第 35 卷第 2 期 ■特约专稿

doi:10.3969/j.issn.0253-9608.2013.02.002

Phase selection rules for complex multi-component alloys

with equiatomic or close-to-equiatomic compositions
① ②
GUO Sheng , LIU Chain T.
① Research Fellow; ②Fellow of National Academy of Engineering, Center of Advanced Structural Materials,
Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of
Hong Kong, Kowloon, Hong Kong, China

Key words phase selection, multi-component alloys, amorphous phase, solid solution, intermetallic
compounds

Abstract Alloying greatly expands the amount of available materials beyond the naturally existing
ones, and more importantly offers the material scientists opportunities to initiatively control the
composition-structure-property relationship in materials. Since commonly used metallic materials are
mostly multi-component alloys, the know-how of alloying through compositional control, certainly plays
a critical role in designing materials with desired structure and properties. However, alloying in
multi-component alloys is an extremely complicated issue, as the alloyed products could be the
amorphous phase, various solid solutions and intermetallic compounds containing two or more alloy
components. By narrowing down the scope of the multi-component alloys to those with equiatomic or
close-to-equiatomic compositions only, and also aiming at framing out the rules that govern the phase
selection upon alloying in multi-component alloys in a broad sense, we have identified here a simple and
easily executable two-parameter scheme that can effectively predict the formation of the amorphous
phase, solid solutions and intermetallic compounds, in multi-component alloys, simply from the given
alloy compositions. We believe this scheme reveals a clear physical scenario governing the phase
selection in multi-component alloys, helps to simplify the alloy design, and benefits the future
development of advanced metallic alloys like bulk metallic glasses and high entropy alloys.

discovery in the ancient time, as copper ores mixed

1 Introduction
The English word, alloy, originates from the
Latin word, alligare (bind), and later the Old
French, aloier (combine). Intuitively, alloying
means combining two or more elements. For
example, bronze is an alloy coming from the
combining of copper and tin, or we can say the
alloying of copper and tin can make bronze.
Alloying of copper and tin was an accidental
with ores of arsenic, zinc and tin in the primitive
fires in the caves[1]. Today, we know that this
accidental discovery brought the Bronze Age, as
people started to use bronze widely after they found
that bronze was superior to other materials (stones
and pure copper) in terms of the mechanical and
physical properties. The discovery of steel, an alloy
of iron and carbon, is another milestone in the
human history and steel is still the most widely

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Chinese Journal of Nature Vol. 35 No. 2
used material nowadays. The purpose of alloying is
always to achieve better properties, as pure metals
have few uses but their mechanical, physical or
chemical properties can be improved by alloying.
Alloys can exist in different forms: solid
solution, the amorphous phase, intermetallic
compound, or a mixture of them. Solid solution is
the most commonly seen form of alloys. A solid
solution is a solid-state solution of one or more
solutes in a solvent. Such a mixture is regarded as a
solution rather than a compound, when the crystal
structure of the solvent remains unchanged by
adding (alloying) the solutes, and when the mixture
remains in a single homogeneous phase. Certainly,
depending on the solvent or the principle element,
the solid solution can have various crystal
structures, like face-centered cubic (fcc), body-
centered cubic (bcc) or hexagonal close packed
(hcp) structure. The solute atoms may incorporate
into the solvent crystal lattice substitutionally, by
replacing the solvent atoms in the lattice, or
interstitially, by fitting into the space between
solvent atoms. Intermetallic compound essentially
is also a solid-state solution of one or more solutes
in a solvent, but it differs with the solid solution in
which its crystal structure is neither the same as that
of the solvent nor that of the solutes. In
intermetallic compounds, different elements are
ordered into different sites in the structure, with
distinct local environments and often a well-defined
and fixed stoichiometry. Complex structures with
very large unit cells can be formed in intermetallic
compounds[2]. Intermetallic compounds are
generally hard and brittle, and they have high
melting points. They also present desirable
magnetic, superconducting and chemical properties,
due to their strong internal order and mixed
(metallic and covalent/ionic) atomic bonding.
Intermetallic compounds have found applications in
various novel materials. For example, Ni3Al is the
hardening phase in the nickel-base superalloys, and
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TiAl has been used in recent turbine blade
applications; SmCo5 is an outstanding permanent
magnetic material and LaNi5 has good hydrogen
storage properties[3]. Both the solid solution and
intermetallic compound are crystalline alloys, in
which the atoms are arranged in the so-called lattice
exhibiting long range order and symmetry. On the
contrast, an amorphous alloy has a disordered and
non-crystalline atomic-scale structure; as a result, it
is also known as the metallic glass. Actually, the
English word amorphous comes from the Greek
amorphos (shapeless), from a- (without) + morphē
(form). The amorphous alloys without a crystalline
form have many unique properties that are superior
to their crystalline counterparts, including high
strength, high elastic strain and good corrosion
resistance. More detailed introduction to the
amorphous alloys is to be covered in Section 2.
Commonly used metallic alloys are mostly
multi-component alloys, i.e., having more than
three constituent elements. Alloying in the multi-
component alloys can be an extremely complicated
issue, as there exist so many possibilities of the
alloyed products depending on the alloy
compositions, and this is certainly beyond the
capability of phase diagrams, which vividly tell the
formed phases at particular compositions but are
only valid for limited binary and ternary alloy
systems[4]. The phase diagrams are still of help if
there are less than three major elements in the
alloys, as other minor alloying elements are less
likely to alter the phase constitution significantly.
Indeed, most conventional alloys are based on one
element, like Fe, Al, Mg, Cu, Ti, Ni, or two
elements, like FeAl or TiAl. As a result, the Fe-C
binary phase diagram can still be used as a
guidance to study steels although there exist many
more alloying elements in steels apart from Fe and
C. The situation changes dramatically in high
entropy alloys (HEAs), a recently emerged multi-
component alloys where the alloying elements are

mixed in equiatomic ratio or close-to-equiatomic
ratio[1,5-6]. In HEAs, there is no well-defined
principle element and there is no clue to what the
alloyed products can be. In addition, phase
diagrams give the phase information in the
equilibrium conditions, and although non-
equilibrium conditions can now be taken into
account, they cannot be used directly to guide the
design of amorphous alloys. Admittedly, the
eutectic compositions[5] or sometimes intermetallic
compound compositions[6] have been suggested to
be indicators of good glass formers, and phase
diagrams can help in these conditions.
Framing out workable rules to predict the
phase selection in multi-component alloys upon
alloying is a daunting task, considering the
complexity of the possible alloyed products as
briefly mentioned above. However, the vision of
possessing the capability to predict the phase
selection in complex multi-component alloys
through simple compositional control, is
tremendously attractive as it will greatly simplify
the alloy design. This work aims at sheding some
light on this important issue, by narrowing down
the scope of studied alloy systems and defining the
phase selection in a broader sense. Specifically,
inspired by HEAs, only multi-component alloys
with equiatomic or close-to-equiatomic
compositions are considered. In equiatomic alloys
the relative composition of each element is not a
concern as in conventional multi-component alloys,
which on one hand makes the target alloy systems
(at least apparently) simple, but on the other hand
means none of the alloying elements is playing a
negligible role. Since equiatomic multi-component
alloys are still a novel metallurgy concept and
discussions on the phase selection issue in this new
alloy system are few[7-10], it justifies an informative
discussion here. By saying to define the phase
selection in a broader sense, we mean to
differentiate here only the amorphous phase, solid
第 35 卷第 2 期 ■特约专稿
solution and intermetallic compound, and do not
further differentiate different types of solid
solutions or different intermetallic compounds. To
make a fair comparison, all the alloying covered
here follows the liquid-solid route, using the copper
mould casting or melt spinning methods. The
statistical analysis of the phase selection in multi-
component alloys with equiatomic or close-to-
equiatomic compositions comes after a brief
introduction to two intensively studied and both
scientifically and technically important multi-
component alloys: bulk metallic glasses (BMGs)
and high entropy alloys (HEAs). Understanding the
phase selection is of great importance to the future
development of the BMGs and HEAs.
2 Bulk metallic glasses (BMGs)
In the 1960s, amorphous alloys, or more
commonly referred to as metallic glasses, were
discovered by Duwez et al. unintentionally[11] as
they initially aimed at testing the solid solubility of
two components that normally cannot form a solid
solution under the rapid cooling condition. In the
early time of the development of metallic glasses,
the amorphous phase could only be achieved with
high cooling rates of 103～106 K·s-1. Although bulk
metallic glasses (BMGs), with the smallest
dimension over 1 mm were reported at some
noble-metal based alloys like Pd-Cu-Si and Pd-Ni-P
with low cooling rates of ~10 K·s-1, the high cost of
these alloys did not generate a general interest
toward them in the materials community[12]. The
discovery of multi-component BMGs with low
critical cooling rates (the lowest cooling rates to
achieve the fully amorphous condition) by Inoue
and his colleagues in the late 1980s marked the
second milestone in the history of the metallic
glasses[13-14]. Noble metals were not a must in these
multi-component BMGs. Since then, a large
amount of BMGs have been developed in various
alloy systems[15] and as seen in Fig. 1, the largest
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BMGs up to today have a diameter of 80 mm and a
length of 85 mm in the Pd-Cu-Ni-P system, made
by a water quenching method[16].
Fig. 1 (a) and (b) side and top views of the world’s largest
glassy Pd42.5Cu30Ni7.5P20 alloy, with a cylindrical form
of 80 mm in diameter and 85 mm in length[16]
BMGs have been intensively studied over the
past two decades, as they present many unique
mechanical and functional properties that are absent
in crystalline alloys[15,17-21]. BMGs have a high
hardness and high fracture strength, and noticeably
the Co-based BMGs can have a hardness of 17.1
GPa[22] and compressive fracture strength of 6 GPa;
they have a large elastic strain of ~2%, compared
with ~0.2% for conventional crystalline alloys[21];
their fracture toughness can reach 200 MPa·m1/2[23];
they have good soft magnetic properties[24],
corrosion resistance[25-26] and wear resistance[17];
they have excellent flowability and accurate mould
formability in the supercooled liquid region (i.e.,
between the glass transition temperature and the
crystallization temperature[27]). Although the ductility,
especially the tension ductility is still restricting their
structural applications, BMGs have found many
unique applications such as in kinetic energy
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penetrators (KEP)[28], biodegradable implants[29],
micro fuel cell[30], solar wind collector[18,31], surgical
instruments[32] and micro- gear[33-34].
3 High entropy alloys (HEAs)
HEAs emerge as a new type of advanced
metallic materials and have received increasing
attentions from the materials community. The
concept of HEAs was initiated by Yeh and his
colleagues in the mid 1990s[1,35], and basically HEAs
are defined as multi-component alloys having at least
5 principle elements and all the principle elements
are mixed in equiatomic or close-to-equiatomic
ratios[36]. HEAs micro-alloyed with some minor
elements can still be termed as HEAs[36-37] and this
makes no conflict with the atomic percentage
requirements for the principle elements.
As mentioned in the Introduction, HEAs differ
with conventional multi-component alloys in which
there is no dominant principle element in HEAs.
This metallurgy concept is a brand new one, as in
the past people thought such a high percentage of
alloying elements would lead to the formation of
many unwanted phases, particularly the hard
intermetallic compounds, and hence embrittle the
material. Surprisingly, in many HEAs only simple
solid solutions with fcc and/or bcc structures
(schematically shown in Fig. 2) are obtained and no
intermetallic compounds form at all[7,36,38].
The preferred formation of solid solutions over
intermetallic compounds is believed to come from
the high configuration entropy of HEAs, as
thermodynamically a high entropy helps to decrease
the Gibbs energy at elevated temperatures and
hence to win the phase selection between solid
solution phases and intermetallic compounds . The
configuration entropy of multi-component alloy
systems assuming at a fully random state, can be
n
defined as ΔS = − R ∑ c ln c
i i
[39]
, where R is the
i =1
gas constant, n is the number of the alloying elements,
 第 35 卷第 2 期 ■特约专稿

ci is the atomic percentage for the ith element. It is

pointed out here that throughout the paper, the
configuration entropy refers to the configuration
entropy of the alloys at the fully random state. This
enables and also justifies the direct comparison of
configuration entropies among different alloys, as if
without this premise, the unknown atomic
configurations in the real phases (solid solution, the
amorphous phase, or intermetallic compound) make
the comparison meaningless. The configuration
entropy reaches the maximum of ΔS = R ln n at
the equiatomic condition. HEAs have much higher
configuration entropies compared with
conventional multi- component alloys (see Table 1
for a quick comparison) and here comes their
name[36].
HEAs present some excellent mechanical and
physical properties[36]. Their hardness can range
from 100 to 1 100 HV; their microstructures can
Fig. 2 Schematic illustrations of crystalline structures of (a)
have good thermal stability; they have excellent
bcc and (b) fcc solid solutions composed of five
resistance to temper softening; they can present
multi-principal elements[60]

Table 1 Comparison of the configuration entropy, ΔS, between HEAs and some conventional multi- component alloys
System Alloy ΔS at the fully random state Classification of ΔS
Low-alloy steel 4340 0.22R Low
304 0.96R Low
Stainless steel
316 1.15R Medium
High-speed steel M2 0.73R Low
Mg alloy AZ91D 0.35R Low
2024 0.29R Low
Al alloy
7075 0.43R Low
Cu alloy 7-3 Brass 0.61R Low
Inconel 718 1.31R Medium
Ni-base superalloy
Hastelloy X 1.37R Medium
Co-base superalloy Stellite 6 1.13R Medium
Cu47Zr11Ti34Ni8 1.17R Medium
BMGs
Zr53Ti5Cu16Ni10Al16 1.30R Medium
CoCrCuFeNi 1.61R High
Al0.3CoCrCuFeNi 1.74R High
HEAs
6FeNiCoSiCrAlTi 1.59R High
AlCo0.5CrCuFe1.5Ni1.2B0.1C0.15 1.87R High

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high-temperature precipitation hardening; they can
have excellent corrosion, wear and oxidation
resistance; they can have high electrical resistivity
with a low or even negative temperature coefficient.
To give two specified examples here, a bcc typed
AlCoCrFeNiTi0.5 (for the expression of the
compositions of HEAs, the subscripts indicate its
atomic portion and is 1 if not particularly indicated.
In this case, Al, Co, Cr, Fe and Ni each accounts for
1/5.5 and Ti accounts for 0.5/5.5 of the constituent
elements) alloy has the yield stress, fracture
strength, and compressive plastic strain of 2.26 GPa,
3.14 GPa, and 23.3%, respectively[40], which are
superior to most of the high-strength alloys such as
bulk metallic glasses; two refractory high entropy
alloys NbMoTaW and VNbMoTaW have a single-
phase bcc structure that remains not only stable
after exposure to 1 400℃, but also disordered[41],
and more interestingly, they still keep a yield
strength of 407 MPa and 477 MPa, respectively at
1 600℃, much higher than those of the Ni-base
superalloys at the same temperature[41]. HEAs have
great potentials to be used as high temperature
materials, coating materials requiring high hardness
and high wear resistance, and corrosion resistant
materials with high strength. Some unique
applications include the diffusion barrier material
between copper interconnects and the Si substrate[42].
4 Phase selection in multi-
component alloys with equiatomic or
close-to-equiatomic compositions
4.1 High entropy effect
The formation of simple solid solution phases
and absence of intermetallic compounds in the
seemly complex multi-component alloys with
equiatomic or close-to-equiatomic compositions, is
somewhat unexpected. The phase selection is
essentially determined by the Gibbs energies of the
competing phases and intuitively the preferred
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INVITED SPECIAL PAPER
formation of the solid solution phases can be related
to the high configuration entropy of HEAs, as at
high temperatures the contribution from the entropy
to the Gibbs energy becomes significant. However,
such a qualitative understanding does not help to
predict the phase selection. In terms of the role of
the entropy on the formed phases upon alloying,
there is a well-known confusion principle[10] which
articulates that the more alloying elements are
involved, the lower the chance that the alloy can
form well defined crystal structures. The confusion
principle works well to explain why BMGs are
mostly discovered in multi-component alloys with
more than three alloying elements, and it can also
be used to explain the formation of disordered solid
solution in HEAs. From the perspective of the
disorder, disordered solid solutions are chemically
disordered and topologically ordered, while the
amorphous phases are at least topologically
disordered (in the long range). Naturally, the
confusion principle raises a question: when the
entropy is high, is the formation of the random solid
solution or amorphous phase preferred? As a matter
of fact, in many HEAs solid solutions tend to form,
but in some other HEAs the amorphous phase does
form, and even BMGs can form[43-47]. For example,
a PdPtCuNiP BMG with a maximum diameter of
10 mm was fabricated by the fluxed water
quenching technique[47], as shown in Fig. 3. These
BMGs with high entropy are termed as HE-BMGs.
In addition, the high entropy does not necessarily
lead to the formation of the amorphous phase or
disordered solid solutions, as intermetallic
compounds or ordered solid solutions have been
widely observed in multi-component alloys with
equiatomic or close-to-equiatomic compositions[7-9].
The available experimental evidences clearly
suggest that apart from the entropy effect, there are
other factors controlling the phase selection. It is
thus the target of this paper to identify those factors
playing the decisive roles.

Fig. 3 Pd20Pt20Cu20Ni20P20 alloy cylinders with diameters of
(a) 12 mm and (b) 10 mm prepared by water
quenching and a B2O3 flux treatment; (c) X-ray
diffraction patterns for the two alloys, showing a fully
amorphous state for the 10 mm sized one[47]
4.2 A parametric approach
Considering the complexity of the phase
selection issue in multi-component alloys, physical
metallurgy (semi-empirical) rules rather than
strictly robust scientific principles are more likely
to act as an effective guidance. Historically, it is
also these physical metallurgy rules that lead to the
development of many new alloy systems. They are
not always right, but they work. In the context of
this paper, two well known physical metallurgy
rules give some clues to the decisive factors
controlling the phase selection in multi-component
alloys.
First, the Hume-Rothery rules[48-49] on the
formation of binary solid solutions. Hume-Rothery
himself listed five factors affecting the stability of
alloy phases: electronegativity, atomic size factor,
第 35 卷第 2 期 ■特约专稿
electron concentration, position of the elements in
the periodical table, and the orbital type[49-50], and
among them the first three factors are more widely
recognized. The electron concentration effect is
evident when the electronegativity and the size
factor are of minor importance[50]. Also, the famous
Darken-Garry plot[48] also utilizes only the
electronegativity and the size factor to consider the
solid solubility issue. Basically, both the
Hume-Rothery rules and the Darken-Garry plot
claim that, in order to have a large solubility of
element A in element B, these two elements shall
have a small difference in the electronegativity and
atomic size.
Second, Inoue’s three empirical rules to form
the bulk metallic glasses[13]. As mentioned in
Section 2, it is the feasibility of fabricating BMGs
using cost effective elements that actually ignited
the frenzy of massive research activities towards
BMGs. According to Inoue, to form BMGs the
alloy compositions shall have more than three
elements, the atomic size difference among the
three main elements (A, B, C) needs to be large
enough (>12%), and the mixing enthalpies between
the main elements (A-B, A-C, B-C) have to be very
negative. A similar principle has also been proposed
by Johnson[51].
Hume-Rothery rules and Inoue’s rules seem to
suggest that three factors are controlling the phase
selection: (1) topology, mainly the atomic size; (2)
chemistry, the electronegativity, electron
concentration or the mixing enthalpy; and (3)
complexity, simply put the genre and amount of the
constitution elements. We then attempt to use three
parameters characteristic of these three controlling
factors to search for the phase selection rules, based
on a statistical analysis of the available experimental
evidences in multi-component alloys with
equiatomic or close-to-equiatomic compositions.
The atomic size difference is a simple and
effective parameter to reflect the topological factor,
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Chinese Journal of Nature
and it appears in both the Hume-Rothery rules and
Inoue’s rules. For the multi-component alloys, the
atomic size polydispersity, δ, can be a good
parameter to represent the atomic size difference
among the constituent elements[7-8,52]. It is defined
as
n
δ= ∑ c (1 − r / r )
i =1
i i
n
where r = ∑c r , c
i =1
i i i and ri are the atomic percent-
age and atomic radius of the ith element, and n is
the number of alloying elements. We choose the
mixing enthalpy to reflect the chemical factor, since
on one hand this parameter appears in Inoue’s rules,
and it actually includes the contribution from the
electronegativity that is in the Hume-Rothery
rules[53], and on the other hand it has been shown
that compared to the electronegativity and electron
concentration, the mixing enthalpy shows a better
performance to separate the formation of solid
solutions, the amorphous phase and intermetallic
compounds[7]. For simplicity, we use the weight
averaged mixing enthalpies of different pairs of
alloying elements to represent the mixing enthalpy,
ΔH mix , of the alloy. ΔH mix is defined as
n Figure 4 shows the result from the statistical
ΔH mix = ∑
i =1,i ≠ j
Ωij ci c j ,
where Ωij = 4Δ ABmix , Δ mix is the mixing enthalpy
AB
of binary liquid AB alloys[54]. The entropy concept
is naturally appropriate to describe the complexity,
and we use the mixing entropy for this purpose. It is
approximated as the configuration entropy as we
defined in Section 3:
n
ΔSmix = − R ∑ ci ln ci .
i =1
It is emphasized here again that the configuration
entropy defined here assumes the alloys being at the
fully random state and ignores the actual atomic site
occupancy in the specified phase (solid solution, the
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Vol. 35 No. 2 INVITED SPECIAL PAPER
amorphous phase or intermetallic compound). As
the target of this work is multi-component alloys
with equiatomic or close-to-equiatomic
compositions, differences in ΔS mix among the
analyzed alloys (all with high ΔS mix ) are small[7]
and hence ΔS mix is not considered here. However,
the high ΔS mix should be the necessary though
2
, not the sufficient condition, for the solid solution to
be the preferred phase in some alloy systems[36,55].
In addition, it has been shown that ΔS mix has a
close correlation to the glass forming ability (how
easy to form the BMGs) and a higher ΔS mix
generally favors the easy glass formation[7]. This is
in line with Inoue’s rules on the complexity of the
alloying elements to form BMGs. We then evaluate
how δ and ΔH mix can act as controlling factors
for the phase selection in multi-component alloys
with equiatomic or close-to-equiatomic
compositions. The selection of these two
parameters is also based on a statistical analysis[7],
from which we identified the key factors that
control the phase selection in multi-component
alloys with equiatomic or close-to-equiatomic
compositions.
4.3 Statistical analysis
analysis of the available experimental evidences on
the phase selection in multi-component alloys with
equiatomic or close-to-equiatomic compositions,
using the two parameters, a topology natured δ and
a chemistry natured ΔH mix (source data given in
Ref. [56]). It is surprising to see that the phase
selection can be very reasonably delineated by
these two parameters alone. Basically, solid
solutions can form when δ is small (δ<～0.066),
and ΔH mix is either slightly positive or
insignificantly negative (~ −11.6 kJ·mol-1 < ΔH mix
<3.2 kJ·mol-1); exactly contrary to these
requirements, the amorphous phase can form when
δ is large (δ >0.064), and ΔH mix is noticeably

negative ( ΔH mix < −12.2 kJ·mol-1); interestingly,
intermetallic compounds can form in the
intermediate conditions in terms of δ and ΔH mix .
It is noted here that the intermetallic compound
forming region does not indicate that intermetallic
compounds are the sole alloyed products, but rather
refer to the condition where the amount of
intermetallic compounds is sufficient to be detected
by the X-ray diffraction.
Fig. 4 A δ -ΔHmix plot delineating the formation conditions
for solid solutions, the amorphous phase and
intermetallic compounds. The shadowed blocks
indicate the crossover values on δ and ΔHmix, where
the formation of both the solid solution and
amorphous phase is possible. The olive dash-dotted
ellipse indicates the intermetallic compound forming
region defined by δ and ΔHmix
The atomic size difference, δ, apparently plays
a critical role determining the phase selection. Solid
solutions forming at small δ in the multi-
component alloys can be seen as an extension of the
Hume-Rothery rules on the solid solubility of
binary solid solutions. The necessity of a large δ to
form the amorphous shall originate from the
requirement on the sufficient atomic-level stress to
destabilize the solid solution phase[57-58]. According
to Egami[57], the amorphous phase is stabilized
partly because the solid solution phase of the
corresponding composition is topologically
unstable, which explains why the formation of the
第 35 卷第 2 期 ■特约专稿
solid solution phase and amorphous phase has an
opposite requirement from the topology perspective.
Previous studies also suggest that a large δ is
required to form BMGs, for non-equiatomic
multi-component alloys[7-9]. In other words, δ is
related not only to the glass formation, but also to
the glass forming ability.
The requirement on ΔH mix to form the solid
solution phase is also contrary to that of the
amorphous phase. A small ΔH mix favoring the
solid solution is still in line with the Hume-Rothery
rules in that elements with similar chemistry
natured properties have larger solid solubility.
However, a large ΔH mix favoring the amorphous
phase rather than the intermetallic compound, is
surprising at the first sight. On the one hand, it is
noted here that the mixing enthalpy defined in this
work is the weight averaged mixing enthalpies of
different pairs of alloying elements, and the large
mixing enthalpy of an individual pair is hence not
sensitively reflected by this averaged parameter. A
large mixing enthalpy of an individual pair still
promotes the intermetallic compound formation,
and this happens to explain the competition
between the amorphous phase and intermetallic
compounds in the intermediate conditions in terms
of ΔH mix . Our experimental results (see Ref. [56])
have proved that, in cases intermetallic compounds
inhibit the fully amorphorization, the intermetallic
compounds are formed between those elements
with very negative ΔH mix , and further the fully
amorphorization can be achieved by avoiding the
formation of these unwanted intermetallic
compounds through the compositional adjustment.
For example, the melt-spun CoCrCuFeNiZr was
mainly amorphous, but intermetallic compounds
ZrX5 (X=Cu, Co or Ni) also formed[56], since Zr-Cu,
Zr-Co and Zr-Ni have the mixing enthalpy of −23,
−41 and −49 kJ·mol-1, respectively, much more
negative compared to the mixing enthalpy of other
combinations of elements[54]. Simply reducing the
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Chinese Journal of Nature Vol. 35 No. 2
Zr concentration in this alloy and making it to a
composition of CoCrCuFeNiZr0.6, the fully
amorphous phase was obtained[56]. On the other
hand, the formation of intermetallic compounds or
the amorphous phase is determined simultaneously
by ΔS mix (actually T· ΔS mix ) and ΔH mix . In the
case of forming intermetallic compounds, the more
negative ΔH mix dominates as ΔS mix is
negligible (note that ΔS mix here apparently cannot
assume a fully random state of the atomic
distribution); ΔS mix plays an important role when
forming the amorphous phase and in cases when
ΔSmix is high and at the same time ΔH mix is very
negative, the stabilization of the amorphous phase
is possible. The very negative ΔH mix might also
favor the formation of atomic clusters that stabilize the
amorphous phase[59]. The revealing of intermediate
conditions where the amorphous phase and
intermetallic compounds can compete, and
furthermore the proposing of convenient solutions to
avoid the formation of unwanted intermetallic
compounds, are thus of significant importance and
provide new perspectives to design amorphous alloys.
5 Conclusions
(1) The phase selection in the seemingly
complex multi-component alloys with equiatomic
or close-to-equiatomic compositions, can
reasonably predicted using a parametric approach
based on two parameters: the atomic size
polydispersity parameter, δ, and the mixing
enthalpy, ΔH mix .
(2) When the mixing entropies are comparable,
solid solutions can form when δ is small and
ΔH mix is either slightly positive or insignificantly
negative; in the contrary, the amorphous phase is
stable when δ is large and ΔH mix is significantly
negative.
(3) Intermetallic compounds can be formed in
the intermediate condition in terms of δ and
ΔH mix . The formation of intermetallic compounds
94
INVITED SPECIAL PAPER
or the amorphous phase is dependent on the
competition between ΔS mix and ΔH mix .
Intermetallic compounds are formed when ΔH mix
dominates, while the amorphous phase can be
stabilized when ΔS mix is high and at the same
time ΔH mix is very negative. In cases when
intermetallic compounds compete with the
amorphous phase, the full amorphorization can be
achieved via the compositional adjustment to avoid
the formation of intermetallic compounds.
(4) The phase selection rules proposed in this
work reveals a clear physical scenario that is not
seen previously, and it will help to simplify the
alloy design of multi-component alloys, and benefit
the future development of advanced metallic alloys,
such as BMGs, HEAs, BMG composites, and
intermetallic compound strengthened high
temperature alloys.
Acknowledgements This work is financially supported by
the Research Grant Council (RGC), the Hong Kong
Government, through the General Research Fund (GRF) under
the project number CityU/521411, with City University of
Hong Kong.
(2013 年 1 月 16 日收稿)■
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(编辑：方守狮)

■自然信息 地球这样的行星的呢？有证据证 着数千亿颗星球的星系来说，太阳

明太阳是由银河系构成物的残余 兄妹的数量实在是微乎其微。但是
寻找太阳长期失散的同胞兄妹 碎砾生成的一批天体中的一个。这 历史对他们并不仁慈。一个新的星
些原始的陨石保留了某些成分，而 团一旦形成，它就会融入到一个星
我们的太阳是一颗孤独的恒 这些成分只有当一颗恒星发生超 系之中，星系就会把它弄得支离破
星，它发出的光要经过 4 年多的时 新星爆炸，产生放射性同位素衰变 碎。最大的星云质量是太阳质量的
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年前，形成太阳的同一团气体和尘 太阳相仿或略小一些的恒星组成， 力聚集在一起的，因此当恒星爆炸
埃也同样孕育了一大堆别的天体， 或者有几个巨大的星云组成，星云 向太空抛射物质时，质量的损失会
也就是太阳的同胞兄妹。产生太阳 内的恒星质量相差悬殊。这个陨石 使得星团的引力减小。从星团穿过
的星际云早已消失，但是由它生成 保留了一个巨大恒星的残留物，从 的恒星也会拽拉云团，它们的拉力
的大多数恒星仍在银河系的某些 而指证了太阳的婴儿期也曾是一 会吸引单独的恒星离开星团，最终
地方闪烁发光。“我被历史上发生 个巨大的星云团。 结果是星团里恒星之间的相互作
的事情完全迷倒了！”位于新威尔 2010 年，在 Ann Arbor 的 用会把最轻的个体甩出星团。46
士的悉尼大学研究小组成员 Joss Michigan 大学的 Fred Adams 回顾 亿年后，星团里相互作用的力耗尽
Bland Hawthorn 说：
“我想知道我 了现存的太阳系演化历史的全部 了孕育太阳的云团，夺走了云团里
能不能分辨出那些是与太阳一起 信息资料，得出结论：太阳的恒星 的恒星，甚至包括位于云团另一侧
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96