EP0088604B1 - Nickel/titanium/copper shape memory alloys - Google Patents

Nickel/titanium/copper shape memory alloys Download PDF

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Publication number
EP0088604B1
EP0088604B1 EP83301168A EP83301168A EP0088604B1 EP 0088604 B1 EP0088604 B1 EP 0088604B1 EP 83301168 A EP83301168 A EP 83301168A EP 83301168 A EP83301168 A EP 83301168A EP 0088604 B1 EP0088604 B1 EP 0088604B1
Authority
EP
European Patent Office
Prior art keywords
atomic percent
titanium
nickel
alloys
shape memory
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
EP83301168A
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German (de)
English (en)
French (fr)
Other versions
EP0088604A2 (en
EP0088604A3 (en
Inventor
John David Harrison
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.)
Raychem Corp
Original Assignee
Raychem Corp
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 Raychem Corp filed Critical Raychem Corp
Priority to AT83301168T priority Critical patent/ATE28669T1/de
Publication of EP0088604A2 publication Critical patent/EP0088604A2/en
Publication of EP0088604A3 publication Critical patent/EP0088604A3/en
Application granted granted Critical
Publication of EP0088604B1 publication Critical patent/EP0088604B1/en
Expired legal-status Critical Current

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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
    • C22C14/00—Alloys based on titanium

Definitions

  • Alloys which exhibit the shape memory effect are now well-known, and include a number of alloys comprising nickel and titanium. See, e.g., U.S. Pat. Nos. 3,174,851; 3,351,463; and 3,753,700.
  • a wide variety of useful articles, such as electrical connectors, actuators, and pipe couplings can be made from such alloys. See e.g. U.S. Pat. Nos. 3,740,839; 4,035,077; and 4,198,081.
  • Shape memory alloys also find use in switches, such as are disclosed in U.S. Patent No. 4,205,293, and actuators, etc.
  • As temperature should be above ambient, so that the alloy element will remain in its martensitic state unless heated either externally or by the passage of an electric current through it.
  • the desired M 50 will generally be above 0°C for an As above, say, 20°C.
  • shape memory alloy element may be subject to repeated cycling between the austenitic and martensitic states under load
  • shape memory "fatigue” may be a problem.
  • shape memory alloys are unstable in the range of 100°C to 500°C if the titanium content is below 49.9 atomic percent (See Wasilewski et al., Met. Trans., v. 2, pp. 229-38 (1971)).
  • the instability manifests itself as a change (generally an increase) in M s , the temperature at which the austenite to martensite transition begins, between the annealed alloy and the same alloy which has been further tempered.
  • Annealing means heating to a sufficiently high temperature and holding at the temperature long enough to give a uniform, stress-free condition, followed by sufficiently rapid cooling to maintain that condition. Temperatures around 900°C for about 10 minutes are generally sufficient for annealing, and air cooling is generally sufficiently rapid, though quenching in water is necessary for some of the low Ti compositions.
  • Tempering here means holding at an intermediate temperature for a suitably long period (such as a few hours at 200-400°C). The instability thus makes the low titanium alloys disadvantageous for shape memory applications, where a combination of high yield strength and reproducible M s is desired.
  • this invention provides a shape memory alloy having an M s of at least 0°C and consisting, apart from impurities, of nickel, titanium and copper within an area defined on a nickel, titanium, and copper ternary phase diagram by a quadrilateral with its first vertex at 42 atomic percent nickel, 49.5 atomic percent titanium, and 8.5 atomic percent copper; its second vertex at 35.5 atomic percent nickel, 49.5 atomic percent titanium, and 15 atomic percent copper; its third vertex at 41 atomic percent nickel, 44 atomic percent titanium, and 15 atomic percent copper, and its fourth vertex at 44.25 atomic percent nickel, 47.25 atomic percent titanium, and 8.5 atomic percent copper.
  • the alloys according to the invention advantageously display the properties of high strength and an M 50 (138 MPa) (20 ksi) temperature above 0°C. The alloys also display unexpectedly good temper stability, workability and machinability.
  • Shape memory alloys according to the invention may conveniently be produced by the methods described in, for example, U.S. Pats. No. 3,753,700 and 4,144,057.
  • the following example illustrates the method of preparation and testing of samples of memory alloys.
  • the resulting ingots were hot swaged and hot rolled in air at approximately 850°C to produce strip of approximately 0.5 mm (0.025 ins) thickness. After de-scaling, samples were cut from the strip and vacuum annealed at 900°C.
  • the annealed samples were cooled and re-heated while the change in resistance was measured. From the resistance-temperature plot, the temperature at which the martensitic transformation was complete, the M f temperature, was determined. The transformation temperature of each alloy was determined as the temperature at which 50% of the total deformation had occurred under 138 MPa (20 ksi) load, referred to as the M 50 (138 MPa) (20 ksi) temperature.
  • composition of the alloy of this invention can be described by reference to an area on a nickel, titanium, and copper ternary composition diagram.
  • the general area of the alloy on the composition diagram is shown by the small triangle in Figure 1. This area of the composition diagram is enlarged and shown in Figure 2.
  • the compositions at the points, A, B, C, and D, are shown in Table II below.
  • the lines AB and BC correspond approximately to the workability limit these alloys, while the lines CD and DA correspond approximately to an M so (138 MPa) (20 ksi) of 0°C.
  • the particularly preferred alloys of this invention will lie nearer line AB (the high titanium line) of the quadrilateral ABCD of Figure 2.
  • the alloys of this invention possess machinability which is unexpectedly considerably better than would be predicted from similar Ni/Ti alloys. While not wishing to be held to any particular theory, it is considered that this free-machining property of the alloys is related to the presence of a second phase, possibly Ti 2 (Ni, Cu) 3 , in the TiNi matrix. It is therefore considered that this improved machinability will manifest itself only when the titanium content is below the stoichiometric value and the Ti:Ni:Cu ratio is such as to favour the formation of the second phase.
  • Alloys obtained by these methods and using the materials described will contain small quantites of other elements, including oxygen and nitrogen in total amounts from about 0.05 to 0.2 percent.
  • the effect of these materials is generally to reduce the martensitic transformation temperature of the alloys.
  • the alloys of this invention possess good temper stability, are hot-workable, and are free-machining; in contrast to prior art alloys. They are also capable of possessing shape memory, and have a M 50 (138 MPa) (20 ksi) temperature above 0°C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Semiconductor Memories (AREA)
  • Chemically Coating (AREA)
  • Conductive Materials (AREA)
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EP83301168A 1982-03-05 1983-03-04 Nickel/titanium/copper shape memory alloys Expired EP0088604B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83301168T ATE28669T1 (de) 1982-03-05 1983-03-04 Nickel-titon-kupfer gedaechtnislegierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35527482A 1982-03-05 1982-03-05
US355274 1982-03-05

Publications (3)

Publication Number Publication Date
EP0088604A2 EP0088604A2 (en) 1983-09-14
EP0088604A3 EP0088604A3 (en) 1984-07-04
EP0088604B1 true EP0088604B1 (en) 1987-07-29

Family

ID=23396877

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83301168A Expired EP0088604B1 (en) 1982-03-05 1983-03-04 Nickel/titanium/copper shape memory alloys

Country Status (9)

Country Link
EP (1) EP0088604B1 (enrdf_load_stackoverflow)
JP (2) JPS58164745A (enrdf_load_stackoverflow)
AT (1) ATE28669T1 (enrdf_load_stackoverflow)
CA (1) CA1223758A (enrdf_load_stackoverflow)
DE (1) DE3372790D1 (enrdf_load_stackoverflow)
GB (1) GB2117401B (enrdf_load_stackoverflow)
HK (1) HK88689A (enrdf_load_stackoverflow)
IL (1) IL68051A0 (enrdf_load_stackoverflow)
SG (1) SG24488G (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60208440A (ja) * 1984-03-30 1985-10-21 Matsushita Electric Ind Co Ltd 熱感応装置
JPH01215948A (ja) * 1988-02-22 1989-08-29 Furukawa Electric Co Ltd:The Ｎｉ−Ｔｉ−Ｃｕ形状記憶合金およびその製造方法
JP3033583B2 (ja) * 1988-10-27 2000-04-17 古河電気工業株式会社 温度センサー兼アクチュエーター
US5044947A (en) * 1990-06-29 1991-09-03 Ormco Corporation Orthodontic archwire and method of moving teeth
EP1831012A2 (en) * 2004-11-24 2007-09-12 Dow Gloval Technologies Inc. Laminated polyisocyanurate foam structure with improved astm e-84 flame spread index and smoke developed index

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7002632A (enrdf_load_stackoverflow) * 1970-02-25 1971-08-27
CH606456A5 (enrdf_load_stackoverflow) * 1976-08-26 1978-10-31 Bbc Brown Boveri & Cie
CH616270A5 (enrdf_load_stackoverflow) * 1977-05-06 1980-03-14 Bbc Brown Boveri & Cie
CH623711B (de) * 1978-12-15 Bbc Brown Boveri & Cie Uhr.

Also Published As

Publication number Publication date
JPS58164745A (ja) 1983-09-29
SG24488G (en) 1988-07-15
JPH04350139A (ja) 1992-12-04
IL68051A0 (en) 1983-06-15
GB2117401A (en) 1983-10-12
GB2117401B (en) 1985-09-11
HK88689A (en) 1989-11-17
GB8306025D0 (en) 1983-04-07
CA1223758A (en) 1987-07-07
JPH0480097B2 (enrdf_load_stackoverflow) 1992-12-17
DE3372790D1 (en) 1987-09-03
ATE28669T1 (de) 1987-08-15
EP0088604A2 (en) 1983-09-14
EP0088604A3 (en) 1984-07-04

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