Material Science

Course No. ME202

Imperfections in Solids
The atomic arrangements in a crystalline lattice
is almost always not perfect.
There are defects in the way atoms are arranged
in the crystalline solids.
So we can say that in crystalline solids some
Lattice Irregularities are always present.
These crystalline defects are not bad. Some are
intentionally introduced to improve the material.

ME202 Material Science

Imperfections in Solids
Solidification- result of casting of molten
material
2 steps
Nuclei form
Nuclei grow to form crystals grain structure

Start with a molten material all liquid

nuclei

liquid

crystals growing

grain structure
Fig.4.14 (b), Callister 7e.

Crystals grow until they meet each other

ME202 Material Science

Imperfections in Solids
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

Fig. 4.7, Callister 7e.

ME202 Material Science

Imperfections in Solids
Grains can be
- equiaxed (roughly same size in all
directions)
- columnar ~
(elongated
grains)
8 cm

heat
flow
Shell of
equiaxed
grains due to
rapid cooling
(greater T)
near wall

Columnar in
area with less
undercooling
Fig. 4.12, Callister 7e.

ME202 Material Science

Types of Crystalline Defects

The study of defects is divided according to their dimension:
0D (zero dimension) Point defects
Vacancies and Interstitials.
Impurities.
1D linear defects:
dislocations (edge, screw, mixed)
2D grain boundaries, surfaces.
3D extended defects: pores, cracks

ME202 Material Science

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
ME202 Material Science

Point Defects
The simplest of the point defect is a
vacancy, or vacant lattice site.
All crystalline solids contain vacancies.
Principles of thermodynamics are used
to 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 Energy required to form vacancy
Total no. of atomic sites
on and increases with
uilibriumdepends
no. of vacancies
T = absolute temperature
temperature as follows:

Nv= N exp(-Qv/kT)
ME202 Material Science

in Kelvin

k = gas or Boltzmanns
constant
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Point Defects
The simplest of the point defect is a
vacancy, or vacant lattice site.
All crystalline solids contain vacancies.
Principles of thermodynamics are used
to 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 Energy required to form vacancy
Total no. of atomic sites
on and increases with
uilibriumdepends
no. of vacancies
T = absolute temperature
temperature as follows:

Nv= N exp(-Qv/kT)
ME202 Material Science

in Kelvin

k = gas or Boltzmanns
constant
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Measuring Activation Energy

Q
Nv
v
exp
kT
N

Q is generally obtained
experimentally.

Nv

Nv
ln
N

N
exponential
dependence!

defect concentration
ME202 Material Science

slope

-Qv /k

1/T

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Point Defects

Impossible to create a material without vacancies due to the

laws of Thermodynamics.
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Point Defects in Metals

Self Interstitial: When an atom

is pushed into an interstitial
site which is normally
unoccupied.
Very small amount in metals
because when it occurs, it
highly distorts the metal.
Much lower concentrations
than vacancies.
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Point Defects in Ceramics

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

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Point Defects in Ceramics

Frenkel Defect

Interstitial

Neighboring
cation vacancy
and cation
interstitial.
Nfr = N exp(Qfr/2kT)
Vacancy

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Point Defects in Ceramics

Shottky Defect

Vacancy

Neighboring
cation vacancy
and anion
vacancy.
Ns = N exp(Qs/2kT)
Vacancy

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Point Defects in Ceramics

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Point Defects in Ceramics

More types of defects than metals because there are more
types of ions.
In order to keep electroneutrality, ions must be lost in
equal amounts of charge. For example: One cation and one
anion.
Two main types: Frenkel Defect, Shottky Defect
Most ceramics stay in a stoichiometric state, that is, they
generally keep the same ratios as predicted by their
empirical formula.
Exceptions occur in atoms like iron: Fe2+and Fe3+

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Point Defects in Polymers

Defects due in part to chain packing errors and impurities
such as chain ends and side chains.

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Point Defects in Polymers

Different from ceramics and metals
Chains can bond together forming loops.
Chains can tie two molecules together.
Impurities may include interstitials, side
branches, or incorrect bending.
Vacancies can occur and alter the chain
sequence.
Every chain end is considered a defect.

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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.
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Second phase particle

--different composition
--often different structure.

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Imperfections in Solids

Hume Rothery rules For Substitutional Solid Solutions

Similar Crystal Structure

Two or more metals should have a similar structures such
as FCC and FCC or BCC and BCC
Relative atomic size
Sizes within 15% of each other
Valency Criteria
Same Valency
Electronegativity
Electronegativity should not be high

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Imperfections in Solids

Hume Rothery rules For Substitutional Solid Solutions

Element

Cu
C
H
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn

Atomic Crystal
Radius Structure
(nm)
0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

Electronegativity

Valence

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

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Imperfections in Solids
Specification of composition
weight percent

m1
C1
x 100
m1 m2

m1 = mass of constituent 1
m2 = mass of constituent 2

atom percent

n m1
C
x 100
nm1 n m 2
'
1

nm1 = number of moles of constituent 1

nm2 = number of moles of constituent 2

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Imperfections in Solids

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
nNi
6.82m
58.69 g / m
9.44
'
CCu
.581 or 58.1%
9.44 6.82
6.82
'
C Ni
.419 or 41.9%
9.44 6.82
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Imperfections in Solids
Converting Between: (Wt% and At%)

C1 A2
C
100
C1 A2 C2 A1
'
1

C2 A1
C
100
C1 A2 C2 A1
'
2

Converts from
Wt% to At%
(Ai is atomic
weight)

C1' A1
C1 '
100
'
C1 A1 C2 A2

Converts from

C2' A2
C2 '
100
'
C1 A1 C2 A2

(Ai is atomic
weight)

ME202 Material Science

At% to Wt%

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Imperfections in Solids

Determining Mass of a Species per Volume

C1"

C1
103
C1 C2

1 2

C2"

C2
103
C1 C2

1 2

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

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