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Solidification Processing: Lecture 10: Thermodynamics 3

1) Thermodynamic driving force is the difference in Gibbs free energy between the solid and liquid phases, and drives solidification. It depends on the temperature difference from the melting point. 2) Increasing pressure raises the melting point slightly for most metals. It can also cause grain refinement during solidification under high pressure. 3) Curvature effects, such as for spheres and cylinders, introduce a pressure difference term related to the curvature radius and interface energies. This affects the driving force for solidification.

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10 views

Solidification Processing: Lecture 10: Thermodynamics 3

1) Thermodynamic driving force is the difference in Gibbs free energy between the solid and liquid phases, and drives solidification. It depends on the temperature difference from the melting point. 2) Increasing pressure raises the melting point slightly for most metals. It can also cause grain refinement during solidification under high pressure. 3) Curvature effects, such as for spheres and cylinders, introduce a pressure difference term related to the curvature radius and interface energies. This affects the driving force for solidification.

Uploaded by

Anonymous T02GVGzB
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Solidification Processing

Lecture 10: Thermodynamics 3


Thermodynamic driving force
Solidification
Thermodynamic driving force
S S S
TS H G =
L L L
TS H G =
S T H
S S T H H
G G G
L S L S
L S
A A =
=
= A
) ( ) (
Thermodynamic driving force
When T is not far away from T
m
m
H H A = A
m
S S A = A
m m m
T H S / A = A
m
m
T
T H
G
A A
= A
When T is far away from T
m
|
.
|

\
|
A A +
A A
= A
T
T
T T C
T
T H
G
m
p
m
m
ln
Effect of pressure on solidification
More general free energy
TS PV U F + =
When pressure changes
T S P V F
L L L
A A = A
T S P V F
S S S
A A = A
Effect of pressure on solidification
At new melting point
S L
G G A = A
( ) ( ) T S S P V V
L S L S
A = A
m
m
m
H
V T
S
V
P
T
A
A
=
A
A
=
A
A
Effect of pressure on solidification
Antimony, Bismuth Most metals
~0.01 K/atm.
Bubble burst
High pressure ->grain refine
Effect of pressure on solidification
Effect of curvature on solidification
Pressure difference
ko o 2
1 1
2 1
=
|
|
.
|

\
|
+ =
r r
P P
L S
Sphere k=1
Cylinder k=1/2
Effect of curvature on solidification
T S P V F
L L L L
A A = A
T S P V F
S S S S
A A = A
T S V T S
S S L
A = A ko 2
k
ko ko
d
H
V T
S
V
T
m
S m S
=
A

=
A

= A
2 2
Capillary length
SL4
T T
m
Magnetic contribution to thermodynamics
Fe, Ni, Co and their alloys
Curie temperature = The temperature
above which a ferromagnetic material
loses its permanent magnetism
Neel temperature = The temperature at
which an antiferromagnetic material
becomes paramagnetic
Magnetic contribution to entropy
( ) t h B RT H
mag
) 1 ln(
0
+ =
Magnetic contribution to enthalpy
Magnetic contribution to Cp
Magnetic contribution to Gibbs energy
Heat capacity of Co and Ni
About the thermodynamics
To predict if the reaction happens
To estimate new processing method

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