EP0419789A1 - Alliage à mémoire de forme - Google Patents
Alliage à mémoire de forme Download PDFInfo
- Publication number
- EP0419789A1 EP0419789A1 EP90114034A EP90114034A EP0419789A1 EP 0419789 A1 EP0419789 A1 EP 0419789A1 EP 90114034 A EP90114034 A EP 90114034A EP 90114034 A EP90114034 A EP 90114034A EP 0419789 A1 EP0419789 A1 EP 0419789A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- shape memory
- memory alloy
- temperature
- alloys
- atom
- 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.)
- Granted
Links
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 40
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910001000 nickel titanium Inorganic materials 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
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 for repeated applications, which contains no precious 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.
- 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 and 7.5 to 22 at.% Zr exists.
- This shape memory alloy can advantageously be further developed in that it still contains up to 8.5 at.% Cu (ie between 0 and 8.5 at.% Cu).
- 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.
- 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 (claim 3) or 24 to 30 at% Ti and 20 to 22 at% Zr (claim 4).
- the A s temperature is above 120 ° C, with a Zr content of 20 at% above 145 ° C.
- the shape memory alloy according to claims 1 and 2 can advantageously be further developed in that the (Ni + Cu) content 47 to 50 at.% (Claim 5) or 48 to 49.5 at.% (Claim 6) or 48.5 to 49 at% (claim 7).
- the Zr content can be modified in such a way that it is between 10 and 19 at% (claim 8) or between 14 and 18 at% ( Claim 9) is.
- a shape memory alloy with particularly favorable properties can be produced by dimensioning the composition ranges in the manner described by claims 1, 7 and 9.
- 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.
- Tables 1 and 2 below list, by way of example, shape memory alloys according to the invention 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 created in the button furnace 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)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3926693 | 1989-08-12 | ||
| DE3926693 | 1989-08-12 | ||
| DE4006076 | 1990-02-27 | ||
| DE4006076A DE4006076C1 (fr) | 1989-08-12 | 1990-02-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0419789A1 true EP0419789A1 (fr) | 1991-04-03 |
| EP0419789B1 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023072B3 (de) * | 2005-04-29 | 2006-09-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Vorrichtung zur Reduzierung von Wolfstönen bei Streichinstrumenten |
Families Citing this family (30)
| 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 |
| US6592724B1 (en) | 1999-09-22 | 2003-07-15 | Delphi Technologies, Inc. | Method for producing NiTiHf alloy films by sputtering |
| 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 |
| 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 |
| AU3441001A (en) * | 1999-12-01 | 2001-06-12 | Advanced Cardiovascular Systems Inc. | Nitinol alloy design and composition for vascular stents |
| US6500282B2 (en) | 2000-03-28 | 2002-12-31 | Honeywell International Inc. | Gold-indium intermetallic compound, shape memory alloys formed therefrom and resulting articles |
| US6464844B1 (en) | 2000-09-21 | 2002-10-15 | Delphi Technologies, Inc. | Sputtering alloy films using a sintered metal composite target |
| US6303008B1 (en) | 2000-09-21 | 2001-10-16 | Delphi Technologies, Inc. | Rotating film carrier and aperture for precision deposition of sputtered alloy films |
| US6402906B1 (en) | 2000-10-19 | 2002-06-11 | Delphi Technologies, Inc. | Sputtering alloy films using a crescent-shaped aperture |
| US6602272B2 (en) * | 2000-11-02 | 2003-08-05 | Advanced Cardiovascular Systems, Inc. | Devices configured from heat shaped, strain hardened nickel-titanium |
| 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 |
| 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 |
| WO2003064717A1 (fr) * | 2002-02-01 | 2003-08-07 | Mide Technology Corporation | Alliages amortisseurs a memoire de forme |
| 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 |
| EA008864B1 (ru) * | 2003-09-30 | 2007-08-31 | Нью Ривер Фармасьютикалз Инк. | Фармацевтические композиции для предотвращения передозировки или неправильного употребления лекарственных средств |
| RU2327753C2 (ru) * | 2006-03-23 | 2008-06-27 | Николай Николаевич Попов | Сплав с эффектом памяти формы |
| FR2942516B1 (fr) | 2009-02-24 | 2015-07-03 | Saint Gobain Ct Recherches | Assemblage affleurant. |
| 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. |
| 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 |
| KR102845720B1 (ko) * | 2020-12-17 | 2025-08-12 | 현대자동차주식회사 | 형상기억합금용 비정질 전구체와 이를 이용한 형상기억합금 및 이의 제조방법 |
| 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 |
| CN116949314B (zh) * | 2023-08-28 | 2025-06-27 | 哈尔滨工业大学 | 兼具高循环稳定性和高温线性超弹性的多主元形状记忆合金及其制备方法和应用 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2105555A1 (de) * | 1970-02-25 | 1971-09-30 | Philips Nv | Formspeicherelement |
| DE2133103A1 (de) * | 1970-07-02 | 1972-02-17 | Raychem Corp | Sich in der Hitze erholende Leigierung |
| FR2389990A1 (fr) * | 1977-05-06 | 1978-12-01 | 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 |
| EP0047639A2 (fr) * | 1980-09-05 | 1982-03-17 | RAYCHEM CORPORATION (a California corporation) | Alliages à mémoires de forme, du type nickel-titane-cuivre |
| EP0086013A2 (fr) * | 1982-02-05 | 1983-08-17 | BBC Brown Boveri AG | Matériau, constitué au moins partiellement d'un composant présentant un effet de mémoire à une voie et procédé pour sa fabrication |
| EP0187452A1 (fr) * | 1984-11-06 | 1986-07-16 | RAYCHEM CORPORATION (a Delaware corporation) | Procédé pour la mise en oeuvre d'un alliage à mémoire à base de nickel-titane et pièce obtenue par ce procédé |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59150069A (ja) * | 1983-02-15 | 1984-08-28 | Hitachi Metals Ltd | 形状記憶合金製造方法 |
| 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
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2105555A1 (de) * | 1970-02-25 | 1971-09-30 | Philips Nv | Formspeicherelement |
| DE2133103A1 (de) * | 1970-07-02 | 1972-02-17 | Raychem Corp | Sich in der Hitze erholende Leigierung |
| FR2389990A1 (fr) * | 1977-05-06 | 1978-12-01 | 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 |
| EP0047639A2 (fr) * | 1980-09-05 | 1982-03-17 | RAYCHEM CORPORATION (a California corporation) | Alliages à mémoires de forme, du type nickel-titane-cuivre |
| EP0086013A2 (fr) * | 1982-02-05 | 1983-08-17 | BBC Brown Boveri AG | Matériau, constitué au moins partiellement d'un composant présentant un effet de mémoire à une voie et procédé pour sa fabrication |
| EP0187452A1 (fr) * | 1984-11-06 | 1986-07-16 | RAYCHEM CORPORATION (a Delaware corporation) | Procédé pour la mise en oeuvre d'un alliage à mémoire à base de nickel-titane et pièce obtenue par ce procédé |
Non-Patent Citations (1)
| Title |
|---|
| SHAPE MEMORY EFFECTS IN ALLOYS, 1975, Seiten 263-265, J. Perkins, Plenum Press, New York, US; "Effects of alloying (Shape memory effect in TiNi)" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023072B3 (de) * | 2005-04-29 | 2006-09-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Vorrichtung zur Reduzierung von Wolfstönen bei Streichinstrumenten |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0372046A (ja) | 1991-03-27 |
| EP0419789B1 (fr) | 1993-07-21 |
| US5108523A (en) | 1992-04-28 |
| DE4006076C1 (fr) | 1990-12-13 |
| DE59002023D1 (de) | 1993-08-26 |
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