open-pore foam bodies or open-pore foam bodies with a closed cover layer can be produced.
  • the foam body can consist of any material that z. B. can be processed by thermal spraying (iron, zinc, aluminum, copper, nickel, gold, silver, platinum, tin or their alloys).
  • ceramic particles tungsten carbide, aluminum oxide, silicon carbide
  • the substrate can be provided with the material completely or only in partial areas.
  • the process according to the invention for producing a metal foam body is based on an open-pore non-metallic substrate which is provided with drops of molten zinc, aluminum, tin, or their alloys, the drops of molten zinc, aluminum, tin, or their alloys at least partially into the penetrate open pores of the non-metallic substrate.
  • the molten zinc, aluminum, tin, or their alloys are applied by thermal spraying, atomization of molten metal or rotational atomization of molten metal.
  • the penetration of the molten zinc, aluminum, tin, or their alloys can be promoted by measures known to the person skilled in the art. These include in particular the variation of the substrate pore size, shape and structure, variation of the droplet size, velocity, temperature, the spraying distance, the spraying duration, the angle of attack of the substrate to the coating unit, multi-layer spraying, generation of a negative pressure on the back of the substrate or a combination thereof Activities.
  • the open-pore non-metallic substrate which can be used in the process according to the invention can be selected from porous inorganic or organic materials.
  • Suitable inorganic materials are in particular those selected from the group consisting of zeolites, silica gels, frits, ceramic materials, mineral fiber wool or combinations thereof.
  • the organic materials are selected in particular from the group consisting of open-pore foamed material made of plastics, such as foamed polyurethane, polyester, polyether foamed polystyrene, open-pore natural or artificial sponges, wood wool or combinations thereof.
  • the drops can consist of molten zinc, aluminum, tin or their alloys.
  • the substrate can be thermally or chemically removed, for example with the droplets of the molten zinc, aluminum, tin, or their alloys. B. by burning out in the case of organic substrates.
  • the metal foam body according to the invention can be formed with two main surfaces, one or both main surfaces being formed with a closed-pore or non-closed-pore layer made of one material.
  • a polyurethane foam serving as a substrate can be provided on one side with an open-pore layer made of a zinc alloy, the zinc alloy not completely penetrating the substrate.
  • the other side is provided with a multilayer structure consisting of a zinc layer and an overlying copper layer with penetration depths, which also do not penetrate completely through the substrate. If a central area in the polyurethane foam remains untreated, this leads to a 3-component composite consisting of a metal foam body made of a zinc alloy, the substrate polyurethane and a metal foam body zinc / copper.
  • the properties of the individual components eg substrate-zinc-layer-copper layer
  • a soft PU foam with a firm "shell" made of metal can be set in the finished sandwich. This makes it possible, for example, to set certain damping properties or bending stiffness with a simultaneous visual design of the surface.
  • the metal foam body according to the invention can be used, for example, in construction, in particular for lightweight structures, mechanical engineering, in vehicle technology, chemical industry, medical technology, electrical engineering, and in principle wherever weight-saving but solid or stiffened materials are important.
  • the metal foam body according to the invention can be used, for example, for insulation boards, covers, sound insulation, components for electromagnetic shielding, vibration damping, crash absorbers, filters, catalysts, battery components, semiconductors.
  • the shape of the foam body is typically determined by the substrate and can thus be easily and precisely prepared before spraying (e.g. plates, balls, rods, spatially demanding, complicated structures made of substrate material; substrate can also be preformed before coating and in this state can be kept by the coating).
  • the foam can also be used as a core for a composite material, for example the metal foam can be made from a cover sheet made of light metal connected with solder material and heated up to the soldering temperature and optionally inserted stiffening ribs are formed as a composite material.
  • the invention also relates to the use of the metal foam body according to the invention as a starting material for further coatings with metallic materials by means of galvanic processes, by separation from the gas or liquid phase or by powder coating.
  • the metal foam body according to the invention is used as a matrix for filling with polymers or metal casting.
  • a substrate in the form of a polyurethane foam with a thickness of 20 mm and 10 pores per 2.54 cm (pores / inch, 10 ppi) is coated with a layer of zinc by wire arc spraying.
  • the result is an open-pore metal foam body with a density of 0.06-0.45 g / cm 3 and a compressive strength of 16 kPa-220 kPa.
  • a metal foam produced according to Example 1 can be embedded as a matrix in a polymer or metal structure.
  • the open-pore metal foam can be filled with a liquid polymer. This gives a metal / polymer composite with the combination of the materials. This can then be used as a crash absorber, for example.
  • a substrate in the form of a polyurethane foam plate with a thickness of 20 mm, 10 pores per 2.54 cm (pores / inch, 10 ppi) is coated with a layer of zinc by wire arc spraying.
  • the result is an open-pore metal foam body with a density of 0.06-0.45 g / cm 3 and a compressive strength of 16 kPa-220 kPa.
  • a second layer of brass or copper is applied by wire arc spraying. This creates a rigid plate with good sound absorption properties and an aesthetic surface design in brass or copper optics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Laminated Bodies (AREA)

Description

Gegenstand der vorliegenden Erfindung ist ein poröser Metallschaumkörper, ein Verfahren zur Herstellung des Metallschaumkörpers sowie dessen Verwendung.The present invention relates to a porous metal foam body, a method for producing the metal foam body and its use.

Metallschäume und deren Herstellung sind bekannt. So werden Metallschäume aus Pulver oder auf schmelzmetallurgischem Weg durch Einrühren von Keimbildnern und Gas hergestellt.Metal foams and their production are known. Metal foams are made from powder or by melt metallurgy by stirring in nucleating agents and gas.

Die DE 102 38 284 A1 beschreibt einen mehrstufigen Prozess, bei dem auf ein nicht-leitendes Substrat mit Schaumstruktur (z.B. PU-Schaum) leitfähige Partikel als Basis für ein nachfolgendes Beschichten durch Galvanisieren aufgebracht werden und danach eine Galvanisierung durchgeführt wird. Als Substrat kann jedes Material genutzt werden, das eine offenporige Schaumstruktur aufweist. Das Substrat dient als Skelett.The DE 102 38 284 A1 describes a multi-stage process in which conductive particles are applied to a non-conductive substrate with a foam structure (eg PU foam) as the basis for a subsequent coating by electroplating and then electroplating is carried out. Any material that has an open-cell foam structure can be used as the substrate. The substrate serves as a skeleton.

In der DE-A-100 13 378 werden poröse Keramiken beschrieben, die mit Metall gefüllt sind. Dabei wird der gesamte poröse Innenraum mit Metall gefüllt und nicht nur die Oberfläche der Poren mit einer Metallschicht versehen.In the DE-A-100 13 378 describes porous ceramics that are filled with metal. The entire porous interior is filled with metal and not only the surface of the pores is provided with a metal layer.

Die DE-A-35 22 287 offenbart zwar einen offenporigen Körper zum Filtern und/oder katalytischen Behandeln von Gasen oder Flüssigkeiten und Verfahren zu seiner Herstellung, weist aber wie die DE-A-102 38 284 darauf hin, dass vor der Metallisierung der Oberfläche die Poren des nicht metallischen Substrats mittels elektrisch leitfähiger Schichten zur Galvanisierung vorbereitet werden müssen. Die Metallschicht gemäß den genannten Druckschriften wird nämlich mittels Galvanisieren aufgetragen.The DE-A-35 22 287 discloses an open-pore body for filtering and / or catalytic treatment of gases or liquids and methods for its manufacture, but points like that DE-A-102 38 284 indicate that before the surface is metallized, the pores of the non-metallic substrate must be prepared for electroplating by means of electrically conductive layers. The metal layer according to the cited documents is namely applied by means of electroplating.

Auch die FR-A-2 679 925 offenbart die Herstellung einer porösen metallischen Struktur mittels dreifacher Metallisierung der Oberfläche eines porösen organischen Substrats.Also the FR-A-2 679 925 discloses the production of a porous metallic structure by triple metallization of the surface of a porous organic substrate.

Die Metallschäume, die aus dem Stand der Technik bekannt sind, weisen entweder geschlossene Poren auf, so dass nicht alle Oberflächenbereiche des Metallschaums zugänglich sind oder im Falle offenporiger Metallschäume nur aufwändig herstellbar sind und mindestens zwei Metalllagen aufweisen.The metal foams, which are known from the prior art, either have closed pores, so that not all surface areas of the Metal foam are accessible or, in the case of open-pore metal foams, are difficult to manufacture and have at least two metal layers.

Eine Aufgabe der vorliegenden Erfindung war es, einen insbesondere offenporigen Metallschaumkörper zu schaffen, der in einem weiten Anwendungsbereich einsetzbar ist, und ein Verfahren zu seiner Herstellung bereitzustellen, das einfach und kostengünstig ist.It was an object of the present invention to provide an open-pore metal foam body, in particular, which can be used in a wide range of applications, and to provide a process for its production which is simple and inexpensive.

Gelöst wird diese Aufgabe durch einen porösen Metallschaumkörper erhältlich durch Aufbringen von geschmolzenem Zink, Aluminium, Zinn, oder deren Legierungen auf ein offenporiges nicht metallisches Substrat und Eindringen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen in die offenen Poren des nicht metallischen Substrats, unter Bildung eines Metallschaumkörpers, wobei das Aufbringen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen durch Aufbringen von Tropfen geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen durch thermisches Spritzen, durch Verdüsung von Metallschmelzen oder Rotationsverdüsung von Metallschmelzen in einer oder mehreren Lagen erfolgt und sich das geschmolzene Zink, Aluminium, Zinn, oder deren Legierungen auf der Oberfläche zumindest einer Teilpopulation der Poren niederschlägt und eine metallisierte Oberfläche der Poren erhalten wird. Die metallische Komponente ist insbesondere zumindest teilweise in das offenporige nicht metallische Substrat eingedrungen.This object is achieved by a porous metal foam body obtainable by applying molten zinc, aluminum, tin or their alloys to an open-pore non-metallic substrate and penetration of the molten zinc, aluminum, tin or their alloys into the open pores of the non-metallic substrate, to form a metal foam body, wherein the application of the molten zinc, aluminum, tin, or their alloys by application of drops of molten zinc, aluminum, tin, or their alloys by thermal spraying, by atomization of molten metals or rotational atomization of molten metals in one or more layers takes place and the molten zinc, aluminum, tin, or their alloys precipitate on the surface of at least a partial population of the pores and a metallized surface of the pores is obtained. The metallic component has at least partially penetrated the open-pore non-metallic substrate.

Der poröse Metallschaumkörper gemäß der Erfindung weist in seinem Lumen Populationen von Poren auf, die mindestens teilweise mit einer Oberfläche mit Zink, Aluminium, Zinn, oder deren Legierungen versehen sind. Dabei kann die Population auch nur teilweise in Form einer Teilpopulation von Poren ausgebildet sein, die an ihrer Oberfläche Zink, Aluminium, Zinn, oder deren Legierungen aufweist, und zwar insbesondere im Außenbereich des nicht metallischen Substrats angeordnet ist. Ein derartiger poröser Metallschaumkörper weist mithin an der Außenseite Poren mit Oberfläche mit Zink, Aluminium, Zinn, oder deren Legierurngen auf, wohingegen im Innenbereich sich keine metallisierten Poren befinden. Dabei kommt es in Abhängigkeit vom Herstellungsverfahren nicht zu einem schroffen Übergang zwischen metallisierten und nicht metallisierten Porenoberflächen, sondern die Häufigkeit der vollständig mit einer metallisierten Oberfläche versehenen Poren nimmt zum Inneren des Lumens des porösen Metallschaumkörpers allmählich ab. Bei entsprechender Verfahrensführung zur Herstellung des porösen Metallschaumkörpers und angepasster Dicke des Metallschaumkörpers gelingt es auch, fast sämtliche für das geschmolzene Metall zugängliche Poren mit einer Oberfläche mit Zink, Aluminium, Zinn, oder deren Legierungen zu versehen.The porous metal foam body according to the invention has populations of pores in its lumen which are at least partially provided with a surface with zinc, aluminum, tin, or their alloys. The population can also be formed only partially in the form of a partial population of pores, which has zinc, aluminum, tin, or their alloys on its surface, and in particular is arranged in the outer region of the non-metallic substrate. Such a porous metal foam body therefore has pores on the outside with a surface with zinc, aluminum, tin, or their alloying alloys, whereas in There are no metallized pores inside. Depending on the manufacturing process, there is no abrupt transition between metallized and non-metallized pore surfaces, but the frequency of the pores completely provided with a metallized surface gradually decreases towards the interior of the lumen of the porous metal foam body. With an appropriate procedure for producing the porous metal foam body and adapted thickness of the metal foam body, it is also possible to provide almost all of the pores accessible to the molten metal with a surface with zinc, aluminum, tin, or their alloys.

Dabei erfolgt das Aufbringen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen erfindungsgemäß durch Aufbringen von Tropfen geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungendurch thermisches Spritzen, durch Verdüsung von Metallschmelze oder durch eine Rotationsverdüsung der Metallschmelze. Als Basismetalle kommen erfindungsgemäß Zink, Aluminium, Zinn oder deren Legierungen in Betracht.The molten zinc, aluminum, tin, or their alloys are applied according to the invention by applying drops of molten zinc, aluminum, tin, or their alloys by thermal spraying, by atomizing molten metal or by rotating atomizing the molten metal. According to the invention, zinc, aluminum, tin or their alloys come into consideration as base metals.

Es können auch mehrere Schichten gleichen oder verschiedenen Metalls aufgebracht werden, um einen mehrlagigen Aufbau der Metallschicht in dem Metallschaumkörper der Erfindung zu erhalten. Insbesondere Zinkbasiswerkstoffe eignen sich als erste Schicht auf dem nicht metallischen Substrat, da sie sowohl eine gute Haftung zu diesem wie auch zu den darüberliegenden Metallschichten gewährleisten.Several layers of the same or different metal can also be applied in order to obtain a multilayer structure of the metal layer in the metal foam body of the invention. Zinc-based materials, in particular, are suitable as the first layer on the non-metallic substrate, since they ensure good adhesion to this as well as to the overlying metal layers.

Der erfindungsgemäße Metallschaumkörper weist beispielsweise eine Porosität von 5 bis 150 Poren pro 2,54 cm (5 ppi, bis 150 ppi, pores per inch) auf, aber auch andere Bereiche sind wählbar.The metal foam body according to the invention has, for example, a porosity of 5 to 150 pores per 2.54 cm (5 ppi to 150 ppi, pores per inch), but other ranges can also be selected.

Die Poren des offenporigen nicht metallischen Substrats werden durch "Stege" gebildet und umschlossen. Die Oberfläche bzw. die Stege des Substrates werden beispielsweise durch thermisches Spritzen oder Verdüsung, z.B. Luftverdüsung, mit einer Schicht überzogen. Die Schichtdicke kann dabei in Abhängigkeit der Parameter der Aufbringungsmethode der Metalltropfen eingestellt werden. Das Resultat ist dann ein Schaumkörper aus dem verspritzten Werkstoff. Es können offenporige Schaumkörper oder auch offenporige Schaumkörper mit einer geschlossenen Deckschicht hergestellt werden. Der Schaumkörper kann dabei aus jedem Material bestehen, welches sich z. B. durch thermisches Spritzen verarbeiten lässt (Eisen, Zink, Aluminium, Kupfer, Nickel, Gold, Silber, Platin, Zinn oder deren Legierungen). Es können aber zum Beispiel auch keramische Partikel (Wolframkarbid, Aluminiumoxid, Siliziumkarbid) insbesondere durch thermisches Spritzen aufgetragen werden.The pores of the open-pore non-metallic substrate are formed and enclosed by "webs". The surface or the webs of the substrate are coated with a layer, for example by thermal spraying or atomization, for example air atomization. The layer thickness can vary depending on the parameters of the application method of the metal drops can be set. The result is a foam body made of the sprayed material. Open-pore foam bodies or open-pore foam bodies with a closed cover layer can be produced. The foam body can consist of any material that z. B. can be processed by thermal spraying (iron, zinc, aluminum, copper, nickel, gold, silver, platinum, tin or their alloys). However, ceramic particles (tungsten carbide, aluminum oxide, silicon carbide) can also be applied, for example, in particular by thermal spraying.

Das Substrat kann dabei vollständig oder aber auch nur in Teilbereichen mit dem Werkstoff versehen werden.The substrate can be provided with the material completely or only in partial areas.

Das erfindungsgemäße Verfahren zur Herstellung eines Metallschaumkörpers geht von einem offenporigen nicht metallischen Substrat aus, das mit Tropfen geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen versehen wird, wobei die Tropfen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen zumindest partiell in die offenen Poren des nicht metallischen Substrats eindringen.The process according to the invention for producing a metal foam body is based on an open-pore non-metallic substrate which is provided with drops of molten zinc, aluminum, tin, or their alloys, the drops of molten zinc, aluminum, tin, or their alloys at least partially into the penetrate open pores of the non-metallic substrate.

Erfindungsgemäß erfolgt das Aufbringen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen durch thermisches Spritzen, durch Verdüsung von Metallschmelze oder Rotationsverdüsung von Metallschmelze. Das Eindringen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen kann durch dem Fachmann bekannte Maßnahmen gefördert werden. Dazu gehören insbesondere die Variation der Substratporengröße, - form und -struktur, Variation der Tropfengröße, -geschwindigkeit, - temperatur, des Spritzabstandes, der Spritzdauer, des Anstellwinkels des Substrates zur Beschichtungseinheit, mehrlagiges Spritzen, Erzeugung eines Unterdruckes an der Substratrückseite oder eine Kombination dieser Maßnahmen.According to the invention, the molten zinc, aluminum, tin, or their alloys are applied by thermal spraying, atomization of molten metal or rotational atomization of molten metal. The penetration of the molten zinc, aluminum, tin, or their alloys can be promoted by measures known to the person skilled in the art. These include in particular the variation of the substrate pore size, shape and structure, variation of the droplet size, velocity, temperature, the spraying distance, the spraying duration, the angle of attack of the substrate to the coating unit, multi-layer spraying, generation of a negative pressure on the back of the substrate or a combination thereof Activities.

Das im erfindungsgemäßen Verfahren einsetzbare offenporige nicht metallische Substrat kann ausgewählt sein aus porösen anorganischen oder organischen Materialien.The open-pore non-metallic substrate which can be used in the process according to the invention can be selected from porous inorganic or organic materials.

Dabei kommen als anorganische Materialien insbesondere solche in Betracht, die ausgewählt sind aus der Gruppe bestehend aus Zeolithen, Kieselgelen, Fritten, keramischen Materialien, Mineralfaserwolle oder Kombinationen davon.Suitable inorganic materials are in particular those selected from the group consisting of zeolites, silica gels, frits, ceramic materials, mineral fiber wool or combinations thereof.

Die organischen Materialien sind insbesondere ausgewählt aus der Gruppe bestehend aus offenporigem geschäumten Material aus Kunststoffen, wie geschäumten Polyurethanen, Polyester, Polyether geschäumten Polystyrolen, offenporigen natürlichen oder künstlichen Schwämmen, Holzwolle oder Kombinationen davon.The organic materials are selected in particular from the group consisting of open-pore foamed material made of plastics, such as foamed polyurethane, polyester, polyether foamed polystyrene, open-pore natural or artificial sponges, wood wool or combinations thereof.

Die Tropfen können erfindungsgemäß aus geschmolzenemZink, Aluminium, Zinn oder deren Legierungen bestehen.According to the invention, the drops can consist of molten zinc, aluminum, tin or their alloys.

In einer Ausführungsform des erfindungsgemäßen Verfahrens kann das Substrat nach dem Versehen mit den Tropfen des geschmolzenen Zinks, Aluminiums, Zinns, oder deren Legierungen thermisch oder chemisch entfernt werden, z. B. durch Ausbrennen im Fall organischer Substrate. Der erfindungsgemäße Metallschaumkörper kann mit zwei Hauptoberflächen ausgebildet sein, wobei eine oder beide Hauptoberflächen mit einer geschlossenporigen oder nicht geschlossenporigen Schicht aus einem Werkstoff gebildet wird.In one embodiment of the method according to the invention, the substrate can be thermally or chemically removed, for example with the droplets of the molten zinc, aluminum, tin, or their alloys. B. by burning out in the case of organic substrates. The metal foam body according to the invention can be formed with two main surfaces, one or both main surfaces being formed with a closed-pore or non-closed-pore layer made of one material.

Im letzteren Fall handelt es sich um eine Sandwich-Konstruktion. Es kann zum Beispiel ein als Substrat dienender Polyurethanschaum einseitig mit einer offenporigen Schicht aus einer Zinklegierung versehen werden, wobei die Zinklegierung das Substrat nicht vollständig durchdringt. Die andere Seite wird mit einem mehrlagigen Aufbau bestehend aus einer Zinkschicht und einer darüber liegenden Kupferschicht mit Eindringungstiefen versehen, die ebenfalls das Substrat nicht vollständig durchdringen. Falls ein Mittenbereich in dem Polyurethanschaum unbehandelt bleibt, führt dies zu einem 3-Komponenten-Verbundwerkstoff bestehend aus einem Metallschaumkörper aus einer Zinklegierung, dem Substrat Polyurethan und einem Metallschaumkörper Zink/Kupfer. Es können je nach Ausführung die Eigenschaften der Einzelkomponenten (z.B. Substrat-Zinkschicht-Kupferschicht) beim fertigen Sandwich eingestellt werden. Zum Beispiel ein weicher PU-Schaum mit einer festen "Schale" aus Metall. Dadurch wird es möglich z.B. bestimmte Dämpfungseigenschaften oder Biegesteifigkeiten bei gleichzeitiger optischer Gestaltung der Oberfläche einzustellen.In the latter case, it is a sandwich construction. For example, a polyurethane foam serving as a substrate can be provided on one side with an open-pore layer made of a zinc alloy, the zinc alloy not completely penetrating the substrate. The other side is provided with a multilayer structure consisting of a zinc layer and an overlying copper layer with penetration depths, which also do not penetrate completely through the substrate. If a central area in the polyurethane foam remains untreated, this leads to a 3-component composite consisting of a metal foam body made of a zinc alloy, the substrate polyurethane and a metal foam body zinc / copper. Depending on the version, the properties of the individual components (eg substrate-zinc-layer-copper layer) can be set in the finished sandwich. For example a soft PU foam with a firm "shell" made of metal. This makes it possible, for example, to set certain damping properties or bending stiffness with a simultaneous visual design of the surface.

Der erfindungsgemäße Metallschaumkörper kann beispielsweise im Bauwesen, insbesondere für Leichtbaukonstruktionen, Maschinenbau, in der Fahrzeugtechnik, chemischen Industrie, Medizintechnik, Elektrotechnik eingesetzt werden, und zwar grundsätzlich dort, wo es auf gewichtssparende, aber feste bzw. versteifte Materialien ankommt. So kommt der erfindungsgemäße Metallschaumkörper beispielsweise für Dämmplatten, Abdeckungen, Schallschutz, Bauelemente für elektromagnetische Abschirmung, Schwingungsdämpfung, Crashabsorber, Filter, Katalysatoren, Batteriebauteile, Halbleiter in Betracht.The metal foam body according to the invention can be used, for example, in construction, in particular for lightweight structures, mechanical engineering, in vehicle technology, chemical industry, medical technology, electrical engineering, and in principle wherever weight-saving but solid or stiffened materials are important. The metal foam body according to the invention can be used, for example, for insulation boards, covers, sound insulation, components for electromagnetic shielding, vibration damping, crash absorbers, filters, catalysts, battery components, semiconductors.

Es ist ebenfalls möglich, einen mehrschichtigen Aufbau durch Spritzen mit verschiedenen Materialien zu erzielen. Auch das Auftragen von verschiedenen Werkstoffen nebeneinander ist möglich.It is also possible to achieve a multilayer structure by spraying with different materials. It is also possible to apply different materials side by side.

Die Form des Schaumkörpers wird typischerweise durch das Substrat vorgegeben und kann so leicht und formgenau vor dem Spritzen vorbereitet werden (z. B. Platten, Kugeln, Stäbe, räumlich anspruchsvolle, komplizierte Strukturen aus Substratmaterial; Substrat kann auch vor dem Beschichten vorgeformt werden und in diesem Zustand durch die Beschichtung gehalten werden).The shape of the foam body is typically determined by the substrate and can thus be easily and precisely prepared before spraying (e.g. plates, balls, rods, spatially demanding, complicated structures made of substrate material; substrate can also be preformed before coating and in this state can be kept by the coating).

Der Schaum kann auch als Kern für einen Verbundwerkstoff genutzt werden, z.B. kann der Metallschaum aus einem mit Lotwerkstoff verbundenen Deckblech aus Leichtmetall über Erwärmen bis zur Lottemperatur und gegebenenfalls eingelegten Versteifungsrippen als Verbundwerkstoff ausgebildet werden.The foam can also be used as a core for a composite material, for example the metal foam can be made from a cover sheet made of light metal connected with solder material and heated up to the soldering temperature and optionally inserted stiffening ribs are formed as a composite material.

Gegenstand der Erfindung ist auch die Verwendung des erfindungsgemäßen Metallschaumkörpers als Vormaterial für weitere Beschichtungen mit metallischen Werkstoffen durch galvanische Verfahren, durch Ausscheidung aus der Gas- oder Flüssigphase oder durch Pulverbeschichtung. In einer bevorzugten Ausführungsform wird der erfindungsgemäße Metallschaumkörper als Matrix für das Füllen mit Polymeren oder Metallguss verwendet.The invention also relates to the use of the metal foam body according to the invention as a starting material for further coatings with metallic materials by means of galvanic processes, by separation from the gas or liquid phase or by powder coating. In a preferred embodiment, the metal foam body according to the invention is used as a matrix for filling with polymers or metal casting.

Beispiele:Examples: Beispiel 1example 1

Ein Substrat in Form eines Polyurethanschaumes mit einer Stärke von 20 mm und 10 Poren pro 2,54 cm (Poren/inch, 10 ppi) wird durch Drahtlichtbogenspritzen mit einer Schicht aus Zink beschichtet. Es ergibt sich ein offenporiger Metallschaumkörper mit einer Dichte von 0,06-0,45 g/cm3 und einer Druckfestigkeit von 16 kPa-220 kPa.A substrate in the form of a polyurethane foam with a thickness of 20 mm and 10 pores per 2.54 cm (pores / inch, 10 ppi) is coated with a layer of zinc by wire arc spraying. The result is an open-pore metal foam body with a density of 0.06-0.45 g / cm 3 and a compressive strength of 16 kPa-220 kPa.

Beispiel 2Example 2

Ein nach Beispiel 1 hergestellter Metallschaum kann als Matrix in Polymer- oder Metallstruktur eingebettet werden.A metal foam produced according to Example 1 can be embedded as a matrix in a polymer or metal structure.

Der offenporige Metallschaum kann mit einem flüssigen Polymer gefüllt werden. Man erhält dadurch einen Verbundstoff Metall/Polymer mit der Kombination der Werkstoffe. Dieser kann dann beispielsweise als Crashabsorber eingesetzt werden.The open-pore metal foam can be filled with a liquid polymer. This gives a metal / polymer composite with the combination of the materials. This can then be used as a crash absorber, for example.

Beispiel 3Example 3

Ein Substrat in Form eines Polyurethanschaumplatte mit einer Stärke von 20 mm, 10 Poren pro 2,54 cm (Poren/inch, 10 ppi) wird durch Drahtlichtbogenspritzen mit einer Schicht aus Zink beschichtet. Es ergibt sich ein offenporiger Metallschaumkörper mit einer Dichte von 0,06-0,45 g/cm3 und einer Druckfestigkeit von 16 kPa-220 kPa. Eine zweite Schicht aus Messing oder Kupfer wird durch Drahtlichtbogenspritzen aufgebracht. Hierduch entsteht eine biegesteife Platte mit guten Schallabsorptionseigenschaften und ästhetischem Oberflächendesign in Messing- oder Kupferoptik.A substrate in the form of a polyurethane foam plate with a thickness of 20 mm, 10 pores per 2.54 cm (pores / inch, 10 ppi) is coated with a layer of zinc by wire arc spraying. The result is an open-pore metal foam body with a density of 0.06-0.45 g / cm 3 and a compressive strength of 16 kPa-220 kPa. A second layer of brass or copper is applied by wire arc spraying. This creates a rigid plate with good sound absorption properties and an aesthetic surface design in brass or copper optics.

Claims (17)

  1. A porous metal foam body obtainable by applying molten zinc, aluminum, tin or their alloys to an open-pore non-metallic substrate and allowing the molten zinc, aluminum, tin or their alloys to penetrate into the open pores of said non-metallic substrate to form a metal foam body, wherein said applying of the molten zinc, aluminum, tin or their alloys is effected by applying droplets of molten zinc, aluminum, tin or their alloys by thermal spraying, by atomizing a molten metal, or by rotational atomization of molten metals in one or more layers, and said molten zinc, aluminum, tin or their alloys is deposited on the surface of at least a partial population of the pores to obtain a metallized surface of the pores.
  2. The metal foam body according to claim 1, wherein said partial population of the pores that have zinc, aluminum, tin or their alloys on their surface is located in the outer region rather than in the inner region of said non-metallic substrate.
  3. The metal foam body according to any of the preceding claims, wherein substantially all pores of said non-metallic substrate are pores whose surface is metallized with zinc, aluminum, tin or their alloys.
  4. The metal foam body according to any of the preceding claims having a porosity of from 5 to 150 pores per 2.54 cm (5 ppi to 150 ppi).
  5. A process for the preparation of a metal foam body according to at least one of the preceding claims, wherein an open-pore non-metallic substrate is provided and coated with one or more layers of molten zinc, aluminum, tin or their alloys, and the molten zinc, aluminum, tin or their alloys penetrates into the open pores of the open-pore non-metallic substrate, wherein said coating with the molten zinc, aluminum, tin or their alloys is effected by applying droplets of molten zinc, aluminum, tin or their alloys by thermal spraying, by atomizing molten metals, or by rotational atomization of molten metals.
  6. The process according to the preceding claim, wherein said penetration by the droplets of molten zinc, aluminum, tin or their alloys is promoted by varying the size, shape and structure of the pores in the substrate, varying the size, speed and temperature of the droplets, the spraying distance, the spraying time, the work angle between the substrate and the coating unit, multilayer spraying and/or generation of a negative pressure on the backside of the substrate.
  7. The process according to any of claims 5 or 6, wherein said open-pore non-metallic substrate is selected from porous inorganic or organic materials.
  8. The process according to any of the preceding claims 5 to 7, wherein said inorganic materials are selected from the group consisting of zeolites, silica gels, frits, ceramic materials, mineral fiber wool or combinations thereof.
  9. The process according to any of the preceding claims 6 to 8, wherein said organic materials are selected from the group consisting of open-pore foamed material consisting of plastics, such as foamed polyurethanes, polyesters, polyethers, foamed polystyrenes, open-pore natural or artificial sponges, wood wool, fabrics, textiles and combinations thereof.
  10. The process according to any of the preceding claims 6 to 9, wherein said molten zinc, aluminum, tin or their alloys have additions of ceramic particles (tungsten carbide, aluminum oxide, silicon carbide).
  11. The process according to claim 9, wherein said organic substrate is removed after having been coated with the molten zinc, aluminum, tin or their alloys.
  12. A metal foam body according to claim 1 to 4 having two major surfaces, wherein one or both major surfaces are formed with a closed-pore layer of a material.
  13. The metal foam body according to claim 12 as a sandwich construction.
  14. Use of a metal foam body according to at least one of claims 1 to 4 in construction, especially for light-weight constructions, engine construction, automotive engineering, chemical industry, medical engineering, electrical engineering.
  15. The use according to claim 14 for components for insulation boards, coverings, sound protection, electromagnetic shielding, vibration damping, crash absorbers, filters, catalysts, battery elements and/or semiconductors.
  16. The use of a metal foam body according to claim 1 to 4 as a substrate material for further coatings with metallic materials by electrodeposition methods, by deposition from the vapor or liquid phase, or by powder coating.
  17. The use of a metal foam body according to claim 1 to 4 as a matrix for the filling with polymers or metal casting.
EP06763358.6A 2005-05-30 2006-05-30 Porous metal foam body Not-in-force EP1888807B1 (en)

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AU2006254135B2 (en) 2010-12-02
JP2008542540A (en) 2008-11-27
ES2816523T3 (en) 2021-04-05
CN101184862B (en) 2011-06-29
US20090081444A1 (en) 2009-03-26
CA2609239A1 (en) 2006-12-07
JP5389439B2 (en) 2014-01-15
WO2006128858A1 (en) 2006-12-07
BRPI0610871A2 (en) 2010-08-03
KR20080015823A (en) 2008-02-20
AU2006254135A1 (en) 2006-12-07
EP1888807A1 (en) 2008-02-20
CN101184862A (en) 2008-05-21
PL1888807T3 (en) 2020-11-16

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