MATERIALS SCIENCE &

ENGINEERING
BITS Pilani
Pilani Campus

Dr. Subrata Bandhu Ghosh

Department of Mechanical Engg.

Imperfections in Solids

In our pervious Lecture when

discussing Crystals we
ASSUMED PERFECT ORDER

In real materials we find:

Crystalline Defects or lattice irregularity
Most real materials have one or more errors in
perfection
with dimensions on the order of an atomic diameter to
many lattice sites
Defects can be classification:
1. according to geometry
(point, line or plane)
2. dimensions of the defect

Imperfections in Solids
The properties of some materials are
profoundly influenced by the
presence of imperfections.
It is important to have knowledge
about the types of imperfections that
exist and the roles they play in
affecting the behavior of materials.

Atom Purity and Crystal Perfection

If we assume a perfect crystal structure
containing pure elements, then
anything that deviated from this
concept or intruded in this uniform
homogeneity would be an
imperfection.
1. There are no perfect crystals.
2. Many material properties are improved
by the presence of imperfections and
deliberately modified (alloying and
doping).

Polycrystalline Materials
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.

Types of Imperfections
Vacancy atoms
Interstitial atoms
Substitutional atoms

Point defects

Dislocations

Line defects

1-2 atoms

1-dimensional

Grain Boundaries

Area defects
2-dimensional

Point Defects
Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

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

selfinterstitial
distortion
of planes

Self Interstitials

In metals, a self interstitial introduces

relatively large distortions (strain) in
the surrounding lattice since the atom
is substantially larger than the
interstitial site.

POINT DEFECTS
The simplest of the point defect is a vacancy, or vacant lattice site.
All crystalline solids contain vacancies.
Principles of thermodynamics is used explain the necessity of the
existence of vacancies in crystalline solids.
The presence of vacancies increases the entropy (randomness) of
the crystal.
The equilibrium number of vacancies for a given quantity of
material depends on and increases with temperature as
follows:
Total no. of atomic sites

Energy required to form vacancy

Equilibrium no. of vacancies

Nv= N exp(-Qv/kT)

T = absolute temperature in Kelvin

k = gas or Boltzmanns constant

Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature.
Activation energy
energy required for formation of vacancy
No. of defects
No. of potential
defect sites

Q
Nv
= exp v
kT
N

Temperature

Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
Each lattice site
is a potential
vacancy site

Measuring Activation Energy

Q
Nv
v

exp
=
kT
N

We can get Qv from

an experiment.
Measure this...

Replot it...

Nv

ln

Nv
N

note:
N=

N A El
AEl

slope
-Qv /k

exponential
dependence!

defect concentration

1/T

Example Problem 4.1

Calculate the equilibrium number of vacancies per cubic meter for
copper at 1000C. 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
8.4 g/cm3, respectively.
Solution.
Use equation 4.1. Find the value of N, number of atomic sites per cubic
meter for copper, from its atomic weight Acu, its density, and
Avogadros number NA.

N A (6.023x10 23 atoms / mol )(8.4 g / cm3 )(10 6 cm3 / m 3 )

N=
=
ACu
63.5 g / mol
= 8.0x10 28 atoms / m 3
Thus, the number of vacancies at 1000o C (1273K ) ie equal to

Continuing:
Qv
N v = N exp

kT

(
0
.
9
eV

= (8.0x10 atoms / m ) exp

(8.62 x10 5 eV / K )(1273K )

28

= 2.2x1025 vacancies/m3
And Note: for MOST MATERIALS just
below Tm
Nv/N = 10-4
Here: 0.0022/8 = .000275 = 2.75*10-4

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.
(e.g., Cu in Ni)

Interstitial solid soln.

(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.

Imperfections in Solids
Conditions for substitutional solid solution (S.S.)
Hume Rothery rules
1. r (atomic radius) < 15%
2. Proximity in periodic table
i.e., similar electronegativities

3. Same crystal structure for pure metals

4. Valency equality
All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency (it provides more electrons to the cloud)

Imperfections in Solids
Application of HumeRothery rules Solid
Solutions
Element
Atomic Crystal
ElectroRadius Structure
(nm)

1. Would you predict

more Al or Ag
to dissolve in Zn?
More Al because size is closer and val. Is
higher but not too much FCC in HCP

2. More Zn or Al
in Cu?
Surely Zn since size is closer thus
causing lower distortion (4% vs 12%)

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

Valence

negativity

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

Table on p. 106, Callister 7e.

Imperfections in Solids
Specification of composition
weight percent

m1
C1 =
x 100
m1 + m2
m1 = mass of component 1

atom percent

n m1
C =
x 100
n m1 + n m 2
'
1

nm1 = number of moles of component 1

Wt. % and At. % -- An example

Typically we work with a basis of 100g or 1000g
given: by weight -- 60% Cu, 40% Ni alloy
600 g
nCu =
= 9.44m
63.55 g / m
400 g
= 6.82m
nNi =
58.69 g / m
9.44
'
CCu =
.581 or 58.1%
9.44 + 6.82
6.82
'
CNi =
.419 or 41.9%
9.44 + 6.82

Converting Between: (Wt% and At%)

C1 A2
C =
100
C1 A2 + C2 A1
'
1

C2 A1
100
C =
C1 A2 + C2 A1
'
2

C A1
C1 = '
100
'
C1 A1 + C2 A2
'
1

C2' A2
C2 = '
100
'
C1 A1 + C2 A2

Converts
from wt% to
At% (Ai is
atomic
weight)
Converts
from at% to
wt% (Ai is
atomic
weight)

Determining Mass of a Species per

Volume

C
1
C1" =
C1 + C2

1
2

103

C
2
C2" =
C1 + C2

1
2

103

i is density of pure
element in g/cc
Computed this way,
gives concentration
of speciesi in kg/m3 of
the bulk mixture
(alloy)