Module:3 Solidification, Diffusion and Phase
Transformation
Solidification, Diffusion and Phase
Module:3 8 hours
Transformation
Nucleation- Homogeneous and Heterogeneous Nucleation- Growth of
crystals - Planar growth – dendritic growth. Diffusion: Introduction – Fick’s
Law of Diffusion – Diffusion Mechanisms, Steady state and non-steady state
diffusion. Basics of phase diagram, Gibb’s phase rule, Lever rule, Unary
phase Diagrams, Binary Isomorphous and Eutectic Systems, Interpretation of
Phase Diagram, Iron – iron carbide phase diagram – Slow cooling of hypo
and hyper eutectoid steels, Phase transformations in steels and cast iron.
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Solidification of Metals
Solidification: It is generalized process
through which a melt change to solid state.
1. During solidification, the liquid changes in to solid.
2. The free energy of liquid is less than that of the solid above the melting point.
Hence liquid is stable above the melting point.
3. Below the melting point, the energy of liquid becomes more than that of the solid.
4. Hence below the melting point, the solid becomes more stable than the liquid.
5. Therefore at the melting point, liquid gets converted in to solid during cooling.
6. This transformation of liquid into solid below melting point is known as
solidification.
Crystallization mechanism
Crystallization is the transition from the liquid to the solid state and occurs in two
stages:
2 steps
Nuclei form
Nuclei grow to form crystals – grain structure
Start with a molten material – all liquid
nuclei crystals growing grain structure
liquid
• Crystals grow until they meet each other
Solidification mechanism
An interface is created when a solid forms from the liquid
For a material to solidify, the liquid need to cools just below its
freezing (or melting) temperature, because the energy associated
with the crystalline structure of the solid is less then the energy of
the liquid
Solidification mechanism –
Nucleation
The Nucleation and Growth Transformation may be
of two types
• 1. Homogeneous Nucleation
• 2. Heterogeneous Nucleation
Homogeneous Nucleation
➢Homogeneous nucleation occurs when there are no special objects inside a phase
which can cause nucleation
➢For instance when a pure liquid metal is cooled below its equilibrium freezing
temperature to a sufficient degree numerous homogeneous nuclei are created by slow-
moving atoms bonding together in a crystalline form.
➢Above melting point Tm, liquid free energy, Fl < Fs (Solid free energy) and free energy
change for solidification ΔF > 0. Below Tm, ΔF < 0 and nuclei of the solid phase form.
F
Homogeneous Nucleation
➢There are two contributions to free energy change, volume free energy ΔFv and surface
free energy, γ due to creation of a new surface.
➢Taking the nucleus as a spherical particle of radius r
ΔF = 4/3πr3ΔFv + 4πr2γ ------------------ (1)
➢The tiny particle of the solid that forms first will be stable only when it achieves a critical
radius (r*). Below the critical radius it is unstable and is called embryo.
Homogeneous Nucleation
r* = critical radius
= surface free energy (solid-liquid interfacial en
Tm = melting temperature
− 2Tm
r* = H = latent heat of solidification (fusion)
H T T = Tm - T = undercooling
Note: H and are weakly dependent on T
r* decreases as T increases
➢ Critical radius (r*) - The minimum size that must be formed by atoms clustering
together in the liquid before the solid particle is stable and begins to grow.
➢ Undercooling - The temperature to which the liquid metal must cool below the
equilibrium freezing temperature before nucleation occurs.
Homogeneous Nucleation
Critical nucleus size - Example
Calculate the size of the critical radius and the number of atoms in the critical nucleus
when solid copper forms by homogeneous nucleation.
Given, Freezing/melting temperature of Cu as 1085 °C, heat of fusion 1628 J/cc,
solid-liquid interfacial energy 177 x 10-7 J/cm2, under cooling for homogeneous
nucleation 236°C and lattice parameter for Cu 3.615 Å. If we increase the
undercooling by 70°C, comment on the critical radius
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Calculation of Number of unit cell for the
Solidification of Copper
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Homogeneous Nucleation
− 2Tm
r* =
H T
r* = critical radius
= surface free energy (solid-liquid interfacial energy)
Tm = melting temperature
H = latent heat of solidification (fusion)
T = Tm - T = undercooling
Solidification mechanism – Nucleation
➢ Homogeneous nucleation - Formation of a critically sized solid from
the liquid by the clustering together of a large number of atoms at a
high undercooling (without an external interface).
➢ Heterogeneous nucleation - Formation of a critically sized solid from
the liquid on an impurity surface
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Heterogeneous Nucleation
• Nucleation on preexisting surfaces is known as heterogeneous nucleation.
• A reduction in the interfacial energy would facilitate nucleation at small values of ∆T.
2
r =−
*
het
GV
−
Cos =
• This process is dependent on the contact angle () for the nucleating phase and the
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surface on which nucleation occurs
Ingot Structure
Al ingot
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Problems
Q1: Calculate the critical radius of a homogeneous nucleus that forms when pure liquid of
copper solidifies at 600oC. (Given data: M.P. of copper = 1083oC; Enthalpy change = 1826
J/cm3 ; surface energy of copper = 177 x 10-7 J/cm2 .
Q2: Calculate the size of the critical radius and the number of atoms in the critical nucleus
when solid Iron (Fe) forms by homogeneous nucleation. Given freezing temperature, heat of
fusion, solid-liquid interfacial energy and undercooling as 1438 °C, 1637 J/cm3, 196 x 10-7
J/cm2 and 250°C. Also given lattice parameter of Fe is 3.76 Å nm.
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Growth mechanisms
Solidification front - Interface between a solid and liquid.
Planar growth - The growth of a smooth solid-liquid interface during
solidification, when no undercooling of the liquid is present
Dendrite - The treelike structure of the solid that grows when an
undercooled liquid solidifies
Specific heat - The heat required to change the temperature of a unit
weight of the material one degree
Latent heat - The heat or energy that is absorbed or released during
a phase change of a substance.
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Cooling Curves
Cooling curve for a pure metal that has not
been well-inoculated.
The liquid cools as specific heat is removed
(between points A and B). Undercooling is
thus necessary (between points B and C). As
the nucleation begins (point C), latent heat of
fusion is released causing an increase in the
temperature of the liquid.
This process is known as recalescence (point
C to point D). The metal continues to solidify
at a constant temperature (Tmelting). At point
E, solidification is complete. The solid casting
continues to cool from this point.
Cooling curve for a well-inoculated, but
otherwise pure, metal.
No undercooling is needed. Recalescence is
not observed.
Solidification begins at the melting
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temperature.
Cooling Curves
Pure metal Alloy
L Soldification L Soldification
begins begins
TL
L S L+S
Tm
TS
Solidification S
S
Region of Thermal arrest complete
Solidification
complete No region of Thermal arrest for alloys
Solid Solutions
When two metals are mixed together they form an alloy if the atoms of solute are
present in the lattice of the solvent, it is known as solid solution. Therefore, an alloy is a
solid solution of two or more metals.
Primarily there are two types of solid solutions -
Substitutional – Solute atoms occupy the regular lattice sites of the parent metal
(solvent). Substitutional solid solutions can be random (Cu-Ni) or ordered (Cu-Au).
Interstitial – Solute atoms occupy the interstitial positions (Steel – C solute atoms in Fe) .
Random substitutional Ordered substitutional Interstitial
Solid solution, mixture of two crystalline solids that coexist as a
new crystalline solid, or crystal lattice. 25
Hume-Rothery Rules
Formation of substitutional solid solutions between two metals is governed by a
set of rules known as
oSize difference between the atoms of solute and the parent metal
should be less than 15%, in order to minimize the lattice strain
oThe electronegetivity difference between the metals should be
small.
oValence: The ions must have the same valence; otherwise, the
valence electron difference encourages the formation of compounds
rather than solutions.
oFor complete solubility over the entire range of compositions
the crystal structures of the solute and the solvent must be the
same.
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Hume-Rothery Rules
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