IMPERFECTIONS/DISORDER

Properties of materials are influenced by the

presence of imperfections
Many are profoundly sensitive to deviations from
crystalline perfections
Disorder accounts for the behavior of
semiconductors, for the ductility of metals.
Disorder also permits the movement of atoms
during heating treatment so that new structures
and enhanced properties may be realized.
• Electrical Resistivity of Copper:

Adapted from Fig. 18.8, Callister 6e.

(Fig. 18.8 adapted from: J.O. Linde,
Ann Physik 5, 219 (1932); and
C.A. Wert and R.M. Thomson,
Physics of Solids, 2nd edition,
McGraw-Hill Company, New York,
1970.)

• Adding “impurity” atoms to Cu increases resistivity.

• Deforming Cu increases resistivity.

4
• Space Shuttle Tiles: • Thermal Conductivity
--Silica fiber insulation of Copper:
offers low heat conduction. --It decreases when
Fig. 19.0, Callister 6e.
you add zinc!
(Courtesy of Lockheed
Missiles and Space
Company, Inc.)

Adapted from Adapted from Fig. 19.4, Callister 6e.

Fig. 19.4W, Callister (Fig. 19.4 is adapted from Metals Handbook:
6e. (Courtesy of Properties and Selection: Nonferrous alloys
Lockheed Aerospace and Pure Metals, Vol. 2, 9th ed., H. Baker,
Ceramics Systems, (Managing Editor), American Society for
Sunnyvale, CA) Metals, 1979, p. 315.)
(Note: "W" denotes
fig. is on CD-ROM.) 5
• Magnetic Storage:
• Magnetic Permeability
--Recording medium vs. Composition:
is magnetized by --Adding 3 atomic % Si
recording head. makes Fe a better
recording medium!

Adapted from C.R. Barrett, W.D. Nix, and

Fig. 20.18, Callister 6e.
(Fig. 20.18 is from J.U. Lemke, MRS Bulletin,
Vol. XV, No. 3, p. 31, 1990.)
A.S. Tetelman, The Principles of
Engineering Materials, Fig. 1-7(a), p. 9,
1973. Electronically reproduced
by permission of Pearson Education, Inc.,
Upper Saddle River, New Jersey.

6
CRYSTALLINE IMPERFECTIONS

•Also known as defects

•a lattice irregularity having one or more of
its dimensions on the order of an atomic
diameter
CRYSTALLINE IMPERFECTIONS are
frequently classified according to geometry or
dimensionality of the defect.

Point defects
Line defects
Interfacial defects
Bulk or volume defects
POINT DEFECTS are associated with one
or two atomic positions.

Point Defects in Metals

a. Vacancy
• vacant lattice site or missing atom from atomic site
• may be formed due to imperfect packing during
solidification or by atomic rearrangement
• may arise from thermal vibration of atoms at
elevated temperatures
VACANCY

Vacancy
distortion
of planes
b. Self-Interstitial

interstitial site – a small void space which

under ordinary circumstances is not
occupied

• an atom from the crystal is positioned in

an interstitial site between the matrix
atoms
• does not generally occur naturally due to
resulting structural distortion
• can be introduced by irradiation
SELF-INTERSTITIAL

self-
distortion interstitial
of planes
POINT DEFECTS in METALS

SELF-INTERSTITIAL
VACANCY
Two-dimensional representations of a
vacancy and a self-interstitial. (From
Callister, Materials Science and
Engineering).
POINT DEFECTS in METALS

SELF-INTERSTITIAL in
BODY CENTERED
CRYSTAL (BCC)
EQUILIBRIUM NUMBER OF
VACANCIES or VACANT LATTICE
SITES for a given quantity of material
depends on and increases with temperature
according to:
 QV 
N V  N  exp    (1)
 kT 
N = total number of atomic sites (defect-free)
Qv = energy required for the formation of a vacancy
T = absolute temperature (in K)
k = Boltzmann’s constant
(1.38 x 10-23 J/atom-K or 8.62 x 10-5 eV/atom-K)
EQUILIBRIUM NUMBER OF
VACANCIES or VACANT LATTICE
SITES
 QV 
N V  N  exp    Slope = -Qv / k
 kT 

ln (Nv / N)
or
 NV  QV  1 
ln    
 N  k T

T-1
Sample Problem:

Calculate the equilibrium number of vacancies per cubic

meter for copper at 1000°C. The energy for vacancy
formation is 0.9 eV/atom; the atomic weight and density
(at 1000°C) for copper are 63.5 g/mol and 8.40 g/cm3,
respectively.

 QV 
N V  N  exp   
 kT 
Solution:

First, determine N (number of atoms per cm3) of a

defect-free Cu at 1000°C.

NA 
N
A Cu

Substitute to equation the expression for N to equation1,

NA   QV 
NV   exp   
A Cu  kT 
Solution:

The number of vacancies at 1000°C (1273 K) is,

N Aρ  QV 
NV   exp   
A Cu  kT 

(6.023 x 10 23 atoms mole)(8.40 g cm 3 )  0.9 eV 

NV   exp   -5 eV

 (8.62 x 10 K )(1273 K) 
g
(63.5 mole)

Nv  2.2 x 1019 vacanciescm 3  2.2 x 10 25 vacancies m3

Sample Problem:

Calculate the energy of vacancy formation in silver, given

that the equilibrium number of vacancies at 800°C is
3.60 x 1023 m-3. The molar mass and density (at 800°C)
for silver are, respectively, 107.9 g/mol and 9.5 g/cm3.
Assuming negligible change in density, at what
temperature (in °C) will the equilibrium number of
vacancies equal to 1.07 x 1023 m-3?
Solution:

Rearrange equation 1
 Qv
Nv  N  e kT

Nv  Qv
 e kT
N
Nv Qv
ln 
N kT
N
Q v  kT  ln
Nv
Solution:

Determine N (number of atoms per cm3) of a defect-free

Ag at 800°C, then solve for Qv

N A  (6.02x10
23 atoms g 6 cm 3
)(9.5 )(10 )
N  cm 3 m3
mole
g
A Ag 107.9 mole
N
Q v  kT  ln
Nv
23 atoms g 6 cm 3
(6.02x10 )(9.5 )(10 )
Q v  (8.62x10 )(1073 K)  ln cm 3 m3
-5 eV mole
atom- K g 23 vacancies
(107.9 mole)(3.60x10 m3
)
Q v  1.1 atom
eV
 1.76x10 19 atom
J
Solution:

Temperature (in °C) where Nv (equilibrium number of

vacancies) equal to 1.07 x 1023 m-3
 Qv
Nv  N  e kT

Qv
T
N
k  ln
Nv
eV
1.1 atom
T g cm 3
(6.02x10 23 atoms )(9.5 )(10 6
)
(8.62x10 -5 eV
atom- K )  ln g
mole cm 3 m3
23 vacancies
(107.9 mole )(1.07x10 m3
)
T  973 K  700 C
 Impurities in Solids
Alloys
•impure metals
•impurity atoms have been intentionally added to impart
specific characteristics to the material
•enhances mechanical properties and corrosion resistance
Solid Solutions
•result from the addition of impurity atoms to a metal, without
the formation of new structures (crystal structure is
maintained)
•they are compositionally homogeneous: the impurity atoms
are randomly and uniformly dispersed in the solid

solute – the element or compound present in minor concentration

solvent or host atom – the element or compound present in the
greatest amount
 Impurity Point Defects in Solid Solutions
a) Substitutional
solute or impurity
atoms replace or
substitute for the host
atoms

b) Interstitial
impurity atoms fill the
voids or interstices
among the host atoms the
normal concentration of
interstitial impurity atoms
is low (less than 10%)
Ex. Carbon in Iron
Hume-Rothery Rules for Solid Solubility:
a. Atomic Size Factor
the difference in atomic radius between the two atoms should be less
than about ± 15 %

b. Crystal Structure
the crystal structure for both metals should be the same for
appreciable solid solubility to occur

c. Electronegativity
similar electronegativity

the more electropositive one element is and the more electronegative

the other is, the greater is the tendency to form an intermetallic
compound than a substitutional solid solution

d. Valences
other factors being equal, a metal will have more of a tendency to
dissolve another metal of higher valency than one of a lower valency
 Hume-Rothery Rules for Solid Solubility:
a. Atomic Size Factor
b. Crystal Structure
c. Electronegativity
d. Valences

Element Atomic Radius, nm Crystal Electronegativity Valence

Structure

Copper 0.128 FCC 1.9 +1

Nickel 0.125 FCC 1.8 +2
b. Interstitial

impurity atoms fill the voids or interstices among the host atoms
the normal concentration of interstitial impurity atoms is low (less
than 10%)
Ex. Carbon in Iron
Sample Problem:

Which of these elements would you expect to form the following with
nickel:
Element R, nm Structure EN Valence
Ni 0.1246 FCC 1.8 +2
a. A substitutional solid solution
C 0.071 --- ---
having complete solubility.
H 0.046 --- ---

b. A substitutional solid solution O 0.060 --- ---

having incomplete solubility. Ag 0.1445 FCC 1.9 +1

Al 0.1431 FCC 1.5 +3

c. An interstitial solid solution Co 0.1253 HCP 1.8 +2

Cr 0.1249 BCC 1.6 +3

Fe 0.1241 BCC 1.8 +2

Pt 0.1387 FCC 2.2 +2

Zn 0.1332 HCP 1.6 +2

POINT DEFECTS in CERAMICS
Defect structure is often used to
designate the types and
concentrations of atomic defects in
ceramics.

Electroneutrality is the state that

exists when there are equal
numbers of positive and negative
charges from the ions.

As a consequence, defects in A unit cell of NaCl crystal (From

Callister, Materials Science and
ceramics do not occur alone. Engineering).
Point Defects in Ceramics

c. Schottky Imperfection
• found in AX materials
• point imperfections in ionic compounds in which a
cation-anion pair are missing
• since both cations and anions have the same
charge, and since for every anion vacancy there
exists a cation vacancy, the charge neutrality of
the crystal is maintained.
Point Defects in Ceramics

c. Schottky Imperfection

Anion
Vacancy
Cation
Vacancy
Point Defects in Ceramics

d. Frenkel Defect
• point defect in ionic crystals in which a cation is
displaced from a lattice site into an interstitial site
• involves a cation-vacancy and a cation-interstitial
pair .
• there is no change in charge because the cation
maintains the same positive charge as an
interstitial.
Point Defects in Ceramics

d. Frenkel Defect

Cation Interstitial
Cation Vacancy
Point Defects in Ceramics

e. Nonstoichiometry
• may occur for some ceramic materials in which
two valence states exist for one of the ion types
(i.e. Fe2+ and Fe3+).

Fe3+

Fe2+

O2-

Fe2+ vacancy
EQUILIBRIUM NUMBER OF CATION-
ANION VACANCY defect pair, Ns, for a
given quantity of ceramic material depends on
and increases with temperature according to:

 Qs 
N s  N  exp    (2)
 2kT 
N = total number of atomic sites (defect-free)
Qs = energy required for the formation of a Schottky defect
T = absolute temperature (in K)
k = Boltzmann’s constant
(1.38 x 10-23 J/atom-K or 8.62 x 10-5 eV/atom-K)
EQUILIBRIUM NUMBER OF CATION-
VACANCY/CATION-INTERSTITIAL
defect pair, Nfr, for a given quantity of
ceramic material depends on and increases
with temperature according to:
 Qfr 
N fr  N  exp    (3)
 2kT 
N = total number of atomic sites (defect-free)
Qfr = energy required for the formation of a Frenkel defect
T = absolute temperature (in K)
k = Boltzmann’s constant
(1.38 x 10-23 J/atom-K or 8.62 x 10-5 eV/atom-K)
Sample Problem:

Calculate the fraction of lattice sites that are Schottky

defects for cesium chloride at 534°C. Assume that the
energy of defect formation is 1.86 eV/cation-anion
vacancy pair.

 Qs 
N s  N  exp   
 2kT 
LINE or ONE-DIMENSIONAL
DEFECTS
The linear size of these defects in one
dimension is considerably greater than the
atomic size, and is commensurable with it in
two other dimensions.

DISLOCATION
• Characterized by an open Burgers circuit
DISCLINATION
• Characterized by a closed Burgers circuit
DISLOCATION is a linear or one-dimensional defect
around which some of the atoms are misaligned.
• significant in plastic deformation by shear
stresses
• may increase the strength of a material when
present in large numbers
a. Edge Dislocation
• occurs when the edge of an extra plane of atoms,
a half plane, terminates within the crystal
 Slip - process of plastic deformation by
dislocation motion
 Slip Plane – crystallographic plane where
dislocation traverses
SLIP PLANE
b. Screw Dislocation
• may be thought of as being formed by a shear
stress that is applied to produce the distortion
SLIP PLANE
c. Mixed Dislocation
• a combination of a screw and edge dislocation
INTERFACIAL DEFECTS are
boundaries that have two
dimensions and normally separate
regions of the materials that have
different crystal structures.

a. External surfaces
b. Grain Boundaries
c. Twin Boundaries
a. External surfaces
• where the crystal structure terminates
• have a higher energy state than the atoms at the
interior positions since they are not bonded to the
maximum number of nearest neighbors

b. Grain Boundaries
• a boundary separating two small regions in
crystals having different crystallographic
orientations in polycrystalline materials
• areas of higher energy due to the presence of
interfacial or grain boundary energy
b. Grain Boundaries
Angle of misalignment

High-angle grain
boundary
Low-angle grain
boundary
 (a) Small crystallite
nuclei. (b) Growth
of the crystallites;
(c) grains having
irregular shapes
have formed. (d)
The grain structure
as it would appear
under the
microscope; dark
lines are the grain
boundaries.
(Adapted from W. Rosenhain, An Introduction to
the Study of Physical Metallurgy, 2nd edition,
Constable & Company Ltd., London, 1915.)
 OPTICAL
MICROSCOPY

Polished and etched

grains

Etching
characteristics
resulting surface
texture varying from
grain to grain
because of the
(Adapted from Callister , 2007, Materials difference in
Science and Engineering – An Introduction. crystallographic
orientation
MICROSTRUCTURE

• Geometric arrangement of grains (single

crystals) and phases in a material.
• Variables: relative amount, size, shape, and
distribution of the grains and phases present.
• Microscope (optical or electron) is
necessary to observe these structural
features
• Micrometer (10-6 m) up to nanometer (10-9
m) in dimensions
GRAIN SIZE is often determined when the
properties of a polycrystalline material are under
consideration.

TECHNIQUES

1. Intercept Method
2. Average number of grains per area
3. ASTM method
INTERCEPT METHOD
Straight lines are drawn through several pictographs
that show the grain structure
Grains intersected by each lines are counted
Average grain diameter, Dave, is computed as:

L  1  L
Dave   
nG M  M
where
L = total length of the lines drawn,
nG = equivalent number of grains intersected,
M = linear magnification of the micrograph.
Magnification: 100X
Magnification: 100X
the grain size can be quantified by the ASTM (American
Society for Testing and Materials) Grain Size Number, n

n 1
N 2
where N is the average number of grains per square inch
at a magnification of 100X
ASTM COMPARATIVE METHOD

Grain size number, n, is determined by comparing the

pictograph of the structure obtained under 100X magnification
with a series of graded standard grain size pictographs.

1 2 3 4

5 6 7 8

The network charts above are essentially idealized

grain boundaries in a hypothetical hexagonal
network.
c. Twin Boundaries
special types of grain boundary across which there is a
specific mirror lattice symmetry
d. Stacking Faults
interruptions in the stacking sequence of close-packed
planes in the FCC structure

FCC HCP
e. Phase Boundaries

boundaries between phases in multiphase materials where

there is a sudden change in physical and/or chemical
characteristics
Bulk or Volume Defects
-three dimensional defects
-normally introduced during processing and fabrication of
the material

ex. pores, cracks, foreign inclusions and other phases-