Imperfections in Solids

All solids contain large number of

imperfections or deviations from crystalline
perfection.
Only single crystals have a near perfect
crystalline structure.
Presence of imperfections has a profound
influence on the material properties (eg. optical,
electrical, thermal, chemical, mechanical, etc.)

Point Defects
Vacancies
Vacant lattice sites which
increase the entropy or
randomness of a crystal.
A vacancy is formed when
an atom is missing from a
normal site during
solidification from high
temperatures or radiation
damage.
The equilibrium number of
vacancies (Nv) increases
with temperature (T):

N = total number of atomic sites

Qv
N v = N exp( )
kT

Qv = energy required to form a vacancy

k = Boltzmanns constant (1.38x10-23 J/atom-K)

Example Problem
Calculate the equilibrium number of vacancies/m3 for copper at 1000C.
The energy for vacancy formation is 0.9 eV/atom; the atomic weight and
density (at 1000C) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively.
N
N= A
ACu

(6.023 10 23 atoms / mol )(8.4 g / cm 3 )(10 6 cm 3 / m 3 )

=
63.5 g / mol

= 8.0 1028 atoms/m3

At 1000C (1273 K)
Q
N v = N exp( v )
kT

0.9eV
= (8.0 10 28 atoms / m 3 ) exp

5
(8.62 10 eV / K )(1273 K )

= 2.2 1025 vacancies/m3

 Self- Interstitials
Host atoms that occupy
interstitial sites and
their presence can
cause large distortions
in the surrounding
lattice.

Self-interstitial and
vacancy.

Impurities /Additives
Foreign atoms that occupy the lattice or
interstitial sites of metals to form alloys.
Presence of impurity atoms can lead to
formation of a solid solution and/or a new
second phase.

Solid Solutions
A solid solution is formed when foreign
atoms are added to the host material.
The crystal structure of the host material is
maintained and no new structures or phases
are formed.

 Substitutional solid
solution
Foreign atoms substitute
for the host atoms.
The degree of substitution
depends on (a) the atomic
size, (b) crystal structure,
(c) electronegativity and
(d) valency of the foreign
atoms.
Get complete solubility if
the foreign atom has a
similar size (R 15%),
crystal structure, and
electronegativity but
higher valency.
eg. Copper/Nickel

small substitutional atom

large substitutional atom

Characteristics of copper and nickel.

Cu

Ni

Atomic size
(nm)

0.128

0.125

Crystal structure

FCC

FCC

Electronegativity

1.9

1.8

Valency

+1

+2

 Interstitial solid solution

Small foreign atoms (eg.
C, N, H) fill the voids or
interstitials among the
host atoms.
eg. carbon (2%)-Iron
(Steel)
RFe = 0.124 nm
RC = 0.071 nm

Line Defects
Dislocations
Line defects around which some of the atoms
are misaligned.
Movement of dislocations leads to deformation
in metals and ceramics.
The direction and distance that a dislocation
moves in each step is known as the Burgers
vector (b).

 Edge Dislocation
()
A dislocation
introduced into
the lattice by
adding an extra
half plane of
atoms.
The Burgers
vector and the
dislocation are
perpendicular to
each other.

Slip system of an edge dislocation.

Screw Dislocation (3)

A dislocation produced by shearing a crystal so that one atomic
plane produces a spiral ramp about the dislocation.
The Burgers vector and the dislocation are parallel to each other.

Mixed Dislocation (,3)

A dislocation that contains partly edge components and partly screw
components.

Electron Micorgraphs of Dislocations

Dislocation loops.

Dislocation network.

Example Problem
Calculate the length of the Burgers vector in copper (nm).
a = 0.36151
The close-packed directions are <110> or
along the face diagonals.
Face diagonal:

4R = a 2 = 2 (0.36151) = 0.51125 nm

b= 2R =

1
(0.51125) = 0.25563
2

nm

Interfacial Defects
Boundaries that have two dimensions which separate
regions of the materials that have different crystal
structures or crystallographic orientations.

External surfaces
Boundaries where the crystal structure terminates.
Due to incomplete bonding, surface atoms have higher
energy and more reactive than the bulk of the material.

Grain Boundaries
Boundaries between two grains
having a different orientations in
a polycrystalline material.
There is lack of regular bonding
and some atomic mismatch or
disorder within the grain
boundary.
Hence grain boundaries have a
higher energy state and are more
chemical reactive than the
grains.

Low-angle and high-angle grain

boundaries.

Bamboo (x-section)

Bamboo (longitudinal section)

Diffraction Patterns of Bamboo with Fibre Bundles Aligned: (a) Parallel and (b) Perpendicular to the Surface.

Tooth Enamel x-section

Tooth Enamel axial section

Nano and Microstructure of CeO2/CuO

Nano/Molecular Level Composite Powder

Layer-by-Layer Lattice Composite in

Li1+x-y Nb1-x-3yTix-4yO3

Ferroelectric
LN cells
Phase
Boundary

A small angle grain boundary is

produced by an array of dislocations
causing a small misorientation of
the lattice across the surface of the
imperfection.

Tilt boundary formed by edge

dislocations
Twist boundary formed by screw
dislocations.

Formation of a tilt boundary

from edge dislocations.

Twin Boundaries
Boundaries across the twins
where there is a mirror image
mis-orientation of the lattice.
Twins are formed from atomic
displacements due to
mechanical shear forces
(mechanical twins) or annealing
heat treatments following
deformation (annealing twins).
Mechanical twins are found in
BCC and HCP metals.
Annealing twins are found in
FCC metals.

Stacking Faults
Surface defects in FCC metals caused by the improper stacking sequence
of close-packed planes.
eg. FCC lattice
ABCABCABCABC..
Stacking fault

ABCABABCBACA.

Surface Energy (J.m-210-3)

Surface
Defect

Al

Cu

Pt

Fe

Grain
boundary

625

645

1000

780

Twin
boundary

120

45

195

190

Stacking
fault

200

75

95

Volume Defects
Cracks, pores, foreign inclusions and other
phases.