EP0136998B1 - Wrought nickel-base alloy and process for its thermal treatment - Google Patents

Wrought nickel-base alloy and process for its thermal treatment Download PDF

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EP0136998B1
EP0136998B1 EP84890149A EP84890149A EP0136998B1 EP 0136998 B1 EP0136998 B1 EP 0136998B1 EP 84890149 A EP84890149 A EP 84890149A EP 84890149 A EP84890149 A EP 84890149A EP 0136998 B1 EP0136998 B1 EP 0136998B1
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wrought nickel
heat treatment
alloy
based alloy
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EP0136998A1 (en
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Herbert Dipl.-Ing. Aigner
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Voest-Alpine Stahl AG Te Linz Ad
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Vereinigte Edelstahlwerke AG
Voestalpine Stahl GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the invention relates to a wrought nickel alloy with the alloy components C, Si, Mn, Cr, Mo, Cu, Ti and Fe with the aim of making a substantial increase in strength possible by a special heat treatment by changing the percentage composition.
  • This alloy is generally used in the solution-annealed state, whereby (the mechanical characteristics refer to RT in the following) a tensile strength of about 600 to max. 700 N / mm 2 and a 0.2% proof stress from about 230 to max. 270 N / mm2.
  • the work hardened condition is also common for pipes and rods, with the work hardening achieved being of the order of magnitude as is the case for austenitic Cr-Ni steels; the tensile strength is accordingly for cold-formed pipes up to about 800 N / mm 2 and the 0.2% proof stress up to about 500 N / mm 2 .
  • Such an alloy also has a permeability below 1.010, with which it can be described as non-magnetic.
  • the invention also includes the heat-treated alloy.
  • a preferred method for the heat treatment of this wrought nickel alloy is characterized in that after solution annealing in the temperature range from 980-1170 ° C. with a holding time of at least 5 minutes in order to achieve a further increase in strength, the temperature is preferably set to 650-800 ° C. 680 - 770 ° C, is carried out for a period of 3 to 20 h, preferably from 6 to 16 h.
  • a further increase in these mechanical parameters can still be achieved in that, after solution annealing, a cold deformation with a degree of deformation of 5 to 15% is interposed.
  • the invention further relates to the use of the alloy as a material for non-magnetic parts, for. B. housing parts, boring bar parts and the like., In particular for the development and / or promotion of gaseous and / or liquid fossil fuels. It was quite surprising that with the increased addition of titanium, in addition to the possible increase in strength values, a permeability is also achieved which allows this material to be used for such components, while at the same time the low susceptibility to stress corrosion cracking makes this material suitable for use in drilling and Conveyor technology, e.g. B. as non-magnetic collars or as a housing for corresponding magnetic measuring devices and the like., Is extremely suitable.
  • melt no. 1 the composition of eleven test melts is compared to that of melt no. 1, the alloys according to the invention, beginning with melt no. 2, differing in particular from an increasing titanium content.
  • the permeability of samples 1 to 12 decreases with increasing titanium content, the permeability coming below approximately 1.01 from a titanium content of 1.2%, so that here a technically as non-magnetic significant material is present.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Furnace Charging Or Discharging (AREA)
  • Forging (AREA)

Abstract

1. A wrought nickel-based alloy with the alloy constituents C, Si, Mn, Cr, Mo, Cu, Ti and Fe, characterized in that it comprises max. 0.1% C, max. 1% Si, max. 1.5% Mn, 36.5 to 46.0% Ni, 18.5 to 26.0% Cr, 1.0 to 4.0% Mo, 1.0 to 4.0% Cu, 1.35 to 2.60% Ti, optionally up to 0.7% Al, and/or 0.3 to 1.2% Nb/Ta, and the rest essentially Fe and impurities determined by production.

Description

Die Erfindung betrifft eine Nickel-Knetlegierung mit den Legierungsbestandteilen C, Si, Mn, Cr, Mo, Cu, Ti und Fe mit der Zielsetzung, durch eine Abänderung der prozentualen Zusammensetzung eine wesentliche Festigkeitssteigerung durch eine spezielle Wärmebehandlung möglich zu machen.The invention relates to a wrought nickel alloy with the alloy components C, Si, Mn, Cr, Mo, Cu, Ti and Fe with the aim of making a substantial increase in strength possible by a special heat treatment by changing the percentage composition.

Die Erfindung geht von einer Nickel-Knetlegierung aus, die im Deutschen Normenblatt DIN 17 744 (Feb. 1983) unter dem Kurzzeichen NiCr 21 Mo/Werkstoff-Nr 2.4858 angeführt ist, u.zw. mit nachfolgender Zusammensetzung:

  • max. 0,025 % C, max. 0,5 % Si, max. 1,0 % Mn, 38,0 - 46,0 % Ni, 19,5 - 23,5 % Cr, 2,5 - 3,5 % Mo, 1,5 - 3,0 % Cu, 0,6 - 1,2 % Ti, gegebenenfalls noch max. 0,2 % Al bzw. max. 1,0 % Co (wobei es sich jedoch bei AI und Co - siehe die Seiten 106 bzw. 107 der "Stahl-Eisen-Liste", 6. Auflage, 1977 - bloß um zulässige Verunreinigungen handelt), Rest im wesentlichen Fe.
The invention is based on a wrought nickel alloy, which is listed in the German standard DIN 17 744 (Feb. 1983) under the abbreviation NiCr 21 Mo / Material No. 2.4858, etc. with the following composition:
  • Max. 0.025% C, max. 0.5% Si, max. 1.0% Mn, 38.0 - 46.0% Ni, 19.5 - 23.5% Cr, 2.5 - 3.5% Mo, 1.5 - 3.0% Cu, 0.6 - 1.2% Ti, possibly max. 0.2% Al or max. 1.0% Co (although AI and Co - see pages 106 and 107 of the "Stahl-Eisen-Liste", 6th edition, 1977 - are merely admissible impurities), the rest essentially Fe.

Diese Legierung wird grundsätzlich im lösungsgeglühten Zustand angewendet, wobei sie (die mechanischen Kennwerte beziehen sich im folgenden grundsätzlich auf RT) eine Zugfestigkeit von etwa 600 bis max. 700 N/mm2 und eine 0,2 %-Dehngrenze von etwa 230 bis max. 270 N/mm2 aufweist. Für Rohre und Stangen ist auch der kaltverfestigte Verwendungszustand gebräuchlich, wobei die erzielte Kaltverfestigung in der Größenordnung derjenigen liegt, wie sie für austenitische Cr-Ni-Stähle gilt; die Zugfestigkeit beträgt demgemäß für kaltverformte Rohre bis etwa 800 N/mm2 und die 0,2 %-Dehngrenze bis etwa 500 N/mm2.This alloy is generally used in the solution-annealed state, whereby (the mechanical characteristics refer to RT in the following) a tensile strength of about 600 to max. 700 N / mm 2 and a 0.2% proof stress from about 230 to max. 270 N / mm2. The work hardened condition is also common for pipes and rods, with the work hardening achieved being of the order of magnitude as is the case for austenitic Cr-Ni steels; the tensile strength is accordingly for cold-formed pipes up to about 800 N / mm 2 and the 0.2% proof stress up to about 500 N / mm 2 .

Wegen ihrer ausgezeichneten Korrosionsbeständigkeit auch in heißen Säuren bzw. Mischsäuren und gegenüber oxidierenden Einflüssen, beispielsweise seien Mischungen aus Salpeter-, Phosphor- und Schwefelsäure genannt, sowie der sehr guten Beständigkeit gegen Lochfraß und Spannungsrißkorrosion erfolgt die Anwendung insbesondere dort, wo ausnehmend heikle Korrosionsprobleme auftreten, wie beispielsweise bei Sulfonieranlagen, für Beizausrüstungen in der Metallindustrie sowie für Anwendungszwecke in der Zellstoff- und Kunstfaserindustrie und anderes mehr.Because of their excellent corrosion resistance even in hot acids or mixed acids and against oxidizing influences, for example mixtures of nitric, phosphoric and sulfuric acid, as well as the very good resistance to pitting and stress corrosion cracking, they are used particularly where particularly delicate corrosion problems occur, such as in sulfonation plants, for pickling equipment in the metal industry and for applications in the pulp and synthetic fiber industry and others.

Eine Beschränkung von Anzahl und Umfang der Anwendungsarten erfährt diese Nickel-Legierung vorwiegend durch den verhältnismäßig hohen Preis und daraus folgert, daß mit einer Festigkeitssteigerung und den damit erzielbaren Einsparungen und der Erschließung neuer Anwendungsgebiete ein sehr bedeutender technischer Fortschritt zu erreichen wäre.A limitation of the number and scope of the types of application experiences this nickel alloy mainly due to the relatively high price and it follows that with an increase in strength and the savings that can be achieved and the opening up of new areas of application, a very significant technical advance could be achieved.

Zur Lösung des Problems und der gestellten Aufgabe wird gemäß dem Erfindungskennzeichen folgende Legierungszusammensetzung für die neue Nickel-Knetlegierung vorgeschlagen:

  • max. 0,1 % C,
  • max. 1 %, vorzugsweise max. 0,6 % Si,
  • max. 1,5 %, vorzugsweise max. 1,2 % Mn,
  • 36,5 bis 46,0, vorzugsweise 38,0 bis 44,0 % Ni,
  • 18,5 bis 26,0 %, vorzugsweise 19,0 bis 24,0 % Cr,
  • 1,0 bis 4,0 %,vorzugsweise 2,0 bis 3,5 % Mo,
  • 1,0 bis 4,0 %,vorzugsweise 1,0 bis 3,0 % Cu,
  • 1,35 bis 2,60 % Ti,

gegebenenfalls bis 0,7 %, vorzugsweise bis 0,5 % Al, und/oder 0,3 bis 1,2 %, vorzugsweise 0,5 bis 1,2 % Nb/Ta, sowie Rest im wesentlichen Fe und herstellungsbedingte VerunreinigungenTo solve the problem and the problem, the following alloy composition for the new wrought nickel alloy is proposed according to the invention:
  • Max. 0.1% C,
  • Max. 1%, preferably max. 0.6% Si,
  • Max. 1.5%, preferably max. 1.2% Mn,
  • 36.5 to 46.0, preferably 38.0 to 44.0% Ni,
  • 18.5 to 26.0%, preferably 19.0 to 24.0% Cr,
  • 1.0 to 4.0%, preferably 2.0 to 3.5% Mo,
  • 1.0 to 4.0%, preferably 1.0 to 3.0% Cu,
  • 1.35 to 2.60% Ti,

optionally up to 0.7%, preferably up to 0.5% Al, and / or 0.3 to 1.2%, preferably 0.5 to 1.2% Nb / Ta, and the remainder essentially Fe and production-related impurities

Eine derartige Legierung weist weiters eine Permeabilität unter 1,010 auf, womit sie als amagnetisch bezeichnet werden kann.Such an alloy also has a permeability below 1.010, with which it can be described as non-magnetic.

Unter Bezugnahme auf den Aluminiumgehalt wird darauf verwiesen, daß geringe, meistens in der Größenordnung von einigen Hunderstel-Prozent liegende Gehalte dieses Legierungselementes oft herstellungsbedingt vorhanden sind, weshalb ein als Legierungszusatz zu wertender Anteil jedenfalls dann vorliegt, wenn ein Prozentanteil von 0,2 % AI in der Legierungszusammensetzung überschritten ist.With reference to the aluminum content, reference is made to the fact that low levels of this alloy element, usually in the order of a few hundredths of a percent, are often present due to the production process, which is why a proportion to be considered as an alloy additive is present when a percentage of 0.2% Al is exceeded in the alloy composition.

Dem alternativ eingeräumten Zusatz von AI kommt insbesondere die Bedeutung zu, daß es sich beim Erschmelzen der Legierung erübrigt, auf eine kritische Einstellung dieses Legierungsbestandteiles hinsichtlich einer einzuhaltenden Höchstmenge etwa bei der Desoxidation Bedacht nehmen zu müssen.The alternatively added addition of Al is of particular importance that, when the alloy melts, there is no need to consider critical adjustment of this alloy component with regard to a maximum amount to be observed, for example during deoxidation.

Die Abwandlung mit Bezug auf einen Zusatz von Nb/Ta erbringt eine kornfeinernoe Wirkung, die sich positiv auf die 0,2 %-Dehngrenze auswirkt.The modification with regard to the addition of Nb / Ta produces a grain-fine effect, which has a positive effect on the 0.2% proof stress.

Wie schon eingangs erwähnt, liegt die Bedeutung des neuen Werkstoffes, insbesondere in der Möglichkeit, durch eine Wärmebehandlung eine beträchtliche Festigkeitssteigerung erreichen zu können. Die Erfindung umfaßt auch die wärmebehandelte Legierung. Ein bevorzugtes Verfahren zur Wärmebehandlung dieser Nickel-Knetlegierung ist dadurch gekennzeichnet, daß nach einem Lösungsglühen im Temperaturbereich von 980 - 1170°C mit einer Haltezeit von zumindest 5 min zur Erzielung einer weiteren Festigkeitssteigerung eine Einstellung der Temperatur auf 650 - 800° C, vorzugsweise auf 680 - 770° C, während eines Zeitraumes von 3 bis 20 h, vorzugsweise von 6 bis 16 h, vorgenommen wird.As already mentioned at the beginning, the importance of the new material lies in particular in the possibility of being able to achieve a considerable increase in strength through heat treatment. The invention also includes the heat-treated alloy. A preferred method for the heat treatment of this wrought nickel alloy is characterized in that after solution annealing in the temperature range from 980-1170 ° C. with a holding time of at least 5 minutes in order to achieve a further increase in strength, the temperature is preferably set to 650-800 ° C. 680 - 770 ° C, is carried out for a period of 3 to 20 h, preferably from 6 to 16 h.

Es gelingt so, eine Erhöhung der Zugfestigkeit bis auf über 1.000 N/mm2 und der 0,2 %-Dehngrenze auf 800 N/mm2 zu erreichen.It is possible to increase the tensile strength up to over 1,000 N / mm 2 and the 0.2% proof stress to 800 N / mm 2 .

Eine weitere Steigerung dieser mechanischen Kennwerte ist gemäß einem weiteren Verfahrensmerkmal noch dadurch erzielbar, daß nach dem Lösungsglühen noch eine Kaltverformung mit einem Verformungsgrad von 5 bis 15 % zwischengeschaltet wird.According to a further feature of the method, a further increase in these mechanical parameters can still be achieved in that, after solution annealing, a cold deformation with a degree of deformation of 5 to 15% is interposed.

Es hat sich nämlich unerwarteterweise gezeigt, daß dadurch der festigkeitssteigernde Effekt der Wärmebehandlung verbessert wird, weil eine noch feinere Verteilung der an den Korngrenzen ausgeschiedenen Partikel damit erreicht wird. Während in diesem Falle eine Abkühlung auf Raumtemperatur nach dem Lösungsglühen zwingend vorgenommen werden muß, kann ansonsten die festigkeitssteigernde Erwärmung gegebenenfalls auch ohne eine solche Abkühlung, also unmittelbar aus dem Temperaturbereich vom Lösungsglühen, vorgenommen werden.It has been shown unexpectedly that this improves the strengthening effect of the heat treatment, because an even finer distribution of the grain boundaries excreted particles is thus achieved. While in this case cooling to room temperature is mandatory after solution annealing, the strength-increasing heating can also be carried out without such cooling, that is, directly from the temperature range of solution annealing.

Die Erfindung bezieht sich weiters auf die Verwendung der Legierung als Werkstoff für amagnetische Teile, z. B. Gehäuseteile, Bohrstangenteile u.dgl., insbesondere für die Erschließung und/oder Förderung von gasförmigen und/oder flüssigen fossilen Brennstoffen. Es war durchaus überraschend, daß mit dem erhöhten Zusatz von Titan neben der möglichen Steigerung der Festigkeitswerte auch eine Permeabilität erreicht wird, die es erlaubt, diesen Werkstoff für derartige Bauteile anzuwenden, wobei gleichzeitig die niedrige Spannungsrißkorrosionsanfälligkeit diesen Werkstoff für den Einsatz in der Bohr- und Fördertechnik, z. B. als amagnetische Schwerstangen oder auch als Gehäuse für entsprechende Magnetmeßvorrichtungen u.dgl., hervorragend geeignet ist.The invention further relates to the use of the alloy as a material for non-magnetic parts, for. B. housing parts, boring bar parts and the like., In particular for the development and / or promotion of gaseous and / or liquid fossil fuels. It was quite surprising that with the increased addition of titanium, in addition to the possible increase in strength values, a permeability is also achieved which allows this material to be used for such components, while at the same time the low susceptibility to stress corrosion cracking makes this material suitable for use in drilling and Conveyor technology, e.g. B. as non-magnetic collars or as a housing for corresponding magnetic measuring devices and the like., Is extremely suitable.

Die Erfindung wird nachfolgend an Hand von Ausführungsbeispielen im Vergleich mit der Basislegierung (Schmelze Nr. 1) näher erläutert.The invention is explained in more detail below on the basis of exemplary embodiments in comparison with the base alloy (melt No. 1).

In der Tabelle ist die Zusammensetzung von elf Versuchsschmelzen derjenigen von Schmelze Nr. 1 gegenübergestellt, wobei die erfindungsgemäßen Legierungen, beginnend mit Schmelze Nr. 2 sich insbesondere durch einen jeweils steigenden Titan-Gehalt unterscheiden.In the table, the composition of eleven test melts is compared to that of melt no. 1, the alloys according to the invention, beginning with melt no. 2, differing in particular from an increasing titanium content.

Alle Probe wurden in gleicher Weise einer Wärmebehandlung gemäß dem Verfahrensanspruch 3 unterzogen, und zwar nach einem Lösungsglühen bei 1150°C mit einer Haltezeit von 30 min, Abkühlung (durch Abschrecken in Wasser) auf RT und Aushärtung während zwölf Stunden bei 740°C, wonach langsam an ruhender Luft auf Raumtemperatur abgekühlt wurde.

Figure imgb0001
All samples were subjected in the same way to a heat treatment according to process claim 3, namely after solution annealing at 1150 ° C. with a holding time of 30 min, cooling (by quenching in water) to RT and curing at 740 ° C. for twelve hours, after which was slowly cooled to room temperature in still air.
Figure imgb0001

In den Schaubildern der Fig. 1 und 2 sind die von den einzelnen Proben 1 bis 12 gemäß vorhergehender Tabelle ermittelten Werte der Zugfestigkeit bzw. der 0,2 %-Dehngrenze jeweils in Relation zum Titangehalt dargestellt, und es zeigt sich, daß die Vergleichsprobe (Schmelze Nr. 1) mit 1,12 % Ti im. Gegensatz zu den erfindungsgemäßen Schmelzen 1 - 12 praktisch keine auf die Wärmebehandlung zurückgehenden Festigkeitssteigerung erkennen läßt.1 and 2, the values of the tensile strength or the 0.2% proof stress determined by the individual samples 1 to 12 according to the previous table are shown in relation to the titanium content, and it is shown that the comparative sample ( Melt No. 1) with 1.12% Ti im. In contrast to the melts 1 to 12 according to the invention, there is practically no increase in strength due to the heat treatment.

Das Diagramm der Fig. 3 zeigt den Einfluß der Aushärtetemperatur auf die Erhöhung der 0,2 %-Dehngrenze. Es sind dort die bei verschiedenen Aushärtetemperaturen erzielten Werte für die Schmelzen 1, 3, 7 und 12 - in dieser Reihenfolge mit vollem Kreis, Dreieck, Quadrat und leerem Kreis symbolisiert - sowie die Ausgangswerte dieser Schmelzen im lösungsgeglühten Zustand - mit L bezeichnet - angegeben; man ersieht daraus, daß im bevorzugten Temperaturbereich von 680 - 770° C die besten Ergebnisse erhalten wurden.3 shows the influence of the curing temperature on the increase in the 0.2% proof stress. The values for melts 1, 3, 7 and 12 - symbolized in this order with a full circle, triangle, square and empty circle - as well as the initial values of these melts in the solution-annealed state - denoted by L - are given there; it can be seen that the best results were obtained in the preferred temperature range of 680-770 ° C.

Wie dem Diagramm der Fig. 4 zu entnehmen, sinkt die Permeabilität der Proben 1 bis 12 mit steigendem Titangehalt, wobei ca. ab einem Titangehalt von 1,2 % die Permeabilität unter 1,01 zu liegen kommt, sodaß hier ein technisch als amagnetisch zu bezeichnender Werkstoff vorliegt.As can be seen from the diagram in FIG. 4, the permeability of samples 1 to 12 decreases with increasing titanium content, the permeability coming below approximately 1.01 from a titanium content of 1.2%, so that here a technically as non-magnetic significant material is present.

Claims (6)

1. A wrought nickel-based alloy with the alloy constituents C, Si, Mn, Cr, Mo, Cu, Ti and Fe, characterized in that it comprises
max. 0.1 % C,
max. 1 % Si,
max. 1.5 % Mn,
36.5 to 46.0 % Ni,
18.5 to 26.0 % Cr,
1.0 to 4.0 % Mo,
1.0 to 4.0 % Cu,
1.35 to 2.60 % Ti,
optionally up to 0.7 % Al, and/or
0.3 to 1.2% Nb/Ta,
and the rest essentially Fe and impurities determined by production.
2. A wrought nickel-based alloy according to claim 1, characterized in that it contains
up to 0.5 % Al, and/or
0.5 to 1.2 % Nb/Ta.
3. A process for the heat treatment of the wrought nickel-based alloy according to claim 1 or 2, characterized in that after a solution heat treatment in the temperature range of 980 - 1170° C with a holding time of at least 5 min until an increase in strength is achieved the temperature is set to 6500 - 800° C for a period of from 3 to 20 h.
4. A process for the heat treatment of the wrought nickel-based alloy according to claim 1 or 2 and 3, characterized in that, in order to achieve an increase in strength, the temperature is set to 680° - 770°C for a period of from 6 to 16 h.
5. A process according to claim 1 or 2 and 3 or 4, characterized in that after the solution heat treatment a cold deformation with a degree of deformation of from 5 to 15 % is included.
6. The use of an alloy, produced according to claims 3 to 5, characterized by a material for magnetic parts, e.g. housing parts, drill rod parts and the like, in particular for discovering and/or extracting gaseous and/or liquid fossil fuels.
EP84890149A 1983-08-10 1984-08-07 Wrought nickel-base alloy and process for its thermal treatment Expired EP0136998B1 (en)

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