Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Tuning element distribution, structure and properties by composition in high-entropy alloys

Nature volume 574, pages 223–227 (2019)Cite this article

Subjects

Abstract

High-entropy alloys are a class of materials that contain five or more elements in near-equiatomic proportions1,2. Their unconventional compositions and chemical structures hold promise for achieving unprecedented combinations of mechanical properties3,4,5,6,7,8. Rational design of such alloys hinges on an understanding of the composition–structure–property relationships in a near-infinite compositional space9,10. Here we use atomic-resolution chemical mapping to reveal the element distribution of the widely studied face-centred cubic CrMnFeCoNi Cantor alloy2 and of a new face-centred cubic alloy, CrFeCoNiPd. In the Cantor alloy, the distribution of the five constituent elements is relatively random and uniform. By contrast, in the CrFeCoNiPd alloy, in which the palladium atoms have a markedly different atomic size and electronegativity from the other elements, the homogeneity decreases considerably; all five elements tend to show greater aggregation, with a wavelength of incipient concentration waves11,12 as small as 1 to 3 nanometres. The resulting nanoscale alternating tensile and compressive strain fields lead to considerable resistance to dislocation glide. In situ transmission electron microscopy during straining experiments reveals massive dislocation cross-slip from the early stage of plastic deformation, resulting in strong dislocation interactions between multiple slip systems. These deformation mechanisms in the CrFeCoNiPd alloy, which differ markedly from those in the Cantor alloy and other face-centred cubic high-entropy alloys, are promoted by pronounced fluctuations in composition and an increase in stacking-fault energy, leading to higher yield strength without compromising strain hardening and tensile ductility. Mapping atomic-scale element distributions opens opportunities for understanding chemical structures and thus providing a basis for tuning composition and atomic configurations to obtain outstanding mechanical properties.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Aberration-corrected TEM imaging and mapping of element distributions in the CrMnFeCoNi Cantor alloy.
Fig. 2: Aberration-corrected TEM imaging and mapping of element distributions in the CrFeCoNiPd alloy.
Fig. 3: TEM observation of dislocations in the CrFeCoNiPd alloy.
Fig. 4: Comparison of mechanical properties of the CrFeCoNiPd alloy with other CrCoNi-based HEAs.

Data availability

All data generated or analysed during this study are included in the published article and Supplementary Information, and are available from the corresponding authors upon reasonable request.

References

  1. Yeh, J. W. et al. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes. Adv. Eng. Mater. 6, 299–303 (2004).

    Article  CAS  Google Scholar 

  2. Cantor, B., Chang, I. T. H., Knight, P. & Vincent, A. J. B. Microstructural development in equiatomic multicomponent alloys. Mater. Sci. Eng. A 375–377, 213–218 (2004).

    Article  Google Scholar 

  3. Gludovatz, B. et al. A fracture-resistant high-entropy alloy for cryogenic applications. Science 345, 1153–1158 (2014).

    Article  CAS  ADS  Google Scholar 

  4. Zhang, Z. J. et al. Nanoscale origins of the damage tolerance of the high-entropy alloy CrMnFeCoNi. Nat. Commun. 6, 10143 (2015).

    Article  CAS  ADS  Google Scholar 

  5. Gludovatz, B. et al. Exceptional damage-tolerance of a medium-entropy alloy CrCoNi at cryogenic temperatures. Nat. Commun. 7, 10602 (2016).

    Article  CAS  ADS  Google Scholar 

  6. Li, Z. M., Pradeep, K. G., Deng, Y., Raabe, D. & Tasan, C. C. Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off. Nature 534, 227–230 (2016).

    Article  CAS  ADS  Google Scholar 

  7. Lei, Z. et al. Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes. Nature 563, 546–550 (2018).

    Article  CAS  ADS  Google Scholar 

  8. Yang, T. et al. Multicomponent intermetallic nanoparticles and superb mechanical behaviors of complex alloys. Science 362, 933–937 (2018).

    Article  CAS  ADS  Google Scholar 

  9. Zhang, Y. et al. Microstructures and properties of high-entropy alloys. Prog. Mater. Sci. 61, 1–93 (2014).

    Article  Google Scholar 

  10. Miracle, D. B. & Senkov, O. N. A critical review of high entropy alloys and related concepts. Acta Mater. 122, 448–511 (2017).

    Article  CAS  Google Scholar 

  11. Khachaturian, A. G. Theory of Structural Transformations in Solids (Dover, 2013).

  12. Gyorffy, B. L. & Stocks, G. M. Concentration waves and Fermi surfaces in random metallic alloys. Phys. Rev. Lett. 50, 374–377 (1983).

    Article  CAS  ADS  Google Scholar 

  13. Gludovatz, B., George, E. P. & Ritchie, R. O. Processing, microstructure and mechanical properties of the CrMnFeCoNi high-entropy alloy. JOM 67, 2262–2270 (2015).

    Article  CAS  Google Scholar 

  14. Widom, M., Huhn, W. P., Maiti, S. & Steurer, W. Hybrid Monte Carlo/molecular dynamics simulation of a refractory metal high entropy alloy. Metall. Mater. Trans. A 45, 196–200 (2014).

    Article  CAS  Google Scholar 

  15. Tamm, A., Aabloo, A., Klintenberg, M., Stocks, M. & Caro, A. Atomic-scale properties of Ni-based FCC ternary, and quaternary alloys. Acta Mater. 99, 307–312 (2015).

    Article  CAS  Google Scholar 

  16. Zhang, F. X. et al. Local structure and short-range order in a NiCoCr solid solution alloy. Phys. Rev. Lett. 118, 205501 (2017).

    Article  CAS  ADS  Google Scholar 

  17. Ma, Y. et al. Chemical short-range orders and the induced structural transition in high-entropy alloys. Scr. Mater. 144, 64–68 (2018).

    Article  CAS  Google Scholar 

  18. Ding, J., Yu, Q., Asta, M. & Ritchie, R. O. Tunable stacking fault energies by tailoring local chemical order in CrCoNi medium-entropy alloys. Proc. Natl Acad. Sci. USA 115, 8919–8924 (2018).

    Article  CAS  ADS  Google Scholar 

  19. Watson, R. E. & Bennett, L. H. Transition metals: d-band hybridization, electronegativities and structural stability of intermetallic compounds. Phys. Rev. B 18, 6439–6449 (1978).

    Article  CAS  ADS  Google Scholar 

  20. Cottrell, A. H. Concepts of the Electron Theory of Alloys (IOM Communications, 1998).

  21. Labusch, R. A statistical theory of solid solution hardening. Phys. Status Solidi 41, 659–669 (1970).

    Article  Google Scholar 

  22. Nabarro, F. R. N. Theory of solution hardening. Philos. Mag. 35, 613–622 (1977).

    Article  CAS  ADS  Google Scholar 

  23. Okamoto, N. L. et al. Size effect, critical resolved shear stress, stacking fault energy, and solid solution strengthening in the CrMnFeCoNi high-entropy alloy. Sci. Rep. 6, 35863 (2016).

    Article  CAS  ADS  Google Scholar 

  24. Hart, E. W. Theory of tensile test. Acta Metall. 15, 351–355 (1967).

    Article  CAS  Google Scholar 

  25. Otto, F. et al. The influences of temperature and microstructure on the tensile properties of a CoCrFeMnNi high-entropy alloy. Acta Mater. 61, 5743–5755 (2013).

    Article  CAS  Google Scholar 

  26. Wu, Z., Bei, H., Pharr, G. M. & George, E. P. Temperature dependence of the mechanical properties of equiatomic solid solution alloys with face-centered cubic crystal structures. Acta Mater. 81, 428–441 (2014).

    Article  CAS  Google Scholar 

  27. Liu, W. H. et al. Ductile CoCrFeNiMox high entropy alloys strengthened by hard intermetallic phases. Acta Mater. 116, 332–342 (2016).

    Article  CAS  ADS  Google Scholar 

  28. Kim, S.-H., Kim, H. & Kim, N. J. Brittle intermetallic compound makes ultrastrong low-density steel with large ductility. Nature 518, 77–79 (2015).

    Article  CAS  ADS  Google Scholar 

  29. Jacques, P. J., Furnémont, Q., Lani, F., Pardoen, T. & Delannay, F. Multiscale mechanics of TRIP-assisted multiphase steels. I. Characterization and mechanical testing. Acta Mater. 55, 3681–3693 (2007).

    Article  CAS  Google Scholar 

  30. Bouaziz, O., Allain, S., Scott, C. P., Cugy, P. & Barbier, D. High manganese austenitic twinning induced plasticity steels: a review of the microstructure properties relationships. Curr. Opin. Solid State Mater. Sci. 15, 141–168 (2011).

    Article  CAS  ADS  Google Scholar 

  31. Ma, S. G. et al. Superior high tensile elongation of a single-crystal CoCrFeNiAl0.3 high-entropy alloy by Bridgman solidification. Intermetallics 54, 104–109 (2014).

    Article  CAS  Google Scholar 

  32. Zaddach, A. J., Scattergood, R. O. & Koch, C. C. Tensile properties of low-stacking fault energy high-entropy alloys. Mater. Sci. Eng. A 636, 373–378 (2015).

    Article  CAS  Google Scholar 

  33. Nöhring, W. G. & Curtin, W. A. Cross-slip of long dislocations in FCC solid solutions. Acta Mater. 158, 95–117 (2018).

    Article  Google Scholar 

  34. Hÿtch, M. J., Snoeck, E. & Kilaas, R. Quantitative measurement of displacement and strain fields from HREM micrographs. Ultramicroscopy 74, 131–146 (1998).

    Article  Google Scholar 

  35. Chatfield, C. The Analysis of Time Series: An Introduction 6th edn (Chapman and Hall/CRC, 2003).

  36. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).

    Article  CAS  ADS  Google Scholar 

  37. Li, Q., Sheng, H. & Ma, E. Strengthening in multi-principal element alloys with local-chemical-order roughened dislocation pathways. Nat. Commun. 10, 3563 (2019).

    Article  ADS  Google Scholar 

Download references

Acknowledgements

Q.Y. was supported by the National Natural Science Foundation of China (51671168), National Key Research and Development Program of China (2017YFA0208200), 111 project under grant no. B16042, and the State Key Program for Basic Research in China under grant no. 2015CB659300. T.Z. was supported by the US National Science Foundation under grant no. DMR-1810720. R.O.R. was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division and under contract no. DE-AC02-05CH11231 to the Mechanical Behavior of Materials program (KC13) at the Lawrence Berkeley National Laboratory. We thank E. Ma for providing the interatomic potential used for Monte Carlo simulations.

Author information

Author notes

  1. These authors contributed equally: Qingqing Ding, Yin Zhang, Xiao Chen

Authors and Affiliations

  1. Center of Electron Microscopy and State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou, China

    Qingqing Ding, Xiaoqian Fu, Sijing Chen, Hongbin Bei, Jixue Li, Ze Zhang & Qian Yu

  2. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Yin Zhang, Dengke Chen, Minru Wen & Ting Zhu

  3. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Xiao Chen & Fei Wei

  4. Beijing National Laboratory for Condensed Matter Physics and Collaborative Innovation Center of Quantum Matter, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Lin Gu

  5. Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN, USA

    Yanfei Gao

  6. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Yanfei Gao

  7. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Robert O. Ritchie

  8. Department of Materials Science and Engineering, University of California Berkeley, Berkeley, CA, USA

    Robert O. Ritchie

Authors
  1. Qingqing Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yin Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaoqian Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dengke Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sijing Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Lin Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Fei Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Hongbin Bei
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Yanfei Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Minru Wen
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Jixue Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Ze Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Ting Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Robert O. Ritchie
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Qian Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Q.Y., T.Z. and R.O.R. designed the research. Q.Y., Q.D., X.F., X.C., S.C., L.G. and F.W. performed TEM and in situ experiments. H.B. synthesized alloys and conducted mechanical testing. Y.Z., D.C., Y.G., M.W., T.Z. and Q.Y. conducted data analysis and modelling. Q.Y., T.Z., R.O.R., Q.D., Z.Z., J.L. and H.B. wrote the manuscript. All authors contributed to the discussion and revision of the paper.

Corresponding authors

Correspondence to Ting Zhu, Robert O. Ritchie or Qian Yu.

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.

Peer review information Nature thanks Elena Pereloma and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Fig. 1

X-ray diffraction characterization showing the single-phase signal of the fcc structure of the CrFeCoNiPd alloy.

Extended Data Fig. 2 Atomistic Monte Carlo simulation.

Simulation shows formation of concentration waves in a model equiatomic ternary alloy under annealing at a temperature of 800 K. a, Initial fcc structure with a random distribution of the three constituent elements; yellow, grey and green atoms represent A, B and C elements, respectively. b, Relaxed structure showing the formation of a mixture of an element-A/B dominant phase (mixed yellow and grey atoms) and an element-C dominant phase (green atom clusters). c, Simulated EDS map for element C based on the structure in b. d, Plots of pair correlation functions S(r) of individual elements against concentration wavelength r.

Extended Data Fig. 3 Atomic structure of a simulated dislocation dipole.

The structure consists of two closely spaced 60° dislocations of opposite signs in an fcc Ni single crystal, for comparison with similar dislocation core structures in Fig. 3a. Atoms are coloured by their coordination numbers (CN = 12, yellow; CN = 11, blue), so as to display 30° and 90° partial dislocations (atoms in blue) in the core of an extended 60° full dislocation.

Extended Data Fig. 4 High-resolution TEM images of the cores of dissociated 60° dislocations in the CrFeCoNiPd alloy.

The number in each image indicates the measured stacking fault width in the core of dissociated dislocation. The average stacking fault width is d = 3.37 nm. The stacking-fault energy γsf can be estimated as \({\gamma }_{{\rm{sf}}}=\frac{\mu {b}_{{\rm{p}}}^{2}}{8{\rm{\pi }}d}\left(\frac{2-\nu }{1-\nu }\right)\left(1-\frac{2\nu \cos 2\theta }{2-\nu }\right)\), where θ is the angle between the dislocation line and the Burgers vector of the full dislocation, bp is the length of the Burgers vector of the partial dislocation, μ is the shear modulus and ν is Poisson’s ratio. The γsf of the CrFeCoNiPd alloy is estimated to be 66 mJ m−2.

Extended Data Fig. 5 Kocks–Mecking plots.

The plots of strain hardening rate against true strain at 293 K and 77 K show the strong hardening capability of the CrFeCoNiPd alloy.

Extended Data Fig. 6 Aberration-corrected TEM imaging and mapping of element distributions in the Cr20Fe20Co18Ni30Al12 alloy.

a, HAADF images and associated EDS maps (taken along the [110] zone axis) for individual elements of Cr, Fe, Co, Ni and Al. b, Line profiles of atomic fraction of individual elements taken from respective EDS maps in a; each line profile represents the distribution of an element in a (002) plane projected along the [110] beam direction. c, Cross-slip of dislocations in the Cr20Fe20Co18Ni30Al12 alloy, from in situ straining experiment.

Extended Data Fig. 7 Comparison of element distributions in CrCoNi alloy and in CrCoNi alloy containing 5 at% W.

a, HAADF image and corresponding EDS maps of the CrCoNi alloy containing 5 at% W, taken along the [110] zone axis, showing the distribution of individual elements of Cr, Co, Ni and W. b, Line profiles of atomic fraction of elements Cr, Co and Ni taken from respective EDS maps in a for the CrCoNi alloy containing 5 at% W; each line profile represents the distribution of an element in a \(\left(1\bar{1}1\right)\) plane projected along the [110] beam direction. c, Line profiles of atomic fraction of individual elements taken from the corresponding EDS maps of the CrCoNi alloy; each line profile represents the distribution of an element in a \(\left(1\bar{1}1\right)\) plane projected along the [110] beam direction.

Extended Data Table 1 Properties of the CrMnFeCoNi, CrFeCoNiPd, Cr10Mn30Fe50Co10 and CrCoNi alloys
Full size table

Supplementary information

Reporting Summary

Video 1

In situ TEM showing the sluggish motion of dislocations in the primary slip plane in the CrFeCoNiPd alloy. The leading dislocation in the pile-up stopped moving in the middle of the strained sample, indicating that the glide of dislocations was strongly hindered (scale bar: 500 nm).

Video 2

In situ TEM showing massive cross slip as the primary slip stopped in the CrFeCoNiPd alloy (scale bar: 200 nm).

Video 3

In situ TEM showing secondary cross slip from the first cross-slipped dislocations in the CrFeCoNiPd alloy (scale bar: 500 nm).

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ding, Q., Zhang, Y., Chen, X. et al. Tuning element distribution, structure and properties by composition in high-entropy alloys. Nature 574, 223–227 (2019). https://doi.org/10.1038/s41586-019-1617-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-019-1617-1

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing