References

1- Principals of Materials Science and Engineering, William F. Smith

2- The Science and Engineering of Materials , Donald R. Askeland and Pradeep P. Phule

3-Materials Science and Engineering - An Introduction, 7th Edition, Callister

Useful website

http://www.doitpoms.ac.uk/tlplib/index.php

http://www.azom.com/

1
 Lectuer1

Introduction

2
 Contents

What is Material Science and Engineering?

Materials and History

Properties of Materials

Classification of Materials

Materials Design and Selection

3
 What is Material Science and Engineering?

Materials Science and Engineering (MSE) is an interdisciplinary

field of science and engineering that studies and manipulates the
composition and structure of materials to control material
properties through synthesis and processing.

Technology development = Materials Development

Materials development depends on the understanding of the

relation between material properties and internal structure. Then
the structure can be altered through the various processing
techniques to achieve the required properties for an application.

4
 What is Material Science and Engineering?

 In materials science, the emphasis is on underlying

relationships between synthesis and processing, structure and
properties.
 In materials engineering, the focus is how to transform
materials into useful devices and structures
 Composition means the chemical make-up of a material.

 Structure means a description of the arrangements of

atoms or ions in a material.

 Synthesis is the process by which materials are made from

naturally occurring or other chemicals.

 Processing means different ways for shaping materials into

useful components or changing their properties.

5
 What is Material Science and Engineering? – cont’d

Application of the
tetrahedron of materials
science and engineering to
sheet steels for automotive
chassis. Note that the
composition,
microstructure, and
synthesis-processing are all
interconnected and affect
the performance-to-
cost ratio

The Science and Engineering of Materials , Donald R. Askeland, et al., 6th edition.

6
 Materials and History

 Materials are very important in development of

human civilization. In respect, their names are
associated in history, e.g. Stone age, Bronze age, Iron
age, etc.

 With time humans discovered new materials and also

techniques to produce known materials. This is an
ongoing process for coming centuries, i.e. no end in
sight!

7
 Materials and History – cont’d

Materials science is at the base of an enabling technology

which affects all aspects of life in a broad sense: how we
feed ourselves, how we communicate with each other,
how we transport ourselves from one place to another.
Materials are necessary for a multitude of functions in
almost all aspects of daily life and work, in the fine arts,
and in all kinds of technology.

M. S. Dresselhaus, MASSACHUSETTS INSTITUTE OF TECHNOLOGY

8
Over the ages the prowess of a
civilization is closely related to its
ability to synthesize and process
materials.

M. S. Dresselhaus, MASSACHUSETTS INSTITUTE OF TECHNOLOGY

9
 Properties of Materials

Why Should We Study Properties of Materials?

Since there are thousands of materials

available it is almost impossible to select a
material for a specific task unless
otherwise its properties are known.

10
 Properties of Materials – cont’d

 Properties are the way the material responds to the

environmental and external forces
 All solid engineering materials are characterized for their
properties.
 Engineering use of a material is reflection of its properties
under conditions of use.
 All important properties can be grouped into six categories:
Mechanical, Electrical, Thermal, Magnetic, Optical, and
Deteriorative.
 Each material possess a structure, relevant properties, which
dependent on processing and determines the performance.

11
 Properties of Materials – cont’d

 Mechanical properties – response to mechanical forces,

strength, loads, etc.
 Electrical and magnetic properties – response to electrical
and magnetic fields, conductivity, etc.
 Thermal properties – are related to transmission of heat and
heat capacity.
 Optical properties – are related to transmission and
scattering of light.
 Deteriorative – chemical stability in contact with
environment (corrosion resistance)

12
 Classification of Materials

Based on atomic bonds, structures and properties; materials

can be classified into five different groups:

 Metals and Alloys

 Ceramics and Glasses
 Polymers
 Semiconductors
 Composites

13
 Classification of Materials – cont’d

Metals and Alloys

 Inorganic substances which are composed of one or more metallic elements
and may also contain some non-metallic elements.
 Examples of metallic elements are Iron, copper, aluminium, nickel,
titanium, magnesium.
 Examples of non-metallic elements are carbon, nitrogen and oxygen.
 Metals have a crystalline structure in which the atoms are arranged in an
orderly manner.
 Metals are strong and ductile at room temperature, and shiny if polished
 Metals are good thermal and electrical conductors.
 Can be divided into Ferrous and Nonferrous metals.

14
 A jet engine (Rolls-Royce
Trent 800), showing the
different stages: intermediate
pressure compressor (IPC),
high pressure compressor
(HPC), high pressure turbine
(HPT), intermediate pressure
turbine (IPT), low pressure
turbine (LPT), and the
pressure and temperature
profiles along the engine.
Image of the Trent 800
(courtesy Rolls-Royce Plc.)

Ref: http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/coatings/index.html

15
 A section through a jet engine. The forward compression section operates at low
to medium temperatures, and titanium parts are often used. The rear
combustion section operates at high temperatures and nickel-based superalloys
are required. The outside shell experiences low temperatures, and aluminum and
composites are satisfactory. (Courtesy of GE Aircraft Engines.)

The Science and Engineering of Materials , Donald R. Askeland, et al., 6th edition.

16
 Classification of Materials – cont’d

Ceramics and Glasses

 They contain both metallic and non-metallic elements.
 Characterized by their higher resistance to high temperatures and harsh
environments than metals and polymers.
 Typically good insulators to passage of both heat and electricity.
 Less dense than most metals and alloys.
 They are harder and stiffer, but brittle in nature.
 They are mostly oxides, nitrides, and carbides of metals.
 Wide range: traditional (clay, silicate glass, cement) to advanced (carbides,
pure oxides, non-silicate glasses).
 E.g.: Glass, Porcelain, Minerals, etc.

17
 Classification of Materials – cont’d

Polymers

Polymers are produced using a Polymerization process that occurs when

small molecules, represented by the circles, combine to produce larger
molecules, or polymers. The polymer molecules can have a structure that
consists of many chains that are entangled but not connected
(thermoplastics) or can form three-dimensional networks in which chains
are cross-linked (thermosets)
The Science and Engineering of Materials , Donald R. Askeland, et al., 6th edition.

18
 Classification of Materials – cont’d

Polymers
 Most polymeric materials consists of organic (carbon-containing)
long molecular chains or networks.
 Very good strength-to-weight ratio
 Good electrical and thermal insulators.
 They decompose at relatively moderate temperatures (100-400 C),
therefore they are NOT suitable for use at high temperatures.
 Application: packaging, textiles, biomedical devices, optical devices,
compact discs (CDs), toys, etc.
 E.g.: Nylon, Teflon, Rubber, Polyester, etc.
 Commercially called plastics (contain additives that enhance the
properties of polymers)

19
 Classification of Materials – cont’d

Semiconductors
 They are a part of broader class of materials known as electronic
materials.
 Their electrical conductivity depends strongly on minute proportions
of contaminates, and it is between that of ceramic insulators and
metallic conductor. Examples: Silicon, Germanium and Gallium-
arsenide.
 Level of conductivity can be controlled to enable electronic devices
(transistor, diodes, etc..) that are used in integrated circuits.

20
 Classification of Materials – cont’d

Composites
 The main idea in developing Composites is to blend the properties of
Different materials
 Consist of more than one kind of material; tailor made to benefit
from combination of best characteristics of each constituent.
 Concrete and fiberglass are composites.
 Sports equipment such as bicycles, golf clubs, tennis rackets, and are
made of different composites that are light and stiff
 Mainly are composed of two phases; one is matrix – which is
continuous and surrounds the other, dispersed phase.
 Classified into many groups: (1) depending on orientation of phases;
such as particle reinforced, fiber reinforced, etc. (2) depending on
matrix; metal matrix, polymer matrix, ceramic matrix.

21
Classification of Materials – cont’d

22
Classification of Materials – cont’d

23
Bar-chart of room temperature density values for various metals,
ceramics, polymers, and composite materials.
Ref. Materials Science and Engineering - An Introduction, 7th Edition, Callister

24
Figure 1.4 Representative strengths of various categories of materials

Ref. Materials Science and Engineering - An Introduction, 7th Edition, Callister

25
Bar-chart of room-temperature resistance to fracture (i.e., fracture toughness)
for various metals, ceramics, polymers, and composite materials.

Ref. Materials Science and Engineering - An Introduction, 7th Edition, Callister

26
Bar-chart of room temperature electrical conductivity ranges for metals,
ceramics, polymers, and semiconducting materials.
Ref. Materials Science and Engineering - An Introduction, 7th Edition, Callister

27
 Materials Design and Selection

A number of factors must be considered when designing a material

for a given applications:-

 1- The material must acquire the desired physical and

mechanical properties.
 2- Capable of being processed or manufactured into the desired
shape.
 3- Must provide an economical solution to the design problem.

Strength-to-weight ratio is the strength of a material

divided by its density; materials with a high strength-to-
weight ratio are strong but lightweight.
28
Materials Design and Selection – cont’d

Materials Selection Charts

29
 Materials Design and Selection – cont’d

Materials Selection Charts

 Allow easy visualisation of properties
 Show lots of different materials
 Can be ‘drilled down’ to specifics
 Show balances of properties
e.g. strength vs. cost
 Ideal for a first ‘rough cut’ selection

30
 Materials Design and Selection – cont’d
Drink Container
What are the requirements?
 Provide leak free environment for storing liquid.
 Comply with food standards & protect liquid from
health hazards.
 For fizzy drinks, withstand pressure.
 Easy to open
 Easy to store & transport
 Cheap for high volumes

Steel, Aluminium, Glass, Plastic, Paper

31
Atomic Bonding and Structure of
Crystalline Materials
 Outline
 Binding Energy and Interatomic Spacing
 Energy and Packing
 Different Types of Bonds
 Crystalline Materials
 Crystal Structures and Systems
 Cubic System
 Theoritical Density
 Crystallographic Points, Directions and
Planes
 Linear and Planar Densities
2
 Binding Energy and Interatomic Spacing

Interatomic spacing is the equilibrium spacing

between the centers of two atoms due to the balance
between the attractive and repulsive forces.
Binding energy is the energy required to separate two
atoms from their equilibrium spacing, OR it is the
strength of the bond between two atoms.
Materials having a high binding energy display high
strength and melting point.

3
 Binding Energy and Interatomic Spacing – cont’d
Atoms or ions are separated by an equilibrium spacing that corresponds to the
minimum inter-atomic energy for a pair of atoms or ions (or when zero force is
acting to repel or attract the atoms or ions)

(a)The dependence of repulsive, attractive, and net forces on interatomic separation for two isolated atoms.
4
 Binding Energy and Interatomic Spacing – cont’d

(b) The dependence of repulsive, attractive, and net potential energies on interatomic separation for two
isolated atoms.

5
Binding Energy and Interatomic Spacing – cont’d
Modulus of elasticity is the slope of the stress-strain curve in the
elastic region (E). It is directly linked to the strength of bonds between
atoms (binding energy).
Yield strength is the level of stress above which a material begins to
show permanent deformation.

The force-distance curve

for two materials,
showing the relationship
between atomic bonding
and the modulus of
elasticity, a steep dFlda
slope gives a high
modulus

6
 Binding Energy and Interatomic Spacing – cont’d

Coefficient of thermal expansion (CTE) is the amount by which a

material changes its dimensions when the temperature
changes.

The inter-atomic energy (IAE)-

separation curve for two
atoms. Materials that display a
steep curve with a deep trough
have low linear coefficients of
thermal expansion
7
 Energy and Packing

• Non dense, random packing

Energy
typical neighbor
bond length
typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy
Dense, ordered packed structures tend to have lower energies.
8
 Types of Bonds

Different types of bonds:

Metallic bond
Covalent bond
Ionic bond
Van der Waals bond

9
 Types of Bonds – cont’d
The Metallic Bond
It forms when atoms give up their valence
electrons, which then form an electron sea
that shields the positively charged ions from
one another.
The positively charged atom cores are
bonded by mutual attraction to the
negatively charged electrons
Relatively high young’s modulus since the
bonds are strong
Good ductility since the bonds are non-
directional
Good thermal conductors
Subjected to corrosion and oxidation due to
their electropostivity
10
 Types of Bonds – cont’d
Metals are good electrical conductors
When voltage is applied to a metal, the electrons in the electron
sea can easily move and carry a current.

11
 Types of Bonds – cont’d
Covalent Bond
Bonds which are formed by sharing valence electrons among
two or more atoms so that each atom has a stable electron
configuration.

Covalent bonds have a certain directional relationship with one

another (when a specific angle between atom bonds form).

It is very strong, consequently, covalently bonded materials are

very strong and hard. (C- diamond and SiC).

These materials display very high melting point.

These materials are brittle (limited ductility), due to the bonds

tend to be directional.

Also, these materials are poor electrical conductors.

1
 Types of Bonds – cont’d

In silicon, with a valence of four, four covalent bonds must be

formed
Covalent bonds are directional. In silicon, a tetrahedral structure is
formed, with angles of 109.5° required between each covalent
bond
2
 Types of Bonds – cont’d
The Ionic Bond
An ionic bond is created between two different atoms
with different electro-negativities due to the
electrostatic attraction between the oppositely
charged ions.
When sodium donates its valence electron to
chlorine, each becomes an ion (+ cation and - anion);
attraction occurs, and the ionic bond is formed

3
When voltage is applied to an ionic material, entire ions must move
to cause a current to flow. Ion movement is slow and the electrical
conductivity is poor.

4
 Types of Bonds – cont’d
Van der Waals Bonding

A secondary and weak bond developed between atoms and

molecules as a result of interactions between dipoles that are
induced or permanent.

Van der Waals bonds are secondary bonds, but the atoms within
the molecule or group of atoms are joined by strong covalent or
ionic bonds.

Van der Waals forces between atoms and molecules play a vital
role in determining the surface tension and boiling points of
liquids.

Van der Waals bonds can dramatically change the properties of

certain materials, for example, graphite and diamond.

5
 Types of Bonds – cont’d
(a) In polyvinyl chloride (PVC), the chlorine atoms attached to the polymer
chain have a negative charge and the hydrogen atoms are positively
charged. The chains are weakly bonded by van der Waals bonds. This
additional bonding makes PVC stiffer.
(b) When a force is applied to the polymer, the van der Waals bonds are
broken and the chains slide past one another.

6
 Types of Bonds – cont’d

EXAMPLE:
Relationships between Arrangements of Atoms and Materials Properties

Diamond
Diamond is one of the highest melting-point materials
known with a melting temperature of 3550°C.
Diamond is the stiffest material with an elastic
modulus of 1100 GPa. (diamond is about ten times
stiffer than titanium and more than fifteen times stiffer
than aluminum).
Diamond is one of the hardest substances known,
which is why it is often used in cutting tools in
industrial applications.

7
 Types of Bonds – cont’d

Diamond is an electrical insulator. All of the valence

electrons of each carbon atom are shared with the
neighboring atoms, leaving no free electrons to
conduct electricity.
Diamond also has one of the highest known thermal
conductivities.
As a material is heated, the atoms vibrate with more
energy. When the bonds are stiff, the vibrations are
transferred efficiently between atoms, thereby
conducting heat.
Usually an electrical insulator is also a poor
conductor of heat because it lacks free electrons, but
diamond is an exception due to its extraordinary
stiffness. 8
 Types of Bonds – cont’d
Graphite
It is like pure diamond, contains only carbon atoms but the properties
of graphite are significantly different from that of diamond.
In graphite, the carbon atoms are arranged in layers. In each layer, the
carbon atoms are arranged in a hexagonal pattern in each graphite
layer, each carbon atom is bonded covalently to only three others
There is a fourth bond between the layers, but this is a much weaker
van der Waals bond
Also, the spacing between the graphite layers is 2.5 times larger than
the spacing between the carbon atoms in the plane
In graphite, it is NOT difficult to separate the individual layers, because
the bonds between the layers are weak (writing with pencil is example)
Graphite has a lower density than diamond because of its layer
structure the atoms are not packed as closely together.
Unlike diamond, graphite is electrically conductive. This is because the
fourth electron of each carbon atom, which is not covalently bonded in
the plane, is available to conduct electricity. 9
 Types of Bonds – cont’d

Diamond: each C-atom Graphite: in each layer,

share four C-atoms each C-atom share three
with covalent bonds C-atoms with covalent
bonds

10
 Crystalline Materials

Crystalline materials: If the atoms or ions of a solid are arranged in

a pattern that repeats itself in three dimensions, they form a solid
which is said to have a crystal structure and is referred to as
crystalline materials. Examples of crystalline materials are metals,
alloys and some ceramic material.

Amorphous: disordered – lack of a systematic atomic arrangement.

Amorphous silicon

Crystalline silicon
Ref. The Science and Engineering of Materials , Donald R. Askeland and Pradeep P. Phule
11
 Crystalline Materials – cont’d

Crystalline Materials
Single crystal is a crystalline material that is made of
only one crystal, atoms are in the same repeating array
over the entire extent of the material.

Polycrystalline is a material comprised of many crystals.

12
 Crystalline Materials – cont’d

Polycrystalline Materials

Grains are the crystals of

different size and
orientation in a
polycrystalline material.

Grain boundaries are

regions between grains
of a polycrystalline
material.

13
 Crystal structure and Systems
Lattice - A collection of points that divide space into smaller
equally sized segments.
Basis - A group of atoms associated with a lattice point.
Crystal structure = Lattice + Basis.
Unit cell - A subdivision of the lattice that still retains the overall
characteristics of the entire lattice.
Hard Sphere Model of Atoms: It is useful to consider atoms as
being hard spheres with well-defined radii. The shortest distance
between two like atoms is one diameter of the hard sphere.

(7) Crystal Systems.

(14) Bravais Lattice (arrangement of lattice points) = the (14)
types of Bravais lattices grouped into (7) crystal system.
14
Crystal structure and Systems – cont’d

15
 Crystal structure and Systems – cont’d
Lattice Parameters and Interaxial Angles
The lattice parameters are the axial lengths or dimensions of the unit
cell and are denoted by convention as a, b, and c. The angles
between the axial lengths, known as the interaxial angles, are
denoted by the Greek letters α, β, and γ.

16
 Crystal structure and Systems – cont’d

Seven Crystal Systems

17
18
19
(14) Bravais
Lattice

20
 Cubic System
Number of Atoms per Unit Cell
Corners contribute 1/8 of an atom,
Faces contribute 1/2 ,
Body-centered positions contribute 1 atom /unit cell.

21
 Cubic System – cont’d
Coordination Number: is the number of atoms touching a particular
atom, or the number of nearest neighbors for that particular atom.
This is one indication of how tightly and efficiently atoms are
packed together.
Each atom has the same number of nearest-neighbor or
touching atoms

Illustration of coordination in (a) SC and (b) BCC unit cells.

6 atoms touch each atom in SC, while
8 atoms touch each atom in the BCC unit cell. 22
 Cubic System – cont’d
Example 1
Determine the number of lattice points per cell in the cubic crystal
systems. If there is only one atom located at each lattice point,
calculate the number of atoms per unit cell.
Solution
In the SC unit cell: lattice point / unit cell = (8 corners)(1/8) = 1
In BCC unit cells: lattice point / unit cell = (8 corners)(1/8) + (1
center)(1) = 2
In FCC unit cells: lattice point / unit cell = (8 corners)(1/8) + (6
faces)(1/2) = 4
The number of atoms per unit cell would be 1, 2, and 4, for the
simple cubic, body-centered cubic, and face-centered cubic, unit
cells, respectively.

23
 Cubic System – cont’d
BCC Crystal Structure
Such as: Chromium, iron, tungsten.
a = b = c; all angles = 90º
Number of atoms/unit cell = 2 atoms
(8 corners)(1/8) + (1 center) = 2 atoms
Lattice parameter & radius relation: a0 = 4r 3
The coordination number (CN) = 8 atoms
Atomic Packing Factor (APF) = 0.68

24
 Cubic System – cont’d
FCC Crystal Structure
Such as: copper, aluminum, silver, and gold
a = b = c; all angles = 90º
Number of atoms/unit cell = 4 atoms
(8 corners)(1/8) + (6 faces)(1/2) = 4 atoms
Lattice parameter & radius relation: a0 = 4r 2
The coordination number (CN) = 12 atoms
Atomic Packing Factor (APF) = 0.74

25
 Cubic System – cont’d

Packing factor - The fraction of space in a unit

cell occupied by atoms.

26
 Cubic System – cont’d
Example
Calculate the packing factor for the FCC unit cell
Solution
In a FCC unit cell, there are four lattice points per cell;
If there is one atom per lattice point, there are also four atoms per
cell.
The volume of one atom is (4πr3/3); and
The volume of the unit cell is a03
4 3
(4 atoms/cell)( πr )
Packing Factor = 3
a03 PF, FCC = 0.74
PF, BCC = 0.68
Since, for FCC unit cells, a 0 = 4r/ 2 PF, SC = 0.52
4 3
(4)( πr )
3 π
Packing Factor = 3
= ≅ 0.74
( 4r / 2 ) 18 27
 Theoretical Density

The theoretical density of a material can be calculated

using the properties of the crystal structure. The
general formula is:

28
 Theoretical Density – cont’d
Example
Determine the density of BCC iron, which has a lattice parameter
of 0.2866 nm.
Solution
For a BCC unit cell:
Atoms/cell = 2, a0 = 0.2866 nm = 2.866 × 10-8 cm
Atomic mass = 55.847 g/mol
Volume of unit cell = = (2.866 × 10-8 cm)3 = 23.54 × 10-24 cm3/cell
Avogadro’s number NA = 6.02 × 1023 atoms/mol
(number of atoms/cell)(atomic mass of iron)
Density ρ =
(volume of unit cell)(Avogadro' s number)
(2)(55.847)
ρ= = 7 . 882 g / cm 3

(23.54 ×10 − 24 )(6.02 ×10 23 )

29
 Theoretical Density – cont’d
Example
Copper has an atomic radius of 0.128 nm, an FCC
crystal structure, and an atomic weight of 63.5 g/mol.
Calculate its theoretical density.

Solution

For FCC, n, the number of atoms per unit cell = 4 atoms.

The atomic weight, A, = 63.5 g/mol.
The unit cell volume (Vc) for FCC = (a0)3 = (4r 2 )3
Avogadro's Number (NA) = 6.02 X 1023
Density of Copper = 8.89 g/cm3
From Literature, density of copper is 8.94 g/cm3,
30
 Crystallographic Points

Example:
Specify point coordinates for all atom
positions for a BCC unit cell.

31
 Crystallographic Directions

Miller indices - A shorthand notation to describe certain

crystallographic directions and planes in a material. Denoted by [ ]
brackets for directions and ( ) parentheses for planes. A negative
number is represented by a bar over the number.

Directions in the Unit Cell: Certain directions in the unit cell are of
particular importance. Miller indices for directions are the shorthand
notation used to describe these directions.

32
 Crystallographic Directions – cont’d

The procedures for finding the Miller indices for directions is as

follows:

1. Using a right-handed coordinate system, determine the

coordinates of two points that lie on the direction.
2. Subtract the coordinates of the “tail” point from the
coordinates of the “head” point to obtain the number of
lattice parameters traveled in the direction of each axis of the
coordinate system.
3. Clear fractions and or reduce the results obtained from the
subtraction to lowest integers.
4. Enclose the numbers in square brackets [ ]. If a negative sign
is produced, represent the negative sign with a bar over the
number.

33
 Crystallographic Directions – cont’d

Determine the Miller indices of directions A,

B, and C in the Figure.
SOLUTION
Direction A
1. Two points are 1, 0, 0, and 0, 0, 0
2. 1, 0, 0 - 0, 0, 0 = 1, 0, 0
3. No fractions to clear or integers to reduce
4. [100]
Direction B
1. Two points are 1, 1, 1 and 0, 0, 0
2. 1, 1, 1 - 0, 0, 0 = 1, 1, 1
3. No fractions to clear or integers to reduce
4. [111]
Direction C
1
1. Two points are 0, 0, 1 and , 1, 0
2
1 1
2. 0, 0, 1 - ,1, 0 = - ,-1, 1
2 2
1
3. 2 (- , - 1, 1) = - 1, - 2, 2
2
4. [ 1 2 2]

34
 Crystallographic Directions – cont’d

Several points should be noted about the use of Miller

indices for directions:
1. Because directions are vectors, a direction and its negative are
−

not identical; [100] is not equal to [10 0]. They represent the same
line, but opposite directions.
2. A direction and its multiple are identical; [100] is the same
direction as [200].
3. Certain groups of directions are equivalent; they have their
particular indices because of the way we construct the
coordinates. For example, in a cubic system, a [100] direction is
a [010] direction if we redefine the coordinate system. We may
refer to groups of equivalent directions as directions of a form or
family.

35
 Crystallographic Directions – cont’d
Equivalent directions: this means that the spacing of atoms along each
direction is the same.
Groups of equivalent directions are referred as directions of a form or
family.
The special brackets are used to indicate this collection of
directions.

For example, in cubic crystals, all the directions represented by the

following indices are equivalent:
− − −
[100], [100], [010], [0 10], [001], and [00 1]
Equivalent directions are grouped to gether into a family,
which are enclosed in angle brackets, thus : 100
36
 Crystallographic Directions – cont’d

Significance of Crystallographic Directions

Crystallographic directions are used to indicate a
particular orientation of a single crystal or of an
oriented polycrystalline material.

Knowing how to describe these can be useful in many

applications. Metals deform more easily, for example, in
directions along which atoms are in closest contact.

Another real-world example is the dependence of the

magnetic properties of iron and other magnetic
materials on the crystallographic directions.

37
 Crystallographic Planes

Planes in the Unit Cell

Certain planes of atoms in a crystal also carry particular significance.

For example, metals deform along planes of atoms that are most tightly
packed together.

Miller indices are used as a shorthand notation to identify these important

planes, as described in the following procedures.
1. Identify the points at which the plane intercepts the x, y, and z
coordinates in terms of the number of lattice parameters. If the plane
passes through the origin, the origin of the coordinate system must be
moved to that of an adjacent unit cell.
2. Take reciprocals of these intercepts.
3. Clear fractions but do not reduce to lowest integers.
4. Enclose the resulting numbers in parentheses (). Again, negative
numbers should be written with a bar over the number.

38
 Crystallographic Plans – cont’d

Determine the Miller indices of planes A, B, and C.

39
 Crystallographic Plans – cont’d
SOLUTION
Plane A
1. x = 1, y = 1, z = 1
2.1/x = 1, 1/y = 1,1 /z = 1
3. No fractions to clear
4. (111)
Plane B
1. The plane never intercepts the z axis, so x = 1, y = 2, and z = ∞
2. 1/x = 1, 1/y =1/2, 1/z = 0
3. Clear fractions: 1/x = 2, 1/y = 1, 1/z = 0
4. (210)
Plane C
1. We must move the origin, since the plane passes through 0, 0, 0.
Let’s move the origin one lattice parameter in the y-direction.
Then, x = ∞ , y = -1, and z = ∞
2. 1/x = 0, -1/y = -1, 1/z = 0
3. No fractions to clear.
−

4. (010) 40
 Crystallographic Plans – cont’d

Important aspects of the Miller indices for planes:

1. Planes and their negatives are identical (this was not the case −

for directions) because they are parallel. Therefore, (020)= 0 2 0 )

2. Planes and their multiples are not identical (again, this is the
opposite of what we found for directions).

3. In each unit cell, planes of a form or family represent groups of

equivalent planes that have their particular indices because of
the orientation of the coordinates. We represent these groups
of similar planes with the notation { }.

4. In cubic systems, a direction that has the same indices as a

plane is perpendicular to that plane.

41
 Crystallographic Plans – cont’d

The planes of the form {110} in cubic systems are

shown.

42
 Close-Packed Planes and Directions

In examining the relationship between atomic radius and lattice

parameter, we looked for close-packed directions, where atoms are
in continuous contact.

43
 Linear and Planar Densities

Directional equivalency is related to linear density in the sense

that, for a particular material, equivalent directions have identical
linear densities.
The corresponding parameter for crystallographic planes is
planar density, and planes having the same planar density
values are also equivalent.

Number of Atoms Centered on Direction Vector

Linear Density = LD =
Length of Direction Vector
Number of Atoms Centered on a Plane
Planar Density = PD =
Area of the Plane
Area of Atoms per Face
Planar Packing fraction =
Area of Face

44
 Linear and Planar Densities – cont’d
EXAMPLE
Calculate the planar density and planar packing fraction
for the (010) and (020) planes in simple cubic polonium,
which has a lattice parameter of 0.334 nm.

The packing fraction for a unit cell, consider 3D, so that the atoms are spheres.
The packing fraction for a plane/direction, consider 2D so that the atoms are circles.
45
 Linear and Planar Densities – cont’d
SOLUTION
The total atoms on each face is one. The planar density is:

atom per face 1 atom per face

Planar density (010) = = 2
area of face (0.334)
= 8.96 atoms/nm 2 = 8.96 × 1014 atoms/cm 2

The planar packing fraction is given by:

area of atoms per face (1 atom) (πr ) 2

Packing fraction (010) = = 2

area of face (a )
0

πr2

= = 0.79
2
( 2r )
No atoms are centered on the (020) planes. Therefore, the planar
density and the planar packing fraction are both zero. The (010) and
(020) planes are not equivalent!
46
 Linear and Planar Densities – cont’d
The linear density of the [110] direction for the FCC crystal
structure

Number of Atoms Centered on Direction Vector

Linear Density = LD =
Length of Direction Vector

LD110 = 2 atoms /4R = 1/ 2R

47
 Linear and Planar Densities – cont’d
The Planar density of the (110) plane for the FCC crystal
structure

4R
(110)
2R √2

Number of Atoms Centered on a Plane

Planar Density = PD =
Area of the Plane

48
Week 6, Cont’d
 HCP Crystal Structure
Such as: cadmium, magnesium, titanium, and zinc
Number of atoms/unit cell = 6 atoms
(12 corners)(1/6) + (2 faces)(1/2) + 3 (mid-plane interior) = 6 atoms
The coordination number (CN) = 12 atoms
Atomic Packing Factor (APF) = 0.74 (H.W.)

2
 HCP Crystal Structure – cont’d
Miller-Bravais Indices for Hexagonal Unit Cells
The procedures for finding the indices of planes is exactly the same as before, but
four intercepts are required, giving indices of the form (hkil).
Directions in HCP cells are denoted with either the three-axis or four-axis system.
With the three-axis system, the procedures are the same as for conventional Miller
indices.

The four coordinate axes (a1, a2, a3 and c) of HCP crystal structure 3
 HCP Crystal Structure
Determine the Miller-Bravais indices for planes A & B and directions C & D.
Plane A
1. a1 = a2 = a3 = ∞ , c = 1
2. 1/a1 = 1/a2 = 1/a3 = 0, 1/c = 1
3. No fractions to clear
4. (0001)
Plane B
1. a1 = 1, a2 = 1, a3 = -1/2, c = 1
2. 1/a1 = 1, 1/a2 = 1, 1/a3 = -2, 1/c = 1
3. No fractions to clear
4. (11 2 1)
Direction C
1. Two points are 0, 0, 1 and 1, 0, 0.
2. 0, 0, 1 - 1, 0, 0 = 1, 0, 1
3. No fractions to clear or integers to reduce.
4. [ 1 01]
Direction D
1. Two points are 0, 1, 0 and 1, 0, 0.
2. 0, 1, 0, -1, 0, 0 = -1, 1, 0
3. No fractions to clear or integers to reduce.
4. [ 1 10] 4
 Close-Packed Planes and Directions

In examining the relationship between atomic radius and lattice

parameter, we looked for close-packed directions, where atoms are
in continuous contact.

5
 Isotropic and Anisotropic Behavior

Because of differences in atomic arrangement in the planes and

directions within a crystal, some properties also vary with direction.
A material is crystallographically anisotropic if its properties depend on
the crystallographic direction along which the property is measured.
If the properties are identical in all directions, the material is
crystallographically isotropic.
Note that a material such as aluminum, which is crystallographically
anisotropic, may behave as an isotropic material if it is in a
polycrystalline form. This is because the random orientations of
different crystals in a polycrystalline material will mostly cancel out any
effect of the anisotropy as a result of crystal structure.
In general, most polycrystalline materials will exhibit isotropic
properties.
Materials that are single crystals or in which many grains are oriented
along certain directions (naturally or deliberately obtained by
processing) will typically have anisotropic mechanical, optical,
magnetic, and dielectric properties. 6
 7
Anisotropy in wood
 Elongated grains
Equiaxed grains

8
 Anisotropic Behavior

During deformation, grains rotate as well as elongate, causing

certain crystallographic directions and planes to become aligned
with the direction in which stress is applied. Consequently,
preferred orientations, or textures, develop and cause
anisotropic behavior.

The Young’s modulus of materials depends upon

crystallographic directions in single crystals. For example, the
Young’s modulus of iron along [111] and [100] directions is 260
and 140 GPa, respectively.

Development of texture not only has an effect on mechanical

properties but also on magnetic and other physical properties of
materials. For example, grain-oriented magnetic steels made
from about 3% Si and 97% Fe used in transformer cores are
textured via thermo-mechanical processing so as to optimize
their electrical and magnetic properties.
9
 Anisotropic Behavior – cont’d

This Figure shows the anisotropic

behavior in a rolled aluminum-lithium
sheet material used in aerospace
applications. The sketch relates the
position of tensile bars to the mechanical
properties that are obtained.

For this alloy, strength is

highest parallel to the
rolling direction, whereas
ductility is highest at a 45°
angle to the rolling
direction.

The strengthening that

occurs by the
development of
anisotropy or of a texture
is known as texture
strengthening. 10
 POLYMORPHISM AND ALLOTROPY

Allotropy: The characteristic of an element being able to exist in

more than one crystal structure, depending on temperature and
pressure.

Polymorphism: Compounds exhibiting more than one type of

crystal structure.

Example is found in carbon: graphite is the stable allotrope at

ambient conditions, whereas diamond is formed at extremely
high pressures.

Another example in pure iron has a BCC crystal structure at

room temperature, which changes to FCC iron at 912ºC.

Most often a modification of the density and other physical

properties accompanies a polymorphic transformation.

11
 POLYMORPHISM AND ALLOTROPY – cont’d

Allotrope of pure iron

Temperature ºC Allotrope
-273 to 912 BCC – α – Fe
912 to 1394 FCC – γ – Fe
1394 to 1539 BCC – δ – Fe
Above 1539 Liquid Fe

12
 POLYMORPHISM AND ALLOTROPY – cont’d
EXAMPLE

Calculate the percent volume change as zirconia ZrO2

transforms from a tetragonal to monoclinic structure.

The lattice constants for the monoclinic unit cell are: a =

5.156, b = 5.191, & c = 5.304 Å, respectively. The angle
β for the monoclinic unit cell is 98.9º.

The lattice constants for the tetragonal unit cell are a =

5.094 and c = 5.304 Å, respectively.

Does the zirconia expand or contract during this

transformation? What is the effect of this transformation
on the mechanical properties of zirconia ceramics?

13
POLYMORPHISM AND ALLOTROPY – cont’d

14
 POLYMORPHISM AND ALLOTROPY – cont’d

SOLUTION
The volume of a tetragonal unit cell is given by
V = a2c = (5.094)2 (5.304) = 137.63 Å3.
The volume of a monoclinic unit cell is given by
V = abc sin β = (5.156) (5.191) (5.304) sin(98.9) = 140.25 Å3.
Thus, there is an expansion of the unit cell as ZrO2 transforms from
a tetragonal to monoclinic form.
The percent change in volume
= (final volume - initial volume)/(initial volume) x 100
= [(140.25 - 137.63 Å3)/137.63 Å3 ]* 100 = +1.9%.

Most ceramics are very brittle and cannot withstand more than a 0.1% change in
volume. The conclusion here is that ZrO2 ceramics cannot be used in their
monoclinic form since, when zirconia does transform to the tetragonal form, it will
most likely fracture.

16
Solidification and Crystalline Imperfections

1
 Outline

Solidification
Solidification Process
Nucleation
Cooling Curves
Growth of Crystals in Liquid Metal

Crystalline Imperfections
Point Defects
Line Defects
Surface Defects
2
 Solidification Process
What is Solidification ?

 It is the process of transformation

of a substance from liquid to
solid state in which the crystal
lattice forms and crystals appear.

 Solidification of metals
and alloys is an
important industrial
process since most
metals are melted and
then cast into a semi-
finished or finished
shape.
3
 Solidification Process – Cont’d
Solidification
• in pure metals and eutectic alloys takes place at
constant temperature
• in solid solution alloys proceeds over a temperature
range.

In general the solidification of a metal or alloy can be

divided into the following steps:

(i) Nucleation: the formation of stable nuclei in the

melt.
(ii) Growth: the growth of nuclei into crystals and the
formation of a grain structure (which depends on
the solidification conditions).

4
 Solidification Process – Cont’d
Grain
Liquid boundaries
Embryo

Nuclei

Crystals which will Grains

form grains

Schematic illustration showing the stages of the solidification of metals:

(a) formation of nuclei, (b) growth of nuclei into crystals, and (c) joining together of crystals
to form grains and associated grain boundaries.
Note that the grains are randomly oriented.

5
 Nucleation
The Formation of Stable Nuclei in Liquid Metals
The two main mechanisms by which nucleation of solid particles in
liquid metal occurs are homogeneous nucleation and heterogeneous
nucleation.
Homogeneous Nucleation
Homogeneous nucleation is the simplest case of nucleation. It occurs
when the metal itself provides the atoms to form nuclei.
Homogeneous nucleation usually requires a considerable amount of
undercooling which may be as much as several hundred degrees
Celsius for some metals.
For a nucleus to be stable so that it can grow into a crystal, it must
reach a critical size. A cluster of atoms bonded together which is less
than the critical size is called an embryo, and one which is larger than
the critical size is called a nucleus. Because of their instability,
embryos are continuously being formed and redissolved in the
molten metal due to the agitation of the atoms. 6
 Nucleation – Cont’d

* 2γTm
600 r =−
ΔHs ΔT
ΔHs = Latent heat of solidification
ΔT = amount of undercooling
ΔT, 0C

300

Nuclei are stable in this region

Embryos form in this region

100 and may redissolve

5x10-7 10-6 1.5 X10-6

Critical radius of particle, r*, cm

As the amount of undercooling increases, the critical
nucleus size decreases 7
 Nucleation – Important terminology

• Nucleation - The physical process by which a new phase is

produced in a material.
• Critical radius (r*) - The minimum size that must be formed by
atoms clustering together in the liquid before the solid particle
is stable and begins to grow.
• Undercooling - The temperature to which the liquid metal must
cool below the equilibrium freezing temperature before
nucleation occurs.
• Homogeneous nucleation - Formation of a critically sized solid
from the liquid by the clustering together of a large number of
atoms at a high undercooling (without an external interface).
• Heterogeneous nucleation - Formation of a critically sized solid
from the liquid on an impurity surface.

8
 Nucleation – Cont’d

(a) An interface is created when a solid forms from the liquid.

(b) The total free energy of the solid-liquid system changes with the size of the solid.
The solid is an embryo if its radius is less than the critical radius and is a nucleus
if its radius is greater than the critical radius. 9
 Nucleation – Cont’d
Heterogeneous Nucleation
Heterogeneous nucleation is nucleation that occurs in a
liquid on the surfaces of its container, insoluble impurities, or
other structural material which lower the critical free energy
required to form a stable nucleus.

Since large amounts of undercooling do not occur during

industrial casting operations and usually range between 0.1
to 10°C, the nucleation must be heterogeneous and not
homogeneous.

For heterogeneous nucleation to take place, the solid

nucleating agent (impurity solid or container) must be
wetted by the liquid metal. Also the liquid should solidify
easily on the nucleating agent. 10
Heterogeneous Nucleation

 It occurs much more often than homogeneous nucleation.

 It applies to the phase transformation between any two phases

of gas, liquid, or solid.

 It forms at preferential sites such as phase boundaries, surfaces

(of container, bottles, etc.) or impurities like dust. At such
preferential sites, the effective surface energy is lower, thus
diminishes the free energy barrier and facilitating nucleation.

 Surfaces promote nucleation because of wetting – contact

angles greater than zero between phases facilitate particles to
nucleate.

11
 Nucleation – Cont’d

The free energy needed for heterogeneous nucleation is equal to the

product of homogeneous nucleation and a function of the contact
angle (θ):

ΔG heterogeneous = ΔG homogeneous *f(θ) where

2 − 3cos𝜃𝜃 + cos3𝜃𝜃 4
f(θ) =
4

12
• The barrier energy needed for heterogeneous nucleation is
reduced.
• The wetting angle determines the ease of nucleation by
reducing the energy needed.

13
(a) Variation of ΔG* with undercooling (ΔT) for homogeneous and
heterogeneous nucleation.
(b) The corresponding nucleation rates assuming the same critical value
of ΔG*.
14
 Cooling Curves

Homogenous nucleation Heterogeneous nucleation 15

 Cooling Curves – Cont’d
Fig (a) Cooling curve for a pure metal that has not been well-
inoculated. The liquid cools as specific heat is removed (between
points A and B).

Undercooling is thus necessary (between points B and C). As the

nucleation begins (point C), latent heat of fusion is released
causing an increase in the temperature of the liquid. This process
is known as recalescence (point C to point D).

The metal continues to solidify at a constant temperature (Tmelting).

At point E, solidification is complete. The solid casting continues

to cool from this point.

Fig (b) Cooling curve for a well-inoculated, but otherwise pure,

metal. No undercooling is needed. Recalescence is not observed.
Solidification begins at the melting temperature.
16
 Growth of Crystals in Liquid
When a relatively pure metal is cast into a stationary mold without the
use of grain refiners two major types of grain structures are usually
produced:
1. Equiaxed grains
2. Columnar grains
Equiaxed grains will be produced, if the nucleation and growth conditions
in the liquid metal during solidification are such that the crystals can grow
approximately equally in all directions. Equiaxed grains require large
amount of undercooling that is present at the mold wall.

Columnar grains are long, thin coarse grains which are created when a
metal solidifies relatively slowly in the presence of a steep temperature
gradient, Relatively few nuclei are available when columnar grains are
produced. 17
 Growth of Crystals in Liquid – Cont’d
Columnar grains

Equiaxed
grains

Mold

a) Schematic drawing of a solidified metal grain structure produced by using a cold

mold, (b) Transverse section through an ingot of aluminium alloy 1100.

18
 Growth of Crystals in Liquid – Cont’d

The number of nucleation sites available to the freezing metal will

affect the grain structure of the solid metal produced.

If relatively few nucleation sites are available during solidification,

a coarse, or large-grain, structure will be produced.

If many nucleation sites are available during solidification, a fine-

grain structure will result. Almost all engineering metals and alloys
are cast with a fine-grain structure since this is the most desirable
type for strength and uniformity of finished metal products.

19
 Growth of Crystals in Liquid – Cont’d

Effect of Grain Refiners

(a) (b)

Parts of transverse sections through two 6-in-diameter ingots of alloy 6063 (AI-
0.7% Mg-0.4% Si) that were direct-chill semicontinuous cast. Ingot section (a)
was cast without the addition of a grain refiner; note columnar grains. Ingot
section (b) was cast with the addition of a grain refiner and shows a fine,
equiaxed grain structure. 20
Crystalline Imperfections

1
 Point Defects
Localized interruptions in perfect atomic or ionic arrangements in a crystal
structure. This interruption affects a region involving several atoms or
ions.
These imperfections may be introduced by movement of the atoms or
ions when they gain energy by heating, during processing of the
material, or by the intentional or unintentional introduction of impurities.
Vacancy - An atom or an ion missing from its regular crystallographic
site.
Interstitial defect - A point defect produced when an atom is placed into
the crystal at a site that is normally not a lattice point.
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.
Frenkel defect - A pair of point defects produced when an ion moves to
create an interstitial site, leaving behind a vacancy.
Schottky defect - A point defect in ionically bonded materials. In order to
maintain a neutral charge, a stoichiometric number of cation and anion
vacancies must form. 2
 Point Defects – Cont’d

(a) vacancy, (b) interstitial atom,

(c) small substitutional atom, (d) large substitutional atom,
(e) Frenkel defect, and (f) Schottky defect.
3
What is Schottky Defect
Schottky defect is a type of point defect which occurs due to the loss of
atoms from a crystal lattice in stoichiometric units. This phenomenon was
named after Walter H. Schottky. The Schottky defect can occur in ionic or
non-ionic crystals. In ionic crystals, the defect is formed when a
stoichiometric unit of atoms leave the lattice. In other words, the defect
arises when one building block leaves the lattice. This leaving creates a
vacancy in the lattice.
However, the overall charge is maintained neutral since the loss occurs in
stoichiometric units. The stoichiometric units are composed of oppositely
charged atoms in equal ratios. For example, in NaCl lattice,
Na+ cation and Cl– anion can leave, forming Schottky defect.

The Schottky defect causes the reduction of density in the lattice. This
defect is highly found in ionic compounds. When it is present in non-ionic
crystals, this is called a vacancy defect. The Schottky defect is usually
found in lattices having ions with nearly equal sizes. This type of defect is
common in lattices like NaCl, KBr, and KCl.

4
What is Frenkel Defect
Frenkel defect is a type of point defect that occurs due to the loss of one
atom or a small ion. This creates a vacant site inside the lattice structure.
This is also called Frenkel pair or Frenkel disorder.
If the leaving chemical species is an ion, it is usually a cation. This atom or
ion then occupy an interstitial site.
Frenkel defect does not have any effect on the density of the lattice. This is
because the leaving atoms or ions occupy a nearby position instead of
leaving the lattice completely. Then both the mass and volume of the lattice
remain unchanged.
The Frenkel defect is found mostly in ionic compounds. Unlike Schottky
defect, the Frenkel defect is found in lattices composed of atoms or ions
that have considerable differences between their sizes.
One or more atoms or ions may undergo Frenkel defect. Therefore, the
number of interstitial sites is equal to the number of defects present in the
lattice.
Here, the number of atoms present in the same volume is the same as it
was before the defect. Therefore, the density is the same. Some examples
for Frenkel defect are AgCl, AgI, CaF2 and ZnS.
5
6
 Line Defects

Dislocations are line imperfections in a perfect crystal.

They typically are introduced into a crystal during
solidification of the material or when the material is
deformed permanently.
Dislocations are particularly useful in explaining
deformation and strengthening in metallic materials.
Types of dislocations:
The edge dislocation, and
The screw dislocation.

7
 Line Defects – Cont’d
Edge Dislocation
An edge dislocation is created in a crystal by the insertion of an extra half
plane of atoms. The slip (Burgers) vector of the edge dislocation is
normal to the dislocation line.

Positive edge dislocation in a crystalline lattice. A linear defect occurs in the region just
above the inverted "tee,Т”, where an extra half plane of atoms has been wedged in
8
 Line Defects – Cont’d
The screw dislocation is Screw Dislocation
created by a cutting plane
undergoing upward and
downward shearing stresses.
A screw dislocation consists
of a spiral ramp of distorted
atoms and is represented by
a line in the drawing. The
extent of the distortion is not
defined but is at least several
atoms or more. The slip
(Burgers) vector of the screw
dislocation is parallel to the
dislocation line. 9
 Line Defects – Cont’d

Strain fields surrounding (a) an edge dislocation and (b) a screw dislocation.

10
 Surface Defects

Grain Boundaries

 Grain boundaries are interfacial imperfections in polycrystalline

materials that separate grains (crystals) of different
orientations.
 In metals, grain boundaries are created during solidification
when crystals formed from different nuclei grow
simultaneously and meet each other.
 The shape of the grain boundaries is determined by the
restrictions imposed by the growth of neighbouring grains.

11
 Surface Defects – Cont’d

Grains Grain Boundaries

12
Surface Defects – Cont’d

Optical Microscope 13
 Surface Defects – Cont’d

The effect of etching a polished surface of a steel metal sample on the microstructure
observed in the optical microscope, (a) In the as-polished condition no microstructural
features are observed, (b) After etching a very low-carbon steel, (c) After etching a
medium-carbon steel polished sample, dark (pearlite) and light (ferrite) regions are
observed in the microstructure. 14
Atomic Diffusion in Solids

1
 Outline

Atomic Diffusion in Solids

Why do we study diffusion?
What is diffusion?
Types of diffusion
Diffusion mechanisms
Activation Energy for Diffusion
Steady-state diffusion
Non-steady state diffusion
Technological applications of diffusion 2
 Why Do We Study Diffusion?

Materials of all types are often heat treated to

improve their properties.

The phenomena that occur during a heat treatment

almost always involve atomic diffusion.

Often, an enhancement of diffusion rate is desired.

On occasion measures are taken to reduce it.

3
 What Is Diffusion?

Diffusion can be defined as the mechanism by which matter is

transported through matter.
Atoms in gases, liquids, and solids are in constant motion and
migrate over a period of time. In gases atomic movement is
relatively rapid as indicated by the rapid movement of cooking
odours or smoke particles.
Atomic movements in liquids are in general slower than in
gases, as evidenced by the movement of coloured dye in liquid
water.
In solids atomic movements are restricted due to bonding to
equilibrium positions. However, thermal vibrations occurring in
solids do allow some atoms to move.

4
 What Is Diffusion? – Cont’d

Diffusion of atoms in metals and alloys is particularly important

since most solid-state reaction involve atomic movements. E.g.
Precipitation of second phase and nucleation and growth in
solid state.
The phenomena that occur during a heat treatment in most
cases involve atomic diffusion.

5
 What Is Diffusion? – Cont’d
Diffusion is the mechanism by which matter is transported through matter.
From an atomic perspective, diffusion is just the stepwise migration of atoms
from lattice site to another lattice site.

(a) (b)

(c)

(a) A Copper–nickel diffusion couple before a high-temperature heat treatment.

(b) Schematic representations of Cu (red circles) and Ni (blue circles) atom locations within
the diffusion couple.
(c) Concentrations of copper and nickel as a function of position across the couple. 6
 What Is Diffusion? – Cont’d

(a) (b)

(c)

(a) A copper–nickel diffusion couple after a high-temperature heat treatment,

showing the alloyed diffusion zone.
(b) Schematic representations of Cu (red circles) and Ni (blue circles) atom
locations within the couple.
(c) Concentrations of copper and nickel as a function of position across the
couple. 7
 Types of Diffusion

(1) Impurity diffusion or inter-diffusion: is a process in

which atoms of one metal diffuse into another.
(2) Self Diffusion: is a process in which atoms of the
same metal are exchanging positions.
Two conditions must be met for an atom to move:
(1) There must be an empty adjacent site (vacancy),
and
(2) The atom must have sufficient energy to break
bonds with its neighbour atoms and then cause
some lattice distortion during the displacement.

8
 Diffusion Mechanisms

Two mechanisms: vacancy and interstitial diffusion

1. Vacancy Diffusion
Which involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice
site or vacancy

9
 Diffusion Mechanisms – Cont’d

2. Interstitial Diffusion
The second type of diffusion involves atoms that migrate
from an interstitial position to a neighboring one that is
empty.

10
 Activation Energy for Diffusion
The activation energy Q is required to squeeze atoms
past one another during diffusion

11
 Activation Energy for Diffusion – Cont’d

A diffusing atom must squeeze past the surrounding atoms to reach its
new site.
In order for this to happen, energy must be supplied to allow the atom
to move to its new position, as shown schematically for vacancy and
interstitial diffusion.
The atom is originally in a low-energy, relatively stable location. In
order to move to a new location, the atom must overcome an energy
barrier. The energy barrier is the activation energy “Q”.
The thermal energy supplies atoms or ions with the energy needed to
exceed this barrier.
The activation energy “Q” is required to squeeze atoms past one
another during diffusion. Generally, more energy is required for a
substitutional atom than for an interstitial atom.

12
 Activation Energy for Diffusion – Cont’d

The activation energy for self-diffusion increases as the melting point of the
metal increases.
13
 Diffusion Flux
Diffusion flux (J), defined as the mass (or, equivalently, the number of
atoms) “M” diffusing through and perpendicular to a unit cross-sectional
area of solid per unit of time. This may be represented as:

where “A” denotes the area across which diffusion is occurring and “t” is the
elapsed diffusion time.
The units for “J” are kilograms or atoms per meter squared per second (kg/m2-s
or atoms/m2-s)

14
 Steady State Diffusion
Fick’s First Law: Diffusion flux for steady-state diffusion

(a) Steady-state diffusion across a thin plate.

(b) A linear concentration profile for the diffusion situation in (a) 15
 Steady State Diffusion – Cont’d

The mathematics of steady-state diffusion in a single (x) direction is

relatively simple, in that the flux is proportional to the concentration
gradient through the expression.
Steady state diffusion: the diffusion flux does not change with time, it
is concentration dependent.

Fick’s first law

The constant of proportionality “D” is called the diffusion coefficient,

which is expressed in square meters per second.
The negative sign in this expression indicates that the direction of
diffusion is down the concentration gradient, from a high to a low
concentration. 16
 Steady State Diffusion – Cont’d

Example:
A plate of iron is exposed to a carburizing (carbon-rich)
atmosphere on one side and a decarburizing (carbon-deficient)
atmosphere on the other side at 700 °C. If a condition of steady
state is achieved, calculate the diffusion flux of carbon through the
plate if the concentrations of carbon at positions of 5 and 10 mm
beneath the carburizing surface are 1.2 and 0.8 kg/m3, respectively.
Assume a diffusion coefficient of 3 *10-11 m2/s at this temperature.

17
 Non-Steady State Diffusion – Cont’d
Fick’s Second Law: Non-Steady-State Diffusion
Diffusion is time dependant and concentration gradient dependant.
Most practical diffusion situations are non-steady-state ones. That is,
the diffusion flux and the concentration gradient at some particular
point in a solid vary with time, with a net accumulation or depletion of
the diffusing species resulting.

Concentration profiles for non-steady-

state diffusion taken at three different
times: t1, t2, t3.
18
 Non-Steady State Diffusion – Cont’d
Solution of Fick’s Second Law
The solution of Fick`s second law in case of a gas diffusing into a solid is
given as the following:

Where Cs = Surface concentration of element in gas diffusing into the surface

C0= Initial uniform concentration of element in solid
Cx = the concentration at depth “x” from the surface at time “t”
X= distance from surface
D= diffusivity of diffusing solute( diffusion coefficient in m2 /sec)
t = time

19
Non-Steady State Diffusion – Cont’d
Tabulation of Error Function Values

20
 Non-Steady State Diffusion – Cont’d
Example:
Determine the carburizing time necessary to achieve a carbon
concentration of 0.45 wt% at a position 2 mm into an iron-carbon
alloy that initially contains 0.2 wt% C. the surface concentration is
to be maintained at 1.3 wt% C, and the treatment is to be
conducted at 1000 °C. Given that (D1273 K = 1.93 x 10-11 m²/s).

21
Non-Steady State Diffusion – Cont’d

22
 Dependence of D on Temperature

Since atomic diffusion involves atomic movements, it is to be expected

that increasing the temperature of a diffusion system will increase the
diffusion rate.
By experiment, it has been found that the temperature dependence
of the diffusion rate of many diffusion systems can be expressed by
the following Arrhenius type equation:

Where D = Diffusivity, m2 /s
D0= Proportionality constant m2 /s
Q= Activation energy of diffusing spices, J/mole
R= molar gas constant = 8.314 J/(mol. K)
T = Temperature, K 23
 Applications

Technological Applications of
Diffusion “Case hardening” or
“Carburizing”

Photograph of a steel gear that has

been “case hardened.”
The outer surface layer was
selectively hardened by a high-
temperature heat treatment during
which carbon from the surrounding
atmosphere diffused into the
surface.

24
 Heat Treatment

Dr. Marwa A. Abbas

Metallurgy and Materials Science dept.

abbas.marwa@outlook.com
Heat Treatment of Metals
• In general three kinds of treatments are: (i) Thermal (heat treatment), (ii)
Mechanical (working), (iii) Chemical (alteration of composition).
• A combination of these treatments are also possible (e.g. thermo-mechanical
treatments, thermo-chemical treatments).
• The treatment may affect the whole sample or only the surface.
• A typical industrial treatment cycle may be complicated with many steps (i.e. a
combination of the simple steps which are outlined in the chapter).c

Thermal (heat treatment)

e.g. heat and quench
Or a combination
Treatments Mechanical (Thermo-mechanical,
e.g. shot peening thermo-chemical)
e.g. case carburizing
Chemical
Bulk

Surface
Heat Treatment is the controlled heating and cooling of
metals to alter their physical and mechanical properties
without changing the product shape.

Common heat treatments:

• Softening
Softening is done to reduce strength or hardness, remove
residual stresses, improve toughness, restore ductility, refine
grain size or change the electromagnetic properties .

• Hardening
Hardening of steels is done to increase the strength and wear
properties. One of the pre-requisites for hardening is sufficient
carbon and alloy content. If there is sufficient Carbon content
then the steel can be directly hardened. Otherwise the surface of
the part has to be Carbon enriched using diffusion treatment
hardening techniques.
• Material Modification (Conditioning)
Heat treatment is used to modify properties of materials in
addition to hardening and softening. These processes modify
the behavior of the steels in a beneficial manner to maximize
service life, e.g., stress relieving, or strength properties,
e.g., cryogenic treatment, or some other desirable properties,
e.g., spring aging.
 1. Softening heat treatments
Annealing
• What does it do?
1. Reduce hardness
2. Remove residual stress (stress relief)
3. Improve toughness
4. Restore ductility
5. Refine grain size

Metals and alloys are usually annealed to reduce the hardness,

improve machinability, facilitate cold-working, produce a
desired microstructure.
• Process Steps: in Steels

1. Heat material into the austenite region–hold steel

for one hour for each one inch of thickness

2. Slowly furnace cool the steel – DO NOT QUENCH

3. Key slow cooling allows the C to precipitate out so

resulting structure is coarse pearlite with excess
ferrite

4. After annealing steel is quite soft and ductile

Full Annealing

 The purpose of this heat treatment is to obtain a material with high ductility. A microstructure
with coarse pearlite (i.e. pearlite having high interlamellar spacing) is endowed with such
properties.
 The range of temperatures used is given in the figure below.
 The steel is heated above A3 (for hypo-eutectoid steels) & A1 (for hyper-eutectoid steels) → (hold) → then the
steel is furnace cooled to obtain Coarse Pearlite.
 Coarse Pearlite has low (↓) Hardness but high (↑) Ductility.
 For hyper-eutectoid steels the heating is not done above Acm to avoid a continuous network of
proeutectoid cementite along prior Austenite grain boundaries (presence of cementite along grain boundaries
provides easy path for crack propagation).

910°C Acm
Ful
l An
A3 ne alin
g
723°C Full Annealing
A1

↑
T

Wt% C
0.8 %
Recrystallization Annealing

 During any cold working operation (e.g. cold rolling), the material becomes harder (due to
work hardening), but loses its ductility. This implies that to continue deformation the material
needs to be recrystallized (wherein strain free grains replace the ‘cold worked grains’).
 Hence, recrystallization annealing is used as an intermediate step in (cold) deformation
processing.
 To
Heat A1 →
belowthis
achieve theSufficient
sample is time →below
heated Recrystallization
A1 and held there for sufficient time for
recrystallization to be completed.

910°C Acm

A3

723°C
Recrystallization Annealing A1

↑
T

Wt% C
0.8 %
Spheroidization Annealing

 This is a very specific heat treatment given to high carbon steel requiring extensive
machining prior to final hardening & tempering. The main purpose of the treatment is to
increase the ductility of the sample.
 The treatment is done just below A1.
 Long time heating leads cementite plates to form cementite spheroids. The driving force for
this (microstructural) transformation is the reduction in interfacial energy.

910°C Acm

A3

723°C
Spheroidization A1

↑
T

Wt% C
0.8 %
 Annealing- Review
• The term annealing is a heat treatment in which a metal or
alloy is heated to a certain high temperature and held for a
certain period of time, followed by slow cooling.

• Annealing is used to reduce hardness, obtain a relatively

near stable microstructure, refine grain size, improve
machinability, and facilitate cold working.

• For hypoeutectoid steels, full annealing consists of heating to

10-40 C above the A3 temperature, and for hypereutectoid
steels, heating above the A1 temperature and followed, in
both cases, by very slow cooling. As a result of the very slow
cooling rates, the microstructure consists of coarse ferrite or
coarse ferrite plus pearlite, depending on the carbon and
alloy content of the steel.
• The temperature and the cooling rate determine the resultant
structure of the steel and hence the mechanical properties, as
illustrated in the time temperature transformation (TTT)
diagram.

Effect of the cooling rate

on microstructure
• To produce a steel in its softest possible condition with
minimum hardness and maximum ductility, it can be
spheroidized by heating just above or just below the A1
eutectoid temperature and then holding at that temperature
for an extended period of time.

• Spheroidizing can also be conducted by cyclic processing, in

which the temperature of the steel is cycled above and below
the A1 line. This process breaks down lamellar pearlite into
small pieces and forms small cementite spheroids through
diffusion in a continuous matrix of ferrite.
Microstructure of spheroidized steel
NORMALIZING

 The sample is heated above A3 | Acm to complete Austenization. The sample is then air cooled
to obtain Fine pearlite. Fine pearlite has a reasonably good hardness and ductility.
 In hypo-eutectoid steels normalizing is done 50°C above the annealing temperature.
 In hyper-eutectoid steels normalizing done above Acm → due to faster cooling, cementite
does not form a continuous film along GB.

910°C at ion Acm

No a liz
rma rm
liz a tio No
A3
n

723°C
A1

↑
T

Wt% C
0.8 %
Refine grain structure prior to hardening

Purposes To harden the steel slightly

To reduce segregation in casting or forgings

 The effect of cold work on the mechanical
properties of copper

There is a maximum amount of cold work or deformation that we

can perform on a metallic material before it becomes too brittle and
breaks.
 Annealing
• Annealing is a heat treatment used to eliminate some or all
of the effects of cold working.
• Annealing at a low temperature may be used to eliminate
the residual stresses produced during cold working
without affecting the mechanical properties of the finished
part.
• Annealing may be used to completely eliminate the strain
hardening achieved during cold working. In this case, the
final part is soft and ductile but still has a good surface
finish and dimensional accuracy.
• By combining repeated cycles of cold working and
annealing, large total deformations may be achieved.
 Three stages of Annealing

The effect of annealing temperature on the microstructure of cold-worked metals.

(a) cold-worked, (b) after recovery, (c) after recrystallization, and (d) after grain
growth.
Photomicrographs showing the effect of annealing temperature on grain size
in brass. Twin boundaries can also be observed in the structures. (a) Annealed at
400C, (b) annealed at 650C, and (c) annealed at 800C.
(Adapted from Brick, R. and Phillips, A., The Structure and Properties of Alloys,
1949: McGraw-Hill.)
Control of Annealing
 Design of a Process to Produce Copper Strip

We wish to produce a 0.1-cm-thick, 6-cm-wide copper strip

having at least 60,000 psi yield strength and at least 5%
elongation. We are able to purchase 6-cm-wide strip only in
thicknesses of 5 cm. Design a process to produce the product.
 Design of a Process to Produce Copper Strip

Solution:
𝑥𝑥 − 0.1
% CW = 40% .4 = X= 0.167 cm
𝑥𝑥
𝑥𝑥 − 0.1
% CW = 45% .45 = X= 0.182 cm
𝑥𝑥
Therefore, the starting thickness must be between 0.167 cm
and 0.182 cm, and this starting material must be as soft as
possible— i.e. in the annealed condition.

But can we successfully cold work from 5 cm to 0.182 cm?

 5 −0.182
% CW = * 100 = 96.4 %
5
A maximum of about 90% cold work is permitted. Therefore,
we must do a series of cold work and anneal cycles.

For example:
1. Cold work the 5-cm strip 80% to 1 cm:
5 −𝑥𝑥1
80% = *100 → x1 = 1 cm
5

2. Anneal the 1-cm strip to restore the ductility.

If we don’t know the recrystallization temperature, we can use the 0.4Tm

relationship to provide an estimate. The melting point of copper is 1085 °C:

Tr = 270 ° C
3. Cold work the 1-cm-thick strip to 0.182 cm:
1 −0.182
% CW = * 100 = 81.8 %
1

4. Again anneal the copper at 270 °C to restore ductility.

5. Finally cold work 45%, from 0.182 cm to the final dimension

of 0.1 cm.

This process gives the correct final dimensions and properties.