EP0035601B1 - Procédé de fabrication d'un alliage-mémoire - Google Patents

Procédé de fabrication d'un alliage-mémoire Download PDF

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Publication number
EP0035601B1
EP0035601B1 EP80200184A EP80200184A EP0035601B1 EP 0035601 B1 EP0035601 B1 EP 0035601B1 EP 80200184 A EP80200184 A EP 80200184A EP 80200184 A EP80200184 A EP 80200184A EP 0035601 B1 EP0035601 B1 EP 0035601B1
Authority
EP
European Patent Office
Prior art keywords
powder
temperature
process according
soft
copper
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
EP80200184A
Other languages
German (de)
English (en)
Other versions
EP0035601A1 (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 DE8080200184T priority Critical patent/DE3065931D1/de
Priority to EP80200184A priority patent/EP0035601B1/fr
Priority to US06/239,626 priority patent/US4365996A/en
Priority to JP2850481A priority patent/JPS56136942A/ja
Publication of EP0035601A1 publication Critical patent/EP0035601A1/fr
Application granted granted Critical
Publication of EP0035601B1 publication Critical patent/EP0035601B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/006Resulting in heat recoverable alloys with a memory effect
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0425Copper-based alloys

Definitions

  • the invention is based on a method for producing a memory alloy according to the preamble of claim 1.
  • Memory alloys of the Cu / Al type or of the Cu / Al type plus at least one of the elements Ni, Fe, Mn and Co are known and have been described in various publications (for example US Pat. No. 3,783,037). Such memory alloys, which belong to the general type with the ⁇ high-temperature phase, are generally produced by melt metallurgy.
  • the invention is based on the object of specifying a production method for memory alloys of the Cu / AI type or of the Cu / AI type plus at least one of the elements Ni, Fe, Mn and Co which results in dense, compact bodies with good mechanical properties and at the same time too precisely reproducible values of the transition temperature and other quantities related to the memory effect.
  • the essence of the new process is not to start from elementary powders or from a starting powder corresponding to the final alloy, but to use a mixture of pre-alloyed powders and specially composed powder mixtures. This allows the required ductility to be optimally adapted to the processing process with extensive freedom in terms of composition.
  • the grain size of the crystallites of the finished body can largely be predetermined. Grain growth is not to be feared. Coherent oxide skins that prevent homogenization and impair mechanical properties are avoided. If a certain small percentage is present, the metal oxides are present in finely divided form as dispersoids and have a beneficial effect on the mechanical properties of the end product, preventing grain growth.
  • a round rod was made from a memory alloy with the following final composition:
  • thermomechanical processing consisted of round hammering at 950 ° C, the diameter of the rod being reduced to 18 mm in the first round hammering stitch and by 2 mm for each further stitch.
  • the procedure was such that homogenization annealing followed after 2 thermomechanical operations.
  • the rod hammered down to 8 mm in diameter was finally subjected to a final annealing in a stream of argon for 15 minutes at a temperature of 950 ° C. and immediately quenched in water.
  • the test showed a density of 99.5-99.8% of the theoretical value for the workpiece.
  • thermomechanical machining / homogenization can be continued for as long as required until the final shape of the workpiece is reached. When the theoretical density is reached, further homogenization is generally no longer necessary.
  • a round rod was made from a memory alloy with the following final composition:
  • Example I The powders given in Example I were weighed out as follows and mixed in a tumble mixer for 15 minutes:
  • a tape was made from a memory alloy of the following final composition:
  • Example I The powders given in Example I were weighed out as follows and mixed in a tumble mixer for 12 minutes:
  • this powder mixture were filled into a soft-annealed tombac tube with an inner diameter of 20 mm and a wall thickness of 1.6 mm and completely encapsulated by covering the ends and soldering under an argon atmosphere.
  • the tube and powder were then isostatically pressed at a pressure of 12,000 bar and the compact was reduced and presintered in a stream of hydrogen at a temperature of 850 ° C. for 11 ⁇ 2 hours and then sintered in a stream of argon at a temperature of 820 ° C. for 22 hours.
  • the workpiece was then reduced in 2 round hammer passes at a temperature of 900 ° C to 18 or 16 mm in diameter and homogenized in a stream of argon at 920 ° C for 1 h. This was followed by two round hammer passes at 900 ° C, so that the rod finally had a diameter of 13 mm.
  • the rod was rolled down in several successive hot rolling operations, each with a 20-25% reduction in cross section, to form a strip 1.5 mm thick and 20 mm wide.
  • a square bar was made from a memory alloy of the following final composition:
  • the powders given under the example were weighed out as follows and mixed in a tumble mixer for 10 min.
  • the reduction ratio (decrease in cross-section) was 11: 1.
  • the rod was then homogenized at a temperature of 920 ° C. for 30 minutes and then pulled down in 2 passes on a warming bench at a temperature of 750 ° C. to an edge length of 6 mm. After the final annealing at 900 ° C. for 15 minutes in a stream of argon, the rod was quenched in water. The density of the finished rod was 99.8% of the theoretical value.
  • a round plate was made from a memory alloy of the following final composition:
  • Example I The powders given in Example I were weighed out as follows and mixed in a tumble mixer for 15 minutes:
  • 1000 g of this powder mixture were filled into a plastic tube with an inner diameter of 66 mm and pressed isostatically at a pressure of 12,000 bar to a cylinder with a diameter of 60 mm and a height of 80 mm.
  • the green body was reduced in a hydrogen / nitrogen stream at a temperature of 880 ° C. for 1 h and presintered and then sintered in a stream of argon at a temperature of 930 ° C. for 25 h.
  • the raw sintered body was turned to a diameter of 58 mm, introduced into a soft-annealed box made of soft iron with an outside diameter of 64 mm and completely encapsulated by putting the lid on and soldering in an argon atmosphere.
  • the workpiece produced in this way was subjected to thermomechanical processing under a hot press, interrupted by homogenization annealing.
  • the height of the cylinder was successively reduced to approx. 32 mm, whereby the material condensed to approx. 95% of the theoretical density and now had a diameter of 70 mm corresponding to the die.
  • the preformed circular plate with parallel flat end faces was inserted in a forging die with a different diameter and in several operations, which were interrupted by intermediate annealing, at temperatures between 1000 ° C and 750 ° C the finished form forged.
  • the 20 mm thick plate had a radial bead of 5 x 5 mm on the upper side and a central recess of 20 mm diameter and 5 mm axial depth on the lower side. After a final annealing at 980 ° C for 15 minutes, the plate was quenched in water. The density was 99.299.5% of the theoretical value.
  • the powder mixtures are within the following limits:
  • Isostatic pressing requires pressures of at least 8000 bar.
  • the compact is advantageously reduced and presintered in the temperature range from 700 to 1000 ° C. for at least 30 minutes in a stream of hydrogen or hydrogen / nitrogen.
  • the sintering of the compact must be above the temperature of the eutectoid transformation, i.e. H. at least 700 ° C for 10 h in a stream of argon to achieve the most homogeneous structure possible.
  • thermomechanical processing which can consist of hot pressing, hot extrusion, hot forging, hot rolling, hot drawing and / or hot round hammering, should be carried out at temperatures between 700 and 1000 ° C, as well as the intermediate homogenization in the inert gas stream (intermediate annealing) at at least 700 ° C for at least 30 min.
  • the final annealing in a stream of argon is carried out at temperatures between 700 and 1050 ° C. ( ⁇ -mixed crystal region) for 10 to 15 minutes and the workpiece is then immediately quenched in water.
  • thermomechanical processing it is expedient to encapsulate the material beforehand in a ductile metallic shell that does not react chemically with it, which is removed mechanically or chemically at the end of the shaping as a surface layer in most applications.
  • Soft-annealed metals and alloys such as copper, copper alloys and soft iron are particularly suitable as materials for the casing. Encapsulation can take place immediately before the thermomechanical processing, in that the sintered body undergoes a mechanical surface treatment beforehand by turning, milling, planing, etc., or the powder can be filled directly into a suitable tube, a can, etc., instead of into a rubber or plastic tube will.
  • the powder metallurgical method according to the invention enables the production of workpieces from a memory alloy of the Cu / Al and Cu / Al / Ni type, which compared to conventional, i.e. H. bodies produced by melt metallurgy have a fine-grained structure and optionally contain dispersoids in the form of finely divided oxide particles.
  • the mechanical properties, in particular the elongation, notch toughness and the working capacity of such workpieces are significantly better than those of cast and / or hot-kneaded bodies. This opens up a further area of application for this type of alloy.

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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)
  • Powder Metallurgy (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)

Claims (8)

1. Procédé de production d'un alliage à mémoire du type Cu/AI ou du type Cu/AI plus au moins l'un des éléments Ni, Fe, Mn, Co, caractérisé en ce qu'il comprend les stades suivants:
a) préparation d'une poudre A d'une granulométrie de 10 à 200 ¡.lm à partir d'un alliage maître riche en cuivre contenant 84 à 99% en poids de cuivre et pour le reste de l'aluminium, préparation d'une poudre B d'une granulométrie de 5 à 100 µm par mélange et/ou alliage de 95 à 99,5% en poids de poudre d'aluminium avec 0,5 à 5% en poids de poudre de cuivre, préparation d'ur,e poudre C d'une granulométrie de 10 à 100 µm à partir d'au moins un des éléments nickel, rer, manganèse, cobalt;
b) mélange de 0,5 à 10% en poids de la poudre B et de 0 à 6% en poids de la poudre C et de la poudre A pour le reste dans un mélangeur à poudres pendant au moins 10 minutes;
c) pressage isostatique du mélange des poudres dans un tube souple en matière synthétique ou en caoutchouc ou dans un tube en cuivre ou en fer adouci par recuit ou en un alliage de cuivre ductile sous une pression d'au moins 8000 bars;
d) réduction et préfrittage de l'ébauche pressée obtenue en c) dans un courant d'hydrogène ou d'hydrogène/azote à une température de 700 à 1000° C pendant au moins 30 minutes;
e) frittage de l'ébauche réduite et préfrittée dans un courant d'argon à au moins 700° C pendant au moins 10 heures;
f) traitement thermomécanique à une température de 700 à 1000° C en alternance avec des homogénéisations dans un courant de gaz inerte à une température d'au moins 700°C pendant au moins 30 minutes;
g) recuit final dans un courant d'argon à une température de 700 à 1050°C pendant 10 à 15 minutes et trempe à l'eau immédiatement ensuite.
2. Procédé suivant la revendication 1, caractérisé en ce que le pressage isostatique est exécuté dans un tube souple en matière synthétique ou en caoutchouc et la pièce frittée est soumise avant le stade f) à un traitement de surface mécanique et est encapsulée ensuite dans une enveloppe en cuivre ou en fer adouci par recuit ou en un alliage de cuivre ductile.
3. Procédé suivant la revendication 2, caractérisé en ce que le traitement de surface mécanique consiste en un tournage et la pièce ainsi travaillée est introduite dans un tube de cuivre adouci par recuit, puis celui-ci est complètement fermé par obturation aux extrémités au moyen de bouchons et soudure en atmosphère d'argon.
4. Procédé suivant la revendication 1, caractérisé en ce que le pressage isostatique en c) est exécuté dans un tube en cuivre ou en fer adouci par recuit ou en alliage de cuivre ductile et l'enveloppe ainsi formée n'est éliminée par voie mécanique ou chimique qu'après le stade g).
5. Procédé suivant la revendication 1, caractérisé en ce que le traitement thermomécanique du stade f) consiste en un pressage à chaud, une extrusion à chaud, un forgeage à chaud, un laminage à chaud ou un étirage à chaud.
6. Procédé suivant la revendication 1, caractérisé en ce que le traitement thermomécanique au stade f) consiste en un martelage circulaire.
7. Procédé suivant la revendication 6, caractérisé en ce que la pièce présente la forme d'un barreau et au cours du stade f) 2 passes de martelage circulaire à 950°C sont exécutées en alternance avec un recuit d'homogénéisation à 950° C de manière à effectuer au total 6 passes de martelage circulaire et 2 à 3 recuits d'homogénéisation.
8. Procédé suivant la revendication 1, caractérisé en ce que le cycle indiqué au stade f) est poursuivi à volonté jusqu'à atteindre la forme finale de la pièce. >n
EP80200184A 1980-03-03 1980-03-03 Procédé de fabrication d'un alliage-mémoire Expired EP0035601B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE8080200184T DE3065931D1 (en) 1980-03-03 1980-03-03 Process for making a memory alloy
EP80200184A EP0035601B1 (fr) 1980-03-03 1980-03-03 Procédé de fabrication d'un alliage-mémoire
US06/239,626 US4365996A (en) 1980-03-03 1981-03-02 Method of producing a memory alloy
JP2850481A JPS56136942A (en) 1980-03-03 1981-03-02 Production of copper - aluminum - nickel memory alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP80200184A EP0035601B1 (fr) 1980-03-03 1980-03-03 Procédé de fabrication d'un alliage-mémoire

Publications (2)

Publication Number Publication Date
EP0035601A1 EP0035601A1 (fr) 1981-09-16
EP0035601B1 true EP0035601B1 (fr) 1983-12-21

Family

ID=8186966

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200184A Expired EP0035601B1 (fr) 1980-03-03 1980-03-03 Procédé de fabrication d'un alliage-mémoire

Country Status (4)

Country Link
US (1) US4365996A (fr)
EP (1) EP0035601B1 (fr)
JP (1) JPS56136942A (fr)
DE (1) DE3065931D1 (fr)

Families Citing this family (19)

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Publication number Priority date Publication date Assignee Title
EP0035070B1 (fr) * 1980-03-03 1985-05-15 BBC Aktiengesellschaft Brown, Boveri & Cie. Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel
EP0045985B1 (fr) * 1980-08-07 1984-02-08 BBC Aktiengesellschaft Brown, Boveri & Cie. Procédé de fabrication d'un alliage à mémoire à base de cuivre
CH659482A5 (de) * 1982-02-05 1987-01-30 Bbc Brown Boveri & Cie Verfahren zur erzeugung eines reversiblen zweiweg-gedaechtniseffekts in einem bauteil aus einer einen einwegeffekt zeigenden legierung.
JPS6029406A (ja) * 1983-07-27 1985-02-14 Tohoku Metal Ind Ltd 焼結体の製造方法
US4464205A (en) * 1983-11-25 1984-08-07 Cabot Corporation Wrought P/M processing for master alloy powder
US4759293A (en) * 1986-06-30 1988-07-26 Davis Jr Thomas O Article using shape-memory alloy to improve and/or control the speed of recovery
US4839479A (en) * 1986-06-30 1989-06-13 Davis Jr Thomas O Article using shape-memory alloy to improve and/or control the speed of recovery
US4836979A (en) * 1988-06-14 1989-06-06 Inco Limited Manufacture of composite structures
US5443615A (en) * 1991-02-08 1995-08-22 Honda Giken Kogyo Kabushiki Kaisha Molded ceramic articles
JPH083133B2 (ja) * 1990-07-12 1996-01-17 日立粉末冶金株式会社 船外機用バルブシート材およびその製造方法
US5344605A (en) * 1991-11-22 1994-09-06 Sumitomo Electric Industries, Ltd. Method of degassing and solidifying an aluminum alloy powder
US6132486A (en) * 1998-11-09 2000-10-17 Symmco, Inc. Powdered metal admixture and process
JP4424810B2 (ja) * 2000-03-27 2010-03-03 株式会社小松製作所 焼結材料
US6548013B2 (en) * 2001-01-24 2003-04-15 Scimed Life Systems, Inc. Processing of particulate Ni-Ti alloy to achieve desired shape and properties
JP4282284B2 (ja) * 2001-08-22 2009-06-17 株式会社小松製作所 履帯
DE102005032544B4 (de) * 2004-07-14 2011-01-20 Hitachi Powdered Metals Co., Ltd., Matsudo Abriebsresistente gesinterte Aluminiumlegierung mit hoher Festigkeit und Herstellugsverfahren hierfür
US10245639B2 (en) * 2012-07-31 2019-04-02 United Technologies Corporation Powder metallurgy method for making components
JP7216842B2 (ja) * 2019-12-11 2023-02-01 株式会社ダイヤメット Cu-Ni-Al系焼結合金の製造方法
CN113684389B (zh) * 2021-08-16 2022-07-29 大连大学 一种控制γ相分布提高Co-Ni-Al磁记忆合金超弹性的方法

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Also Published As

Publication number Publication date
JPS56136942A (en) 1981-10-26
US4365996A (en) 1982-12-28
EP0035601A1 (fr) 1981-09-16
DE3065931D1 (en) 1984-01-26

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