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A highly distorted ultraelastic chemically complex Elinvar alloy

Nature volume 602, pages 251–257 (2022)Cite this article

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Abstract

The development of high-performance ultraelastic metals with superb strength, a large elastic strain limit and temperature-insensitive elastic modulus (Elinvar effect) are important for various industrial applications, from actuators and medical devices to high-precision instruments1,2. The elastic strain limit of bulk crystalline metals is usually less than 1 per cent, owing to dislocation easy gliding. Shape memory alloys3—including gum metals4,5 and strain glass alloys6,7—may attain an elastic strain limit up to several per cent, although this is the result of pseudo-elasticity and is accompanied by large energy dissipation3. Recently, chemically complex alloys, such as ‘high-entropy’ alloys8, have attracted tremendous research interest owing to their promising properties9,10,11,12,13,14,15. In this work we report on a chemically complex alloy with a large atomic size misfit usually unaffordable in conventional alloys. The alloy exhibits a high elastic strain limit (approximately 2 per cent) and a very low internal friction (less than 2 × 10−4) at room temperature. More interestingly, this alloy exhibits an extraordinary Elinvar effect, maintaining near-constant elastic modulus between room temperature and 627 degrees Celsius (900 kelvin), which is, to our knowledge, unmatched by the existing alloys hitherto reported.

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Fig. 1: Structure characterization of single-crystal Co25Ni25(HfTiZr)50 alloy.
Fig. 2: DFT calculation of three structure models for the Co25Ni25(HfTiZr)50 alloy.
Fig. 3: Mechanical properties of the Co25Ni25(HfTiZr)50 alloy.
Fig. 4: The Elinvar effect in the Co25Ni25(HfTiZr)50 alloy.

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The data supporting the findings of this study are available within the article.

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Acknowledgements

D.J.S. gratefully acknowledges the support of the Research Grant Council, Hong Kong Government, through the General Research Fund (GRF) with grant nos HKU 11211019. J.G.W. acknowledges the support of Guangdong Major Project of Basic and Applied Basic Research, China (grant no. 2019B030302010). The research of Y.Y. is supported by the Research Grant Council, Hong Kong Government, through the General Research Fund (GRF) with the grant nos CityU11213118 and CityU11200719 as well as by the City University of Hong Kong with grant no. 9610391. C.W.P. acknowledges the financial support of Academia Sinica Career Development Award with grant no. 2317-1050100. Q.Z. acknowledges the funding from the National Natural Science Foundation of China (Nos. 51871054). C.W.P. is grateful for computational support from the National Center for High-performance Computing, Taiwan. Q.F.H. is grateful for the assistance given by X. K. Xi, X. D. Liu and T. Liu.

Author information

Author notes

  1. These authors contributed equally: Q. F. He, J. G. Wang, H. A. Chen

Authors and Affiliations

  1. Department of Mechanical Engineering, City University of Hong Kong, Kowloon, Hong Kong, China

    Q. F. He, J. G. Wang, Z. Y. Ding, Z. Q. Zhou, J. C. Qiao, C. T. Liu & Y. Yang

  2. College of Mechanical Engineering, Dongguan University of Technology, Dongguan, China

    J. G. Wang

  3. Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei, Taiwan

    H. A. Chen

  4. X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    L. H. Xiong & Y. Ren

  5. Department of Materials Science and Engineering, Hong Kong Institute for Advanced Study, City University of Hong Kong, Kowloon, Hong Kong, China

    J. H. Luan, C. T. Liu & Y. Yang

  6. MATEIS, Université de Lyon, UMR CNRS5510, INSA-Lyon, Villeurbanne, France

    J. M. Pelletier & J. C. Qiao

  7. School of Mechanics, Civil Engineering and Architecture, Northwestern Polytechnical University, Xi’an, China

    J. C. Qiao

  8. Laboratory for Structures, Institute of Materials, Shanghai University, Shanghai, China

    Q. Wang

  9. College of Physics and Materials Science, Tianjin Normal University, Tianjin, China

    L. L. Fan

  10. Department of Physics, City University of Hong Kong, Kowloon, Hong Kong, China

    Y. Ren

  11. Center for High Pressure Science and Technology Advanced Research, Shanghai, China

    Q. S. Zeng

  12. Jiangsu Key Laboratory of Advanced Metallic Materials, School of Materials Science and Engineering, Southeast University, Nanjing, China

    Q. S. Zeng

  13. Research Center for Applied Sciences, Academia Sinica, Taipei, Taiwan

    C. W. Pao

  14. Department of Mechanical Engineering, The University of Hong Kong, Hong Kong, China

    D. J. Srolovitz

  15. International Digital Economy Academy (IDEA), Shenzhen, China

    D. J. Srolovitz

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  1. Q. F. He
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Contributions

Y.Y. supervised the project. Y.Y., C.W.P. and D.J.S. conceived the idea. Q.F.H. fabricated the polycrystalline samples and J.C.Q. prepared the single-crystal samples. Q.F.H. characterized the structures and mechanical properties of the samples. J.G.W., C.W.P. and H.A.C. carried out the atomistic simulations. J.C.Q. and J.M.P. performed the dynamic mechanical spectroscopy analyses. J.H.L. and C.T.L. performed the 3D APT experiments. L.H.X., L.L.F., Q.S.Z. and Y.R. performed the in situ HEXRD experiments. Y.Y., D.J.S., C.W.P., Z.Y.D., Z.Q.Z. and Q.W. contributed to the data analysis. Y.Y., Q.F.H. and C.W.P. wrote the manuscript. All authors participated in the discussion of the results.

Corresponding authors

Correspondence to C. W. Pao, D. J. Srolovitz or Y. Yang.

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Competing interests

Y.Y. and Q.F.H are in the process of applying a patent related to the alloy design described in this work. The remaining authors declare no competing interests.

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Nature thanks David Dye, Andrew Minor and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Characterization of single-crystal Co25Ni25(HfTiZr)50 alloy.

a, A low-magnification backscatter electron image and elemental distributions show that the chemical distribution is homogeneous in the single-crystal samples on a sub-micro scale. b, Low-magnification TEM image and the corresponding diffraction patterns ([001] zone axis) in different regions show that there is no phase separation in the single-crystal samples.

Extended Data Fig. 2 The characterization of the polycrystalline Co25Ni25(HfTiZr)50.

a, The inverse pole figure map showing the grain structure of as-cast polycrystalline Co25Ni25(HfTiZr)50 alloy. b, The pole figures showing that there are no preferred orientations in the as-cast polycrystalline Co25Ni25(HfTiZr)50 alloy. c, The XRD patterns of the Co25Ni25(HfTiZr)50 alloy samples after thermal annealing at 1,273 K for different time durations all exhibit single-phase B2 ordering. d, Compression stress–strain curves of the single-crystal and polycrystal Co25Ni25(HfTiZr)50 alloy after annealing at 1,273 K for 9 h. The results show that the mechanical properties of the Co25Ni25(HfTiZr)50 alloy do not change after the heat treatment. e, A low-magnification SEM image shows the microstructure of the Co25Ni25(HfTiZr)50 alloy after annealing at 1,273 K for 9 h. f, The STEM image and elemental mapping near a grain boundary. No segregation to grain boundaries was observed following a 9-h, 1,273-K anneal in our Co25Ni25(HfTiZr)50 alloy. (AC and HT represent as-cast and heat-treated, respectively.) g, The APT reconstructions of the three-dimensional elemental distributions showing the chemical homogeneity along the grain boundary at the nanometre scale. The black rectangle in the EBSD image indicates the position from which the APT tip was carved.

Extended Data Fig. 3 The monotonic and cyclic microcompression results of the single-crystalline Co25Ni25(HfTiZr)50.

a, The typical monotonic stress–strain curves obtained for different micropillar diameters. The inset shows a typical pillar image. b, The Young’s modulus versus pillar diameter of the micropillars in Fig. 3b. The average Young’s modulus is measured to be 106 GPa. c, The size-dependent yield strength of single-crystal Co25Ni25(HfTiZr)50 micropillars. d, The cyclic stress–strain curves obtained within the elastic regime from the micropillar at different nominal stress rates. Note that no mechanical hysteresis is evident in d. The inset shows the (cyclic) load versus time. Five cycles were performed for each compression.

Extended Data Fig. 4 Loss factors.

The loss factors measured for the single-crystal and polycrystalline Co25Ni25(HfTiZr)50 in comparison with various bulk metallic glasses over a wide temperature range.

Extended Data Fig. 5 Comparison of the first height of the steel ball bouncing back from different alloy surfaces.

a, Photo showing the starting moment of the bouncing experiments. b–e, The first height of the steel ball after bouncing back, as indicated by the white arrow, from single-crystalline Co25Ni25(HfTiZr)50 (b), spark plasma sintered (SPS) Cu50Zr45Al5 metallic glass (c), NiAl alloy with a B2 structure (d), and commercial stainless steel (e). See Supplementary Video 1 for details. We note that all the bulk alloys had a similar size.

Extended Data Fig. 6 The dislocation structure analysis performed in the [111] single-crystalline Co25Ni25(HfTiZr)50 sample after deforming to 4% mechanical strain.

a, \(g=(0\bar{2}0)\) and beam direction Z = [001]. b, \(g=(\bar{1}\bar{1}0)\) and beam direction Z = [001]. c, g = (200) and beam direction Z = [001]. d, \(g=(0\bar{1}1)\) and beam direction \(Z=[\bar{1}11]\). e, \(g=(\bar{1}\bar{1}0)\) and beam direction \(Z=[\bar{1}11]\). f, g = (101) and beam direction \(Z=[\bar{1}11]\). The g · b = 0 out of contrast analyses indicate that the dislocations are of the ⟨001⟩ type. See Supplementary Table 1 for detailed analysis and description of labels A–D.

Extended Data Fig. 7 Stress relaxation and internal friction stress.

a, The typical stress relaxation curve obtained from a single-crystalline Co25Ni25(HfTiZr)50 micropillar with a top diameter of 1 μm. The activation volume is calculated to be ~3.05b3. b, The yield strength of single-crystal Co25Ni25(HfTiZr)50 micropillars at different temperatures. Standard fits to the data (inset equation) yield a Peierls stress of τc ≈ 0.47σc = 2.8 GPa and effective temperature of T0 = 1,107 K. The inset shows the contour plot of the critical stress τc as a function of the correlation length λ and standard deviation Δ for Co25Ni25(HfTiZr)50. Note that  ζ0 stands for a dislocation core size.

Extended Data Fig. 8 The magnetic properties measured for the Co25Ni25(HfTiZr)50 alloy.

a, The magnetization curve of the Co25Ni25(HfTiZr)50 alloy as a function of the applied magnetic field at room temperature. The saturation magnetization Ms of Co25Ni25(HfTiZr)50 is only 1.17 emu g−1. b, The temperature dependence of magnetization of Co25Ni25(HfTiZr)50 under the applied magnetic field of 500 Oe. The result shows that there is an antiferromagnetic (AFM) to ferromagnetic (FM) transition at the transition temperature TN = 851 K. c, The measured magnetostriction coefficient along different directions of single-crystal Co25Ni25(HfTiZr)50 alloy. The magnetostriction coefficient of Co25Ni25(HfTiZr)50 alloy is about zero. The ferromagnetic polycrystalline Ni- and Fe-based metallic glass (MG) are taken for comparison.

Extended Data Fig. 9 The linear thermal expansion coefficient of the Co25Ni25(HfTiZr)50 alloy.

a, The thermal expansion curves obtained from experiments. The average thermal expansion coefficients (α) of the single-crystal and polycrystalline samples are almost the same, about 11.4 × 10−6 K−1. b, The variation of the lattice constant with temperature calculated from the ab initio molecular dynamics simulations. The average thermal expansion coefficient is about 8.1 × 10−6 K−1, which is very close to our experimental measurement.

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Equations, Supplementary Figure 1, Supplementary Table 1, Supplementary References and the legend for Supplementary Video 1

Supplementary Video 1

Demonstration of elasticity of different metals with steel ball bouncing tests.

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He, Q.F., Wang, J.G., Chen, H.A. et al. A highly distorted ultraelastic chemically complex Elinvar alloy. Nature 602, 251–257 (2022). https://doi.org/10.1038/s41586-021-04309-1

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