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CLL141-Introduction to materials

Principles of solidification
Hariprasad Kodamana
IIT DELHI

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 1 / 22

Solidification

solidification is considered one of the most important

manufacturing processes
Materials such as steel, aluminum alloys, copper, and zinc are
produced through solidification
Industry also uses the solidification process as a primary
processing step to produce metallic slabs or ingots (a simple,
and often large casting that is processed later into useful shapes)
The ingots or slabs are then hot and cold worked through
secondary processing steps into more useful shapes (i.e., sheets,
wires, rods, plates, etc.)
Solidification also is applied when joining metallic materials
using techniques such as welding, brazing, and soldering.

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 2 / 22

Nucleation

The term nucleation refers to the formation of the first

nano-sized crystallites from molten material. For example, as
water begins to freeze, nano-sized ice crystals, known as nuclei,
form first
In a broader sense, the term nucleation refers to the initial stage
of formation of one phase from another phase
When a vapor condenses into liquid, the nanoscale sized drops of
liquid that appear when the condensation begins are referred to
as nuclei.

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 3 / 22

Homogeneous nucleation
When a material to solidify when the liquid cools to just below
its freezing (or melting) temperature, the energy associated with
the crystalline structure of the solid is then less than the energy
of the liquid
This energy difference between the liquid and the solid is the
free energy per unit volume △Gv and is the driving force for
solidification
When the solid forms a solid-liquid interface is created, a surface
free energy γ is associated with this interface; the larger the
solid, the greater the increase in surface energy
△Gv and γ are not functions of r
An embryo is a tiny particle of solid that forms from the liquid as
atoms cluster together
The embryo is unstable, and may either grow into a stable
nucleus or redissolve back into the liquid
HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 4 / 22
Homogeneous nucleation
At the temperature where the solid and liquid phases are
predicted to be in thermodynamic equilibrium (i.e., at the
freezing temperature), the free energy of the solid phase and
that of the liquid phase are equal (△Gv = 0), so the total free
energy change (△G) will be positive
When the solid is very small, with a radius less than the critical
radius for nucleation (r ∗ ) , further growth causes the total free
energy to increase
The critical radius (r ∗ ) is the minimum size of a crystal that
must be formed by atoms clustering together in the liquid before
the solid particle is stable and begins to grow
But instead of growing, the solid has a tendency to remelt,
causing the free energy to decrease; thus, the bulk of the
material remains liquid leaving just a small crystal solid
HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 5 / 22
Homogeneous nucleation

The formation of embryos is a statistical process as many

embryos form and redissolve
If by chance an embryo forms which has a radius that is larger
than r ∗ further growth causes the total free energy to decrease
The new solid is then stable and sustainable since nucleation has
occurred, and growth of the nucleus begins
At the thermodynamic freezing temperature, the probability of
forming stable, sustainable nuclei is extremely small
Therefore, solidification does not begin at the thermodynamic
melting or freezing temperature

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 6 / 22

Homogeneous nucleation

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 7 / 22

Homogeneous nucleation
The critical free energy (△G ∗ ) refers to the change in free energy
associated with the formation of a nucleus of a new phase within a
parent phase. Equivalently, it may be considered an energy barrier to
the nucleation process.

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 8 / 22

Homogeneous nucleation
At the equilibrium solidification temperature Tm , the value of △Gv is
zero, and with diminishing temperature its value becomes increasingly
more negative.
This volume free energy change △Gv is the driving force for the
solidification transformation, and its magnitude is a function of
temperature

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 9 / 22

Homogeneous nucleation

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 10 / 22

Homogeneous nucleation

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 11 / 22

Homogeneous nucleation

As liquid cools to temperatures below the equilibrium freezing

temperature, two factors combine to favor nucleation
First, since atoms are losing their thermal energy the probability
of forming clusters to form larger embryos increases
Second, the larger volume free energy difference between the
liquid and the solid reduces the critical size r ∗ of the nucleus
The number of stable nuclei n∗ (having radii greater than r ∗ )

K1 is related to the total number of nuclei of the solid phase

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 12 / 22

Homogeneous nucleation

Another important temperature-dependent step is involved in

and also influences nucleation: the clustering of atoms by
short-range diffusion during the formation of nuclei
Diffusion effect is related to the frequency at which atoms from
the liquid attach themselves to the solid nucleus, vd

Qd is a temperature-independent parameter—the activation

energy for diffusion and K2 is a temperature-independent
constant

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 13 / 22

Homogeneous nucleation

The nucleation rate Ṅ, which has units of nuclei per unit volume
per second, is proportional to the product of n∗ and vd

K3 is the number of atoms on a nucleus surface

With a lowering of temperature from below Tm , the nucleation
rate first increases, achieves a maximum, and subsequently
diminishes.

HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 14 / 22

Homogeneous nucleation

Initially, when the temperature is high △G ∗ > Qd → nucleation rate

is suppressed at high temperatures because of a small activation
driving force. Later, temperature diminishes △G ∗ < Qd → low
atomic mobility suppresses the nucleation rate.
HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 15 / 22
Heterogeneous nucleation
Except in controlled laboratory experiments, homogeneous
nucleation almost never occurs in liquids
Instead, impurities in contact with the liquid, either suspended in
the liquid or on the walls of the container that holds the liquid,
provide a surface on which the solid can form
Now, a radius of curvature greater than the critical radius is
achieved with very little total surface between the solid and liquid
Only a few atoms must cluster together to produce a solid
particle that has the required radius of curvature
Much less undercooling is required to achieve the critical size, so
nucleation occurs more readily
Nucleation on pre-existing surfaces is known as heterogeneous
nucleation
HK (ChE & Yardi ScAI IITD ) CLL141 31-JULY-2024 16 / 22
Heterogeneous nucleation -
Gas-Liquid-Solid