Driving Force for Solidification

Topic 3

M.S Darwish
MECH 636: Solidification 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 defined 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
measure of
Entropy randomness of
Enthalpy Temperature the system

H = E + PV A system is in
equilibrium when it is
measure of at its most stable state
heat content = Internal Energy + Pressure Volume when it has the lowest
of the system value of the Gibbs free
energy
Kinetic + Potential Energy
dG = 0
for condensed phases PV ≈0 and thus H ≈ E
 Equilibirum
dG = 0

Gibbs free
energy, G
dG = 0

B A
metastable equilibrium stable equilibrium

Any transformation that results in a decrease in Gibbs free energy is possible

∆G = G2 - G1 < 0

How fast does a phase transformation occur?

 Free Energy
Specific Heat
Cp

Relations
0 T(K)
Enthalpy
H
H
⎛ ∂H ⎞ T

∫C
Enthalpy
CP = ⎜ ⎟ H= P dT H
⎝ ∂T ⎠ P 298 slope = Cp
slope = Cp

CP ⎛ ∂S ⎞
T T(K)
C
0 =⎜ ⎟ S = ∫ P dT 298

T ⎝ ∂T ⎠ P 0 T
298

TS 0 T(K)

slope = -S

slope = -S Entropy
S

G = H -T S 0 T(K)
 Driving Force for
Solidification
Enthalpy
H (liquid)
H

G Stable Stable
solid liquid L H (solid)

slope = Cp

T(K)
0
solid Tm
298

solid stable liquid stable

G(solid)

Tm slope = -S
Temperature

G(liquid)

G
 Driving Force for
Solidification
GL = HL -TSL
G Stable Stable ∆G = ∆H -T∆S
solid liquid GS = HS -TSS
liquid ∆H = HL - HS
!G
∆S = SL - SS
solid At equilibrium ∆G = 0
GS
∆G = ∆H -Tm∆S = 0
!T GL
∆Hf L entropy of fusion (nearly
∆Sf = =
T Tm Tm Tm a constant ≈ R)
Temperature
L
∆G ≈ L -T
Tm
for small ∆T we get L ∆T
∆G ≈ ≈ ∆Sf ∆T
Tm
undercooling
 Solidification
To get the solidification process started, the liquid
phase must be undercooled, cooled to a
temperature below the freezing point.

G Stable
solid
Stable
liquid
Once a nucleus forms, it can proceed to grow as
liquid
fast as the latent heat of solidification and specific
!G
heat can be carried away.

solid Controlled by:

GS thermal conductivities
relative masses
!T GL
shapes of the melt, the solid, and mold
T Tm
Temperature Nucleation: occurs when a small piece of solid
forms in the liquid and must attain a minimum
critical size before it is stable

Growth: occurs as atoms from the liquid are

attached to the tiny solid until no liquid remains