MICROSTRUCTURAL

PROPERTIES
 DEFECTS IN MATERIALS

ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

 Imperfections in Solids
3

Solidification- result of casting of molten material

 2 steps
 Nuclei form
 Nuclei grow to form crystals – grain structure
 Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig.4.14 (b), Callister 7e.
• Crystals grow until they meet each other
 Polycrystalline Materials
4

Grain Boundaries
 regions between crystals
 transition from lattice of one
region to that of the other
 slightly disordered
 low density in grain
boundaries
 high mobility
 high diffusivity
 high chemical reactivity

Adapted from Fig. 4.7, Callister 7e.

 Defects in Materials
 Descriptions of defects in materials at the basic level focuses,
appropriately on intrinsic defects (vacancies, dislocations).
 For the materials engineer, however, defects include extrinsic
defects such as voids, inclusions, grain boundary films, and other
types of undesirable second phases.
 Vacancy is a type of point defect in a crystal where an atom is
missing from one of the lattice sites.
 Voids are introduced either by gas evolution in solidification or by
incomplete sintering in powder consolidation.
 Inclusions are second phases entrained in a material during
solidification. In metals, inclusions are generally oxides from the
surface of the metal melt, or a slag.
 Grain boundary films are common in ceramics as glassy films
from impurities.
 In aluminum alloys, there is a hierachy of names for second phase
particles; inclusions are unwanted oxides (e.g. Al2O3); dispersoids
are intermetallic particles that, once precipitated, are
thermodynamically stable (e.g. AlFeSi compounds); precipitates are
intermetallic particles that can be dissolved or precipiated
depending on temperature (e.g. AlCu compounds).
 What is meant by Defect Structure?

 The term Defect Structure:

 Defect means-
 imperfection
 lack of something
 structural imperfection etc..
 The following points go on to outline ‘Defect Structure’:
 Kinds of defects present along with their dimensionality (vacancies, dislocations, grain
boundaries etc.)
 Based on association with Symmetry and Symmetry Breaking
 The nature of these defects in terms of their origin: Statistical or Structural
 The nature of these defects in terms of their position: Random or Ordered
 Density and spatial distribution of these defects
 Based on the fact that if the defect is with respect to a geometrical entity or a
physical property
IMPERFECTIONS IN SOLIDS:

There is no such thing as a perfect crystal!

• Thermodynamically “impossible”
• “defects” lower the energy of a crystal & make it more stable
• always have vacancies and impurities, to some extent

Defect does not necessarily imply a bad thing

• addition of C to Fe to make steel
• addition of Cu to Ni to make thermocouple wires
• addition of Ge to Si to make thermoelectric materials
• addition of Cr to Fe for corrosion resistance
• introduction of grain boundaries to strengthen materials
…… and so on

“Defect” (in this context) can be either desirable or

undesirable.
In general, a defect simply refers to a disruption in the crystalline
order of an otherwise periodic material.
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area/Surface defects

10
CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

0D 1D 2D 3D
(Point defects) (Line defects) (Surface / Interface) (Volume defects)

Surface Twins
Vacancy Dislocation
Interphase Precipitate
Impurity Disclination
boundary
Faulted
Frenkel Dispiration Grain
region
defect boundary
Twin Voids /
Schottky
boundary Cracks
defect
Stacking Thermal
faults vibration
Anti-phase
boundaries
• Microscopic defects can occur in crystals,
amorphous solids and polymers.
• In crystals there are:
• Point defects (Vacancies, Interstitials,
Impurities)
• Line defects (Edge and Screw Dislocations)
• Planar defects (Grain boundaries,
Microcracks)
• Volume defects (Voids).

• Microcracks and Voids occur in Amorphous

materials
• Polymers can have partly crystalline regions so
can have all of these defects.
 SYMMETRY ASSOCIATED DEFECTS

Translation Rotation Screw

Atomic
Dislocation Disclination Dispiration
Level

SYMMETRY ASSOCIATED DEFECTS

Mirror Rotation Inversion

Twins Multi-atom
 The operation defining a defect cannot be a
symmetry operation of the crystal.
DEFECTS
Based on A defect “associated” with a symmetry
symmetry operation of the crystal  topological defect
breaking
Topological Non-topological

BASED ON
ENTITY IN
QUESTION

GEOMETRICAL PHYSICAL
E.g. atoms, clusters etc. E.g. spin, magnetic
moment
P O I N T D E F E C T S : W H I C H A R E P L A C E S , W H E R E A N AT O M I S M I S S I N G
(OR) IRREGULARITY PLACED IN THE L AT T I C E STRUCTURE. POINT
DEFECT INCLUDES
 Lattice vacancies
 Self interstitial atoms
 Substitution impurity atoms
 Interstitial impurity atoms

LINEAR DEFECTS: WHICH ARE GROUPS OF AT O M S IN IRREGULAR

P O S I T I O N S . L I N E A R D E F E C T S A R E C O M M O N LY C A L L E D D I S L O C AT I O N S .
T Y P E S O F D I S L O C AT I O N S :
• edge dislocation - movement of a caterpillar
• screw dislocation - Result of Shear stress
P L A N A R D E F E C T S : W H I C H A R E I N T E R FA C E B E T W E E N H O M O G E N E O U S
R E G I O N S O F T H E M AT E R I A L . P L A N A R D E F E C T S I N C L U D E
 Grain boundaries
 Stacking faults
 External surfaces
 Vacancy
Non-ionic Interstitial
Impurity
crystals
Substitutional
0D
(Point defects) Frenkel defect
Ionic
Other ~
crystals
Schottky defect

 Imperfect point-like regions in the crystal about the size of 1-2

atomic diameters
Vacancy

 Missing atom from an atomic site

 Atoms around the vacancy displaced
 Tensile stress field produced in the vicinity

• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortio
n of
planes

Tensile Stress
Fields ?
 -"extra" atoms positioned Relative
between atomic sites. size
Interstitial
Compressive
Impurity Stress
Fields
Substitutional distortion of planes
Foreign atoms replaces
original atomic site

Compressive stress
fields

INTERSTITIAL IMPURITY
Tensile Stress
 Foreign atom sitting in the void of a crystal
Fields
 E.g. C sitting in the octahedral void in HT FCC-Fe
 SUBSTITUTIONAL IMPURITY
 Foreign atom replacing the parent atom in the crystal
 E.g. Cu sitting in the lattice site of FCC-Ni
 Ionic Crystals

 Overall electrical neutrality has to be maintained

Frenkel defect

 Cation (being smaller get displaced to interstitial voids

 E.g. AgI, CaF2
Schottky defect

 Pair of anion and cation vacancies

 E.g. Alkali halides
Other defects due to charge balance

 If Cd2+ replaces Na+ → one cation vacancy is created

Defects due to off stiochiometry

 ZnO heated in Zn vapour → ZnyO (y >1)

 The excess cations occupy interstitial voids
 The electrons (2e) released stay associated to the interstitial cation
 FeO heated in oxygen atmosphere → FexO (x <1)
 Vacant cation sites are present
 Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ → Fe3+ + e
 For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions → provides the 2 electrons required by excess oxygen
Equilibrium Concentration: Point Defects
• Equilibrium vacancy concentration of the material with point defects
varies with temperature! Vacancies occur naturally in all crystalline
materials. At any given temperature, up to the melting point of the
material, there is an equilibrium concentration (ratio of vacant lattice
sites to those containing atoms). At the melting point of some metals
the ratio can be approximately 1:1000.

No. of defects Activation energy

Nv æ -Q ö
No. of potential = expçç v
N è kT ø
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom.K)
(8.62 x 10 -5 eV/atom.K)
Each lattice site is a
23
potential vacancy site
 Measuring Activation Energy
• We can get Qv from Nv æ-Q ö
ç
ç
= exp è v÷
÷
an experiment. N kT ø
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T 1/T
defect concentration
24
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
• Given: Atomic weight
r = 8.4 g/cm 3 A Cu = 63.5 g/mol
Avagadro number
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Nv = æ-Q ö
exp çç v÷
÷ = 2.7 x 10-4
N è kT ø
1273K
8.62 x 10-5 eV/atom-K
NA
For 1 m , N = r x
3 x 1 m3 = 8.0 x 1028 sites
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
25
 Observing Equilibrium Vacancy Conc.
• Low energy electron
microscopic view of
a (110) surface of NiAl.
• Increasing T causes
surface island of
atoms to grow.
• Why? When the equilibrium
vacancy concentration
increases, atoms are expelled
to surface via atom motion from Reprinted with permission from Nature (K.F. McCarty,
J.A. Nobel, and N.C. Bartelt, "Vacancies in
the crystal to the surface, Solids and the Stability of Surface Morphology",
where they join the island. Nature, Vol. 412, pp. 622-625 (2001). Image is
5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
Island grows/shrinks to maintain Publishers, Ltd.
equil. vancancy conc. in the bulk.

26
 ENTHALPY OF FORMATION OF VACANCIES

 Formation of a vacancy leads to missing bonds and distortion of the

lattice
 The potential energy (Enthalpy) of the system increases
 Work required for the formaion of a point defect →
Enthalpy of formation (Hf) [kJ/mol or eV / defect]
 Though it costs energy to form a vacancy, its formation leads to
increase in configurational entropy
  above zero Kelvin there is an equilibrium number of vacancies

Crystal Kr Cd Pb Zn Mg Al Ag Cu Ni
kJ / mol 7.7 38 48 49 56 68 106 120 168
eV / vacancy 0.08 0.39 0.5 0.51 0.58 0.70 1.1 1.24 1.74
 G (perfect crystal) T (ºC) n/N
500 1 x 1010
At a given T
G (G ib b s fre e e n e rg y )

1000 1 x 105
1500 5 x 104
G m in
2000 3 x 103
Hf = 1 eV/vacancy
E q u ilib riu m
c o n c e n tra tio n = 0.16 x 1018 J/vacancy

n (n u m b e r o f v a c a n c ie s )

 Certain equilibrium number of vacancies are preferred at T > 0K

29
 Planar or Surface defects:
o Surface defects are the boundaries or planes that
separate a material into regions.
o Each region having same crystal structures but different
orientations.
o There are different kinds of surface defects, some of
which are described.
 Material surface
 Grain boundaries
 Small angle grain boundaries
 Stacking faults
 Twin boundaries
 Dislocation Edge

Disclination Screw
Intrinsic

Local Edge
Extrinsic Disclination
Defects in surface crystals Edge
Dislocation
Global Extrinsic Edge
Disclination
Screw
35
36
37
38
 Microstructures and classification

Microstructure is the fine structure (in a metal or other material) which can be made

visible when examined with a microscope.
Microstructure is the structure of a material as revealed through microscopic

examination.
Classification

Metallic 
Polymeric 
Ceramic 
Composite
It can strongly influence physical properties such as strength, toughness, ductility,

hardness, corrosion resistance, high/low temperature behavior, wear resistance
Grain Size:
Particle size, also called grain size, refers to
the diameter of individual grains
of sediment, or the lithified particles
in clastic rocks.
The term may also be applied to
other granular materials.
This is different from the crystallite size,
which refers to the size of a
single crystal inside a particle or grain.
A single grain can be composed of
several crystals. 
Granular material can range from very
small colloidal particles,
through clay, silt, sand, gravel, and cobbles,
to boulders.
 Grain Size control:

Grain size can decrease with

increasing deformation carried out
on the material.

Grain size can increase with increasing

annealing temperature.
Grain size can decrease with rate of
cooling. Quenching (rapid cooling)
will result in smaller grain size.
Factors affecting grain size :
• Number and location of the nuclei at the time
of solidification
• Shape of the mould in which the metal
solidifies
• Rate of crystallization
• Rate of cooling
• Cold working
• Nucleating agents
What is nucleation?

 As the metal is cooled, clusters of atoms come together from

the liquid to form solid crystal nuclei.
 This nuclei will be stable and grow into crystallites or grains.
 Nucleation can occur by two processes: Homogenous
nucleation Heterogeneous nucleation.
 Mechanism of crystallization: Crystallization is controlled by
atomic diffusion from melt to the nuclei. Characteristically a
pure metal may crystallize in a tree branch pattern from a
nucleus. Such formations are called dendrites.
 Microstructure of copper-tin alloy showing branch like
dendritic formations
 Microstructure of brass alloy showing branch like dendritic
formations
 What is Growth?

 Grain growth refers to the increase in size of grains

(crystallites) in a materials at high temperature. This occurs
when recovery and recrystallisation are complete.
 This term commonly used in metallurgy, ceramics &minerals
 Grain growth occur by the movement of grain boundaries.
 Consider a phase transformation in which α-phase (parent
phase) changes to β-phase (product phase), after nucleation,
the product phase starts growing at different nucleation sites.
 The growth rate depends on the extent of super cooling ∆T.
 During growth, atoms jump from the parent phase α to the
product phase β.
 Recovery
 Annealing relieves the stresses from cold working –
three
stages: recovery, recrystallization and grain growth.
 Recovery involves annihilation of point defects.
 Driving force for recovery is decrease in stored energy from
cold work.
 During recovery, physical properties of the cold-worked
material are restored without any observable change in
microstructure.
 Recovery is first stage of annealing which takes place at low
temperatures of annealing.
 There is some reduction, though not substantial, in dislocation
density as well apart from formation of dislocation
configurations with low strain energies.
 Recrystallization

 This follows recovery during annealing of cold worked

material. Driving force is stored energy during cold work.
 It involves replacement of cold-worked structure by a new
set of strain-free, approximately equi-axed grains to replace all
the deformed crystals.
 This is process is characterized by recrystallization
temperature which is defined as the temperature at which
50% of material recrystallizes in one hour time.
 The recrystallization temperature is strongly dependent on
the
purity of a material.
 Pure materials may recrystallizes around 0.3 Tm, while impure
materials may recrystallizes around 0.5-0.7 Tm, where Tm is
 Recrystallization laws

 A minimum amount of deformation is needed to cause

recrystallization (Rx).
 Smaller the degree of deformation, higher will be the Rx
temperature.
 The finer is the initial grain size; lower will be the Rx temperature.
 The larger the initial grain size, the greater degree of deformation is
required to produce an equivalent Rx temperature.
 Greater the degree of deformation and lower the annealing
temperature, the smaller will be the recrystallized grain size.
 The higher is the temperature of cold working, the less is the
strain energy stored and thus Rx temperature is correspondingly
higher.
 The Rx rate increases exponentially with temperature.
 Grain growth

 Grain growth follows complete crystallization if the material

is left at elevated temperatures.
 Grain growth does not need to be preceded by recovery and
recrystallization; it may occur in all polycrystalline materials.
 In contrary to recovery and recrystallization, driving force
for this process is reduction in grain boundary energy.
 Tendency for larger grains to grow at the expense of smaller
grains is based on physics.
 In practical applications, grain growth is not desirable.
 Incorporation of impurity atoms and insoluble second
phase particles are effective in retarding grain growth.
 Grain growth is very strongly dependent on temperature.
Rules Of Grain Growth:
Grain growth has long been studied primarily by the examination of
sectioned, polished and etched samples under the optical microscope.
The following rules became well established features of grain growth:
 Grain growth occurs by the movement of grain boundaries and not
by coalescence (i.e, like water droplets).
 Boundary movement is discontinuous and the direction of motion
may change suddenly.
 One grain may grow into one grain whilst being consumed from
the other side.
 The rate of consumption often increases when the grain is nearly
consumed.
 A curved boundary typically migrates towards its centre of
curvature.
 The grain included by the more acute angle will be consumed so
that the angles approach 120º
Normal Grain Growth:
 It is the growth where all grains grow at roughly the same rate.

Discontinuous(abnormal) Growth:
 Grain growth is one in which some grain grows at a much

greater rate than its neighbors.

Continuous Discontinuous
Aging:
Aging (the process of growing old) process at room

temperature is called natural aging.

Aging at elevated temperature is called artificial

aging
Aging can be reinitiated by heating the solid solution

to a temperature where the process will be faster and

can be controlled easily.
Two Common Types of Grain Structures:

Equiaxed Grains: These grains grow equally in all directions. If the

nucleation and growth conditions are suitable in the liquid metal

which is cooling slowly, one obtains equiaxed grains.

Equiaxed grains are grown near a cold wall. Large amount of super
cooling results in the formation of large number of nuclei.
Grain boundary:

A grain boundary is the interface between two grains,

or crystallites, in a polycrystalline material. Grain boundaries
are 2D defects in the crystal structure, and tend to decrease
the electrical and thermal conductivity of the material. Most
grain boundaries are preferred sites for the onset of corrosion
and for the precipitation of new phases from the solid. They are
also important to many of the mechanisms of creep. On the
other hand, grain boundaries disrupt the motion
of dislocations through a material, so reducing crystallite size is
a common way to improve mechanical strength.
 55
GRAIN BOUNDARIES

They are the imperfections which separate crystals or grains of

different orientation in a poly crystalline solid during nucleation or
crystallization.
It is a two dimensional imperfection. During crystallization, new
crystals form in different parts and they are randomly oriented with
respect to one another.
They grow and impinge on each other.
The atoms held in between are attracted by crystals on either side
and depending on the forces, the atoms occupy equilibrium
positions.
PH 0101 UNIT 4 LECTURE 7
 56
GRAIN BOUNDARIES

These positions at the boundary region between two

crystals are distorted. As a result, a region of transition
exists in which the atomic packing is imperfect.
The thickness of this region is 2 to 10 or more atomic
diameters.
The boundary region is called a crystal boundary or a
grain boundary.
The boundary between two crystals which have different
crystalline arrangements or different compositions, is
called as interphase boundary or commonly an interface.

PH 0101 UNIT 4 LECTURE 7

 57
GRAIN BOUNDARIES

PH 0101 UNIT 4 LECTURE 7

58
 59
TILT BOUNDARIES

This is called low-angle boundary as the orientation

difference between two neighbouring crystals is less than 10°.
The disruption in the boundary is not so severe as in the
high-angle boundary. In general low-angle boundaries can be
described by suitable arrays of dislocation.
Actually a low-angle tilt boundary is composed of edge
dislocation lying one above the other
The angle or tilt will be b

D
where b = Burgers vector and
D = the average vertical distance between dislocations.

PH 0101 UNIT 4 LECTURE 7

 60
TILT BOUNDARIES

PH 0101 UNIT 4 LECTURE 7

 TWIN BOUNDARIES
61

If the atomic arrangement on one side of a boundary is

a mirror reflection of the arrangement on the other side,
then it is called as twin boundary.
As they occur in pair, they are called twin boundaries.
At one boundary, orientation of atomic arrangement
changes.
At another boundary, it is restored back. The region
between the pair of boundaries is called the twinned
region.
These boundaries are easily identified under an optical
microscope.

PH 0101 UNIT 4 LECTURE 7

 TWIN BOUNDARIES
62

PH 0101 UNIT 4 LECTURE 7

63
64
Grain boundaries and precipitates
66
 STACKING FAULTS
67

Whenever the stacking of atomic planes is not in a

proper sequence throughout the crystal, the fault caused
is known as stacking fault.
For example, the stacking sequence in an ideal FCC
crystal may be described as A-B-C-A-B-C- A-B-C-…….
But the stacking fault may change the sequence to A-B-
C-A-B-A-B-A-B-C. The region in which the stacking
fault occurs (A-B-A-B) forms a thin region and it
becomes HCP.
This thin region is a surface imperfection and is called
a stacking fault.

PH 0101 UNIT 4 LECTURE 7

 STACKING FAULTS
68

PH 0101 UNIT 4 LECTURE 7

 VOLUME IMPERFECTIONS
69

Volume defects such as cracks may arise in crystals when

there is only small electrostatic dissimilarity between the
stacking sequences of close packed planes in metals.
Presence of a large vacancy or void space, when cluster of
atoms are missed is also considered as a volume
imperfection.
Foreign particle inclusions and non crystalline regions
which have the dimensions of the order of 0.20 nm are also
called as volume imperfections.

PH 0101 UNIT 4 LECTURE 7