EP2154261B1 - Alliage résistant aux températures élevées - Google Patents

Alliage résistant aux températures élevées Download PDF

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Publication number
EP2154261B1
EP2154261B1 EP09165678A EP09165678A EP2154261B1 EP 2154261 B1 EP2154261 B1 EP 2154261B1 EP 09165678 A EP09165678 A EP 09165678A EP 09165678 A EP09165678 A EP 09165678A EP 2154261 B1 EP2154261 B1 EP 2154261B1
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EP
European Patent Office
Prior art keywords
weight
alloys
temperature alloy
alloy
alloy according
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.)
Not-in-force
Application number
EP09165678A
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German (de)
English (en)
Other versions
EP2154261A1 (fr
Inventor
Mohamed Nazmy
Andreas KÜNZLER
Giuseppe Bandiera
Hanspeter Zinn
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.)
General Electric Technology GmbH
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Alstom Technology AG
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Publication of EP2154261A1 publication Critical patent/EP2154261A1/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
    • C22C38/18—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
    • C22C38/002—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron

Definitions

  • the invention relates to the field of materials technology. It relates to a high-temperature alloy based on iron, which contains about 20% by weight of Cr and several% by weight of Al and minor amounts of other constituents, and which has good mechanical properties and a very good oxidation resistance at use temperatures of up to 1200 ° C.
  • ODS oxide-dispersion-strengthened, oxide dispersion strengthened
  • iron z. B. ferritic ODS FeCrAl alloys
  • They are due to their excellent mechanical properties at high temperatures preferred for thermally and mechanically highly stressed components, eg. B. for gas turbine blades used.
  • thermocouple protection tubes which are used, for example, in sequential combustion gas turbines for temperature control where they are exposed to extremely high temperatures and oxidizing atmospheres.
  • Table 1 sets forth the nominal chemical compositions (in weight%): Table 1: Nominal composition of known ODS-FeCrAlTi alloys component Fe Cr al Ti Si Addition of reactive elements (in the form of an oxide dispersion) alloy designation Kanthal APM rest 20.0 5.5 12:03 12:23 ZrO 2 -Al 2 O 3 MA 956 rest 20.0 4.5 0.5 - Y 2 O 3 -Al 2 O 3 (0.5 Y 2 O 3 ) PM 2000 rest 19.0 5.5 0.5 - Y 2 O 3 -Al 2 O 3 (0.5 Y 2 O 3 )
  • the materials mentioned have very high creep ruptures at very high temperatures and also excellent high-temperature oxidation resistance by forming an Al 2 O 3 protective film, as well as a high resistance to sulfidation and steam oxidation. They have strong directional characteristics. For example, in pipes, the creep strength in the transverse direction is only about 50% of the creep strength in the longitudinal direction.
  • WO 01/49441 a FeCrAl alloy produced by powder metallurgy is known, which, inter alia, is still alloyed with up to 0.7% by weight of Si and 0.5% by weight of Mn. Further, various Ni-base wrought alloys are known, such as Hastelloy X and Haynes 214, which can be made cheaper than the above-mentioned materials and have no anisotropic properties.
  • the Haynes 214 material is said to be the oxidation, carburization and chlorination resistant alloy commercially available as wrought alloy, with effective use at 2200 ° F (about 1205 ° C) for long term stress or 2400 ° F (approx 1316 ° C) is possible for short-term stress.
  • 2200 ° F about 1205 ° C
  • 2400 ° F approximately 1316 ° C
  • the properties of this alloy at very high temperatures do not match the excellent properties of the abovementioned ODS alloys.
  • the aim of the invention is to avoid the mentioned disadvantages of the prior art.
  • the object of the invention is to develop an iron-based material which is suitable for the abovementioned applications (protective tubes for thermocouples which can be used in gas turbines at extremely high temperatures), which is less expensive than the material PM 2000 known from the prior art is, but has at least as good oxidation resistance.
  • the material according to the invention should be readily heat-moldable and have very good mechanical properties.
  • the high proportion of Cr (20% by weight) ensures that the material shows good oxidation and corrosion behavior. Cr also positively affects ductility.
  • the alloy contains 5-6, preferably 5.5% by weight Al.
  • an Al 2 O 3 protective film is formed on the material surface, which enhances the high-temperature oxidation resistance.
  • the contents of Ta and Mo are less than the specified values of 4% by weight each, the high-temperature strength is excessively reduced, if they are higher, the oxidation resistance is undesirably reduced, and the material becomes too expensive.
  • Ta, Zr and B are elements which act as precipitation strengthening agents.
  • Rhenium A special meaning comes to the Rhenium.
  • An addition of 3-4% by weight of Re results in improving the creep rupture strength of the material at very high temperatures, while at the same time increasing the oxidation resistance.
  • Re is a solid solution hardener and has a very strong effect in improving creep properties at high temperatures. It increases the activity of Al to form Al 2 O 3 .
  • Re has a hexagonal close-packed crystal structure, which is very different from the cubic lattice structure of Fe, Mo, Al, Ta, Cr. This difference in the crystal structure of Re causes it to function as a solid solution hardener.
  • the material according to the invention Due to its chemical composition (combination of the specified elements in the stated ranges), the material according to the invention has outstanding properties at temperatures of 1200 ° C., in particular good creep rupture strength and extremely high oxidation resistance.
  • the sole FIGURE shows the oxidation behavior at 1200 ° C./12 h for two high-temperature alloys according to the invention in comparison with the alloys PM 2000, Hastelloy X and Haynes 214 known from the prior art.
  • novel alloys were prepared by arc melting of the specified elements and then rolled at temperatures of 900-800 ° C. From these samples were prepared to determine the oxidation resistance and the mechanical properties.
  • the weight change at 1200 ° C as a function of time over a period of 12 hours is shown for the specified alloys.
  • the comparative powder metallurgy PM 2000 known from the prior art but very expensive, has the lowest weight changes and thus the best oxidation resistance under these experimental conditions.
  • the inventive alloy 2022 which differs from the other alloy 2025 according to the invention only in that on the one hand it contains no carbon and on the other hand the Re content is higher by 1% by weight.
  • the other known wrought alloys known from the prior art (Hastelloy X and Haynes 214) behave much worse than the alloys according to the invention under the experimental conditions mentioned above with regard to the oxidation behavior.
  • the change in weight of Hastelloy samples, for example, after 12 hours of aging at 1200 ° C adversely about 2-2.5 times as large as in the inventive alloys.
  • the yield strength at 1000 ° C. is about 60 MPa for the alloys according to the invention, while the comparative alloy PM 2000 has a yield strength at 1000 ° C. of about 90 MPa. However, if this is combined with the excellent oxidation behavior of these alloys at 1200 ° C (see figure), then this is a very good combination of properties.
  • the lower strength of the inventive alloys compared to PM 2000 is also completely sufficient for the intended use (protective tube for jacket thermocouple).
  • novel materials can also be hot rolled well, they have a good plastic deformability.
  • a combination of Mo and Ta in equal proportions has a particularly good effect on the oxidation behavior at 1200 ° C.
  • Ta increases the activity of Al in the specified range and improves the oxidation resistance.
  • thermocouples can advantageously be produced from the materials according to the invention.
  • Such thermocouples are used for example in gas turbines with sequential combustion for temperature control and exposed there to oxidizing atmospheres.
  • the alloys according to the invention have a very high oxidation resistance at 1200 ° C. Although the strength values of the alloys according to the invention are slightly lower than those of the alloy PM 2000 at high temperatures, they are still sufficiently high. Since the alloys according to the invention are also cheaper than PM 2000 (cheaper components, easier production), they are outstandingly suitable as a replacement for PM 2000 for the fields of application described above.

Claims (7)

  1. Alliage à base de fer, résistant aux températures élevées, caractérisé par la composition chimique suivante (données en % en poids):
    20 Cr,
    5-6 Al,
    4 Ta,
    4 Mo,
    3-4 Re,
    0,2 Zr,
    0,05 B,
    0,1 Y,
    0,1 Hf,
    0-0,05 C,
    le reste étant du fer et des impuretés inévitables.
  2. Alliage résistant aux températures élevées selon la revendication 1, caractérisé par 5,5 % en poids Al.
  3. Alliage résistant aux températures élevées selon l'une quelconque des revendications 1 et 2, caractérisé par 0,05 % en poids C.
  4. Alliage résistant aux températures élevées selon l'une quelconque des revendications 1 à 3 caractérisé par 3 % en poids Re.
  5. Alliage résistant aux températures élevées selon l'une quelconque des revendications 1 à 3, caractérisé par 4 % en poids Re.
  6. Alliage résistant aux températures élevées selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il est utilisé pour des tubes de protection de thermocouples.
  7. Procédé de fabrication d'un alliage résistant aux températures élevées selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les éléments correspondant à la composition de l'alliage sont fondus à l'arc électrique et sont ensuite laminés à 900-800°C.
EP09165678A 2008-07-25 2009-07-16 Alliage résistant aux températures élevées Not-in-force EP2154261B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH01174/08A CH699206A1 (de) 2008-07-25 2008-07-25 Hochtemperaturlegierung.

Publications (2)

Publication Number Publication Date
EP2154261A1 EP2154261A1 (fr) 2010-02-17
EP2154261B1 true EP2154261B1 (fr) 2011-11-02

Family

ID=39884286

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09165678A Not-in-force EP2154261B1 (fr) 2008-07-25 2009-07-16 Alliage résistant aux températures élevées

Country Status (5)

Country Link
US (1) US8153054B2 (fr)
EP (1) EP2154261B1 (fr)
JP (1) JP5522998B2 (fr)
AT (1) ATE531831T1 (fr)
CH (1) CH699206A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102822022B (zh) 2010-03-04 2015-06-03 本田技研工业株式会社 车辆的转弯控制装置
EP3339482A1 (fr) * 2016-12-26 2018-06-27 Nuctech Company Limited Film sensible pour la détection de neutrons et son procédé de formation

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS508974B1 (fr) * 1970-12-14 1975-04-09
JPS55461B2 (fr) * 1971-11-09 1980-01-08
BE794801A (fr) * 1972-01-31 1973-07-31 Int Nickel Ltd Procede de recuit en zones d'alliages
US4277374A (en) * 1980-01-28 1981-07-07 Allegheny Ludlum Steel Corporation Ferritic stainless steel substrate for catalytic system
US4334923A (en) * 1980-02-20 1982-06-15 Ford Motor Company Oxidation resistant steel alloy
DE3926479A1 (de) * 1989-08-10 1991-02-14 Siemens Ag Rheniumhaltige schutzbeschichtung, mit grosser korrosions- und/oder oxidationsbestaendigkeit
JPH04354850A (ja) * 1991-05-29 1992-12-09 Nisshin Steel Co Ltd 耐高温酸化性に優れた高Ａｌ含有フェライト系ステンレス鋼
JP2682335B2 (ja) * 1992-06-01 1997-11-26 住友金属工業株式会社 フェライト系ステンレス鋼熱延鋼帯の製造法
JPH06108268A (ja) * 1992-09-30 1994-04-19 Sumitomo Metal Ind Ltd フェライト系ステンレス鋼箔およびその製造法
US5340415A (en) * 1992-06-01 1994-08-23 Sumitomo Metal Industries, Ltd. Ferritic stainless steel plates and foils and method for their production
JPH11511203A (ja) * 1995-08-16 1999-09-28 シーメンス アクチエンゲゼルシヤフト 高温酸化性ガスの案内部品
US5939204A (en) * 1995-08-16 1999-08-17 Siemens Aktiengesellschaft Article for transporting a hot, oxidizing gas
JP2000097779A (ja) * 1998-09-18 2000-04-07 Daido Steel Co Ltd 熱電対保護管
DE19937577A1 (de) * 1999-08-09 2001-02-15 Abb Alstom Power Ch Ag Reibungsbehaftete Gasturbinenkomponente
DE19941228B4 (de) * 1999-08-30 2009-12-31 Alstom Eisenaluminidbeschichtung und deren Verwendung
SE0000002L (sv) 2000-01-01 2000-12-11 Sandvik Ab Förfarande för tillverkning av ett FeCrAl-material och ett sådant marerial
US6346134B1 (en) * 2000-03-27 2002-02-12 Sulzer Metco (Us) Inc. Superalloy HVOF powders with improved high temperature oxidation, corrosion and creep resistance
SE527742C2 (sv) * 2004-02-23 2006-05-30 Sandvik Intellectual Property Ferritiskt stål för högtemperaturtillämpningar, sätt att framställa detta, produkt och användning av stålet

Also Published As

Publication number Publication date
ATE531831T1 (de) 2011-11-15
US8153054B2 (en) 2012-04-10
JP2010047836A (ja) 2010-03-04
EP2154261A1 (fr) 2010-02-17
CH699206A1 (de) 2010-01-29
JP5522998B2 (ja) 2014-06-18
US20100021338A1 (en) 2010-01-28

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