Ferrous Polycrystalline Shape-Memory Alloy Showing Huge Superelasticity Y. Tanaka, et al. Science 327, 1488 (2010); DOI: 10.


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27. Chem. 2Institute of Multidisciplinary Research for Advanced Materials. this ferrous alloy has a very large damping capacity and exhibits a large reversible change in magnetization during loading and unloading. Tolbert. Supporting Online Material www.org on May 31. 56 (2007). Soc. L. Chung et al. 7282 (2005).sciencemag. although the g/a′ martensitic transformation in this system is not thermoelastic. Figure 1E shows a series of optical micrographs taken from the NCATB alloy during 11% tensile strain cycle (movie S1). Phys. 14444 (2006). B.1 T. An SS curve obtained from a commercial Ni-Ti superelastic wire (Ni-49. which is approximately 20 times larger than that obtained in the Fe-Ni-Co-Ti alloy and almost twice that of the commercial Ni-Ti alloy. lastic strain in metallic materials is usually limited to about 0. J.” which. Ni-Ti–based polycrystalline SMA specimens are easily fractured. accepted 2 February 2010 Published online 18 February 2010. It is known that Fe-Pd (9) and Fe-Pt (10) alloys exhibit a thermoelastic fcc/face-centered tetragonal (fct) transformation.1 Y. Beverina et al. have been E 1 Department of Materials Science. Omori. It was also found that a 7-carbon polymethine with thiopyrylium terminal groups (S-7C) exhibited slightly lower nonlinearities but comparable two-photon FOMs to Se-7C (Table S3). Furthermore. because of their better workability and lower cost. J.ac. hereafter notated as NCATB] is mechanically strengthened by fine and coherent precipitates of a g′-(Ni. J. 26. Marder. and stents. are basically nonthermoelastic.2%. Am. S1) and a strong recrystallization {035}<100> texture obtained by thermomechanical treatment. which is almost twice the maximum superelastic strain obtained in the Ni-Ti alloys. spectacle frames. 6. 119.tohoku. J. Exhibiting some ductility and a superelastic strain of more than 7%.org/cgi/content/full/science. 295 (1984). E-mail: kainuma@tagen.Fe. the Ni-Ti–based polycrystalline SMAs are used for many products. 29. which is significantly smaller than that of nonthermoelastic transformations in steels and general ferrous alloys (~ 400 K) but is comparable to that reported in the Fe-Ni-Co-Ti alloy (8). Sendai 980-8579. One drawback of existing ferrous SMAs is that superelasticity can barely be obtained at room temperature. Marder et al. Chem. Chem.. 25. most polycrystalline SMAs that have an atomically ordered structure are extremely brittle..Co)3Ti phase with a L12 structure (6). R. It is known that in the Fe-Ni-Al ternary alloy. the superelastic strain obtained by a bending test at 240 K is only 0. for example. 128. 28. namely. For applied strains up to approximately 15%. 279. B 24. which is insufficient for practical use.1 R. The Fe-Mn-Si–based alloys are now used for pipe couplings and fishplates. Tohoku University. The cyclic tensile stress-strain (SS) curves obtained at room temperature for NCATB superelastic alloy are shown in Fig. M. Maki and others have succeeded in obtaining a thermoelastic g/a′ (bct) transformation in a polycrystalline Fe-Ni-Co-Ti alloy by the precipitation of a g′-(Ni. Polycrystalline alloys. Soc. Tohoku University. and the DARPA ZOE Program (W31P4Q-09-1-0012). with a tensile strength above 1 gigapascal. 22. Fu et al. such as Fe-Mn-Si (2. Am. Many shape-memory alloys (SMAs). 7. Mater. Opt. Am. X.jp developed as “ferrous SMAs. H.1126/science. Chem. Dyes Pigments 5.%). J. However. by large deformations of over 30% that occur after cold rolling without intermediate annealing. show a large reversible strain of greater than several percent due to “pseudoelasticity” or “superelasticity” (1). 179 (2002).5Ta-0. The NCATB alloy shows a very high tensile strength of 1200 MPa. S. Tanaka. which exhibits some ductility and excellent superelastic strain. 14). Ishida1 Shape-memory alloys. We present here a ferrous polycrystalline SMA showing a large superelastic strain of over 13% at room temperature due to a thermoelastic g/a′ transformation. We herein describe a ferrous polycrystalline. Figure 2A shows an electrical resistivity curve for the NCATB superelastic alloy in the temperature region of the martensitic transformation. 3). which has a thermoelastic transformation. 30. Kainuma.sciencemag. The martensitic transformation start temperature Ms and the reverse transformation finish temperature Af are 187 and 211 K. Am. shape-memory alloy exhibiting a superelastic strain of more than 13%. the texture intensity of the <100>g component in the rolling VOL 327 SCIENCE direction is 25. J. Scherer et al. but in spite of extensive studies. This strain relies on the occurrence of a thermoelastic martensitic transformation and arises from a combination of stress-induced transformation upon loading and its reverse transformation upon unloading. 47.1185117/DC1 Materials and Methods SOM Text Figs. medical guidewires. S2).1185117 Include this information when citing this paper. J. 24. M. 7095 (2008). S.sciencemag. Zhao. Soc. 1C.2* Y. The origin of the thermoelastic transformation observed in the NCATB alloy can be understood on the basis of the arguments put forward by Maki and others for the Fe-Ni-Co-Ti alloy (1. Anderson. high hardness (Vickers hardness = 402) large tetrag- 1488 19 MARCH 2010 www. Chem. such as Ni-Ti and Cu-Zn-Al. Before the present study. However. Angew. respectively. Japan. the NCATB exhibits almost complete superelasticity (Fig. Science 276. we examined the effects of alloying elements and of microstructures controlled by various thermomechanical treatments on the ductility and the superelasticity for the Fe-Ni-Al alloys. Ed. We thank W. 12). the Ni-Ti–based alloy. 21. Hales. S. the Defense Advanced Research Projects Agency (DARPA) MORPH Program and Office of Naval Research (N00014-04-0095 and N00014-06-1-0897). and Fe-Ni-Co-Ti (5–8). Japan. as well as in the Fe-Ni-Co-Ti alloy. L. Himuro..5Al-2. the g′-phase with the L12 structure coherently precipitates in the g matrix by aging (11. Graduate School of Engineering. 23. A to C (13). is only 24 K. D.% Ti) is also presented in Fig. 1233 (1997).1 K. Reduced productivity and the high cost of fabrication caused by the low cold-workability impede further application of these materials to other fields. Ferrous Polycrystalline Shape-Memory Alloy Showing Huge Superelasticity Y. Here. 1B). A. 2011 . L. The maximum superelastic strain obtained is about 13. C.. Hermann for helpful discussions and corroborative nonlinear optical characterization measurements.5%.. Sendai 980-8579. J. This ferrous shape-memory alloy has great potential as a high-damping and sensor material. is the only superelastic material available for practical applications at present. 215 (1995). The microstructural evolution indicates that stress-induced a′ martensites appear and vanish during the strain cycle and that this pseudoelastic behavior is caused by stress-induced thermoelastic transformation. R. S1 to S8 Tables S1 to S4 References 24 November 2009. Int. This ferrous superelastic alloy with a composition of Fe-28Ni-17Co-11. In particular. This material is based on work supported in part by the Science and Technology Centers Program of NSF under agreement DMR-0120967. The thermal hysteresis of the transformation. Furthermore. are commercially more attractive than the Ni-Ti–based SMAs.05B [atomic percent (at. no superelasticity at room temperature has been reported since the discovery of Fe-Ni-Co-Ti alloy in 1984.REPORTS 20.4 at. Chem. *To whom correspondence should be addressed. such as cellular phone antennae. Perry. K. high-strength. Soc. Ta) phase with a L12 structure due to aging (fig.7% (7). 1. W. Thorley. such as Ni-Ti and Cu-Zn-Al. J. and application of stress over a critical value causes plastic deformation due to slip or twin boundary motion.org Downloaded from www. show a large reversible strain of more than several percent due to superelasticity. Sutou. Fe-Ni-C (4). their ductility is not sufficient for most applications. 127. 10. defined as Th ≡ Af – Ms. 3253 (1997).Fe..4 (fig. because their martensitic transformations—g [facecentered cubic (fcc)]/e [hexagonal close packed (hcp)] and g/a′ [body-centered cubic (bcc) or body-centered tetragonal (bct)].Co)3(Al. We have now found a combination of composition and microstructure suitable to obtain the high level of superelasticity [supporting online material (SOM) text]. D. Kachkovski et al. However. Gorman.

the grain boundary precipitation of the b phase cannot be suppressed without the doping of boron.REPORTS onality of the bct martensite phase (c/a = 1.3604 nm and a = 0.1%. 2A. If the bcc martensite appearing in the final stage has the same molar volume as that of the bct martensite. Electrical resistance curves obtained from (A) NCATB sheet with strong {035}<100> texture. One possible explanation for this discrepancy is the occurrence of a two-step transformation. respectively. respectively. 2B.org on May 31.11) → bcc. which drastically changes the transformation behavior from nonthermoelastic to thermoelastic (Fig. In the present alloy. Figure 2.% Ti). however. the g/a′ transformation is nonthermoelastic. improvement in the mechanical properties was obtained by the suppression of the grain boundary precipitation of the b phase (Fig. inset). and that from the random textured NCAT alloy is in the inset of (C). producing a volume change due to the transformation of +0. The result for the <100>g direction.Co)3(Al. 2. does not agree with the superelastic strain of 13. The optical micrographs taken from the random and {035}<100> textured NCATB alloys are shown in the inset of (A). Tensile SS curves at room temperature obtained in the NCATB alloy (A to C) with strong {035}<100> texture and (D) with random texture and [inset of (C)] commercial Ni-Ti superelastic wire (Ni-49. in the B-free NCAT alloy. Hence.11. According to theoretical calculation based on a phenomenological theory.5%. a strong g′forming element. exhibiting a large thermal hysteresis greater than 500 K. where most of the grain boundaries (about 90%) are composed of high-angle boundaries covered by the b phase. Ta)–ordered fcc phase (table S1). the superelastic strains expected in directions <110>g and <111>g are about 4.5Al-2.sciencemag. 2C. c = 0. increases the volume fraction of the g′ phase and heightens the hardness and tetragonality of martensite (table S1). the fraction of high-angle boundaries (about 40%) could be lowered by a strong {035}<100> recrystalization texture developed because of thermomechanical treatment (fig. showing stress-induced martensite and its reverse transformation.0. and the partial atomic ordering of the parent phase because of coherent precipitates of the g′-(Ni. 2C).1 and 2. B and C. 19 MARCH 2010 1489 Downloaded from www. In the NCA quaternary alloy shown in Fig.2867 nm and the emax becomes 12. 2A. the tensile superelastic strain expected in the <100>g direction is simply evaluated from the lattice correspondence by pffiffiffi 2a − a0 emax ≈ ð1Þ 100 a0 In the case of single crystal NCATB. which may be due to a small amount of the g′ precipitates because of its low g′ solvus temperature (table S1).7%.3069 nm.2771 nm. The NCATB alloy with a random texture. and the strain in the direction <100>g has a maximum value (fig S3). The addition of a small amount of boron results in a drastic suppression of the undesirable b phase. It is known that both the shape memory and superelastic properties are also influenced by control of the texture. (E) A series of optical micrographs taken from the NCATB superelastic alloy during the 11% tensile strain cycle.org SCIENCE VOL 327 Fig. the <100>g direction of the {035}<100> textured sheet. The lattice parameters of the g and a′ phases of NCATB. as determined by x-ray diffraction. the emax 100 is 8. that is. superelasticity cannot be obtained. 100 which is almost comparable to the experimental Fig. Therefore. Consequently.). www.68%. However.5Ta (NCAT) alloys. are a0 = 0. additions of Ta and B are necessary for obtaining excellent superelastic properties.4 at. 1C).sciencemag. 2011 . is still brittle and fractures before showing superelasticity (Fig. In the NCATB alloy. 1D). S2).5% experimentally obtained in the rolling direction <100>g for the {035}<100> textured sheet (Fig. although the precipitation of the b phase cannot be completely suppressed at high-angle boundaries (Fig. and the ductility of the alloy rapidly decreases because of intergranular fracture. because the transformation strain is strongly dependent on the deformation direction in crystals (16–19).5Al (NCA) and Fe-28Ni-17Co-11. 1. The electrical resistivity ratio at 298 K is scaled as 1. such as small-angle and coincidence grain boundaries (15). b-NiAl– ordered bcc phase precipitates along the grain boundaries in the matrix phase (Fig. Although the strong {035}<100> texture develops due to a similar thermomechanical treatment in the B-free NCAT alloy. The addition of Ta. inset). respectively. The tensile direction is parallel to the rolling direction. shows the electrical resistivity curves for Fe-28Ni-17Co-11. and (C) NCAT sheets with random texture. the lattice parameter of the bcc phase is a = 0. The appearance of the nonthermoelastic transformation is a result of its low hardness and small tetragonality of martensite. fcc → bct (c/a = 1. inset). respectively. (B) NCA.Fe. It is known that sheet specimens with a strong texture have many low-energy grain boundaries. where c and a are the lattice parameters for the c and a axes.

T. Watanabe. 186 (1979). Shape Memory Materials (Cambridge Univ. 855 (1980). 15. T. Figure 4 shows the magnetizationversus–magnetic field curves at room temperature obtained under some fixed tensile strains for an NCATB superelastic sheet specimen. 2026 (2008). Cambridge. This physical property can be used practically as a noncontact strain sensor covering a large repeatable strain of over 10% and is detectable in the magnetization. Metall.0% strains. E. Ziebeck at Cambridge University for his help in critical reading. Kajiwara. Mayer.% Ti. 137 (1973). 6. There is a possibility that in the second stage over the ec1 of about 10%. Proc. C. C. Scr. unloading process. whereas some hysteresis occurs between the loading and unloading curves. dotted lines. Kakeshita et al. and sensor materials in various fields. T. V. Ganzula. Metall. The NCATB alloy sheet with a strong texture exhibits an excellent superelastic effect of more than 13%. Metall. Mech. The magnetization after unloading is almost the same as that before loading.sciencemag. Tohoku University. 22. In contrast to the Ni-Ti–based SMAs. 10. M. M. and Global COE Program. 1105 (1984). This work was supported by Grant-in-Aids from the Japanese Society for the Promotion of Science (JSPS). 4. 179 (2006). No apparent change in magnetization due to thermal martensitic transformation was detected in the thermomagnetization curves (fig. because the transformation hardly proceeds during cooling (Fig. P.% Ti-6Nb (23). Metall. 2011 . 9. Arai. Trans. S. I. The authors are grateful to K. Chernenko. J. 13. R. compared with those for conventional superelastic nonferrous polycrystalline SMAs (17. One of them is an excellent mechanical damping property due to the large energy absorption in the superelastic cycle. Sutou. Kajiwara. VOL 327 SCIENCE 1490 19 MARCH 2010 www. even by a 99% reduction in cold rolling without intermediate annealing. Plotted in Fig. Because they absorb a large amount of energy during a superelastic cycle. Fujita. McCormik. 584 (1967). A 273–275. Phys. the c/a ratio of the bct a′ martensite continuously decreases with applying stress. Baruj. Ishida. Tyber. Kikuchi. which yields the recoverable strain. 2. Ni-46. S.sciencemag. 67 (1999). Di Sarno. Acta Metall. Therefore. Eng.4 at. N. however. as shown in comparison between the micrographs 4 and 5 with 10. 46. 3 is the energy absorbed by a superelastic cycle per unit volume as a function of applied tensile strain for the NCATB superelastic alloy. and the strain region with the low gradient given by De01 = ec1 – ec0. 4. 2817 (2002). 60 (2003). Prog. Soma. T. 23). 23. J. K. Trans. Japan. S1 to S4 Table S1 References Movie S1 12 October 2009. Wayman. Shevchenko. Chishima. S4). 133. N. tubes. where the absorbed energy corresponds to the area enclosed by hysteresis loop in the SS curve.org on May 31. Mater. N.2Al-3Ni (17) superelastic polycrystalline SMAs. Phys. Eng. which shows the largest energy absorption of all nonferrous SMAs (38 MJ/m3 in 8% superelastic cycle) (23) and is also almost 5 times larger than that in the Ni-Ti alloy (16 MJ/m3 in 8% superelastic cycle). Press.REPORTS value. 4. Kajiwara. K. loading process. V. If this alloy is used as a mechanical damper in constructions. has not been observed. Met. 67. It is seen that the spontaneous magnetization drastically increases with increasing applied strain and reaches 140 electromagnetic units (emu)/g at a strain of 12%. 21. T. K. K. A. Mater. Bhatacharya. Acta Metall. 18. Appl. 1B). which is more than twice as large as that in the Ni-Ti-Nb alloy. MEXT. J. Acta Metall. J. These results support the conjecture that the origin of the large superelastic strain is due to the two-step transformation. Solid lines. Structures 24.4 at. Trans. 5457 (1998). Eds. This alloy also has excellent cold-workability. 58. 5. I. This alloy shows several unique physical properties. 3. H. 1A). Metallk. 250 (2003). R.. The two-step transformation caused by the appearance of a second martensite phase. 202 (1989). 372 (1967). S. The superelastic Ni-Ti alloys have drawn attention as high-damping materials with a recentering capacity due to their superelasticity. 30. M. the NCATB alloy has many physical properties besides the large superelastic strain that are useful for practical applications. 1998). Metall. K. Dunne. N. Kokorin. K. Japan Science and Technology Agency (JST). Shu. Minato. Z. Ni-49. Thus. Dadda et al. respectively (Fig. which is about 3. 19. 973 (1985). 5. 47.% Mn-9. the gradient of the superelastic curve in the plateau region drastically changes at a strain of ec1 (Fig. various shapes. and the costs for fabrication can be lowered because of the advantages of the processing cost. Given these properties. a large change in magnetization and electric resistance during loading. and thin foils.5 at. Furthermore. Y. M. V. Hornbogen. Sohmura. 847 (1990).1183169 Fig. 7. although there is some residual strain perhaps due to slip deformation. DesRoches. Eng. F. Hornbogen. such as wires. Fig. 15. M. Sehitoglu et al. Kokorin. Acta Metall. K. Yu. Materials and methods are available as supporting material on Science Online. E. Delemont. Mater.5 times larger than that before loading. 18. SPIE 5053. can be obtained more easily compared with the Ni-Ti alloys fractured by deformation of over 30%. damping materials. Core Research for Evolutional Science and Technology (CREST). Energy absorbed by one superelastic cycle at room temperature as a function of applied tensile strain for NCATB.. and Cu-16. Eng. K. Sato. E. Oikawa. 2A). L. The NCATB superelastic alloy also undergoes a large change in spontaneous magnetization induced by the martensitic transformation. A. Takagi. but further work is required to confirm this. E. Koval. H. The spontaneous magnetization decreases during unloading. R.. the present ferrous superelastic alloy is expected to be used for many practical applications such as superelastic materials. accepted 25 January 2010 10. Otsuka. This value is roughly the same as the theoretical value for the <100>g direction in the bct martensite. R.3 and 11.. I. 941 (1989). T. 17. Acta Metall. 16. such as a large superelastic hysteresis. V. Omori. The maximum energy absorbed by a complete superelastic cycle for the present ferrous alloy with applied strains up to 15% is 81 MJ/m3. T. N. Shinya. M. Tamura. O. Kainuma. Acta Metall. 12. Ishida. S. V. Sci. Kainuma. the stressinduced a′ martensite has a spontaneous magnetization larger than 140 emu/g at room temperature. 38. Ono. one can nondestructively and noncontactually monitor the strain in the damper through magnetization measurements. Elnashai. Magnetization curves examined at room temperature under some fixed tensile strains for NCATB superelastic alloy.org Downloaded from www.5%. 3. Wayman. Biomater. D. Mayer. Met. 39A. 1E and movie S1). Scr. Sutou. R. 76B. Kobayashi. is about 8. H. Gall. 1019 (2007). Oshima. A. 325 (2002). Maier. where ec0 is the critical strain of stress-induced transformation. R. 14. Yamauchi. J. 3311 (2000). Scr. The polycrystalline specimens before aging are not fractured.sciencemag. and an excellent ductility. K. 48. Kikuchi. Y. Mori. 20. they have been considered for seismic applications such as dampers in buildings and bridges (20–22). A. Maki. 37. 11. T. Metall.1126/science. H. Samsonov. C. Y.org/cgi/content/full/327/5972/1488/DC1 Materials and Methods SOM Text Figs. where the magnetic field was applied in the direction perpendicular to the tensile direction. W. Fujii. M. T. References and Notes 1. W. Struct. 33A. The hysteresis in the SS curves of the NCATB superelastic alloy is considerably larger than that of the Ni-Ti superelastic alloys (Fig. DesRoches. Y. 14. 8. 1177 (1982). 24. Mater. Supporting Online Material www. New Energy and Industrial Technology Development Organization (NEDO). 19. and the change in magnetization of the alloy in the superelastic cycle is reversible.

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