Chapter 8

( Solidification and Grain Size Strengthening)

Solidification:
It requires two steps
1- Nucleation
2- Growth
Nucleation:
It occurs when a small piece (particle) of solid called (embryo) with a
critical size forms from liquid.
Growth of the solid occurs when more atoms from liquid are attached to
it until no more liquid remains.
\

Solidification takes place when the free energy of the solid is less than of
the liquid at the freezing temperature.
- As the free energy difference becomes larger, the solid will be more
stable. This energy difference is Fv (volume free energy)

In order for the solid to form, an interface must be created separating

the solid from the liquid.

 A surface free energy is associated with this interface As the interface gets
larger, the greater the increase in .

The total change in free energy G Produced when the embryo forms is:
G

Where
4 3
r
3

4 3
r Fv 4r 2
3

= volume of a spherical embryo of radius r.

4r 2 = surface area of the spherical embryo.

= surface free energy

Fv

= volume free energy (which is a negative change)

The total change in the free energy depends on the size of the embryo.
If the embryo is small, further growth will cause the free energy to increase,
so it will remelt and causes the free energy to decrease.
No nucleation and no growth. So, the metal remains liquid
Since the liquid is present below the equilibrium freezing temperature, the
liquid is undercooled.
If the embryo is large (greater the critical radius), the total energy
decreases when the size of the embryo increase, nucleation has occurred
and growth of the nucleus begins.

Homogeneous Nucleation:
It occurs when the undercooling becomes large enough to cause formation
of a stable nucleus. Thats when embryo to exceed the critical size..
Estimating the Size of the Stable Nucleus:
The size of the critical radius (r*) is given by:
r*

2Tm
H f T

H f = the heat latent of fusion (it represents the heat that is given up during
the liquid-solid transformation) of the metal
T = Tm T (is the undercooling when the liquid temperature is T)
Tm = the equilibrium freezing temperature in K

Q) Calculate the size of the critical radius and the number of atoms in
the critical nucleus when solid copper forms by homogeneous nucleation.
Solution:
From the table:
T 236 0 C
Tm = (1085 + 273) = 1358 K
H f = 1628 J / cm 3

= 177 x10 -7 J / m 2
r* =

2Tm
( 2)(177 x 10-7 )(1358)
=
= 12.51x10-8 cm
H f T
(1628)(236)

The lattice parameter for FCC copper is:

a= 3.615 = 3.615 x 10-8 cm
Vunit cell = (a)3 = (3.615 x 10-8 )3 = 47.24 x 10-24 cm3

4 3 4 -8 3 -24 3
Vr* = r = (12.51x10 ) = 8200x10 cm
3 3
The number of unit cells in the critical nucleus is:
8200 x 10 -24
= 174 unit cells
47.24 x10 -24

In FCC there are 4 atoms/unit cells.

So, No. of atoms in r* = (4 atoms/cell x 174 cells/nucleus) = 696
atoms
Heterogeneous Nucleation:
It occurs on the surface of impurities in the molten metal.
Impurities provide a surface on which the solid can form.

Grain Size strengthening by Nucleation:

It occurs by adding impurities to the liquid metal.
It is called grain refinement or inoculation
Titanium or Boron added to Al liquid
- Very small particles of Al3Ti or TiB2 forms
- These particles are sites for heterogeneous nucleation
5

Grain refining produces large number of grains.

So, more grain boundaries,
Grain size strengthening occurs.

Glasses:
In certain cases of very rapid cooling, nucleation of the crystalline
solid never occurs. Instead an unstable amorphous (noncrystalline) solid
forms.

Growth:
After the formation of nuclei, growth occurs as atoms are attached
to the solid surface.
It depends on the removal of heat during solidification.
a) Specific heat of the liquid:
- It is the heat required to change the temperature of a unit weight of
the material by one degree.
- It must be removed either by radiation or conduction, until the
liquid cools to the freezing temperature.
b) Latent heat of fusion
It represents the energy that evolved as the disordered liquid
structure transforms to a more stable crystal structure.

Types of growth mechanisms:

The difference between the two types of growth mechanisms arises
because of the different sinks for the latent heat.
1) Planar Growth
It occurs by the movement of smooth solid-liquid interface into the

Liquid, where the container or mold must absorb the heat.

2) Dendritic Growth:
When nucleation is poor, the liquid undercools to a temperature below
the freezing temperature before the solids forms. The undercooled
liquid absorbs the heat.

 Under this condition, a small solid protuberance (dendrite) forms at the

interface.
Secondary and tertiary dendrite arms can also form on the primary
stalks to speed the evolution of the latent heat.
In pure metals, dendritic growth normally represents only a small
fraction of the total growth.
Dendritic.. fraction f

cT
H f

c=specific heat of the liquid, T = heat that the undercooled liquid can absorb
Hf = latent heat represents the total heat that must be given up during
solidification.

As the undercooling T increases, more dendritic growth occurs.

Q76) Calculate the fraction of growth that occurs dendritically in copper

which (a) nucleates homogeneously and (b) nucleates heterogeneously with
100C undercooling. Where latent heat of fusion for copper is
1628x10 6 J/m3, specific heat is 4.4x106 J/m3, undercooling for homogeneous
nucleation is 2360C
:Solution
(a) For homogeneous nucleation
f

cT ( 4.4 x10 6 )(236)

0.638
H f
1628 x10 6

(b) For 100 C undercooling

f

cT (4.4 x10 6 )(10)

0.027
H f
1628 x10 6