Solidification

Solidification

 Solidification of pure metals also known as crystallization is the

transformation from liquid state to solid state.

 In molten metal, atoms will be in constant motion due to their high

kinetic energy owing to high temperature.

 As the temperature of molten metal decreases sufficiently, the atomic

movement also decreases.

 The properties of the material depends upon the nature of the

solidification process (microstructure).
Heating/Cooling curve

 A heating/cooling curve shows how the temperature of a substance

changes as heat is liberated at a constant rate.

 Temperature remains constant during phase transformation in a pure

metal.

 Phase transformation in alloys happens at a range of temperature.

Cooling curve

Sensible heat

Latent heat

Sensible heat

Pure metal Alloy

Nucleation and grain
growth
 As temperature of molten metal decrease atoms group together in
positions corresponding to space lattice and are known as embryos.

 Embryos co-exist with molten metal and develop into nuclei.

 The progress of solidification may be broken down into two distinct stages:
o Nucleation
When the liquid metal is cooled solidification occurs by formation
of numerous small particles of the new phase.
o Growth
The increase in particle size until the transformation complete.
 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 the parent liquid phase.
Driving force for nucleation
 A transformation from liquid to solid will occur spontaneously only
when a change in free energy (G) has a negative value

G G= H-TS
G (T)
r
G = GS - GL

gL gS
Each nucleus is assumed as
T Tm spherical in geometry and
has a radius r
Undercoolin
g

Sensible heat

Latent heat Undercooling

Sensible heat
 Undercoolin
gDuring the cooling of a
liquid, an appreciable
nucleation rate (i.e.,
solidification) will begin
only after the
temperature has been
lowered to below the Undercooling
melting temperature.

 This phenomenon is
termed supercooling (or
undercooling),
Types of nucleation

 Homogeneous nucleation
o Occurs uniformly through out the liquid at sufficiently low
temperature

o Requires undercooling

 Heterogeneous nucleation
o Nucleation facilitated by the presence of impurity atoms,
imperfection or grain boundary.

o Lower level of undercooling only required.

Homogeneous nucleation

 For a solid to nucleate from liquid, it needs to create an interface

 Total free energy change (G) is contributed by two factors

First:

 Free energy difference between the solid and liquid phases, or the
volume free energy
4 3
 The volume free energy =  r (G ) v
3 Free energy change per unit volume

 The value will be negative if the temperature is below the equilibrium

solidification temperature.
Second:

 Free 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, which is

positive (must be supplied).

 The surface free energy = 4  r 

2
𝛾- Surface energy per unit area

4 3
G   r (G ) v + 4  r 
2

3
 4𝜋𝑟 2 𝛾
 r* is called critical radius
Solid particles of radius r < r*
cannot grow as it will lead to an
𝜟𝑮*
increase in the free energy of the
system! (embryos).
Free energy, ∆G

Δ𝐺

r
r*  When r > r* nuclei will grow
Δ𝐺* is called activation-free
energy, which is the free
 r Gv 
4 3 energy required for the
3
formation of a stable
4 3
G   r (G ) v + 4  r 
2
nucleus.
3
 4 3
G   r (G ) v + 4  r 
2
4𝜋𝑟 2 𝛾
3

Differentiate the equation with

Δ𝐺* respect to ‘r’ and the resulting
Δ𝐺 expression is set to zero to obtain
Free energy, ∆G

Embryo Nuclei
r the maximum value
r*

 r Gv  2 16   3
4 3
3
r*   G* 
Gv 3 (Gv ) 2
 Volume-free energy is a <

function of temperature

where ∆Hf is the latent heat of fusion

∆Gv = 0, at T= Tm
Substitute this expression of (Δ𝐺)𝑣 into the previous

 2  Tm  1  16   3  1 
r*      G*  
 
2 
 Tm
2

 H  T  T 3 (H f )  Tm  T  
2
 f  m 
 Critical radius and activation free energy decrease as temperature T
decreases.
 The number of stable nuclei n* (having radii
greater than r*) as a function of temperature
is given by Maxwell-Boltzmann statistics

n* = Number of nuclei having critical size per unit

volume
K1= Total number of nuclei per unit volume

As T decreases, the number of nuclei having critical size (n*) increases

 Clustering of atoms takes place by short-range
diffusion during the formation of nuclei

 Diffusion effects the frequency at which atoms

from the liquid attach themselves (vd) to the
solid nucleus

Qd Is the activation energy for diffusion (temperature

independent)
K2 temperature-independent constant
The frequency at which atoms attach themselves decreases as temperature
decreases
 Nucleation rate, N
(nuclei per unit volume per second)

K3 is the number of atoms on a nucleus surface

 Hence with a lowering of temperature from below

Tm, the nucleation rate first increases, achieves a
maximum, and subsequently diminishes

 For the upper region of the curve, a sudden and dramatic increase with decreasing T
 At much lower temperatures, a low atomic mobility suppresses the nucleation rate
Heterogeneous nucleation
 The formation of nuclei within its own melt with the help of foreign
substances or substrates is known as heterogeneous nucleation.

 Inclusions of foreign particles in the liquid and walls of the container

holding the liquid provide preferred nucleation sites.

 Activation-free energy (energy barrier) for nucleation is lowered when

nuclei form on the preexisting surfaces, which in turn increases
nucleation

 The probability of nucleation occurring at certain preferred sites will

be much greater than at other sites.
 Consider the nucleation, on a flat surface, of a solid particle from a liquid
phase

 At first both liquid and solid phases wet the surface

 Three interfacial energies (represented as surface tension vectors) exist

at phase boundaries, 𝜸𝑰𝑳 , 𝜸𝑺𝑰 , 𝜸𝑺𝑳
 Taking a surface tension force balance

γ𝐼𝐿 = γ𝑆𝐼 + γ𝑆𝐿 cos 𝜃

 The total free energy is contributed by free energies associated with the
formation of all these surface and volume free energy
The critical radius r* and activation free energy (Δ𝐺*) can be obtained are:

2 ∗ 16𝜋𝛾 3 2−3cos𝜃 + cos3𝜃

r*   Δ𝐺 =
Gv 3(Δ𝐺𝑣 )2 4

Δ𝐺𝐻𝑒𝑡 * = Δ𝐺𝐻𝑜𝑚𝑜 * 𝑓 𝜃 0 < 𝑓 𝜃 <1

 Activation energy barrier for
Perfect wetting
heterogeneous nucleation is smaller than  = 0°
the homogeneous barrier by an amount
corresponding to 𝑓 𝜃
  90°
Δ𝐺𝐻𝑒𝑡 * = Δ𝐺𝐻𝑜𝑚𝑜 * 𝑓 𝜃

Case 1: only point contact, θ = 180°

 > 90°
f(θ) = 1, Δ𝐺𝐻𝑒𝑡 * = Δ𝐺𝐻𝑜𝑚𝑜 *,
Foreign particles do not play any role
 = 180° No wetting
Case 2: completely wets, θ = 0°
f(θ) = 0, Δ𝐺𝐻𝑒𝑡 * = 0, no barrier for nucleation (no undercooling)

In all other angles Δ𝐺𝐻𝑒𝑡 * < Δ𝐺𝐻𝑜𝑚𝑜 *

Small value of contact angle promote heterogeneous nucleation
• The surface energy of a pure metal liquid, g, is 600 dynes/cm2; the
volume of an atom of this metal in the liquid is 2.7 3 10225 cm3; and
the free-energy difference between an atom in the vapor and liquid,
Δgvl, is 22.37 J. Under these conditions, what would be the critical
radius of a droplet, r* , in nm and the free energy of the droplet, ΔGr*,
in J.
 Criteria for selecting nucleation agent:
Similar crystal structure and nearly equal lattice parameters, low
interfacial energy (γ𝑆𝐼 ) and hence low contact angle (θ), increases
nucleation rate
Eg: AgI is used to increase the nucleation rate of ice crystals (atomic planes that
match those of the ice crystal) and subsequently melt to form raindrops

Nucleation rate versus

temperature for both
homogeneous and
heterogeneous
Schematic free energy- versus-embryo/nucleus radius plot nucleation
Grain growth
 The growth in a phase transformation begins once an embryo has
exceeded the critical size, and becomes a stable nucleus
 Particle growth occurs by long-range
atomic diffusion

= Growth rate

Q is the activation energy, and C is the

preexponential constant which is
independent of temperature
 Transformations near to Tm :

low nucleation and high growth

rates >>
large phase particles (coarse
grains)

 Transformations at lower
temperatures (near to maximum
transformation rate):

High nucleation and low growth

rates >>
small particles (fine grains)
Grain structure

(a) Nucleation:
It begins at foreign particles.
(b) Crystal Growth:
Crystal begins to grow from
each nucleus
(c) Grain Formation:
Interface Develops
(d) Polycrystalline Structure:
Grain Growth is limited by
another grain, creating
boundary between them.
Phase
Diagrams
Phase
 A phase may be defined as a homogeneous portion of a system/matter
that has uniform physical and chemical characteristics.

 Characteristics:
o It has the same structure (atomic arrangement) and roughly the
same composition and properties throughout.

o There exists a definite interface between it and its surroundings or

adjoining phases.

 The conversion of one phase to another by either heating/cooling is

known as phase transformation.
Liquid mixture of sugar and water Liquid mixture of oil and water
(Single phase) (Two phase)
Component

 A chemical constituent (element, ion or compound) of a system that

may be used to specify its composition.

 A system having one component is called a unary system.

 Systems having two or three components are called binary or ternary

systems.

 Eg. In steel, the components are Fe and C

Equilibrium
 A state of Balance
 A system is in equilibrium if its free energy is at a minimum under some
specified combination of temperature, pressure and composition.
 In a macroscopic sense, this means that the characteristics of the system
do not change with time but persist indefinitely

Phase Equilibrium:
 Refers to equilibrium as it applies to a system in which more than one
phase may exist.

Metastable: A state of equilibrium is never completely achieved.

Gibbs phase rule
 The Gibbs phase rule establishes the relationship between the number
of components (C), the number of phases (P), and the number of
degrees of freedom (F) in a system.

 The degrees of freedom refer to the independent variables like

temperature, pressure or concentration, which can be changed without
affecting other variables.

 Ignoring pressure, the phase rule can be mathematically expressed as:

P+F=C+1
Phase diagrams

 A diagram or map that give the relationships between phases in

equilibrium in a system as a function of any two among temperature,
pressure, and composition.

 These diagrams are also know as equilibrium diagrams or constitutional

diagrams.

 The phase diagram shows the phases that exist in equilibrium

corresponding to any combination of temperature and composition of
an alloy.
One component/unary phase diagram
 Phase diagram containing only one component
 . Composition is held constant. Pressure and temperature are the variables
 Sometimes also called a pressure-temperature (or P–T) diagram

Pressure–temperature phase diagram for H2O

Binary phase diagram

 When pressure is held constant with temperature and composition as

variables, it leads to a binary phase diagram with two components.
 The two components can be pure elements or compounds.
 The most commonly used phase diagram
 If an alloy contains more than two components, a binary phase diagram
between the two major components is useful for interpreting the phase
relationships of the alloy.
 Binary phase diagrams are helpful in predicting phase transformations
and the resulting microstructures.
Construction of binary phase diagram

Weight % of B

Series of cooling curves for different alloys Phase diagram

Cooling curve

Sensible heat

Latent heat

Sensible heat

Pure metal Alloy

Isomorphous system
 When two components are mixed,
they could be completely soluble
in the liquid as well as solid state.

 Such a binary system is called an

isomorphous system. Eg: Cu-Ni
phase diagram

 For metallic alloys, solid solutions

are commonly designated by
lowercase Greek letters (𝛼, 𝛽, 𝛾,
etc.)
  Three different phase regions exist
L (L, ⍺, L + ⍺)

 Each region is separated by phase

boundaries

 Corresponding to a Temperature
⍺ and composition point, the phases
present can be identified, and the
composition of different phases
(single or two phases) can also be
determined.
 Determination of Phase Compositions(concentrations of the components)
in two phase region:

 Tie-lines are drawn horizontally

and intercepts on the solidus and
liquidus are noted

 Perpendiculars are drawn from

these intersections to the
horizontal composition axis, from
which the composition of each of
the respective phases is read.
 To compute the relative amount of phases (as fractions or as
percentages), the lever rule is applied.

oThe tie line is constructed across the two-phase region at the

temperature of the alloy.
oThe overall alloy composition is located on the tie line.
oThe fraction of one phase is computed by taking the length of the tie
line from the overall alloy composition to the phase boundary for the
other phase and dividing by the total tie line length.
lever rule
L α

R S
 Exercise:
Calculate the amount of  phase and
L phase present in a Cu - 40% Ni alloy
at 1250 oC

Ans:
 (62%), L (38%)
Specification of composition
 Two most common ways to specify composition are weight percent and atom percent

m1 m1 = mass of component 1
o weight percent C1  x 100
m1 + m2 m2 = mass of component 2

nm1 nm1 = number of moles of component 1

o Atom percent C 
'
x 100
nm1 + nm 2
1
nm2 = number of moles of component 2

m1'
nm1 
A1
Development of microstructure
 Equilibrium Cooling:

o Condition in which the

cooling occurs very slowly.

o Phase equilibrium is
continuously maintained.
 Nonequilibrium Cooling:

o Rapid cooling rate.

o No time for compositional
readjustments and maintenance
of equilibrium.
o Present in all practical
solidification situations.

oThe degree of displacement of the

nonequilibrium solidus curve
from the equilibrium one depends
on the rate of cooling.
o Slower the cooling rate, the
smaller this displacement

o Nonequilibrium Cooling
results in a structural
inhomogeneity called coring

o The center of the grain

becomes rich in higher
melting point component.

o Grains formed will have a

concentration gradient.
Cored structure
Eg: Cu-Ni
Slow rate of cooling High rate of cooling

First  to solidify has C = 46 wt% Ni.

Last  to solidify has C < 35 wt% Ni.
Uniform C:
35 wt% Ni First  to solidify:
46 wt% Ni
Last  to solidify:
< 35 wt% Ni

Equilibrium structure Cored structure