Major classes of materials

Metals
Atoms are located in
regularly defined, repeating positions - a crystal
Structure has free electrons making metals good electrical
conductors
Strong but very dense
Moderate temperature resistance
Metals resist brittle fracture by bending - ductile
Ceramics
Combination of metallic and non-metallic atoms
Many but not all ceramics are crystalline
Bonding does not permit free electrons
Very strong, moderate density
High temperature stability, chemically resistant
Ceramics bend little before they break - brittle
Major classes of materials
Polymers
Long chain molecules with repeating groups
Relatively low strength, temperature sensitive
Easy to form into complex shapes
Low density, can be ductile or brittle
Inexpensive
Composites
2 or more materials are combined
Structural applications where rigidity, strength, and low
density are critical
Semiconductors
Bonding similar to ceramics
Mechanical properties similar to ceramics
Used in electronic and optical devices

Correlation Between Strength and
Ductility
S
t
r
e
n
g
t
h

Measure of Ductility
Structure-Property-Process
relationship
Structure
Atomic / Nano / Micro / Macro
Property
Mechanical
Physical (electrical, magnetic, optical, thermal,
elastic, chemical)
Process
Material history

Atomic Structure
E
n
e
r
g
y

Principal quantum number, n
1
2 3 4 5 6 7
s
p
s
p
s
p
s
p
s
p
s
p
s
d
d
d
d
d f
f
f
Schematic representation of
the relative energies of the
electrons for the various shells
and subshells.
Atomic Structure
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d 6f
7s 7p 7d 7f
8s 8p 8d 8f
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d 6f
7s 7p 7d 7f
8s 8p 8d 8f
Order of filling: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s,
4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ...
Schematic representation of the filled
energy states for an isolated sodium atom
Atomic number of sodium is 11
I
n
c
r
e
a
s
i
n
g

E
n
e
r
g
y

1s
2s
2p
3s
3p
Energy-level diagram for the orbital electrons in a
12
C atom.
E
n
e
r
g
y
,

e
V

1s
2(sp
3
)
0
-6.5
-283.9
Electronic Structure
Compare the electronic structures of
Silicon and Germanium with Carbon
Atomic number of Carbon- 6
Atomic number of Silicon- 14
Atomic number of Germanium- 32
These electronic configurations lead to
similar crystal structure for the three
elements
Electronic Structure
Carbon, 6 electrons- 1s
2
, 1s
2
, 2s
2
, 2p
2
When hybridized- 1s
2
, 2(sp
3
)
4
Silicon, 14 electrons- 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
2
When hybridized- 1s
2
, 2s
2
2p
6
, 3(sp
3
)
4
Germanium, 32 electrons- 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
10
, 4p
2

When hybridized- 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 3d
10
, 4(sp
3
)
4
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d 6f
7s 7p 7d 7f
8s 8p 8d 8f
Order of filling:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s,
4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ...
2
1 2
2
( )
( )
4
a
o
Z Z q
F x
x tc
=
( )
r
m
K
F x
x
=
m > 2
Origins of Thermal Expansion as
Captured in the Bond-Energy Curve
E
n
e
r
g
y

E
n
e
r
g
y

x
x
Average separation distance Materials with different bond
energy behaviors
Bond-Force Curves for Two Hypothetical
Materials
Evaluate the slope at F = 0
for each material
Atom
Cation
r
atom
> r
cation

Atom
r
atom
< r
anion

Anion
Neutral atoms are shown in green, cations are red, and anions are blue. Note the
relative change when a neutral atom becomes a cation, compared to an anion.
Relative Sizes of Atoms and Ions
C=C
H H
H H
Basic building
block
C C
H H
H H
. .
Polyethylene
monomer
C C
H H
H H
C C
H H
H H
C C
H H
H H
C C
H H
H H

C C
H H
H H
C C
H H
H H
C C
H H
H H
C C
H H
H H

Polyethylene
chain
Single chains of polyethylene pack well because the side groups
are only hydrogen and the result is high density polyethylene
C C
H H
H H
C C
H H
H H
C C
H H
H H
. .
Formation of Polyethylene from
a Basic Chemical Unit of C
2
H
4

C C
H
H
H
Cl
C C
H
H
H
Cl
C
C
C
C
C
C
C
C
C
C
Cl Cl Cl Cl Cl
H H H H H H H H H H
H H H H H
n
Formation of Polyvinylchloride from
a Basic Chemical Unit of C
2
H
3
Cl


C
C
C
C
C
C
C
C
C
C
Cl Cl Cl Cl Cl
H H H H H H H H H H
H H H H H
n
C
C
C
C
C
C
C
C
C
C
Cl Cl Cl Cl Cl
H H H H H H H H H H
H H H H H
n
Hydrogen
bonding
Strongly electronegative chlorine develops
hydrogen bonding between polymer chains
Formation of Polyvinylchloride from
a Basic Chemical Unit of C
2
H
3
Cl


C C
R H
H
C C
H H
H
C C
R H
H
C C
H H
H

C C
R
H
H
C C
H
H H
C C
R
H
H
C C
H
H H

Double
bonds


C C
R H
H
C C
H H
H
C C
R H
H
C C
H H
H

C C
R
H
H
C C
H
H H
C C
S H
H
C C
H S
H

S S
Cross-linked
Primary Bonds
H H
Structure of Cross-linked Rubber
Geometry of the hard Sphere BCC
Structure
Fractions of
atoms in the
unit cell
Hard Sphere Packing
Number of atoms/unit cell =
8 corners x (1/8) + 1 in center = 2
Packing factor, pf, =
(Number of spheres x vol. of sphere)/vol. of unit cell
3
3
4
2
3
r
pf
a
t
| |
| |
|
|
\ .
= |
|
|
\ .
3 4 a r =
4
3
r
a =
3
3
4
2
3
4
3
r
pf
r
t
| |
| |
|
|
\ .
|
=
|
| |
|
|
|
\ .
\ .
Density of Selected Elements, Hard
Sphere Approximation
BCC- Hard sphere packing
FCC- Hard sphere packing
uc
uc
M
Density
V
=
#
uc
atoms mass
M
uc atom
| || |
=
| |
\ .\ .
3
uc
V a =
4
2
r
a =
4
3
r
a = 2 atoms/uc
4 atoms/uc
Coordinates of a Point
Directions in a Crystal, Miller Indices- [hkl]
1. Get 2 points that
lie in the direction.
2. Subtract coordinates
of the tail from tip.
3. Clear fractions.
4. Write integers in
square brackets.
5. Negative integers are
indicated by putting a
bar over the integer.
Directions in a Crystal, Miller Indices- [hkl]
Planes in a Crystal, Miller Indices- (hkl)
Plane A
Plane B
Plane C
Plane D
Plane F
Plane
E
1. Identify coordinate intercepts of the plane.
2. Take the reciprocal of the intercepts.
3. Clear fractions by multiplying, but do not reduce to
lowest integers.
4. Write integers in parentheses, no commas.
5. Negative integers are indicated by a bar over the integer.
Planes in a Crystal, Miller Indices- (hkl)
Plane A
Plane B
Plane C
Plane D
Plane F
Plane
E
Crystals with Multiple Atoms Per Lattice Site
Diamond Cubic Structure Geometry-
2 atoms/lattice point
FCC lattice
8 atoms/unit cell
C
Si
Ge
6
14
32
Group
IVB
Crystals with Multiple Atoms Per Lattice Point
Perovskite Structure
Alternate representations of the structure
CaTiO
3

Crystals with Multiple Atoms Per Lattice Site
BaTiO
3

Simple tetragonal
Offset between top
plane of Ba
+
ions and
top of center O
2-
ion
Offset between central
Ti
4+
ions and
mid-plane of O
2-
ions
Crystals with Multiple Atoms Per Lattice Site
Crystalline
polyethylene
Liquid Crystals
Chain ends unaligned
Chain ends aligned
Wave Interference
Destructive interference
Constructive interference
X-Ray Diffraction
Path length 2a -
Path length 1a = 0
Path length 3c -
Path length 1a = 2(AB + BC)
Path length 2b -
Path length 1a = AB + BC
u
u u
u
d
AB = BC = dsin u
AB + BC = 2 dsin u
n = 2 dsin u, Braggs Law
Point Defects
Vacant lattice site
AG = AH - TAS
The Effect of Temperature on the
Vacancy Concentration of Nickel
-40
-35
-30
-25
-20
-15
-10
-5
0
0 0.001 0.002 0.003 0.004
1/T, 1/K
l
n
(
V
c
)
Room Temperature,
25 C
Melting Temperature,
1083 C
fr
Q
slope
R
| |
=
|
\ .
( )
exp
exp
1
ln
fr
v t
fr
v
fr
v
Q
N N
RT
Q
C
RT
Q
C
R T
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
Point Defects
Schottky defect
2V
Cl
and 1V
Mg

-
2+

Schottky defect
1V
Cl
and 1V
Na

-
+

Cation-anion pair
Schottky defect
, ,
exp
2
fvc
v cat v an
Q
C C
RT

| |
= =
|
\ .
Point Defects
The defect involves a cation The defect involves an anion
The cation defect is more common because of the
size of the cation compared to the size of the anion.
Vacancy-Interstitial Pair
Frenkel defect in AgCl
exp
2
fvi
v i
Q
C C
RT

| |
= =
|
\ .
A atoms
B atoms
Ficks First Law
Factors affecting
atomic transport:
dc
J D
dx
=
Leads to:
J = D(C
1
C
2
)/Ax
Concentration gradient
Jump distance, Ax
Temperature
Structure
Mechanisms of Atomic Transport
Interstitial solid solution
Substitutional solid solution
Counter flow of
Vacancies and solute
E
n
e
r
g
y

Position
Polycrystalline material composed of many grains
separated by thin regions called grain boundaries.
Unit cell
orientations
in grain A
Unit cell
orientations
in grain A
Grain boundary
Single and Polycrystalline Materials
Grain Boundary Structure
Grain 1
Grain 2
Grain
Boundary
Region
Unsatisfied bonds are the source for grain boundary energy
Grain Boundary Structure
Grain 1
Grain 2
Grain
Boundary
Region
Provides more open regions for transport by diffusion.
Short circuit
diffusion path
Grain Boundary Diffusion versus Bulk
Diffusion
l
n
D

1/T, K
-1
Increasing T Decreasing T
lnD
o,bulk +
+
+
bulk
Q
slope
R
| |
=
|
\ .
gb
Q
slope
R
| |
=
|
\ .
lnD
o,gb
+
Bulk diffusion
dominates
GB diffusion
dominates
Q
bulk
> Q
gb
exp
exp
bulk
bulk o
gb
gb o
Q
D D
RT
Q
D D
RT
| |
=
|
\ .
| |
=
|
\ .
Decreasing the grain
size increases the
temperature where
grain boundary
diffusion dominates
Grain Boundary Structure
Grain 1
Grain 2
Grain
Boundary
Region
Provides more open regions for solute segregation.
Grain Boundary Structure
Grain 1
Grain 2
Grain
Boundary
Region
Provides more open regions for solute segregation.
Impurities in a Polymer Chain
Crystalline
regions
Amorphous
regions
Impurities randomly distributed
Impurities largely excluded
Entanglement
points with
other polymer
chains
Mechanisms of Diffusion in Polymers
exp
o
Q
D D
RT
| |
=
|
\ .
Diffusion in a polymer
Melt- D
o
scales
inversely as the square
of the length of the
polymer chain.
Diffusion in Natural Rubber
-2.5
-2
-1.5
-1
-0.5
0
0.5
1
1.5
-6 -4 -2 0 2 4 6
Distance from interface
c
,
c
'
,
c
'
'
Thin-Film
2
2
C C
D
t x
c c
=
c c
Composition decreases
with time
Composition increases
with time
Edge Dislocation
Edge
dislocation
line
Extra half plane
of atoms
Role of Dislocations in Plastic Deformation


Types of Dislocations
Edge Screw
Mixed
Loop
Hardening Mechanisms
Solute
Dislocations
Grain size
Precipitation

Specific Volume for a Variety of Materials
Liquid to glass solid
transformation in a pure
substance. The glass transition
temperature, Tg, is not an
equilibrium transformation
temperature.
Liquid to crystalline solid
transformation for a pure
substance. T
m
is an equilibrium
transformation temperature
The Effect of Cooling Rate on the Glass
Transition Temperature, T
g
S
p
e
c
i
f
i
c

V
o
l
u
m
e

T
g1
T
g2
T
m
Temperature
T
1
.
T
2
.
T
1
.
T
2
.
Liquid
Solid
Glass
Super-cooled liquid
>
Comparison of the Response of a Solid and a
Liquid to a Shear Stress
F dy
A dx
G
t
t

=
( )
( )
dy
d
dt
dx
dy
d
dx
dt
t
t

d
dt

t q q = =
Temperature Dependence of
Viscosity
Fluidity


Viscosity




exp
o
Q
RT
| |

(
=
(

1
exp
o
Q
RT
q q
|
+
(
= =
(

Repeat Units
SiO
4
-4
tetrahedron

C
2
H
4
mer in polyethylene
Classification of Polymers
The degree of polymerization
The nature of the bond
Thermoplastics (TP), possible secondary bonds
between chains
Thermoset (TS), cross-links between chains
Molecular weight
Molecular weight
Number average molecular weight
Weight average molecular weight
Polydispersity
Conformation
Configuration- Tacticity and branching
One-Component Phase Diagrams
F = C P + 2
C- Components
P- Number of phases
F- Degrees of freedom
F = 2
F = 1
F = 0
Two-Component Phase Diagrams
Composition, X
B
T
e
m
p
e
r
a
t
u
r
e

( )
( )
( )
( )
1
1
1
l s
o l l s s
l s
o l s s s
o l l s s s
o l s s l
o l
s
s l
f f
X X f X f
f f
X X f X f
X X X f X f
X X f X X
X X
f
X X
+ =
= +
=
= +
= +
=

( )
( )
s o
l
s l
X X
f
X X

The Lever Rule in a Two-Component System

Eutectic Phase Diagrams
Composition, X
B
T
A
T
B
X
1
X
E
X
2
A B
T
e
m
p
e
r
a
t
u
r
e

X
o
X
|
T
X
s
X
l
F = 1, must
specify temperature
or the composition
of one of the phases
F = 1
F = 1
F = 1
T
X
s
X
l
T
X
o
X
|
Analysis of a Eutectic Phase Diagram
Alloy 1 Alloy 5 Alloy 2 Alloy 3 Alloy 4
T
e
m
p
e
r
a
t
u
r
e

Composition
A B
l o | = +
Labeling Complex Phase Diagrams
Fe-C System
Eutectic
Peritectic
Eutectoid
6m
Phase Transformations in Steels-
Decomposition of Austenite to form Pearlite
Microstructure of pearlite
formed at different isothermal
hold temperatures.
Decreasing the isothermal
hold temperatures decreases
the interlamellar spacing
655 C
534 C 487 C
600 C
Phase Transformations in Steels
Bainite that forms isothermally
495 C
410 C

Fe
3
C
o
Schematic of
bainite formation


10m
Phase Transformations in Steels
Progress of athermal martensite in an Fe-1.8C wt %C
alloy after cooling to various temperatures
T= 25 C T= -60 C T= -100 C
Decreasing temperature, increasing fraction of transformed martensite


Martensite
plates
4140 4340
IT Diagrams
Continuous Cooling Curve in a Eutectoid Steel
Phase Transformations in Steels
Phase Transformations in Steels
Recovery and Recrystallization
Recrystallization at higher Temperatures
Grain with high dislocation density
Nucleate new grain with a lower dislocation density.
Elastic Deformation
t
a
t
o
a
o
d
d
l
l
c
v
c
c
c
=
A
=
A
=
where
and
Poissons Ratio
2(1 )
E
G
v
=
+
For an isotropic material
Tensile Testing
Permanent
plastic
deformation
Recoverable
elastic
deformation
Tensile Testing
Onset of Necking
or plastic instability
Reduction
in stress
Tensile Testing
Formation of the neck begins
and continues to propagate
through the gage until failure.
True
Engineering
Tensile Testing
Tensile Testing
Typical FCC Metal
Like Aluminum
Typical Behavior
for Carbon Steels
Indicator of Toughness
0
f
U d
c
o c =
}
Area under the stress-strain response is an indicator of
toughness. The units are:
(force per unit area) x (length per unit length) =
(force x length)per unit volume = energy per unit volume
1
2
3
Mechanical Behavior
Metal
Ceramic
Ceramic
Ceramic
Compressive
Stress-strain
Tensile
Stress-strain
Tensile
Stress-strain
Four-Point Bend Test
Mechanical Behavior
Thermosets, thermoplastics below T
g
; and
thermoplastic polymers aligned prior
to testing along the tensile axis
Region I
Region II
Region III
Crystalline lamella
Interlamellar
noncrystalline
polymer
Semicrystalline spherulites
Semicrystalline
spherulites
starting to unravel
Charpy Impact Testing
Charpy Impact Testing- The Ductile-to-Brittle
Transition Temperature (DBTT)
S
t
r
a
i
n

Time
Fracture Fracture
Fracture
Creep
strain
slope
time
c = =
Orowan Modification
Orowan noticed that fracture in metals
occurred at constant:
a o t
2
e s p
e
s
p
e p
e
f
Effective surface energy
True surface energy
Energy dissipated around crack
E
a

o
t
= +



=
( )
2
y
K
f
r
o u
t
| |
=
|
\ .
Tunnel crack
Penny crack
Wedge-opened crack Eccentrically loaded
Fracture Toughness Comparison
Fracture toughness values for different materials are
shown below. Assume that very wide panels are made
from these materials. Assume that the panels contain
cracks of length 2a and are subjected to a stress of 350
MPa. Compare the maximum size crack that could be
present in each of the panels.
Material Fracture Toughness
MPa m
1/2
7075-T6 Al 28
300 Maraging steel 66
Alumina 2.5
For the maximum crack size the panel is about to crack.
2
2
1
2
2
IC
IC
IC
K a
K
a
K
a
o t
t o
t o
=
| |
=
|
\ .
| |
=
|
\ .
2 3
3
7075 6
2
300
5
2 4.07 10
2 2.26 10
2 3.25 10
T
Maraging
Al O
a x m
a x m
a x m

=
=
=
max
a
o

Application in Ceramics
a is the crack length
is the radius of the crack tip
Toughing Mechanisms for Ceramics
Crack blunting
Compressive
stresses
clamping the
crack
The Influence of Alloying on Conductivity
( )
( )
d
i i
T = +

| |
(1 )
d AB B B
AB BA
b x x
b b
=
=
In the dilute solution range
Charge Mobility
Collisions
v at
v E
v E
=

=
Charge
Mobility
0
T
c
<
c
Thermal vibrations
Foreign atoms
Vacancies
0
D
N
c
<
c
Energy Band Diagram for Three Classes of
Electrical Materials at 0K
Conductor
Semiconductor
Insulator
Bonding in an n-type Semiconductor
Behavior of a n-type Semiconductor
Behavior of a p-type Semiconductor
Boron atom
Missing electron
1/T
lno
2-Dimensional Silicate Structures
Silica glass Crystalline silica
Types of Conductors and the Conductivity
Equations
Metallic conductors




Ionic conductors




( ) exp
e e e h h ion ion ion
i
cat cat cat cat
cat
total total
ion ion ion o
q N N N Z
N Z
t
Q
T N Z
RT
o
o
o o
o o
(
= + +
(

= =
| |
= =
|
\ .

| |
e e e
q N o =
Types of Conductors and the Conductivity
Equations
Semiconductors
(Intrinsic behavior)



Semiconductors
(Extrinsic behavior)
n-type


p-type
| |
e e e h h
q N N o = +
| |
exp
2
exp
2
g
e o
g
e o e h
E
N N
kT
E
q N
kT
o
| |
=
|
\ .
| |
= +
|
\ .
| |
exp
c d
e o e
E E
q N
kT
o

| |
=
|
\ .
e e e e
N q o =
| |
exp
a
h o h
E
q N
kT
o
| |
=
|
\ .
h h h h
N q o =
Superconductivity