PRINCIPLES OF

SOLIDIFICATION
 OVERVIEW:
 Solidification in Metal Alloys.
o Nucleation.
o Nuclei growth mechanisms.
o Solidification defects.
 Concept of Diffusion:
o Self diffusion.
o Vacancy diffusion.
o Substitutional diffusion.
o Factors influencing diffusion in materials.
o Diffusion coefficient.
 OVERVIEW:
 The solidification of metals and their
alloys is an important industrial process.
 Not only do structural alloys start with
the casting of ingots for processing into
reinforcing bars or structural shapes, but
when a metal is welded a small portion of
the metal near the weld melts and
resolidifies.
 It also serves as a model to represent
first order phase transformations in
general.
 SOLIDIFICATION
 What is Solidification?
 Nucleation:
o Homogeneous Nucleation.
o Heterogeneous Nucleation.
o Nuclei growth mechanisms.
o Solidification defects.
 Transformation Kinetics:
o Self diffusion.
 SOLIDIFICATION
 What is Solidification?
o Refers to a phase
change of matter that
results in the
production of a solid.
o This generally occurs
when the temp of a
liquid substance is
lowered below its
freezing point.
 Solidification controls the
microstructure of the
component/material.
 SOLIDIFICATION
 Metals exists as
‘aggregates’ of atoms or
molecules; found in more
of three basic states:
 Solid.
 Liquid
 Vapour (Gas).
 Normally, when a material
solidifies, multiple crystals
begin to grow (form) in the
liquid; ‘Nucleation’.
 That leads to a
‘polycrystalline’ (many
crystals) solid forming.
NUCLEATION DURING
SOLIDIFICATION
 NUCLEATION DURING
SOLIDIFICATION
 Stages during
the solidification
in metals.
 NUCLEATION DURING
SOLIDIFICATION:
 Phase transformation –
normally occurs at high temp
(ΔG* - thermally activated).
 If ‘embryo’ forms randomly
within lattice – homogeneous
nucleation (no preferred
position/direction).
 System must have ‘driving
 Nucleation: Main mechanism of ‘Phase force’ – provided by the ‘free
Transformation’ – invariably accompanied by energy change of
large-scale atom rearrangement. transformation’ (ΔG).
 Phase transformation – cannot occur if ‘system’  Nuclei formed randomly –
cannot decrease its free energy in the process. arranged differently within
the lattice  ‘retarding
 System has to temporarily increase its energy
forces’ from interfaces
(ΔG*) before gaining ‘ΔG’ in solidifying from
(surface energy - γs).
liquid to solid.
 NUCLEATION: DRIVING AND
RETARDING FORCES:
 The total energy change for
solidification must incorporate the net
driving force of formation and the
energy required to overcome the
retarding forces.
4
 Thus: Δ𝐺 = Δ𝐺𝑓 π𝑟 3 + γ𝑠 π𝑟 2
3
 Solidification cannot occur at T = Tm.
Significant “undercooling”
(supercooling) must be attained first
=> significant ‘ΔT’.
 Critical nucleus radius, r*, must be
achieved to form a stable embryo or
crystal.
TYPES OF NUCLEATION:

 Nucleation can either be

‘homogeneous’ or ‘heterogeneous’.
 Homogeneous Nucleation: New
phase or ‘crystal embryo’ forms
spontaneously (randomly) within the
undercooled matrix.
 Heterogeneous Nucleation: The new
phase forms ‘selectively on specific
locations’ of the undercooled matrix
(e.g. on the walls of the container).
 CONTROLLED NUCLEATION:
 Sometimes, for grain refinement
purposes, nucleating particles are
deliberately added  act as
heterogeneous nucleation sites.
 Referred to as Inoculation or grain
refinement or grain engineering.
 Similarly, precipitation of a
second-phase in a metallic alloy
can lead to similar strengthening
effects (dispersion strengthening
or second-phase strengthening).
 The ultra-fine precipitates formed
leads to dislocation pile-up =>
strengthening.
CRITICAL STAGES IN
STEEL PRODUCTION –
VIDEO:
 DIFFUSION CONCEPT:
 Thermodynamically – any inhomogeneous
single phase system  becomes
homogeneous => equilibrium.
 In-fact, many reactions & processes in the
treatment of materials rely on ‘mass
transport’.
 Hence, ‘diffusion’  material transport by
atomic motion.
 From ‘an atomic perspective’, atoms in
solid material are always in ‘constant
motion’ – change position.
 For atoms to make such a move – two
conditions ‘MUST’ be met:
o There must be an ‘empty adjacent site’.
o Atom must have sufficient energy to
break bonds with neighbouring atoms –
cause lattice distortion.
 DIFFUSION CONCEPT –
STEADY-STATE DIFFUSION:
 Diffusion – time dependent
=> quantity of element
transported within another
is a function of time.
 Often important to know
‘how fast’ diffusion occurs
 ‘rate of mass transfer’ –
diffusion flux (J).
𝑀
 𝐽 = 𝐴𝑡
1 𝑑𝑀
 In differential form: 𝐽 = 𝐴 𝑑𝑡
 M = mass (equivalently, no.
of atoms).
 Flux for steady-state Concentration
𝑑𝐶 𝒅𝑪
diffusion: 𝐽 = −𝐷 ; D = Gradient, =
𝑑𝑥 𝒅𝒙
Diffusion Coefficient (Fick’s Δ𝑪
=
𝑪𝑨 −𝑪𝑩
1st Law – Adolph Fick). Δ𝒙 𝒙𝑨 −𝒙𝑩
DIFFUSION CONCEPT – NON-
STEADY-STATE DIFFUSION:
 Most practical diffusion situation are
non-steady; i.e. the diffusion flux &
concentration gradient vary with time.
 This leads to a ‘net accumulation or
depletion’ of diffusing species.
 1st Law of Mass Transport can no longer
𝝏𝐶 𝝏 𝝏𝐶
hold; hence Fick’s 2nd Law: = 𝝏𝑥 𝐷 𝝏𝑥
𝝏𝑡
 If the diffusion coefficient is independent
of composition, the above expression
𝝏𝐶 𝝏2 𝐶
then simplifies to: 𝝏𝑡
= 𝐷 𝝏𝑥 2
 Solutions to this expression 
concentration in terms of position &
time possible with some boundary
conditions specified.
 For boundary conditions, we must first
make some assumptions:
 DIFFUSION CONCEPT – NON-
STEADY-STATE DIFFUSION:
1. Before diffusion, diffusing solute atoms in the solid are
uniformly distributed  Concentration = C0.
2. Value of ‘x’ at the surface is ‘zero’ – increases with
distance into solid.
3. Time before diffusion process begins  taken to be ‘zero’.
 Thus; boundary conditions then become:
For t = 0, C = C0; at 0 ≤ x ≤ ∞.
For t > 0, C = Cs (constant surface concentration); at x = 0.
C = C0; at x = ∞.
 Application of these boundary conditions to Fick’s 2nd Law
𝑪𝒙 −𝑪𝟎 𝒙
above yields: = 𝟏 − 𝒆𝒓𝒇 ; where Cx represents the
𝑪𝒔 −𝑪𝟎 𝟐 𝑫𝒕
concentration at depth ‘x’ after time t.
𝑥
 The expression 𝑒𝑟𝑓 is known as the ‘Gaussian Error
2 𝐷𝑡
Function’, with values given in some mathematical tables.
 FACTORS INFLUENCING
DIFFUSION:
 Diffusion increases exponentially with
time:
𝑄𝑑
D = 𝐷0 exp(− )
𝑅𝑇
 D0 = temp independent pre-
exponential constant.
 Qd = Activation energy for diffusion.
 Temperature:  diffusion rate
increases rapidly with temp.
 Diffusion mechanism:  E.g.
Interstitial mechanism usually faster
than vacancy diffusion.
 Host Species: D0 and Qd are different
for every solute and solvent pair.
 Microstructure: diffusion faster in
polycrystalline material than single
crystals.
 TYPES OF DIFFUSION:
 Self Diffusion: Migration of atoms within
the same matrix to an adjacent vacancy
position.
 Vacancy Diffusion:  Mainly involves the
interchange of substitutional atoms from a
normal lattice position to an adjacent
vacant lattice site or vacancy. Thus, the
extent to which this mechanism can occur
is dependent on the presence or formation
of vacancies in the lattice.
 Interstitial Diffusion:  Involves migration
of atoms from an interstitial position to an
adjacent empty interstitial position.
Mechanism common in the diffusion of
impurities in steel alloys (e.g. hydrogen,
carbon, nitrogen and oxygen). It occurs
much rapidly than vacancy diffusion
(impurity atoms are smaller & hence more
mobile).
 GROWTH MECHANISMS
PLANAR:
 Well inoculated liquid cooling
under equilibrium conditions 
NO need for ‘undercooling’ =>
heterogeneous nucleation can
occur.
 => Temp of liquid ahead of
solidification front (solid-liquid
interface) > freezing temp.
 Any protuberance that grows
on interface is surrounded by
liquid above freezing temp 
protuberance growth stops =>
smooth solid-liquid interface
(planar growth).
 GROWTH MECHANISMS
DENDRITIC:
o Poor inoculation = poor
nucleation => liquid has to be
undercooled before solid forms.
o Thus, in this case a small
protuberance that forms on
interface is encouraged to grow
– liquid ahead of the
solidification front is
undercooled.
o Results in dendrite (dendron =
tree) structure formation.
o Diff btwn planar & dendritic
growth – diff sinks of Latent
Heat of Fusion.
 GROWTH MECHANISMS
DENDRITIC:
 SOLIDIFICATION ZONES
DURING FREEZING OF
INGOTS:
 CHILL ZONE: Nucleation
an Growth.
 COLUMNAR ZONE:
Predominantly Dendritic
Growth.
 CENTRAL ZONE:
Constitutional
Supercooling.
 SOLIDIFICATION TIME -
CHVORINOV’S RULE:
NB: The rate at • Chvorinov’s Rule:
which a solid 𝑉 𝑛
occurs depends on • 𝑡𝑠 = 𝐵
𝐴
the cooling rate or • V = volume of casting.
rate of heat • A = surface area of the
extraction. casting in contact with
Thus, high cooling the mould.
rate = rapid • B = mould constant.
solidification = • n = material constant
short solidification (usually about 2 for
most materials).
time.
COMMON SOLIDIFICATION
DEFECTS:
COMMON SOLIDIFICATION
DEFECTS:
 SUMMARY - STEEL
PRODUCTION PROCESS:
 Casting of Molten Metals – Is an old ancient
tradition which then requires some controlled
solidification of the molten substance into
defined shape.
 Solidification – Leads to nucleation
(homogeneous or heterogeneous) and/or
recrystallization of the alloy’s host parent
atoms, which has a direct consequence on its
resultant metallurgical properties.
 Solidification relies on the concept of mass
transport by atomic motion (diffusion – high
concentration to lower concentration down a
concentration gradient).