Abstract
As proposed in the 1920s, the empirical Hume-Rothery rules have been guiding the alloy design for random solid solutions. In contrast, the recent proposal by Yeh et al. (Adv Eng Mater 6(5):299–303, 2004) suggested that formation of random solid solution could be attributed to the maximized configurational entropy of mixing of multicomponent alloys, also known as high entropy alloys. By taking into account the non-ideal mixing of atoms with inter-atomic correlations (correlated mixing), here we suggest that the idea of entropic stabilization could be theoretically connected with the Hume-Rothery rules. The non-ideal formulation of the configurational entropy of mixing of a multicomponent alloy rationalizes the recent data obtained from experiments and simulations, which show the temperature dependence of the configurational entropy of mixing, the metastability of random solid solution observed at a low temperature, and the coupled effect of atomic size and chemical bond misfit on the stability of random solid solution. Finally, we discuss the measures that one can take to maximize the configurational entropy of a multicomponent alloy by considering the possible correlations among their constituent elements.
Similar content being viewed by others
References
J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau, and S.Y. Chang, Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes, Adv. Eng. Mater., 2004, 6(5), p 299-303
U. Mizutani, Hume-Rothery Rules for Structurally Complex Alloy Phases, CRC Press, Boca Raton, 2016
Y.F. Ye, C.T. Liu, and Y. Yang, A Geometric Model for Intrinsic Residual Strain and Phase Stability in High Entropy Alloys, Acta Mater., 2015, 94, p 152-161
Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen, P.K. Liaw, and Z.P. Lu, Microstructures and Properties of High-Entropy Alloys, Prog. Mater Sci., 2014, 61, p 1-93
J.D. Eshelby, The Continuum Theory of Lattice Defects, Solid State Phys., 1956, 3, p 79–144. doi:10.1016/S0081-1947(08)60132-0
T. Egami, Atomic Level Stresses, Prog. Mater. Sci., 2011, 56(6), p 637-653
T. Egami and Y. Waseda, Atomic Size Effect on the Formability of Metallic Glasses, J. Non-Cryst. Solids, 1984, 64(1-2), p 113-134
B. Cantor, I.T.H. Chang, P. Knight, and A.J.B. Vincent, Microstructural Development in Equiatomic Multicomponent Alloys, Mater. Sci. Eng. A, 2004, 375-377, p 213-218
E.J. Pickering and N.G. Jones, High-Entropy Alloys: A Critical Assessment of Their Founding Principles and Future Prospects, Int. Mater. Rev., 2016, 61(3), p 183-202
D.B. Miracle and O.N. Senkov, A Critical Review of High Entropy Alloys and Related Concepts, Acta Mater., 2017, 122, p 448-511
S. Guo and C.T. Liu, Phase Stability in High Entropy Alloys: Formation of Solid-Solution Phase or Amorphous Phase, Prog. Nat. Sci. Mater. Int., 2011, 21(6), p 433-446
Y.F. Ye, Q. Wang, J. Lu, C.T. Liu, and Y. Yang, High-Entropy Alloy: Challenges and Prospects, Mater. Today, 2016, 19(6), p 349-362
G. Adam and J.H. Gibbs, On Temperature Dependence of Cooperative Relaxation Properties in Glass-Forming Liquids, J. Chem. Phys., 1965, 43, p 139-146
P.G. Debenedetti and F.H. Stillinger, Supercooled Liquids and the Glass Transition, Nature, 2001, 410(6825), p 259-267
L. Angelam and G. Foffi, Configurational Entropy of Hard Spheres, J. Phys. Condens. Matter, 2007, 19, p 256207
I. Ford, Statistical Models of Entropy, Statistical Physics, Wiley, New York, 2013, p 119-135
L.K. Nash, Elements of Statistical Thermodynamics, 2nd ed., Dover Publication Inc, Mineola, 2006
J.-W. Yeh, Alloy Design Strategies and Future Trends in High-Entropy Alloys, JOM, 2013, 65(12), p 1759-1771
D. Ma, B. Grabowski, F. Körmann, J. Neugebauer, and D. Raabe, Ab Initio Thermodynamics of the CoCrFeMnNi High Entropy Alloy: Importance of Entropy Contributions Beyond the Configurational One, Acta Mater., 2015, 100, p 90-97
Q.F. He, Y.F. Ye, and Y. Yang, The Configurational Entropy of Mixing of Metastable Random Solid Solution in Complex Multicomponent Alloys, J. Appl. Phys., 2016, 120(15), p 154902
G.A. Mansoori, N.F. Carnahan, K.E. Starling, and T.W. Leland, Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres, J. Chem. Phys., 1971, 54(4), p 1523-1525
Y.F. Ye, Q. Wang, J. Lu, C.T. Liu, and Y. Yang, The Generalized Thermodynamic Rule for Phase Selection in Multicomponent Alloys, Intermetallics, 2015, 59, p 75-80
Y. Zhang, Y.J. Zhou, J.P. Lin, G.L. Chen, and P.K. Liaw, Solid-Solution Phase Formation Rules for Multi-component Alloys, Adv. Eng. Mater., 2008, 10(6), p 534-538
Y.F. Ye, Q. Wang, J. Lu, C.T. Liu, and Y. Yang, Design of High Entropy Alloys: A Single-Parameter Thermodynamic Rule, Scr. Mater., 2015, 104, p 53-55
Y.F. Ye, X.D. Liu, S. Wang, C.T. Liu, and Y. Yang, The General Effect of Atomic Size Misfit on Glass Formation in Conventional and High-Entropy Alloys, Intermetallics, 2016, 78, p 30-41
L. Ma, L. Wang, T. Zhang, and A. Inoue, Bulk Glass Formation of Ti-Zr-Hf-Cu-M (M = Fe Co, Ni) Alloys, Mater. Trans., 2002, 43(2), p 277-280
Z. Wu, H. Bei, F. Otto, G.M. Pharr, and E.P. George, Recovery, Recrystallization, Grain Growth and Phase Stability of a Family of FCC-Structured Multi-component Equiatomic Solid Solution Alloys, Intermetallics, 2014, 46, p 131-140
M. Widom, Prediction of Structure and Phase Transformations, High-Entropy Alloys: Fundamentals and Applications, M.C. Gao, J.-W. Yeh, P.K. Liaw, and Y. Zhang, Ed., Springer International Publishing, Cham, 2016, p 267-298
Z. Liu, Y. Lei, C. Gray, and G. Wang, Examination of Solid-Solution Phase Formation Rules for High Entropy Alloys from Atomistic Monte Carlo Simulations, JOM, 2015, 67(10), p 2364-2374
M.C. Troparevsky, J.R. Morris, P.R.C. Kent, A.R. Lupini, and G.M. Stocks, Criteria for Predicting the Formation of Single-Phase High-Entropy Alloys, Phys. Rev. X, 2015, 5(1), p 011041
Y.F. Ye, Q. Wang, Y.L. Zhao, Q.F. He, J. Lu, and Y. Yang, Elemental Segregation in Solid-Solution High-Entropy Alloys: Experiments and Modeling, J. Alloy. Compd., 2016, 681, p 167-174
Z. An, H. Jia, Y. Wu, P.D. Rack, A.D. Patchen, Y. Liu, Y. Ren, N. Li, and P.K. Liaw, Solid-Solution CrCoCuFeNi High-Entropy Alloy Thin Films Synthesized by Sputter Deposition, Mater. Res. Lett., 2015, 3(4), p 203-209
E.J. Pickering, R. Muñoz-Moreno, H.J. Stone, and N.G. Jones, Precipitation in the Equiatomic High-Entropy Alloy CrMnFeCoNi, Scr. Mater., 2016, 113, p 106-109
F. Otto, A. Dlouhý, K.G. Pradeep, M. Kuběnová, D. Raabe, G. Eggeler, and E.P. George, Decomposition of the Single-Phase High-Entropy Alloy CrMnFeCoNi After Prolonged Anneals at Intermediate Temperatures, Acta Mater., 2016, 112, p 40-52
B. Linder, Thermodynamics and Introductory Statistical Mechanics, Wiley, New York, 2004
O.N. Senkov, G.B. Wilks, J.M. Scott, and D.B. Miracle, Mechanical Properties of Nb25Mo25Ta25W25 and V20Nb20Mo20Ta20W20 Refractory High Entropy Alloys, Intermetallics, 2011, 19(5), p 698-706
X. Yang, Y. Zhang, and P.K. Liaw, Microstructure and Compressive Properties of NbTiVTaAlx High Entropy Alloys, Procedia Eng., 2012, 36, p 292-298
O.N. Senkov, G.B. Wilks, D.B. Miracle, C.P. Chuang, and P.K. Liaw, Refractory High-Entropy Alloys, Intermetallics, 2010, 18(9), p 1758-1765
M.C. Gao, B. Zhang, S.M. Guo, J.W. Qiao, and J.A. Hawk, High-Entropy Alloys in Hexagonal Close-Packed Structure, Metall. Mater. Trans. A, 2016, 47(7), p 3322-3332
A. Takeuchi, K. Amiya, T. Wada, K. Yubuta, and W. Zhang, High-Entropy Alloys with a Hexagonal Close-Packed Structure Designed by Equi-Atomic Alloy Strategy and Binary Phase Diagrams, JOM, 2014, 66(10), p 1984-1992
M. Feuerbacher, M. Heidelmann, and C. Thomas, Hexagonal High-Entropy Alloys, Mater. Res. Lett., 2015, 3(1), p 1-6
Y.J. Zhao, J.W. Qiao, S.G. Ma, M.C. Gao, H.J. Yang, M.W. Chen, and Y. Zhang, A Hexagonal Close-Packed High-Entropy Alloy: The Effect of Entropy, Mater. Des., 2016, 96, p 10-15
J.-W. Yeh, S.-Y. Chang, Y.-D. Hong, S.-K. Chen, and S.-J. Lin, Anomalous decrease in X-ray Diffraction Intensities of Cu-Ni-Al-Co-Cr-Fe-Si Alloy Systems with Multi-principal Elements, Mater. Chem. Phys., 2007, 103(1), p 41-46
Y.X. Zhuang, H.D. Xue, Z.Y. Chen, Z.Y. Hu, and J.C. He, Effect of Annealing Treatment on Microstructures and Mechanical Properties of FeCoNiCuAl High Entropy Alloys, Mater. Sci. Eng. A, 2013, 572, p 30-35
Y. Zhang, S.G. Ma, and J.W. Qiao, Morphology Transition from Dendrites to Equiaxed Grains for AlCoCrFeNi High-Entropy Alloys by Copper Mold Casting and Bridgman Solidification, Metall. Mater. Trans. A, 2012, 43(8), p 2625-2630
C. Li, J.C. Li, M. Zhao, and Q. Jiang, Effect of Alloying Elements on Microstructure and Properties of Multiprincipal Elements High-Entropy Alloys, J. Alloy. Compd., 2009, 475(1-2), p 752-757
O.N. Senkov, J.D. Miller, D.B. Miracle, and C. Woodward, Accelerated Exploration of Multi-principal Element Alloys with Solid Solution Phases, Nat. Commun., 2015, 6, p 6529
X. Yang and Y. Zhang, Prediction of High-Entropy Stabilized Solid-Solution in Multi-component Alloys, Mater. Chem. Phys., 2012, 132(2-3), p 233-238
C.-J. Tong, Y.-L. Chen, J.-W. Yeh, S.-J. Lin, S.-K. Chen, T.-T. Shun, C.-H. Tsau, and S.-Y. Chang, Microstructure Characterization of Al x CoCrCuFeNi high-Entropy Alloy System with Multiprincipal Elements, Metall. Mater. Trans. A, 2005, 36(4), p 881-893
Z. Hu, Y. Zhan, G. Zhang, J. She, and C. Li, Effect of Rare Earth Y Addition on the Microstructure and Mechanical Properties of High Entropy AlCoCrCuNiTi Alloys, Mater. Des., 2010, 31(3), p 1599-1602
Y.J. Zhou, Y. Zhang, Y.L. Wang, and G.L. Chen, Solid Solution Alloys of AlCoCrFeNiTix with Excellent Room-Temperature Mechanical Properties, Appl. Phys. Lett., 2007, 90(18), p 181904
X.F. Wang, Y. Zhang, Y. Qiao, and G.L. Chen, Novel Microstructure and Properties of Multicomponent CoCrCuFeNiTix Alloys, Intermetallics, 2007, 15(3), p 357-362
J.-W. Yeh, S.-J. Lin, T.-S. Chin, J.-Y. Gan, S.-K. Chen, T.-T. Shun, C.-H. Tsau, and S.-Y. Chou, Formation of Simple Crystal Structures in Cu-Co-Ni-Cr-Al-Fe-Ti-V Alloys with Multiprincipal Metallic Elements, Metall. Mater. Trans. A, 2004, 35(8), p 2533-2536
X.Q. Gao, K. Zhao, H.B. Ke, D.W. Ding, W.H. Wang, and H.Y. Bai, High Mixing Entropy Bulk Metallic Glasses, J. Non-Cryst. Solids, 2011, 357(21), p 3557-3560
A. Takeuchi, N. Chen, T. Wada, Y. Yokoyama, H. Kato, A. Inoue, and J.W. Yeh, Pd20Pt20Cu20Ni20P20 High-Entropy Alloy as a Bulk Metallic Glass in the Centimeter, Intermetallics, 2011, 19(10), p 1546-1554
H.Y. Ding and K.F. Yao, High Entropy Ti20Zr20Cu20Ni20Be20 Bulk Metallic Glass, J. Non-Cryst. Solids, 2013, 364, p 9-12
Acknowledgments
The research of Y.Y. is supported by the City University of Hong Kong through the UGC Block Grant with the Project No 9610366. Y.Y. is also thankful to Prof. David Srolovitz (University of Pennsylvania, PA, USA) for the insightful discussions during his short visit of Hong Kong.
Author information
Authors and Affiliations
Corresponding author
Appendix
Appendix
For a microcanonic ensemble, let us assume the occurrence probability of the individual microstate being equal. Furthermore, the number (Ω) of the microstate corresponding to the equilibrium macrostate is overwhelmingly large compared to others, which can be expressed as \(\ln \varOmega = \ln N! + \sum\limits_{i} {n_{i} \ln g_{i} } - \sum\limits_{i} {\ln n_{i} !}\). For a large N, we can take Stirling’s approximation \(\ln N! = N\ln N - N\) and, therefore, \(\ln \varOmega = N\ln N + \sum\limits_{i} {n_{i} \ln \frac{{g_{i} }}{{n_{i} }}}\). Maximizing ln Ω subjected to the two constraints dE = ∑ i ɛ i dn i = 0 and dN = ∑ i dn i = 0 leads to
where E is the potential energy; α and β are the Lagrangian multipliers. For any arbitrary change of dn i , (8) holds only if \(\ln \frac{{g_{i} }}{{n_{i} }} - \alpha - \beta \varepsilon_{i} = 0\). This leads to the Maxwell–Boltzmann distribution \(n_{i} = g_{i} e^{{ - \alpha - \beta \varepsilon_{i} }}\). Define the partition function \(Z = \sum\limits_{i} {g_{i} e^{{ - \beta \varepsilon_{i} }} }\), the particle number N of the system can be expressed as \(N = \sum\limits_{i} {g_{i} e^{{ - \alpha - \beta \varepsilon_{i} }} = e^{ - \alpha } Z}\) or e −α = N/Z. As a result, the expression of ln Ω can be simplified to ln Ω = N ln Z + βE. Furthermore, for a canonic ensemble (constant temperature and constant volume), it can be shown that β = 1/k B T[35] and thus \(\ln \varOmega = N\ln Z + \frac{E}{{k_{B} T}}\). Taking a small fluctuation in the configurational energy E, we have \(d\left( {\ln \varOmega } \right) = \frac{dE}{{k_{B} T}}\). According to the first law of thermodynamics, dE = δQ. Thus \(d\left( {\ln \varOmega } \right) = \frac{\delta Q}{{k_{B} T}} = \frac{dS}{{k_{B} }}\). Finally, we obtain:
Here, it is worth noting that Ω in the Boltzmann entropy formula corresponds to the fixed potential energy E. Any disturbance in the potential energy E will cause a change in the Ω and thus the configurational entropy S.
Rights and permissions
About this article
Cite this article
He, Q.F., Ye, Y.F. & Yang, Y. Formation of Random Solid Solution in Multicomponent Alloys: from Hume-Rothery Rules to Entropic Stabilization. J. Phase Equilib. Diffus. 38, 416–425 (2017). https://doi.org/10.1007/s11669-017-0560-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11669-017-0560-9