1

Mid-term exam -1 : %20

Mid-term exam -2 : %20
Final exam : %60
%100


SOLIDIFICATION
Prof. Dr. . Aydn ATASOY
Department of Metallurgical and
Materials Engineering
Technical University of stanbul

2



141p
THERMODYNAMIC EQUILIBRIUM
The Sum of a) mechanical, b) chemical and c) thermal equilibrium
Net forces on the ball are zero
(Constant pressure)
A ball at the bottom
of the valley -
minimum
potential energy
position
Mechanical equilibrium
Si Ge
T ~ 1000 C
Chemical Equilibrium
C
Si
C
Ge
t = 0
t =
x
x
t =
t = 0
Potential energy for a given
atom in the system is the same
everywhere and will remain
fixed in time. (Constant
chemical composition)
Thermal equilibrium
+
=
Hotter (T )
Colder (T )
1
2
Isothermal (T)
T > T > T
1 2
Temperature is
the same
everywhere
in the system
(Constant temperature)
t = 0
t =
0
0
0 < t <<
0 << t <
0 << t <
0 < t <<
Complete dissolution


3


141r
GIBBS FREE ENERGY
For reactions at constant temperature and pressure
the relative stability of a system is determined by its Gibbs free energy:
H : enthalpy (heat content) of the system
T : absolute temperature (Kelvin)
E : internal energy of the system (kinetic energy from atomic vibrations +
potential energy from bonds between the atoms)
p : pressure
v : volume
S : entropy (measure of the randomness of the system; degree of disorder)
T S : mixing energy
p v : For condensed systems (i.e. solids and liquids) p v is relatively small
T = constant
p = constant
S T H G =
v p E H + =
S T E G ~ E H~


Liquid - Solid Phase Transformation 141-0
Liquid Solid For T = T , G = G
T
L s
,
G
T
G G
L
Temperature
G = G G
L s
A
G = E T AS A
= 0
A
T< T For
AG =
AE AT
T
Undercooling
AT= (T T) > 0
AE < 0 AG < 0
Solidification Nucleation + Growth
v
v
v v
m
m
m
v
m
AS =
AE
T
m
v
v
v v
v
s m
T
AT

AT = T T
T
T
Solid grains
Time
T
e
m
p
e
r
a
t
u
r
e
0
141-1
Cooling Curve and Nucleation
m n
m
n
Liquid
Liquid + First nuclei
n


4

141b
r
A Spherical solid particle called embryo forms homogeneously
from the liquid
Liquid atoms
Embryo/liquid interfacial
area :
A= 4t r
2
Volume of a spherical
embryo of radius r :
3
4t r
3
V=

DEFINITION OF THE VOLUME FREE ENERGY CHANGE
Solid (s)
Liquid()
: volume of liquid phase : volume of solid phase
Free energy of the system : Free energy of the system:
Total free energy change of the system after the solidification of a solid phase
Volume free
energy change =
free energy change
per unit volume
: free energy per unit
volume of liquid phase
: free energy per unit
volume of solid phase
141aa
: Solid-liquid interfacial area
: Solid-liquid interfacial free energy
Liquid ()
G
v

G
s
v
) v v (
s

v
s
o + + =

s s
s
v s v s 2
A G v G v v G ) (
G v A G v G ) v v ( G G G
v s s
s
v s v s 1 2

o + + = = A
A
s
o
s
G G G
v
s
v v

= A
o + A = o + =

s s v s s s v
s
v s
A G v A ) G G ( v
) v (

G v G
v 1

=
T
n
1 2

Homogeneous NUCLEATION in Liquids 141
Liquid Solid For T =T AG = AE T AS
v
= 0
r* = critical size For T< T AG =(AE AT
n
) / T
undercooling
AG
AG
r*
r (radius of particle)
(4/3)t rAG
V
4t ro
s
surface
free energy
change
volume free energy change
Total free energy change
a < r < r* embryo
r > r* stable nucleus (cAG
T
/ cr) = 0
0
For r = r*
T
m
m
m
*
m v
v v
v
T T T
n m n
= A
: Latent heat of solidification 0 L E
m v
< ~ A
(AG
T
)
o t + A t = A
s
2
v
3
T
r 4 G r ) 3 / 4 ( G
T E
T 2
r
n v
m s *
A A
o
=

T E 3
) T 16 (
G
2
n
2
v
2
m
3
s
*
A A
o t
=
A

a
0


5

141 aaa
of radius r*
Stable embryo( nucleus)
of radius (r* + A r)
1 atom
from the liquid
]
[
] [
+
AG < 0
T
Unstable embryo
+
[ ]
141a
The number of critical nuclei per unit volume of liquid , n*,
at any temperature is given by
n* = N exp(
AG*
k T
)
N : the number of atoms per unit volume of liquid
(The number of sites available for nuclei formation in the liquid)
L
L
Two-dimensional representation of an
instantaneous picture of the liquid
structure. Many close-packed
crystal-like embryos(coloured) are
present
B


6

141e
Homogeneous Nucleation Rate in Liquids
N

=
N v
L
exp(
A
AG*
k T
G
D
k T
) exp( )
N
L
: Number of available nucleation sites ( here; each atom)
in the unit volume of the liquid.(The number of atoms per
unit volume of the liquid.)
v : Thermal vibration frequency of the atoms in the liquid
AG
D
: Activation free energy for the diffusion of atoms in the
liquid
The addition of one more atom to each of the critical-sized embryos
will convert them into stable nuclei :

hom.
hom.
B B
0 K
T
m
n*
N

n*
N

T
T
4 3
2
1
T
T
T
AT
T : For small undercoolings AG* is large
but the rate of diffusion is rapid
and hence number of critical nuclei (n*)
is small. (Large grains)
1
T
3
:
For large undercoolings A G* is small
but the rate of diffusion is very slow
and hence the nucleation rate is again
low.
T
4
: At intermediate undercoolings, diffusion
rate is fairly rapid and AG* is not too large
and there is a maximum in the nucleation
rate. (Small grains)
T :
2
For very large undercoolings,
the diffusion rate and A G* are
extremely small and hence no embryo
can reach the crystal unit cell size (r*< a )
(Amorphous solid)
141d
0

7


8

100 m
Hyper-eutectic Al-wt%15Si alloy
Primary dendrites of oAl
Primary dendrites of Si
Fine eutectic
microstructure
grows on
primary
dendrites of o Al

9


10



11

HETEROGENEOUS NUCLEATION IN LIQUIDS
Nucleation rather occurs heterogeneously on the walls of the container or foreign particles (substrate)
acting as a site for nucleation in the melt during solidification. In commercial practice heterogeneous
nucleation is often enhanced by the addition of inoculants ( VC , TiC , TiB , AlB , ZrC , NbC , W C
powders ) to the melt in order to refine the final grain size.
2 2 2
u
Liquid
Substrate
Crystal embryo
Liquid
Crystal
embryo
o
o
LC
LS
A
CS
A
LC
h
Substrate r
o
CS
u
The shape of the crystal
embryo is a spherical cap
Volume =
t
3
r ( 2 3 Cos u + Cos u )
3 3
A = 2 t r (1 Cos u)
LC
2
A = t r (1 Cos )
CS
2 2
u
u : wetting angle
Interfacial tensions balance in the plane of the substrate:
LS
o = o + o Cos u
CS
LC
Cos u =
o
LC
LS
o
CS
o
141 i
Heterogeneous nucleation in liquids ...
141j
If o < o
CS
LS
, then the crystal embryo precipitates on
the substrate, because the average surface
energy of the crystal embryo decreases.
AG = 2tr (1 Cos u)
2
T
o
LC
o
t
3
r (2 3 Cos u + Cos u) AG +
3
3
v
t r (1 Cos u)(
2
2
o
CS
o )
LS
For
c(AG )
T
cr
= 0
r* =
2o
LC
AG
v
het.
AG* =
het.
4t
3
LC
( 2 3Cosu + Cos u)
3
3AG
v
2
AG* < AG*
het. hom.
(o
CS
o ) < 0
LS

12

141m
= N v exp( ) exp( )
Heterogeneous Nucleation Rate in Liquids
het.
s

D
D
AG*
k T
AG
k T

N : Number of sites available for heterogeneous nuclei

formation per unit volume of the liquid
s
v : Thermal vibration frequency of the atoms in the liquid
AG : Activation free energy for the diffusion of atoms in the
liquid
N
het.
B
B
u
u
u =0
r~

(excellent wetting)
AG* = 0
0<u<180
(partial wetting)
AG* < AG*
het. hom.
u = 180
(no wetting)
AG* = AG*
het.
hom.
141k
0
N

A T
het.
hom.


13

T
Water
V
Water Water
M
e
t
a
l
l
i
c

s
u
b
s
t
r
a
t
e
(
c
h
i
l
l
)
a
b
H
e
a
t
e
r
C
o
o
l
e
r
H
e
a
t

i
n
s
u
l
a
t
o
r
z
T
I
T
E
V
T A
0 (t) V > = f
T
q
Liquid
Liquid
0
0

T
ss
T
fs
W
a
t
e
r
G

~
G

C C
E 1
=
) t ( T
I
f =
0

0 (t)
T
G
q
> =
(
(

c
c
~

0 . onst C G
z
T
G
0 z
q
> = =
(
(

c
c
~
=

0 C > = ~ . onst V V
pot
. Const T
I
=
V
pot
V
con
T
ft
T
ct
) t ( V f =
Liquid
cru.
V
cru
Basic Techniques of Directional Solidification
Bridgman technique Directional casting technique

: System coordinates
: Coordinate system moving with the solid-liquid interface y x
V : Rate of interface movement
T
q : Temperature imposed by the temperature gradient (G) arising from
the heat flow occurring in the casting.


14





15





b
T T
k k
A < A
- -
T T
k k
A >> A
-
5nm
2 ) T k ( /
I B
= 10 ) T k ( /
I B
~ 12 ) T k /( L
I B f
=

16


141
At equilibrium the free energy reaches an absolute minimum
and the entropy reaches the maximumvalue that the system can exhibit.
Free energy change for the reaction:
T= constant
G
l
E
G
s
E
S S
AG = G G =
s l
AE = E E =
AS = S S =
All spontaneous reactions occur when the system can lower its free energy
l s
Free energy change
Activation energy
Entropy change
In an isolated system:
For condensed systems (i.e. solids and liquids) Av is relatively small
H H AH = H H
=
Entalpy change
E v p E H A ~ A + A = A
l
l
l
s
s
s
s
s
s
l
l
l
0 S T E S T H
G G
G
s
< A A ~ A A = = A
l

141t
REACTION RATE (How fast does a reaction occur?)
1 2 3
An atom is vibrating about the position 1
To lower the free energy the atom
must move into position 3 (free energy
change : AG)
But it must first overcome the energy
barrier which is called as
activation free energy barrier
Activation free energy to overcome the energy barrier can be supplied to
the atom as thermal energy in the form of atomic vibrations.
G
a
A
G
a
A
Arrangement of atoms
a
2
3
Stable
solid
Unstable
G
s
G
l
G
*
G
i
b
b
s

f
r
e
e

e
n
e
r
g
y
1
0 )
G G
(
G
*
a
> =
A
l
AT > 0
0
G G
G
s
< = A
l
T T
I
=
AG
Meta-
stable
Liquid Solid
G
0

17



141u
Statistical Thermodynamics
Probability that atom has sufficient thermal energy to overcome
the barrier of AG :
R = molar gas constant = 8.314 J/(mol K) = 1.98 cal/(mol K)
k = Boltzmanns constant =
N = number of Avogadro
A
Here, the particle is an atom!
Joule 10 6 . 1 eV 1
18
=

) K particle /( J 10 38 . 1 N / R
23
A
=

) K particle /( cal 10 3 . 3
24
=

mol / particles 10 02 . 6
23
=
|
|
.
|

\
|
=
A
T k
I B
G
a
exp P
a
141
v : vibration frequency of an atomin a system (number of
attempts per unit time to overcome the energy barrier;
typically
The rate at which the atoms overcome the barrier (number of
successful jumps per unit time):
s 10
1 13
|
|
.
|

\
|
A
v =

T k
r
I B
a
) hkl ( ) s (
G
exp
f
l
|
|
.
|

\
|
A +
A

v =

T k
r
I B
a
) hkl ( ) (s
G
G
exp
f
l
v
v v
= ~
s
f
) hkl (
: Crystallographic factor; the ratio of the number of
growth sites occupied by the liquid atoms to the number
of sites available in the solid at interface.

18




(
(

|
|
.
|

\
|
A

|
|
.
|

\
|
A
v = =

T k T k
r r
I B I B
a
) hkl ( s
G
exp 1
G
exp a ) ( a V
f
l s l
a
D
T k
G
exp
2
I
I B
a
I
=
|
|
.
|

\
|
A
v =
v
(
(

|
|
.
|

\
|
A
~
(
(

|
|
.
|

\
|
A
=
T k T k
I B
D
I B
I
) hkl (
G
exp 1
V
G
exp 1
a
D
V
f
a
D f
a
D
a
D
V
0
I ) hkl (
0
I I
D
~ ~ =
Continuous growth

19


20



21


22


23


24




1.5
T k N
G
A B s
C

A
f
) hkl (
5 = o
3 = o
2 = o
5 . 1 = o
1 = o
a
0
2
1
0.5
0.5
10 = o
0.2 0 0.4 0.6 0.8 1.0
0
o = 10
o = 5
o = 3
o = 1
b
f
) hkl (
)
T k N
( /
G
A B s C

A

25





26



27

a-4
7

a1
b
c
kiz dzlemleri
219 141
) 0 1 10 (
) 0001 (
{
1
1
1
}
{
1
1
1
}
{
1
1
1
}
<
1
1
2
>
219
141
a2
r 4
c
t r 2
c
r
c

r 19
c
(0001)
c
(0001)

a1
b
c
kiz dzlemleri
219 141
) 0 1 10 (
) 0001 (
{
1
1
1
}
{
1
1
1
}
{
1
1
1
}
<
1
1
2
>
219
141
a2
r 4
c
t r 2
c
r
c

r 19
c
(0001)
1
a-1
b
b
r
C
y
0
V
b-1 b-2
1
2
3
4
5
6
a-2
a-3
.
b
.
b
141
141
219
219
(
1
1
1
)
kiz dzlemleri
B
A
| |A 2 1 1 | |A 1 2 1
| |A 1 1 2
| | B 2 11
(
1
1
1
)
A
(
1
1
1
)
B
B
) 111 (
| | 2 1 1
| | 1 2 1
| | 1 1 2
| | 2 11
| | 1 2 1
| | 11 2
Twin planes
Repeatable growth defects in faceted crystals : Screw dislocation with a spiral ramp,
twinning with re-entrant corner, and twist boundary with steps. Depending upon
the type of defect present, the faceted crystal can exhibit various morphologies:
needles in the case of screw dislocations, or plates in the case of twinnings (Si in Al-Si)
or twist boundaries (graphite in cast iron).

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