Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

9. Thermodynamics of solidification 2


9.1 Entropy

Entropy is defined as T q S / = where q is the amount of heat absorbed or
evolved in an isothermal and reversible process in which the system goes from
one state to another, and T is the absolute temperature at which the process is
occurring. 0 =

S when system passes through a series of reversible,

equilibrium and isothermal steps and arriving back to the initial state.

This thermodynamic definition of entropy is only valid for a system in equilibrium
(because temperature is defined only for a system in equilibrium), while statistical
definition of entropy applies to any system. Thus the statistical definition is
usually considered fundamental definition of entropy.

Kelvin and Boltzmann considered that the entropy is related to the probability of a
system by

W k S ln = (8.1)

where k=1.3806502x10
-23
Joule/Kelvin is Boltzmann constant and W is the
possibility (a measure of disorder). Eq. (8.1) means that the maximum entropy is
associated with the greatest disorder. When the temperature of the system
approached absolute zero the entropy of the system would approach zero.

The 3
rd
law of thermodynamics: The entropy of a condensed system would be
zero at a temperature of absolute zero.


9.2 Entropy of solution at ideal mixing

Alloy is solution which is made up of components. There is solubility between the
various components. For an alloy in which there is no repulsive and attractive
interactions between various components, atoms (or molecules) can be mixed up
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

ideally. Suppose that n atom or molecule of component A is mixed up with N-n
number of component B, the possibility is given by

)! ( !
!
n N n
N
W

= (8.2)

The possibility is demonstrated in figure 1 for a binary crystal (N=9, n=1).

Figure 1. Possibility

Inserting eq. (8.2) into eq. (8.1) gives the entropy

|
|

\
|

=
)! ( !
!
ln
n N n
N
k S (8.3)

Using Stirling approximation N N N N = ln ) ! ln( eq (8.3) becomes

[ ]
(

\
|
+
|

\
|
=
=
N
n N
N
n N
N
n
N
n
Nk
n N n N n n N N k S
ln ln
) ln( ) ( ln ln
(8.4)

Let N n x
A
/ = and ( ) N n N x
B
/ = ,
A
x and
B
x are molar fraction of components A
and B in the solution. The molar entropy in ideal solution is

( )
B B A A
x x x x R S ln ln + = (8.5)

If there are no repulsive or attractive interactions between atoms A and B the
solution is called ideal and the Gibbs energy of mixing is given by
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

( )
B B A A
ideal
mix
x x x x RT G ln ln + = (8.6)

Generally, it takes the following format for multicomponent solution

=
i
i i
ideal
mix
x x RT G ln (8.7)
where
i
x is the molar fraction of component i .


9.3 Entropy of solution at non-ideal mixing

Normally there are interactions between different atoms or molecules of various
components. The excess mixing energy,
xs
mix
G , should be considered. The
simplest way to consider is via the regular solution model where

=
B A
xe
mix
x x G (8.8)

where is the regular solution interaction energy parameter and is related to the
energy of bonds between A and B atoms or molecules. >0 corresponds to
repulsive interaction, such as Cu-Ag. <0 corresponds to the attractive
interaction, such as Fe-Ni. The total mixing Gibbs energy of binary alloy is given
by combination of eqs. (8.6) and (8.8).

( ) + + =
B A B B A A mix
x x x x x x RT G ln ln (8.9)
(a) (b)
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0 0.2 0.4 0.6 0.8 1
MOLAR FRACTION B
G
I
B
B
S

M
I
X
I
N
G

E
N
E
R
G
Y
G-ideal
G-xe
G-mix
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0 0.2 0.4 0.6 0.8 1
MOLAR FRACTION B
G
I
B
B
S

M
I
X
I
N
G

E
N
E
R
G
Y
G-ideal
G-xe
G-mix

Figure 2. Gibbs mixing energy at RT=1 (a) =-2 and (b) =2
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Eq. (8.9) is plotted with parameters of RT=1 (which means that the energy unit is
in RT ), =-2 (figure 2a) and =2 (figure 2b). It can be found from figure 2b that
the two-phase structure will be formed to reduce the system free energy. One is
A-rich and another is B-rich phases.

In general,
xs
mix
G is expressed by a expression of following

[ ]

=
+
+ =
+ + + =
n
i
n
i j
j i ij j i ij ij j i
xe
mix
x x x x x x G
1
1
1
2 2 1 0
... ) ( ) ( (8.10)


9.4 Gibbs energy of solution

To describe the Gibbs energy of solution, the reference states must be added to
the mixing Gibbs energy. The reference Gibbs energy is

=
i
i i ref
G x G (8.11)

where

i
G is the Gibbs energy of the phase at pure i . The Gibbs energy of
solution, therefore, is expressed at

[ ]

=
+
+ =
+ + + + + =
n
i
n
i j
j i ij j i ij ij j i
i
i i
i
i i
x x x x x x x x RT G x G
1
1
1
2 2 1 0
... ) ( ) ( ln (8.12)
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0 0.2 0.4 0.6 0.8 1
MOLAR FRACTION B
G
I
B
B
S

M
I
X
I
N
G

E
N
E
R
G
Y
G-ideal
G-xe
G-mix
G

Figure 3. Gibbs energy ( 3 . 0 05 . 0 = =
b A
G G , other parameters are same as in figure 2a)
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Equation (8.12) is plotted for a binary alloy with following parameters

RT=1
G
A
=0.05
G
B
=0.3

AB
0
=-2

AB
1
=
AB
2
==0

The result is the blue line in figure 3.


9.5 Solidification of binary alloy

Alloy solidification should follow the routine that free energy goes to minimum. In
equilibrium, the solute concentration in solid should be
E
S
x and in liquid should be
E
L
x . The free energy minimization is demonstrated in figure 4. The chemical
potentials of components A and B are defined as

B
x P T
A
A
x
G
, ,
|
|

\
|

= and
A
x P T
B
B
x
G
, ,
|
|

\
|

= (8.13)

At equilibrium, the free energy achieves minimum and the chemical potentials of
all components are equivalent. Here
B A
=

Figure 4. Free energy minimization during solidification
Solid
Liquid
x
0

x
S
E

x
L
E

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

E
L
E
S
x
x
k = is called equilibrium partition ratio. The solute concentration profile in
steady state equilibrium solidification is illustrated in Figure 5. The method of
calculation for the solution distribution profile has been given in lecture 7.


Figure 5. Solute concentration distribution in binary solidification


In non-equilibrium casting such as rapid quench, free energy minimization is
restricted by kinetics and metastable solid forms. For example the metal glasses.

REFERENCES

1. M.C. Flemings, Solidification processing, 1974.
2. N. Saunders and A.P. Miodownik, CALPHAD, 1998.




x
S
E

x
L
E

K<1
x
S
E

x
L
E

K>1