Materials Science and Engineering

Course Code: BMEE209L

Vivek Kumar Barnwal, PhD

Associate Professor, SMEC, VIT-Vellore
[email protected]
CBMR Building, 102J
 Module -3
Solidification, Diffusion and Phase transformation

Solidification – Solidification is a generalized process through which a

melt is changed to a solid state from liquid state

Examples
 Glass formation
 Ice formation
 Metal or plastic solidification

Objective is to know
 Solidification mechanism
 Nucleation mechanism

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Importance of solidification
 The properties of metals depend on its microstructure, and the microstructure depends on
solidification mechanism
 Common variables : Cooling rate, temperature, mould etc.

Types of processing

Primary processing Secondary processing

Processes such as rolling,

It is the process involving
extrusion, etc. used to
casting of molten metals into
process
ingots or semi-finished useful
ingots or slabs to other semi-
shapes such as slabs
finished shapes

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 Mechanism of solidification
Equilibrium
Non-equilibrium

Nucleation
Supersaturation
Growth Crystal
A state of a solution that contains more of
Growth of nuclei Completely
the dissolved material than could be
solidified state
dissolved by the solvent under normal
circumstances
Clustering of atoms

Liquid melt Nucleation Grain formation Solidified crystal

Growth
with GB
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Solidification mechanism : Nucleation
 Nucleation – first step in the process of solidification – formation of the first nano-crystallites
from molten state
 Metal in molten state possesses high energy and atoms are in random state
 As the metal cools, atoms lose their energy and begin to collide with each other
 Due to these collisions, energy is released and attractive forces cause formation of small cluster of
atoms, called nuclei, at several locations
 These nuclei (seeds) act as templates on which crystals grow

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Solidification mechanism : Nucleation
 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

Types of 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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 Solidification mechanism : Nucleation
 Phase transformation occurs spontaneously only when change in Gibb’s free energy (∆G) has a negative value

Total change in free energy

Change in volume free- Surface free energy (γ)

energy (∆Gv)

Due to the formation of the

Free energy difference
solid–liquid phase boundary
between the solid and
during the solidification
liquid phases
transformation
magnitude
magnitude

Product of (∆Gv) and Product of γ and the

volume of spherical surface area of the
nucleus (4/3)πr3 nucleus 4πr2
Total free
energy change
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Solidification mechanism : Nucleation
Total free
energy change

4𝜋𝑟 𝛾 Critical radius (r*) – growth will continue with the accompaniment of
a decrease in free energy

Embryo and nucleus – A cluster of radius less than the critical radius
r* will shrink and redissolve. This subcritical particle is an embryo,
whereas the particle of radius greater than critical radius r* is termed a
nucleus.

Activation free energy – corresponds to critical free energy (G*),

which is the free energy required for the formation of a stable nucleus
4
𝜋𝑟 Δ𝐺
3 ΔGv – Driving force for the nucleation
γ– Obstacle for the nucleation
(∆Gv) will always be negative at temperature below
the equilibrium solidification temperature
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 Solidification mechanism : Nucleation
…………………………………………………………………………………………………..Equation 1

or
……………..Equation 2
After substituting Eq-2 in to Eq-1
Activation free energy required for
the formation of a stable nucleus …………………………………………....Equation 3

The term ΔGv is function of temperature and expressed by …………..…………....Equation 4

Hf – latent heat of fusion per unit volume;
Tm – melting point (in K)
T – temperature of liquid (in K)
(Tm – T) is the undercooling

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Solidification mechanism : Nucleation
After substituting Eq-4 in to Eq-2 and Eq-3

and

 A lowering of temperature at temperatures below the

equilibrium solidification temperature (Tm), nucleation
occurs more readily
or
 As the undercooling (Tm – T) increases, the critical radius
A schematic of ΔG-vs-r plot required for nucleation decreases

γ and Hf are relatively insensitive to

temperature changes
1
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Exercise

Melting point of gold = 1064°C; Undercooling = 230°C

1
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Exercise

In FCC cell, 4 atoms per unit cell

Hence number of atoms = 137 X 4 = 548 atoms/critical nucleus Degree of supercooling for
various metals

1
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 Heterogeneous nucleation
 Nucleation on pre-existing surfaces is known as
heterogeneous nucleation

 Nucleation occurs with lesser activation energy

resulting in much less undercooling and smaller critical
radius required

 A radius of curvature greater than the critical radius is

achieved with very little total surface between the solid
and liquid

 Relatively few atoms must cluster together to produce a

solid particle that has the required radius of curvature

 This process is dependent on the contact angle (θ) for

the nucleating phase and the surface on which
nucleation occurs
Free energy vs radius plot
1
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 Heterogeneous nucleation

Grain structure of ingots

 Heterogeneous solidification occurs at mold walls and
impurities

 With heterogeneous solidification, the solid is not uniform,

instead having three distinct regions within the solid

 These regions are the chill zone, columnar zone, and

equiaxed zone

 The chill zone is nearest to the mold wall and contains a

band of randomly oriented grains

 The columnar zone consists of long columnar grains that

grow opposite to the direction of heat flow

 The equiaxed zone is in the center of the mold and has

uniform equiaxed grains and controlled nucleation

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 Growth mechanism
 Grain growth – After nucleation, more atoms get attached to the solid interface. This
process is called growth wherein size of the nuclei begins to increase

 Nucleation continues to occur simultaneously with growth of the new phase

particles

 The flow of latent heat of fusion determines the growth mechanism

 Solidification front - Interface between a solid and liquid

Growth mechanisms
 Planar growth – smooth solid-liquid interface, occurs at no undercooling/low undercooling
 Dendritic growth – Tree like structure, occurs for undercooled liquid

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 Planar growth

/bulge

 No undercooling
 Heterogeneous nucleation
 Slow cooling rate

 When the temperature of the liquid is above the freezing temperature, a bulge on the solid-liquid
interface will not grow, until the remainder of the interface catches up leading to maintenance of a
planar interface
 Latent heat is removed from the interface through the solid to the surroundings
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 Dendritic growth

 Undercooling required
 Poor nucleation

SEM micrograph of steel

 If the liquid is undercooled, a protuberance on the solid-liquid interface can grow rapidly as a
dendrite. The latent heat of fusion is removed by raising the temperature of the liquid back to the
freezing temperature
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 Applications of controlled solidification
 Grain refinement - The addition of heterogeneous nuclei in a controlled manner to
increase the number of grains in a casting

 Dispersion strengthening - Increase in strength of a metallic material by

generating resistance to dislocation motion by the introduction of small clusters of a
second material

 Solid-state phase transformation - A change in phase that occurs in the solid state

 Rapid solidification processing - Producing unique material structures by

promoting unusually high cooling rates during solidification

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 Diffusion

Diffusion – A flow process that governs the movement of atoms and molecules in
solids is called diffusion

Driving force
 Thermal energy
 Stress gradient
 Electric, magnetic and
concentration gradient
Objective is to know
 Diffusion Mechanisms
 Fick’s Law of Diffusion
 Steady state and non-steady state diffusion
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 Importance of diffusion
 The control over properties of metals makes them attractive for various applications
 Usually, change in phase is one common method to tailor the properties of metals
 Often, diffusion plays an important role in phase change

Diffusion couple Cu Ni

Cu (red circles) and Ni (blue circles)

atoms within the diffusion couple
The process, whereby
Position of atoms after heating
atoms of one metal diffuse
followed by cooling into another, is termed
inter-diffusion

Concentration of Copper and Nickel

with respect to position

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Diffusion controlled applications
 Carburization and other heat treatment processes
 Oxidation of metals
 Doping of semiconductors
 Microstructural phase transformation
 Processing of materials by diffusion binding (such as cladding) etc.

Diffusion mechanisms
 Liquid and gaseous state – random motion of atoms
 Solid state – Vacancy and interstitial diffusions
 For an atom to make a move
i. there must be an empty adjacent site
ii. the atom must have sufficient energy to break the bonds with its neighbor atoms and then cause
some lattice distortion during the displacement
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Vacancy diffusion
 This involves the interchange of an atom from a normal lattice position to an adjacent vacancy
 Vacancy diffusion is a function of the number of vacant sites; significant concentrations of vacancies may exist in
metals at elevated temperatures
 Because diffusing atoms and vacancies exchange positions, the diffusion of atoms in one direction corresponds to
the motion of vacancies in the opposite direction
 Both self-diffusion and inter-diffusion occur by this mechanism; for the latter, the impurity atoms must substitute
for host atoms

2
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Interstitial diffusion
 This involves atoms that migrate from an interstitial position to a neighboring one that is empty.
 This mechanism is found for inter-diffusion of impurities such as hydrogen, carbon, nitrogen, and oxygen, which
have atoms that are small enough to fit into the interstitial positions
 In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion by the vacancy mode, because
the interstitial atoms are smaller and thus more mobile
 Moreover, there are more empty interstitial positions than vacancies; hence, the probability of interstitial atomic
movement is greater than for vacancy diffusion

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Measurement of diffusion
 Diffusion rate is measured in terms of diffusion flux (J)

Unit area

Diffusion flux (J) is mass (or number of atoms)

per unit area per unit time

Unit

kilogram (or atoms) per meter square per unit

second

𝐽= or in differential form ( )

where, M – mass; A – area; t – elapsed time

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Steady state diffusion (is measured by Fick’s first law)

 In steady state condition, when diffusion flux (J) does not change with time (t)

𝐶 −𝐶 𝑑𝐶
𝐽∝ or 𝐽∝ Concentration, C1
𝑥 −𝑥 𝑑𝑥
Concentration, C2
or 𝐽 = −𝐷 x1 x2
x-direction
where
D – Diffusivity or diffusion constant or diffusion coefficient in (m2/s)

The negative sign indicates that the atoms are flowing in the direction of lower concentration

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Non-steady state diffusion (is measured by Fick’s second law)
 Fick’s first law does not consider the fact that the gradient and local concentration of the diffusing
mass in a material changes with respect to time
 Fick’s second law states that the change in the concentration over time is equal to the change in
local diffusion flux

𝜕𝐶 𝜕𝐽
Mathematically – =
𝜕𝑡 𝜕𝑥
where is the rate of change of
concentration with respect to time

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 Phase diagram

Objective
Important terms and definition related to phase
diagram

2
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Typical phase diagrams

Phase diagram for pure H2O

Iron–iron carbide phase diagram

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Terminologies
 Component: Components are pure metals and/or compounds of which an alloy is composed

 Phase: Physically distinct, mechanically separable, and chemically homogeneous portion of a

system

 Equilibrium: The state of a system at any specified condition when the system possesses
minimum free energy

 Degree of freedom: The number of independent variables required to describe the state of a
system

 Solubility Limit: At some specific temperature, there is a maximum concentration of solute atoms
that may dissolve in the solvent to form a solid solution

 Phase diagram (or equilibrium diagram): Plots showing relations between phases in
equilibrium with respect to composition, pressure and temperature

 What is single phase system and multi-phase system?

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What is alloy?
 An alloy is composed of two or more elements of which at least one element is a metal
Usually: Alloy = Base metal + alloying additions
 Alloying additions are added deliberately whereas impurities inhibit into the base metal
accidentally
 Generally pure metals don’t have required mechanical properties to be used at industrial scale;
therefore, alloying additions are added in base metal to attain required properties
 Alloys are found in the form of (i) solid solution (ii) intermetallic compound (iii) Intermediate
compound

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Solid solution
 Solid solution: A homogeneous mixture of atoms of two or more elements in solid state is called as
solid solution. In a solid solution, atoms of different elements cannot be either mechanically
separated or physically distinguished

 Solid solutions are of mainly two types

i. Substitutional solid solution
ii. Interstitial solid solution Substitutional Interstitial
solid solution solid solution

 Interstitial solid solution – Small solute atoms occupy the interstitial space amongst big solvent
atoms; for example, carbon in α-iron
 Substitutional solid solution – Solute substitutes the solvent in the crystal lattice without
structural changes
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Are alloys, solid solutions and mixture same?
Materials Science and Engineering 31
Substitutional solid solution
 The arrangement of the solute atoms may be disordered (random) or ordered

Random substitutional solid solution Ordered substitutional solid solution

 Some alloy systems exhibit complete solid solution (e.g. Cu-Ni, Cd-Mg), others show only limited solubility at
any temperature
 Solubility of solute in solvent is governed by a set of rules called Hume-Rothery’s rule
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Hume-Rothery’s rule
 Size factor: The atoms or ions must be of similar size, with no more than a 15% difference in atomic radius,
in order to minimize the lattice strain (i.e., to minimize, at an atomic level, the deviations caused in
interatomic spacing)

 Crystal structure: The materials must have the same crystal structure; otherwise, there is some point at
which a transition occurs from one phase to a second phase with a different structure

 Valence: The ions must have the same valence; otherwise, the valence electron difference encourages the
formation of compounds rather than solutions

 Electronegativity: The atoms must have approximately the same electronegativity. Electronegativity is the
affinity for electrons. If the electro-negativities differ significantly, compounds form—as when sodium and
chloride ions combine to form sodium chloride.

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Gibb’s phase rule
 J. W. Gibbs enunciated an expression that describes the number of phases that can coexist in equilibrium in a
given system. This equation is called Gibbs phase rule.

P+F=C+N

where P – Number of phases

F – Degree of freedom
C – Number of component
N – system variables

 Degrees of freedom indicates number of variables that can be changed without changing the number of phases
 System variables are pressure and temperature

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 Phase diagram

Objective
Interpretation of different types of phase diagrams

3
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Types of phase diagram
 Unary phase diagram – Single component  Ternary phase diagram – Three component
 Binary phase diagram – Two component  Quaternary phase diagram – Four component

Unary phase diagram Things to note

 Oa, Ob and Oc are phase boundaries
 Point – 2 is melting point/freezing point
 Point – 3 is boiling point/condensing point
 Point – O is triple point/invariant point

At point O (as per Gibb’s rule)

P+F=C+γ
3 + F = 1 + 2; or F = 0
Phase diagram for H2O Zero independent variable is required to describe the state of a system

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Binary phase diagram (for isomorphous system)
Isomorphous system – When two components have
unlimited solubility, i.e. they always form a solid solution
regardless of the ratio of atoms/molecules.
Liquidus line – The line above which only liquid phase
exists
Solidus line – The line below which only solid phase exists
Tie line – A horizontal line drawn at temperature of interest
is called tie line (or isotherm line)
A phase diagram provides following three information:
i. Phases that are present
ii. Compositions of the phases
iii. Fractions of the phases
Phase diagram of copper-nickel
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Binary phase diagram
i. Name and number of phases – Solid phases are designated
by lower Greek letters, for example – α, β, λ etc.
D

ii. Composition of phases – Amount of components in

different phases at a particular point – by drawing a tie line

iii. Fractions of the phases – Individual amount of phases at a

particular point – calculated using lever rule

For point B (@ 35% of Ni)

CL C0 Cα
31.5 % 42.5 %
31.5 42.5
35%

42.5 − 35 35 − 31.5
Phase diagram of copper-nickel 𝑊 = = 0.68; 𝑊 = = 0.32
42.5 − 31.5 42.5 − 31.5
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Derivation of lever rule

31.5 42.5

Phase diagram of copper-nickel

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 Phase diagram

Objective
Interpretation of different types of phase diagrams
continued…

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Microstructure development

Equilibrium cooling (slow cooling) Non-equilibrium cooling (fast cooling)

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Reactions in phase diagram
 Mainly following four invariant reactions that depend on solubility and melting
point of components
Example – Pb- c
1. Eutectice reaction L⇌
h
α+β
Sn, Cu-Au, Bi-Cd
Decomposition of one
phase in two phases
Example – Cu- 2. Eutectiod reaction c
γ⇌ α+β
h
Be, Al-Mn, Cu-Al

Example – Ag- c
3. Peritectic reaction α+L⇌
h
β
Pt, Cu-Au, Bi-Cd Transformation of two
phases in a single phase
c
4. Peritectoid reaction α+β⇌
h
γ

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Binary eutectic phase diagram
Also, at point E
c
Liquid ⇌
hα+β
Eutectic phase reaction

 Eutectic reaction occurs when the melting point of

the two components are not far from each other
TE
 Point E is called eutectic point
 Temperature corresponding to point E (i.e. TE) is
called eutectic temperature
hyper-  Composition at point E is called eutectic
hypo-eutectic eutectic
composition
 Composition on the left hand side of eutectic point is
The copper–silver phase diagram called hypo-eutectic composition
At point E (as per Gibb’s rule):  Composition on right hand side of eutectic point is
P + F = C + γ; 3 + F = 2 + 1; or F = 0 called hyper-eutectic composition
Zero6 independent variable is required to describe the state of
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Materials Science and Engineering 43
Binary peritectic phase diagram
At point P
c Peritectic reaction
Liquid +β ⇌
h α

 Peritectic reaction occurs when the melting point of the

two components are too much different
 Point P is called peritectic point
 Temperature corresponding to point P is called
peritectic temperature
 Composition at point P is called peritectic composition

The silver-platinum phase diagram

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Exercise
For a 40 wt% Sn–60 wt% Pb alloy at 150°C, (a) what phase(s) is (are) present? (b) What is (are) the
composition(s) of the phase(s)? (c) fraction of each phase

Solution
(a) α and β phases are present at point O
(b) Cα is approximately 11 wt% of Sn and
remaining Pb; Cβ is approximately 98 wt% Sn and
remaining Pb
(c) Mass fraction can be calculated using lever rule
O
CO
Cα Cβ

Wα = (Cβ – CO)/(Cβ – Cα) = (98-40)/(98-11) = 0.67

Wβ = (CO – Cα)/(Cβ – Cα) = (40-11)/(98-11) = 0.33

Phase diagram Pb-Sn

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 Phase diagram

Objective
A detailed study of iron-carbon phase diagram
Phases, their structure and solubility
Invariant reactions
Microstructure development

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 Important points to know
Voids
The vacant space available between
atoms is called void

Tetrahedral voids Octahedral voids

BCC FCC
Tetrahedral 0.29r 0.225r
Octahedral 0.15r 0.414r

 Iron is called an allotrope because it can exist in more than one crystal structure
 Is allotropy same as polymorphism?
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Important points to know

Table : Various micro-constituent of iron-carbon

Phase Structure Hardness Ductility
α – Ferrite BCC RB ≈ 90 ≈ 40%
γ - Austenite FCC RC ≈ 40 ≈ 10%
Fe3C – Cementite Orthorhombic RC ≈ 65 – 68 Brittle
δ-ferrite BCC No practical applications
Martensite BCT RC ≈ 30 – 65 Brittle

Cooling curve for pure iron

 α – ferrite, δ-ferrite, γ – austenite and martensite are interstitial solid solution of carbon in iron

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A typical Fe-Fe3C diagram
Important phases

δ-ferrite – max solubility of carbon is 0.1% at 1493°C

γ – austenite – max solubility of carbon is 2.04% at

1147°C

α – ferrite – max solubility of carbon is 0.02% at 723°C

Cementite (Fe3C) – Metastable compound of iron and

Fe-Fe3C diagram carbon, hardest phase

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A typical Fe-Fe3C diagram
Invariant reactions
Peritectic
0.1 0.16 0.51
Peritectic (at 1493°C) – L
δ γ
L0.51 + δ0.1 → γ0.16
Eutectic

2.14 4.3 6.7

Eutectic (1147°C) – γ L
Fe3C
Eutectoid
L4.3 → γ2.14 + Fe3C6.7
Ledeburite
a eutectic mixture of γ and cementite

0.02 0.76 6.7

Eutectoid (727°C) – α Fe3C
γ
Hypo- Hyper-
eutectoid eutectoid γ0.76 → α0.02 + (Fe3C)6.7
Steel Cast iron

Fe-Fe3C diagram Pearlite

eutectoid mixture of α-ferrite and cementite
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Slow cooling in eutectoid compositions
 At point ‘a’, only austenite phase exists
 After crossing the eutectoid point while cooling, layers of ferrite (α)
and cementite (Fe3C), called as pearlite, are formed
 The relative thickness of layers is 7:1 (in some references 8:1)
 Pearlite exists as colonies; within each colony the layers are
oriented in the same direction

Microstructure evolution for  The redistribution of carbon from austenite phase to pearlite
eutectoid compositions occurs by diffusion
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Slow cooling in hypo-eutectoid compositions
 At point c, the microstructure will consist only grains of the γ–phase
 In cooling to point d, small particles of α–phase will form along the
grain boundaries
 Cooling from point d to e, will produce an increased fraction of the
α–phase: the α–phase will have grown larger
 Cooling to point f, the γ–phase will transform to pearlite. There will
be virtually no change in the α–phase that existed at point e in
crossing the eutectoid temperature
 The α–phase present in the pearlite is called eutectoid
ferrite
 The α–phase that formed while cooling through the α + γ phase
Microstructure evolution
hypo-eutectoid compositions region is termed proeutectoid ferrite
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Slow cooling in hyper-eutectoid compositions

 At point g only the γ–phase will be present; therefore,

microstructure will have only γ–grains
 Upon cooling into the γ+Fe3C phase field, to point h, the cementite

phase will begin to form along the grain boundaries

 This cementite is called proeutectoid cementite (formed before the
eutectoid reaction).
 On further cooling to point i, all remaining austenite of eutectoid
composition is converted into pearlite; thus, the resulting
microstructure consists of pearlite and proeutectoid cementite

Microstructure evolution
hyper-eutectoid compositions
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Influence of alloying additions

The dependence of eutectoid temperature on alloy The dependence of eutectoid composition (wt% C) on
concentration for several alloying elements in steel alloy concentration for several alloying elements in steel

 Alloying additions change both the temperature of the eutectoid reaction and eutectoid composition in terms of
carbon, which changes relative fractions of pearlite and the proeutectoid phases
 Steels are usually alloyed either to improve their corrosion resistance or to render them amenable to heat treatment

6 September 2025 Materials Science and Engineering 54

 Thank you
and
Your questions?