Chapter-4

Imperfections/Defects
in
Solids (Atomic and Ionic Arrangements)
 Table of Contents Learning Outcomes

• Introduction to Imperfections You will be able to-

• Describe various point defects in a
in Solids crystalline material (Vacancy,
substitutional defect, interstitial defect).
• Types of imperfections in
• Explain the concept and geometry of
Solids the edge dislocation and the screw
dislocation and how dislocations
Point Defects strengthen crystalline materials.
• Identify the likely slip system for a given
1D Line Defects crystal structure.
• Explain how grain boundaries
2D Area Defects strengthen polycrystalline materials.
• Explain the role of grain size in
3D Volume Defects strengthening polycrystalline materials.
• Explain the process of work hardening
• Slip and how it affects the strength of
crystalline materials.
• Significance of Atomic
Vibration
 Any deviation from completely ordered arrangement of

constituent particles in a crystal is called disorder or a defect.

Crystalline defect refers to a lattice irregularity having one or more of its

dimensions on the order of an atomic diameter. Classification of

crystalline imperfections is frequently made according to geometry or

dimensionality of the defect.

The properties of materials are profoundly influenced by the presence of

imperfections. Consequently, it is important to have a knowledge about the types
of imperfections that exist and the roles they play in affecting the behavior of
materials.
For example, the mechanical properties of pure metals experience significant
alterations when alloyed (i.e., when impurity atoms are added)-
-Brass (70% copper/30% zinc) is much harder and stronger than pure copper.
-Sterling Silver (92.5% Silver and 7.5% Copper) is harder and strong than pure Silver)
The Defects have a profound Deviations from ideal are called
impact on the macroscopic DEFECTS
properties of materials

Bonding
+
Structure Properties
+ These imperfections result from deformation of the solid, rapid cooling from
high temperature, or high-energy radiation striking the solid
Defects
Significance of Atomic Vibration
Every atom in a solid material is vibrating very rapidly about its lattice position within the crystal. In a
sense, these atomic vibrations may be thought of as imperfections or defects. At any instant of time not all
atoms vibrate at the same frequency and amplitude, nor with the same energy. At a given temperature
there will exist a distribution of energies for the constituent atoms about an average energy.
Over time the vibrational energy of any specific atom will also vary in a random manner. With rising
temperature, this average energy increases, and, in fact, the temperature of a solid is really just a measure
of the average vibrational activity of atoms and molecules. At room temperature, a typical vibrational
frequency is on the order of 1013 vibrations per second, whereas the amplitude is a few thousandths of a
nanometer.
Many properties and processes in solids are manifestations of this vibrational atomic motion.
For example, melting occurs when the vibrations are vigorous enough to rupture large numbers of atomic
bonds.
 Why Defects are Important

There are a lot of properties that are controlled or affected by

defects, for example:

Electric and thermal conductivity in metals (strongly reduced by

point defects).

Electronic conductivity in semi-conductors (controlled by

substitution defects).

Diffusion (controlled by vacancies).

Ionic conductivity (controlled by vacancies).

Plastic deformation in crystalline materials (controlled by

dislocation).

Colors (affected by defects).

Mechanical strength (strongly depended on defects).

Types of Imperfections
 Point defects
- The simplest type of imperfection
- those associated with one or two atomic positions
Point defects are accounted for when the *crystallization process occurs at a very fast
rate. These defects mainly happen due to deviation in the arrangement of
constituting particles. In a crystalline solid, when the ideal arrangement of solids is
distorted around a point/ atom, it is called a point defect.
A point defect occurs when one or more atoms of a crystalline solid leave their
original lattice site and/or foreign atoms occupy the interstitial position /
lattice site of the crystal. There are several types of point defects
Vacancy, Self-Interstitial, Substitutional or Interstitial Impurity
Vacancies and self-interstitial defects are also called intrinsic defects, while substitutional or interstitial
impurities are extrinsic defects.

Schematic representation of point defects in a pure solid chemical element:

V- Vacancy
Is- Substitutional Impurity
SI- Self-interstitial
Ii- interstitial impurity
the crosses mark the vacant interstitial sites
 Vacancy
The simplest point defect is the Vacancy– an atom site from which an atom is
missing

*Crystallization or crystallisation is the process by which a solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some of the ways
by which crystals form are precipitating from a solution, freezing, or more rarely deposition directly from a gas
 Self-Interstitial An interstitial defect is a type of point crystallographic defect where an
atom of the same or of a different type, occupies a normally unoccupied
site in the crystal structure. When the atom is of the same type as those
already present they are known as a self-interstitial defect

-"extra" atoms positioned between atomic sites.

Self-
interstitial
distortion
of planes
https://www.tf.uni-kiel.de/matwis/amat/iss/kap_5/backbone/r5_2_2.html
Impurity

Impurities in Solids
Solute

Solvent
 Point Defects
Two outcomes if impurity (B) added to host (A):
in Alloys
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
--different composition
--often different structure.

17
 Line defects
- The simplest type of imperfection
- those associated with one or two atomic positions

Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

• before deformation • after tensile elongation

slip steps
 Linear Imperfections/Line defects
DISLOCATIONS
A dislocation is a linear or one-dimensional defect around which
some of the atoms are misaligned. One type of dislocation is
represented in Fig given by side, an extra portion of a plane of
atoms, or half-plane, the edge of which terminates within the
crystal, an edge dislocation exists.
This is termed an edge dislocation; it is a linear defect that
centers on the line that is defined along the end of the extra half-
plane of atoms. This is sometimes termed the dislocation line,
which, for the edge dislocation in Figure, is perpendicular to
the plane of the page. Within the region around the dislocation
line there is some localized lattice distortion. The atoms BELOW
the dislocation line in Figure are squeezed together, and those
ABOVE are pulled apart; this is reflected in the slight curvature
for the vertical planes of atoms as they bend around this extra
half-plane.
The magnitude of this distortion decreases with distance away
from the dislocation line; at positions far removed, the crystal
lattice is virtually perfect. Sometimes the edge dislocation in
Figure is represented by the symbol which also indicates the
position of the dislocation line.
https://www.youtube.com/watch?v=2ICZW0eJltg
https://www.youtube.com/watch?v=quGSfmt4V6Y
https://www.youtube.com/watch?v=iKKxTP6xp74
Another type of dislocation, called a screw
dislocation, may be thought of as being
formed by a shear stress that is applied to
produce the distortion shown in Figure (a)
shown: 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 (b).
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. Sometimes the symbol is
used to designate a screw dislocation.

Screw dislocation
Within a Crystal
Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw

31
The magnitude and direction of the lattice distortion associated

with a dislocation is expressed in terms of a Burgers vector,

denoted by b. Burgers vectors are indicated in previous Figures
for edge and screw dislocations, respectively. Furthermore, the
nature of a dislocation (i.e., edge, screw, or mixed) is defined by
the relative orientations of dislocation line and Burgers vector.
For an edge, they (Burger Vector and Dislocation Line) are
perpendicular.
 2D or Area Defects Or 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.
These imperfections include external surfaces,
grain boundaries, phase boundaries, twin
boundaries, and stacking faults.
Grain Boundaries
Another interfacial defect, as the boundary separating
two small grains or crystals having different
crystallographic orientations in polycrystalline materials.
A grain boundary is represented schematically from an
atomic perspective in Figure shown. 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.
Various degrees of crystallographic misalignment
between adjacent grains are possible (see Figure. When
this orientation mismatch is slight, on the order of a few
degrees, then the term small- (or low-) angle grain
boundary is used.
 The permanent deformation of metal
comes from the movement of
Given enough stress and thermal energy, dislocations
crystalline imperfections, known as
will easily move throughout the crystalline grains,
dislocations, through the grains in the
resulting in permanent distortion of the grain itself.
metal. We will examine the
However, once a dislocation reaches a grain
improvement of a metal’s strength by
boundary, it has nowhere to go. In other words, grain
limiting the movement of these
boundaries stop dislocations (see Figure 1).
dislocations by controlling grain size.
Thus, an easy way to improve the strength of a
material is to make the grains as small as possible,
increasing the amount of grain boundary.
Smaller grains have greater ratios of surface area to
volume, which means a greater ratio of grain
Fig. 1 boundary to dislocations. It means there is a much
greater chance for a dislocation to be stopped at
a grain boundary in the smaller grain.
“The more grain boundaries that exist, the higher the
strength becomes”.
Decreasing grain size decreases the amount of possible pile up at the boundary, increasing the amount of
applied stress necessary to move a dislocation across a Grain boundary. The higher the applied Stress needed
to move the dislocation, the higher the yield strength.

A fine grain size will certainly improve yield strength, fatigue strength,
and formability etc. 1. Work hardening.
However, there are practical limits to how small the grains can be 2.alloying.
Solid solution strengthening and

made. Fortunately, there are several other strengthening 3. Precipitation hardening.

mechanisms that are even more effective than grain size 4.5. Dispersion strengthening.
Grain boundary strengthening.
refinement. 6. Transformation hardening.
The following example illustrates this principle. Figure 2
shows a crude representation of two grains. For
the sake of simplicity, the grains are illustrated as
perfect rectangular prisms. Each prism is made up of
several cubic units. For the sake of this analysis, each
unit contains exactly six dislocations. For the larger
grain, there are 2 x 3 x 4 = 24 cubic units, and the
smaller grain is one cubic unit. The larger grain will
have 24 x 6 = 144 dislocations, and the smaller grain
has six. The larger grain has a total surface area of 2
x (2 x 4) + 2 x (2 x 3) + 2 x (3 x 4) = 52 square units.
The smaller grain has a surface area of 6 square
units. For every dislocation in the large grain, there is
0.36 square units of grain boundary. In the smaller
grain, there is one square unit of grain boundary for
each dislocation. There is a much greater chance for a
dislocation to be stopped at a grain boundary in the
smaller grain. Therefore, the smaller grain is stronger.
In the larger grain, a dislocation can travel up to 4 units
without being stopped by a grain boundary,
indicating the potential for extensive plastic flow. In the
small grain, no dislocation can travel more than 1
unit of distance.
Grain Size
•Why do we care?
Because Smaller grains lead to stronger materials
 BULK OR VOLUME DEFECTS
Other defects exist in all solid materials that are much
larger than 1D and 2D defects. These include pores,
cracks, foreign inclusions, and other phases. They are
normally introduced during processing and fabrication
steps.

Significance of Atomic Vibration

Every atom in a solid material is vibrating very rapidly about its lattice position within
the crystal. In a sense, these atomic vibrations may be thought of as imperfections
or defects. At any instant of time not all atoms vibrate at the same frequency and
amplitude, nor with the same energy. At a given temperature there will exist a
distribution of energies for the constituent atoms about an average energy.
Over time the vibrational energy of any specific atom will also vary in a random
manner. With rising temperature, this average energy increases, and, in fact, the
temperature of a solid is really just a measure of the average vibrational activity of
atoms and molecules. At room temperature, a typical vibrational frequency is on
the order of 1013 vibrations per second, whereas the amplitude is a few thousandths
of a nanometer.
Many properties and processes in solids are manifestations of this vibrational atomic
motion. For example, melting occurs when the vibrations are vigorous enough to
rupture large numbers of atomic bonds.
Nonconductivity

Ordinarily, ceramics are poor conductors of electricity and therefore make excellent insulators.
Nonconductivity arises from the lack of “free” electrons such as those found in metals. In ionically
bonded ceramics, bonding electrons are accepted by the electronegative elements, such as
oxygen, and donated by the electropositive elements, usually a metal. The result is that all
electrons are tightly bound to the ions in the structure, leaving no free electrons to conduct
electricity.
In covalent bonding, bonding electrons are similarly localized in the directional orbitals between
the atoms, and there are no free electrons to conduct electricity.

There are two ways that ceramics can be made electrically conductive. At sufficiently high
temperatures point defects such as oxygen vacancies can arise, leading to ionic conductivity. In
addition, the introduction of certain transition-metal elements (such as iron, copper, manganese,
or cobalt), lanthanoid elements (such as cerium), or actinoid elements (such as uranium) can
produce special electronic states in which mobile electrons or electron holes arise. The copper-
based superconductors are a good example of conductive transition-metal oxide ceramics—in
this case, conductivity arising at extremely low temperatures.
Brittleness
Unlike some metals, nearly all ceramics are brittle at room temperature; i.e., when subjected to tension,
they fail suddenly, with little or no plastic deformation prior to fracture. Metals, on the other hand, are
ductile (that is, they deform and bend when subjected to stress), and they possess this extremely
useful property owing to imperfections called dislocations within their crystal lattices. There are many
kinds of dislocations. In one kind, known as an edge dislocation, an extra plane of atoms can be
generated in a crystal structure, straining to the breaking point the bonds that hold the atoms together.
If stress were applied to this structure, it might shear along a plane where the bonds were weakest, and
the dislocation might slip to the next atomic position, where the bonds would be re-established. This
slipping to a new position is at the heart of plastic deformation. Metals are usually ductile because
dislocations are common and are normally easy to move.
In ceramics, however, dislocations are not common (though they are not nonexistent), and they are
difficult to move to a new position. The reasons for this lie in the nature of the bonds holding the
crystal structure together.
In ionically bonded ceramics some planes—such as the so-
called (111) plane shown slicing diagonally through the rock
salt structure in Figure, top—contain only one kind of ion
and are therefore unbalanced in their distribution of
charges. Attempting to insert such a half plane into a
ceramic would not favour a stable bond unless a half plane
of the oppositely charged ion was also inserted. Even in the
case of planes that were charge-balanced—for instance,
the (100) plane created by a vertical slice down the middle
of the rock salt crystal structure, as shown in Figure ,
bottom—slip induced along the middle would bring
identically charged ions into proximity. The identical charges
Barriers to slip in ceramic crystal structures would repel each other, and dislocation motion would be
impeded. Instead, the material would tend to fracture in the
manner commonly associated with brittleness.
In order for polycrystalline materials to be ductile, they must possess more than a minimum number
of independent slip systems—that is, planes or directions along which slip can occur. The presence
of slip systems allows the transfer of crystal deformations from one grain to the next (by movement of
dislocations). Metals typically have the required number of slip systems, even at room temperature.
Ceramics, however, do not, and as a result they are notoriously brittle.

Slip, in engineering and physics, sliding displacement along a plane of one part of a crystal relative
to the rest of the crystal under the action of shearing forces—that is, forces acting parallel to that
plane. Much of the permanent, or plastic, deformation of materials under stress is the result of slip
within the individual crystals that constitute the material. Slip and an alternate mode of
deformation, twinning, are the only ways that crystals in solids can be permanently deformed. In
slip, all the atoms on one side of the slip (or glide) plane do not slide simultaneously from one set of
positions to the next. The atoms move sequentially one row at a time into the next position along the
plane because of structural defects or spaces, called edge dislocations, in the crystal that move at
the same rate in the opposite direction.
Viewed as a large-scale phenomenon as in the deformation of a piece of metal, slip involves the
passage of a large number of dislocations on nearby slip planes within many of the individual
crystals. Slip lines in crystals, seen with the aid of an optical microscope, appear as bands of many
slip planes under the greater magnification of the electron microscope.
 • Identify the likely slip system for a given crystal structure

On a macroscopic scale, plastic deformation corresponds to the net movement of large numbers of
atoms in response to an applied stress.

In an edge dislocation, localized lattice distortion exists along the end of an extra half-plane of
atoms. • A screw dislocation results from shear distortion. • Many dislocations in crystalline
materials have both edge and screws components; these are mixed dislocations.
 The caterpillar movement resembles the
dislocation movement. Its hump is the
representation of extra half plane of atoms
The process by which plastic deformation is produced by dislocation motion is called SLIP,
that is movement of dislocations.
The extra half plane moves along the Slip Plane
Slip Systems
Dislocations move more easily on specific planes and in specific
directions.

Ordinarily, there is a preferred plane (slip plane), and specific

directions (slip direction) along which dislocations move.
12 slip systems
The combination of slip plane and slip direction is called the slip FCC slip occurs on close-packed
system. planes in close-packed directions.
There are 4 octahedral planes,
The slip system depends on the crystal structure of the metal. (111), (111), (111), and (111), six
<110> directions, each one
The slip plane is the plane that has the most dense atomic packing common to two octahedral planes,
(the greatest planar density). giving 12 slip systems.

The slip direction is most closely packed with atoms (highest linear
density).

Slip Plane {111}: most Slip Direction ‹110› (pink

dense atomic packing arrows): highest linear density
 Stress and Dislocation Motion
• Edge and screw dislocations move in response to Deformation in a Single Crystal
shear stresses applied along a slip plane in a slip • For a single crystal in tension, slip will occur
direction. along a number of equivalent & most favorably
• Even though an applied stress may be tensile, shear oriented planes and directions at various positions
components exist in directions other than the ones along the specimen.
parallel or perpendicular to the stress direction.
• Each step results from the movement of a large
• These are called resolved shear stresses number of dislocations along the same slip plane.

Critical Resolved Shear

Stress is the minimum
shear stress required to
begin plastic deformation
or slip.
What do we need to move
dislocation

In response to an applied tensile or compressive stress,

slip in a single crystal begins when the resolved shear
stress reaches some critical value,
• It represents the minimum shear stress required to
initiate slip and is a property of the material that
determines when yielding occurs.
 Work Hardening

Strain hardening or work hardening is the

phenomenon of increasing hardness and
strength of a ductile material as a result of
plastic deformation at temperatures far
below its melting point during cold working.
 Resistance to continuing plastic flow as a metal is
worked is termed 'work hardening'. When work is
performed below hot working temperatures (i.e. below
about 0.5Tm, where Tm is the melting point), and the
Work hardening, also known as strain
crystal structure is forced to deform to accommodate
hardening, is the strengthening of a the strain, microscopic shearing (or slip) occurs along
metal or polymer by plastic definite crystalline planes. Discontinuities in the crystal
deformation. ... This strengthening structure, present in all metals and known as
occurs because of dislocation dislocations, increase in density during plastic flow and
those moving on intersecting slip planes tangle and pile
movements and dislocation generation
up. This means that an ever increasing shear stress is
within the crystal structure of the required for deformation, increasing the yield stress.
material. Eventually the stress required to move dislocations is
Work hardening may be desirable, high enough for a crack to initiate and subsequently
undesirable, or inconsequential, propagate, and the material breaks
depending on the context.

Work hardening improves tensile strength,

yield strength and hardness at the expense of
reduced ductility. These effects can only be
removed by annealing or normalising.

effect of work hardening during a tensile test

Cold Working Operations
What Does Work Hardening Mean?
Work hardening, is the strengthening of a metal by plastic deformation. In the plastic region, the true stress increases continuously,
meaning that when a metal is strained beyond the yield point, more and more stress is required to produce additional plastic
deformation and the metal seems to have become stronger and more difficult to deform. This implies that the metal is becoming
stronger as the strain (work) increases.

Work hardening is a process that can help to reduce the potential for cracking along the surface of a strengthened metal or metal
alloy. By employing the process, it is possible to use metals in the creation of devices that are designed to withstand a specific
amount of load for a certain period of time. Since work hardening is not a process that can be reversed, the strength is easily
measured, making it possible to choose the right metal or alloy for the manufacture of the product.

Some metals like aluminum and alloys like austenitic stainless steels cannot be heat treated or tempered to a higher hardness.
However, they can be work hardened by putting some energy into them by processes such as by peening, rolling, forging or drawing.

Disadvantages associated with work hardening make it undesirable in some situations. The metal will be somewhat less ductile after
the treatment, making it unfit for the production of certain types of products. In addition, a great deal of force is required as part of
the process, whether heat or cold is employed. The directional properties of the metal may also be adversely affected, another factor
that may render the metal unusable for certain purposes. For this reason, work hardening may be desirable, based on the nature of
the products that will be made from the metal, or be completely undesirable as an event that unintentionally occurs during a
manufacturing process.
Grain Size Refinement
 Solid Solution Strengthening
(Alloying)

= strengthening by deliberate
additions of impurities (alloying
elements) which act as barriers
to dislocation movement.
Example: addition of zinc to
copper making the alloy brass
(copper dissolves up to 30%
Zinc added to copper = zinc). Zinc atoms replace
brass. Zinc atoms are copper atoms to form random
bigger and therefore substitutional solid solution.
distort lattice! The zinc atoms are bigger than
copper and by squeezing into
the copper lattice, they distort it
Cr and Ni to Fe, etc…
making it harder for dislocations
to move.
Dispersion and Precipitate Strengthening
(Heat Treat):

Disperse small strong

particles (i.e. carbon) to
impede dislocations
This is dispersion and
precipitate strengthening

This is solution hardening

(alloying)
How to strengthen
metals:
Other strengthening methods include
remelt to remove impurities, hot roll to
reduce grain size
 Microscopic Examination
• Crystallites (grains) and
grain boundaries. Vary
considerably in size. Can
be quite large
– ex: Large single crystal of
quartz or diamond or Si
– ex: Aluminum light post or
garbage can - see the
individual grains
• Crystallites (grains) can be
quite small (mm or less) –
necessary to observe with
a microscope.

60
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister 7e.
(Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
61
Grain boundaries...
Optical Microscopy
• are imperfections,
• are more susceptible
to etching,
• may be revealed as polished surface
dark lines,
• change in crystal surface groove
orientation across grain boundary
(a)
boundary. Adapted from Fig. 4.14(a) and
(b), Callister 7e.
ASTM grain (Fig. 4.14(b) is courtesy
of L.C. Smith and C. Brady, the
size number National Bureau of Standards,
Washington, DC [now the
N = 2 n -1 National Institute of Standards
and Technology, Gaithersburg,
MD].)
Fe-Cr alloy
number of grains/in2
at 100x (b)
magnification
 Optical Microscopy
• Polarized light
– metallographic scopes often use polarized light
to increase contrast
– Also used for transparent samples such as
polymers
 Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from the
work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged on

molecules arranged on a copper (111) surface.
a platinum (111) These Kanji characters
surface. represent the word
“atom”.
 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
– X-Rays? Difficult to focus.
– Electrons
• wavelengths ca. 3 pm (0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.