WO2005049876A2 - High-purity titanium-nickel alloys with shape memory - Google Patents
High-purity titanium-nickel alloys with shape memory Download PDFInfo
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- WO2005049876A2 WO2005049876A2 PCT/US2004/034972 US2004034972W WO2005049876A2 WO 2005049876 A2 WO2005049876 A2 WO 2005049876A2 US 2004034972 W US2004034972 W US 2004034972W WO 2005049876 A2 WO2005049876 A2 WO 2005049876A2
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- Shape memory materials are materials which can recover a shape after heating.
- shape memory properties of shape memory alloys such as, for example, nickel-titanium based shape memory alloys, can overlap with super-elastic properties.
- super-elastic properties which exist over a temperature range specific to the particular material allow shape memory materials to have great flexibility.
- the unique properties of shape memory alloys make them particularly useful for applications in fields such as automotive, aerospace, thin-film, robotics, and medical fields.
- Exemplary applications for these materials include implantable medical devices, precision tools and medical instruments, and actuators.
- Nickel-titanium based alloys are currently being used in place of stainless steel in many applications.
- Other exemplary applications for these materials include sputtering targets which in turn can be utilized to produce thin films such as those used in the manufacture of micro-electromechanical systems (MEMS).
- MEMS micro-electromechanical systems
- Shape memory, super-elasticity and other metallurgical properties of a material can be affected by contaminants in the material. For example, contaminants such as metallic impurities and/or gases can impair mechanical properties by forming inclusions that can lower fatigue life and can shift phase transformation temperatures out of specification.
- Nickel-titanium alloys having limited purities attainable utilizing conventional methodologies typically have high work hardening rates which limit the cross-sectional reduction during many fabrication operations. These conventional materials require numerous in-process heat treatments to regain ductility. Further, the presence of contaminants can affect the biocompatibility of materials. Accordingly, it is desirable to develop methods to produce high-purity shape memory alloys.
- the invention encompasses an alloy containing atomically equivalent amounts of nickel and titanium.
- the alloy has a shape memory and has a metallic purity of at least about 99.995%, by weight, and comprises less than about 200 ppm of gases.
- the invention encompasses an alloy comprising titanium and nickel where the titanium and nickel amounts are non-equivalent.
- the alloy has shape memory and has a metallic purity of at least 99.995%, by weight, and contains less than about 200 ppm of gases.
- the invention encompasses a method of producing a shape memory alloy. Titanium is provided which has a metallic purity of at least 99.999%, by weight.
- Nickel is provided which has a metallic purity of at least 99.99%, by weight, and the titanium and nickel are combined to form the alloy.
- the combining utilizes a first melting event and a second melting event where each of the first and second melting events can be e-beam melting, vacuum arc melting, vacuum induction melting, induction skull melting or plasma melting.
- DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0008]
- the invention encompasses high-purity titanium alloys and methodology for producing high-purity titanium alloys.
- the methodology of the invention can be utilized for producing shape-memory and/or super-elastic titanium alloy materials.
- the high-purity alloy materials of the invention have improved cold-ductility allowing fewer in- process heat treatments relative to conventional materials.
- the term 'shape memory' as used in the description of the invention refers to materials which recover an original shape after heating to above a temperature at which the material begins to undergo a solid state phase change from martensite to austenite.
- the temperature at which this transformation begins can be referred to as the phase transformation temperature or critical temperature, and can be dependent upon the particular alloy or material.
- phase transformation temperature critical temperature
- a shape memory material is cooled to below the critical temperature it exists in the martensite phase and is malleable and deformable. Upon heating through the critical temperature, a shape memory material that has been deformed in the martensite phase will regain the austenite phase and substantially resume a shape that it held prior to the cooling and deformation.
- super-elastic properties present in shape memory materials can allow a martensite phase to be induced by placing stress upon the material without subjecting the material to a temperature below the critical temperature. The material can then be deformed in the martensite phase. Relief from the stress upon the material can induce return to the austenite phase and recovery of the earlier shape that existed prior to the stress/deformation process.
- Methodology of the invention can be useful for production of numerous titanium alloys and can be particularly useful for production of high-purity nickel-titanium based (nitinol) binary and higher order alloys.
- the term high-purity can refer to a metallic purity of greater than 99.995% (4N5), where such material contains a total metallic impurity content of less than or equal to about 50 ppm, by weight.
- high-purity materials of the invention will have a purity of greater than or equal to 99.998% (4N8), by weight, such material containing less than or equal to 20 ppm total metallic impurities.
- the methodology of the invention can be utilized to produce binary, ternary or higher order Ni-Ti based high-purity materials.
- the high-purity Ni-Ti alloy produced by methodology of the invention can have a 1 :1 atomic ratio of nickel and titanium.
- a binary Ni-Ti alloy will contain an atomic equivalent of nickel and titanium which can be alternatively referred to as a 50% nickel binary alloy.
- Ternary and higher order alloys can also be produced having an atomic equivalence of nickel and titanium.
- the total atomic percent of nickel and titanium can depend upon the amount of additional elements added to the alloy.
- the invention additionally encompasses alloys having an atomic excess of nickel relative to titanium, or an atomic excess of titanium over the amount of nickel present. For example, excess nickel of up to about 1 at% can be utilized to adjust the transformation temperature of a material and/or to increase the yield strength.
- Ni or Ti is not limited to a particular value.
- additional elements can be added to affect various properties.
- one or more non-Ti/Ni metallic elements can be added to increase or decrease the transformation temperature of the material, affect the deformation stress, and/or decrease the hysteresis of the material.
- the addition of one or more non-Ni/Ti elements can be utilized in higher order alloys having an atomic equivalence of nickel and titanium or alloys having an atomic excess of either nickel or titanium.
- one or more metallic elements can be utilized for production of higher order alloys according to the invention. The amount of added element(s) is not limited to a particular value.
- High-purity alloys of the invention can be produced to contain from 0 to less than about 200 ppm of gases. As utilized in the present description, ppm refers to parts per million by weight.
- gases as utilized in the present description can refer to contaminant elements which are generally considered to be interstitial elements, including O, C, S, N, and H.
- the alloys of the present invention can preferably contain from 0 to less than 100 ppm of total gases, and more preferably less than about 50 ppm.
- the C content can preferably be less than 50 ppm and more preferably less than 20 ppm.
- the S content can be preferably less than 5 ppm and more preferably less than 2 ppm.
- the H content can be preferably less than 5 ppm and more preferably less than 2 ppm.
- the indicated preferred values for gas contaminants are values as measured by the LECO technique.
- alloys of the present invention can contain 0 ppm of one or more of these gases or can contain one or more gases below the corresponding detection limit of the technique.
- alloys of the present invention can preferably contain less than or equal to 50 ppm of total metallic impurities, where metallic impurities refers to any metallic element present which is not intentionally added.
- the alloys of the present invention contain no more than 50 ppm Fe, and preferably from 0 to less than 10 ppm Fe.
- Any chromium present can preferably be less than 5 ppm and more preferably less than 1 ppm.
- Any cobalt present can preferably be less than 1 ppm and more preferably less than 0.5 ppm.
- Any tungsten present can preferably be less than 10 ppm, and more preferably from 0 to less than 5 ppm.
- a total of all other metallic impurities present in the alloys of the invention can preferably be from 0 to less than 5 ppm each.
- the indicated content of metallic impurities within alloys of the invention reflects values as measured utilizing glow discharge mass spectrometry (GDMS).
- GDMS glow discharge mass spectrometry
- Methodology of the invention for producing the described titanium alloys includes utilizing high-purity titanium during the alloying process.
- high-purity titanium can preferably be titanium having a purity of at least 99.999% with ultra low dissolved gases and carbon levels.
- ultra pure titanium can be produced utilizing methodology and apparatus described in U.S. Patent Nos. 6,063,254 and 6,024,847, the contents of which are hereby incorporated by reference.
- the described high- purity titanium can be combined with a high-purity source of nickel.
- the high-purity nickel source can preferably have a purity of at least 99.99%.
- non- titanium/nickel alloying elements are preferably provided utilizing a high-purity source, and most preferably from a source having a purity level of sufficient to enable an alloy purity of at least 99.995%, preferably 99.998%, by weight.
- Production of titanium-nickel based high-purity alloys of the invention can comprise combination of high-purity titanium with high-purity nickel, and optionally with one or more high-purity sources of additional elements.
- the combining can, in particular instances, utilize a single melting event, the combining preferably comprises at least two melting events.
- Such melting events can include, for example, e-beam melting, vacuum arc remelting, vacuum induction melting, induction skull melting, plasma melting, or combinations thereof.
- the invention contemplates alloy production utilizing multiple applications of a single melting technology or utilization of more than one melting technology. It can be advantageous to utilize multiple melting events to provide improved purity and homogeneity of the resulting material. Including at least one high vacuum melting event can beneficially preserve the purity of the source materials by avoiding imparting impurities during processing. Accordingly, alloys of the invention can have a purity equivalent to that of the staring materials.
- Particular applications of the invention can advantageously include at least one e-beam melting operation and at least one additional melting event for production of high-purity nickel-titanium based alloys.
- the use of e-beam melting can, in some instances further increase the purity by removing at least some of the impurities present in the source materials.
- alloys prepared in accordance with the invention can have an increased purity relative to the starting materials.
- Example: Production of a high-purity Ni-Ti alloy [0024] Titanium having a 99.9997% purity and nickel having a purity of 99.997% were combined and were vacuum arc re-melted to form a Ni-Ti binary alloy containing approximately 55.8 wt% Ni.
- Ni-Ti binary alloy had a purity of 99.997%, by weight.
- Purity analysis of the Ni-Ti binary alloy presented in Tables 1 and 2.
- Table 1 Ni-Ti Binary Alloy (approximately 55.8 wt% NiJ; Analysis of Metallic Impurities
- Processing in accordance with the invention can additionally include various thermo-mechanical processing steps, including but not limited to, forging, rolling, drawing, and annealing.
- the described thermo-mechanical processing of the high- purity alloys can be utilized to produce materials having desired shape memory and super-elastic properties with purity levels that exceed levels attainable utilizing conventional alloy formation and processing methods.
- alloy production in accordance with the methodology of the invention can be particularly useful for minimizing or eliminating incorporation of any contaminants into high-purity materials during alloy formation. Due to the use of high-purity source metals in combination with melting techniques that can maintain or increase purity, alloys produced by methodology of the present invention can have a level purity equal to or exceeding the original high-purity source materials.
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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)
- Manufacture And Refinement Of Metals (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US51431703P | 2003-10-24 | 2003-10-24 | |
US60/514,317 | 2003-10-24 | ||
US10/969,600 US20060037672A1 (en) | 2003-10-24 | 2004-10-19 | High-purity titanium-nickel alloys with shape memory |
US10/969,600 | 2004-10-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005049876A2 true WO2005049876A2 (en) | 2005-06-02 |
WO2005049876A3 WO2005049876A3 (en) | 2005-08-04 |
Family
ID=34623001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/034972 WO2005049876A2 (en) | 2003-10-24 | 2004-10-22 | High-purity titanium-nickel alloys with shape memory |
Country Status (3)
Country | Link |
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US (1) | US20060037672A1 (en) |
KR (1) | KR20060126896A (en) |
WO (1) | WO2005049876A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009070784A1 (en) | 2007-11-30 | 2009-06-04 | Abbott Laboratories | Fatigue-resistant nickel-titanium alloys and medical devices using same |
US8430981B1 (en) | 2012-07-30 | 2013-04-30 | Saes Smart Materials | Nickel-titanium Alloys, related products and methods |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6569194B1 (en) | 2000-12-28 | 2003-05-27 | Advanced Cardiovascular Systems, Inc. | Thermoelastic and superelastic Ni-Ti-W alloy |
US20070073374A1 (en) * | 2005-09-29 | 2007-03-29 | Anderl Steven F | Endoprostheses including nickel-titanium alloys |
US7923836B2 (en) * | 2006-07-21 | 2011-04-12 | International Business Machines Corporation | BLM structure for application to copper pad |
KR101334287B1 (en) | 2009-11-02 | 2013-11-29 | 사에스 스마트 머티리얼즈 | Ni-Ti SEMI-FINISHED PRODUCTS AND RELATED METHODS |
KR101665170B1 (en) * | 2014-01-17 | 2016-10-12 | 순천대학교 산학협력단 | METHOD FOR MANUFACTURING Ni-Ti SHAPE MEMORY ALLOY |
CN104278167B (en) * | 2014-09-15 | 2017-02-08 | 安泰科技股份有限公司 | Manufacturing method of high-quality titanium-aluminum alloy target |
KR101615158B1 (en) | 2014-11-14 | 2016-04-25 | 경상대학교산학협력단 | Ti-Ni-Si BASED SHAPE MEMORY ALLOY |
KR101640324B1 (en) * | 2014-12-29 | 2016-07-18 | 순천대학교 산학협력단 | METHOD OF MANUFACTURING Ni-Ti SHAPE MEMORY ALLOY BY USING DOUBLE MELTING |
CN107245606B (en) * | 2017-05-26 | 2018-09-25 | 西安赛特思迈钛业有限公司 | A kind of preparation method of Ti-Ni alloy large-scale casting ingot |
Citations (3)
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US4631094A (en) * | 1984-11-06 | 1986-12-23 | Raychem Corporation | Method of processing a nickel/titanium-based shape memory alloy and article produced therefrom |
US4740253A (en) * | 1985-10-07 | 1988-04-26 | Raychem Corporation | Method for preassembling a composite coupling |
US5114504A (en) * | 1990-11-05 | 1992-05-19 | Johnson Service Company | High transformation temperature shape memory alloy |
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US3660082A (en) * | 1968-12-27 | 1972-05-02 | Furukawa Electric Co Ltd | Corrosion and wear resistant nickel alloy |
US5951793A (en) * | 1995-07-12 | 1999-09-14 | The Furukawa Electric Co., Ltd. | Ni-Ti-Pd superelastic alloy material, its manufacturing method, and orthodontic archwire made of this alloy material |
EP1011889B1 (en) * | 1996-01-30 | 2002-10-30 | Medtronic, Inc. | Articles for and methods of making stents |
US6569194B1 (en) * | 2000-12-28 | 2003-05-27 | Advanced Cardiovascular Systems, Inc. | Thermoelastic and superelastic Ni-Ti-W alloy |
US7316753B2 (en) * | 2003-03-25 | 2008-01-08 | Questek Innovations Llc | Coherent nanodispersion-strengthened shape-memory alloys |
-
2004
- 2004-10-19 US US10/969,600 patent/US20060037672A1/en not_active Abandoned
- 2004-10-22 KR KR1020067002776A patent/KR20060126896A/en not_active Application Discontinuation
- 2004-10-22 WO PCT/US2004/034972 patent/WO2005049876A2/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4631094A (en) * | 1984-11-06 | 1986-12-23 | Raychem Corporation | Method of processing a nickel/titanium-based shape memory alloy and article produced therefrom |
US4740253A (en) * | 1985-10-07 | 1988-04-26 | Raychem Corporation | Method for preassembling a composite coupling |
US5114504A (en) * | 1990-11-05 | 1992-05-19 | Johnson Service Company | High transformation temperature shape memory alloy |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009070784A1 (en) | 2007-11-30 | 2009-06-04 | Abbott Laboratories | Fatigue-resistant nickel-titanium alloys and medical devices using same |
US8398789B2 (en) | 2007-11-30 | 2013-03-19 | Abbott Laboratories | Fatigue-resistant nickel-titanium alloys and medical devices using same |
EP2801632A1 (en) * | 2007-11-30 | 2014-11-12 | Abbott Laboratories | An endoprosthetic device including at least one structural member formed from a fatigue-resistant superelastic or shape-memory alloy |
US9272376B2 (en) | 2007-11-30 | 2016-03-01 | Abbott Laboratories | Fatigue-resistant nickel-titanium alloys and medical devices using same |
US8430981B1 (en) | 2012-07-30 | 2013-04-30 | Saes Smart Materials | Nickel-titanium Alloys, related products and methods |
WO2014021951A1 (en) | 2012-07-30 | 2014-02-06 | Saes Smart Materials | Nickel-titanium alloys, related products and methods |
Also Published As
Publication number | Publication date |
---|---|
US20060037672A1 (en) | 2006-02-23 |
WO2005049876A3 (en) | 2005-08-04 |
KR20060126896A (en) | 2006-12-11 |
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