Solidification

What is solidification?
• Solidification is the process where liquid
metal transforms into solid upon cooling
• The produced by solidification,
particularly
structure the grain size and grain shape, affects to a large
extent the properties of the products
• At any temp, the thermodynamically stable state is the one
which has the lowest free energy and consequently, any other
state tends to change the stable form.
 The terms
Latent must be Super
heat known
heat
The heat that is added to The heat is further
convert all the solid into added for the metal to
liquid at the constant remain in molten state
temperature

Entropy

Is a thermodynamic property
that is the measure of a system’s
thermal energy per unit
temperature that is unavailable
for doingHuarisPerafsuadl-Awssisotarnkt Professor
• Gibbs free energy (G) of any system said to
be minimum when the same is at
equilibrium.
G = H-TS
• ‘G’ is a function of ‘H’ (enthalpy) and
‘S’ (entropy)
• Important parameter is change in
free energy ‘𝞓G’
• A transformation will occur
spontaneously only when G has a negative
value
Ice melting in
a warm room
is a common
example of
increasing
entropy
• A crystalline solid has lower internal energy
and high degree of order, or lower entropy as
compared to the liquid-phase
i.e.,
• Liquid has higher internal energy (equal to the
heat of fusion) and higher entropy due to the
more random structure
• Transformation from liquid metal to solid metal
is accompanied by a shrinkage in the volume
• This volume takes place in three
shrinkage stages:
1. Liquid – Liquid
2. Liquid – Solid
3. Solid – Solid
 Melting of Metals

Temp

Solid + Liquid
Tm
Latent Super Heat
Heat

Time, Enthalpy
 Freezing of Metals

Super Heat Solid + Liquid

Temp Latent Heat

Time
 Solidification
Melting
Free energy (G)

∆
𝐆

Free energy
curve
for solid (Gx
)
Free energy curve
∆ for liquid(Gl)
𝑻

Temp
• If we take a simple case of pure metal
transforming to solid crystal of pure metal X as:
L  X (Solid)
• A crystalline solid has the lower internal energy
and high degree of order, or low entropy as
compared to the liquid phase
i.e.,
• Liquid has higher internal energy (equal to the
heat of fusion) and higher entropy
 • With the increase of temperature, the free-energy curve of the liquid phase falls more
steeply than the solid-phase
• At Tm, the equilibrium melting point, the free energies of both the phases are equal
• Above Tm, the liquid has a lower free energy than the crystalline solid ‘X’, i.e., liquid is more
stable
The solidification reaction will not occur
under such conditions as the free energy
change, ∆ 𝑮 for the reaction is positive
Solidification At the melting temperature, where the two
curves cross, the solid and liquid phases are in
Melting
equilibrium.
Below Tm, the free energy of
Free energy (G)

crystalline
the solid X, is less than the liquid
phase.
The free energy change for the reaction is
negative
∆
𝐆

Free energy curve

for solid (Gx )

Free energy curve

∆ for liquid(Gl)
𝑻

Temp
 Undercooling (or) Supercooling
in pure
Supercooling, also known as
undercooling, is the process of lowering
the temperature of metals
a liquid or a gas below its
freezing point without it becoming a solid

• In alloys, commencement of solidification is easy since

the foreign atoms act as source of nucleation
• But pure metals experience difficulties in
commencing solidification. (there are no foreign
atoms to form nuclei)
• In such cases the metal cools below its freezing
temperature and actual solidification begins at the
same point (shown in pic in the next slide)
Undercooling (or) Supercooling
in pure
metals

Hari Prasad-Assistant Professor

 Solidification of alloys
• Solidification in alloys takes place in the same manner
but with exceptions
• They solidify over a range of temp rather than at a constant
temp
i. Begin solidification at one temp and end at
another temp (Solid solution)
ii. Begin and end solidification at a constant temp
just like in pure metals (pure eutectics)
iii. Begin solidification like a solid-solution and
end it like a eutectic
The local solidification time can be calculated using Chvorinov's rule, which is:
�
��
𝒕= 𝑩 �
�
Where t is the solidification time, V is the volume
� of the casting, A is the surface area of
the casting that contacts the mould, n is a constant, and B is the mould constant.
It is most useful in determining if a riser will solidify before the casting, because if the
riser does solidify first then it is worthless
 Solid solution

Temp b
c

Time
Solid solution
 Pure eutectic

Temp b c

Time
 Partly solution and partly eutectic

b
Temp c d

Time
Understanding solidification

Nucleation
Solidification
Growth
• The basic solidification process involves nucleation
and growth
• Nucleation involves the appearance of very small
particles, or nuclei of the new phase (often
consisting of only a few hundred atoms), which are
capable of growing.
• During the growth stage these nuclei increase in
size, which results in the disappearance of some (or
all) of the parent phase.
• The transformation reaches completion if the
growth of these new phase particles is allowed to
proceed until the equilibrium fraction is attained
 a) Nucleation of crystals,
b) crystal growth,
c) irregular grains form as
crystals grow together,
d)grain boundaries as
seen in a microscope.
 Types of Nucleation

Homogeneous Heterogeneous
Nucleation Nucleation

Nuclei form
preferentially at
Nuclei of the structural
new phase inhomogeneities,
form uniformly insoluble impurities,
throughout grain boundaries,
the parent dislocations, and so
phase on.
 Homogeneous nucleation
• Prominent is pure metals
• Nuclei of the solid phase form in the interior of
the liquid as atoms cluster together
• Each nucleus is spherical and has a radius ‘r’.
• This situation is represented schematically

4
𝑉𝑜𝑙𝑢𝑚𝑒 = 𝜋𝑟3
3
Solid

Solid-Liquid
interface 𝐴𝑟𝑒𝑎 = 4𝜋𝑟2
• There are two contributions to the total free energy
change that accompany a solidification transformation.
• The first is the free energy difference between the solid and
liquid phases, or the volume free energy 𝞓Gv and the
volume of spherical nucleus
𝟒
𝟑
𝝅 𝒓 𝟑

• The second energy contribution results from the

formation of the solid–liquid phase boundary during the
solidification transformation.
• Associated with this boundary is a surface free energy 𝜸
(positive)
∆𝑮𝒔 = 𝟒 𝝅 𝒓 𝟐 𝜸
• Latent heat released by atoms is:
𝟒
∆𝑮 𝒗 = − 𝝅 𝒓𝟑
𝟑
∆𝑮
*Negative value is taken since the temp is considered below the
equilibrium solidification temperature
• Finally, the total free energy change is
equal to the sum of these two contributions—
that ∗is: 𝟒 𝟑
∆𝐺 = ∆𝑮 𝒗 + ∆𝑮 𝒔 = − 𝝅𝟐𝒓 ∆ 𝑮 +
These volume, surface, and total free𝟑 energy contributions are
𝟒 𝝅 𝒓schematically
plotted 𝜸 as a function of nucleus radius in
Figures
• From the fig. it is clear
that as the particle radius
increases, the net free
energy ∆ G also increases
till the nucleus reaches a
critical radius ‘r*’.
• Further increase in
particle radius the free
energy decreases and even
goes to negative.
• In order for grain growth
to take place around a
particular nucleus, it
should have the
reached critical
radius
• The size of the critical radius can be estimated
∗
by differentiating ∆ 𝐺 with respect to ‘r’ and
equating by zero
� 𝟒
𝒅 𝝅 𝒓 𝟑 ∆𝑮 + 𝟒 𝝅 𝒓 𝟐 𝜸 = 𝟎
𝒅� ∆𝑮 = 𝒅 𝒓
∗
𝟑
𝒓 − −𝟒𝝅 𝒓 𝟐 ∆𝑮 + 𝟖 𝝅 𝒓 𝜸
=𝟎 𝟐𝜸
r = r* = ∆𝑮
If we substitute ∆𝑮
r/r* in 𝟏𝟔𝝅𝜸
∗
∆𝑮 ∗
𝟑 ∗𝟐
𝟑
= ∆𝑮
 Heterogeneous nucleation
• It is easier for nucleation to occur at surfaces
and interfaces than at other sites.
• Nucleation occurs with the help of impurities
or chemical inhomogeneities.
• Impurities can be insoluble like sand particles
or alloying elements
• Nuclei are formed on the surfaces of the above
possible surfaces often called the ‘substrate’
Nucleation of carbon dioxide bubbles around a finger
Two essential things must happen:
1. The substrate must be wetted by the liquid metal
2. The contact angle/wetting angle (𝜽 ) of the
cap- shaped nucleus should be less than 90o
𝛾𝑆𝐼 = 𝑆𝑜𝑙𝑖𝑑 𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑖𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 ( 𝜸 𝞫 𝞭 )
𝛾SL = Solid-liquid interfacial energy (𝜸 𝞪 𝞫 )
𝛾IL = Liquid interfacial energy (𝜸 𝞪 𝞭 )

Liquid 𝜶

𝜽 = 𝟑𝟔𝟎 𝒐

Solid 𝜷
Cap

Substrate 𝜹

𝜸 𝞪 𝞭 = 𝜸 𝞫 𝞭 + 𝜸 𝞪 𝞫 𝒄𝒐𝒔𝜽 or 𝜸𝑰𝑳 = 𝜸𝑺𝑰 + 𝜸 𝑺 𝑳 𝒄𝒐𝒔𝜽

 A typical cast metal structure

Coarse grain structure can be converted into fine grain structure by

grain refinement. This can be achieved by high cooling rates, low
pouring temp, and addition of inoculating agent
• The chill zone is named so because it occurs at the walls of
the mould where the wall chills the material.
• Here is where the nucleation phase of the solidification
process takes place.
• As more heat is removed the grains grow towards the
centre of the casting.
• These are thin, long columns that are perpendicular to the
casting surface, which are undesirable because they have
anisotropic properties.
• Finally, in the centre the equiaxed zone contains spherical,
randomly oriented crystals.
• These are desirable because they have isotropic properties.
• The creation of this zone can be promoted by using a low
pouring temperature, alloy inclusions, or inoculants
 b) Partially columnar and
a) Columnar grains c) Equiaxed grains
partially equiaxed grains