EP0236823A2 - Demi-produit métallique, procédé pour sa fabrication et utilisation du demi-produit - Google Patents

Demi-produit métallique, procédé pour sa fabrication et utilisation du demi-produit Download PDF

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Publication number
EP0236823A2
EP0236823A2 EP87102472A EP87102472A EP0236823A2 EP 0236823 A2 EP0236823 A2 EP 0236823A2 EP 87102472 A EP87102472 A EP 87102472A EP 87102472 A EP87102472 A EP 87102472A EP 0236823 A2 EP0236823 A2 EP 0236823A2
Authority
EP
European Patent Office
Prior art keywords
semi
finished product
metal
stem
oxide
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.)
Granted
Application number
EP87102472A
Other languages
German (de)
English (en)
Other versions
EP0236823B1 (fr
EP0236823A3 (en
Inventor
Hans-Joachim. Dr.-Ing. Fleischer
Klaus Lohscheidt
Dieter Görres
Friedrich Dr.-Ing. Behr
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.)
Thyssen AG
Original Assignee
Thyssen AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thyssen AG filed Critical Thyssen AG
Priority to AT87102472T priority Critical patent/ATE65552T1/de
Publication of EP0236823A2 publication Critical patent/EP0236823A2/fr
Publication of EP0236823A3 publication Critical patent/EP0236823A3/de
Application granted granted Critical
Publication of EP0236823B1 publication Critical patent/EP0236823B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt

Definitions

  • the invention relates to semi-finished metal products in the form of wire, rods, billets, tubes, in particular sheet metal or strips, for applications in which high thermal shock resistance and a large surface area and / or chemical resistance and / or low thermal conductivity of the surface layer is required, in particular for catalyst supports, Soot filters, heating conductors, aerosol filters, linings of chemical and energy converting plants.
  • the invention also includes a method for producing and using the semi-finished product.
  • the alloys mentioned are known to form either layers of chromium oxide or aluminum oxide with high selectivity or layers composed of Al 2 O 3 chromium mixed crystals. At use temperatures of around 900 ° C and more, the alloys that form Al 2 O 3 layers are selected.
  • a ferritic stainless steel which can be processed hot and is resistant to temperature changes, oxidation and scaling at elevated temperatures.
  • the iron-chromium-aluminum alloy contains cerium, lanthanum and other rare earth metals and is suitable for forming a textured aluminum oxide film on the surface.
  • the alloy is produced in the usual way by melting.
  • the typical steel impurities such as oxygen, nitrogen and sulfur are reduced before the rare earth metals are added to the melt.
  • Any conventional process, including arc furnaces, AOD and vacuum induction melting processes, is applicable.
  • the melt is poured into blocks, bars, strips or sheets.
  • the steel is then hot and / or cold rolled and subjected to the usual procedures such as descaling and annealing.
  • the ferritic stainless steel is then heat treated to form an alumina surface.
  • the object of the invention is to provide a semi-finished metal product which, preferably without an intermediate layer (wash coat), represents a temperature change-resistant adhesive base for a catalytically active coating.
  • the task also includes the creation of a method which leads in the simplest possible way to a metallic semi-finished product with the property mentioned.
  • a semi-finished metal product based on iron and / or nickel and / or cobalt with 2 to 16% aluminum, 12 to 30% chromium and up to 4% of at least one highly reactive element from the group Y, Zr, Ti , Ce, Sm, Hf, La, Th, U, V, W, Ta, Nb, Mo, Gd, Si, Mg, Ca and / or their dispersed oxides, preferably at least 0.01% of these elements or oxides, and Inevitable impurities proposed according to the invention that metallic stem crystals are formed at least in the surface area of the semifinished product, from which stem crystals consisting predominantly of aluminum oxide and / or chromium oxide have grown, the axes of both types of stem crystal being predominantly perpendicular to the geometric surface of the semifinished product.
  • Normal steel contaminants are carbon, nitrogen, oxygen, phosphorus, sulfur, manganese, copper and nickel.
  • the method according to the invention is characterized in that the semi-finished product is solidified from the molten state in a front that is predominantly parallel to the geometric surface with a cooling rate of 10 3 to 10 6 K / s, then first at one Temperature of 800 to 1000 ° C for a short time in an oxygen contained in bound form gas, in particular C0 2 , under the resulting reducing conditions and then in the temperature range from 800 to 1000 ° C for up to 25 h in air.
  • the invention provides a semi-finished metal product in which metal stem crystallites are formed at least in the surface area by the directional solidification of the metal alloy. Due to the high cooling rate and thermal treatment, the additional elements from the aforementioned group X, which are highly reactive, i.e. are highly oxygen-affine, or their oxides, which are present in finely divided form in the surface area, as germs in the subsequent heat treatment. At the same time, as a kind of dowel, they ensure a high level of adhesive strength for the thermally grown oxidic stem crystallites. A further improved nucleation is achieved by briefly heating as the first thermal treatment stage under reducing conditions or those that occur during this treatment.
  • the long-term annealing treatment under oxidizing conditions, preferably in air, in which the oxidic stem crystallites grow, which predominantly consist of aluminum oxide and / or chromium oxide, the axes of which are also predominantly perpendicular to the geometric surface of the semi-finished product. Due to this stem crystal formation, an extraordinarily large surface is created, in which a metallic and / or ceramic coating can be very well anchored.
  • profiled, finely crystalline strips of approximately 20 to 200 ⁇ m can be produced in this way, with the aid of cooled copper rolls, possibly up to approximately 500 ⁇ m and more. It is preferable to produce tapes approximately 40 to 70 ⁇ m thick.
  • stem crystals at least in the surface area of the auxiliary device, can alternatively be achieved by briefly melting a surface layer of the cast or rolled semifinished product with subsequent self-cooling, in addition to the above-mentioned pouring onto cooled rolls.
  • a metal strip of 50 ⁇ m thickness was produced at a cooling rate of 10 5 to 10 4 K / s.
  • the material composition is 20% chromium, 5% aluminum, 0.15% cerium, 0.01% lanthanum, the rest iron with small amounts of Si, Mn, C, S, P, Ni as trace elements.
  • the tape was then preheated to 900 ° C dry carbon dioxide gas for one minute and then held in air at 925 ° C for 16 hours.
  • a cold rolled sheet of the same material composition was also treated after recrystallization annealing.
  • the stalk-shaped oxide grains of the cast strip have diameters of approximately 0.2 ⁇ m and lengths of on average approximately 4 ⁇ m and that they are arranged almost uniformly perpendicular to the surface of the metal grains, while the sample produced by rolling is scaly , partially in contact with each other grains of different orientation and length of up to about 3 microns.
  • Example 1 A 10 mm thick plate made of the material described in Example 1 was bombarded with an electron beam in such a way that a spot approximately 0.5 mm in diameter was melted down to a depth of 100 ⁇ m. The plate was then treated in CO 2 gas at 900 ° C. for 1 minute. The procedure was as in Example 1.
  • the sample was subjected to several temperature changes, being heated to approximately 1000 ° C. and quenched in an oil bath.
  • the stem oxide grains in the area of the melting spot were not attacked by the treatment, the oxide layer on the rest of the sample surface shows individual flaking.
  • Example 2 A plate was produced according to Example 2 with a similar melting spot, then an etching was carried out so that the grain boundaries were exposed to a depth of 20 pm and the procedure according to Example 1 was then continued. It was found that a radiation-like oxide-grain layer of the same quality as in Example 1 had grown on the metal grains which had been partially exposed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Continuous Casting (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Adornments (AREA)
  • Forging (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
EP87102472A 1986-03-01 1987-02-21 Demi-produit métallique, procédé pour sa fabrication et utilisation du demi-produit Expired - Lifetime EP0236823B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87102472T ATE65552T1 (de) 1986-03-01 1987-02-21 Metallenes halbzeug, verfahren zur herstellung und verwendung des halbzeugs.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3606804 1986-03-01
DE19863606804 DE3606804A1 (de) 1986-03-01 1986-03-01 Metallisches halbzeug und verfahren zu seiner herstellung sowie verwendung

Publications (3)

Publication Number Publication Date
EP0236823A2 true EP0236823A2 (fr) 1987-09-16
EP0236823A3 EP0236823A3 (en) 1988-05-25
EP0236823B1 EP0236823B1 (fr) 1991-07-24

Family

ID=6295321

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87102472A Expired - Lifetime EP0236823B1 (fr) 1986-03-01 1987-02-21 Demi-produit métallique, procédé pour sa fabrication et utilisation du demi-produit

Country Status (6)

Country Link
US (1) US4798631A (fr)
EP (1) EP0236823B1 (fr)
JP (1) JPH0660386B2 (fr)
KR (1) KR940003503B1 (fr)
AT (1) ATE65552T1 (fr)
DE (2) DE3606804A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358309A1 (fr) * 1988-09-06 1990-03-14 General Motors Corporation Procédé pour accélérer la croissance de trichites sur une feuille d'alliage fer-chrome-aluminium
EP0625585A1 (fr) * 1993-05-20 1994-11-23 Kawasaki Steel Corporation Feuille mince d'alliages fer-chrome-aluminium résistant à l'oxydation pour substrat de catalyseur d'un convertisseur et sa méthode de production

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6411957A (en) * 1987-07-04 1989-01-17 Kawasaki Steel Co Manufacture of stainless steel having high-temperature oxidation film excellent in corrosion resistance
JP3386848B2 (ja) * 1992-06-10 2003-03-17 株式会社島津製作所 排気ガス浄化装置及びその製造方法
JP3374173B2 (ja) * 1999-10-21 2003-02-04 独立行政法人物質・材料研究機構 室温延性のある耐熱性金属間化合物Ｎｉ３Ａｌ箔の製造方法および室温延性のある耐熱性金属間化合物Ｎｉ３Ａｌ箔
JP3611107B2 (ja) * 2000-04-12 2005-01-19 セイコーエプソン株式会社 冷却ロール
JP3728396B2 (ja) 2000-04-12 2005-12-21 セイコーエプソン株式会社 磁石材料の製造方法
JP3587140B2 (ja) 2000-07-31 2004-11-10 セイコーエプソン株式会社 磁石粉末の製造方法、磁石粉末およびボンド磁石
JP4554794B2 (ja) * 2000-08-23 2010-09-29 日本冶金工業株式会社 絶縁層を有するステンレス鋼
EP1344907A1 (fr) * 2002-03-12 2003-09-17 Capital Technology GmbH Dispositif pour enlever des particules de carbone des gases d'échappement
GB2394959A (en) * 2002-11-04 2004-05-12 Doncasters Ltd Hafnium particle dispersion hardened nickel-chromium-iron alloys
WO2004042100A2 (fr) * 2002-11-04 2004-05-21 Doncasters Limited Alliages haute temperature
JP4614063B2 (ja) * 2004-05-20 2011-01-19 日産自動車株式会社 ウィスカー形成体及びウィスカー形成体の製造方法
JP4788878B2 (ja) * 2004-07-01 2011-10-05 日産自動車株式会社 ウィスカー被覆材料及びその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3027252A (en) * 1959-09-29 1962-03-27 Gen Electric Oxidation resistant iron-chromium alloy
US3298826A (en) * 1964-04-06 1967-01-17 Carl S Wukusick Embrittlement-resistant iron-chromium-aluminum-yttrium alloys
EP0091526A2 (fr) * 1982-04-12 1983-10-19 Allegheny Ludlum Corporation Alliage fer-chrome-aluminium, article réalisé avec cet alliage et procédé pour sa fabrication
EP0232793A1 (fr) * 1986-01-30 1987-08-19 Nippon Steel Corporation Ruban en acier inoxydable utilisable comme support de catalyseur pour les gaz d'échappement des moteurs à combustion interne et procédé pour sa fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4945456B1 (fr) * 1969-06-25 1974-12-04
US4331631A (en) * 1979-11-28 1982-05-25 General Motors Corporation Enhanced oxide whisker growth on peeled Al-containing stainless steel foil
GB2158746A (en) * 1984-05-14 1985-11-20 Olin Corp Apparatus and process for rolling spin cast strip

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3027252A (en) * 1959-09-29 1962-03-27 Gen Electric Oxidation resistant iron-chromium alloy
US3298826A (en) * 1964-04-06 1967-01-17 Carl S Wukusick Embrittlement-resistant iron-chromium-aluminum-yttrium alloys
EP0091526A2 (fr) * 1982-04-12 1983-10-19 Allegheny Ludlum Corporation Alliage fer-chrome-aluminium, article réalisé avec cet alliage et procédé pour sa fabrication
EP0232793A1 (fr) * 1986-01-30 1987-08-19 Nippon Steel Corporation Ruban en acier inoxydable utilisable comme support de catalyseur pour les gaz d'échappement des moteurs à combustion interne et procédé pour sa fabrication

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. ELECTROCHEM. SOC., Solid-State Science and Technology, Band 131, Nr. 4, Seiten 923-931; T.A. RAMANARAYANAN et al.: "The characteristics of alumina scales formed on FE-based Yttria-dispersed alloys" *
K.N. STRAFFORD, "High Temperature Technology, vol. 1, No. 6, Nov. 1983, p. 307-318 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358309A1 (fr) * 1988-09-06 1990-03-14 General Motors Corporation Procédé pour accélérer la croissance de trichites sur une feuille d'alliage fer-chrome-aluminium
EP0625585A1 (fr) * 1993-05-20 1994-11-23 Kawasaki Steel Corporation Feuille mince d'alliages fer-chrome-aluminium résistant à l'oxydation pour substrat de catalyseur d'un convertisseur et sa méthode de production

Also Published As

Publication number Publication date
DE3606804C2 (fr) 1989-03-30
JPH0660386B2 (ja) 1994-08-10
KR940003503B1 (ko) 1994-04-23
DE3606804A1 (de) 1987-09-10
DE3771526D1 (de) 1991-08-29
KR870009050A (ko) 1987-10-23
EP0236823B1 (fr) 1991-07-24
JPS62290857A (ja) 1987-12-17
EP0236823A3 (en) 1988-05-25
ATE65552T1 (de) 1991-08-15
US4798631A (en) 1989-01-17

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