Driving Force for Solidication

Topic 3
M.S Darwish
MECH 636: Solidication Modelling
Definitions

In the study of phase transformations we will be dealing

with the changes that can occur within a given system
e.g. an alloy that can exist as a mixture of one or more
phases

A phase can be dened as a portion of the system whose

properties and composition are homogeneous and which
is physically distinct from other parts of the system

The components of a system at the different elements or

chemical compound which make up the system
Gibbs Free Energy
G = H - T S
for condensed phases PV !0 and thus H ! E
Enthalpy
Temperature
Entropy
H = E + PV
Internal Energy
Kinetic + Potential Energy
Pressure Volume
measure of
heat content
of the system
+ =
A system is in
equilibrium when it is
at its most stable state
when it has the lowest
value of the Gibbs free
energy
measure of
randomness of
the system
dG = 0
Equilibirum
B A
Gibbs free
energy, G
dG = 0
dG = 0
metastable equilibrium stable equilibrium
Any transformation that results in a decrease in Gibbs free energy is possible
"G = G
2
- G
1
< 0
How fast does a phase transformation occur?
Free Energy
Relations
Specific Heat
Cp
T(K)
0
Enthalpy
H
T(K)
298
0
slope = Cp
Entropy
S
T(K) 0

C
P
=
!H
!T
"
#
$
%
&
'
P

H = C
P
dT
298
T
!

C
P
T
=
!S
!T
"
#
$
%
&
'
P

S =
C
P
T
dT
0
T
!
Enthalpy
H
T(K)
298
0
slope = Cp
G
TS
slope = -S
slope = -S
H
G
G = H - T S
Driving Force for
Solidification
Enthalpy
H
T(K)
298
0
slope = Cp
G
slope = -S
liquid stable
H (liquid)
G(liquid)
Tm
H (solid)
L
G(solid)
solid stable
G
Temperature
Stable
solid
Stable
liquid
solid
Tm
Driving Force for
Solidification
G
Temperature
Stable
solid
Stable
liquid
solid
liquid
Tm
G
S
!G
G
L
T
!T
G
L
= H
L
-TS
L
G
S
= H
S
-TS
S
"G

= "H -T"S
"H = H
L
- H
S
"S = S
L
- S
S
At equilibrium "G = 0
"G

= "H -T
m
"S = 0
entropy of fusion (nearly
a constant ! R)
for small "T we get
=
L
T
m
"S
f


=
"H
f
T
m
"G

! L -T
L
T
m
"G

!
L "T
T
m
! "S
f
"T
undercooling
Solidification
Growth: occurs as atoms from the liquid are
attached to the tiny solid until no liquid remains
To get the solidication process started, the liquid
phase must be undercooled, cooled to a
temperature below the freezing point.
G
Temperature
Stable
solid
Stable
liquid
solid
liquid
Tm
G
S
!G
G
L
T
!T
Nucleation: occurs when a small piece of solid
forms in the liquid and must attain a minimum
critical size before it is stable
Controlled by:
thermal conductivities
relative masses
shapes of the melt, the solid, and mold
Once a nucleus forms, it can proceed to grow as
fast as the latent heat of solidication and specic
heat can be carried away.