Defects / Imperfections in

Crystalline Materials
 Defects/ Imperfections
 Real Crystals are not perfect – Imperfect Crystal
 Perfect Crystal = Ideal Crystal = Where the atoms are
oriented across a particular direction and regular fashion
with no defects
 Defects alter the mechanical and physical properties of
the material
 Crystalline defect is meant as a lattice irregularity having
one or more of its dimension in the order of an atomic
diameter
 Defects may be created intentionally to produce desired
set of electronic, magnetic, optical and mechanical
properties
 Cont…
Crystal lattice imperfections are
classified according to the geometry and
shape
 Point Defects / Zero Dimensional Defects
Line Defects / Linear Defects / Dislocations / One
Dimensional Defects
Planar Defects / Surface Defects /
Two Dimensional Defects
Volume Defects / Bulk Defects/
Macroscopic Defects/ Three dimensional Defects
Point Defects / 0-D defects
 Localized disruptions in a perfect atomic / ionic
arrangements in a crystal structure
 These imperfections may be introduced by the
movement of atoms/ions when they gain energy
by heating during processing of material, by
introducing impurities
 Point Defects – Category
◦ Vacancy Defects
◦ Interstitialcy Defects
◦ Schotky Defects
◦ Frenkel Defects
Vacanc
y One / more atoms is missing from its normal site in the crystal

 When atoms are missing from the site, the overall entropy of the
material which increases the thermodynamic stability of the
material
 Vacancy, a point defect, may occur due to various reasons, as enlisted
below:
 For not allowing directional solidification, usually during casting.
 Due to increase in temperature of the solid for various processing like
heat treatment, coating, etc. Number of vacancies in a specific amount
of solid increases exponentially as indicated by the expression
provided below.
 Due to irradiation or sputtering effect.
 Due to presence of residual tensile stress within the solid
 Vacancies are equilibrium defects in metals and their formation is
1 eV
 At elevated temperatures, the mobility of atoms is greater
 At room temperatures, the concentration of vacancies are smaller
but it increases exponentially as temperature increases
We can estimate that at room temperature in copper there is one vacancy
pet 1015 lattice atoms, whereas just below the melting point there is one
vacancy for every 10,000 atoms – very strong temperature dependence
Why are vacancies referred to as equilibrium thermodynamic defects?
In these discussion, we will keep in view metallic crystals like Fe, Cu,
Zn, etc.
 Formation of a vacancy leads to ‘missing bonds’ and distortion of the lattice.
 The potential energy (Internal energy & Enthalpy) of the system increases.
 Work required for the formation 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 (the crystal without vacancies represents just one
state, while the crystal with vacancies can exist in many energetically
equivalent states, corresponding to various positions of the vacancies in the
crystal → ‘the system becomes configurationally rich’).
  at some temperature above zero Kelvin there is an equilibrium
concentration/number of vacancies (at ‘low’ temperatures no vacancies may be stable).
 These type of vacancies are called Thermal Vacancies (and will not leave
the crystal on annealing at a temperature at which these are stable→
Thermodynamically stable).
Contd…
 Non-equilibrium concentration of vacancies can
be generated by:
 quenching from a higher temperature
 bombardment with high energy particles
 plastic deformation.
Interstitialc
y site between the surrounding atoms in normal sites
Sometimes an atom in a crystal can occupy the interstitial


 Interstitial Atoms may be

 Self Interstitial
 Substitutional impurity
 Interstitial impurity

A self interstitial atom is an atom from

the crystal that is crowded into an
interstitial site creating a small void
space that doesn’t happen under normal
circumstances
At elevated temperatures, this type of
crowning of self interstitial atoms occur
 Cont..
 Substitutional Impurity
In Substitutional type, solute or the
impurity atom replace the host atoms.
Eg. Cu - Ni

 Interstitial Impurity
• Interstitial impurity atom fills
the void
• between
For the host materials
atoms that hav
relatively
metallic highAPFs, interstitial
e
these
positions are relatively
small
• Eg. Fe-C
Solid
Solution
 A solid solution forms as when the solute atoms are
added to the host material, the crystal structure is
maintained and no new strcutures are formed
 A solid solution is compositionally homogeneous; the
impurity atoms are uniformly / randomly distributed
within the solid
Schotky Defects Frenkel Defects
 Di-vacancy defect  If a positive cation moves
 When 2 oppositely charged into an interstitial site in an
ions are missing from the ionic crystal, a cation
ionic crystal, a cation – vacancy is created in the
anion divacancy is created normal ion site
 This vacancy – interstitialcy
pair is known as Frenkel defect
 Dislocations /
One Dimensional defects /
Linear defects / Line Defects
Dislocations
 Dislocations are a type of topological defect,
sometimes called a soliton (Wave pocket or simply a pulse)
 A dislocation may be defined as a disturbed region
between two substantially perfect parts of a crystal.
 A dislocation is a linear defect around which some of the atoms
are misaligned.
 There are two basic types of dislocations, the edge dislocation
and the screw dislocation.
 Edge and Screw dislocations are just extreme forms of
the
possible dislocation structures that can occur
 Responsible for large mechanical deformation in crystalline
solids; They occur in high densities and strongly influence the
mechanical properties of material.
 Dislocations are non-equilibrium defects and they store energy
in the distorted region of the crystal lattice around the
dislocation
 Can be visualized using TEM, Field Ion Microscopy (FIM)
 Dislocation is a boundary
between the slipped and
Slipped Unslipped the unslipped parts of the
part part crystal lying over a slip
of the of the plane
crystal crystal
Edge Dislocations or Taylor-Orowan
dislocation

The motion of dislocations is

the principle mechanism
whereby metals deform
 Edge
dislocations
 It may be described as an edge of an extra plane of
atoms within a crystal structure.
 Thus regions of compression and tension are associated
with an edge dislocation.
 Because of extra incomplete plane of atoms, the atoms
above the dislocation line are squeezed together and are
in state of compression whereas atoms below are pulled
apart and experience tensile stresses.
 Edge dislocation

Direction of tt vector

dislocation line vector

Direction of b
b vector
Compressive stress
field

Tensile stress
field
Edge Dislocations

 Edge Dislocation motion is

analogous to movement of a
caterpillar.
 The caterpillar would have to
exert a large force to move its
entire body at once.
 Instead it moves the rear
portion of its body forward a
small amount and creates a
hump.
 The hump then moves forward
and eventual moves all of the
body forward by a small amount.
Incrementally breaking bonds  Similarly the edge dislocations
•If dislocations don't move, deformation doesn't move incrementally by breaking
happen! (But fracture will, like in a ceramic) by the bonds
Mechanism of Mechanism of
Glide Climb

Dislocation motion by climb occurs when the

When the dislocation moves in the dislocation moves out of the glide plane, and
plane which contains both its line thus normal to the Burgers vector
and its Burgers vector
SCREW DISLOCATIONS
 There is a second basic type of dislocation, called screw dislocation.
 Screw dislocation is slightly more difficult to visualize.
 The motion of a screw dislocation is also a result of shear stress, but the defect
line movement is perpendicular to direction of the stress and the atom
displacement, rather than parallel.
 Screw dislocation was named for continuous, pivotal motion around a given
point, but with each circumnavigation reaching a different plane than the
previous one, not unlike the motion along a [Link] each turn of a screw,
an elevation of one step is made.
Contd…
A screw dislocation is like a spiral ramp with an
imperfection line down its axis.
 Screw dislocations result when displacing planes relative
to each other through shear.
 Shear stresses are associated with the atoms adjacent to
the screw dislocation
 A screw dislocation does not have a preferred slip plane,
as an edge dislocation has, and thus the motion of a
screw dislocation is less restricted than the motion of an
Edge dislocation.
 As there is no preferred slip plane, screw dislocation can
cross-slip on to another plane, and can continue its glide
under favorable stress conditions.
Contd….
 Unlike point defects, these are not thermodynamically
stable.
 They can be removed by heating to high temperatures
where they cancel each other or move out through the
crystal to its surface
Burger’s
Vector
 The Burgers vector of a dislocation is a crystal vector,
specified by Miller indices, that quantifies the difference
between the distorted lattice around the dislocation and
the perfect lattice.
 Equivalently, the Burgers vector denotes the direction
and magnitude of the atomic displacement that occurs
when a dislocation moves.
 A dislocation is characterized by its ‘Burgers vector’,
which is defined by what is known as the ‘Burgers
circuit’. A dislocation has two properties – a line
direction and its Burgers vector.
 In an edge dislocation, the Burgers vector is
perpendicular to the line direction, whereas, in screw
dislocations, it is parallel
Cont…
The Burger vector can be found by the gap in the Burger
circuit which is obtained by moving equal distances in
each direction around the dislocation
Characteristics of Dislocations
 Mixed
Dislocations

Components characterizes most dislocations in crystals

Dislocation
• Pure screw type where it enters the crystal (at left)
• Pure edge type where it leaves the crystal (on the right)
• Mixed type, with edge and screw components within the
crystal
Dislocations and
Ductility
 A largenumber of independent slip systems are required
for good ductility in polycrystalline materials so grains
can deform to accommodate their neighboring grains
 Common in many metal structures (bcc and fcc)

Dislocations are very complex in ceramic structures.

 This complications of like charged ions encountering
each other during slip make dislocation movement
almost impossible in ceramics
 Therefore ceramics are not ductile, they are brittle
Grain boundaries other dislocations impede the
and movement of
dislocation causing “hardenin
s g”