- Physical Review Journals
All JournalsPhysics Magazine
Access Provided by Xinjiang University

Physical Review Materials

Export citation

Export citation

Choose format for download:

Download Citation
  • Access by Xinjiang University

Suppression of vacancy clustering in nonequiatomic NiFeMnCrAl high-entropy alloys

Xiaoyu Gui1, Xudong An2, Kenichiro Mizohata1, Ilja Makkonen1,5, Roger Castellote-Alvarez3, Wenyi Huo4, Isaac Toda-Caraballo3, David San-Martin3, Filip Tuomisto1,5 et al.

Eryang Lu1,*

  • *Contact author: eryang.lu@helsinki.fi
PDF

Phys. Rev. Materials 10, 055201 – Published 26 May, 2026

DOI: https://doi.org/10.1103/96qn-zfbs

Abstract

The investigation of vacancy diffusivity in metallic materials is crucial for advancing predictive models of radiation damage under extreme environmental conditions. In this work, positron annihilation spectroscopy was employed to systematically investigate the formation and diffusion mechanisms of irradiation-induced vacancies in cobalt-free NiFeMnCrAl high-entropy alloys (HEAs) and Ni subjected to 6 MeV proton irradiation. A broad activation energy spectrum for monovacancy migration, from 1.55 to 1.90 eV, is found owing to the lattice distortions and chemical complexity in HEAs. Vacancy clustering, which occurs in pure metals during thermal treatment, is suppressed in the HEAs. A complex energy landscape stems from the chemical diversity, and inherent lattice distortion leads to instability of vacancy clusters, slowing down long-distance defect diffusion – sluggish diffusion – thereby suppressing the formation of large vacancy clusters. This mechanism underpins the pronounced void swelling resistance under irradiation in multiple-component alloy systems.

View figure in article

Physics Subject Headings (PhySH)

Article Text

References (73)

  1. B. Wang, C. Yang, D. Shu, and B. Sun, A review of irradiation-tolerant refractory high-entropy alloys, Metals 14, 45 (2023).
  2. Z. Cheng, J. Sun, X. Gao, Y. Wang, J. Cui, T. Wang, and H. Chang, Irradiation effects in high-entropy alloys and their applications, J. Alloys Compd. 930, 166768 (2023).
  3. S. Shuang, Y. Hu, X. Li, F. Yuan, G. Kang, H. Gao, and X. Zhang, Tuning chemical short-range order for simultaneous strength and toughness enhancement in NiCoCr medium-entropy alloys, Int. J. Plast. 177, 103980 (2024).
  4. B. Zhang, Z. Zhang, K. Xun, M. Asta, J. Ding, and E. Ma, Minimizing the diffusivity difference between vacancies and interstitials in multi-principal element alloys, Proc. Natl. Acad. Sci. USA 121, e2314248121 (2024).
  5. S. Ge, H. Fu, L. Zhang, H. Mao, H. Li, A. Wang, W. Li, and H. Zhang, Effects of Al addition on the microstructures and properties of MoNbTaTiV refractory high entropy alloy, Mater. Sci. Engin. A 784, 139275 (2020).
  6. S. Xia, M. C. Gao, T. Yang, P. K. Liaw, and Y. Zhang, Phase stability and microstructures of high entropy alloys ion irradiated to high doses, J. Nucl. Mater. 480, 100 (2016).
  7. N. A. P. K. Kumar, C. Li, K. J. Leonard, H. Bei, and S. J. Zinkle, Microstructural stability and mechanical behavior of FeNiMnCr high entropy alloy under ion irradiation, Acta Mater. 113, 230 (2016).
  8. F. Marques, M. Balcerzak, F. Winkelmann, G. Zepon, and M. Felderhoff, Review and outlook on high-entropy alloys for hydrogen storage, Energy Environ. Sci. 14, 5191 (2021).
  9. B. Jiang, Y. Yu, J. Cui, X. Liu, L. Xie, J. Liao, Q. Zhang, Y. Huang, S. Ning, B. Jia, B. Zhu, S. Bai, L. Chen, S. J. Pennycook, and J. He, High-entropy-stabilized chalcogenides with high thermoelectric performance, Science 371, 830 (2021).
  10. V. Chaudhary, R. Chaudhary, R. Banerjee, and R. V. Ramanujan, Accelerated and conventional development of magnetic high entropy alloys, Mater. Today 49, 231 (2021).
  11. N. Kumar Katiyar, K. Biswas, J.-W. Yeh, S. Sharma, and C. Sekhar Tiwary, A perspective on the catalysis using the high entropy alloys, Nano Energy 88, 106261 (2021).
  12. W.-Y. Chen, X. Liu, Y. Chen, J.-W. Yeh, K.-K. Tseng, and K. Natesan, Irradiation effects in high entropy alloys and 316H stainless steel at 300∘C, J. Nucl. Mater. 510, 421 (2018).
  13. E. J. Pickering, A. W. Carruthers, P. J. Barron, S. C. Middleburgh, D. E. J. Armstrong, and A. S. Gandy, High-entropy alloys for advanced nuclear applications, Entropy (Basel) 23, 98 (2021).
  14. Q. Xu, H. Guan, Z. Zhong, S. Huang, and J. Zhao, Irradiation resistance mechanism of the CoCrFeMnNi equiatomic high-entropy alloy, Sci. Rep. 11, 608 (2021).
  15. Y. Chen, D. Chen, J. Weaver, J. Gigax, Y. Wang, N. A. Mara, S. Fensin, S. A. Maloy, A. Misra, and N. Li, Heavy ion irradiation effects on CrFeMnNi and AlCrFeMnNi high entropy alloys, J. Nucl. Mater. 574, 154163 (2023).
  16. C. Lu, T. Yang, K. Jin, N. Gao, P. Xiu, Y. Zhang, F. Gao, H. Bei, W. J. Weber, K. Sun, Y. Dong, and L. Wang, Radiation-induced segregation on defect clusters in single-phase concentrated solid-solution alloys, Acta Mater. 127, 98 (2017).
  17. A. Iwase, S. Sasaki, T. Iwata, and T. Nihira, Defect production and defect saturation behavior in nickel irradiated with heavy ions in the energy range 84–120 MeV, J. Nucl. Mater. 155–157, 1188 (1988).
  18. S.-M. Liu and W.-Z. Han, Mechanism of interaction between interface and radiation defects in metal, Acta Phys. Sin. 68, 13 (2019).
  19. R. Voskoboinikov, Statistics of primary radiation defects in pure nickel, Nucl. Instrum. Methods Phys. Res. Sect. B 478, 201 (2020).
  20. Y. Zhang, S. Zhao, W. J. Weber, K. Nordlund, F. Granberg, and F. Djurabekova, Atomic-level heterogeneity and defect dynamics in concentrated solid-solution alloys, Curr. Opin. Solid State Mater. Sci. 21, 221 (2017).
  21. K. Ma, B. Décamps, A. Fraczkiewicz, F. Prima, and M. Loyer-Prost, Inversion of dislocation loop nature driven by cluster migration in self-ion irradiated nickel, Scr. Mater. 208, 114338 (2022).
  22. K. Ma, L. Guo, A. Dartois, E. Meslin, C. Ophus, B. Décamps, A. Fraczkiewicz, A. J. Knowles, L. Wang, O. Tissot, F. Prima, F. Gao, H. Deng, and M. Loyer-Prost, Decoding the interstitial/vacancy nature of dislocation loops with their morphological fingerprints in face-centered cubic structure, Sci. Adv. 11, eadq4070 (2025).
  23. F. Tan, L. Li, L. Jia, B. Liu, P. Liaw, and Q. Fang, Multiscale modelling of irradiation damage behavior in high entropy alloys, Adv. Powder Mater. 2, 100114 (2023).
  24. Y. Liu, Y. Chen, J. Li, B. Liu, R. Zhang, J. Xia, and Q. Fang, Irradiation hardening and creep modeling of high-entropy alloy at high temperature and dose, Acta Mech. Solida Sin. 38, 588 (2025).
  25. H. S. Do and B. J. Lee, Origin of radiation resistance in multi-principal element alloys, Sci. Rep. 8, 16015 (2018).
  26. H. Pommerenke, J. Duan, N. Curtis, V. DeLibera, A. Bratten, A. Hoffman, M. Buchely, R. O'Malley, and H. Wen, A strong and ductile cobalt-free solid-solution Fe30Ni30Mn30Cr10 multi-principal element alloy from hot rolling, J. Alloys Compd. 948, 169566 (2023).
  27. C. Li, X. Hu, T. Yang, N. A. P. K. Kumar, B. D. Wirth, and S. J. Zinkle, Neutron irradiation response of a Co-free high entropy alloy, J. Nucl. Mater. 527, 151838 (2019).
  28. X. An, E. Lu, Q. Wang, X. Gui, Q. Yang, T. Zhu, X. Cao, P. Zhang, H. Deng, W. Hu, and T. Yang, Effects of alloying elements on the hydrogen behaviors of FCC Co-free concentrated solid solution alloys, Acta Mater. 289, 120879 (2025).
  29. J. Zhang, H. Qiu, H. Zhu, and Z. Xie, Effect of Al additions on the microstructures and tensile properties of AlxCoCr3Fe5Ni high entropy alloys, Mater. Charact. 175, 111091 (2021).
  30. S. Gangireddy, B. Gwalani, V. Soni, R. Banerjee, and R. S. Mishra, Contrasting mechanical behavior in precipitation hardenable AlXCoCrFeNi high entropy alloy microstructures: Single phase FCC vs dual phase FCC-BCC, Mater. Sci. Engin. A 739, 158 (2019).
  31. Y. Lu, Y. Dong, S. Guo, L. Jiang, H. Kang, T. Wang, B. Wen, Z. Wang, J. Jie, Z. Cao, H. Ruan, and T. Li, A promising new class of high-temperature alloys: Eutectic high-entropy alloys, Sci. Rep. 4, 6200 (2014).
  32. R. Castellote-Alvarez, D. San-Martin, C. Fernandez-Jimenez, J. A. Jimenez, C. Petersson, E. Urones-Garrote, P. Szakalos, and I. Toda-Caraballo, Corrosion behavior in liquid lead of a novel FCC nonequiatomic high-entropy alloy capable of forming an alumina protective oxide scale, Corros. Sci. 262, 113651 (2026).
  33. F. Tuomisto, I. Makkonen, J. Heikinheimo, F. Granberg, F. Djurabekova, K. Nordlund, G. Velisa, H. Bei, H. Xue, W. J. Weber, and Y. Zhang, Segregation of Ni at early stages of radiation damage in NiCoFeCr solid solution alloys, Acta Mater. 196, 44 (2020).
  34. Z. Su, J. Ding, M. Song, L. Jiang, T. Shi, Z. Li, S. Wang, F. Gao, D. Yun, E. Ma, and C. Lu, Enhancing the radiation tolerance of high-entropy alloys via solute-promoted chemical heterogeneities, Acta Mater. 245, 118662 (2023).
  35. C. Wang, L. Guo, R. Li, and Q. Peng, Atomistic insights into the irradiation resistance of co-free high entropy alloy FeMnNiCr, Acta Metall. Sin. (English Letters) 37, 1657 (2024).
  36. T. Yang, S. Xia, S. Liu, C. Wang, S. Liu, Y. Fang, Y. Zhang, J. Xue, S. Yan, and Y. Wang, Precipitation behavior of AlxCoCrFeNi high entropy alloys under ion irradiation, Sci. Rep. 6, 32146 (2016).
  37. Y. Yu and Y. Yu, Simulations of irradiation resistance and mechanical properties under irradiation of high-entropy alloy NiCoCrFe, Mater. Today Commun. 33, 104308 (2022).
  38. S. Zhao, Y. Osetsky, A. V. Barashev, and Y. Zhang, Frenkel defect recombination in Ni and Ni-containing concentrated solid-solution alloys, Acta Mater. 173, 184 (2019).
  39. F. Niessen, T. Nyyssonen, A. A. Gazder, and R. Hielscher, Parent grain reconstruction from partially or fully transformed microstructures in MTEX, J. Appl. Crystallogr. 55, 180 (2022).
  40. P. C. Hautojärvi and Positron C, Spectroscopy at defects in metals and semiconductors, in positron spectroscopy of solids, in Proceedings of the International School of Physics Enrico Fermi Course CXXV (IOS Press, Amsterdam, 1995), pp. 491-532.
  41. F. Tuomisto and I. Makkonen, Defect identification in semiconductors with positron annihilation: Experiment and theory, Rev. Mod. Phys. 85, 1583 (2013).
  42. Y. Shu, R. Wang, Z. Chen, Y. Lin, Z. Liu, H. Deng, W. Hu, and T. Yang, Ab initio study of effects of Al on the defect behaviors of AlxCoCrFeNi high entropy alloys, J. Appl. Phys. 133, 21 (2023).
  43. A. Zunger, S. Wei, L. G. Ferreira, and J. E. Bernard, Special quasirandom structures, Phys. Rev. Lett. 65, 353 (1990).
  44. E. Boronski and R. M. Nieminen, Electron-positron density-functional theory, Phys Rev B 34, 3820 (1986).
  45. M. Alatalo, B. Barbiellini, M. Hakala, H. Kauppinen, T. Korhonen, M. J. Puska, K. Saarinen, P. Hautojärvi, and R. M. Nieminen, Theoretical and experimental study of positron annihilation with core electrons in solids, Phys. Rev. B 54, 2397 (1996).
  46. E. Lu, I. Makkonen, K. Mizohata, Z. Li, J. Räisänen, and F. Tuomisto, Effect of interstitial carbon on the evolution of early-stage irradiation damage in equiatomic FeMnNiCoCr high-entropy alloys, J. Appl. Phys. 127, 2 (2020).
  47. B. Barbiellini, P. Genoud, and T. Jarlborg, Calculation of positron lifetimes in bulk materials, J. Phys. Condens. Matter 3, 7631 (1991).
  48. J. Čížek, O. Melikhova, T. Vlasák, P. Hruška, D. Starý, and F. Lukáč, Characterization of lattice distortions in refractory metal complex concentrated alloys using positron annihilation spectroscopy, Materialia 23, 101450 (2022).
  49. E. Lu, J. Zhao, I. Makkonen, K. Mizohata, Z. Li, M. Hua, F. Djurabekova, and F. Tuomisto, Enhancement of vacancy diffusion by C and N interstitials in the equiatomic FeMnNiCoCr high entropy alloy, Acta Mater. 215, 117093 (2021).
  50. H. Rajainmaki, S. Linderoth, H. E. Hansen, and R. M. Nieminen, Defect recovery and hydrogen-vacancy interactions in nickel between 20 and 650 K, J. Phys. F 18, 1109 (1988).
  51. M. J. Puska and R. M. Nieminen, Theory of positrons in solids and on solid surfaces, Rev. Mod. Phys. 66, 841 (1994).
  52. J. Heikinheimo, K. Mizohata, J. Räisänen, T. Ahlgren, P. Jalkanen, A. Lahtinen, N. Catarino, E. Alves, and F. Tuomisto, Direct observation of monovacancy and self-interstitial recovery in tungsten, APL Mater. 7, 021103 (2019).
  53. M. Elsayed, R. Krause-Rehberg, C. Eisenschmidt, N. Eißmann, and B. Kieback, Defect study in CoCrFeMnNi high entropy alloy by positron annihilation lifetime spectroscopy, Phys. Status Solidi 215, 11 (2018).
  54. K. Sugita, N. Matsuoka, M. Mizuno, and H. Araki, Vacancy formation enthalpy in CoCrFeMnNi high-entropy alloy, Scr. Mater. 176, 32 (2020).
  55. X. An, E. Lu, I. Makkonen, G. Wei, J. Byggmästar, J. Zhu, K. Mizohata, Z. Chen, F. Djurabekova, W. Hu, H. Deng, T. Yang, and F. Tuomisto, Enhanced migration of monovacancies in AlxFeCoCrNi high entropy alloys, J. Alloys Compd. 1010, 177704 (2025).
  56. S. Abhaya, R. Rajaraman, R. M. Sarguna, P. K. Parida, C. David, and G. Amarendra, Defect microstructure in high temperature Ni+ implanted FeCrCoNi-a positron beam study, J. Alloys Compd. 806, 780 (2019).
  57. A. Fellman, J. Byggmästar, F. Granberg, F. Djurabekova, and K. Nordlund, Radiation damage and phase stability of AlxCrCuFeNiy alloys using a machine-learned interatomic potential, Phys. Rev. Mater. 10, 023801 (2026).
  58. C. Gao, S. Wang, X. Liu, and C. V. Singh, Defect energetics in an high-entropy alloy fcc CoCrFeMnNi, Mate. Adv. 5, 4231 (2024).
  59. D. C. Look, D. C. Reynolds, J. W. Hemsky, R. L. Jones, and J. R. Sizelove, Production and annealing of electron irradiation damage in ZnO, Appl. Phys. Lett. 75, 811 (1999).
  60. F. Tuomisto, K. Saarinen, D. C. Look, and G. C. Farlow, Introduction and recovery of point defects in electron-irradiated ZnO, Phys. Rev. B 72, 085206 (2005).
  61. K. G. Lynn, J. C. L. Snead, and J. J. Hurst, Positron lifetime studies of pure Ni from 4.2 to 1700 K, J. Phys. F 10, 1753 (1980).
  62. M. I. Baskes, C. L. Bisson, and W. D. Wilson, Calculations of the trapping and migration of vacancies and nickel self-interstitials in the presence of rare gases and dislocations, J. Nucl. Mater. 83, 139 (1979).
  63. P. Wynblatt, Calculation of the vacancy migration energy in cubic crystals, J. Phys. Chem. Solids 29, 215 (1968).
  64. P. Hautojärvi, J. Johansson, A. Vehanen, J. Yli-Kauppila, and P. Moser, Vacancy-carbon interaction in iron, Phys. Rev. Lett. 44, 1326 (1980).
  65. E. Kuramoto, H. Abe, M. Takenaka, F. Hori, Y. Kamimura, M. Kimura, and K. Ueno, Positron annihilation lifetime study of irradiated and deformed Fe and Ni, J. Nucl. Mater. 239, 54 (1996).
  66. B. Luo, X. Ren, X. Feng, L. Gong, and G. Peng, Ab initio investigation of energetics and stability of vacancy clusters in the FCC high-entropy alloy FeCrCoNi, J. Nucl. Mater. 609, 155744 (2025).
  67. S. Zhao, G. Velisa, H. Xue, H. Bei, W. J. Weber, and Y. Zhang, Suppression of vacancy cluster growth in concentrated solid solution alloys, Acta Mater. 125, 231 (2017).
  68. Z. Wang, C. T. Liu, and P. Dou, Thermodynamics of vacancies and clusters in high-entropy alloys, Phys. Rev. Mater. 1, 043601 (2017).
  69. Y.-Z. Wang and Y.-J. Wang, Disentangling diffusion heterogeneity in high-entropy alloys, Acta Mater. 224, 117527 (2022).
  70. H. Guan, H. Cui, N. Ding, K. Yang, S. Jiang, and Y. Sui, Significantly enhanced vacancy diffusion in Mn-containing alloys, arxiv:2404.03339.
  71. Z. Zhang, Z. Su, B. Zhang, Q. Yu, J. Ding, T. Shi, C. Lu, R. O. Ritchie, and E. Ma, Effect of local chemical order on the irradiation-induced defect evolution in CrCoNi medium-entropy alloy, Proc. Natl. Acad. Sci. USA 120, e2218673120 (2023).
  72. C. Li, J. Yin, K. Odbadrakh, B. C. Sales, S. J. Zinkle, G. M. Stocks, and B. D. Wirth, First principle study of magnetism and vacancy energetics in a near equimolar NiFeMnCr high entropy alloy, J. Appl. Phys. 58, SCCD15 (2019).
  73. S. Zhao, T. Egami, G. M. Stocks, and Y. Zhang, Effect of d electrons on defect properties in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys, Phys. Rev. Mater. 2, 013602 (2018).

Outline

Information

Phys. Rev. Materials 10, 055201– Published 26 May, 2026
  • Received 11 February 2026
  • Accepted 4 May 2026
Crossmark - Check for updates button

©2026 American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation