EP0419789B1 - Alliage à mémoire de forme - Google Patents
Alliage à mémoire de forme Download PDFInfo
- Publication number
- EP0419789B1 EP0419789B1 EP90114034A EP90114034A EP0419789B1 EP 0419789 B1 EP0419789 B1 EP 0419789B1 EP 90114034 A EP90114034 A EP 90114034A EP 90114034 A EP90114034 A EP 90114034A EP 0419789 B1 EP0419789 B1 EP 0419789B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- shape memory
- memory alloy
- temperature
- alloys
- composition
- 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 - Lifetime
Links
Classifications
-
- 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 shape memory alloy with A s temperatures above 100 ° C for repeated applications, which contains no noble metals.
- NiTi shape memory alloys are known to have excellent properties. With an almost stoichiometric composition, they are characterized by a particularly high amount of reversible deformation in the one-way and two-way effect, by high tensile strength and ductility and by very good corrosion resistance. In addition, these shape memory alloys have an excellent stability of the effect size against thermal cycles. In addition, they can be heated relatively far above the temperature A f (temperature at the end of the austenite formation) without harmful irreversible structural changes occurring, which reduce the size of the shape memory effect or inadvertently shift the transformation temperature.
- a f temperature at the end of the austenite formation
- the A s temperature (temperature at the start of austenite formation) should be relatively high, for example at temperatures above 100 ° C. However, the maximum A s temperatures that can be achieved with NiTi shape memory alloys for repeated applications are below 100 ° C. In the following there will be considered as coming A s temperature that A s temperature indicated that appears after several thermal cycles.
- a shape memory alloy based on Ni-Ti is known from FR-A-2 389 990 (for example according to Table I), which may contain up to 30% by weight of Zr and up to 5% of Zr in addition to Cu. -% contains. With the composition mentioned here, however, this Zr fraction only makes up about 3.5 at%.
- the invention has for its object to propose a shape memory alloy based on NiTi, which has good values for the two-way effect, elongation at break, overheatability and reversible deformation at an A s temperature of more than 100 ° C.
- the object is achieved by a shape memory alloy with A s temperatures above 100 ° C., which consists of 41.5 to 54 at.% Ni, 24 to 42.5 at.% Ti, 14 to 22 at.% Zr and 0 to 8.5 at% Cu; Within the framework of the teaching according to the invention, Zr can be replaced by Hf.
- the shape memory alloys in question are obtained in a known manner from suitable starting melts or master alloys by remelting in a vacuum induction furnace under an argon atmosphere in graphite crucibles; the starting melts or master alloys are composed such that a reaction with the graphite crucible is largely suppressed. Contrary to expectations, it was found that shape memory alloys in the composition range mentioned have shape memory properties with significantly higher transition temperatures than binary NiTi shape memory alloys.
- the shape memory alloys are ductile and can be deformed at room temperature, provided that their composition has a single-phase structure.
- a composition formula Ni 1-x TiZr x is given for a memory alloy with the alloy components nickel, titanium and zircon, whose x value can be between 0 and 0.21.
- shape memory alloys with advantageous properties can also be designed in such a way that they range from 24 to 34 at.% Ti and 16 to 22 at.% Zr or Hf (claim 2) or 24 to 30 at% of Ti and 20 to 22 at% of Zr or Hf (claim 3).
- the A s temperature is above 120 ° C, with a Zr content of 20 at% above 145 ° C.
- the shape memory alloy according to claim 1 can advantageously be further developed in that the (Ni + Cu) content 47 to 50 at.% (Claim 4) or 48 to 49.5 at.% (Claim 5) or 48, 5 to 49 at% (claim 6).
- the Zr or Hf content can be modified in such a way that it can contain up to 19 at% (claim 7) or up to 18 at% (Claim 8).
- a shape memory alloy with particularly favorable properties can be produced by dimensioning the composition ranges in the manner described by claims 1, 6 and 8.
- Such a shape memory alloy therefore has the following composition: 48.5 to 49 at.% Ni; 24 to 42.5 at% Ti and 14 to 18 at% Zr or Hf.
- Tables 1 and 2 below list, by way of example, primarily shape memory alloys of the claimed composition with their A s temperatures.
- Table 2 also shows an example of a binary NiTi shape memory alloy whose A s temperature is expected to be below 100 ° C.
- the exemplary embodiments in Tables 1 and 2 show that the A s temperatures increase with increasing Zr content: with more than 16 at.% Zr, the A s temperature is above 120 ° C., with more than 20 at. -% Zr higher than 150 ° C.
- the size of the shape memory effect ie the extent of the reversible deformation, is another important feature. Since the shape memory effect decreases with increasing Zr content, the shape memory alloys given in the tables only have Zr contents in the order of 20 at%, taking into account the opposite tendency of the properties.
- Master alloys of the claimed composition are produced in the button port and remelted in the vacuum induction furnace under argon atmosphere in graphite crucibles to cylindrical samples.
- the transition temperatures A s and A f given in the tables were determined calorimetrically on the samples in the as-cast state after several thermal cycles.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Powder Metallurgy (AREA)
- Continuous Casting (AREA)
Claims (8)
- Alliage à mémoire de forme dont la température As est supérieure à 100°C, comprenant de 41.5 à 54 en parties pour cent de Ni, de 24 à 42.5 en parties pour cent de Ti et de 14 à 22 en parties pour cent de Zr ou de Hf et de 0 à 8.5 en parties pour cent de Cu.
- Alliage à mémoire de forme selon la revendication 1, caractérisé en ce qu'il renferme de 24 à 34 en parties pour cent de Ti et de 16 à 22 en parties pour cent de Zr ou de Hf.
- Alliage à mémoire de forme selon la revendication 1, caractérisé en ce qu'il renferme de 24 à 30 en parties pour cent de Ti et de 20 à 22 en parties pour cent de Zr ou de Hf.
- Alliage à mémoire de forme selon la revendication 1, caractérisé en ce qu'il renferme de 47 à 50 en parties pour cent Ni+Cu.
- Alliage à mémoire de forme selon la revendication 1, caractérisé en ce qu'il renferme de 48 à 49.5 en parties pour cent de Ni+Cu.
- Alliage à mémoire de forme selon la revendication 1, caractérisé en ce qu'il renferme de 48,5 à 49 en parties pour cent de Ni+Cu.
- Alliage à mémoire de forme selon au moins une des revendications 1 et 4 à 6, caractérisé en ce qu'il renferme jusqu'à 19 en parties pour cent de Zr ou de Hf
- Alliage à mémoire de forme selon au moins une des revendications 1 et 4 à 6, caractérisé en ce qu'il renferme jusqu'à 18 en parties pour cent de Zr ou de Hf.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3926693 | 1989-08-12 | ||
DE3926693 | 1989-08-12 | ||
DE4006076A DE4006076C1 (fr) | 1989-08-12 | 1990-02-27 | |
DE4006076 | 1990-02-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0419789A1 EP0419789A1 (fr) | 1991-04-03 |
EP0419789B1 true EP0419789B1 (fr) | 1993-07-21 |
Family
ID=25883963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90114034A Expired - Lifetime EP0419789B1 (fr) | 1989-08-12 | 1990-07-21 | Alliage à mémoire de forme |
Country Status (4)
Country | Link |
---|---|
US (1) | US5108523A (fr) |
EP (1) | EP0419789B1 (fr) |
JP (1) | JPH0372046A (fr) |
DE (2) | DE4006076C1 (fr) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6165292A (en) * | 1990-12-18 | 2000-12-26 | Advanced Cardiovascular Systems, Inc. | Superelastic guiding member |
US6682608B2 (en) * | 1990-12-18 | 2004-01-27 | Advanced Cardiovascular Systems, Inc. | Superelastic guiding member |
US5419788A (en) * | 1993-12-10 | 1995-05-30 | Johnson Service Company | Extended life SMA actuator |
US5904480A (en) * | 1995-05-30 | 1999-05-18 | Ormco Corporation | Dental and orthodontic articles of reactive metals |
US6358380B1 (en) | 1999-09-22 | 2002-03-19 | Delphi Technologies, Inc. | Production of binary shape-memory alloy films by sputtering using a hot pressed target |
US6592724B1 (en) | 1999-09-22 | 2003-07-15 | Delphi Technologies, Inc. | Method for producing NiTiHf alloy films by sputtering |
US6596132B1 (en) | 1999-09-22 | 2003-07-22 | Delphi Technologies, Inc. | Production of ternary shape-memory alloy films by sputtering using a hot pressed target |
WO2001039695A2 (fr) * | 1999-12-01 | 2001-06-07 | Advanced Cardiovascular Systems, Inc. | Conception et composition de nitinol pour stents vasculaires |
US6500282B2 (en) | 2000-03-28 | 2002-12-31 | Honeywell International Inc. | Gold-indium intermetallic compound, shape memory alloys formed therefrom and resulting articles |
US6303008B1 (en) | 2000-09-21 | 2001-10-16 | Delphi Technologies, Inc. | Rotating film carrier and aperture for precision deposition of sputtered alloy films |
US6464844B1 (en) | 2000-09-21 | 2002-10-15 | Delphi Technologies, Inc. | Sputtering alloy films using a sintered metal composite target |
US6402906B1 (en) | 2000-10-19 | 2002-06-11 | Delphi Technologies, Inc. | Sputtering alloy films using a crescent-shaped aperture |
US7976648B1 (en) | 2000-11-02 | 2011-07-12 | Abbott Cardiovascular Systems Inc. | Heat treatment for cold worked nitinol to impart a shape setting capability without eventually developing stress-induced martensite |
US6602272B2 (en) * | 2000-11-02 | 2003-08-05 | Advanced Cardiovascular Systems, Inc. | Devices configured from heat shaped, strain hardened nickel-titanium |
US6855161B2 (en) * | 2000-12-27 | 2005-02-15 | Advanced Cardiovascular Systems, Inc. | Radiopaque nitinol alloys for medical devices |
US6454913B1 (en) | 2001-07-12 | 2002-09-24 | Delphi Technologies, Inc. | Process for deposition of sputtered shape memory alloy films |
DE10142998B4 (de) * | 2001-09-03 | 2005-02-24 | Stiftung Caesar Center Of Advanced European Studies And Research | Formgedächtnisverbund mit inhärentem Bewegungsablauf |
US20040025985A1 (en) * | 2002-02-01 | 2004-02-12 | Mide Technology Corporation | Energy absorbing shape memory alloys |
EP1629134B1 (fr) * | 2003-03-25 | 2012-07-18 | Questek Innovations LLC | Alliages a memoire de forme renforces par nanodispersion et coherents |
US7942892B2 (en) * | 2003-05-01 | 2011-05-17 | Abbott Cardiovascular Systems Inc. | Radiopaque nitinol embolic protection frame |
MXPA06003619A (es) * | 2003-09-30 | 2008-01-14 | New River Pharmaceuticals Inc | Composiciones farmaceuticas para prevencion de sobredosis o abuso. |
DE102005023072B3 (de) * | 2005-04-29 | 2006-09-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Vorrichtung zur Reduzierung von Wolfstönen bei Streichinstrumenten |
FR2942471A1 (fr) | 2009-02-24 | 2010-08-27 | Saint Gobain Ct Recherches | Piece ceramique revetue. |
FR2942515B1 (fr) * | 2009-02-24 | 2015-07-03 | Saint Gobain Ct Recherches | Dispositif d'assemblage. |
FR2942516B1 (fr) | 2009-02-24 | 2015-07-03 | Saint Gobain Ct Recherches | Assemblage affleurant. |
US10081969B2 (en) * | 2014-04-16 | 2018-09-25 | Dynalloy, Inc. | Lockable latching device |
RU2613835C1 (ru) * | 2015-10-22 | 2017-03-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Композиционный материал на основе нитинола |
CN115927915B (zh) * | 2022-11-30 | 2024-05-17 | 西安赛特思迈钛业有限公司 | 一种Ti-Ni-Zr形状记忆合金及其制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7002632A (fr) * | 1970-02-25 | 1971-08-27 | ||
US3753700A (en) * | 1970-07-02 | 1973-08-21 | Raychem Corp | Heat recoverable alloy |
CH616270A5 (fr) * | 1977-05-06 | 1980-03-14 | Bbc Brown Boveri & Cie | |
DE3007307A1 (de) * | 1980-01-18 | 1981-07-23 | BBC AG Brown, Boveri & Cie., Baden, Aargau | Schrumpfverbindung und verfahren zu deren herstellung |
US4283233A (en) * | 1980-03-07 | 1981-08-11 | The United States Of America As Represented By The Secretary Of The Navy | Method of modifying the transition temperature range of TiNi base shape memory alloys |
US4337090A (en) * | 1980-09-05 | 1982-06-29 | Raychem Corporation | Heat recoverable nickel/titanium alloy with improved stability and machinability |
CH660882A5 (de) * | 1982-02-05 | 1987-05-29 | Bbc Brown Boveri & Cie | Werkstoff mit zweiweg-gedaechtniseffekt und verfahren zu dessen herstellung. |
JPS59150069A (ja) * | 1983-02-15 | 1984-08-28 | Hitachi Metals Ltd | 形状記憶合金製造方法 |
CA1269915A (fr) * | 1984-11-06 | 1990-06-05 | John A. Simpson | Methode de traitement d'un alliage de nickel et titane a memoire de forme, et article qui en est derive |
US4950340A (en) * | 1987-08-10 | 1990-08-21 | Mitsubishi Kinzoku Kabushiki Kaisha | Intermetallic compound type alloy having improved toughness machinability and wear resistance |
-
1990
- 1990-02-27 DE DE4006076A patent/DE4006076C1/de not_active Expired - Lifetime
- 1990-07-21 EP EP90114034A patent/EP0419789B1/fr not_active Expired - Lifetime
- 1990-07-21 DE DE9090114034T patent/DE59002023D1/de not_active Expired - Fee Related
- 1990-07-24 US US07/557,629 patent/US5108523A/en not_active Expired - Fee Related
- 1990-08-10 JP JP2210555A patent/JPH0372046A/ja active Pending
Non-Patent Citations (2)
Title |
---|
Journal of Metals, vol.34 (1982), Seiten 14-20, Duerig et al. "A Shape-Memory Alloy for High-Temperature Applications" * |
Kleinherenbrink und Beyer "Control of the transformation temperatures of TiNi Shape memory alloys by tertiary additions" (Conference: The martensitic transformation in science and technology, Bochum, BRD, 09-10.03.89, DGM Informationsgesellschaft m.b.H. Verlag, W-6370 Oberursel, Seiten 187-190) * |
Also Published As
Publication number | Publication date |
---|---|
DE4006076C1 (fr) | 1990-12-13 |
US5108523A (en) | 1992-04-28 |
DE59002023D1 (de) | 1993-08-26 |
EP0419789A1 (fr) | 1991-04-03 |
JPH0372046A (ja) | 1991-03-27 |
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