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EP0035069B1 - Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité - Google Patents

Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité Download PDF

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Publication number
EP0035069B1
EP0035069B1 EP19800200183 EP80200183A EP0035069B1 EP 0035069 B1 EP0035069 B1 EP 0035069B1 EP 19800200183 EP19800200183 EP 19800200183 EP 80200183 A EP80200183 A EP 80200183A EP 0035069 B1 EP0035069 B1 EP 0035069B1
Authority
EP
European Patent Office
Prior art keywords
temperature
memory alloy
way effect
weight
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19800200183
Other languages
German (de)
English (en)
Other versions
EP0035069A1 (fr
Inventor
Keith Dr. Melton
Olivier Dr. Mercier
Helmut Dr. Riegger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BBC Brown Boveri AG Switzerland
Original Assignee
BBC Brown Boveri AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BBC Brown Boveri AG Switzerland filed Critical BBC Brown Boveri AG Switzerland
Priority to EP19800200183 priority Critical patent/EP0035069B1/fr
Priority to DE8080200183T priority patent/DE3065930D1/de
Priority to PT7259081A priority patent/PT72590B/pt
Priority to JP2850381A priority patent/JPS56136945A/ja
Publication of EP0035069A1 publication Critical patent/EP0035069A1/fr
Application granted granted Critical
Publication of EP0035069B1 publication Critical patent/EP0035069B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • 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 is based on a shape memory alloy according to the preamble of claim 1 and on a method for stabilizing the two-way effect according to the preamble of claims 6 and 7.
  • Copper-rich shape memory alloys which have a ⁇ -phase ( ⁇ -brass type) capable of martensitic transformation have been known for a long time, e.g. B. from: R. Haynes, Some Observations on Isothermal Transformations of Eutectoid Aluminum Bronzes Below Their M s Temperatures, Journal of the Institute of Metals 1954-55, Vol. 83, pages 357-358; WA Rachinger, A "super-elastic" single crystal calibration bar, British Journal of Applied Physics, Vol. 9, June 1958, pages 250-252; RP Jewett, DJ Mack, Further Investigation of Copper-Aluminum Alloys in the Temperature Range below the Eutectoid, Journal of the Institute of Metals 1963-64, Vol.
  • these alloys show a clear memory effect compared to the also known Ni / Ti alloys in a temperature range of more than 100 ° C (which is particularly interesting for temperature monitoring devices and overcurrent switches), they are metastable. This means that they are subjected to diffusion-related phase changes in the desired temperature range. At the response temperature or just above it, the high-temperature ß phase changes and the memory effect is lost.
  • the invention is based on the object of specifying aging-resistant memory alloys of the Cu / Al or Cu / Al / Ni type at temperatures above 100 ° C. and a method for their production or stabilization of the two-way effect.
  • the method of stabilization consists essentially in a heat treatment of the alloy in the cast or hot-kneaded state after the last annealing in the ⁇ mixed crystal region in the temperature range from 600 to 950 ° C. (5 to 60 min) and before the induction of the two-way effect.
  • the heat treatment is an annealing in the temperature range of 200 to 350 ° C, which can in principle be carried out in two ways. In a first process, the alloy is quenched to room temperature after the last annealing in the ⁇ mixed crystal region and then tempered in the temperature range from 200 to 350 ° C. for 0.1 to 10 h.
  • the alloy is quenched from the ⁇ mixed crystal region directly into an oil, salt, metal or sand bath at 250 to 350 ° C. after the last annealing, held here for 0.5 to 10 min and finally at the Air cooled to room temperature.
  • this heat treatment is followed by a deformation of 1 to 6% in the range from 30 ° C. above to 50 ° C. below the point of the martensitic transformation M s in order to induce the two-way memory effect.
  • the process extends to the entire alloy group of the ⁇ -type Cu / Al and Cu / Al / Ni, in particular to alloys with 10 to 15% by weight aluminum, 0 to 6% by weight nickel, the rest copper.
  • the nickel in the alloys of the Cu / Al / Ni type can be partially or completely replaced by manganese, iron, cobalt or a mixture of at least two of these elements. Alloys produced by this process are resistant to aging up to 300 ° C, i. H. they mainly consist of the ⁇ high-temperature phase and show a stable two-way effect.
  • the alloy was produced by melt metallurgy, cast into an ingot and then hot-worked at 700 ° C. in such a way that a rod of 10 mm in diameter was produced. The rod was then subjected to annealing in the ⁇ mixed-crystal region for 10 min at 750 ° C. and quenched in water. Torsion samples with a total measuring length of 40 mm and a measuring length of 22 mm and a diameter of 3 mm were worked out from the rod. The two-way effect was induced by subjecting the samples to torsional stress near the martensitic transformation point M S (150 ° C) such that the torsional strain was gradually increased to 4 to 5% while going through a heating / cooling cycle. The samples were then heated at a temperature of Annealed at 300 ° C. The check showed that the memory effect had completely disappeared.
  • Example 1 An alloy according to Example 1 was melted, cast, thermoformed, annealed and quenched in water in a manner similar to Example 1. The rod obtained was then additionally tempered at 300 ° C. for 3 hours. After working out the samples according to Example I, the two-way effect was induced in the same way. After an additional annealing of the samples for 8 hours at 300 ° C, the two-way effect had not subsided in any way. Even after an annealing period of 500 h at 300 ° C, a two-way effect was still detectable - albeit weaker.
  • Example II An alloy according to Example I was melted, cast and thermoformed into a 10 mm diameter rod. A strip 1.5 mm thick and 10 mm wide was produced from this rod by hot rolling. Bending samples of 60 mm in length were cut from this and subjected to the usual annealing at 750 ° C. for 10 minutes. The samples were then quenched directly into a salt bath at 300 ° C., held at this temperature for 2 minutes and then cooled in air. During the cooling process, the samples were bent through an angle of 90 ° C, which induced the two-way effect. After heating to 300 ° C for several hours, the effect could be demonstrated in undiminished size.
  • the invention is not limited to the examples above.
  • the method can in principle be applied to all ß-copper alloys of the Cu / Al or Cu / Al / Ni type.
  • Another cheap legation has the following composition:
  • the level of the transition temperature Ms can apparently be greatly influenced by small variations in the aluminum content.
  • the above-mentioned substitutes manganese, iron, cobalt can also be used.
  • the method according to the invention creates memory alloys which are resistant to aging beyond the range of temperature monitoring customary in electrical engineering and in many industrial and household applications and have a stable two-way effect. In doing so, they are closing a previously existing gap in surveillance technology.

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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)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
  • Adornments (AREA)
  • Heat Treatment Of Articles (AREA)

Claims (7)

1. Alliage à mémoire de forme du type Cu/AI ou Cu/AI/Ni, caractérisé en ce qu'il est stable au vieillissement jusqu'à une température de 300° C, consiste principalement en la phase de haute température ß et manifeste un effet de réversibilité stable dans l'intervalle de température de 100 à 250° C.
2. Alliage à mémoire de forme suivant la revendication 1, caractérisé en ce qu'il consiste en 10 à 15% en poids d'aluminium, en 0 à 6% en poids de nickel et pour le reste en cuivre.
3. Alliage à mémoire de forme suivant la revendication 2, caractérisé en ce qu'il consiste en 13,25% en poids d'aluminium, en 3% en poids de nickel et pour le reste en cuivre.
4. Alliage à mémoire de forme suivant la revendication 2, caractérisé en ce qu'il consiste en 13% en poids d'aluminium, en 3% en poids de nickel et pour le reste en cuivre.
5. Alliage à mémoire de forme suivant la revendication 1, caractérisé en ce que le nickel dans les alliages du type Cu/AI/Ni est remplacé partiellement ou complètement par au moins un des éléments manganèse, fer et cobalt.
6. Procédé de stabilisation de l'effet de réversibilité jusqu'à une température de 300° C, d'un alliage à mémoire de forme, du type Cu/AI ou Cu/AI/Ni qui peut être présenté à l'état coulé ou à l'état travaillé à chaud, caractérisé en ce qu'on recuit l'alliage d'abord pendant 5 à 60 minutes dans l'intervalle de température de 600 à 950°C, on le trempe à l'eau et on le maintient pendant 0,1 à 10 heures à une température de 200 à 350°C et finalement, pour induire l'effet de réversibilité, on le déforme à raison de 1 à 6% dans l'intervalle de température de 30°C au-dessus à 50°C en dessous de la température de transformation Ms.
7. Procédé de stabilisation de l'effet de réversibilité jusqu'à une température de 300° C d'un alliage à mémoire de forme du type Cu/AI ou Cu/AI/Ni qui peut être présenté sous forme coulée ou sous forme travaillée à chaud, caractérisé en ce qu'on chauffe l'alliage d'abord pendant 5 à 60 minutes dans l'intervalle de température de 600 à 950° C, on le trempe dans un bain de métal, de sel, d'huile ou de sable à une température de 250 à 350°C, on le maintient à cette température pendant 0,5 à 10 minutes et on le refroidit ensuite à l'air, puis, pour induire l'effet de réversibilité, on le soumet à une déformation à raison de 1 à 6% dans l'intervalle de température de 30°C au-dessus à 50°C en dessous de la température de transformation Ms.
EP19800200183 1980-03-03 1980-03-03 Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité Expired EP0035069B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19800200183 EP0035069B1 (fr) 1980-03-03 1980-03-03 Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité
DE8080200183T DE3065930D1 (en) 1980-03-03 1980-03-03 Memory alloy based on cu-al or on cu-al-ni and process for the stabilisation of the two-way effect
PT7259081A PT72590B (de) 1980-03-03 1981-02-27 Harzmischung
JP2850381A JPS56136945A (en) 1980-03-03 1981-03-02 Shaped memory alloy based on cu al or cu al ni and stabilization of said alloy in two-direction effect

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19800200183 EP0035069B1 (fr) 1980-03-03 1980-03-03 Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité

Publications (2)

Publication Number Publication Date
EP0035069A1 EP0035069A1 (fr) 1981-09-09
EP0035069B1 true EP0035069B1 (fr) 1983-12-21

Family

ID=8186965

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800200183 Expired EP0035069B1 (fr) 1980-03-03 1980-03-03 Alliage à mémoire de forme à base de Cu-Al ou de Cu-Al-Ni et procédé pour la stabilisation de l'effet de réversibilité

Country Status (4)

Country Link
EP (1) EP0035069B1 (fr)
JP (1) JPS56136945A (fr)
DE (1) DE3065930D1 (fr)
PT (1) PT72590B (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416706A (en) * 1982-02-05 1983-11-22 Bbc Brown, Boveri & Company Limited Process to produce and stabilize a reversible two-way shape memory effect in a Cu-Al-Ni or a Cu-Al alloy
US4654092A (en) * 1983-11-15 1987-03-31 Raychem Corporation Nickel-titanium-base shape-memory alloy composite structure
US4533411A (en) * 1983-11-15 1985-08-06 Raychem Corporation Method of processing nickel-titanium-base shape-memory alloys and structure
JPS6130643A (ja) * 1984-07-20 1986-02-12 Kobe Steel Ltd 加工性の良好な硬質形状記憶合金
FR2590048B1 (fr) * 1985-07-19 1992-05-15 Souriau & Cie Dispositif de declenchement mecanique sequentiel
FR2617187B1 (fr) * 1987-06-24 1989-10-20 Cezus Co Europ Zirconium Procede d'amelioration de la ductilite d'un produit en alliage a transformation martensitique et son utilisation
FR2618163B1 (fr) * 1987-07-15 1992-04-30 Trefimetaux Procede d'education d'un objet en alliage a memoire de forme, permettant d'assurer la precision et la stabilite de l'effet memoire reversible.
EP0382109B1 (fr) * 1989-02-08 1993-12-08 Nivarox-FAR S.A. Procédé de conditionnement d'une pièce en alliage métallique à mémoire de forme présentant deux états de mémoire de forme réversibles
CH677677A5 (fr) * 1989-02-08 1991-06-14 Nivarox Sa
FR2643086B1 (fr) * 1989-02-10 1991-05-24 Nivarox Sa Procede de conditionnement d'une piece en alliage metallique a memoire de forme presentant deux etats de memoire de forme reversibles
CN108384984B (zh) * 2018-04-09 2020-01-03 天津理工大学 一种低成本高温形状记忆合金的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB433534A (en) * 1934-02-12 1935-08-12 Thomas Bolton And Sons Ltd Improved trolley wheels and the like devices for collecting electric current
BE758862A (fr) * 1969-11-12 1971-04-16 Fulmer Res Inst Ltd Perfectionnements relatifs au traitement d'alliages
GB1346047A (en) * 1969-11-12 1974-02-06 Fulmer Res Inst Ltd Treatment of alloys
JPS5818427B2 (ja) * 1974-07-05 1983-04-13 大阪大学長 繰り返し形状記憶性を有する金属物品の製法
JPS5337129A (en) * 1976-09-17 1978-04-06 Matsushita Electric Works Ltd Conductible spring material

Also Published As

Publication number Publication date
JPH0138867B2 (fr) 1989-08-16
DE3065930D1 (en) 1984-01-26
EP0035069A1 (fr) 1981-09-09
PT72590B (de) 1982-02-12
PT72590A (de) 1981-03-01
JPS56136945A (en) 1981-10-26

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