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What the Darken–Gurry Plot Means About

the Solubility of Elements in Metals


YOSHIHARU MAE

The solubility of elements in metals is a classical subject but still an important one. There are
Hume-Rothery rules, which describe the solubility of elements in metals. The Darken–Gurry
plot is a diagrammatical representation of Hume-Rothery rules in which the atomic radius is
taken as the abscissa and the electronegativity as the ordinate. Apart from the existing methods,
the author introduced the ‘‘thermal conductivity-Young’s modulus’’ (TC-YM) diagram in
which thermal conductivity is taken as the abscissa and the Young’s modulus as the ordinate.
The maximum solubilities of elements in c-Fe, a-Fe, Cu, and Al are shown on both the
Darken–Gurry plot and the TC-YM diagram. The TC-YM diagrams showed clear patterns of
solubility on the diagram, while the Darken–Gurry plots showed only vague ones. According to
the TC-YM diagram, the atomic radius and electronegativity, which are factors in the
Darken–Gurry plot, were proven to be similar factors of the same trend. This is why the
Darken–Gurry plot shows vague trends on the figure. On the other hand, the TC-YM diagram
shows a clear trend of the solubility of elements. The same crystal structure, nearness to the
matrix metal on the diagram, and similar Young’s modulus are concluded to be main factors for
the large solubility.

DOI: 10.1007/s11661-016-3730-1
Ó The Minerals, Metals & Materials Society and ASM International 2016

I. INTRODUCTION II. REPRESENTATION OF SOLUBILITY OF


ELEMENTS IN METALS BY THE
SOLUBILITY of elements in metals is still one of the DARKEN–GURRY PLOT
primary concerns in metallurgy. The conditions for the
solubility in metals are known as Hume-Rothery rules Figure 1 shows the Darken–Gurry plot for most of
and are as follows.[1] the solid elements. Elements of the largest electronega-
tivity are nonmetallic elements, and those of the smallest
(1) Size factor: The difference in atomic radius must electronegativity are alkali metals. General metallic
be less than 15 pct. elements are located in between.
(2) Crystal structure: The element must have the
same structure as the base metal.
(3) Valence: The element must have the same valence A. Maximum Solubility of Elements in c-Fe
as the base metal. The solubility of elements varies with temperature;
(4) Electronegativity: The element must have elec- therefore, the maximum solubility in the c phase at high
tronegativity similar to the base metal. temperature was adopted as the maximum solubility in
As one of the derivatives of the Hume-Rothery rules, c-Fe.[6] The maximum solubility varies from 100 to 0
the Darken–Gurry plot has been used to explain the mol pct and is classified into several ranks. Figure 2
solubility of elements in metals.[2–5] In the Darken– shows the maximum solubility of elements in c-Fe, in the
Gurry plot, the size factor is taken as the abscissa and neighborhood of Fe on the Darken–Gurry plot.
the electrochemical factor (electronegativity) as the The figures in the legend show the range of solubility
ordinate. It is understood that the Darken–Gurry plot in mol percent. The vertical lines show the boundaries of
takes into consideration the first and fourth items of the ±15 pct difference in atomic radius. The elements Ni
Hume-Rothery rules. Recently, the author introduced and Co near Fe show 100 pct solubility, but other
the diagram with thermal conductivity on the abscissa elements near Fe show only small solubility. On the
and Young’s modulus on the ordinate to explain the contrary, elements Rh, Ir, Pt, and Pd, relatively far from
various behaviors of elements. Using this diagram, what Fe, show 100 pct solubility. It cannot be said that the
the Darken–Gurry plot means was studied and is Darken–Gurry plot is effective in regard to the solubility
reported here. of elements in c-Fe.

B. Maximum Solubility of Elements in a-Fe


YOSHIHARU MAE, President, is with Maetech, 685-8, Mimuro, The maximum solubility of elements in the a phase of
Midori-ward, Saitama-city, 336-0911, Japan. Contact email: Fe at high temperature was adopted as the maximum
yoshimae@hotmail.com
Manuscript submitted November 6, 2015.
solubility of elements in a-Fe. Figure 3 shows the

METALLURGICAL AND MATERIALS TRANSACTIONS A


3 C. Maximum Solubility of Elements in Cu
The maximum solubility of elements in Cu at high
I
temperature was adopted as the maximum solubility in
Se Cu. Figure 4 shows the maximum solubility of elements
2.5 C
in Cu, in the neighborhood of Cu on the Darken–Gurry
S plot. Nickel is the only element near Cu that shows 100
P pct solubility. Other elements of 100 pct solubility, Rh,
Pt, Pd, and Mn, are located relatively far from Cu. It
Electronegativity

2 B
cannot be said that the Darken–Gurry plot is effective in
showing the solubility of elements in Cu. The interesting
finding is that the patterns of c-Fe and Cu are similar,
probably because c-Fe and Cu have the same fcc
1.5 structure and are located near each other in the
Be
Darken–Gurry plot, as shown in Figures 2 and 4.

1
D. Maximum Solubility of Elements in Al
The maximum solubility of elements in Al at high
temperature was adopted as the maximum solubility of
K Rb Cs elements in Al. Figure 5 shows the maximum solubility
0.5 of elements in Al, in the neighborhood of Al on the
0.5 1 1.5 2 2.5 3
Darken–Gurry plot. Only the element Zn shows large
–10
Atomic radius (10 m) solubility among the elements near Al. The elements Cu
and Mg, the most important alloying elements for
Fig. 1—Darken–Gurry plot for solid elements. industry, are relatively far from Al. It cannot be said
that the Darken–Gurry plot is effective in showing the
solubility of elements in Al.
100 50–20 20–10 10 0 0 Fe
2.5

2.4 –15% W +15% III. WHAT THE DARKEN–GURRY PLOT MEANS


Ru From the results in Figures 2 through 5, it can be said
2.3
Rh Pt
that the effects of atomic radius on the solubility of
P
2.2 As Os elements in the matrix metals are rather recognized,
Pd while the effects of electronegativity are rarely recog-
Ir
Electronegativity

2.1 Mo Te nized. What is the reason for it?


Bi
Ge Sb
2 Sn A. Introduction of the Thermal Conductivity-Young’s
Si Modulus Diagram
Cu Ag
1.9 Ni
Tc Re The author has introduced a new diagram to explain
Co
1.8 the behaviors of elements. In general, the main charac-
Fe Ga teristics of the metallic elements are crystal structures
1.7 Zn Cd
and the existence of free electrons. Among many
Cr physical properties, the Young’s modulus was selected
1.6 Al as an index representing the strength of lattice and the
V
Be
Nb thermal conductivity as an index representing the
1.5 characteristics of free electrons. Consequently, a dia-
1 1.1 1.2 1.3 1.4 1.5 1.6 gram with the thermal conductivity on the abscissa and
Atomic radius(10
–10
m) the Young’s modulus on the ordinate was made, and
each element was plotted on the diagram. This diagram
Fig. 2—Maximum solubility of elements in c-Fe (mol pct) shown on will be referred to as the ‘‘thermal conductivity-Young’s
the Darken–Gurry plot. modulus’’ (TC-YM) diagram.
The Young’s modulus is generally thought to be an
engineering factor, but it is a physically fundamental
factor: The Young’s modulus is proportional to the
maximum solubility of elements in a-Fe, in the neigh- gradient of the tangent of the curve of the Condon-
borhood of Fe on the Darken–Gurry plot. The elements Morse force between atoms at an equivalent atomic
Cr and V show 100 pct solubility, though they are not distance,[7] i.e., proportional to the second-order differ-
located in the nearest position to Fe. It cannot be said ential of the binding potential between two atoms at
that the elements near Fe show the largest solubility. equivalent atomic distance.[8] Therefore, the Young’s

METALLURGICAL AND MATERIALS TRANSACTIONS A


100 100–50 50–20 20–10 10–0 0 Fe 70–60 30–10 3–1 1–0 0 Al
2.5 2
S
Sn
–15% Si Ni
2.4 W +15% 1.9 Cu
Ag
Co
Ru Ga
2.3 Pt 1.8
Fe In
P Rh Cd
2.2 Pd 1.7 Cr Zn
As
Electronegativity

Electronegativity
2.1 Mo 1.6 V Al
Sb Nb
Ge
2 Be Mn
1.5
Ni
Si Cu Sn
1.9 Co 1.4
Ga Zr
1.8 Fe
1.3 Ti
Mg
1.7 Cr Zn
V Al 1.2
Be
1.6 Nb
Mn 1.1
Ta –15% +15%
1.5 Ca
1 1.1 1.2 1.3 1.4 1.5 1.6 1
1 1.2 1.4 1.6 1.8 2
Atomic radius (10 –10m) –10
Atomic radius (10 m)
Fig. 3—Maximum solubility of elements in a-Fe (mol pct) shown on
the Darken–Gurry plot. Fig. 5—Maximum solubility of elements in Al (mol pct) shown on
the Darken–Gurry plot.

100 50–20 20–10 10–0 0 Cu


2.5
can reflect the essential properties of atoms of the
metallic and semimetallic elements.
2.4
–15% W +15% The thermal conductivity is said to come from both
Ru the free electron transfer and the lattice vibration.[9] The
2.3
ratio of the thermal conductivity to the electrical
Rh Pt conductivity is constant at room temperature and is
2.2 As Os Pd called the Wiedemann–Franz law.[10] Figure 6 shows the
Ir
Electronegativity

Mo Te
relationship of solid elements between the thermal
2.1
conductivity and the electrical conductivity.
Sb Bi
Ge Cu Except the semiconductor elements Ge and Si, the
2
Sn
thermal conductivity is proportional to the electrical
Ni Re conductivity in all solid elements. Figure 6 shows that
1.9
Si
Co Ag the thermal conductivity is covered by the free electrons
1.8 Ga
in the solid elements. Then, how about the contribution
Fe of the lattice vibration to the thermal conductivity? To
Cd examine this, the result of taking the correlation between
1.7 Cr Zn
V
the thermal conductivity and the Young’s modulus as
1.6 Be Al
the factor of lattice vibration is this TC-YM diagram.
The result is shown in Figure 7.
Mn Nb
1.5
In this case, the semiconductor elements Ge and Si are
1 1.1 1.2 1.3 1.4 1.5 1.6 contained in the figure. Moreover, Ge and Si show
–10 behaviors similar to the nearby elements as the alloying
Atomic radous (10 m)
elements, as shown subsequently. Further, the half-metal-
lic elements, such as As, Se, Te, and I, show the intrinsic
Fig. 4—Maximum solubility of elements in Cu (mol pct) shown on
the Darken–Gurry plot.
characteristics according to their positions in the TC-YM
diagram. In this way, the TC-YM diagram shows the
characteristics of most solid elements, including metallic,
modulus is a good index to represent the binding state of semiconductor, and half-metallic.
atoms. Thermal conductivity can be considered to be As shown in Figure 7, there is an element group of
related to the mobility of free electrons in atoms. This is Mg, Al, Au, and Cu in which the thermal conductivity
also a physically fundamental factor. A diagram with abruptly increases with only a slight increase of the
thermal conductivity on the abscissa and Young’s Young’s modulus, and there is an element group of Ta,
modulus on the ordinate (TC-YM diagram), therefore, Fe, Ni, Co, Cr, Mo, and W in which the thermal

METALLURGICAL AND MATERIALS TRANSACTIONS A


80 enabling elements of high thermal conductivity and low
Young’s modulus and those of low thermal conductivity
Ag and high Young’s modulus.
70
Cu Then the law that allows the distribution of the
Young’s moduli of the elements is the subject of this
Electrical conductivity (10 / cm)

60 work.
Figure 8 shows the distribution of the crystal struc-
Au
tures of various elements in a TC-YM diagram. The
4

50
crystal structures are classified as body-centered-cubic
Al (bcc), face-centered-cubic (fcc), hexagonal-close-packed
40 (hcp), diamond structured, and ‘‘others’’ for miscella-
Ca neous structures.[11] The most remarkable feature of
Be
Figure 8 is that the bcc-structured elements mostly lie on
30
a straight line connecting V, Ta, Cr, Mo, and W, which
can be called the straight line of refractory metals. Iron is
20 W located near this line. Additionally, elements with fcc
Nb structures lie on a clear curve, which can be called the
Ru curve of fcc metals. In contrast, bcc-structured alkali
10 metals lie on a curve near the abscissa (the curve of alkali
Cr metals). Elements with hcp and other structures are
Ge Si distributed elsewhere. Lanthanides gather tightly in the
0
0 100 200 300 400 500 low Young’s modulus and low thermal conductivity
Thermal conductivity (W/mK)
region.
The TC-YM diagram, therefore, shows clear patterns
Fig. 6—Relationship in the elements between the thermal conductiv-
with respect to the crystal structures of elements. Other
ity and the electrical conductivity. elemental properties, such as atomic radius, melting
point, thermal expansion, boiling point, heat of fusion,
vapor pressure, heat capacity, electronegativity, and
600
ionization energy, also show clear patterns in TC-YM
Os diagrams.
Ir
For comparison, the same data of crystal structures
500 Re were plotted on the Darken–Gurry plot and are shown
in Figure 9. There is no recognizable order in the figure.
This is the fatal defect of the Darken–Gurry plot for the
Young's modulus (GPa)

400 W explanation of solubility of elements.

Mo
300 B. Analysis of the Darken–Gurry Plot by the TC-YM
Be
Cr Diagram
Fe
In the Darken–Gurry plot, the atomic radius is taken
200 Ni Co as the abscissa and the electronegativity as the ordinate.
Ta What are the natures of the atomic radius and elec-
Si
Zn Cu tronegativity? The atomic radii of elements are plotted
100 Ge
Al
Au in the TC-YM diagram and are shown in Figure 10.
Mg The figures in the legend show the range of atomic
Ag radii in units of 10 10 m. There seems to be a clear trend
0 in the diagram. The elements Be, Cr, Fe, Ni, Co, Si, and
0 100 200 300 400 500 Cu, which form a gulf near the center of the diagram,
Thermal conductivity (W/mK) show the smallest atomic radii. These elements will be
referred to as ‘‘gulf elements.’’ They show common
Fig. 7—Relationship in the elements between the thermal conductiv- behaviors to each other in other properties. Note that
ity and the Young’s modulus. the semiconductor element Si is included in this element
group and behaves as a metallic element, as shown
conductivity increases modestly with the increase of the subsequently.
Young’s modulus. However, there are many additional The elements of the next smallest atomic radii are
elements that are randomly distributed in the TC-YM located as if they were surrounding the gulf elements.
diagram. The elements with far larger atomic radii are located
As shown in Figure 6, the thermal conductivity is outside those elements. Most of the elements distribute
covered by the transfer of the free electrons; therefore, in the form of a concentric circle according to their
the Young’s modulus is freed from the contribution to atomic radii. Such a property will be called ‘‘the
the thermal conductivity and is able to take free values, property of thermal conductivity type.’’

METALLURGICAL AND MATERIALS TRANSACTIONS A


bcc diamond fcc hcp others 0.7–1.1 1.1–1.3 1.3–1.5 1.5–1.7 1.7–1.9
600 1.9–2,1 2.1–2.7
600
Os Os
Ir
500 Straight line of Ir
Re refractory metals 500
B
Ru Re Straight line of
B refractory metals
Young's modulus (GPa)

Young's modulus (GPa)


Ru
400 W 400
W
Rh Tc
Tc Rh
Mo
300 Mo Be
Be 300
Cr
Cr
Ni Co Mn
Mn Ta
200 200
U Fe Curve of fcc metals Fe Ni Co
Pt Si Si Cu
V Cu
Pd Au Zn
100 100
Zn Al Ge
Th Mg
Ca Ag Al Au Ag
Pb As Mg
0 0
0 100 200 300 400 500 0 100 200 300 400 500
Thermal conductivity (W/mK) Thermal conductivity (W/mK)

Fig. 8—Crystal structures of elements shown on the TC-YM dia- Fig. 10—Distribution of atomic radius of elements on the TC-YM
gram. diagram.

bcc diamond fcc hcp others fact, electronegativity is a mixture of properties of


3
‘‘thermal conductivity type’’ and ‘‘Young’s modulus
I
type,’’ which is stated next. Consequently, both the
atomic radius and electronegativity have a common
Se
S Au property classified as thermal conductivity type. They
2.5
have a common trend; therefore, when they are plotted
C
Pb on the same diagram, a correlation is expected. Practi-
P cally, the Darken–Gurry plot shows a rather good
correlation between the atomic radius and electronega-
Electronegativity

2
B tivity, as shown in Figure 1. The atomic radius and
electronegativity are not independent factors of each
other. In the description of solubility, the atomic radius
is effective to the solubility of elements, but the effect of
1.5 electronegativity is covered by the effect of the atomic
radius.
This is the reason why the Darken–Gurry plot does
Sr
not clearly show the solubility of elements in metals. It is
1 difficult to explain the solubility by only one factor. As
Li Rb Cs
was shown, the atomic radius and electronegativity
Na Ba
belong to the property of thermal conductivity type;
K
moreover, the heat capacity and ionization energy are
0.5 included in this type. As the atomic radius decreases, the
0.5 1 1.5 2 2.5 3
Coulomb force between the nucleus and electrons
–10
Atomic radius(10 m) increases. Consequently, electronegativity, the capacity
to attract electrons, increases, and ionization energy, the
Fig. 9—Crystal structures of elements shown on the Darken–Gurry work to deprive electrons from the atom, increases. The
plot. correlation between the atomic radius and electronega-
tivity is reasonable physically.
Next, values of electronegativity were plotted on the Figure 12 shows the distribution of the melting
TC-YM diagram and are shown in Figure 11. temperature of elements in the TC-YM diagram. The
In Figure 11, gulf elements show the largest values of figures in the legend show the range of the melting
electronegativity. Most of the elements distribute in the temperature in Kelvin. In the melting temperature, the
enlarging concentric circle with decreasing electronega- elements of high Young’s modulus, Re, Os, Ir, Ru, W,
tivity, except the elements of high Young’s modulus. In and Mo, show the highest values, and the trend

METALLURGICAL AND MATERIALS TRANSACTIONS A


3–2.5 2.5–2.0 2.0–1.5 1.5–1.0 1.0–0.5 The remarkable and common fact through the ther-
600 mal conductivity type and Young’s modulus type is that
Os the gulf elements show common properties in both
Ir types.
Straight line of
500 refractory metals
B

Ru C. Application of the TC-YM Diagram to the Solubility


Young's modulus (GPa)

400 of Elements in Metals


W
Rh Representations of solid solubility of elements in
metals on the Darken–Gurry plot were insufficient.
Mo
300 Be What happens if the TC-YM diagram is applied to the
Cr solubility of elements in metals?
Figure 13 shows the distribution of solubility of
Ta elements in c-Fe on the TC-YM diagram. The data of
200 Fe Ni Co solubility are the same as in Figure 2. The figures in the
Pt legend show the range of solubility in mol percent. Iron
Cu is located near the center of the diagram. Most of the
Pd Zn Si Au
100 elements show a clear distribution. Elements of 100 pct
Ge
Cd solubility lie on the curve of fcc metals and are relatively
Sn Ag near Fe. They have the same fcc structure as c-Fe. The
Al
0 other fcc elements of lower Young’s modulus, Cu, Au,
0 100 200 300 400 500 and Al, and those of other crystal structures and of
Thermal conductivity (W/mK) similar Young’s modulus, Si, Zn, Sn, As, Th, Ga, Zr,
Pu, Ti, and V, show small solubility.
Fig. 11—Distribution of electronegativity of elements on the TC-YM Figure 14 shows the distribution of solubility of
diagram. elements in a-Fe in the TC-YM diagram. Most of the
elements show a clear distribution in this case also. The
elements near Fe and on the straight line of refractory
>3500 3500–3000 3000–2500 2500–2000 metals Cr and V show 100 pct solubility. The elements
2000–1500 1500–1000 1000–500 500–0 on the straight line of refractory metals have the same
600 bcc structure as a-Fe. However, the elements Mo and W
Os
far from Fe show small solubility, although they are
located on the straight line of refractory metals. The
500 Ir
Straight line of elements Mo, Be, Si, and Zn surrounding the elements
B Re refractory metals Cr and V of 100 pct solubility show the next largest
Ru solubility. The farther elements show small or no
Young's modulus (GPa)

400 W
solubility. Especially, the elements of low Young’s
Rh
modulus show no solubility.
Tc Figure 15 shows the distribution of solubility of
Mo Be elements in Cu. Some of the elements on the curve of
300
Cr
fcc metals, Au, Pd, Pt, Ni, and Rh, show 100 pct
solubility. They have the same fcc structure as Cu.
Ta Among other fcc elements, Al of smaller Young’s
200 Ni Co
Fe
modulus and smaller thermal conductivity shows small
Hf
Pt
Cu solubility, while the elements Ca, Pb, and Th of much
Si
V Pd Au
smaller Young’s modulus and thermal conductivity
100
Zn Ag show no solubility. The element of the highest Young’s
Th Mg modulus, Ir, on the curve of fcc metals shows small
Ca Al
Na solubility. The farthest elements show no solubility.
0 Figure 16 shows the distribution of solubility of
0 100 200 300 400 500
elements in Al. Aluminum has no elements of 100 pct
Thermal conductivity (W/mK)
solubility. This is probably because Al has lower
Young’s modulus and smaller thermal conductivity
Fig. 12—Distribution of melting point of elements (Kelvin) in the
TC-YM diagram.
than Cu. The elements near Al and with equivalent
Young’s modulus, Ag, Mg, and Zn, show relatively
decreases gradually along the straight line of refractory large solubility. Aluminum has fcc structure, but it
metals and reaches the elements of low Young’s cannot dissolve most of the fcc elements, except Cu and
modulus, Ta and Hf. This type of property will be Ag. This is also because Al has low Young’s modulus
called a property of Young’s modulus type. Thermal and the resulting low alloying capacity. Aluminum only
expansion, boiling point, heat of fusion, and heat of dissolves the elements near Al and with the equivalent or
vaporization are included in this type. slightly higher Young’s modulus.

METALLURGICAL AND MATERIALS TRANSACTIONS A


100 50–20 20–10 10–1 0 Fe 100 50–20 20–10 10–0 0 Cu
600 600
Os Os
Ir Ir
500 500
Re Straight line of
refractory metals
Young's modulus (GPa)

Re Ru

Young's modulus (GPa)


B Ru W
400 400
Rh W
Rh
Mo Mo
300 Be
Fe 300 Be
Cr Cr
Mn
200 Ni Co Mn Ni Co
200
Si Cu Fe
Pt Al
Ti
V Pd Pt Cu
Nb Au
100 Pd
Zn 100 Si Au
Ag Zn
As Sn Ge
Mg Cd Al Ag
0 Sn Mg
0 100 200 300 400 500 0
0 100 200 300 400 500
Thermal conductivity (W/mK)
Thermal conductivity (W/mK)
Fig. 13—Maximum solubility of elements in c-Fe shown on the
TC-YM diagram. Fig. 15—Maximum solubility of elements in Cu shown on the
TC-YM diagram.

100 100–50 50–20 20–10 10–0 0 Fe


600 70–60 30–15 3–1 1–0 0 Al
600

Os
500 Straight line of
Ir refractory metals 500 Straigt line of
Re refractory metals
Young's modulus (GPa)

400 Ru
Young's modulus (GPa)

W 400
Rh W

300 Be
Mo Mo
Cr 300 Be
Fe
Mn Cr
200 Mn
Ni Co
Ni Co 200
Pt Cu Fe
V Si V
Pd
100 Au
Ti Si Cu
Zn
100 Zn
Al Ge Al
Sn Mg Zr Ag
Au
0
0 100 200 300 400 500 Mg
0
Thermal conductivity (W/mK) 0 100 200 300 400 500
Thermal conductivity (W/mK)
Fig. 14—Maximum solubility of elements in a-Fe shown on the
TC-YM diagram.
Fig. 16—Maximum solubility of elements in Al shown on the
TC-YM diagram.
IV. DISCUSSION AND CONCLUSIONS
is because the Darken–Gurry plot does not show the
As shown in Figures 2 through 5, in the Darken– trend of crystal structures schematically, as shown in
Gurry plot, most of the elements of large solubility are Figure 9. Second, electronegativity has a correlation
included within the range of ±15 pct difference in with atomic radius and is not an independent factor
atomic radius, as the Hume-Rothery rules teach. How- from atomic radius. As a consequence, the Darken–
ever, simultaneously, other elements of small and no Gurry plot begins to show the solubility of elements by
solubility are also included in the same range. First, this only one factor.

METALLURGICAL AND MATERIALS TRANSACTIONS A


In contrast to this, in the TC-YM diagram proposed the solute, and the atomic size factor are important.[12]
by the author, the trends of crystal structures, atomic The electronegativity was ignored, because it was noted
radius, and electronegativity are shown schematically, as that the electronegativity is not an independent param-
illustrated in Figures 8, 10, and 11, respectively. The eter; it depends upon the radius and valence, as the
diagram covers three of the four items in the author also recognized in this study.
Hume-Rothery rules. Summarizing the results of Zhang used the artificial neural networks (ANNs) and
Figures 13 through 16, the following can be said about simulated the process that Hume-Rothery had used to
the factors affecting the solubility of elements in metals. derive the Hume-Rothery rules from experiments.[13]
It is said as follows: When the functionized values
1. The crystal structure of the solute atom is the were used as input parameters, the ANN gave good
primary factor in determining the atom’s solubility performance. As a result, it was recognized that the
in matrix metals. The crystal structure must be the atomic size factor has the largest influence, followed
same as the matrix metal to have large solubility. next by electronegativity. However, these parameters are
The elements c-Fe, Cu, and Al primarily dissolve not independent of each other, making the determina-
the elements of the same fcc structure, as shown in tion of solubility difficult. The structural parameter
Figures 13, 15, and 16, while a-Fe primarily dis- seemed not to play a very important role. In conclusion,
solves the elements of the same bcc structure, as new parameters and laws should be explored.
shown in Figure 14. The main difference from the conclusion in this article
2. The elements near the matrix metal on the TC-YM is that, in the previous studies, the structural parameter
diagram generally show large solubility. This is is not important. However, in this article, the same
because the element in the neighborhood of the crystal structure is the most dominant factor. Further-
matrix metal is apt to have similar atomic radius more, in those previous studies, the item representing
and electronegativity, as shown in Figures 10 and the bonding force of the atoms is not commonly
11. Besides, to be near the matrix metal means that included. The Young’s modulus plays an important
the binding force of atoms represented by the role, as shown in this study. Further, the other studies
Young’s modulus and the configuration of electrons generally cannot display the results in a diagram. The
represented by the thermal conductivity are similar Darken–Gurry plot exhibits them in a diagram, but the
between the solute atoms and the matrix atoms. results are not correct. The TC-YM diagram can
Additionally, the elements that dissolve elements systematically show the solubility in a diagram.
most are Fe, Ni, Co, Pt, and Pt. This is because they On the other hand, there has been research in
have rather high Young’s modulus and the most which the phase diagram was obtained by calculation
nearby elements, as shown in Figures 13 and 14. (CALPHAD), for example, the Ni-Sb binary phase
3. In matrix metals such as Al and Cu, which have diagram.[14] The calculation result corresponds well with
high conductivity and low Young’s modulus, ele- the experimental diagram. The Sb dissolves into Ni by
ments of similar Young’s modulus are apt to have 10 mol pct as the maximum solubility. However, this
large solubility. In general, elements of low Young’s method cannot systematically show the solubility of the
modulus (indicated by 9) are unlikely to dissolve elements in Ni, but only shows it individually. In
into the matrix metals of higher Young’s modulus, contrast to this, on the TC-YM diagram, the maximum
as shown in Figures 15 and 16. solubility of the elements can be shown on one chart. As
4. The matrix metal should have high Young’s mod- Ni and c-Fe have the same fcc structure and they are
ulus or high thermal conductivity, so that it may very close to each other in the TC-YM diagram, the
have elements of large solubility. TC-YM diagrams become very similar between c-Fe and
The capacity of the matrix metal to dissolve other Ni. Antimony is located at the position of 26 W/mK and
elements decreases with its decreasing Young’ modulus 78 GPa and belongs to the element group with the
and thermal conductivity, as shown in Figures 15 and solubility of 1 to 10 mol pct in c-Fe. Similarly, it belongs
16, comparing Cu and Al. Aluminum has fewer elements to the element group with the solubility of 1 to 10 mol
of high solubility than Cu. The elements of very low pct in Ni also. In this way, the TC-YM diagram can
Young’s modulus and thermal conductivity, Pb and Sn, show the total tendency of the solubility, differently
only dissolve the elements near themselves in the from CALPHAD.
TC-YM diagram. The solubility in the high entropy alloy system has
In this way, the solubility of elements in the matrix been studied using the KKR-CPA method.[15] It is noted
metal can be well displayed in the TC-YM diagram that Hume-Rothery substitutions—replacing one ele-
schematically, while the Darken–Gurry plot cannot. ment with another of a similar atomic size, electroneg-
Besides, it should be noted that the preceding items, ativity, and crystal structure—similarly can fail to
except number 1, are all related to the Young’s modulus. preserve the single phase. It is concluded that the
The binding force of atoms is the next largest factor for enthalpy of formation of binary compounds rules the
the solubility of elements following the crystal structure. formation of single-phase, high-entropy alloys.
After the development of the Darken–Gurry plot, However, this method does not show the total
Gschneidner and Verkade introduced the semiempirical tendency of the solubility among elements either.
electronic, crystal structure, size model and noted that Furthermore, the significance of the TC-YM diagram
the compatibility of the crystal structure, the valence of can be considered as follows:

METALLURGICAL AND MATERIALS TRANSACTIONS A


As mentioned in Section III-A, the thermal conduc- REFERENCES
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METALLURGICAL AND MATERIALS TRANSACTIONS A