CHAPTER 5:

IMPERFECTIONS IN SOLIDS
TOPICS
Types of imperfections-
Point: Vacancy, interstitial and substitution
Line defects: Dislocations
Area defects: External surfaces, grain boundaries,,
Volume defects: Cracks, pores
Estimation of no of defects, energy of formation of a defect
Edge dislocation, screw dislocation, Burger vectors
Tilt boundaries, Twin boundaries, other defects
Defects in ceramics and ionic crystals, defects in polymers
TYPES OF IMPERFECTIONS
Vacancies
Interstitial sites
Substitutional atoms
Dislocations
Grain Boundaries
External Surfaces
Point defects
Line defects
Area defects
Volume defects
Cracks, Pores,
other phases
POINT DEFECTS
Vacancies:
-vacant atomic sites in a structure.
Self-Interstitials:
-"extra" atoms positioned between atomic sites.
Vacancy
distortion
of planes
self-
interstitial
distortion
of planes
INTRODUCTION
Vacancies are equilibrium defects! i.e., they will
always be present in a crystal at finite temperature.
They are not created due to any shortcomings in
the process of crystal growth.
An amount of energy Q
d
is required to create a
single defect. Then why are there defects?
To increase the entropy (disorder) of the crystal!
Any system at equilibrium has the maximum
possible entropy.
The equilibrium configuration of a system (crystal)
is found by minimizing the Gibbs Free energy (G= H-
T
S
) of a crystal.
EQUIL. CONCENTRATION: POINT DEFECTS
Boltzmann's constant
(1.38 x 10
-23
J/atom K)
(8.62 x 10
-5
eV/atom K)
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
No. of defects
No. of potential
defect sites.
Activation energy
Temperature
Each lattice site
is a potential
vacancy site
Activation Energy: Energy required
for the formation of a vacancy. kJ/mol
-1

, ev/point imperfection

Given:
ESTIMATING VACANCY CONCENTRATION
8.62 x 10
-5
eV/atom-K
0.9eV/atom
1273K
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
For 1m
3
, N =
N
A
A
Cu
x
x 1m
3
= 8.0 x 10
28
sites
= 2.7 10
-4
Find the equil. # of vacancies in 1m
3
of Cu at
1000
o
C.
We can get Q
v
from experiments.
|
N
v
N
=
exp

Q
v
k T
|
\

|
.
|
MEASURING ACTIVATION ENERGY
Measure this...
N
v
N
T
exponential
dependence!
defect concentration
Re plot it...
1/T
N
N
v
ln
-
Q
v
/k
slope
5.1 Calculate the fraction of atom sites that are vacant for Cu
at its melting temp of 1048
o
C (1347 K) Assume an energy of
vacancy formation of 0.90 eV/atom
5.2 Calculate the number of vacancies per cubic meter in gold
at 900
o
C. The energy for formation of vacancy is 0.98
eV/atom. Density= 18.63 g/cm3 and at. Wt= 196.9 g/mol.
POINT DEFECTS IN ALLOYS
Two outcomes if impurity (B) added to host
Solid solution of B in A (i.e., random dist. of point defects)
Solid solution of B in A plus particles of a new phase (usually
for a larger amount of B)
OR
Substitutional solid soln.( Cu in Ni)
Interstitial solid soln.(e.g., C in Fe)
Second phase particle
--different composition
--often different structure.
An ordered alloy becomes disordered (random) at a higher
temperatures.
SOLID SOLUTION
A solid solution is a solid-state solution of one
or more solutes in a solvent.
Such a mixture is considered a solution rather
than a compound when the crystal structure of
the solvent remains unchanged by addition of
the solutes, and when the mixture remains in a
single homogeneous phase.
This often happens when the two elements
(generally metals) involved are close together
on the periodic table.
FACTORS AFFECTING SOLID SOLUTION
Atomic size factor: Appreciable solubility of a solute
when the difference between the two atom sizes are
within +/- 15%. Failing which lattice distortions and
new phases are formed.
Crystal Structure: For appreciable solubility the
crystal structures of solute and solvent should be
the same.
Electronegativity: Large electronegativity differences
can lead to an intermetallic compound rather than a
substitution solid solution.
Valences: More tendency to dissolve a higher
valency metal than a lower valency.
EXAMPLES
Substitutional solid solution: Cu & Ni
Same atomic radii (0.128 nm for Cu & 0.125 nm for
Ni)
Both have same crystal structure (FCC)
Same electronegativities (1.9 and 1.8)
Interstitial Solid Solution: (impurity atoms fill in voids
or interstices among the host atoms)
Maximum solubility is less than 10% if atom is
bigger than interstitial site.
Eg: Solubility limit of C in Fe is 2 %
Atomic radius of C = 0.071 nm and that of Fe =
0.124nm
Which of these elements would you expect to form the following
with Nickel.
a)A substitutional solid solution having complete solubility.
b) A substitutional solid solution having incomplete solubility.
c) An interstitial solution.
5.4
Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
Cu 0.1278 FCC 1.9 +2
C 0.071
H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
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
Pt 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
a) Pt is the only element that meets all of the criteria and
thus forms a substitutional solid solution having complete
solubility. At elevated temperatures Co and Fe experience
allotropic transformations to the FCC crystal structure, and
thus display complete solid solubility at these
temperatures.
b) Ag, Al, Co, Cr, Fe, and Zn form substitutional solid
solutions of incomplete solubility. All these metals have
either BCC or HCP crystal structures, and/or the difference
between their atomic radii and that for Ni are greater than
15%, and/or have a valence different than 2+.
c) C, H, and O form interstitial solid solutions. These
elements have atomic radii that are significantly smaller
than the atomic radius of Ni.

5.5 For both BCC and FCC crystal structures, there are
two different types of interstitial sites. In each case, one
site is larger that the other, and is normally occupied by
impurity atoms. For FCC, this larger one is located at
center of each edge of the unit cell; it is termed as
octahedral interstitial site. And for BCC structure, the
larger site is found at 0 positions that is lying on
{100} faces, situated midway between two unit cell edges
on those face and one-quarter of the distance between
the other two unit cell edges; it is termed as tetrahedral
interstitial site.
For both FCC and BCC structures, compute the radius r of
an impurity atom that will just fit into one of these sites in
terms of the atomic radius R of the host atom.

FCC structure: (100) plane
From the geometry
a = 2r + 2R
For FCC, a = 2R(2)
1/2
After substitution, r= 0.41 R
BCC structure: (100) plane
From the geometry
(R + r)
2
= (a/2)
2
+ (a/4)
2
For BCC, a = 4R/(3)
1/2
After solving, r = 0.291R
Thus, for a host atom of radius R, the size of an interstitial site for
FCC is approximately 1.4 times that for BCC.
COMPOSITION/CONCENTRATION
Definition: The relative content of a specific element or
constituent in an alloy.
Concentration of weight % of element 1 is
Concentration of atoms (atom %) present in element 1
100
2 1
1
1

+
=
m m
m
C
100
2 1
1
1

+
=
'
m m
m
n n
n
C
where nm1 are number of moles of the element in the alloy.
m
1
-- mass of the element, A
1
atomic weight of element 1
1
1
1
A
m
n
m
=
CONVERSION BETWEEN WT % AND AT %
100
2 2 1 1
1 1
1

'
+
'
'
=
A C A C
A C
C
100
1 2 2 1
2 1
1

+
=
'
A C A C
A C
C
100
2 2 1 1
2 2
2

'
+
'
'
=
A C A C
A C
C
100
1 2 2 1
1 2
2

+
=
'
A C A C
A C
C
Weight % Atoms%
100 ' '
100
2 1
2 1
= +
= +
C C
C C
Since there are only two atoms, we can write as
CONVERSION BETWEEN WT % AND AT% IN AN A-
B ALLOY
Total mass (say in grams)

Since or


From the equation we can write as

since

Substituting we get the
100
2 1
1
1

+
=
'
m m
m
n n
n
C
100
2
'
2
1
'
1
1
'
1
1

+
=
'
A
m
A
m
A
m
C
100
2 1
1
1

+
=
m m
m
C
100
1 1
'
1
M C
m =
' '
2
'
1
M m m = +
100
100 100
100
2
'
2
1
'
1
1
'
1
1

+
=
'
A
M C
A
M C
A
M C
C
100
1 2 2 1
2 1
1

+
=
'
A C A C
A C
C
'
2
'
1
'
m m M + =
1000
2
2
1
1
1
1
X
C C
C
C
|
|
|
|
.
|

\
|
+
=
' '

where C
1

= mass of element 1 per unit volume (kg/m

3
)
C
1
= weight percent of element 1, density in g/cm
3
1000
2
2
1
1
2
2
X
C C
C
C
|
|
|
|
.
|

\
|
+
=
' '

Conversion of concentration from weight % to mass % of
one component per unit volume of material. (from wt% to
kg/m
3
)
Used in diffusion computations.
|
|
|
|
.
|

\
|
+
=
2
2
1
1
100

C C
ave
|
|
|
|
.
|

\
|
'
+
'
'
+
'
=
2
2 2
1
1 1
2 2 1 1

A C A C
A C A C
ave
|
|
|
|
.
|

\
|
+
=
2
2
1
1
100
A
C
A
C
A
ave
100
2 2 1 1
A C A C
A
ave
'
+
'
=
Approximate relations (alloy density & atomic weight)
5.8 What is the composition, in weight % of an alloy that
consists of 5 at% of Cu and 95 at% of Pt? (At wt Cu= 63.55
g/mol, at wt Pt= 195.08 g/mol.)
5.17 Calculate the unit cell edge length for a 80 wt% Ag-
20wt% Pd alloy. All of the Palladium is in solid solution, the
crystal structure for this alloy is FCC. The At wt -Ag and Pd
are 107.9 and 106.4 g/mol, whereas the densities for the Ag
and Pd are 10.49 g/cm
3
and 12.02 g/cm
3
Sol: Average density relation as =

or

Since the crystal structure is
FCC, the value of n= 4.
a can be estimated to be 4.050 x 10
-8
cm
|
|
|
|
.
|

\
|
+
=
2
2
1
1
100

C C
ave
|
|
|
|
.
|

\
|
+
=
2
2
1
1
100
A
C
A
C
A
ave
5.19. For a solid solution consisting of two elements,
sometimes it is desirable to determine the no of atoms per
cubic centimeter of one element in a solid solution, N1,
given the concentration of that element specified in wt %,
C1. Derive the above equation the following expression:

1
=

1
+

2
(100
1
)

Solution: Let the concen., of component 1 in atom %
1
is
just 100*
1

where
1

is the atom fraction of component 1.

Furthermore, it is defined as = N
1
/N where N
1
and N are,
respectively, the number of atoms of component 1 and total
number of atoms per cubic cm.

The above expression can be written as
Substituting in the equation (N is the no of atoms present per
cubic cm or m) =

we get
From relation between C1 and C1 and the relation of
averages, we get,


5.20 Molybdenum forms a substitutional solid solution with
Tn. Compute the no of Mo atoms per cubic cm for a Mo-Tn
alloy that contains 16.4 wt% of Mo. The densities of Mo and
Tnare 10.22 and 19.30 gm/cubic cm.
DEFECTS IN CERAMIC STRUCTURES
Electro neutrality: Equal number of + and - ve charged ions.
Stoichiometry: Defined as a state of ionic compounds where
there is exact number of cations to anions ratio.
Schematic
representation of
cation and anion
vacancies and a
cation interstitial.
Frenkel Defect -- a paired set of cation vacancy and a
cation interstitial is out of place.
Schottky Defect -- a paired set of cation vacancy and
anion vacancy is out of place.




Schottky
Defect:
Frenkel
Defect
Is charge neutrality
maintained in either
of the cases?
Non- stoichiometry occurs for ceramic materials in
which two valence (or ionic) states exist for one of the
ion types. Eg: Fe
2+
and Fe
3+
.
What happens if one Fe
2+
is converted to Fe
3+
?



One Fe
2+
vacancy formed for every two Fe
3+
formed.
Hence chemical formula is Fe
1-x
O.
The equilibrium number of both the defects increase
with and depend on Temperature in a manner similar to
the number of vacancies in metals.
The factor 2 represents two defects (a missing cation
and an interstitial cation) are associated with each
Frankel defect. Similarly with Schottky defect.

= exp (

2
)

= exp (

2
)
N= NA /(At1+At2)
Where N is the number of lattice sites per cubic meter.
Impurities must also satisfy charge balance (Electroneutrality)
Ex: NaCl
Impurities in Ceramics
Na
+
Cl
-
initial geometry Ca
2+
impurity resulting geometry
Ca
2+
Na
+
Na
+
Ca
2+
cation
vacancy
Substitutional anion impurity
initial geometry O
2-
impurity
O
2-
Cl
-
an ion vacancy
Cl
-
resulting geometry
Calculate the number of Schottky defects per cubic meter
in potassium chloride at 500
o
C. The energy required to
form each Schokkty defect is 2.6 eV, while the density of
KCL (at 500
o
C) is 1.95 g/cm
3
. AK=39.10, ACl=35.54 g/mol
Solution:
Number of lattice sites per cubic meter is
N= NA /(AK+ACl)
From the formula we have

= exp (

2
)
LINES DEFECTS
Dislocations:
are line defects,
cause slip between crystal planes when they
move
produce permanent (plastic) deformation.
are of two types
Edge dislocation
Screw dislocation


1. EDGE DISLOCATION
Extra half plane of atoms

Dislocation line Burgers vector
http://www.youtube.com/wa
tch?v=iKKxTP6xp74
2. SCREW DISLOCATION : DISLOCATION LINE ||
BURGERS VECTOR
Figure showing Burger Vector in both the imperfections
3. MIXED DISLOCATION
Edge
Screw
Dislocations were postulated to explain the discrepancy
between the experimental and the theoretical values of the
elastic limit for (single) crystalline solids.
Experimental value of elastic limit ~ 10
6
N/m
2
Theoretically calculated value ~ 10
10
N/m
2
(assuming
relative motion of entire planes)
If dislocations are present, plastic deformation involves only
the motion of the dislocation, which requires lesser applied
stress.
Analogy: Moving a kink across a carpet is easier than
dragging the entire carpet across a room.
INTERFACIAL DEFECTS
Dislocations (unlike vacancies) are non-equilibrium
defects. However they help in the growth of crystals and
hence are normally present in crystals.
Density of dislocations cannot be predicted and can
increase with applied stress!
Without screw dislocations
crystal growth will be a very
slow process.

Screw dislocation and
growth of crystals
INTERFACIAL DEFECTS
Defined as boundaries that have 2d imperfections in
crystalline solids, have different crystal structures and/or
crystallographic orientations on either side of them.
Distortions lie about a surface having thickness of a few
atomic diameters.
Ex: External surfaces, grain boundaries, twin boundaries,
stacking faults, and phase boundaries.
Not thermodynamically stable, rather they are meta-stable
imperfections.
Arise from the clustering of line defects into a plane.
EXTERNAL SURFACES
The environment of an atom at a surface differs from that
of an atom in the bulk.
The number of neighbors (coordination #) at surface is
less. Thus the unsaturated bonds of surface atoms give
rise to a surface energy.
This results in relaxation (the lattice spacing is decreased)
or reconstruction (the crystal structure changes).
To reduce the energy, materials tend to minimize, if
possible, the total surface area.
This is similar to a liquid drop changing its shape to
spherical.
GRAIN BOUNDARIES
Boundaries separated by two small grains or crystals
having different crystallographic orientation in
polycrystalline materials.
There is mismatch in transition from crystalline orientation
of one grain to that of an adjacent one.
When this misalignment is slight, on the order of few
degrees (< 10), it is called low angle grain boundary.
Low grain boundary formed by edge dislocations is called
tilt boundary; where as twist boundary if formed of screw
dislocations.
Atoms are bonded less regularly along the boundaries; thus
having GB energy, function of degree of mis orientation.
Schematic diagram of grain
boundaries.
A tilt boundary having an
angle of mis-orientation
results from an alignment of
edge dislocation
5.36 For a given material, would you expect the surface
energy to be >/ </ = that of grain boundary energy. Why?
Why GBE for small GBAngle < that of for larger GBAngle?
More atoms
bond across
the
boundary
for the
small-angle,
thus, there
are fewer
unsatisfied
bonds
Tilt and twist boundaries are planar surface imperfections in
contrast to high angle grain boundaries.
Less irregularity in bond formation along the grain boundary that
results in interfacial or grain boundary energy.
Grain boundaries are chemically more reactive because of grain
boundary energy. Impurities segregate along these areas.
Polycrystalline solids are still very strong as cohesive forces
present within and across the boundary.
Twin Boundaries: (A mirror lattice symmetry is found.)
Results from atomic displacements produced from shear forces
also during annealing heat treatments following deformation.
Twinning occurs on a definite crystallographic planes and
on specific directions. These depend on crystal structure.
Annealing twins found in FCC structure.
Mechanical Twins in BCC and HCP structures.
BULK OR VOLUME DEFECTS
Larger in size. Ex pores, cracks, foreign inclusions and
other phases. Occurs during processing and fabrication
steps.
Atomic Vibrations: Atoms vibrate very rapidly about its
lattice positions. At any instant not all atoms vibrate at the
same amplitude and frequency.
At a given Temp, there exists a distribution of energies for
the constituent atom about an average energy.
As temp increases, average energy increases.
Many properties and processes in solids are manifestations
of this vibrational atomic motion.
Melting occurs when vibration are vigorous enough to
rupture large number of atomic bonds.
Miscellaneous defects:
Stacking faults in HCP & FCC crystals
Phase boundaries, pores, cracks
Atomic vibrations
DEFECTS IN POLYMERS
5.29 Using the data given below that relate to the formation
of Schottky defects in some oxide ceramic (chemical
formula MO), determine
a) The energy for defect formation (in eV)
b) The eqvlnt. no., of Schottky defects /cubic m at 1000
o
C
c) The identity of the oxide (identify metal M)
T (
o
C) (g/cm
3
) Ns (m
-3
)
750 3.50 5.7 x 10
9
1000 3.45 ?
1500 3.40 5.8 x 10
17
Solution: From the given data, the Schottky defects at 750
and 1500
o
C are known. For an alloy system, we can write
the relations as


As we do not know the metal oxide, from the two equations,
we can find the relation between the number of defects and
temperature by eliminating the atomic weights


Dividing the two equations we
get:
Taking natural log on both the
sides:
Rearranging for Qs (energy of
defect formation):
b)
From the above equation of
Ns
1
/Ns
2
, we can take Ns
2
and T
2

at 750
o
C and since we know T
1
=
1000
o
C, we can get Ns
1
.
c) Rearranging the first equation
to get N from Ns, we have:

Rearranging the above equation
for AM we get:
SUMMARY
Types of imperfections-
Point: Vacancy, interstitial and substitution
Line defects: Dislocations
Area defects: External surfaces, grain boundaries,,
Volume defects: Cracks, pores
Estimation of no of defects, energy of formation of a defect
Edge dislocation, screw dislocation, Burger vectors
Tilt boundaries, Twin boundaries, other defects
Defects in ceramics and ionic crystals, defects in polymers
Problems of interest: 5.26, 5.28, 5.31, 5.34, 5.38