EP2584058A1 - Alliage a faible teneur en nickel resistant a temperatures elevees - Google Patents

Alliage a faible teneur en nickel resistant a temperatures elevees Download PDF

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Publication number
EP2584058A1
EP2584058A1 EP11186244.7A EP11186244A EP2584058A1 EP 2584058 A1 EP2584058 A1 EP 2584058A1 EP 11186244 A EP11186244 A EP 11186244A EP 2584058 A1 EP2584058 A1 EP 2584058A1
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EP
European Patent Office
Prior art keywords
weight
alloy
nickel
high temperatures
alloys
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
EP11186244.7A
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German (de)
English (en)
Other versions
EP2584058B1 (fr
Inventor
José María Deu Ibarz
Jacques Pierre Marius Brissot
Nuria Llorca Isern
Désirée Viladot Gatnau
Michel Louis Marcel Baron
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.)
METALOGRAFICA SA
SCIENCE ET SURFACE Sas
Original Assignee
METALOGRAFICA SA
SCIENCE ET SURFACE Sas
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Publication date
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Priority to ES11186244.7T priority Critical patent/ES2477994T3/es
Priority to EP11186244.7A priority patent/EP2584058B1/fr
Priority to DK11186244.7T priority patent/DK2584058T3/da
Priority to PT111862447T priority patent/PT2584058E/pt
Priority to SI201130205T priority patent/SI2584058T1/sl
Priority to PL11186244T priority patent/PL2584058T3/pl
Publication of EP2584058A1 publication Critical patent/EP2584058A1/fr
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Publication of EP2584058B1 publication Critical patent/EP2584058B1/fr
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/005—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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • the present invention belongs to the metallurgical sector and relates in particular to an alloy based on iron, chromium and aluminum (FeCrAl) having a nickel content of less than 3% by weight.
  • the alloy of the present invention has improved strength properties at high temperatures (800-1200 ° C), as well as chemical resistance to corrosive agents.
  • Nickel-based alloys are divided into three major groups: nickel-based alloys, cobalt-based alloys and iron-nickel alloys.
  • Nickel-based and cobalt-based superalloys have high toughness, good resistance to corrosion and work at elevated temperatures, and are much more expensive than iron-nickel-based alloys.
  • Iron-nickel superalloys of the conventional FeNi type, normally contain between 20% and 30% by weight of nickel and between 13% and 22% by weight of chromium and are very useful in high temperature applications because of their good resistance to corrosion. These alloys are used in electrical resistances, automotive catalytic converter parts and are part of the own heat treatment furnaces for metal parts.
  • alloys of the FeCrAl type having a high resistance to temperatures of between 900 ° C. and 1100 ° C., form, at high temperatures and in most of the atmospheres, an adhesive and impermeable layer which essentially consists of Al 2 O 3 .
  • This oxide protects the metal against oxidation, as well as against other types of corrosion, such as carburizing, sulfurization and the like.
  • the objective of the present invention is to provide an FeCrAl type alloy, which has a low nickel content (less than or equal to 3% by weight) and which has a better mechanical strength at high temperatures than the alloys.
  • the iron-based alloy of the present invention comprises 15% to 20% by weight of chromium, 4% to 8% by weight of aluminum, 1.5% to 3% by weight of nickel and 0.2% to 0.3% silicon. Furthermore, the alloy of the present invention contains minor fractions of Y (0.5-1% by weight), Hf (0.3-1% by weight), Ru (0.05-0.2% by weight), weight) and La (0.02-0.07% by weight).
  • the alloy of the present invention may be prepared by any method known in the art. It can in particular be prepared by melting in an electric arc furnace. The melting mixture is prepared directly by mixing the materials to be used in the form of shot.
  • the parts obtained are then subjected to different surface oxidation treatments and a quenching mass treatment in order to improve the mechanical properties.
  • the alloy of the present invention has better mechanical strength at elevated temperatures (800-1200 ° C) than conventional FeCrAl alloys.
  • An iron-based alloy according to the present invention was prepared by melting in an electric arc furnace, performing several remakes of the test pieces to ensure their homogeneity.
  • the resulting alloy was then subjected to a high temperature (> 1000 ° C) creep test, with a constant charge of 2.8 MPa for 1070 hours.
  • a commercial alloy (800HT) having the following composition was used: 30-35% by weight of Ni, 39.5% by weight of Fe, 19-23% by weight of Cr, 0.85-1 , 2% by weight of Al and 1.0% by weight of Si.
  • the final deformation of the RFT alloy according to the present invention was 4% and that of the 800HT commercial alloy was 9%.
  • Creep at elevated temperatures gave very similar results on both alloys, despite the fact that the 800HT alloy contains a proportion of nickel (30-35% by weight) much higher than that of the alloy of the present invention. (2% by weight). On the other hand, the rupture tends to occur more rapidly for the 800HT alloy than for the alloy of the present invention.
  • the alloy of the present invention exhibits better mechanical behavior at elevated temperatures than conventional FeCrAl alloys despite a much lower nickel content.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Contacts (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention appartient au secteur de la métallurgie et concerne en particulier un alliage à base de fer, de chrome et d'aluminium (FeCrAl) ayant une teneur en nickel inférieure à 3 % en poids. L'alliage de la présente invention possède des propriétés améliorées en matière de résistance à températures élevées (800-1200°C), ainsi que de résistance chimique à des agents corrosifs.

Description

  • La présente invention appartient au secteur de la métallurgie et concerne en particulier un alliage à base de fer, de chrome et d'aluminium (FeCrAl) ayant une teneur en nickel inférieure à 3 % en poids. L'alliage de la présente invention possède des propriétés améliorées en matière de résistance à températures élevées (800-1200°C), ainsi que de résistance chimique à des agents corrosifs.
  • Les superalliages sont divisés en trois grands groupes : les alliages à base de nickel, les alliages à base de cobalt et les alliages à base de fer-nickel. Les superalliages à base de nickel et à base de cobalt présentent une ténacité élevée, une bonne résistance à la corrosion et au travail à des températures élevées et leur prix est bien supérieur à celui des alliages à base de fer-níckel.
  • Les superalliages à base de fer-nickel, du type FeNi classiques, contiennent normalement entre 20 % et 30 % en poids de nickel et entre 13 % et 22 % en poids de chrome et sont très utiles dans des applications à températures élevées, en raison de leur bonne résistance à la corrosion. Ces alliages sont utilisés dans des résistances électriques, des parties de pots catalytiques automobiles et font partie des propres fours de traitement thermique de pièces métalliques.
  • Par ailleurs, les alliages du type FeCrAl, ayant une résistance élevée à des températures comprises entre 900°C et 1100°C environ forment, à des températures élevées et dans la majeure partie des atmosphères, une couche adhésive et imperméable qui est essentiellement constituée d'Al2O3. Cet oxyde protège le métal contre les oxydations, ainsi que contre d'autres types de corrosion, tels que la cémentation, la sulfuration et similaires.
  • On sait dans la technique qu'un alliage qui ne contient que du fer, du chrome et de l'aluminium possède une faible résistance mécanique aux températures élevées et tend à se fragiliser lorsqu'il est refroidi à de basses températures, une fois qu'il a été soumis à des périodes relativement longues de températures élevées. Ceci provient fondamentalement de la croissance du grain. Ce problème a été résolu dans la technique antérieure par la formation par précipitation d'inclusions intermétalliques dans la microstructure de l'alliage, permettant d'obtenir un effet de durcissement et d'homogénéisation de la structure par précipitation.
  • Il existe actuellement sur le marché divers alliages FeNi qui présentent des propriétés adéquates de résistance mécanique aux températures élevées, mais ces alliages FeNi contiennent des quantités élevées de nickel dans leur composition (> 20 % en poids). En raison de cette teneur élevée en nickel, ces alliages sont très coûteux et sont sujets à la forte fluctuation du prix du nickel sur le marché mondial.
  • Au vu de ce qui précède, il est souhaitable d'obtenir un alliage FeCrAl qui présente une faible teneur en nickel, mais qui présente les propriétés mécaniques souhaitables pour des applications à températures élevées, permettant ainsi une amélioration du prix de l'alliage.
  • De ce fait, l'objectif de la présente invention est de proposer un alliage du type FeCrAl, qui a une faible teneur en nickel (inférieure ou égale à 3 % en poids) et qui présente une meilleure résistance mécanique à températures élevées que les alliages FeCrAl connus jusqu'ici et qui présentent un comportement intermédiaire entre les superalliages à base de nickel ou à base de cobalt et les alliages à base de fer-nickel avec forte teneur en nickel qui sont disponibles sur le marché, permettant d'améliorer son prix de commercialisation.
  • L'alliage à base de fer de la présente invention comprend 15 % à 20 % en poids de chrome, 4 % à 8 % en poids d'aluminium, 1,5 % à 3 % en poids de nickel et 0,2 % à 0,3 % de silicium. Par ailleurs, l'alliage de la présente invention contient des fractions minoritaires de Y (0,5-1 % en poids), Hf (0,3-1 % en poids), Ru (0,05-0,2 % en poids) et La (0,02-0,07 % en poids).
  • L'alliage de la présente invention peut être préparé au moyen de n'importe quel procédé connu dans la technique. Il peut en particulier être préparé par fusion dans un four à arc électrique. Le mélange de fusion est préparé directement, en mélangeant les matériaux à utiliser sous forme de grenaille.
  • Les pièces obtenues sont ensuite soumises à différents traitements superficiels d'oxydation et à un traitement massique de trempe en vue d'améliorer les propriétés mécaniques.
  • L'alliage de la présente invention présente une meilleure résistance mécanique à températures élevées (800-1200°C) que les alliages FeCrAl classiques.
  • La présente invention est décrite ci-après en plus amples détails en référence à un exemple de réalisation. Cet exemple n'a toutefois pas pour but de limiter la portée technique de la présente invention.
    • Exemple : Préparation d'un alliage du type FeCrAl selon la présente invention
  • Un alliage à base de fer selon la présente invention a été préparé par fusion dans un four à arc électrique, en accomplissant plusieurs refontes des éprouvettes pour assurer leur homogénéité.
  • L'alliage obtenu a ensuite été soumis à un essai de fluage à température élevée (>1000°C), avec une charge constante de 2,8 MPa pendant 1 070 heures. Pour comparaison, on a utilisé un alliage du commerce (800HT) ayant la composition suivante : 30-35 % en poids de Ni, 39,5 % en poids de Fe, 19-23 % en poids de Cr, 0,85-1,2 % en poids d'Al et 1,0 % en poids de Si. La déformation finale de l'alliage RFT selon la présente invention était de 4 % et celle de l'alliage du commerce 800HT était de 9 % .
  • Le fluage à des températures élevées a donné des résultats très similaires sur les deux alliages, malgré le fait que l'alliage 800HT contienne une proportion de nickel (30-35 % en poids) bien supérieure à celle de l'alliage de la présente invention (2 % en poids). D'autre part, la rupture tend à se produire plus rapidement pour l'alliage 800HT que pour l'alliage de la présente invention.
  • En conclusion, l'alliage de la présente invention présente un meilleur comportement mécanique à températures élevées que les alliages FeCrAl classiques malgré une teneur en nickel bien inférieure.

Claims (4)

  1. Alliage résistant à des températures élevées caractérisé en ce qu'il contient du fer, du chrome, de l'aluminium, du silicium et du nickel, dans lequel la concentration en nickel est inférieure ou égale à 3 % en poids.
  2. Alliage, selon la revendication 1, caractérisé en ce que la concentration en chrome est dans la plage de 15 % à 20 % en poids, la concentration en aluminium est dans la plage de 4 % à 8 % en poids et la concentration en silicium est dans la plage de 0,2 % à 0,3 % en poids.
  3. Alliage selon la revendication 1 ou 2, caractérisé en ce qu'il comprend en outre Y (0,5-1 % en poids), Hf (0,3-1 % en poids), Ru (0,05-0,2 % en poids) et La (0,02-0,07 % en poids).
  4. Alliage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il présente une meilleure résistance mécanique à températures élevées (800-1200°C) que les alliages FeCrAl classiques.
EP11186244.7A 2011-10-21 2011-10-21 Alliage à faible teneur en nickel résistante à températures élevées Not-in-force EP2584058B1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES11186244.7T ES2477994T3 (es) 2011-10-21 2011-10-21 Aleación de bajo contenido en níquel resistente a elevadas temperaturas
EP11186244.7A EP2584058B1 (fr) 2011-10-21 2011-10-21 Alliage à faible teneur en nickel résistante à températures élevées
DK11186244.7T DK2584058T3 (da) 2011-10-21 2011-10-21 Legering med lavt nikkelindhold og bestandighed mod høje temperaturer
PT111862447T PT2584058E (pt) 2011-10-21 2011-10-21 Liga de baixo teor de níquel resistente a altas temperaturas
SI201130205T SI2584058T1 (sl) 2011-10-21 2011-10-21 Zlitina z nizko vsebnostjo niklja, ki je odporna proti povišanim temperaturam
PL11186244T PL2584058T3 (pl) 2011-10-21 2011-10-21 Stop o niskiej zawartości niklu wytrzymały w wysokich temperaturach

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11186244.7A EP2584058B1 (fr) 2011-10-21 2011-10-21 Alliage à faible teneur en nickel résistante à températures élevées

Publications (2)

Publication Number Publication Date
EP2584058A1 true EP2584058A1 (fr) 2013-04-24
EP2584058B1 EP2584058B1 (fr) 2014-04-09

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EP11186244.7A Not-in-force EP2584058B1 (fr) 2011-10-21 2011-10-21 Alliage à faible teneur en nickel résistante à températures élevées

Country Status (6)

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EP (1) EP2584058B1 (fr)
DK (1) DK2584058T3 (fr)
ES (1) ES2477994T3 (fr)
PL (1) PL2584058T3 (fr)
PT (1) PT2584058E (fr)
SI (1) SI2584058T1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207870A (zh) * 2018-11-16 2019-01-15 陈万勤 一种Fe-Cr-Al系合金及其生产方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4222026C1 (en) * 1992-07-04 1993-04-15 Thyssen Edelstahlwerke Ag, 4000 Duesseldorf, De Semi-finished prod. mfr. used as catalyst supports - by coating starting material, e.g. ferritic stainless steel, with at least one chromium@ layer and diffusion heat treating
DE10159408A1 (de) * 2000-12-04 2002-06-06 Hitachi Metals Ltd Fe-Cr-Ni-Al-Legierung mit hervorragender Oxidationsbeständigkeit und hoher Festigkeit sowie aus dieser Legierung hergestellte Platte
DE10233624A1 (de) * 2001-07-27 2003-02-13 Kawasaki Steel Co Stranggießverfahren für einen Stahl mit hohem Cr- und Al-Gehalt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4222026C1 (en) * 1992-07-04 1993-04-15 Thyssen Edelstahlwerke Ag, 4000 Duesseldorf, De Semi-finished prod. mfr. used as catalyst supports - by coating starting material, e.g. ferritic stainless steel, with at least one chromium@ layer and diffusion heat treating
DE10159408A1 (de) * 2000-12-04 2002-06-06 Hitachi Metals Ltd Fe-Cr-Ni-Al-Legierung mit hervorragender Oxidationsbeständigkeit und hoher Festigkeit sowie aus dieser Legierung hergestellte Platte
DE10233624A1 (de) * 2001-07-27 2003-02-13 Kawasaki Steel Co Stranggießverfahren für einen Stahl mit hohem Cr- und Al-Gehalt

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207870A (zh) * 2018-11-16 2019-01-15 陈万勤 一种Fe-Cr-Al系合金及其生产方法

Also Published As

Publication number Publication date
DK2584058T3 (da) 2014-07-14
EP2584058B1 (fr) 2014-04-09
PT2584058E (pt) 2014-07-15
SI2584058T1 (sl) 2014-08-29
ES2477994T3 (es) 2014-07-18
PL2584058T3 (pl) 2014-09-30

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