EP1436440B1 - Acier ferritique et utilisation de ce dernier dans la fabrication de produits resistant aux hautes temperatures - Google Patents

Acier ferritique et utilisation de ce dernier dans la fabrication de produits resistant aux hautes temperatures Download PDF

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Publication number
EP1436440B1
EP1436440B1 EP02783530A EP02783530A EP1436440B1 EP 1436440 B1 EP1436440 B1 EP 1436440B1 EP 02783530 A EP02783530 A EP 02783530A EP 02783530 A EP02783530 A EP 02783530A EP 1436440 B1 EP1436440 B1 EP 1436440B1
Authority
EP
European Patent Office
Prior art keywords
steel
strip
hot
ferritic stainless
pipes
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.)
Expired - Lifetime
Application number
EP02783530A
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German (de)
English (en)
Other versions
EP1436440A1 (fr
Inventor
Gianni Songini
Massimo Centro Sviluppo Materiali S.P.A. Barteri
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.)
Acciai Speciali Terni SpA
Original Assignee
ThyssenKrupp Acciai Speciali Terni SpA
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Publication date
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Publication of EP1436440A1 publication Critical patent/EP1436440A1/fr
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Publication of EP1436440B1 publication Critical patent/EP1436440B1/fr
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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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • 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

Definitions

  • the present invention refers to the field of the ferritic stainless steels usable in the manufacture of high temperature resistant products.
  • Object of the present invention is a ferritic stainless steel that, by virtue of its composition and of suitable thermo-mechanical treatments, is suitable for the manufacture of products exhibiting high performances at high temperatures, in particular for the manufacture of vehicle exhaust manifold systems.
  • ferritic stainless steels In the manufacture of vehicle exhaust system components, ferritic stainless steels, by virtue of their smaller thermal expansion coefficient, are preferred to the austenitic ones. In the development of the related technological field, ferritic stainless steels are adopted for the manufacture of vehicle exhaust system components working at temperatures reaching 750°C. For the manufacture of a manifold, subjected to temperatures higher than 800°C, cast iron had longtime been preferred to ferritic stainless steels. However, the adoption of the former material proved unsatisfactory due to the occurrence of drawbacks related to the weight increases, the entailed fuel consumption, and the design difficulty due to the high thickness of the component thus manufactured.
  • object of the present invention is a ferritic stainless steel, comprising the following chemical elements expressed in percentage by weight:
  • the ferritic stainless steel according to the present invention may also comprise Yttrium and/or rare earth elements in a percentage by weight comprised in the range 0.10-0.30.
  • the present invention further encompasses strips or sheets made of steel according to the invention, weldable, formable and highly resistant to oxidation and creep.
  • a further object of the present invention is a process for the preparing of the strips or sheets, wherein the steel according to the invention is subjected to the following steps:
  • the present invention encompasses the use of the ferritic stainless steel according to the invention for the manufacture of products in form of flat bloom, strip, ingot, casting, forging or semimanufactured item, as well as the flat blooms, the strips, the ingots, the castings, the forgings and the semimanufactured items made therewith.
  • the present invention further refers to the use of the steel strip or sheet according to the invention for the production of pipes or of pipe-derivable products.
  • the pipes thus manufactured can be weldless or welded, even longitudinally welded. Also the pipes and the pipe-derivable products manufactured with said steel strips or sheets are an object of the present invention.
  • the invention also refers to high temperature exhaust system components, in particular to vehicle exhaust manifolds.
  • the ferritic stainless steel of the invention exhibits the desired features, in particular a resistance to hot cyclic oxidation, by virtue of an apt synergy of chemical elements like Chromium, Aluminum, Zirconium, Silicon, Titanium, Niobium, Carbon, Nitrogen and optionally Yttrium and/or rare earth elements.
  • These features, desired at high temperatures are enhanced by the hot and/or cold rolling and by the subsequent annealing treatment of sheets and/or strips thus obtainable, during which a Zircon carbonitride precipitation occurs, optionally followed by a pickling treatment.
  • the Inventors deem the functions of the main chemical elements forming the alloy of the present invention to be as follows.
  • Chromium in the indicated percentages by weight, remarkably increases resistance to oxidation without promoting the formation of brittle phases.
  • Silicon and Aluminum stabilize the ferritic matrix and are accountable for the increase of resistance to hot oxidation.
  • An employ of these elements above the upper limits set forth is detrimental to steel quality in terms of formation of intermetallic phases and of increased manufacturing problems.
  • Zircon forms stable carbonitrides, whose presence influences the microstructural development during annealing of the cold-rolled items.
  • Titanium and Niobium form stable carbides and nitrides, and prevent the precipitation of Chromium nitrides and carbides onto the edge of the grains and the entailed dechroming (sensitizing) of the matrix in the vicinities thereof, further promoting the presence of an entirely ferritic structure at all temperatures, as reducing the dissolved Carbon and Nitrogen quantities.
  • Yttrium and/or rare earth elements enhance the resistance to hot oxidation in the presence of thermal and mechanical shocks due to the increased adhesion of the oxide onto the metal substrate.
  • Figure 1 shows the weight variation per surface unit effected on samples of austenitic and of ferritic steels in order to identify a steel known to the state of the art apt to provide the best features in terms of resistance to hot cyclic oxidation, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000°C.
  • Fig. 2 shows the weight variation per surface unit in an AISI 441 steel sample of a composition known to the art, identified as apt to provide the best features to hot cyclic oxidation, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000°C.
  • Fig. 3 shows the weight variation per surface unit in a steel sample according to the invention, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000°C.
  • Ferritic stainless steels 441, 436, 429, and austenitic steels 321, 309, 310, 4828 operating at a 1000°C temperature were tested.
  • Fig. 1 shows the weight variation per surface unit of the various steel types according to the number of cycles.
  • austenitic steels exhibit a worse behavior, with a swift weight decrease due to spalling.
  • steel 321 has a high instability and decays over a very short time.
  • steel 441 undergoes a slight weight increase, with respect to 436 and 429 steels that instead exhibit a slight weight decrease after the test.
  • the steel 441 apt to provide the best performances among known steels, was used as comparison to the steel advanced according to the present invention.
  • This conventional steel AISI 441 was prepared according to the following composition expressed as percentage by weight: C 0.016; Cr 18.18; Si 0.60; Al 0.09; Nb 0.42; Ti 0.18; Mn 0.18; Cu 0.08; N 0.012, and iron q.s. to 100.
  • the hot strips were forwarded to cold rolling down to a 1.5 mm thickness and then annealed 40 sec at a 1080°C temperature.
  • the resistance to cyclic oxidation of the strip thus obtained was tested at 1000°C and at 1050°C, in a 1000-cycle test, each cycle consisting of 25 min heating /in-oven permanence and 5 min air cooling. Test results are shown in Fig. 2.
  • the end-test measuring highlighted a permanent deflection of over 40 mm, well beyond the 18 mm threshold generally adopted by the current technology.
  • a steel according to the present invention is prepared, having the following composition expressed as percentage by weight: Cr 17.68; Al 0.94; Zr 0.15; Si 1.16; Ti 0.21; Nb 0.40; C 0.022; N 0.013, and substantially iron q.s. to 100.
  • the steel is cast by a casting process into flat blooms having thin thicknesses typically ranging from 50 to 90 mm, and in the example being equal to 60 mm.
  • This flat bloom obtained according to the abovedisclosed composition was heated to 1150°C, and by a subsequent hot rolling thereof strips having a thickness equal to 5 mm were produced.
  • the hot strips were forwarded to cold rolling down to a 1.5 mm thickness and then annealed 40 sec at a 1080°C temperature.
  • the resistance to cyclic oxidation of the strip thus obtained was tested at 1000°C and at 1050°C, in a 1000-cycle test, each cycle consisting of 25 min heating/in-oven permanence and 5 min air cooling.
  • the test results are shown in Fig. 3.
  • a steel according to the present invention is prepared, having the following composition expressed as percentage by weight:
  • the steel was cast by a traditional casting process into flat blooms that were first heated to 1150°C. Then, by a subsequent hot-rolling, 5mm thick strips were made.
  • the hot strips were forwarded to cold rolling, down to a 1.5 mm thickness, and then annealed 40 sec at a 1080°C temperature.
  • the resistance to cyclic oxidation of the strip thus obtained was tested at 1000°C and at 1050°C, in a 1000-cycle test, each cycle consisting of 25 min heating/in-oven permanence and 5 min air cooling.
  • the test results are substantially equivalent to those shown in Fig. 3.

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

Claims (10)

  1. Acier inoxydable ferritique, caractérisé en ce qu'il comprend les éléments chimiques suivants exprimés en pourcentage en poids :
    Cr 14,0 à 20,0
    Al 0,50 à 1,50
    Zr 0,10 à 0,50
    Si 0,30 à 1,50
    Ti 0,10 à 0,35
    Nb 0,25 à 0,55
    C < 0,035
    N < 0,035
       comprenant éventuellement de l'yttrium et/ou des éléments de terres rares dans un pourcentage en poids compris dans la plage de 0,10 à 0,30, du moment que la teneur en Ti, Nb, C et N satisfait à la relation suivante : %Ti + %Nb/1,94 > 9(%C + %N),    le reste étant du fer et des impuretés.
  2. Bande ou feuille d'acier, caractérisées en ce qu'elles sont faites d'acier selon la revendication 1, et en ce qu'elles sont soudables, formables, et hautement résistantes à l'oxydation et au fluage.
  3. Procédé de fabrication de la bande ou de la feuille d'acier selon la revendication 2, caractérisé en ce que l'acier de la revendication 1 est soumis aux étapes suivantes :
    le laminage à chaud et/ou à froid ;
    le recuit, après le laminage à chaud et/ou à froid, à une température allant de 900°C à 1200°C et pendant des temps inférieurs à 3600 s.
       le décapage éventuel après le laminage à chaud et/ou à froid.
  4. Utilisation de l'acier inoxydable ferritique selon la revendication 1 dans la fabrication de produits sous forme de bloom, de bande, de lingot, de pièce coulée, de pièce forgée ou d'objet semi-manufacturé plats.
  5. Blooms, bandes, lingots, pièces coulées, pièces forgées et objets semi-manufacturés plats, caractérisés en ce qu'ils sont faits d'acier selon la revendication 1.
  6. Utilisation de la bande ou de la feuille d'acier selon la revendication 2 pour la production de tuyaux ou de produits dérivés de tuyaux.
  7. Utilisation de la bande ou de la feuille d'acier selon la revendication 6, pour la production de tuyaux sans soudure ou de tuyaux soudés, et même de tuyaux soudés longitudinalement.
  8. Tuyaux et produits dérivés de tuyaux, caractérisés en ce que qu'ils sont fabriqués avec la bande ou la feuille selon la revendication 2.
  9. Produit dérivé de tuyaux selon la revendication 8, adapté pour constituer un composant d'un système d'échappement à haute température.
  10. Produit selon la revendication 9, adapté pour constituer un collecteur d'un système d'échappement de véhicule.
EP02783530A 2001-09-26 2002-09-26 Acier ferritique et utilisation de ce dernier dans la fabrication de produits resistant aux hautes temperatures Expired - Lifetime EP1436440B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT2001RM000584A ITRM20010584A1 (it) 2001-09-26 2001-09-26 Acciaio inossidabile ferritico e suo uso nella fabbricazione di manufatti per impieghi ad elevate temperature.
ITRM20010584 2001-09-26
PCT/IT2002/000613 WO2003027343A1 (fr) 2001-09-26 2002-09-26 Acier ferritique et utilisation de ce dernier dans la fabrication de produits resistant aux hautes temperatures

Publications (2)

Publication Number Publication Date
EP1436440A1 EP1436440A1 (fr) 2004-07-14
EP1436440B1 true EP1436440B1 (fr) 2005-07-27

Family

ID=11455801

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Application Number Title Priority Date Filing Date
EP02783530A Expired - Lifetime EP1436440B1 (fr) 2001-09-26 2002-09-26 Acier ferritique et utilisation de ce dernier dans la fabrication de produits resistant aux hautes temperatures

Country Status (9)

Country Link
US (1) US20040265162A1 (fr)
EP (1) EP1436440B1 (fr)
CN (1) CN1274864C (fr)
AT (1) ATE300627T1 (fr)
CA (1) CA2461869A1 (fr)
DE (1) DE60205269T2 (fr)
ES (1) ES2248625T3 (fr)
IT (1) ITRM20010584A1 (fr)
WO (1) WO2003027343A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE528027C2 (sv) * 2004-04-16 2006-08-08 Sandvik Intellectual Property Användning av ett ferritiskt stål i katalysatorer för dieselmotorer
CN103710631B (zh) * 2011-08-11 2016-01-20 丹阳市华龙特钢有限公司 成本较低廉的机车制动电阻带的制备方法
RU2603519C2 (ru) * 2012-09-03 2016-11-27 Аперам Стейнлесс Франс Листовая ферритная нержавеющая сталь, способ ее производства и ее применение, особенно в выхлопных системах
MX2018011206A (es) * 2016-03-30 2018-11-22 Nisshin Steel Co Ltd Hoja de acero inoxidable ferritico que contiene nb y metodo de fabricacion de la misma.
JP6278160B1 (ja) * 2017-02-28 2018-02-14 新日鐵住金株式会社 フェライト系ステンレス鋼板、ホットコイルおよび自動車排気系フランジ部材

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2161954A1 (de) * 1971-12-14 1973-06-20 Deutsche Edelstahlwerke Gmbh Ferritischer hitzebestaendiger stahl
US3923696A (en) * 1973-08-22 1975-12-02 Int Nickel Co Catalyst structure
DE3480602D1 (de) * 1983-12-12 1990-01-04 Armco Advanced Materials Warmfester ferritischer stahl.
JPS61117251A (ja) * 1984-11-09 1986-06-04 Daido Steel Co Ltd 耐熱鋼
JP3541458B2 (ja) * 1993-10-15 2004-07-14 Ｊｆｅスチール株式会社 高温塩害特性に優れたフェライト系ステンレス鋼
FR2790485B1 (fr) * 1999-03-05 2002-02-08 Usinor Procede de coulee continue entre cylindres de bandes d'acier inoxydable ferritique a haute ductilite, et bandes minces ainsi obtenues

Also Published As

Publication number Publication date
CN1274864C (zh) 2006-09-13
EP1436440A1 (fr) 2004-07-14
DE60205269T2 (de) 2006-05-24
ATE300627T1 (de) 2005-08-15
CA2461869A1 (fr) 2003-04-03
CN1575347A (zh) 2005-02-02
DE60205269D1 (de) 2005-09-01
ITRM20010584A1 (it) 2003-03-26
US20040265162A1 (en) 2004-12-30
WO2003027343A1 (fr) 2003-04-03
ITRM20010584A0 (it) 2001-09-26
ES2248625T3 (es) 2006-03-16

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