EP0035070B1 - Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel - Google Patents

Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel Download PDF

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Publication number
EP0035070B1
EP0035070B1 EP80200185A EP80200185A EP0035070B1 EP 0035070 B1 EP0035070 B1 EP 0035070B1 EP 80200185 A EP80200185 A EP 80200185A EP 80200185 A EP80200185 A EP 80200185A EP 0035070 B1 EP0035070 B1 EP 0035070B1
Authority
EP
European Patent Office
Prior art keywords
nickel
weight
powder
memory alloy
diameter
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
EP80200185A
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German (de)
English (en)
Other versions
EP0035070A1 (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
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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 DE8080200185T priority Critical patent/DE3070639D1/de
Priority to EP80200185A priority patent/EP0035070B1/fr
Priority to US06/239,646 priority patent/US4389250A/en
Priority to JP2850281A priority patent/JPS56136943A/ja
Publication of EP0035070A1 publication Critical patent/EP0035070A1/fr
Application granted granted Critical
Publication of EP0035070B1 publication Critical patent/EP0035070B1/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
    • 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
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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 is based on a memory alloy according to the preamble of claim 1.
  • Copper-rich memory alloys are known and have been described in various publications (e.g., U.S. Patent 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 has for its object to provide memory alloys based on Cu / Al, Cu / Al / Ni and NiAI, which form dense, compact bodies with good mechanical properties and at the same time to reproducible values of the transition temperature and others related to the memory effect Have sizes processed.
  • the essence of the invention consists in the presence of metal oxides which are embedded in the form of finely divided dispersoids in the metallic matrix of the alloys.
  • Metal oxides of this type can be introduced into the end product both as separate powders and as natural contents of the starting substances, the production of which is advantageously carried out by powder metallurgy.
  • An essential feature of the process consists in neither starting from elementary powders nor from a starting powder corresponding to the final alloy, but instead using 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 crystallite of the finished body can largely be predetermined. Grain growth is not to be feared thanks to the presence of the dispersoids. Coherent oxide skins that prevent homogenization and impair mechanical properties are avoided.
  • the dispersoids are Y 2 0 3 and Ti0 2 or any mixtures of these oxides. Their content is 0.5 to 2% by weight of the total mass of the alloy and their particles have an average diameter of 10 ⁇ (1 nm) to 1 ⁇ m.
  • Y 2 0 3 and Ti0 2 are separately mixed into the metal powders in the form of very fine particles and ground and mechanically alloyed under an organic solvent (toluene, ethyl alcohol) which keeps out atmospheric oxygen in a ball mill or attritor.
  • organic solvent toluene, ethyl alcohol
  • a round rod was made from a memory alloy with the following final composition:
  • the powder mixture was dried and then 240 g were poured into a soft annealed copper tube with an inside diameter of 18 mm and a wall thickness of 2 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 10,000 bar and the compact was reduced and presintered in a hydrogen / nitrogen stream at a temperature of 750 ° C. for 2 hours and then in a stream of argon at a temperature of 800 ° C. for 25 hours finish sintered.
  • the workpiece was then alternately subjected to 2 round hammer operations and a homogenization anneal at 900 ° C each.
  • the rod hammered down to 6 mm was subjected to a final annealing at 1000 ° C. for 10 minutes in a stream of argon and quenched in water.
  • the density of the matrix was 99.5% of the theoretical value.
  • the martensitic transformation temperature Mg was 150 ° C.
  • the average crystallite diameter was 28 ⁇ m.
  • a square bar was made from a memory alloy of the following final composition:
  • the powders A, B, C and D * (100% titanium dioxide) were weighed out as follows and mixed, ground and mechanically alloyed in a ball mill for 12 hours under ethyl alcohol:
  • 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 warm drawing 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 matrix of the finished rod was 99.8% of the theoretical value.
  • the transition temperature M s was 170 ° C.
  • the average crystallite diameter was 26 ⁇ m with a Vickers hardness (HV10) of 280 units.
  • a round plate was made from a memory alloy of the following final composition:
  • the raw sintered body was turned to a diameter of 58 mm, introduced into a soft-annealed can made of soft iron with an outside diameter of 64 mm and completely encapsulated by placing 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. By alternating upsetting and annealing at 1200 ° C, the height of the cylinder was successively reduced to approximately 32 mm, the material condensing to approximately 95% of the theoretical density and now having 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 reduced diameter and in several operations, which were interrupted by intermediate annealing, at temperatures between 1 220 ° C and 1 100 ° C forged to the finished shape.
  • 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.
  • the plate was quenched in water.
  • the density of the matrix was 99.2-99.5% of the theoretical value.
  • the temperature Mg of the martensitic transformation was 130 ° C.
  • a sheet was made from a memory alloy of the following final composition:
  • the raw sintered body was turned to a diameter of 58 mm, inserted into a soft-annealed tube made of corrosion-resistant steel with an outside diameter of 64 mm and completely encapsulated by putting on lids 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. By alternating upsetting and annealing at 1,180 ° C, the height of the cylinder was successively reduced to approx. 64 mm, the material condensing to approx. 95% of the theoretical density and now having a diameter of 70 mm corresponding to the recipient of the extrusion press . After an additional homogenization annealing at 1200 ° C.
  • the preformed circular body was inserted into an extrusion press and pressed at a temperature of 1200 ° C. to form a flat bar of rectangular cross section of 10 ⁇ 50 mm.
  • the reduction ratio (decrease in cross section) was 7.8: 1.
  • the rod was then homogenized at a temperature of 1,300 ° C. for 30 minutes and then a piece of 250 mm in length was cut out. This piece was rolled down in several successive hot rolling operations with corresponding intermediate annealing at 1,250 to 1,150 ° C. to a sheet of 2 mm thickness.
  • Each 2 stitches of cross rolls, each with a 20% reduction in cross-section were interrupted by 1 stitch each of longitudinal rolls with a 5% reduction in cross-section (stitch for straightening the sheet).
  • the dispersion memory alloys according to the invention produced by the aforementioned processes have a fine-grained structure with a crystallite diameter of at most 100 ⁇ m.
  • a crystallite diameter of at most 100 ⁇ m In general - depending on the choice of the starting powder - an average crystallite diameter of 30 I Lm and less can be achieved.
  • the invention is not restricted to the parameters specified in the examples. In general, the powder compositions and mixtures can be varied and substituted in such a way that the following material limits for the metallic matrix are reached:
  • Nickel can also be partially or completely replaced by at least one of the following elements:
  • Nickel can also be partially or completely replaced by cobalt.

Claims (2)

1. Alliage à mémoire contenant des dispersoïdes, à base d'un cristal mixte qui est présent sous la phase β, caractérisé en ce qu'il est fabriqué, par la métallurgie des poudres, à partir de préalliages et de prémélanges, en ce que sa matrice formée par la phase β se compose, en poids, de 10,5 à 15 % d'aluminium, de 0 à 6 % de nickel, le reste étant du cuivre, où le nickel peut être remplacé en partie ou en totalité par au moins un des éléments manganèse, fer, cobalt, ou en poids, de 17 à 26 % d'aluminium, le reste étant du nickel plus du cobalt, en ce qu'il présente une structure à grain fin avec un diamètre de cristaux de 100 µm maximum et en ce que, dans la matrice formée par la phase β, il se trouve de 0,5 à 2 % en poids de Y203 et/ou Ti02 sous la forme de dispersoïdes finement dispersés ayant un diamètre moyen de particules de 10 A (1 nm) à 1 µm.
2. Alliage à mémoire suivant la revendication 1, caractérisé en ce que sa structure présente un diamètre moyen de cristaux de 30 µm, qui subsiste encore après un recuit d'une durée quelconque à une température pouvant atteindre 950 °C.
EP80200185A 1980-03-03 1980-03-03 Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel Expired EP0035070B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE8080200185T DE3070639D1 (en) 1980-03-03 1980-03-03 Memory alloy based on a highly cupriferous or nickelous mixed crystal
EP80200185A EP0035070B1 (fr) 1980-03-03 1980-03-03 Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel
US06/239,646 US4389250A (en) 1980-03-03 1981-03-02 Memory alloys based on copper or nickel solid solution alloys having oxide inclusions
JP2850281A JPS56136943A (en) 1980-03-03 1981-03-02 Memory alloy based on solid solution rich in copper or nickel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP80200185A EP0035070B1 (fr) 1980-03-03 1980-03-03 Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel

Publications (2)

Publication Number Publication Date
EP0035070A1 EP0035070A1 (fr) 1981-09-09
EP0035070B1 true EP0035070B1 (fr) 1985-05-15

Family

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Family Applications (1)

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EP80200185A Expired EP0035070B1 (fr) 1980-03-03 1980-03-03 Alliage-mémoire à base d'une solution solide riche en cuivre ou en nickel

Country Status (4)

Country Link
US (1) US4389250A (fr)
EP (1) EP0035070B1 (fr)
JP (1) JPS56136943A (fr)
DE (1) DE3070639D1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4752334A (en) * 1983-12-13 1988-06-21 Scm Metal Products Inc. Dispersion strengthened metal composites
US5320800A (en) * 1989-12-05 1994-06-14 Arch Development Corporation Nanocrystalline ceramic materials
AUPN317095A0 (en) * 1995-05-24 1995-06-22 Unisearch Limited Manufacture of intermetallic compounds
US6106642A (en) * 1998-02-19 2000-08-22 Boston Scientific Limited Process for the improved ductility of nitinol
JP4709296B2 (ja) 2009-04-17 2011-06-22 日立電線株式会社 希薄銅合金材料の製造方法
JP5077416B2 (ja) * 2010-02-08 2012-11-21 日立電線株式会社 軟質希薄銅合金材料、軟質希薄銅合金線、軟質希薄銅合金板、軟質希薄銅合金撚線およびこれらを用いたケーブル、同軸ケーブルおよび複合ケーブル
JP5589754B2 (ja) 2010-10-20 2014-09-17 日立金属株式会社 希薄銅合金材料、及び耐水素脆化特性に優れた希薄銅合金材料の製造方法
CN103547691B (zh) * 2011-05-26 2016-08-17 泰尔茂株式会社 医疗用具用复合材料及其制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035602A1 (fr) * 1980-03-03 1981-09-16 BBC Aktiengesellschaft Brown, Boveri & Cie. Procédé de préparation par métallurgie des poudres d'un alliage-mémoire à base de cuivre, de zinc et d'aluminium
EP0035601A1 (fr) * 1980-03-03 1981-09-16 BBC Aktiengesellschaft Brown, Boveri & Cie. Procédé de fabrication d'un alliage-mémoire

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
DD2444A (fr) *
US2947068A (en) * 1958-04-18 1960-08-02 John S Nachtman Aluminum base powder products
DE1433100A1 (de) * 1961-04-25 1968-10-10 Grant Nicholas John Dispersionsverfestigte Metalle und Verfahren zu ihrer Herstellung
US3143789A (en) * 1962-08-31 1964-08-11 Du Pont Dispersion strengthened metal composition
BE758862A (fr) * 1969-11-12 1971-04-16 Fulmer Res Inst Ltd Perfectionnements relatifs au traitement d'alliages
US3909309A (en) * 1973-09-11 1975-09-30 Int Nickel Co Post working of mechanically alloyed products
JPS5619393B2 (fr) * 1974-01-24 1981-05-07
JPS53925B2 (fr) * 1974-05-04 1978-01-13
JPS5319109A (en) * 1976-08-06 1978-02-22 Nok Corp Sintered c# alloy for sliding material
JPS5393115A (en) * 1977-01-26 1978-08-15 Hiroyasu Mitani Method of making aluminum bronze with sound insulating and vibration absorbing property
JPS5393107A (en) * 1977-01-26 1978-08-15 Hiroyasu Mitani Soun arresting and vibration dampening aluminium and bronze sintered alloy
NL7714494A (nl) * 1977-12-28 1979-07-02 Leuven Res & Dev Vzw Werkwijze voor het maken van vaste lichamen uit koper-zinkaluminiumlegeringen.
US4292079A (en) * 1978-10-16 1981-09-29 The International Nickel Co., Inc. High strength aluminum alloy and process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035602A1 (fr) * 1980-03-03 1981-09-16 BBC Aktiengesellschaft Brown, Boveri & Cie. Procédé de préparation par métallurgie des poudres d'un alliage-mémoire à base de cuivre, de zinc et d'aluminium
EP0035601A1 (fr) * 1980-03-03 1981-09-16 BBC Aktiengesellschaft Brown, Boveri & Cie. Procédé de fabrication d'un alliage-mémoire

Also Published As

Publication number Publication date
DE3070639D1 (en) 1985-06-20
US4389250A (en) 1983-06-21
EP0035070A1 (fr) 1981-09-09
JPS56136943A (en) 1981-10-26

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