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Introduction to Materials Science

and Engineering

Dr. Ranjit Bauri


Department of Metallurgical & Materials Engineering
IIT Madras, Chennai 600 036
The objective of Materials Science Study

At some point of time or the other an engineering problem


involves issues related to material selection. Understanding
the behavior of materials, particularly structure-property
correlation, will help selecting suitable materials for a
particular application.
The objective of studying materials science is to develop
this understanding .
Objective and Scope of the present course
Primary objective is to present the basic fundamentals of
materials science and engineering.
Expose the reader community to different classes of
materials, their properties, structures and imperfections
present in them.
Help understand the subject with ease by presenting the
content in a simplified and logical sequence at a level
appropriate for students/teachers/researchers.
Aid the teaching learning process through relevant
illustrations, animations, web content and practical examples.
Highlight important concepts for each topic covered in the
subject
Provide opportunity of self-evaluation on the understanding
of the subject matter.
Historical perspective

Materials Science
and
Human Civilization
Materials in day to day life
What would life be like without Materials??
Materials: The Milestones of Progress
Development and advancement of Human societies-
closely related with materials
Civilizations have been named based on the level of their
materials development Stone age, Bronze age etc.
Quest for newer materials:
The driving force for the progress- stone age to IT age

Quest for more advanced materials to meet the growing


needs as the civilization progressed.
A look at the history of materials chronologically clearly
reveals this
Stone age
Stone age People living in caves and
hunting with stone-made weapons

200,000 BC Discovery of fire Said to be the most


significant discovery in human civilization.
However, till the time the fire was controlled
to contain and utilize the heat, it was not
significant.

Containing the fire Was not possible


without materials. Started with clay (a
ceramic material) pots and now we have all
kinds of means to control and contain fire.
Introduction of metals

First metals to be discovered Copper and Gold

Material processing - Annealing and Shaping.


Throwing copper into camp fire and hammering
in early days

Melting and casting of metals. Melting of Gold


to give it different shapes

Reduction of copper from its ore Nile Valley


The dawn of metallurgy.
Perhaps discovered by chance much before by
early potters
Discovery of Alloy - Metal Combinations

The discovery of alloy combination of metals

Mixing of Tin with Copper Bronze


Copper ore invariably contains some Tin Mixing of
different ores having different Tin content produced the first
Bronzes.
Iron and Steel Building blocks of human civilization

Iron wheels discovery of iron making.


Revolution in warfare and cultivation

Invention of Blast furnace Production of pig iron


from ores

Sir Henry Bessemer (1813-1898)


Bessemer steel making patent
Many other steel making processes LD,
20th Century
Electric Arc, VAR for making high quality
steels
Early 20th Century The golden era

Hall process- Electrochemical process for


extraction of Aluminium from Alumina (Al2O3)

Revolution in Transportation Discovery


1890 - 1910 AD
of automobiles and Aero plane

Process for making Nylon Introduction of


plastics
The Electronic revolution

Zone refining A metallurgical


process to produce ultra pure Si

Ultra pure Si through zone refining Si


chip, the heart of electronics. Smaller and
smaller Si wafers - Miniaturization
Superconductors

High temperature ceramic MRI Machine, Brain Scan


superconductors Advancement in Medical science

Magnetic Levitation: Maglev train :


300 500 kmph
(See Lecture # 15)
Further reading

http://neon.mems.cmu.edu/cramb/Processing/history.html
http://materialiaindica.wordpress.com/2009/02/16/a-brief-
history-of-materials1metallurgical-heritage-of-india/

Key words: History of materials science; Material development;


Progress of human civilization
The Impact of Materials on
Progress
Revolution in Transportation
Road Transport in the 18th and a major part of 19th century
was mainly horse carriages.
By 1890 we had Copper, Bronze, Iron, Steel , Aluminum
and Rubber in addition to Wood. This paved the way for
series of inventions leading to a paradigm shift in the road
transport from horse carriages to motorized vehicles
Karl Benz in Germany came up with a viable motor
vehicle called Velo in 1894
Ford Motors made the first assembly line for mass
production of commercial vehicles
The Ford T-model was the first successful and affordable
commercial vehicle
Materials had a very important role to play in this
transformation from Velo or T to modern cars (see the next
slide)
Automobile and Materials
We have come of ages, developed new materials and
technologies based on them

The application of these materials has led to the modern


day cars
Automobile and Materials
Engine and Interior
From Cast iron blocks to more compact, lighter and
powerful engine blocks Material development has made it
all possible
Engine components are traditionally made from ferrous
alloys. Emphasis on weight reduction for higher fuel
efficiency has increased usage of aluminum for cylinder
blocks, cylinder heads, and other engine components.
Some engine covers and intake manifolds are made of
magnesium. Titanium is also used in high-speed engines
connecting rods to reduce reciprocating mass.
Materials like synthetic rubber, variety of polymers, foams
have provided new dimension and aesthetic look to
automotive interiors
Invention of Aeroplane
From Wright Brothers invention in 1902 To todays Aircraft
Materials played a very important role in this case also
Use of advanced materials - Stronger, lighter and better
aerodynamic design, greater speed.
Boeing 777, for example, used 75% aluminum whereas half
of the materials used in the advanced version 787 is fiber
reinforced composite.
Total materials used by weight

Boeing 777 (Source: Boeing) Boeing 787


Impact of Materials
As the aircraft design improved, the load on the engine and
hence, its operating temperature also increased.
Need of materials that can sustain such harsh conditions.
The advent of High-temperature materials (Ni base super
alloys) has made it possible.
(www.cmse.ed.ac.uk/AdvMat45/SuperEng.pdf)
Waterways Transport and Safety
RMS Titanic, a classic example
On its maiden voyage from Southampton, UK to New York
city, RMS titanic sank in the North Atlantic on April 15, 1912
on colliding with an iceberg
An analysis done on the hull steel years later provided the
materials aspects of this tragedy.
The hull of the ship was made of riveted steel plates
The quality and the composition of the steel is crucial for
the required properties and performance.

Hull made of Riveted


steel plates

Rivet joint
Metallurgical aspects of failure

Poor Steel quality, high S and P and low Mn:S ratio


A metallurgical analysis done on the hull steel revealed a
Mn:S ratio of 6.8:1 which was too low compared to a quality
steel like ASTM A36 (Mn:S 15:1)
Low Mn:S ratio cannot remove the sulfur from steel
As a result sulphides form. The brittle sulfides reduces the
impact properties
At lower temperature metals and alloys loose their ductility
and becomes brittle Ductile to Brittle Transition
Temperature (DBTT) is the deciding factor
Failure analysis
Formation of brittle sulphide inclusions due to Low Mn:S
ratio
High Ductile to brittle transition temperature (DBTT)
The steel became very brittle at low temperature
Impact property testing of the titanic steel exhibited brittle
behavior.
Brittle fracture on collision with ice berg in the chilling
water temperature (-2 C at the time of collision).
Breakage of ship and sinking
The modern cruise ship
Modern cruise: As or more Luxurious as Titanic
Use of advanced materials such as fiber reinforced
composite (FRP), laminated composites, high-strength steels,
non-ferrous alloys
Better safety due to improved design and materials used
therein combined with advanced navigation system
The Electronics Revolution
Silicon the heart of every electronic component
Before invention of the Si chip Electro-mechanical
computers were developed
Harvard MarkI Electro-mechanical computer, 1940 5 tons,
8 x 51 feet and 500 miles of wire
IBM Computer,1959, 33 feet long
Invention of a metallurgical process, Zone refining, that can
produce high purity Si led to the development of
semiconductor chips.
Development of smaller and smaller Si chips helped
miniaturization that led to todays computers
Communication and Entertainment
Smaller and smaller microchips have brought the whole
world on our palm top

The advent of new electronic, optical and optoelectronic


materials has given new dimension to entertainment
Further reading

Katherine Felkins et al. The Royal Mail Ship Titanic: Did a


Metallurgical Failure Cause a Night to Remember? JOM
50 (1) (1998) 12-18
Zygmont, Jeffrey Microchip: An Idea, Its Genesis, and The
Revolution It Created (Cambridge, MA: Perseus, 2003).
http://www.computersciencelab.com/ComputerHistory/Hist
oryPt3.htm

Key words: Role of Materials; Impact on progress;


Transportation and Electronic revolution
Materials Science
What is Materials Science??

Material Science Tetrahedron


Material Science can be broadly defined as correlation
between microstructure and properties.
The Materials Science Tetrahedron :-
Microstructure depends on the processing route while
performance is dictated by properties.
Materials Science and Engineering (MSE)

Physics
Technology Chemistry

Engineering MSE Maths

Medicals Geology
Biology

Materials Science is an interdisciplinary area where


many science and engineering streams merge together
Atomic structure
In order to understand the structure of materials and its
correlation to property, we have to start form the basic
element of matter The Atom
An atom consists of a nucleus composed of protons and
neutrons and electrons which encircle the nucleus.
Protons and electrons have same and opposite charge of
1.6 x 10-19 C.
Atomic number (Z) = Number protons = number of electrons.
Atomic mass (A) = proton mass + neutron mass.
Isotopes are the same element having different atomic
masses. Number of protons in isotopes remains same while
number of neutrons varies.
Atomic structure

Atomic mass unit (amu) = 1/12 mass of Carbon 12 (12C)

1 mol of substance contains 6.023 x 1023 (Avogadros


number) atoms or molecules.

Atomic weight = 1 amu/atom (or molecule) = 1 g/mol = Wt.


of 6.023 x 1023 atoms or molecules.

For example, atomic weight of copper is 63.54 amu/atom


or 63.54 g/mole
Atomic structure
The Bohr Model

(a) (b)

Electrons revolve around a positively charged nucleus in


discrete orbits (K, L, M or n=1, 2, 3 respectively) with specific
levels of energy.
Electrons positions are fixed as such, however, an electron
can jump to higher or lower energy level by absorption or
emission of energy respectively as shown in Fig. (b)
Atomic structure
Limitations of the Bohr Model

Although the Bohrs model was the first and best model
available at the time of its discovery, it had certain limitations
and could not explain many phenomena involving electrons.
Heisenbergs uncertainty principle:
The position and momentum of an electron can not be
determined simultaneously.
This also disapproves the hypothesis in the Bohr model
that electrons revolve around certain circular orbits.
Wave-Mechanical Model
The wave-mechanical or wave-particle model was
proposed to address the limitations in the Bohr model.

The basic premise of this model is the wave-particle


duality of electrons i.e. electrons are considered to have
both wave-like and particle-like characteristics.

The position of an electron is defined as the probability


of finding it at different locations in an electron cloud
around the nucleus i.e. position of an electron is described
by a probability distribution instead of discrete orbits.
Wave-Mechanics Model
Probability distribution of
electrons

The Bohr radius, r =

Probability of finding an electron


is maximum at the Bohr radius

Probability distribution vs. distance from nucleus


Quantum numbers
Four parameters or numbers called Quantum numbers are
needed to describe the distribution and position of electrons
in an atom.
The first three of them (n, l, ml) describe the size, shape,
and spatial orientation of the probability density distribution
of electrons .
Principal quantum number, n
It describes electron shells as shown in the Bohr model.
Values of n can be 1, 2, 3, 4 corresponding to electron
shells K, L, M, N ..
The value of n also determines the size or distance of the
shells from the nucleus.
Number of electrons in a shell = 2n2.e.g. number of electrons
in K shell (n =1)= 2. 12 = 2, L shell (n =2) 8 (2. 22) and so on
Quantumnumbers
Azimuthal or Angular quantum number, l
It signifies subshell or electron orbital s, p, d, f and so on.
l can take values of from 0 to n-1. K shell, n = 1, one s
orbital. L , n =2, two orbitals, s, p. M, n =3, three orbitals s, p,
d. N, n =4, four orbitals s, p, d, f and so on.
The value of l decides the shape of the orbital as shown in the
figure below. s orbital (l = 0) spherical, p (l = 1) polar or
dumbbell shaped, d (l =2 ) double-dumbbell shaped
Quantum numbers
Magnetic quantum number, ml
Orbitals are associated with energy states. Magnetic
quantum number determines the number of energy states in
each orbital.
This number depends on the value of l . ml Can take values
from l to + l e.g. l = 1 (p orbital) ml = -1, 0, +1 ( three
states). Only one state for the s orbital (l = 0), as ml can take
only one value (0). In general no. of states = 2 l +1

Orbital s p d f
No. of states 1 3 5 7
Quantum numbers
Spin quantum number, ms
Each electron is associated with a spin moment. The fourth
quantum number, ms is related to this spin moment of
electrons. It can have only two values, + and

Paulis exclusion principle:


It states that not more than two electrons having opposite
spin can occupy the same energy state.
Based on this principle, number of electrons in different
orbitals (s, p, d .) can be obtained. For example, s orbital
has only one energy state, so it can accommodate only
two electrons having opposite spins.
Electron Configuration
The quantum mechanic principles as discussed before allow
determination of electron configuration i.e. the manner in
which electron states are occupied in a given atom.
n 1
2(2l 1)
l 0

Electron configuration based on quantum n 1


numbers. Total
number of electrons in a shell is 2n2 or 2(2l 1)
l 0
Electron Configuration
The manner or sequence of filling of electron orbitals is
decided a by a set of two principles/rules:

1. Aufbau (German meaning building up) principle


It states that lower energy states will be filled up first.

2. Madelungs rule:
Orbitals fill in the order of increasing (n+l). 4s (n+l = 4+0 = 4)
will be filled before 3d (n+l = 3+2 = 5) and 5s (n+l = 5+0 = 5)

For orbital with same values of (n+l), the one with lower
n will be filled first. 3d will be filled before 4p
Electron Configuration
The Aufbau principle and Madelung rule

Aufbau principle
Madelung rule
Electron Configuration
Based on the foregoing discussion, it is now possible to find
the electron configuration for a given atom. For example,

Sodium, ( Na 11
23 ) has 11 electrons the configuration is
shown in the first figure. The second picture shows the Bohr
configuration.
11
Na
23

Valence electrons
The electrons in the outer most shell are known as valence
electrons. Na has one valence electron (the 3s electron).
These electrons are responsible for chemical reaction and
atomic bonding
Electron configuration of elements
Atomic Symbol Electron Atomic Symbol Electron Atomic Symbol Electron
No. configuration No. configuration No. configuration
1 H 1s1 21 Sc [Ar] 4s23d1 41 Nb [Kr] 5s14d4
2 He 1s2 22 Ti [Ar] 4s23d2 42 Mo [Kr] 5s14d5
3 Li [He] 2s1 23 V [Ar] 4s23d3 43 Tc [Kr] 5s24d5
4 Be [He] 2s2 24 Cr [Ar] 4s13d5 44 Ru [Kr] 5s14d7
5 B [He] 2s22p1 25 Mn [Ar] 4s23d5 45 Rh [Kr] 5s14d8
6 C [He] 2s22p2 26 Fe [Ar] 4s23d6 46 Pd [Kr] 4d10
7 N [He] 2s22p3 27 Co [Ar] 4s23d7 47 Ag [Kr] 5s14d10
8 O [He] 2s22p4 28 Ni [Ar] 4s23d8 48 Cd [Kr] 5s24d10
9 F [He] 2s22p5 29 Cu [Ar] 4s13d10 49 In [Kr] 5s24d105p1
10 Ne [He] 2s22p6 30 Zn [Ar] 4s23d10 50 Sn [Kr] 5s24d105p2
11 Na [Ne] 3s1 31 Ga [Ar] 4s23d104p1 51 Sb [Kr] 5s24d105p3
12 Mg [Ne] 3s2 32 Ge [Ar] 4s23d104p2 52 Te [Kr] 5s24d105p4
13 Al [Ne] 3s23p1 33 As [Ar] 4s23d104p3 53 I [Kr] 5s24d105p5
14 Si [Ne] 3s23p2 34 Se [Ar] 4s23d104p4 54 Xe [Kr] 5s24d105p6
15 P [Ne] 3s23p3 35 Br [Ar] 4s23d104p5 55 Cs [Xe] 6s1
16 S [Ne] 3s23p4 36 Kr [Ar] 4s23d104p6 56 Ba [Xe] 6s2
17 Cl [Ne] 3s23p5 37 Rb [Kr] 5s1 57 La [Xe] 6s25d1
18 Ar [Ne] 3s23p6 38 Sr [Kr] 5s2 58 Ce [Xe] 6s24f15d1
19 K [Ar] 4s1 39 Y [Kr] 5s24d1 59 Pr [Xe] 6s24f3
20 Ca [Ar] 4s2 40 Zr [Kr] 5s24d2 60 Nd [Xe] 6s24f4
Stable Configuration
Look at the electron configuration of inert gases (He, Ne, Ar,
Kr, Xe) in the previous table. Their valence electron cell is
completely filled unlike any other element.

Argon (Ar) for example has 18 electrons and 3s and 3p


orbitals of its valence shell are completely filled.
This is known as stable configuration. Since it is the lowest
energy configuration, the valence electrons do not take part
in any chemical reaction and hence, the inertness.
See the structure-property correlation here
Electron Configuration

Note that the configuration of higher atomic number


elements can be expressed by the previous inert element
configuration (see the previous table)

It is the tendency of every element to attain the lowest


energy stable configuration that forms the basis of chemical
reactions and atomic bonding
Atomic Bonding
Atomic interaction

(a)

When two neutral atoms are brought close to each other,


they experience attractive and or repulsive force
Attractive force is due to electrostatic attraction between
electrons of one atom and the nucleus of the other.
Atomic interaction
Repulsive force arises due to repulsion between electrons
and nuclei of the atoms.

The net force, FN (Fig. a), acting on the atoms is the


summation of attractive and repulsive forces.

The distance, at which the attraction and repulsion forces


are equal and the net force is zero, is the equilibrium
interatomic distance, ro. The atoms have lowest energy at
this position.

Attraction is predominant above ro and repulsion is


dominant below ro (see Fig. a).
Atomic interaction
Lennard-Jones potential

(b)

The interaction energy between the pair of atoms is given by


the Lennard-Jones potential, Vr or VLJ
1
2

6
VL



Atomic interaction
is the distance at which the interaction energy is zero. is
the depth of the potential well (see Fig. b) and is a measure of
the bonding energy between two atoms.

L-J potential can be also expressed in the simplified form as


VLJ = A/r12 B/r6 and hence, is also known as 6-12 potential.

A/r12 is predominant at short distances and hence,


represents the short-range repulsive potential due to overlap
of electron orbitals and B/r6 is dominant at longer distance
and hence, is the long range attractive potential.
Atomic Bonding
The mechanisms of bonding between the atoms are
based on the foregoing discussion on electrostatic inter-
atomic interaction.
The types of bond and bond strength are determined by
the electronic structures of the atoms involved.
The valence electrons take part in bonding. The atoms
involved acquire, loose or share valence electrons to
achieve the lowest energy or stable configuration of noble
gases.
Atomic bonding can be broadly classified as i) primary
bonding ii) secondary bonding
Atomic Bonding
Primary Bonds
Three types primary bonds are found in solids

oIonic
oCovalent
oMetallic

Majority of the engineering materials consist of one of these


bonds. Many properties of the materials depend on the
specific kind of bond and the bond energy.
Ionic Bond
Ionic bonds are generally found in compounds composed of
metal and non-metal and arise out of electrostatic attraction
between oppositely charged atoms (ions).

Number of electron in outer shell is 1 in Na and 7 in Cl .


Therefore, Na will tend to reject one electron to get stable
configuration of Ne and Cl will accept one electron to obtain
Ar configuration. The columbic attraction between Na+ and
Clions thus formed will make an ionic bond to produce NaCl.
Some other examples are CaF2, CsCl , MgO, Al2O3.
Covalent Bond
In this type of bonding, atoms share their valence electrons
to get a stable configuration.
Methane (CH4): Four hydrogen atoms share their valence
electrons with one carbon atom and the carbon atom in turn
shares one valence electron with each of the four hydrogen
atoms. In the process both H and C atoms get stable
configuration and form a covalent bond.
Covalent bond

Covalent bonds are formed between atoms of similar


electronegativity.

C atoms in diamond are covalently bonded to each other.

Si also has valency of four and forms SiC through


covalent bonding with C atoms.
Metallic Bond
In metals the valence electrons are not really bound to one
particular atom, instead they form a sea or cloud of valence
electrons which are shared by all the atoms. The remaining
electrons and the nuclei form what is called the ion core
which is positively charged. The metallic bond arises out of
the columbic attraction between these two oppositely
charged species the electron cloud and the ion cores.

Electrons
sea
Ion core
Characteristics of primary bonds
Structure-property correlation
Ionic and covalent bonds posses high bond energy
450 1000 kJ/mole
High bond strength in ionic and covalent solids results in
high melting point, high strength and hardness. e.g. diamond
As the electrons are tightly bound to the atoms they are
generally poor conductors of heat and electricity
Are brittle in nature
Most of the ceramics consist of covalent (SiC) or ionic bonds
(Al2O3) or a mix of both and hence, exhibit all the properties
described above.
Structure-property correlation
Metallic bonds on the other hand provide good thermal and
electrical conductivities as the valence electrons are free to
move.
The metallic bond energy is 68 kJ/mol (Hg) on the lower
side and 850 kJ/mol (W, tungsten) on the higher side.
Bond strength increases with atomic number as more
electrons are available to form the bonds with the ion cores.
As a result melting point, hardness and strength increases
with atomic number.
Metals are ductile as the free moving electrons provides
agility to the bonds and allows plastic deformation.
Secondary Bonds
Van der Waals bonding
Van der Waals bonding between molecules or atoms arise
due to weak attraction forces between dipoles

The natural oscillation of atoms leading to momentary


break down of charge symmetry can generate temporary
dipoles

Dipoles can induce dipoles and attraction between


opposites ends of the dipoles leads to weak bonding
Van der Waals Bonding

An ion can also induce a dipole

Some molecules like HCl have permanent dipoles due


to asymmetrical arrangement of +ve and ve charges.

Van der Waals bonding is much weaker compared to


primary bonds. Bond energy lies in the range of 2 10
kJ/mol.

Molecules in liquid and gas are held by weak Van der


Waals forces
Van der Waals bonds
The atomic layers in graphite are held together by weak
van der Waals bonds. Therefore, the layers can move easily
over each other and this imparts the lubricating property
graphite is known for.
Hydrogen bonding
Hydrogen bond is a type of secondary bond found in
molecules containing hydrogen as a constituent.
The bond originates from electrostatic interaction between
hydrogen and another atom of high electronegativity such
as fluorine or oxygen.
The strength of hydrogen bonds is in the range of 10 - 50
kJ/mol.
Water molecules, for example, are connected by hydrogen
bonds (dashed lines in the picture).

H 2O
Evaluation and Examples
At this point one should be able to

Understand two quantum mechanics models of atomic


structure and their fundamental differences.

Understand quantum numbers and their significance.

Find out electronic configuration of a given element.

Understand atomic interactions and different types of


atomic bonding.
Explain some properties based on atomic bonding

Some examples are given next for further assistance


Examples
Example 1. How many Fe atoms are there in 1 g of Fe?
Solution: Atomic mass of Fe = 55.85 g/mol.
1 mol of substance has 6.023 x 1023 atoms (Avogadros
number).
Therefore, 1 mol or 55.85 g of Fe has 6.023 x 1023 atoms.
Hence, 1 g Fe has (6.023 x 1023) 55.85 = 10.78 x 1021
atoms

Example 2. Find the electronic configuration of Lead (Pb82)


Solution: Atomic number of Pb = 82. No. of electrons is 82.
The noble gas closest to Pb is Xe (54 [Kr]4d105s25p6).
Therefore electronic configuration of Pb can be expressed as
[Xe] 4f14 5d10 6s2 6p2
Examples
Example 3: What is the attractive force between Na+ and
Cl- ions just touching each other?
Solution:
Fattractive = -(Z1Z2e2)/4oro. Z1 and Z2 are valency of the ions
(+1 for Na and -1 for Cl), ro is the interatomic separation, e
is the charge of an electron (1.60 x 10-19 C) and o is the
permittivity of vacuum (8.85 x 10-12 F/m)
As the ions just touch each other, ro is the sum of the radii
of the ions.
Ionic radius of Na and Cl are 0.095 nm and 0.181 nm
respectively.
Substituting these values in the equation will yield
Fattractive = 3.02 x 10-9 N
Quiz
1. What is Materials science? What is material science
tetrahedron?
2. What is atomic mass unit (amu)?
3. Briefly describe the Bohr atomic model.
4. Find out the Bohr radius for an hydrogen atom (see slide #8).
5. What is wave-particle duality? Briefly explain the wave
mechanical model of atomic structure.
6. What is Heisenbergs uncertainty principle?
7. What is Paulis exclusion principle
8. What are Aufbau and Madelung rules?
9. Show that energy of an electron in hydrogen atom E =
22me4/n2h2 = - 13.6/n2 eV
Clue: Refer to slide #8, equate centrifugal force of the electron,
mv2/r to Coulomb force keZe2/r2 (ke = 1/4o), Energy is the sum
of kinetic energy and the attractive energy.
Quiz
10. What is stable electron configuration?
11. Why are noble gases inert?
12. What is Lennard-Jones potential?
13. Briefly explain the primary bonds in solids.
14. How do secondary bonds form? What is hydrogen bond?
15. Why is graphite lubricating?
16. Why are ceramics hard and brittle? Why are they not
conductive?
17. Why is boiling point of methane (CH4) lower than water?
18. How many atoms are there in 1 g of copper?
19. Write the electron configuration of tungsten (74)
20. Why is Tungsten (74) much stronger than Aluminium (13)
though both are metallic?
21. Calculate the attractive force between two K+ and Br- ions
that just touch each other. Atomic radii of K+ and Br- are 0.133
and 0.196 nm respectively.
Quiz
22. If the attractive force between a pair of Cs+ and I- ions is
2.83 x 10-9 N and the ionic radius of Cs+ is 0.165 nm, what is
the ionic radius of I- ion?
23. Calculate the attractive force between a pair of Ba2+ and S2-
ions which just touch each other. Ionic radius of Ba and S are
0.143 nm and 0.174 nm respectively. o = 8.85 x 10-12 C2/N.m2
24. Does the size of Na and Cl atoms remain same when they
react to from NaCl? Give reasons for your answer.
25.If energy of an electron, E = - 13.6/n2 eV, find out the energy,
wavelength and frequency of the photon emitted for a jump from
M to L shell. h = 4.14 x 10-15 eV.s
References
http://www.virginia.edu/bohr/mse209/chapter2.htm
http://www.chemguide.co.uk/atommenu.html
http://www.youtube.com/watch?v=QqjcCvzWwww
http://phet.colorado.edu/en/simulation/atomic-interactions

Key words: Materials tetrahedron; Atomic structure; Bohr


model; Quantum numbers; Atomic bonding; Ionic, Covalent,
Metallic bonding; Van der Waals bonds
Crystal Structure
Preface
Crystal structure is one of the most important aspects of
materials science and engineering as many properties of
materials depend on their crystal structures. The basic
principles of many materials characterization techniques
such as X-ray diffraction (XRD), Transmission electron
microscopy (TEM) are based on crystallography. Therefore,
understanding the basics of crystal structures is of
paramount importance.
Atomic arrangement
Solid

Crystalline Amorphous

Crystalline periodic arrangement of atoms: definite


repetitive pattern
Non-crystalline or Amorphous random arrangement of
atoms.
The periodicity of atoms in crystalline solids can be
described by a network of points in space called lattice.
Space lattice
A space lattice can be defined as a three dimensional array
of points, each of which has identical surroundings.
If the periodicity along a line is a, then position of any point
along the line can be obtained by a simple translation, ru = ua.
Similarly ruv = ua + vb will repeat the point along a 2D plane,
where u and v are integers.
a

b
Symmetry
Symmetry
Symmetry refers to certain pattern or arrangement. A body is
symmetrical when it is reproduced by certain operation.

The symmetry word (somewhat distorted) itself shows 2-fold


rotation symmetry (restored by 180o rotation)
In the picture below the plane looks identical after a 90o
rotation. The plane has 4 fold rotation symmetry as it repeats
itself 4 times (shown by the red dot) in a full 360o rotation.
Symmetry operations

1. Translation
2. Rotation
3. Reflection
4. Inversion
Translation
uT

The first point is repeated at equal distances along a line by a


translation uT, where T is the translation vector and u is an
integer.

Translation on a point with coordinates xyz x+a y+b z+c


where, a, b and c are the unit vectors in x, y and z directions
respectively.
Symmetry operations
Rotation
A rotation can be applied on the translation vector T in all
directions, clock or anti-clock wise, through equal angles
in the 2D space.
If two rotation operations, one each in clock and anti-clock
direction, are applied on the translation vector T, it will
create two more lattice points. Because of the regular
pattern, the translation between these two points will be
some multiple of T (pT).


Symmetry operations
Rotation
T = T cos + pT + T cos = pT +2T cos
T T cos = (1 p)/2

p n-fold Symbol
pT 0 60 6
Tcos Tcos 1 90 4
T
2 120 3
3 180 2
-1 0/360 1

An n-fold rotation symmetry means rotation through an


angle of 2/n will repeat the object or motif n times in a full
360o rotation. n =1 means no symmetry.
Rotation
1-Fold Rotation Axis - An object that
requires rotation of a full 360o to repeat
itself has no rotational symmetry.

2-fold Rotation Axis - If an object appears identical after


a rotation of 180o, that is twice in a 360o rotation, then it is
said to have a 2-fold (2/180) rotation symmetry

2 2 2
Rotation
Similarly we have 3, 4 and 6-fold rotational symmetry

3 fold 2/120

4 fold 2/90

6 fold 2/60
Rotation
Is it possible to have 5, 7 or 8-fold rotation symmetry?
Objects with 5, 7 and 8 or higher order symmetry do exist in
nature, e.g. star fish (5-fold), flowers with 5 or 8-fold symmetry.

However, these are not possible in crystallography as they


cannot fill the space completely

5 fold 8 fold
Reflection or Mirror symmetry
An object with a reflection symmetry will be a mirror image of
itself across a plane called mirror plane (m).

y
-xy xy
m

Reflection operation: xyz -x y z (x y z ) across a mirror


plane perpendicular to x axis
Symmetry and Space lattice
Symmetry elements discussed so far define five types of 2D
space lattices. When a translation is applied to the third
direction these lattices create a total of 7 crystal systems.

2-fold 3, 6-fold
a2
Parallelogram Hexagonal

a1 a2, = Any a1 = a2, = 120
a1

4-fold: Square Centered-Rectangular Primitive-Rectangular


a1 = a2, = 90 a1 a2, = 90 a1 a2, = 90
Inversion Center of symmetry
In this operation, every part of the object is reflected through
an inversion center called center of symmetry which is
denoted as i. The object is reproduced inverted from its
original position.
1 4

2 5
6 i 3
i i
3 6
5 2

4 1
i
xyz -x -y -z (xyz)
Combined operations
Combined symmetry operations also exist. For example,
rotation can be combined with inversion which is called
roto-inversion. The roto-inversion axis is denoted as n.
For example, a 6-fold roto-inversion (6 ) involves rotating
the object by 60o (360/6), and inverting through a symmetry
center.
6

Inversion
center

Rotation axis
Point and Space groups
Symmetry operations generate a variety of arrangements of
lattice points in three dimensions. There are 32 unique ways
in which lattice points can be arranged in space. These
non-translation elements are called point-groups.

A large number of 3D structures are generated when


translations [linear translation, translation + reflection (glide
plane) and translation + rotation (screw axis)] are applied to
the point groups. There are 230 unique shapes which can
be generated this way. These are called space groups.
Hermann-Mauguin Symbols
The 32 point groups are denoted by notations called
Hermann-Mauguin symbols. These symbols basically
describe the unique symmetry elements present in a body.
The shape in Fig.(a) contains 1 4-fold axis, 4 2-fold axes, 5
mirror planes. 3 mirror planes and 2 2-fold axes are unique as
others can be produced by a symmetry operation. Therefore,
point group symbol for this shape is 4/m2/m2/m. The /
between 4 or 2 and m indicates that they are perpendicular to
each other.

m
m

4/m2/m2/m (b)
(a)
2/m2/m2/m
Summary
Space lattice is arrangement of points with each point having
exactly same surroundings.
Symmetry operations restore a body to its original position.
There are four symmetry operations Translation, reflection,
rotation and inversion.
There are 32 point groups and 230 space groups.
Hermann-Mauguin symbols are used to denote point groups.

References
http://www.tulane.edu/~sanelson/eens211/index.html#Lecture
Notes
http://www.tulane.edu/~sanelson/eens211/introsymmetry.pdf
http://www.tulane.edu/~sanelson/eens211/32crystalclass.pdf
Crystal Systems
The space lattice points in a crystal are occupied by atoms.
The position of any atom in the 3D lattice can be described
by a vector ruvw = ua + vb + wc, where u, v and w are integers.

(a) (b)

Unit Cell
The three unit vectors, a, b, c can define a cell as shown by the
shaded region in Fig.(a) This cell is known as unit cell (Fig. b)
which when repeated in the three dimensions generates the
crystal structure.
Crystal Systems
Bravais Lattice

The unit vectors a, b and c are called lattice parameters.


Based on their length equality or inequality and their
orientation (the angles between them, , and ) a total of 7
crystal systems can be defined. With the centering (face,
base and body centering) added to these, 14 kinds of 3D
lattices, known as Bravais lattices, can be generated.
Crystal Systems
Cubic: a = b = c, = = = 90o

Simple Body-centered Face-centered


cubic cubic (BCC) cubic (FCC)

Tetragonal: a = b c, = = = 90o

Simple Body-centered
Tetragonal Tetragonal (BCT)
Crystal Systems
Orthorhombic: a b c, = = = 90o

Simple Body-centered Base-centered Face-centered

Monoclinic: a b c, = = 90o

Simple Base-centered
monoclinic monoclinic
Crystal Systems

Triclinic
Rhombohedral Hexagonal
abc
a=b=c a=bc
90o
= = 90o = = 90 = 120
o o
Crystal Systems

Crystal system Example


Triclinic K2S2O8,K2Cr2O7
Monoclinic As4S4, KNO2,CaSO4.2H2O, -S
Rhombohedral Hg, Sb, As, Bi, CaCO3
Hexagonal Zn, Co, Cd, Mg, Zr, NiAs
Orthorhombic Ga, Fe3C, -S
Tetragonal In, TiO2, -Sn
Cubic Au, Si, Al, Cu, Ag, Fe, NaCl
Point Coordinates
Position of any point in a unit cell is given by its coordinates
or distances from the x, y and z axes in terms of the lattice
vectors a, b and c.
Thus the point located at a/2 along x axis, b/3 along y axis
and c/2 along z axis, as shown in the figure below, has the
111
coordinates
232
Crystal Planes
Miller Indices
Planes in a crystal are described by notations called Miller
indices
Miller indices of a plane, indicated by h k l, are given by the
reciprocal of the intercepts of the plane on the three axes.

The plane, which intersects X axis at 1 (one lattice


parameter) and is parallel to Y and Z axes, has Miller indices
h = 1/1 = 1, k = 1/ = 0, l = 1/ = 0. It is written as (hkl) =
(100).

Miller indices of some other planes in the cubic system are


shown in the figures in the next slide
Crystal Planes

To find the Miller Indices of a plane, follow these steps:


Determine the intercepts of the plane along the crystal axes
Take the reciprocals
Clear fractions
Reduce to lowest terms and enclose in brackets ()
Ex: Intercepts on a, b, c : , , (h k l) = (4/3, 2, 4) = (2 3 6)
Crystal Planes
Planes can also have negative intercept e.g. 1, -1/2, 1

h k l = 1 -2 1. This is denoted as ( 1 2 1 )

Family of planes {hkl}


Planes having similar indices are equivalent, e.g. faces
of the cube (100), (010) and (001). This is termed as a
family of planes and denoted as {100} which includes
all the (100) combinations including negative indices.
Some other equivalent planes are shown in the next
slide.
Equivalent Planes

Note the shift of origin from blue to red circle for the negative indices
Planes in Hexagonal system

In the cubic system all the faces of the cube are equivalent,
that is, they have similar indices.
However, this is not the case in the hexagonal system. The
six prism faces for example have indices (1 0 0), (0 1 0),
(1 1 0 ), (1 0 0 ), (01 0), (11 0 ), which are not same.

In order to address this, a fourth axis (a3) (1 1 0 )

which is opposite to the vector sum of a1


and a2 is used and a corresponding fourth

(010)
(100)
index i is used along with hkl. Therefore
the indices of a plane is given by (hkil)
whre i = -(h+k). Sometime i is replaced
with a dot and written as (h k . l)
Planes in Hexagonal system

The indices of six faces now become (1 01 0), (0 11 0),


(1 1 0 0), (1 0 1 0), (01 1 0), (11 0 0 ) which are now
equivalent and belong to the {1 01 0 } family of planes.

(1 1 0 0)

(0 11 0)
(1 01 0)
Interplanar spacing
The spacing between planes in a crystal is known as
interplanar spacing and is denoted as dhkl
In the cubic system spacing between the (hkl) planes is

l
1 1 2 2
d

a
given as 2
2 2

a
/
For example, dhkl of {111} planes d111 = 3

l
1 1 2 1
d

c
In Tetragonal system 2
2 2
2
2

h
k
l

l
1
1 2 1 2 1 2
d

c
In Orthorhombic system 2 2
2 2

h
k
l

h
k
h

l
1 4 1
d

c
In Hexagonal system 2 2 2 2 2 2

3
h
k
l


Crystal Directions
The directions in a crystal are given by specifying the
coordinates (u, v, w) of a point on a vector (ruvw) passing
through the origin. ruvw = ua + vb + wc. It is indicated as
[uvw]. For example, the direction [110] lies on a vector r110
whose projection lengths on x and y axes are one unit (in
terms of unit vectors a and b).
Directions of a form or family like [110], [101], [011] are
written as <110>

<100> and <110> family <111> family


Crystal Directions
The line which passes through uvw will also pass through
2u2v2w and u v w. Hence [uvw], [2u2v2w] and
[ u v w] are same and written as [uvw].

Fractions are converted in to integers (as shown in the


figure below) and reduced to lowest terms.
Crystal Directions
To determine a direction of a line in the crystal:

Find the coordinates of the two ends of the line and


subtract the coordinates (Head Tail) OR draw a line from
the origin parallel to the line and find its projection lengths on
x, y and z axis in terms of the unit vectors a, b and c.

Convert fractions, if any, in to integers and reduce to


lowest term.

Enclose in square brackets [uvw]


Directions in Hexagonal Crystal
Like planes, directions in the hexagonal system are also
written in terms of four indices as [uvtw].

If [UVW] are indices in three axes then it can be


converted to four-axis indices [uvtw] using the following
relations.
U=ut V=vt W=w
u = (2U-V)/3 v = (2V-U)/3 t = -(u + v) = -(U + V)/3
w=W

Ex: [100] = [211 0], [210] = [1 0 1 0]


Relationship between direction and planes
In the cubic system planes and directions having same
indices are perpendicular to each other i.e. if [uvw] direction
is perpendicular to (hkl) plane then h = u, k = v and l = w
Ex: {100} planes and <100> directions are perpendicular to
each other.

If [uvw] direction is parallel to (hkl), that is if [uvw] lies in the


plane (hkl) then hu + kv + lw = 0. For example, [1 1 0 ] lies
in the plane (111) since 1.(-1) + 1.1 + 1.0 = 0
Coordination number
Coordination number is the number of nearest neighbor
to a particular atom in the crystal

In the FCC lattice each atom is in contact with 12 neighbor


atoms. FCC coordination number Z = 12
For example, the face centered atom in the front face is in
contact with four corner atoms and four other face-centered
atoms behind it (two sides, top and bottom) and is also
touching four face-centered atoms of the unit cell in front of
it.
Coordination number

The coordination number of BCC crystal is 8.

The body centered atom is in contact with all the eight


corner atoms. Each corner atom is shared by eight unit
cells and hence, each of these atoms is in touch with
eight body centered atoms.
Coordination number

In Hexagonal lattice Z = 12. The center atom of the top


face is in touch with six corner atoms, three atoms of the
mid layer and other three atoms of the mid layer of the
unit cell above it.
Atomic packing factor

Atomic packing factor (APF) or packing efficiency


indicates how closely atoms are packed in a unit cell and
is given by the ratio of volume of atoms in the unit cell
and volume of the unit cell

V
o
l
m
e
f
o
a
t
o
m
s
A
P
F
V
o
l
u
m
e
o
f
u
n
i
t
c
e
l
l

Atomic packing factor
FCC lattice
In the FCC unit cell effective number of atoms = 8 corner
atoms x (1/8) (each atom is shared by 8 unit cells) + 6 face-
centered atoms x1/2 (each shared by two unit cells) = 4

The corner atom C is shared


1
F 2 by unit cells 1, 2, 3, 4 and
four more in front of each of
3
C them. The face-centered
atom, F is shared between
4
cells 1 and 2.

Click here for animation


Atomic packing factor
FCC lattice
Considering the atoms as hard spheres of radius R
T
o
t
a
l
v
o
l
u
m
e
o
f
a
t
o
m
s
4 3
R
4
3
The relation between R and the FCC cell side a as shown in
the figure below is 2a 4 R

4 3
4 R
3 16 2 2 a3
APF ( FCC ) 0.74
a 3
3 64a 3
Atomic packing factor
BCC
For BCC crystals effective number of atoms per unit cell is
8 x 1/8 + 1 = 2 and the relation between R and a is
3a 4 R

4 3
2 R
3 8 3 3 a
3

APF ( BCC ) 0.68


a 3
3 64a 3
Atomic packing factor
Hexagonal lattice
In the Hexagonal unit cell, number of atoms = 12 corner
atoms x 1/6 (shared by six unit cells) + Two face atoms x 1/2
+ 3 interior = 6.
2R = a
Unit cell volume = (6 x x a x h) x c = (3 x a x a sin60) x c
= 3a2 c sin60
Atomic packing factor

The face-centered atom and the three


mid-layer atoms form a tetrahedron
MNOP which has sides equal to a (as
atoms at vertices touch each other) and
height of c/2. Using this tetrahedron it
can be shown that for an ideal
hexagonal crystal c/a ratio = 1.633

4
6 R3
8 a
3

APF ( HCP ) 2 3 0.74


3a c sin 60 3 8 1.414a 3
Planar density
Planar density (PD) refers to density of atomic packing
on a particular plane.

N
u
m
b
e
r
f
o
a
t
o
m
s
o
n
a
p
l
a
n
e
P
l
a
n
a
r
D
e
n
s
i
t
y

A
r
e
a
o
f
p
l
a
n
e

For example, there are 2 atoms (1/4 x 4 corner atoms +


1/2 x 2 side atoms) in the {110} planes in the FCC lattice.
Planar density of {110} planes in the FCC crystal
2 2
PD(110 ) 2
a 2a a

2a
Planar density
In the {111} planes of the FCC lattice there are 2 atoms
(1/6 x 3 corner atoms + 1/2 x 3 side atoms). Planar density
of {111} planes in the FCC crystal
2 4
PD(111)
1 3 3a 2
2a 2a
2 2
This is higher than {110} and any other plane. Therefore,
{111} planes are most densely packed planes in the FCC
crystal

2a
Linear Density
Linear density (LD) is the number of atoms per unit
length along a particular direction

N
u
m
b
e
r
o
f
a
t
o
m
s
o
n
t
h
e
d
i
r
e
c
t
i
o
n
v
e
c
t
o
r
L
i
n
e
a
r
D
e
n
s
i
t
y

L
e
n
g
t
h
o
f
t
h
e
d
i
r
e
c
t
i
o
n
v
e
c
t
o
r

<110> directions in the FCC lattice have 2 atoms (1/2 x 2


corner atoms + 1 center atom) and the length is 2a
2 2
LD[110 ]
2a a
This is the most densely packed direction in the FCC lattice
Close-Packed Structure
FCC and hexagonal crystal structures are most highly
packed with packing efficiency of 74% (APF= 0.74). Such
structures can be described in terms of close-packed
atomic planes.
In FCC, {111} planes are close-packed and the basal
plane (0001) is the close-packed one in hexagonal
close-packed (HCP) system. Therefore, both of these
structures can be generated by stacking of these planes.
A portion of such a stack is shown in the picture below.
Close-Packed Structure
There are two types of voids between the atoms
vertex up (b), and vertex down (c). The atoms in the next
layer sit on the b sites (See animation below).
In FCC, atoms in the third layer sit over the c sites and this
repeats giving rise to ABC ABC ABC type of stacking.
Close-Packed Structure
In HCP system, centers of atoms of the third layer lie
directly over centers of atoms of the first layer (a positions)
giving rise to AB AB AB type of stacking.
Structure-Property correlation
Aluminium (Al) is ductile while iron (Fe) and magnesium
(Mg) are not. This can be explained from their crystal
structures.
Al is FCC where as Fe is BCC and Mg is HCP.

Plastic deformation in metals takes place mainly by a


process called slip. Slip can broadly be visualized as sliding
of crystal planes over one another. Slip occurs on most
densely packed planes in the most closely packed directions
lying on that plane.
The slip plane and the direction together is called a
Slip system
Structure-Property correlation
In FCC, {111} planes are close-packed and there are four
unique {111} planes. Each of these planes contains three
closely packed <110> directions. Therefore, there are
4 x 3 = 12 slip systems
In HCP, the basal plane, (0001) is the close-packed and it
contains three <1 12 0> directions. Hence, number of slip
system = 1 x 3 = 3
Slip in more number of slip systems allows greater plastic
deformation before fracture imparting ductility to FCC
materials
Structure-Property correlation
Close-packed planes are also planes with greatest
interplanar spacing and this allows slip to take place easily
on these planes.

BCC structure on the other hand has 48 possible slip


systems. However, there is no close-packed plane. Hence,
plastic deformation before fracture is not significant. Slip
might occur in {110}, {112} and {123} planes in the <111>
directions.
Evaluation
At the end of this chapter on crystallography, one should be
able to
Understand Space lattice, Unit cells,7 crystal structure
and 14 Bravais lattices.
Understand atomic arrangement and packing in different
unit cells.
Derive point coordinates
Find out miller indices of crystallographic planes and
directions.
Correlate some properties to crystal structure.
Web References

http://www.youtube.com/watch?v=qh29mj6uXoM&feature=relmfu
http://www.youtube.com/watch?v=8zWySdeXB0M&feature=relmfu
http://www.youtube.com/watch?v=Rm-i1c7zr6Q&feature=related
http://www.youtube.com/watch?v=PWQ89UoxOK8&feature=related
http://www.youtube.com/watch?v=mQy2CdKYqX0&feature=related

Key words: Symmetry; Space lattice; Crystal structure; Miller


indices; Close pack structure; Slip system
Examples
Ex. 1: Theoretical density calculation from crystal structure.
nA
Theoretical density,
VC N A
n = number of atoms in the unit cell
A = atomic weight
VC = volume of unit cell
NA = Avogadros number (6.023 x 1023 atoms/mol)
Calculate the theoretical density of Al.
Al is FCC, lattice parameter, a = 4.05 , n = 4.
Atomic weight of Al is 26.98 g/mol
.

g
c
c
.

/
4 26 98
.

2 697
4 05 10
8 3
6 023 10 23
Examples
Ex. 2: Show the point having coordinates 1/2, 1, 1/3 .
Solution: Select one of the corners of the unit cell as the
origin. Move a/2 from the origin along the x axis and mark
this point. From this point move b units along the y axis
and then c/3 units along the z axis.
Ex. 3: Draw the plane ( 31 2) in a cubic unit cell.
z

c/2
y
a/3

b
x
Examples
Ex. 4: Draw the directions [236] and [203] and [21 1] in a
cubic unit cell.

[211]

c/2

-b/2

Ex. 5: The atomic radius of Fe is 0.124 nm. Find the


lattice parameter of Fe.
R

Solution: Fe is BCC at room temperature. Therefore,


.
a
a

.
4 4 0 124
3 4 and 0 286 nm
3 3
Quiz
1. Show that only four types of rotational symmetry are
possible.
2. Why it is not possible to have 5, 7 or higher order
symmetry in crystallography?
3. What is point group? How many point-groups are possible?
4. Find out the Hermann-Mauguin symbol for a cube.
5. For a point at xyz write a translation, a reflection and an
inversion operation.
5. What is unit cell? What is lattice parameter?
6. What is Bravais lattice? How are the Bravais lattices
obtained from the primitive cell? How many types of Bravais
lattices are there?
7. What is the effective number of atoms in a simple cubic unit
cell?
Quiz
8. What is coordination number (CN)? Show that CN for FCC
and HCP structure is 12 while it is 8 for BCC.
9. Show that packing efficiency of FCC is 74% and that of
BCC is 68%.
10. Show that the ideal c/a ratio in a hexagonal unit cell is
1.633 and calculate the packing efficiency.
11. What are the coordinates of the center atom in the BCC
unit cell.
12. What is miller index? How is it obtained?
13. Draw the planes (11 0), (12 1), (23 4), (1 12 ) and
directions[1 11], [123], [120], [1 2 1] in a cubic unit cell.
14. Why it is necessary to include a fourth miller index in the
hexagonal system?
15. Convert the directions [112], [12 3], [110], [111], [130] to
four indices in a hexagonal lattice.
Quiz
16. What is family of planes? Draw the {111} family of planes
in cubic system?
17. What is linear density? What is planar density?
18. Find the planar of density {111} planes and linear density
of <110> directions in FCC system.
19. What is the linear density of <111> directions in the
BCC crystal.
20. What is interplanar spacing? Find the interplanar spacing
of the vertical planes in the HCP system?
21. What is the stacking sequence of FCC and HCP crystals?
22. What is slip system?
23. Why FCC metals are ductile while BCC and HCP metals
are not?
24. Calculate the theoretical density of Cu from its crystal
structure.
Quiz
25. Lattice constant of Al is 4.05 . What is the atomic
radius of Al?
26. Calculate the theoretical density of Mg, Cu and Fe and
compare them to the standard values.
27. A metal has a density of 10.22 g/cc, atomic weight of
95.94 and atomic radius of 0.136 nm. Is it BCC or FCC?
28. Calculate the volume of the unit cell of Zn crystal. a and
c of Zn are 266.5 pm and 494.7 pm respectively.
29. Calculate the planar density of {110} planes in -Fe
(BCC) crystal. a = 0.287 nm.
30. Calculate the linear density of [110] direction in a Cu
crystal. a = 0.361 nm.
Polycrystalline, single crystal and
Non crystalline Materials
Polycrystalline
Polycrystalline material Aggregate of several crystals or
grains
The boundary between the grain is the grain boundary across
which the orientation of the crystal changes.
The point at which three boundaries meet is called the triple
junction.
Triple junction
Grain size determination
Line intercept method
This is one of the most commonly used methods. Number of
grains intersecting a given length of a random line is counted.
Grain size D = Length of the line/no of grains intersected
Grain size measurement
ASTM grain size number, G Number of grains per unit
area at a particular magnification
ASTM Grains/mm2 Grains/mm3 Avg. grain
No. size, mm G = -2.9542 + 1.4427 ln N
-1 3.9 6.1 0.51 where, N is number of
0 7.8 17.3 0.36 grains/mm2
1 15.5 49.0 0.25 G is compared in ASTM
2 31.0 138 0.18
grain size chart to obtain
3 62.0 391 0.125
the grain size.
4 124 1105 0.09
5 248 3126 0.065
6 496 8842 0.045
7 992 25010 0.032
8 1980 70700 0.022
9 3970 200000 0.016
10 7940 566000 0.011
Grain size measurement

Calculate the grain size from the micrographs using the line
intercept method
Grain size Property relationship
Hall-Petch Relation
A general relationship between mechanical properties and
grain size is given by the Hall-Petch equation

k
d
/

o

i
1 2

o is the yield strength, d is the grain size and i and k are


material dependent constants.

Finer grain size means more grain boundaries or higher grain


boundary area per unit volume. Deformation in metals takes
place by dislocation motion and grain boundaries act as
obstacles to dislocation motion. Hence, presence of more
grain boundaries (finer grain size) will increase the resistance
to deformation and enhance the strength.
Single Crystals
Single crystal only one grain or crystal and hence, no
grain boundaries.
Useful for applications where grain boundaries are harmful.
For example, high temperature deformation or creep
resistance (as creep takes place by grain boundary sliding) -
single crystal turbine blades
(http://blog.makezine.com/2012/01/16/single-crystal-
superalloys/)(www.cmse.ed.ac.uk/AdvMat45/SuperEng.pdf)
Silicon single crystals for semi conductors
Non crystalline or Amorphous materials

Amorphous random arrangement of atoms: Silicate glass,


Polymers

Metallic amorphous materials


Bulk Metallic Glass (BMG)
A metallic system can be made amorphous by decreasing the
chance of crystallization : Allow less time for crystallization
during solidification Rapid solidification processing (RSP)
Increase confusion for a particular crystal form by increasing
the number of components (alloying elements).
Bulk Metallic Glass
Multi component elements with different chemical nature
and atomic size and number together reduce the chance of
crystallization

Zr41.2Ti13.8Cu12.5Ni10Be22.5 [=(Zr3Ti)55(Be9Cu5Ni4)45], commonly


referred to as Vitreloy 1 (Vit1)

Processing routes:
RSP - Melt spinning
Ball milling
Solid-state amorphisation reaction
Nuclear irradiation
Properties of BMGs
Mechanical properties High strength, low ductility
Formation of small crystallites in glassy matrix by annealing
can improve ductility.
Some Properties of Vit1 (R D Conner et al. Scripta mater. 1997;37:13738)
Elastic Tensile Youngs Shear Hardness Fracture
strain strength Modulus Modulus toughness
2% 1.9 GPa 96 GPa 34.3 GPa 534 VHN 55 MPa m1/2

Magnetic properties excellent soft magnetic properties due


to absence of crystalline magnetic anisotropy FINEMET
Fe-Si-B-Cu-Nb
Excellent corrosion resistance
Good acoustic properties
Applications of BMGs
Golf heads BMG golf heads can transfer 99% energy
compared to 60% for steel heads and 70% for Ti heads
Thin yet strong electronic casing MP3 player, mobile
phones, digital cameras, PDA
Surgical instruments, Prosthetic implants (Biomaterials)
Sensors for electronic article surveillance, cores for high
frequency transformers
Self-sharpening tank armor penetrator
Nano Materials
Nanometer = 10-9 m
micrometer = 10-6 m
mm = 10-3 m
Nano Materials
Nano Structured Material (NSM) At least one component
of the microstructure e.g. grains, particles or dispersoids, is
nano meter in size.
Nano particles possess very high surface area /unit volume
which gives rise to unique physical and chemical properties.
In a nano-grained material the grain boundary width is
comparable with the grain size.

Nano particles Nano Ni-ZrO2 composite Nano grains in Al


Nano -Structured Materials (NSM)

A two-dimensional representation of a nanostructured


material. Red circles indicate atoms in the grain while
open circles indicate atoms in the grain boundary region
Classification of NSMs

Classification of NSMs according to their chemical


composition and shape
Processing Routes

Inert gas condensation


Vapour phase condensation
Wet chemical method
High energy mechanical alloying
Plasma processing
Combustion synthesis
Super critical liquid
Chemical vapor deposition (CVD)
Physical vapor deposition (PVD)
Properties of NSMs
Superior functional properties Photoluminescence,
Electroluminescence, Electronic and magnetic peoperties
Enhanced catalytic activity Very high surface area per unit
volume
Structural properties Very high strength Hall-petch
equation 0 = i + kd-1/2
Ultrafine grain size - Superplasticity
High Hardness Nanocrystalline WC-Co composites
High stiffness - CNTs
Applications
Sunscreens Lotions - Many sunscreens contain nano
particles of zinc oxide or titanium oxide.

Self-cleaning glass: Activ Glass - uses nanoparticles to make


the glass photocatalytic and hydrophilic.
Clothing: coating fabrics with a thin layer of zinc oxide
nanoparticles, better protection from UV radiation.
Stain resistant clothes - have nanoparticles in the form of little
hairs or whiskers that help repel water and other materials
Glossy colors Nano particles of pigments (CoAl2O4).
Shiny, better looking colors for cars
Scratch resistant coatings addition of aluminum silicate
nanoparticles to scratch-resistant polymer coatings. Scratch-
resistant coatings for cars and eye lenses.
NSMs in Electronics Better and Smaller

The advent of the nano technology has immensely helped


in miniaturization which is an essential part in many
electronic gadgets.
The nano technology is already in use in many electronic
gadgets like mobile phones, I-pads, cameras, palm tops and
so on.
Quantum dots - nano-scale semiconductor crystals.
Dramatic improvement in digital storage (Flash memory)
Less power consumption, better resolution (in visuals),
smaller size.
Applications of NSMs

Flash memory: Conventional tunneling film must be


sufficiently insulating to store the charge. Limits thickness
reduction and thus miniaturization. Cannot work with defects
in the film.
Nano dot or quantum dot flash memory allows for higher
defect tolerance, lower thickness (and hence
miniaturization). Less power consumption
Quantum dots display - By altering the size of the nano
particles, the color they emit can be changed.
6 nm red, 2 nm - blue
Quantum dot display in place of LCDs or OLEDs less
power consumption, better quality pictures.
Applications of NSMs contd.

IBM has developed Microscopic LED: A thin indium-nitride


nanowire that emits infrared light when a current is applied
(http://www.technologyreview.in/communications/19129/)

It is believed that the nanowire LEDs could eventually be


used for telecommunications and for faster communications
between devices on microchips.
References
http://www.iue.tuwien.ac.at/phd/holzer/node39.html
http://science.howstuffworks.com/nanotechnology3.htm
http://203.208.166.84/mjrahman/Class%20Note_Jellur.pdf
http://en.wikipedia.org/wiki/Single_crystal
http://www.appropedia.org/Single_Crystal_Turbine_Blades

Processing Techniques
http://www2.mmae.ucf.edu/~sury/Online_Pub/Nano-
Hyperfine.pdf
http://library.iyte.edu.tr/tezler/master/kimyamuh/T000294.pdf

Key words: Polycrystalline; Grain boundary; Amorphous;


Bulk Metallic Glass; Single crystal; Nano Materials
Quiz
1. What aspect of the crystals changes across the grain
boundaries?
2. How is the gain size measured in a polycrystalline material?
3. What is effect of grain boundaries on strength of metals?
4. Are grain boundaries desirable for high temperature
structural application? Give reasons for your answer.
5. What is meant by amorphous material?
6. How can a metallic system be made into an amorphous
material?
7. Why bulk metallic glasses (BMG) are generally
multicomponent?
8. What is nanostructured material? What imparts unique
properties to these materials?
9. Classify nanostructured materials.
10. What are the processing routes of nano materials?
Lattice Defects
Types of lattice defects
Point defects
Line defects
Surface defects
Volume defects
Point defects
Vacancy An atom missing from regular lattice position.
Vacancies are present invariably in all materials.
Interstitialcy An atom trapped in the interstitial point (a
point intermediate between regular lattice points) is called
an interstitialcy.
An impurity atom at the regular or interstitial position in
the lattice is another type of point defect.

Vacancy Interstitialcy Impurity


Point defects

Frenkel defect Schottky defect

In ceramic materials point defects occur in pair to maintain


the electroneutrality.
A cation-vacancy and a cation-interstitial pair is known as
Frenkel defect.
A cation vacancy-anion vacancy pair is known as a Schottky
defect.
Line defects
Dislocations
Dislocation is the region of localized lattice distortion which
separates the slipped and unslipped portion of the crystal.
The upper region of the crystal over the slip plane has
slipped relative to the bottom portion. The line (AD) between
the slipped and unslipped portions is the dislocation.
The magnitude and direction of slip produced by dislocation
(pink shaded) is the Burger vector, b, of the dislocation.
Edge Dislocations

In one type of dislocations, the Burger vector is


perpendicular to the dislocation line and the distortion
produces an extra half-plane above the slip plane.

Extra half-plane

Slip vector
Screw Dislocations
The other type of dislocation is the screw dislocation where
the Burger vector is parallel to the dislocation line (AD).
The trace of the atomic planes around the screw dislocation
makes a spiral or helical path (pink shade) like a screw and
hence, the name.
Atomic positions along a screw dislocation is represented in
Fig. (b)

(a) (b)
Burger Circuit
The Burger vector can be found by the gap in the Burger
circuit which is obtained by moving equal distances in each
direction around the dislocation.
Dislocation movement and deformation

The theoretical shear stress to produce plastic deformation


in metals, = G /2
G, the shear modulus for metals is in the range of = 20 -
150 GPa yielding = 3 30 GPa
However, actual measured values of = 0.5 10 MPa.
This discrepancy can be explained by the presence of
dislocations in the lattice.
Dislocations assist in plastic deformation since it is easier
to move the atoms at the dislocations core.
The movement of dislocations produces a slip step of one
Burger vector or one interatomic distance.
Dislocation movement
Dislocations move in steps. The edge dislocation at P moves
to Q in steps as depicted by the red (half-plane) and blue atoms.
This movement is analogous to movement of a caterpillar.
When the half-plane reaches a free surface it produces a slip
step.
Edge dislocations can move only on the slip plane while screw
dislocations do not have a fixed glide plane.
Since plastic deformation takes place by movement of
dislocations, any hindrance to their motion will increase the
strength of metals.

Slip plane
Observing dislocations

Dislocations appear as lines when observed under


transmission electron microscope (TEM)
Surface defects
Grain Boundaries
Most crystalline solids are an aggregate of several
crystals. Such materials are called polycrystalline.
Each crystal is known as a grain. The boundary between
the grains is the grain boundary (the irregular lines in Fig.a)
A grain boundary is a region of atomic disorder in the
lattice only a few atomic diameter wide.
The orientation of the crystals changes across the grain
boundary as shown schematically in Fig. b.
Grain boundaries act as obstacles to dislocation motion.
Hence, presence of more grain boundaries (finer grain size)
will increase the strength.
Grain boundaries
Grain
boundaries

Grain 1 Grain 2

Grain 3

(b) Schematic of orientation


(a) Optical micrograph of change across the grain
a polycrystalline material boundary
Bulk or volume defects

Porosity
Inclusions
Cracks
These defects form during manufacturing processes for
various reasons and are harmful to the material.
Bulk defects

Weld defect Casting defect Shrinkage cavity


Casting blow holes, porosity Gas entrapment during melting
and pouring. Improper welding parameters/practice
Shrinkage cavity due to improper risering
Non-metallic inclusions Slag, oxide particles or sand
entrapment
Cracks Uneven heating/cooling, thermal mismatch,
constrained expansion/contraction all leading to stress
development
Evaluation
At the end of this chapter one should

Understand different types of lattice defects.


Be able to differentiate between screw and edge
dislocation.
Be able to describe Burger vector and dislocation
movement.
Understand grain and grain boundaries
References
http://www.ndt-ed.org/EducationResources/CommunityCollege
/Materials/Structure/linear_defects.htm
http://people.virginia.edu/~lz2n/mse201/mse201-defects.pdf
http://www.public.iastate.edu/~micromech/Courses/EM590-
F/Lecture-notes/Defects%20in%20crystals.pdf
http://henry.wells.edu/~cbailey/solidstate/Defects.ppt

Key words. Lattice defects; Point defects; Line defects;


Dislocations; Edge dislocation; Screw dislocation; Burger
vector; Slip; Surface defects; Grain boundary.
Quiz
1.How many types of latiice defects exist?
2.What is an interstitialcy and how it is different from an impurity
atom?
3. What is dislocation? What is Burger vector?
4. Draw the atomic arrangement around an edge dislocation
and show the extra half-plane.
5. What is the fundamental difference between edge and
screw dislocation?
6. What is Burger circuit?
7. Why the ideal strength of metals is less than the actual
measured values?
8. Why is the movement of dislocations compared to caterpillar?
9. How does dislocation movement produce plastic
deformation?
Quiz
10. How do dislocations appear when observed an electron
microscope?
11. From a dislocation mechanism point of view how can one
increase the strength of metals?
12. What is meant by a polycrystalline material?
13. What is a grain?
14. Is the orientation of the crystal across a grain boundary
same?
15. How do grain boundaries affect strength of a material?
Diffusion
Diffusion Phenomena
Diffusion is a process of mass transport by atomic
movement under the influence of thermal energy and a
concentration gradient.
Atoms move from higher to lower concentration region.
If this movement is from one element to another e.g. Cu to
Ni, then it is termed inter-diffusion. If the movement is within
similar atoms as in pure metals, it is termed self-diffusion.
Diffusion Mechanism
Diffusion of atoms involves movement in steps from one
lattice site to the another. An empty adjacent site and
breaking of bonds with the neighbor atoms are the two
necessary conditions for this.
Vacancy Diffusion
This mechanism involves movement of atoms from a regular
lattice site to an adjacentt vacancy. Since vacancy and
atoms exchange position, the vacancy flux is in the opposite
direction.
Diffusion Mechanism
Interstitial Diffusion
This mechanism involves migration of atoms from one
interstitial site to a neighbouring empty interstitial site.
This mechanism is more prevalent for impurity atoms such
as hydrogen, carbon, nitrogen, oxygen which are small
enough to fit in to an interstitial position.
For substitutional diffusion atoms exchange their places
directly or along a ring (ring diffusion mechanism).
Interstitial
atom

Interstitial Diffusion
Kirkendall Effect
If the diffusion rates of two metals A and B in to each other
are different, the boundary between them shifts and moves
towards the faster diffusing metal as shown in the figure.

A-rich B-rich
Diffusion rate
B A> B
A t = t1 t = time
t=0

This is known as Kirkendall effect. Named after the inventor


Ernest Kirkendall (1914 2005).
It can be demonstrated experimentally by placing an inert
marker at the interface.
This is a direct evidence of the vacancy mechanism of
diffusion as the other mechanisms do not permit the flux of
diffusing species to be different.
Kirkendall effect
Zn diffuses faster into Cu than Cu in Zn. A diffusion couple of
Cu and Zn will lead to formation of a growing layer of Cu-Zn
alloy (Brass).

Same will happen in a Cu-Ni couple as Cu diffuses faster in


Ni than vice versa.
Since this takes place by vacancy mechanism, pores will
form in Cu (of the Cu-Ni couple) as the vacancy flux in the
opposite direction (towards Cu) will condense to form pores.
Ficks Law
Steady-state diffusion
Steady-state diffusion is the situation when the diffusion flux
is independent of time (e.g. diffusion of a gas through solid
medium where concentration/pressure of the gas is kept
constant at both the end).
Ficks first law describes steady-state diffusion and is given

dd
Cx
by
J

Where, J is the diffusion flux or the mass transported per unit


time per unit area and dC/dx is the concentration gradient. D
is known as the diffusion coefficient.
Ficks Second Law
Non- Steady state diffusion
In most practical situations, diffusion is non-steady state i.e.
diffusion flux and concentration gradient varies with time.
This is described by Ficks second law

Ct

Cx
2
D

2

A solution to this equation can be obtained for a semi-infinite
solid with the following boundary conditions.
For t = 0, C = Co at 0 x . For t > 0, C = Cs (surface
concentration) at x = 0 and C = Co at x =
CxCs
CoCo

xD
e
r
f
1


t C
2 Cx

xD
x
,
t
A
B
e
r
f

2
t
The more generalized form is

Factors affecting Diffusion
Diffusing species
The magnitude of the diffusion coefficient, D, is an indication of
the rate at which atoms diffuse. As the value of D is fixed for a
given element in a given material, the extent of diffusion is first
decided by the diffusing species itself.

Temperature
Temperature is a major factor which affects diffusion.
Temperature dependence of the diffusion coefficient is
expresses as
QR
D
Do
e
x
p

T


Where, Do is the pre-exponential factor and the Q is the
activation energy for diffusion
Example
Ex.1. The carbon content of a steel at the surface is 0.9%.
The steel is being carburized at 927 C. The nominal C
content in the steel is 0.2%. Calculate the time needed to
increase the carbon content to 0.4% at 0.5 mm depth.
D = 1.28 x 10-11 m2/s at 927 C.
CxCs
CoCo

xD
e
r
f
Solution. 1
------ (1)

t
2


Cs = 0.9%, Co = 0.2%, Cx = 0.4%, x = 0.5 mm = 5 x 10-4 m
Substituting these values in equation (1)
6
9
.
8t
8

6
9
.
8t
8
e
r
f

0
.
7
1
4
3

0
.
7
5
5

or

t = 8567 s = 143 min
References
http://dev.matter.org.uk/matscicdrom/manual/df.html
http://highered.mcgraw-
hill.com/sites/0072495855/student_view0/chapter2/animation_
_how_diffusion_works.html
http://web.mse.uiuc.edu/courses/mse280/notes/06/ch06_diffu
sion.ppt
http://www.msm.cam.ac.uk/phase-trans/abstracts/L1-2.pdf
http://www.msm.cam.ac.uk/phase-trans/kirkendall.html
http://www.eng.utah.edu/~lzang/images/lecture-6.pdf
http://people.virginia.edu/~lz2n/mse209/Chapter5.pdf

Key words: Diffusion; Atomic diffusion; Ficks law of diffusion;


Self-diffusion; Kirkendall effect; Diffusivity
Quiz
1. What is diffusion?
2. What are the two necessary conditions for diffusion to
occur?
3. What are the mechanisms of diffusion?
4. What is self-diffusion?
5. What is steady state diffusion? Describe Ficks first law of
diffusion.
6. What is Ficks second law of diffusion?
7. What is the effect of temperature on diffusion? How is the
activation energy obtained?
8. What other factors affect diffusion rate in metals?
9. Give an example of an industrial process which uses
diffusion.
10. Calculate the diffusivity of carbon in -Fe at 927 C.
Do = 2 x 10-5 m2/s and Q = 142 kJ/mol
Quiz
11. The diffusivity of Ag atoms in Ag metal is 1.0 x 10-17 m2/s at
500 C and 7.0 x 10-13 m2/s at 1000 C. Calculate the activation
energy for diffusion of Ag atoms in the temperature range 500
1000 C.
12. A plain carbon steel (0.18% C) is to be carburized at 927 C.
What is the time needed to make the carbon content 0.35% at a
depth of 0.4 mm? Take C content at surface to be 1.15 wt%.
D = 1.28 x 10-11 m2/s.
13. If the same steel is carburized for 7 hrs at 927 C what will
be the carbon content at a depth of 1mm from the surface?
Solid Solutions
Solid Solution
When two metals are mixed together they form an alloy if
one metal is soluble in the other one in solid state. Therefore,
an alloy is a solid solution of two or more metals.
Primarily there are two types of solid solutions -
Substitutional Solute atoms occupy the regular lattice
sites of the parent metal (solvent). Substitutional solid
solutions can be random (Cu-Ni) or ordered (Cu-Au).
Interstitial Solute atoms occupy the interstitial positions
(Steel C solute atoms in Fe) .

Solvent
Solute

Random substitutional Ordered substitutional Interstitial


Hume-Rothery Rules
Formation of substitutional solid solutions between two metals
is governed by a set of rules known as
Hume-Rothery rules
Size difference between the atoms of solute and the parent
metal should be less than 15%.
The electronegetivity difference between the metals should
be small (minimum chemical affinity to each other).
The solubility of a metal with higher valence in a solvent of
lower valence is more compared to the reverse situation e.g.
Zn is much more soluble in Cu than Cu in Zn.
For complete solubility over the entire range of compositions
the crystal structures of the solute and the solvent must be the
same.
Ordering in Solid solutions
As stated before substitutional solid solutions can be either
ordered or random. This depends on a thermodynamic
parameter called enthalpy of mixing, Hmix
Gmix = Hmix - T Smix
Gmix is the Gibbs free energy change and Smix entropy of
mixing. For an ideal solution Hmix = 0.
If Hmix> 0, formation of like bonds (A-A or B-B) is preferred
in a solid solution between metals A and B. This known as
clustering.
If Hmix< 0, unlike bonds (A-B) are preferred. This leads to
ordering which may exist over short range or long range (at
lower temperatures).
Intermediate Phases
As the name suggest intermediate structures formed
between two metals are neither the parent metals nor like an
alloy.
Intermetallic compounds
If two elements have high difference in electronegetivity, they
tend to from a system called intermetallic compound.
Intermetallic compounds like MgSe, PbSe, Mg2Si, Cu2S are
cubic whereas NiAs, MnSe, CuSn are hexagonal.
Electron or Hume Rothery phases
These compounds have wide range of solubility and occur at
certain values of valence electrons to atom ratio such as 3:2
(CuZn), 21:13 (Cu5Zn8), 7:4 (CuZn3).
Intermediate Phases
Laves phase
Laves phases have a general formula of AB2, for example
MgCu2 (cubic), MgZn2 (hexagonal), MgNi2 (hexagonal)
Sigma phase
Sigma phase has a very complex crystal structure and is very
brittle. This phase can act as a source of embrittlement in
some alloys such as steels.
Metal carbides and nitrides
Metals which have high chemical affinity for carbon and
nitrogen form carbides and nitrides such as VC, NbC, VN,
NbN, TiC, TiN. They can act as source of hardening in many
alloys.
References
http://www.newagepublishers.com/samplechapter/000627.pdf
http://www.ul.ie/~walshem/fyp/Solid%20solution.htm
http://www.csun.edu/~bavarian/mse_528.htm
Physical Metallurgy - Google Books Result, Robert W. Cahn

Key words: Solid solutions; Alloys; Hume-Rothery rules;


Intermediate phases
Quiz
1. What is a solid solution?
2. How many types of solid solutions are there? Give examples
for each of them?
3. What are Hume-Rothery rules?
4. If two metals have very different electronegetavity will they
form a solid solution?
5. How does valence of an element affect the solid solubility?
6. What is an ideal solution?
7. What is clustering?
8. What is ordering?
9. What is an intermetallic compound?
10. What is Hume-Rothery phase?
11. What is Laves phase?
12. What is sigma phase?
13. What kind of metals form carbides?
Quiz
14. The atomic radius of Cu is 0.128 nm and electronegativity
is 1.8. What is the probability of lead, Pb (atomic radius 0.175
nm, electronegativity 1.6) and zinc, Zn (atomic radius 0.133
nm, electronegativity 1.7) forming solid solution with copper?

15. Predict the relative degree of solid solubility of the


following elements in Fe (r = 0.124 nm, electronegativity 1.7).
Ni (atomic radius, r = 0.125 nm, electronegativity 1.8), Cr (r =
0.125 nm, electronegativity 1.6), Ti (r = 0.147 nm,
electronegativity 1.3)
Phase diagrams
Phase
A phase can be defined as a physically distinct and chemically
homogeneous portion of a system that has a particular
chemical composition and structure.
Water in liquid or vapor state is single phase. Ice floating on
water is an example two phase system.
Gibbs Phase rule
The number of degrees of freedom, F (no. of independently
variable factors), number of components, C, and number of
phases in equilibrium, P, are related by Gibbs phase rule as
F=CP+2
Number of external factors = 2 (pressure and temperature).
For metallurgical system pressure has no appreciable effect on
phase equilibrium and hence, F = C P + 1
Phase Diagrams
One component system
The simplest phase diagram is the water which is a one
component system. It is also known as pressure-temperature or
P-T diagram. Two phases exist along each of the three phase
boundaries. At low pressure (0.006 atm) and temperature (0.01
C) all the three phases coexist at a point called triple point.

Water phase
diagram
Binary Phase diagrams
A binary phase is a two component system. Binary phase
diagrams are most commonly used in alloy designing.
The simplest binary system is the Cu-Ni which exhibits
complete solubility in liquid and solid state.

Cu-Ni equilibrium
phase diagram
Binary Phase diagrams
The line above which the alloy is liquid is called the liquidus
line. At temperature just below this line crystals of solid
solution start forming.
The line below which solidification completes is called
solidus line. Hence, only solid solution exists at any
temperature below the solidus line.
The intermediate region between liquidus and solidus lines
is the two-phase region where liquid and solid coexist.
It can be noted that the two metals are soluble in each other
in the entire range of compositions in both liquid and solid
state. This kind of system is known as Isomorphous system.
The Tie line
The composition of phases in the two-phase region is not
same.
To find the composition of the individual phases in the two-
phase region, a horizontal line (XY), called tie line, is drawn and
its intercepts on the liquidus and solidus lines, Cl and Cs, are
taken as the composition of the liquid and solid respectively.
Lever rule
The relative fractions of the phases at a given temperature for
an alloy composition Co is obtained by the lever rule. This rule
gives the fraction of a phase by the ratio of the lengths of the tie
line between Co and composition of the other phase to the total
length of the tie line. For example, fraction solid, fs is given by

MX
XY
CoCs
ClCl
fs


Similarly fraction liquid, fl

MX
YY
CsCs
CoCl
fl



Cooling curves
Upon cooling from liquid state, the temperature of the pure
metal (A or B) drops continuously till melting point at which
solidification starts. Solidification happens at a constant
temperature (line PQ) as F =0 (F = 1 2 +1 = 0). The
temperature drops again on completion of solidification.
For any alloy (1, 2, 3 etc.) temp. drops till the liquidus (L1, L2,
L3). However, in this case, solidification proceeds over a range
of temperature as F = 1 (2 2 + 1 = 1). Once solidification
completes at the solidus (S1, S2, S3) the temp. drops again.
Phase diagrams- Limited solubility
Not all metals are completely soluble in each other.
Distinctions can be made between two types solid solutions
with limited solubility (i) Eutectic and (ii) Peritectic.
When the melting points of two metals are comparable, a
eutectic system forms while a peritectic results when melting
points are significantly different.
A eutectic reaction is defined as the one which generates
two solids from the liquid at a given temperature and
composition, L +
Peritectic is Liquid + Solid 1 Solid 2 (L + )
In both the cases three phases (two solids and a liquid)
coexist and the degrees of freedom F = 2 3 + 1 = 0. This is
known as invariant (F = 0) reaction or transformation.
Eutectic Phase diagram
In the eutectic system between two metals A and B, two
solid solutions, one rich in A () and another rich in B () form.
In addition to liquidus and solidus lines there are two more
lines on A and B rich ends which define the solubility limits B in
A and A in B respectively. These are called solvus lines.
Eutectic Phase diagram
Three phases (L++) coexist at point E. This point is called
eutectic point or composition. Left of E is called hypoeutectic
whereas right of E is called hypereutectic.
A eutectic composition solidifies as a eutectic mixture of
and phases. The microstructure at room temperature (RT)
may consist of alternate layers or lamellae of and .
In hypoeutectic alloys the phase solidifies first and the
microstructure at RT consists of this phase (called
proeutectic ) and the eutectic (+) mixture. Similarly
hypereutectic alloys consist of proeutectic and the eutectic
mixture.
The melting point at the eutectic point is minimum. Thats
why Pb-Sn eutectic alloys are used as solders. Other eutectic
systems are Ag-Cu, Al-Si, Al-Cu.
Eutectic Cooling curves
While cooling a hypoeutectic alloy from the liquid state, the
temp. drops continuously till liquidus point, a, at which crystals
of proeutectic begins to form.
On further cooling the fraction of increases. At any point, b,
in the two-phase region the fraction is given by the lever rule
as bn/mn.
Eutectic Cooling curves
Solidification of proeutectic continues till the eutectic
temperature is reached. The inflection in the cooling curve
between points a and e is due to evolution of the latent heat.
At the eutectic point (e) the solidification of eutectic mixture
(+) begins through the eutectic reaction and proceeds at a
constant temperature as F = 0 (2 3 + 1).
The cooling behavior in hypereutectic alloy is similar except
that proeutectic forms below the liquidus.
For a eutectic composition, the proeutectic portion is absent
and the cooling curve appears like that of a pure metal.
Any composition left of point c or right of point d ( and
single phase region respectively) will cool and solidify like an
isomorphous system.
Peritectic Phase diagram
L + . An alloy cooling slowly through the peritectic
point, P, the phase will crystallize first just below the liquidus
line. At the peritectic temperature, TP all of the liquid and will
convert to .
Any composition left of P will generate excess and similarly
compositions right of P will give rise to an excess of liquid.
Peritectic systems Pt - Ag, Ni - Re, Fe - Ge, Sn-Sb (babbit).
Monotectic Phase diagram
Another three phase invariant reaction that occurs in some
binary system is monotectic reaction in which a liquid
transforms to another liquid and a solid. L1 L2 + .
Two liquids are immiscible like water and oil over certain
range of compositions. Cu-Pb system has a monotectic at 36%
Pb and 955 C.

Cu-Pd system
Monotectic portion
Phase diagrams with intermediate phases

Binary system can have two types of solid solutions/phases


terminal phases and intermediate phases.
Terminal phases occur near the pure metal ends, e.g. and
phases in the eutectic system.
Intermediate phases occur inside the phase diagram and are
separated by two-phase regions.
The Cu-Zn system contains both types of phases. and
are terminal phases and , , and are intermediate phases.
Intermediate phases form in ceramic phase diagrams also.
For example, in the Al2O3 SiO2 system an intermediate
phase called mullite (3Al2O3.2SiO2) is formed.
Intermediate phases - Cu-Zn Phase diagram

Cu-Zn phase diagram. and are terminal phases and


, , and are intermediate phases.
Phase diagrams with compounds
Sometimes a crystalline compound called intermetallic
compound may form between two metals.
Such compounds generally have a distinct chemical formula
or stoichiometry.
Example Mg2Pb in the Mg-Pb system (appear as a vertical
line at 81% Pb ), Mg2Ni, Mg2Si, Fe3C.

Mg - Pb phase
diagram
Ternary Phase diagram
A ternary or three component phase diagram has the form of
an triangular prism with an equilateral triangle as a base.
Pure components are at each vertex, sides are binary
compositions and ternary compositions are within the triangle.
The composition lines on the triangle is constructed from
projections of surfaces.

Wt.% C
Ternary phase diagram
The temperature varies along the height of the prism. The
composition triangle is an isothermal section. Alternatively
projections of different surfaces and lines can be shown as
temperature contours.
The composition of any point in the triangle is determined by
drawing perpendiculars from corners to the opposite sides and
measuring the distance of the point along the perpendicular.
Point p, for example, lies on the isocomoposition line 25% A
along the perpendicular A-50. Hence, percentage of A in the
alloy is 25%. Similarly B is 50% and C is 25%.
Examples
Ex.1. A 53% Ni Cu-Ni alloy is cooled from liquid state to
1300 C. Calculate the % of Liquid and solid at 1300 C.
Solution: The tie line at 1300 C intersects solidus at 58% Ni
and liquidus at 45% Ni.
Apply the lever rule to get the liquid fraction
% Liquid = 100* (58 53)/(58 45) = 38%
%Solid = 100* (53 45)/(58 45) = 62% (100 %Liquid))

Ex.2. A 34.6% Pb-Sn alloy is cooled just below the eutectic


temperature (183 C). What is the fraction of proeutectic
and eutectic mixture ( +)?
Solution: The eutectic point is at 61.9% Sn and boundary
is at 19.2% Sn. Apply the lever rule
% proeutectic = 100*(61.9 34.6)/(61.9 19.2) = 64%
% ( +) = 100* (34.6 19.2)/(61.9 19.2) = 36%
References
1. M. Hansen & K. Anderko, Constitution of Binary Alloys,
McGraw-Hill, 1958
2. ASM International, ASM Handbook Volume 3: Alloy Phase
Diagrams, 1992
Web References
http://serc.carleton.edu/research_education/equilibria/phaserule.ht
ml
http://www.sjsu.edu/faculty/selvaduray/page/phase/binary_p_d.pdf
http://www.soton.ac.uk/~pasr1/eutectic.htm
http://www.ce.berkeley.edu/~paulmont/CE60New/alloys_steel.pdf
http://www.substech.com/dokuwiki/doku.php?id=phase_transformat
ions_and_phase_diagrams
http://www.sjsu.edu/faculty/selvaduray/page/phase/ternary_p_d.pdf
Key words

Key Words: Phase; phase rule; phase diagrams; isomorphous;


eutectic; peritectic; monotectic; intermetallic compound; ternary
phase diagram.
Quiz
1. Define a phase? What is Gibbs phase rule?
2. What is isomorphous system? Give example of an
ispmorphous sytem.
3. Why does a liquid metal solidify at constant temperature?
4. What is a tie line. What is lever rule?
5. How is the liquidus and solidus curves of a binary
isomorphous system determined experimentally? (Clue: Refer
to the cooling curves)
6. What is an invariant reaction? Give some examples.
7. What kind of system will result when melting points two
metals having limited solubility in each other are (i) comparable
(ii) significantly different?
8. What is a solvus line?
9. What is eutectic? Why there is infliction in the cooling curve
of a hypoeutectic alloy in the two-phase region?
Quiz
10. Why does the eutectic reaction happen at a constant
temperature?
11. Why Pb-Sn alloys are used as solders?
12. What are terminal and intermediate phases?
13. What is an intermetallic compound?
14. What are the typical phases present in Brass (Cu-Zn)?
15. How is the composition of an alloy determined in a ternary
system?
16. What is monotectic reaction?
17. A Pb-Sn alloy contains 64 wt% proeutectic and rest
eutectic (+) just below 183 C. Find out the average
composition. (Consult Example #2)
18. A 35 wt% Ni Cu-Ni alloy is heated to the two-phase region.
If the composition of the phase is 70% Ni find out (i) the
temperature, (ii) the composition of the liquid phase and (iii) the
mass fraction of both phases. (Consult a Cu-Ni phase diagram)
Phase Transformation
Phase transformation
Phase transformation Formation of a new phase having a
distinct physical/chemical character and/or a different structure
than the parent phase.
It involves two phenomena Nucleation and Growth
Nucleation formation of a nucleus or tiny particles of the
new phase.
A nucleus is formed when the Gibbs free energy, G, of the
system decreases i.e. G becomes negative.
Two types of nucleation Heterogeneous and Homogeneous
Growth Increase in size of the nucleus at the expense of the
parent phase.
Homogeneous nucleation
In homogeneous nucleation the probability of nucleation is
same throughout the volume of the parent phase.
The simplest example of nucleation is solidification of a metal.
Above melting point Tm, liquid free energy, Gl < Gs (Solid free
energy) and free energy change for solidification G > 0.
Below Tm, G < 0 and nuclei of the solid phase form.
Homogeneous nucleation
There are two contributions to free energy change, volume
free energy Gv and surface free energy, due to creation of a
new surface.
Taking the nucleus as a spherical particle of radius r
G = 4/3r3Gv + 4r2 ------------------ (1)
The tiny particle of the solid that forms first will be stable only
when it achieves a critical radius (r*). Below the critical radius it
is unstable and is called embryo.
Since this happens at the maximum of the G vs. r curve
dG /dr = 4r2Gv + 8r = 0
2
r
*

16 3
Gv

This yields and G *


3( Gv )2
Heterogeneous nucleation
Here, the probability of nucleation is much higher at certain
preferred sites such as mold wall, inclusions, grain boundaries,
compared to rest of the parent phase.
Example - Solidification of a liquid on an inclusion surface

IL = IS + SL cos

2
r

SG
L v
With a similar approach it can be shown that and

4 3
G *Het ( 2 3 cos cos 3
) G *Hom S( )
3( Gv ) 2

The small value of ensures that the energy barrier (G) is


effectively lowered in heterogeneous nucleation.
Nucleation and Growth Kinetics
Once the embryo exceeds the critical size r*, the growth of
the nucleus starts. Nucleation continues simultaneously.
Nucleation and growth rates are function of temp. Nucleation
rate increases with cooling rate and degree of undercooling (T
= Tm T).
High nucleation rate and low growth Finer grain size.
The over all transformation rate is the product of nucleation
and growth rates.
Fe-C Phase diagram
Phases in Fe-C system
-ferrite Interstitial solid solution of C in BCC iron. Max
solubility of C is 0.025%. Exists from 273C to 910C.
Austenite () - Interstitial solid solution of C in FCC iron. Max
solubility of C is 2.1%. Exists from 910C - 1394C.
-ferrite (BCC) exists over the temp range of 1394C to
1539C. Max solubility of C is 0.09%.
Cementite, Fe3C - is an intermetallic compound. C content in
Fe3C is 6.67%.
Graphite, the free form of C, also exists in the Fe-C system.
Bainite (B) is another phase which forms in steels at higher
cooling rates.
The hard phase martensite (M) forms below the bainitic
temperature range at high cooling rates.
Critical temperatures in Fe-C system
The eutectoid temperature (727C) during heating and
cooling is Ac1 and Ar1 respectively. A for arrt (arrest), c for
chauffage (heating) and r for refroidissement (cooling).
At normal rates of heating or cooling Ac1 > Ar1.
A2 at 768 C is the currie temp above which Fe turns
paramagnetic while heating.
The temperatures corresponding to ( +)/ and ( +Fe3C)/
phase boundaries are function of carbon content and are
represented as A3 and Acm respectively.
The eutectic temperature is 1146 C.
The peritectic temperature is at 1495 C.
Phase transformation in Fe-C system
Peritectic reaction at 1495 C
L (0.53% C) + (0.09% C) (0.17% C)
Eutectic reaction at 1146C
L (4.3% C) (2.1 % C) + Fe3C (6.67% C). The eutectic
mixture of austenite () and cementite (Fe3C) is called
Ledeburite. Compositions right and left of 4.3% are called hyper
and hypoeutectic steels (Cast iron) respectively.
Eutectoid reaction at 727C
(0.8 % C) (0.025% C) + Fe3C (6.67% C). The eutectoid
mixture of ferrite () and cementite (Fe3C) is called Pearlite.
Compositions right and left of 0.8% are called hyper and
hypoeutectoid steels respectively.
Compositions up to 2.1% C are steels and beyond this it is
considered as cast iron.
Microstructures
A eutectoid steel (0.8% C) will have 100% pearlite (p) at room
temperature (RT). The pearlite formed under equilibrium
conditions consists of alternate lamellas of ferrite and Fe3C.

Schematic of Pearlite White areas are

Hypoeutectoid steels + p; hypereutectoid Fe3C + p.


Hypoeutectic cast irons consist of + ledeburite (Le) below
the eutectic temp and p + Fe3C + Le at RT as the transforms
to Fe3C and p at the eutectoid temp. Similarly hyper eutectic
cast irons will have a structure of Fe3C + Le.
T-T-T diagram
The relation between temperature and time for the formation
of a phase is given by T-T-T or temp time transformation
diagrams also known as isothermal-transformation diagram.
A typical T-T-T diagram is shown below. The phases formed
on isothermal holding at a given temp for a certain period of
time are indicated.
T-T-T diagram
At normal cooling rates pearlite (P) forms, higher cooling
rates generates bainite (B). The size of pearlite or bainite
depends on the transformation temp.
Martensite (M) forms when the steel is cooled below the
maternsite start (Ms) temp at much higher cooling rate so that
the nose of the T-T-T curve (shown dotted) is avoided (the long
blue arrow) .
Diffusion rates below Ms is so low that M transformation
is a diffusionless process (the C content remains same).
However, the crystal structure changes from FCC () to body
centered tetragonal (BCT).
C-C-T diagram
In actual practice a steel is generally cooled continuously.
Continuous-cooling-transformation (C-C-T) diagrams depict this
situation.
The C-C-T curve (Blue) is shifted to the right of the T-T-T
(dashed) curve as continuous cooling transformation occurs at
lower temperature and longer time compared isothermal holding.
C-C-T diagram
Bainite generally does not form in steels during continuous
cooling and hence the C-C-T curve ceases just below the
nose.
The microstructure (fine or coarse) depends on the cooling
rate. Higher the cooling rate finer the microstructure is.
Finer size pearlite is called sorbite and very fine size
pearlite is called troostite.
The critical cooling rate is the one at which the cooling
curve just touches the nose of the C-C-T curve.
A cooling rate higher than the critical rate is needed to form
martensite.
Examples
Ex.1. A eutectoid steel is slowly cooled from 750 C to a
temperature just below 727 C . Calculate the percentage of
ferrite and cementite.
Solution: Eutectoid composition 0.8% C, Ferrite composition
- 0.025% C and cementite 6.67% C.
Apply the lever rule to get the percentages as
% Ferrite = 100* (6.67 0.80)/(6.67 0.025) = 88.3%
%Cementite = 100* (0.80 0.025)/(6.67 0.025) = 11.7%
Ex.2. A carbon steel cooled from austenitic region contains
9.1% ferrite. What is the C content in the steel?
Let c be C content. Apply the lever rule
0.091 = (6.67 c)/(6.67 0.025)
c = 0.1% C
References
http://www.ce.berkeley.edu/~paulmont/CE60New/heat_treatm
ent.pdf
http://www.ce.berkeley.edu/~paulmont/CE60New/transformati
on.pdf
http://www.synl.ac.cn/org/non/zu1/knowledge/phase.pdf
http://www.youtube.com/watch?v=3xP1U_oDnfU

Key words. Phase transformation; Nucleation; Homogeneous


and heterogeneous nucleation; Growth; Fe-C phase diagram;
Eutectoid reaction; T-T-T diagram; C-C-T diagram
Quiz
1. What are the different stages of phase transformation?
2. What are homogeneous and heterogeneous nucleation?
3. Derive the expression for critical radius of the nucleus?
4. What are the different phases present in the Fe-C system?
5. How many invariants reactions are present in the Fe-C
system and what are those?
6. What are microstructure of eutectoid, hypoeutectoid and
hypereuctectoid steels obtained under equilibrium
conditions?
7. What are T-T-T and C-C-T diagrams? What is the
fundamental difference between them?
8. What should be the conditions for forming martensite in
steels?
9. Why is the martensitic transformation in steels a
diffusionless process?
Quiz
10. What are sorbite and troostite?
11. A plain-carbon steel contains 93 wt% ferrite and 7 % Fe3C.
What is the average carbon content in the steel?
12. A 0.9% C steel is slowly cooled from 900 C to a
temperature just below 727 C . Calculate the percentages of
proeutectoid cementite and eutectoid ferrite?
13. A 0.4% C steel is slowly cooled from 940 C to (A) just
above 727 C (B) just below 727 C.
Calculate the amount of austenite and proeutectoid ferrite for
case (A).
Calculate the amount of proeutectoid ferrite and eutectoid
ferrite and cementite for case (B).
Strengthening Mechanisms
Slip in single crystals

PA

PA
cc
oo
ss

c
o
s
c
o
s

Cylindrical single crystal of area A under tensile load P.


Area of the slip plane A/cos and load on the plane P cos.
Shear stress for slip to occur is called the critical resolved
shear stress (CRSS), R.
Effect of Grain boundaries
Grain boundaries act as obstacles to dislocations and hence,
dislocations pile up at the grain boundaries

Number of dislocations in the pile-up, n = ksL/Gb (G, shear


modulus, b, Burger vector, s, avg. resolved shear stress).
A pile-up of n dislocations One big dislocation with Burger
vector nb.
Stress at the tip of the pile up = nbs
Grain boundary strengthening
For a dislocation source at the center of a grain diameter D,
n = ksD/4Gb
The critical shear stress to cross the grain boundary barrier,
c = ns = s2 D/4Gb
s = i (i is the lattice resistance to dislocation motion)
c = ( i)2D/4Gb = i + (c4Gb/D)1/2 = i + kD-1/2
Expressing this in terms of normal stresses gives rise to the

k
D
1
/
2
o

i

Hall-Petch relationship
k is known as locking parameter, which is a measure of the
relative hardening contribution of grain boundaries and i is
known as friction stress which represents overall resistance
of the lattice to dislocation motion.
Solid solution strengthening
Solute atoms introduce lattice strain as their size is different
from the host atoms.
A larger substitutional solute atom will impose a compressive
stress (Fig. a) while a smaller interstitial atom will cause tensile
stresses in the lattice (Fig. b).
Interstitial atoms are often bigger than the interstitial space
they occupy, resulting in a compressive stress field.

(a) (b)
Solid solution hardening
Dislocations have strain field at their cores due to lattice
distortion
Solute atoms with a tensile strain field will diffuse to the
dislocation core to nullify part of the compressive strain field of
the dislocation to reduce the strain energy.
This hinders motion of the dislocation and hence, the
strength increases.

Solid solution hardening


Dislocation strain field
Precipitation hardening
Strength and hardness of some alloys can be increased by
formation of fine precipitates.
The solute should have increasing solubility with increasing
temperature (e.g. Al-Cu) for the precipitation to occur.
Heat treatment Solutionizing or heating to single phase
region. Quenching - rapid cooling to get a superstaurated solid
solution (SSS) (Normal cooling Coarse equilibrium CuAl2
phase below TN). Isothermal holding at certain temperature.
Precipitation Sequence
When the supersaturated solid solution is held isothermally
(aging), fine particles of precipitates form in several steps.
The precipitation sequence Guiner-Preston (GP) zones
(cluster of Cu atoms)
and have different crystal structures than the parent
phase () and are coherent with the parent lattice, while the
equilibrium phase , which forms on prolonged aging
(Overaging) is not coherent.
Hardening mechanism
and have different crystal structures but maintain
coherency with parent lattice resulting in lattice strain. This
impedes dislocation motion and hence, the hardness and
strength increases.
Further aging for longer time dissolves the phase and the
equilibrium phase (CuAl2) forms. This phase is no longer
coherent with parent lattice and as a result hardness decreases,
a phenomenon called overaging.

Coherent precipitate Incoherent precipitate


Strain Hardening
Increasing strength and hardness by plastic deformation is
called strain hardening or work hardening. Also referred as cold
working as deformation takes place at RT.
Extent of strain hardening increases with degree of cold
working (% area reduction).
Since the metal is deformed in a certain direction, grains are
elongated in the direction of working.

Initial structure Cold-worked


Strain Hardening mechanism
Cold working generates dislocations dislocation density
increases. Higher density of dislocations impedes their motion
due to interactions of dislocation strain fields.
Hence the strength increases according to the relation
o = i + Gb1/2. is the dislocation density, b, Burger vector,
G, shear modulus and is a constant.
The ductility decreases after cold working.
Examples
Ex.1 Calculate the resolved shear stress for an FCC single
crystal on the (111) [01 1] slip system if a stress of 14 MPa
is applied in [001] direction.

Solution: The angle between two direction vectors [u1v1w1]

uv 0
u
v
v
w
wv c
and [u2v2w2] is given as
c
o
s

1

2

1
2

2
ua 2

w
u

w

2

a3
1

2
c
o
s

.
7
0
7

o
s

0
.
5
7
7
a

a
Therefore, and

R = 14 cos cos = 14 x 0.707 x 0.577 = 5.7 MPa


Quiz
1. What is critical resolve shear stress? Derive the expression
for CRSS.
2. Calculate the resolved shear stress for an Ni single crystal
on the (111) [01 1] slip system if a stress of 15 MPa is applied
in [001] direction.
3. A stress of 5 MPa is applied to a single crystal FCC metal in
the [0 01] direction. Calculate the CRSS on (1 11) plane in
[1 01], [011] and [1 1 0] directions.
4. What is the mechanism of grain refinement strengthening?
5. Show that strength is proportional to D-1/2 (D = grain dia).
6. An iron rod has a grain size of 0.01 mm and yield strength
of 230 MPa. The strength is 275 MPa at a grain size of 0.006
mm. In order achieve a yield strength of 310 MPa what should
be the grain size?
7. Why is strain hardening also called cold working?
8. What kind of microstructure develops after cold working?
Quiz
9. Why does hardness and strength increase on clod working?
What is the effect of cold working on ductility?
10. How is dislocation density related to strength?
11. What is the mechanism of strengthening by solid solution?
12. What kind of strain field interstitial atoms generally
introduce?
13. What kind of strain fields are associated with dislocations?
14. What are the different stages of precipitation hardening?
15. What kind of alloy system hardens by precipitation?
16. Will precipitation hardening occur if the alloy is cooled
slowly from the single phase region?
17. What is supersaturated solid solution?
18. How does the strength increase by precipitation?
19. What is coherent and incoherent precipitate?
20. What is the main strengthening phase in Al-Cu alloys.
References
http://www.soton.ac.uk/~engmats/xtal/deformation/control.htm
http://people.virginia.edu/~lz2n/mse209/Chapter7.pdf
http://kth.diva-portal.org/smash/get/diva2:9474/FULLTEXT01
http://imechanica.org/files/handout4.pdf

Key words. Strengthening mechanism, Hall-Petch equation,


Solid solution hardening, precipitation hardening, strain
hardening.
Mechanical Properties
Hardness
Hardness can be defined as resistance to deformation or
indentation or resistance to scratch.

Hardness

Indentation Scratch Rebound

Indentation hardness is of particular interest to engineers


and is most commonly used.
Indentation hardness can be measured by different
methods.
Classified based on how it is measured.
Mohs scale of hardness
Mohs Absolute
Mineral Chemical formula
hardness hardness
1 Talc Mg3Si4O10(OH)2 1
2 Gypsum CaSO42H2O 3
3 Calcite CaCO3 9
4 Fluorite CaF2 21
5 Apatite Ca5(PO4)3(OH,Cl,F) 48
Orthoclase
6 KAlSi3O8 72
Feldspar
7 Quartz SiO2 100
8 Topaz Al2SiO4(OH,F)2 200
9 Corundum Al2O3 400
10 Diamond C 1600
Rockwell Hardness
In this type of test, depth of indentation at a constant load is
taken as the measure of Hardness.
A minor load of 10 kg is first applied for good contact
between the indenter and the sample surface.
The major load is then applied and the depth of indentation
is recorded on a dial gage in terms of an arbitrary number.
The dial consists of 100 divisions, each division representing
a penetration depth of 0.002 mm.
Rockwell Hardness
Indenter and Hardness Scale
Two types of indenters 120 diamond cone called Brale
indenter and 1.6 and 3.2 mm diameter steel balls
Combination of indenter and major load gives rise to
different hardness scales.
C - Scale Brale indenter + 150 kg load, designated as RC.
Range is RC 20 RC 70. Used for hard materials like
hardened steels.
B-Scale Steel ball indenter + 100 kg load, written as RB.
Range is RB 0 to RB 100.
Minor loads in RC and RB scales are 10 kg and 3 kg
respectively.
Brinell Hardness
Indentation is done with 10 mm diameter steel ball.
A load of 3000 kg (500 kg for softer materials) is applied for
10 30 s.
Dia of the indentation is measured to obtain the hardness
(Brinell Hardness No.) from the relationship
P

PD
B
H
N

t

D

d
(kgf/m2) (1)


2 2

2 D

P = Applied load
D = Diameter of ball
d
d = Dia of indentation
t = Depth of impression
Brinell Hardness
BHN varies with load. P/D2 value needs to be kept
constant according to eqn. (2). P1/D12 = P2/D22 = P3/D32

D
P
B
H
N

c
o
s (2)


2
1 d
2
d = D sin
Vickers Hardness
Vickers test uses a square-base diamond pyramid indenter
having an angle of 136 between the opposite faces. This angle
approximates the ideal d/D ratio (0.375) in Brinell test (Fig. a)
The hardness, called DPH or VHN (Diamond pyramid
hardness no. or Vickers Hardness no.), is obtained by dividing
the load (1 120 kg) with the surface area of the indentation.
The surface area is calculated from the diagonals length of
the impression. D

(b)
(a)

d
P

P
s
i
nL
/

.
D
P
H
V
H
N

2 2 1 854

L

2
2
Microhardness
Sometime hardness determination is needed over a very small
area.
For example, hardness of carburised steel surface, coatings or
individual phases or constituents of a material.
The load applied is much smaller compared to macrohardness.
The indentation is very small. An optical microscope is used to
observe it. Sample preparation is needed.
Two methods are used for microhardness testing.
Microhardness
Knoop Indentation
Knoop indenter is a diamond pyramidal indenter. Produces
diamond shaped indentation with long and short diagonal
lengths in the ratio of 7:1
The hardness is called Knoop Hardness number (KHN) and
is obtained by dividing the load (25 - 300 g) with the projected
surface area of the indentation.
P Ap

PL
K
H
N

2
(kgf/m2)

Ap = Projected area of indentation


L = Longer diagonal length
C = Indenter specific constant
Microhardness
Vickers Microhardness
This is same as Vickers hardness except that the applied
load is much smaller so as to cover a small area.
The applied load range is 1 100 g.
Tensile Properties
Stress and Strain
Stress, s = P/A --------------- (1)
where P is the applied load and A is the original area of the
cross section of the sample.

L Lo
L
Lo
e

Lo
Strain, -------------- (2)

Lo = Original length
L = Final length
L = L Lo is the elongation

These are called engineering stress and engineering strain.


Elastic and Plastic behavior
All materials deform when subjected to an external load.
Up to a certain load the material will recover its original
dimensions when the load is released. This is known as
elastic behavior.
The load up to which the materials remains elastic is the
elastic limit. The deformation or strain produced within the
elastic limit is proportional to the load or stress. This is known
as Hooks Law , Stress Strain or Stress = E*Strain. E is
known as the Elastic Modulus.
When the load exceeds the elastic limit, the deformation
produced is permanent. This is called plastic deformation.
Hooks law is no longer valid in the plastic region.
Tensile Testing
Load is applied uniaxially in a tensile testing frame and the
displacement is recorded.
The stress and strain are derived using equations (1) and
(2)
The stress is plotted against strain to generate the stress-
strain curve.
Different properties are calculated from this curve.
Tensile Testing
(a)
(b)
Tensile Properties
EL = Elastic limit, up to which Hooks Law (Stress Strain)
is valid. The material comes back to original shape when the
load is released.
Elastic limit is difficult to determine. The proportional limit,
PL, the load at which the curve deviates from linearity, is
taken as the elastic portion.
The slope of the linear region is the Youngs Modulus or
Elastic Modulus (E).
Loading beyond PL produces permanent or plastic
deformation. The onset point of plastic deformation is known
as Yield stress (YS).
In some materials like mild steel the yield point is prominent
(Curve 1 in Fig. b)
Tensile Properties
In many other metals and alloys the yield point is not
distinct (Curve 2, Fig. b). In such cases, a line parallel to the
linear region is drawn at a strain = 0.002 (0.2%) and its
intercept on the plastic region is taken as the yield stress
(Fig. b). This is called 0.2% Proof stress.
The stress at the maximum load is called ultimate tensile
strength (UTS).
The strain up to UTS is the uniform plastic strain. Beyond
this the cross sectional area reduces and necking takes
place.
The fracture strain ef = (Lf - Lo)/Lo, where Lf is the length
after fracture, is taken as the measure of Ductility.
Tensile Properties
Resilience:
The ability of a material to absorb energy in the elastic region.
This is given by the strain energy per unit volume
Uo = soeo (= so2/2E) which is the area of the elastic region
Toughness:
Ability to absorb energy in the plastic range. This is given by
the total area under the stress-strain curve.

High resilience is a
property required in spring
steels whereas structural
steels have high toughness
but lower resilience.
Ductile Vs. Brittle Fracture
The fracture strain ef = (Lf - Lo)/Lo, or reduction of area at
fracture, q = (A Ao)/Ao, is taken as the measure of Ductility.
A ductile material exhibits high fracture strain, that is, it
undergoes significant plastic deformation before fracture.
A brittle material is the one which exhibits little or no plastic
deformation before fracture.
True Stress and Strain
The engineering stress and strain are based on the
original sample dimensions which change during the test.
True stress and strain on the other hand are based on the
actual or instantaneous dimensions and hence, are better
representation of the deformation behavior of the material.
L
L
L
L
L
L
o

.
.
.
.
.
.
.
1 2 1 3
L

LL

L
2
True strain,
odL
1 2
L

e
l
n

l
n
L


L
o
1
Lo

Engineering stress, s = P/Ao


True stress, = P/A = (P/Ao)(Ao/A) = s (Ao/A)
Volume, AL, remains constant, AoLo = AL Ao/A = L/Lo = (e+1)
= s (e+1)
True Stress-Strain Curve
Since the engineering stress-strain curve is based on
original area, it descends after maximum load as the load
bearing ability of the sample decreases due to reduction in
area.
The true stress-strain curve (blue) however, continues to go
up till fracture as it is based on the actual area.
The Flow Curve
The true stress-strain curve is also known as flow curve.
The plastic region of the flow curve can be described as
= K n
n is known as strain-hardening exponent and K is the strength
coefficient. A log-log plot up to maximum load will yield a
straight line. The slope of the line is n. K is the true stress at
= 1. n = 0, perfectly plastic solid, n = 1, elastic solid. For
most metals n = 0.1 0.5
Poissons ratio
A tensile force in the x direction produces an extension along
that axis while it produces contraction along the transverse y
and z axis.
The ratio of the lateral to axial strain is the Poisson's ratio, .
For most metals it is around 0.33

x
Shear Stress and Strain
The deformation in a body may also result in change in the
initial angle between any two lines.
The angular change is known as the shear strain, , which is
produced by a shear stress, .
ah
t
a
n

=G
G is the shear modulus
a


h
Structure-Property Correlation
Structure-insensitive: Elastic modulus
Structure-sensitive properties: Yield stress, UTS, Ductility.
These properties vary with the structure of the material.
For example, the same material having a finer grain size will
have higher strength as per the relation -

k
d
/
1 2
o

i
This is known as the Hall-Petch equation which relates the
yield strength to grain size.
o is the yield strength, d is the grain size and i and k are
material dependent constants.
Finer grain size large grain boundary area/unit volume. As
grain boundaries hinder dislocation motion, stress required to
move the dislocations increases in the fine grained material
and hence the strength increases.
Mechanical Properties of some commonly used materials
Material E,GPa YS,MPa UTS,MPa %Elong. Poisson's
ratio
Csteel 207 220 250 400 500 23 0.30
Stain lesssteel 193 515 850 10 0.30
Alloy steels 207 860 1280 12 0.30
Al 70 34 90 40 0.33
Alalloys 72 85 250500 300 550 1020 0.34
Ti 103 170 240 30 0.34
Tialloy 114 1100 1170 10 0.34
Mg 45 25 40 50 60 8 10 0.35
Mgalloys 45 220 290 15 0.35
Ni 204 148 460 47 0.31
Nisuperalloy 207 517 930 0.21
Al2O3 380 550 0.16
PET 2.7 4 60 70 30300 0.39
References

Mechanical Metallurgy, George E Dieter. McGraw Hill, London


http://www.virginia.edu/bohr/mse209/chapter6.htm
http://web.utk.edu/~prack/mse201/Chapter%206%20Mechanica
l%20Properties.pdf
http://nptel.iitm.ac.in/courses/IIT-
MADRAS/Design_Steel_Structures_I/1_introduction/3_properti
es_of_steel.pdf

Key words: Mechanical properties; Hardness; True stress;


True strain; Strain hardening exponent; Flow curve ; Poissons
ratio; Hall-Petch relationship
Examples
Ex.1. A 15 mm long and 13 mm diameter sample shows the
following behavior in a tensile test. Load at 0.2% offset 6800
kg, maximum load 8400 kg, fracture occurs at 7300 kg,
diameter and length after fracture 8 mm and 65 mm
respectively. Find the standard mechanical properties.

Solution: Ao = (13)2/4 = 132.7 mm2, Af = (8)2/4 = 50.3 mm2


UTS = Pmax/Ao = (8400 x 9.8)/132.7 = 620 N/mm2 = 620 MPa
0.2% proof stress = (6800 x 9.8)/132.7 = 502 N/mm2 = 502 Mpa
Breaking stress = (7300 x 9.8)/132.7 = 539 Mpa
%elongation = 100*(Lf Lo)/Lo = 100 x (65 50)/50 = 30%
% area reduction = 100*(Af Ao)/Lo = 100(132.7 50.3)/132.7 =
62%
Examples
Ex.2. A metal experiences a true strain of 0.16 at a true stress
of 500 MPa. What is the strain hardening exponent of the
metal? K = 825 MPa. What will be the true strain at a stress of
600 MPa?

Solution: n = (log - logK)/log = (log 500 log 825)/log 0.16


= 0.271
= K n
Strain at 600 MPa: 600 = 825 ()0.271 , strain = 0.3
Quiz
1. Define hardness. What is Mohs scale of hardness?
2. Why it is necessary to specify load-indenter combination in
Rockwell hardness test?
3. How is Brinell hardness measured. Show that BHN varies
as P/D2 where P is the load and D is the indenter diameter.
4. Why is the included angle between opposite faces of the
Vickers indenter 136?
5. What is microhardness? Why sometime it is necessary?
6. What is engineering stress and strain?
7. What is Hooks law?
8. What is elastic and proportional limit?
9. How is the elastic modulus measured from the stress-strain
curve?
10. What is yield stress?
Quiz
11. What is 0.2% proof stress?
12. How is the ductility measured?
13. What is ductile and brittle behavior?
14. What is resilience? What is toughness?
15. What is true stress and strain. Deduce the relationship
between true and engineering stress ad strain.
16. Why does the engineering stress-strain curve peak and
drop where as the true stress-strain curve keep on going up?
17. What is a flow curve?
18. What is shear stress and strain
19. What is Poisson's ratio?
20. What are structure-sensitive and structure insensitive
properties?
21. What is Poisson's ratio?
Quiz
22. A 15 mm long and 120 mm dia cylindrical rod is subjected
to a tensile load of 35 kN. It must not experience either plastic
deformation or a diameter reduction of more than 0.012 mm.
Which of the listed materials is suitable for such a requirement
and why? Al (E= 70 GPa, YS = 250 MPa, = 0.33), Ti (E= 105
GPa, YS = 850 MPa, = 0.36), Steel (E= 205 GPa, YS = 550
MPa, = 0.27), Mg (E= 45 GPa, YS = 170 MPa, = 0.35).

23. A metal experiences a true strain of 0.1 at a true stress of


415 MPa. What is the strain hardening exponent of the metal?
K = 1035 MPa. What will be the true strain at a stress of 600
MPa?
Quiz
24. The following data were obtained in a tensile test of a low-
carbon steel of diameter 12 mm and gage length 50 mm.
Load, kN Elongation, mm Load, kN Elongation, mm
2 0.0041 25.2 0.51
4 0.0082 28 1.52
6 0.0132 30 2.03
8 0.0183 34 3.05
10 0.0226 38.4 4.57
12 0.0267 40 6.60
14 0.0310 40.4 7.62
16 0.0351 40.8 12.7
18 0.0391 40.2 14.7
20 0.0445 38.6 15.7
22 0.0485 36.4 17.8
24 0.0518 32.4 19.3

Plot Engineering and True stress-strain curve and find the


tensile properties.
Thermal Property
Thermal Property
Heat capacity
Thermal Property Response of material to application of heat
Manifestation Rise in temperature and change in dimension.
Temperature rise Heat absorption
Heat capacity is the ability of a material to absorb heat
Heat capacity, C, is defined as the amount of energy required
dd
qT

to produce a unit temperature rise


C

(J/mol-K or cal/mol-K), q is energy, T is temperature.


Specific heat, c, is heat capacity per unit mass (J/kg-K or
cal/g-K)
Constant pressure or constant volume heat capacity, Cp and
Cv respectively.
Thermal Conductivity
If there is a temperature gradient, heat will flow from higher to
lower temperature region. This is Thermal conduction.
The ability of a material to transfer the heat is the Thermal
conductivity, k.

dd
TX
q

k q is steady state heat flux i.e.



heat flow per unit area per unit
time (W/m2)
k is thermal conductivity of the
medium (W/m-K)
dT/dX is the thermal gradient in
the medium.
Conduction Mechanism
Atoms vibrate about their equilibrium positions with high
frequency and low amplitudes. Amplitude increases with rise in
temperature.
The vibrations of adjacent atoms are coupled due to atomic
bonding and this leads to generation of elastic waves which
move through the lattice at the velocity of sound and thus carries
the heat.
Each quantum of the wave is known as phonon.
Conduction Mechanism
Free electrons gain kinetic energy in the hotter region and
move towards the colder region thus transferring the heat.
Therefore, thermal conductivity k = kl (lattice) + ke (electron)
Since a large number free valence electrons are available in
metals, the electron mechanism is much more efficient. This
imparts great thermal conductivity that metals are known for.
Thermal and electrical conductivities in metals are related by
WiedemannFranz law: L= k/T, L is a constant, is electrical
conductivity.
Ceramics do not have free electrons as all electrons are tightly
bound in the atomic bonds and hence, are poor conductors of
heat.
Polymers conduct heat by vibrational and rotational motion of
chain molecules and hence, are poor conductors of heat.
Thermal Conductivity
Thermal conductivity of ceramics generally decreases with
increasing temperature due to phonon scattering. At very high
temperature it increases again due to change in heat transfer
mode from conduction to radiation.
Determination of Thermal conductivity
Experimental set up
Heat generation/conduction unit with controls
Thermocouples and Data logger
Maintain two ends of the sample at constant temperatures
Insert five to six thermocouples along the length at different
locations
Plot temperature as a function of distance and find dT/dX from
the slope.
Find the thermal conductivity, k (q = - k dT/dX) [Experimental
techniques to find q can be found at
http://www.physics.uoguelph.ca/~detong/phys3510_4500/Ther
mal%20expansion%20and%20conductivity.pdf
http://www.the-
three.net/documents/portfolio/thermal_conductivity_report.pdf
Thermal Expansion
Most of the solids expand when heated. This is known as

L Lo
thermal expansion.

T

It can be expressed as l
Where, L is the change in length due to a temperature rise of
T. l is known as linear coefficient of thermal expansion (CTE).
l (C-1) is a material property which depends on the type of
atomic bonding. The extent to which a material expands on
heating will depend on its l .
The atomic mechanism of thermal expansion can be viewed
as an increase in the inter-atomic separation.
Therefore, it will depend on the shape of the energy vs. inter-
atomic distance curve.
Thermal Expansion
The energy and vibrational amplitude (width of the potential
energy trough) increase with increasing temperature and so
does the interatomic separation (indicated by the open circles).
For a material with a broader potential curve, the increase in
the interatomic distance is more (Fig. a) and hence thermal
expansion is more.
The increase in atomic distance and hence, the expansion is
much lower for a deep and narrow potential trough (Ceramics).
(a) (b)
Low/Zero Thermal Expansion
Coefficient of thermal expansion (CTE) for metals is in the
range of 5 x 10-6 25 x 10-6/C.
For a typical ceramic like Al2O3 CTE = 7.6 x 10-6/C
There is a class of materials which have very low or near-zero
thermal expansion.
Invar (64Fe 36Ni) has CTE of 1.6 x 10-6/C (Up to 230 C,
the temperature can be increased by heat treatment).
Super Invar (63Fe-32Ni-5Co) 0.72 x 10-6/C.
This is believed to be caused by magnetostriction a
phenomena which lead to volume change on magnetization.
Negative Thermal Expansion
Some materials contract on heating (negative CTE).
Zirconium tungstate (ZrW2O8) for example contracts
continuously from 2 to 1050 K.
A composite (mix) of positive and negative expansion
materials may give rise to a zero expansion material.
Thermal Properties of some materials
Material cp (J/kg-K) l (C-1 x 10-6) k (W/m-K)
Metals
Alumnium 900 23.6 247
Copper 386 17.0 398
Silver 235 19.7 428
Steel 502 16 15.9
Super Invar 500 0.72 10
Ceramics
Alumina (Al2O3) 775 7.6 39
Fused Silica (SiO2) 740 0.4 1.4
Pyrex glass 850 3.3 1.4
Polymers
Polyethylene 1850 106 - 198 0.50
Polystyrene 1170 90-150 0.13
Teflon 1050 126-216 0.25
Thermal Stress
Thermal stresses arise due to
Constrained expansion or contraction e.g. heating or
cooling a rod with fixed rigid ends.
Uneven heating/cooling
Thermal expansion mismatch inside the solid.
Thermal stress due to temperature change from To to Tf
= El(To Tf) = ElT
E is the elastic modulus.

Upon heating, the stress is compressive and tensile while


cooling if the expansion/contraction is restrained.
Example
A steel rod is to be used with its ends held rigid. What is the
maximum temperature the rod can be heated to without the
compressive stress in it exceeding 180 MPa. Elastic modulus
of the rod E = 190 GPa.

Solution:
-180 x 106 Pa (Compressive) = El(To Tf)
l for steel 14 x 10-6 C-1. To = room temperature = 25 C
1 1
8 0
0 9
1 1
0
6
Tf

C
2
5

9
2
o

1
9
0

4
1
0

6


Thermal Shock
Thermal stresses might cause fracture in brittle materials like
ceramics due to rapid heating or cooling if the
expansion/contraction is restrained. This is known as thermal
shock.
The ability of material to withstand such shocks is known as
thermal shock resistance (TSR)k
T
S
R

, f is the fracture stress.



l

Thermal shock can be prevented by controlling the external


conditions like lowering heating and cooling rates and
controlling the thermal/mechanical parameters such as CTE
and fracture stress as per the equation above.
References
http://neon.mems.cmu.edu/rollett/27301/L8_therm_cond-
Nov07.pdf
http://www.engineersedge.com/properties_of_metals.htm
http://www4.ncsu.edu/~pamaggar/403_Thermal.pdf
www.claisse.info/student/Powerpoints/1.3%20Thermal.ppt
http://www.cmse.ed.ac.uk/MSE3/Topics/ThermalProperties.pdf

Key words: Thermal properties; Heat capacity; Thermal


conductivity; Thermal expansion; Thermal shock
Quiz
1. What is heat capacity? What is specific heat?
2. Briefly explain the mechanism of heat conduction in solids?
3. What is phonon?
4. Why do metals have good thermal conductivity?
5. Why are ceramics poor conductors of heat?
6. What is the origin of thermal expansion in solids?
7. Why thermal expansion of ceramics is much lower
compared to metals?
8. What kind of stresses will be developed if the ends of a
solid are constrained while (i) heating (ii) while cooling?
9. Is it possible to have zero or negative thermal expansion?
10. What causes thermal shock?
11. What is thermal shock resistance? How can it be
improved?
Quiz
12. A brass rod is to be used with its ends held rigid. What is
the maximum temperature the rod can be heated to from
room temp without the compressive stress in it exceeding
172 MPa. Elastic modulus of brass E = 100 GPa and
l = 20 x 10-6
13. A 0.35 m long brass rod is heated from 15 to 85 C with
its ends held rigid. Find out the magnitude and type of stress
developed if it was free of stress at 15 C. Elastic modulus of
brass is 100 GPa and of brass is 20 x 10-6/C
Electrical Properties
Electrical Conduction
R

Ohms law V = IR I
l

Area, A V

where I is current (Ampere), V is voltage (Volts) and R is the


resistance (Ohms or ) of the conductor
Resistivity
Resistivity, = RA/l ( -m), where A is the area and l is the
length of the conductor.
Electrical conductivity
Conductivity, = 1/ = l/RA ( -m)-1
Band Theory
Electrons occupy energy states in atomic orbitals
When several atoms are brought close to each other in a
solid these energy states split in to a series of energy states
(molecular orbitals).
The spacing between these states are so small that they
overlap to form an energy band.
Band Theory
The furthest band from the nucleus is filled with valence
electrons and is called the valence band.
The empty band is called the conduction band.
The energy of the highest filled state is called Fermi energy.
There is a certain energy gap, called band gap, between
valence and conduction bands.
Primarily four types of band structure exist in solids.
Band Theory
In metals the valence band is either partially filled (Cu) or the
valence and conduction bands overlap (Mg).
Insulators and semiconductors have completely filled
valence band and empty conduction band.
It is the magnitude of band gap which separates metals,
semiconductors and insulators in terms of their electrical
conductivity.
The band gap is relatively smaller in semiconductors while it
is very large in insulators.
Conduction Mechanism
An electron has to be excited from the filled to the empty
states above Fermi level (Ef) for it to become free and a charge
carrier.
In metals large number of free valence electrons are
available and they can be easily excited to the empty states
due to their band structure.
On the other hand a large excitation energy is needed to
excite electrons in Insulators and semiconductors due the large
band gap.
Empty states

Ef

Conduction in Metals
Filled states
Intrinsic Semiconductors
Semiconductors like Si and Ge have relatively narrow band
gap generally below 2 eV.
Therefore, it is possible to excite electrons from the valence to
the conduction band. This is called intrinsic semi conductivity.
Every electron that is excited to the conduction band leaves
behind a hole in the valence band.
An electron can move in to a hole under an electrical potential
and thus holes are also charge carriers.
Conduction band

Band gap
Hole

Valence band
Intrinsic conductivity
Electrical conductivity of a conductor primarily depends on two
parameters charge carrier concentration, n, and carrier
mobility, . Conductivity, = n e
e is absolute charge (1.6 x 10-19 C).
Intrinsic semiconductors have two types charge carriers,
namely electrons and holes
=n e e+p e h
where, n and p are concentration of electron and hole charge
carriers respectively and e and h are their mobility.
Since each electron excited to conduction band leaves behind
a hole in the valence band, n = p = ni and
= n e ( e + h) = p e ( e + h) = ni e ( e + h)
Extrinsic Semiconductors
The conductivity is enhanced by adding impurity atoms
(dopant) in extrinsic semi conductors . All semi conductors for
practical purposes are extrinsic.
A higher valence dopant e.g. P (5+) in Si (4+) creates an extra
electron (n-type) while a lower valence dopant like B (3+) creates
a hole (p-type) as shown in the atomic bonding model below.
This increases the charge carrier concentration and hence the
enhancement in conductivity.

Si Si Si Si Si Si Si Si
Free Hole
electron
Si P Si Si Si B Si Si

Si Si Si Si Si Si Si Si

n-type p-type
Extrinsic Semiconductors
The band theory model of n-type and p-type extrinsic
semiconductors are shown below.
In n-type, for each impurity atom one energy state (known as
Donor state) is introduced in the band gap just below the
conduction band.
In p-type, for each impurity atom one energy state (known as
acceptor state) is introduced in the band gap just above the
valence band.
Conduction band

Donor
state Band gap Acceptor
state

Valence band

n-type p-type
Extrinsic conductivity
Large number of electrons can be excited from the donor state
by thermal energy in n-type extrinsic semiconductors.
Hence, number of electrons in the conduction band is far
greater than number of holes in the valence band, i.e. n >> p
and
=n e e
In p-type conductors, on the other hand, number of holes is
much greater than electrons (p >> n) due to the presence of the
acceptor states.
=p e h
Effect of Temperature
Metals
Increasing temperature causes greater electron scattering due
to increased thermal vibrations of atoms and hence, resistivity,
, (reciprocal of conductivity) of metals increases (conductivity
decreases) linearly with temperature.
Effect of Temperature
Metals contd
The resistivity of metals depends on two other factors namely,
impurity level and plastic deformation as these generate
scattering centers for electrons.
Increase in impurity level results in more scattering centers
and decreases the conductivity.
Similarly plastic deformation introduces more dislocations
which act as scattering centers and increase the resistivity.

total = t + i + d
Effect of Temperature
Intrinsic Semiconductors
In intrinsic semiconductors the carrier concentration increases
with temperature as more and more electrons are excited due to
the thermal energy.
Effect of Temperature
Extrinsic Semiconductors
Temperature dependence of extrinsic semiconductors, on the
other hand is totally different.
For example, an n-type conductor exhibits three regions in the
temperature vs. carrier concentration curve.
Effect of Temperature
Extrinsic Semiconductors contd..
In the low temperature region known as Freeze-out region,
the charge carriers cannot be excited from the donor level to
conduction band due to insufficient thermal energy.
In the intermediate temperature range ( 150 450 K) almost
all the donor atoms are ionized and electron concentration is
approximately equal to donor content. This region is known as
Extrinsic region.
In the high temperature region sufficient thermal energy is
available for electrons to get excited from the valence to the
conduction band and hence it behaves like an intrinsic semi
conductor.
Electrical properties of some metals at RT

Metal Conductivity Resistivity


( -1-m-1) ( -m)
Silver 6.8 x 107 1.59 x 10-8
Copper 6.0 x 107 1.68 x 10-8
Gold 4.3 x 107 2.44 x 10-8
Aluminum 3.8 x 107 2.82 x 10-8
Nickel 1.43 x 107 6.99 x 10-8
Iron 1.0 x 107 9.0 x 10-8
Platinum 0.94 x 107 1.06 x 10-7
Electrical properties of some semi conductors

Material Band gap Conductivity n p


(eV) ( -1-m-1) (m2/V-s) (m2/V-s)

Si 1.11 4 x 10-4 0.14 0.05


Ge 0.67 2.2 0.38 0.18
GaP 2.25 - 0.03 0.015
GaAs 1.42 1 x 10-6 0.85 0.04
InSb 0.17 2 x 104 7.7 0.07
CdS 2.40 - 0.03 -
ZnTe 2.26 - 0.03 0.01
Dielectric Property
A dielectric material is an insulating material which can
separate positive and negatively charged entities.
Dielectric materials are used in capacitors to store the
electrical energy.
Capacitance
Capacitance, C, is related to charge stored, Q, between two
oppositely charged layers subjected to a voltage V. C = Q/V
If two parallel plates of area, A, are separated by a distance l
in vacuum, then C = o A/l. o, permittivity of vacuum = 8.85 x
10-12 F/m.
If a dielectric material is present between the plates,
C = A/l, is the permittivity of the dielectric medium.
Relative permittivity r = / o, also known as dielectric
constant.
Capacitance and Polarization
The orientation of a dipole along the applied electric field is
called polarization (P).
It causes charge density to increase over that of a vacuum
due to the presence of the dielectric material so that
D= o + P. is the electric field.
D is surface charge density of a capacitor, also called
dielectric displacement.
Types of Polarization
Four types of polarization: Electronic, Ionic, Orientation, and
Space charge (interfacial).
Electronic polarization is due to displacement of the centre of
the electron cloud around the nucleus under the applied field.
Ionic polarization occurs in ionic material as the applied
electric filed displaces the cations and anions in opposite
directions resulting in a net dipole moment.
Orientation polarization can only occur in materials having
permanent dipole moments. The rotation of the permanent
moment in the direction of the applied field causes the
polarization in this case.
Space charges polarization arises from accumulation of
charge at interfaces in a heterogeneous material consisting of
more than one phase having different resistivity.
Ferro-electricity
Ferro-electricity is defined as the spontaneous alignment
of electric dipoles in the absence of an external field.
The spontaneous polarization results from relative
displacement of cations and anions from their symmetrical
positions. Therefore, ferroelectric materials must posses
permanent dipoles.
Examples of ferroelectric materials: BaTiO3, Rochelle salt
(NaKC4H4O6.4H2O), potassium dihydrogen phosphate
(KH2PO4), potassium niobate (KNbO3), lead zirconate
titanate [Pb (ZrO3, TiO3)].
These materials have extremely high dielectric constants
at relatively low applied field frequencies. Hence,
capacitors made from ferroelectric materials are smaller
than those made from other dielectric materials.
Piezoelectricity
Piezo-electricity is defined as conversion of electrical
energy into mechanical strain and vice versa.
It arises due to polarization induced by an external force.
Thus by reversing the direction of external force, direction of
the established field can be reversed i.e. the application of an
external electric field alters the net dipole length causing a
dimensional change.
Application for these materials includes microphones,
ultrasonic generators, sonar detectors, and mechanical strain
gauges.
Examples: Barium titanate, lead titanate, lead zirconate
(PbZrO3),ammonium dihydrogen phosphate (NH4H2PO4),
and quartz.
Evaluation
At the end of this chapter one should be able to understand
The source of electrical conductivity
Band theory, energy bands and band gap
Reasons for high conductivity of metals
Semi conductivity Intrinsic and Extrinsic
Effect of temperature on conductivity
Dielectric behavior
Ferro and Piezo-electricity

Key words: Electrical conductivity; Band theory; Band gap;


Metallic conductors; Semi conductors; Dielectric;
Ferroelectricity; Piezoelectricity.
Web References
http://hyperphysics.phy-astr.gsu.edu/hbase/solids/band.html#c3
http://hyperphysics.phy-astr.gsu.edu/hbase/solids/intrin.html
http://en.wikipedia.org/wiki/Electronic_band_structure
http://www.youtube.com/watch?v=03j4ZvQCKWY&feature=related
http://www.youtube.com/watch?v=AgkQrCeJF1Y&feature=relmfu
http://www.virginia.edu/bohr/mse209/chapter19.htm
http://simple-semiconductors.com/1.html
www.exo.net/~jillj/activities/semiconductors.ppt
http://free-zg.t-com.hr/Julijan-Sribar/preview/semicond.pdf
Quiz
1. What is Ohms Law?
2. What is resistivity?
3. Briefly explain the band theory of electrical conduction.
4. What is Fermi energy?
5. Why are metals highly conductive?
6. Briefly explain the conduction mechanism in metals?
7. What is the difference between band structure of Cu and
Mg?
8. How is the conductivity of metals affected by impurity level?
9. What is the role of dislocations on conductivity of metals?
10. Why does the metallic conductivity decrease with
increasing temperature?
11. What is the typical band gap in semiconductors?
12. What is intrinsic semi conductivity?
Quiz
13. Show that the conductivity in intrinsic semi conductors,
= ni e ( e + h)
14. What is extrinsic semi conductivity? Which factors control
the conductivity in these semi conductors?
15. What are acceptor and donor levels?
16. Explain the atomic and band theory models of extrinsic
semi conductivity.
17. What is the effect of temperature on extrinsic semi
conductivity?
18. How does the carrier concentration in intrinsic semi
conductors depend on temperature?
19. Name some compound semi conductors.
20. Calculate the electrical conductivity of intrinsic Si at 150 C.
The carries concentration in Si at 150 C is 4 x 1019 m-3 and
2 2
e = 0.06 m /V-s and h = 0.022 m /V-s.
Quiz
21. If the electrical conductivity = oe-Eg/2kT then calculate the
conductivity of GaAs at Room temp (27 C) and 70 C.
ni = 1.4 x 1012 m-3, e = 0.72 m2/V-s and h = 0.02 m2/V-s for
GaAs at RT. Eg of GaAs is 1.47 eV. k = 8.62 x 10-5 eV/K
22. Find the electrical conductivity of pure Si at 200 C.
Electrical resistivity of Si at RT is 2.3 x 103 -m and Eg = 1.1 eV.
23. Find the electrical conductivity of pure Ge (Eg = 0.67 eV) at
250 C. Electrical resistivity of Ge at RT is 45 x 10-2 -m
24. What is dielectric constant?
25. What is polarization? How many types are there?
26. What is ferro-electricity? Give some examples of ferro-
electric materials.
27. What is piezoelectricity?
Magnetic Properties
Magnetic field
Magnetic field is a force which is generated due to energy
change in a volume of space.
A magnetic field is produced by an electrical charge in
motion e.g. current flowing in a conductor, orbital movement
and spin of electrons.
The magnetic field can be described by imaginary lines as
shown in the figure below for a magnet and a current loop.
Magnetic lines of force

Current
Magnetic field Strength
If a magnetic field, H, is generated by a cylindrical coil
(solenoid) of n turns and length l, H = nI/l (A/m)
Magnetic flux density, B: It is the magnitude of the field
strength within a substance subjected to a field H
B = H (Tesla or Weber/m2)
, called the permeability, is the measure of the degree to
which a material can be magnetized.
In vacuum B = oH. o is the permeability of vacuum and is a
universal constant. o = 4 x 10-7(H/m). r = /o is the relative
permeability.
Magnetic moments
Being a moving charge, electrons produce a small magnetic
field having a magnetic moment along the axis of rotation.
The spin of electrons also produces a magnetic moment
along the spin axis.
Magnetism in a material arises due to alignment of magnetic
moments.
Magnetic Dipole and Monopole
Analogous to electric dipole, a magnetic dipole can be
defined as two monopoles of opposite and equal strength
separated by a certain distance.
A magnetic monopole, however, is not observed in nature.
If there are N monopoles each located at a point given by a
vector , then the magnetic dipole moment can be defined as
a vector, N
u m ia i
i 1

Two monopoles of strength +m and m separated by


distance l, will give a dipole = m1 m2 = m(1 2) = m
A bar magnet can be thought of consisting of two opposite
and equal poles at its two ends.
Magnetization
With the application of a magnetic field magnetic moments
in a material tend to align and thus increase the magnitude of
the field strength.
This increase is given by the parameter called magnetization,
M, such that B = oH + oM.
M = mH.
m is called magnetic susceptibility.
m = r 1
Magnetism
Depending on the existence and alignment of magnetic
moments with or without application of magnetic field, three
types of magnetism can be defined.

Magnetism

Diamagnetism Paramagnetism Ferromagnetism


Diamagnetism
Diamagnetism is a weak form of magnetism which arises
only when an external field is applied.
It arises due to change in the orbital motion of electrons on
application of a magnetic field.
There is no magnetic dipoles in the absence of a magnetic
field and when a magnetic field is applied the dipole moments
are aligned opposite to field direction.
The magnetic susceptibility, m (r 1) is negative i.e. B in a
diamagnetic material is less than that of vacuum.
H =0 H
Diamagnetic materials:
Al2O3, Cu, Au, Si, Zn
Paramagnetism
In a paramagnetic material the cancellation of magnetic
moments between electron pairs is incomplete and hence
magnetic moments exist without any external magnetic field.
However, the magnetic moments are randomly aligned and
hence no net magnetization without any external field.
When a magnetic field is applied all the dipole moments are
aligned in the direction of the field.
The magnetic susceptibility is small but positive. i.e. B in a
paramagnetic material is slightly greater than that of vacuum.
H=0 H
Paramagnetic materials:
Al, Cr, Mo, Ti, Zr
Ferromagnetism
Certain materials posses permanent magnetic moments in
the absence of an external magnetic field. This is known as
ferromagnetism.
Permanent magnetic moments in ferromagnetic materials
arise due to uncancelled electron spins by virtue of their
electron structure.
The coupling interactions of electron spins of adjacent atoms
cause alignment of moments with one another.
The origin of this coupling is attributed to the electron
structure. Ferromagnetic materials like Fe (26 [Ar] 4s23d6)
have incompletely filled d orbitals and hence unpaired electron
spins.
Antiferromagnetism
If the coupling of electron spins results in anti parallel
alignment then spins will cancel each other and no net
magnetic moment will arise.
This is known as antiferromagnetism. MnO is one such
example.
In MnO, O2- ions have no net magnetic moments and the
spin moments of Mn2+ ions are aligned anti parallel to each
other in adjacent atoms.

O2-
Mn2+
Ferrimagnetism
Certain ionic solids having a general formula MFe2O4, where
M is any metal, show permanent magnetism, termed
ferrimagnetism, due to partial cancellation of spin moments.
In Fe3O4, Fe ions can exist in both 2+ and 3+ states as
Fe2+O2 (Fe3+)2(O2-)3 in 1:2 ratio. The antiparallel coupling
between Fe3+ (Half in A sites and half in B) moments cancels
each other. Fe2+ moments are aligned in same direction and
result in a net magnetic moment.
Octahedral Tetrahedral

Fe3+

Fe2+
Domains
Ferromagnetic materials exhibit small-volume regions in
which magnetic moments are aligned in the same directions.
These regions are called domains.
Adjacent domains are separated by domain boundaries. The
direction of magnetization changes across the boundaries.
The magnitude of magnetization in the material is vector sum
of magnetization of all the domains.
Domains

Domain
wall
Magnetization and Saturation
When a magnetic field is applied to a ferromagnetic material,
domains tend to align in the direction of the field by domain
boundary movement and hence, the flux density or magnetization
increases.
As the field strength increases domains which are favorably
oriented to field direction grow at the expense of the unfavorably
oriented ones. All the domains are aligned to the field direction at
high field strengths and the material reaches the saturation
magnetization, Ms.

The initial slope of the B-H


curve at H =0 is called initial
permeability, i, which is a
material property.
Hysteresis
If the field is reduced from saturation by magnetic reversal, a
hysteresis develops.
As the field is reversed the favorably oriented domains tend to
align in the new direction. When H reaches zero some of the
domains still remain aligned in the previous direction giving rise
to a residual magnetization called remanence, Mr.

Hc, the reverse filed strength at


which magnetization is zero, is
called Coercivity
Hard and Soft magnets
Based on their hysteresis characteristics ferro and
ferrimagnetic materials can be classified as hard and soft
magnets.
Soft magnets have a narrow hysteresis curve and high initial
permeability and hence easy to magnetize and demagnetize. It
is just opposite for the Hard magnets.
Hard and Soft magnets
The magnetic hardness is expresses by a term called energy
product which is the area of the largest rectangle that can be
drawn in the second quadrant (red-hatched).
Conventional hard magnetic materials like steel, Cunife(Cu-
Ni-Fe) alloys, Alnico (Al-Ni-Co) alloy have BHmax values in the
range of 2 80 kJ/m3. High-energy hard magnetic materials
like Nd2Fe14B, SmCo5 exhibit BHmax 80 kJ/m3.
Hard magnets are used in all permanent magnets in
applications such as power drills, motors, speakers.
Soft magnets like Fe, Fe-Si are useful when rapid
magnetization and demagnetization is required as in
transformer cores.
Impurity and other defects should be low for this purpose as
they may hinder the domain wall movement through which
domains align.
Magnetic anisotropy
The magnetic properties of a crystalline material are not
isotropic i.e. properties are not the same in all crystallographic
direction.
There always happens to be a preferred direction in which
magnetization is easier. For example, [0001] direction is the
preferred magnetization direction in Co. For Fe it is [100] as
shown in the diagrams below.
Effect of Temperature
The atomic vibration increases with increasing temperature
and this leads to misalignment of magnetic moments. Above a
certain temperature all the moments are misaligned and the
magnetism is lost. This temperature is known as Curie
temperature, Tc.
Ferro and ferrimagnetic materials turn paramagnetic above
curie point. For Fe Tc = 768 C, Co 1120 C, Ni 335 C.

Mo

magnetization
Saturation

Below Tc Above Tc 0
Temperature Tc
Superconductivity
Superconductivity is disappearance of electrical resistance
below a certain temperature.
The temperature below which superconductivity is attained is
known as the critical temperature, TC.
The superconducting behavior is represented in a graphical
form in the figure below.
Bardeen-Cooper-Schreiffer (BCS) Theory
John Bardeen, Leon Cooper and John Schreiffer BCS
theory, Noble prize for Physics in 1972 .
The temperature dependence of metals arises out of
scattering of electrons due to atomic vibrations which increase
with temperature.
Cooper pair Below TC two electrons can pair through the
lattice phonon which causes a slight increase in the positive
charge around an electron and since thermal energy to scatter
is low, this pair can move through the lattice.

Motion of Cooper pair


through the lattice
BCS Theory contd..
Thus the charge carrier in a superconductor is a pair of
electrons instead of a single electron.
BCS theory applies well to conventional superconductors like
Al (TC = 1.18 K), Nb3Ge (TC = 23 K).
High temp. superconductors Recently a number of ceramic
superconductors such as YBa2Cu3O7 have been discovered
whose TC is much higher.

Material TC (K)
Aluminum 1.18
Nb-Ti alloy 10.2
Nb3Al 18.9
Nb3Ge 23.0
YBa2Cu3O7 92
Tl2Ba2Ca2Cu3O10 125
Superconductivity and Magnetism
The Meissner effect
A material in its superconducting state will expell all of an
applied magnetic field (Fig. b). This is Meisnner effect.
A magnet placed over a superconductor will thus float, a
phenomenon known as magnetic levitation.

(a) T>TC (b) T<TC


Messner effect. (a) Above TC , normal conducting state, magnetic flux
penetrates. (b) below TC, superconducting, the magnetic field is
expelled.
Types of Superconductors
If the field is increased, some of the superconducting materials
come back to normal conducting state above a critical magnetic
field HC (Fig. c) These are Type I superconductors. Ex. Al , Pb
In another class of materials the field begins to intrude above a
critical value of the applied field (HC1) and at a higher field (HC2) it
turns into a normal conductor (Fig. d). The transition is gradual
here unlike Type I. These are called Type II superconductors.
Ex. Nb3Sn, YBa2Cu3O7
(d) Type II
(c) Type I
Applications

Superconductors are used in


Maglev trains which can reach very high velocity
MRI scan machines (Medical science, Brain imaging)
High efficiency electric generators
Energy storage
Superconducting Quantum Interference Device (SQUID)
The Large Hadron Collider (LHC) for generating high
velocity particles travelling at speed of light
Key Words
Magnetism; Magnetic properties; Diamagnetism;
Paramagnetism; Ferromagnetism; Ferrimagnetism;
Antiferromagnetism; Hysteresis; Soft and Hard magnets;
Curie point; Superconductivity; BCS theory; Meissner effect.
References
http://www.ndted.org/EducationResources/HighSchool/Magneti
sm/magnetismintro.htm
http://www.ee.ucla.edu/~jjudy/classes/magnetics/
http://media.wiley.com/product_data/excerpt/22/07803103/0780
310322.pdf
http://phy.ntnu.edu.tw/~changmc/Teach/SS/SS_note/chap11.pdf
http://teachers.web.cern.ch/teachers/archiv/HST2001/accelerat
ors/superconductivity/superconductivity.htm
http://katzgraber.org/teaching/SS07/files/burgener.pdf
http://chabanoiscedric.tripod.com/NSCHSS.PDF
Quiz
1. What is a magnetic field?
2. What is the source of a magnetic field?
3. What is magnetic flux?
4. What is permeability?
5. What is relative permeability?
6. What is the origin of magnetic moments in materials?
7. What are the different kinds of magnetism?
8. How is electron configuration related to magnetism?
9. What is ferrimagnetism? How is it different from
ferromagnetism?
10. Explain the origin of ferrimagnetism taking the example of
Fe3O4
11. What is antiferromagnetism?
12. What is a magnetic domain?
13. What is magnetic susceptibility?
Quiz
14. Why do ferromagnets reach saturation on application of a
magnetic field of sufficient strength?
15. Why does a residual magnetism remains even at H = 0
during magnetic reversal in ferromagnets?
16. What is Coercevity?
17. What is meant by hard and soft magnets?
18. Which parameter decides the magnetic hardness?
19. Give examples of soft and hard magnets.
20. What is initial permeability? How is it related to
magnetization?
21. Why should soft magnets for transformer core application
be free of defects and impurities?
22. Why the magnetism is lost when ferromagnets are heated
above a certain temperature?
23. What is magnetic anisotropy? What are hard and soft axis
of magnetization?
Quiz
24. What is superconductivity?
25. What is BCS theory of superconductivity?
26. What is High-temperature superconductor?
27. What is Meissner effect?
28. What is Type I and Type II superconductors?
Properties and Applications of
Materials
Classification of Materials

Materials

Metals Polymers Ceramics


Metals

Metals

Ferrous Non-Ferrous

Steel and Cast Irons Al, Cu, Mg etc.


Ferrous Materials

Ferrous

Steels Cast iron

Low Alloy High Alloy

Stainless Tool steel


steel
Ferrous Materials - Steels
Steels - alloys of iron-carbon.
May contain other alloying Steels
elements.
Several grades are available. Low High
alloy alloy
Low Alloy (<10 wt%)
Low Carbon (<0.25 wt% C) Low
Carbon Stainless
Medium Carbon (0.25 to 0.60
wt%)
Medium
High Carbon (0.6 to 1.4 wt%) Carbon Tool
High Alloy
High
Stainless Steel (> 11 wt% Cr)
Carbon
Tool Steel
Low Carbon Steel
Plain carbon steels - very low content of alloying elements
and small amounts of Mn.
Most abundant grade of steel is low carbon steel - greatest
quantity produced; least expensive.
Not responsive to heat treatment; cold working needed to
improve the strength.
Good Weldability and machinability
High Strength, Low Alloy (HSLA) steels - alloying elements
(like Cu, V, Ni and Mo) up to 10 wt %; have higher strengths
and may be heat treated.
Low carbon steel
Compositions of some low carbon and low alloy steels
Properties and typical application of some low carbon and
low alloys steels
Medium Carbon Steel
Carbon content in the range of 0.3 0.6%.
Can be heat treated - austenitizing, quenching and then
tempering.
Most often used in tempered condition tempered martensite
Medium carbon steels have low hardenability
Addition of Cr, Ni, Mo improves the heat treating capacity
Heat treated alloys are stronger but have lower ductility
Typical applications Railway wheels and tracks, gears,
crankshafts.
Composition of some alloyed medium carbon steels
High Carbon Steel
High carbon steels Carbon content 0.6 1.4%
High C content provides high hardness and strength.
Hardest and least ductile.
Used in hardened and tempered condition
Strong carbide formers like Cr, V, W are added as alloying
elements to from carbides of these metals.
Used as tool and die steels owing to the high hardness and
wear resistance property
Compositions and Application of some Tool steels
Effects of Alloying Elements on Steel
Manganese strength and hardness; decreases ductility and
weldability; effects hardenability of steel.
Phosphorus increases strength and hardness and decreases
ductility and notch impact toughness of steel.
Sulfur decreases ductility and notch impact toughness
Weldability decreases. Found in the form of sulfide inclusions.
Silicon one of the principal deoxidizers used in steel
making. In low-carbon steels, silicon is generally detrimental to
surface quality.
Copper detrimental to hot-working steels; beneficial to
corrosion resistance (Cu>0.20%)
Nickel - ferrite strengthener; increases the hardenability and
impact strength of steels.
Molybdenum increases the hardenability; enhances the creep
resistance of low-alloy steels
Stainless steel
Stainless steels - A group of steels that contain at least 11% Cr.
Exhibits extraordinary corrosion resistance due to formation of a
very thin layer of Cr2O3 on the surface.
Categories of stainless steels:
Ferritic Stainless Steels Composed of ferrite (BCC)
Martensitic Stainless Steels Can be heat treated.
Austenitic Stainless Steels Austenite () phase field is extended
to room temperature. Most corrosion resistant.
Precipitation-Hardening (PH) Stainless Steels Ultra high-
strength due to precipitation hardening.
Duplex Stainless Steels Ferrite + Austenite

Composition and Properties of some stainless steels are given


in the next slide
Applications of Stainless steels
Cast Irons
Carbon 2.1- 4.5 wt% and Si (normally 1-3 wt%).
Lower melting point (about 300 C lower than pure iron) due
to presence of eutectic point at 1153 C and 4.2 wt% C.
Low shrinkage and good fluidity and casting ability.
Types of cast iron: grey, white, nodular, malleable and
compacted graphite.
Grey Cast Iron
Grey cast iron contains graphite in the form of flakes. Named
after its grey fractured surface. C:3.0 4.0 wt%, Si: 1.0 3.0 %
Microstructure: graphite flakes in a ferrite or pearlite matrix
Weak & brittle in tension (the graphite flake tips act as stress
concentration sites).Stronger in compression,
Excellent damping capacity, wear resistance.
Microstructure modification by varying silicon content and
cooling rate
Casting shrinkage is low
Nodular or Ductile Iron
Addition of Mg and/or Cerium to grey iron converts the
graphite flakes to nodules.
Normally a pearlite matrix.
Castings are stronger and much more ductile than grey iron
as the stress concentration points existing at the flake tips are
eliminated.
White Cast Iron
White cast iron C: 2.5 3 wt.%, Si: 0.5 1.5%. Most of the
carbon is in the form of cementite. Named after its white
fracture surface.
Results from faster cooling. Contains pearlite + cementite,
not graphite. Thickness variation may result in nonuniform
microstructure from variable cooling
Very hard and brittle
Used as intermediate to produce malleable cast iron.
Malleable Cast Iron
Malleable cast iron Carbon: 2.3 2.7 wt%, Si: 1.0 1.75 %
Obtained by heat treating white iron for a prolonged period
that causes decomposition of cementite into graphite.
Heat treatment : Two stages Isothermal holding at 950 C
and then holding at 720 C.
graphite forms in the form of rosettes in a ferrite or pearlite
matrix.
Reasonable strength and improved ductility (malleable)

Heat
treatment

White iron Malleable


Compact Graphite Iron (CGI)
CGI graphite occurs as blunt flakes or with a worm-like shape
(vermicular). Carbon: 3.1 4.0 wt%, Silicon: 1.7 3.0 wt %.
Microstructure and properties are between gray and ductile iron.
Alloying addition may be needed to minimize the sharp edges
and formation of spheroidal graphite. Matrix varies with alloy
additions or heat treatment.
As castable as grey iron, but has a higher tensile strength and
some ductility.
Relatively high thermal conductivity, good resistance to
thermal shock, lower oxidation at elevated temperatures.
Applications of Cast iron
Cast irons are used in wide variety of application owing to
the properties like good fluidity, ease of casting, low
shrinkage, excellent machinability, wear resistance and
damping capacity.
Applications
Car parts cylinder heads, blocks and gearbox cases.
Pipes, lids (manhole lids)
Foundation for big machines (good damping property)
Bridges, buildings
Cook wares Excellent heat retention
Nonferrous Metals
Cu Alloys Al Alloys
Brass: Cu-Zn alloy. -low : 2.7 g/cm3
Corrosion resistant. Used in -Cu, Mg, Si, Mn, Zn additions
costume jewelry, coins -solid solution or precipitation
Bronze : Cu with Sn, strengthened (structural
Al, Si, Ni aircraft parts
Cu-Be: & packaging)
precipitation hardened Mg Alloys
Nonferrous
(bushings, landing gear) -very low : 1.7g/cm3
-ignites easily
-aircraft, missiles
Ti Alloys
relatively low : 4.5 g/cc Refractory metals
reactive at high Ts Noble metals -high melting Ts
space and biomedical - Ag, Au, Pt -Nb, Mo, W, Ta
oxidation/corrosion
application
resistant
Copper
Copper is one of the earliest metals discovered by man.
The boilers on early steamboats were made from copper.
The copper tubing used in water plumbing in Pyramids was
found in serviceable condition after more than 5,000 years.
Cu is a ductile metal. Pure Cu is soft and malleable, difficult
to machine.
Very high electrical conductivity second only to silver.
Copper is refined to high purity for many electrical
applications.
Excellent thermal conductivity Copper cookware most
highly regarded fast and uniform heating.
Electrical and construction industries are the largest users
of Cu.
Copper
The second largest use of Cu is probably in coins.
The U.S. nickel is actually 75% copper. The dime, quarter,
and half dollar coins contain 91.67% copper and the Susan B
Anthony dollar is 87.5% copper.
The various Euro coins are made of Cu-Ni, Cu-Zn-Ni or
Cu-Al-Zn-Sn alloys.
Copper Alloys
Brasses and Bronzes are most commonly used alloys of Cu.
Brass is an alloy with Zn. Bronzes contain tin, aluminum,
silicon or beryllium.
Other copper alloy families include copper-nickels and nickel
silvers. More than 400 copper-base alloys are recognized.
Family of Cu Alloys
Alloy Alloying element UNS numbers

Brass Zinc (Zn) C1xxxxC4xxxx,C66400


C69800
Phosphor bronze Tin (Sn) C5xxxx
Aluminium bronzes Aluminium (Al) C60600C64200
Silicon bronzes Silicon (Si) C64700C66100
Copper nickel, Nickel (Ni) C7xxxx
nickel silvers
Copper Alloys - Brass
Brass is the most common alloy of Cu Its an alloy with Zn
Brass has higher ductility than copper or zinc.
Easy to cast - Relatively low melting point and high fluidity
Properties can be tailored by varying Zn content.
Some of the common brasses are yellow, naval and
cartridge.
Brass is frequently used to make musical instruments (good
ductility and acoustic properties).
Bronze
Copper alloys containing tin, lead, aluminum, silicon and
nickel are classified as bronzes.
Cu-Sn Bronze is one of the earliest alloy to be discovered as
Cu ores invariably contain Sn.
Stronger than brasses with good corrosion and tensile
properties; can be cast, hot worked and cold worked.
Wide range of applications: ancient Chinese cast artifacts,
skateboard ball bearings, surgical and dental instruments.

Bronze bearing
Beryllium copper
Cu-Be alloys are heat treatable. Max solubility of Be in Cu is
2.7% at 866 C. Decreasing solubility at lower temp. imparts
precipitation hardening ability.
Cast alloys - higher Be. Wrought alloys lower Be and some
Co
Cu-Be is ductile, weldable and machinable. Also resistant to
non-oxidizing acids (HCl or H2CO3), abrasive wear and galling.
Thermal conductivity is between steels and aluminum.
Applications
Used in springs, load cells and other parts subjected to
repeated loading. Low-current contacts for batteries and
electrical connectors. Cast alloys are used in injection molds.
Other applications include jet aircraft landing gear bearings and
bushings and percussion instruments.
Compositions, Properties and Application of some Cu Alloys
Name UNS Compos. Condition YS UTS %El Applications
No. (wt.%) (MPa) (MPa)
Eletrolytic C11000 0.04 O Annealed 69 220 45 Electrical wires,
Copper roofing, nails, rivets
Cartridge C26000 30.0 Zn Cold- 435 525 8 Automotive radiator
brass rolled core, lamp fixture,
ammunition.
Phosphor C51000 5.0 Sn, Annealed 130 325 64 Bellows, clutch disk,
bronze 0.25 P diaphragm, fuse clips,
springs
Yellow C85400 29 Zn, As cast 83 234 35 Furniture, radiator
bras 3.0 Pb, fittings, battery clamps,
(Leaded) 1 Sn light fixtures
Al bronze C95400 11 Al, As cast 241 586 18 Bearings, bushings,
4 Fe valve seats and guards
Beryllium C17200 1.9 Be Precipita. 965 1140 10 Electrical, valves,
copper 0.2 Co hardened pumps
Cu - Ni C71500 30 Ni Annealed 125 380 36 Condenser, heat-
exchanger, piping,
valves
Tin bronze C90500 10 Sn, As cast 152 310 25 Bearings, bushing,
2 Zn piston rings, gears
Aluminum
Aluminum is a light metal ( = 2.7 g/cc); is easily machinable;
has wide variety of surface finishes; good electrical and thermal
conductivities; highly reflective to heat and light.
Versatile metal - can be cast, rolled, stamped, drawn, spun,
roll-formed, hammered, extruded and forged into many shapes.
Aluminum can be riveted, welded, brazed, or resin bonded.
Corrosion resistant - no protective coating needed, however it
is often anodized to improve surface finish, appearance.
Al and its alloys - high strength-to-weight ratio (high specific
strength) owing to low density.
Such materials are widely used in aerospace and automotive
applications where weight savings are needed for better fuel
efficiency and performance.
Al-Li alloys are lightest among all Al alloys and find wide
applications in the aerospace industry.
Aluminum Alloys
Aluminum alloys are classified into two categories Cast
and Wrought alloys.
Wrought alloys can be either heat-treatable or non-heat
treatable.
Alloys are designated by a 4 digit number. Wrought the 1st
digit indicates the major alloying element. Cast The last digit
after the decimal indicates product from( casting - 0 or ingot -1)
Wrought As Cast
Alloy Principal Alloying Element Alloy Principal Alloying Element
Series Series
1xxx 1xx.x Aluminum, 99.00% or greater
Minimum99.00% Aluminum
2xxx Copper 2xx.x Copper
3xxx Manganese 3xx.x Silicon with Copper and/or Magnesium
4xxx Silicon 4xx.x Silicon
5xxx Magnesium 5xx.x Magnesium
6xxx Magnesium and Silicon 6xx.x Unused Series
7xxx Zinc 7xx.x Zinc
8xxx Other Elements 8xx.x Tin
9xx.x Other Elements
Temper Designations
F As fabricated - products in which no thermal treatments
or strain-hardening.
H Strain-hardened (wrought products) strain hardened
with or without additional thermal treatment.
H1 Strain-hardened only - strain-hardened without thermal
treatment.
O Annealed, recrystallized
T Thermally treated with or without strain-hardening to
produce stable tempers other than F, O or H.
T3 Solution heat-treated and then cold worked.

Solution heat treatment heating to the single phase region


and isothermal holding.
Compositions, Properties and Application of some Al Alloys
Al Ass. Composition Condition YS UTS %El Applications
No (wt.%) (MPa) (MPa)
1100 0.12 Cu Annealed 35 90 45 Food/chemical handling
(O) equipment, heat exchangers
light reflectors
3003 0.12 Cu,1.2 Annealed 40 110 30 Utensils, pressure vessels and
Mn, 0.1 Zn piping
5052 2.5 Mg, 0.25 Strain-hardn. 195 230 14 Bellows, clutch disk,
Cr (H32) diaphragm, fuse clips, springs
2024 4.4 Cu, 1.5 Heat treated 325 470 20 Aircraft structure, rivets, truck
Mg, 0.6 Mn (T4) wheels, screw
6061 1 Mg, 0.6 Si, T4 145 240 22 Trucks, canoes, railroad cars,
0.3 Cu, 0.2 Cr furniture, pipelines
7075 5.6 Zn, 2.5 Peak-aged 505 570 11 Aircraft structures and other
Mg, 1.6 Cu, (T6) highly loaded applications
0.23 Cr
359.0 7 Si, 0.3 Mg T6 164 228 4 Aircraft pump parts,
automotive transmission
cases, cylinder blocks
8090 2.0 Li. 1.3 Heat treated 360 465 - Damage tolerant aircraft
Cu, 0.95 Mg, cold-worked structures
0.12 Zr (T651)
Titanium
Pure titanium melts at 1670 oC and has a low density of 4.51
g/cc (40% lighter than steel and 60% heavier than aluminum).
Titanium has high affinity to oxygen strong deoxidiser. Can
catch fire and cause severe damage
Ti is stronger than Al - high strength and low weight makes
titanium very useful as a structural metal.
Excellent corrosion resistance due to a presence of a
protective thin oxide surface film. Can be used as biomaterial.
Can be used in elevated temperature components.
Limitation of pure Ti is its lower strength. Alloying is done to
improve strength.
Titanium
Oxygen, nitrogen, and hydrogen can cause titanium to
become more brittle. Care should be taken during processing.
Titanium can also be cast using a vacuum furnace.
Because of its high strength to weight ratio and excellent
corrosion resistance, titanium is used in a variety of
applications:
Aircraft Body structure, Engine parts
sporting equipment, chemical processing, desalination,
turbine engine parts, valve and pump parts, marine hardware
Medical implants - prosthetic devices.
Recently use of Ti in bikes and automotives is increasing
Titanium alloys
Pure Ti exhibits two phases Hexagonal -phase at room
temperature and BCC -phase above 882 C.
Strength of Titanium is improved by alloying. Alloying
elements are either or stabilizer.
Elements with electron/atoms ratio < 4 stabilizer (Al, O,
Ga), = 4 neutral (Sn, Zr) and > 4 stabilizer (V, Mo,Ta, W).
( + ) two-phase alloys can be obtained with right
proportions of alloying elements.
alloys have low density, moderate strength, reasonable
ductility and good creep resistance.
Metastable alloys are heavier, stronger and less ductile
than alloys. Creep strength reduces with increasing content
( + ) alloys show a good strength-ductility combination
Compositions, Properties and Application of some Ti Alloys
Alloy Comp . wt.% Condition YS UTS %El Applications
type (UNS No) (MPa) (MPa)
CP Ti 99.1Ti Annealed 414 484 45 Airframe skins, marine
(R50500) and chemical processing
equipments
Ti-5Al-2.5Sn Annealed 784 826 16 Gas turbine engine casing
(R54520) and rings, chemical
processing equipment
Near- Ti-8Al-1Mo- Annealed 890 950 15 Forged jet engine
1V (R54810) components compressor
disc, plate, hubs
- Ti-6Al-4V Annealed 877 947 14 Prosthetic implants,
(R56400) airframe components
- Ti-6Al-6V - Annealed 985 1050 14 Rocket engine case,
2Sn (R56620) airframe structure
Ti-10V -2Fe- Heat treated 1150 1223 10 High-strength airframe
3Al (aging) components, parts
requiring uniform tensile
stresses
Nickel
Nickel is a high-density, high-strength metal with good
ductility and excellent corrosion resistance and high
temperature properties.
Ni has may unique properties including its excellent
catalytic property. Nickel Catalyst for Fuel Cells: Nickel-
cobalt is seen as a low-cost substitute for platinum catalysts.
Two-thirds of all nickel produced goes into stainless steel
production. Also used extensively in electroplating various
parts in variety of applications.
Ni-base super alloys are a unique class of materials
having exceptionally good high temperature strength, creep
and oxidation resistance. Used in many high temperature
applications like turbine engines.
Nickel
Shape Memory Alloys: Ni base (Ni-Ti) and Ni containing
(Cu-Al-Ni) shape memory alloys that can go back to original
form, are an important class of engineering materials finding
widespread use in many applications.

Nickel-containing materials are used in buildings and


infrastructure, chemical production, communications, energy
(batteries: Ni-Cd, Ni-metal hydrides), environmental
protection, food preparation, water treatment and
transportation.
Applications of Nickel

Turbine engine Electroplating Batteries


Magnesium
Magnesium - Lightest among commonly used metals ( 1.7
g/cm3). Melting point is 650 C and it has HCP structure.
Is very reactive and readily combustible in air. Can be used
as igniter or firestarter.
Thermal conductivity is less than Al while their CTE is almost
same.
Pure Mg has adequate atmospheric resistance and moderate
strength.
Properties of Mg can be improved substantially by alloying.
Favorable atomic size - Can be alloyed with many elements.
Most widely used alloying elements are Al, Zn, Mn and Zr.
Mg Alloys Cast, Wrought
Wrought alloys are available in rod, bar, sheet, plate, forgings
and extrusions.
Magnesium Alloys
Mg alloys: Impact and dent resistant, have good damping
capacity - effective for high-speed applications.
Due to its light weight, superior machinability and ease of
casting, Mg and its alloys are used in many applications:
Auto parts, sporting goods, power tools, aerospace equipment,
fixtures, electronic gadgets, and material handling equipment.
Automotive applications include gearboxes, valve covers, alloy
wheels, clutch housings, and brake pedal brackets.
Compositions, Properties and Application of some Mg Alloys
ASTM Compos. Condition YS UTS %El Applications
No (wt.%) (MPa) (MPa)
Wrought Alloys
AZ31B 3.0 Al, Extruded 200 262 15 Structure and tubing,
1.0Zn, 0.2 cathodic protection
Mn
HK31A 3.0Th, 0.6Zr Strain hard. 200 255 9 High temp applications
Annealed (high strength to 315 C)
ZK60A 5.5 Zn, Aged 285 350 11 Forging of max strength
0.45Zr for aircrafts

Cast Alloys
AZ91D 9.0Al, 0.15 As cast 150 230 3 Die-cast parts for
Mn, 0.7 Zn automobile, luggage and
electronic devices
AM60A 9.0Al, As cast 130 220 6 Automotive wheels
0.13Mn,
AS41A 4.3Al, 1.0 Si, As cast 140 210 6 Die-cast parts requiring
0.35Mn good creep strength
Ceramics Materials

Ceramics

Refractory Advanced
Abrasives Glass
Materials Ceramics
Refractory Materials
Refractory - retains its strength at high temperatures > 500C.
Must be chemically and physically stable at high temperatures.
Need to be resistant to thermal shock, should be chemically
inert, and have specific ranges of thermal conductivity and
thermal expansion.
Are used in linings for furnaces, kilns, incinerators, crucibles
and reactors.
Aluminium oxide (alumina), silicon oxide (silica), calcium oxide
(lime) magnesium oxide (magnesia) and fireclays are used to
manufacture refractory materials.
Zirconia - extremely high temperatures.
SiC and Carbon also used in some very severe temperature
conditions, but cannot be used in oxygen environment, as they
will oxidize and burn.
Composition of some common refractory materials

Composition (wt%)
Al2O3 SiO2 MgO Cr2O3 Fe2O3 CaO TiO2 %Porosity
Refractory
Fireclay 25-45 50-70 0-1 0-1 0-1 1-2 10-25
High-alumina 90-50 10-45 0-1 0-1 0-1 1-4 18-25
fireclay
Silica 0.2 96.3 0.6 2.2 25
Periclase 1.0 3.0 90 0.3 3.0 2.5 22
Periclase - 9.0 5.0 73 8.2 2.0 2.2 21
chrome ore
Advanced Ceramics: Automobile Engine parts
Advantages:
Operate at high temperatures high efficiencies; Low frictional
losses; Operate without a cooling system; Lower weights than
current engines
Disadvantages:
Ceramic materials are brittle; Difficult to remove internal voids
(that weaken structures); Ceramic parts are difficult to form and
machine
Potential materials: Si3N4 (engine valves, ball bearings), SiC
(MESFETS), & ZrO2 (sensors),
Possible engine parts: engine block & piston coatings
Microelectromechanical systems (MEMS)
MEMS These micron-sized structures such as beams, cantilevers,
diaphragms, valves, plates and switches that can function as tiny
sensors and actuators.
Fabricated by integrated circuit (IC) manufacturing processes: bulk
and surface micromachining.
Thousands of micromachines can be fabricated on a single silicon
wafer with supporting circuits integrated on the chip. Can be mass-
produced in the millions at low prices.
Low-cost, commercial MEMS devices developed for: Corrosion
detectors and monitors; Instrumentation for automotive and aerospace;
Biological and medical devices; Chemical and environmental sensors;
Manufacturing and process control devices ;Virtual reality systems
Abrasive Ceramics
Abrasives are used in cutting and grinding tools.
Diamonds - natural and synthetic, are used as abrasives,
though relatively expensive. Industrial diamonds are hard and
thermally conductive. Diamonds unsuitable as gemstone are
used as industrial diamond
Common abrasives SiC, WC, Al2O3 (corundum) and silica
sand.
Either bonded to a grinding wheel or made into a powder and
used with a cloth or paper.

Silicon carbide
Glass
Glass - inorganic, non-crystalline (amorphous) material.
Range - soda-lime silicate glass for soda bottles to the
extremely high purity silica glass for optical fibers.
Widely used for windows, bottles, glasses for drinking,
transfer piping and receptacles for highly corrosive liquids,
optical glasses, windows for nuclear applications.
The main constituent of glass is silica (SiO2). The most
common form of silica used in glass is sand.
Sand fusion temp to produce glass - 1700 C. Adding other
chemicals to sand can considerably reduce the fusion
temperature.
Sodium carbonate (Na2CO3) or soda ash, (75% SiO2 + 25%
Na2O) will reduce the fusion temperature to 800 C.
Other chemicals like Calcia (CaO) and magnesia (MgO) are
used for stability. Limestone (CaCO3) and dolomite (MgCO3)
are used for this purpose as source of CaO and MgO.
Key Properties of Glass

Glass-ceramic materials should have:


Relatively high mechanical strengths
Low coefficients of thermal expansion
Relatively high temperature capabilities
Good dielectric properties
Good biological compatibility
Thermal shock resistance
Compositions and Characteristics of some common Glasses
Polymers
Polymers Chain of H-C molecules. Each repeat unit of H-C
is a monomer e.g. ethylene (C2H4), Polyethylene (CH2
CH2)n
Polymers: Thermosets Soften when heated and harden on
cooling totally reversible. Thermoplasts Do not soften on
heating
Plastics moldable into many shape and have sufficient
structural rigidity. Are one of the most commonly used class of
materials.
Are used in clothing, housing, automobiles, aircraft,
packaging, electronics, signs, recreation items, and medical
implants.
Natural plastics hellac, rubber, asphalt, and cellulose.
Characteristics and Applications of some common
Thermoplastics
Material Characteristics Applications
Polyethylene Chemically resistant, tough, low Flexible bottles, toys, battery parts,
friction coeff., low strength ice trays, film wrapping materials
Polyamide Good strength and toughness, Bearings, gears, cams, bushings and
(Nylon) abrasion resistant, liquid jacketing for wires and cables
absorber, low friction coeff.
Fluorocarbon Chemically inert, excellent Anticorrosive seals, chemical pipes
(Teflon) electrical properties, relatively and valves, bearings, anti-adhesive
weak coatings, high temp electronic parts
Polyester Tough plastic film, excellent Recording tapes, clothing, automotive
(PET) fatigue and tear strength, tyre cords, beverage containers
corrosion resistant
Vinyl Low-cost general purpose Floor coverings, pipe, electric al wire
material, rigid, can be made insulation, garden hose, phonograph
flexible records
Polystyrene Excellent electrical prop and Wall tile, battery cases, toys, lighting
optical clarity, good thermal and panels, housing appliances
dimensional stability
Characteristics and Applications of some common
Thermosetting Polymers
Material Characteristics Applications
Epoxy Excellent mechanical Electrical moldings, sinks,
(Araldite) properties and corrosion adhesives, protective coatings,
resistance, good electrical fiber reinforced plastic (FRP),
prop., good adhesion and laminates
dimensional stability
Phenolic Excellent thermal stability Motor housings, telephones,
(Bakelite) (>150C), inexpensive, auto distributors, electrical
can be compounded with fixtures
many resins
Polyester Excellent electrical Helmets, fiberglass boats, auto
(Aropol) properties, low cost, can body components, chair fans
formulated for room or
high temperature, often
fiber reinforced
Elastomers

Elastomer a polymer with rubber-like elasticity.


Each of the monomers that link to form the polymer is
usually made of carbon, hydrogen, oxygen and/or silicon.
Cross-linking in the monomers provides the flexibility.
Glass transition temperature, Tg, is the temperature at
which transition from rubbery to rigid state takes place in
polymers.
Elastomers are amorphous polymers existing above their
Tg. Hence, considerable segmental motion exists in them.
Their primary uses are in seals, adhesives and molded
flexible parts.
Characteristics and Applications of some commercial Elastomers
Material Characteristics Applications
Natural Useful temp. range : - 60 Pneumatic tyres and tubes, heels
rubber (NR) 120Cgood resistance to and soles, gaskets
cutting abrasion, resistant to
oil, ozone, elng. 500- 700%
Styrene- Temp. range: - 60 120 C, Same as natural rubber
butadiene Good physical properties,
copolymer elongation 450 500%
(SBR))
Acrylonitrile- Temp. range: - 50 150 C. Gasoline, chemicals and oil hose,
butadiene Excellent resistance to oils, seals and O-rings, soles and heels
copolymer elongation 400 600%
(NBR)

Chloroprene Temp. range: - 50 105 C. High and low temp. insulation,


(CR) Excellent resistance to high seals, diaphragm, tubing for food
and low temp. excellent and medical uses
electrical prop. Elng. 100
800%
Liquid Crystal Polymers (LCP)
LCPs are a group of chemically complex structure having
unique properties. Primarily used in LCDs (liquid crystal
displays) on watches, flat panel computer monitors, televisions
and clocks.
Advantages - LCDs are thinner and lighter and consume much
less power than cathode ray tubes (CRTs).
The name "liquid crystal" arises out of their characteristics. It
takes a fair amount of heat to change a suitable substance from
a solid into a liquid crystal, and it only takes a little more heat to
turn the liquid crystal into a real liquid.
LCDs use these liquid crystals because they react predictably
to electric current in such a way as to control light passage.
A particular sort of nematic liquid crystal, called twisted
nematics (TN), is naturally twisted. Applying an electric current
to these liquid crystals will untwist them to varying degrees,
depending on the applied electrical potential.
Advanced Polymers
Ultrahigh Molecular Weight Polyethylene (UHMWPE)

Molecular weight ca. 4 x 106 g/mol


Outstanding properties
high impact strength
resistance to wear/abrasion
low coefficient of friction
self-lubricating surface UHMWPE
Important applications
bullet-proof vests
golf ball covers
hip implants (acetabular cup)
References
http://www.titaniuminfogroup.co.uk/tech-data-links.php
http://www.msm.cam.ac.uk/phase-trans/ 2004/titanium/
titanium.html
http://www.nickelinstitute.org/NickelUseInSociety/
http://www.keytometals.com/Article58.htm
http://www.alcotec.com/us/en/solutions/-Understanding-the-
Aluminum-Alloy-Designation-System.cfm
http://www.efunda.com/materials/alloys/aluminum/temper.cfm
http://www.howstuffworks.com/lcd.htm

Key words: Application of materials, Ferrous and Noferrous


alloys, Stainless steel, Cast iron, aluminium alloys, temper
designation, titanium, nickel, magnesium, ceramics, polymers
Quiz
1. Classify materials. Classify metals.
2. What are the typical grades of steel? What is the effect of
different alloying elements in steel?
3. Why are tool steels hard? What is HSLA steel?
4. What are the major alloying elements in stainless steels?
Why are stainless steels resistant to corrosion?
5. What is 17-7PH steel? What is the source of high strength
in these steels?
6. What should be minimum carbon content in a cast iron?
7. Why is grey cast iron so brittle? Why is it resistant to wear?
8. How can the ductility of cast irons be increased?
9. What is the shape of graphite in malleable cast iron?
10. What are the useful properties of cast iron?
11. Why is copper used extensively in electrical and thermal
applications?
Quiz
12. What is Brass? What are typical alloying elements in
bronze?
13. Which is the heat treatable alloy of copper?
14. How are Alumium alloys classified and designated?
15. What are the different temper designation of aluminum
alloys?
16. Why is titanium resistant to corrosion?
17. What are the typical phases in Ti alloys? What is and
stabilizer?
18. Why Ti alloys are preferred for high temperature
applications?
19. What are the different categories of ceramic materials?
20. What are the main constituents in refractory ceramics?
What are the main constituents of glass?
21. What are the key properties of glass-ceramics?
Quiz
22. What are thermosets and thermoplasts?
23. Why do plastics find widespread applications?
24. What is elastomer? What are their typical characteristics
and applications?
25. What is glass transition temperature?
26. What is UHMWPE polymer?
27. What is LCP?
28. Why are LCPs used in LCD displays?
29. What is twisted nematics?
30. Name some natural plastics.

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