1.

0 DEFECTS IN CRYSTALS

Any deviation from the perfect atomic arrangement in a crystal is said to contain
imperfections or defects.

An ideal crystal is a perfect crystal in which each atom has identical surroundings.
Real crystals are not perfect, but contain imperfections that are classified according
to their geometry and shape into point, line, and planar defects.

• A real crystal always has a large number of imperfections in the lattice.

The study of imperfections has a two-fold purpose, namely,

- A better understanding of crystals and how they affect the properties of

metals.
- Exploration of possibilities of minimizing or eliminating these defects.

A crystal is a solid composed of atoms, ions, or molecules arranged in a repetitive 3-

D pattern. In an ideal crystal the atomic arrangement is perfectly regular and
continuous where as in real crystal, there is a lattice distortion and various
imperfections, irregularities and defects are present.

A crystal structure is built of atoms. A crystal lattice is an infinite pattern of points,

each of which must have the same surroundings in the same orientation.

The properties of materials are profoundly influenced by the presence of

imperfections.

1. The conductivity of some semiconductors is due to entirely trace amount of

chemical impurities.
2. Colour, luminescence of many crystals arise from impurities and
imperfections.
3. Atomic diffusion may be accelerated enormously by impurities or
imperfections.
4. Mechanical and plastic properties are usually controlled by imperfections.
Crystal imperfections can be classified on the basis of their geometry (point, line or
plane) or dimensions of the defect as,

1.1 POINT DEFECTS

Points defects are defects of atomic dimensions that usually result from the presence
of an impurity atom, the absence of a matrix atom, or the presence of a matrix atom
in the wrong place. They are zero-dimensional lattice defects, meaning they have
no lattice structure in any dimension.

Point defects may be created as follows:

i. By thermal fluctuations
ii. By quenching (fast cooling) from a higher temperature
iii. By severe deformation of the crystal lattice e.g., by hammering or rolling.
While the lattice still retains its general crystalline nature, numerous
defects are introduced. (Plastic deformation)

There are different kinds of point imperfections;

1.1.1 VACANCY

A vacant site is referred to as VACANCY. A vacancy exists in a crystal where a normal

lattice site is unoccupied.

• All crystalline solids contain vacancies.

• Principles of thermodynamics is used explain the necessity of the existence

of vacancies in crystalline solids.

• The presence of vacancies increases the entropy (randomness) of the

crystal.

• The equilibrium number of vacancies for a given quantity of material depends

on and increases with temperature as follows: (an Arrhenius model)

∆𝐸𝑑
𝑁𝑑 = 𝑁 𝑒𝑥𝑝 [− ( )]
𝐾𝑇
Where:

𝑁𝑑 = Equilibrium number of point defects (vacancies)

𝑁 = the number of atomic sites per cubic metre or per mole (total number of atomic
sites)

∆𝐸𝑑 = the activation energy necessary to form the defect

𝑇 = the absolute temperature

𝐾 = the Boltzmann constant (= 1.38 × 10−23 𝐽 ∕ 𝑎𝑡𝑜𝑚 − °𝐾)

• If an atom is missing from its normal site in the matrix, the defect is called
a vacancy defect.

• It may be a single vacancy, divacancy or a trivacancy.

Fig. 1.1 Point defects

In metals, vacancies are created by thermal excitation (vibrations) of atoms at high

temperatures.

• When the temperature is sufficiently high, as the atoms vibrate around their
regular positions, some acquire enough energy to leave the site completely.

• When the regular atom leaves, a vacancy is created.

1.1.2 SUBSTITUTIONAL IMPURITY

• It refers to a foreign atom that substitutes for or replaces a parent atom in

the crystal.
 • Pentavalent or trivalent impurity atoms doped in Silicon or Germanium are
also substitutional impurities in the crystal.

Fig. 1.2 Substitutional impurity - Cu in Ni

1.1.3 INTERSTITIAL IMPURITY

• An interstitial defect arises when an atom occupies a definite position in the

lattice that is not normally occupied in the perfect crystal. Interstitials are
atoms lying between lattice sites. They can be impurities or matrix
constituent atoms.

• In crystals, packing density is always less than 1.

• If a small sized atom occupies the void space in the parent crystal without
disturbing the parent atoms from their regular sites, then it is called as
‘interstitial impurity’.
Fig. 1.3 C in Fe as Interstitial impurity atom

1.1.4 SELF-INTERSTITIAL IMPURITY

Here an "extra" atom is positioned between atomic sites. A matrix atom in an

interstitial site is called self-interstitial.

This defect occurs when an atom from the crystal occupies the small void space
(interstitial site) that under ordinary circumstances is not occupied.

In metals, a self-interstitial introduces relatively (very) large distortions in the

surrounding lattice.

SELF-INTERSTITIAL: very rare occurrence but may be introduced into a structure by

radiation.

Fig. 1.4 Forms of Point defects

Point defects in ionic structure differ from those found in pure elements because of
their charge requirement in ionic solids. Examples of such defects are Frenkel and
Schottky.

1.1.5 FRENKEL DEFECTS

A cation is displaced from its lattice position to an interstitial site. Frenkel defect
is related to interstices.

Fig. 1.5 Frenkel defect

As no ions are missing from the crystal lattice as a whole, therefore density of the
solid remains the same.

Defects can be found in silver halides such as AgCl, AgBr, AgI, ZnS, etc. So far as of
the small size of the Ag ions and ions, these ions can move into the interstitial sites.

1.1.6 SCHOTTKY DEFECT

This defect is caused whenever a pair of positive and negative ions are missing from
a crystal. This type of imperfection maintains a charge neutrality.
Fig. 1.6 Schottky defect

1.2 LINE IMPERFECTIONS

Are one-dimensional defects around which atoms are misaligned. Dislocation are line
defects, that leads to the atom misalignment-

• causes slip between crystal planes when it moves and

• produces permanent (plastic) deformation.

Dislocations are very important imperfections in real materials. They are formed
during solidification or when the material is deformed.

Dislocations strongly affect the mechanical, electronic and photonic properties of

materials.

The two types of dislocations are,

• Edge dislocation

• Screw dislocation

1.2.1 EDGE DISLOCATION

• In perfect crystal, atoms are arranged in both vertical and horizontal planes
parallel to the side faces.
 • If one of these vertical planes does not extend to the full length, but ends in
between within the crystal it is called ‘edge dislocation’.

• In the perfect crystal, just above the edge of the incomplete plane the atoms
are squeezed and are in a state of compression.

• Just below the edge of the incomplete plane, the atoms are pulled apart and
are in a state of tension.

• The distorted configuration extends all along the edge into the crystal.

• Thus, as the region of maximum distortion is centred around the edge of the
incomplete plane, this distortion represents a line imperfection and is called
an edge dislocation.

• Edge dislocations are represented by ‘⊥’ (inverted tee) or ‘Τ‘ depending on

whether the incomplete plane starts from the top or from the bottom of the
crystal.

• These two configurations are referred to as positive and negative edge

dislocations respectively.

Edge dislocation is where an extra half plane of atoms is “inserted” into the crystal
lattice (i.e., half plane of atoms disrupts the overall crystal structure). Due to the
edge dislocations metals possess high plasticity characteristics. The magnitude and
the direction of the displacement are defined by a vector called the Burgers Vector.
It indicates the extent of lattice distortion caused by the dislocation and direction
in which the slip will occur.
Fig. 1.11 Edge dislocation
The plane in which a dislocation moves through the lattice is called a SLIP PLANE.

With an applied shear stress the dislocation moves, atomic row by atomic row, and
one part of the crystal is displaced relative to the other. When the dislocation has
passed through the crystal, the portion of the crystal above the slip plane has shifted
one atomic distance relative to the portion below the slip plane. In other words, the
motion of the dislocation has caused the crystal to change its shape - to be
permanently deformed. As in Fig. 1.12,

Fig 1.12 Plastic deformation of crystalline solid by slip associated with stress induced motion of

dislocation

1.2.2 SCREW DISLOCATION

• In this dislocation, the atoms are displaced in two separate planes

perpendicular to each other.

• It forms a spiral ramp around the dislocation.

• The Burgers Vector is parallel to the screw dislocation line.

• Speed of movement of a screw dislocation is lesser compared to edge

dislocation. Normally, the real dislocations in the crystals are the mixtures of
edge and screw dislocation.
This is another type of line defect or line imperfection. In this case, there is no extra
half plane of atoms (as in the case of edge dislocation), but a screw dislocation
(atoms distorted along a helix of a screw) is formed when a part of the crystal
displaces angularly over the remaining part, as if a shear stress has produced this
dislocation. A screw dislocation is when a half twist disrupts the overall crystal structure.

A mixed dislocation is a dislocation that combines both an edge and screw

dislocation together.
A dislocation can interact with either another dislocation or a solute atom. When
dislocations interact with each other, they can either repel (if they have the same
sign) or annihilate (if they have opposite signs). On the other hand, when a
dislocation interacts with a solute atom, an energetically favorable arrangement is
formed, leading to solute-solution strengthening.

By dislocation annihilation, i.e. the dislocation arrangement remains constant. on

an average during deformation. Annihilation does not mean immobilization, but
mutual destruction of dislocations of opposite sign.
Dislocations on the same slip plane but of opposite sign can annihilate each other
when they collide. Dislocations on different slip planes need to change planes before
annihilation can occur. This process takes place by edge dislocation climb and screw
dislocation cross slip.

1.2.3 MOVEMENT OF DISLOCATION

DISLOCATION SLIP

• SLIP - The process by which a dislocation moves and deforms a material i.e. the

parallel movement of two adjacent crystal planes relative to one another.

Dislocations do not move with the same degree of ease on all crystallographic planes
of atoms and in all crystallographic directions.

• Slip direction - The direction in which a dislocation moves.

• Slip plane - The plane of preferred dislocation movement.

• Slip systems - The combination of the slip direction and slip plane makes up the
slip system. The slip system depends on the crystal structure.
Dislocation Climb:

Climb is the mechanism of moving an edge dislocation from one slip plane to another
through the incorporation of vacancies or atoms. The climb process is not a motion
of the plane, but rather its growth or shrinking as a result of the addition of atoms
or “vacancies” respectively from the environment of the dislocation. As in Fig. 1.13

Figure 1.13 Dislocation climb by (a) loss of atoms to surrounding vacancies and (b) incorporation of

interstitial atoms.

The movement of atoms and vacancies at high temperature is the cause of this
motion.

Screw dislocation cannot climb up or climb down. The edge dislocation climb is a
diffusion-controlled process.

The positive climb causes the vacancies to annihilate while the negative climb
generates vacancies.

• In positive climb (vacancy diffusion): Atoms are removed from the extra half
plane of atoms at a positive edge dislocation, so that this extra half plane
moves up one atom spacing.
• In negative climb: A row of atoms is added below the extra half plane so that
the dislocation lines move down one spacing.

The climb motions require more energy than glide motions, because these are
associated with migration of vacancies. Stress helps the climb motion. A compressive
stress causes a positive climb and a tensile stress causes a negative climb.
The dislocation climb is necessary for polygonization and creep processes. Creep
occurs due to diffusion of vacancies.

Glide:

Glide is the motion of dislocation in its own slip plane. Dislocation moves in the
surface defined by its line and Burger’s vector. At low temperatures where diffusion
is difficult and the in the absence of non-equilibrium concentration point defects,
the movement of dislocation is restricted almost entirely to glide.

Only edge dislocation and mixed dislocations can have glide motion, i.e. crystal
glides over the slip plane. [Figure 1.14(a)]. The dislocation moves or glides over the
slip plane and disappears when it reaches free surface as shown in Figure 1.14(b).
There is no gliding motion of screw dislocation.

Fig. 1.14 Dislocation disappears on reaching the surface.

Cross Slip:

Cross slip is the process by which a screw dislocation can move from one slip plane
to another.

• A screw dislocation can slip on any plane! The slip planes and slip directions are
specific crystallographic planes and directions.
1.3 INTERFACIAL/PLANAR DEFECTS

Interfacial defect is an imperfection in form of a plane between uniform parts of the

material. They are two-dimensional regions in crystal and arise from change in
stacking of atomic planes on or across boundary. 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.

The most important interfacial defect is a grain boundary. The grain boundary
separates two small grains or crystals having different crystallographic orientations
in polycrystalline materials.

Formation of a boundary between two grains may be imagined as a result of rotation

of crystal lattice of one of them about a specific axis. Depending on the rotation
axis direction, two ideal types of a grain boundary are possible:

▪ Tilt boundary – rotation axis is parallel to the boundary plane;

▪ Twist boundary - rotation axis is perpendicular to the boundary plane:

Misalignment between adjacent grains may be of various degrees (small or high angle
grain boundaries). Boundaries between two phases of different chemical
compositions and different crystal structure are similar to HIGH-ANGLE
BOUNDARIES (misorientation of two neighboring grains exceeds 10º-15º), while
boundaries between different phases with similar crystal structures and
crystallographic orientations are analogous to LOW-ANGLE GRAIN BOUNDARIES
(misorientation of two neighboring grains is 5º or less).
Interfaces between regions where there is a change in electronic structure but not
in atomic arrangement, known as DOMAIN BOUNDARIES.

Grains, divided by small-angle boundaries are also called subgrains. Grain

boundaries accumulate crystal lattice defects (vacancies, dislocations) and other
imperfections; therefore, they effect on the metallurgical processes, occurring in
alloys and their properties.

Since the mechanism of metal deformation is a motion of crystal dislocations

through the lattice, grain boundaries, enriched with dislocations, play an important
role in the deformation process.
The boundary between two crystals which have different crystalline arrangements
or different compositions, is called as INTERPHASE BOUNDARY or commonly an
interface.
Fig. 1.15 Polycrystalline material

1.4 VOLUME IMPERFECTIONS

• 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.
They can greatly affect electrical, mechanical, optical properties.

Problem 1

Calculate the equilibrium number of vacancies per cubic meter for copper at 1000 oC.
The energy for vacancy formation is 0.9eV/atom; the atomic weight and density (at
1000oC) for copper are 63.5 g/mol and 8.4 g/cm3, respectively.
Problem 2

g/cc meaning → grams per cubic centimetre [(g/cc or g/cm3)

QUESTIONS

1. Even under equilibrium condition, a metal contains vacant lattice sites.

Explain why this is so and discuss briefly two examples of metallurgical
phenomena in which vacancies play a prominent part.
2. The energy of formation of a vacancy in copper is 0.9eV. estimate the fraction
of vacant sites at 1250 and 300oK. What would be the fraction of vacant sites
at 300oK? comment on the results.
3. Calculate the activation energy formation in silver, given that the equilibrium
number of vacancies at 800oC is 3.6 X 1023m-3. The atomic weight and density
(at 800oC) for silver are respectively 107.9 g/mol and 9500kg/m3.
4. The vacancy concentration at equilibrium at 600 oC for magnesium is 3.5 X
1023m-3. Calculate the formation energy of vacancies in electron volts and in
kilojoules per mole. The density of magnesium is 1740kg/m3.
5. Show how two edge dislocation of opposite sign on the same slip plane can
annihilate each other. Can two screw dislocations of opposite sign also
annihilate each other?
6. The motion of dislocation is known to proceed by slip, climb and cross slip.
Account for each of these and specify the type of involved in each case.
7. Determine the number and type of vacancies produced by the following
substitutions in substitutional solid solutions: MgCl2 for LiCl, MgO for FeO, LiCl
for CaCl2, CaO for ZrO2, Al2O3 for NiO.