MME309 SCIENCE OF MATERIALS

Lecturer: Prof. David Esezobor

Metallurgical and Materials Engineering Dept


Email: [email protected]
Course Outline

SESSION TOPIC


WEEK 1

Course Outline, Laboratory
Experiments, Term Paper Topics
Types of Materials
Material Properties
Laboratory: Introduction to
Laboratory Experiments

WEEK 2
Material Structure (Atomic)
Electronic Structure
Nuclear Model of the atom
Atomic Bonds


WEEK 3
Crystal Structure
Crystallization
Crystal Imperfections
Laboratory: Rockwell and Brinell
Hardness Tests


WEEK 4


Plastic Deformation (Slip and
Twinning)
Cold Work
Annealing
Laboratory: Cold Working

WEEK 5
Phase Diagrams (Part 1)
Phase Diagrams (Part 2)
Laboratory: Annealing






WEEK 6

Polymorphism and Allotropy
Iron-Iron Carbide Diagrams
Iron-Iron Carbide Applications
Optical Microscope and the Crystal Structures found in
Iron-Iron Carbide Diagrams
Definition of Structures on the Iron-iron carbide
diagram
Sample Preparation, Etching and Preparation Artifacts
Laboratory: Metallography

WEEK 7
Effect of Carbon on the Strength and Hardness of Steel
Effect of Alloying on the Properties of Steel Cast iron
Classification of Steels
Stainless Steels
Laboratory: Coldwork micrographs
Laboratory: Annealing Micrographs




WEEK 8

TTT Diagrams
Heat Treatment of Steel
Annealing
Normalizing
Review for the test
Laboratory: Phase Diagram of Lead and Tin
Alloys
WEEK 9 TEST 1
WEEK 10
Quenching and Tempering
Case Hardening
Deep Cryogenic Tempering
Solution Heat Treatment and Age Hardening
Laboratory: Nondestructive Testing
Methods




WEEK 11

Tool Steels
Nonferrous Metal Alloys
Laboratory: Solution Heat Treatment and
Age Hardening
Laboratory: Conventional Quenching and
Tempering
WEEK 12
Composites
Ceramics
Polymers
Thermoplastics and Thermosets
Laboratory: Jominy End Quench Test
WEEK 13
TERM PAPER PRESENTATIONS
WEEK 14
Review
WEEK 15
FINAL EXAM
Grading
Test 20 %
Final Exam 60 %
Lab reports 20 %

REFERENCES
1 James P. Schaffer et al. The Science and
Design of Engineering Materials. 2
nd
Edition,
McGraw-Hill, 1999
2 J.C. Anderson et al. Materials Science. 2
nd

Edition, E.L.B.S., 1974
3 John, Introduction to engineering Materials.
Macmillan
4 D.J. Davies, L.A. Oelmann. The Structure,
Properties and Heat Treatment of Metals.
Pitman, 1983
5 Atkins, Physical Chemistry

Types of Materials
Metals:
good electrical and thermal conductivity.
high strength, high stiffness, and have good
ductility.
Some metals, such as iron, cobalt and nickel are
magnetic.
At extremely low temperatures, some metals and
intermetallic compounds become superconductors.

Pure metals:
Pure metals are elements which come from a
particular area of the periodic table.
Examples of pure metals include copper in
electrical wires and aluminum in cooking foil
and beverage cans.
Metal Alloys:
Metal Alloys contain more than one metallic
element. Their properties can be changed by
changing the elements present in the alloy.
Examples of metal alloys include stainless
steel which is an alloy of iron, nickel, and
chromium; and gold jewelry which usually
contains an alloy of gold and nickel.
The most important properties of metals include
density, fracture toughness, strength and plastic
deformation. The atomic bonding of metals also
affects their properties. In metals, the outer
valence electrons are shared among all atoms,
and are free to travel everywhere. Since electrons
conduct heat and electricity, metals make good
cooking pans and electrical wires.
Many metals and alloys have high densities and
are used in applications which require a high
mass-to-volume ratio.
Some metal alloys, such as those based on
Aluminum, have low densities and are used in
aerospace applications for fuel economy.
Many metal alloys also have high fracture
toughness, which means they can withstand
impact and are durable.

Polymers
A polymer has a repeating structure, usually based on a carbon
backbone. The repeating structure results in large chainlike
molecules.
Polymers are useful because they are lightweight, are corrosion
resistant, are easy to process at low temperatures, and are
generally inexpensive.
Some important characteristics of polymers include their size
(or molecular weight), softening and melting points, crystallinity,
and structure. The mechanical properties of polymers generally
include low strength and high toughness. Their strength is often
improved using reinforced composite structures.
One of the distinct properties of polymers is that they are poor
conductors of electricity and heat, which makes them good
insulators.
One of the distinct properties of polymers is that they are poor
conductors of electricity and heat, which makes them good
insulators.

Ceramics
A ceramic is often broadly defined as any inorganic
nonmetallic material. Examples of such materials
can be anything from NaCl (table salt) to clay (a
complex silicate). Some of the useful properties of
ceramics and glasses include high melting
temperature, low density, high strength, stiffness,
hardness, wear resistance, and corrosion
resistance. Many ceramics are good electrical and
thermal insulators.
Some ceramics have special properties: some
ceramics are magnetic materials; some are
piezoelectric materials; and a few special ceramics
are superconductors at very low temperatures.
Ceramics and glasses have one major drawback:
they are brittle
Glasses
A glass is an inorganic non-metallic
material that does not have a
crystalline structure. Such materials
are said to be amorphous.

Examples of glasses range from the
soda-lime silicate glass in soda
bottles to the extremely high purity
silica glass in optical fibers.
Composites
Composites are formed from two or more
types of materials. Examples include
polymer/ceramic and metal/ceramic
composites.
Composites are used because overall
properties of the composites are superior to
those of the individual components. For
example: polymer/ceramic composites have a
greater modulus than the polymer
component, but aren't as brittle as ceramics.

Tensile Test:
Tensile test determines the strength of the
material when subjected to a simple
stretching operation. Typically, standard
dimension test samples are pulled slowly
at a uniform rate in a testing machine
while the strain is defined as :
Engineering Strain = Change in Length / Original
Length
The engineering stress is defined as:
Engineering Stress = Applied Force / Original
Area
Slide 1 shows the stress-strain diagram of a ductile
material where the linear portion of the graph indicates
elastic deformation.
Modulus of Elasticity: The initial slope of the
curve, related directly to the strength of the
atomic bonds. This modulus indicates the
stiffness of the material. (Modulus Elasticity
is also known as Young's Modulus)
Modulus of Elasticity, E = Change in Stress/ Change in Strain
Slide 1. Stress-strain diagram
Slide 2. Fracture of a flat
tensile test specimen
Tensile Strength: The maximum stress applied to the specimen.
Tensile strength is also known as Ultimate Strength. (The highest
point on the stress-strain diagram)
Ductility: The total elongation of the specimen due to
plastic deformation, neglecting the elastic stretching.

Toughness: The total area under the curve, which
indicates the energy absorbed by the specimen in the
process of breaking.
Extensometer: The instrument that measures the
elongation of a material while applying tension.
Extensometer
Tensile Test Machine
Measurement of Elongation
Comparison of Breaks
Material Structure
All matter is considered to be composed of unit substances known as
chemical elements. These are the smallest units that are
distinguishable on the basis of their chemical activity and physical
properties. The elements are composed of atoms which have distinct
structure characteristic of each element.
Matter: Anything that has weight and that takes up space.
Forms of Matter: Solid, Liquid, Gas
Molecule: The smallest particle of matter that retains the same
properties of that matter. Example: Water
Compound: A substance that can be broken down into two or more
simpler substances. (A compound is made of millions of molecules)
Element: The smallest part of a substance that retains the same
properties of that substance and can not be broken down any further.
Elements are composed of atoms which have a distinct structure
characteristic of each element.
Atom: The smallest particle of an element which retains the distinct
structure characteristic of an element.
Figure 1. Atomic Model
Atomic Structure:
The free atom is composed of electrons, protons,
and neutrons. Almost the entire mass of the atom
is concentrated in the nucleus, which contains
the protons (positive charges) and neutrons
(electrically neutral particles). The electrical
charge q carried by each e and p is 1.60x10
-19

coulombs. An atom consists of a minute
positively charged nucleus surrounded by a
sufficient number of electrons (negative charges)
to keep the atom as a whole neutral. The nucleus
is 10
-14
m in diameter. Since the electron and
proton have equal but opposite electrical charge,
the neutral atom must contain an equal number
of electrons and protons.
Atomic Mass Number:
Atomic Mass Number, A = Number of electrons, e + Number of
neutrons, N or it can be equal to Number of Protons, p + Number of
Neutrons, N i.e.
A = e + N or A = p + N
The mass of each proton and neutron is about 1.67x10
-24
g which is
referred to a.m.u, but the mass of each electron is 9.11x10
-28
g which
makes a negligible contribute to the atomic mass of the element.
Mp is greater than Me by 1876
Mass Number has a mass very close to the atomic mass unit. The
mass number of an atom approximately expresses its ATOMIC
MASS.
Mass Number is the mass of Avogadro number, NA= 6.02x10
23
mol
-1

is the number of atoms or molecule in a g mole. The unit of atomic
mass is g/g mole or a.m.u, which is the mass of carbon 12.
Atomic Number:
Atomic Number, Z = Number of electrons = Number of protons
Z = e = p.
The number of p in the nucleus of an atom is the characteristic of the
element in which that atom belongs and is called the ATOMIC
NUMBER of that element.
Proton Neutron Electron
Symbol p N e
Mass , kg 1.67x10
-27
1.67x10
-27
9.11x10
-31

Charge, C 1.6x10
-19
0 1.6x10
-19

Mass relative to e 1876 1876 1
Charge relative to p +1 0 -1

The electrons, spinning on their own axes as they rotate around the
nucleus, are arranged in definite shells. The maximum number of electrons
that can fit in each shell is 2n
2
where n is the shell number.
The maximum number of electrons that can fit in the first shell (K) is two,
the second shell (L) eight, the third shell (M) eighteen, the fourth shell (N)
thirty two, etc.
ISOTOPES
Atoms of the same element that contain a different number of N in the nucleus, and
thus have different atomic mass.
Atomic mass = average (means) of the proportion (abundances) isotopes.



All the elements in the periodic table exhibit isotopic character except Be, Fe, Na,
Al, P, Sc, Mn, Co, As, Y, Nb, Rh, I Cs, Pr, Ts, Ho, Tm, Au. ISOTOPES
All the elements in the periodic table exhibit isotopic character except Be, Fe, Na,
Al, P, Sc, Mn, Co, As, Y, Nb, Rh, I Cs, Pr, Ts, Ho, Tm, Au.
37 % 43 . 2 35 % 53 . 75 .
43 . 35
17
37
17
35
17
of of e i
Cl Cl Cl
+
= +
PHYSICAL MODELS OF THE ATOM
(ELECTRONIC STRUCTURE)
An e has the lowest energy when it is in the orbit
closest to the nucleus (i.e. normal or ground state of
an atom)
The energy of an e can take on only definite
allowed values, in other words it is quantized i.e.
electron occupy discrete energy levels within the
atom. Each e possesses a particular energy, with no
more than 2 e in each atom having the same energy.
The energy level to which each e belongs determined
by the 4 quantum number.
The number of POSSIBLE ENERGY levels is
determined by the 1st 3 quantum number
FIRST (PRINCIPAL) QUANTUM number, n

The possible energy states of an electron in an atom are determined
by the volume of the principal quantum number, n that can take
1,2,3., etc. An e has the smallest energy at n=1. It grows with n
increases. At n=1, e is the 1st on ground energy level, at n=2, it is at
2nd level etc .

n determines the dimension of the electron cloud. A greater value
of n corresponds to greater dimensions of the dimensions of the
electron cloud (layers or shells).
A DISCRETE number of e is situated in every level and is equal to

N = 2n
2
where N total number of e
1st level N = 2x1
2
=2 electrons
2nd level N = 2x2
2
= 8 electrons
3rd level N = 2x3
2
= 18 electrons and etc.

Principal quantum number, n 1 2 3 4 5 6 7
Designation of energy level K L M N O P Q
K Shell
(n=1) 2e
L Shell
(n=2)
N= 8:8e
M Shell
(n=3)
Figure 1. The atomic structure of sodium Na
23
11
l
l
The shape of the e cloud is determined
by
2
nd
(ORBITAL) or AZIMUTHAL Quantum number,
that can take the value of o to (n-1). It determines
the value of ORBITAL ANGULAR MOMENTUM of
an electron.
=O when n=1 does not mean an electron at rest, but a motion
that does not give rise to a resultant angular momentum, L
L = m v r
m is the mass of the particle, v is the velocity and r is the
position vector connecting the center of revolution to the
particle.
l
) 1 ( (
2
+ = q q
n
h
L
m
q
The angular momentum of the electron

h-planks constant = 6.626x10
-34
Js

the charge of the electron.
m v
r
L
(1)
The azimuthal quantum numbers are customarily
called the ENERGY SUBLEVELS OR
SUBSHELLS of an electron in an atom. They are
designated by lowercase letters
Orbital q. no 0 1 2 3 4 5 6 7
Designation of energy level s p d f g h i j
s-sharp, p-principal, d-diffuse, f-fundamental.
when n=2 we have either 0 or -1 i.e. 2 sublevels
In general, in the nth level, there will be n sublevels
with equals to 0, 1, 2, 3,, n-1
THIRD (MAGNETIC) QUANTUM number, m
l
indicates the orientation of an electron. It gives the
number of energy levels or orbital for each azimuthal
quantum number. The total of for each is 2l+1. The
values of m
l
are given by whole numbers between
n e and +e. for example 3 different values of (-1,
0, +1) are possible for p electron (=1) and s for M,
(-2,-1,0,+1,+2) for d electron (=2) which is 2(2) +1=5.

m
l
is called magnetic because of the interact of the
magnetic field set up by an electron with which the
external magnetic field depends on its value.
SHAPE AND ARRANGEMENTOF ELECTRONS IN SPACE
Electron clouds of 1s, 2p and 3d electrons

X
Z
Y
1S
i) Since m
l
= (0) =1 for s state
l =0, then any possible
arrangement of an S electron
cloud in space are identical
X
2px
Z
Y
ii) p orbital l = 1; m
l
(-1, 0, 1) = 3, accordingly
they can be arranged in space in 3 ways
Z
Y
X
2py
2pz
Z
Y
X
The 3 p electron clouds are oriented along mutually
perpendicular direction, which are conventionally taken
as the direction of the coordinate axes (x, y or z); the
corresponding states of the electrons are designated
px, py, and pz
iii) For d orbital l = 5; m
l
= (-2,-1,0,+1,+2) = 5 values of the magnetic quantum number
are possible and accordingly, 5 different orientations of the d electron clouds in space.
FOURTH QUANTUM NUMBER,
(SPIN QUANTUM NUMBER)
m
s
or simply the spin is used to determine the INTRINSIC
state of an electron. Unlike n, l , and m
l
, m
s
is not
associated with motion of the electron about the nucleus.
can be loosely associated with the spin of the electron
about its own axis. This can have only 2 values + or
depending on the direction of rotation of the electron about
its axis (m
s
= + or - ). Two electrons in the same orbital
having values of + and - are said to be paired; both of
them would have the same amount of energy.
NOTE: The possible values of the spin quantum number
differ by UNITY.
PAULI EXCLUSION PRINCIPLE
It specifies that no more than 2 electrons, each with oppositely
electronic spins, may be present in each orbital. The spin
quantum number is assigned values + to reflect the different
spins .
Summary
Table 1.2 Maximum number of electrons in atom energy levels and sublevels
Energy
Level
Energy
sublevel
Possible Values
of Magnetic
Quantum
Number
Number of
orbitals
Number of
electrons
In
sublevel
In
level
In
sublevel
In
level
K (n=1) s(l=O)
0
1 1
2
2
L (n=2) s(l=O)
p(l=1)
0
-1, 0, +1
1
3

4
2
6

8
M (n=3) s(l=0)
p(l=1)
d(l=2)
0
-1, 0, +1
-2,-1,0,+1,+2
1
3
5

9
2
6
10

18
N=(n=4)

s(l=0)
p(l=1)
d(l=2)
f(l=3)
0
-1, 0, +1
-2,-1,0,+1,+2
-3,-2,-1,0,+1,+2,+3
1
3
5
7

16
2
6
10
14


32
CONCLUSION
Each principal level of quantum number, n contains a total n
sublevels
Each sublevel of quantum No, l contains a total 2l + 1 orbitals
Each orbital can hold two electrons
The maximum number of e in each energy level is 2n
2
The shorthand notation frequently used to donate the electronic
structure of an atom combines the numerical value of the
principal quantum No, n, the lowercase letter rotation for the
azimuthal quantum No and a superscript showing the number
of electrons in each orbital. Thus, the shorthand notation for the
electronic structure of bromine which has an atomic number of
35 is 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 3d
10
, 4s
2
4p
5
NOTE
The energy state of the electrons depends not only on the principal
quantum number n, but also on the orbital quantum number. This is associated
with the circumstance that an electron in an atom is not only attracted by the
nucleus, but is also repelled by the electrons between the given electron and the
nucleus. The internal electron layers form a peculiar shield that weakens the
attraction to the nucleus

l
.
ORBITAL DIAGRAMS HUNDS RULE
Orbital diagram indicates the number of
electrons in each orbital and their
respective spins:
1s
2
2s
2
2p
1

Electron configuration of boron

Definition (Hunds Rule)
In an atom in which orbitals of equal energy
are to be filled by electrons, the order of
filling is such that as many electrons remain
unpaired as possible
B
C
C
C
II
I
III
2s
2p
I: Ms are the same, while their spin
are antiparallel




II: 2p electrons occupy different
orbitals (i.e. have different Ms and
their spins are opposite)



III Different orbits correspond to the 2
s p electrons while their spins are
parallel
Among the 3 diagrams, the third is correct and it corresponds to the greatest
value of the total spin of an atom. (In I & II the sum of the spin of all electrons is
zero while, for the third diagram it is unity.
Therefore Hunds rule states that the maximum value of the total
spin of an atom corresponds to the stable i.e. unexcited state in
which the atom has the smallest possible energy; at any other
distribution of the electrons, the energy of the atom will be higher, so
that it will be in an excited, unstable state. In other words the
distribution of the electrons within the limits of an energy sublevel at
which the absolute value of the total spin of he atom is maximum
corresponds to the stable state of an atom.

1st Rule
The sequence of filling of the atomic electron orbitals depends
on the values of the principal and orbital quantum number. And
the energy of an electron rises as the sum of these 2 quantum
number increases, i.e. with increasing n+l. With an increase in
the charge of the nucleus of an atom, the electron orbitals are
filled consecutively from orbitals with a smaller value of the
sum of the principal and orbital quantum (n + l) to orbitals with
a greater value of this sum.

2nd Rule
At identical values of the sum n+l the orbital are filled
consecutively in the direction of the growth in the value of the
principal quantum number, n
Note:
The chemical properties of the elements are
determined first of all by the structure of the outer
electron layer of their atom and depend only to a
smaller content on the content on the structure of the
preceding (inner) electron layers.
All the d (transition) elements are METALS whereas
the filling of the outer P sublevel result in a transit from
a metal to a typical non-metal and finally, to a noble
gas.
The outer orbitals of d metals are filled in order of
energy stability and an increased energy stability is a
property of electrons configurations with exactly a
HALF-FILLED or TOTAL-FILLED sublevel (e.g.
structures containing 3 electrons in the outer layer,
five d electrons in the layer preceding the outer one, or
seven f electrons in a still deeper layer).
Violation
The violations of the normal sequence of filling the energy states in
(lanthanum (Z =57) (the appearances of a 5d instead of a 4f electron) and
cesium (the simultaneous appearance of two 4f election). This can be
explained as follows: upon an increase in the charge of the nucleus the
electrostatic attraction to it of an electron in a given energy sublevel
becomes stronger and the energy of the electron diminishes. The energy of
the electron in different sublevels changes differently because the charge of
the nucleus is increased to a different extent with respect to these electrons.
In particular, the energy of 4f of electrons diminishes with a growth in the
charge of the nucleus more sharply than the energy of the 5d electrons.
57 58
5d
4f
Dependence of the energy of the 4f and 5d electrons on the nuclear charge.
E
Z
Consequently in La (Z =57), the energy of the
5d electrons is found to be lower and in cesium
(Z=58) higher than that of the 4f electrons.
Accordingly, the electron that in La is in the
sublevel 5d in cesium passes to the sublevel 4f

57
La 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10

5s
2
5p
6
5d
1
6s
2

58
Ce 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10

4f
2

5s
2
5p
6
6s
2

The most stable state of an electron in an atom
corresponds to the minimum possible value of
its energy
Periodic Table
Valence: The valence of an atom is the ability of the atom to enter
into chemical combination with other elements and is often
determined by the number of electron in the outer most combined s
p level. O
2
-referred valence and H
2
-referred Mg-2; Al-3; Ge-4; Na-1;
P-3,5; Mn-2,3,4,6,7
ELECTRONEGATIVITY: Describes the tendency of an atom to gain
an electron. Atoms with almost completely filled outer energy level,
like Cl are strongly electronegative and readily accept electron.
EXCITATION, IONIZATION AND IONIZATION ENERGIES: When
atoms are exposed to high energy high temperature or exposed to
fast-moving electrons from nearly any source, they tend to become
excited and to give off energy in the form of radiation. The nature of
the radiation emitted depends on the excitation which is used. When
atoms through collisions, absorb energy and become excited, they
move in the process to higher allowed electronic energy levels.
Once excited the atoms will be unstable and will tend to return to
lower electronic energy levels, ultimately reaching the lower energy
level, the ground state of the atom. Under excitation the atom will
quickly reach a state of dynamic equilibrium in which some atoms
are releasing energy at the same rate that it is being absorbed by
other.



In a process in which an excited atom makes a
transition to a lower energy level, a photon of
light may be emitted (A ray of light can be
considered to consist of photons which appear
to have some properties characteristic of
particles).
The wavelength of the photon is related to the
magnitude of the change in energy (E) of the
atom by


where h is a physical constant, called = Plancks constant 6.626 x 10
-34
J.S,
c is the speed of light = 2.998 x 10
8
m/s and the wavelength of the photon in
meters.

hc
E E
Photon atom
= = A
(2)
IONIZATION ENERGY and AFFINITY ELECRON
The amount of energy needed to detach an electron from an atom with conversion of the latter
into a positive ion is called ionization energy.
The smallest voltage of the field at which the speed of the electrons becomes sufficient for
ionization of the atoms is the ionization potential of the atoms and is expressed in volts.
The energy of an electron is often expressed in electron volts (eV)
1eV is the energy acquired by an electron in an accelerating electric field with a potential
difference of one volt
1eV = 1.6x10
-19
J = 96.5KJ/mol
The ionization energy expressed in electron-volts numerically equals the ionization potential
expressed in volts.
The first ionization energy, of an atom is the energy change of the formation of positive ion from
the gaseous atom;
X(g) = X
+
(g)
+e 1
st
E-ionization energy
The magnitude of the E, can be a measure of the greater as smaller metallicity of an element
the smaller the E, the easier it is to detach an electron from the atom and the stronger should
the metallic properties of the element be empresses.
An increase in the atomic number of element is attended by diminishing of the ionization energy
in the groups. This fronts to an increase in the metallic properties and accordingly, a decrease
in the non-metallic properties of the relevant element.
This regularity is associated with the growth in the atomic radii. - the smaller the atom, the more
tightly its electrons are held to the nucleus and the more difficulty they are to be removed. In
addition, an increase in the number of intermediate electron layers between the nucleus of an
atom and the outer electrons leads to greater screaming of the nucleus, i.e. diminishing its
effective charge. Both these factors (the growing of its effective charge) lead to weakening of
the bond of the outer electrons with the nucleus and consequently, to lowering of the ionization
energy. Large atoms such as those of the alkali metals have relatively low ionization energies
because the outer electrons are far away from the positive charge of the nucleus.
Summary
The properties of an atom are determined by
the following factors:
The atomic number that corresponds to the
number of electrons or protons in a neutral atom
The mass of the atom
The spatial distribution of the electrons in orbits
around the nucleus
The energy of the electrons in the atom and
The ease of adding or removing one or more
electrons from the atom to create a charged ion.
Problem: Determine the electron configuration for a sulfur
atom, a selenium atom and a tellurium atom. Explain why
these three elements display similar characteristics?
STRUCTURE AND PROPERTIES OF ATOMIC
NUCLEI. RADIOACTIVITY
Radioactivity: This is the name given to the phenomenon of the emission
of radiation by certain element capable of penetrating through a
substance, ionizing air, and of causing photographic plates to dasher.
This phenomenon was first discovered in uranium compounds by the
French physicist A. Becquerel.
Investigation of the Curies (Pierre) and of the British physicist Rutherford
showed that radioactive radiation is not homogeneous: a magnetic field
causes it to divide into three beams, one of which does not change its
original direction, while the other 2 deviate in opposite directions.
The rays that do no deviate in a magnetic field and, consequently, have
no electric charge, were called GRAMMA RAYS. They are
electromagnetic radiation similar to X-rays and having a very high
penetrability.
The deflection of the other outer 2 teams under the action of magnetic
field indicates that these beams consist of electrically charged particles.
The opposite direction of the observed deflecting witness that one beam
contains negatively charged particles (BETA RAYS), while the other
(ALPHA RAYS) CONTAINS POSITIVELY CHARGED PARTICLES. The
beta rays were found to be a stream of rapidly moving electrons.
The positively charged alpha rays were found to consist of particles
whose mass equals that of a helium atom and whose charge is absolute
value is double that of an electron.
Rutherford proved by direct experiments that these
particles are charged helium atoms. The results of
the experiment proved that Radium atoms in the
process of radioactive mission disintegrate (decay),
transforming into atom of other elements, particularly
into helium atoms
n
R He Ra
222
86
4
2
226
88
+
o
NUCLEAR MODEL OF THE ATOM

According to the model proposed in 1903 by J.J Thomas,
an atom consists of a positive charge uniformly distributed over
the entire volume of the atom and electron migrating inside this
charge.
To verify Thomsons hypothesis and establish more
accurately the internal structure of an atom, E-Rutherford
performed series of experiments involving scattering of alpha
particles by thin metal plates (gold foil)
Source S of alpha rays was placed in lead capsule C with a borehole drilled in it in
order to obtain a pencil of alpha particles flying in a definite direction. Upon reaching
screen be coated with zinc sulphide, the alpha particles cause to grow this gold foil F
was placed between the radiation source and the screen. The flashes on the screen
allowed the experimentalist to assess the deflection of the particles from the original
direction, although the thickness of the foil was hundreds of thousands of atomic
diameters. But a certain fraction of the particles was nevertheless deflected through
small angles while from time to time the particles sharply changed the direction of
their motion, and some of them even rebounded from the foil as if they had
encountered a massive obstacle.
If followed from these results that the predominating part of the space occupied by an
atom of a metal contains no heavy particles only electrons can there. And the mass
of main alpha particles is almost 7500 times greater than that of an electron, so that
a collision with the latter cannot virtually affect the direction of the motion. Cases of
where deflection and even rebounding of the alpha particles however signify that an
atom contains heavy particles in which the predominating part of the entire mass of
the atom is concentrated. This nucleus occupies a very small volume and must have
a positive charge. This is why that nucleus repels the positively charged alpha
particles.

S
C
Thin gold
foil
F
Se
A
M
Set-up of alpha particle scattering experiment
On the basis of these considerations, Rutherford in 1911
proposed the following model of the structure of an atom
which is known as the structure of an atom which is known as
the nuclear model of the atom. An atom consists of a
positively charged nucleus in which the predominating part of
the atoms mass is concentrated, and of electrons orbiting
around it. The positive charged of the nucleus is neutralized
by the total negative charge of the electrons, so that the atom
as a whole is electrically neutral. The centrifugal force
produced owing to rotation of the electrons around the
nucleus is balanced by the force or electrostatic attraction of
the electrons to the appositively charged nucleus. The size of
the nucleus is very small in comparison with that of an atom
is of the order of 10
-8
cm, whereas the diameter of the nucleus
is of the order of 10
-13
to 10
-12
cm.
This experiment made it possible not only to detect an atomic
nucleus, but also to determine its charge. It followed that the
charge of a nucleus (expressed in units of electron charge of
a nucleus (expressed in units of electron charge) numerically
equals the atomic number) of the element in the periodic
table.

The physical meaning of the atomic number of an element in
the periodic table was found to be a very important constant
of an element expressing the positive charge of its atoms
nucleus. It can be seen from their electrons orbiting about the
nucleus also equals to the atomic number of the element.
This discovery eliminated an apparent contradiction in the
periodic table the position of some of the elements with a
greater atomic mass ahead of elements with a smaller atomic
mass

There is no contradiction here because the placement of an
element in the table is determined by the charge of the atomic
nucleus. The charge of a Fe atom is 52, and that of an iodine
atom 53-established experimentally.
Thus, the charge of the atomic nucleus is the basic quantity
determining the properties of an element and its position in
the periodic table.
The determination of the atomic number of the element
according to the charges of the nuclei of their atoms made it
possible to establish the total number of position in the
periodic table.

( ) Ni and Co K and Ar I and Fe
7 . 58
28
9 . 58
27
39
19
9 . 39
18
9 . 126
53
6 . 127
52
,.. ,..
CONTRADICTIONS IN RUTHERFORDS THEORY
The theory could not explain the stability of the atom. An
electron orbiting about a positively charged nucleus ought to
emit electromagnetic energy in the form of high waves. And by
so doing, the electron lose part of its energy which would result
in the violation of equilibrium between the centrifugal force
associated with the rotation of the electron and the force of
electrostatic attraction of the electron to the nucleus. To restore
equilibrium, the electron must move closer to the nucleus.
Thus, an electron continuously emitting electromagnetic energy
and moving along spiral will approach the nucleus. After
exhausting all its energy, it should fall onto the nucleus, and
the atom will stop existing. This conclusion contradicts the real
properties of atomic, without decay for an exceedingly long
time.
The model led to improper conclusions on the nature of atomic
spectra. The radiation of a glowing solid or liquid body consists
of electromagnetic waves of every possible frequency
continuous spectrum.
An appreciable step in the development of the atomic structure concept was
made by NEILS BOHR who proposed a theory combining the nuclear model
of the atom with the quantum theory of light.
QUANTUM THEORY OF LIGHT
Max Planck showed that radiant energy is emitted and
absorbed by bodies not continuously, but discretely i.e. in
separate portions (quanta).
Frequency of the energy emitted or absorbed, is given by the
Einstein equation (Planck)
E = E
2
E
1
= h .--------------------------- (3)
The proportionality constant h-the Planck constant, E
2
-the final
energy of the atom after the jump, E
1
- the initial energy of the
atom before the jump, a negative E means that energy is
emitted.
Einstein concluded that electromagnetic (radiant) energy exists
only in the form of quanta and that consequently radiation is a
stream of indivisible material particles (photons) whose
energy is determined by the Planck equation.
It follows from the quantum theory of light that a photon
behaves like a particle i.e. displays corpuscular properties. It
however, also has wave properties. It has wave - particle
duality
Bohr theory failed to predict properly the energy levels of some other simple
systems such as vibrating or rotating diatomic molecules.
WAVE MECHANICS QUANTUM MECHANICS
AND WAVE FUNCTION
The particle properties of the photon are expressed by
the Planck equation
E = h ------------------------(4)
according to which the photon is indivisible and exists
as a discrete formation. The wave properties of the
photon, on the other hand are expressed in the
equation.
= c -------------------------(5)
Relating the wavelength of electromagnetic oscillation
to its frequency and the speed of propagation, c
Thus
-----------------------(6)

hc
E =
But a photon having the energy, E also possesses a certain mass in accordance
with the Einstein equation
E = mc
2
-------------------------------------------(7)

but

Whence


The product mc is called the momentum of the body
-----------------------------------------(8)

Eq. 8 was first derived by de Broglie by assuming that a photon has both wave
and particle properties.
He assumed that wave-particle duality is a property of electrons in addition to
photons. Consequently, an electron must display wave properties and like a
photon, it must obey the last equation, which is often called de Broglie equation

The fact that an electron has a wavelength does not necessarily mean that it is a
wave; it does mean that the motion of the electron is governed by the same
differential equations that describe wave motion

----------------------(9)

Eq 9 Schrodinger standing waves equation. Where s is the max. transverse displacement,
or amplitude, of a segment of string dx, x is the distance along the string, and is the wavelength.

hc
mc =
2
mc
h
=
p
h
=
0
4
2
2
2
2
= + s
dx
s d

t
WAVE FUNCTION
Based on the concept of Schrdinger that the state of an electron moving in an
atom must be described by the equation of a standing electromagnetic wave.
By substituting the wave function for the amplitude s, the de Broglie wavelength,
h/(mv) = h/p, for , and E-V for the kinetic energy mv
2
. The result is

-------------------------------(10)

where E-represents total energy and V represents potential energy.
The three - dimensional form will be

-----------------------------(11)

wave functions are sinusoidal for the particle in the given system.
The wave function is of special significance for characterizing the state of an
electron. Like the amplitude of any wave process, it can take on both positive and
negative values.
The quantity
2
however, is always positive. The higher the values
2
in a given
region, the greater is the probability of an electron displaying its action here i.e. if its
existence being detected in a physical process.
To be more precisely, the probability of detecting an electron in a certain small
volume is expressed by
2
V. Thus, the quantity
2
itself expresses the DENSITY
OF THE PROBABILITY of finding an electron in the corresponding region of space
The density of an electron cloud is proportional to the square of the wave function.
From the properties of waves, the latter can have finite amplitudes only inside the
system, the amplitude at the walls must the zero.

0 ) (
8
2
2
2
2
= +
t
V E
h
m
dx
d
0 ) (
8
2
2
2
2
2
2
2
2
= + + +
t
V E
h
m
dz
d
dy
d
dx
d

1
=2d =2d/1

2
=d =2d/2

4
=d =2d/4
d
n
n = 4
n=2
n=1
n
n
n
n n
n
A
A
-A
Antinodes maximum amplitude
Nodes n amplitude of the oscillation vanishes
If the length of a one-dimensional atom (the distance
between the walls is d and n is an integer equal to 1,2,3,
The wavelength, of the allowed waves

--------------(12)
n
d 2
=
Some wave functions of a particle in
one-dimensional box
By combining de Broglies equation
or
n
d
mv
h 2
= =
d
nh
2
=
Energy, E to certain allowed values
2
2
2
2
8 2 2
1
n
md
h
d
nh
m
E =
|
.
|

\
|
=
( )
2
2
2
1
2
1
mv mv E =
|
.
|

\
|
=
----(13)
This equation tells us that a particle, of any kinds confined to
move in a region of any length will have only certain energies
allowed to it.
Those energies (from Eq. 13) depend on the mass, m of the
particle, the interval d through which it can move, and the
quantum number, n.

Implications of de Broglie relation
1. A confined particle cannot have zero energy since n cannot be
zero if a wave is to be present. Since n can equal 1,2,3.. the
particles may take on many energies, the lowest value will be
when n=l
2. The lowest energy available to a particle depends markedly on
its mass and on the size of the space to which it is confined.
This energy varies inversely with the mass every time the
mass is decreased by a factor of 2 the energy is doubled. The
minimum energy also varies inversely with the square of the
length through which the particle can move.
ISOTOPES
From the Greek words isos which means same and topes place.
Atoms having an identical charge of their nucleus (and, consequently, identical
chemical properties) , but a different numbers of neutron and (and, therefore, a
different mass number) are known as isotopes.
The chemical properties of isotopes are identical. This means that if there does
exist a certain difference between isotopes with respect to their chemical
properties, it is so small that it is virtually not detected, only those involving mass
effects would be noticed.
An exception is the hydrogen isotopes
1
H and
2
H. Owing to the enormous relative
difference in their atomic masses (the mass of an atom of one isotope is double
that of an atom of the other isotope) the properties of these isotopes differ quite
appreciable. The
2
H is called Deuterium (D). The deuterium content in ordinary
hydrogen is about 0.015%.
Also known is the radioactive hydrogen isotope
3
H-Tritium (T) (with half-life of about
12 years) prepared only artificially. Tritium is unstable. The elements of higher Z
contain at least as many neutrons as protons, but because of the shielding effect of
the innermost electrons this does not affect the material properties. In the atoms of
higher Z, the number of neutrons considerable exceeds the number of protons, and
these elements are often referred to as the heavy elements. E.g. of
natural uranium which is artificially produced by
neutron bombardment of thorium.
The nucleus itself eventually becomes unstable and the addition of a further
neutron may cause nuclear fission. The atom then disintegrates with the
production of two new atoms and a debris of elementary particles and radiations.
% 99
238
92
U
U and U
233
92
235
92
% 7 . 0
ISOTOPIC INDICATIORS (TRACERS)
Isotopic indicators or labeled atoms (tracer atom) are widely used in studying the
mechanism of chemical and biological processes. This use is based on the possibility
of tracing the ways of transition of an element in chemical transformation by
measuring the concentration of one of its isotopes in one of the substances taken for
a reaction. Since all the isotopes of the same element behave virtually identically in
chemical reactions, by determining the change in the composition of the isotopes of a
given element in the various products, we can trace its path.
For example, the use of the heavy oxygen isotope
18
O in studying how carbon
dioxide is assimilated by plants. (Carbon dioxide and water enriched with
18
O were
used for the experiments) showed that the process occurs according to the following
reaction, in which the isotope
18
O is marked with an asterisk.

6CO
2
+ 12H
2
O* = C
6
H
12
O
6
+ 6H
2
O + 6O
2
*

6CO
2
* + 12H
2
O = C
6
H
12
O
6
* + 6H
2
O* + 6O
2

It was thus established that the oxygen returned by plants to the atmosphere is taken
completely from water and not from carbon dioxide.

18
O a stable isotope which is quite rare in nature (abundance = 0.20%). This isotope
is readily detected by using a mass spectrometer.
Carbon-14 can be used also.
In Medicine: The high-energy radiation given off by Radium is used in the treatment
of cancer.
RADIOACTIVITY NUCLEAR REACTIONS
Nuclear reactions differ form ordinary chemical reactions.
1. In ordinary reactions, the different isotopes of an element show virtually
identical chemical properties; in nuclear reactions they behave quite
differently.
The chemical properties of and are very similar but the nucleus is
extremely stable while the nucleus decomposes spontaneously.
2. The nuclear reactivity of an element is essentially independent of its state of
chemical combination. E.g. Ra
2+
ion in RaCl
2
and elementary Radium
behave similarly from a nuclear stand point. In ordinary chemical reaction on
the other hand, the radium atom and the Ra
2+
ion behave quite differently
since they have different outer electronic structures.
3. Nuclear reaction frequently involve the conversion of one element to another
(with a change in the number of protons in the nucleus. Elements in ordinary
chemical reaction retain their identity.


4. Nuclear reactions are accompanied by energy changes which exceed by
several orders of magnitude, those associated with ordinary chemical
reaction. The energy evolved when a gram of radium undergo radioactive
decay is about 500,000 times as great as that given off when an equal
amount of radium reacts with chlorine to form radium chloride.
C
12
6
C
14
6
C
14
6
C
12
6
Rn He Ra
222
86
4
2
226
88
+
o
RADIOACTIVITY
By radioactivity is meant the spontaneous transformation of an
unstable isotope of one chemical element into an isotope of
another element attended by the emission of elementary
particles or nuclei (for instance alpha particles).
The rate of radioactive transformations is characterized by the
radioactive decay constant which shows part of the total
number of atom of a radioactive isotopes decays in one
second. The greater the radioactive decays, the more rapidly
does an isotope decay.
The number of atoms of a radioactive isotope decaying in unit
time is propositional to the total number of atom of this isotope
present at the given moment.
The time needed for half of the original amount of a radioactive
element to decay is called the HALF-LIFE. This quantity
characterizes the lifetime of an element. It ranges from fraction
of a second to hundreds of millions of years. E.g., the half-life of
Radium is 3.85 days, of Radium is 1620 years, of uranium 4500
million years.
The main kinds of radioactive radiation include alpha, beta and
gamma radiation.
Negatively
charge plate
Positively
charge
plate
Gamma particles
No charge
Beta particles
negatively
charged
Alpha particles
positive charge
2
He +2e
Radioactive
sample
Alpha Radiation which consists of a stream of
positively charge particles (alpha particles) that carry
a charge of +2 and have a mass of 4 on the atomic
mass scale. In alpha decay, the nucleus of an atom
emits 2 protons and 2 neutrons bound in a nucleus
of the helium atom
4
2
He. The result is lowering of the
charge of the initial radioactive nucleus by 2, and of
its mass number by 4. Thus alpha decay results in
the formation of an atom of an element having an
atomic number two less than the original isotope.

Th He U
234
90
4
2
238
92
+ =
Beta Radiation (decay) which is made up of a stream
of negatively charged particles (beta particles) that
have all the properties of electrons. (mass charge -1)
Beta particles results from the transformation of a
neutron (mass =l charge =o) at the surface of the
nucleus into a proton (mass=l, charge = +1).
Consequently beta-emission leaves the mass number
unchanged but increases the atomic number by one
unit

The process of beta decay can be written as
neutron proton + electron or n P+e-. The electron
appearing in this transformation flies out of the nucleus,
and the positive charge of the letter grows by unity.
Pa e Th
234
91
0
1
234
90
+ =

A proton may also transform into a neutron as:

Protons neutron +Positron or P n+e
+

A positron, whose symbol is e
+
, is an elementary particle with a mass equal
to that of an electron, but carrying a positive electric charge. The charges of
an electron and a positron are identical in absolute value.
A proton may transform into a neutron with the formation of a positron when
the instability of the nucleus is due to an excess content of protons in it. One
of the protons in the nucleus transforms into a neutron, the positron that
appears flies out of the nucleus, and the charge of the nucleus diminishes by
unity. This kind of radioactive decay is called POSITRON. BETA DECAY (|+
decay) in contrast to the previously considered ELECTRON BETA DECAY
(|- decay).
As a result of beta decay the atom is transformed into a new element whose
atomic number is one greater (with |- decay) or one less (with |+ decay)
than that of the original isotope.

(|+ decay)

(|- decay)

(|+ decay)

(|- decay)


e Si P
0
1
30
14
30
15
+
e Si Al
0
1
28
14
28
13
+
e B C
0
1
11
5
11
6
+
e N C
0
1
14
7
14
6
+
GAMMA Radiation, electromagnetic radiation of very short wavelength (=0.0005 to 0.1nm)
i.e. high energy photons. The emission of gamma radiation accompanies virtually all
nuclear reaction as the result of an energy change within the nucleus, whereby an unstable,
excited nucleus remitting form alpha or beta-emission given off a photon and drop to a
lower more stable energy state (no mass change, no change in Z).

INTERACTION OF RADIATION
The commonly instrument used to detect and measure radiation is the Scintillation counter.
We have also Geiger Muller counter.
The harmful effect of radiation upon human beings is caused by its ability to ionize and
ultimately destroy the organic molecules of which body cells are composed. The extent of
damage depends upon
1. the energy and the
2. types of radiation. The former is expressed in GRAYS. A gray corresponds to the
absorption of one joule per kilogram of tissue. The total biological effect of radiation is
expressed in rems.
Number of Rems = n x (number of grays) where n is 100 for |, , and x radiation and 1000
for o radiation or high energy neutrons.
Effect of exposure to a single dose of radiation
Dose (Rems) Probable effect
0 to 25 No observable effect
25 to 50 Small decrease in white blood cell count
50 to 100 Lesions, marked decrease in white blood cells
100 to 200 Nausea, vomiting, loss of hair
200 to 500 Hemorrhaging, ulcers, possible death
5000 + Fatal.
Radiation can produce mutations in plants and animals by bringing about changes in
chromosomes. Federal research council has set an upper limit of 0.17 per year above
background as the max. dosage to which major population group can be exposed.
USE FULNESS
In Medicine
Treatment of cancer to destroy or arrest the growth of malignant tissue (Radium).
Even cheaper cobalt-60. Sodium iodine containing radioactive iodine (
131
I or
126
I)
used to destroy the malignant cells (cancer of the thyroid) in human beings.

RATE OF RADIOACTIVE DECAY
FIRST ORDER RATE LAW
The first order equation reaction
X- products; rate = =k (conc. X)


log
10
conc. X = log
10
(conc. X)
o
Kt / 2.30
(Conc x = conc of x at t conc of x at t = zero; conc x (conc x)
0
(t = t 0 = t)

where (conc. X)
o
is the initial concentration and t is the elapsed time (Xo is the
amount of radioactive substance at zero time (when the counting process starts )
and X is the amount remaining after time t. The first order rate constant K, is the
characteristic of the isotope undergoing radioactive decay.

----------------------------------(14)

t
x conc
A
A .
t k
x conc
x conc
A =
A
.
.
30 . 2 ) .
) . (
log
10
kt
x Conc
x conc
o
=
Derivation of Eq. 14 is as follows:



Integrating from t = 0 to t and from x
0
to x



or

-----------(15)

kx
dt
dx
Rate = =
kdt
x
dx
=
K K
t
693 . 0
2 log
30 . 2
10
5 . 0 = =
} }
=
x
x
t
dt K
x
dx
0
0
ln x ln x
0
= - Kt and ln X = 2.30 log
10
X
30 . 2
log log
0 10 10
Kt
x x =
30 . 2
log
0
10
Kt
x
x
=
t
x
x
K
=
0
10
log
30 . 2
Since X = X
0
/2;
X
0
= 2X;
X
0
/X = 2
ATOMIC BONDING
There are two types of bonds:
Primary
Secondary
Primary Bonds:
Primary bonds are the strongest bonds
which hold atoms together. The three types
of primary bonds are:
Ionic Bonds
Covalent Bonds
Metallic Bonds
bonding is achieved when atoms fill their outer s and p
levels.

THE IONIC BOND
Lost and gain of electrons
Ionic bond is created between 2 unlike atoms with
different electronegativities i.e. one atom donate its
valence electrons to a different atom. Both atoms now
have filled (or empty) outer energy levels but both have
acquired an electrical charge and as ions.
The donor of the electron is left with a positive charge
and is a cation while the electron accepter acquires a net
negative charge and is an anion. The oppositely charged
ions are then attracted to one another to produce the
ionic bond.

Na
+

Na
+

Na
+

Na
+

Cl
-

Cl
-
Cl
-

Cl
-
Cl
-
The ionic bond between
Na and Cl
The ionic bond is non-directional. A positively charged Na+
will attract any adjacent Cl- equally in all directions.
The more electropositive the metal and the more
electronegative the non-metal, the greater the ionic
contribution to bonding. LiFl is almost completely ionic
MgO has a little covalent character in its bond sand
SiO
2
is about half conic half covalent.
The non-directional of ionic bond is due to the
spherically symmetry of the electric field of an iron, i.e.
diminishes with the distance according to the same
way regardless of directions.
When a force is applied to NaCl crystal the electrical balance between the ions is
upset. Partly for this reason, ionically bonded materials behave in a brittle manner.
Electrical conductivity is also poor; when a voltage is applied the electrical charge is
transferred by the movement of entire ion which does not move as easily as
electrons.
Ionic bond does not have saturability. The oppositely attracted charge ions retain
their ability to interact electrostatically with other ions.
The forces of attraction of oppositely charged ions must predominate over the force
of mutual repulsion exerted between ions of the same sign.
The absence of directionality and saturability in an ionic bond is the reason why ionic
molecules tends to associate i.e. to combine with one another.
COVALENT BOND
Covalent bonding requires that electron be shared
between atoms in such a way that each atom has its
outer sp orbital filled. For example, a silicon atom,
which has a valence of 4 obtains 8 electrons in its
outer energy shell by sharing its electrons with 4
surrounding silicon atoms. Therefore in Si 4 covalent
bonds must be formed.
In order for the covalent bonds to occur the Si atoms
must be arranged as the bonds have a fixed
DIRECTIONAL relationship with one another. In Si, C
the arrangement produces a tetrahedron with angles
of about 109
o
between the covalent
Si
Si Si Si
o
o o
o o
o
Si Si
Si
In Si, C a tetrahedral structure is formed with angles of about 109
o

required between ach covalent bond.
A covalent chemical bond is formed by 2 electrons with anti parallel spins , this
electron pair belonging to 2 atoms. The strength of a covalent bond grows with an
increasing degree of overlapping of the interaction electron clouds.
The ability of atoms to participate in the formation of a restricted number of covalent
bonds is called SATURABILITY of covalent bond.
The formation of a covalent bond is a result of overlapping of the valence electron
clouds of the interaction atoms. But such overlapping is possible only with a definite
mutual orientation of the electron cloud; here the overlap region is arranged in a
definite direction with respect to the interacting atoms. In other words, a covalent
bond is DIRECTIONAL.
109
0
DIRECTION OF A COVALENT BOND
The properties of a molecule, its ability to enter into chemical reactions with
other molecules (its reactivity) depend not only on the strength of the chemical
bonds in the molecule, but to a considerable extent on its dimensional structure
too.
In a hydrogen molecule, the atomic S-electron clouds overlaps near the
imaginary straight line joining the nuclei of the interacting atoms (i.e. the bond
axis). A covalent bond formed in such a way is known as a o (sigma) bonds.



If p-electron clouds are oriented along the bond axis, they can also participate in
the formation of a sigma bond. Overlapping of the 2p-electron cloud of the
fluorine atom and the Is-electron cloud of the hydrogen atom in the
formation of a sigma bond in the molecule HF
Note: In the formation of a chemical bond energy is always evolved as a result
of the decrease in the potential energy of the system of interacting electrons and
nuclei this is why the potential energy of a particle formed a (a molecule or
crystal) is always less than the total potential energy of the initial free atom.
The chemical bond in the molecule F
2
is also sigma bond, it is formed by the 2p-
electron clouds of the F atoms.
overlapping of atomic
electron clouds in a
hydrogen molecule.
Overlapping of the 2p-electron cloud of the
fluorine atom and the Is-electron cloud of the
hydrogen atom in the formation of a sigma
bond in the molecule HF
When P- electron clouds oriented
perpendicularly to the bond axis interact, two
overlaps regions are formed at both rides of this
axis instead of a single region. Such a covalent
bond is called a (pi) (Bond)
-
-
o - Bond
(b)
+
z
x
y
z
y
-
+ +
-
y
z
- Bond
- Bond
Overlapping of the 2p-electron clouds in the molecule N
2
a sigma bond and 2-pi bonds
HYBRIDIZATION OF ATOMIC ELECTRON
ORBITALS
The method of hybridization of atomic orbital proceeds from the
assumption that in the formation of a molecule, instead of the
initial atomic s-, p-, and d-electron clouds, equivalent blended
or hybrid electron clouds are formed that are stretched out in a
direction towards the neighboring atoms, the result being their
more complete overlapping with the electron clouds of these
atoms. The more complete overlapping of the valence electron
clouds the stronger the chemical bond formed and
consequently to additional gain in energy. If this gain in energy
is sufficient to more than compensate the expenditure of energy
for the deformation of initial atomic electron clouds, such
hybridization in the long run leads to diminishing of potential
energy of the molecule formed and consequently to an increase
in its stability.
+ + -
+ + - -
sp-hybridization Hybridization of 1s and 2p
orbital leading to the formation of two sp orbital
BeF
2
linear orientation
Overlapping of the 2p electron clouds of the
fluorine atoms with the 2s and 2p electron
clouds of Beryllium atom.
2p
Be
F
B
F
F

F
F
F Be
BeF
2
straight line 180
o

equilateral triangle 120
o
BF
3
CH
4
Tetrahedron 109.5
o
i) 4 pairs of electrons around the central atom are all shared, the
molecule is tetrahedral
ii) when one pair is unshared, the structure is that of a pyramid
with an equilateral triangle as large
iii) 2 unshared pairs lead to a bent.
sp
3
-hybridization
METALLIC BOND
The metallic bond involves sharing of delocalized electron given
a non-directional bond high electrical conductivity. The metallic
bond forms when atom give up their valence electron, which
then form an electron sea (or gas) leaving behind a core
consisting of the nucleus and inner electron and the core
becomes an ion with a positive charge. The positively charge
atom cores are bonded by mutual attraction to the negatively
charged electron.
Metallic bonds are non directional; the electron holding he
atoms together are not fixed in one position. This properly
permit metals to have good ductility and to be deformed into
useful shapes since when the former is bent and the atoms
attempt to change their relationships to one another, the
direction of the bond merely shifts rather then the bond
breaking.
Since the electrons are free to move, they lead to good thermal
and electrical conductivity.
Metallic bond and electron cloud
Metallic bond.
Secondary Bonds:
Secondary bonds are much weaker than primary bonds. They often provide
a "weak link" for deformation or fracture. Example for secondary bonds are:
Hydrogen Bonds and Van der Waals Bonds
Hydrogen Bonds

Hydrogen bonds are common in covalently bonded
molecules which contain hydrogen, such as water
(H2O). Since the bonds are primarily covalent, the
electrons are shared between the hydrogen and
oxygen atoms. However, the electrons tend to spend
more time around the oxygen atom. This leads to a
small positive charge around the hydrogen atoms,
and a negative charge around the oxygen atom.
When other molecules with this type of charge
transfer are nearby, the negatively charged end of
one molecule will be weakly attracted to the
positively charged end of the other molecule. The
attraction is weak because the charge transfer is
small.

Hydrogen bonds.
Van Der Waals bonding is a secondary bonding, which exists between virtually all atoms
or molecules, but its presence may be obscured if any of the three primary bonding
types is present. Secondary bonding forces arise from atomic or molecular dipoles. In
essence, an electron dipole exists whenever there is some separation of positive and
negative portions of an atom or molecule. When an electron cloud density occurs at one
side of an atom or molecule during the electron flight about the nucleus, Van Der Waals
forces are generated. This creates a dipole wherein one side of the atom becomes
electrically charged and the other side has deficiency of electrons and is considerably
charged positive.

Van der Waals Bonds

Van der Waals bonds are very weak compared to other
types of bonds. These bonds are especially important in
noble gases which are cooled to very low temperatures.
The electrons surrounding an atom are always moving.
At any given point in time, the electrons may be slightly
shifted to one side of an atom, giving that side a very
small negative charge. This may cause an attraction to a
slightly positively charged atom nearby, creating a very
weak bond. At most temperatures, thermal energy
overwhelms the effects of Van der Waals bonds.

Crystal Lattice Structures
Atoms are the building blocks of all materials.
They are bonded or "held together" by cohesive forces in a manner
characteristic of a particular material.
In a liquid state the atoms of metal are of random arrangement, having
short-range order. At times several unlike atoms will arrange themselves in
the characteristic pattern of a particular metal.
There is the phenomenon of random grouping, scattering, and regrouping for
short periods of time is characteristic of the liquid state. As the random
grouping mechanism becomes less frequent and the atomic movement of
unlike atoms become more agitated, the material may become a gas.
As the energy input decreases, the random movement of the unlike atoms
becomes less frequent, the bonding becomes stronger, and ordered arrays
of atoms form lattices.

A crystal is a repeating array. In describing this structure we must
distinguish between the pattern of repetition (the lattice type) and what is
repeated (the unit cell). The most fundamental property of a crystal lattice is
its symmetry. In three-dimensions, unit cells stack like boxes, filling the
space, making the crystal. A Crystal: A repetitive, three dimensional
arrangement of atoms or ions in a solid. It possess a periodicity that
produces long-range order i.e. the local atomic (ionic) arrangement is
repeated at regular intervals millions of times in the 3 dimensions of
space.
The most stable arrangement of atoms in
a crystal will be that which minimizes the
energy per unit volume or in other words,
the one that
Preserves electrical neutrality
Satisfies the directionality and discreteness of
all covalent bonds
Minimizes strong-ion-ion repulsion
Packs the atoms as closely as possible
consistent with (1), (2) and (3)

Cubic Lattice Structure
Hexagonal Lattice Structure
Orientation of the unit cells in a lattice.
Unit Cell: When a solid has a crystalline structure, the
atoms are arranged in repeating structures called unit
cells, which are the smallest units that show the full
symmetry of a crystal.

Lattice: The three dimensional array formed by the unit
cells of a crystal is called lattice.
Face-centered cubic (F.C.C.)
Body-centered cubic (B.C.C.
Hexagonal-close-packed (H.C.P.)
Lattice pt: The vertices of the unit cell
Lattice parameter: The length of the unit
cell edges
The angles and lengths within the repeat
unit determine the class to which the
lattice cell belongs
Basis: group of things located on a lattice
Lattice + Basis = Crystal Structure
Crystal Systems
7 systems (7 unique unit cell shapes) to describe crystal
structures. Lattice pts can be arranged in only 14
different arrays called Bravais lattices
Body Centered Cubic (B.C.C)
Lattice Structure
Face Centered Cubic (F.C.C) Lattice Structure
Closed Packed Hexagonal (C.P.H)
Lattice Structure
a
b
a
b
c
c

Cl
-1
Cl
-1
Cl
-1
Cl
-1
Cl
-1
Cl
-1
Cl
-1 Cl
-1
Cs
+1
Simple Cubic (S.C)
CN = 8
Brass SC r/R >0.73
CaTiO
3
SC
a
SC
= 2(r
Cs+
+R
Cl-
)/3

Relationship between the radius, r and
lattice parameters
3
4
) ( 0
r
a
BCC
=
a
b
a
b
c
c

a
0
3
a
0
2
a
0
3
2
a
b
a
b
c
c

a
0
2
a
0
2
CN=8
2
4
) ( 0
r
a
FCC
=
CN=12
C
r a a c
HCP
266 . 3 633 . 1 )
6
4
(
0 ) ( 0
= = =
CN=12
Fe-, V, Cr, Mo, Na, W, SiF
4
, Mg(OH)
2
Al, Ni, Ag, Fe-, Cu, Au, CH
4
, NaCl, LiF
MgO, CH
4
Cd
Zn
Mg
Co
Zr
Ti
Be
Al
2
O
3
,
ZnS,
NiAs,
CdI
2
Miller Indices
Indices of Directions
Determine the coordinates of 2 pts that lie in the direction of
interest h
1
, k
1
, l
1
and h
2
, k
2
, l
2
Subtract the coordinates of the 2
nd
pt from those of the 1
st

pt: h = h
2
- h
1
, k = k
2
- k
1
and l = l
2
- l
1
,
Clear fractions from the differences h, k and l to give
indices in lowest integer values, h, k, l
Write the indices in square brackets without commas: [h k l]
If h < 0, we write [ k l]
Directions Indices [h k l ]
OA [1 0 0]
OB [1 1 0]
OC [1 1 1]
OD [2 0 1]
OE [0 1 0]
OF [1 1 2]
CB [0 0 1]
C
z
y
x
0
B
F
A
D
E
To determine the angle
between directions
If A = ui + vj + wk and B =
uI + vj +wk, then,
A
.
B = A B cos where
is the angle between
the 2 vectors
(

+ + + +
+ +
=

2
1
2
1
) ( ) (
cos
12 12 12 2 2 2
1 1 1
1
w v u w v u
ww vv uu

Indices of Planes
Identify the coordinates intercepts of the plane. If the plane is
parallel to one of the axes, the intercept is taken as infinity
Take the reciprocal of the intercepts
Clear fractions, but do not reduce to lowest integers
Cite planes in parentheses (h k l).
A
B
C
Plane Intercepts Indices
A ,,1 (0 0 1)
B 1,1,1 (1 1 1)
C 1,1, (1 1 0)
D ,,1 (3 4 6)
D
a
3

C
a
1

a
2

a
1
, a
2,
a
3,
C
(h k i l)


I = -(h + k)
Linear density,
L
is the ratio of the
number of atoms centered along direction
within one unit to the length of the line
contained within one unit
Planar density,
P
is the ratio of the
number of atoms centered on a plane
within one unit to the area of the plane
contained within one unit
Volumetric density,
V
is the number of
atoms per unit volume
Atomic Packing Factor, APF is the ratio of
the volume of atoms in a unit cell to the
volume of unit cell; or APF is the product
of atoms in cell and volume of an atom per
unit volume of the cell; or
(

|
.
|

\
|
=
3
3
4
r APF
V
t
DCS, Perovskite Structure
SC, Crystobalite Structure
STACKING SEQUENCE
The manner in which close-packed
planes are stacked on top of one another
in a particular structure; planes stacked
so their atoms are directly above one
another are represented by the same
letter, for example ABABABA
represents HCP stacking and
ABCABCABC represents FCC stacking
(0002)
A
B
(0001)
A
A A
A
A
A
A
B
B
B
Stacking of
(0002) planes
A
A A
A
A
A
A
B
B
B
C
C
C
Stacking of
(111) planes
A
B
C
(111)
Significance of local packing arrangement
A coordination polyhedron behaves as a tightly bound
unit when the valence of the central atom is more than
half the total valence of the atoms bonded to it. If the
valence of the central atom equals the total valence of
the surrounding atoms, the subunit is really a molecule
When polyhedral subunits are discrete atomic groups
bonded to one another by secondary bonds than
when they are bonded together with primary bonds,
the melting or softening temperature will be lower. For
example in SiF
4
each silicon is tetrahedrally
coordinated by 4 fluorine atoms and in SiO
2
each
silicon is tetrahedrally coordinated by 4 oxygen atoms
yet SiF
4
melts at -90
o
C and SiO
2
melts at 1710
o
C
Polyethylene melts at about 125
o
C. But if adjacent
polyethylene chains are bonded together by some C-C
bonds produced by irradiation, the polymer may keep
its shape and thermal stability up to 300
o
C

Influence of bond type on structure and properties
The non-directionality of metallic and ionic bond
allows metal atoms to be packed closely
together in a regular crystalline array. The
major of them have ligancy of either 12 (CPH or
FCC systems) or 8 (BCC systems). The CN of
ionic crystals is frequency of 4, 6, or 8 and so,
on average, ionic crystals possess lower
packing densities than metals. This is due to
the fact that ionic compound contains at least 2
types of ion which may be of different sizes,
compared to a pure metal where all atoms are
identical, and secondly the ions possess
opposing charges.

Metals and ceramics are fully crystalline but polymers
and glasses are either partially crystalline or
completely amorphous. In amorphous structures,
the atoms or molecules are not packed in a regular
and symmetrical pattern and the amount of void
space is greater than within a crystal.
As the atomic number of the element increases and
the distance of the outer shell or valence, electrons
from the nucleus becomes greater, the bond
strength of covalently bonded crystals reduces.
The melting pt of C, Si, Ge, Sn are 3800, 1420, 937
and 232oC respectively.
The melting pt of ceramics materials mainly oxides,
carbides and nitrides of the lower atomic number
elements such as Al, B, Mg, Si are all high being in
the order of 1000 3000oC. The presence of weak
van der waals bond within the covalently bonded
molecules influences the melting temperatures.
The polymides (nylons) have higher m.p than other
polymers such as polyethylene because of the
presence of hydrogen bonds.
The close packing of atoms in metals leads towards
relatively high m.p. the strength of bond may be
less compare to that of ionic and covalent bonds

FCC & HCP
SIMILARITIES:
Both FCC & HCP Structures have atomic packing factors of 0.74. The two
structures are each regular stacking of close-packed planes. In the case of
fcc metals, the (111) planes are closed packed. These are identical to the
(0002) planes of the hcp structure

DIFFERENCES
The fundamental difference between Al (FCC) and Mg(HCP) relates
directly to the different crystal structures for Al and Mg in their sequence of
packing of layers. Al structure follows a cubic packing arrangement - fcc
stacking as an ABCABC---- sequence, and the Mg a hexagonal one hcp
stacking as ABAB---- Sequence. This subtle difference leads to significant
differences in their properties ductility which depends on mechanical
deformation. This, is turn, is related to planes and directions of high atomic
density in the metals crystal structure. There are 12 plane/ direction
combinations for Al and only 3 for Mg. There are, therefore, 4 times as
many combinations for mechanical deformation in the Al crystal structure
as in Mg. This is equivalent to having 4 times, the number of avenues
available for ductility in aluminum based alloys as in Mg based alloys.
NOTE: The mechanical behavior of a given type of metal alloy can
be affected by heat treatment.
DIAMOND CUBIC (DC) CRYSTAL STRUCUTRE
The diamond cubic crystal structure is a fcc lattice with
2 atoms per lattice pt., some spheres are tetrahedrally
coordinated by other spheres inside the cell.
These are 8 atoms per unit cell for an average of 2
atoms per fcc position . Experiments show that the
C C interatomic difference is 0.154nm in this
structure. The body diagonal is 4 times this value.
Thus
(b.d) Diamond = 4 (C-C) = a
diamond

a
diamond
=4 (0.154nm) /3 =
0.356nm
C
diamond
, Gallium arsenide
(GaAs), Ge and grey Sn
Diamond
Graphite
DIFFERENCES
Two crystalline forms (allotropes) of the element carbon graphite and diamond.
Both allotropes are macromolecular, which explains why both graphite and
diamond have very high melting points above 3500
0
c.
The graphite crystal is PLANAR with the carbon atoms arranged in a HEXAGONAL
pattern. Each carbon atom is bonded to 3 others, forming one double bond and 2
single bonds. The forces between the layers in graphite are are of the dispersion
type and are quite weak. Consequently, the layers can readily slide past one
another so that graphite is soft and slippery to the touch. When you write with a
lead pencil; which is really made of graphite, than layers of graphite rub off onto
the paper.
In diamond, each carbon atom forms single bonds with four other carbon atoms
arranged tetrahedrally around it. The bonds are strong enough (bond energy C C
= 347 KJ mol
-1
) to produce a rugged three dimensional lattice. Diamond is one of
the very hardest of substances, and is used industrially in cutting tools and quality
grindstones.
The light elements in group IV have crystal structures in which all the bonds that
hold the crystal together are covalent. The bonds are the results of overlapping sp
3

hybrid orbitals and the structure that results is the diamond cubic (DC) crystal
structure of diamond, Si, Ge and Grey Sn.
Some of the group IV elements can also have structures in which all the bonds
that hold the crystal together are not covalent. Graphite crystal structures; as earlier
stated, in it the atom are covalently bonded in planar hexagonal arrays with weak
secondary bonds between the planes. The primary covalent bonds are between the
sp
2
orbital; the weaker bonds between the planes are much more metallic in
characters with the result that graphite conducts electricity and heat much more
easily parallel to the planes than perpendicular to them.

POLYMORPHISM
Diamond Graphite
Diamond and graphite are the two polymorphs of carbon.
Diamond is hard, transparent, and an electrical insulator.
Graphite has lubricating characteristics and conducts an
electric current. These contracts arise from differences in
bonding, and therefore differences in structure. Diamond has a
3 dimensional structure of covalent bonds. Graphite has
element that possesses mobility in the crystal layers of a 2-
dimensional structure.
Diamond will change to graphite if it is heated sufficiently for the
thermal energy to break the bonds and coordinate the atoms
with new neighbors. The reaction is reversible.
15000C
C
diamond
C graphite
2000
0
C 10000atm

Crystal Imperfections
These are 3 basic types of lattice imperfections
point defects,
line defects (or dislocations) and
surface defects.
These defects are intentionally added to produce a
desired set of mechanical and physical properties.
POINT DEFECTS
Point defects are localized disruption of the lattice
involving one as possibly several atoms.
Consider a hypothetical crystal structure.
O O O O
O O O O
O O O O
O O O O
O O O O
O O O O
O O O
O O O O
O O O O
O O O O
O O O O
O O O O
O O O O
O O O O
O O O
O O O O
Vacancy Interstitial impurity
Substitutional
T n
RT
Q
n n
V V
o
|
.
|

\
|

= exp
n
v
the number of vacancies per cm
3
n is the number of lattice points per cm
3
Q is the energy required to produce a vacancy
in J/mole
R- is the gas constant, 8.31 J/mole.K and
T is the temperature in degrees kelvin
O O O O
O O O
O O O O
O O O O
O O O O
O O
O O O
O O O O
O O O O
O O
O O O O
O O O O
Schottky defect formed in order to
maintain neutral charge
Vacancy
Interstitial
ion
Pt defects disturb the perfect arrangement of
the surrounding atom. When a vacancy or a
small substitutional atom is present, the
surrounding atom collapse towards the Pt.
defect, stretching the bonds between the
surrounding atom and producing a tensile
stress field. An interstitional and large
substitutional atom produce the surrounding
atoms together, producing a compressive
stress field. The disruption accounts for the
strength of the metal.
LINE DEFECT (DISLOCATIONS)
Dislocations are line imperfections in a perfect lattice. There are
2 types of dislocations:
the screw dislocation and the edge dislocation. Considering the
diagram below, if a force or stress F is applied parallel to and
along the y- axis, we have a motion.
F
F
F
a
EDGE DISLOCATION
If the force F is applied as shown above and
the whole line moves by a distance a we have
an edge dislocation.
This is when the burger vectors is perpendicular
to the line vector of the dislocation.
SCREW DISLOCATION
A dislocation produced by skewing a crystal so
that one atomic plane produces a special ramp
about the dislocation
When the burgers vector is parallel to the line
vector
SIGNIFICANCE OF DISLOCATIONS
The process by which dislocation moves and causes a
metal to deform is called slip.
This slip explain why the strength of metals is much
lower than the value predicted from the metallic load
Slip provides ductility in metals, if no dislocation were
present, the metal (bar) is brittle, the materials can not
be shaped by various metalworking processes such as
forging into useful shapes.
The mechanical properties of a metal or alloy can be
controlled by interfering with the movement of
dislocations. An alloy or obstacle introduced into the
crystal prevents a dislocation from slipping.
Dislocation densities of 10
6
cm/cm
3
are typical of the
softer metals while densities upto 10
12
cm/ cm
3
can be
achieved by deforming the materials.
SCHMIDS LAW
A resolved shear stress may be produced on a slip
system, causing the dislocation to move on the slip plane in
the slip direction.

where Resolved shear stress in the slip direction;
F
r
= F Cos resolved shear force; = F/A
o
unidirectional stress
applied; F unidirectional force
| o t Cos Cos =

t
A
F
r
= t

A
Slip direction
Shear stress
is the angle between the slip direction and the applied force and is
the angle between the normal to the slip plane and the applied force
t
crss
t
The critical resolved shear stress is the shear stress required to
break enough metallic bonds in order for slip to occur. Thus slip occurs
causing the metal to deform, when the applied stress produces a resolved
shear stress that equals the critical resolved shear stress


Note When the slip plane is perpendicular to the applied stress . Then
= O
0
, = 90
0
and Cos = 0, therefore =0
That is, even if is great, no resolved shear stress develop along the slip
direction and the dislocation cannot move.

We can use Schmids law to compare the properties of metals having Bcc,
Fcc and Hcp crystal structures. (see table below)

Schmids law : slip in a metal crystal begins when the stress resolved on
the slip plane in the slip direction reaches a certain value termed the
critical resolved shear stress
crss r
t t =
Factors affecting slip in perfect metallic structures
Factor Bcc Fcc Hcp
1. Critical resolved
shear stress (MPa) 35-70 0.35-0.70 0.35-0.70
2. Number of slip
Systems 48 12 3
3. Cross-slip` Can occur Can occur Cannot
4. Properties Strong Ductile Relatively
Brittle
Critical resolved shear stress in metal is very high, the must be high in
order for resolved stress to equal to critical. If is large, the metal must
have a high strength. In Fcc (closed packed planes) is low (0.35
0.70 mpa)
Fcc metals are expected to have low srengths.
Bcc contains no close packed planes, much as (110), (112) and (123)
planes and (70MPa) Bcc metals have high strength, Hcp metals contains
close-packed planes and therefore expected to have low critical resolved
shear stress.
Number of slip systems: ideal Hcp metals possess only one set of parallel
close packed planes, the (0001) planes, and three close packed
directions, giving three slip systems. Consequently, the probability of the
close packed planes and directions being oriented with and near 45
0
is
very low. The latter is needed so that we could obtain at low applied
stress. The Hcp crystal may fail in a bristle manner without a significant
amount of slip.
Fcc metals contain 4 non parallel close packed planes of the form (111)
and 3 close packed directions of the form (110) within each plane, giving a
total of 12 slip systems. At least one slip system is favorably oriented for slip
to occur at low applied stresses causing Fcc metals to have low strength but
high ductilities.
Bcc metals have as many as 48 slip systems that are nearly close packed.
Dislocation moving on one slip plane may interfere with movement of
dislocation on other active slip planes. This interference leads to high
strength in Bcc metals yet still permits at least some ductility as well.
crss r
t t =
Cross-slip: A change in the slip system of a dislocation when
dislocation shift to a second intersecting slip system, also
properly oriented and continue to move.
In many Hcp metals cross-slip cannot occur since the plane are
parallel, not intersecting. Therefore the Hcp metals tend to
remain brittle. Cross slip is possible in both Fcc and Bcc
metals because a number of intersecting slip system is present.
Cross-slip consequently helps maintain ductility in these metals.
Note
Dislocations are more difficult to move in ionic and covalent
materials. In covalent materials of Si, the directionality of the
bonds prevents easy movement of dislocations behaves in a
rather brittle manner.
In ionic materials including most ceramics, dislocations are
present and are observed to move , however movement of a
dislocation disrupts the charge balance around the anions and
cations, requiring that bonds between anions and cations be
broken. Slip is much more difficult and ceramic materials
normally display bristle behavior.

SURFACE DEFECTS
Surface imperfections of a structural nature arise
from a change in the stacking of atomic planes
across a boundary.
STACKING FAULTS
A surface defect in Fcc materials caused by the
improper stacking sequence of close-packed planes.
Normally, a stacking sequence ABCABCABC is
produced in a perfect Fcc lattice. But suppose the
following sequence is produced ABCABABABC. The
small region ABAB which has an Hcp stacking
sequence instead of the Fcc stacking sequence
represents a stacking fault. Stacking faults interfere
with the slip process.
TWIN BOUNDARIES
A twin boundary is a surface defect across
which there is a mirror image misorientation of
the lattice. It can also move and cause
deformation of the material. The twin
boundaries interfere of the metal.

Crystal Formation
Crystallization
Crystallization is the transition from the liquid to the solid state
and occurs in two stages:
1. Nucleus formation
2. Crystal growth
Atomic motion in the liquid state of a metal is almost completely
disordered. Although the atoms in the liquid state do not have
any definite arrangement, it is possible that some atoms at any
given instant are in positions exactly corresponding to the
space lattice they assume when solidified. As the energy in the
liquid system decreases, the movement of the atoms decreases
and the probability increases for the arrangement of a number
of atoms into a characteristic lattice for that material. The
energy level at which these isolated lattices form is called the
freezing point.
Mechanism of solidification (square grids represent the unit cells)
(d) (c) (b) (a)
(a) Nucleus formation; (b), (c) Growth of the crystallites; (d) Grain boundaries
Now consider a pure metal at its freezing point where both the liquid and solid states
are at the same temperature. The kinetic energy of the atoms in the liquid and the solid
must be the same, but there is a significant difference in potential energy. Kinetic
energy is related to the speed at which the atoms move and is strictly a function of
temperature. The higher the temperature, the more active are the atoms and the
greater is their kinetic energy. Potential energy, on the other hand, is related to the
distance between atoms. The greater the average distance between the atoms, the
greater is their potential energy. The atoms in the solid are much closer together, so
that solidification occurs with a release of energy. This difference in potential energy
between the liquid and solid states is known as the latent heat of fusion.
When the temperature of the liquid metal has dropped sufficiently below its freezing
point, stable aggregates or nuclei appear spontaneously at various points in the liquid.
These nuclei, which have now solidified, act as centers for further crystallization. As
cooling continues, more atoms tend to freeze, and they may attach themselves to
already existing nuclei or form new nuclei of their own. Each nucleus grows by the
attraction of atoms from the liquid into its space lattice.
Crystal growth continues in three
dimensions, the atoms attaching
themselves in certain preferred directions,
usually along the axes of a crystal. This
gives rise to a characteristic treelike
structure which is called dendrite.
Process of crystallization by nucleation and dendritic growth.
The crystal axes are pointed at random because Each
nucleus is formed by chance, and therefore the dendrites
will grow in different directions in each crystal. As the
amount of liquid decreases, the gaps between the arms of
the dendrite will be filled and the growth of the dendrite will
be mutually obstructed by that of its neighbors. This leads
to a very irregular external shape. The crystals found in all
commercial metals are commonly called grains because of
this variation in external shape. The area along which
crystals meet, known as the grain boundary, is a region of
mismatch. The boundaries are formed by materials that are
not part of a lattice, such as impurities, which do not show
a specific grain pattern. This leads to a noncrystalline
(amorphous) structure at the grain boundary with the
atoms irregularly spaced. Since the last liquid to solidify is
generally along the grain boundaries, there tends to be a
higher concentration of impurity atoms in that area.
Grain Boundary

Formation of dendrites in
a molten metal.

Dendrites observed
at a magnification of
250x
Plastic Deformation
When a material is stressed below its elastic limit,
the resulting deformation or strain is temporary.
Removal of stress results in a gradual return of
the object to its original dimensions. When a
material is stressed beyond its elastic limit, plastic
or permanent deformation takes place, and it will
not return to its original shape by the application
of force alone. All shaping operations such as
stamping, pressing, spinning, rolling, forging,
drawing, and extruding involve plastic
deformation of metals. Various machining
operations such as milling, turning, sawing, and
punching also involve plastic deformation.
Plastic deformation may take place by :
Slip
Twinning
Combination of slip and twinning
Deformation by Slip:
When the plastic deformation is due to slip, the atoms
move a whole interatomic space (moving from one
corner to another corner of the unit cell). This means
that overall lattice structure remains the same. Slip is
observed as thin lines under the microscopes and
these lines can be removed by polishing.
The effect of slip on the lattice structure.
Deformation by Twinning:
When mechanical deformation is created by twinning,
the lattice structure changes. The atoms move only a
fraction of an interatomic space and this leads to a
rearrangement of the lattice structure. Twinning is
observed as wide bands under the microscope. These
wide bands can not be removed by polishing.
Two kinds of twins are of interest to the metallurgists:

1. Deformation or mechanical twins, most prevalent in close
packed hexagonal metals (magnesium, zinc, iron with large
amount of ferrite)

2. Annealing twins, most prevalent in F.C.C. (Face centered
cubic) metals (aluminum, copper, brass, iron with austenite).
These metals have been previously worked and heat
treated. The twins are formed because of a change in the
normal growth mechanism.
The effect of twinning on the lattice structure.
Twin bands
Twin bands in zinc.
Slip Twinning
Atomic movement Atoms move a whole
number of atomic
spacing.
Atoms move
fractional atomic
spacing.
Microscopic
appearance
Thin lines Wide bands or broad
lines
Lattice orientation No change in lattice
orientation. The steps
are only visible on the
surface of the crystal
and can be removed by
polishing. After polishing
there is no evidence of
slip.
Lattice orientation
changes. Surface
polishing will not
destroy the evidence
of twinning.
Slip versus Twinning
Cold Work
A material is considered to be cold worked if its grains are in a
distorted condition after plastic deformation is completed. All the
properties of a metal that are dependent on the lattice structure are
affected by plastic deformation or cold working. The following
properties are affected by cold work significantly:
Tensile Strength
Hardness
Yield Strength
Ductility
Tensile strength, yield strength and hardness are increased, while
ductility is decreased. Although both strength and hardness increase,
the rate of change is not the same. Hardness generally increases most
rapidly in the first 10 percent reduction (cold work), whereas the tensile
strength increases more or less linearly. The yield strength increases
more rapidly than the tensile strength, so that, as the amount of plastic
deformation is increased, the gap between the yield and tensile
strengths decreases. This is important in certain forming operations
where appreciable deformation is required. In drawing, for example, the
load must be above the yield point to obtain appreciable deformation
but below the tensile strength to avoid failure. If the gap is narrow, very
close control of the load is required.
Effect of cold working on tensile
and yield strength of copper.
Effect of cold working on tensile
strength, hardness, ductility and grain
size. (The curve below ductility
represents the change in grain size)
Ductility follows a path opposite to that
of hardness. A large decrease in the first
10 percent reduction and then a decrease
at a slower rate is observed. Distortion of
the lattice structure hinders the passage
of electrons and decreases electrical
conductivity in alloys. The increase in
internal energy, particularly at the grain
boundaries, makes the material more
susceptible to inter granular corrosion,
SCC
Annealing
As a result of cold working, the hardness, tensile
strength, and electrical resistance increase, while
ductility decreases. There is also a large increase in
the number of dislocations, and certain planes in the
crystal structure are severely distorted. Most of the
energy used to cold work the metal is dissipated in
heat, and a finite amount of energy is stored in the
crystal structure as internal energy associated with the
lattice defects created by the deformation.
Full annealing is the process by which the distorted
cold worked lattice structure is changed back to one
which is strain free through the application of heat.
This process is carried out entirely in the solid state
and is usually followed by slow cooling in the furnace
from the desired temperature.
The annealing process may be divided into three stages:
Recovery
Recrystallization
Grain growth

Recovery:
This is primarily a low temperature process, and the property changes
produced do not cause appreciable change in microstructure or the
properties, such as tensile strength, yield strength, hardness and
ductility. The principal effect of recovery is the relief of internal
stresses due to cold working.
When the load which causes plastic deformation is released, all the
elastic deformation does not disappear. This is due to the different
orientation of crystals, which will not allow some of them to move back
when the load is released. As the temperature is increased, there is
some spring back of these elastically displaced atoms which relieve
most of the internal stresses. Electrical conductivity is also increased
appreciably during the recovery stage.
Since the mechanical properties of the metal are essentially
unchanged, the main purpose of heating in the recovery range is
stress relieving cold worked alloys to prevent stress corrosion
cracking or to minimize the distortion produced by residual stresses.
Commercially, this low temperature treatment in the recovery range is
known as stress relief annealing or process annealing.
Recrystallization:
As the temperature of the recovery range is reached,
minute new crystals appear in the microstructure. These
new crystals have the same composition and lattice
structure as the original undeformed grains and are not
elongated but are uniform in dimensions. The new crystals
generally appear at the most drastically deformed portions
of the grain, usually the grain boundaries and slip planes.
The cluster of atoms from which the new grains are formed
is called a nucleus. Recrystallization takes place by a
combination of nucleation of strain free grains and the
growth of these nuclei to absorb the entire cold worked
material.
The term recrystallization temperature does not refer to a
definite temperature below which recrystallization will not
occur, but refers to the approximate temperature at which
a highly cold worked material completely recrystallizes in
one hour.
Material Recrystallization
Temperature (
o
F)
Copper ( 99.99 %) 250
Copper (5 % Zinc) 600
Aluminum (99.99 %) 175
Aluminum alloys 600
Low carbon steel 1000
Zinc 50
Tin 25
Lead 25
Recrystallization temperatures for various metals and alloys.
The greater the prior deformation, the lower the
temperature for the start of recrystallization.
Increasing the annealing time decreases the
recrystallization temperature for the start of
recrystallization.
During recrystallization stage, there is a
significant drop in tensile strength, hardness and
a large increase in the ductility of the material.
Grain Growth:
In this stage the tensile strength and hardness
continue to decrease but at a much less rate than
the recrystallization stage. The major change
observed during this stage is the growth of the
grain boundaries and reaching the original grain
size (See Figure below).
Effect of annealing on tensile strength, hardness, ductility and grain size.
Phase Diagrams
Part 1
The properties of a material depend on the type,
number, amount, and form of the phases present, and
can be changed by altering these quantities. In order
To make these changes, it is essential to know the
conditions under which these quantities exist and the
conditions under which a change in phase will occur.
The best method to record the data related to phase
changes in many alloy systems is in the form of phase
diagrams, also known as equilibrium diagrams or
constitutional diagrams.
Simple Phase Diagram
In order to specify completely the state of a system in equilibrium, it is necessary
to specify three independent variables. These variables, which are externally
controllable, are temperature, pressure and composition. With pressure assumed
to be constant at atmospheric value, the equilibrium diagram indicates the
structural changes due to variation of temperature and composition. Phase
diagrams show the phase relationships under equilibrium conditions, that is,
under conditions in which there will be no change with time. Equilibrium
conditions may be approached by extremely slow heating and cooling, so that if a
phase change is to occur, sufficient time is allowed.
Phase diagrams are usually plotted with temperature as the ordinate, and the alloy
composition as the abscissa as shown in the Figure above.
Phase Diagrams
Part 2
Inverse Lever Rule:
Inverse lever rule is used to determine the percentage of each
phase that is present at various temperatures.
The length of line XY represents the sum of the two phases as
100 percent. The inverse lever rule states that liquid phase can
be calculated by taking the length of the line XZ and dividing
this by XY.
The solid phase can be calculated by taking the length of the
line ZY and dividing it by XY. To get the percentages, the
values are multiplied by 100.
Phase diagram of a mixture with
complete solubility in liquid and
solid states.
Eutectic System:
Eutectic system is a phase
transformation that takes
place when a single-phase
liquid transforms directly to
a two-phase solid.
L ---> S1 + S2
Liquid ---> Solid 1 + Solid 2
(This is a reversible phase
transformation)
Eutectoid System:
The eutectoid phase
transformation occurs when
a single-phase solid
transforms directly to two-
phase solid.
S1 --->S2 + S3
Solid 1 ---> Solid 2 + Solid 3
(This is a reversible phase
transformation)
Eutectic phase transformation
Eutectoid phase transformation
Polymorphism and Allotropy
Polymorphism is a physical phenomenon where a
material may have more than one crystal structure. A
material that shows polymorphism exists in more than
one type of space lattice in the solid state. If the change
in structure is reversible, then the polymorphic change is
known as allotropy. The prevailing crystal structure
depends on both the temperature and the external
pressure.
One familiar example is found in carbon: graphite is the
stable polymorph at ambient conditions, whereas
diamond is formed at extremely high pressures.
The best known example for allotropy is iron. When iron
crystallizes at 2800
o
F(1538
o
C) it is B.C.C. ( -iron), at
2554
o
F(1400
o
C) the structure changes to F.C.C. ( -iron
or austenite), and at 1670
o
F(910
o
C) it again becomes
B.C.C. ( -iron or ferrite).
-iron (alpha) :
Figure 2. Alpha iron (B.C.C) unit cell
The other name for -iron is ferrite. This crystal has body
centered cubic structure. The unit cell and the micrograph of
the crystal are shown in the Figures below.
Cooling curve for pure iron. (Allotropic behavior of pure iron)
Alpha iron (B.C.C) unit cell
Fig. 2
Ferrite crystals.
-iron (Gamma):
Face centered cubic crystal unit
cell. The other name for -iron is
austenite. This crystal has face
centered cubic (F.C.C) structure.
The unit cell and the micrograph
of the crystal are shown in the
Figures below.
Austenite crystals.
Iron-Iron Carbide Diagram
Iron-iron carbide diagram
CEMENTITE (Fe
3
C):
Cementite is also known as iron carbide which has a chemical formula, Fe
3
C.
It contains 6.67 % Carbon by weight. It is a typical hard and brittle interstitial
compound of low tensile strength (approximately 5,000 psi) but high
compressive strength. Its crystal structure is orthorhombic.
AUSTENITE ( iron):
It is also known as ( ) gamma-iron, which is an interstitial solid solution of
carbon dissolved in iron with a face centered cubic crystal (F.C.C) structure.
Average properties of austenite are:


Tensile strength 150,000 psi.
Elongation 10 % in 2 in gage length.
Hardness Rockwell C 40
Toughness High
Table 1. Properties of Austenite
Austenite (gamma iron) crystal structure
Austenite is normally unstable at room temperature. Under certain conditions it
is possible to obtain austenite at room temperature.
FERRITE (o iron):
It is also known as (o ) alpha -iron, which is an interstitial solid solution of a
small amount of carbon dissolved in iron with a Body Centered Cubic (B.C.C.)
crystal structure. It is the softest structure on the iron-iron carbide diagram.
Average properties are:


Tensile Strength 40,000 psi
Elongation 40 % in 2 in gage length
Hardness Less than Rockwell C 0 or
less than Rockwell B 90.
Toughness Low
Table 2. Properties of Ferrite.
Ferrite (alpha iron) crystal structure
PEARLITE (o + Fe
3
C)
It is the eutectoid mixture containing 0.83 % Carbon and is formed at 1333
o
F(726
o
C)
on very slow cooling. It is very fine platelike or lamellar mixture of ferrite and
cementite. The structure of pearlite includes a white matrix (ferritic background)
which includes thin plates of cementite. Average properties are:


Tensile Strength 120,000 psi
Elongation 20 % in 2 in gage
length
Hardness Rockwell C 20 or
BHN 250-300
Table 3. Properties of pearlite.
Pearlite microstructure
A fixed amount of carbon and a fixed amount of iron are needed to form cementite
(Fe
3
C). Also, pearlite needs fixed amounts of cementite and ferrite. If there is not
enough carbon, that is less than 0.83 %, the C and the Fe will combine to form Fe
3
C
until all the C is consumed. This cementite will combine with the required amount of
ferrite to form pearlite. The remaining amount of ferrite will stay in the structure as free
ferrite. Free ferrite is also known as proeutectoid ferrite. The steel that contains
proeutectoid ferrite is referred to as hypoeutectoid steel. If, however, there is an excess
of C above 0.83 % in the austenite, pearlite will form, and the excess C above 0.83 %
will form cementite. The excess cementite deposits in the grain boundaries. This excess
cementite is also known as proeutectoid cementite.
(Light background is the ferrite matrix,
dark lines are the cementite network)
LEDEBURITE ( + Fe3C)
It is the eutectic mixture of austenite and
cementite. It contains 4.3 % Carbon and
represents the eutectic of cast iron. Ledeburite
exists when the carbon content is greater than 2
%, which represents the dividing line on the
equilibrium diagram between steel and cast iron.

() DELTA IRON:
Delta iron exists between 2552 and 2802
o
F. It may
exist in combination with the melt to about 0.50 %
Carbon, in combination with austenite to about
0.18 % Carbon and in a single phase state out to
about 0.10 % carbon. Delta iron has the Body
Centered Cubic (B.C.C) crystal structure and is
magnetic.
Effect of Carbon on the Physical Properties of Steel
In general, as the carbon content increases the hardness of the
steel also increases. The tensile strength and the yield strength
also increase to about 0.83 % carbon. Thereafter, they level
out. This is shown in Figure1.





Figure 1. Effect of carbon on hardness, tensile strength and yield strength of steels.
The tensile strength and hardness are affected as the ratio of
ferrite to cementite in the structure of steel changes. As the
percentage of pearlite increases in the hypoeutectoid steels,
the tensile strength increases. The hardness does not increase
dramatically. The hypereutectoid steels show only a slight
increase in strength as the cementite-to-ferrite ratio increases.
The elongation and the reduction in area represent how ductile
or brittle a material is. Figure 2 indicates the effect of carbon on
the ductility and impact resistance (toughness) of steels. The
elongation and the reduction in area drop sharply with increase
in carbon content, going almost to zero at about 1.5 % carbon.
This indicates that the carbon content of 1.5 % or more will
cause high brittleness. The impact resistance also decreases
very sharply up to about 0.83 % carbon and then levels out.
Figure 2. Effect of carbon on the impact resistance and ductility of steels.
Composites
Composites are combinations of two materials in which one of the
materials, called the reinforcing phase, is in the form of fibers,
sheets, or particles, and is embedded in the other materials called
the matrix phase. The reinforcing material and the matrix material
can be metal, ceramic, or polymer. Composites are used because
overall properties of the composites are superior to those of the
individual components. For example: polymer/ceramic composites
have a greater modulus than the polymer component, but aren't as
brittle as ceramics. The following are some of the reasons why
composites are selected for certain applications:
High strength to weight ratio (low density high tensile strength)
High creep resistance
High tensile strength at elevated temperatures
High toughness
Typically, reinforcing materials are strong with low densities while
the matrix is usually a ductile, or tough, material. If the composite is
designed and fabricated correctly, it combines the strength of the
reinforcement with the toughness of the matrix to achieve a
combination of desirable properties not available in any single
conventional material. The downside is that such composites are
often more expensive than conventional materials. Examples of
some current application of composites include the diesel piston,
brake-shoes and pads, tires and the Beechcraft aircraft in which
100% of the structural components are composites.
The strength of the composite depends primarily
on the amount, arrangement and type of fiber (or
particle) reinforcement in the resin. Typically, the
higher the reinforcement content, the greater the
strength. In some cases, glass fibers are
combined with other fibers, such as carbon or
aramid (Kevlar29 and Kevlar49), to create a
"hybrid" composite that combines the properties
of more than one reinforcing material. In addition,
the composite is often formulated with fillers and
additives that change processing or performance
parameters.
Three types of composites are:
Particle-reinforced composites
Fiber-reinforced composites
Structural composites

Particle Reinforced Composites:

Particles used for reinforcing include ceramics and
glasses such as small mineral particles, metal particles
such as aluminum, and amorphous materials, including
polymers and carbon black. Particles are used to increase
the modulus of the matrix, to decrease the permeability of
the matrix, to decrease the ductility of the matrix. Particles
are also used to produce inexpensive composites.
Reinforcers and matrices can be common, inexpensive
materials and are easily processed. An example of particle
reinforced composites is an automobile tire which has
carbon black particles in a matrix of polyisobutylene
elastomeric polymer. Another example is spheroidized
steel where cementite is transformed into a spherical
shape which improves the machinability of the material.
Another example for particle-reinforced composite is
concrete where the aggregates ( sand and gravel) are the
particles and cement is the matrix. Particle reinforced
composites support higher tensile, compressive and shear
stresses.

Fiber-reinforced Composites:
Reinforcing fibers can be made of metals, ceramics,
glasses, or polymers that have been turned into graphite
and known as carbon fibers. Fibers increase the modulus
of the matrix material. The strong covalent bonds along the
fiber's length gives them a very high modulus in this
direction because to break or extend the fiber the bonds
must also be broken or moved. Fibers are difficult to
process into composites which makes fiber-reinforced
composites relatively expensive.
Fiber-reinforced composites are used in some of the most
advanced, and therefore most expensive, sports
equipment, such as a time-trial racing bicycle frame which
consists of carbon fibers in a thermoset polymer matrix.
Body parts of race cars and some automobiles are
composites made of glass fibers (or fiberglass) in a
thermoset matrix.
The arrangement or orientation of the fibers relative to one
another, the fiber concentration, and the distribution all
have a significant influence on the strength and other
properties of fiber-reinforced composites. Applications
involving totally multidirectional applied stresses normally
use discontinuous fibers, which are randomly oriented in
the matrix material. Consideration of orientation and fiber
length for a particular composites depends on the level
and nature of the applied stress as well as fabrication cost.
Production rates for short-fiber composites (both aligned
and randomly oriented) are rapid, and intricate shapes can
be formed which are not possible with continuous fiber
reinforcement.
Modulus of Fiber-Reinforced Composites:
Fibers have a very high modulus along their axis, but have
a low modulus perpendicular to their axis. If the fibers are
all parallel, the modulus of a fiber reinforced composite
depends upon which direction you're measuring. The
modulus of the entire composite, matrix plus reinforcer, is
governed by the rule of mixtures when measuring along
the length of the fiber:
E
c
= E
f
V
f
+ E
m
V
m

E
c
is the modulus of the entire composite
along the length of the fiber.
E
f
is the modulus of the fiber along the
length of the fiber.
V
f
is the volume percent occupied by the
fibers.
Em is the modulus of the matrix (usually
not dependent upon direction)
Vm is the volume percent occupied by the
matrix (equal to (1-V
f
)).
Tensile strength and elastic modulus
when fibers are parallel to the
direction of stress.
tensile strength and elastic modulus
when fibers are perpendicular to the
direction of stress.
POLYMERS
An alternative name for this category is PLASTICS,
which describes the extensive formability of many
polymers during fabrication. The mer in a polymer is
a single hydrocarbon molecule such as ethylene
(C
2
H
4
).
Polymers are long chain molecules composed of
many mers bonded together. The most common
commercial polymer is POLYETHYLENE (C
2
H
4
)
n
-
where n can range from approximately 100 to 1000.

C ==C C C C C C -

Conversion of the C = C double bond into 2 C C
single bonds
Strong covalent bonds exist along the
straight lines between C and C and between
C and H. Only weak, secondary bonding
occurs between adjacent section of the long
molecular chains. This secondary bonding
that acts as weak link leading to the low
strength and low melting joint for traditional
polymers.
Polymers are contained within animal (wool,
leather), insect (silk) and vegetable (wood,
cotton) products.
TYPES OF POLYMERISATION
There are 2 types of polymers: thermoplastics and the thermosets. Rubber
or elastomers form another group of polymeric materials.
Thermoplastic polymers, in which the long molecular chains are not rigidly
connected, have good ductility and formability; thermosetting polymers are
stronger but more brittle because the molecular chains are tightly linked.
COPOLYMER: When 2 or more kinds of mers are mixed within a single
polymeric chain as in the case of alloying in metal system, and similarly
yields materials that potentially combine the beneficial properties of each
component. There are 3 types alternating, random and flock, grafting and
terpolymers.
Thermosets and Elastomers
In thermosets and elastomers, the entire network is interconnected through
primary bonds in a non-regular (non-crystalline) fashion. The networks are
of two folds:
1. There in which small molecules link linear chains and 2) those in
which small molecules (including short polymer chains) react directly to
produce chain branching.
Elastomers (Rubber): The main constituent of new natural rubber is
polyisoprene which belong to the first category of materials stated above. It
contains unsaturated C=C bonds, and when vulcanizing rubber, sulfur is
added to promote crosslinks.
Without vulcanization, rubber is soft and sticky and flows viscously even at
room temperature. By crosslinking about 10% of the sites, the rubber
attains mechanical stability while preserving its flexibility.
Polymer Trade Names Major Application Characteristics Typical Applications
Acrylics(Polym
thylmethacrylate)
Lucite, Plexiglas Outstanding light transmission and
resistance to weathering
Lenses, transparent aircraft
enclosures, drafting equipment,
outdoor signs
Fluorocarbons
(PTFE or
TFE)
Teflon, TFE,
Halon TFE
Chemically inert in almost all environments;
excellent electrical properties; low coefficient of
friction; may be used to 500 F; relatively weak
Anticorrosive seals, chemical pipes and
valves, bearings, antiadhesive coatings,
high temperature electronic parts
Nylons Zytel, Plaskon Good mechanical strength, abrasion
resistance, and toughness; low coefficient of
friction; absorbs water and some other Liquid
Bearings, gears, cams, bushings,
handles, and jacketing for wires and
cable
Polycarbonates Merlon, Lexan Dimensionally stable; low water absorption;
transparent; very good impact resistance and
ductility; chemical resistance not outstanding
Safety helmets; lenses, light globes,
base for photographic film
Polyethylene Alathon,
Petrothene,
Hi-fax
Chemically resistant, and electrically
insulating; tough and relatively low coefficient
of friction; low strength and poor resistance
to weathering
Flexible bottles, toys, tumblers, battery
parts, ice trays, film wrapping
materials
Polypropylene Pro-fax, Tenite,
Moplen
Resistant to heat distortion; excellent electrical
properties and fatigue strength; chemically inert;
relatively inexpensive; poor resistance to UV light
Sterilizable bottles, packaging film, TV
cabinets, luggage
Poylstyrene Dtyron, Lustrex,
Rexolite
Excellent electrical properties and optical clarity;
good thermal and dimensional stability; relatively
Inexpensive
Wall tile, battery cases, toys, indoor
lighting panels, appliance housings
Vinyls PVC, Pliovic, Saran,
Tygon
Good low cost, general purpose materials; ordinarily rigid,
but may be made flexible with plasticizers; often
copolymerized; susceptible to heat distortion
Floor coverings, pipe, electrical wire
insulation, garden hose
Polyester (PET) Mylar, Dacron,
Celanar
One of the toughest of plastic films; excellent fatigue and tear
strength, and resistance to humidity, acids, greases, oils, and
solvents
Magnetic recording tapes, clothing, auomotove
tire cords
Thermoplastics and Thermosets
Thermoplastics
Thermosets

Polymer Trade Names Major Application
Characteristics
Typical Applications
Epoxies Epon, Epi-rez,
Araldite
Excellent combination of
mechanical properties and
corrosion resistance;
dimensionally stable; good
adhesion; relatively inexpensive;
good electrical properties
Electrical moldings, sinks,
adhesives, protective
coatings, used with
fiberglass laminates
Phenolics Bakelite, Durez,
Resinox
Excellent thermal stability to
over 300 F; may be compound
with a large number of resins,
fillers, etc.; inexpensive
Motor housings, telephones,
auto distributors, electrical
fixtures
Polyesters Selectron,
Laminac,
Paraplex
Excellent electrical properties
and low cost; can be formulated
for room -or high temperature
use; often fiber reinforced
Helmets; fiberglass boats,
auto body components,
chairs, fans
Silicones DC resins Excellent electrical properties;
chemically inerts, but
susceptible to attack by steam;
outstanding heat resistance;
relatively expensive
Laminates, terminal strips,
high temperature insulation
CERAMICS & GLASSES
Greek word Keramos referring to pottery or earthen
ware. It includes various hand, bristle corrosion resistant
materials made by firing clay and other minerals consisting
of one or more metals and one or more non metals; oxygen
present in the form of oxides. Ceramic materials are joined
together by ionic and covalent bonds. Ceramic typically are
hard, brittle, high melting point materials with low electrical
and thermal conductivity, good chemical and thermal
stability, and high comprehensive strengths.
Ceramic materials have a wide range of applications,
ranging from pottery; Brick, tile, cooking ware, and soil pipe
to glass, refractories, magnets, electrical devices and
abrasives. The tiles that protect the space shuttle (Rocket)
are silica, a ceramic material. The newly discovered
superconductive and load bearing materials are also
ceramic such as impellers in turbine engines.
STONE & ROCK e.g. granite (a mixture of feldspar
(aluminosilicate containing sodium, potassium or calcium),
quartz and mica (aluminosilicate), limestone and marble.
The brittle nature of these materials facilitates quarrying
and polishing, while their low coefficient of thermal
expansion, relatively low density and low tendency to
absorb water are beneficial attributes in structural
applications.
CLAY PRODUCTS (filed whiteware and structural clay
products). Clay consists of electrically neutral
aluminosilicate layers in the form of tiny crystalline platelets
that readily slide over each other. In combination with water
they form plastic masses that are easily shaped.
White-ware includes porcelain, sanitary-ware, electrical
insulators and dishes. They are made from mixtures of clay,
feldspar and flint.
Structural clay products includes bricks tiles and sewer
pipes.

GLASSES
Note: Glasses and ceramics are distinct materials. Silica
glasses are , however, generally classified as a subgroup of
ceramics. For example lithium aluminosilicate which have low-
thermal expansion coefficients, making them resistant to
fracture due to rapid temperature changes. They are mostly
used as cookware.
REFRACTORIES
These ceramics largely provide the thermal insulation, crucibles
and hardware in all kind of casting operations as well as
elevated temperature processing and heat treatment furnaces.
Refractories include fireclays containing alumina silicates with
varying Al
2
0
3
Si0
2
, proportions, MgO rich compositions,
relatively pure silica and zircona (Zr 0
2
)
ABRASIVES
Materials used as abrasives include silicon carbide, tungsten
carbide, alumina, silica and industrial diamond dust. They are
most commonly bonded to grinding wheels or to paper and
cloth (e.g.. Sandpaper), but are also used to loose form as well
as embedded in pastes and waxes.


CATEGORIES
Ceramics and glasses can be divided into 3 categories
crystalline ceramics, glasses (non crystalline) and glass
ceramics
CERAMIC CRYSTALLINE MATERIALS
They include the traditional silicates and the many oxide and
non-oxide compounds.

Compositions of some silicate ceramics Composition (wt %)
Ceramic SiO
2
Al
2
O
3
K
2
O mqO CaO others

Silica refractory 96 - - - - 4
Fireclay 50-70 45-25 5
Mullite 28 72 -
Electrical porcelain 61 32 6 1
Steatite porcelain 64 5 30 1
Portland cement 25 9 64 2
Some nonsilicate oxides and nonoxide ceramic

primary comportion Common product names
Al
2
O
3
Alumina, alumina refractory
MgO Magnesia, magnesia refractory
MgO. Al
2
O
3
Spinel
UO
2
Uranium dioxide
ZrO
2
Zirconia
BaTiO
3
Baruim titanate
* Si C Silicon carbide
* Si
3
N
4
Silicon nitride
TiC Titanium carbide
WC Tungsten carbide
C Graphite

GLASSES NON CRYSTALLINE MATERIALS
These are commercially silicates glassware.
Composition of some silicate glasses, Composition (wt %)
Glass Si0
2
B
2
0
3
Al
2
0
3
Na
2
0 Ca0 Mg0 K
2
0 Zn0 Pb0 other
Vitreous silica 100
Window 72 1 14 8 4 1
Container 73 2 14 10 1
Fiber (E-glass) 54 15 22 1
Copper enamel 35 3 4 17 42 -
Vitreous purely Si0
2
can withstand series temperature in
excess of 1000
0
C. Thigh temperature crucibles and furnace
windows are typical applications.
GLASS CERAMICS
The most important example of glass ceramic is the
Li
2
0 Al
2
0
3
Si0
2
system which consists of 74%Si0
2
,
4%Li
2
0, 16%Al
2
0
3
and 6%Ti0
2
. These materials
exhibit excellent thermal shock resistance due to the
low expansions coefficient of the crystallized ceramic.
Uses: missile nose cones, domestic ovenware
bearings and ceramic - to glass seal.
APPLICATIONS AND PROPERTIES OF CERAMICS
CLAY PRODUCTS.
Clay improve the forming characteristics, permitting
more complicated ceramic bodies to be produced.
High feldspar contents reduce the liquidus
temperature and consequently the firing temperature
REFRACTORIES used to contain molten metals.





APPLICATIONS AND PROPERTIES OF MATERIALS
APPLICATIONS PROPERITES
METALS
Copper Electrical conductor were light electrical conductivity, good formability
Gray cast Automobile engine blocks castability, mechinability, vibration damping
Alloy steels Wrenches Good strengthening by heat treatment
CERAMICS
SiO2-Na2O-CaO Window glass Good optical properties and thermal insulation
Al2O3, mgO, AiO2 Refractories for
Containing molten metal thermal insulation, high melting temperature, relatively inert to
molten
Basium titanate Transducers for metal
Stereo record players piezoelectric bahaviour converting sound to
electricity
POLYMERS
Polyethylene food packaging Easily formed into thin, flexible airtight film
Epoxy Encapsulation of integrated
Circuits Good electrical insulation and moisture resistance
Phenolic Adhesives to join plies in
Plywood Strength and moisture resistance
SEMICONDUCTORS
Silicon Transistors and integrated circuits Unique electrical behaviour
GaAs Fiber-optic systems Converts electrical signals to light
COMPOSITES
Graphite-epoxy Aircraft components High strength-to-weight ratio
Tungsten carbide
Cobalt Carbide cutting tools for High hardness yet good shock resistance
Machining
Titanium-clad
Steel Reactors vessels low cost and high strength of steel with good corrosion
resistance of Titanium