EP0185452B1 - Nickel-Titan-Niob-Formgedächtnislegierung und daraus gefertigter Gegenstand - Google Patents

Nickel-Titan-Niob-Formgedächtnislegierung und daraus gefertigter Gegenstand Download PDF

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EP0185452B1
EP0185452B1 EP85308079A EP85308079A EP0185452B1 EP 0185452 B1 EP0185452 B1 EP 0185452B1 EP 85308079 A EP85308079 A EP 85308079A EP 85308079 A EP85308079 A EP 85308079A EP 0185452 B1 EP0185452 B1 EP 0185452B1
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atomic percent
niobium
titanium
nickel
alloy
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EP0185452A1 (de
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John A. Simpson
Tom Duerig
Keith Melton
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Raychem Corp
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Advanced Metal Components Inc
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    • 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
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent

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  • This invention relates to the field of nickel/titanium-based shape memory alloys and particularly to those alloys containing niobium.
  • the ability to possess shape memory is a result of the fact that the alloy undergoes a reversible transformation from an austenitic state to a martensitic state with a change of temperature. Also, the alloy is considerably stronger in its austenitic state than in its martensitic state. This transformation is sometimes referred to as a thermoelastic martensitic transformation.
  • An article made from such an alloy for example, a hollow sleeve, is easily deformed from its original configuration to a new configuration when cooled below the temperature at which the alloy is transformed from the austenitic state to the martensitic state.
  • the temperature at which this transformation begins is usually referred to as M s and the temperature at which it finishes M f .
  • a s A f being the temperature at which the reversion is complete
  • Shape-memory alloys have found use in recent years in, for example, pipe couplings (such as are described in U.S.P. 4,035,007 and 4,198,081 to Harrison and Jervis), electrical connectors (such as are described in U.S.P. 3,740,839 to Otte and Fischer), switches (such as are described in U.S.P. 4,205,293 to Melton and Mercier),.
  • the alloy austenitic at the service temperature which is often but not necessarily near room temperature, since the austenite phase is stronger than the martensite phase.
  • Military Specification MIL-F-85421 requires a product that is functional to about -55°C. If the product comprises a shape memory alloy, then for convenience in shipping the product in the heat-unstable configuration, the product should not recover prior to about 50°C. It is a matter of commercial reality, within and without the military, that the product satisfy these or similar requirements.
  • the alloy be martensitic in the vicinity of room temperature so that the article can be fabricated, stored, and shipped at or near room temperature.
  • the reason for this is that in the case of an article made from the alloy, a coupling, for example, the article would not recover prematurely.
  • an alloy that is martensitic near room temperature and which is also austenitic over a large range of temperatures including room temperature is to have an alloy which exhibits a sufficiently wide tranformation hysteresis, say, greater than about 125°C. If the hysteresis were sufficiently wide and room temperature could be located near the middle of the hysteresis, then the alloy could be fabricated and conveniently stored while in the martensitic condition. Since the hysteresis is sufficiently wide, the alloy would not transform to austenite until heated Substantially above room temperature.
  • the commercially viable near equiatomic binary nickel-titanium alloys can have a hysteresis width of about 30°C.
  • the location of the hysteresis for this alloy is also extremely composition sensitive so that while the hysteresis can be shifted from sub-zero temperatures to above-zero temperatures, the width of the hysteresis does not appreciably change.
  • the alloy were martensitic at room temperature, the service temperature must be above room temperature.
  • the alloy would be martensitic below room temperature so that the alloy would require special cold-temperature equipment for fabrication, shipping, and storage.
  • room temperature should be located near the middle of the transformation hysteresis.
  • the width of the hysteresis in the binary alloy is so narrow, the range of service temperatures for any particular alloy is necessarily limited. As a practical matter, the alloy would have to be changed to accommodate any change in service temperatures.
  • Nickel/titanium/iron alloys e.g., those in Harrison et al., USP 3,753,700, while having a wide hysteresis, up to about 70°C, are the typical cryogenic alloys which always undergo the martensite/austenite transformation at sub-zero temperatures.
  • the colder shape-memory alloys such as the cryogenic alloys have a wider transformation hysteresis than the warmer shape memory alloys.
  • the alloys In the case of the cryogenic alloys, the alloys must be kept very cold, usually in liquid nitrogen, to avoid the transformation from martensite to austenite. This makes the use of shape memory alloys inconvenient, if not uneconomical.
  • the nickel/titanium/copper alloys of Harrison et al., U.S. Patent Application No. 537,316, filed September 28, 1983, which served to establish a priority date for EP-A-88604, and the nickel/titanium/vanadium vanadium alloys of Quin, U.S. Patent Application Serial No. 541,844, filed October 14, 1983, which served to establish a priority date for EP-A-140621, are not cryogenic but their hysteresis may be extremely narrow (10-20°C) such that their utility is limited for couplings and similar articles.
  • Nickel/titanium/niobium alloys are largely unexplored.
  • the ternary phase diagram has been determined [see "Ternary Intermetallic Compounds in the System Ni-Ti-Nb", Poroshkovaya Metallurgiya , No. 8(44), pp. 61-69(1966)] but there has been no study of the physical properties in this system.
  • U.S. Naval Ordinance Laboratory Report NOLTR 64-235 (August, 1965) examined the effect upon hardness of ternary additions of from 0.08 to 16 weight percent of eleven different elements (including niobium) to stoichiometric nickel/titanium.
  • a brazing alloy of percentage weight composition Ti 22.8-36.4%, Ni 26.9-42.9%, Nb 20.7-50.3% is described without reference to shape memory effects in US-A-3662455.
  • expansion of the hysteresis should generally be understood to mean that A s and A f have been elevated to A s ' and A f ' while at least M s and usually also M f remain essentially constant. Aging, heat treatment, composition, and cold work can all effectively shift the hysteresis. For example, if the stress is applied to the shape memory alloy at room temperature the hysteresis may be shifted so that the martensite phase can exist at a temperature at which there would normally be austenite. Upon removal of the stress, the alloy would isothermally (or nearly isothermally) transform from martensite to austenite.
  • nickel/titanium-based shape memory alloys Another problem common to nickel/titanium-based shape memory alloys is their notoriously poor machinability. Of course, while nickel/titanium-based shape memory alloys can be machined, it is only with expensive tooling and then only in relatively simple shapes.
  • the shape memory alloy While it is certainly desirable that the shape memory alloy have a wide transformation hysteresis, be free-machining and not exhibit a deleterious R phase transformation, it is important to appreciate and understand that recovery strength, ductility, and stability also remain important considerations when choosing a shape memory alloy.
  • nickel/titanium-based shape memory alloy which is exemplary with respect to recovery strength, ductility, and stability.
  • nickel/titanium/niobium alloys that are extremely susceptible to a widening of their transformation hysteresis and that do not exhibit a deleterious R phase transformation. For the most part, these alloys are also free-machining.
  • the disclosed alloys contain about 2.5 to 30 atomic percent niobium.
  • One aspect of the present invention accordingly provides the use of niobium in a nickel-titanium shape memory alloy to widen the transformation hysteresis (As'-Ms) of the strained alloy to more than 100°C, (preferably more than 125°C), the alloy consisting essentially of nickel, titanium and niobium within an area defined on a nickel, titanium, and niobium pseudo-binary phase diagram by a quadrilateral with its first vertex at 48 atomic percent titanium, 49.5 atomic percent nickel, and 2.5 (preferably 4.5) atomic percent niobium; its second vertex at 37.5 atomic percent titanium, 32.5 atomic percent nickel, and 30 (preferably 20) atomic percent niobium; its third vertex at 33.7 atomic percent titanium, 36.3 atomic percent nickel, and 30 (preferably 20) atomic percent niobium; and its fourth vertex at 45.5 atomic percent titanium, 52 atomic percent nickel, and 2.5 (preferably 4.5) atomic percent niobium.
  • a second aspect of the invention provides a shape memory alloy which consists essentially of nickel, titanium, and niobium within an area defined on a nickel, titanium, and niobium pseudo-binary phase diagram by a quadrilateral with its first vertex at 48 atomic percent titanium, 49.5 atomic percent nickel, and 2.5 atomic percent niobium; its second vertex at 41.32 atomic percent titanium, 38.68 atomic percent nickel, and 20 atomic percent niobium; its third vertex at 38 atomic percent titanium, 42 atomic percent nickel, and 20 atomic percent niobium; and its fourth vertex at 45.5 atomic percent titanium, 52 atomic percent nickel, and 2.5 atomic percent niobium.
  • a third aspect of the invention provides a shape memory alloy which consists essentially of nickel, titanium and niobium within an area defined on a nickel, titanium, and niobium pseudo-bonary phase diagram by a quadrilateral with its first vertex at 48 atomic percent titanium, 49.5 atomic percent nickel, and 2.5 atomic percent niobium; its second vertex at 37.5 atomic percent titanium, 32.5 atomic percent nickel, and 30 atomic percent niobium; its third vertex at 33.7 atomic percent titanium, 36.3 atomic percent nickel, and 30 atomic percent niobium; and its fourth vertex 45.5 atomic percent titanium, 52 atomic percent nickel, and 2.5 atomic percent niobium, the alloy having been deformed to impart non-recoverable (at the deformation temperature) strain thereto, as a result of which the strained alloy has a transformation hysteresis (As'-Ms) of at least 100°C.
  • As'-Ms transformation hysteresis
  • FIG. 1 there is illustrated a composition diagram for the nickel/titanium/ niobium system.
  • the titanium composition may be read on the horizontal axis and the niobium composition may be read on the vertical axis.
  • the nickel composition may be obtained by adding the titanium and niobium compositions and subtracting from 100. All compositions are in atomic percent.
  • the claimed composition in Figure 1 is generally bounded by area ADEH.
  • the composition for each of the vertices is given in Table 1.
  • Table 1 Ti(a/o) Ni(a/o) Nb(a/o) A 48 49.5 2.5 D 37.5 32.5 30 E 33.7 36.3 30 H 45.5 52 2.5
  • compositions to the left of AD have an M s temperature that is too high and compositions to the right of EH have an M s temperature that is too cold (substantially below liquid nitrogen).
  • alloys within area ADEH are very susceptible to having their transformation hysteresis enlarged; however, in those compositions below line AH, the enlargement is too small to be of practical utility.
  • compositions with higher niobium contents above line DE have too little shape memory effect to be of practical utility as will become apparent hereafter.
  • a particularly preferred composition is circumscribed by area BDEG on Figure 1.
  • the composition for each of the vertices is given in Table 2.
  • Table 2 Ti(a/o) Ni(a/o) Nb(a/o) B 47.24 48.26 4.5 D 37.5 32.5 30 E 33.7 36.3 30 G 44.64 50.86 4.5
  • lines BD and EG provide boundaries for compositions having the proper range of M s temperatures.
  • line DE provides the upper limit of the niobium content.
  • Line BG now provides the lower boundary for the free-machining alloys such that all alloys within BDEG are free-machining. It is expected that alloys with higher niobium contents above line DE would also be free-machining but are excluded from the alloys according to the invention due to the small shape memory effect present, as mentioned above. The fact that the alloys according to the invention are free-machining was surprising and totally unexpected.
  • compositions for each of the vertices is given in Table 3.
  • line CF provides a boundary between compositions having different recovery forces as well as different machinabilities, as just discussed. On Figure 1, those compositions below line CF have a higher recovery force than those compositions above line CF. The import of this will become apparent hereafter.
  • compositions are those in area BCIJ.
  • the bounds of this area are given in Table 4.
  • Table 4 Ti(a/o) Ni(a/o) Nb(a/o) B 47.24 48.26 4.5 C 41.32 38.68 20 I 39 41 20 J 45.5 50 4.5
  • Lines CI and BJ have been drawn to optimize recovery force and machinability.
  • Lines BC and IJ have been drawn to optimize the desired M s temperatures and the expansion of the transformation hysteresis.
  • the resulting ingots were hot swaged and hot rolled in air at approximately 850°C to produce a strip of approximately 0.025-in. (0.635 mm thickness. Samples were cut from the strip, descaled and vacuum annealed at 850°C for 30 minutes and furnace cooled.
  • compositions to the left of line AD have an M s of about 30°C or higher. Since this M s is higher than room temperature, the utility of those alloys to the left of line AD is necessarily limited for coupling, fastener, or similar type applications.
  • compositions to the right of line EH have an M s substantially less than -196°C.
  • these alloys may have some utility (e.g., as replacement for the Ni/Ti/Fe cryogenic alloys of Harrison, et al. as noted in the Background of the Invention) but for the instant invention, these compositions will not fulfill the objects of the invention.
  • Line IJ defines a constant M s of about -80°C. Compositions to the right of line IJ will have a colder M s and compositions to the left of line IJ will have a warmer M s .
  • An M s of -80°C is an important number since this means that the composition will have acceptable strength at about -55°C (there being a strength minimum at M s ) and thus will meet the previously noted Military Specification.
  • compositions between lines IJ and BC define the most preferred range based on the M s temperature.
  • each sample was elongated. After elongation the stress was removed and the strip was heated unrestrained so as to effect recovery of the shape memory alloy. The recovery was monitored and plotted as a function of temperature. When the transformation was complete, the sample was cooled and then reheated so as to complete the measurement of the martensite and austenite transformation temperatures before recovery and after recovery.
  • the elongation of the sample will act to expand the transformation hysteresis such that the austenite transformation temperatures, A s and A f will be temporarily raised to A s ' and A f '.
  • the martensite transformation temperatures, M s and M f will remain essentially constant.
  • the measure A s ' minus M s defines an operating range. That is, the M s value will be indicative of the lower temperature limit of functionality of the sample and A s ' is indicative of the highest temperature the sample may be exposed to before the sample will transform to austenite. After the sample transforms to austenite, the hysteresis will shrink to A s -M s .
  • a s '-M s is a useful indicator of the expansion of the hysteresis.
  • a s '-M s will also be useful in indicating the preconditionability of each composition wherein the transformation hysteresis can be temporarily expanded prior to use.
  • Line AH at the bottom of Figure 2 was determined to be the dividing line between those compositions having practical preconditionability and those compositions not having practical preconditionability.
  • the preconditionability number (A s '-M s ) is the top number in parentheses at each data point and M s is the bottom number. The other number at each data point is the alloy number.
  • the preconditionability does not substantially change until about 2.5% niobium (line AH).
  • Compositions to the left of line AD and above 2.5% niobium have a preconditionability of less than about 100°C and are unsuitable, in any event, since they have an M s that is too warm.
  • Compositions to the right of line AD and above 2.5% niobium have a preconditionability over about 100°C.
  • preconditionability will increase from low niobium content toward higher niobium content for any given constant M s value.
  • composition 24 (15% niobium) is more preconditionable than composition 6 (12% niobium), even though both have a similar M s .
  • preconditionability will increase with decreasing titanium content for any given niobium content.
  • compositions 8, 46, and 48 all of which have a niobium content of 10 atomic percent, the preconditionability increases from 109 to 263 while titanium content decreases from 45 to 43 atomic percent.
  • Alloys to the left of line BD contain a third, coarse phase in addition to the primary (shape memory) phase and the eutectic.
  • the eutectic structure if present, tends to be rather coarse, too. In this regard, see Figure 4 (alloy 51).
  • Table 7 Alloy No. Ti Ni Nb 35 46 51 3 51 49 43 8 30 39 39 22 14 44 47 9 21 39 43 18
  • Alloys below line BG exemplified by alloy 35, contain very small amounts of eutectic, usually less than about 5 volume percent.
  • the microstructure can be seen in Figure 5.
  • alloys having a niobium content above line CF such as alloy 30, contain primarily the eutectic plus a second phase consisting of almost pure niobium (see Figure 6).
  • the area within BCFG in Figure 3 is exemplified by alloy 14 and alloy 21.
  • the microstructures can be seen in Figures 7 and 8, respectively.
  • the microstructure is characterized by the primary (shape-memory) phase in the form of dendrites plus an interdentritic eutectic network.
  • the eutectic appears to consist of the primary phase plus essentially pure niobium.
  • the eutectic network is broken up and the alloy becomes more homogeneous on a microscopic scale.
  • the volume fraction of eutectic increases with increasing niobium.
  • the eutectic appears to coarsen with increasing titanium content.
  • alloy 14 has a very fine eutectic.
  • alloys with this microstructure have excellent formability and, for example, may be cold worked at room temperature.
  • an alloy having the nominal composition of 44 atomic percent titanium, 47 atomic percent nickel, and 9 atomic percent niobium, (the above alloy 14) was cold drawn to 0.025-inch (0,635mm) diameter wire from 0.5-inch (12,7mm) bar with interpass anneals at 850°C.
  • the same alloy could also be hot rolled to form sheet which could then be cold rolled as a finishing operation.
  • the alloys having enhanced machinability are located within area BDEG, the area having the greatest amount of the eutectic composition. Even more unexpectedly, the alloys within area BCFG have greatly enhanced machinability for reasons which will become apparent shortly. Generally, it has been found that machinability increases with increasing eutectic.
  • the eutectic in area BCFG is presented as a phase with different mechanical properties much the same way as a free-machining steel or brass. It was found that when the volume percent of eutectic was 5% or greater, improved machinability was observed. With the eutectic less than about 5 volume percent, the desired effect was not observed. In area CDEF, the eutectic is presented as the major constituent, which has better machinability than the primary shape memory phase (as found, e.g., in normal nickel/titanium-based alloys), but not as good as where it surrounds the primary shape memory phase as in area BCFG.
  • Samples were prepared in the same manner as those in Examples I. Each sample was deformed 14% (except where noted), unloaded, heated, and then allowed to freely recover 3%. Each sample was then restrained (strain rate set at zero) so as to build up a stress, which was then measured.
  • the purpose of this test was to simulate the behavior of a coupling.
  • the 3% free recovery was for the purpose of demonstrating the taking up of tolerances. After the 3% free recovery, the coupling would come up against the substrate (the pipe) which would act as a virtually immovable object. At this point, the coupling would continue to attempt to recover, thereby building up to a maximum stress.
  • the maximum stress ( ⁇ max ) measured is a reliable indicator of the recovery force of the coupling.
  • the first four samples are located below line CF.
  • the last four samples are above line CF.
  • the comparison of the two sets of samples is most revealing.
  • compositions above line CF clearly have less recovery force than those below line CF. Thus, it is expected that the latter compositions will have somewhat greater utility than the former compositions. It should be understood, however, that compositions above line CF (but below line DE) will still have practical utility and will also satisfy the objects of the invention.
  • Alloy 38 is on the border between the alloys according to the invention and the alloys not within the scope of the invention. The reason for this demarcation can be explained as follows. It is noted that alloy 38 had zero recovery force. This result is due to the fact that the shape memory effect in this particular composition (as well as other compositions having greater than about 30 percent niobium) is so small that there was not enough shape memory recovery to take up the 3 percent simulated tolerance. The small shape memory effect is due, it is believed, to the reduced volume fraction present of the shape memory phase. Accordingly, it is believed that compositions beyond line DE will have little practical utility.
  • the properties of the alloys according to the invention can be influenced to varying degrees by processing. As will become apparent hereafter, the properties of any particular alloy can be tailored to fit a particular set of requirements by application of the following preferred processing methods.
  • the zero load M s temperature was determined as a function of processing temperature for an alloy consisting essentially of 44 atomic percent titanium, 47 atomic percent nickel, and 9 atomic percent niobium. Three of the samples were warm worked and warm annealed at temperatures ranging from 400-600°C and three of the samples were hot worked at temperatures between 850 and 900°C and then hot annealed at temperatures between 850 and 1050°C. The results are tabulated in Table 9. Table 9 Sample No.
  • thermo-mechanical processing can be applied to these alloys to control the temperature of transformation.
  • preconditionability is also improved by warm working and warm annealing. Rings of the above alloy were enlarged 16% at -50°C after warm working/warm annealing at 600°C or hot working/hot annealing at 850°C. The rings were heated and allowed to freely recover so that A s ' could be measured.
  • the warm worked/warm annealed ring had an A s ' of 40°C. From Table 9, M s was -170°C. Therefore A s '-M s is 210°C.
  • the hot worked/hot annealed ring had an A s ' of 52°C and an M s of -94°C so that A s '-M s is 146°C.
  • the operating range of the alloy, A s '-M s has been increased by 64°C by optimizing processing conditions.
  • the effect of processing upon austenitic yield strengths was studied.
  • two samples were made from an alloy consisting essentially of 45 atomic percent Ti, 47 atomic percent nickel, and 8 atomic percent niobium.
  • One sample was hot worked and hot annealed (for 30 minutes) at 850°C and the other was warm worked and warm annealed (for 30 minutes) at 500°C.
  • the M s at 10 ksi (68,95 N/mm2) and the austenitic yield strengths were measured.
  • the hot worked/hot annealed sample had an M s of -5°C and an austenitic yield strength of 82 ksi.
  • the warm worked/warm annealed sample had an M s of -47°C and an austenitic yield strength of 96 ksi. (661,9 N/mm2)
  • processing can be used to control the strength, as well as the transformation temperature, of the disclosed alloys.
  • the samples were made from an alloy consisting essentially of 46 atomic percent nickel, 46 atomic percent titanium, and 8 atomic percent niobium.
  • One sample had a 10 ksi M s of 24°C after hot working and hot annealing at 850°C.
  • Another sample had a 10 ksi M s of 3°C after cold rolling and then warm annealing at 500°C.
  • the room temperature austenitic yield strength was raised from 78 ksi (537,8 N/mm2) hot worked/hot annealed) to 132 ksi (910,11 N/mm2) by cold rolling and warm annealing.
  • cold working combined with an appropriate annealing temperature can also be used to control the strength and transformation temperature of the disclosed alloys.
  • M s can be either raised or lowered by heat treatment.

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Claims (11)

  1. Verwendung von Niob in einer Nickel-Titan-Legierung mit Formgedächtnis, um die Umwandlungshysterese (As'-Ms) der gedehnten Legierung auf mehr als 100 °C (bevorzugt mehr als 125 °C) auszudehnen, wobei die Legierung im wesentlichen aus Nickel, Titan und Niob innerhalb eines Bereichs besteht, der in einem quasibinären Nickel-Titan-Niob-Phasendiagramm definiert ist durch ein Viereck mit seinem ersten Scheitel bei 48 Atom-% Titan, 49,5 Atom-% Nickel und 2,5 (bevorzugt 4,5) Atom-% Niob; seinem zweiten Scheitel bei 37,5 Atom-% Titan, 32,5 Atom-% Nickel und 30 (bevorzugt 20) Atom-% Niob; seinem dritten Scheitel bei 33,7 Atom-% Titan, 36,3 Atom-% Nickel und 30 (bevorzugt 20) Atom-% Niob; und seinem vierten Scheitel bei 45,5 Atom-% Titan, 52 Atom-% Nickel und 2,5 (bevorzugt 4,5) Atom-% Niob.
  2. Legierung mit Formgedächtnis, die im wesentlichen aus Nickel, Titan und Niob innerhalb eines Bereichs besteht, der in einem quasibinären Nickel-Titan-Niob-Phasendiagramm definiert ist durch ein Viereck mit seinem ersten Scheitel bei 48 Atom-% Titan, 49,5 Atom-% Nickel und 2,5 Atom-% Niob; seinem zweiten Scheitel bei 41,32 Atom-% Titan, 38,68 Atom-% Nickel und 20 Atom-% Niob; seinem dritten Scheitel bei 38 Atom-% Titan, 42 Atom-% Nickel und 20 Atom-% Niob; und seinem vierten Scheitel bei 45,5 Atom-% Titan, 52 Atom-% Nickel und 2,5 Atom-% Niob.
  3. Legierung mit Formgedächtnis, die im wesentlichen aus Nickel, Titan und Niob innerhalb eines Bereichs besteht, der in einem quasibinären Nickel-Titan-Niob-Phasendiagramm definiert ist durch ein Viereck mit seinem ersten Scheitel bei 48 Atom-% Titan, 49,5 Atom-% Nickel und 2,5 Atom-% Niob; seinem zweiten Scheitel bei 37,5 Atom-% Titan, 32,5 Atom-% Nickel und 30 Atom-% Niob; seinem dritten Scheitel bei 33,7 Atom-% Titan, 36,3 Atom-% Nickel und 30 Atom-% Niob; und seinem vierten Scheitel bei 45,5 Atom-% Titan, 52 Atom-% Nickel und 2,5 Atom-% Niob, wobei die Legierung deformiert worden ist, um ihr eine (bei der Deformierungstemperatur) nichtrückstellbare Dehnung zu erteilen, aufgrund deren die gedehnte Legierung eine Umwandlungshysterese (As'-Ms) von wenigstens 100 °C hat.
  4. Legierung nach Anspruch 3, die nicht mehr als 20 Atom-% Niob enthält.
  5. Legierung nach einem der Ansprüche 2 bis 4, die wenigstens 4,5 Atom-% Niob enthält.
  6. Legierung mit Formgedächtnis nach Anspruch 2 oder 3 innerhalb eines Bereichs, der in dem genannten quasibinären Nickel-Titan-Niob-Phasendiagramm definiert ist durch ein Viereck mit seinem ersten Scheitel bei 47,24 Atom-% Titan, 48,26 Atom-% Nickel und 4,5 Atom-% Niob; seinem zweiten Scheitel bei 41,32 Atom-% Titan, 38,68 Atom-% Nickel und 20 Atom-% Niob; seinem dritten Scheitel bei 39 Atom-% Titan, 41 Atom-% Nickel und 20 Atom-% Niob; und seinem vierten Scheitel bei 45,5 Atom-% Titan, 50 Atom-% Nickel und 4,5 Atom-% Niob.
  7. Legierung nach einem der Ansprüche 2 bis 6 mit Ms nicht weniger als -80 °C.
  8. Verfahren zum Herstellen einer Nickel-Titan-Legierung mit Formgedächtnis, gekennzeichnet durch (a) die Zugabe von 2,5 (bevorzugt 4,5) bis 30 (bevorzugt 20) Atom-% Niob, um eine Zusammensetzung nach Anspruch 3 zu erhalten zu dem Zweck, es der Martensit/Austenit-Umwandlungshysterese der Legierung zu ermöglichen, durch Dehnung der Legierung auf wenigstens 100 °C ausdehnbar zu sein, und durch (b) das Deformieren der Legierung, um ihr eine (bei der Deformierungstemperatur) nichtrückstellbare Dehnung zu erteilen, wodurch die Hysterese auf wenigstens 100 °C ausgedehnt wird.
  9. Gegenstand, der aus einer Legierung nach einem der Ansprüche 2 bis 7 gebildet ist.
  10. Band, Stab, Draht, Flächenkörper oder hohle Hülse, die aus einer Legierung nach einem der Ansprüche 2 bis 7 gebildet sind.
  11. Rohrkupplung, elektrischer Verbinder oder Schalter, die einen Gegenstand nach Anspruch 9 oder 10 aufweisen.
EP85308079A 1984-11-06 1985-11-06 Nickel-Titan-Niob-Formgedächtnislegierung und daraus gefertigter Gegenstand Expired - Lifetime EP0185452B1 (de)

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AT85308079T ATE89871T1 (de) 1984-11-06 1985-11-06 Nickel-titan-niob-formgedaechtnislegierung und daraus gefertigter gegenstand.

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US66877784A 1984-11-06 1984-11-06
US668777 1984-11-06

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EP0185452B1 true EP0185452B1 (de) 1993-05-26

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4872713A (en) * 1987-02-19 1989-10-10 Raychem Corporation Coupling device
JP2802385B2 (ja) * 1989-03-22 1998-09-24 清原 まさ子 制御器
JPH09511281A (ja) 1994-03-31 1997-11-11 エー． ベッセリンク，ペトルス Ｎｉ−Ｔｉ−Ｎｂ合金の処理方法と該合金から作られた物品
US20040193257A1 (en) * 2003-03-31 2004-09-30 Wu Ming H. Medical devices having drug eluting properties and methods of manufacture thereof
EP2339040B1 (de) 2006-03-17 2014-10-08 University of Tsukuba Aktuator und Motor
WO2007108180A1 (ja) 2006-03-20 2007-09-27 University Of Tsukuba 高温形状記憶合金、アクチュエータおよび発動機
JP2008031545A (ja) * 2006-07-31 2008-02-14 Shuichi Miyazaki ピストンリング

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US3662455A (en) * 1970-12-10 1972-05-16 Sanders Associates Inc Method for preparing an anti-oxidizing, active alloy brazing composition
JPS58157934A (ja) * 1982-03-13 1983-09-20 Hitachi Metals Ltd 形状記憶合金
JPS59150069A (ja) * 1983-02-15 1984-08-28 Hitachi Metals Ltd 形状記憶合金製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SCIENTIFIC AMERICAN, vol. 241, no. 5, November 1979; pp. 68-76# *

Also Published As

Publication number Publication date
JPS61119639A (ja) 1986-06-06
ATE89871T1 (de) 1993-06-15
DE3587365T2 (de) 1993-09-02
DE3587365D1 (de) 1993-07-01
JP2539786B2 (ja) 1996-10-02
CA1259826A (en) 1989-09-26
EP0185452A1 (de) 1986-06-25

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