EP0570072A2 - Method of producing a chromium-base alloy - Google Patents

Method of producing a chromium-base alloy Download PDF

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Publication number
EP0570072A2
EP0570072A2 EP93201342A EP93201342A EP0570072A2 EP 0570072 A2 EP0570072 A2 EP 0570072A2 EP 93201342 A EP93201342 A EP 93201342A EP 93201342 A EP93201342 A EP 93201342A EP 0570072 A2 EP0570072 A2 EP 0570072A2
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Prior art keywords
weight
chromium
based alloy
alloy
alloy according
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German (de)
French (fr)
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EP0570072B1 (en
EP0570072A3 (en
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Ralf Dr. Eck
Günter Dr. Kneringer
Wolfgang Dr. Köck
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Plansee SE
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Plansee SE
Metallwerk Plansee GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen

Definitions

  • the invention relates to a chromium-based alloy.
  • a major disadvantage of pure chromium is the brittleness of the material, which usually begins at around 400 ° C., depending on the shaping, so that the use of the material in practice is often only possible due to increased manufacturing and construction costs.
  • DE-OS 16 08 116 describes a chromium alloy which contains up to 45% by weight of iron and / or nickel and / or cobalt and up to a total of 5% by weight of Al, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Y and rare earths and up to 1% by weight of C, N, B and Si.
  • the alloying of iron in particular, but also of nickel and cobalt is said Oxidation and corrosion resistance increased and the deformability at low temperatures can be improved.
  • the addition of Al, Ti, Zr, Hf, V, Nb, Ta as well as Y and rare earths is said to significantly reduce the ductile-brittle transition temperature. In fact, the transition temperature of this alloy is still too ductile-brittle, so that this alloy has no practical significance.
  • DE-OS 21 05 750 relates to a cast body made of a chromium-based alloy, which consists of a single crystal or of directed crystals.
  • the alloy preferably contains 5-50% by weight of iron and / or cobalt and / or nickel and 1-25% by weight of niobium and / or tantalum and / or molybdenum and / or tungsten and / or rhenium and up to 2% by weight.
  • Y and / or rare earths and / or aluminum as well as up to 1% by weight boron and / or carbon and / or nitrogen and / or silicon in conjunction with additives on metals which form boride, carbide, nitride or silicide.
  • This prior publication also describes that this alloy in the monocrystalline state enables a transition temperature which was at that time reduced by several 100 ° C. in a ductile, brittle manner and a relatively high impact strength at room temperature.
  • this alloy no information can be found in the previous publication.
  • the main disadvantage of this alloy is that it is no longer mechanically formable as a cast alloy, so that not all workpieces can be produced in any dimensions. In particular, the production of semi-finished products, such as sheets, rods and wire, is not possible.
  • US 3 591 362, US 3 874 938 and DE-AS 23 03 802 generally describe dispersion-strengthened metal alloys which can contain up to 25% by volume of a dispersoid, including oxides of rare earth metals. Chromium contents of the alloy of up to 65% by weight are described in the claims. From the examples and the description, however, it appears that the invention is primarily based on alloys with a significantly lower chromium content, in particular is aimed at ODS superalloys with a chromium content between approximately 10 and 20% by weight. US 3 909 309 describes a method for improving the flexural strength in ODS superalloys. Chromium contents of up to 65% by weight are mentioned in a subclaim.
  • ODS superalloys are primarily used in hot gas turbine construction, where good corrosion resistance to vanadium pentoxide is not so important.
  • the dispersoids are primarily added to increase the strength properties of the alloy.
  • US Pat. No. 3,841,847 shows a chromium-based alloy with at least 70% by weight of chromium, which in addition to yttrium, aluminum and silicon can also contain up to 18% by weight of yttrium oxide. With this alloy too, the transition temperature is ductile and brittle, so that the production of semi-finished products and parts by forming processes is problematic.
  • the object of the present invention is to provide a chromium-based alloy which has good corrosion resistance, in particular to combustion gases and non-volatile combustion residues of fossil fuels, and which at the same time has a ductile-brittle transition temperature which is sufficiently low for forming processes and good heat resistance properties .
  • a chromium-based alloy with a chromium content of more than 65% by weight which in addition to the usual impurities consists of 0.005-5% by weight of one or more rare earth oxides and 0.1 to 32% by weight of one or more Metals from the group iron, nickel and cobalt.
  • rare earth oxides are known for various alloys to increase the heat resistance through dispersion strength.
  • yttrium oxide and / or lanthanum oxide as oxides of the rare earths with a proportion of 0.5 to 2% by weight and of iron and nickel with a proportion of 5 to 25% by weight has proven particularly advantageous.
  • the alloy according to the invention is particularly suitable as a material for stationary but also moving parts in all systems in which temperatures of about 800 to over 1200 o C occur and in which contact with gases and residues from the combustion, in particular fossil fuels and pure or polluted air.
  • the alloy has a high heat resistance and a high recrystallization temperature as well as a coefficient of thermal expansion which, compared to known chrome alloys, is much better adapted to other high-temperature materials, such as ceramics, which further increases the area of application of the alloy according to the invention expanded.
  • the optional addition of up to 30% by weight of one or more metals from the group aluminum, titanium, zirconium and hafnium primarily improves the oxidation resistance of the alloy.
  • Aluminum and / or titanium and / or zircon with a proportion of 3 to 10% by weight have been found to be particularly suitable.
  • the optional addition of up to 10% by weight of one or more metals from the group vanadium, niobium, molybdenum, tantalum, tungsten and rhenium increases the dimensional stability at high temperatures in components made from the alloy according to the invention, which is particularly long when it occurs Continuous stresses that act on the components is important.
  • the light and ductile metals vanadium and niobium are preferred.
  • the addition of the refractory metals tungsten and rhenium can reduce the oxidation resistance of the alloy, which is why they are advantageously used only in relatively small amounts.
  • Vanadium, niobium and molybdenum individually or in combination with a total content of 3 to 8% by weight, have proven to be particularly advantageous.
  • the mixture of the starting powder is pressed to a minimum compression density of 65% and the compact is sintered at a sintering temperature between 1500 and 1600 o C under an H2 atmosphere for 15-20 hours.
  • the sintered plates were cut into steel sheet with a thickness of 2 mm on all sides.
  • the forged plates were forged by 35% and cooled from the forging end temperature in the furnace to room temperature within 12 hours.
  • the plates were rolled into sheets of 4.5 mm thickness and cooled from the final roll temperature in the furnace to room temperature within 12 hours.
  • the sheets were heated to 1250 o C and rolled to a thickness of 2 mm and the edges trimmed.
  • the sheets were again heated to 1250 ° C. and annealed at this temperature for one hour.
  • the sheets were 1.3 mm thick finish rolled and then subjected to final annealing at 1600 o C for one hour.
  • samples with the dimensions 100 mm ⁇ 100 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm.
  • the alloys according to the invention have a corrosion resistance which is improved by a factor of 2 compared to pure chromium.
  • samples with the dimensions 20 mm ⁇ 30 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm. After weighing, the samples were oxidized in air once at a temperature of 1000 ° C. and once at a temperature of 1200 ° C. over a period of 7 days. At 1000 o C a well adhering oxide layer formed on the samples, so that the average Weight gain of the samples was used as a measure of the oxidation resistance.

Abstract

The invention relates to a chromium-base alloy having a chromium content of more than 65% by weight, and the following composition: 0.005 to 5% by weight of one or more rare earth oxides and 0.1 to 32% by weight of one or more metals from the group comprising iron, nickel and cobalt, the remainder being chromium. In addition, the alloy can contain up to 30% by weight of one or more metals from the group comprising Al, Ti, Zr and Hf, up to 10% by weight of one or more metals from the group comprising V, Nb, Mo, Ta, W and Re, and also up to 1% by weight of C and/or N and/or B and/or Si. As compared with pure chromium, the alloy has a markedly improved oxidation resistance and improved corrosion resistance, in particular against vanadium pentoxide.

Description

Die Erfindung betrifft eine Legierung auf Chrombasis.The invention relates to a chromium-based alloy.

Reines Chrom mit einer derzeit technisch möglichen Reinheit von 99,97 % kommt vielfach dort zum Einsatz, wo es auf eine gute Korrosionsbeständigkeit ankommt. Es hat jedoch den Nachteil, daß es je nach Herstellungsverfahren bei relativ tiefen Temperaturen zwischen 700 und 800oC rekristallisiert und damit keine Festigkeitszunahme durch Umformung erlaubt, wie das üblicherweise für derartige metallische Werkstoffe gegeben ist.Pure chrome with a currently technically possible purity of 99.97% is used in many cases where good corrosion resistance is important. However, it has the disadvantage that, depending on the production process, it recrystallizes at relatively low temperatures between 700 and 800 ° C. and thus does not permit an increase in strength due to deformation, as is usually the case for such metallic materials.

Ein wesentlicher Nachteil des reinen Chroms ist die in der Regel je nach Umformung unter etwa 400oC beginnende Sprödigkeit des Werkstoffes, so daß eine Verwendung des Werkstoffes in der Praxis vielfach nur durch erhöhten fertigungstechnischen und konstruktiven Aufwand ermöglicht wird.A major disadvantage of pure chromium is the brittleness of the material, which usually begins at around 400 ° C., depending on the shaping, so that the use of the material in practice is often only possible due to increased manufacturing and construction costs.

Man hat daher in der Vergangenheit versucht, durch Legieren von Chrom mit anderen Elementen die Übergangstemperatur duktil-spröde zu senken, ohne daß die gute Korrosionsbeständigkeit verlorengeht, was bisher jedoch noch nicht in vollständig befriedigendem Umfang erreicht worden ist.Attempts have therefore been made in the past to lower the transition temperature in a ductile-brittle manner by alloying chromium with other elements, without losing the good corrosion resistance, but this has not yet been achieved to a completely satisfactory extent.

Die DE-OS 16 08 116 beschreibt eine Chromlegierung, die bis zu 45 Gew.% Eisen und/oder Nickel und/oder Kobalt sowie bis zu insgesamt 5 Gew.% an Al, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Y und Seltene Erden sowie bis zu 1 Gew.% an C, N, B und Si enthält. Bei dieser Legierung soll insbesondere durch das Zulegieren von Eisen, aber auch von Nickel und Kobalt die Oxidations- und Korrosionsbeständigkeit gesteigert und die Verformbarkeit bei tiefen Temperaturen verbessert werden. Darüberhinaus soll durch den Zusatz von Al, Ti, Zr, Hf, V, Nb, Ta sowie von Y und Seltenen Erden die Übergangstemperatur duktil-spröde erheblich gesenkt werden. Tatsächlich liegt bei dieser Legierung die Übergangstemperatur duktil-spröde immer noch zu hoch, sodaß diese Legierung keine praktische Bedeutung erlangt hat.DE-OS 16 08 116 describes a chromium alloy which contains up to 45% by weight of iron and / or nickel and / or cobalt and up to a total of 5% by weight of Al, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Y and rare earths and up to 1% by weight of C, N, B and Si. In this alloy, the alloying of iron in particular, but also of nickel and cobalt, is said Oxidation and corrosion resistance increased and the deformability at low temperatures can be improved. In addition, the addition of Al, Ti, Zr, Hf, V, Nb, Ta as well as Y and rare earths is said to significantly reduce the ductile-brittle transition temperature. In fact, the transition temperature of this alloy is still too ductile-brittle, so that this alloy has no practical significance.

Die DE-OS 21 05 750 bezieht sich auf einen Gußkörper aus einer Chrombasislegierung, die aus einem Einkristall oder aus gerichteten Kristallen besteht. Die Legierung enthält vorzugsweise 5 - 50 Gew.% Eisen und/oder Kobalt und/oder Nickel sowie 1 - 25 Gew.% Niob und/oder Tantal und/oder Molybdän und/oder Wolfram und/oder Rhenium und bis zu 2 Gew.% an Y und/oder Seltenen Erden und/oder Aluminium sowie zu bis 1 Gew.% Bor und/oder Kohlenstoff und/oder Stickstoff und/oder Silizium in Verbindung mit Zusätzen an borid-, karbid-, nitrid- oder silizidbildenden Metallen.DE-OS 21 05 750 relates to a cast body made of a chromium-based alloy, which consists of a single crystal or of directed crystals. The alloy preferably contains 5-50% by weight of iron and / or cobalt and / or nickel and 1-25% by weight of niobium and / or tantalum and / or molybdenum and / or tungsten and / or rhenium and up to 2% by weight. on Y and / or rare earths and / or aluminum as well as up to 1% by weight boron and / or carbon and / or nitrogen and / or silicon in conjunction with additives on metals which form boride, carbide, nitride or silicide.

Auch in dieser Vorveröffentlichung ist beschrieben, daß sich durch diese Legierung im einkristallinen Zustand eine zum damaligen Zeitpunkt um mehrere 100oC erniedrigte Übergangstemperatur duktil-spröde sowie eine relativ hohe Kerbschlagzähigkeit bei Raumtemperatur erreichen läßt. Hinsichtlich der Korrosions- und Oxidationsfestigkeit dieser Legierung sind der Vorveröffentlichung keine Hinweise zu entnehmen.
Nachteilig bei dieser Legierung ist vor allem, daß sie als Gußlegierung mechanisch nicht mehr umformbar ist, sodaß sich nicht alle Werkstücke in beliebigen Abmessungen herstellen lassen. Insbesondere die Herstellung von Halbzeug, wie Bleche, Stäbe und Draht, ist nicht möglich.This prior publication also describes that this alloy in the monocrystalline state enables a transition temperature which was at that time reduced by several 100 ° C. in a ductile, brittle manner and a relatively high impact strength at room temperature. With regard to the corrosion and oxidation resistance of this alloy, no information can be found in the previous publication.
The main disadvantage of this alloy is that it is no longer mechanically formable as a cast alloy, so that not all workpieces can be produced in any dimensions. In particular, the production of semi-finished products, such as sheets, rods and wire, is not possible.

Die US 3 591 362, US 3 874 938 sowie die DE-AS 23 03 802 beschreiben allgemein dispersionsverfestigte Metallegierungen, die bis zu 25 Vol.% eines Dispersoids, unter anderem auch Oxide der Seltenen Erdmetalle enthalten können. Von den Ansprüchen her sind dort Chromgehalte der Legierung bis zu 65 Gew.% beschrieben. Aus den Beispielen und der Beschreibung geht jedoch hervor, daß die Erfindung in erster Linie auf Legierungen mit einem wesentlich niedrigeren Chromgehalt, insbesondere auf ODS-Superlegierungen mit einem Chromgehalt zwischen etwa 10 und 20 Gew.%, ausgerichtet ist.
Die US 3 909 309 beschreibt ein Verfahren zur Verbesserung der Biegebruchfestigkeiten bei ODS-Superlegierungen. In einem Unteranspruch sind Chromgehalte von bis zu 65 Gew.% genannt. Aber auch hier ist aus den Beispielen zu ersehen, daß der praktische Chromgehalt bei ODS-Superlegierungen wesentlich niedriger, bei etwa 20 Gew.% liegt. ODS-Superlegierungen werden in erster Linie im Heißgasturbinenbau eingesetzt, wo es nicht so sehr auf gute Korrosionsfestigkeit gegenüber Vanadiumpentoxid ankommt. Die Dispersoide werden in erster Linie zur Steigerung der Festigkeitseigenschaften der Legierung zugegeben.US 3 591 362, US 3 874 938 and DE-AS 23 03 802 generally describe dispersion-strengthened metal alloys which can contain up to 25% by volume of a dispersoid, including oxides of rare earth metals. Chromium contents of the alloy of up to 65% by weight are described in the claims. From the examples and the description, however, it appears that the invention is primarily based on alloys with a significantly lower chromium content, in particular is aimed at ODS superalloys with a chromium content between approximately 10 and 20% by weight.
US 3 909 309 describes a method for improving the flexural strength in ODS superalloys. Chromium contents of up to 65% by weight are mentioned in a subclaim. But here too it can be seen from the examples that the practical chromium content in ODS superalloys is considerably lower, at about 20% by weight. ODS superalloys are primarily used in hot gas turbine construction, where good corrosion resistance to vanadium pentoxide is not so important. The dispersoids are primarily added to increase the strength properties of the alloy.

Aus der US 3 841 847 ist eine Legierung auf Chrombasis mit mindestens 70 Gew.% Chrom zu entnehmen, die neben Yttrium, Aluminium und Silizium noch bis zu 18 Gew.% Yttriumoxid enthalten kann. Auch bei dieser Legierung liegt die Übergangstemperatur duktil-spröde noch sehr hoch, so daß die Herstellung von Halbzeug und Teilen durch Umformprozesse problematisch ist.US Pat. No. 3,841,847 shows a chromium-based alloy with at least 70% by weight of chromium, which in addition to yttrium, aluminum and silicon can also contain up to 18% by weight of yttrium oxide. With this alloy too, the transition temperature is ductile and brittle, so that the production of semi-finished products and parts by forming processes is problematic.

Aufgabe der vorliegenden Erfindung ist es, eine Legierung auf Chrombasis zur Verfügung zu stellen, die eine gute Korrosionsbeständigkeit, insbesondere gegenüber Verbrennungsgasen und nicht flüchtigen Verbrennungsrückständen fossiler Brennstoffe, aufweist und die gleichzeitig eine für Umformprozesse ausreichend tiefe Übergangstemperatur duktil-spröde sowie gute Warmfestigkeits-Eigenschaften besitzt.The object of the present invention is to provide a chromium-based alloy which has good corrosion resistance, in particular to combustion gases and non-volatile combustion residues of fossil fuels, and which at the same time has a ductile-brittle transition temperature which is sufficiently low for forming processes and good heat resistance properties .

Erfindungsgemäß wird dies durch eine Chrombasislegierung mit einem Chromgehalt von mehr als 65 Gew.% erreicht, die neben üblichen Verunreinigungen aus 0,005 - 5 Gew.% von einem oder mehreren Oxiden der Seltenen Erden und 0,1 bis 32 Gew.% von einem oder mehreren Metallen aus der Gruppe Eisen, Nickel und Kobalt besteht.According to the invention, this is achieved by a chromium-based alloy with a chromium content of more than 65% by weight, which in addition to the usual impurities consists of 0.005-5% by weight of one or more rare earth oxides and 0.1 to 32% by weight of one or more Metals from the group iron, nickel and cobalt.

Die Zugabe von Oxiden der Seltenen Erden ist bei verschiedenen Legierungen zur Erhöhung der Warmfestigkeit durch Dispersionsfestigkeit bekannt. Völlig überraschend war jedoch die Erkenntnis, daß bei einer Chrombasislegierung mit einem Chromgehalt von mehr als 65 Gew.% durch einen bestimmten Legierungsanteil an Oxiden der Seltenen Erden bei einem gleichzeitigen Zulegieren von einem bestimmten Anteil von Eisen, Nickel und/oder Kobalt eine verbesserte Beständigkeit gegen Oxidation und verminderte Korrosion, insbesondere gegenüber Vanadiumpentoxid, das in großem Maß bei der Verbrennung fossiler Brennstoffe entsteht, erreicht wird und gleichzeitig die Übergangstemperatur duktil-spröde abgesenkt wird, so daß die Umformbarkeit der Chromlegierung bei tiefen Temperaturen und auch die Duktilität im Anwendungsfall bei tiefen Temperaturen verbessert ist.The addition of rare earth oxides is known for various alloys to increase the heat resistance through dispersion strength. Completely surprising, however, was the finding that, in the case of a chromium-based alloy with a chromium content of more than 65% by weight, a certain alloy content of rare earth oxides while simultaneously alloying a certain amount of iron, nickel and / or cobalt improved resistance to Oxidation and reduced corrosion, in particular compared to vanadium pentoxide, which occurs to a large extent in the combustion of fossil fuels, is achieved and at the same time the transition temperature is ductile-brittle, so that the malleability of the chromium alloy at low temperatures and also the ductility in the application at low temperatures is improved.

Unter einem Anteil von 0,005 Gew.% zeigt eine Zugabe von Seltenen Erdoxiden praktisch keine Wirkung. Die Obergrenze für ihre Zugabe liegt bei 5 Gew.%, da bei darüberhinausgehenden Anteilen die Verarbeitbarkeit der Legierung in einem unzumutbaren Ausmaß verschlechtert wird.
Die Legierungselemente Eisen, Nickel und Kobalt bewirken erst ab einem Mindestgehalt von 0,1 Gew.% ihre duktilisierende Wirkung auf die Legierung, während bei einem Überschreiten der Obergrenze von 32 Gew.% die Korrosionseigenschaften der Legierung in einem Ausmaß verschlechtert werden, daß eine derartige Legierung praktisch nicht mehr interessant ist.With a proportion of 0.005% by weight, addition of rare earth oxides shows practically no effect. The upper limit for their addition is 5% by weight, since if the proportions exceed this, the processability of the alloy is deteriorated to an unacceptable extent.
The alloying elements iron, nickel and cobalt only have a ductile effect on the alloy from a minimum content of 0.1% by weight, while if the upper limit of 32% by weight is exceeded, the corrosion properties of the alloy are deteriorated to such an extent that such Alloy is practically no longer interesting.

Als besonders vorteilhaft hat sich die Verwendung von Yttriumoxid und/oder Lanthanoxid als Oxide der Seltenen Erden mit einem Anteil von 0,5 bis 2 Gew.% sowie von Eisen und Nickel mit einem Anteil von 5 bis 25 Gew.% bewährt.The use of yttrium oxide and / or lanthanum oxide as oxides of the rare earths with a proportion of 0.5 to 2% by weight and of iron and nickel with a proportion of 5 to 25% by weight has proven particularly advantageous.

Die erfindungsgemäße Legierung ist besonders als Werkstoff für ruhende, aber auch bewegte Teile in allen Anlagen geeignet, in denen Temperaturen von etwa 800 bis über 1200oC auftreten und in denen gleichzeitig Kontakt zu Gasen und Rückständen aus der Verbrennung, insbesondere fossiler Brennstoffe und reiner oder verunreinigter Luft, besteht.The alloy according to the invention is particularly suitable as a material for stationary but also moving parts in all systems in which temperatures of about 800 to over 1200 o C occur and in which contact with gases and residues from the combustion, in particular fossil fuels and pure or polluted air.

Neben der vielseitigen Korrosionsbeständigkeit weist die Legierung eine hohe Warmfestigkeit und eine hohe Rekristallisationstemperatur sowie einen Wärmeausdehnungs-Koeffizienten auf, der im Vergleich zu bekannten Chromlegierungen wesentlich besser an andere Hochtemperatur-Werkstoffe, wie zum Beispiel Keramik, angepaßt ist, was den Einsatzbereich der erfindungsgemäßen Legierung nochmals erweitert.In addition to the versatile corrosion resistance, the alloy has a high heat resistance and a high recrystallization temperature as well as a coefficient of thermal expansion which, compared to known chrome alloys, is much better adapted to other high-temperature materials, such as ceramics, which further increases the area of application of the alloy according to the invention expanded.

Durch das wahlweise Zulegieren von bis zu 30 Gew.% von einem oder mehreren Metallen aus der Gruppe Aluminium, Titan, Zirkon und Hafnium wird in erster Linie die Oxidationsfestigkeit der Legierung nochmals verbessert.The optional addition of up to 30% by weight of one or more metals from the group aluminum, titanium, zirconium and hafnium primarily improves the oxidation resistance of the alloy.

Als besonders geeignete Elemente haben sich hierbei Aluminium und/oder Titan und/oder Zirkon mit einem Anteil von 3 bis 10 Gew.% herausgestellt.Aluminum and / or titanium and / or zircon with a proportion of 3 to 10% by weight have been found to be particularly suitable.

Durch das wahlweise Zulegieren von bis zu 10 Gew.% von einem oder mehreren Metallen aus der Gruppe Vanadium, Niob, Molybdän, Tantal, Wolfram und Rhenium wird bei Bauteilen aus der erfindungsgemäßen Legierung die Formbeständigkeit bei hohen Temperaturen erhöht, was vor allem beim Auftreten lang andauernder Spannungen, die auf die Bauteile einwirken, wichtig ist. Den leichten und duktilisierenden Metallen Vanadium und Niob wird dabei der Vorzug gegeben. Der Zusatz der hochschmelzenden Metalle Wolfram und Rhenium kann die Oxidationsbeständigkeit der Legierung herabsetzen, weshalb sie vorteilhafterweise nur in verhältnismäßig geringen Mengen eingesetzt werden.The optional addition of up to 10% by weight of one or more metals from the group vanadium, niobium, molybdenum, tantalum, tungsten and rhenium increases the dimensional stability at high temperatures in components made from the alloy according to the invention, which is particularly long when it occurs Continuous stresses that act on the components is important. The light and ductile metals vanadium and niobium are preferred. The addition of the refractory metals tungsten and rhenium can reduce the oxidation resistance of the alloy, which is why they are advantageously used only in relatively small amounts.

Als besonders vorteilhaft haben sich Vanadium, Niob und Molybdän, einzeln oder in Kombination mit einem Gesamtgehalt von 3 bis 8 Gew.% erwiesen.Vanadium, niobium and molybdenum, individually or in combination with a total content of 3 to 8% by weight, have proven to be particularly advantageous.

Für Anwendungen, bei denen die Festigkeit für einen Temperaturbereich über 1000oC weiter erhöht werden soll, ist es vorteilhaft, der Legierung bis zu 1 Gew.% Kohlenstoff und/oder Stickstoff und/oder Bor und/oder Silizium zuzulegieren. Diese Hartphasen bildenden Elemente erhöhen die Festigkeit, ohne die gute Korrosionseigenschaft der Legierung zu verschlechtern und ohne die Duktilität wesentlich zu vermindern.For applications in which the strength is to be increased further for a temperature range above 1000 ° C., it is advantageous to add up to 1% by weight of carbon and / or nitrogen and / or boron and / or silicon to the alloy. These hard phase-forming elements increase the strength without impairing the good corrosion properties of the alloy and without significantly reducing the ductility.

Besonders vorteilhaft ist es hierbei, Kohlenstoff und/oder Stickstoff mit einem Anteil von 0,03 bis 0,3 Gew.% einzusetzen.It is particularly advantageous to use carbon and / or nitrogen in a proportion of 0.03 to 0.3% by weight.

In einem vorteilhaften pulvermetallurgischen Verfahren zur Herstellung der erfindungsgemäßen Legierung wird die Mischung des Ausgangspulvers auf eine Mindestpreßdichte von 65 % gepreßt und der Preßling bei einer Sintertemperatur zwischen 1500 und 1600oC unter H₂-Atmosphäre während 15 - 20 Stunden gesintert.In an advantageous powder metallurgical process for the preparation of the alloy according to the invention, the mixture of the starting powder is pressed to a minimum compression density of 65% and the compact is sintered at a sintering temperature between 1500 and 1600 o C under an H₂ atmosphere for 15-20 hours.

Nachfolgend wird die Erfindung anhand von Beispielen näher erläutert.The invention is explained in more detail below with the aid of examples.

HerstellungsbeispielManufacturing example

Zur Herstellung von Blech aus der Legierung Cr-4Fe-5Ti-1Y₂O₃ wurden 60 kg einer Pulvermischung aus 4 Gew.% Eisenpulver mit einer mittleren Korngröße von 26 µm, 5 Gew.% Titanhydridpulver mit einer mittleren Korngröße von 2 µm, 1 Gew.% Y₂O₃-Pulver mit einer mittleren Korngröße von 0,35 µm, Rest Chrompulver mit einer mittleren Korngröße von 30 µm in einem Attritor 12 Stunden unter Argon mit einem Druck von einer Atmosphäre gemahlen. Die Pulvermischung wurde dann in einer Stahlmatrize zu Platten mit den Abmessungen 80 mm x 300 mm x 40 mm mit einem Preßdruck von 3000 bar kaltisostatisch gepreßt und anschließend ohne Vorsinterung bei 1600oC 20 Stunden unter Wasserstoff gesintert. Danach wurden die gesinterten Platten in Stahlblech mit einer Dicke von 2 mm allseitig eingekannt. Nach einem Anwärmen auf 1250oC wurden die eingekannten Platten durch Schmieden um 35 % umgeformt und von der Schmiedeendtemperatur im Ofen innerhalb von 12 Stunden auf Raumtemperatur abgekühlt. Nach Anwärmen auf 1250oC wurden die Platten zu Blechen von 4,5 mm Stärke gewalzt und von der Walzendtemperatur im Ofen innerhalb von 12 Stunden auf Raumtemperatur abgekühlt. Dann wurden die Bleche auf 1250oC angewärmt und auf eine Stärke von 2 mm weitergewalzt und die Ränder besäumt. Unmittelbar danach wurden die Bleche wiederum auf 1250oC angewärmt und eine Stunde lange bei dieser Temperatur geglüht. Nach einem Abkühlen auf 500oC wurden die Bleche auf eine Stärke von 1,3 mm fertiggewalzt und danach einer Endglühung bei 1600oC während einer Stunde unterzogen.To produce sheet metal from the alloy Cr-4Fe-5Ti-1Y₂O₃, 60 kg of a powder mixture of 4% by weight iron powder with an average grain size of 26 µm, 5% by weight titanium hydride powder with an average grain size of 2 µm, 1% by weight Y₂O₃ powder with an average grain size of 0.35 µm, the rest of chrome powder with an average grain size of 30 µm in an attritor milled for 12 hours under argon with a pressure of one atmosphere. The powder mixture was then mm in a steel die to form plates with dimensions of 80 x 300 mm x 40 mm with a molding pressure of 3000 bar cold isostatically pressed and subsequently sintered without preliminary sintering at 1600 o C for 20 hours under hydrogen. After that, the sintered plates were cut into steel sheet with a thickness of 2 mm on all sides. After warming up to 1250 o C the forged plates were forged by 35% and cooled from the forging end temperature in the furnace to room temperature within 12 hours. After warming to 1250 o C, the plates were rolled into sheets of 4.5 mm thickness and cooled from the final roll temperature in the furnace to room temperature within 12 hours. Then the sheets were heated to 1250 o C and rolled to a thickness of 2 mm and the edges trimmed. Immediately afterwards, the sheets were again heated to 1250 ° C. and annealed at this temperature for one hour. After cooling to 500 o C, the sheets were 1.3 mm thick finish rolled and then subjected to final annealing at 1600 o C for one hour.

Mit denselben Fertigungsschritten und -bedingungen wurden 1,3 mm starke
Bleche aus den Legierungen
Cr - 0,15 Fe - 1 Y₂O₃
Cr - 0,15 Fe - 1 La₂O₃
Cr - 24 Fe - 5 Al - 1 Y₂O₃
sowie aus reinem Chrom gefertigt.
Bei den Aluminium enthaltenden Legierungen wurde Aluminiumpulver mit einer mittleren Korngröße von 28 µm verwendet.With the same manufacturing steps and conditions, 1.3 mm thick
Sheets from the alloys
Cr - 0.15 Fe - 1 Y₂O₃
Cr - 0.15 Fe - 1 La₂O₃
Cr - 24 Fe - 5 Al - 1 Y₂O₃
as well as made of pure chrome.
Aluminum powder with an average grain size of 28 µm was used for the aluminum-containing alloys.

Prüfung der KorrosionsbeständigkeitCorrosion resistance test

Zur Prüfung der Korrosionsbeständigkeit der erfindungsgemäßen Legierungen im Vergleich mit reinem Chrom gegenüber Vanadiumpentoxid wurden aus den nach dem Herstellungsbeispiel gefertigten Blechen Proben mit den Abmessungen 100 mm x 100 mm geschnitten. Die Proben wurden dann beidseitig unter Entfernung der oberflächlichen Stahlschichten auf eine Enddicke von 1 mm geschliffen.To test the corrosion resistance of the alloys according to the invention in comparison with pure chromium against vanadium pentoxide, samples with the dimensions 100 mm × 100 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm.

Nach dem Abwiegen wurden die Proben im Feuerungsraum einer Ölverbrennungsanlage bei 900oC 3 Stunden lang der Verbrennungsschlacke ausgesetzt.
Dann wurden die Proben abgekühlt, mit Wasser gewaschen und erneut abgewogen. Dabei wurden im Schnitt folgende durchschnittliche Gewichtsverluste als Maß der jeweiligen Korrosion festgestellt: Material Gewichtsverlust (mg/cm²) Chrom 3,7 Cr - 4 Fe - 5 Ti - 1 Y₂O₃ 1,8 Cr - 0,15 Fe - 1 Y₂O₃ 2,4 Cr - 0,15 Fe - 1 La₂O₃ 2,8 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 3,2 After weighing, the samples were exposed to the combustion slag in the furnace of an oil combustion plant at 900 o C for 3 hours.
The samples were then cooled, washed with water and weighed again. The following average weight losses were determined as a measure of the respective corrosion: material Weight loss (mg / cm²) chrome 3.7 Cr - 4 Fe - 5 Ti - 1 Y₂O₃ 1.8 Cr - 0.15 Fe - 1 Y₂O₃ 2.4 Cr - 0.15 Fe - 1 La₂O₃ 2.8 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 3.2

Daraus ist zu ersehen, daß die erfindungsgemäßen Legierungen eine bis um den Faktor 2 verbesserte Korrosionsbeständigkeit gegenüber reinem Chrom aufweisen.It can be seen from this that the alloys according to the invention have a corrosion resistance which is improved by a factor of 2 compared to pure chromium.

Prüfung der WarmfestigkeitTesting the heat resistance

Zur Ermittlung der Warmfestigkeitseigenschaften der erfindungsgemäßen Legierungen wurden Bleche mit 3 mm Stärke gefertigt und bei 1000oC auf Zugfestigkeit und Bruchdehnung geprüft. Werkstoff Blech 3 mm Zugfestigk. (N/mm²) bei 1000o C Bruchdehnung (%) bei 1000o C Übergangst. duktil/spröde (o C) Cr 40 62 365 Cr - 0,15 Fe - 1 Y₂O₃ 140 24 107 Cr - 0,15 Fe - 1 La₂O₃ 115 44 203 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 90 16,5 nicht gem. To determine the heat resistance properties of the alloys according to the invention, sheets with a thickness of 3 mm were produced and tested for tensile strength and elongation at break at 1000 ° C. Material sheet 3 mm Tensile strength (N / mm²) at 1000 o C Elongation at break (%) at 1000 o C Transitional ductile / brittle ( o C) Cr 40 62 365 Cr - 0.15 Fe - 1 Y₂O₃ 140 24th 107 Cr - 0.15 Fe - 1 La₂O₃ 115 44 203 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 90 16.5 not acc.

Es ist die gegenüber reinem Chrom deutlich verbesserte Warmzugfestigkeit bei einer wesentlichen Absenkung der Übergangstemperatur duktil/spröde zu erkennen.The warm tensile strength, which is significantly better than that of pure chrome, can be seen with a significant reduction in the ductile / brittle transition temperature.

Prüfung der OxidationsbeständigkeitTesting the resistance to oxidation

Zur Prüfung der Oxidationsbeständigkeit der erfindungsgemäßen Legierungen im Vergleich mit reinem Chrom wurden aus den nach dem Herstellungsbeispiel gefertigten Blechen Proben mit den Abmessungen 20 mm x 30 mm geschnitten. Die Proben wurden dann beidseitig unter Entfernung der oberflächlichen Stahlschichten auf eine Enddicke von 1 mm geschliffen. Nach dem Abwiegen wurden die Proben an Luft einmal bei einer Temperatur von 1000oC und einmal bei einer Temperatur von 1200oC über einen Zeitraum von 7 Tagen oxidiert. Bei 1000oC bildete sich an den Proben eine gut haftende Oxidschicht aus, so daß die durchschnittliche Gewichtszunahme der Proben als Maß für die Oxidationsbeständigkeit herangezogen wurde.
Bei 1000oC wurde darüberhinaus innerhalb einer Oxidationszeit von 112 Stunden der Kurvenverlauf der Oxidation ermittelt und daraus die Geschwindigkeitskonstante errechnet.
Bei 1200oC bildete sich an den Proben eine nur mehr schlecht haftende Oxidschicht, die durch Abbürsten und Waschen der Proben in Wasser entfernt wurde, so daß die durchschnittliche Gewichtsabnahme der Proben als Maß für die Oxidationsbeständigkeit herangezogen wurde.

Figure imgb0001
Oxidationsbedingungen: Luft bei 1200oC Werkstoff Gewichtsabnahme nach 168 Std. (g/cm²) Cr 14 Cr - 0,15 Fe - 1 Y₂O₃ 3 Cr - 0,15 Fe - 1 La₂O₃ 6 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 2 In order to test the oxidation resistance of the alloys according to the invention in comparison with pure chromium, samples with the dimensions 20 mm × 30 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm. After weighing, the samples were oxidized in air once at a temperature of 1000 ° C. and once at a temperature of 1200 ° C. over a period of 7 days. At 1000 o C a well adhering oxide layer formed on the samples, so that the average Weight gain of the samples was used as a measure of the oxidation resistance.
At 1000 o C, the course of the oxidation was also determined within an oxidation time of 112 hours, and the rate constant was calculated from this.
At 1200 o C, the samples formed a poorly adhering oxide layer, which was removed by brushing and washing the samples in water, so that the average weight loss of the samples was used as a measure of the oxidation resistance.
Figure imgb0001
 Oxidation conditions: air at 1200 o C material Weight loss after 168 hours (g / cm²) Cr 14 Cr - 0.15 Fe - 1 Y₂O₃ 3rd Cr - 0.15 Fe - 1 La₂O₃ 6 Cr - 24 Fe - 5 Al - 1 Y₂O₃ 2nd

Die deutlich verbesserte Oxidationsbeständigkeit der erfindungsgemäßen Legierung gegenüber reinem Chrom ist zu ersehen.The clearly improved oxidation resistance of the alloy according to the invention compared to pure chromium can be seen.

Claims (8)

Legierung auf Chrombasis mit einem Chromgehalt von mehr als 65 Gew.%, die neben üblichen Verunreinigungen aus der folgenden Zusammensetzung besteht:
0,005 bis 5 Gew.% von einem oder mehreren Oxiden aus der Gruppe der Seltenen Erden,
0,1 bis 32 Gew.% von einem oder mehreren Metallen aus der Gruppe Eisen, Nickel und Kobalt,
bis zu 30 Gew.% von einem oder mehreren Metallen aus der Gruppe Aluminium, Titan, Zirkon und Hafnium,
bis zu 10 Gew.% von einem oder mehreren Metallen aus der Gruppe Vanadium, Niob, Molybdän, Tantal, Wolfram und Rhenium,
bis zu 1 Gew.% Kohlenstoff und/oder Stickstoff und/oder Bor und/oder Silizium,
Rest Chrom.Chromium-based alloy with a chromium content of more than 65% by weight, which consists of the following composition in addition to usual impurities:
0.005 to 5% by weight of one or more oxides from the group of rare earths,
0.1 to 32% by weight of one or more metals from the group iron, nickel and cobalt,
up to 30% by weight of one or more metals from the group aluminum, titanium, zirconium and hafnium,
up to 10% by weight of one or more metals from the group vanadium, niobium, molybdenum, tantalum, tungsten and rhenium,
up to 1% by weight of carbon and / or nitrogen and / or boron and / or silicon,
Rest chrome. Legierung auf Chrombasis nach Anspruch 1, dadurch gekennzeichnet, daß sie 0,3 bis 2 Gew.% Yttriumoxid und/oder Lanthanoxid enthält.Chromium-based alloy according to Claim 1, characterized in that it contains 0.3 to 2% by weight of yttrium oxide and / or lanthanum oxide. Legierung auf Chrombasis nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie 5 bis 25 Gew.% Eisen und/oder Nickel enthält.Chrome-based alloy according to Claim 1 or 2, characterized in that it contains 5 to 25% by weight of iron and / or nickel. Legierung auf Chrombasis nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie 3 bis 10 Gew.% Aluminium und/oder Titan und/oder Zirkon enthält.Chromium-based alloy according to one of Claims 1 to 3, characterized in that it contains 3 to 10% by weight of aluminum and / or titanium and / or zircon. Legierung auf Chrombasis nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie 3 bis 8 Gew.% Vanadium und/oder Niob und/oder Molybdän enthält.Chromium-based alloy according to one of Claims 1 to 4, characterized in that it contains 3 to 8% by weight of vanadium and / or niobium and / or molybdenum. Legierung auf Chrombasis nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie 0,03 bis 0,3 Gew.% Kohlenstoff und/oder Stickstoff enthält.Chromium-based alloy according to one of Claims 1 to 5, characterized in that it contains 0.03 to 0.3% by weight of carbon and / or nitrogen. Legierung auf Chrombasis nach Anspruch 1 mit der Zusammensetzung 24 Gew.% Eisen, 5 Gew.% Aluminium, 1 Gew.% Yttriumoxid, Rest Chrom.Chromium-based alloy according to Claim 1 with the composition 24% by weight iron, 5% by weight aluminum, 1% by weight yttrium oxide, the rest chromium. Pulvermetallurgisches Verfahren zur Herstellung einer Legierung auf Chrombasis nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Mischung der Ausgangspulver auf eine Mindestpreßdichte von 60 % gepreßt und der Preßling bei einer Sintertemperatur zwischen 1500 und 1600oC unter H₂-Atmosphäre während 15 - 20 Stunden gesintert wird.Powder-metallurgical process for producing a chromium-based alloy according to one of Claims 1 to 7, characterized in that the mixture of the starting powders is pressed to a minimum compression density of 60% and the compact at a sintering temperature between 1500 and 1600 o C under an H₂ atmosphere for 15- Is sintered for 20 hours.
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