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MATERIALS
ENGINEERING
Introduction
Dr. Aneela Wakeel (Lec-1)
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Evolution of materials

A familiar item that is

fabricated from three
different material types is
the beverage container.
Beverages are marketed
in aluminum (metal) cans
(top), glass (ceramic)
bottles (center), and
plastic (polymer) bottles
(bottom).
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• Materials closely connected our culture.

• Development and advancement of societies are dependent on the available
materials and their use.
• Early civilizations designated by level of materials development.
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Materials ages

• Initially natural materials

• Develop techniques to produce materials with superior qualities (heat
treatments and addition of other substances)
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Materials Science and Engineering

• arrangement of internal components
structure • subatomic
• atomic
• microscopic
• macroscopic (bulk)

characterization
processing properties
• material characteristic
• method of preparing
• response to external
material
stimulus
• mechanical, electrical,
performance thermal, magnetic,
• behavior in a optical, deteriorative
particular application
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Processing Structure Properties Performance

Aluminum Oxide (Al O ) 2 3

single-crystal polycrystalline, polycrystalline,

(transparent) fully dense 5% porosity
(translucent) (opaque)
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Why study materials?

• Applied scientists or engineers must make material choices
• materials selection
• in-service performance (properties-trade off)
• Deterioration (elevated temp, Corrosion)
• Economics (glass-plastic)
Classification of Materials
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Metals
Metals
• good conductors of
electricity and heat
• lustrous appearance
• susceptible to
corrosion
• strong, but
deformable
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Ceramics
Ceramics are compounds between metallic and nonmetallic elements; they are
most frequently oxides, nitrides, and carbides. materials include aluminum
oxide (or alumina,Al2O3), silicon dioxide (or silica,SiO2),
silicon carbide (SiC), silicon nitride (Si3N4)

Traditional ceramics—those composed of

clay minerals (i.e., porcelain), as well as
cement, and glass

• relatively stiff and strong

• thermally and electrically insulating
• resistant to high temperatures and
harsh environments
• hard, but brittle
Common objects that are made of ceramic
materials:
scissors, a china tea cup, a building brick, a floor
tile, and a glass vase.
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Polymers-plastic and rubber materials

Some of the common and familiar polymers are polyethylene (PE), nylon,
poly(vinyl chloride) (PVC), polycarbonate (PC), polystyrene (PS), and
silicone rubber

• low density,
• Mechanical property may be
extremely flexible ductile and
pliable (i.e., plastic), which means
they are easily formed into
complex shapes
• have low electrical conductivities
and are nonmagnetic
Figure. Several common objects that are made of polymeric
materials: plastic tableware (spoon, fork, and knife), billiard
balls, a bicycle helmet, two dice, a lawnmower wheel (plastic
hub and rubber tire), and a plastic milk carton
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Composite
A composite is composed of two (or more) individual materials, which come from
(metals, ceramics, and polymers).
The design goal of a composite is to achieve a combination of properties that is not
displayed by any single material, and also to incorporate the best characteristics of
each of the component materials

Fiber glass: (glass fiber-reinforced

polymer GFRP)
Small glass fibers are embedded
within a polymeric material
(normally an epoxy or polyester).
The glass fibers are relatively
strong and stiff (but also brittle),
whereas the polymer is ductile (but
also weak and flexible). Thus, the naturally-occurring
resulting fiberglass is relatively materials are also
considered to be
stiff, strong, flexible, and ductile. In composites—for
addition, it has a low density example,
wood and bone
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Composite
carbon fiber reinforced
polymer” (or “CFRP”)
composite—carbon fibers that
are embedded within a
polymer. These materials are
stiffer and stronger than the
glass fiber-reinforced materials
.
They are more expensive.
The CFRP composites are
used in some aircraft and
aerospace applications, as well
as high-tech sporting
equipment (e.g., bicycles, golf
clubs, tennis rackets, and
skis/snowboards) fiberglass surfboards
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Classification of Materials: A Few Additional Categories

Biomaterials Semiconductors
• implanted in human • electrical properties
body between conductors
• compatible with and insulators
body tissues • electrical properties
can be precisely
controlled

Intel Pentium 4
hip replacement
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Smart materials
Smart(or intelligent) materials are a group of new and state-of-the-art
materials now being developed that will have a significant influence on
many of our technologies
Components of a smart material (or system) include some type of sensor
(that detects an input signal), and an actuator (that performs a responsive
and adaptive function).
Actuators may be called upon to change shape, position, natural
frequency, or mechanical characteristics in response to changes in
temperature, electric fields, and/or magnetic fields.

Four types of materials are commonly used for actuators:

shape memory alloys,
piezoelectric ceramics,
magnetostrictive materials, and
electrorheological/magnetorheological fluids
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• Shape memory alloys are metals that, after having been

deformed, revert back to their original shapes when
temperature is changed.
• Piezoelectric ceramics expand and contract in response to
an applied electric field (or voltage); conversely, they also
generate an electric field when their dimensions are altered.
• The behavior of magnetostrictive materials is analogous to
that of the piezoelectrics, except that they are responsive to
magnetic fields.
• Electrorheological and magnetorheological fluids are liquids
that experience dramatic changes in viscosity upon the
application of electric and magnetic fields, respectively.
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Density comparison
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Stiffness or young’s modulus

Figure
Bar-chart of room temperature stiffness (i.e., elastic modulus) values for
various metals, ceramics, polymers, and composite materials.
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Tensile strength
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Fracture toughness
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Electrical conductivity
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Levels of Structure structure

processing properties

performance

STRUCTURE (length scale)

Sub-atomic
< 0.2 nm
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Fundamentals of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons
Charges:
Electrons (-): protons(+) 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.

Masses:
Protons and Neutrons ~1.67 × 10-27 kg.
Electron 9.11 × 10-31 kg
Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons

chemical identification of element

Isotope number  # neutrons

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Atomic mass units. Atomic weight.
Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).
The atomic mass of 12C atom is 12 amu.

Atomic weight: A
Weighted average of atomic masses of naturally occurring isotopes.
Atomic weight of carbon is 12.011 amu.

Atomic weight is often in mass per mole.

A mole
Amount of matter with mass in grams equal to the atomic mass in amu
(A mole of carbon has a mass of 12 grams).

One Mole contains Avogadro’s number of atoms,

Nav = 6.023 × 1023.

Nav = 1 gram/1 amu.

Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
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Some simple calculations
Number density, n: (number of atoms per cm3)
Mass density, ρ (g/cm3)
Atomic mass, A (g/mol):
n = Nav × ρ / A

Graphite (carbon): ρ = 2.3 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol
= 1.15 × 1023 atoms/cm3

Diamond (carbon): ρ = 3.5 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol
= 1.75 × 1023 atoms/cm3

Water (H2O) ρ = 1 g/cm3, A = 18 g/mol

n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3

SIZE of a Atom or Molecule

If n = 6 × 1022 atoms/cm3
Mean separation between atoms L = (1/n)1/3 = 0.25 nm.
 scale of atomic structure in solids – a fraction of 1 nm
or a few Angstroms
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How many number of atoms per

cm3 in 2.5gram/cm3 of iron.
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Electrons in Atoms (I)- Bohr atomic model

• Electrons are assumed to revolve

around the atomic nucleus in discrete
orbitals
• The position of any particular electron
is more or less well defined in terms of
its orbital

• The energies of electrons are quantized;

that is, electrons are permitted to have
only specific values of energy.
• An electron may change energy, but in
doing so it must make a quantum jump
either to an allowed higher energy (with
absorption of energy) or to a lower
energy (with emission of energy)
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Wave mechanical model

A wave-mechanical model, in
which the electron is considered to
exhibit both wave-like and
particle-like characteristics. With
Figure 2.3 Comparison of
the (a) Bohr and (b) wave mechanical
atom models
in terms of electron
distribution. (Adapted from
Z. D. Jastrzebski,The
Nature and Properties of
Engineering Materials,3rd
edition, p. 4.

this
model, an electron is no longer
treated as a particle moving in a
discrete orbital; rather, position is
considered to be the probability of
an electron’s being at various
locations around the nucleus. In
other words, position is described
by a probability distribution or
electron cloud.
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Quantum numbers
Using wave mechanics, every electron in an atom is characterized by four
parameters called quantum numbers.
The size, shape, and spatial orientation of an electron’s probability density are
specified by three of these quantum numbers.
(n) Shells are specified by a principal
quantum number n, which may take on (l) The second quantum number, signifies the
integral values beginning with unity; subshell, which is denoted by a
sometimes these shells are designated by lowercase letter—an s, p, d,or f; it is related to
the letters K, L, M, N, O, and so on. This the shape of the electron subshell.
quantum number is related to the distance
of an electron from the nucleus, or its
position.

(ml) The number of energy states for each
subshell is determined by the third quantum
number, For an s subshell, there is a single
energy state, whereas for p, d, and f subshells,
three, five, and seven states exist, respectively
a spin moment, which must be oriented either
up or down. Related to this spin moment is the
fourth quantum number ms, for
which two values are possible ( +1/2 and -1/2 ),
one for each of the spin orientations.
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Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
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Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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The Periodic Table

inert gases
give up 1e-
• Columns: Similar Valence Structure
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
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Atomic bonding in solids

=+ (net force which is function of

interatomic separation)

+=0 (state of equilibrium)

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Force-potential
r
energy relationship for two atoms
0

Repulsive energy ER

Interatomic separation r

Net energy EN

A B
EN = EA + ER = - +
r rn
Attractive energy EA

Stable at minimum energy E0 for radius r0.

Force = dE/dr = 0 at r0
r0
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Bonding Forces and Energies

Example: Calculate the force of attraction between a K+
and an O2- ion the centers of which are separated by a
distance of r0 =1.5 nm.
Solution
The attractive force between two ions FA is just the derivative with respect to
the interatomic separation of the attractive energy expression, Equation 2.8,
which is just

 A 
d-  The constant A=(). Since the valences of the
dEA  r  A K+ and
FA = =  = O2- ions
dr dr r2
(Z1 and Z2) are +1 and -2, respectively,
Z1 = 1 and Z2 = 2, then


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(Z1e) (Z 2 e)
FA   =  
40r 2

(1)(2)(1.602   10-19   C) 2
= 
(4)() (8.85   10-12  F/m) (1.5   10-9  m) 2

=2.05  10^(-10 ) N
Calculate the force of attraction between a and on ion
the centers of which are separated by a distance of
1.25nm.
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The electron volt (eV)

Energy unit convenient for atomic bonding

Electron volt –
energy lost / gained when an electron is taken through a potential
difference of one volt.
E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt

1 eV = 1.6 x 10-19 J
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Metals
Metallic Bond + + + + “sea of electrons”
• one, two, or three valence electrons
• valence electrons free to drift through the + + + +
entire material forming a “sea of electrons”
surrounding net positive ionic cores + + + + ionic
• non-directional bond cores
+ + + +

Properties
• good conductors of
electricity and heat
• lustrous appearance
• susceptible to
corrosion
• strong, but
deformable
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Metallic bonding
• Occurs with atoms that easily give up electrons.
• In a solid, these “conduction” electrons form a cloud or sea.
• No two electrons can have exactly the same quantum number, and so
they have a range of energies. Each “exists” throughout the solid.
• The attraction between the positively charged metal ions and the
electron cloud is what causes metallic bonding.
• Non directional.
• These “conduction” electrons
carry electric current and heat.
• Mixtures of metals sometimes
form intermetallic compounds.
• Animation (in full-screen
projection mode):

Another animation: http://mypchem.com/myp9/myp9c/myp9c_swf/metal_vib.htm

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Ceramics and Glasses Coulombic bonding force

Ionic Bond
• composed of metallic and non-metallic elements + +
• metallic elements give up valence electrons to
+ +
non-metallic elements
• all atoms have filled “inert gas” configuration + +
• ionic solid
• non-directional bond + +

Ceramics & Glasses

• thermally and
electrically insulating
• resistant to high
temperatures and
harsh environments
• hard, but brittle
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Ionic bonding in a crystal

• In a crystal, a cation (+ charge) is attracted not only by the nearest

anions, but to a lesser extent by those farther away.
• Similarly, it is repelled by all other cations.
• The sum of the energy due to all attractions and repulsions is known
as the Madelung energy. This is approximately 60% greater than the
energy of attraction for isolated ions the same distance apart as in the
lattice.
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Polymers H
Covalent Bond shared electron
shared electron
from hydrogen
• electrons are shared between adjacent from carbon
atoms, each contributing at least one
electron H C H
• shared electrons belong to both atoms
• directional bond

H methane (CH4)

Polymers
• very large molecules
• low density, light
weight materials
• maybe extremely
flexible
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Mixed Ionic-Covalent Bonding

• Ionic-Covalent Mixed Bonding  -
( X A - X B )2 
• Approximate fraction ionic character  1 - e 4 
 
where XA & XB

are the two Pauling electronegativities.


Example: MgO. Using the 1960 values in the text,

XMg = 1.2 and XO = 3.5,
the equation above predicts that the bond between Mg and O has
about 73% ionic character and 27% covalent.
Using the revised values given on Wikipedia,
XMg = 1.31 and XO = 3.44,
the equation above predicts that the bond between Mg and O has
about 68% ionic character and 32% covalent.
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Secondary Bonding (I)

Secondary = physical bond
(as opposite to chemical bond that involves e- transfer) Interaction of dipoles
Is weak, ~0.1 eV/atom or ~10 kJ/mol.

_ _
+ + -two dipoles attract
Permanent dipoles exist in some molecules
polar molecules: e.g. HCl, H2O
Due to asymmetry of positive and negative regions Strongest among secondary bonds.

Polar molecule induces a dipole in adjacent non-polar molecule.

Attraction between the permanent and induced dipoles.

Fluctuations of electron density distribution in one atom A is felt by the electrons of an

adjacent atom:
Mutual dipoles induced (van der Waals)
This bond is the weakest (He-Ne, H2 - H2).
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Secondary Bonding (II)

Example: hydrogen bond in water. The H end of the molecule is

positively charged and can bond to the negative side of another
H2O molecule (the O side of the H2O dipole)

H H

-
+ +
Dipole

“Hydrogen bond” – secondary bond formed between two

permanent dipoles in adjacent water molecules.
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Secondary (van der Waals) bonds

Arises from interaction between electric dipoles

• Dipoles fluctuating rapidly and interacting

asymmetric electron e.g. liquid H2
clouds H2 H2

+ - + - H H H H

• Permanent dipoles
-general case: + - + -

-ex: liquid HCl H Cl H Cl

secon Within an organic molecule the bonding is

-ex: polymer dary
bond
in g mostly covalent, while between molecules
the bonding is mostly van der Waals.
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Hydrogen bonds
• Between hydrogen atoms and the nearby negative end of a molecular dipole, to
strongly electronegative atoms such as O or N.
• Partly covalent and partly electrostatic.
• Much stronger than van der Waals bonds.
• Determines the unusual properties of water liquid and solid.
• Also occurs with other molecules, and even between parts of complex molecules
such as proteins.
• http://en.wikipedia.org/wiki/Hydrogen_bond
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Table 2.3.
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Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
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Properties From Bonding: Melting point

Interaction energy E Melting Temperature, Tm

versus atomic separation r Energy
Energy

unstretched bond length ro

ro r
r
Eo smaller Tm
“bond energy”
larger Tm
Atomic separation r
Tm is larger when Eo is larger

r
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Properties From Bonding: Thermal expansion

Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
DL DL
= a(T2 -T1)
heated, T2 Lo

Energy

ro
r a is larger when Eo is smaller

Eo larger a
Eo smaller a
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Boundary-property summary
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
secon
da ry bo
nding
small E
large a
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Levels of Structure structure

processing properties

performance

STRUCTURE (length scale)

Sub-atomic Atomic
< 0.2 nm 0.2-10 nm
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Atomic Arrangement: Ordered vs. Disordered

Crystalline:
atoms are arranged in a 3D, periodic array giving the material “long range order”

• stacking can effect

properties (i.e.
ductility)
• anisotropic materials

hexagonal close-packed

Non-crystalline or amorphous:
atoms only have short-range, nearest neighbor order
• viscous materials (generally complex formulas) or rapid
cooling
• isotropic materials
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Levels of Structure structure

processing properties

performance

STRUCTURE (length scale)

Sub-atomic Atomic Microscopic

< 0.2 nm 0.2-10 nm 1-1000 mm
1 nm = ?

Microstructure
Single Crystal
• the periodic arrangement of atoms
extends throughout the entire
sample
• difficult to grow, environment must
be tightly controlled
• anisotropic materials
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Polycrystalline
• many small crystals or grains
• small crystals misoriented with
respect to on another
• several crystals are initiated and
grow towards each other
• anisotropic or isotropic materials
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Single and polycrystalline

Figure 3.4 (a) Photograph of a silicon
single crystal. (b) Micrograph of a
polycrystalline stainless steel showing
grains and grain boundaries (Courtesy
Dr. M. Hua, Dr. I. Garcia, and Dr. A.J.
Deardo.)

Figure 3.5 Liquid

crystal display. These
materials are
amorphous in one
state and undergo
localized
crystallization in
response to an
external electric field
and are widely used
in liquid crystal
displays. (Courtesy of
Nick
Koudis/PhotoDisc/Ge
tty Images.)
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Bulk Properties
Mechanical: Electrical:
elastic modulus conductivity
shear modulus resistivity
hardness capacitance

+ -

Thermal:
Optical: thermal expansion
reflectivity heat capacity
absorbance thermal conductivity
emission
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Processing Structure Properties

Performance
Performance Goal: increased strength from a metallic material
In actuality, crystals are NOT perfect. There are defects!
In metals, strength is determined by how easily defects can move!
OFF

slow cooling

quenching