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WO2000008223A1 - Feuille metallique resistant a l'oxydation - Google Patents

Feuille metallique resistant a l'oxydation Download PDF

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Publication number
WO2000008223A1
WO2000008223A1 PCT/EP1999/004678 EP9904678W WO0008223A1 WO 2000008223 A1 WO2000008223 A1 WO 2000008223A1 EP 9904678 W EP9904678 W EP 9904678W WO 0008223 A1 WO0008223 A1 WO 0008223A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal foil
iron
produced
annealing
rolling
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.)
Ceased
Application number
PCT/EP1999/004678
Other languages
German (de)
English (en)
Inventor
Angelika Kolb-Telieps
Ralf Hojda
Ulrich Heubner
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.)
Krupp VDM GmbH
Original Assignee
Krupp VDM GmbH
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 Krupp VDM GmbH filed Critical Krupp VDM GmbH
Publication of WO2000008223A1 publication Critical patent/WO2000008223A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • B21B2001/383—Cladded or coated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/001—Aluminium or its alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/02—Rolling special iron alloys, e.g. stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2251/00—Treating composite or clad material
    • C21D2251/02—Clad material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment

Definitions

  • the invention relates to a method for producing an iron-chromium-aluminum-metal foil with high resistance to high temperatures.
  • the US-A 4,414,023 describes a steel with 8.0-25.0% Cr, 3.0-8.0% Al, 0.002-0.06% Se, max. 4.0% Si, 0.06-1.0% Mn, 0.035-0.07% Ti, 0.035-0.07% Zr, including inevitable impurities.
  • EP-A 0 387 670 is an alloy with 20-25% Cr, 5-8% Al, max. 0.01% P, max. 0.01% Mg, max. 0.5% Mn, max. 0.005% S, remainder Fe, including unavoidable impurities, from which further alloying elements such as 0.03% Y, 0.004% N, 0.02 - 0.04% C, 0.035 - 0.07% Ti, 0.035-0.07% Zr and 0.035-0.14% Hf are added.
  • 5,336,139 specifies a method in which foils made of iron-chromium-aluminum alloys are produced by coating a suitable iron-chromium steel on both sides by roll-cladding with aluminum or aluminum alloys. This composite is exclusively cold rolled and finally diffusion annealed so that a homogeneous structure is created.
  • the core material can be made of AISI 434 stainless steel, optionally with Ce and La additives.
  • EP-B 0 204423 describes another way of producing multilayer metal foils, namely that of fire aluminizing.
  • this document is based on an iron-chromium alloy without reactive additives. Now, as described in Example 2 below, it has been shown that such materials are inadequate for use as catalysts because they are not sufficiently resistant to oxidation. Additions of reactive elements are absolutely necessary for use as a catalyst. Furthermore, the cited document describes that aluminum alloys containing silicon have not given satisfactory results in practice.
  • EP-B 0 516 097 has disclosed a scale-resistant Fe-Cr-Al alloy with additions of La, Y and Hf, which can be produced by coating, in particular roll cladding.
  • the invention is based on the object of providing an iron-chromium-aluminum material which has an oxidation resistance which is up to 1,100 ° C. better than that of conventional materials, in order in particular to take account of the requirements for environmental protection.
  • the material should be able to be varied in such a way that the electrical resistance increases, which is necessary for preheating, in particular of catalysts in the cold start phase, for example in the case of certain types of the pre-catalyst connected upstream of the actual main catalyst.
  • the material should also be able to be produced inexpensively.
  • the dimensions of a sheet made from this material should only change slightly in terms of final thickness even in the case of annealing up to approximately 1,150 ° C. This object is achieved by a method according to claim 1.
  • the temperature and holding time must be selected so that on the one hand rolling to the final thickness is possible without any problems. H. the formation of intermetallic phases should be suppressed as far as possible. On the other hand, such an intermediate annealing can be used to diffuse part of the aluminum into the carrier strip. Surprisingly, this has the advantage that the change in volume during the heat treatment to the final thickness can be significantly reduced.
  • the metal foil according to the invention can be obtained, for example, by block casting, but can be produced even more cost-effectively by continuous casting, as well as subsequent hot and cold forming.
  • this tape With a thickness between 0.5 and 2 mm, this tape is coated on each side with a layer made of aluminum with 8 - 13% silicon. The coating is applied by way of fire aluminizing.
  • the composite produced in this way is preferably cold-rolled with at least one intermediate annealing to form a film and then also contains the mechanical requirements for the further processing steps, such as for example the corrugation which is required in the production of the catalyst.
  • a final heat treatment is advantageously carried out at temperatures between 700 and 1200 ° C.
  • a further development which is meaningful in terms of economical production is that the heat treatment in the form of the diffusion annealing known per se after the final shaping of the end products produced from the metal composite foil and " in situ " after the completion of the catalyst devices, or only on the finished catalyst carrier body.
  • the diffusion annealing is carried out directly on the film.
  • a further advantageous embodiment of the invention consists in further alloying the iron-chromium-aluminum alloys described above with the aid of the coating with aluminum and silicon in order to increase their oxidation resistance and their electrical resistance. This is also possible if you start with a carrier tape that already contains up to 6% aluminum and then only requires a thinner coating.
  • Example 1 stands out from the other, more common alloys in terms of its oxidation resistance, as is necessary for applications in the catalyst and heating conductor area.
  • a carrier material with the composition in mass% is
  • the alloy according to the invention was produced by fire aluminizing and has the following chemical composition (in% by mass):
  • the change in mass at 1,100 ° C. is 25% less than in the case of a comparative alloy which was produced in the conventional way, for example as described in Example 1.
  • Another advantage is that the cost of manufacturing by fire aluminizing is only about 75% of the cost of conventional alloys.
  • a strip was cut out from the tape produced according to Example 3 at a thickness of 0.11 mm. Individual pieces were annealed at temperatures shown in the table below and then rolled to a final thickness of 50 ⁇ m. During the subsequent final annealing at 1,100 ° C, the length and width changed by less than 0.5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

L'invention concerne un procédé de production d'une feuille métallique constituée d'un alliage de fer, de chrome et d'aluminium, présentant une grande résistance à l'oxydation à température élevée, qui est produite par aluminiage à chaud d'une bande de support en alliage de fer et de chrome avec un alliage d'aluminium et de silicium, la feuille obtenue présentant en % en masse la composition suivante: 18-25 % de Cr, 4-10 % de Al, 0,03-0,08 % de Y, max. 0,01 % de Ti, 0,01-0,05 % de Zr, 0,01-0,05 % de Hf, 0,5-1,5 % de Si, le solde étant constitué de fer et d'impuretés résultant du procédé. La teneur totale en aluminium de la feuille métallique recouverte est, à proximité de la surface, d'au moins 7 % et ne tombe pas à une valeur inférieure à 3 % en direction du coeur de la feuille métallique. Le matériau composite est laminé, et, pendant le laminage, soumis à un recuit intermédiaire, à une température d'environ 800 DEG C, grâce auquel le changement de volume résultant d'un recuit final suivant le processus de laminage est réduit à </= 0,5 %.
PCT/EP1999/004678 1998-07-31 1999-07-06 Feuille metallique resistant a l'oxydation Ceased WO2000008223A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19834552.6 1998-07-31
DE1998134552 DE19834552A1 (de) 1998-07-31 1998-07-31 Oxidationsbeständige Metallfolie

Publications (1)

Publication Number Publication Date
WO2000008223A1 true WO2000008223A1 (fr) 2000-02-17

Family

ID=7875978

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004678 Ceased WO2000008223A1 (fr) 1998-07-31 1999-07-06 Feuille metallique resistant a l'oxydation

Country Status (2)

Country Link
DE (1) DE19834552A1 (fr)
WO (1) WO2000008223A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0209166B1 (pt) * 2001-04-26 2011-01-11 liga de ferro-cromo-alumìnio.
DE10310865B3 (de) * 2003-03-11 2004-05-27 Thyssenkrupp Vdm Gmbh Eisen-Chrom-Aluminium-Legierung
DE102008006039B4 (de) * 2008-01-25 2018-04-26 Elringklinger Ag Verfahren zum Verbinden von metallischen Bauteilen eines Brennstoffzellenstacks und Baugruppe für einen Brennstoffzellenstack
DE102008006038B4 (de) * 2008-01-25 2013-02-21 Elringklinger Ag Verfahren zur Herstellung einer Bipolarplatte für eine Brennstoffzelleneinheit und Bipolarplatte
DE102009061021B4 (de) 2009-05-20 2015-05-07 VDM Metals GmbH Verfahren zur Herstellung einer Metallfolie

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2224288A (en) * 1988-11-01 1990-05-02 British Steel Plc Improvements in and relating to hafnium-containing alloy steels
EP0387670A1 (fr) * 1989-03-16 1990-09-19 Krupp VDM GmbH Alliage d'acier ferritique
EP0516097A1 (fr) * 1991-05-29 1992-12-02 Kawasaki Steel Corporation Alliage fer-chrome-aluminium, substrat de catalyseur utilisant cet alliage et le procédé pour sa fabrication
EP0688882A1 (fr) * 1993-12-28 1995-12-27 Nisshin Steel Co., Ltd. Tole d'acier inoxydable plaquee d'aluminium presentant une excellente resistance a l'oxydation a haute temperature
EP0837151A1 (fr) * 1996-10-15 1998-04-22 Krupp VDM GmbH Procédé pour la fabrication d'une feuille de fer-chrome-aluminium et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2224288A (en) * 1988-11-01 1990-05-02 British Steel Plc Improvements in and relating to hafnium-containing alloy steels
EP0387670A1 (fr) * 1989-03-16 1990-09-19 Krupp VDM GmbH Alliage d'acier ferritique
EP0516097A1 (fr) * 1991-05-29 1992-12-02 Kawasaki Steel Corporation Alliage fer-chrome-aluminium, substrat de catalyseur utilisant cet alliage et le procédé pour sa fabrication
EP0688882A1 (fr) * 1993-12-28 1995-12-27 Nisshin Steel Co., Ltd. Tole d'acier inoxydable plaquee d'aluminium presentant une excellente resistance a l'oxydation a haute temperature
EP0837151A1 (fr) * 1996-10-15 1998-04-22 Krupp VDM GmbH Procédé pour la fabrication d'une feuille de fer-chrome-aluminium et son utilisation

Also Published As

Publication number Publication date
DE19834552A1 (de) 2000-02-03

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