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CHAPTER 5:
IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...

Chapter 5
Imperfections in Solids

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 5 - 2
Thanks to Jeff DePue, Greg Dykes, Alex Eaton

5.1 Imperfections in Solids

5.1 Introduction
Solidification- result of casting of molten material
Every single solid has defects and
imperfections.
Sometimes the imperfections are purposely
created and used for a specific purpose.
Types of defects:
Point Defects (One or two atomic positions)
Linear Defects (One Dimensional)
Interfacial Defects (Boundaries)

2 steps
Nuclei form
Nuclei grow to form crystals grain structure

Start with a molten material all liquid

nuclei

crystals growing
liquid

grain structure

Adapted from Fig. 5.19 (b), Callister & Rethwisch 3e.

Crystals grow until they meet each other

Chapter 5 - 4

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Solidification

Polycrystalline Materials

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

- columnar (elongated grains)
~ 8 cm

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

heat
flow
Shell of
equiaxed grains
due to rapid
cooling (greater
T) near wall

Columnar in
area with less
undercooling
Adapted from Fig. 5.17,
Callister & Rethwisch 3e.

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

Adapted from Fig. 5.12,

Callister & Rethwisch 3e.
Chapter 5 - 5

Imperfections in Solids

Chapter 5 - 6

Types of Imperfections

There is no such thing as a perfect

crystal.
What are these imperfections?
Why are they important?

Vacancy atoms
Interstitial atoms
Substitutional atoms

Point defects

Dislocations

Line defects

Many of the important properties of

materials are due to the presence of
imperfections.

Grain Boundaries

Area defects

Chapter 5 - 7

Chapter 5 - 8

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I. Point
defects

5.2 Point Defects in Metals

Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

Self-Interstitials:
-"extra" atoms positioned between atomic sites.

selfinterstitial
distortion
of planes

Chapter 5 - 9

Chapter 5 - 10

Equilibrium Concentration:
Point Defects

Measuring Activation Energy

Equilibrium concentration varies with temperature!

No. of defects
No. of potential
defect sites

Activation energy

Q
Nv
v

exp

N
kT

We can get Qv from

an experiment.

Q
Nv
v
= exp
kT
N

Measure this...

Replot it...

Nv

Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)

ln

slope
-Qv /k

exponential
dependence!

Each lattice site

is a potential
vacancy site

Nv

1/T

defect concentration
Chapter 5 - 11

Chapter 5 - 12

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Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
Given:
= 8.4 g/cm3
ACu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Q
Nv
v

-4

exp

For 1 m3 , N = x

kT = 2.7 x 10
NA
ACu

1273 K
8.62 x 10-5 eV/atom-K
x 1 m3 = 8.0 x 1028 sites

Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Chapter 5 - 13

5.2 Point Defects in Metals

5.2 Point Defects in Metals

Vacancies:
Impossible to create a
material without vacancies
due to the laws of
Thermodynamics.
The number of vacancies (Nv)
calculated from
Nv = N exp(-Q/kT)
N = number of atomic sites;
Q = energy for vac.
formation;
http://www.matter.org.uk/matscicdrom/manual/po.html
k = boltzmanns constant
= 1.3810-23 J/atom-K
= 8.6210-5 eV/atom-K
T = absolute temperature (K)

5.3 Point Defects in Ceramics (i)

Vacancies
-- vacancies exist in ceramics for both cations and anions
Interstitials
-- interstitials exist for cations

Self Interstitial:
When an atom is
pushed into an
interstitial site
which is normally
unoccupied.
Very small amount
in metals because
when it occurs, it
highly distorts the
metal.
Much lower
concentrations than
vacancies.

-- interstitials are not normally observed for anions because anions

are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

http://www.substech.com/dokuwiki/doku.php?id=imp
erfections_of_crystal_structure

Anion
Vacancy

Adapted from Fig. 5.2, Callister &

Rethwisch 3e. (Fig. 5.2 is from
W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Chapter 5 - 16

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Point Defects in Ceramics (ii)

5.3 Point Defects in Ceramics

Frenkel Defect
-- a cation vacancy-cation interstitial pair.
Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect:

Adapted from Fig. 5.3, Callister &

Rethwisch 3e. (Fig. 5.3 is from
W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)

Frenkel
Defect

Equilibrium concentration of defects e

QD /kT

Chapter 5 - 17

Frenkel Defect
Neighboring cation
vacancy and cation
interstitial.
Nfr = N exp(-Qfr/2kT)

More types of defects than metals because

there are more types of ions.
In order to keep electroneutrality, ions must
be lost in equal amounts of charge. For
example: One cation and one anion.
Two main types: Frenkel Defect, Shottky
Defect
Most ceramics stay in a stoichiometric state,
that is, they generally keep the same ratios
as predicted by their empirical formula.
Exceptions occur in atoms like iron: Fe2+ and
Fe3+

Shottky Defect
Neighboring
cation vacancy
and anion
vacancy.
Ns=N*exp(Qs/2kT)
http://mrsec.wisc.edu/Edetc/SlideShow/slides/defects/
Schottky_Frenkel.html

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Impurities in Solids

5.4 Impurities in Solids

METALS: 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.
(e.g., Cu in Ni)

Interstitial solid soln.

(e.g., C in Fe)

Solid Solutions:
Substitutional
replacement of ions
Interstitial
filling of voids
Impurities in
Dependent on:
Ceramics

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 5 - 21

Atomic size factor

Crystal Structure
Electronegativity
Valences

Both types as
well Can occur
for the cations
or for the
anions
Usually both
occur at same
time (one
cation + one
http://www.chem.ufl.edu/%7Eitl/2045/lectures/lec_i.html

Impurities in Metals

Impurities in Metals

Conditions for substitutional solid solution (SS)

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

Chapter 5 - 24

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Imperfections in
Metals

Element Atomic Crystal Electro- Valence

Radius Structure nega(nm)
tivity

Cu
C
H
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn

1. Would you predict

more Al or Ag
to dissolve in Zn?
2. More Zn or Al
in Cu?

0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

FCC

1.9

+2

FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP

1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6

+1
+3
+2
+3
+2
+2
+2
+2

Imperfections in
Metals
1. Would you predict
more Al or Ag
to dissolve in Zn?
2. More Zn or Al
in Cu?

Element Atomic Crystal Electro- Valence

Radius Structure nega(nm)
tivity

Cu
C
H
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn

0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

FCC

1.9

+2

FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP

1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6

+1
+3
+2
+3
+2
+2
+2
+2

Chapter 5 - 25

Chapter 5 - 26

Table on p. 159, Callister & Rethwisch 3e.

Table on p. 159, Callister & Rethwisch 3e.

Imperfections in Ceramics

5.5 Point Defects in Polymers

Electroneutrality (charge balance) must be maintained

when impurities are present

Cl Ex: NaCl Na+
Substitutional cation impurity

Defects due in part to chain packing errors and impurities such

as chain ends and side chains
Adapted from Fig. 5.7,
Callister & Rethwisch 3e.

cation
vacancy

Adapted from Fig. 5.7,

Callister & Rethwisch 3e.

Ca 2+
Na +
Na +
without impurity

Ca 2+ impurity

Substitutional anion impurity

O2-

without impurity

Cl Cl O2- impurity

Ca 2+
with impurity
anion vacancy

with impurity
Chapter 5 - 27

Chapter 5 - 28

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5.5 Point Defects in Polymers

5.6 Specification of Composition

(or concentration)
Specification of composition

Different from ceramics and metals

Chains can bond together forming loops.
Chains can tie two molecules together.
Impurities may include interstitials, side
branches, or incorrect bending.
Vacancies can occur and alter the chain
sequence.
Every chain end is considered a defect.

weight percent

C1

m1
x 100
m1 m2

m1 = mass of component 1

atom percent

C1'

nm1
x 100
nm1 nm2

nm1 = number of moles of component 1

m = mass; n = moles (Compositions are easily converted
from one type to the other by manipulating m to n, or vice
versa, using the atomic weight, A)

Chapter 5 30

5.7 Line Defects

II.
Miscellaneous
Imperfections
Chapter 5 - 31

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

Chapter 5 - 32

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Imperfections in Solids

Imperfections in Solids

extra half-plane of atoms inserted

in a crystal structure

Linear Defects (Dislocations)

Are one-dimensional defects around which atoms are
misaligned

Edge dislocation:

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
Burgers vector, b: measures the magnitude and direction of
the lattice distortion
Fig. 5.8, Callister & Rethwisch 3e.

Chapter 5 - 33

Imperfections in Solids

Chapter 5 - 34

Edge, Screw, and Mixed Dislocations

Mixed

Screw Dislocation: b || dislocation line

Screw
Dislocation

Dislocation
line
Burgers
vector b

Edge

b
(b)
(a)

Adapted from Fig. 5.10, Callister & Rethwisch 3e.

Screw

Adapted from Fig. 5.9, Callister & Rethwisch 3e.

Chapter 5 - 35

Chapter 5 - 36

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Imperfections in Solids
Dislocations are visible in electron micrographs; TEM
Titanium alloy, dark lines are dislocations 51,450x

5.7 Dislocations Linear

Defects
A dislocation is a linear (one dimensional) defect
around which other atoms are misaligned
Edge Dislocation where an extra plane or half
plane of atoms stops
Screw Dislocation where a shear stress causes a
region of a crystal to shift
Mixed Dislocation a combination of edge and
screw dislocations
Burges Vector the magnitude and direction of
lattice distortion associated with a dislocation

Fig. 5.11, Callister & Rethwisch 3e.

Chapter 5 - 37

5.8 Interfacial defects

2D Boundaries
Separate xtal structures & xtalographic orientations
Examples:
-external surfaces
-Lower nearest neighbors
-Atoms in higher energy states
-Tend to minimize the total surface area
- grain boundaries
-Low angle
example: tilt boundary
-High angle
- twin boundaries
- stacking faults
- phase boundaries (in multiphased materials)

Chapter 5 -

Chapter 5 - 40

10

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Twin boundary (plane)

Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 5.14,

Callister & Rethwisch 3e.

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC

Chapter 5 - 41

5.8 Interfacial Defects

Interfacial defects are two dimensional boundaries
with different crystal structures and/or orientations
External Surfaces where the crystal terminates
Grain Boundaries crystals often form groups of
atoms known as grains, which when combined with
other grains in a large crystal, often have
misalignments that form boundaries
Phase Boundaries where a crystal forms more
than one phase (i.e. solid and liquid)
Twin Boundaries A special grain boundary where
one grain forms a mirror lattice symmetry with
another
Other miscellaneous interfacial defects include
stacking faults and ferromagnetic domain walls.

Catalysts and Surface Defects

A catalyst increases the
rate of a chemical
reaction without being
consumed
Active sites on catalysts
are normally surface
defects

Fig. 5.15, Callister & Rethwisch 3e.

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 5.16, Callister & Rethwisch 3e.
Chapter 5 - 42

5.8 Interfacial Defects

Grain Boundary

http://www.corrosionlab.com/Failure-Analysis-Studies/Failure-Analysis-Images/20030.SCC.304Hpipeline/20030.microstructure-ditched-grain-boundaries.jpg

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5.9 Bulk or Volume Defects

Much larger defects than the previous
ones, usually introduced during
processing and fabrication steps
Examples include:
Pores
Cracks
Foreign Inclusions
Other Phases
http://www.fossil.energy.gov/images/education/rockpore.jpg

5.10 Atomic Vibrations

Every atom vibrates even at zero Kelvin
(OK?)
Frequencies in the order of 10 THz
At any given time, each atom in a crystal is
vibrating about its lattice position within the
crystal
The amplitudes and frequencies of the
vibrations vary between atoms and can be
considered imperfections or defects
The vibrations change with temperature and
influence many properties of the crystal such
as melting point
Chapter 5 - 46

III.Microscopic
Examination

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 5 - 47

Chapter 5 - 48

12

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5.11 Microscopic Examination

5.11 Microscopic Examination
The grains of many crystals have diameters
in the order of microns (10-6 meters)
Microstructure Structural features subject to
observation under a microscope
Microscopy Use of a microscope in
studying crystal structure
Photomicrograph A picture taken by a
microscope

5.12
Microscopic
Techniques

Electron Microscope

Optical Microscope
Scanning Probe Microscope

http://science.kukuchew.com/wp
content/uploads/2008/06/moder
nmicroscope.jpg

http://img.directindustry.com
/images_di/photog/scanning-probemicroscope-spm-47975.jpg

Optical Microscopy

Optical Microscopy
Useful up to 2000X
magnification.
Polishing removes
surface features (e.g.,
scratches)
Etching changes
reflectance, depending
on crystal orientation.
Adapted from Fig. 5.18(b) and (c), Callister
& Rethwisch 3e. (Fig. 5.18(c) is courtesy
of J.E. Burke, General Electric Co.)

http://rsic.puchd.ac.in/images/
image002.jpg

crystallographic
planes

Micrograph
of brass (a
Cu-Zn alloy)

0.75mm

Chapter 5 - 51

Uses a series of lenses

Three basic lenses (4x,
10x, and a third ranging
from 20x - 100x)

polished surface

surface groove
(a)

grain boundary
Adapted from Fig.
5.19(a) and (b),
Callister &
Rethwisch 3e.
(Fig. 5.19(b) is
courtesy
of L.C. Smith and
C. Brady, the
National Bureau of
Standards,
Washington, DC
[now the National
Institute of
Standards and
Technology,
Gaithersburg,
MD].)

Grain boundaries
are imperfections,
are more susceptible
to etching,
may be revealed as
dark lines,
change in crystal
orientation across
boundary.

Fe-Cr alloy

(b)

Chapter 5 - 52

13

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Optical Microscopy

Microscopy

Polarized light

Optical resolution ca. 10-7 m = 0.1 m = 100 nm

For higher resolution need higher frequency
X-Rays? Difficult to focus.
Electrons

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

wavelengths ca. 3 pm (0.003 nm)

(Magnification - 1,000,000X)

Atomic resolution possible

Electron beam focused by magnetic lenses.

Cast iron with spherulitic graphite,

polished, C-DIC; Dr. H.-L. Steyer,
Kesselsdorf, Germany
Chapter 5 - 53

Chapter 5 - 54

Scanning Tunneling Microscopy (STM)

Atoms can be arranged and imaged!
Carbon monoxide
molecules arranged
on a platinum (111)
surface.
Photos produced from the work of
C.P. Lutz, Zeppenfeld, and D.M.
Eigler. Reprinted with permission
from International Business Machines
Corporation, copyright 1995.

Iron atoms arranged

on a copper (111)
surface. These Kanji
characters represent
the word atom.

MicroscopyfromCarlZeiss
Chapter 5 - 55

Chapter 5 - 56

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Microscopic Techniques:
Electron Microscopy
Uses focused beam of electrons to
magnify target
Magnification up to 2,000,000x
4 main types
TEM, SEM, REM, STEM
A TEM
image of
the polio
virus. The
polio virus
is 30 nm in
size

Transmission Electron
Microscopy (TEM)
Original form of
electron microscope
Utilizes an electron
gun with a tungsten
filament
Image projected unto
a phosphor viewing
screen

http://www.engr.uky.edu/~bjhinds/facil/images/2010.jpg

Microscopic Techniques
Scanning Electron Microscopy (SEM)
Scans rectangular area by using a
focused beam of electrons
Electrons give off differing energies
based on structure of target
Microscope reads these energies and
produces a visual representation

Microscopic Techniques
Reflection Electron Microscopy (REM)
REM study of Co electrodeposition on Pt(111) surfaces

Like TEM, uses a

beam of electrons to
develop a picture of
the target
Reads the reflected
beam of electrons to
form visual
representation
http://www.zaiko.kyushu-u.ac.jp/z9/Letter/PL1.JPG

15

2/29/2012

Microscopic Techniques
Scanning Transmission Electron
Microscope (STEM)
A type of Transmission
Electron Microscope
Electrons focus on a small area
of specimen
Electrons pass through the
sample, and a visual is formed

5.13

Grain size determination

n = ASTM grain size number

N = 2n-1
N = number of grains/in2 at 100 magnification

American Society for Testing and Materials

Chapter 5 - 62

Grain Size Determination

Section 5.13

Photomicrographic techniques used for

determination
Two techniques used:

Grain Size Determination

Intercept comparison
Standard comparison

http://www.scielo.br/img/revistas/mr/v11n1/11f1a.gif

http://www.eos.ubc.ca/courses/eosc221/images/sed/sili/pic/sedsize.gif

16

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Grain Size Determination

Grain Size Method

Intercept Method

Standard Method

Draw straight lines through photograph

of grain structure
Count number of grains that pass
through each line
Line length divided by number of
intersected grains

Developed by American Society for

Testing and Materials (ASTM)
Photograph specimen at 100x
Compare grain size to a set of charts
with grain size scale 1-10
ASTM grain size (n) is determined by
number of grains per square inch (N)
at 100x from the equation,
N = 2n-1

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.)

Chapter 5 - 67

17