EP1083013B1 - Preparation of foamable metal bodies and metal foams - Google Patents

Preparation of foamable metal bodies and metal foams Download PDF

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Publication number
EP1083013B1
EP1083013B1 EP00119602A EP00119602A EP1083013B1 EP 1083013 B1 EP1083013 B1 EP 1083013B1 EP 00119602 A EP00119602 A EP 00119602A EP 00119602 A EP00119602 A EP 00119602A EP 1083013 B1 EP1083013 B1 EP 1083013B1
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EP
European Patent Office
Prior art keywords
powder
metal
blowing agent
gas
powder mixture
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EP00119602A
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German (de)
French (fr)
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EP1083013A2 (en
EP1083013A3 (en
Inventor
Peter Dipl.-Ing. Heinrich (Fh)
Heinrich Prof. Dr. Kreye
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Linde GmbH
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Linde GmbH
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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
    • B22F7/00—Manufacture 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
    • B22F7/002—Manufacture 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
    • B22F7/004—Manufacture 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
    • B22F7/006—Manufacture 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
    • 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
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • 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
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a method for the production of foamable metal bodies, wherein from a powder mixture containing at least one metal powder and at least a gas-releasing propellant powder, which when heated to a temperature equal to or above the decomposition temperature of the propellant gas splits comprises, a compact body is made.
  • metal powder is used together with a propellant Powder processed by cold gas spraying into a compact body.
  • the compact body can be present as a layer or as a shaped body.
  • the blowing agent remains at least substantially bound. It will if desired, only free to foam during subsequent heating.
  • Decisive in the technical spraying method used according to the invention is that the blowing agent powder splits off substantially no gas during the injection process. In cold gas spraying, this is also due to the short residence time of the powder due to the low process temperature of the cold gas spraying with a few 100 ° C ensure heated carrier gas jet.
  • the invention provides a simple and versatile method for the production the foamable metal body provided.
  • the so produced Metal bodies may be the same or preferred by heating to a temperature above the decomposition temperature of the propellant and subsequent cooling be used for the production of porous Metallkörpem or metal foams.
  • the decomposition temperature of the propellant is not a sharp temperature value but a temperature range.
  • the decomposition temperature of the blowing agent is therefore under a Temperature equal to or preferably above the decomposition temperature of the blowing agent in these cases a temperature in the decomposition temperature range or preferably understood above the decomposition temperature range of the blowing agent.
  • the powder mixture of metal plus blowing agent be sprayed in almost any mixing ratios. This allows, that the mixing ratio of metal powder and propellant powder respectively to the adapted to desired conditions.
  • the powder mixture of metal powder and propellant powder in the preparation of the foamable metal body with respect to its Parameters such as the composition, but especially with respect to the mixing ratio to be changed.
  • a propellant in the powder mixture between 0.01 and 1.0% by weight, preferably between 0.05 and 0.5% by weight, especially preferably between 0.1 and 0.3 wt .-%, is suitable.
  • the gas-releasing propellant powder comprises metal hydrides such as titanium hydride (TiH 2 ), carbonates such as calcium carbonate, potassium carbonate, sodium carbonate or sodium bicarbonate, hydrates such as aluminum sulfate hydrate, alum, aluminum hydroxide or light volatiles such as mercury compounds or powdered propellants organic substances or mixtures of the aforementioned substances.
  • metal hydrides such as titanium hydride (TiH 2 )
  • carbonates such as calcium carbonate, potassium carbonate, sodium carbonate or sodium bicarbonate
  • hydrates such as aluminum sulfate hydrate, alum, aluminum hydroxide or light volatiles such as mercury compounds or powdered propellants organic substances or mixtures of the aforementioned substances.
  • the powder mixture can be sprayed onto a substrate carrier, wherein at least temporarily, a relative movement between the substrate carrier and the device for thermal spraying of the powder mixture by means Cold gas spraying takes place. It can, for example, with the Powder mixture moldings are sprayed, for example, the spray gun of the Device for thermal spraying and / or the substrate carrier to be moved.
  • the powder mixture can be applied to any suitable substrate carrier in particular on a carrier material of metal, plastic, ceramic and / or glass be sprayed.
  • the compact body can be detached from the carrier material before, by heating, gas release from the propellant Foaming of the compact body takes place.
  • the compact body before the gas separation the foaming agent for foaming the compact body while changing the Pressure and / or the temperature deformed or reshaped.
  • transformations For example, extrusion or rolling are possible.
  • the powder mixture is on the inside sprayed in a mold that is completely or partially foamed with metal foam shall be.
  • the metal foam is made.
  • At least two layers are injected, wherein at least one layer with the metal powder and gas-releasing propellant powder comprehensive powder mixture and at least one further layer with metal powder be thermally sprayed without gas-releasing propellant.
  • at least one layer with the metal powder and gas-releasing propellant powder comprehensive powder mixture and at least one further layer with metal powder be thermally sprayed without gas-releasing propellant.
  • the powder mixture of metal and propellant only in layers between two metal layers be sprayed.
  • the propellant and by a subsequent cooling can a Metal foam are produced.
  • Preference is given to heating the compact Body at a temperature above the melting temperature of the metal or above the Sollidustemperatur the metal alloy. In this case, this foams as gas escaping propellant to the molten metal. This foam forms after the Cool a porous hollow body. Preference is thus given to the decomposition of the Propellant released gas, the metal or metal alloy as a melt lather.
  • Moldings can be produced which comprise at least one metal foam.
  • composite bodies can be produced which comprise at least one metal foam Layer on or between a substrate carrier.
  • at least one foamed metal layer at least a further thermally sprayed layer may be present.
  • Titanium hydride (TiH 2 ) is particularly suitable as blowing agent.
  • titanium hydride may be sprayed by cold gas spraying along with other metal powders of aluminum (Al), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), and alloys containing one or more of these metals.
  • Al aluminum
  • Cu copper
  • Ni nickel
  • Fe iron
  • Ti titanium
  • alloys containing one or more of these metals a relatively small proportion of the blowing agent is sufficient for foaming the compact body.
  • a powder mixture with 0.2 wt .-% TiH 2 and with essentially Al as a metal powder to a foam body with about five times volume increase.
  • a propellant content of 1.0 wt% TiH 2 increases the volume of Al by more than ten times.
  • the gas needed for the thermal spraying can be nitrogen, helium, argon, neon, Krypton, xenon, a hydrogen-containing gas, a carbon-containing gas, especially carbon dioxide, oxygen, an oxygen-containing gas, air, Water vapor or mixtures of the aforementioned gases.
  • air and / or helium are also suitable for the powdery filler gas carrying a nitrogen, argon, neon, krypton, Xenon, oxygen, a hydrogen-containing gas, a carbon-containing gas, in particular carbon dioxide, water vapor or mixtures of the aforementioned gases and mixtures of these gases with helium.
  • the proportion of helium in the total gas can up to 90 vol .-% amount.
  • a helium content of 10 to 50% by volume is preferred Gas mixture complied.

Abstract

Production of a expandable metal body comprises using a powder mixture made of a metal powder and a gas-splitting propellant powder to form a compact body by thermally spraying the powder mixture, by high pressure flame spraying or cold gas spraying. An Independent claim is also included for a device for the production of metal foams comprising an apparatus for introducing a powder mixture made of a metal powder and a gas-splitting propellant powder; an apparatus for producing a compact body from the mixture by thermally spraying the powder mixture by high pressure flame spraying or cold gas spraying; and an apparatus for heating the compact body to a temperature which is the same or above the decomposition temperature of the propellant with splitting of the gas.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von aufschäumbaren Metallkörpern, wobei aus einem Pulvergemisch, welches zumindest ein Metallpulver und zumindest ein gasabspaltendes Treibmittelpulver, welches bei Aufheizen auf eine Temperatur gleich oder oberhalb der Zersetzungstemperatur des Treibmittels Gas abspaltet, umfasst, ein kompakter Körper hergestellt wird.The invention relates to a method for the production of foamable metal bodies, wherein from a powder mixture containing at least one metal powder and at least a gas-releasing propellant powder, which when heated to a temperature equal to or above the decomposition temperature of the propellant gas splits comprises, a compact body is made.

Die Erfindung betrifft ferner eine Vorrichtung zum Herstellen von Metallschäumen, umfassend

  • Mittel zur Zufuhr eines Pulvergemisches, welches zumindest ein Metallpulver und zumindest ein gasabspaltendes Treibmittelpulver beinhaltet,
  • Mittel zur Herstellung eines kompakten Körpers aus dem Pulvergemisch und
  • Mittel zum Aufheizen des kompakten Körpers auf eine Temperatur gleich oder oberhalb der Zersetzungstemperatur des Treibmittels unter Abspaltung von Gas. Die industrielle Fertigung von Metallschäumen oder porösen Metallkörpern ist seit langem bekannt. So ist beispielsweise in der Patentschrift US-3,087,807 A ein Herstellungsverfahren für Metallschäume beschrieben. Ein Metallpulver wird mit einem Treibmittel gemischt und unter einem Preßdruck von größer 80 MPa kalt kompaktiert und anschließend durch Strangpressen um mindesten 87,5 % umgeformt (extrudiert), damit die Pulverpartikel fest miteinander verbunden (verschweißt) sind. Die Temperatur beim Strangpressen muß unterhalb der Zersetzungstemperatur des Treibmittels liegen. Der stranggepreßte Stab wird anschließend in einer Form auf mindestens die Schmelztemperatur des Metalls erwärmt. Der Stab wird dabei zu einem porösen Metallkörper aufgeschäumt. Die Aufschäumung kann in verschiedenen Formen erfolgen, so dass der fertige poröse Metallkörper die gewünschte Form aufweist.Aus der Patentschrift DE 40 18 360 C1 ist ein das oben beschriebene Verfahren verbesserndes Herstellungsverfahren für poröse Metallkörper bekannt, wobei mindestens ein Metallpulver und mindestens ein gasabspaltendes Treibmittelpulver gemischt werden und die Mischung durch Heißkompaktieren zu einem Halbzeug geformt wird. Das Halbzeug wird dann zum Aufschäumen auf Temperaturen oberhalb der Zersetzungstemperatur des Treibmittels, vorzugsweise im Temperaturbereich des Schmelzpunkes des verwendeten Metalles, aufgeheizt. Anschließend findet ein Abkühlen des so aufgeschäumten Körpers statt.Aus der Patentschrift DE 41 01 630 C2 ist ein Herstellungsverfahren für aufschäumbare Metallkörper bekannt, bei dem beim Kompaktierungsvorgang die Temperatur so hoch gewählt wird, dass die Verbindung zwischen den einzelnen Metallpulverteilchen überwiegend durch Diffusion erfolgt und der Druck beim Heißkompaktieren so hoch gewählt wird, dass die Zersetzung des Treibmittels verhindert wird. Aus der DE-C-195 01 659 ist ein zweistufiges Verfahren zur Herstellung eines Metallschaumteiles durch Hochgeschwindigkeitsflammspritzen bekannt.Die bekannten Verfahren sind noch nicht in jeder Hinsicht zufriedenstellend, insbesondere ist die damit zur Verfügung stehende Variationsbreite nicht befriedigend.Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren und eine Vorrichtung der eingangs genannten Art aufzuzeigen, durch welche die Herstellung von aufschäumbaren Metallkörpem vereinfacht und/oder die Variabilität bei der Herstellung von aufschäumbaren Metallkörpem vergrößert wird.Diese Aufgabe wird für das Verfahren erfindungsgemäß dadurch gelöst, dass die Herstellung des kompakten Körpers durch thermische Spritzen des Pulvergemisches mittels Kaltgasspritzens erfolgt.Die Aufgabe wird für die Vorrichtung dadurch gelöst, dass die Mittel zur Herstellung des kompakten Körpers aus dem Pulvergemisch eine Vorrichtung zum thermischen Spritzen mittels Kaltgasspritzens umfassen.Thermische Spritzverfahren zeichnen sich im wesentlichen dadurch aus, dass sie gleichmäßig aufgetragene Beschichtungen von hoher Qualität und Güte ermöglichen. Durch thermische Spritzverfahren aufgetragene Beschichtungen können durch Variation der Spritzmaterialien und/oder der Verfahrensparameter an unterschiedliche Anforderungen angepaßt werden. Die Spritzmaterialien können dabei grundsätzlich in Form von Drähten, Stäben oder als Pulver verarbeitet werden. Es kann zusätzlich eine Nachbehandlung vorgesehen sein.Details zum thermischen Spritzen sind beispielsweise der europäischen Norm EN 657 zu entnehmen.In jüngerer Zeit wurde darüber hinaus ein weiteres thermisches Spritzverfahren entwickelt, welches auch als Kaltgasspritzen bezeichnet wird. Es handelt sich dabei um eine Art Weiterentwicklung des Hochgeschwindigkeits-Flammspritzens. Dieses Verfahren ist beispielsweise in der europäischen Patentschrift EP 0 484 533 B1 beschrieben. Beim Kaltgasspritzen kommt ein Zusatzwerkstoff in Pulverform zum Einsatz. Die Pulverpartikel werden beim Kaltgasspritzen jedoch nicht im Gasstrahl geschmolzen. Vielmehr liegt die Temperatur des Gasstrahles unterhalb des Schmelzpunktes der Zusatzwerkstoffpulverpartikel (EP 0 484 533 B1). Im Kaltgasspritzverfahren wird also ein im Vergleich zu den herkömmlichen Spritzverfahren "kaltes" bzw. ein vergleichsweise kälteres Gas verwendet. Gleichwohl wird das Gas aber ebenso wie in den herkömmlichen Verfahren erwärmt, aber in der Regel lediglich auf Temperaturen unterhalb des Schmelzpunktes der Pulverpartikel des Zusatzwerkstoffes.Beim Kaltgasspritzen können die Pulverpartikel auf eine Geschwindigkeit von 300 bis 1600 m/s beschleunigt werden. Es eignen sich dabei insbesondere Geschwindigkeiten der Pulverpartikel zwischen 500 und 1200 m/s zur Erzielung besonders hoher Auftragswirkungsgrade und Schichtdichten.Als Materialien für das Metallpulver können im Rahmen der Erfindung alle geeigneten metallhaltigen Spritzpulver, insbesondere
  • reine Metalle,
  • Metallegierungen,
  • Metalle und/oder Metallegierungen mit Zusätzen an Hartstoffen wie Metalloxide (insbesondere Al2O3 und/oder TiO2), Carbide, Boride und/oder mit Zusätzen an Kunststoffen
    oder
  • Mischungen der vorgenannten Stoffe
verwendet werden. The invention further relates to an apparatus for producing metal foams, comprising
  • Means for supplying a powder mixture which comprises at least one metal powder and at least one gas-releasing propellant powder,
  • Means for producing a compact body from the powder mixture and
  • Means for heating the compact body to a temperature equal to or above the decomposition temperature of the blowing agent with elimination of gas. The industrial production of metal foams or porous metal bodies has long been known. For example, US Pat. No. 3,087,807 A describes a production process for metal foams. A metal powder is mixed with a blowing agent and cold compacted under a pressure of greater than 80 MPa and then converted by extruding at least 87.5% (extruded), so that the powder particles are firmly bonded together (welded). The temperature during extrusion must be below the decomposition temperature of the blowing agent. The extruded rod is then heated in a mold to at least the melting temperature of the metal. The rod is thereby foamed to a porous metal body. The foaming may take various forms such that the finished porous metal body has the desired shape. Patent DE 40 18 360 C1 discloses a method for producing porous metal bodies which improves the method described above, wherein at least one metal powder and at least one gas-releasing propellant powder are mixed and the mixture is formed by hot compacting to a semi-finished product. The semifinished product is then heated to foaming to temperatures above the decomposition temperature of the blowing agent, preferably in the temperature range of the melting point of the metal used. From the patent DE 41 01 630 C2, a manufacturing method for foamable metal body is known in which the temperature is chosen so high in the Kompaktierungsvorgang that the connection between the individual Metallpulverteilchen takes place mainly by diffusion and the Pressure when hot compacting is chosen so high that the decomposition of the propellant is prevented. From DE-C-195 01 659 a two-stage process for producing a metal foam part by high-speed flame spraying is known. The known processes are not yet satisfactory in every respect, in particular the range of variation available is not satisfactory. The present invention is based on the object to show a method and a device of the type mentioned, by which simplifies the production of foamable Metallkörpem and / or the variability in the production of foamable Metallkörpem is increased.This object is achieved for the method according to the invention that the production of the compact body The object is achieved for the device in that the means for producing the compact body from the powder mixture, a device for thermal spraying by means of Kaltgasspr Essentially, thermal spray processes are characterized by the ability to provide uniformly applied coatings of high quality and goodness. By thermal spraying applied coatings can be adapted by varying the spray materials and / or the process parameters to different requirements. The spray materials can basically be processed in the form of wires, rods or as a powder. In addition, a post-treatment can be provided. Details of thermal spraying can be found, for example, in European Standard EN 657. More recently, a further thermal spraying process has also been developed, which is also referred to as cold gas spraying. It is a kind of further development of high-speed flame spraying. This process is described, for example, in European Patent EP 0 484 533 B1. In cold gas spraying, an additional material in powder form is used. The powder particles are melted during cold gas spraying but not in the gas jet. Rather, the temperature of the gas jet is below the melting point of the filler material powder particles (EP 0 484 533 B1). In the cold gas spraying method, therefore, a "cold" or a comparatively colder gas is used in comparison to the conventional spraying method. However, the gas is heated as well as in the conventional method, but usually only to temperatures below the melting point of the powder particles of Zusatzstoffstoffes.Beim cold gas spraying, the powder particles can be accelerated to a speed of 300 to 1600 m / s. In particular, speeds of the powder particles between 500 and 1200 m / s are suitable for achieving particularly high application efficiencies and layer densities. Suitable materials for the metal powder in the context of the invention include all suitable metal-containing spray powders, in particular
  • pure metals,
  • Metal alloys,
  • Metals and / or metal alloys with additions of hard materials such as metal oxides (in particular Al 2 O 3 and / or TiO 2 ), carbides, borides and / or with additions of plastics
    or
  • Mixtures of the aforementioned substances
be used.

Gemäß der Erfindung wird Metallpulver zusammen mit einem das Treibmittel enthaltende Pulver durch Kaltgasspritzen zu einem kompakten Körper verarbeitet. Der kompakte Körper kann dabei als Schicht oder als Formkörper vorliegen. Wegen der kurzen Verweilzeit des Pulvers (üblicherweise liegt diese im Bereich einiger Millisekunden) beim Hochgeschwindigkeits-Kaltgasspritzen in dem aufgeheizten Trägergasstrahl bleibt das Treibmittel zumindest im wesentlichen gebunden. Es wird falls gewünscht erst beim anschließenden Aufheizen zum Aufschäumen frei. Entscheidend beim erfindungsgemäß eingesetzten technischen Spritzverfahren ist, dass das Treibmittelpulver beim Spritzvorgang im wesentlichen kein Gas abspaltet. Beim Kaltgasspritzen wird dies außer durch die kurze Verweilzeit des Pulvers auch durch die niedrige Prozeßtemperatur des Kaltgasspritzens mit einem auf wenige 100°C aufgeheizten Trägergasstrahl gewährleisten.According to the invention, metal powder is used together with a propellant Powder processed by cold gas spraying into a compact body. Of the compact body can be present as a layer or as a shaped body. Because of the short residence time of the powder (usually in the range of some Milliseconds) in high-speed cold gas spraying in the heated Carrier gas jet, the blowing agent remains at least substantially bound. It will if desired, only free to foam during subsequent heating. Decisive in the technical spraying method used according to the invention is that the blowing agent powder splits off substantially no gas during the injection process. In cold gas spraying, this is also due to the short residence time of the powder due to the low process temperature of the cold gas spraying with a few 100 ° C ensure heated carrier gas jet.

Durch die Erfindung wird ein einfach und vielseitig anwendbares Verfahren zur Herstellung der aufschäumbaren Metallkörper zur Verfügung gestellt. Die so hergestellten Metallkörper können durch Aufheizen auf eine Temperatur gleich oder bevorzugt oberhalb der Zersetzungstemperatur des Treibmittels und anschließendem Abkühlen zur Herstellung von porösen Metallkörpem oder Metallschäumen verwendet werden. In der Regel ist die Zersetzungstemperatur des Treibmittels keine scharfer Temperaturwert sondern ein Temperaturbereich. Im Rahmen der Erfindung wird daher unter einer Temperatur gleich oder bevorzugt oberhalb der Zersetzungstemperatur des Treibmittels in diesen Fällen eine Temperatur im Zersetzungstemperaturbereich oder bevorzugt oberhalb der Zersetzungstemperaturbereichs des Treibmittels verstanden.The invention provides a simple and versatile method for the production the foamable metal body provided. The so produced Metal bodies may be the same or preferred by heating to a temperature above the decomposition temperature of the propellant and subsequent cooling be used for the production of porous Metallkörpem or metal foams. In As a rule, the decomposition temperature of the propellant is not a sharp temperature value but a temperature range. In the context of the invention is therefore under a Temperature equal to or preferably above the decomposition temperature of the blowing agent in these cases a temperature in the decomposition temperature range or preferably understood above the decomposition temperature range of the blowing agent.

Beim erfindungsgemäßen Verfahren kann die Pulvermischung aus Metall plus Treibmittel in nahezu beliebigen Mischungsverhältnissen gespritzt werden. Das ermöglicht, daß das Mischungsverhältnis von Metallpulver und Treibmittelpulver jeweils an die gewünschten Bedingungen angepaßt wird.In the method according to the invention, the powder mixture of metal plus blowing agent be sprayed in almost any mixing ratios. This allows, that the mixing ratio of metal powder and propellant powder respectively to the adapted to desired conditions.

In Ausgestaltung der Erfindung kann das Pulvergemisch aus Metallpulver und Treibmittelpulver bei der Herstellung des aufschäumbaren Metallkörpers bezüglich seiner Parameter wie der Zusammensetzung, aber insbesondere bezüglich des Mischungsverhältnisses verändert werden. Besondere Vorteile ergeben sich, wenn das Pulvergemisch mit verändertem Treibmittelanteil gespritzt wird. Denn durch eine Veränderung des Mischungsverhältnisses von Metall und Treibmittel können Schichten und Strukturen mit einem sich vorzugsweise definiert verändernden Treibmittelanteil gespritzt werden (gradierte Schichten, Strukturen).In an embodiment of the invention, the powder mixture of metal powder and propellant powder in the preparation of the foamable metal body with respect to its Parameters such as the composition, but especially with respect to the mixing ratio to be changed. Special advantages arise when the powder mixture is injected with modified blowing agent. Because by a change The mixing ratio of metal and blowing agent can be layers and Structures injected with a preferably defined changing propellant content become (graded layers, structures).

Im Rahmen der Erfindung hat sich gezeigt, daß ein Treibmittelanteil im Pulvergemisch zwischen 0,01 und 1,0 Gew.-%, vorzugsweise zwischen 0,05 und 0,5 Gew.-%, besonders bevorzugt zwischen 0,1 und 0,3 Gew.-%, geeignet ist.In the context of the invention has been shown that a propellant in the powder mixture between 0.01 and 1.0% by weight, preferably between 0.05 and 0.5% by weight, especially preferably between 0.1 and 0.3 wt .-%, is suitable.

In Ausgestaltung der Erfindung umfaßt das gasabspaltende Treibmittelpulver als Treibmittel Metallhydride, wie beispielsweise Titanhydrid (TiH2), Karbonate, wie beispielsweise Calziumkarbonat, Kaliumkarbonat, Natriumkarbonat oder Natriumbikarbonat, Hydrate, wie beispielsweise Aluminiumsulfathydrat, Alaun, Aluminiumhydroxid oder leicht verdampfende Stoffe wie beispielsweise Quecksilberverbindungen oder pulverisierte organische Substanzen oder Mischungen der vorgenannten Stoffe.In an embodiment of the invention, the gas-releasing propellant powder comprises metal hydrides such as titanium hydride (TiH 2 ), carbonates such as calcium carbonate, potassium carbonate, sodium carbonate or sodium bicarbonate, hydrates such as aluminum sulfate hydrate, alum, aluminum hydroxide or light volatiles such as mercury compounds or powdered propellants organic substances or mixtures of the aforementioned substances.

Mit Vorteil kann das Pulvergemisch auf einen Substratträger gespritzt werden, wobei zumindest zeitweise eine Relativbewegung zwischen dem Substratträger und der Vorrichtung zum thermischen Spritzen des Pulvergemisches mittels Kaltgasspritzens erfolgt. Es können beispielsweise mit dem Pulvergemisch Formteile gespritzt werden, wobei beispielsweise die Spritzpistole der Vorrichtung zum thermischen Spritzen und/oder der Substratträger bewegt werden. Advantageously, the powder mixture can be sprayed onto a substrate carrier, wherein at least temporarily, a relative movement between the substrate carrier and the device for thermal spraying of the powder mixture by means Cold gas spraying takes place. It can, for example, with the Powder mixture moldings are sprayed, for example, the spray gun of the Device for thermal spraying and / or the substrate carrier to be moved.

Das Pulvergemisch kann erfindungsgemäß auf jeden geeigneten Substratträger insbesondere auf ein Trägermaterial aus Metall, Kunststoff, Keramik und/oder Glas gespritzt werden. Mit Vorteil kann der kompakte Körper vom Trägermaterial gelöst werden, bevor durch Erwärmung eine Gasabspaltung aus dem Treibmittel zum Aufschäumen des kompakten Körpers erfolgt.According to the invention, the powder mixture can be applied to any suitable substrate carrier in particular on a carrier material of metal, plastic, ceramic and / or glass be sprayed. Advantageously, the compact body can be detached from the carrier material before, by heating, gas release from the propellant Foaming of the compact body takes place.

In Weiterbildung der Erfindung kann der kompakte Körper vor der Gasabspaltung aus dem Treibmittel zum Aufschäumen des kompakten Körpers unter Änderung des Druckes und/oder der Temperatur verformt oder umgeformt werden. Als Umformungen kommen beispielsweise Strangpressen oder Walzen in Frage.In a further development of the invention, the compact body before the gas separation the foaming agent for foaming the compact body while changing the Pressure and / or the temperature deformed or reshaped. As transformations For example, extrusion or rolling are possible.

In einer anderen Weiterbildung der Erfindung wird das Pulvergemisch auf die Innenseite einer Form gespritzt, die mit Metallschaum ganz oder teilweise ausgeschäumt werden soll. Durch Aufheizen auf eine Temperatur gleich oder bevorzugt oberhalb der Zersetzungstemperatur des Treibmittels wird der Metallschaum gefertigt.In another embodiment of the invention, the powder mixture is on the inside sprayed in a mold that is completely or partially foamed with metal foam shall be. By heating to a temperature equal to or preferably above the Decomposition temperature of the blowing agent, the metal foam is made.

In einer anderen Weiterbildung der Erfindung werden zumindest zwei Lagen gespritzt, wobei zumindest eine Lage mit dem Metallpulver und gasabspaltendes Treibmittelpulver umfassenden Pulvergemisch und zumindest eine weitere Lage mit Metallpulver ohne gasabspaltendes Treibmittels thermisch gespritzt werden. Beispielsweise kann das Pulvergemisch aus Metall und Treibmittel nur lagenweise zwischen zwei Metallschichten gespritzt werden.In another embodiment of the invention, at least two layers are injected, wherein at least one layer with the metal powder and gas-releasing propellant powder comprehensive powder mixture and at least one further layer with metal powder be thermally sprayed without gas-releasing propellant. For example, can the powder mixture of metal and propellant only in layers between two metal layers be sprayed.

Durch Aufheizen des kompakten Körpers, der nach dem oben beschriebenen Verfahren hergestellt ist, auf eine Temperatur gleich oder bevorzugt oberhalb der Zersetzungstemperatur des Treibmittels und durch eine nachfolgende Abkühlung kann ein Metallschaum hergestellt werden. Bevorzugt erfolgt ein Aufheizen des kompakten Körpers auf eine Temperatur oberhalb der Schmelztemperatur des Metalls oder oberhalb der Sollidustemperatur der Metallegierung. In diesem Fall schäumt das als Gas entweichende Treibmittel die Metallschmelze auf. Dieser Schaum bildet nach dem Erkalten einen porösen Hohlkörper. Bevorzugt wird also das beim Zersetzen des Treibmittels frei werdende Gas das Metall oder die Metallegierung als Schmelze aufschäumen. By heating the compact body, following the procedure described above is prepared, to a temperature equal to or preferably above the decomposition temperature the propellant and by a subsequent cooling can a Metal foam are produced. Preference is given to heating the compact Body at a temperature above the melting temperature of the metal or above the Sollidustemperatur the metal alloy. In this case, this foams as gas escaping propellant to the molten metal. This foam forms after the Cool a porous hollow body. Preference is thus given to the decomposition of the Propellant released gas, the metal or metal alloy as a melt lather.

Es können Formteile hergestellt werden, die zumindest einen Metallschaum umfassen. Andererseits sind Verbundkörper herstellbar, die zumindest einen Metallschaum als Schicht auf oder zwischen einem Substratträger umfassen. Bei Formteilen oder Verbundkörpern können neben der zumindest einen aufgeschäumten Metallschicht zumindest eine weitere thermisch gespritzte Schicht vorhanden sein.Moldings can be produced which comprise at least one metal foam. On the other hand, composite bodies can be produced which comprise at least one metal foam Layer on or between a substrate carrier. For molded parts or composites In addition to the at least one foamed metal layer at least a further thermally sprayed layer may be present.

Als Treibmittel eignet sich insbesondere Titanhydrid (TiH2).Titanium hydride (TiH 2 ) is particularly suitable as blowing agent.

Titanhydrid kann beispielsweise mittels Kaltgasspritzens zusammen mit anderen Metallpulvern aus Aluminium (Al), Kupfer (Cu), Nickel (Ni), Eisen (Fe), Titan (Ti) sowie Legierungen die eines oder mehrere dieser Metalle enthalten, gespritzt werden. In der Regel reicht ein relativ kleiner Mengenanteil des Treibmittels zum Aufschäumen des kompakten Körpers aus. Beispielsweise führt ein Pulvergemisch mit 0,2 Gew.-% TiH2 und mit im wesentlichen Al als Metallpulver zu einem Schaumkörper mit etwa fünffacher Volumenvergrößerung. Ein Treibmittelanteil von 1,0 Gew.-% TiH2 vergrößert das Volumen von Al um mehr als das Zehnfache.For example, titanium hydride may be sprayed by cold gas spraying along with other metal powders of aluminum (Al), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), and alloys containing one or more of these metals. As a rule, a relatively small proportion of the blowing agent is sufficient for foaming the compact body. For example, a powder mixture with 0.2 wt .-% TiH 2 and with essentially Al as a metal powder to a foam body with about five times volume increase. A propellant content of 1.0 wt% TiH 2 increases the volume of Al by more than ten times.

Das für das thermische Spritzen benötigte Gas kann Stickstoff, Helium, Argon, Neon, Krypton, Xenon, ein Wasserstoff enthaltendes Gas, ein kohlenstoffhaltiges Gas, insbesondere Kohlendioxid, Sauerstoff, ein Sauerstoff enthaltendes Gas, Luft, Wasserdampf oder Mischungen der vorgenannten Gase enthalten. Neben den aus der EP 0 484 533 B1 bekannten Gasen Luft und/oder Helium eignen sich auch für das den pulverförmigen Zusatzwerkstoff tragende Gas ein Stickstoff, Argon, Neon, Krypton, Xenon, Sauerstoff, ein Wasserstoff enthaltendes Gas, ein kohlenstoffhaltiges Gas, insbesondere Kohlendioxid, Wasserdampf oder Mischungen der vorgenannten Gase und Mischungen dieser Gase mit Helium. Der Anteil des Helium am Gesamtgas kann bis zu 90 Vol.-% betragen. Bevorzugt wird ein Heliumanteil von 10 bis 50 Vol.-% im Gasgemisch eingehalten.The gas needed for the thermal spraying can be nitrogen, helium, argon, neon, Krypton, xenon, a hydrogen-containing gas, a carbon-containing gas, especially carbon dioxide, oxygen, an oxygen-containing gas, air, Water vapor or mixtures of the aforementioned gases. In addition to the from the EP 0 484 533 B1 known gases air and / or helium are also suitable for the powdery filler gas carrying a nitrogen, argon, neon, krypton, Xenon, oxygen, a hydrogen-containing gas, a carbon-containing gas, in particular carbon dioxide, water vapor or mixtures of the aforementioned gases and mixtures of these gases with helium. The proportion of helium in the total gas can up to 90 vol .-% amount. A helium content of 10 to 50% by volume is preferred Gas mixture complied.

Claims (13)

  1. Process for producing foamable metal bodies comprising forming a compact body from a powder mixture which comprises at least one metal powder and at least one gas-detaching blowing agent powder which detaches gas upon heating to a temperature equal to or above the decomposition temperature of the blowing agent, characterized in that the forming of the compact body is effected by thermal spraying of the powder mixture by cold gas spraying.
  2. Process according to Claim 1, characterized in that the mixing ratio of metal powder and blowing agent powder is conformed to the desired conditions in each case.
  3. Process according to Claim 1 or 2, characterized in that the powder mixture of metal powder and blowing agent powder is changed especially with regard to the mixing ratio in the course of the forming of the foamable metal body.
  4. Process according to Claim 3, characterized in that the powder mixture is spray dispensed using a varying blowing agent content.
  5. Process according to any one of Claims 1 to 4, characterized in that the blowing agent content in the powder mixture is between 0.01 and 1.0 wt.-%, preferably between 0.05 and 0.5 wt.-% and more preferably between 0.1 and 0.3 wt.-%.
  6. Process according to any one of Claims 1 to 5, characterized in that the gas-detaching blowing agent powder comprises a blowing agent selected from the group consisting of metal hydrides, carbonates, hydrates, alum, aluminium hydroxide and/or mercury compounds and/or pulverized organic substances.
  7. Process according to any one of Claims 1 to 6, characterized in that the powder mixture is sprayed onto a substrate support while a relative movement between the substrate support and the apparatus for thermal spraying of the powder mixture takes place at least temporarily.
  8. Process according to any one of Claims 1 to 7, characterized in that the powder mixture is sprayed onto a support material composed of metal, plastic, ceramic and/or glass.
  9. Process according to Claim 8, characterized in that the compact body is released from the support material before gas detachment from the blowing agent to foam the compact body.
  10. Process according to any one of Claims 1 to 9, characterized in that the compact body is shaped and/or reshaped by changing the pressure and/or the temperature before gas detachment from the blowing agent to foam the compact body.
  11. Process according to any one of Claims 1 to 10, characterized in that the powder mixture is sprayed onto the inside surface of a mould which is to be wholly or partly foamed out with metal foam.
  12. Process according to any one of Claims 1 to 11, characterized in that at least two plies are spray produced, at least one ply being thermally spray produced using the powder mixture comprising metal powder and gas-detaching blowing agent powder and at least one further ply being spray produced using metal powder without gas-detaching blowing agent.
  13. Apparatus for producing metal foams which comprises
    means for feeding a powder mixture comprising at least one metal powder and at least one gas-detaching blowing agent powder,
    means for forming a compact body from the powder mixture and
    means for heating the compact body to a temperature equal to or above the decomposition temperature of the blowing agent by detachment of gas,
    characterized in that
    the means for forming the compact body from the powder mixture comprise an apparatus for thermal spraying of the powder mixture by cold gas spraying.
EP00119602A 1999-09-08 2000-09-07 Preparation of foamable metal bodies and metal foams Expired - Lifetime EP1083013B1 (en)

Applications Claiming Priority (2)

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DE19942916 1999-09-08
DE19942916A DE19942916A1 (en) 1999-09-08 1999-09-08 Manufacture of foamable metal bodies and metal foams

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EP1083013A2 EP1083013A2 (en) 2001-03-14
EP1083013A3 EP1083013A3 (en) 2004-01-21
EP1083013B1 true EP1083013B1 (en) 2005-07-27

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EP (1) EP1083013B1 (en)
AT (1) ATE300378T1 (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013210198A1 (en) * 2013-05-31 2014-12-04 Siemens Aktiengesellschaft Method for producing a metal foam and method for producing particles suitable for the aforesaid method

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6464933B1 (en) * 2000-06-29 2002-10-15 Ford Global Technologies, Inc. Forming metal foam structures
US6733958B2 (en) * 2000-08-30 2004-05-11 Dainippon Ink And Chemicals, Inc. Material for photo-alignment layer, photo-alignment layer and method of manufacturing the same
US20030002043A1 (en) * 2001-04-10 2003-01-02 Kla-Tencor Corporation Periodic patterns and technique to control misalignment
ATE388778T1 (en) * 2002-05-20 2008-03-15 Liquidmetal Technologies FOAMED STRUCTURES OF GLASS-FORMING AMORPHIC ALLOYS
DE10246454A1 (en) * 2002-10-04 2004-04-15 Rwth Aachen Making coated foamed components used in e.g. automobile or building industries, employs surface treatment, coating and profiling by thermal foaming
US7621314B2 (en) * 2003-01-17 2009-11-24 California Institute Of Technology Method of manufacturing amorphous metallic foam
US7560170B2 (en) * 2003-04-04 2009-07-14 Intelligent Energy, Inc. Surface modification of porous metal substrates using cold spray
EP1613465B1 (en) * 2003-04-04 2014-07-09 Intelligent Energy, Inc. Surface modification of porous metals
US7077889B2 (en) * 2003-04-04 2006-07-18 Intelligent Engery, Inc. Surface modification of porous metal substrates
WO2004091828A1 (en) * 2003-04-14 2004-10-28 Liquidmetal Technologies, Inc. Continuous casting of foamed bulk amorphous alloys
KR100723538B1 (en) 2004-12-24 2007-06-04 고경현 Method of preparing disperse-strengthened alloys and disperse-strengthened alloys prepared by the same
AU2006243447B2 (en) * 2005-05-05 2010-11-18 H.C. Starck Surface Technology and Ceramic Powders GmbH Method for coating a substrate surface and coated product
US7402277B2 (en) * 2006-02-07 2008-07-22 Exxonmobil Research And Engineering Company Method of forming metal foams by cold spray technique
CN101063204B (en) * 2006-04-30 2010-10-13 宝山钢铁股份有限公司 Method for manufacturing galvanized steel sheet
DE102006020860B4 (en) * 2006-05-04 2008-02-07 Alulight International Gmbh Process for the production of composite bodies and composite bodies produced therefrom
EP1903127A1 (en) * 2006-09-21 2008-03-26 Siemens Aktiengesellschaft Process of manufacturing of workpieces by cold gas spraying and turbine workpiece
US20080078268A1 (en) 2006-10-03 2008-04-03 H.C. Starck Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
NZ576664A (en) * 2006-11-07 2012-03-30 Starck H C Gmbh Method for coating a substrate surface and coated product
US20080145688A1 (en) 2006-12-13 2008-06-19 H.C. Starck Inc. Method of joining tantalum clade steel structures
US8197894B2 (en) 2007-05-04 2012-06-12 H.C. Starck Gmbh Methods of forming sputtering targets
US8246903B2 (en) 2008-09-09 2012-08-21 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
US8043655B2 (en) * 2008-10-06 2011-10-25 H.C. Starck, Inc. Low-energy method of manufacturing bulk metallic structures with submicron grain sizes
DE102008058141A1 (en) * 2008-11-20 2010-05-27 Mtu Aero Engines Gmbh Method for producing a blade for a rotor of a turbomachine
DE102008058142A1 (en) * 2008-11-20 2010-05-27 Mtu Aero Engines Gmbh Method for producing and / or repairing a rotor of a turbomachine and rotor for this purpose
DE102009037894A1 (en) * 2009-08-18 2011-02-24 Mtu Aero Engines Gmbh Thin-walled structural component and method for its production
US8974588B2 (en) 2011-09-29 2015-03-10 General Electric Company Coating composition, a process of applying a coating, and a process of forming a coating composition
US8703233B2 (en) 2011-09-29 2014-04-22 H.C. Starck Inc. Methods of manufacturing large-area sputtering targets by cold spray
US8475882B2 (en) 2011-10-19 2013-07-02 General Electric Company Titanium aluminide application process and article with titanium aluminide surface
US9033024B2 (en) 2012-07-03 2015-05-19 Apple Inc. Insert molding of bulk amorphous alloy into open cell foam

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087807A (en) 1959-12-04 1963-04-30 United Aircraft Corp Method of making foamed metal
DE2112751B2 (en) * 1971-03-17 1973-05-17 PROCESS FOR MANUFACTURING INSULATING AND CORROSION-PROTECTED FOAM-METAL COMPOSITE ELEMENTS
US3940252A (en) * 1972-03-27 1976-02-24 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Apparatus for the releasing of materials from voluminous precipitates or suspensions
EP0484533B1 (en) 1990-05-19 1995-01-25 Anatoly Nikiforovich Papyrin Method and device for coating
DE4101630A1 (en) 1990-06-08 1991-12-12 Fraunhofer Ges Forschung METHOD FOR PRODUCING FOAMABLE METAL BODIES AND USE THEREOF
US5266099A (en) * 1992-08-11 1993-11-30 The United States Of America As Represented By The Secretary Of The Navy Method for producing closed cell spherical porosity in spray formed metals
DE19501659C1 (en) * 1995-01-20 1996-05-15 Daimler Benz Ag Method for producing component made of metal foam
DE19651197C2 (en) * 1995-12-15 1999-10-28 Susan Dietzschold Material for producing porous metal bodies

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013210198A1 (en) * 2013-05-31 2014-12-04 Siemens Aktiengesellschaft Method for producing a metal foam and method for producing particles suitable for the aforesaid method

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DE50010812D1 (en) 2005-09-01
US6408928B1 (en) 2002-06-25
DE19942916A1 (en) 2001-03-15
EP1083013A2 (en) 2001-03-14
ATE300378T1 (en) 2005-08-15
EP1083013A3 (en) 2004-01-21

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