Adama Science and Technology University

Introduction to Engineering Materials

(MScE2101)
Department of Materials Science and Engineering

Target Group: Second year

Academic year: 2023/2024

Instructor: Gebisa Bekele(PhD)

 Chapter-4 :
 Imperfections in Solids

Introduction

Point defects

Impurities in solids

Dislocations – Line Defects

Interfacial – Planar Defects

Objective
Describe both vacancy and self-interstitial crystalline defects.
Calculate the equilibrium number of vacancies in a material at
some specified temperature, given the relevant constants.
Name the two types of solid solutions and provide a brief written
definition and/or schematic sketch of each.
For each of edge, screw, and mixed dislocations: (a) describe and
make a drawing of the dislocation, (b) note the location of the
dislocation line, and (c) indicate the direction along which the
dislocation line extends.
Describe the atomic structure within the vicinity of (a) a grain
boundary and (b) a twin boundary.
 Introduction
A perfect crystal is an idealization, there is no such thing in
nature. Atom arrangements in real materials do not follow perfect
crystalline patterns.

Most real crystals contain large numbers of various defects or

imperfections.

Controlling the defects is one of the main goal of materials

science and engineering.

Many of the properties of materials are greatly influenced by the

presence of defects.

For example carbon which forms an interstitial solid solution

when added to iron, many of the mechanical properties depends
on the amount of carbon.
 Introduction
Defects can be classified into four categories depending on

geometry and dimension as:

Point defects (0D)

Line defects (1D)

Area defects (2D)

Volume defects (3D)

 Point Defects
Vacancies and Self-interstitials metal
These includes vacancies, self-interstitial atoms, interstitial
impurities and substitutional impurities

Vacancies: absence of an atom from its normal lattice position

in a crystal structure

Self-interstitial: an atom from the crystal occupies the interstitial

site that under ordinary circumstance is not occupied.
 Point Defects
All crystalline solids contain vacancies , in fact, it is impossible to
create such a material that is free of defects.

The higher the temperature, often times atoms are jumping from
one equilibrium position to another and leaving empty lattice sites
behind.

The equilibrium number of vacancies for a given quantity of

material depends on the temperature.

Nv = number of vacancies

 - Qv  N = number of atomic sites

N v  N exp  Qv = activation energy
 kT  T = temperature in Kelvin
k = Boltzmann constant
 Point Defects
The number of vacancies increases exponentially with
temperature

For most metals, the fraction of vacancies Nv/N just below the Tm
is the order of 10-4 (That is, one lattice site out of 10,000 will be
empty).

Example_1

Calculate the equilibrium number of vacancies per cubic meter for

copper at 1000 C. 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.
  Point Defects
Solution
 = 8.4 g/cm3 ACu = 63.5 g/mol

T = 1000 C = 1273 K Qv = 0.9 eV/atom

NA = 6.02 x 1023 atoms/mol

The number of atomic sites per cubic meter for copper.

N A  Cu
N
ACu

 23 atoms  g  106 cm3 

 6.02x10  8.4 
3 
 atoms
 mol  cm  m 3
  8.0x1028
N m3
atoms
63.5
mol
 Point Defects
The number of equilibrium vacancies per cubic meter at 1273 K:
 Q 
N v  N exp  v 
 kT 

 eV 
atoms  0.9 
 8.0 x1028 exp - atoms 
 8.62x10-5 1273 K 
3
m eV
 atoms - K 

vacancies
 2.2 x1025
m3
  Point Defects
Example_2

a) Calculate the fraction of atom sites that are vacant for copper (Cu)
at its melting temperature of 1084 C. Assume an energy for
vacancy formation of 0.90 eV/atom

b) Repeat this calculation at room temperature (298 K).

c) What is the ratio of N v/N (1357 K) and Nv /N(298 K)?

Solution
Qv = 0.90 eV/atom

T1= 1084C = 1357 K

T2= 298K

k = 8.62x10-5 eV/atom-K
  Point Defects
Example_2

a) Calculate the fraction of atom sites that are vacant for copper (Cu)
at its melting temperature of 1084 C. Assume an energy for
vacancy formation of 0.90 eV/atom

b) Repeat this calculation at room temperature (298 K).

c) What is the ratio of N v/N (1357 K) and Nv /N(298 K)?

Solution (a)

Nv  0.90 eV/atom 

 exp  
N 
 8.62x10 eV/atom - K 1357 k  
-5

 4.56x104
  Point Defects
Example_2

a) Calculate the fraction of atom sites that are vacant for copper (Cu)
at its melting temperature of 1084 C. Assume an energy for
vacancy formation of 0.90 eV/atom

b) Repeat this calculation at room temperature (298 K).

c) What is the ratio of N v/N (1357 K) and Nv /N(298 K)?

Solution (b)

Nv  0.90 eV/atom 

 exp  
N 
 8.62x10 eV/atom - K 298 k  
-5

 6.08x1016
  Point Defects
Example_2

a) Calculate the fraction of atom sites that are vacant for copper (Cu)
at its melting temperature of 1084 C. Assume an energy for
vacancy formation of 0.90 eV/atom

b) Repeat this calculation at room temperature (298 K).

c) What is the ratio of N v/N (1357 K) and Nv /N(298 K)?

Solution (c)

 Nv 
  4
 N 1357  4.56 x10
 7.50 x1011

 Nv  6.08x1016
 
 N  298
  Point Defects
Example_3

Calculate the energy for vacancy formation in nickel (Ni), given

that the equilibrium number of vacancies at 850 oC is 4.7x1022 m-3.
The atomic weight and density (at 850 oC) for Ni are, respectively,
58.69 g/mol and 8.80 g/cm3.

Solution

Nv = 4.7x2022 m-3 A = 58.69 g/mol

T = 850 C = 1123 K  = 8.80g/cm3

NA = 6.02 x 1023 atoms/mol

  Point Defects
Example_3

Calculate the energy for vacancy formation in nickel (Ni), given

that the equilibrium number of vacancies at 850 oC is 4.7x1022 m-3.
The atomic weight and density (at 850 oC) for Ni are, respectively,
58.69 g/mol and 8.80 g/cm3.

Solution

 23 atoms  g  106 cm3 

 6.02x10  8.80 
3 

 mol  cm  m 3
 atoms
N
atoms
 9.0x1028

58.69 m3
mol
 Impurities in Solids (metal and ceramics)

Impurities  a pure metal consisting small foreign atoms

Maximum purity of metals is ca 99.9999%

At this level, on the order of 1022 to 1023 impure atoms are present
in a 1 m3 of materials.

Alloys  impure atoms have been added intentionally to impart

specific characteristics to the material.

Originally, alloying is used in metals to improve mechanical

strength and corrosion resistance.

E.g., sterling silver is 92.5% silver and 7.5% copper alloy (alloying
with copper significantly enhance mechanical properties of silver
without losing its corrosion resistance appreciably).
 Impurities in Solids (metal and ceramics)

The addition of impurity atoms to a metal will result in the

formation of a solid solution and/or a new second phase,

depending of kind of impurity, their concentration and

the temperature of the alloy.

Solvent – element or compound that is present in the large

amount.

Solute – element or compound that is present in minor

amount.
 Impurities in Solids (metal and ceramics)

Solid Solutions

A solid solution forms when, as the solute atoms are

added to the host material, the crystal structure is
maintained and no new structures are formed.

Impurity point defects are found in solid solutions, of

which there are two types substitutional and interstitial.

Subsitututional SS, a solute or impurity atoms replaced

or substitute the hosting atoms

Interstitial SS, a solute or impurity atoms fill the void or

interstitial sites among the hosting atoms
 Impurities in Solids (metal and ceramics)

Solid Solutions

A solid solution is also compositionally homogeneous; the

impurity atoms are randomly and uniformly dispersed within
the solid.

Second phase are formed when a solute atoms added, new

compounds or structures are formed or solute forms local
precipitate.
 Impurities in Solids (metal and ceramics)

Substitution Solid Solutions

There are several features of the solute and solvent atoms
determine the solubility limit of the solute in solvent (Hume-
Rothery rules)

1. Atomic size factor: the difference in atomic radii between the

two atom types is less than about ~  15%,Solute atom creates
substantial lattice distortions and a new phase forms

2. Crystal structure: the crystal structures for metals of both

atom types must be the same.

3. Electronegativity factor: the electronegativity hosting and

foreign atoms should be comparable (otherwise new
intermetallic compound formed)
 Impurities in Solids (metal and ceramics)

Substitution Solid Solutions

There are several features of the solute and solvent atoms

determine the solubility limit of the solute in solvent (Hume-

Rothery rules)

3. Valences: if other factors being equal, a metal has more of a

tendency to dissolve another metal of higher valancy.

 Impurities in Solids (metal and ceramics)

Substitution Solid Solutions

4. Valences: if other factors being equal, a metal has more of a

tendency to dissolve another metal of higher valancy.

An example of a substitutional solid solution is found for copper and

nickel alloy:
These two elements are completely soluble in one another at all
proportions. With regard to the aforementioned rules that govern
degree of solubility.

Atomic radii for Cu and Ni are 0.128 and 0.125 nm (%R = 2.3%)

Both have the FCC crystal structure

Electronegativity of Cu is 1.9 and 1.8 for Ni

most common valancy Cu is+1 (or +2) and +2 for Ni

 Impurities in Solids (metal and ceramics)

Interstitial Solid Solutions

Metallic materials have relatively high atomic packing factors, which

means that these interstitial positions are relatively small.

For both FCC and BCC crystal structure, there are two types of
interstitial sites: tetrahedral and octahedra

The impurity atoms fill the interstices among the hosting atoms.

Atomic radius of solute should be significantly less than solvent

The maximum allowable concentration of impurity atoms should be less

than 10%.

For example, carbon forms an interstitial solid solution when added to

iron in steal making
 The atomic radius of the carbon atom is very small: (0.071 and 0.124 nm for
C and Fe, respectively)  max. concentration ~ 2%
 Summary on point defects:
Types of point defects
 (1) vacancies
 (2) self-interstitial
 (3) interstitial impurity
 (4,5) substitutional impurities

Arrows  local stress introduced by defect Due

to the local stresses introduced by point
defects, they can feel each other (interact) and
feel external stresses.

Self-interstitials in metals induced large

distortions in surrounding lattice.

Energy of self-interstitial formation is ~ 3

x larger than for vacancies (Qi ~ 3Qv)

Low equilibrium self-interstitial

concentration.
 Dislocations – Linear Defects
Edge Dislocations

A dislocation is a linear or one-dimensional defect around which

some of the atoms are misaligned.
 Dislocations – Linear Defects
Edge Dislocations

The magnitude and direction of the lattice distortion associated

with a dislocation are expressed in terms of a Burgers vector,
denoted by b.

The magnitude of the burger vector, can be determined by making a

burger circuit around dislocation, is equal to interatomic spacing.
 Dislocations – Linear Defects
Screw Dislocations
A dislocation is a linear or one-dimensional defect around which some of the
atoms are misaligned.

The dislocation is being formed by the applied shear stress to produce a

distortion

The upper front region of the crystal is shifted one atomic distance to the
right relative to the bottom portion.
 Dislocations – Linear Defects
Mixed Dislocations

Most dislocations found in crystalline materials are probably neither

pure edge nor pure screw, but exhibits components of both types.

These are termed as mixed dislocations

In mixed dislocation, the dislocation lines are neither perpendicular

nor parallel to the burgers vector b.
 Dislocations – Linear Defects
Grain Boundary

The boundary separating two small grains or crystals having different

crystallographic orientations in polycrystalline materials.

Within the grain boundary, several atomic distance wide, there is some

mismatch angle () between two adjacent grains.

Low (small) angle grain boundary

Tilt boundary – formed when an edge dislocations are aligned.

Large (high) angle grain boundary

Twist boundary – can be described by an array of aligned screw

dislocations.
 Dislocations – Linear Defects
Grain Boundary

The atoms are bonded less regularly along a grain and

consequently there is an grain boundary energy similar to the
surface energy.

Surfaces and interfaces are reactive, as a consequence of surface

or grain boundary energy.

Therefore the impurities atoms often preferentially segregate along

these boundaries.

The total grain boundary energy is lower in large or coarse-grained

materials than in small or fine-grained materials. This is because in
large grains, the total grain boundary area is smaller that the grain
boundary of fine grains.
 Dislocations – Linear Defects
Twin Boundary

A twin boundary is a special type of grain boundary across which

there is a specific mirror lattice symmetry.

That is, atoms on one side of the boundary are located in mirror-
image positions of the atoms on the other side
 Dislocations – Linear Defects
Phase Boundary

Phase boundaries exist in multiphase materials, in which a different

phase exists on each side of the boundary, each of the constituent
phases has its own physical and/or chemical characteristics.
 Chapter-5 :
 Diffusion

Diffusion Mechanisms

Fick‟s First and Second Laws of Diffusion

Diffusion in Semiconducting Materials