Polymer Processing EG-M106

Polymer Morphology and Structure

Learning outcomes

- Polymer morphology:

- Structure of glassy polymers

- Semi crystalline structure
- Orientation
- Mixed materials

*Morphology identifies the structure of a material

 Let’s start with a polymer liquid
Chains are long but separate
Chains are very mobile and flexible
Random chain structure is most stable

Will behave as a liquid,

but very thick
 Let’s start with a polymer liquid
Chains are long but separate
Chains are very mobile and flexible
Random chain structure is most stable

If polymer liquid is flowing fast,

chains can become oriented
 Let’s start with a polymer liquid
Chains are long but separate
Chains are very mobile and flexible
Random chain structure is most stable

chains can become oriented,

but will quickly revert
 Solid Structure
2 (3) types of morphology in
their solid state:

Amorphous Semi
crystalline
Glass Rubber
Some limitations
- Semi-crystalline structure only possible with
thermoplastics

- Glass structure possible with both

thermoplastics and thermosets

- Rubber structure mostly with thermosets, but

can be thermoplastic
 Thermoplastics morphology
Some regions where molecules
are presented in a highly ordered
Random structured manner

structure
 Amorphous Glassy Structure
Characteristics:

- Randomly arranged molecular structure

(much like liquid)

- No major chemical bonds between chains

- Entanglement structure provides strength and

stiffness (so need stiff chains)
 Amorphous Thermoplastics
Typical properties:

- Poor chemical resistance

Fairly open chain structure and external
chemicals can penetrate structure

- Have a smooth and glossy surface, with low

shrinkage, so give good aesthetic appearance
(a bit more on this later)
 Amorphous Thermoplastics
Typical properties:

- Often quite brittle (why?)

To get a good stiffness and strength, chains
need to be quite stiff
Very little yielding to blunt cracks
 Amorphous Thermoplastics
Typical properties:

- Can be transparent
Unless they include pigments
Why?:
Light atoms don’t absorb or reflect light
Uniform structure with no features on the scale
of light wavelength – so no scattering of light

Some will absorb some light (coloured), but

some are optically clear.
 Amorphous Thermoplastics
Amorphous thermoplastics include:

Polystyrene – cheap mouldings, packaging foams,

PMMA (Perspex) – windows, light covers

PVC – packaging, window frames, pipes,

Polycarbonate – tough glazing, electrical goods.

 What about rubbers?
These have a random chain structure, but:

- Chains are flexible at operating temperature

(like a liquid)

- Cross-links hold the structure together and

prevent and flow like a liquid

- Typical properties: low stiffness, high elastic

limit
 Crystallisation

In the case of crystalline polymers, there are certain regions of the sample
where the molecules are present in a highly ordered and structured
manner. Each of these regions is called a crystallite. Few polymers are
completely crystalline and there are always areas where the molecules are
present in a random manner. A polymer is therefore semi-crystalline in
nature, where crystallites are present in the midst of amorphous regions.
 Semi-crystalline Thermoplastics
Characteristics:

- The molecular structure aligns in an ordered

crystal structure

- The crystalline structure is part of a lamellar

crystal which in turn forms the spherulites.
 Semi-crystalline Thermoplastics
Characteristics:

- The crystal microstructure can vary with

processing

- With no flow, round spherulites form

- With orientation, different structures {PIC}
 Semi-crystalline Thermoplastics
Characteristics:

- The crystal microstructure can vary with

processing

- With orientation, different structures

Orientation
-
 Semi-Crystalline Structure
Characteristics:

- Regular arranged molecular structure in areas

- Stronger secondary bonds between chains in

crystals
Most strength and stiffness comes from crystal
bonds

- Amorphous areas between crystals can be

stiff (glassy) or flexible (more rubbery)
Rubbery amorphous regions give toughness
 Semi-Crystalline Thermoplastics
Typical properties:

- Good chemical resistance

Crystal structure is more closed and external
chemicals can’t easily penetrate structure

- Have a rougher and matt surface, with high

shrinkage, so give worse aesthetic appearance
(a bit more on this later)
 Semi-Crystalline Thermoplastics
Typical properties:

- Often tougher (why?)

Stiffness and strength comes from crystals, so
amorphous material in between can be flexible
and allow yielding to blunt cracks
 Semi-crystalline Thermoplastics
Typical properties:

- Generally translucent or opaque

Unless very thin
Why?:
The lamellae structure has a characteristic
size of 50 to 500μm. This is much larger than
the wavelength of visible light, so light gets
scattered at each boundary
Makes semi-crystalline materials translucent or
opaque, not transparent.
 Avoiding confusion
The term “crystal clear” is quite wrong with polymers

Maybe it should be “semi-crystal cloudy”?

You can buy “crystal polystyrene”

This is transparent, and it is amorphous, so has no
crystallinity!
 Semi-crystalline Thermoplastics
Semi-crystalline thermoplastics include:

Polyethylene – packaging, bottles, toys, pipes

Polypropylene – crates, automotive heating and air

conditioning units

Nylons (polyamides) – gears, zips, wheels

CHAIN STRUCTURE: Configuration
Benzene ring

SAME POLYMER
 CHAIN STRUCTURE: Configuration

Isotactic – side groups all on same side

Syndiotactic – side groups alternate

Atactic – side groups random

 Amorphous v’s crystalline
There are 2 main reasons why a polymer can be
amorphous or crystalline:

- The monomer geometric regularity

- The strength of the intermolecular forces

between them
 Amorphous v’s crystalline
Geometric regularity

- The arrangement of the groups on the main chain

- Monomer segments that are arranged in same regular

manner help pack closer and easier together

Game of Tetris
 Amorphous v’s crystalline
Geometric regularity

- Where monomer segments are not arranged in the

same regular order the chance to pack the molecules
closer together is reduced.

Game of Tetris
CHAIN STRUCTURE: Configuration

Sometimes crystalline
Normally crystalline

Never crystalline
What polymer morphology would you expect to see in the
configurations above?
 Amorphous v’s crystalline
How the morphology effects properties?

- For some polymers it is

possible to control the
orientation of the monomer
during polymerisation
 Amorphous v’s crystalline
How the morphology effects properties?

- Regular polystyrene is atactic therefore amorphous

- However during polymerisation a metallocene catalyst

can be used to form a isotactic or syndiotatic polymer

- The properties of crystalline polystyrene are far superior

and their mechanical and chemical properties excel.
 Amorphous v’s crystalline
There are 2 main reasons why a polymer can be
amorphous or crystalline:

- The geometric regularity

- The strength of the intermolecular forces

between them
(eg nylons)
Amorphous v’s crystalline
 Crystallinity
The proportion of the material that is crystalline (percentage
crystallinity) can have important effects on properties.

Higher crystallinity gives:

Strength
Stiffness
Chemical resistance
Toughness
Light transmission
Density
 Crystallinity
The proportion of the material that is crystalline (percentage
crystallinity) can have important effects on properties.

Higher crystallinity gives:

Strength
Stiffness
Chemical resistance
Toughness
Light transmission
Density
 Crystallinity in PE
Polyethylene

Polyethylene Polyethylene
(linear) (branched)

High crystallinity Low crystallinity

High density / higher Low density / lower stiffness

stiffness and strength and strength
HDPE – eg pipes LDPE – flexible packaging
Molecular weight and crystallinity
The relationship between the percentage crystallinity and
molecular weight defines the use of the polymer. This
explains the vast use of polyethylene based on this
relationship.

Low molecular weight and low crystallinity polyethylene is

typically used more in soft waxes and greases, whereas high
molecular weight and highly crystalline materials tend to
be hard plastics.
 Mixed Materials
Plastic materials are often more complex mixtures

- Copolymers and blends – mix of more than one

polymer

- Reinforced with fibres, particles

- Plasticised to increase flexibility

 Mixed Materials
Effects on processing

- Wider ‘melting’ range

- Higher viscosity so higher pressure needed

- More effects of orientation

- More wear of equipment

How is this made?