Prepared by,

Philip Jacob Perakathu

Assistant Professor – Mechanical Engineering Department
Saintgits College of Engineering, Pathamuttom
 Deviations from the orderly arrangement of
atoms in lattice structures are known as
imperfections/defects.
 Based on the bond strength most perfect
materials should have a strength of about 106
psi but in reality the strength is much lower in
the order of only 4x104 psi.
 It was found that this large variation in
strength values was due to the presence of
imperfections.
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 Impurities
 Elements or compounds that are present from raw
materials or processing.
 Dopants
 Elements or compounds that are deliberately added (in
known concentrations), at specific locations in the
microstructure, with an intended beneficial effect on
properties.
 In general, the effect of impurities is deleterious,
whereas the effect of dopants on the properties of
materials is useful.
 Phosphorus (P) and boron (B) are examples of dopants
that are added to silicon crystals to improve the electrical
properties of pure silicon (Si).
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 Types of imperfections:
 Point or Zero-dimensional defects
▪ Atoms missing or present in irregular places in the
lattice (associated with one or two atomic positions).
 Line or One-dimensional defects
▪ Group of atoms in irregular positions.
 Surface or Two-dimensional defects
▪ This arise due to the clustering of line defects into a
plane.
 Volume or Three-dimensional defects
▪ Extended defects
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 Point or Zero-dimensional defects
 Point defects, as the name implies, are imperfect
point-like regions in the crystal.
 Localized disruptions in a perfect atomic or ionic
arrangements in a crystal structure.
 Typical size of a point defect is about 1-2 atomic
diameters.

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 Point defects (cont…)
 Different types are:
▪ Vacancy
▪ Interstitial defect
▪ Substitutional defect
▪ Frenkel defect
▪ Schottky defect

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 Point defects (cont…)
 Vacancy
▪ An atom missing from regular lattice position.
▪ Vacancies are present invariably in all materials.
▪ Vacancies are introduced into metals and alloys during
solidification at high temperatures, or as a consequence of
radiation damage.
▪ At room temperature the concentration of vacancies is small,
but the concentration of vacancies increases as the
temperature is increased.
▪ Vacancies play an important role in determining the rate at
which atoms or ions move around or diffuse in a solid
material, especially in pure metals.
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 Point defects (cont…)
 Vacancy (cont…)
▪ According to Arrhenius type behavior

where
nv – Number of vacancies per cm3
n – Number of atoms per cm3
Qv – Energy required to produce one mole of vacancies in
cal/mol or Joules/mol
R – Gas constant (8.31 Joules/mol K or 1.98 cal/Mol K)
T – Temperature in Kelvin (K).
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 Point defects (cont…)
 Vacancy (cont…)
▪ Possible ways of forming vacancies:
▪ Raising the temperature
▪ During solidification
▪ By extensive plastic deformation
▪ Bombardment with high energy nuclear particles.

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 Point defects (cont…)
 Interstitial defect
▪ Formed when an extra ion or atom is inserted into the crystal
structure
▪ Interstitials tend to push the surrounding atoms farther apart
and also produce distortion of the lattice planes.
▪ Interstitial atoms may be produced by the severe local
distortion during plastic deformation.
▪ Unlike vacancies, once introduced, the number of interstitial
atoms or ions in the structure remains nearly constant, even
when the temperature is changed.
▪ Interstitial atoms such as hydrogen are often present as
impurities, whereas carbon atoms are intentionally added to
iron to produce steel.

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 Point defects (cont…)
 Substitutional defect
▪ The atom of one element will replace the atom of other
element in the lattice, while the atom of second element
will get settled in the vacant space created by the first
atom.
▪ Number of defect is independent on temperature.
▪ Promotes atomic diffusion and phase transformations
▪ Thermal and electric conductivities are also affected.

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 Point defects (cont…)
 Substitutional defect
▪ Substitutional atoms or ions may either be larger than the
normal atoms or ions in the crystal structure, in which case
the surrounding interatomic spacings are reduced, or smaller
causing the surrounding atoms to have larger interatomic
spacings.
▪ Examples of substitutional defects include
▪ incorporation of dopants such as phosphorus (P) or boron (B) into Si.
▪ Similarly, if we add copper to nickel, copper atoms will occupy
crystallographic sites where nickel atoms would normally be present.
The substitutional atoms will often increase the strength of the
metallic material.

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 Point defects (cont…)
 Frenkel defect
▪ The atoms exist as charged ions, when defect structures are
considered, conditions of electroneutrality must be
maintained.
▪ Electroneutrality is the state that exists when there are equal
numbers of positive and negative charges from the ions.
▪ Defect involves a cation–vacancy and a cation–interstitial pair
is called a Frenkel defect. It might be thought of as being
formed by a cation leaving its normal position and moving
into an interstitial site.
▪ There is no change in charge because the cation maintains
the same positive charge as an interstitial.
▪ Frenkel defect can occur in metals and covalently bonded
materials.
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 Point defects (cont…)
 Schottky defect
▪ A cation vacancy–anion vacancy pair known as a Schottky
defect.
▪ This defect might be thought of as being created by
removing one cation and one anion from the interior of the
crystal and then placing them both at an external surface.
▪ Since both cations and anions have the same charge, and
since for every anion vacancy there exists a cation vacancy,
the charge neutrality of the crystal is maintained.
▪ Schottky defect is unique to ionic materials and is commonly
found in many ceramic materials.
▪ For example, one Mg2+ vacancy and one O2- vacancy in MgO
constitute a Schottky pair. In ZrO , for one Zr4+vacancy, there
2

will be two O2- vacancies

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 When a material is subjected to an external
force/load, the material suffers a change in
shape, which is called deformation.
 If the deformation is temporary (disappears on
removal of the load) – elastic deformation.
 If the deformation is permanent (persists on
removal of the load) – plastic deformation.

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 Elastic deformation
 The displacement of atoms is by relatively small amounts, the
removal of the applied load allows the atoms to return to their
normal equilibrium position.
 Elastic deformation is reversible.
 Plastic deformation
 Yielding involves the possibility that some of the atoms, under
distortion produced by the applied load, move to a new
equilibrium position.
 New bonds are formed in the new positions, so no tendency for
atoms to return to their original positions.
 Deformation is permanent.
 There are two common mechanism of plastic deformation
▪ Slip
▪ Twinning.
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 Types of loads
 Tensile loads
▪ Forces applied normal to the sample surface
▪ Elongation –positive linear strain

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 Types of loads (cont…)
 Compressive loads
▪ Forces applied normal to the sample surface
▪ Elongation – negative linear strain

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 Types of loads (cont…)
 Pure shear load
▪ The shear angle θ
▪ Applied force is parallel to the both sample faces

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 Types of loads (cont…)
 Torsional deformation
▪ Twist angle, φ
▪ Torsion is a variation of pure shear
▪ Torsion load produces a rotational motion (twist) around
axis of symmetry

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 Slip
 Slip occurs most readily in specific directions on
certain crystallographic planes.
 The plane on which slip occurs is known as slip plane
and the direction in which slip takes place is known as
slip direction.
 The combination of slip plane and slip direction is
known as slip system.
 Generally slip plane is the plane of greatest atomic
density and the slip direction is the closed packed
direction within the slip plane
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 Crystal Slip plane Slip direction
structure
SC {100} <100>
BCC {110} <111>
FCC {111} <110>
HCP {0001} <1120>

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 Schmid’s Law
 Schmid's law defines the relationship between
shear stress, the applied stress, and the
orientation of the slip system.
 It is an equation for finding the stress in the slip
plane given an axial force and the angle of the slip
plane.
 Schmid's law can help to explain the differences in
behavior of different metals when subjected to a
unidirectional force.

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 Twinning
 In certain metals when shear stress is applied, planes of
atoms in the lattice move parallel to a specific plane so
that the lattice is divided into two symmetrical parts which
are differently oriented.
 This phenomenon is known as twinning and the planes
parallel to which atomic movement has taken place are
know as twinning planes
 The differently oriented region within the crystal and
between the twinning planes is know as twinned region.
 The amount of movement of each plane of atoms in the
twinned region is proportional to its distance from the
twinning plane, so that the mirror image is formed across
the twin plane.
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 SLIP TWINNING
Atoms move a whole number of inter Atoms movement is fractional amounts.
atomic distance.

Appears thin lines Broad lines or bands

Little change is lattice orientation Different lattice orientation in the

twinned region

Steps are visible on surface Polishing will not destroy the evidence of
twining-due to difference in lattice
Steps can be removed by polishing-no orientation
evidence of slip

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 Line or One-Dimensional defects
 Also known as Dislocations.
 A dislocation is a linear or one-dimensional defect
around which some of the atoms are misaligned.
 Although dislocations are present in all materials,
including ceramics and polymers, they are particularly
useful in explaining deformation and strengthening in
metallic materials.
 Three types of dislocations
▪ Edge dislocations
▪ Screw dislocations
▪ Mixed dislocations
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 Burger vector
 The magnitude and direction of the lattice
distortion associated with a dislocation is
expressed in terms of a Burgers vector, denoted
by a ‘b’.

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 Line defects (cont…)
 Edge dislocations
▪ A linear defect that centers around the line that is
defined along the end of the extra half-plane of atoms.
▪ This is termed the dislocation line.
▪ Within the region around the dislocation line there is
some localized lattice distortion.

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 Line defects (cont…)
 Edge dislocations (cont…)
▪ As the dislocation moves, the extra half plane will break
its existing bonds and form new bonds with its neighbor
opposite of the dislocation motion.
▪ This step is repeated in many discreet steps until the
dislocation has moved entirely through the lattice.
▪ After all deformation, the extra half plane forms an edge
that is one unit step wide also called a Burger’s Vector.

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 Line defects (cont…)
 Screw dislocations
▪ It can be thought of as being formed by a shear stress
that is applied to produce the distortion.
▪ The upper front region of the crystal is shifted one
atomic distance to the right relative to the bottom
portion.
▪ The atomic distortion associated with a screw
dislocation is also linear and along a dislocation line, line
AB in figure.
▪ The screw dislocation derives its name from the spiral or
helical path or ramp that is traced around the dislocation
line by the atomic planes of atoms. 49
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 Think of screw dislocation this way …….

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It’s an Atomic Force Microscopy image of a thin film of a block copolymer – a molecule with
a long section thatcan crystallise (poly ethylene oxide), attached to a shorter length of a
non-crystallisable material (poly vinyl pyridine).

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 Line defects (cont…)
 Mixed dislocations
▪ Most dislocations found in crystalline materials are
probably neither pure edge nor pure screw, but exhibit
components of both types; these are termed mixed
dislocations.

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 In general, there can be any angle between the
Burgers vector b (magnitude and the direction
of slip) and the line vector t (unit vector
tangent to the dislocation line).
 bt - Edge dislocation
 b  t - Screw dislocation
 b not  t , b not  t - Mixed dislocation

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 Surface or Two-Dimensional defects
 Also known as Interfacial defects.
 Interfacial defects are boundaries that have two
dimensions and normally separate regions of the
materials that have different crystal structures
and/or crystallographic orientations.
 External surface
▪ One of the most obvious boundaries is the external
surface, along which the crystal structure terminates.
▪ Surface atoms have higher energy state than the atoms
at interior positions.
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 Surface defects (cont…)
 Grain Boundaries
▪ The boundary separating two small grains or crystals
having different crystallographic orientations in
polycrystalline materials
▪ Within the boundary region, which is probably just
several atom distances wide, there is some atomic
mismatch in a transition from the crystalline orientation
of one grain to that of an adjacent one.

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 Surface defects (cont…)
 Grain Boundaries (cont…)
▪ When this orientation mismatch is slight, on the order of a
few degrees, then the term small- (or low- ) angle grain
boundary is used.
▪ These boundaries can be described in terms of dislocation
arrays.
▪ One simple small-angle grain boundary is formed when edge
dislocations are aligned, and this type is called a tilt boundary.
▪ When the angle of mis-orientation is parallel to the boundary,
a twist boundary results, which can be described by an array
of screw dislocations. This type is called a twist boundary.
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 Surface defects (cont…)
 Twin Boundaries
▪ A twin boundary is a special type of grain boundary
across which there is a specific mirror lattice symmetry;
that is, atoms on one side of the boundary are located in
mirror-image positions of the atoms on the other side.
▪ The region of material between these boundaries is
appropriately termed a twin.
▪ Twins result from atomic displacements that are
produced from applied mechanical shear forces
(mechanical twins), and also during heat treatment
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 Surface defects (cont…)
 Stacking fault
▪ Stacking faults are found in FCC metals when there is an
interruption in the ABABAB . . . stacking sequence of
close-packed planes.
▪ When stacking fault occurs, the stacking sequence may
be ABC ABC AB AB ABC or ABC ABC AC ABC

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 Volume or Three-Dimensional defects
 Also known as bulk defect.
 Defects which exist in all solid materials and are
much larger than those discussed.
 These include pores, cracks, foreign inclusions,
and other phases.
 They are normally introduced during processing
and fabrication steps.

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 During plastic deformation, the dislocation
density in the crystal increases by two to six
orders of magnitude, depending on the amount
of deformation undergone by crystal.
 A lightly cold worked crystal may have a
dislocation density of 1012 cm of dislocation line
per cubic centimeter of metal.
 This indicates there are sources within the
crystal, which generate new dislocations during
plastic deformation.
 One such source is called Frank-Read Source.
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 Frank-Read Source
 Segment of moving dislocation is pinned at points A
and B, at a distance L.
 Applied shear stress causes the segment to bow out
between points A and B with a radius of R (radius of
curvature).

 Bowing continues until R=L/2. At this point the loop

becomes unstable and begins to bend around upon
itself.
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 Frank-Read Source (cont…)
 This continues until the loop pinches off at point
CC’, which are screw dislocations of opposite
signs.
 The loop continues to grow.
 New dislocation will repeat if applied stress is
sufficient.

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 The motion of a large number of dislocations
within a crystal results in plastic deformation.
 The process by which plastic deformation is
produced by dislocation movement is termed
as slip.
 Dislocations also move by the processes of
cross slip and climb.
 When moving dislocations intersect each
other, jogs and kinks are formed.
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 Slip
 During slip, atomic bonds at one point are broken and
re-established at another point.
 Slip occurs most readily in specific directions on
certain crystallographic planes.
 The plane on which slip occurs is known as slip plane
and the direction in which slip takes place is known as
slip direction.
 The combination of slip plane and slip direction is
known as slip system.
 Generally slip plane is the plane of greatest atomic
density and the slip direction is the closed packed
direction within the slip plane.
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 Cross Slip
 When a screw dislocation moving along a slip
plane encounters an obstacle, it is blocked from
further movement along the plane.
 The dislocation can now shift to another
intersecting slip plane and continue to move
along this plane.
 This is called cross slip.

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 Dislocation Climb
 An edge dislocation can move out of its slip plane
to another parallel slip plane just above or below
it.
 This type of dislocation movement is called
dislocation climb.
 If the slip plane shifts up in a positive edge
dislocation, it is called positive climb.
 If the slip plane shifts up in a negative edge
dislocation, it is called negative climb.
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 Intersection of dislocations
 The intersection of two dislocations produces a
sharp break (a few atom spacing in length) in
dislocation line.
 This break can be of two types:
▪ Jog
▪ Sharp break in the dislocation moving it out of the slip plane.
▪ They are steps on the dislocation which move it from one atomic
slip plane to another.
▪ Kink
▪ Sharp break in the dislocation line which remains in the slip plane.
▪ They are steps which displace it on the same slip plane.
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 Intersection of two dislocations with Burgers
vectors at right angle to each other:
 An edge dislocation XY with Burgers vector b1 is
moving on plane Pxy and cuts through dislocation
AB with Burgers vector b2.
 The intersection causes jog PP’ in dislocation AB
parallel to b1 and has Burgers vector b2 and with
the length of the jog = b1.
 It can readily glide with the rest of dislocation.
 Note: b1 is normal to AB and jogs AB, while b2 is
parallel to XY and no jog is formed.
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 Intersection of two dislocations with Burgers
vectors parallel to each other:
 Both dislocations are jogged.
 The length of jog PP’ is b1 and the length of jog
QQ’ is b2.
 The jogs both have a screw orientation and lie in
the original slip plane. This is called Kink (not
stable)

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 Dislocations often pile up on slip planes at
barriers i.e., grain boundaries or second
phase particles.
 High stress concentration on the leading
dislocations in the pile-up.

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 A phase transition is the transformation of a
thermodynamic system from one phase or
state of matter to another one by heat
transfer.
 A variety of phase transformations are
important in the processing of materials, and
usually they involve some alteration of the
microstructure.

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 VAPORISATION
GAS
SUBLIMATION
CONDENSATION
DESUBLIMATION

LIQUID
MELTING

SOLID FREEZING

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 Basically, these transformations can be divided into
three:
 In one group are simple diffusion-dependent
transformations in which there is no change in either the
number or composition of the phases present. These
include solidification of a pure metal, allotropic
transformations, and recrystallization and grain growth.
 In another type of diffusion-dependent transformation,
there is some alteration in phase compositions and often
in the number of phases present; the final microstructure
ordinarily consists of two phases. Eg: Eutectoid reaction.
 The third kind of transformation is diffusionless, wherein a
metastable phase is produced. Eg: Martensitic
transformation.
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 Solidification of pure metals, is the transition
from liquid state to solid state.
 Solidification is the transition from the liquid
to the solid state and occurs in two stages:
 Nuclei formation
 Crystal growth

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 The nucleus can be regarded as the small cluster of
atoms having the right crystalline arrangement.
 When the melt is cooled below its melting point,
nuclei begin to form in many parts of the melt at the
same time.
 The rate of nuclei formation depends on the rate of
under cooling and also on the presence of impurities
which considerably facilitate nucleation.
 The extent of under cooling varies from metal to
metal.
 At any temperature below the melting point a nucleus
has to be of a certain minimum size, called the critical
size, so that it will grow. 99
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 The critical size is greatest near the melting
point, but the probability of forming such a
large size is less.
 Particles smaller than the critical size will be
dissolved by the vigorous bombardment of
neighboring atoms and cannot grow are
known as embryos.
 Growth of nucleus occurs by diffusion process
which is also a function of temperature and
hence the rate of nucleation and rate of
growth are functions of temperatures. 100
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 Nucleation involves the appearance of very small
particles (nuclei), of the new phase which are capable
of growing.
 There are two types of nucleation: homogeneous and
heterogeneous.
 The distinction between them is made according to
the site at which nucleating events occur.
 For the homogeneous type, nuclei of the new phase
form uniformly throughout the parent phase.
 Whereas for the heterogeneous type, nuclei form
preferentially at structural inhomogeneities, such as
container surfaces, insoluble impurities, grain
boundaries, dislocations, and so on. 101
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 Let us first consider the solidification of a pure
material, assuming that nuclei of the solid phase form
in the interior of the liquid as atoms cluster together
so as to form a packing arrangement similar to that
found in the solid phase.
 It will be assumed that each nucleus is spherical in
geometry and has a radius r.

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 When a liquid cools down just below its
freezing temperature, energy associated with
the crystalline structure of the solid is less
than the energy of the liquid.
 This energy difference is free energy per unit
volume.
 This force is the driving force for
solidification.

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 There are two contributions to the total free
energy change that accompany a solidification
transformation.
 The first is the free energy difference between
the solid and liquid phases, or the volume free
energy, Gv .
 Its value will be negative if the temperature is
below the equilibrium solidification
temperature, and the magnitude of its
contribution is the product Gv and the volume
of the spherical nucleus (i.e., 4/3 r3)
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 The second 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; furthermore,
the magnitude of this contribution is the
product of  and the surface area of the
nucleus (i.e., 4r2 ).
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 Finally, the total free energy change is equal
to the sum of these two contributions that is,

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 These volume, surface and total free energy
contributions are plotted schematically as a
function of nucleus radius.

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 A solid particle begins to form as atoms in the
liquid cluster together, its free energy first
increases.
 If this cluster reaches a size corresponding to the
critical radius r*, then growth will continue with
the accompaniment of a decrease in free energy.
On the other hand, a cluster of radius less than
the critical will shrink and re-dissolve.
 This subcritical particle is an embryo, whereas
the particle of radius greater than r* is termed a
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 A critical free energy, G*, occurs at the
critical radius and, consequently, at the
maximum of the curve.
 This corresponds G* to an activation free
energy, which is the free energy required for
the formation of a stable nucleus.

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 Differentiate w.r.t r

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 This volume free energy change Gv is the
driving force for the solidification
transformation, and its magnitude is a function
of temperature.
 At the equilibrium solidification temperature Tm,
the value of Gv is zero.
 It can be shown that Gv is a function of
temperature as

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 Substituting …

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 Thus, from the two equations, both the
critical radius r* and the activation free
energy G* decrease as temperature T
decreases.
 Physically, this means that with a lowering of
temperature at temperatures below the
equilibrium solidification temperature (Tm),
nucleation occurs more readily.

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 Although levels of super cooling for
homogeneous nucleation may be significant (on
occasion several hundred degrees Celsius), in
practical situations they are often on the order
of only several degrees Celsius.
 The reason for this is that the activation energy
for nucleation is lowered when nuclei form on
pre-existing surfaces or interfaces, since the
surface free energy is reduced.
 In other words, it is easier for nucleation to occur
at surfaces and interfaces than at other sites.
Again, this type of nucleation is termed
heterogeneous.
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 Let us consider the nucleation, on a flat
surface, of a solid particle from a liquid phase.
 It is assumed that both the liquid and solid
phases “wet” this flat surface, that is, both of
these phases spread out and cover the
surface.

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 Also noted in the figure are three interfacial
energies (represented as vectors) that exist at
two-phase boundaries— SL,SI and IL —as well
as the wetting angle  (the angle between the SI
and SL vectors)
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 Taking a surface tension force balance in the
plane of the flat surface leads to the following
expression

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 Most crystalline solids are composed of a
collection of many small crystals called
grains, and such materials are termed as
polycrystalline materials.

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 Grain Boundaries
 The boundary separating two small grains or crystals
having different crystallographic orientations in
polycrystalline materials
 When this orientation mismatch is slight, on the order of a
few degrees, then the term small- (or low- ) angle grain
boundary is used.
 These boundaries can be described in terms of dislocation
arrays.
 This type is called a tilt boundary.
 When the angle of mis-orientation is parallel to the
boundary, a twist boundary results, which can be
described by an array of screw dislocations.
 This type is called a twist boundary.
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 In the solidification process, two types of heat must be
removed:
 The specific heat of the liquid and
 The latent heat of fusion.
 The specific heat must be removed first, either by radiation
into the surrounding atmosphere or by conduction into the
surrounding mold, until the liquid cools to its freezing
temperature.
 The manner in which we remove the latent heat of fusion
determines the material’s growth mechanism and final
structure of a casting.

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 The growth of crystal is different in different
crystallographic directions.
 The resultant preferred direction of growth is
responsible for crystal orientation in cast
metals.
 Slow cooling favors growth of crystals
uniformly in all the directions of the growth
and gives equiaxed crystals, whereas rapid
cooling favors tree-like crystals, called
dendrites.
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 During the process of solidification, each
nucleus grows by attracting atoms from the
liquid into the space lattice.
 Crystal growth continues in three
dimensions, the atoms attaching themselves
in certain preferred directions, usually along
the axes of the crystal.
 This gives rise to a tree-like characteristic
structure which is called dendrites.
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Magnesium dendrites growing from liquid
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Dendrites in a nickel-based super alloy single-crystal weld
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 Dendrites of ice on window
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 The size of the grains in a casting is determined by the
relation between the rate of growth G and the rate of
nucleation N.
 If the number of nuclei formed is high, a fine-grain
material will be produced, and if only a few nuclei are
form, a coarse-grain will be produced.
 Factors increasing the rate of nucleation, thus promoting
the formation of fine grains are
 Rapid rate of cooling such as chill casting
 Presence of insoluble impurities such as Al and Ti thus form
insoluble oxides in steel
 Stirring the melt during solidification which tends to break up
the crystals before they have a chance to grow very large
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 The rate of growth relative to the rate of
nucleation is greatest at are just under the
freezing point.
 In general fine-grained materials exhibit
better toughness or resistance to shock.
 They are harder and stronger than coarse
grained materials because the deformation
path is greater in fine grained material when
compared to coarse grained material
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 Schematic illustration of three cast structures
of metals solidified in a square mold
 (a) pure metals
 (b) solid solution alloys
 (c) structure obtained by using nucleating agents.

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 The specimen is prepared and etched then the
image of the microstructure is projected at a
magnification of 100x.
 It is compared with a series of graded standard
grain size charts (American Society of Testing of
Materials - ASTM).
 By trial and error a match is secured and the
grain size of the metal is then designated by a
number corresponding to the index number of
the matching chart.

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 Metals showing a mixed grain size are rated
in a similar manner, and it is customary in
such cases to report the grain size in terms of
two numbers denoting the approximate
percentage of each size present.
 A grain size number below ASTM no 3
represents a coarse grained material while
that of above 3 are fine grained material.
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ASTM grain Avg. no. of Avg. diameter of
size no. grains per sq equivalent spherical
inch at 100x grains in microns.
1 1 287.0

2 2 203.0

3 4 144.0

4 8 101.0

5 16 71.8

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 The comparison method is most convenient
and sufficiently accurate for specimens
consisting of equiaxed grains.
 The ASTM grain-size number n may be
obtained as follows
N = 2(n-1)
where N is the number of grains observed per
square inch at 100x magnification.

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Different grain sizes for the materials are shown
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 At ambient conditions, yield strength rises as the grain
size decreases.
 The variation in strength can be described by a power-
law relationship:

where σ0 yield strength, D is the average diameter of the

grains, and σi and k are constants for the metal.
 The Hall-Petch effect quantifies the trend of increasing
strength and toughness with decreasing grain size.
 That is to say, fine grain size strengthens the material.
 Hence, presence of more grain boundaries (finer grain
size) will increase the resistance to deformation and
enhance the strength.
 This equation is not valid for both very large and
extremely fine grain materials. 145
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 Specimen preparation involves the different
stages:
 Selection of specimen
 Cutting
 Rough grinding
 Intermediate and Fine grinding
 Polishing
 Etching

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 Optical Microscope
 Transmission Electron Microscope
 Scanning Electron Microscope

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 X-ray diffraction
 X-rays are electromagnetic radiation with typical
photon energies in the range of 100 eV - 100 keV.
 For diffraction applications, only short wavelength x-
rays (hard x-rays) in the range of a few angstroms to
0.1 angstrom (1 keV - 120 keV) are used.
 Because the wavelength of x-rays is comparable to
the size of atoms, they are ideally suited for probing
the structural arrangement of atoms and molecules in
a wide range of materials.
 The energetic x-rays can penetrate deep into the
materials and provide information about the bulk
structure.
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 X-ray diffraction (cont…)
 Bragg’s Law
▪ Diffraction can occur whenever Bragg's law is satisfied. X-rays
primarily interact with electrons in atoms.
▪ When x-ray photons collide with electrons, some photons
from the incident beam will be deflected away from the
direction where they original travel.
▪ Diffracted waves from different atoms can interfere with
each other and the resultant intensity distribution is strongly
modulated by this interaction.
▪ Measuring the diffraction pattern therefore allows us to
deduce the distribution of atoms in a material.
▪ The peaks in a x-ray diffraction pattern are directly related to
the atomic distances. 150
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 X-ray diffraction (cont…)
 Bragg’s Law
▪ Consider the two parallel planes of atoms A– A’ and B–B’ in,
which have the same h, k, and l Miller indices and are
separated by the interplanar spacing dhkl.
▪ Now assume that a parallel, monochromatic, and coherent
(in-phase) beam of x-rays of wavelength, λ is incident on
these two planes at an angle .
▪ Two rays in this beam, labeled 1 and 2, are scattered by atoms
P and Q. Constructive interference of the scattered rays 1 and
2 occurs also at an angle to the planes, if the path length
difference between 1–P–1’ and 2–Q–2’ (i.e., ) is equal to a
whole number, n, of wavelengths. 151
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 X-ray diffraction (cont…)
 Bragg’s Law
2dhklsinθ = n λ
where, λ is the wavelength of the x-ray, θ the scattering angle,
and n an integer representing the order of the reflection.
 With monochromatic radiation, an arbitrary setting of
a single crystal in an x-ray beam will not generally
produce any diffracted beams. There would therefore
be very little information in a single crystal diffraction
pattern from using monochromatic radiation.

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 X-ray diffraction (cont…)
 This problem can be overcome by continuously
varying λ or θ over a range of values, to satisfy
Bragg's law. Practically this is done by:
▪ Using a range of x-ray wavelengths or
▪ By rotating the crystal or, using a powder or
polycrystalline specimen.

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 Diffusion is a process of mass transport by
atomic movement under the influence of
thermal energy and a concentration gradient.
 Diffusion is the phenomenon of material
transport by atomic motion.
 Atoms move from higher to lower concentration
region.
 If this movement is from one element to another
e.g. Cu to Ni, then it is termed inter diffusion /
impurity diffusion.
 If the movement is within similar atoms as in
pure metals, it is termed self-diffusion.
 Volume diffusion
 The atoms move through the crystal from one regular or
interstitial site to another.
 Because of the surrounding atoms, the activation energy is
large and the rate of diffusion is relatively slow.
 Grain boundary diffusion
 Atoms at the grain boundaries diffuse
 Atoms diffuse easily because the atom packing is
disordered and less dense in the grain boundaries
 Surface diffusion
 Diffusion through surface
 Definition of terms
 Diffusion Flux (J)
▪ Mass flow per unit area per unit time.
▪ Number of atoms of one plane moving to unit area of
another plane per unit time.
 Concentration Gradient (dC/dx)
▪ When Concentration of an element (C) is plotted versus
position within the solid, the resulting curve is
concentration profile, and the slope of the curve is
concentration gradient.
 Terms (cont…)
 Steady state and Non-steady state diffusion
▪ In steady state, the diffusion flux doesn’t change with
time.
▪ In non-steady state diffusion, at any given instant, the
flux varies with time.
 Diffusion Co-efficient/Diffusivity (D)
▪ It is an index of the rate or intensity at which the atoms
diffuse.
 Terms (cont…)
 Activation Energy (Qv)
▪ The energy required by an atom to overcome barriers and
resistance to atomic movements, is known as activation
energy.
 Diffusion Couple
▪ Many reactions and processes that are important in the
treatment of materials rely on the transfer of mass either
within a specific solid or from a liquid / gas or another solid
phase.
▪ Accomplished by diffusion
▪ This phenomenon is demonstrated with the use of a diffusion
couple, which is formed by keeping two metal bars together.
 Diffusion mechanism
 Diffusion of atoms involves movement in steps
from one lattice site to the another.
 For an atom to make such a move, two conditions
must be met
▪ There must be an empty adjacent site.
▪ The atoms must have sufficient energy to break bonds
with its neighboring atoms.
 Vacancy Diffusion
 This mechanism involves movement of atoms
from a regular lattice site to an adjacent vacancy.
 Since vacancy and atoms exchange position, the
vacancy flux is in the opposite direction.
 Interstitial Diffusion
 This mechanism involves migration of atoms from
one interstitial site to a neighboring empty
interstitial site.
 This mechanism is more prevalent for impurity
atoms such as hydrogen, carbon, nitrogen,
oxygen which are small enough to fit in to an
interstitial position.
 For substitutional diffusion atoms exchange their
places directly or along a ring (ring diffusion
mechanism).
 According to Arrhenius type behavior

where
nv – Number of vacancies per cm3
n – Number of atoms per cm3
Qv – Energy required to produce one mole of
vacancies in cal/mol or Joules/mol
R – Gas constant (8.31 Joules/mol K or 1.98 cal/Mol
K)
T – Temperature in Kelvin (K).
 Fick’s first law for steady state diffusion
 At steady state diffusion, diffusion flux is
proportional to concentration gradient.
 Fick’s second law for non-steady state
diffusion
 Factors affecting diffusion
 Temperature
 Nature of diffusing species
 Crystal structure
 Presence of crystal imperfections
 Grain size
 Impurities