Chapter

4 CHAPTER 4
Imperfections
in
Solids
Chapter
4 Topic Contents
Introduction
Point Defect
Vacancies and Self-Interstitials
Impurities in Solid
Specification of Composition
Miscellaneous Imperfections
Dislocations – Linear Defects
Interfacial Defects
Bulk or Volume Defects
Atom Vibrations
Microscopic Examination
General
Microscope Techniques
Chapter
4 TOPIC OUTCOMES
At the end of the lecture, students will be able:
1. Describe both vacancy and self-interstitial crystalline
defects.
2. Calculate the equilibrium number of vacancies in a
material at same specified temperature, given the
relevant constants.
3. Name the two types of solid solutions, and provide a
brief written definition and/or schematic sketch of each.
4. Given the masses and atomic weights of two or more
elements in a metal alloy, calculate the weight percent
and atom percent for each element
Chapter
4 TOPIC OUTCOMES
5. For each of edge, screw and mixed dislocations:
(a) describe and make a drawing of the dislocation.
(b) note the location of the dislocation line, and
(c) indicate the direction along which the
dislocation line extends
6. Describe the atomic structure within the vicinity of
(a) a grain boundary and
(b) a twin boundary
Chapter
4 INTRODUCTION
ISSUES TO ADDRESS...

• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

Chapter
4 Solidification
• The solidification of metal & alloy - important industrial process
• Most metal are melted & then cast into semifinished or finished
shape.
• Solidification- result of casting of molten material
– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid
• Crystals grow until they meet each other

nuclei crystals growing grain structure

liquid
Chapter
4 Solidification
• In each solidifying crystal the atoms are
arranged in a essentially regular
pattern, but orientation of each crystal
varies.
• Solidified metal containing many
crystal is said to be polycrystalline.
• The crystal in the solidified metal are
called grains and the surface between
them, grain boundaries.
Chapter
4
Solidification
• The number of nucleation sites
available to the freezing metal will
affect the grain structure of the solid
metal produced.
• If a few nucleation sites are available
during solidification, a coarse, or large-
grain, structure will be produced.
• If many nucleation sites – fine-grain
structure
Chapter
4
Solidification
Example 1: ~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall

Grains can be - equiaxed (roughly same size in all directions)

- columnar (elongated grains)
Grain Refiner - added to make smaller, more uniform, equiaxed grains.
Chapter
4
Solidification
Example 2:
Chapter
4
Imperfections in Solids
 Before this we assume the arrangement of
atoms were perfect.
 But, in reality crystals are never perfect.
 Imperfection/defect – affect many of their
physical & mechanical properties.

 So, good or not to us?

 Example:
- Sterling silver (92.5% Silver, 7.5%
copper (impurities)
- strong & hard compared to pure silver.
Chapter
4
Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Chapter
4 Point Defects

i. vacancy
ii. self-interstitial
Chapter
4
i. Vacancies

• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes
Chapter
4
i. Vacancies

• The simplest of the point defect – vacancy

or vacant lattice site.
• One normally occupied from which an atom
is missing
• All crystalline solids contain vacancies.
• Vacancies – during crystal growth, vibrates
• Vacancies can moves and exchange site
with neighbors
Chapter Equilibrium Concentration:
4 Point Defects

• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q 
No. of potential  exp 
 v 
N  kT 
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
Chapter
4
ii. Self-Interstitials
• Self-Interstitials:

-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes
Chapter
4
ii. Self-Interstitials
• An atom from crystal that is crowded into
interstitial site.
• A small void space that under ordinary
circumstances is not occupied.
• In metal – self-interstitial introduces
relatively large distortions in the
surrounding lattice.
• Atom is substantially larger than the
interstitial position.
• self-interstitial lower than vacancies.
Chapter
4
Ionic Crystals Point Defects
• In ionic crystal defects are more complex due to the
necessity to maintain electrical neutrality.

1. Schottky Imperfection
when two oppositely charged ions are missing
from an ionic crystal, a cation-anion divacancy is
created.

2. Frenkel Imperfection
if a positive cation moves into an interstitial site in
an ionic crystal, a cation vacancy is created in the
normal ion site.
Chapter
4
Ionic Crystals Point Defects
• 2D representation of an ionic crystal illustrating a Schottky defect
and a Frenkel defect.
Chapter
4
Impurity of atoms in Solid
• Impurity atoms of the substitution or
interstitial type are also point defects and
may be present in metallic or covalent
bonded crystals.

• For example,
– Very small amounts of subtitutional impurity
atoms in pure silicon can greatly affect its
electrical conductivity for use in electrical
conductivity for use in electronic device.

• Impurity ions are also point defect ion ionic

crystals.
Chapter
4
Impurity of atoms in Solid
Terms:
1. Solvent – the element or compound that is present in
the greater amount. Also called host atom.

2. Solute – used to denote an element or compound

present in a minor concentration.

3. Alloy – a metallic substance that is composed of two

or more elements

4. Solid solution – as solute atoms are added to the host

material, the crystal structure is maintained and no
new structures are formed
Chapter
4 Point Defects in Alloys
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.
Chapter
4
Point Defects in Solid Solution

Impurity point defect in solid solution:

i. Subtitutional
ii. Interstitial
Chapter
4
i. Substitutional

 Solute/impurity atom replace or substitute

for the host atoms

Factors:
i. Atomic size factor – solute may be
accommodated of solid solution only when
the difference in atomic radii between the
two types less ± 15%.
ii. Crystal structure – for both atom types
must be the same.
iii. Electronegativity - must be the same
iv. Valences - must be the same
Chapter Example:
4

A substitutional solid solution for Cu and Ni

Cu Ni
Atomic Radius (nm) 0.128 0.125
Crystal Structure FCC FCC
Electronegativity 1.9 1.8
Valence +1/+2 +2
Chapter ii. Interstitial
4

 Impurities atoms fill the voids or

interstices among the host atoms.
 The atomic diameter of an
interstitial impurities < host atoms.
 For metallic materials with high
atomic packing factors – interstitial
relatively small.
Chapter
4
2. Linear defects – Dislocations
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.

Chapter
4
Imperfections in Solids

Linear Defects (Dislocations)

– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b  to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b  to dislocation line
• Mixed dislocation:
– Combination of edge and screw dislocation
Chapter Edge dislocation
4

Burger’s vector, b:
measure of lattice
distortion
Chapter
4 Edge Dislocation
• Created by insertion of extra half planes of atoms.

• Positive edge dislocation

• Negative edge dislocation

Burgers vector
• Burgers vector
Shows displa-
cement of
atoms (slip).

31
Chapter
4 Motion of Edge Dislocation

• 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.
Chapter Screw dislocation
4

Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Chapter
4
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.

34
Chapter
4 Edge, Screw, and Mixed Dislocations

Mixed

Edge

Screw
Chapter
4

Dislocation structure of iron deformed

14% at –1950C
Chapter
4
Interfacial Defects:

• Boundaries that have two dimensions

and normally separate regions that have
different crystal structures and/or
crystallographic orientation.
• Examples:
– External surfaces, grain boundaries,
twin boundaries, stacking faults and
phase boundaries.
• Most obvious - grain boundaries, twin
boundaries
Chapter
4

3D view of
grains

Grain Boundaries
In 1018 steel
Chapter
4
Grain Boundaries

• regions between crystals

• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity

Adapted from Fig. 4.7, Callister 7e.

Chapter
4 Planar Defects in Solids

• twin boundary (plane)

– Essentially a reflection of atom positions across the twin plane.
• Twins result from:
– atomic displacements that are produced from applied
mechanical shear forces (mechanical twins)
– Also during annealing heat treatments following deformation
(annealing twins)
Chapter
4

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
Chapter Bulk or Volume Defects
4

• Theses include pores, cracks foreign

inclusion and other phases
• They are normally introduced during
processing and fabrication steps.
Chapter
4 Atomic Vibrations

• Every atom in a solid material is vibrating

very rapidly about its lattice position within
the crystal.
• So we may be thought as imperfections
• At any instant of tome not all atoms vibrate
at the same frequency and amplitude nor
with the same energy
Chapter
4
Composition

Two most command ways to specify

composition in alloy are:

1. weight (or mass) percent and

2. atom percent
Chapter
4 composition

• Specification of
composition m1
C1  x 100
– weight percent
m1  m2
m1 = mass of component 1

nm1
– atom percent C 
'
1 x 100
nm1  nm 2

nm1 = number of moles of component 1

m1 m1 = mass (gram)

A1 A1 = atom weight
Chapter
4
Composition
Chapter
4 Problem 1:

Determine the composition, in

atom percent, of an alloy that
consist of 97 wt.% aluminium and
3 wt.% copper
(Atomic mass Al = 26.98 g/mol,
Cu = 63.55 g/mol)
Chapter
4 Solution 1:

• C’Al = CAlACu x 100

CAlACu + CCuAAl

= 98.7 at %

• C’Cu = CCuAAl x 100

CAlACu + CCuAAl

= 1.30 at %
Chapter
4 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.
Chapter
4 Copper grain structure
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Observing Grain Boundaries - Metallography

• To observe grain boundaries, the metal sample must be

first mounted for easy handling
• Then the sample should be ground and polished with
different grades of abrasive
paper and abrasive solution.
• The surface is then etched
chemically.
• Tiny groves are produced
at grain boundaries.
• Groves do not intensely
reflect light. Hence
observed by optical
microscope.
After M. Eisenstadt, “Introduction to Mechanical Properties of Materials,” Macmillan, 1971, p.126
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Virtual Lab Modules

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Effect of Etching

Unetched Etched
Unetched Etched
Brass Brass
Steel Steel
200 X 200 X
200 X 200 X

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Virtual Lab Modules

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Virtual Lab Modules

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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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Measuring Grain Size

• ASTM grain size number ‘n’ is a measure of grain size.

N = 2 n-1 N = Number of grains per
2
square 2.54 x10 m
n < 3 – Coarse grained of a polished and etched
4 < n < 6 – Medium grained specimen at 100 x.
7 < n < 9 – Fine grained
n = ASTM grain size number.
n > 10 – ultrafine grained

200 X 200 X

1018 cold rolled steel, n=10 1045 cold rolled steel, n=8
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Measuring ASTM Grain Size Number

• Click the Image below to play the tutorial.

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Foundations of Materials Science and Engineering, 5th Edn. in SI units Smith and Hashemi
Chapter
4 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
Chapter
4 Optical Microscopy
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.
ASTM grain
size number

N = 2n-1

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification
Chapter
4 Optical Microscopy

• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers
Chapter
4 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.
Chapter Scanning Tunneling Microscopy (STM)
4

• Atoms can be arranged and imaged!

Carbon monoxide Iron atoms arranged

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

• Electron Microscope:
i. The Scanning Electron Microscope
(SEM)
ii. Transmission Electron Microscopy
(TEM)
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The Scanning Electron Microscope

• 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.
SEM of fractured metal end
65
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Transmission Electron Microscope

• Electron produced by
heated tungsten
filament.
• Accelerated by high
voltage (75 - 120 KV)
• Electron beam passes
through very thin Collagen Fibrils
of ligament as
specimen.
seen in TEM
• Difference in atomic
arrangement change
directions of electrons.
• Beam is enlarged and
focused on fluorescent
screen.

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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 Probe Microscopy

• Scanning Tunneling Microscope (STM) and

Atomic Force Microscope (AFM).
• 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.

68
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Atomic Force Microscope

• Similar to STM but tip attached to cantilever

beam.
• When tip interacts with surface, van der waals
forces deflect the beam.
• Deflection detected by laser
and photodetector.
• Non-conductive materials
can be scanned.
• Used in DNA research and
polymer coating technique.

69
Foundations of Materials Science and Engineering, 5th Edn. in SI units Smith and Hashemi
Chapter
4 i. The Scanning Electron Microscope (SEM)

• The upper limit of optical microscope ~2000x.

• but, some structural elements are too fine/small.
• need higher magnification
• An image of the structure under investigation is
formed using beams of electrons instead of light
radiation.

• The surface of a specimen to be examined is

scanned with an electron beam, and the reflected
(or back-scattered) beam of electron is collected,
then displayed at the same scanning rate on a
cathode ray tube (similar to a CRT TV screen)
Chapter
4 ii. Transmission Electron Microscopy (TEM)

• The image seen with a TEM is formed by

an electron beam that passes through
specimen.
• Details of internal microstructural
features are accessible to observation
• Since solid materials are highly
absoptive to electron beams, a
specimen must be very thin.
• Magnification 1 000 000x are possible.
Chapter
4 Scales
Chapter
4 Summary
• 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.)