EME 1166

MATERIALS SCIENCE

CHAPTER 4
CRYSTAL DEFECTS

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 INTRODUCTION
Crystalline defect: 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.

This chapter discusses:

• Point defects
• Specification of composition
• Miscellaneous dislocation
• Interfacial defects
• Grain size
• Microscopic techniques
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 POINT DEFECTS:
Vacancies & Self-interstitials

Figure 1: Two-dimensional representations

of a vacancy and a self-interstitial
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Vacancy:
A point imperfection in a crystal lattice
where an atom is missing from an atomic
site.

Self-interstitial
An atom from the crystal that is crowded
into an interstitial site, a small void space
that under ordinary circumstances is not
occupied.

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• In metals, a self-interstitial exists in very
small concentrations (not highly
probable):

Because self-interstitial introduces relatively

large distortions in the surrounding lattice
because the atom is substantially larger
than the interstitial position in which it is
situated.

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• The equilibrium number of vacancies, Nv for a
given quantity of material depends on and
increases with temperature according to

 Q 
N v  N exp   v  (2.1)
 kT 

where:
N = Total number of atomic sites
Qv= Energy required for the formation of a vacancy
T = Absolute temperature (in kelvins, K)
k = Boltzmann’s constant = 1.38 x 10-23 J/atom.K or
8.62 x 10-5 eV/atom
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• Number of atomic sites per unit volume:

N A
N (2.2)
A

where:
NA = Number of Avogadro = 6.022 x 1023 atoms/mol
 = Density
A = Atomic weight

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Example:
Calculate the number of vacancies per cubic
meter in iron at 855°C. The energy for
vacancy formation is 1.08 eV/atom.
Furthermore, the density and atomic weight
for Fe are 7.65 g/cm3 and 55.85 g/mol,
respectively.

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  Qv  N A   Qv 
N v  N exp    exp   
 kT  A  kT 

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10
 LIQUID SOLUTION

Figure 2: Forming a liquid solution of water and alcohol. Mixing occurs

on the molecular scale. 11
• For liquid solution;
• 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.

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 SOLID SOLUTION

A solid solution forms when the solute

atoms are added to the host material, the
crystal structure is maintained, and no
new structures are formed.

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• The addition of impurity atom to a metal will
result in the formation of solid material and/or a
new second phase.
• With regard to alloys, solute and solvent are
terms that are commonly employed.
• Solvent: the element or compound that is
present in the greatest amount; on occasion,
solvent atoms are also called host atoms.
• Solute: used to denote an element or compound
present in a minor concentration.

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Figure 3: Solid solution of nickel in copper shown along a plane.
This is a substitutional solid solution with nickel atoms
substituting for copper atoms on FCC atom sites.

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 SOLID SOLUTION

Figure 4: Interstitial solid solution of carbon in α-iron. The carbon atom

is small enough to fit with some strain in the interstice (or opening)
among adjacent Fe atoms in this structure of importance to the steel
industry.

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 POINT DEFECTS:
Interstitial & Substitutional

Figure 5: Two-dimensional representations of substitutional and

interstitial impurity atoms 17
• Interstitial:
Impurity atoms fill the voids or interstices among
the host atoms.

• Substitutional:
Solute or impurity atoms replace or substitute
for the host atoms.

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 HUME-ROTHERY RULES
To form metallic solid solutions:
1. Atomic size factor
– Less than ± 15% difference in atomic radii.
– Or the solute atoms will create substantial lattice
distortions and a new phase will form.
2. Crystal structure
- The same crystal structures
3. Electronegativity (the ability of the atom to attract an
electron)
– Similar electronegativity.
– Or intermetallic compound will form.
4. Valences
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- The same valence
 Specification of Composition

The two most common ways to specify composition

(or concentration) of an alloy are:

i. Weight (or mass) percent (wt%)

ii. Atom percent (at%)

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Composition in weight percent (wt%):
• The basis for weight percent (wt%) is the weight of a
particular element relative to the total alloy weight.
• For an alloy that contains two hypothetical atoms
denoted by 1and 2, the composition of 1 in wt%, C1,
is defined as

(2.3)

Where m1 and m2 represent the weight (or mass) of

elements 1 and 2.
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Composition in atom percent (at%):
• The basis for atom percent (at%) calculations is the number of
moles of an element in relation to the total moles of the
elements in the alloy.
• The number of moles in some specified mass of a hypothetical
element 1, nm1, may be computed as follows:

(2.4)

Here, m1 and A1 denote the mass (in grams) and atomic weight,
respectively for element 1.

Composition in term of atom percent of element 1 in an alloy

containing element 1 and 2 atoms, C1’ is defined by

(2.5)
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 Composition Conversions
• Conversion from weight percent to atom percent:

(2.6a)

(2.6b)

• Conversion from atom percent to weight percent:

(2.7a)

(2.7b)
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• Since we are considering only two
elements, computations involving the
preceding equations are simplified when it
is realized that

C1 + C2 = 100 (2.8a)
C1’ + C2’ = 100 (2.8b)

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• Conversion from weight percent to mass per unit volume:

(2.9a)

(2.9b)

• Average density of a two-component alloy:

(2.10a)

• Average atomic weight of a two-component alloy:

(2.10b)
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26
 Miscellaneous Imperfections:
Dislocations – Linear Defects

Dislocations:
A linear or one-dimensional crystalline defects of
which some of the atoms are misaligned.

• There are 2 pure types:

i) Edge dislocation
ii) Screw dislocation

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 Dislocations – Linear Defects
i. Edge dislocation:
• A linear defect that centers on the line that is
defined along the end of the extra half-plane of
atoms.
• The Burgers vector, b is perpendicular to the
edge dislocation line.
• Symbol:

The atom positions around an edge dislocation; extra

half-plane of atoms shown in perspective.
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i. Edge dislocation:
• The atoms above the dislocation line are
squeezed together, and those below are pulled
apart.
• The magnitude of this distortion decreases with
distance away from the dislocation line; at
positions far removed, the crystal lattice is virtually
perfect.

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 Edge Dislocation
• Created by insertion of extra half planes of atoms.
Positive edge dislocation

Negative edge dislocation

• Burgers vector shows displacement of atoms (slip).

Burgers vector

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ii. Screw dislocation:
• A linear crystalline defect associated with the
lattice distortion created when normally parallel
planes are joined together to form a helical
ramp.
• The upper front region of the crystal is shifted
one atomic distance to the right relative to the
bottom portion.
• The Burgers vector is parallel to the dislocation
line.
• Symbol:
31
ii. Screw dislocation:

(a) screw dislocation within a crystal. (b) The screw dislocation in (a) as
viewed from above. The dislocation line extends along line AB. Atom positions
above the slip plane are designated by open circles, those below by solid
circles. 32
 ii. Screw Dislocation
• Created due to shear stresses applied to regions of
a perfect crystal separated by cutting plane.
• Distortion of lattice in form of a spiral ramp.
• Burgers vector is parallel to dislocation line.

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 iii. Mixed Dislocation
• Most crystal have components
of both edge and screw
dislocation.

• Dislocation, since have

irregular atomic arrangement
will appear as dark lines
when observed in electron
microscope. Dislocation structure of iron deformed
14% at –1950C 34
iii. Edge, screw and mixed dislocation:

(a) (b)
Figure 5 (a) Schematic representation of a dislocation that has edge, screw, and mixed
character. (b) Top view, where open circles denote atom positions above the slip plane, and
solid circles, atom positions below.

i.At point A: pure screw dislocation.

ii.At point B: pure edge dislocation.
iii.For regions in between where there is curvature in the dislocation line, 35
the
character is mixed edge and screw.
• The relative orientations of Burgers vector
and dislocation line are:

i) Perpendicular for edge,

ii) Parallel for screw, and
iii) Neither perpendicular nor parallel for
mixed.

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 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.

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 Interfacial Defects
• Grain boundaries, twin boudaries, low/high
angle boundaries, twists and stacking faults
• Free surface is also a defect : Bonded to atoms
on only one side and hence has higher state of
energy Highly reactive
• Nanomaterials have small clusters of atoms
and hence are highly reactive.

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 Grain Boundaries
• Grain boundaries separate grains.
• Formed due to simultaneously growing crystals meeting
each other.
• Width = 2-5 atomic diameters.
• Some atoms in grain boundaries have higher energy.
• Restrict plastic flow and prevent dislocation movement.

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3D view of
grains

Grain Boundaries
In 1018 steel
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 Grain Boundaries

Schematic diagram showing small and high-angle grain boundaries and the
adjacent atom positions.
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 Twin Boundaries
• Twin: A region in which mirror image of structure
exists across a boundary.
• Formed during plastic deformation and
recrystallization.
• Strengthens the metal.
Twin
Plane

Twin

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 Grain Size
• Affects the mechanical properties of the material
• The smaller the grain size, more are the grain
boundaries.
• More grain boundaries means higher resistance
to slip (plastic deformation occurs due to slip).
• More grains means more uniform the
mechanical properties are.

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 Microscopic Examination
• Many of the important defects and structural elements of
materials are of microscopic dimensions, and observation
is possible only with the aid of a microscope.

• Both optical and electron microscopes are employed,

usually in conjunction with photographic equipment.

• More recent scanning probe microscopic techniques have

been developed that generate topographical maps
representing the surface features and characteristics of
the specimen. Examinations on the atomic and molecular
levels are possible using these techniques.
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 Microscopic Examination

Cross-section of a cylindrical copper ingot. The small needle-

shaped grains may be observed, which extend from the center
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radially outward.
 Optical Microscopy

(a) Polished and etched grains as they might appear when viewed with an optical
microscope. (b) Section taken through these grains showing how the etching
characteristics and resulting surface texture vary from grain to grain because of
differences in crystallographic orientation. 46
(c) Photomicrograph of a polycrystalline brass specimen.
 Optical Microscopy

(a) Section of a grain boundary and its surface groove produced by etching; the
light reflection characteristics in the vicinity of the groove are also shown.
(b) Photomicrograph of the surface of a polished and etched polycrystalline
specimen of an iron chromium alloy in which the grain boundaries appear dark.47
 Transmission Electron Microscope (TEM)
• Electron produced
by heated tungsten
filament.
• Accelerated by
high voltage (75 -
120 KV)
• Electron beam
passes through Collagen
very thin specimen. Fibrils
of ligament as
• Difference in atomic seen in TEM
arrangement
change directions
of electrons.
• Beam is enlarged
and focused on
fluorescent screen. 48
 TEM (..Cont)
• TEM needs complex sample preparation
• Very thin specimen needed ( several hundred
nanometers)
• High resolution TEM (HRTEM) allows resolution of
0.1 nm.
• 2-D projections of a crystal with accompanying
defects can be observed.
Low angle
boundary
As seen
In HTREM

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Scanning Electron Microscope (SEM)
• Electron source
generates electrons.
• Electrons hit the
surface and
secondary electrons
are produced.
• The secondary
electrons are
collected to produce
the signal.
• The signal is used
to produce the
image.
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 Scanning Probe Microscopy (SPM)
• Scanning Tunneling Microscope (STM)
• Sub-nanometer magnification.
• Atomic scale topographic map of surface.
• STM uses extremely sharp tip.
• Tungsten, nickel, platinum
- iridium or carbon nanotubes are used for tips.

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 Scanning Tunneling Microscope

• Tip placed one atom diameter from surface.

• Voltage applied across tip and surface.
• Electrons tunnel the gap and produce current.
• Current produced is proportional to change in
gap.
• Can be used only for conductive materials.

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Constant height and current modes Surface of platinum with defects

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Bar chart showing size ranges for several structural features found in materials

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Bar chart showing the resolution ranges for different microscopic techniques

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