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.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
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
Otsuka, K. & Wayman, C. M. Shape Memory Materials (Cambridge Univ. Press, 1999).
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).
Ortin, J. & Delaey, L. Hysteresis in shape-memory alloys. Int. J. Non-Linear Mech. 37, 1275–1281 (2002).
Omori, T. et al. Superelastic effect in polycrystalline ferrous alloys. Science 333, 68–71 (2011).
Lemaitre, J. & Chaboche, J. L. Mechanics of Solid Materials (Cambridge Univ. Press, 1990).
Otsuka, K. & Ren, X. Physical metallurgy of Ti-Ni-based shape memory alloys. Prog. Mater. Sci. 50, 511–678 (2005).
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).
Wang, D. P. et al. Transition in superelasticity for Ni55-xCoxFe18Ga27 alloys due to strain glass transition. Europhys. Lett. 98, 46004 (2012).
Taylor, G. F. A method of drawing metallic filaments and discussion of their properties and uses. Phys. Rev. 23, 655–660 (1924).
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).
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).
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).
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).
Andrews, T. On the continuity of the gaseous and liquid states of matter. Phil. Trans. R. Soc. Lond. 159, 575–590 (1869).
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).
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).
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).
Fujimoto, M. The Physics of Structural Phase Transitions 2nd edn (Springer, 2005).
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).
Sikka, S. K., Vohra, Y. K. & Chidambaram, R. Omega phase in materials. Prog. Mater. Sci. 27, 245–310 (1982).
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).
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).
Nelson, D. R. Defects and Geometry in Condensed Matter Physics (Cambridge Univ. Press, 2002).
Bokov, A. A. & Ye, Z. G. Recent progress in relaxor ferroelectrics with perovskite structure. J. Mater. Sci. 41, 31–52 (2006).
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).
Sarkar, S., Ren, X. & Otsuka, K. Evidence for strain glass in the ferroelastic-martensitic system Ti50-xNi50+x. Phys. Rev. Lett. 95, 205702 (2005).
Wang, Y., Ren, X. & Otsuka, K. Shape memory effect and superelasticity in a strain glass alloy. Phys. Rev. Lett. 97, 225703 (2006).
Greaves, G. N., Greer, A. L., Lakes, R. S. & Rouxel, T. Poisson’s ratio and modern materials. Nature Mater. 10, 823 (2011).
Vitos, L. Computational Quantum Mechanics for Materials Engineers: The EMTO Method and Applications (Springer, 2007).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Gyorffy, B. L. Coherent-potential approximation for a nonoverlapping-muffin-tin-potential model of random substitutional alloys. Phys. Rev. B. 5, 2382–2384 (1972).
Vitos, L., Abrikosov, I. A. & Johansson, B. Anisotropic lattice distortions in random alloys from first-principles theory. Phys. Rev. Lett. 87, 156401 (2001).
Soven, P. Coherent-potential model of substitutional disordered alloys. Phys. Rev. 156, 809–813 (1967).
Skriver, H. L. Crystal structure from one-electron theory. Phys. Rev. B. 31, 1909–1923 (1985).
Liu, Z. H. et al. Electronic structure and ferromagnetism in the martensitic-transformation material Ni2FeGa. Phys. Rev. B. 69, 134415 (2004).
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.
Author information
Authors and Affiliations
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
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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.
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.
a–c, 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
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-020-0645-4
This article is cited by
-
Organic radical ferroelectric crystals with martensitic phase transition
Nature Communications (2023)
-
Computer simulation of super-magnetoelastic behavior near critical region of magnetic materials based on phase-field method
Rare Metals (2023)
-
Heterogeneous Structure-Induced Excellent Functional Properties in Shape Memory Alloys: A Review
JOM (2023)
-
Cyclic Stability of Superelasticity in [001]-Oriented Quenched Ni44Fe19Ga27Co10 and Ni39Fe19Ga27Co15 Single Crystals
Acta Metallurgica Sinica (English Letters) (2023)
-
Strain-magnetization property of Ni-Mn-Ga (Co, Cu) microwires
Rare Metals (2023)