I.

Miscibility Gap (MG) Between Two Liquid Metals

1. EXPERIMENTAL FACTS AND CONVENTIONAL THEORY

For a collection of atoms, whether monatomic or not, to come together to form an

alloy, the first step is to heat the metals to a temperature where the metals turn into their
liquid state. However experimentally it is often observed as shown in Table I, that the metals
are not always miscible in their liquid states to one another. That is, two metals in their
liquid state do not form a homogeneous solution but rather separate out in two distinct
regions (phases) - much like water and oil. Despite the abundance of these cases in metallic
systems, physicists, chemists, and metallurgists alike choose to ignore this prevailing
phenomenon. The miscibility gap (MG) between oil and water is understood readily in
terms of their electronic bonding differences; water being ionic whereas oil being
exclusively covalent bond. However, in the intermetallic system based on the "free" electron
theory, the miscibility gap (MG) is totally unexpected and defies a conventional theoretical
explanation. This is because the "free" electron theory is based on a 'sea' of free-electrons
that are roaming about among the positively charged nuclei. Thus, there is no reason for
two metals in their liquid state to exist in MG state. It is even more perturbing when
chemists find lithium (Li) and sodium (Na) both of which are I-A elements and therefore
chemically identical to form a MG. In fact, a MG also exists between potassium (K) and
sodium (Na).
As is well known to all material scientists, the phase Diagram is the "road map" to the
understanding and the ultimate usage of binary or ternary system of alloys. In fact, they are
so important that many Ph.D. degrees have been awarded (including my own) to those who
are willing to spend a couple of years of their lives in determining phase diagrams
experimentally. Approximately 3000 binary alloy systems have been obtained in this
manner. For more than thirty years, a group of scientists devoted their time to find a way to
calculate phase diagrams from a small amount of data. This effort led to the scientific
journal, CALPHAD, which is devoted to the possible calculation of phase diagrams.
If two metals do not mix in their liquid state, there would be no phase diagram to draw
and thus no understanding of how to utilize the alloy. A good example of how a phase
diagram can help us in utilizing an alloy is amply demonstrated in the formation of stainless
steel. Without phase diagram, we would not know at what temperature the alloy should be
annealed or to what temperature it should be quenched. Without this knowledge, we would
not have created 'hard-steel' vs. 'soft-steel' etc. to make special steel to suit specific
application. In summary, existence of MG is not a trivial matter and should be understood
before we can embark on trying to understand other observations.

10

Bonding Theory for Metals and Alloys

Table 1
List of binary metallic systems found to have Miscibility Gap (MG). Each system is symbolized by
atomic notation (the range of MG in at. % referring to the second element is indicated numerically).

Ag-Cr
Ag-Mn
Ag-Ni
Ag-PUi
Ag-Se
Ag-Te
Ag-U
Al-Bi
Al-Cd
Al-In
Al-K
Al-Na
Al-Pb
As-Tl
Au-Re
Ba-Mn
Be-Ga
Bi-Co
Bi-Cr
Bi-Ga
Bi-Mn
Bi-Si
Bi-U
Ca-Cd

(10-100)
(50-100)
(0-100)
(5-80)
(10-100)
(10-30)
(0-100)
(0-100)
(0-100)
(5-90)
(0-100)
(0-100)
(0-100)
(30-60)
(17-70)
(6-99)
(2-85)
(1-85)
(1-80)
(1-75)
(52-90)
(1-98)
(50-98)
(20-70)

Ca-U
Cd-Ga
Cd-Pu
Ce-Mn
Co-Pb
Co-Se
Cr-Cu
Cr-Cd
Cr-Pb
Cr-Sn
Cu-Pb
Cu-Se
Cu-Te
Cu-Tl
Cu-U
Cu-V
Er-V
Ga-Hg
Ga-K
Ga-Pb
G a - Ta
Ga-Tl
Hg-Se
Fe-Sn

(1-98)
(20-95)
(40-99)
(1-99)
(0-100)
(3-30)
(6-56)
(2-62)
(10-60)
(2-100)
(15-67)
(3-30)
(4-30)
(14-80)
(23-95)
(27-98)
(27-98)
(2-96)
(38-95)
(3-94)
(1-33)
(0-100)
(71-85)
(31-70)

K-Na
K-Pb
K-Zn
La-Mn
La-Pu
La-V
Li-Mn
Li-Na
Mg-Na
Mg-U
Mg-Pu
Mn-Pb
Mn-Sr
Mn-Tl
Na-Zn
Nb-Y
Ni-Pb
Ni-Tl
Pb-U
Sb-Se
Se-Sn
Te-Tl
Th-U
Tl-Zn

(4-96)
(25-63)
(0-100)
(14-40)
(22-90)
(2-88)
(0-100)
(3-92)
(0-100)
(0-100)
(15-90)
(3-63)
(0-100)
(3-92)
(2-93)
(1-54)
(2-98)
(3-92)
(38-95)
(16-47)
(53-85)
(69-98)
(27-92)
(10-98)

2. UNDERSTANDING THE M G BASED ON THE THEORY PROPOSED

The theory being proposed states that metals and alloys are consisted of covalent bond
as well as metallic (quasi-free electron) band. Also, it has been pointed out that covalent
bond has many faces. Therefore, it can be said that while the 'free'-electron part from both
lithium metal and sodium metal are indistinguishable and may mix freely, the covalent bond
part may be distinct from one another to the extent that they are prevented from mixing and
forming a homogeneous solution. As stated in the proposed theory, the covalent bond is far
more susceptible to the temperature change than the 'free'- electrons. Therefore at higher
temperature, the covalent bond may loose its covalency completely and no longer prevent

Miscibility Gap (MG) Between Two Liquid Metals

11

the intermixing of two metals. At this point MG is expected to disappear - this is indeed the
case is exempHfied in the Li-Na phase diagram as shown in Fig. 4.
The reason that covalent bond is sensitive to temperature change is the fact that
electrons can be moved (excited) from one atomic orbital to another with the temperature
change. Readers who are not familiar with covalent bond should read VALENCE BOND by
C.A.Coulson (Oxford University Press, 1979) [1] or CHEMICAL BONDS by H. B Gray
(Benjamin/Cummings, Pub.Co.l973) [2].

20

\SO

40

450 r

WEIGHT PER CENT SODIUM

80

90
1

THERMAL ANALYSIS
4001

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350

300
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200

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REF.'5

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CHEMICA L ANALY SIS
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150

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97.8

: 96.3
(98.9)

50

0
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Li

10

20

30

40
50
60
ATOMIC PER CENT SODIUM

70

80

90

100
No

Fig. 4. The phase diagram of Li-Na system showing the MG disappearing at about 380C.