EP2154261A1 - High temperature alloy - Google Patents

High temperature alloy Download PDF

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Publication number
EP2154261A1
EP2154261A1 EP09165678A EP09165678A EP2154261A1 EP 2154261 A1 EP2154261 A1 EP 2154261A1 EP 09165678 A EP09165678 A EP 09165678A EP 09165678 A EP09165678 A EP 09165678A EP 2154261 A1 EP2154261 A1 EP 2154261A1
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Prior art keywords
alloys
temperature alloy
weight
alloy
high temperature
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German (de)
French (fr)
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EP2154261B1 (en
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Mohamed Nazmy
Andreas KÜNZLER
Giuseppe Bandiera
Hanspeter Zinn
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General Electric Technology GmbH
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Alstom Technology AG
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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 FeCrAI 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 Alloy designation Fe Cr al Ti Si Addition of reactive elements (in the form of an oxide dispersion) 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 (0.5Y 2 O 3 ) PM 2000 rest 19.0 5.5 0.5 - Y 2 O 3 -Al 2 O 3 (0.5Y 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.
  • Ni-base wrought alloys such as Hastelloy X and Haynes 214, which can be made cheaper than the above-mentioned materials and have no anisotropic properties.
  • These alloys have the following chemical compositions: Table 2: Nominal composition of known Ni-base wrought alloys component Alloy designation Ni Cr Co Not a word W Fe Mn Si C al Y Hastelloy X rest 22 1.5 9 0.6 18.5 0.5 0.5 0.1 0.3 - Haynes 214 rest 16 - - - 3 - - 12:04 4.5 12:01
  • 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.

Abstract

An iron-based high temperature alloy comprises (in wt.%) chromium (20), aluminum (5-6, preferably 5.5), tantalum (4), molybdenum (4), rhenium (3-4, preferably 4), zirconium (0.2), boron (0.05), yttrium (0.1), hafnium (0.1), carbon (0-0.05, preferably 0.05) and remaining iron and unavoidable impurities. An independent claim is included for manufacture of the high temperature alloy.

Description

Technisches GebietTechnical area

Die Erfindung bezieht sich auf das Gebiet der Werkstofftechnik. Sie betrifft eine Hochtemperaturlegierung auf Eisenbasis, welche ca. 20 Gew. -% Cr und mehrere Gew. -% Al sowie geringfügige Mengen anderer Bestandteile enthält, und welche bei Einsatztemperaturen bis zu 1200 °C gute mechanische Eigenschaften, sowie einen sehr guten Oxidationswiderstand aufweist.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.

Stand der TechnikState of the art

Seit einiger Zeit sind ODS (oxide-dispersion-strengthened, oxiddispersionsverfestigte) Werkstoffe auf Eisenbasis, z. B. ferritische ODS-FeCrAI-Legierungen, bekannt. Sie werden aufgrund ihrer hervorragenden mechanischen Eigenschaften bei hohen Temperaturen bevorzugt für thermisch und mechanisch höchstbeanspruchte Bauteile, z. B. für Gasturbinenschaufeln, verwendet.For some time ODS (oxide-dispersion-strengthened, oxide dispersion strengthened) materials based on iron, z. B. ferritic ODS FeCrAI alloys, known. 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.

Die Anmelderin setzt derartige Materialien auch für Rohre zum Schutz von Thermoelementen ein, welche beispielsweise in Gasturbinen mit sequenzieller Verbrennung zur Temperaturkontrolle verwendet werden und dort extrem hohen Temperaturen und oxidierenden Atmosphären ausgesetzt sind.Applicant also uses such materials for 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.

Für bekannte ferritische ODS-Legierungen auf Eisenbasis sind in der Tabelle 1 die nominalen chemischen Zusammensetzungen (in Gew.- %) angegeben: Tabelle 1: Nominale Zusammensetzung von bekannten ODS-FeCrAlTi-Legierungen Bestandteil
Legierungs-bezeichnung Fe Cr Al Ti Si Zugabe reaktiver Elemente (in Form einer Oxiddispersion) Kanthal APM Rest 20.0 5.5 0.03 0.23 ZrO2-Al2O3 MA 956 Rest 20.0 4.5 0.5 - Y2O3-Al2O3 (0.5 Y2O3) PM 2000 Rest 19.0 5.5 0.5 - Y2O3-Al2O3 (0.5 Y2O3) For known iron-based ferritic ODS alloys, Table 1 sets forth the nominal chemical compositions (in weight%): Table 1: Nominal composition of known ODS-FeCrAlTi alloys component
Alloy designation Fe Cr al Ti Si Addition of reactive elements (in the form of an oxide dispersion) 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 (0.5Y 2 O 3 ) PM 2000 rest 19.0 5.5 0.5 - Y 2 O 3 -Al 2 O 3 (0.5Y 2 O 3 )

Die Einsatztemperaturen dieser metallischen Werkstoffe reichen bis ca. 1350°C. Sie haben ein Eigenschaftspotential, welches eher für keramische Werkstoffe typisch ist.The operating temperatures of these metallic materials reach up to 1350 ° C. They have a property potential which is more typical for ceramic materials.

Die genannten Werkstoffe weisen sehr hohe Zeitstandfestigkeiten bei sehr hohen Temperaturen auf und ausserdem eine hervorragende Hochtemperatur-Oxidationsbeständigkeit durch Bildung eines Al2O3-Schutzfilmes, sowie einen hohen Widerstand gegen Sulfidierung und Dampfoxidation. Sie haben stark ausgeprägte richtungsabhängige Eigenschaften. So beträgt beispielsweise in Rohren die Kriechfestigkeit in Querrichtung nur ca. 50 % der Kriechfestigkeit in Längsrichtung.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.

Die Herstellung solcher ODS-Legierungen erfolgt auf pulvermetallurgischem Wege unter Verwendung mechanisch legierter Pulvermischungen, die auf bekannte Weise, z. B. durch Strangpressen oder durch heissisostatisches Pressen, kompaktiert werden. Anschliessend wird der Pressling stark plastisch verformt, meist durch Warmwalzen, und einer Rekristallisationsglühbehandlung unterworfen. Diese Art der Herstellung, aber auch die beschriebenen Materialzusammensetzungen bedeuten u.a. nachteilig, dass diese Legierungen sehr teuer sind und anisotrope Eigenschaften aufweisen.The production of such ODS alloys by powder metallurgy using mechanically alloyed powder mixtures, the known manner, for. B. by extrusion or by hot isostatic pressing, compacted. Subsequently, the compact is strongly plastically deformed, usually by hot rolling, and subjected to recrystallization annealing. This type of production, but also the described material compositions mean, inter alia, disadvantageous that these alloys are very expensive and have anisotropic properties.

Weiterhin sind verschiedene Knetlegierungen auf Ni-Basis bekannt, wie beispielsweise Hastelloy X und Haynes 214, die im Vergleich zu den oben genannten Materialien preiswerter hergestellt werden können und keine anisotropen Eigenschaften aufweisen. Diese Legierungen haben folgende chemische Zusammensetzungen: Tabelle 2: Nominale Zusammensetzung von bekannten Ni-Basis-Knetlegierungen Bestandteil
Legierungs-bezeichnung Ni Cr Co Mo W Fe Mn Si C Al Y Hastelloy X Rest 22 1.5 9 0.6 18.5 0.5 0.5 0.1 0.3 - Haynes 214 Rest 16 - - - 3 - - 0.04 4.5 0.01 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. These alloys have the following chemical compositions: Table 2: Nominal composition of known Ni-base wrought alloys component
Alloy designation Ni Cr Co Not a word W Fe Mn Si C al Y Hastelloy X rest 22 1.5 9 0.6 18.5 0.5 0.5 0.1 0.3 - Haynes 214 rest 16 - - - 3 - - 12:04 4.5 12:01

Das Material Haynes 214 soll gemäss Firmenprospekt die oxidations-, aufkohlungs- und chlorierungsbeständigste Legierung sein, die kommerziell als Knetlegierung zur Verfügung steht, wobei ein effektiver Einsatz bei 2200 °F (ca. 1205 °C) für Langzeitbeanspruchung bzw. 2400 °F (ca. 1316 °C) für Kurzzeitbeanspruchung möglich ist. Die Eigenschaften dieser Legierung bei sehr hohen Temperaturen reichen aber nicht an die hervorragenden Eigenschaften der oben genannten ODS- Legierungen heran.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. However, the properties of this alloy at very high temperatures do not match the excellent properties of the abovementioned ODS alloys.

Darstellung der ErfindungPresentation of the invention

Ziel der Erfindung ist es, die genannten Nachteile des Standes der Technik zu vermeiden. Der Erfindung liegt die Aufgabe zu Grunde, ein für die oben angegebenen Anwendungen (Schutzrohre für Thermoelemente, welche in Gasturbinen bei extrem hohen Temperaturen eingesetzt werden können) geeignetes Material auf Eisenbasis zu entwickeln, welches kostengünstiger als das aus dem Stand der Technik bekannte Material PM 2000 ist, aber einen mindestens ebenso guten Oxidationswiderstand aufweist. Das erfindungsgemässe Material soll ausserdem gut warmumformbar sein und sehr gute mechanische Eigenschaften aufweisen.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. In addition, the material according to the invention should be readily heat-moldable and have very good mechanical properties.

Erfindungsgemäss wird dies dadurch erreicht, dass die Hochtemperaturlegierung vom Typ FeCrAl folgende chemische Zusammensetzung (Angaben in Gew. -%) aufweist:

  • 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,
  • Rest Fe und herstellungsbedingte Verunreinigungen.
According to the invention, this is achieved by the fact that the high-temperature alloy of the FeCrAl type has the following chemical composition (in% by weight):
  • 20 Cr,
  • 5-6 Al,
  • 4 days,
  • 4 mo,
  • 3-4 Re
  • 0.2 Zr,
  • 0.05 B,
  • 0.1 Y,
  • 0.1 Hf,
  • 0-0.05 C,
  • Remaining Fe and production-related impurities.

Der hohe Anteil an Cr (20 Gew.- %) sorgt dafür, dass das Material ein gutes Oxidations- und Korrosionsverhalten zeigt. Cr beeinflusst ausserdem positiv die Duktilität.The high proportion of Cr (20% by weight) ensures that the material shows good oxidation and corrosion behavior. Cr also positively affects ductility.

Die Legierung enthält 5-6, bevorzugt 5.5 Gew.- % Al. Damit wird ein Al2O3-Schutzfilm auf der Materialoberfläche gebildet, der die Hochtemperatur-Oxidationsbeständigkeit erhöht.The alloy contains 5-6, preferably 5.5% by weight Al. Thus, an Al 2 O 3 protective film is formed on the material surface, which enhances the high-temperature oxidation resistance.

Sind die Gehalte von Ta und Mo geringer als die angegebenen Werte von je 4 Gew.- %, dann wird die Hochtemperaturfestigkeit zu stark reduziert, sind sie höher, dann wird in unerwünschter Weise der Oxidationswiderstand reduziert und das Material wird ausserdem zu teuer.If 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.

Überraschenderweise hat sich gezeigt, dass es nicht nötig ist, wie es bei den aus dem Stand der Technik bekannten und oben beschriebenen ODS-Legierungen der Fall ist, Titan zuzugeben. Ti und Cr wirken als Mischkristall-Verfestiger. Mo hat im Bereich von 4 Gew.- % eine ähnliche Wirkung, ist aber wesentlich billiger als Ti. Hinzu kommt, dass Mo, wenn es zusammen mit Zr zugegeben wird, wie es bei der vorliegenden Erfindung der Fall ist, zu verbesserten Zugfestigkeiten und Zeitstandfestigkeiten führt.Surprisingly, it has been found that it is not necessary, as is the case with the prior art ODS alloys described above, to add titanium. Ti and Cr act as solid solution hardeners. Mo has a similar effect in the range of 4% by weight, but is much cheaper than Ti. In addition, Mo, when added together with Zr, as in the present invention, results in improved tensile strengths and creep strengths leads.

Ta, Zr und B sind Elemente, welche als Ausscheidungs-Verfestiger wirken. Das Zusammenspiel dieser Bestandteile mit den anderen Bestandteilen, insbesondere dem Cr und dem Mo und dem Ta, führt zu guten Festigkeitswerten, während Al, Y und auch Zr sowie Hf die Oxidationsbeständigkeit erhöhen. Cr beeinflusst positiv die Duktilität.Ta, Zr and B are elements which act as precipitation strengthening agents. The interaction of these constituents with the other constituents, in particular the Cr and the Mo and the Ta, leads to good strength values, while Al, Y and also Zr and Hf increase the oxidation resistance. Cr positively influences ductility.

Eine besondere Bedeutung kommt dem Rhenium zu. Eine Zugabe von 3-4 Gew.- % Re führt dazu, dass die Zeitstandfestigkeit des Materials bei sehr hohen Temperaturen verbessert wird, aber gleichzeitig auch die Oxidationsbeständigkeit erhöht wird. Re ist ein Mischkristallverfestiger und hat einen sehr starken Effekt in der Verbesserung der Kriecheigenschaften bei hohen Temperaturen. Es erhöht die Aktivität von Al zur Bildung von Al2O3. Re weist eine hexagonal dicht gepackte Kristallstruktur auf, welche sich von der kubischen Gitterstruktur des Fe, Mo, Al, Ta, Cr sehr unterscheidet. Dieser Unterschied in der Kristallstruktur von Re bewirkt seine Funktion als Mischkristall-Verfestiger.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.

Das erfindungsgemässe Material weist aufgrund seiner chemischen Zusammensetzung (Kombination der angegebenen Elemente in den angegebenen Bereichen) hervorragenden Eigenschaften bei Temperaturen von 1200 °C, insbesondere eine gute Zeitstandfestigkeit und eine extrem hohe Oxidationsbeständigkeit auf.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.

Kurze Beschreibung der ZeichnungenBrief description of the drawings

In der Zeichnung sind Ausführungsbeispiele der Erfindung dargestellt.In the drawings, embodiments of the invention are shown.

Die einzige Figur zeigt das Oxidationsverhalten bei 1200 °C/12 h für zwei erfindungsgemässe Hochtemperaturlegierungen im Vergleich zu den aus dem Stand der Technik bekannten Legierungen PM 2000, Hastelloy X und Haynes 214.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.

Wege zur Ausführung der ErfindungWays to carry out the invention

Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen und den Zeichnung näher erläutert.The invention will be explained in more detail with reference to embodiments and the drawing.

Es wurden die aus dem Stand der Technik bekannten Legierungen (auf pulvermetallurgischem Wege hergestellte ODS FeCrAl-Vergleichslegierung PM 2000, sowie die Knetlegierungen Hastelloy X und Haynes 214 - Zusammensetzung siehe Tabelle 1) und die in Tabelle 2 aufgeführten erfindungsgemässen Legierungen im Hinblick auf das Oxidationsverhalten bei sehr hohen Temperaturen, hier 1200 °C, untersucht. Die Legierungsbestandteile der erfindungsgemässen Legierungen 2025 und 2022 sind in Gew.- % angegeben: Tabelle 2: Zusammensetzungen der untersuchten erfindungsgemässen Legierungen Bestandteil
Legierungs-bezeichnung Fe Cr Al Ta Mo Re Zr B Y Hf C 2022 Rest 20 5.5 4 4 4 0.2 0.05 0.1 0.1 - 2025 Rest 20 5.5 4 4 3 0.2 0.05 0.1 0.1 0.05 There were known from the prior art alloys (powder produced by powder metallurgy ODS FeCrAl comparative alloy PM 2000, and the wrought alloys Hastelloy X and Haynes 214 - composition see Table 1) and the novel alloys listed in Table 2 with respect to the oxidation behavior at very high temperatures, here 1200 ° C, examined. The alloy constituents of the alloys 2025 and 2022 according to the invention are given in% by weight: Table 2: Compositions of the investigated alloys according to the invention component
Alloy designation Fe Cr al Ta Not a word re Zr B Y Hf C 2022 rest 20 5.5 4 4 4 0.2 12:05 0.1 0.1 - 2025 rest 20 5.5 4 4 3 0.2 12:05 0.1 0.1 12:05

Die erfindungsgemässen Legierungen wurden durch Lichtbogenschmelzen der angegebenen Elemente hergestellt und dann bei Temperaturen von 900-800°C gewalzt. Daraus wurden Proben zur Ermittlung der Oxidationsbeständigkeit und der mechanischen Eigenschaften hergestellt.The 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.

In der einzigen Figur ist für die angegebenen Legierungen die Gewichtsänderung bei 1200°C in Abhängigkeit von der Zeit über einen Zeitraum von 12 Stunden dargestellt. Erwartungsgemäss weist die aus dem Stand der Technik bekannte, aber sehr teure pulvermetallurgisch hergestellte Vergleichslegierung PM 2000 bei diesen Versuchsbedingungen die geringsten Gewichtsveränderungen und damit den besten Oxidationswiderstand auf. Nahezu einen gleich guten Verlauf dieser Eigenschaft zeigt auch die erfindungsgemässe Legierung 2022, die sich von der anderen erfindungsgemässen Legierung 2025 nur dadurch unterscheidet, dass sie einerseits keinen Kohlenstoff enthält und andererseits der Re-Anteil um 1 Gew.- % höher ist. Die aus dem Stand der Technik bekannten anderen untersuchten Knetlegierungen (Hastelloy X und Haynes 214) verhalten sich unter den oben genannten Versuchsbedingungen in Bezug auf das Oxidationsverhalten viel schlechter als die erfindungsgemässen Legierungen. Die Gewichtsänderung der Hastelloy-Proben ist beispielsweise nach 12 Stunden Auslagerung bei 1200 °C nachteilig ca. 2-2.5 mal so gross wie bei den erfindungsgemässen Legierungen.In the single figure, the weight change at 1200 ° C as a function of time over a period of 12 hours is shown for the specified alloys. As expected, 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. Almost equally good course of this property is also shown by 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.

Die Streckgrenze bei 1000 °C beträgt für die erfindungsgemässen Legierungen ca. 60 MPa, während die Vergleichslegierung PM 2000 eine Streckgrenze bei 1000 °C von ca. 90 MPa aufweist. Bringt man das aber in Verbindung mit dem hervorragenden Oxidationsverhalten dieser Legierungen bei 1200°C (siehe Figur), dann ist dies eine sehr gute Eigenschaftskombination. Die geringere Festigkeit der erfindungsgemässen Legierungen gegenüber von PM 2000 ist für den vorgesehenen Einsatzzweck (Schutzrohr für Mantelthermoelement) zudem völlig ausreichend.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).

Die erfindungsgemässen Materialien lassen sich ausserdem gut warmwalzen, sie weisen eine gute plastische Verformbarkeit auf.The novel materials can also be hot rolled well, they have a good plastic deformability.

Offenbar wirkt sich eine Kombination von Mo und Ta in gleichen Anteilen besonders gut auf das Oxidationsverhalten bei 1200°C aus. Insbesondere Ta erhöht im angegebenen Bereich die Aktivität von Al und verbessert den Oxidationswiderstand.Apparently, a combination of Mo and Ta in equal proportions has a particularly good effect on the oxidation behavior at 1200 ° C. In particular, Ta increases the activity of Al in the specified range and improves the oxidation resistance.

Aus den erfindungsgemässen Materialien lassen sich vorteilhaft Schutzrohe für Mantelthermoelemente herstellen. Derartige Thermoelemente werden beispielweise in Gasturbinen mit sequentieller Verbrennung zur Temperaturkontrolle verwendet und dort oxidierenden Atmosphären ausgesetzt.Protective straws for jacket 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.

Zusammenfassend ist festzustellen, dass die erfindungsgemässen Legierungen einen sehr hohen Oxidationswiderstand bei 1200°C aufweisen. Die Festigkeitswerte der erfindungsgemässen Legierungen sind zwar bei hohen Temperaturen etwas geringer als diejenigen der Legierung PM 2000, aber immer noch ausreichend hoch. Da die erfindungsgemässen Legierungen zudem billiger als PM 2000 sind (billigere Bestandteile, einfachere Herstellung) sind diese für die oben beschriebenen Einsatzgebiete hervorragend als Ersatz für PM 2000 geeignet.In summary, it should be noted that 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)

Hochtemperaturlegierung auf Eisenbasis gekennzeichnet durch folgende chemische Zusammensetzung (Angaben in Gew.-%): 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, Rest Fe und herstellungsbedingte Verunreinigungen. Iron-based high-temperature alloy characterized by the following chemical composition (in% by weight): 20 Cr, 5-6 Al, 4 days, 4 mo, 3-4 Re 0.2 Zr, 0.05 B, 0.1 Y, 0.1 Hf, 0-0.05 C, Remaining Fe and production-related impurities. Hochtemperaturlegierung nach Anspruch 1 gekennzeichnet durch 5.5 Gew. -% Al.High-temperature alloy according to claim 1, characterized by 5.5% by weight of Al. Hochtemperaturlegierung nach einem der Ansprüche 1 und 2 gekennzeichnet durch 0.05 Gew.- % C.High-temperature alloy according to one of Claims 1 and 2, characterized by 0.05% by weight of C. Hochtemperaturlegierung nach einem der Ansprüche 1 bis 3 gekennzeichnet durch 3 Gew. % Re.High-temperature alloy according to one of claims 1 to 3, characterized by 3 wt.% Re. Hochtemperaturlegierung nach einem der Ansprüche 1 bis 3 gekennzeichnet durch 4 Gew. % Re.High-temperature alloy according to one of claims 1 to 3 characterized by 4 wt.% Re. Hochtemperaturlegierung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie für Thermoelement-Schutzrohre verwendet wird.High-temperature alloy according to one of claims 1 to 5, characterized in that it is used for thermocouple protective tubes. Verfahren zur Herstellung einer Hochtemperaturlegierung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die der Legierungszusammensetzung entsprechenden Elemente mittels Lichtbogen geschmolzen und anschliessend bei ca. 900-800 °C gewalzt werden.Process for producing a high-temperature alloy according to one of claims 1 to 5, characterized in that the elements corresponding to the alloy composition are melted by means of an arc and subsequently rolled at about 900-800 ° C.
EP09165678A 2008-07-25 2009-07-16 High temperature alloy Not-in-force EP2154261B1 (en)

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