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Scripta Materialia 94 (2015) 28–31
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Atomic-size effect and solid solubility of multicomponent alloys

⇑
Zhijun Wang,a,b Yunhao Huang,b Yong Yang,a Jincheng Wangb and C.T. Liua,
a
Center of Advanced Structural Materials, Department of Mechanical and Biomedical Engineering,
City University of Hong Kong, Kowloon, Hong Kong, China
b
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China
Received 27 August 2014; accepted 14 September 2014
Available online 26 September 2014

In physical metallurgy, solid solubility of alloys is known to play a vital role in determining their physical/mechanical properties. Hume–Rothery
rules show the great effect of size difference between solvent and solute atoms on the solid solubility of binary alloys. However, modern multicom-
ponent systems, such as high-entropy alloys, defy the classic atomic size effect due to the absence of solvent and/or solute atoms. Here, we propose an
effective atomic size parameter by considering atomic packing misfitting in multicomponent systems.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Alloy solubility; High entropy alloys; Atomic-size effect; Atomic packing

The solubility of a solute element in an alloy is an
important aspect of alloy design. Through the addition of
soluble elements, one may obtain a solid solution effect that
can significantly improve the alloy’s performance. For a
substitutional binary alloy, the Hume–Rothery rules pro-
vide the key guidance to evaluating whether a solid solution
can be formed [1]. These include: (i) the relative atomic size
difference between the solute and solvent elements should
be less than 15%; (ii) the formation of stable intermediate
compounds should be restricted by carefully choosing the
combination of metallic elements; and (iii) the electron con-
centration of the constituent elements should be tuned in
favor of the formation of solid solutions, not otherwise.
The Hume–Rothery rules have been used extensively for
more than half a century [2–6]. However, the rules are poses
a challenge with the recent design of multicomponent alloys
[7–10], in some of which the molar fractions of the constitu-
ent elements are equal or nearly equal, such as high-entropy
alloys (HEAs) [9–13]. As a result, there is no distinct identity
of “solvent” or “solute” atoms in such alloys. Therefore, the
atomic size factor as defined by the Hume–Rothery rules
cannot be applied directly to HEAs. Despite this, some
empirical parameters have been suggested as extensions of
the Hume–Rothery rules to explain the solid solubility of
HEAs [14]; however, they do not do so satisfactorily when
compared with experimental data [15].
The atomic size difference is of primary importance in
determining the solubility of alloys. The critical value of
15% atomic size difference in binary alloys was confirmed
⇑ Corresponding author. Tel.: +852 3442 7213; e-mail: chainliu@
cityu.edu.hk
by the continuum elastic theory [16]. However, it is difficult
to define an atomic size parameter in relation to solubility
of HEAs. For simplicity, the polydispersity resulting from
the atomic size difference has been commonly used for pre-
dicting the solid solubility of a given multicomponent alloy
[14], which is:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Xn ffi X
n
2
d¼ i
c i ð1  r i =r Þ ; r ¼ ci ri ð1Þ
i
where ci is the atomic concentration of the ith atom and ri
is the atomic radius of the ith atom. It has been widely
applied in the systems of hard-sphere fluids [17], metallic
glasses [18] and HEAs [14,15]. In the hard-sphere fluid,
d ¼ 0:06 is the criterion used to predict crystalline structure
formation, and this criterion was also claimed in the HEA
investigation. However, this parameter does not describe
the solubility of HEAs very well; as a result, many interme-
tallics have been detected around d ¼ 0:06 [15]. Basically,
the d parameter takes the average effect of the atomic size
difference of all elements in the alloy. However, the solid
solution instability may essentially be determined by the
largest and smallest atoms in multicomponent alloy sys-
tems. Moreover, the physical meaning of d in determining
the solubility is also not well understood, and it cannot
return to the Hume–Rothery limit. Therefore it is necessary
to explore the new and physically acceptable parameter of
the atomic size effect on the solubility of multicomponent
alloys, especially HEAs, which have received increasing
attention recently from the materials community [9,11].
In this letter, we address this issue by considering the
atomic size effect based on atomic packing behavior. The
proposed parameter not only has a clear physical meaning,

http://dx.doi.org/10.1016/j.scriptamat.2014.09.010
1359-6462/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 Z. Wang et al. / Scripta Materialia 94 (2015) 28–31
but is also consistent with the 15% atomic size difference in
the Hume–Rothery rules. In particular, this parameter is
more effective in describing the solubility of HEAs.
In solid solutions, the atomic size difference influences
the topological instability of atomic packing. Egami [19]
presented the topological instability of atomic packing in
dilute binary alloys to discuss the structural instability
involving glasses, and Miracle et al. [20] discussed the
atomic packing efficiency in metallic glasses. Random pack-
ing in colloidal suspensions has also been studied exten-
sively [21]. To date, however, there has been no report on
the random atomic packing in HEAs. The instability of
atomic packing is more complicated in multicomponent
solid solutions with difference atomic sizes. However, the
atoms with the largest and smallest sizes certainly play a
dominant role in determining the stability of a lattice.
Therefore, the packing state around the atoms with the
largest and smallest sizes in HEAs should be the most
important factor used to reveal how far away from the ideal
case the atomic packings are. Hence, the packing states
around the largest and smallest atoms affect the stability
of the solid solutions.
The solid angles of atomic packing for the elements with
the largest and smallest atomic sizes are chosen to quanti-
tatively describe the atomic packing effect in multicompo-
nent alloys. The solid angles around the largest and
smallest atoms in respect to the surrounding atoms are
described geometrically by
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðrS þ rÞ2  r2 ðrL þ rÞ2  r2
xL ¼ 1  ; xS ¼ 1 
ðrS þ rÞ2 ðrL þ rÞ2
where rL and rs are the radii of the largest and smallest
atoms (see Fig. 1). A normalized parameter of the geomet-
ric packing state should be a good candidate to reveal the
atomic packing instability. Here, we chose the ratio
between the solid angles of the smallest and largest atoms
c ¼ xS =xL
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!, sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
ðrS þ rÞ2  r2 ðrL þ rÞ2  r2
¼ 1 2
1
ðrS þ rÞ ðrL þ rÞ2
as an indictor to reveal the atomic packing misfitting and
topological instability. It is also important to point out that
the Hume–Rothery rule of 15% of the atomic size difference
in binary alloys corresponds to a critical value of packing
misfitting of c ¼ 1:167.
(a)
r r
ωL
rL
Figure 1. Sketch of the atomic packing around an atom via a solid angle: (a) around a largest atom; (b) around a smallest atom. r is the average
atomic radius.
29
1.5
Solid solution
Intermetallics
1.4 Metallic glass
1.3
γ=1.175
γ
1.2
δ=0.06
1.1
1.0
0.00 0.04 0.08 0.12
δ
Figure 2. Statistics of the atomic packing parameter c and the
polydispersity parameter d of atomic size difference from representa-
tive experimental results on the phase selection in HEAs. c ¼ 1:17
clearly distinguishes the solid solutions from the intermetallics. All the
alloys are from Table 1 in Ref. [9].
Figure 2 shows the c  d plot from a statistical analysis
of representative experimental results regarding the phase
selection in HEAs reported recently by Guo et al. [15]. All
of the alloys analyzed were prepared by suction and
injection casting in metal molds by arc or induction
melting. The figure shows that there are many solid
solutions and intermetallics coexisting in the region of
0:04 < d < 0:08. Even taking into consideration the mix-
ing enthalpy, it is still impossible to distinguish the two
different kinds of phases in the coexistence region [15].
ð2Þ
Therefore, d is clearly not a good parameter for separating
the solid solutions and intermetallics. It appears that d is
not competent enough to describe the solubility in HEAs.
On the other hand, Figure 2 shows that the atomic pack-
ing parameter c can clearly distinguish solid solutions
from multiphase regions with intermetallics. All of the
solid solutions are in the region of c < 1:175. Most of
the multiphase regions with intermetallics together with
metallic glasses are all distributed in the region of
c > 1:175. Note that metallic glasses are in a metastable
ð3Þ state, prepared by relatively fast cooling, the glass phases
of which mainly change to intermetallic phases during
equilibrium treatments.
A total of 95 kinds of HEAs are included in Figure 2.
The critical value of c ¼ 1:175 can distinguish nearly all
the 59 solid solution alloys. The previous parameter,
d ¼ 0:06, misses six solid solutions, with a 10% error for
(b)
ωS
rS
30 Z. Wang et al. / Scripta Materialia 94 (2015) 28–31

all 59 solid solution alloys. There are alloys with the same d
but different c around d ¼ 0:06, indicating that the alloying
elements may have the same distribution of atomic size
differences but with different atomic packing statuses.
Furthermore, it is important to note that the criterion of
1.175 in HEAs agrees very well with the 15% limit of the
Hume–Rothery rules for binary alloys. Comparison of
the parameters of d and c reveals clearly that c is more effec-
tive in distinguishing solid solutions from multiphases with
intermetallics.
From the viewpoint of physical foundation, the atomic
packing parameter c has a more distinct meaning, refer-
ring to the topological instability, than the polydispersity
parameter d. Firstly, c presents the normalized packing
density discrepancy between the smallest and largest
atoms which predominantly determine the atomic packing
instability, whereas d reveals only the average effect of
atomic size differences on the phase selection. Secondly,
c also reasonably considers the atomic size effect of atoms
with medium sizes through atomic packing with the
average atomic radius r, as shown in Eq. (3). Finally, its
criterion of c < 1:175 can return to the 15% limit of the
Hume–Rothery rules in binary alloys. Note that we care-
fully analyzed other atomic size effects in this study; how-
ever, no other size parameters have the merit of the c
parameter.
We explored several dozen superalloys in order to fur-
ther confirm the application of the effect of this new atomic
packing parameter on the solid solubility of multicompo-
nent alloys. We considered 83 kinds of commercial superal-
loys, as shown in Table 1. As is known, superalloys
generally contain disordered face-centered cubic (fcc) (solid
solution) and ordered fcc (L12) structures. The results are
shown in Figure 3, where alloying elements with an atomic
fraction larger than 1% are considered. The figure shows
that the criterion of c ¼ 1:175 still works very well in distin-
guishing the solid solution phases in the superalloys, much
better than d parameter. There are two exceptions in the

Table 1. The superalloys presented in Figure 3.

Superalloys (solid solution) d c Superalloys (solid solution + precipitation) d c
Haynes 188 0.04727 1.1115 Jetalloy1570 0.05189 1.19912
Haynes25 0.03617 1.11153 A-286 0.05958 1.19993
MAR_M918 0.03046 1.1644 Discaloy 0.03562 1.19954
MP159 0.03806 1.19866 Incoloy 903 0.03844 1.19926
MP35N 0.02204 1.10313 Incoloy 907 0.03538 1.19929
s-816 0.06003 1.16859 Incoloy 909 0.03575 1.19932
Stellite B 0.08298 1.11228 Pyromet CTX-1 0.04032 1.19908
UMCo-50 0.02862 1.00868 Thermo-Span 0.03424 1.19922
Incoloy 801 0.02709 1.19982 V-57 0.04344 1.19936
Illim G 0.04175 1.10336 W-545 0.0446 1.19949
Inconel 690 0.01367 1.03229 AM-1 0.05446 1.19229
Hastelloy B 0.0417 1.10745 AM-3 0.05621 1.1922
Hastelloy B-2 0.03999 1.10746 B-1900 0.07968 1.60503
Hastelloy C-276 0.03243 1.11136 C-1023 0.06605 1.19256
Hastelloy C-4 0.03787 1.16791 Ford 406 0.0528 1.19766
Hastelloy G 0.03134 1.10808 GMR-235 0.05969 1.19864
Hastelloy G-3 0.02788 1.10798 Inconel 100 0.0681 1.19227
Hastelloy N 0.03775 1.10779 Inconel 713LC 0.05642 1.16492
Hastelloy S 0.03018 1.10776 Inconel 713C 0.06097 1.16497
Hastelloy W 0.04663 1.10758 Inconel 718 0.0397 1.19902
Hastelloy X 0.04847 1.17099 Inconel 738 0.0638 1.19291
Haynes 214 0.048 1.17069 Inconel 792 0.06749 1.19274
Haynes 230 0.03946 1.1116 M22 0.06448 1.16468
Nimonic 86 0.0299 1.10321 M-252 0.0532 1.19348
Haynes HR-120 0.02884 1.10819 MAR-M 200 0.06456 1.19764
Haynes HR-160 0.0259 1.00869 MAR-M 246 0.06447 1.19246
Inconel 600 0.02351 1.00695 MAR-M 421 0.06058 1.19288
Inconel 601 0.03072 1.17146 MC2 0.05202 1.19263
Inconel 617 0.03698 1.16605 MS2 0.05437 1.19229
Inconel 625 0.0329 1.11154 N-4 0.05575 1.1923
Inconel 690 0.01554 1.06592 PWA 1480 0.05598 1.19222
Nimonic 75 0.03216 1.00694 Nimonic 105 0.05391 1.19293
RA333 0.02446 1.10817 Jetalloy1650 0.05856 1.19354
19–9D 0.04898 1.09664 Incoloy 901 0.04388 1.19924
Haynes 556 0.02485 1.10809 Incoloy 925 0.03195 1.19929
Incoloy 800 0.03391 1.17169 Inconel 783 0.04898 1.17022
Incoloy 800H 0.03391 1.1717 Inconel 939 0.05719 1.19857
Incoloy 800HT 0.0349 1.17169 Inconel 706 0.0341 1.19942
Hastelloy X 0.03472 1.10807 Inconel 718 0.04309 1.19906
Incoloy 802 0.05785 1.1719 Udimet 630 0.04472 1.19871
N-155(Multimet) 0.04034 1.10817 C-263 0.03991 1.19381
REX-78 0.02477 1.10817
 Z. Wang et al. / Scripta Materialia 94 (2015) 28–31
1.2
1.15
1.1
γ
1.05
solid solution+precipitation
solid solution
1 Rev. B 25 (1982) 907.
0.02 0.04 0.06 0.08
δ
Figure 3. Application of the atomic packing parameter on the solid
solubility of superalloys.
solid solution superalloys – the MP159 and Incoloy 801
superalloys – which contain 3.7 and 1.3 at.% Ti, respec-
tively. These two superalloys have single solid solution
phases at high temperatures, which are retained after
cooling to room temperature, possibly due to the sluggish
phase transformation.
In conclusion, we have revealed a new parameter of the
atomic size difference, c, based on the random atomic
packing in multicomponent alloy systems of HEAs and
superalloys. The proposed parameter has a clear physical
meaning in determining the solubility of these multicom-
ponent alloys, and is consistent to the 15% limit of
Hume–Rothery rules commonly used in binary alloys.
Also, the application of c to phase selection in HEAs
and superalloys indicates that it is more efficient at distin-
guishing solid solutions from intermetallics than the previ-
ous polydispersity parameter of atomic size difference d.
Through a comprehensive analysis of the existing data,
it is shown that the newly proposed parameter is able to
capture the general trend of phase selection in multicom-
ponent alloys much better than the classic one. It should
be noted that c < 1:175 is one of the necessary conditions
for determining the solubility of multicomponent alloys
but not a sufficient one, and that the mixing enthalpy,
electronegativity and electron concentration should also
be considered in order to confirm the solubility of multi-
component alloys.
This research is supported by the Research Grant Coun-
cil (RGC), the Hong Kong Government, through the General
Research Fund (GRF) under project number CityU/521411.
Z.W. is also supported by the Hong Kong Scholar Program and
the National Science Foundation for Post-doctoral Scientists of
China under project number 2013M542385.
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31
[1] R.W. Cahn, P. HaasenPhysical Metallurgy, vol. 1, North-
Holland, Amsterdam., 1996.
[2] W. Hume-Rothery, B.R. Coles, The transition metals and
their alloys, Adv. Phys. 3 (1954) 149.
[3] J. Chelikowsky, Solid solubilities in divalent alloys, Phys.
Rev. B 19 (1979) 686.
[4] J. Alonso, S. Simozar, Prediction of solid solubility in alloys,
Phys. Rev. B 22 (1980) 5583.
[5] V.A. Singh, A. Zunger, Phenomenology of solid solubilities
and ion-implantation sites: an orbital-radii approach, Phys.
0.10
[6] B.-W. Zhang, Semi-empirical theory of solid solubility in
binary alloys, Z. Metallkd. 76 (1985) 264–270.
[7] B. Smola, I. Stulı́ková, F. von Buch, B.L. Mordike, Structural
aspects of high performance Mg alloys design, Mater. Sci.
Eng. A 324 (2002) 113–117.
[8] B. Geddes, Superalloys: Alloying and Performance, ASM
International, Materials Park, OH, 2010.
[9] Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen,
P.K. Liaw, Z.P. Lu, Microstructures and properties of high-
entropy alloys, Prog. Mater. Sci. 61 (2014) 1–93.
[10] B. Cantor, Multicomponent and high entropy alloys, Entropy
16 (2014) 4749–4768.
[11] M.-H. Tsai, J.-W. Yeh, High-entropy alloys: a critical review,
Mater. Res. Lett. (2014) 1–17.
[12] J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T.
Shun, C.H. Tsau, S.Y. Chang, Nanostructured high-entropy
alloys with multiple principal elements: novel alloy design
concepts and outcomes, Adv. Eng. Mater. 6 (2004) 299–303.
[13] B. Cantor, I.T.H. Chang, P. Knight, A.J.B. Vincent, Micro-
structural development in equiatomic multicomponent alloys,
Mater. Sci. Eng. A 375–377 (2004) 213–218.
[14] Y. Zhang, Y.J. Zhou, J.P. Lin, G.L. Chen, P.K. Liaw, Solid-
solution phase formation rules for multi-component alloys,
Adv. Eng. Mater. 10 (2008) 534–538.
[15] S. Guo, Q. Hu, C. Ng, C.T. Liu, More than entropy in high-
entropy alloys: forming solid solutions or amorphous phase,
Intermetallics 41 (2013) 96–103.
[16] J.D. Eshelby, The continuum theory of lattice defects, in: S.
Frederick, T. David (Eds.), Solid State Physics, Academic
Press, New York, 1956, pp. 79–144.
[17] P. Pusey, The effect of polydispersity on the crystallization of
hard spherical colloids, J. Phys. 48 (1987) 709–712.
[18] S. Fang, X. Xiao, L. Xia, W. Li, Y. Dong, Relationship
between the widths of supercooled liquid regions and bond
parameters of Mg-based bulk metallic glasses, J. Non-Cryst.
Solids 321 (2003) 120–125.
[19] T. Egami, Universal criterion for metallic glass formation,
Mater. Sci. Eng. A 226–228 (1997) 261–267.
[20] D.B. Miracle, W.S. Sanders, O.N. Senkov, The influence of
efficient atomic packing on the constitution of metallic
glasses, Philos. Mag. 83 (2003) 2409–2428.
[21] M. Clusel, E.I. Corwin, A.O.N. Siemens, J. Brujic, A
“granocentric” model for random packing of jammed emul-
sions, Nature 460 (2009) 611–615.