Understanding atomic structure

and arrangement will allow us

to better understand how to
control the microstructure and
properties of materials.
Bohr Model
Electrons - Wave or Particle?
Electrons display characteristics
of both. Not all observed
phenomena can be explained by
the particle definition of electrons.
Particle theory cannot explain
specific heat, tunnel diodes,
scanning electron microscopes,
etc.
 Wave Mechanics
• The motion of the electron is
described by mathematics that
describe wave motion
• The energy/position of an electron is
described by a probability distribution
(Fermi-Dirac Statistics)
• Heisenberg Uncertainty Principle: the
closer we know the momentum of the
electron, the larger the uncertainty in
the position of the electron. z  p = h
The energy/position of an electron is described exactly by
the Bohr particle model

The energy/position of an electron is described by a

probability distribution (Fermi-Dirac Statistics)
 Ionic Bonding
• Electrons are transferred to form a bond
• Often found in compounds composed
of electropositive elements (metals)
and electronegative elements (non-
metals)

Na Cl
Valence +1 Valence -1
 Ionic Bonding
General Characteristics
• Bonding Energy: 150-370 Kcal/mol
• Nondirectional Bond - strength of
bond equal in all directions
• Low electrical conductivity - entire
ion must move to conduct electricity
• Transparent, brittle, high melting
temperature
• Examples: NaCl 183 Kcal/mol, LiF
240 Kcal/mol
 Covalent Bonding

Electrons are shared to form a bond

 Covalent Bonding
General Characteristics

• Bonding Energy: 75-300 Kcal/mol

• Directional Bond - strength of bond is
not equal in all directions
• Low electrical conductivity
• Very hard, high melting temperature
• Examples: Si 84 Kcal/mol, GaAs 75
Kcal/mol, Diamond 170 Kcal/mol
 Metallic Bonding

Valence
electrons form
an electron
cloud for
bonding
 Metallic Bonding
General Characteristics
• Bonding Energy: 25-200 Kcal/mol
• Nondirectional Bond - strength of
bond is equal in all directions
• Good electrical conductivity - cloud of
electrons are free to move to conduct
electricity
• Ductile, opaque
• Examples: Na 26 Kcal/mol, Al 74
Kcal/mol, Cu 81 Kcal/mol
 Secondary Bonding
Van der Waals Bonding
• Weak secondary bond (<10 Kcal/mol)
• Often bonding force between molecules
• Example - PVC can be deformed by breaking
Van der Waals bonds between the molecules
that have strong covalent bonds

Hydrogen Bonding
• Special type of secondary bond between
some molecules containing H
• Example - bonds between molecules of water
 Cohesive Energy

Atoms are held together by bonds

that behave like springs

Cohesive energy is a measure of

the strength of the bonds

Bond Stiffness

Figure 4.19
Potential Well Concept Ionic Bonding

Coulombic Attractive
Force 1/r2FA

Energy=Force dr

Nuclear Repulsive
a0
Force 1/r10FR
 Relative Strength of
Bonding Types
Van der Waals

distance
Metallic
Covalent
Ionic
 Table 4.1

Bond stiffness largely determines the value

of the modulus - E
Modulus of Elasticity
Based on the bond energy curve
shown, determine which material
should be used for the applications
given below.
distance

1) Beam that shows little deflection

under load
2) A crucible to be used at high
temperatures
3) A device designed to sense
temperature changes by changing its
dimension
 What Determines Density
Density is mostly dependent on atomic weight
• Metals are dense because their atoms are heavy – iron
has an atomic weight of 56
• Polymers have low densities because they are made of
light atoms – carbon has an atomic weight of 12 while
hydrogen has an atomic weight of 1

The size of atoms and the way in which they are packed
also influence density, but to a much lesser degree
 Atomic Packing
Most materials are crystalline – have a regularly
repeating pattern of structural units

Atoms often behave as if they are

hard and spherical

Layer A represents the close-packed

layer – there is no way to pack the atoms
more closely than this
 Short-Range Order versus
Long-Range Order
1. No Order
Example: gases where atoms randomly fill whatever space is
available
2. Short-Range Order (SRO)
Example: glasses and many polymers where order only extends
to first nearest neighbors. Also called noncrystalline or
amorphous
3. Long-Range Order (LRO)
Example: atomic order that extends to large distances (> 100
nm) typical of metals and all “crystalline” materials
4. Liquid Crystals
Example: LCD’s where the material can change from amorphous
(SRO) to crystalline (LRO) under stimulus
Atomic structures are close-packed in three dimensions

Close-packed hexagonal: ABABAB stacking sequence

Face-centered cubic: ABCABC stacking sequence

Packing fraction for CPH and FCC structures is 0.74 – meaning

spheres occupy 74% of all available space

Figure 4.8
 B and C represent
alternative
positions for atoms
in the next close-
packed plane

If the next plane of

atoms lie in the same
position as the A atoms,
the stacking sequence
will be ABABAB. If the
next plane instead
occupy the depressions
marked C, the stacking
sequence will be
ABCABC.
 Unit Cell
Red lines define the cell while spheres represent
individual atoms

Shaded regions represent close or closest packed plane

Figure 4.11

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
Face-Centered Cubic Crystal
Body-Centered Cubic Crystal
Close-Packed Hexagonal Crystal
 Crystal Lattice

Figure 4.12

(a): hexagonal cell

Lattice points are the
(b): cubic cell
points at which cell
edges meet (c): cell with different
length edges
 Non Close-Packed Structures

Body-centered cubic:
ABABAB packing sequence
Packing fraction = 0.68

Figure 4.9

Amorphous structure:
Packing fraction ≤ 0.64

Figure 4.10
Atomic Packing in Ceramics

Figure 4.13

(a): Hexagonal unit cell with a W-C atom pair associated

with each lattice point

(b): Cubic unit cell with a Si-C atom pair associated with each
lattice point
 Atomic Packing in Glasses
Amorphous silica is the bases of most glasses

Rapid cooling allows material to maintain amorphous

structure achieved after melting

Figure 4.14
 Atomic Packing
in Polymers

Figure 4.15

Polymers have a
carbon-carbon
backbone with
varying side-groups

Figure 4.16
 Figure 4.17

Polymer chains bond to each other through weak hydrogen

bonds

Red lines indicate strong cross-linked carbon-carbon bonds

 Polymer Structure

(a): No regular repeating pattern of

polymer chains – results in a
glassy or amorphous structure
(b): Regions in which polymer chains
line up and register – forms
crystalline patches
(c): Occasional cross-linking allowing
they polymer to stretch – typical
of elastomers
(d): Heavily cross-linked polymers
exhibit chain sliding – typical of
epoxy
Figure 4.18
Elastic Moduli of Elastomers

Undeformed polymer chains

has high randomness (entropy)

Stretched polymer chains

resemble more of a crystalline
structure and has a lower
entropy

Moduli of elastomers is
generally low and unlike
metals, increases with
Figure 4.20 temperature
 Rule of Mixtures
Modifying the modulus and density is most effective when
done at a macro scale such as creating a hybrid rather than
a micro scale such as alloying a metal

Density of solid solution or hybrid material

f volume fraction of material or element A

ρA density of material or element A
ρB density of material or element B
 Composites –
Density and Modulus

Polymer matrix composite (PMC)

Ceramic matrix composite (CMC)
Metal matrix composite (MMC)

Modulus can be altered by

combining stiff fibers with a
less-stiff matrix

Figure 4.21
 ρr – density of reinforcement
ρm – density of matrix

Modulus of composite bracketed by two bounds:

• Upper bound: assumes that, on loading, both components strain
by the same amount, like springs in parallel
• Lower Bound: assumes that, on loading, each component carries
the same stress, like springs in series
Range of modulus and density properties for composites
with a ceramic reinforcement and polymeric matrix

Figure 4.22