1

Chapter 6
Noncrystalline and Semicrystalline Materials
2
Introduction
The emphasis thus far has been on crystalline materials.

There are numerous engineering materials that lack the long range
translational periodicity of a crystalline material.

These non-crystalline materials are referred to as either- amorphous,
glassy, or super-cooled liquids.

Theoretically, any material can form an amorphous structure if the
cooling rate from the melt is sufficiently rapid to suppress crystal
formation.

This chapter will emphasize the structural considerations that
facilitate the development of an amorphous structure.
3
N-th Order Phase Transition
The order of a phase transition can be understood by investigating the
behavior of derivatives of the Gibbs free energy (G).

An n-th order transition is the one in which discontinuities appear only in the
n-th and higher derivatives of G with respect to T and p.
The ordinary first-order transition has discontinuities in
T
p
G
V
|
|
.
|

\
|
c
c
=
p
T
G
S
|
.
|

\
|
c
c
=
The ordinary second-order transition has discontinuities in
p
T
p
p
G
T V T
V
V
(
(

|
|
.
|

\
|
c
c
c
c
=
|
.
|

\
|
c
c
=
1 1
o
T T
T
p
G
V p
V
V
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
2
2
1 1
k
V
p V
V
T
G
T
T
T
S
T C
(
(

|
.
|

\
|
c
c
c
c
=
|
.
|

\
|
c
c
=
p
p
p
T
G
T
T
S
T C
|
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
2
2
4
Glass Transition Temperature
3. Glassy State
A state of material in the absence of long-range order below the glass
transition temperature large scale mobility is frozen atomic movement
requires time.
(Liquid-like structure and molecular mobility is frozen)
Window glass vs. Rubber band
What if you hammer them?
Glass transition temperature: the temperature below which the physical
properties of amorphous materials vary in a manner similar to those of a
solid phase (glassy state), and above which amorphous materials behave
like liquids (rubbery state).
2. Rubbery State
A state of material in the absence of long-range order above the glass
transition temperature atomic movement takes shorter time.
(Liquid-like structure and liquid-like molecular mobility)
1. Liquid State
5
Specific Volume for a Variety of Materials
Liquid to glass solid transformation in a
pure substance. The glass transition
temperature, T
g
, is not an equilibrium
transformation temperature.
Liquid to crystalline solid transformation
for a pure substance. T
m
is an
equilibrium transformation temperature
Glass Transition
The slope normalized by the volume V is the volumetric thermal expansion
coefficient (o
v
)
dT
dV
V
v
1
= o
Decrease of specific volume of liquid with decreasing temperature
6
Glass Transition
Below T
m
, material tends to crystallize.

The crystal formation (crystallization)
occurs over a period of time because
the establishment of long-range order
(LRO) requires atomic rearrangement
by diffusion.


It is possible to avoid crystallization
by cooling at a sufficiently high rate
so as to suppress the diffusion
necessary to establish LRO in the
crystal.
The volume of the collection of
atoms continues to decrease with
the slope characteristic of the liquid
below the melting temperature,
forming a super-cooled liquid.
7
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
.
Liquid
Solid
Glass
Super-cooled liquid
T
1
.
T
2
.
>
Glass Transition
Kinetic aspect of T
g
T
1
.
T
2
.
Super fast fast
9
Liquid to Semi-crystalline Solid Transformation
T
m
<T: Liquid state, molecular motion is very large.
T
g
<T<T
m
: Rubbery state (super-cooled liquid), molecular motion is relatively large.
T<T
g
: Glassy state, molecular motion is very small. Frozen state
10
Structure and Properties of Amorphous and
Semicrystalline Polymers
Ethylene
Basic building
block
Poly (ethylene)
monomer
Poly (ethylene)
chain
Poly (ethylene) chains pack well
because the side groups are only
hydrogen
Formation (polymerization) of Poly (ethylene) from a Basic
Chemical Unit of C
2
H
4
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
. .
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
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
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
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
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
C C
H H
H H

Glass transition temperature: -78 C.
Melting temperature: 100 C.
Amorphous density at 25 C: 0.855 g/cm
3
.
Crystalline density at 25 C: 1.00 g/cm
3
.
Molecular weight of repeat unit: 28.05 g/mol
used in making translucent, lightweight, and
tough plastics, films, containers, insulation,
etc
11
C
H
H
C
H
H
C C C C
H
H
H
H
H
H
H
H
... ...
C
H
H
C
H
H
n
Degree of Polymerization (DP)
n: the number of monomeric unit
~10,000 to ~1,000,000
The degree of polymerization
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
Another Example: Poly (vinyl chloride)
12
Poly (ethylene terephthalate), PET or PETE, one of the polyesters
Film, fibers, clothing, drink bottle
Density 1370 kg/m
3

Young modulus (E) 28003100 MPa
Tensile strength (t) 5575 MPa
Glass temperature 75 C
melting point 260 C
Poly (styrene), PS
Density 1050 kg/m
Specific Gravity 1.05
Young's modulus (E) 3000-3600 MPa
Tensile strength (st) 4660 MPa
Glass temperature 95 C
Melting point 240 C
Containers and toys
13
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
N
H
N
H
C
O
C
H
2
C
H
2
C
H
2
C
H
2
C
O
n
Nylon 66, one of the polyamides
Carpet fiber, apparel, airbags, tires,
ropes, conveyor belts, and hoses
Poly (p-phenyleneterephthalamide), PPTA or Kevlar
Fibers and bulletproof vests
One of the most strong polymers
C
F
F
C
F
F
n
Poly (tetrafluoroethylene), PTFE
bearings, bushings, gears, slide plates
One of the most hydrophobic polymers
With the lowest frictional coefficient
14
semi-crystalline structure of polymer amorphous structure of polymer
15
Thermoplastic Polymer and Thermoset Polymer
Thermoplastic polymer: capable of softening or fusing (melting) when
heated and of hardening again when cooled

e.g.) various linear polymers (no chemical crosslinking)
poly (ethylene), poly (propylene), and Poly (ethylene terephthalate)
Thermoset polymer: not capable of softening or fusing (melting) when
heated and of hardening again when cooled The curing (crosslinking)
process makes three-dimensional network structure in polymeric material

e.g.) various polymers with chemical crosslinking
Vulcanized rubber
Bakelite, a Phenol Formaldehyde Resin (used in electrical insulators and plastic wear)
Urea-formaldehyde foam (used in plywood, particleboard and medium-density fibreboard)
Melamine resin (used on worktop surfaces)
Polyester Resin (used in glass-reinforced plastics/fibreglass (GRP))
Epoxy Resin

16
Thermoplastic Polymer and Thermoset Polymer
Polyester with saturated
bonds along the chain
Polyester with unsaturated
bonds along the chain
Crosslinking with a
polystyrene monomer
Thermoplastic
Thermoset polymer
PET
PET
PET-based thermoset
polymer
17
Structure of Cross-linked Rubber
Thermoplastic Polymer and Thermoset Polymer
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
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
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
Unsaturated bonds are used to form cross-links with cross-linker.
Vulcanized rubber
Thermoset polymers do not crystallize well. Why?
18
Factors Affecting Crystallinity in Polymers
The size of the side groups

The extent of chain branching

Tacticity

The complexity of the repeat unit

The degree of secondary bonding
Factors influencing the efficiency of packing polymer chains
19
The size of the side groups
Bulky side group?
C
H
H
C
H
H
n
C
H
H
C
H
H
n
CH
3
CH
2
CH
n
The extent of chain branching
HDPE is defined by a density of greater or equal to 0.941 g/cm
3
. HDPE has a low degree of
branching and thus stronger intermolecular forces and tensile strength. HDPE can be
produced by chromium/silica catalysts, Ziegler-Natta catalysts or metallocene catalysts. The
lack of branching is ensured by an appropriate choice of catalyst (e.g. chromium catalysts or
Ziegler-Natta catalysts) and reaction conditions. high crystallinity
LDPE is defined by a density range of 0.910 - 0.940 g/cm
3
. LDPE has a high degree of short and
long chain branching, which means that the chains do not pack into the crystal structure as well.
It has therefore less strong intermolecular forces as the instantaneous-dipole induced-dipole
attraction is less. This results in a lower tensile strength and increased ductility. LDPE is created
by free radical polymerization. The high degree of branches with long chains gives molten LDPE
unique and desirable flow properties low crystallinity
20
21
Tacticity
crystallizable
The complexity of the repeat unit
C
H
H
C
H
H
n V.S.
The degree of secondary bonding
CH
2
CH
n
OH
C
H
H
C
H
H
n
CH
3
V.S.
C
O
O CH
2
CH
2
C
O
O
n
Not crystallizable
22
Rubbers
C
H
2
C
C H
3
C
C
H
2
n
H
Cis-1,4-poly (isoprene)
Natural Rubber
Synthetic Rubber
CH
2
CH CH CH
2
n
CH
2
CH CH CH
2
n
CH
2
CH CH CH
2
CH
2
CH CH CH
2
CH
2
CH CH CH
2
S S
S S
CH
2
CH CH CH
2
Poly (butadiene)
Sulfur bridge
Sulfur cross-link
Poly(isoprene) : Tg=~-70C
Poly(butadiene) : Tg=~-70C