Materials Chemistry and Physics 132 (2012) 233–238

Contents lists available at SciVerse ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Materials science communication

Prediction of high-entropy stabilized solid-solution in multi-component alloys

X. Yang, Y. Zhang ∗
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: Phase formation for the multi-component alloys has been predicted by calculating parameter ˝ and ı
Received 24 February 2011 for typical multi-component alloys reported. Here, ˝ is defined as a parameter of the entropy of mixing
Received in revised form 10 June 2011 timing the average melting temperature of the elements over the enthalpy of mixing, ı is the mean square
Accepted 13 November 2011
deviation of the atomic size of elements. It shows that the high-entropy (HE) stabilized solid-solution is
located at ˝ ≥ 1.1 and ı ≤ 6.6%.
Keywords:
© 2011 Elsevier B.V. All rights reserved.
High-entropy
Solid-solution
Bulk-metallic glass
Multi-component alloys

1. Introduction
In recent years, high-entropy alloys (HEAs) have attracted
increasing attentions, because they have been reported to exhibit
unique microstructures and special properties [1–35]. According
to Yeh et al. [2,3,6], HEAs are defined as alloys that generally have
at least 5 major metallic elements, each of which has an atomic
percentage between 5% and 35%.
It has been reported that HEAs usually intend to form FCC and/or
BCC solid solutions rather than intermetallic compounds or other
complex ordered phases owing to HE of mixing [2,11]. This HE sta-
bilized solid-solution is a very strong solution, and we cannot know
which one is the solvent atom and which ones are solute atoms.
People are usually interested in prediction what the phases and
micro/nano structures will be formed for the multi-component
HEAs before doing the experiments. However, up to now, only
a few studies have been carried out on phase formation rule for
multi-component HEAs because of the absence of information
about multi-component alloys in phase diagrams. Zhang et al. [15]
proposed that small atomic size differences and near-zero val-
ues of the absolute enthalpy of mixing facilitate the formation of
solid-solutions for multi-component alloys, that is, the atomic size
differences should be less than 6.5%, the enthalpy of mixing should
be in the range of −15 to 5 kJ mol−1 and the entropy of mixing
should be in the range of 12–17.5 J K−1 mol−1 .
However, as a wide range of new multi-component HEAs sys-
tems have been explored lately, these proposed phase formation
rules should be revised accordingly. Hence, further investigation is
∗ Corresponding author. Tel.: +86 10 62334927; fax: +86 10 62333447.
E-mail addresses: drzhangy@ustb.edu.cn, yongzhangustb@gmail.com (Y. Zhang).
necessary to obtain a more precise phase formation rule for multi-
component HEAs.
In the present study, a literature search of microstructure in var-
ious multi-component alloy systems has been carefully conducted,
and the corresponding atomic size differences, enthalpy of mix-
ing and entropy of mixing have been calculated. On the basis of all
available data, a solid-solution formation rule for multi-component
HEAs has been proposed in this paper.
2. Theory analysis and discussion
As reported previously [10,36,37], besides solid-solutions
phases, multi-component HEAs may form intermetallic com-
pounds and amorphous phases. Simple solid-solution phases are
most expected to form in multi-component HEAs owing to their
promising properties [2,16]. In order to predict the solid-solution
formation rule in multi-component alloys, Gibbs free energy for
multi-component alloy systems has been considered firstly.
For the analysis of solidification, the difference in Gibbs free
energy between solid- and liquid-state, G (=Gs − Gl ), must be
required in the undercooled state.
However, for multi-component systems, it is difficult to cal-
culate G accurately at a certain composition and temperature.
Takeuchi and Inoue [38] have proposed an assumption for
multi-component alloy systems: G at a certain composition is
proportional to the free energy of mixing Gmix of the liquid phase,
and successfully utilize it to calculate critical cooling rate for metal-
lic glasses. In the present study, this assumption has still been
adopted, and Gmix can be expressed as:
Gmix = Hmix − TSmix (1)

0254-0584/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2011.11.021
234 X. Yang, Y. Zhang / Materials Chemistry and Physics 132 (2012) 233–238
Here, T is the absolute temperature, Hmix is the enthalpy of
mixing and Smix is the entropy of mixing.
In this paper, a regular solution model has been adopted in order
to simplify the calculation for free energy of multi-component
HEAs. The enthalpy of mixing for multi-component alloy system
with n elements can be determined from the following equation
[38]:

n
Hmix = ˝ij ci cj (2)
i=1, i =
/ j
where ˝ij (= 4HAB mix ) is the regular solution interaction parameter
between the ith and jth elements, ci or cj is the atomic percentage
of the ith or jth component, and HAB mix is the enthalpy of mixing
of binary liquid alloys. In the calculation, the values of enthalpy
of mixing HAB mix on the basis of Miedema macroscopic model for
binary liquid alloys can be obtained in the Ref. [39].
According to Boltzmann’s hypothesis, the entropy of mixing of
an n-element regular solution is as follows:

n
Smix = −R (ci ln ci ) (3)
i=1
n
where ci is mole percent of component, c = 1, and
i=1 i
R (=8.314 J K−1 mol−1 ) is gas constant. For the equi-atomic
ratio alloy, the entropy of mixing would be the maximum.
Therefore equal/near-equal atomic ratio multi-component HEAs
have much higher entropy of mixing than conventional
alloys.
Clearly, the free energy of mixing for multi-component system
is described as a function of composition and temperature on the
basis of the regular solution model, and Gmix of solid-solution
formation during the solidification in a multi-component alloy can
be easily calculated. If solid-solution phase possesses the lowest
Gmix among all possible formed phases, it will be most possible
to form and the most stable during the solidification. However, it
is impossible to calculate Gmix of all possible formed phases for a
multi-component alloy. Hence, a simple approach to predict solid
solution formation is necessary.
Fortunately, it is found that Hmix and TSmix items in Eq. (1)
play the different roles during the solid-solution formation, and
the ratio of TSmix and Hmix is used to estimate the solid-solution
formation ability in the present study. The detailed analysis is as
follows.
The experiment information shows that the enthalpy of mixing
Hmix in liquid alloy could evidently affect the phase formation
in the binary alloy system [40]. If Hmix < 0, one or more com-
pounds exist stably in the binary alloy; if Hmix > 0, there is a
central miscibility gap in the liquid phase which causes no com-
pounds in the solid phase or both substantial terminal solubility
of solid-solution to be severely restricted. For multi-component
alloy, although the number of factors affecting the phase formation
increases obviously, Hmix has similar effect for the phase forma-
tion. The negative Hmix is inclined to make the different elements
combine to be intermetallic compound. Moreover, the more nega-
tive Hmix means the larger binding force between elements. The
more positive Hmix means the less miscibility of the different ele-
ments in the liquid alloy, which leads to separation or segregation
of different elements in alloy. Whatever the sign of Hmix is, the
larger absolute value of Hmix will make solid-solution form hardly.
Only when the value of Hmix is close to zero, the different ele-
ments can randomly distribute in the alloy, and the solid-solution
phases can stably occur in the solid phase. It is consistent with the
experimental results in Ref. [40].
Consequently, the absolute value of the enthalpy of mixing
(|Hmix |) is adopted to describe the resistance for solid-solution
formation. Here, an assumption is proposed: the positive Hmix
and negative Hmix have the same effect for restraining the solid-
solution formation. The following discussion will show that this
assumption can accord with the calculated data from literature
search.
At the same time, the entropy contribution for solid-solution
formation also has to be taken into account due to the high Smix
for multi-component HEAs. The value of Smix is always positive
in multi-component alloy. The high Smix can effectively increase
the extent of confusion in alloy system and significantly lower
Gmix , thus the different elements would randomly distribute in
the crystal lattice and the tendency of ordering and segregation
of alloy elements is lowered by the high Smix . Consequently, the
high Smix can make random solid-solution form easily and more
stable than intermetallic compounds or other ordered phases dur-
ing solidification in alloys. In addition, in terms of the knowledge
of thermodynamics, the effect of Smix becomes more and more
prominent as the temperature increases. Therefore, the large value
of TSmix would facilitate forming solid-solutions. The value of
TSmix can be used to evaluate the driving force for forming solid-
solution.
According to the above analysis, the important factor affecting
the solid-solution formation can be judged by comparing the value
of TSmix and |Hmix |. Although the enthalpy of mixing is abso-
lute larger, which is often in kJ mol−1 , TSmix could be compared
with the enthalpy of mixing at high temperature. It implies that the
effect of the HE of mixing could balance the effect of the enthalpy
of mixing for forming solid-solution at certain temperature, that
is, the driving force is equal to the resistance. Above this temper-
ature, the effect of the HE of mixing could overcome the effect of
the enthalpy of mixing, TSmix become the main factor affecting
the solid-solution formation. Thus the solid-solution could be prior
to ordered phase to form. Ignoring the solid-state phase transition,
the phase formation generally occurs near the melting temperature
(Tm ) of alloy. Hence, Tm is adopted for the entropy term TSmix , and
a parameter ˝ is defined for predicting the solid-solution formation
for various multi-component alloys as:
Tm Smix
˝=   (4)
Hmix 
The melting temperature of n-elements alloy, Tm , is calculated
using the rule of mixtures:

n
Tm = ci (Tm )i (5)
i=1
Here, (Tm )i is the melting point of the ith component of alloy.
As analyzed above, the value of ˝ is positive, and ˝ = 1 should
be proposed as a critical value to form the solid solution. If ˝ > 1, the
contribution of TSmix will exceed that of Hmix for solid-solution
formation, and the multi-component HEAs are mainly composed
of the solid solutions; if ˝ ≤ 1, Hmix is the predominant part of
the free energy, and intermetallic compounds and segregations are
prior to solid-solution phases to form in multi-component HEAs.
Thus the value of ˝ could be used to estimate the solid-solution
formation ability.
However, the calculation of ˝ is based on a quasi-chemical
approach, the atomic size mismatch effect of component atoms
has not been considered. In multi-component HEAs, owing to
the similar concentration of elements, all atoms are expected to
randomly occupy the crystal lattice sites on the basis of a statisti-
cal average probability of occupancy. Therefore, each component
element can be regarded as the solute element for forming solid-
solution. But the large atomic size difference between so many
 X. Yang, Y. Zhang / Materials Chemistry and Physics 132 (2012) 233–238 235

Table 1
The microstructure and the parameters, ı, Hmix , Smix , Tm and ˝ for typical multicomponent HEAs reported.

Alloys Structure ı (%) Hmix (kJ mol−1 ) Smix (J K−1 mol−1 ) Tm (K) ˝ Ref.

CoCrFeNiAl BCC 5.25 −12.32 13.38 1675.10 1.83 [1]

CoCrFeNiCu FCC 1.07 3.20 13.38 1760.00 7.36 [2]
CoCrFeNiCuAl0.3 FCC 3.15 1.56 14.43 1713.22 15.85 [2]
CoCrFeNiCuAl0.5 FCC 3.82 −1.52 14.70 1684.86 16.29 [2]
CoCrFeNiCuAl0.8 BCC + FCC 4.49 −3.61 14.87 1646.00 6.78 [2]
CoCrFeNiCuAl BCC + FCC 4.82 −4.78 14.90 1622.25 5.06 [2]
CoCrFeNiCuAl1.3 BCC + FCC 5.19 −6.24 14.85 1589.45 3.78 [2]
CoCrFeNiCuAl1.5 BCC + FCC 5.38 −7.04 14.78 1569.27 3.30 [2]
CoCrFeNiCuAl1.8 BCC + FCC 5.54 −8.08 14.65 1541.22 2.79 [2]
CoCrFeNiCuAl2 BCC + FCC 5.71 −8.65 14.53 1523.86 2.56 [2]
CoCrFeNiCuAl2.3 BCC 5.84 −9.38 14.35 1499.60 2.29 [2]
CoCrFeNiCuAl2.5 BCC 5.91 −9.78 14.21 1484.50 2.15 [2]
CoCrFeNiCuAl2.8 BCC 5.99 −10.28 14.01 1463.31 1.99 [2]
CoCrFeNiCuAl3 BCC 6.09 −10.56 13.86 1450.06 1.90 [2]
CoCrFeNiCuAlSi BCC + FCC 4.51 −18.86 16.18 1631.50 1.40 [3]
MnCrFeNiCuAl BCC 4.73 −5.11 14.90 1580.58 4.62 [4]
CoCrFeNiMnGe BCC + FCC 3.25 −15.17 14.90 1695.50 1.67 [5]
CoCrFeNiMn FCC 0.92 −4.16 13.38 1792.40 5.77 [5]
CoCrFeNiMnCu FCC 0.99 1.44 14.90 1720.00 17.80 [5]
CoCrNiCu0.5 Al BCC 5.74 −10.17 13.15 1609.67 2.08 [6]
TiCoCrFeNiCuAlV BCC + FCC 5.87 −13.94 17.29 1735.19 2.15 [6]
CoCrFeNiCu0.5 FCC 1.06 0.49 13.15 1804.67 48.44 [7]
CoCrNiCuAl BCC + FCC 5.19 −6.56 13.38 1584.50 3.23 [3]
CoCuNiAl BCC + FCC 5.77 −8.00 11.52 1447.40 2.08 [3]
CuNiAl BCC + FCC 6.20 −8.44 9.13 1339.80 1.45 [3]
CuNi FCC 1.63 4.00 5.76 1543.00 2.22 [3]
Co0.5 CrFeNiCuAl BCC + FCC 4.91 −4.50 14.70 1608.82 5.26 [9]
CoCr0.5 FeNiCuAl BCC + FCC 5.02 −5.02 14.70 1572.82 4.61 [9]
CoCrFe0.5 NiCuAl BCC + FCC 5.00 −5.55 14.70 1605.09 4.25 [9]
CoCrFeNi0.5 CuAl BCC + FCC 4.91 −3.90 14.70 1612.64 6.08 [9]
CoCrFeNiCu0.5 Al BCC 5.02 −7.93 14.70 1646.27 3.05 [9]
Ti0.5 CoCrFeNiCu FCC 4.46 −3.70 14.70 1776.91 7.05 [10]
Ti0.5 CoCrFeNiAl BCC1 + BCC2 6.11 −17.92 14.70 1699.73 1.39 [1]
TiCoCrFeNiAl BCC1 + BCC2 6.58 −21.56 14.90 1720.25 1.19 [1]
Al11.1 (TiCoCrFeNiCuVMn)88.9 BCC + FCC 5.75 −12.74 18.27 1711.28 2.45 [11]
Al20 (TiCoCrFeNiCuVMn)80 BCC 6.01 −15.44 17.99 1633.50 1.91 [11]
TiCr0.5 FeNiCuAl BCC + FCC 6.45 −15.40 14.70 1640.55 1.56 [8]
TiCrFeNiCuAl BCC + FCC 6.29 −13.67 14.90 1681.58 1.83 [8]
TiCr1.5 FeNiCuAl BCC + FCC 6.14 −12.26 14.78 1716.31 2.08 [8]
TiCr2 FeNiCuAl BCC + FCC 5.99 −11.10 14.53 1746.07 2.29 [8]
TiCr3 FeNiCuAl BCC + FCC 5.72 −9.31 13.86 1794.44 2.67 [8]
TiCoCrFeNiCuAl BCC1 + BCC2 + FCC 6.23 −13.80 16.18 1668.50 1.95 [12]
CoCrFeNiCuAlV BCC + FCC 4.69 −7.76 16.18 1705.07 3.56 [12]
Ti0.5 Co1.5 CrFeNiAl BCC + FCC 6.02 −17.17 14.54 1705.58 1.45 [13]
Ti0.5 Co2 CrFeNiAl BCC + FCC 5.91 −16.43 14.23 1710.54 1.49 [13]
Ti0.5 Co3 CrFeNiAl BCC + FCC 5.69 −14.93 13.49 1718.47 1.55 [13]
Ti0.5 CoCrFeNiCu0.75 Al0.25 FCC 5.03 −7.28 15.55 1757.61 3.76 [14]
Ti0.5 CoCeFeNiCu0.5 Al0.5 BCC + FCC 5.25 −10.84 15.75 1738.32 2.52 [14]
Ti0.5 CoCrFeNiCu0.25 Al0.75 BCC1 + BCC2 5.83 −15.26 15.55 1719.02 1.75 [14]
CoCrFeNiCu0.25 Al BCC 5.13 −9.94 14.34 1660.00 2.39 [15]
CoFeNiCuV FCC 2.63 −1.78 14.90 1833.67 15.35 [15]
CoCrFeNiCu0.75 Al0.25 FCC 3.00 −0.71 14.32 1738.78 35.07 [16]
CoCrFeNiCu0.5 Al0.5 FCC 4.00 −4.60 14.54 1717.55 5.43 [16]
CoCrFeNiCu0.25 Al0.75 BCC + FCC 4.71 −8.47 14.32 1696.33 2.87 [16]
Ti0.5 CoCrFeNiCu0.25 Al BCC1 + BCC2 6.01 −15.50 15.54 1684.87 1.68 [17]
Ti0.5 CoCrFeNiCu0.5 Al BCC1 + BCC2 5.90 −13.42 15.86 1671.25 1.97 [17]
CoCrFeNi FCC 1.06 −3.75 11.53 1860.50 5.71 [7]
CoCrFeNiAl0.25 FCC 3.25 −6.75 12.71 1805.97 3.40 [18]
CoCrFeNiAl0.375 FCC 3.80 −7.99 12.97 1781.04 2.89 [18]
CoCrFeNiAl0.5 BCC + FCC 4.22 −9.09 13.15 1757.50 2.55 [18]
CoCrFeNiAl0.75 BCC + FCC 4.83 −10.90 13.33 1714.13 2.09 [18]
CoCrFeNiAl0.875 BCC + FCC 5.06 −11.66 13.37 1694.12 1.95 [18]
CoCrFeNiAl1.25 BCC 5.55 −13.42 13.34 1639.79 1.62 [18]
CoCrFeNiAl1.5 BCC 5.77 −14.28 13.25 1607.68 1.50 [18]
CoCrFeNiAl2 BCC 6.04 −15.44 12.98 1551.50 1.30 [18]
CoCrFeNiAl2.5 BCC 6.19 −16.09 12.63 1503.96 1.17 [19]
CoCrFeNiAl3 BCC 6.26 −16.41 12.26 1463.21 1.10 [19]
MnCrFe1.5 Ni0.5 Al0.3 BCC 3.32 −5.51 12.31 1747.34 3.90 [20]
MnCrFe1.5 Ni0.5 Al0.5 BCC 4.03 −6.77 12.67 1711.17 3.20 [20]
MoCrFeNiCu FCC 2.92 4.64 13.38 1985.00 5.72 [19]
Ti0.5 Co1.5 CrFeNi1.5 FCC 4.60 −10.74 12.86 1848.00 2.22 [21]
Ti0.5 Co1.5 CrFeNi1.5 Mo0.1 FCC 4.72 −10.64 13.38 1866.70 2.35 [21]
CoCrFeNiCuAl0.5 V0.2 FCC 3.87 −2.50 15.44 1703.01 10.52 [22]
236 X. Yang, Y. Zhang / Materials Chemistry and Physics 132 (2012) 233–238

Table 1 (Continued)

Alloys Structure ı (%) Hmix (kJ mol−1 ) Smix (J K−1 mol−1 ) Tm (K) ˝ Ref.

CoCrFeNiCuAl0.5 V0.4 BCC + FCC 3.80 −3.34 15.76 1719.92 8.12 [22]
CoCrFeNiCuAl0.5 V1.2 BCC + FCC 3.99 −5.73 15.98 1777.49 4.96 [22]
CoCrFeNiCuAl0.5 V1.4 BCC + FCC 4.00 −6.14 15.91 1789.79 4.64 [22]
CoCrFeNiCuAl0.5 V1.6 BCC + FCC 4.00 −6.50 15.82 1801.40 4.38 [22]
CoCrFeNiCuAl0.5 V1.8 BCC + FCC 4.00 −6.81 15.72 1812.38 4.19 [22]
CoCrFeNiCuAl0.5 V2 BCC + FCC 3.99 −7.08 15.60 1822.77 4.01 [22]
MnCrFeNiCu BCC + FCC 0.92 2.72 13.38 1710.00 8.41 [19]
Mn2 CrFeNi2 Cu FCC 0.99 0.44 12.98 1713.00 50.53 [23]
MnCr2 Fe2 NiCu BCC + FCC 0.84 2.61 12.89 1784.86 8.82 [23]
Mn2 Cr2 Fe2 Ni2 Cu FCC 0.91 0.10 13.14 1749.11 229.83 [23]
Mn2 CrFe2 NiCu2 BCC + FCC 0.83 4.69 12.97 1654.88 4.58 [23]
MnCrFe2 Ni2 Cu2 FCC 0.95 3.88 12.97 1680.88 5.61 [23]
Mn2 Cr2 FeNi2 Cu2 BCC + FCC 0.97 2.37 13.14 1697.00 9.40 [23]
MnCr2 Fe2 Ni2 Cu2 BCC + FCC 0.94 3.56 13.14 1729.33 6.38 [23]
W27.3 Nb22.7 Mo25.6 Ta24.4 BCC 2.27 −6.49 11.50 3177.60 5.62 [24]
W21.1 Nb20.6 Mo21.7 Ta15.6 V21 BCC 3.18 −4.54 13.33 2950.49 8.67 [24]
Ti0.3 CoCrFeNi FCC + HCP 4.06 −8.89 12.83 1866.47 2.69 [25]
Ti0.1 CoCrFeNiAl0.3 FCC 4.06 −8.93 13.47 1799.24 2.72 [26]
TiCoNiCuAlZn BCC 6.43 −17.89 14.90 1680.12 1.39 [27]
CoCrFeNiMo0.3 FCC 2.92 −4.15 12.83 1932.67 5.97 [25]
CoCrFeNiAl0.3 Mo0.1 FCC 3.74 −7.26 13.44 1820.81 3.37 [25]
CoCrFeNiCuAlMo0.2 BCC + FCC 4.95 −4.47 15.60 1633.31 5.70 [28]
Ti0.8 CoCrFeNiCu FCC + Laves phase 5.26 −6.75 14.89 1785.66 3.95 [10]
TiCoCrFeNiCu FCC + Laves phase 5.65 −8.44 14.90 1791.00 3.17 [10]
Ti1.5 CoCrFeNiAl BCC1 + BCC2 + Laves 6.93 −23.91 14.78 1737.62 1.08 [1]
phase
CoCrFeNiCuAlMn BCC + FCC + unknown 4.57 −5.63 16.18 1607.64 4.61 [12]
phase
CrFeNiCuZr BCC + compounds 9.91 −14.40 13.38 1831.60 1.70 [19]
Ti0.5 Co1.5 CrFeNi1.5 Mo0.5 FCC + ␴ phase 5.09 −10.25 14.17 1935.25 2.67 [21]
Ti0.5 Co1.5 CrFeNi1.5 Mo0.8 FCC + ␴ phase 5.28 −9.96 14.21 1980.95 2.83 [21]
TiCoCrNiCuAl BCC + Cu + Cr 6.50 −16.67 14.58 1644.75 1.43 [31]
CoCrFeNiCuAl0.5 V0.6 BCC + FCC + ␴ phase 3.94 −4.07 15.92 1735.73 6.79 [22]
CoCrFeNiCuAl0.5 V0.8 BCC + FCC + ␴ phase 3.97 −4.71 16.00 1750.53 5.95 [22]
CoCrFeNiCuAl0.5 V BCC + FCC + ␴ phase 3.98 −5.25 16.01 1764.42 5.38 [22]
CoCrFeNiCuAl0.5 B0.2 FCC + boride 5.77 −4.00 15.44 1708.73 6.60 [32]
CoCrFeNiCuAl0.5 B0.6 FCC + boride 8.07 −8.01 15.92 1751.76 3.48 [32]
CoCrFeNiCuAl0.5 B FCC + ordered 9.52 −11.03 16.01 1789.50 2.60 [32]
FCC + boride
TiCoCrFeNiCuVMn FCC + BCC + ␴ 5.19 −8.13 17.29 1808.50 3.85 [11]
phase + unknown
phase
Al40 (TiCoCrFeNiCuVMn)60 BCC + Al3 Ti + unknown 6.09 −18.29 15.97 1458.50 1.27 [11]
phase
CoCrFeNiCuAlMn BCC + FCC + unknown 4.57 −5.63 16.18 1607.64 4.61 [12]
phase
CoCrFe0.6 NiAlMo0.5 BCC + ␴ phase 5.61 −12.32 14.61 1784.04 2.12 [33]
CoCrFeNiAlMo0.5 BCC + ␴ phase 5.47 −11.44 14.70 1786.00 2.29 [33]
CoCrFe1.5 NiAlMo0.5 BCC + ␴ phase 5.30 −10.50 14.53 1788.08 2.47 [33]
CoCrFe2 NiAlMo0.5 BCC + ␴ phase 5.15 −9.70 14.23 1789.85 2.63 [33]
Co0.5 CrFeNiAlMo0.5 BCC + ␴ phase 5.54 −11.72 14.53 1787.60 2.22 [34]
Co1.5 CrFeNiAlMo0.5 BCC + ␴ phase 5.39 −11.08 14.53 1784.67 2.34 [34]
Co2 CrFeNiAlMo0.5 BCC + FCC + ␴ phase 5.29 −10.70 14.23 1783.54 2.37 [34]
TiCoCrNiCuAl BCC + Cu + Cr 6.50 −16.67 14.90 1946.58 1.73 [31]
CoCrNiCuAlAu FCC + AuCu 6.14 −6.45 14.90 1543.42 3.57 [35]
CoCrFeNiCuAlMo0.4 BCC + ␣ phase 5.05 −4.20 15.91 1701.80 6.45 [28]
CoCrFeNiCuAlMo0.6 BCC + ␣ phase 5.13 −3.95 16.08 1737.95 7.07 [28]
CoCrFeNiCuAlMo0.8 BCC + ␣ phase 5.20 −3.72 16.16 1771.99 7.69 [28]
CoCrFeNiCuAlMo BCC + ␣ phase 5.25 −3.51 16.18 1804.07 8.32 [28]
ZrHfTiCuFe Compounds 9.84 −15.84 13.38 1949.40 1.64 [29]
ZrHfTiCuCo Compounds 10.21 −23.52 13.38 1941.20 1.11 [29]
AlCrMoSiTi Ordered BCC + Mo5 Si3 4.91 −34.08 13.38 1918.90 0.75 [30]
Ti2 CoCrFeNiCu Compounds 6.69 −14.04 14.53 1813.14 1.87 [15]
AlTiVYZr Conpounds 10.35 −14.88 13.38 1802.10 1.62 [15]
ZrTiVCuNiBe Compounds 11.09 −24.89 14.90 1820.67 1.09 [15]
TiCoCrNiCuAlY0.5 Cu2 Y + AlNi2 Ti + Cu + Cr 7.53 −18.32 16.00 1935.38 1.68 [31]
TiCoCrNiCuAlY0.8 Cu2 Y + AlNi2 Ti + Cu + Cr 12.73 −19.00 16.16 1929.45 1.64 [31]
TiCoCrNiCuAlY Cu2 Y + AlNi2 Ti + Cu + Cr + unknown
13.45 −19.37 16.18 1925.79 1.62 [31]
phase

components would significantly affect solid-solution formation in
multi-component alloy. On one hand, the large atomic size dif-
ference could cause serious lattice distortion in alloy and the
corresponding strain energy could increase. Hence, the large atomic
size differences could result in the increase of free energy in alloy,
which could lower the stability of solid-solution. On the other
hand, significant difference in atomic size ratios could lead to the
sluggish diffusion of atoms in the matrix, which lowers the phase
transformation rate and makes the atoms segregate in the alloy,
even causes nanocrystalline and amorphous structures to form.
 X. Yang, Y. Zhang / Materials Chemistry and Physics 132 (2012) 233–238 237

Table 2
The parameters, ı, Hmix , Smix , Tm , ˝, together with the critical cooling rate Rc and the critical section thickness Zc for typical multicomponent bulk metallic glasses (BMGs).

Alloys Zc (mm) Rc (K s−1 ) ı (%) Hmix (kJ mol−1 ) Smix (J K−1 mol−1 ) Tm (K) ˝ Reference

Zr57 Ti5 Al10 Cu20 Ni8 20 10 9.69 −31.50 10.18 1813.45 0.59 [43,44]
Zr38.5 Ti16.5 Cu15.25 Ni9.75 Be20 1.4 13.36 −33.20 12.47 1828.35 0.69 [45]
Zr39.88 Ti15.12 Cu13.77 Ni9.98 Be21.25 1.4 13.59 −34.27 12.34 1834.26 0.66 [45]
Zr42.63 Ti12.37 Cu11.25 Ni10 Be23.75 5 14.05 −36.90 11.97 1844.44 0.60 [45]
Zr41.2 Ti13.8 Cu12.5 Ni10 Be22.5 50 1.4 13.82 −36.72 12.18 1839.28 0.61 [45,46]
Zr44 Ti11 Cu10 Ni10 Be25 12.5 14.27 −37.07 11.73 1849.48 0.59 [45]
Zr45.38 Ti9.62 Cu8.75 Ni10 Be26.25 17.5 14.49 −37.23 11.46 1845.09 0.57 [45]
Zr46.75 Ti8.25 Cu7.5 Ni10 Be27.5 28 14.70 −37.03 11.16 1848.95 0.56 [45,47]
La55 Al25 Ni5 Cu10 Co5 >9 18.8 16.19 −32.31 10.02 1200.78 0.37 [43]
Nd60 Al15 Ni10 Cu10 Fe5 4–6 17.11 −27.37 9.99 1313.18 0.48 [43]
Nd61 Al11 Ni8 Co5 Cu15 6 17.46 −27.43 9.82 1307.13 0.47 [43]
Cu47 Ti33 Zr11 Si1 Ni8 4 8.46 −17.56 10.07 1669.63 0.96 [48]
Cu47 Ti33 Zr11 Si1 Ni6 Sn2 6 8.36 −17.02 10.45 1645.17 1.01 [48]
Fe61 B15 Mo7 Zr8 Co7 Y2 >5 13.20 −30.13 10.30 1992.27 0.68 [49]
Fe61 B15 Mo7 Zr8 Co6 Y2 Al1 >5 13.24 −30.30 10.54 1983.91 0.69 [49]
Fe61 B15 Mo7 Zr8 Co5 Y2 Cr2 >5 37 13.20 −29.97 10.65 1999.53 0.71 [49–51]
Au49 Ag5.5 Pd2.3 Cu26.9 Si16.3 >5 5.30 −29.39 10.35 1377.64 0.49 [50]
Dy46 Al24 Co18 Fe2 Y10 5 40 13.71 −33.26 10.95 1533.60 0.50 [52]
Ti40 Zr25 Ni3 Cu12 Be20 3.2 12.03 −25.88 11.60 2010.40 0.90 [53]
Ti40 Zr25 Cu9 Ni8 Be18 8 12.31 −28.26 11.98 1852.02 0.79 [54]
Ti45 Cu25 Ni15 Sn3 Be7 Zr5 5 9.08 −21.22 11.90 1705.29 0.96 [54]
Ti50 Ni24 Cu20 B1 Si2 Sn3 1 7.89 −27.87 10.31 1731.86 0.64 [55]
Ti50 Zr15 Cu9 Ni8 Be18 6 11.64 −26.37 11.30 1833.82 0.79 [56]
Ti55 Zr10 Cu9 Ni8 Be18 6 11.18 −25.43 10.70 1824.72 0.77 [56]
Ti53 Cu15 Ni18.5 Al7 Hf3 Si3 B0.5 2 7.28 −32.23 11.28 1757.66 0.62 [57]
Ti53 Cu15 Ni18.5 Al7 Sc3 Si3 B0.5 2 7.54 −31.75 11.28 1697.36 0.60 [57]
Ti53 Cu15 Ni18.5 Al7 Ta3 Si3 B0.5 <1.5 6.96 −31.28 11.28 1781.33 0.64 [57]
Ti53 Cu15 Ni18.5 Al7 Nb3 Si3 B0.5 <1.5 6.96 −31.22 11.28 1765.04 0.64 [57]
ZrHfTiCuNi 1.5 10.21 −27.36 13.38 1932.80 0.95 [29]
Mg65 Cu20 Zn5 Y10 6 12.70 −5.98 8.16 1085.64 1.48 [58]
Mg65 Cu15 Ag5 Pd5 Y10 7 9.27 −13.24 9.10 1074.86 0.74 [59]
Mg65 Cu15 Ag5 Pd5 Gd10 10 0.7 9.27 −13.24 9.10 1053.49 0.72 [60]
Mg65 Cu7.5 Ni7.5 Zn5 Ag5 Y10 >4 9.53 −7.35 9.96 1107.24 1.50 [61]

Here, in order to describe the comprehensive effect of the atomic and amorphous phases form at a larger value of ı and a smaller
size difference in n-element alloy, the parameter ı is expressed as value of ˝. These results coincide with previous theory analysis.
follows: Fig. 1 presents the relationship between ı and ˝ for all multi-
 component alloys listed in Tables 1 and 2. Clearly, the alloys which
 n 
 r 2
only form simple solid-solution phases are distributed in the trian-
ı= ci 1 − i (6) gular zone marked by S. In this zone, the multi-component alloys
r̄
i=1 possess the relative small atomic size difference and large value
of ˝, which indicates that the strain energy caused by lattice dis-
where ci is the atomic percentage of the ith component, r̄ = tortion is lower in alloy and the effect of Smix is large enough
 n
c r is the average atomic radius and ri is the atomic radius
i=1 i i
which could be obtained in Ref. [41].
Both the parameter ˝ and ı are important for predicting the
solid-solution formation rule, the more ˝ and less ı would facilitate
solid-solution formation. In the following section, we shall propose
a criterion for forming HE stabilized solid-solution by analyzing the
readily available experimental data.

3. Results

Table 1 presents the values of ı, Hmix , Smix , Tm and ˝,

which are calculated based on Eqs. (2)–(6), for the reported typi-
cal multi-component HEAs. It is necessary to point out that only the
multi-component HEAs which are synthesized by normal casting or
casting into copper mould are shown in the table in order to lower
the influence of dynamic factors. The number of the phases and
their structures also depend on processing conditions besides ı and
˝, such as the splat quenching with rapid cooling rate could facili-
tate the formation of simple structures [42]. For comparison, Table 2
lists the values of ı, Hmix , Smix , Tm , ˝, the critical cooling rate Fig. 1. The relationship between parameters ı an ˝ for multi-component alloys
Rc and the critical section thickness Zc for typical multi-component (“Solid Solutions” indicates the alloy contains only solid solution; “Intermetallics”
indicates the alloy mainly contains intermetallic compound and other ordered
glass-forming alloys. For forming solid-solutions, the newly defined
phases; “S + I” indicates that not only the solid solution could form, but also the
˝ value is in the range from 1.1 to 229.8 and ı is in the range of 0.8% ordered compounds could precipitate in multi-component alloys; and “BMGs” indi-
to 6.6%. Comparing with solid-solutions, the intermetallic phases cates the alloy can form amorphous phase).
238 X. Yang, Y. Zhang / Materials Chemistry and Physics 132 (2012) 233–238
to exceed that of Hmix for the solid-solution formation. Thus the
component atoms can randomly distribute in the alloy and simple
solid solution is stable and easily forms during solidification.
In the zone marked by S + I, not only the solid solution could
form, but also the ordered compounds could precipitate in multi-
component alloys. Compared with the zone S, the value of ˝
decreases and the value of ı is relative large. As the formation of
ordered phases, the extent of ordering for multi-component alloys
increases until the ordering is complete. The zone S + I has par-
tial superposition with the zone S and the zone I, in which the
atomic size difference and the effect of Hmix are larger enough
for multi-component alloys to form intermetallic compounds and
other ordered phases, it implies that the zone S + I is a transition
zone between the solid solutions and ordered phases.
The multi-component bulk-metallic glasses (BMGs) are located
in the zone marked as B. We can see that multi-component
BMGs have larger values of ı and smaller ˝ than those of multi-
component HEAs.
It is apparent that ı and ˝, which can be calculated before
preparing the alloy, are two key factors for predicting the solid-
solution formation in multi-component alloys. According to Fig. 1,
˝ ≥ 1.1 and ı ≤ 6.6% should be proposed as a criterion for forming
solid-solution phase.
4. Conclusions
A parameter ˝, defined as Tm Smix /|Hmix |, has been proposed
to estimated solid-solution formation ability in multi-component
alloy systems. By calculating parameters of ı and ˝ for typical
multi-component HEAs reported, a solid-solution formation rule
for multi-component HEAs has been proposed, and ˝ ≥ 1.1, ı ≤ 6.6%
should be expected as the criteria for forming HE stabilized solid-
solution phase.
Acknowledgments
The authors would like to acknowledge financial support by
the National Natural Science Foundation of China (NNSFC, no.
50971019).
References
[1] Y.J. Zhou, Y. Zhang, Y.L. Wang, G.L. Chen, Appl. Phys. Lett. 90 (2007)
181904.
[2] J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau, S.Y. Chang,
Adv. Eng. Mater. 6 (2004) 299–303.
[3] J.W. Yeh, S.Y. Chang, Y.D. Hong, S.K. Chen, S.J. Lin, Mater. Chem. Phys. 103 (2007)
41–46.
[4] H.Y. Chen, C.W. Tsai, C.C. Tung, J.W. Yeh, T.T. Shun, C.C. Yang, S.K. Chen, Ann.
Chim. Sci. Mater. 31 (2006) 685–698.
[5] B. Cantor, I.T.H. Chang, P. Knight, A.J.B. Vincent, Mater. Sci. Eng., A 375–377
(2004) 213–218.
[6] J.W. Yeh, S.J. Lin, T.S. Chin, J.Y. Gan, S.K. Chen, T.T. Shun, C.H. Tsau, S.Y. Chou,
Metall. Mater. Trans. A 35 (2004) 2533–2536.
[7] Y.J. Hsu, W.C. Chiang, J.K. Wu, Mater. Chem. Phys. 92 (2005) 112–117.
[8] M. Chen, Y. Liu, Y.X. Li, X. Chen, Acta Metall. Sin. 43 (2007) 1020–1024.
[9] C.C. Tung, J.W. Yeh, T.T. Shun, S.K. Chen, Y.S. Huang, H.C. Chen, Mater. Lett. 61
(2007) 1–5.
[10] X.F. Wang, Y. Zhang, Y. Qiao, G.L. Chen, Intermetallics 15 (2007) 357–362.
[11] Y.J. Zhou, Y. Zhang, Y.L. Wang, G.L. Chen, Mater. Sci. Eng. A 454–455 (2007)
260–265.
[12] B.S. Li, Y.R. Wang, M.X. Ren, C. Yang, H.Z. Fu, Mater. Sci. Eng. A 498 (2008)
482–486.
[13] F.J. Wang, Y. Zhang, Mater. Sci. Eng. A 496 (2008) 214–216.
[14] F.J. Wang, Y. Zhang, G.L. Chen, J. Alloys Compd. 478 (2009) 321–324.
[15] Y. Zhang, Y.J. Zhou, J.P. Lin, G.L. Chen, P.K. Liaw, Adv. Eng. Mater. 10 (2008)
534–538.
[16] Y.J. Zhou, Y. Zhang, F.J. Wang, G.L. Chen, Appl. Phys. Lett. 92 (2008) 241917.
[17] Y.J. Zhou, Y. Zhang, F.J. Wang, Y.L. Wang, G.L. Chen, J. Alloys Compd. 466 (2008)
201–204.
[18] H.P. Chou, Y.S. Chang, S.K. Chen, J.W. Yeh, Mater. Sci. Eng., B 163 (2009) 184–189.
[19] C. Li, J.C. Li, M. Zhao, Q. Jiang, J. Alloys Compd. 475 (2009) 752–757.
[20] K.C. Hsieh, C.F. Yu, W.T. Hsieh, W.R. Chiang, J.S. Ku, J.H. Lai, C.P. Tu, C.C. Yang, J.
Alloys Compd. 483 (2009) 209–212.
[21] Y.L. Chou, J.W. Yeh, H.C. Shih, Corros. Sci. 52 (2010) 2571–2581.
[22] M.R. Chen, S.J. Lin, J.W. Yeh, M.H. Chuang, S.K. Chen, Y.S. Huang, Metall. Mater.
Trans. A 37 (2006) 1363–1369.
[23] B. Ren, Z.X. Liu, D.M. Li, L. Shi, B. Cai, M.X. Wang, J. Alloys Compd. 493 (2010)
148–153.
[24] O.N. Senkov, G.B. Wilks, D.B. Miracle, C.P. Chuang, P.K. Liaw, Intermetallics 18
(2010) 1758–1765.
[25] T.T. Shun, C.H. Hung, C.F. Lee, J. Alloys Compd. 493 (2010) 105–109.
[26] T.T. Shun, C.H. Hung, C.F. Lee, J. Alloys Compd. 495 (2010) 55–58.
[27] S. Varalakshmi, M. Kamaraj, B.S. Murty, Mater. Sci. Eng. A 527 (2010)
1027–1030.
[28] J.M. Zhu, H.F. Zhang, H.M. Fu, A.M. Wang, H. Li, Z.Q. Hu, J. Alloys Compd. 497
(2010) 52–56.
[29] L.Q. Ma, L.M. Wang, T. Zhang, I. Akihisa, Mater. Trans. JIM 43 (2002) 277–280.
[30] H.W. Chang, P.K. Huang, A. Davison, J.W. Yeh, C.H. Tsau, C.C. Yang, Thin Solid
Films 516 (2008) 6402–6408.
[31] Z.H. Hu, Y.Z. Zhan, G.H. Zhang, J. She, C.H. Li, Mater. Des. 31 (2010) 1599–1602.
[32] C.Y. Hsu, J.W. Yeh, S.K. Chen, T.T. Shun, Metall. Mater. Trans. A 35 (2004)
1465–1469.
[33] C.Y. Hsu, T.S. Sheu, J.W. Yeh, S.K. Chen, Wear 268 (2010) 653–659.
[34] C.Y. Hsu, W.R. Wang, W.Y. Tang, S.K. Chen, J.W. Yeh, Adv. Eng. Mater. 12 (2010)
44–49.
[35] U.S. Hsu, U.D. Hung, J.W. Yeh, S.K. Chen, Y.S. Huang, C.C. Yang, Mater. Sci. Eng.
A 460–461 (2007) 403–408.
[36] K.B. Zhang, Z.Y. Fu, J.Y. Zhang, W.M. Wang, H. Wang, Y.C. Wang, Q.J. Zhang,
Mater. Sci. Forum 620–622 (2009) 383–386.
[37] Y.J. Zhou, Y. Zhang, T.N. Kim, G.L. Chen, Mater. Lett. 62 (2008) 2673–2676.
[38] A. Takeuchi, A. Inoue, Mater. Sci. Eng. A 304–306 (2001) 446–451.
[39] A. Takeuchi, A. Inoue, Mater. Trans. JIM 46 (2005) 2817–2829.
[40] A.R. Miedema, P.F. de Châtel, F.R. de Boer, Physica B+C 100 (1980) 1–28.
[41] C. Kittel, Introduction to Solid State Physics, seventh ed., Wiley, New York, 1996.
[42] S. Singh, N. Wanderka, B.S. Murty, U. Glatzel, J. Banhart, Acta Mater. 59 (2011)
182–190.
[43] Z.P. Lu, H. Tan, S.C. Ng, Y. Li, Scripta Mater. 42 (2000) 667–673.
[44] L.Q. Xing, P. Ochin, M. Harmelin, F. Faudot, J. Bigot, J.P. Chevalier, Mater. Sci.
Eng. A 220 (1996) 155–161.
[45] T.A. Waniuk, J. Schroers, W.L. Johnson, Appl. Phys. Lett. 78 (2001) 1213-1–1213-
3.
[46] W.L. Johnson, Mater. Sci. Forum 225–227 (1996) 35–50.
[47] J.F. Löffler, P. Thiyagarajan, W.L. Johnson, J. Appl. Crystallogr. 33 (2000)
500–503.
[48] E.S. Park, H.K. Lim, W.T. Kim, D.H. Kim, J. Non-Cryst. Solids 298 (2002) 15–22.
[49] Z.P. Lu, C.T. Liu, W.D. Porter, Appl. Phys. Lett. 83 (2003) 2581.
[50] J. Schroers, B. Lohwongwatana, W.L. Johnson, A. Peker, Appl. Phys. Lett. 87
(2005) 061912.
[51] S. Guo, Z.P. Lu, C.T. Liu, Intermetallics 18 (2010) 883–888.
[52] W.H. Wang, J. Appl. Phys. 99 (2006) 093506.
[53] Y.J. Huang, J. Shen, J.J.J. Chen, J.F. Sun, J. Alloys Compd. 477 (2009) 920–924.
[54] Y.C. Kim, W.T. Kim, D.H. Kim, Mater. Sci. Eng. A 375–377 (2004) 127–135.
[55] T. Zhang, A. Inoue, Mater. Sci. Eng. A 304 (2001) 771–774.
[56] J.M. Park, Y.C. Kim, W.T. Kim, D.H. Kim, Mater. Trans. JIM 45 (2004) 595–598.
[57] M.X. Xia, H.X. Zheng, J. Liu, C.L. Ma, J.G. Li, J. Non-Cryst. Solids 351 (2005)
3747–3751.
[58] H. Men, Z.Q. Hu, J. Xu, Scripta Mater. 46 (2002) 699–703.
[59] K. Amiya, A. Inoue, Mater. Trans. JIM 41 (2000) 1460–1462.
[60] H. Men, W.T. Kim, D.H. Kim, Mater. Trans. JIM 44 (2003) 2141–2144.
[61] H. Ma, J. Xu, E. Ma, Appl. Phys. Lett. 83 (2003) 2793.