Slides are based in:

“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 4: Imperfections in Solids
Chapter 7: Dislocations and Strengthening
Mechanisms

“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 4: Crystal Defects and Non-
crystalline Structure - Imperfection
IMPERFECTIONS IN SOLIDS

Dislocations in a photonic crystal arrangement of polystyrene nanospheres

 Defects in Solids
• Only ideal solids are defect-free

• All materials have structural flaws

• No material can be prepared without

some chemical impurity
Even a single crystal of maximum
purity has concentrations of defects
that greatly exceeds
a trillion defects per cm3
 Structural Flaws
are called
Defects
impurities
• Point Defects

• Dislocations

• Interfacial Defects

• Bulk Defects
 Point Defects (0-D Imperfections)
• Vacancy
• Self Interstitials
• Which one of
these two types
of defects would
be more
common?

• How would
Temperature
affect each of
them?
Equilibrium Number of Vacancies

NV = Equilibrium number of vacancies

N = Number of atomic sites

QV = energy for vacancy formation

k = Boltzmann’s constant = 8.62 x 10-5 eV/atom-K

T = absolute temperature (K)

What is the shape of the exp (-Qv / kT) curve
as a function of T ?

Very wide T range Typical T

range
For calculating Nv and Qv it is more convenient to
work on a semi-log plot

Nv = N exp-(Qv / kT)
then, ln Nv = ln N – Qv / kT
plotting ln Nv vs. 1 /T

intercept = ln N
ln Nv

slope = -Qv/k

1/T
 Example 1
At 400ºC, the fraction of lattice sites vacant in a metal M is
2.29x10-5. What is this fraction at 600ºC?
Nv = =NNexp(-Q
fraction of lattice sites vacant v / N v / kT)

then ln (Nv / N) k= =
- Q8.62
v / kT
x 10-5 eV/K
that is, Qv = - kT ln (Nv / N)

= - 8.62 x 10-5 . 673 . ln (2.29x10-5)

= 0.62 eV
therefore,

(Nv / N)600C = exp-(Qv / kT) = exp-(0.62/(873* 8.62 x 10-5))

= 2.64 x 10-4
 Example 2
At 400ºC, the number of vacant metal sites in a metal
sample is 2.33x1018 atoms/cm3. At 660ºC, just below
the melting point, the number is 4.30x1019 atoms/cm3.
What is this number at 550ºC?
Nv1 = N exp(-Qv / kT1)
= exp (-Qv/k) [ 1/T1 – 1/T2 ]
Nv2 = N exp(-Qv / kT2)

Nv1 = N exp(-Qv / kT1)

Nv3 = N exp(-Qv / kT3)
 Example 3
At 400ºC, the concentration of vacancies in aluminum
is 1.39 1018 sites/cm3. We do not know:
What is this concentration at 600ºC?
Qv or N
Finally, at 873 K
- ln ( Nv / N ) = Qv / kT
-ln ( Nv / N ) = 0.619 / (8.62E-5 * 873)
= 8.226
So, Nv (873) = N exp (- 8.226)
= 1.62E+19
 Point Defects: Impurities
▪ Foreign Atoms within the crystal
▪ Pure Metals and ceramics are rare.
Purity > 99.9999% are extremely difficult
to obtain
▪ Alloys = impurities are added to
intentionally affect material properties
 Solid Solutions
▪ Occur when an impurity is added to a crystal but
the crystal structure is maintained

▪ Solid Solution =
Solute (Impurity) + Solvent (Crystal)

Solute =
Impurity

Solvent = Crystal Solid

Solution
Substitutional Solid Solutions
Substitutional Solid Solutions
Solute Atoms replace host atoms when the following
criteria are met.

1) Atomic Size
Difference between atomic radii < + 15%
2) Crystal Structure
Solute and Solvent have same crystal structure
3) Electronegativity
Solute and Solvent have similar electronegativities
4) Valences
Similar valences
 Example of a
Substitutional Solid Solution
Copper and Nickel
🟂These two elements are completely soluble in
each other
🟂RCu = 0.128 nm and RNi = 0.125 nm
🟂Both are FCC
🟂+1 and +2 valence for Cu and +2 for Ni
🟂electronegativities are similar 1.9 and 1.8
Interstitial Solid Solutions
 Interstitial Solid Solutions
▪ Impurity atoms fill the void (interstitial sites)
among the host atoms

▪ Atom Size
Solute radii must be much smaller than the solvent
radii and able to fit into voids
Ex: Carbon in Iron: RCarbon = 0.071nm
RFe = 0.124nm

▪ Concentrations are usually < 10%

Carbon’s Maximum Concentration in Iron is 2%
 Example:
A Ti-Al alloy has the composition 90wt%Ti–10wt%Al.
Express this composition in atomic fractions.

C’ Ti = (CTi AAl )

(CTi AAl + CAl ATi)

C’Ti = (0.9 x 26.98) = 0.835 = 83.5 %

(0.9 x 26.98 + 0.1 x 47.88)

C’Al = ( 1 - C’Ti ) = 0.165 16.5 %

 In the design of an aircraft, we need to prepare a Li-Al
Design Problem alloy with an overall density of 2.55 g/cm3. What
Assume Li and Al are totally composition should we use ?
immiscible

ρT = MT / VT or 1/ρT = VT / MT
then
1/ρT = VT / (mLi + m Al)
= (vLi + v Al) / (mLi + m Al) (1)
but, vLi = mLi / ρLi = CLi MT/ ρLi
then in (1):
1/ρT = CLi MT/ ρLi + CAl MT/ ρAl
CLi MT + CAl MT
MT cancels out

1/ρT = CLi / ρLi + CAl / ρAl = CLi / ρLi + CAl / ρAl

CLi + CAl
1/ρT = CLi / ρLi + (1- CLi) / ρAl

= CLi ( 1/ρLi - 1/ρAl ) + 1/ρAl

Therefore:
CLi = 1/ρT - 1/ρAl
( 1/ρLi - 1/ρAl )

CLi = (1/2.55 - 1/2.71)

(1/0.534 - 1/2.71)

CLi = 0.0154 1.54 wt % Li

98.46 wt % Al
 Structural Flaws
are called
Defects
• Point Defects

• Dislocations

• Interfacial Defects

• Bulk Defects
 What happens if we insert a new half-plane here?

Let’s draw this rectangle

as a reference before the
insertion of the plane
 What happens if we insert a new half-plane here?

Jan Burgers proposed to

use a vector to quantify
distortion

compression

expansion
 Dislocations (1-D Imperfections)
• Edge an extra half-plane is inserted
Dislocation inside the crystal
Burgers vector
describes the
magnitude of
distortion to the
lattice

distortion
around
this line
Burgers
Vector
Is
Perpendicular
To dislocation
Dislocations (1-D Imperfections)
• Screw
Some atoms
Dislocation slightly out of
position.

This defect is due

to unequal growth
while the crystal
forms.
Dislocations (1-D Imperfections)
• Screw
Dislocation
Dislocations (2-D Imperfections)
• Screw
Dislocation

Burgers
Vector
Is Parallel
To
dislocation
 Slip
The process by which a dislocation moves and
deforms a material.

When a shear force acts along

the direction of the Burger's
vector, the dislocation can
move.

The direction of that movement

is the slip direction.

Slip occurs on densely packed planes and directions

 Slip and Plastic Deformation
dislocation produces deformation Not every plane is equally
effective for slip
Planar defects(2-D Imperfections)
• Screw
Dislocation
Planar defects
(2-D Imperfections)

• Defects at surfaces

Importance:
- Heterogeneous catalysis
- Adsorption
- Drying
- Chemical Vapor Deposition
 Defects

• Point Defects

• Dislocations

• Interfacial Defects

• Bulk Defects
What would you see if you cut a metal
bar and polish the cut surface?
Interfacial Defects
(2-D Imperfections)
• Grain
Boundaries
Grain Boundaries How are
they
formed?
During Solidification from the molten
state
 Bulk Defects
(3-D Imperfections)

• Pores

• Cracks
 Out class problem - Porosity of Solids

A porous membrane has :

- pore volume : 1 cm3/g

- surface area : 200 m2/g

A) Calculate the average pore

radius assuming cylindrical
pores

B) Calculate the pore length in a

gram of membrane

Remember that the distance Earth to

Moon is 384,000 km –
so … Be realistic !
 Please read:

“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 3: Imperfections in Solids
Chapter 7: Dislocations and Strengthening
Mechanisms

“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 3: Crystalline Structure – Perfection
Ceramic structures