MEEG213 Lecturenote1

MEEG213 Material Science & Engineering
MEEG213 Material Science & Metallurgy

Chap.1
Introduction to
Materials Science
and Engineering
Materials and Engineering
What do engineers do?
Engineers adapt materials and energy for societys need
Engineers design products and system,
make them, and monitor their use.
An Automobile
Power distribution system Internal structure of mobile phone
Building
Silicon solar cell
Organic solar cell
Every product is made with materials; and
energy is involved in production, in use, and
even in communication.

This association with design, production, and
usage is the reason that engineering students
take a course in materials as part of their
undergraduate curricula.
-The materials that are specified must have
the correct properties

- Costs of the processed materials must be acceptable.
- Durability, reliability.
- The choice of materials must be compatible
with the environmental standard
from raw-material sources, through manufacturing steps
and product usage, to eventual discard.
Necessary condition for selecting materials.
Light energy (photons) Electrical energy
When sunlight is absorbed by some materials, the solar energy knocks electrons
loose from their atoms, allowing the electrons to flow through the material to
produce electricity. This process of converting light (photons) to electricity (voltage)
is called the photovoltaic (PV) effect.
Whats PVs
Greenhouse Gas Effect
Why Solar energy?
Advantages of Organic PVs (OPVs)
-Processed easily over large area using
-spin-coating
-doctor blade techniques (wet-processing)
-evaporation through a mask (dry processing)
-printing
-Low cost
-Low weight
-Mechanical flexibility and transparency
-Band gap of organic materials can be
easily tuned chemically by incorporation
of different functional group
Why OPVs?
Structure, Properties,
Performances
Properties of a material originate from the internal
structures of that material.
The internal structures of materials comprise atoms
associated with their neighbors in crystals, molecules,
and microstructures.
The manufacturing process
(machining, rolling, wiring, heat treating. etc)
changes the internal structure of the material.
The engineer must consider not only the initial demand
but also those service conditions that will alter the
internal structure and hence the properties of a material.
(ex. Rubber, Steel for boiler, Magnet)
Property Symbol Definition Units
Conductivity
(electrical)
o Charge flux along a voltage
gradient
Ohm
-1
m
-1
Conductivity
(thermal)
k Energy flux along a thermal
gradient
W/m
o
C
Resistivity Reciprocal of electrical
conductivity
Ohm m
Strength S Critical stress for failure
N/m
2
, lb/in
2
Ductility Plastic strain prior to
fracture
%
Elastic modulus E Ratio of stress to elastic
strain
N/m
2
, lb/in
2
Hardness Resistance to penetration
Toughness Energy absorbed prior to
fracture
Selected Engineering Properties
Structure
Properties
Performance
During process
During Service
Types of Materials
Based on atomic bonds and structure
-metals, polymer, and ceramics

Based on the electrical property
-conductors, semiconductors, and insulators

We can classify also based on the mechanical,
optical, magnetic properties.
Metals
1. High thermal, electrical conductivities-
Because the valence electrons are not bound
2. Opaque, Higher luster being polished.
3. Usually heavy and deformable.
Jet Engine
Ni base super alloy
Ti-Al-V alloy
Al super alloy
Polymers (Plastics)
1. Low density, insulator both thermal and electrical.
2. Poor reflector of light. Transparent or translucent.
3. Flexible, subject to deformation.
Ceramics : compounds that contain metallic
and nonmetallic element
1. Relatively hard, brittle
2. Higher resistance to high temperature
than metal or polymer
3. Chemically resistant
We also can group materials as conductors.
Conductors are predominately metals.
Their valence electrons are delocalized; in contrast,
insulators have tightly bound electrons,
which are characteristic of many polymers and ceramics.

Semiconductors feature elemental silicon, but also include a
growing number of ceramic materials and a few polymers.
Conductors, Semiconductors, and Insulator
MEEG213 Material Science & Metallurgy
Chap.2
Atomic Bonding
and Coordination
Atomic structure include

-Electronic structure of the atoms making up the material
-Binding forces between the atoms
-The three dimensional arrangement of the atoms
(Example) Carbon Steel
The strength of a carbon-steel was very dependent on the rate of
cooling from an elevated temperature. In this instance the strength
is determined by the exact atom arrangement, which in turn
depends on the rate of cooling.

Then the logical starting point in our study of materials is
to consider the possible ways in which atoms can join together.
And the force that bind atoms together find their origins
in the electronic structures of atoms.
2-1 Individual Atoms and Ions
It is the electrons-particularly the outermost
ones (valence electron)-that affect most
properties of interest to engineers
They determine the chemical properties, the
nature of inter atomic bonding, size of the
atom, electrical conductivity and optical
characteristics.
Electrons
One electrons has negative electrical charge :
1.6x10
-19
Coulomb
Several features of electron behavior

1) With individual atoms, electrons have specific energy
state, called orbital.
-the available electron energy states around a hydrogen
can be identified definitely=> There are large ranges of
intermediate energies not available for the electrons.
The values in these ranges are forbidden because the
corresponding frequencies do not permit standing waves.
Atomic Mass Unit : amu is defined as one-twelfth of the
atomic mass of carbon 12.
2) Valence electron
The top most occupied orbital contains valence electron.

Ionization result from removing of valence electron by
outer electric field.
Ionized atom becomes cation.

Anion : When the valence orbital are not filled, the atom
may accept a limited number of extra electrons within
these unfilled energy states, to become a negative ion
or anion.
Ex. 2-1.1
Sterling silver contains approximately 7.5w/o copper
and 92.5w/o silver what are the a/o copper and a/o
silver?
2-2. Molecules
Fig2-2.1
The atoms are held together by strong intra molecular
attractive forces that produce covalent bonds.
The intermolecular bonds between molecules are weak,
consequently each molecule is free to act more or less
independently.
Properties originated from above.
- Each of these molecules compounds has a low melting
and a low boiling temp. compared with other material.
- The molecular solid are soft because the molecules
can slide past each other with small stress applications.
- The molecules remain intact in liquid and gases.
Covalent Bonding
1) Covalent bonds are stereo specific 3 dimensional
and can be sketched in several ways.
a) bond lines : C-C
b) pairs of dot : C:C
c) regions of high electron probability
The probability of an electrons position is greatest along
the line between atoms. (Sharing electron)
2) Coordination Number (CN)
Number of closest ionic or atomic neighbors
Carbon (diamond structure) CN=4(maximum CN
possessed by covalently bonded carbon.
Carbon (in ethylene) CN=3
Table 2.-2.1 Covalent Bonds per Atom
H H
C= C
H H
3) Typically, covalent bond are very strong.
Example : The hardness of diamond
Each carbon atom is covalently bonded with four
neighboring atoms, and each neighbor is bonded with an
equal number of atoms to form a rigid three-dimensional
structure.
Fig. 2-2.3
Bond Length and Energies
The strength of bonds between atoms in a molecule
depends on the kind of atoms and other neighboring
bonds.
Table 2-2.2

The energy reported is the amount required to break
1mole(Avogadros number) of bonds.
For example, 370,000J of energy are required to break
6.02X10
23
C-C bond.
This same amount of energy is released if one mole of
these C-C is formed.
Bond Angles (hybrid sp
3
orbital)
Methane(CH
4
),
carbon tetrachloride
(CCl
4
), and diamond
provide examples of
sp
3
orbital that
connect four identical
atoms to the central
carbon.
We find the atoms
equally spaced
around the central
carbon at 109.5
o
from
each other.

However if the orbitals do not bond identical atoms to the
central carbon, these time-averaged angels are distorted
slightly. CH
3
Cl : 110.1
o
Delocalized Electrons
Stereospecific covalent bond is called sigma bond.

Fig.2-2.7
The six electrons that are not included in the sigma
bonds develop standing waves across the whole
molecule. These electrons, which are called pi electrons,
respond to and electric field by moving their center of
oscillation toward the side of the molecule that is nearer
the positive electrode. However they can not leave the
molecule.
There are as many wave patterns for these delocalized
electrons as there are carbon atoms in the ring.
Example 2-2.1
How much energy is required, +,(or released -) if
2.6kg of acetylene,C
2
H
2
, react with hydrogen to
produce ethylene, C
2
H
4
?
Sol)
C
2
H
2
+ H
2
= C
2
H
4

For each molecule of C2H4 to be produced, one H-H
bond and C C are eliminated, conversely one C=C
and two C-H bonds are formed.
H-C
C-H
H-H
H H
C= C
H H
Example 2-2.2
The structure of naphthalene is a double benzene
ring with two carbons of each ring in common.
(a)How many delocalized electrons are there?
(b) How many wave patterns (electrons states) are
available to the delocalized electrons?
Sol)
(a)Total valence electron : 4/CX10C+1/HX8H=48
electrons in bonds : C-H : 8X2=16
C-C (sigma)= 11X2=22
delocalized electrons=48-(16+22)=10
(b) 10 (because there are 10 carbon atoms.)
-> 20 delocalized electrons could be accommodated.
2-3 Macromolecule(Polymer)
Natural macromolecule
: cellulose in wood, cotton, fibrous plants.

Industrially made macromolecules : polyethylene,
polyvinylchloride, polystyrene.
Mer : the smallest repetitive unit in a polymer.
Fig.2-3.1
(b) produced by
the joining of
many single units
into a Molecular
chain.
Linear Molecules
Polymer : There is no theoretical limit to its length.
Strong covalent bonds exist along its length.
Numerous commercial polymers are linear.
Ex) polyvinyls and polyesters
Polyvinyls are a family of polymers that have C2H3R
mers.
N is the degree of polymerization : the number of mers
per molecule.
In polystyrene, R is a benzene ring.
In Polyethylene, R is a simple hydrogen atom.
Table 2-3.1
Secondary Bonds

Weak (<40kJ/mol) inter atomic bonds
arising from dipoles within the atoms or molecules
1) Van der waals bonding
Arises from electron oscillations within the atom or
molecule.
In brief, the center of negative charges for the electrons
is displaced momentarily(<10
-15
s) from the center of
positive charges that accompanies the protons in the
nuclei-> producing of small electric dipoles.
The positive side of one atom or molecule is attracted to
the negative side of an adjacent atom or molecule ->the
resulting dipoles provide the only forces of attraction in
many of our ambient vapors and gases.
Non directional force due to fluctuating character of the
dipoles.
Low bonding energy-> very low melting point.
Ex) Ne, Ar, CH
4
, Kr, Cl
2

2) Secondary bond in asymmetric
molecules
Ex) CH
3
Cl (Chloromethane)
In general the dipole moments are greater than are
those for comparable values in atoms and in non-polar
molecule->materials possessing polar molecules
remains solid to relatively high temperature.
3) Hydrogen Bridge
(Strongest secondary forces of attraction)
Ex)H
2
O
These bare proton can easily be attracted to negative
charges of other molecules, because the protons are not
shielded by electrons.
The properties of water originated from the hydrogen bridge
- the bridge are of sufficient strength that water has the
highest melting point of any molecule of its size.
(18amu and Tm=0
o
C)
- the heat of vaporization is very high.(2250J/g)
- the freezing expansion of water also can be related to the
stereo specific nature of this type of bonding in solid ice.
Thermo plastic properties of Linear
Molecule.
Being soften on heating (not melting).
Being reharden on cooling.
Relatively weak intermolecular forces along the
molecular chain hold the molecules together.
As the temperature is increased, shear stresses can
break these weaker secondary bonds and permit the
molecules to move by each other.
Continued increases in temp. accelerate the flow,
because the secondary bond becomes still less effective
against the added thermal energy.
We can use thermoplastic properties to mold polymers,
but thermoplastics can not be used where service
conditions exceed the softening temp.
The spoon after it
has been used to
stir hot coffee.
(Polyvinyl spoon)
Example 2-3.1
Teflon, with a mer of C
2
F
2
polymerizes to
polytetrafluoroethylene (C
2
F
4
)n
(a)What is the degree of polymerization if the mass of the
molecule is 33000amu(or 33000 g/mol)
(b) How many molecules are there per gram?

Sol)
(a)Atomic mass of mer is 4(19)+2(12)=100amu
(33000amu/molecule)/(100amu/mer)=330mers/molecule
n= 330

(b) 6.02X10
23
molecules/33000g=1.8X10
19
molecule/g
Primary Bond

Strong (>200 kJ/mol) inter atomic bonds of
the covalent, ionic, and metallic types
2-4 Three-dimensional bonding
Network Structures.
Polymerization can lead to a network structure if some of
the units are polyfunctional.
Ex) phenol-formaldehyde.(PF), the first synthetic
polymers, market name Bakelite Fig2-4.2
CH
2
O(formaldehyde), C
6
H
5
OH(phenol)
The formaldehyde has supplied a CH
2
bridge between
benzene ring of two phenols.-> rigid three-dimensional
network.
PF is a thermosetting product. Reheating will not soften the three-
dimensional network significantly. (until 1200-1500
o
C)
Low thermal expansion coefficient because of open space can
accommodate intense thermal vibration.
Those mechanical properties that are related to strength are
improved if the primary bonds develop in all three dimensions.
Ionic Bonding
Bonding between strongly electropositive elements (metal)
and strongly electronegative elements (non metal)
The electropositive atom gives up one or more electrons
to the electronegative atom, producing two opposite
charged ions.
The coulomb force of attraction and repulsion can
produce polyatomic structures.
Negative ions are coordinated directly with positive ions.
The anion-to-anion distances and cation-to-cation are
greater. Therefore, the attractive forces predominate, and
unlimited numbers of ions can be bonded to produce a
solid material with primary bonds in three dimensions.

Coulomb forces between ions
-2 Z 2, Z MgO
-1 Z 1, Z NaCl example for
/ 10 9 or
4
1
: k
valences ionic the are z , z
S A 10 1.6 of charge electron the : q
) )( (
2 1
2 1
9
O
2 1
19
2
2 1
= + =
= + =

=
S A m V
x
q Z q Z k
F
o
o
C
tc
The inter-atomic bonding is much greater in MgO than NaCl
Melting Temp. of MgO : 2800
o
C
Melting Temp. of NaCl : 800
o
C
Ionic Coordination Numbers
Usually, covalently bonded solids are loosely packed,
and posses considerable free space.
In general, ionic solids are close packed with less free
space, because coulombic attraction are omni-directional.
Table2-4.1
The maximum coordination number is dictated by the
ratio of the radii. r/R
r : the radius of the small ion
R: the radius of the lager ion
(a)Coordination with r/R>0.41. The smaller cation is
coordinated with four anions (CN=4 for two dimension)
(b) Coordination with r/R<0.4. The positive ion does not
have maximum contact with all four neighboring negative
ions. Likewise, there is repulsion between the contacting
anions.
(c) When r/R<0.4, then CN=3 is favored.
Metallic Bonding
The metallic bond occurs between atoms with only a few
electrons in their outer s and p orbitals. The bonding
electrons in metal are essentially free.
Metal has a periodic structure of positive ions surrounded
by a sea of delocalized (free) electrons. The attraction
between the two provides the bond.
The valence electron of metals are free (delocalized).
They move in a wavelike pattern through the total metal.
Furthermore, there are as many wave patterns as there
are atoms in the contiguous metal. An electrical field will
shift the electrons forward the positive electrode, and if an
external connection is made, conductivity occurs.
CN of metallic bond can be as high as 12, because a pure
metal has atoms of only one size.-> efficient packing
Cu: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
10

2-5 Interatomic distances
Attractive forces pull down atom together into solid (and
into liquid)

For polyethylene : the distance between carbon nulcei
is 0.1544nm.
For iron : center-to-center distance is 0.2482nm at 20
o
C
Material has specific inter atomic distance, Why?

2
x F
C
Electronic repulsion

-Very strong, short-range repulsive forces appears.
-When the atoms approach within a nanometer of each other,
these forces develop because each atom is accompanied by
numerous electrons-sub valence as well as valence electrons.
-When atoms are brought into close proximity, there is mutual
electronic repulsion.
-At greater distance of atomic separation, the coulombic forces
predominate.
- At closer inter atomic spacing, repulsive forces predominate.
10 ~ 9
constant al proportion : b
=
n
x
b
F
n
R
When F
C
+F
R
=0,
the equilibrium spacing
being resulted in.
Fig.2-5.2
The equilibrium spacing is a very
Specific distance for a given pair of atoms, or ions.
It can be measured to five significant figures by
X-ray diffraction.
Equilibrium
spacing
The depth of this energy well
represent the bonding energy
min
E E
x
=
0
separation atomic infinite of state in the
) (
energy Bonding
=
+ =
=
}
x
x
R C
E
dx F F E
Hard ball model for metallic atoms
To stretch or compress inter atomic distance as much as 1
percent. 2000MPa is required for iron.

-> So, hard ball model for atom is useful for many
purposes where strength or atom arrangements are
considered.
Fig. 2-5.3 Energy and Expansion
Strongly bonded solid Weakly bonded solid
Since energy well is asymmetrical
the mean value of x is increased
with increasing temp.
With equal additions of thermal energy, above absolute zero,T
0
,
the mean interatomic spacing changes less in a material with
a deeper energy well-> low thermal expansion.
Atomic and Ionic radii
Several factors can change the distance between atom
centers.
1) Temperature
2) Ionic valence : example Fe
2+ :
Since the two outer valence
electrons of the iron ion have been removed the remaining
24 electrons are pulled in closer to the nucleus.
3) The number of adjacent atom : With a larger number of
adjacent atoms, there is more electronic repulsion, from
neighboring atoms -> the interatomic distances are increased.
4) We generally do not speak of atomic radii in covalently
bonded materials because the electron distributions may be
far from spherical.-> bond distance
Table 2-5.1

2-6. Generalization based on
atomic bonding
Melting, boiling temp. can be correlated with the depth of
the energy well.
Hardness : Strength is influenced by the height of the
total force or sum curve of Fig.2-5.2(a) observation.
Higher melting point, harder material.
Lower melting point, softer material.
Elasticity : E(modulus of elasticity) is related to the slope
of the sum curve of Fig.2-5.2(a)
Thermal expansion vary inversely with the melting
temperatures of those materials.
Conductivity of metals
- Ionic and covalently bonded materials are poor
conductor, because electrons are not free to leave their
host atoms.
- Delocalized electrons of metals move easily along the
potential gradient.

Thermal conductivity is high in metallic bonds. Because
delocalized electrons are efficient carriers of thermal
energy as well as electrical energy.

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