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Unprecedented non-hysteretic superelasticity of [001]-oriented NiCoFeGa single crystals

Abstract

Superelasticity associated with the martensitic transformation has found a broad range of engineering applications1,2. However, the intrinsic hysteresis3 and temperature sensitivity4 of the first-order phase transformation significantly hinder the usage of smart metallic components in many critical areas. Here, we report a large superelasticity up to 15.2% strain in [001]-oriented NiCoFeGa single crystals, exhibiting non-hysteretic mechanical responses, a small temperature dependence and high-energy-storage capability and cyclic stability over a wide temperature and composition range. In situ synchrotron X-ray diffraction measurements show that the superelasticity is correlated with a stress-induced continuous variation of lattice parameter accompanied by structural fluctuation. Neutron diffraction and electron microscopy observations reveal an unprecedented microstructure consisting of atomic-level entanglement of ordered and disordered crystal structures, which can be manipulated to tune the superelasticity. The discovery of the large elasticity related to the entangled structure paves the way for exploiting elastic strain engineering and development of related functional materials.

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Fig. 1: Superelastic behaviour of Ni55-xCoxFe18Ga27 alloys.
Fig. 2: In situ synchrotron characterization of the superelasticity in NiCoFeGa fibres.
Fig. 3: Temperature-dependent neutron diffraction measurements at different temperatures for a Co20 single crystal.
Fig. 4: Microstructure and mechanical behaviour for alloy annealing at different temperatures.

Data availability

The data that supports the plots within this paper and the findings of this work are available from the corresponding author on reasonable request.

Code availability

The open-source and commercial software used for data analysis are referenced in the Methods.

References

  1. Otsuka, K. & Wayman, C. M. Shape Memory Materials (Cambridge Univ. Press, 1999).

  2. Jani, J. M., Leary, M., Subic, A. & Gibson, M. A. A review of shape memory alloy research, applications and opportunities. Mater. Desig. 56, 1078–1113 (2014).

    Article  Google Scholar 

  3. Ortin, J. & Delaey, L. Hysteresis in shape-memory alloys. Int. J. Non-Linear Mech. 37, 1275–1281 (2002).

    Article  Google Scholar 

  4. Omori, T. et al. Superelastic effect in polycrystalline ferrous alloys. Science 333, 68–71 (2011).

    Article  CAS  Google Scholar 

  5. Lemaitre, J. & Chaboche, J. L. Mechanics of Solid Materials (Cambridge Univ. Press, 1990).

  6. Otsuka, K. & Ren, X. Physical metallurgy of Ti-Ni-based shape memory alloys. Prog. Mater. Sci. 50, 511–678 (2005).

    Article  CAS  Google Scholar 

  7. Otsuka, K., Wayman, C. M., Nakai, K., Sakamoto, H. & Shimizu, K. Superelasticity effects and stress-induced martensitic transformations in Cu-Al-Ni alloys. Acta Metall. 24, 207–226 (1976).

    Article  CAS  Google Scholar 

  8. Wang, D. P. et al. Transition in superelasticity for Ni55-xCoxFe18Ga27 alloys due to strain glass transition. Europhys. Lett. 98, 46004 (2012).

    Article  Google Scholar 

  9. Taylor, G. F. A method of drawing metallic filaments and discussion of their properties and uses. Phys. Rev. 23, 655–660 (1924).

    Article  Google Scholar 

  10. Kaya, I., Karaca, H. E., Souri, M., Chumlyakov, Y. & Kurkcu, H. Effects of orientation on the shape memory behavior of Ni51Ti49 single crystals. Mater. Sci. Eng. A. 686, 73–81 (2017).

    Article  CAS  Google Scholar 

  11. Saghaian, S. M. et al. Effects of aging on the shape memory behavior of Ni-rich Ni50.3Ti29.7Hf20 single crystals. Acta Mater. 87, 128–141 (2015).

    Article  CAS  Google Scholar 

  12. Karaca, H. E., Acar, E., Basaran, B., Noebe, R. D. & Chumlyakov, Y. I. Superelastic response and damping capacity of ultrahigh-strength [111]-oriented NiTiHfPd single crystals. Scr. Mater. 67, 447–450 (2012).

    Article  CAS  Google Scholar 

  13. Chumlyakov, Y. I. et al. Shape memory effect and superelasticity in the [001] single crystals of a FeNiCoAlTa alloy with γ-α′ thermoelastic martensitic transformations. Russ. Phys. J. 56, 920–929 (2013).

    Article  CAS  Google Scholar 

  14. Andrews, T. On the continuity of the gaseous and liquid states of matter. Phil. Trans. R. Soc. Lond. 159, 575–590 (1869).

    Google Scholar 

  15. Xiao, F., Fukuda, T. & Kakeshita, T. Critical point of martensitic transformation under stress in an Fe-31.2Pd (at.%) shape memory alloy. Phil. Mag. 95, 1390–1398 (2015).

    Article  CAS  Google Scholar 

  16. Kosogor, A. et al. Hysteretic and anhysteretic tensile stress–strain behavior of Ni-Fe(Co)-Ga single crystal: experiment and theory. Acta Mater. 66, 79–85 (2014).

    Article  CAS  Google Scholar 

  17. Seiner, H. et al. Evolution of soft-phonon modes in Fe-Pd shape memory alloy under large elastic-like strains. Acta Mater. 105, 182–188 (2016).

    Article  CAS  Google Scholar 

  18. Fujimoto, M. The Physics of Structural Phase Transitions 2nd edn (Springer, 2005).

  19. Devaraj, A. et al. Experimental evidence of concurrent compositional and structural instabilities leading to ω precipitation in titanium–molybdenum alloys. Acta Mater. 60, 596–609 (2012).

    Article  CAS  Google Scholar 

  20. Sikka, S. K., Vohra, Y. K. & Chidambaram, R. Omega phase in materials. Prog. Mater. Sci. 27, 245–310 (1982).

    Article  CAS  Google Scholar 

  21. Williams, J. C., De Fontaine, D. & Paton, N. E. The ω-phase as an example of an unusual shear transformation. Metall. Trans. A. 4, 2701–2708 (1973).

    Article  CAS  Google Scholar 

  22. De Fontaine, D., Paton, N. E. & Williams, J. C. The omega phase transformation in titanium alloys as an example of displacement controlled reactions. Acta Metall. 19, 1153–1162 (1971).

    Article  Google Scholar 

  23. Nelson, D. R. Defects and Geometry in Condensed Matter Physics (Cambridge Univ. Press, 2002).

  24. Bokov, A. A. & Ye, Z. G. Recent progress in relaxor ferroelectrics with perovskite structure. J. Mater. Sci. 41, 31–52 (2006).

    Article  CAS  Google Scholar 

  25. Kowley, R. A., Gvasaliya, S. N., Lushnikov, S. G., Roessli, B. & Rotaru, G. M. Relaxing with relaxors: a review of relaxor ferroelectrics. Adv. Phys. 60, 229–327 (2011).

    Article  Google Scholar 

  26. Sarkar, S., Ren, X. & Otsuka, K. Evidence for strain glass in the ferroelastic-martensitic system Ti50-xNi50+x. Phys. Rev. Lett. 95, 205702 (2005).

    Article  Google Scholar 

  27. Wang, Y., Ren, X. & Otsuka, K. Shape memory effect and superelasticity in a strain glass alloy. Phys. Rev. Lett. 97, 225703 (2006).

    Article  Google Scholar 

  28. Greaves, G. N., Greer, A. L., Lakes, R. S. & Rouxel, T. Poisson’s ratio and modern materials. Nature Mater. 10, 823 (2011).

    Article  CAS  Google Scholar 

  29. Vitos, L. Computational Quantum Mechanics for Materials Engineers: The EMTO Method and Applications (Springer, 2007).

  30. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  31. Gyorffy, B. L. Coherent-potential approximation for a nonoverlapping-muffin-tin-potential model of random substitutional alloys. Phys. Rev. B. 5, 2382–2384 (1972).

    Article  Google Scholar 

  32. Vitos, L., Abrikosov, I. A. & Johansson, B. Anisotropic lattice distortions in random alloys from first-principles theory. Phys. Rev. Lett. 87, 156401 (2001).

    Article  CAS  Google Scholar 

  33. Soven, P. Coherent-potential model of substitutional disordered alloys. Phys. Rev. 156, 809–813 (1967).

    Article  CAS  Google Scholar 

  34. Skriver, H. L. Crystal structure from one-electron theory. Phys. Rev. B. 31, 1909–1923 (1985).

    Article  CAS  Google Scholar 

  35. Liu, Z. H. et al. Electronic structure and ferromagnetism in the martensitic-transformation material Ni2FeGa. Phys. Rev. B. 69, 134415 (2004).

    Article  Google Scholar 

Download references

Acknowledgements

We thank M.-L. Saboungi, D. Price, S. Coppersmith, Y. Zheng, L. Yu and D. Khomskii for fruitful discussions and critical comments. The financial support from the National Science Foundation of China (grant nos. 51831003 and 51527801), the Funds for Creative Research Groups of China (grant no. 51921001), the 111 project (grant no. B170003), the Fundamental Research Funds for the Central Universities (grant nos. 06111020 and 06111040) and the fundamental research fund at the State Key Laboratory for Advanced Metals and Materials (2017Z-09) is acknowledged. L.V. acknowledges the Swedish Research Council (grant no. 2017-06474) and the Hungarian Scientific Research Fund (OTKA 128229). We thank D. Phelan for help in resistivity measurements. The use of Oak Ridge National Laboratory’s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. Work in the Materials Science Division of Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The use of the APS and Center for Nanoscale Materials was supported by the US Department of Energy, Office of Science, Office of Basic Energy Science, under contract no. DE-AC02-06CH11357.

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Authors and Affiliations

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Contributions

Y.D.W. and Y.R. designed the experiments and proposed the theory. H.C. prepared materials and performed mechanical testing. Z.N., M.Z., R.L., Y.R., W.L., X.Z. and S.L. performed the synchrotron measurements. X.S., R.Y. and Y.L. conducted the (S)TEM characterization. F.Y. performed the neutron diffraction measurements. P.C., F.T. and L.V. performed the calculations. H.Z. and J.F.M. performed resistivity and magnetic property measurements. Y.D.W., Y.R., H.C., W.L. and D.C. analysed the experimental data. Y.D.W., Y.R. and H.C. wrote the manuscript with the input of all other coauthors. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yan-Dong Wang or Yang Ren.

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The authors declare no competing interests.

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Extended data

Extended Data Fig. 1 Three-dimensional atom probe (3DAP) atomic reconstruction of a Co20 alloy annealed at 523 K for 30 min.

The results show a homogeneous distribution of all chemical elements without any indication of elemental segregation and precipitation.

Extended Data Fig. 2 Characterization of thermally induced martensitic transformation (TIMT).

a, Contour plot of temperature-dependent synchrotron XRD patterns of Co6, Co10 and Co20 fibres, respectively. The Co6 and Co10 fibres show a TIMT at 250 K and 170 K, respectively, but non TIMT down to 100 K for Co20 fibre. The color bar is the same for the three contour plots. The lattice parameters for Co6: a = b = c = 5.751(6) Å at room temperature for the cubic austenitic structure and are a = b = 3.810(4) Å and c = 6.507(7) Å at 200 K for the tetragonal martensitic structure. b, Resistivity and magnetization versus temperature curves of a Co20 fibre, which does not show any indication of the TIMT until 1.8 K.

Source data

Extended Data Fig. 3 Diffraction geometry for alloys during in situ synchrotron X-ray diffraction measurements.

The (004) and (400) planes are perpendicular to the loading direction (LD) and transverse direction (TD), respectively, for the single crystal fibre subjected to the in situ tensile test.

Extended Data Fig. 4 Two-dimensional synchrotron X-ray diffraction pattern taken along \([110]_{L2_1}\) zone axis.

The weak spots can be indexed by a trigonal ω–like structure. The marked red circle regions corresponding to \((0\bar 112)_{\upomega}\) and (0002)ω reflections.

Extended Data Fig. 5 High-resolution transmission electron microscopy (HRTEM) images of Co20 fibre annealed at 523 K for 30 min.

ac, The HRTEM images taken along \([110]_{L2_1}\) and \([100]_{L2_1}\) zone axes show stripe features. d, The enlarged stripe of the HRTEM taken along \([110]_{L2_1}\) zone axis shows a partial collapse of the {111} planes along <111> direction of the body-centered cubic structure which results in the ω-like transition (the motif of L21 and ω-like structure are highlighted by magenta and blue rectangles respectively).

Supplementary information

Supplementary Information

Supplementary note, Figs. 1–6 and references.

Source data

Source Data Fig. 1

Statistical Source Data

Source Data Fig. 2

Statistical Source Data

Source Data Fig. 3

Statistical Source Data

Source Data Fig. 4

Statistical Source Data

Source Data Extended Data Fig. 2

Statistical Source Data

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Chen, H., Wang, YD., Nie, Z. et al. Unprecedented non-hysteretic superelasticity of [001]-oriented NiCoFeGa single crystals. Nat. Mater. 19, 712–718 (2020). https://doi.org/10.1038/s41563-020-0645-4

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