EP0045985A1 - Method of manufacturing a copper-based memory alloy - Google Patents

Method of manufacturing a copper-based memory alloy Download PDF

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Publication number
EP0045985A1
EP0045985A1 EP81200691A EP81200691A EP0045985A1 EP 0045985 A1 EP0045985 A1 EP 0045985A1 EP 81200691 A EP81200691 A EP 81200691A EP 81200691 A EP81200691 A EP 81200691A EP 0045985 A1 EP0045985 A1 EP 0045985A1
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Prior art keywords
copper
powder
hot
alloy
starting material
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French (fr)
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EP0045985B1 (en
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Gernot Dr. Gessinger
Olivier Dr. Mercier
Helmut Dr. Riegger
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BBC Brown Boveri AG Switzerland
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    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • 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
    • C22C1/0425—Copper-based alloys
    • 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
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect

Definitions

  • the invention relates to a method for producing a copper-based memory alloy according to the preamble of claim 1.
  • the invention is based on the object of specifying a production method for copper-based memory alloys which combines high reproducibility with the greatest possible simplicity and economy, is suitable for mass production and enables homogeneous, dense products in the form of semi-finished or finished products.
  • the coarse powder (grain size> 0.05 by plasma spheroidization, rotating electrode method, dropletization of a melt by means of ultrasonic excitation, atomization of a melt at high speed or by any other known method.
  • the blank was subjected to hot forming by open die forging at a temperature of approx. 800 ° C.
  • the diameter of the workpiece was essentially reduced so that a rod of 18 mm in diameter was finally available.
  • the process is in no way limited to this variant.
  • the starting powder can also consist of powders of different compositions, which together form the final alloy.
  • the grain diameter (particle size) of the powder can in principle be between 0.05 and 0.8 mm.
  • the pressure used in isostatic pressing can be 50 to 300 MPa, depending on the conditions and size of the workpiece to be produced, the associated pressing temperature, depending on the alloy, 750 to 950 ° C and the time period Y2 h to 5 h.
  • the hot-forming operation which can consist of forges, presses, rotary hammers, rollers, etc., is advantageously carried out in the temperature range between 750 and 850 ° C.
  • a hollow cylinder made of copper or a ductile copper alloy can also be used to encapsulate the powder.
  • the powder encapsulated in the rubber tube was subjected to a cold isostatic pressing process:
  • the cold-pressed blank was encapsulated in a copper cylinder of the following dimensions after removal from the rubber hose:
  • the copper cylinder was covered with a lid and sealed and welded under vacuum.
  • the capsule sealed in this way was then subjected to a hot isostatic pressing process with the following characteristics:
  • the blank was subjected to a heat treatment, which corresponded to a homogenization anneal under the following conditions:
  • Example 1 After homogenization, the workpiece was subjected to a forging operation similar to Example 1.
  • the method is not exhausted in this embodiment variant. Any mixture of master alloys and / or elementary powder in any number (two or more types of powder) can be used as the starting powder. The only requirement is that the desired final composition is achieved by mixing the powder.
  • a suitable plastic hose for cold isostatic pressing which is advantageously carried out at pressures of 300 to 800 MPa for 1 to 10 minutes, can also be used.
  • the Homogenization annealing can be carried out in the temperature range of 900 to 950 ° C for 1 to 20 h.
  • Alloys of the following composition are particularly suitable as alloys for this process:
  • the powder metallurgical process according to the invention and the semi-finished and finished products produced thereafter enable the production of workpieces from a memory alloy of the Cu / Al or Cu / Al / Ni type, which have better homogeneity compared to bodies produced by melt metallurgy or by conventional powder metallurgy methods, and allow economical production.

Abstract

Cu Al- oder Cu Al Ni-Gedächtnislegierungen werden pulvermetallurgisch dadurch hergestellt, dass unter Verwendung von Grobkornpulvern aus Vor- oder Endlegierungen mit 0,05 bis 0,8 mm Partikeldurchmesser eine Mischung erzeugt und diese in einen Metallbehälter unter Vakuum abgefüllt wird, worauf der Behälter verschlossen, verschweisst und heiss-isostatisch gepresst, sowie der entstandene Rohling warmverformt wird. Als Variante wird das Pulver in einen Gummischlauch abgefüllt und zunächst kalt-isostatisch gepresst, worauf der Rohling in einen Kupferzylinder gesteckt, der letztere verschlossen, heiss-isostatisch gepresst, homogenisiert und der entstandene Rohling warmverformt wird.Cu Al or Cu Al Ni memory alloys are manufactured by powder metallurgy by using coarse-grain powders made from pre- or final alloys with a particle diameter of 0.05 to 0.8 mm to produce a mixture and this is filled into a metal container under vacuum, whereupon the container sealed, welded and hot-isostatically pressed, and the resulting blank is thermoformed. As a variant, the powder is filled into a rubber tube and first cold-isostatically pressed, whereupon the blank is placed in a copper cylinder, the latter is closed, hot-isostatically pressed, homogenized and the resulting blank is thermoformed.

Description

Die Erfindung geht aus von einem Verfahren zur Herstellung einer Kupferbasis-Gedächtnislegierung nach der Gattung des Anspruchs 1.The invention relates to a method for producing a copper-based memory alloy according to the preamble of claim 1.

Gedächtnislegierungen des β-Sondermessingtyrps wurden bisher vorwiegend schmelzmetallurgisch hergestellt. Ferner sind Verfahren zur pulvermetallurgischen Herstellung derartiger Legierungen bekannt geworden (z.B. M. Follon, E. Aernoudt, Powder-metallurgically processed shape-memcry alloys, 5th European Symposium on Powder Metallurgy, Stockholm 1978, S. 275 - 231). Diese meist mit feinen bis sehr feinen Pulvern arbeitenden Methoden sind ganz allgemein aus der Pulvermetallurgie bekannt. Andererseits sind auch Herstellungsverfahren bekannt, welche verhältnismässig grobkörnige Pulver als Ausgangsmaterialien verwenden. Dies gilt vor allem für die Pulvermetallurgie von Titanlegierungen und von Nickelsuperlegierungen (z.B. G.H.Gessinger, Brown Boveri Research Center, "Titanium powder metallurgy and composites", Int. Tivankonferenz, Kyoto , Mai 1980; G.H.Gessinger and M.J.Eomford, "Powder metallurgy of superalloys", International Metallurgical Reviews 1974, Versucht man, nach den üblichen pulvermetallurgischen Methoden, d.h. durch Mischen, Pressen, Sintern, ev. abwechslungsweises mehrmaliges Pressen und Sintern von groben Pulvern aus Kupferlegierungen Werkstücke herzustellen, so erhält man bestenfalls filterähnliche poröse Gebilde, die für Sonderzwecke bereits seit einiger Zeit im Handel sind. Es besteht daher ein Bedürfnis nach einem Verfahren, welches kompakte, dichte Erzeugnisse liefert.Memory alloys of the β special brass tyre have so far mainly been produced by melt metallurgy. Furthermore, processes for the powder metallurgical production of such alloys have become known (for example M. Follon, E. Aernoudt, Powder-metallurgically processed shape-memcry alloys, 5th European Symposium on Powder Metallurgy, Stockholm 1978, pp. 275-231). These methods, which mostly work with fine to very fine powders, are generally known from powder metallurgy. On the other hand, manufacturing processes are also known which use relatively coarse-grained powders as starting materials. This applies above all to the powder metallurgy of titanium alloys and nickel super alloys (e.g. GHGessinger, Brown Boveri Research Center, "Titanium powder metallurgy and composites", Int. Tivankonferenz, Kyoto, May 1980; GHGessinger and MJEomford, "Powder metallurgy of superalloys", International Metallurgical Reviews 1974, If you try to manufacture workpieces using the usual powder metallurgical methods, i.e. by mixing, pressing, sintering, possibly alternately pressing and sintering coarse powders from copper alloys several times, the best you can get are filter-like porous structures that have been on the market for special purposes for some time . There is therefore a need for a process that provides compact, dense products.

Der Erfindung liegt die Aufgabe zugrunde, ein Herstellungsverfahren für Kupferbasis-Gedächtnislegierungen anzugeben, welches hohe Reproduzierbarkeit mit grösstmöglicher Einfachheit und Wirtschaftlichkeit verbindet, sich für die Massenerzeugung eignet und homogene, dichte Produkte in Form von Halbzeug oder Fertigerzeugnissen ermöglicht.The invention is based on the object of specifying a production method for copper-based memory alloys which combines high reproducibility with the greatest possible simplicity and economy, is suitable for mass production and enables homogeneous, dense products in the form of semi-finished or finished products.

Diese Aufgabe wird erfindungsgemäss durch die Merkmale des Anspruchs 1 gelöst.According to the invention, this object is achieved by the features of claim 1.

Die Erfindung wird anhand der nachfolgenden, durch Figuren erläuterten Ausführungsbeispiele beschrieben.The invention is described on the basis of the following exemplary embodiments explained by figures.

Dabei zeigt:

  • Fig. 1 das Fliessbild (Blockdarstellung) der grundsätzlichen Verfahrensschritte,
  • Fig. 2 das Fliessbild einer Ausführungsvariante des Verfahrens mit zusätzlichem kalt-isostatischem Pressen und Homogenisieren.
It shows:
  • 1 shows the flow diagram (block diagram) of the basic method steps,
  • 2 shows the flow diagram of an embodiment variant of the method with additional cold isostatic pressing and homogenization.

Grundsätzlich können die groben Pulver (Korngrösse>0,05 durch Plasma-Sphäroidisierung, Verfahren der rotierenden Elektrode, Zertropfen einer Schmelze mittels Ultraschallanregung, Verdüsen einer Schmelze unter hoher Geschwindigkeit oder durch jedes beliebige andere bekannte Verfahren hergestellt werden.Basically, the coarse powder (grain size> 0.05 by plasma spheroidization, rotating electrode method, dropletization of a melt by means of ultrasonic excitation, atomization of a melt at high speed or by any other known method.

Ausführungsbeispiel I:Embodiment I: Siehe Fliessbild Fig. 1See flow diagram Fig. 1

Nach dem Verfahren der rotierenden Elektrode wurde ein der endgültigen Legierung entsprechendes Grobkornpulver folgender Zusammensetzung und Partikelgrösse hergestellt:

Figure imgb0001
A coarse-grain powder of the following composition and particle size, corresponding to the final alloy, was produced using the rotating electrode method:
Figure imgb0001

1500 g des Grobkornpulvers wurde gemischt und unter vakuum in ein metallenes Gefäss abgefüllt. Im vorliegenden Fall bestand letzteres aus einem dünnwandigen Hohlzylinder aus rostfreiem Stahl mit den folgenden Abmessungen:

Figure imgb0002
1500 g of the coarse grain powder was mixed and filled into a metal container under vacuum. In the present case, the latter consisted of a thin-walled hollow cylinder made of stainless steel with the following dimensions:
Figure imgb0002

Der Stahlzylinder wurde mit einem Deckel versehen und unter Vakuum verschlossen und verschweisst. Die auf diese Weise mit Pulver gefüllte Kapsel wurde einem heiss-isostatischen Pressvorgang mit folgenden Kenndaten unterworfen:

  • Isostatischer (hydrostatischer) Druck: 50 MPa
    Figure imgb0003
The steel cylinder was provided with a lid and sealed and welded under vacuum. The capsule filled with powder in this way was subjected to a hot isostatic pressing process with the following characteristics:
  • Isostatic (hydrostatic) pressure: 50 MPa
    Figure imgb0003

Nach erfolgtem Pressen wurde der Rohling einer Warmverformung durch Freiformschmieden bei einer Temperatur von ca. 800°C unterworfen. Dabei wurde im wesentlichen der Durchmesser des Werkstücks reduziert, so dass schliesslich ein Stab von 18 mm Durchmesser-vorlag.After pressing, the blank was subjected to hot forming by open die forging at a temperature of approx. 800 ° C. The diameter of the workpiece was essentially reduced so that a rod of 18 mm in diameter was finally available.

Das Verfahren ist.keineswegs auf diese Ausführungsvariante begrenzt. Das Ausgangspulver kann auch aus Pulvern verschiedener Zusammensetzung bestehen, welche gesamthaft die Endlegierung ergeben. Der Korndurchmesser (Partikelgrösse) des Pulvers kann prinzipiell zwischen 0,05 und 0,8 mm liegen. Der beim isostatischen Pressen angewandte Druck kann je nach Verhältnissen und Grösse des zu erzeugenden Werkstücks 50 bis 300 MPa, die dazugehörige Presstemperatur je nach Legierung 750 bis 950°C und die Zeitdauer Y2 h bis 5 h betragen. Die Warmverformungsoperation, welche in Schmieden, Pressen, Rundhämmern, Walzen etc. bestehen kann, wird vorteilhafterweise im Temperaturbereich zwischen 750 und 850°C durchgeführt. Statt eines Gefässes aus rostfreiem Stahl kann auch ein Hohlzylinder aus Kupfer oder einer duktilen Kupferlegierung zur Einkapselung des Pulvers verwendet werden.The process is in no way limited to this variant. The starting powder can also consist of powders of different compositions, which together form the final alloy. The grain diameter (particle size) of the powder can in principle be between 0.05 and 0.8 mm. The pressure used in isostatic pressing can be 50 to 300 MPa, depending on the conditions and size of the workpiece to be produced, the associated pressing temperature, depending on the alloy, 750 to 950 ° C and the time period Y2 h to 5 h. The hot-forming operation, which can consist of forges, presses, rotary hammers, rollers, etc., is advantageously carried out in the temperature range between 750 and 850 ° C. Instead of a stainless steel vessel, a hollow cylinder made of copper or a ductile copper alloy can also be used to encapsulate the powder.

Ausführungsbeispiel II:Working example II: Siehe Fliessbild Fig. 2.See flow diagram Fig. 2.

Nach dem Verfahren der rotierenden Elektrode wurden 2 grobkörnige Vorlegierungspulver der nachfolgenden Zusammensetzung und Partikelgrösse hergestellt:

Figure imgb0004
Figure imgb0005
 Two coarse-grained master alloy powders with the following composition and particle size were produced using the rotating electrode method:
Figure imgb0004
Figure imgb0005

Je 500 g der beiden Pulver wurden gemischt und von der Mischung 800 g unter Vakuum in einen Gummischlauch von 88 mm Innendurchmesser und 110 mm Länge abgefüllt. Die Pulvermischung entsprach somit einer Legierung folgender Endzusammensetzung:

Figure imgb0006
500 g each of the two powders were mixed and 800 g of the mixture were filled under vacuum into a rubber tube with an inside diameter of 88 mm and a length of 110 mm. The powder mixture thus corresponded to an alloy with the following final composition:
Figure imgb0006

Das im Gummischlauch eingekapselte Pulver wurde einem kalt-isostatischen Pressvorgang unterworfen:

Figure imgb0007
The powder encapsulated in the rubber tube was subjected to a cold isostatic pressing process:
Figure imgb0007

Der kalt vorgepresste Rohling wurde nach Entnahme aus dem Gummischlauch in einen Kupferzylinder folgender Abmessungen eingekapselt:

Figure imgb0008
The cold-pressed blank was encapsulated in a copper cylinder of the following dimensions after removal from the rubber hose:
Figure imgb0008

Der Kupferzylinder wurde mit einem Deckel versehen und unter Vakuum verschlossen und verschweisst. Hierauf wurde die auf diese Weise abgeschlossene Kapsel einem heiss-isostatischen Pressvorgang mit folgenden Kenndaten unterworfen:

Figure imgb0009
The copper cylinder was covered with a lid and sealed and welded under vacuum. The capsule sealed in this way was then subjected to a hot isostatic pressing process with the following characteristics:
Figure imgb0009

Nach dem Pressen wurde der Rohling einer Warmbehandlung unterworfen, welche in einer Homogenisierungsglühung unter folgenden Bedingungen entsprach:

Figure imgb0010
After pressing, the blank was subjected to a heat treatment, which corresponded to a homogenization anneal under the following conditions:
Figure imgb0010

Nach erfolgter Homogenisierung wurde das Werkstück einer Schmiedeoperation ähnlich Beispiel 1 unterworfen.After homogenization, the workpiece was subjected to a forging operation similar to Example 1.

Das Verfahren erschöpft sich nicht in dieser Ausführungsvariante. Als Ausgangspulver können beliebige Mischungen von Vorlegierungen und/oder Elementarpulver in beliebiger Anzahl (zwei oder mehr Pulverarten) Verwendung finden. Bedingung ist lediglich, dass durch das Mischen des Pulvers die gewünschte Endzusammensetzung erzielt wird.The method is not exhausted in this embodiment variant. Any mixture of master alloys and / or elementary powder in any number (two or more types of powder) can be used as the starting powder. The only requirement is that the desired final composition is achieved by mixing the powder.

Statt eines Gummischlauches kann auch ein geeigneter Kunststoffschlauch zum kalt-isostatischen Pressen, welches vorteilhafterweise bei Drücken von 300 bis 800 MPa während 1 bis 10 min durchgeführt wird, verwendet werden. Die Homogenisierungsglühung kann im Temperaturbereich von 900 bis 950°C während 1 bis 20 h durchgeführt werden.Instead of a rubber hose, a suitable plastic hose for cold isostatic pressing, which is advantageously carried out at pressures of 300 to 800 MPa for 1 to 10 minutes, can also be used. The Homogenization annealing can be carried out in the temperature range of 900 to 950 ° C for 1 to 20 h.

Als Legierungen für dieses Verfahren eignen sich insbesondere solche der nachfolgenden Zusammensetzung:

Figure imgb0011
Alloys of the following composition are particularly suitable as alloys for this process:
Figure imgb0011

Durch das erfindungsgemässe pulvermetallurgische Verfahren sowie die danach erzeugten Halbfabrikate und Fertigerzeugnisse wird die Herstellung von Werkstücken aus einer Gedächtnislegierung des Cu/Al- oder Cu/Al/Ni-Typs ermöglicht, welche gegenüber schmelzmetallurgisch oder nach herkömmlichen pulvermetallurgischen Methoden hergestellten Körpern eine bessere Homogenität aufweisen und eine wirtschaftliche Fertigung erlauben.The powder metallurgical process according to the invention and the semi-finished and finished products produced thereafter enable the production of workpieces from a memory alloy of the Cu / Al or Cu / Al / Ni type, which have better homogeneity compared to bodies produced by melt metallurgy or by conventional powder metallurgy methods, and allow economical production.

Claims (7)

1. Verfahren zur Herstellung einer Kupferbasis-Gedächtnislegierung auf pulvermetallurgischem Weg, dadurch gekennzeichnet, dass als Ausgangsmaterial ein grobkörniges Legierungspulver mit einer Partikelgrösse von 0,05 bis 0,8 mm Korndurchmesser benutzt wird, dass das Legierungspulver gemischt, in ein Gefäss abgefüllt, unter Vakuum verschlossen und unter einem Druck von 50 bis 300 MPa im Temperaturbereich von 750 bis 950°C während Y2 h bis 5 h heiss-isostatisch gepresst wird und dass der Pressling anschliessend bei einer Temperatur von 750 bis 850°C einer Warmverformungsoperation durch Schmieden, Pressen, Rundhämmern oder Walzen unterworfen wird.1. A process for producing a copper-based memory alloy by powder metallurgy, characterized in that a coarse-grained alloy powder with a particle size of 0.05 to 0.8 mm grain diameter is used as the starting material, that the alloy powder is mixed, filled into a vessel, under vacuum sealed and under a pressure of 50 to 300 MPa in the temperature range of 750 to 950 ° C during Y2 h to 5 h is hot isostatically pressed and that the compact is then at a temperature of 750 to 850 ° C a hot forming operation by forging, pressing, Round hammers or rollers is subjected. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Ausgangsmaterial ein Legierungspulver der Endzusammensetzung der Gedächtnislegierung benutzt wird.2. The method according to claim 1, characterized in that an alloy powder of the final composition of the memory alloy is used as the starting material. 3. Verfahren nach Anspruch l,'dadurch gekennzeichnet, dass als Ausgangsmaterial zwei oder mehrere Vorlegierungspulver benutzt werden.3. The method of claim l, 'characterized in that are used as starting material comprises two or more master alloy. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Gefäss eine Kapsel aus rostfreiem Stahl oder Kupfer benutzt und vakuumdicht verschweisst wird.4. The method according to claim 1, characterized in that a capsule made of stainless steel or copper is used as the vessel and is welded in a vacuum-tight manner. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Gefäss ein Gummischlauch benutzt und das Legierungspulver zunächst unter einem Druck von 300 bis 800 MPa während 1 bis 10 min kalt-isostatisch gepresst und der so erhaltene Pressling vor dem heiss-isostatischen Pressen in einen Kupferzylinder eingekapselt wird.5. The method according to claim 1, characterized in that a rubber tube is used as the vessel and the alloy powder is first cold-isostatically pressed under a pressure of 300 to 800 MPa for 1 to 10 minutes and the compact obtained in this way before the hot-isostatic pressing Copper cylinder is encapsulated. 6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Pressling nach dem heiss-isostatischen Pressen und vor der Warmverformungsoperation einer Homogenisierungsglühung unter Schutzgasatmosphäre im Temperaturbereich von 900 bis 9500C während einer Zeit von 1 bis 20 h unterworfen wird.6. The method according to claim 1, characterized in that the compact after the hot isostatic pressing and before the thermoforming operation is subjected to a homogenization annealing under a protective gas atmosphere in the temperature range from 900 to 950 0 C for a period of 1 to 20 h. 7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Ausgangsmaterial ein Legierungspulver benutzt wird, welches in der Endzusammensetzung einer Gedächtnislegierung mit 10,5 bis 15 Gew.-% Aluminium, 0 bis 6 Gew.-% Nickel, Rest Kupfer entspricht.7. The method according to claim 1, characterized in that an alloy powder is used as the starting material, which corresponds to the final composition of a memory alloy with 10.5 to 15 wt .-% aluminum, 0 to 6 wt .-% nickel, the rest copper.
EP81200691A 1980-08-07 1981-06-19 Method of manufacturing a copper-based memory alloy Expired EP0045985B1 (en)

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DE2856082A1 (en) * 1977-12-28 1979-07-12 Leuven Res & Dev Vzw METHOD FOR PRODUCING SOLID BODIES FROM COPPER-ZINC-ALUMINUM ALLOYS
EP0035601A1 (en) * 1980-03-03 1981-09-16 BBC Aktiengesellschaft Brown, Boveri & Cie. Process for making a memory alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH664515A5 (en) * 1984-12-20 1988-03-15 Bbc Brown Boveri & Cie Powder metallurgical prodn. of shape memory article - of beta brass type copper alloy contg. metal oxide dispersoid
GB2181745A (en) * 1985-08-28 1987-04-29 Avesta Nyby Powder Ab Hot-deformed powder metallurgy articles
GB2181745B (en) * 1985-08-28 1990-03-21 Avesta Nyby Powder Ab A process for the production of powder-metallurgy articles
WO2009043323A1 (en) * 2007-10-04 2009-04-09 Forschungszentrum Jülich GmbH Method for producing semi-finished products from niti shape memory alloys
US8916091B2 (en) 2007-10-04 2014-12-23 Forschungszentrum Juelich Gmbh Method for producing semi-finished products from NiTi shape memory alloys

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DE3162167D1 (en) 1984-03-15
US4410488A (en) 1983-10-18
EP0045985B1 (en) 1984-02-08

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