Imperfections/Defects in

Solids
An ideal crystal can be described in terms
a three-dimensionally periodic
arrangement of points called lattice and an
atom or group of atoms associated with
each lattice point called motif:
Crystal = Lattice + Motif
However, there can be deviations from this
ideality.
These deviations are known as crystal defects or
imperfections.
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.
3
4
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).
5
Vacancy atoms
Interstitial atoms
Substitutional atoms
Point defects
1-2 atoms
Types of Imperfections
Dislocations
Line defects
1-dimensional
Grain Boundaries
Area defects
2-dimensional
6
o Point defects essentially zero dimensional imperfections,
such as vacancies, that are located typically at one (in some
cases a few) sites in the crystal.
o Vacancy - An atom or an ion missing from its regular
crystallographic site.
o Interstitial defect - A point defect produced when an atom is
placed into the crystal at a site that is normally not a lattice
point. Also an alien atom in one of the interstitials in a
structure
o Substitutional defect - A point defect produced when an
atom is removed from a regular lattice point and replaced with
a different atom, usually of a different size.
o Extended defects - Defects that involve several atoms/ions
and thus occur over a finite volume of the crystalline material
(e.g., dislocations, stacking faults, grain boundary).
Vacancy: A point defect
Point Defects
Interstitial defect
Formed when an extra atom or
ion is inserted into the crystal
structure at a normally
unoccupied position.
Substitutional defect
Introduced when one atom or
ion is replaced by a different
type of atom or ion.
9
Vacancies:
-vacant atomic sites in a structure.
Self-Interstitials:
-"extra" atoms positioned between atomic sites.
Point Defects in Metals
Vacancy
distortion
of planes
self-interstitial
distortion
of planes
10
Vacancies
-- vacancies exist in ceramics for both cations and anions
Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites
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.)
Point Defects in Ceramics
Cation Interstitial
Cation Vacancy
Anion Vacancy
Point Defects: Impurities
12
Frenkel Defect
To maintain the charge neutrality, a cation vacancy-cation interstitial
pair occur together. The cation leaves its normal position and moves to the
interstitial site.
Schottky Defect
To maintain the charge neutrality, remove 1 cation and 1 anion;
this creates 2 vacancies.
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.)
Point Defects: Frenkel and Schottky
Schottky
Defect
Frenkel
Defect
vacancy
Interstitial
impurity
Substitutional
impurity
Point Defects
14
Boltzmann's constant
(1.38 x 10
-23
J/atom-K)
(8.62 x 10
-5
eV/atom-K)
|
N
v
N
=
exp

Q
v
k T
|
\

|
.
|
No. of defects
No. of potential
defect sites
Activation energy
energy required for formation of vacancy
Temperature
Each lattice site
is a potential
vacancy site
Equilibrium concentration varies with temperature.
Equilibrium Concentration:
Point Defects
15
We can get Q
v
from
an experiment.
|
N
v
N
=
exp

Q
v
k T
|
\

|
.
|
Measuring Activation Energy
Measure this...
N
v
N
T
exponential
dependence!
defect concentration
Replot it...
1/ T
N
N
v
ln
-
Q
v
/k
slope
16
Find the equil. # of vacancies in 1 m
3
of Cu at 1000C.
Given:
A
Cu
= 63.5 g/mol
= 8.4 g / cm
3
Q
v
= 0.9 eV/atom N
A
= 6.02 x 10
23
atoms/mol
Estimating Vacancy Concentration
For 1 m
3
, N =
N
A

A
Cu

x x 1 m
3
= 8.0 x 10
28
sites
8.62 x 10
-5
eV/atom-K
0.9 eV/atom
1273 K
|
N
v
N
=
exp

Q
v
k T
|
\

|
.
|
= 2.7 x 10
-4


Answer:
N
v
= (2.7 x 10
-4
)(8.0 x 10
28
) sites = 2.2 x 10
25
vacancies
Line Defects
Dislocations
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o Dislocation - A line imperfection in a crystalline
material.
o Screw dislocation - A dislocation resulting from
complicated processes it looks like a spiral ramp
about the dislocation in the plane perpendicular to
it
o Edge dislocation - A dislocation resulting from
complicated processes it looks like an extra half
plane of atoms.
o Mixed dislocation - A dislocation that contains partly
edge components and partly screw components.
o Slip Plastic, i.e. permanent, deformation of a
metallic material by the movement of dislocations
through the crystal.
Dislocations
Missing half plane A Defect
An extra half plane
or a missing half plane
What kind of
defect is this?
A line defect?
Or a planar defect?
Extra half plane
No extra plane!
Missing plane
No missing plane!!!
An extra half plane
or a missing half plane
Edge
Dislocation
This is a line defect called an
EDGE DISLOCATION
26
In order to make up a model of an edge dislocation:
perfect crystal in (a) is cut and an extra plane of
atoms is inserted (b). The bottom edge of the extra
plane is the edge dislocation (c). The Burgers vector
b closes the loop of equal atom spacings around the
edge dislocation.
27
In order to make up a model of a screw dislocation:
perfect crystal (a) is cut and sheared one atom spacing,
(b) and (c). The line along which shearing occurs is the
screw dislocation. The Burgers vector b of the dislocation
closes the loop of equal atom spacings around the screw
dislocation.