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Chapter 4
Imperfections in solids

Outline

Introduction
Points defects
Impurities in solids
Microscopy

Materials Science – 101734-Ch4 Dr. Muayad Esaifan 1

Imperfections or Defects in a Solid

Crystalline solids are formed by the well-ordered
replication of a volumetric number of unit cells in all
directions.
An ionic crystal that consists of a single unit cell with
identical lattice points throughout the crystal is known as an
ideal crystal.
Regardless of whether such ideal crystals exist only at
absolute zero (0K) temperature. At any temperature above 0
K, the crystals are somewhat out of a completely arranged
arrangement.
Any deviation from the perfectly arranged arrangement of
constituent particles in a crystal is called a disorder or
defect.
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Imperfections or Defects in a Solid

Imperfection in solids refers to any abnormality in the
pattern of crystal arrangement in solids. When crystals form,
faults develop. It can happen very quickly or at a slower
pace. Because particles don’t have enough time to arrange
themselves in a regular manner, this happens.

Additional defects may occur in the crystal due to the

presence of certain impurities. The term disorder or
imperfection is widely practiced to refer to an intimate way
of going from the perfectly arranged state of the
constituents of a crystal. These imperfections will not only
alter the properties of the crystal but will also give rise to
new properties.
Materials Science – 101734-Ch4 Dr. Muayad Esaifan 3

Imperfections or Defects in a Solid

Causes of Imperfections or Defects in a Solid:

 The different types of Impurities are found in the crystal

lattice or in a solid.
 Vacancies in the lattice
 Nonstoichiometric proportions of the ions
 Dislocation of a particle in the lattice

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Imperfections or Defects in a Solid

Types of Defects
The defects are of two types as:
1. Point Defects: Defects arising due to irregularities or
deviations from the ideal arrangement of atoms around a
point or an atom in a crystalline material are called point
defects or atomic defects.
2. Line or Dislocation Defects: The defects that roll out
due to irregularities or deviations from the ideal
arrangement in an entire row of lattice points are called
line defects.
3. Grain Boundaries or Area Defects:
These irregularities are called crystal defects of crystal
imperfections
Materials Science – 101734-Ch4 Dr. Muayad Esaifan 5

Imperfections or Defects in a Solid

Types of Defects
The defects are of two types as:
1. Point Defects: Defects arising due to irregularities or
deviations from the ideal arrangement of atoms around a
point or an atom in a crystalline material are called point
defects or atomic defects.
2. Line or Dislocation Defects: The defects that roll out due to
irregularities or deviations from the ideal arrangement in an
entire row of lattice points are called line defects.
3. Grain Boundaries or Area Defects: are two-dimensional
defects in the crystal structure, and tend to decrease the
electrical and thermal conductivity of the material.
These irregularities are called crystal defects of crystal
imperfections
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Point Defect in Solid

When crystallisation occurs quickly, point defects arise,
preventing a perfect crystal structure from forming. It should
be noted, however, that even during a slow crystallisation,
there exist defects.

Point Defects can be divided into three categories:

1. Stoichiometric defect
2. Impurity defect
3. Non-stoichiometric defect

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Point Defect in Solid

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Point Defect in Solid

1. Stoichiometric defect

Stoichiometric compounds are those in which the number

of positive and negative ions are in the ratio indicated by
their chemical formulas.
For the sake of simplicity, we can consider AB-type
compounds that have an equal number of A+ and B– ions.
Defects in these types of compounds are called
stoichiometric defects.
Generally, two types of defects are observed in these
compounds:
(a) Schottky defect
(b) Frenkel defect

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Point Defect in Solid

1. Stoichiometric defect

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Point Defect in Solid

1. Stoichiometric defect

(a) Schottky defect: The Schottky defect arises if some of

the atoms or ions are missing from their normal lattice sites.
The lattice sites which are abortively are called lattice
vacancies or holes. So far as the crystal has to be
electrically neutral, an equal number of cations and anions
are missing. The ideal AB crystal is shown above. Presence
of two holes one due to missing cation and the other due to
missing. It is par excellence a vacancy defect in ionic solids.

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Point Defect in Solid

1. Stoichiometric defect

Schottky defect
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1. Stoichiometric defect
There are three different kinds of Schottky defects as:
1. Vacancy defect– When the umpteenth of the lattice sites
are vacant, the crystal is said to have vacancy defects. This
defect consequence in a deficiency in the density of the
substance. This type of defect can also develop on heating
material and hence, it is also called a thermodynamic defect.

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1. Stoichiometric defect
There are three different kinds of Schottky defects as:
2. Interstitial defect- When some constituent particles
(atoms or molecules) surround vacant interstitial positions,
the crystal is aforenamed to have interstitial defects. This
defect increases the density slightly.

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1. Stoichiometric defect
Conditions causing Schottky defects- This type of defect
is usually seen in strong ionic compounds having
1. high coordination number
2. Ions of approximately the same size.

For example, NaCl, KCI, KBr, CsCl, and AgBr ionic solids
have Schottky defects. It has been ascertained that in NaCl,
there are about 106 Schottky pairs per cm³ at room
temperature. In 1cm³ there are about 1022 ions and this
means that there will be one Schottky defect per 1016 ions in
NaCl. Whereas of the impendence of a broad number of
vacancies in crystals, its density is markedly lowered.

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1. Stoichiometric defect

(b) Frenkel defect: The Frenkel defect occurs when an ion

disappears from its normal state and occupies an interstitial
site between lattice points. The existence of hale due to a
missing cation from its normal position and occupying the
interstitial position is shown. In this case, also, the crystal
remains electrically neutral because the number of anions
and cations remains the same This defect is also known as
an interstitial defect. It creates vacancy defects. It has its
original position and an interstitial defect in its new
location.

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1. Stoichiometric defect
(b) Frenkel defect:

Conditions causing Frenkel defects- This defect generally

occurs in compounds in which coordination number is low,
anions are much larger than the cations.

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Defects in Ionic Solids

Frenkel
defect
Cation vacancy
+
cation interstitial

Schottky
defect
Cation vacancy
+
anion vacancy

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1. Stoichiometric defect

In perfect alkali metal halides, these defects are not very

common because the ions cannot move to the interstitial
state due to their large size. 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.
Vacancies or holes exist in crystals that have a Schottky
well as well as a Frenkel defect, but the former decreases
the overall density of the substance, but the latter does not.
, another hybrid type of defect can also arise from a
combination of both.

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1. Stoichiometric defect
Defects in Schottky and Frank crystals give some interesting results:
1. The presence of these defects increases the electrical conductivity
of crystals. When an electric field is about the experiment, an
adjoining ion moves from its lattice site to occupy a hole. As a
result, a new hole is created and another nearby ion moves into it,
and so on. This process continues and thus h moves from one end
to the other. Thus, it conducts electricity throughout the crystal.
2. Due to the impendence of pores in the crystal, its density decreases.
It presumably noted that the density decreases only for crystals
with Schottky defects.
3. The presence of pores also reduces the lattice energy or
stabilization of the crystal. The presence of too many pores can
cause partial collapse of the lattice.
4. In Frenkel defects, the dielectric constant of the crystal is increased
by placing it in a pattern of equal charges.
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Point Defect in Solid

2. Impurity defects:
These defects arise when some foreign atoms or ions are
present in the lattice space or interstitial site, e.g. Molten
NaCl with a little SrCl2 and a solid solution of CdCl2 and
AgCl.

Fundamental concepts
• alloy
• solute
• solvent
• solid solution

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Point Defect in Solid

Two outcomes if impurity (B) added to host (A):

• 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.

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Point Defect in Solid

2. Impurity defects:
Substitutional Solid Solutions
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rules
– 1. r (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valency
• All else being equal, a metal will have a greater
tendency to dissolve a metal of higher valency than
one of lower valency
Materials Science – 101734-Ch4 Dr. Muayad Esaifan 23

Point Defect in Solid

2. Impurity defects:
Hume-Rothery Rules
Application of Hume–Rothery rules – Solid Solutions
Element Atomic Crystal Electro- Valence
Radius Structure nega-
1. Would you predict (nm) tivity

more Al or Ag Cu
C
0.1278
0.071
FCC 1.9 +2

to dissolve in Zn? H 0.046

O 0.060
More Al ! Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
2. More Zn or Al Co
Cr
0.1253
0.1249
HCP
BCC
1.8
1.6
+2
+3
Fe 0.1241 BCC 1.8 +2
in Cu? Ni 0.1246 FCC 1.8 +2
More Al ! Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Table on p. 106, Callister 7e.

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Point Defect in Solid

2. Impurity defects:

Specification of Impurities/Solutes

• Specification of composition
m1
C1  x 100
– weight percent m1  m2

m1 = mass of component 1

– atom percent n m1
C1'  x 100
n m1  n m 2
nm1 = number of moles of component 1
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Point Defect in Solid

3. Defects in non-stoichiometric crystals:

Non-stoichiometric defects unsettle the stoichiometry of

solids. The ionic sites occupied by unpaired electrons are
called F-centers (Farbenzenter or color center). They impart
color to alkali metal halide crystals. The colors are
produced by the excitation of these electrons when they
absorb energy from visible light falling on the crystal.
Excess of Na turns NaCl crystals yellow, excess of Li
makes LICI pink, excess of potassium turns KCl crystals
purple.

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Point Defect in Solid

3. Defects in non-stoichiometric crystals:

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Point Defect in Solid

3. Defects in non-stoichiometric crystals:
(a) Metal excess defect due to anionic vacancies is shown
by alkali halides like NaCl and KCl. In such defects, a
negative ion is missing from its lattice site leaving a hole
which is occupied by an electron to maintain electrical
neutrality.

(b)The excess of metal due to the presence of additional

cations at the interstitial sites is shown by zinc oxide on
heating. On heating, zinc oxide (white) loses its oxygen and
turns yellow.
ZnO + Heating → Zn²+ + O₂ +2e–

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Missing half plane A Defect

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An extra half plane…

…or a missing half plane

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What kind of defect is

this?

A line defect?

Or a planar defect?

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Extra half plane No extra plane!

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Missing plane No missing plane!!!

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An extra half plane…

Edge
Dislocatio
n

…or a missing half plane

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This is a line defect called an

EDGE DISLOCATION
Materials Science – 101734-Ch4 Dr. Muayad Esaifan 35

Callister FIGURE 4.3

The atom positions around an edge

dislocation; extra half-plane of atoms
shown in perspective. (Adapted from
A. G. Guy, Essentials of Materials
Science, McGraw-Hill Book Company,
New York, 1976, p. 153.)

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

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Adapted from Fig. 7.8, Callister 7e.

Materials Science – 101734-Ch4 Dr. Muayad Esaifan 37

• Dislocation motion requires the successive bumping

of a half plane of atoms (from left to right here).
• Bonds across the slipping planes are broken and
remade in succession.

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

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Glide of 
an Edge
Dislocation


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Glide of
an Edge
Dislocation

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Glide of
an Edge
Dislocation

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Glide of
an Edge
Dislocation

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Glide of
an Edge
Dislocation

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Glide of
an Edge
Dislocation

A surface
step of b is
created if
a
dislocation
sweeps Surface step,
over the not a
entire slip dislocation
plane

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Dislocation Motion

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45

Figure 4.6 A transmission electron micrograph of a titanium alloy in which the dark lines are dislocations.
(Courtesy of M. R. Plichta, Michigan Technological University.)

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Burgers Vector

Johannes
Martinus
BURGERS
Burger’s vector Burgers vector
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The magnitude and direction of the lattice distortion

associated with a dislocation is expressed in terms of a
Burgers vector, denoted by a b.

For metallic materials, the Burgers vector for a dislocation

will point in a close-packed crystallographic direction and
will be of magnitude equal to the interatomic spacing.

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In general, there can be any angle

between the Burgers vector b (magnitude
and the direction of slip) and the line
vector t (unit vector tangent to the
dislocation line)
b  t  Edge dislocation

b  t  Screw dislocation

b  t , b  t  Mixed dislocation

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Edge & Screw Dislocations

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b || t

3
2 51
1

S 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F 1
9
2
8
3
7 A closed
4
6 Burgers
5 Circuit in an 5

4 ideal crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

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F b
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

9 S 1
2
8
3
7
Map the  same 4
6
5
Burgers circuit on a 5

4 real crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F
9 S 1
2
8
3
7  4
6
5
5
6
4
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

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If b || t

Then parallel planes  to the dislocation line

lose their distinct identity and become one
continuous spiral ramp

Hence the name SCREW DISLOCATION

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Screw Dislocation

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Edge, Screw, and Mixed Dislocations

Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

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Energy of a dislocation line

is proportional to b2.

Thus dislocations with

b is a lattice translation
short b are preferred.

b is the shortest lattice

translation
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A dislocation line cannot end

abruptly inside a crystal
It can end on

Free surfaces

Grain boundaries

On other dislocations at a point called a node

On itself forming a loop

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Dislocations & Plastic Deformation

Dislocations & plastic deformation
• Cubic & hexagonal metals - plastic deformation by plastic
shear or slip where one plane of atoms slides over
adjacent plane by defect motion (dislocations).

• If dislocations don't move, Adapted from Fig. 7.1,

Callister 7e.
deformation doesn't occur! 60

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Dislocations & Crystal Structures

• Structure: close-packed view onto two

planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

• Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
Mg (HCP)
• Specimens that
were tensile tensile direction
tested.
Al (FCC)

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Deformation Mechanisms
Slip System
– Slip plane - plane allowing easiest slippage
• Wide interplanar spacings - highest planar densities
– Slip direction - direction of movement - Highest linear
densities

Adapted from Fig.

7.6, Callister 7e.

– FCC Slip occurs on {111} planes (close-packed) in <110> directions

(close-packed)
=> total of 12 slip systems in FCC
– in BCC & HCP other slip systems occur
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Dislocation Motion
• Dislocation moves along slip plane in slip direction
perpendicular to dislocation line
• Slip direction same direction as Burgers vector

Edge dislocation

Adapted from Fig. 7.2,

Callister 7e.

Screw dislocation

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Click to edit Master title style

• Metals: Disl. mvt easier.
+ + + + + + + +
-non-directional bonding + + + + + + + +
-close-packed directions + + + + + + + +
for slip. electron cloud ion cores

• Covalent Ceramics
(Si, diamond): Movement
difficult.
-directional (angular) bonding
• Ionic Ceramics (NaCl):
+ - + - + - +
Movement difficult.
- + - + - + -
-need to avoid ++ and - -
neighbors. + - + - + - +

64

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Positive Negative

Extra half Extra half

Edge plane above plane below
Dislocation the slip plane the slip plane

Left-handed Right-handed
spiral ramp spiral ramp
Screw
Dislocation b parallel to t b parallel to t

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Surface Defects

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Surface Defects

External Internal

Free surface Grain boundary

Twin boundary Same
Stacking fault phase

Domain Wall

Interphase boundary Different

phases
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Surface energy is anisotropic

Surface energy depends on the orientation,

i.e., the Miller indices of the free surface

nA, nB are different for different surfaces

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Is a lattice finite or
Is ainfinite?
crystal finite or infinite?

Free
surface: a
2D defect

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Surface Defects

High-resolution transmission electron

micrograph that shows single crystals of
(Ce0.5Zr0.5)O2;
this material is used in catalytic converters for
automobiles. Surface defects represented
schematically
in Figure 4.10 are noted on the crystals.

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Internal surface: grain boundary

Grain
Boundary

Grain 2
Grain 1

A grain boundary is a boundary between two regions

of identical crystal structure but different orientation
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Grain Boundaries and Dislocations

The atoms are bonded less regularly along

a grain boundary (e.g., bond angles
are longer), and consequently, there is an
interfacial or grain boundary energy similar
to the surface energy.

The magnitude of this energy is a function

of the degree of misorientation, being
larger for high-angle boundaries.
Impurity atoms often preferentially
segregate along these boundaries because
of their higher energy state.

The total interfacial energy is lower in large

or coarse-grained materials than in fine-
grained ones, since there is less total
boundary area in the former.
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Grain boundaries...
• 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,
size number the National Bureau of
Standards, Washington, DC

N = 2n-1 [now the National Institute of

Standards and Technology,
Gaithersburg, MD].)

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification

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Planar Defects in Solids

• One case is a twin boundary (plane)
– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 4.9, Callister 7e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
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Strategies for Strengthening:

Reduce Grain Size

• Grain boundaries are

barriers to slip.
• Barrier "strength"
increases with
Increasing angle of
misorientation. Adapted from Fig. 7.14, Callister 7e.
(Fig. 7.14 is from A Textbook of Materials
• Smaller grain size: Technology, by Van Vlack, Pearson Education,
Inc., Upper Saddle River, NJ.)
more barriers to slip.

76
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• Impurity atoms distort the lattice & generate stress.

• Stress can produce a barrier to dislocation motion.
• Smaller substitutional • Larger substitutional
impurity impurity

A C

B D

Impurity generates local stress at A Impurity generates local stress at C

and B that opposes dislocation and D that opposes dislocation
motion to the right. motion to the right.

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Strengthening by Alloying
• small impurities tend to concentrate at dislocations
• reduce mobility of dislocation  increase strength

Adapted from Fig.

7.17, Callister 7e.

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Strengthening by alloying

• large impurities concentrate at dislocations on low density

side

Adapted from Fig.

7.18, Callister 7e.

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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 - see the individual grains
• Crystallites (grains) can be quite small (mm or
less) – necessary to observe with a microscope.

Photograph of xyz positioning microstage, Quartz Single Crystal

realized in single crystal silicon.
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Microscopic Examination
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystallographic
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

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Polarized Light
– metallographic scopes often use polarized light
to increase contrast
– Also used for transparent samples such as
polymers

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Concept Check

• Does the grain size number (n of Equation 4.16)

increase or decrease with decreasing grain size?
Why?
• Answer: Taking logarithms of Equation 4.16 and then
rearranging such that the grain size number n is the
dependent variable leads to the expression!
n = 1 + log N / log 2
• In other words, the value of n increases with
decreasing grain size.

Electron 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 (10-12m ~0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

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Scanning Probe Microscopy

• Neither light nor electrons are used to form an image!

• The microscope generates a topographical map, on an atomic
scale, that is a representation of the surface features and
characteristics of the specimen.
• Examination on the nanometer scale is possible,
magnifications as high as109x are possible;
• Three-dimensional magnified images are generated that
provide topographical information about features of interest.
• Some SPMs may be operated in a variety of environments
(e.g., vacuum, air,liquid); thus, a particular specimen may be
examined in its most suitable environment.

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Scanning Tunneling Microscopy

(STM)

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Scanning Electron Microscopy

Pollen Seed Space Shuttle Tile

Lead-Tin Solder
Ceramic with pores Fracture Surface
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Scanning Electron Microscopy

Dislocations in Ti Zirconia/Alumina Interface

Ant’s Head Alloy at 51,450X

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• 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

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

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Scanning Tunneling Microscopy

(STM)

(110) Surface of Ni 2 point defects on (111)

plane of Cu lattice

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• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied and

controlled (e.g., T controls vacancy conc.)
• Defects affect material properties (e.g., grain
boundaries control crystal slip).
• Defects may be desirable or undesirable (e.g., dislocations
may be good or bad, depending on whether plastic deformation is
desirable or not.)
• Strength can be increased by making dislocationmotion
difficult.
• Heating (annealing) can reduce dislocation density and increase
grain size. This decreases the strength.

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