US20120141670A1 - Open-porous metal foam body and a method for fabricating the same - Google Patents

Open-porous metal foam body and a method for fabricating the same Download PDF

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Publication number
US20120141670A1
US20120141670A1 US13/197,867 US201113197867A US2012141670A1 US 20120141670 A1 US20120141670 A1 US 20120141670A1 US 201113197867 A US201113197867 A US 201113197867A US 2012141670 A1 US2012141670 A1 US 2012141670A1
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US
United States
Prior art keywords
iron
metal foam
open
porous metal
chrome
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.)
Abandoned
Application number
US13/197,867
Other languages
English (en)
Inventor
Gunnar Walther
Burghardt KLÖDEN
Juliane BÖHM
Tilo BÜTTNER
Thomas WEISSGÄRBER
Bernd KIEBACK
Arne BODEN
Hans-Dietrich BÖHM
Hyuntae Kim
James Choi
Myungjoon JANG
Alexander Böhm
Stefan Fröhlich
Winfried Dölling
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Alantum Corp
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Alantum Corp
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Alantum Corp filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Assigned to ALANTUM, FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWANDTEN FORSCHUNG E.V. reassignment ALANTUM ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOI, JAMES, JANG, MYUNGJOON, KIM, HYUNTAE, BODEN, ARNE, BOHM, ALEXANDER, BOHM, HANS-DIETRICH, BOHM, JULIANE, BUTTNER, TILO, DOLLING, WINFRIED, FROHLICH, STEFAN, KIEBACK, BERND, KLODEN, BURGHARDT, WALTHER, GUNNAR, WEISSGARBER, THOMAS
Publication of US20120141670A1 publication Critical patent/US20120141670A1/en
Priority to US14/011,939 priority Critical patent/US9346240B2/en
Abandoned legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • B22F3/1146—After-treatment maintaining the porosity
    • 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
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • 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
    • 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
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]

Definitions

  • the present invention relates to a metal foam, and more particularly, to an open-porous metal foam.
  • a metal foam may be used in various fields due to a low weight and porosity.
  • the metal foam may be catalytically activated for the purpose of a chemical process or may be used in an environmental engineering, and may be used for the purpose of filtration.
  • the metal foam is frequently used at a relatively high temperature and a severe environment.
  • the metal foam should endure the high temperature of 700° C. or more, and particularly, even the temperature at which it is difficult to make most metals and metal alloys stable for a long time such as the high temperature of 1000° C. or more.
  • the metal foam is advantageous in that the metal foam is applied for the purpose of high temperature as compared to a general heat resistant metal or heat resistant metal alloy in terms of manufacturing costs.
  • the metal foam may be manufactured by various methods.
  • a cost may be more reduced by sintering a green body manufactured in a powder form by using each metal.
  • the surface of the metal foam is subsequently coated and reformed. This is required in a metal foam that is generally formed of nickel.
  • an open-porous shaped body that is coated by another metal formed of nickel or iron, and a mixed crystal of at least iron or nickel, or an intermetallic phase is disclosed.
  • the completed open-porous shaped body is formed of at least two phases having different thermal, mechanical and chemical characteristics.
  • the use of the metal foam formed of an iron-chrome-aluminum alloy is disclosed, and a metal oxide layer acting as a catalyst is formed on the metal foam.
  • the used alloy is not disclosed in detail, and a ratio at which each metal is included in the alloy and a manufacturing process of the metal foam are not disclosed.
  • the present invention has been made in an effort to provide an open-porous metal foam that has improved material characteristics as compared to a known metal foam, and particularly, is used at a higher temperature and is stable to oxidation.
  • An exemplary embodiment of the present invention provides an open-porous metal foam made of an iron-based alloy including 15 wt % or more of chrome and 5 wt % or more of aluminum.
  • a web element of the foam is formed in an air-tight manner.
  • the iron-based alloy includes nickel, and a maximum content of nickel is maintained so as to have an alpha ( ⁇ )-structure in a structure.
  • a specific surface area is 10 mm 2 /mm 3 to 25 mm 2 /mm 3
  • surface roughness of the web element facing an open pore is 50 ⁇ m to 200 ⁇ m.
  • At least one alloy element selected from yttrium (Y), hafnium (Hf), manganese (Mn), silicon (Si) and zirconium (Zr) is included in an amount of greater than 0 wt % to less than 1 wt %.
  • Another exemplary embodiment of the present invention provides a method for manufacturing an open-porous metal foam, including: providing a semi-product that does not include chrome and aluminum or include a smaller amount than an amount in powder of an iron-chrome-aluminum alloy and is formed of iron or an iron-based alloy; uniformly coating a surface and an opened pore of the semi-product that is formed of the iron or the iron-based alloy with the powder of the iron-chrome-aluminum alloy and an organic binding agent; discharging organic components by heat treating the semi-product that is formed of the coated iron or iron-based alloy under a reducing atmosphere at a temperature of 300 to 600° C.; and sintering the semi-product that is formed of the iron or the iron-based alloy from which the organic components are discharged at the temperature of 900° C. or more.
  • the semi-product uses a foam in which the iron or the iron-based alloy is deposited on the organic open-porous foam by an electroplating manner.
  • An average particle size of the powder is 20 ⁇ m to 50 ⁇ m.
  • the metal foam that is formed of the iron-chrome-aluminum alloy is formed by compensating concentrations of alloy elements between the semi-product and the powder by diffusion, and a content of chrome and aluminum in the metal foam is smaller than a content of chrome and aluminum included in a starting alloy of the used powder.
  • the sintering is heated at a heating speed of 5 K/min to 1300° C., and the temperature is maintained for at least 30 min.
  • an open-porous metal foam is formed of a single-phase material, the foam has uniform thermal, mechanical and chemical characteristics, excellent malleability and low brittleness.
  • an anti-aging property may be improved by forming a protective aluminum oxide layer by preliminary oxidation in the air.
  • FIG. 1 is a transverse cross-sectional view that illustrates an extended surface of a web element (factor) of a metal foam according to an exemplary embodiment of the present invention.
  • An open-porous metal foam according to an exemplary embodiment of the present invention is made of an iron-based alloy including 15 wt % or more of chrome and 5 wt % or more of aluminum.
  • Corrosion resistance and high temperature oxidation resistance under various atmospheres may be provided by including chrome (Cr) in the iron-based alloy.
  • oxides of aluminum may be formed on a surface of an iron-based alloy under the environment that is exposed to the high temperature by including aluminum (Al) in the iron-based alloy.
  • Fecralloy As the iron-based alloy in which chrome and aluminum are included, Fecralloy may be used.
  • the open-porous metal foam may be used as a semi-product that is formed of iron or an iron-based alloy.
  • the alloy may not include chrome and aluminum, or the content of at least chrome and aluminum may be smaller than the content of chrome and aluminum included in the powder used in another manufacturing method.
  • the surface and the open pore of the semi-product are uniformly coated with a suspension solution formed by the powder of the iron-chrome-aluminum alloy and the organic binding agent.
  • the sintering process is performed at the temperature of 900° C. or more.
  • the metal foam body that is formed of the iron-chrome-aluminum alloy is formed by compensating concentrations of alloy elements between the semi-product and the powder by diffusion when sintering, and a content of chrome and aluminum in the metal foam is smaller than a content of chrome and aluminum included in a starting alloy of the used powder.
  • the alloy in a the powder state and a volume thereof may be selected so that desired contents of alloy elements are included in the completed metal foam, in consideration of the material volume of the semi-product and an alloy composition thereof in the case of the iron-based alloy.
  • Nickel may be included in addition to iron in the material of the semi-product.
  • the maximum content of nickel in the iron-based alloy should be selected so as to have an alpha ( ⁇ )-structure in the structure frame.
  • ⁇ alpha
  • ⁇ gamma
  • the alpha ( ⁇ )-structure in the structure frame very preferably acts to form a protective oxide layer in the heat treatment performed under an oxidizing atmosphere after the sintering process, particularly, in diffusion of elements such as aluminum.
  • the compensation of the concentration between the semi-product material and the powder alloy in the sintering is simplified and accelerated by improving the diffusion.
  • all web elements of the foam are formed in an air-tight manner. This may be implemented by using the foam in which the iron or the iron-based alloy is deposited on the organic open-porous foam body as the semi-product.
  • a specific surface area may be 10 mm 2 /mm 3 to 25 mm 2 /mm 3
  • surface roughness of the web elements (factors) facing an open pore may be in the range of 50 ⁇ m to 200 ⁇ m.
  • alloy elements may be included in a content of greater than 0 wt % to less than 1 wt %.
  • This element may be at least one selected from yttrium (Y), hafnium (Hf), manganese (Mn), silicon (Si) and zirconium (Zr).
  • a method for manufacturing an open-porous metal foam according to another exemplary embodiment of the present invention includes providing a semi-product that does not include chrome and aluminum or include a smaller amount than an amount in powder of an iron-chrome-aluminum alloy and is formed of iron or an iron-based alloy; uniformly coating a surface and an opened pore of the semi-product that is formed of the iron or the iron-based alloy with the powder of the iron-chrome-aluminum alloy and an organic binding agent; discharging organic components by heat treating the coated semi-product that is formed of iron or iron-based alloy under a reducing atmosphere at a temperature of 300 to 600° C.; and sintering the semi-product that is formed of the iron or the iron-based alloy from which the organic components are discharged at the temperature of 900° C. or more.
  • the powder having the average particle size of 20 ⁇ m to 50 ⁇ m may be used.
  • heating may be performed at a heating speed of 5 K/min to the maximum temperature of 1300° C., and the maximum temperature may be maintained for at least 30 min and preferably, 60 min.
  • the concentration compensation is very preferably implemented between the metal elements included in the semi-product material and the metal elements included in the powder alloy by diffusion implemented for a short time in the sintering.
  • the concentration compensation of the alloy elements is implemented by diffusion.
  • the metal alloy of the completed metal foam is uniform over the entire volume and has resistance to the high temperature oxidation.
  • the air-tight web element (factor) for forming the support structure frame has increased mechanical strength.
  • the surface on which the suspension solution including the powder is provided is a rough surface corresponding to a shape of powder particles. Therefore, the specific surface area of the metal foam may be increased, and fluidizing movement characteristics applied to various fields may be improved.
  • corrosion resistance may be improved because the foam is manufactured by only the sintering by the air-tight property of the web element of the metal foam as compared to the metal foam in which residual porosity cannot be avoided.
  • the foam since a metal foam is formed of a single-phase material, the foam has uniform thermal, mechanical and chemical characteristics, excellent malleability and low brittleness.
  • a protective aluminum oxide layer for increasing an anti-aging property may be formed by preliminary oxidation in the air.
  • the open-porous metal foam was manufactured, first, the semi-product that was formed of the iron-based alloy including 5% of nickel on the organic foam that was formed of polyurethane by the electroplating method was used.
  • Porosity was 94%.
  • the dimension of width L * length B * thickness T was 300 mm * 200 mm * 1.5 mm.
  • the metal foam In order to manufacture the metal foam, 50 g of the metal powder of the iron-chrome-aluminum alloy including 35 wt % of chrome and 9.5 wt % of aluminum was used. In addition, 50 ml of 1% polyvinylpyrrolidone aqueous solution was manufactured.
  • the semi-product processed as described above was fixed into the vibration device, and the metal powder was scattered on the surface thereof.
  • the metal powder was uniformly distributed in the porous net and on the web factor surfaces by vibration, and as a result, the open-porous was maintained while the entire web element surface was completely covered with the powder particles.
  • the pretreated semi-product was heat treated under the hydrogen atmosphere.
  • the temperature was increased at the heating speed of 5 K/min.
  • the organic components were discharged in the temperature range of 300 to 600° C.
  • the sintering temperature for the sintering process was set to the temperature of 900° C.
  • the temperature was maximally increased to 1300° C., and maintained for 60 min.
  • the alloy elements of the used powder were diffused into the material of the semi-product, that is, the web element of the semi-product until the complete compensation of the element concentration was implemented.
  • the completed open-porous metal foam was formed of the iron-chrome-aluminum alloy including 22 wt % of chrome, 6 wt % of aluminum and less than 3 wt % of nickel in addition to iron.
  • the content of oxygen was less than 0.2 wt %, which was very slight, and the content of hydrogen was 0.05 wt %, which was very low.
  • the metal foam had the porosity of 91%, and the web factors had the air-tight property.
  • the metal foam had the oxidation resistance at the temperature of 1100° C. or less in the air.
  • FIG. 1 is a transverse cross-sectional view that illustrates a surface of a web element of a metal foam manufactured as described above. Through FIG. 1 , it could be confirmed that the surface at the cavity of the web factor, which was not changed by the manufacturing process according to the exemplary embodiment of the present invention in the art was smooth and had very low surface roughness.
  • the external surface of the web element became rougher by the sintered powder particles thereon.
  • the recesses between adjacent particles had the depth of 50 ⁇ m to 200 ⁇ m.
  • the densities of the materials were the same and uniform over the entire web factor volume.
  • the exemplary embodiment of the present invention may provide an open-porous metal foam that has improved thermal, mechanical and chemical characteristics, and particularly, may provide an open-porous metal foam body that is used at a higher temperature and is stable to oxidation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
US13/197,867 2010-08-10 2011-08-04 Open-porous metal foam body and a method for fabricating the same Abandoned US20120141670A1 (en)

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KR1020100077032A KR101212786B1 (ko) 2010-08-10 2010-08-10 개방-다공성 금속폼 및 그의 제조방법
KR10-2010-0077032 2010-08-10

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JP (1) JP2012036503A (ko)
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CN107723519A (zh) * 2017-10-20 2018-02-23 湘潭大学 抗高温氯化腐蚀Ni‑Cr‑Si多孔材料及其制备方法
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CN104959612B (zh) * 2015-05-26 2017-10-27 成都易态科技有限公司 多孔过滤薄膜及多孔过滤薄膜的制备方法
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DE102017216566A1 (de) 2017-09-19 2019-03-21 Alantum Europe Gmbh Verfahren zur Herstellung eines offenporösen Formkörpers mit modifizierter Oberfläche, der mit einem Metall gebildet ist und einen mit dem Verfahren hergestellten Formkörper
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EP3597295A1 (en) 2018-07-20 2020-01-22 Alantum Europe GmbH Catalyst material and method of manufacturing the same
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US11784299B2 (en) 2019-05-07 2023-10-10 Agency For Defense Development Anode for thermal battery, apparatus for manufacturing the anode for thermal battery, and method of manufacturing the anode for thermal battery
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