Crystal Imperfection

A perfect crystal, with every atom of the same type in the

correct position, does not exist.
There always exist crystalline defects, which can be point
defects occurring at a single lattice point; line defects occurring
along a row of atoms; or planar defects occurring over
a two-dimensional surface in the crystal. There can also be
three-dimensional defects such as voids.

Crystalline Defects:

Imperfections or defects:
Any deviation from the perfect atomic arrangement in a crystal
is said to contain imperfections or defects. Or a crystalline
defect is a lattice irregularity having one or more of its
dimensions on the order of an atomic dimension.

There are 4 major categories of crystalline defects:

Zero dimensional: Point defects occurring at a single lattice

point.
One dimensional: Linear defects (dislocations) occurring
along a row of atoms.

Two dimensional: Planar (surface) defects occurring over a

two-dimensional surface in the crystal.

Three dimensional: Volume (bulk) (void) defects

Defects influence the electrical and mechanical properties of

solids; in fact it is the defects that are usually responsible for the
existence of useful properties. While is it perhaps intuitive to
think of defects as bad things, they are in fact necessary, even
crucial, to the behavior of materials: Almost, or perhaps all,

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technology involving materials depends on the existence of
some kind of defects.
Adding alloying elements to a metal is one way of introducing a
crystal defect.
Crystal imperfections have strong influence upon many
properties of crystals, such as strength, electrical conductivity
and hysteresis loss of ferromagnetism. Thus some important
properties of crystals are controlled by as much as by
imperfections and by the nature of the host crystals.

The conductivity of some semiconductors is due to entirely

trace amount of chemical impurities.

Color, luminescence of many crystals arise from impurities

and imperfections

Atomic diffusion may be accelerated enormously by

impurities or imperfections
Mechanical and plastic properties are usually controlled by
imperfections.

Crystal Defects Classification:

1. Point defects:

a. Vacancy
b. Schottky
c. Self interstitial
d. Frenkel
e. Colour centers
f. Polarons
g. Excitons

2. Line defects

a. Edge dislocation
b. Screw dislocation

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 3. Surface defects

a. Grain boundaries
b. Tilt boundaries
c. Twin boundaries
d. Stacking faults
4. Volume defects
a. Inclusions
b. Voids

Point Defects:

Point defects are where an atom is missing or is in an irregular

place in the lattice structure.

Vacancies

A perfect crystal with regular arrangement of atoms can not

exist. There are always defects, and the most common defects
are point defects. This is especially true at high temperatures
when atoms are frequently and randomly change their positions
leaving behind empty lattice sites, called vacancies. Or
Vacancies are empty spaces where an atom should be, but is
missing. In most cases diffusion (mass transport by atomic
motion) - can only occur because of vacancies.

How many vacancies are there? The higher is the temperature,

more often atoms are jumping from one equilibrium position to
another and larger number of vacancies can be found in a
crystal. Actually, the equilibrium number of vacancies, Nv,
increases exponentially with the absolute temperature, T, and
can be estimated using the equation

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(Boltzmann Distribution):
Nv =N exp(-Qv/kT)

Where N is the number of regular lattice sites, k is the

Boltzmann constant (1.38 x 10-23 J/atom.K), and Qv is the
energy needed to form a vacancy in a perfect crystal.
Using this simple equation we can estimate that at room
temperature in copper there is one vacancy per 1015 lattice
atoms, whereas at high temperature, just below the melting point
(1358 K)
there is one vacancy for every 10,000 atoms. These are the
lower end estimations, a large numbers of additional vacancies
can be introduced in a growth process or as a result of
further treatment (plastic deformation, quenching from high
temperature to the ambient one, etc.).

Babylon university , engineering college, engineering material,Maithem H- Rasheed

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

Babylon university , engineering college, engineering material,Maithem H- Rasheed

A Schottky defect
is a type of vacancy in which an atom being free from regular
site, migrates through successive steps and eventually settles at
the crystal surface. a pair of anion and cation vacancies.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

Impurities:
A pure metal consisting of only one type of atom just isnt
possible; impurity or foreign atoms will always be present, and
some will exist as crystalline point defects.

In fact, even with relatively sophisticated techniques, it is

difficult to refine metals to purity in excess of 99.9999%. At this
level, on the order of 1022 to 1023 impurity atoms will be
present in one cubic meter of material.

Metals which have impurity called alloys.

alloying is used in metals to improve mechanical strength
and corrosion resistance
The addition of impurity atoms to a metal will result in the
formation of a solid solution and/or a new second phase,
depending on the kinds of impurity, their concentrations, and the
temperature of the alloy.

Several terms relating to impurities and solid solutions

deserve mention. (solute and solvent )

Solvent represents the element or compound that is

present in the greatest amount host atoms.

Solute is used to denote an element or compound present

in a minor concentration.

Solid Solutions:

A solid solution forms when, as the solute atoms are added

to the host material, the crystal structure is maintained, and no
new structures are formed.
If two liquids, soluble in each other (such as water and
alcohol) are combined, a liquid solution is produced as the
molecules intermix, and its composition is homogeneous
throughout.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

A solid solution is also compositionally homogeneous; the
impurity atoms are randomly and uniformly dispersed within the
solid.

Impurity point defects are found in solid solutions, of which

there are two types:

Substitutional :

solute or impurity atoms replace or substitute for the host atoms

Interstitial.
There are several features of the solute and solvent atoms
that determine the degree to which the former dissolves in the
latter, as follows:

1. Atomic size factor.

Appreciable quantities of a solute may be accommodated
in this type of solid solution only when the difference in
atomic radii between the two atom types is less than about.
Otherwise the solute atoms will create substantial lattice
distortions and a new phase will form.

2. Crystal structure.
For appreciable solid solubility the crystal structures for metals
of both atom types must be the same.

3. Electronegativity.
The more electropositive one element and the more
electronegative the other, the greater is the likelihood that they
will form an intermetallic compound instead of a substitutional
solid solution.

4. Valences.

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 Other factors being equal, a metal will have more of a tendency
to dissolve another metal of higher valency than one of a lower
valency.

Interstitials atoms that are squeezed in between regular lattice

sites. If the interstitial atom is of the same species as the lattice
atoms, it is called self-interstitial. Creation of a self-interstitial
causes a substantial distortions in the surrounding lattice and
costs more energy as compared to the energy for creation of a
vacancy (Qi > QV) and, under equilibrium conditions, self-
interstitials are present in lower concentrations than vacancies.
Foreign, usually smaller atoms (carbon, nitrogen, hydrogen,
oxygen) are called interstitial impurities. Interstitial impurity
atoms are much smaller than the atoms in the bulk matrix.
Interstitial impurity atoms fit into the open space between the
bulk atoms of the lattice structure. An example of interstitial
impurity atoms is the carbon atoms that are added to iron to
make steel.

Carbon atoms, with a radius of 0.071 nm, fit nicely in the open
spaces between the larger (0.124 nm) iron atoms. They
introduce less distortion to the lattice and are more common
in real materials and more mobile. If the foreign atom replaces
or substitutes for a matrix atom, it is called a substitutional
impurity. A substitutional impurity atom is an atom of
a different type than the matrix atoms, which has replaced one
of the bulk (matrix) atoms in the lattice. Substitutional impurity
atoms are usually close in size (within approximately 15%) to
the bulk atom. An example of substitutional impurity atoms is
the zinc atoms in brass. In brass, zinc atoms with a radius of
0.133 nm have replaced some of the copper atoms, which have a
radius of 0.128 nm.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

A Frenkel defect
is a pair of cation (positive ion) vacancy and a cation
interstitial. Or it may also be an anion (negative ion) vacancy
and anion interstitial. Or the combination of a vacancy and
interstitial is called a Frankel defect. However anions are much
larger than cations and it is not easy for an anion interstitial to
form. In both Frenkel and Schottky defects, the pair of point
defects stays near each other because of strong coulombic
attraction of their opposite charges.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

2- Linear Defects (Dislocations):

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In linear defects groups of atoms are in irregular positions.
Linear defects are commonly called dislocations. Any deviation
from perfectly periodic arrangement of atoms along a line is
called the line imperfection.
A line defect is a lattice distortion created about a line formed
by the solidification process, plastic deformation, vacancy
condensation or atomic mismatch in solid solutions.

The line imperfection acting as boundary between the slipped

and un-slipped region, lies in the slip plane and is called a
dislocation.

Dislocations are generated and move when a stress is applied.

The strength and ductility of metals are controlled by
dislocations.

Two extreme types of dislocations are distinguish as

1. Edge dislocations and

2. Screw dislocations.

Edge Dislocations:
The inter-atomic bonds are significantly distorted only in the
immediate vicinity of the dislocation line. As shown in the set of
images below, the dislocation moves similarly a small amount at
a time. The dislocation in the top half of the crystal is slipping
one plane at a time as it moves to the right from its position in
image (a) to its position in image (b) and finally image (c). In
the process of slipping one plane at a time the dislocation
propagates across the crystal.
Edge dislocation is considered positive when compressive
stresses present above the stresses exist below the dislocation
line, it is considered as negative edge dislocation, and\

Babylon university , engineering college, engineering material,Maithem H- Rasheed

represented by . A schematic view of edge dislocations are
shown in figure below.

(a) Model of a simple cubic lattice; the atoms are represented by

filled circles, and the bonds between atoms by springs.

(b) positive edge dislocation DC formed by inserting an extra

half-plane of atoms in ABCD.

(c) Atomic arrangement in a plane normal to an edge dislocation.

- The atomic arrangement results in compressive stress above
the slip plane and a tensile stress below the slip plane.

- An edge dislocation with the extra plane of atoms above the

slip plane, is called a positive edge dislocation and if the extra
plane of atoms lies below the slip plane, the dislocation is a
negative edge dislocation.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

(d) Dislocation moves along slip plane in slip direction
perpendicular to dislocation line CD. A pure edge dislocation
can glide or slip in a direction perpendicular to its length. It may
move vertically by a process known as climb, if diffusion of
atoms or vacancies can take place.

2- Screw or Burgers dislocation:

The 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.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

To visualize a screw dislocation, imagine a block of metal with
a shear stress applied across one end so that the metal begins to
rip. Then the bonds are broken .
As was the case with the edge dislocation, movement in this
manner requires a much smaller force than breaking all the
bonds across the middle plane simultaneously.

If the shear force is increased, the atoms will continue to slip .

(a) left-handed screw dislocation DC formed by displacing the faces ABCD

relative to each other in direction AB; The dislocation line is parallel to its,
slip vector or (Burgers vector)
(b) spiral of atoms adjacent to the line DC in (a).

Babylon university , engineering college, engineering material,Maithem H- Rasheed

3- Interfacial defects
Interfacial defects can be defined as boundaries that have two
dimensional imperfections in crystalline solids, and have
different crystal structures and/or crystallographic orientations
on either side of them. They refer to the regions of distortions
that lie about a surface having thickness of a few atomic
diameters. For example: external surfaces, grain boundaries,
twin boundaries, stacking faults, and phase boundaries. These
imperfections are not thermodynamically stable, rather they are
meta-stable imperfections. They arise from the clustering of line
defects into a plane.
External surface:
The environment of an atom at a surface differs from that of an
atom in the bulk; especially the number of neighbors
(coordination) at surface is less. Thus the unsaturated bonds of
surface atoms give rise to a surface energy. This result in

Babylon university , engineering college, engineering material,Maithem H- Rasheed

relaxation (the lattice spacing is decreased) or reconstruction
(the crystal structure changes). To reduce the energy, materials
tend to minimize, if possible, the total surface area.

Grain boundaries:
Crystalline solids are, usually, made of number of grains
separated by grain boundaries. Grain boundaries are several
atoms distances wide, and there is mismatch of orientation of
grains on either side of the boundary as shown in figure below.
When this misalignment is slight, on the order of few degrees (<
10), it is called low angle grain boundary. These boundaries
can be described in terms of aligned dislocation arrays. If the
low grain boundary is formed by edge dislocations, it is called
tilt boundary, and twist boundary if formed of screw
dislocations. Both tilt and twist boundaries are planar surface
imperfections in contrast to high angle grain boundaries. For
high angle grain boundaries, degree of disorientation is of large
range (> 15). Grain boundaries are chemically more reactive
because of grain boundary energy.

At ambient temperatures, grain boundaries give strength to a

material. So in general, fine grained materials are stronger than
coarse grained ones because they have more grain boundaries
per unit volume. However, at higher temperatures, grain
boundaries act to weaken a material due to corrosion and other
factors.

Babylon university , engineering college, engineering material,Maithem H- Rasheed

Twin boundaries:
It is a special type of grain boundary across which there is
specific mirror lattice symmetry. Twin boundaries occur in pairs
such that the orientation change introduced by one boundary is
restored by the other (figure below). The region between

the pair of boundaries is called the twinned region. Twins which

forms during the process of recrystallization are called
annealing twins, whereas deformation twins form during plastic
deformation. Twinning occurs on a definite crystallographic
plane and in a specific direction, both of which depend on the
crystal structure. Annealing twins are typically found in metals
that have FCC crystal structure (and low stacking fault energy),
while mechanical/deformation twins are observed in BCC and
HCP metals. Annealing twins are usually broader and with
straighter sides than mechanical twins. Twins do not extend
beyond a grain boundary.

Babylon university , engineering college, engineering material,Maithem H- Rasheed