Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

• Cracks Volume defects

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 Point Defects in Metals
• Vacancies: All crystalline solids contain vacancies
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials: They are highly improbable and exist in low concentrations

-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

2
Equilibrium Concentration of vacancies

No. of defects Activation energy

Nv Q v 
No. of potential = exp  
defect sites N  k T 
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)

(8.62 x 10 -5 eV/atom-K)

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 Point defects: impurities
• Impurity: a foreign atom that occupies a normal lattice site
(substitution impurity) or goes to the interstitial position (interstitial
impurity).

Substitution impurity Interstitial impurity

 Alloying – Addition of two or more elements to make a solid material e.g.

Cu + Zn → Brass
Fe+ C→ Steel

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 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 (compound)
-- often different structure.
(e.g., Carbide in steel)

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 Differences between second phase and solid solution

• Second phase:
 different composition
 different structure

• Solid solution:
 homogeneous
 maintain crystal structure
 contain randomly dispersed impurities

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 Solid solution
 A solid solution forms if the crystal structure of the host material is
maintained as impurity atoms are added to it. This implies that no
new crystal structure is formed.
 Solid solution can therefore be defined as a homogenous crystalline
phase that contains two or more chemical species, which are mutually
soluble in one another. The ability to dissolve is called solubility.
 The host material is called the solvent while the impurity atom that is
present in minor concentration is called the solute
 Impurity point defects that are found in solid solutions may be
substitutional or interstitial

OR

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 Substitutional Solid Solutions

 Factors for high solubility:

 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

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 Cu and Ni forms substitutional solid solution.

The two elements are completely soluble in each other at all

proportions

Copper Nickel

Atomic radius 0.128 nm 0.125 nm

Crystal structure FCC FCC
Electronegativity 1.9 1.8
Valence +1 or +2 +2

9
1. Would you predict Element Atomic Crystal Electro- Valence
more Al or Ag Radius Structure
(nm)
nega-
tivity
to dissolve in Zn? Cu 0.1278 FCC 1.9 +2
C 0.071
H 0.046
O 0.060
2. More Zn or Al Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
in Cu? Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 118, Callister & Rethwisch 8e.

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 Interstitial Solid Solutions

• Factors for high solubility:

 For fcc, bcc, hcp structures the voids (or interstices) between the host atoms are relatively
small ⇒ atomic radius of solute should be significantly less than solvent

 Even small interstitial impurity atoms are usually bigger than the
interstitial sites and will introduce lattice strains on the adjacent host
atoms.
 Maximum allowable concentration of interstitial solute atoms in an
interstitial solid solution is usually less than 10 % (e.g., C in BCC Fe
< 2%).
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 Composition/Concentration
 Weight percent (wt%), useful when making the solution (mass ratio)
m1
C1 =  100
m1  m2
 Atom percent (at%), useful when trying to understand the material at the
atomic level (atom number ratio)
nm1
C =
'
 100
nm1  nm 2
1

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 Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation,
• can be observed in crystalline materials using electron microscope.

Dislocations are introduced into materials

(a) during casting solidification,
(b) during mechanical deformation

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 Description of Dislocations: Burgers Vector
 To find the Burgers vector, we should make a circuit
from atom to atom counting the same number of atomic
distances in all directions. If the circuit encloses a
dislocation it will not close. The vector that closes the loop
is the Burgers vector b.

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• Edge dislocation:
– extra half-plane of atoms inserted in a crystal
structure
– b perpendicular () to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear
deformation
– b parallel () to dislocation line

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Edge dislocation
 In edge dislocation, the edge of an extra portion of a plane of atoms terminates within
the crystal
 Burgers vector is perpendicular to the dislocation line
 Edge dislocation is defined by the dislocation line, which represents the end of the extra
half-plane of atoms
 Lattice distortions exist in region around the dislocation line: the atoms above are
squeezed together, while those below are pulled apart
 The symbol  is used to represent edge dislocation. If the extra plane of atoms is located
in the lower portion of the dislocation line the designation of edge dislocation will be

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Screw dislocation
 Screw dislocation can be imagined as being formed by a shear stress that is
applied to produce a distortion such that the upper front region of the crystal is
shifted by one atomic distance to the right relative to the bottom portion
 Burgers vector is parallel to the dislocation line

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Mixed/partial dislocations
• The exact structure of most dislocations in real crystals has mixed
edge/screw character.

18
 Interfacial defects

Interfacial defects are two dimensional

boundaries which normally separate regions of
materials that have different crystallographic
structures and/or crystallographic orientations.

19
 Interfacial Defects

External surface
Grain boundary
Twin boundary
Stacking Fault
Phase boundaries

20
• External Surfaces (Free surfaces)
– This refers to the surface along which the crystal structure
terminates.
– Surface atoms have unsatisfied atomic bonds, and higher energies
than the bulk (interior) atoms
– Solid surfaces can “reconstruct” to satisfy atomic bonds
– Surface atoms tend to minimize (e.g., liquid drop)

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• Grain boundaries
 Grain boundaries are the regions
that separate two grains or crystals
having different crystallographic
orientations in a polycrystalline
material.
 Atomic mismatch, which
represents the transition from the
orientation of one grain to the
other, occurs at the grain
boundaries.
 Depending on misalignments of
atomic planes between adjacent
grains, we can distinguish between
the low (< 11o) and high (> 11o)
angle grain boundaries.

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 As a result of irregular bonding of atoms (number of nearest
neighbor less than coordination number) at the grain boundaries,
grain boundary regions are high-energy area.

 The value of grain boundary energy depends on the degree of

crystallographic misalignment.

 The higher the degree of misorientation, the greater the magnitude

of grain boundary energy

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 Tilt and Twist Grain Boundaries
• Tilt Grain Boundaries
Tilt boundaries result from an array of edge dislocations.
• Twist Grain Boundaries
Twist boundaries can be described by an array of screw dislocations.

• Mixed-type Grain Boundaries

Tilt GB

Twist GB

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Twin Boundaries
 A twin boundary is formed when the crystal structure on one side of the boundary is a
mirror image of the adjoining grain on the other side.
 Twining can occur as a result of
a. applied mechanical shear force – common in
BCC and HCP metals
b. annealing heat treatment after deformation –
common in FCC metals
 Twinning occurs on a definite crystallographic plane and in a specific direction, which
depend on the crystal structure.

Twin boundaries in Cu
Lu et al., Science 2004

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 Stacking Faults
 Stacking fault is an irregularity in
the stacking of atomic planes.

 For example, HCP metals are

arranged in regular. . . ABABAB. .
. stacking of the atomic planes, and
FCC metals are arranged in
…..ABC ABC ABC sequence.

 Stacking fault will occur when

there is interruption in this stacking
sequence.
http://amadm.unileoben.ac.at/SFE_Steel.html

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 Phase boundaries
 A phase boundary refers to the region between two adjoining phases in a
multiphase material.
 There is a change in physical and chemical characteristics across a phase
boundary.
’ phase

 phase matrix
Phase boundary in a high-temperature Aerospace Superalloy

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 Bulk or Volume Defects

 These are three dimensional defects such as pores, cracks, foreign

inclusions and other second phase particles.
 They are much larger than the all aforementioned defects and are
introduced during material processing.

Cracks
Commercial 361L steel Courtesy of Dr. Mesquita

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 Atomic Vibrations
Every atom in a solid (or any material) is vibrating rapidly about
its lattice position!

• Heat causes atoms to vibrate

• Vibration amplitude increases with temperature
• Melting occurs when vibrations are sufficient to rupture bonds
• Vibration frequency ~ 1013 Hz
• Average atomic energy due to thermal excitation is of order kT

29
Microscopy

30
The macrostructures and microstructures
The structural elements and defects of a material, which can be observed with
unaided eyes, form the macrostructure.
The structural elements or defects, which are so small that they can only be
observed with the aid of a microscope constitute the microstructure of a material

Microscopic examination
 Microscopic examination involves using microscope to examine the
microstructure of a material and taking the picture (Micrograph) of the structure
for analysis.
 Several techniques that are used for microscopic examination include optical
microscopy, electron microscopy and scanning probe microscopy
 Prior to microscopic examination, the sample must be ground and polished to
obtain a smooth mirror-like surface finish followed by etching.

31
Sample Preparation
• Prior to optical microscopic examination, the sample must
be well prepared through the following major steps.

Mounting – for easy handling

Grinding and Polishing – to obtain mirror-like flat

smooth surface

Etching – to delineate internal features

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Etching
 Etching involves surface treatment
of the polish surface in which the
grain boundaries are attacked
polished surface
more chemically due to their high
chemical reactivity resulting in
surface groove
formation of groves along grain
boundaries. grain boundary
(a)
 The groves make it easier to Adapted from Fig. 4.14(a) and
(b), Callister & Rethwisch 8e.
discern the grain boundaries when (Fig. 4.14(b) is courtesy
the material is viewed under of L.C. Smith and C. Brady, the
National Bureau of Standards,
microscope Washington, DC [now the
National Institute of Standards
 For a multi-phase alloy, etchant is and Technology, Gaithersburg,
selected to produce different MD].)

texture for each phase so that the Fe-Cr alloy

phases can be distinguished from (b)
one another

33
 Optical Microscopy

• Reflected light is used to

observe the polish surface of
the sample to be examined
• Useful up to 2000X
magnification crystallographic planes
• Polishing removes surface
features (e.g., scratches)
• Etching changes reflectance,
depending on crystal Micrograph of
orientation. brass (a Cu-Zn alloy)

0.75mm
Adapted from Fig. 4.13(b) and (c), Callister &
Rethwisch 8e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.)

34
 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.

De Broglie matter wave:

l=h/p
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Electron microscopy
 In electron microscopy, the image of the surface to be examined is
formed using electron beams instead of light radiations
 High velocity electron behave like wave whose wave-length can
be in the range of 0.003 nm when accelerated across large voltages
 Higher magnification and higher resolution are possible by
electron microscope as a result of the short wave length of electron
beams
 There are two types of electron microscopy: Transmission and
scanning electron microscopy

36
 Scanning Electron Microscopy (SEM)

 In SEM, the image is produced by

reflected electron beam from the surface
of the material on a fluorescence screen
 The surface may or may not be polished
or etched, but must be electrically
conductive
 Magnification ranging from 10 to 50,000
times and high depths of field are
possible using SEM

http://www.vcbio.science.ru.nl/en/fesem/info/principe/

37
http://en.wikipedia.org/wiki/Scanning_electron_microscope

38
 Transmission Electron Microscopy (TEM)

 In TEM, the image is formed by

an electron beam that passes
through a very thin foil of the
material on a fluorescence screen
or a photo graphic film
 Magnifications as high as
1,000,000 X are possible with
transmission electron microscopy
 Unlike SEM, you can determine
crystallographic structure by
TEM

http://www.vcbio.science.ru.nl/en/fesem/info/principe/

39
http://en.wikipedia.org/wiki/Transmissio
n_electron_microscopy

40
 Scanning Probe Microscopy (SPM)
 In scanning probe microscopy, neither electrons beam nor light radiation is used to
form an image
 SPM involves scanning a tiny probe with extremely sharp tip across the specimen’s
surface, line by line
 The scanning produces a topographic map, on atomic scale, that is a representation of
surface features of the specimen
 The movements of the probe tip are detected by sensors and transferred to computer
which then generates the image representing the feature of the scanned specimen
 Advantages of SPM over other techniques are:
a. Magnification of the order of 109 times (examination on nanoscale) is possible
b. Three-dimensional magnified images can be generated

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Scanning Probe Microscopy (SPM)
 Scanning Tunneling Microscope (STM)

http://en.wikipedia.org/wiki/Scanning_tunneling_microscopy

42
Scanning Probe Microscopy (SPM)
 Atomic Force Microscope (AFM)

http://en.wikipedia.org/wiki/Atomic_force_microscopy

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