EP2044230B1 - Verfahren zur herstellung von metallschäumen - Google Patents

Verfahren zur herstellung von metallschäumen Download PDF

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Publication number
EP2044230B1
EP2044230B1 EP07785573A EP07785573A EP2044230B1 EP 2044230 B1 EP2044230 B1 EP 2044230B1 EP 07785573 A EP07785573 A EP 07785573A EP 07785573 A EP07785573 A EP 07785573A EP 2044230 B1 EP2044230 B1 EP 2044230B1
Authority
EP
European Patent Office
Prior art keywords
melt
metal
process according
particles
added
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
EP07785573A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2044230A2 (de
Inventor
Norbert BABCSÁN
Goarke Sanjeeviah Vinod Kumar
John Banhart
Budaraju Srinivasa Murty
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.)
Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
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Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
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Publication of EP2044230A2 publication Critical patent/EP2044230A2/de
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Publication of EP2044230B1 publication Critical patent/EP2044230B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/005—Casting metal foams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C22C1/083—Foaming process in molten metal other than by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C22C1/083—Foaming process in molten metal other than by powder metallurgy
    • C22C1/086—Gas 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
    • 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
    • B22F3/1103—Making porous workpieces or articles with particular physical characteristics
    • B22F2003/1106—Product comprising closed porosity

Definitions

  • the invention relates to a process for the production of metal foams with stabilizing particles.
  • Metal foams are of great interest as materials because of their possible combinations of different properties.
  • metal foams are very light on the one hand, and on the other hand have high rigidity and considerable strength. You can z. B. are used for thermal insulation, noise and vibration damping or compression element.
  • a slurry is prepared at room temperature to produce steel foam from steel powder, water and a stabilizer.
  • Phosphoric acid is added to this mixture as a binding and blowing agent.
  • Two reactions then take place in the slurry, leading to the formation of a stable foam structure.
  • hydrogen gas bubbles are produced which cause foaming.
  • a metal phosphate is formed, which solidifies the pore structure by its adhesive effect. The foam thus produced is dried and then sintered free of pollutants to the metallic composite.
  • a melt metallurgical process is used, for example, in EP 1 288 320 A2 described by gas bubbles are introduced into a melt.
  • the size of the bubbles is controlled by the adjustment of the Einströmparameter of the gas.
  • a disadvantage of these melt metallurgical processes is that a molten metal in the pure state can not be foamed.
  • the melt before carrying out the foaming, the melt must be mixed with a viscosity-increasing agent, for example an inert gas ( GB 1,287,994 ) or with ceramic particles ( EP 0 666 784 B ).
  • a viscosity-increasing agent for example an inert gas ( GB 1,287,994 ) or with ceramic particles ( EP 0 666 784 B ).
  • a viscosity-increasing agent for example an inert gas ( GB 1,287,994 ) or with ceramic particles ( EP 0 666 784 B ).
  • a powder metallurgical process for producing porous metal bodies is disclosed in US Pat DE 101 15 230 C2 in which a mixture comprising a powdered metallic material containing at least one metal and / or one metal alloy and a gas-releasing propellant-containing powder is compacted into a semi-finished product.
  • This semifinished product is foamed under the action of temperature, wherein a propellant-containing powder is used, in which the temperature of the maximum decomposition is less than 120 K below the melting temperature of the metal or the solidus temperature of the metal alloy.
  • a foamable semifinished product consisting of metal and at least one blowing agent releasing gas at elevated temperature be produced first.
  • the foamable semifinished product contains a substantially closed matrix in which propellant particles are embedded.
  • An increased quality of a created metal foam body is to be achieved with a semi-finished product in which the metal matrix enclosing the blowing agent particles is formed by diffusion and / or pressure welding of metal particles.
  • Another method for producing foam metal bodies is in WO 2004/063406 A2 described.
  • This method can be used as a powder metallurgy or as a melt metallurgical process.
  • a sufficient gas supply of the melt is achieved in order of the Solidification of the same can cause the formation of a metal foam body low density.
  • JP 01-127631 also describes a process in which hydrogen, nitrogen, oxygen is introduced into the liquid metal analogously to the abovementioned solution under atmospheric pressure, or blowing agent particles, such as nitride, hydride or oxide, release gas into the melt by thermal cracking.
  • the gasified liquid metal is placed in a mold and kept under reduced pressure, 53.320 to 101.308 kPa for a period of time.
  • a method for producing stabilized metal foams is in US 5,112,697 released.
  • solid stabilizing particles are added to the starting material for the metal matrix, mixed and heated to a temperature greater than the liquidus temperature of the metal matrix. Subsequently, gas is added to the mixture and the mixture is cooled. The stabilizing particles are then incorporated into the metal matrix.
  • attention is drawn to the correct selection of these solid stabilizing particles, as these can lose their shape and their identity by dissolution in the metal or chemical combination with the metal.
  • stabilizing particles are called: metal oxides, carbides, nitrides or borides, in particular Al, TiB 2 , Zr, SiC, SiN, which are contained in the metal foam to ⁇ 25%, preferably 5 to 15%.
  • the size of the particles is given as 0.1 to 100 ⁇ m. It should be noted that the right size selection is important because too small particles are very difficult to mix. On the other hand, too large particles precipitate. If the volume fraction of these stabilizing particles is too low, the foam stability is too weak; if the volume fraction is too high, the viscosity is too high.
  • the method described produces a metal foam having typical cell sizes of 250 ⁇ m to 50 mm.
  • Such metal foams containing ⁇ m-sized stabilizing particles in their metal matrix are brittle and are difficult to cut clean with a saw.
  • the starting materials are very expensive and a large amount of these particles is necessary to achieve good stability.
  • the object of the invention is to provide a further process for the production of metal foams having stabilizing particles, in particular the amount of stabilizing particles necessarily used should be reduced and the metal foams produced should be easier to process.
  • the object is achieved for a method of the type mentioned in that the stabilizing particles are generated in the preparation of the foamable starting material in an in situ reaction of molten reactive liquids and a molten metal, wherein the molten metal, the components of the submicroscopic particles or Nanoparticles are added at least as fluoride salt, then mixed and heated above the melting temperature of the mixture components.
  • the solution according to the invention in which the stabilizing submicroscopic particles or nanoparticles are produced during the preparation of the foamable starting material by means of an in situ reaction, makes it possible to provide and cooperate with such elements which are required for the formation of an interface layer between the melt and the stabilizing particles a contact angle of 10 to 100 grd, preferably from 60 to 80 grd are necessary. As has surprisingly been found, this angle is essential for the formation of metal foams according to the inventive solution and depending on the alloys used and also essential for the grain refining during solidification.
  • the metal foams produced by the method according to the invention less material has to be used in order to achieve the same stabilization compared with the prior art of known metal foams, since the stabilizing particles produced in an in situ step have a greater specific surface area.
  • the metal foams produced in this way are less brittle, since their metal matrix has better mechanical properties, and can be processed more easily.
  • K x AF y is used as fluoride salt, where A is an element of Ti, B, Zr, Nb, V, W, Ta or Ce, preferably K 2 TiF 6 or KBF 4 is used or both salts are used as a mixture.
  • a further constituent of the stabilizing particles to be produced in the in situ reaction for example carbon in the form of graphite, is added.
  • the metal used for the melt is aluminum or an aluminum alloy.
  • the starting material is cooled to 700 ° C and for foaming the same powdered metal hydride, preferably TiH 2 , from 1 to 3 wt. % added as an intumescent at 700 ° C.
  • the same powdered metal hydride preferably TiH 2 , from 1 to 3 wt. % added as an intumescent at 700 ° C.
  • reactive gases can also be used for foaming, for example CH 4 , NH 3 and O 2 , preferably O 2 in a concentration of 0.1 to 10 vol.%, In particular of 1 to 2 vol.%.
  • the temperature here is 600 to 1,000 ° C, preferably 700 ° C.
  • the foaming of the starting material can also be carried out by other methods known from the prior art, for example by means of a gas injection directly into the melt.
  • metal foams having stabilizing particles in a metal matrix, wherein the stabilizing particles less than 10 vol.% Are contained in the metal matrix.
  • These stabilizing particles have a size of less than 1 ⁇ m and are arranged at a contact angle of 10 to 100 °, preferably 60 to 80 °.
  • the metal matrix is formed of uniformly arranged polygonal closed cells with an average diameter of 2 to 10 mm.
  • the metal foam produced by the process according to the invention has a porosity of at least 75%.
  • the stabilizing particles contain Ti or B or Zr or Nb or V or W or Ta or Ce or C or Al in combination with a second element of this group and are preferably formed from TiC or AlB 2 or TiB 2 .
  • Fig. 1 shows an SEM image of a section through a cell of the Al foam, on the surface, ie on its cell wall, the TiC particles are very well recognizable in their dense and relatively homogeneous arrangement.
  • Fig. 2 The X-ray image shown shows the entire sample of the same Al foam with TiC particles. The diameter of this sample is 40 mm.
  • a mixture of KBF 4 and K 2 TiF 6 is added to an Al melt produced at 800 ° C. and mixed. After the reaction, the unwanted components are removed again except for the Al-TiB 2 mixture. Cooling and foaming process is carried out as in Example 1.
  • the Al foam thus produced with a porosity of about 75% contains TiB 2 particles in a concentration of 4 vol.% And a size of less than 1 micron.
  • Al is melted at 800 ° C. This melt is added to KBF 4 and mixed again. After removal of the undesirable components after the reaction, the Al-AlB 2 mixture - as described - cooled and foamed. The result of this process is once again an Al foam with a porosity of about 75%, the stabilizing particles of which are formed here from AlB 2 and are contained in the foam in a concentration of 4.3% by volume.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Powder Metallurgy (AREA)
EP07785573A 2006-07-03 2007-06-27 Verfahren zur herstellung von metallschäumen Not-in-force EP2044230B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006031213A DE102006031213B3 (de) 2006-07-03 2006-07-03 Verfahren zur Herstellung von Metallschäumen und Metallschaum
PCT/DE2007/001140 WO2008003290A2 (de) 2006-07-03 2007-06-27 Verfahren zur herstellung von metallschäumen und metallschaum

Publications (2)

Publication Number Publication Date
EP2044230A2 EP2044230A2 (de) 2009-04-08
EP2044230B1 true EP2044230B1 (de) 2010-11-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP07785573A Not-in-force EP2044230B1 (de) 2006-07-03 2007-06-27 Verfahren zur herstellung von metallschäumen

Country Status (4)

Country Link
EP (1) EP2044230B1 (https=)
AT (1) ATE486971T1 (https=)
DE (2) DE102006031213B3 (https=)
WO (1) WO2008003290A2 (https=)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007041775B3 (de) * 2007-09-04 2008-10-02 Eads Deutschland Gmbh Verfahren zum Herstellen eines Formkörpers mit schaumartiger Struktur
DE102008000100B4 (de) 2008-01-18 2013-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines leichtgewichtigen Grünkörpers, danach hergestellter leichtgewichtiger Grünkörper und Verfahren zur Herstellung eines leichtgewichtigen Formkörpers
DE102008023481B4 (de) * 2008-05-14 2013-10-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeleitfähige Komposit-Adsorbentien sowie Verfahren zu deren Herstellung und deren Verwendung
DE102009011763B4 (de) * 2009-03-04 2012-11-08 Bpe International Dr. Hornig Gmbh Verfahren zur Herstellung einer offenporigen metallischen Gitterstruktur und hieraus bestehender Leichtbauwerkstoff
DE102010024669B3 (de) * 2010-06-18 2011-12-08 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Verfahren zur Herstellung von Metallschäumen und Metallschaum
EP3083105B1 (en) * 2013-12-17 2017-11-15 Taskin, Nilhan Urkmez Continuous composite metal foam production and method and device for stirring particle reinforced composite metal
DE102015004609B4 (de) 2014-04-03 2020-10-22 Technische Universität Ilmenau Verfahren zur Herstellung von Metallschaum, Metallschaum und seine Verwendung
CA2954019C (en) 2014-07-01 2019-10-15 Siemens Aktiengesellschaft Clamping assembly having a pressure element
KR101967562B1 (ko) 2014-08-06 2019-04-09 지멘스 악티엔게젤샤프트 발포 금속을 포함하는 전기 안전 장치, 및 상기 안전 장치를 이용하여 전류를 차단하는 방법
CN116005039B (zh) * 2022-12-30 2024-09-03 安徽工业大学 一种泡沫铝及其制备方法

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
US3816952A (en) * 1969-02-19 1974-06-18 Ethyl Corp Preparation of metal foams with viscosity increasing gases
DE2006445C3 (de) * 1969-02-19 1975-01-02 Ethyl Corp., Richmond, Va. (V.St.A.) Verfahren zur Herstellung von Aluminiumschaumformkörpern
GB8505904D0 (en) * 1985-03-01 1985-04-11 London Scandinavian Metall Producing titanium carbide
DE3665739D1 (en) * 1985-07-19 1989-10-26 Agency Ind Science Techn Foamed metal and method of producing same
US5112697A (en) * 1989-09-06 1992-05-12 Alcan International Limited Stabilized metal foam body
GB2259308A (en) * 1991-09-09 1993-03-10 London Scandinavian Metall Metal matrix alloys
US5281251A (en) * 1992-11-04 1994-01-25 Alcan International Limited Process for shape casting of particle stabilized metal foam
DE10115230C2 (de) * 2000-03-28 2002-11-28 Fraunhofer Ges Forschung Verfahren zur Herstellung poröser Metallkörper und Verwendung derselben
US20040163492A1 (en) * 2001-05-17 2004-08-26 Crowley Mark D Method for producing foamed aluminum products
CZ302631B6 (cs) * 2001-06-15 2011-08-10 Hütte Klein-Reichenbach Gesellschaft M. B. H. Zarízení a zpusob k výrobe kovové peny
AT411768B (de) * 2002-09-09 2004-05-25 Huette Klein Reichenbach Gmbh Verfahren und vorrichtung zur herstellung von fliessfähigem metallschaum
AT413344B (de) * 2003-01-13 2006-02-15 Arc Leichtmetallkompetenzzentrum Ranshofen Gmbh Verfahren zur herstellung von metallschaumkörpern
AT412876B (de) * 2003-08-05 2005-08-25 Arc Leichtmetallkompetenzzentrum Ranshofen Gmbh Schäumbares halbzeug und verfahren zur herstellung von metallteilen mit innerer porosität

Also Published As

Publication number Publication date
DE502007005568D1 (https=) 2010-12-16
DE102006031213B3 (de) 2007-09-06
ATE486971T1 (de) 2010-11-15
EP2044230A2 (de) 2009-04-08
WO2008003290A3 (de) 2008-02-28
WO2008003290A2 (de) 2008-01-10

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