Topic 3

Polymers
Materials Technology
 Topic 3 Polymers

3.1 Overview of Polymers

3.2 Molecular Structures and Properties of Polymers
3.3 Additives to Polymers
3.4 Common Polymers and Applications
3.5 Processing of polymers
 Topic 3 Polymers

3.1 Overview of Polymers

3.2 Molecular Structures and Properties of Polymers
3.3 Additives to Polymers
3.4 Common Polymers and Applications
3.5 Processing of polymers
 Overview of Polymers
A macro-molecule
What is Polymer?
 The term Polymer is in Greek.
 The word “poly” in Greek stands for “many”.
 The word “mer” in Greek stands for “a unit”.
 As such polymer stands for a “collection of
many units”.
 In the context of material sciences, a
polymer is a long-chained molecule or
macromolecule.

www.accelrys.com/consortia/
polymer/permod/
 Overview of Polymers
 Polymers are macromolecules formed by the chemical bonding
of large numbers of smaller molecules, or repeating units,
called monomers.
 An example of a polymer is polyethene (PE).

Mer (repeating unit)

The repeating unit for PE is [–CH2-CH2-]

Polyethene molecule-CH2-CH2-CH2-CH2-……
 Overview of Polymers

Do you know hair, DNA, spider silk are also polymers?

They are Naturally Occurring Polymers

Example of naturally occurring polymers:

Hair Spider Silk

DNA
 Overview of Polymers

• For non-naturally occurring or man-made polymers, they are called

Synthetic Polymers.
• Most of the plastics encountered in our daily life (tyres, cups, synthetic
rubber).
 Polymerization

Synthetic polymers are produced using a chemical reaction known as

a polymerization reaction.
A polymerization reaction takes place inside a controlled reaction
chamber. In the reaction chamber, the temperature, pressure and
input of reactants are controlled.
Under favorable environments in the
reaction chamber, the monomers are
linked up to form polymers.

This Photo by Unknown Author is licensed under CC BY-SA-NC

 Polymerization
 Polyethylene or polyethene is a polymer
that is widely used in the industry for
producing a wide range of plastic
products.

 Polyethylene is produced from its monomer ethene which

exist as a gas in room temperature.
 In its gaseous form, ethene molecules move randomly in
space and interact with one another through weak Van der
Waals forces of attraction.
 Each ethene molecule has 2 carbon atoms held by a double
covalent bond. The double bond is unstable and can be
broken through heating.

 Industrial sources for ethene gas – isolated from natural

gas or produced from by product of petroleum refining.
 Polymerization

Example of polymerisation – Polyethene (PE)

 During polymerization, the C=C break apart.
 The 2 free electrons from the broken double bond combine with 2
other ethene molecules to form a chain.
Monomer: Ethene Polymer: Polyethene

 As the reaction progresses, more and more ethene molecules are

added to the chain resulting in a macro-molecule.
 Overview of Polymers
Classification of Polymeric Materials

Polymeric
Materials

Plastics Elastomers

Thermoplastic Thermosets
 Overview of Polymers
• Polymeric materials: combination of carbon with oxygen,
hydrogen, nitrogen and other organic or inorganic elements.
Easily shaped into forms under heat and pressure.

• Plastics: Large and varied group of synthetic materials formed

or molded into shape.
• Thermoplastic: Polymer that can be melted.
• Thermoset: Cross-linked polymer that cannot be melted (Eg.
silicone, phenolics)

• Elastomers: Lightly cross-linked macromolecules with rubbery

viscoelastic properties (ie. extremely flexible). (Eg. Butyl,
natural rubber (polyisoprene), EPDM, neoprene, nitrile etc)
 Overview of Polymers
• Thermoplastics
• Soften when heated and harden when
cooled – process is totally reversible;
melt and solidify without chemical
change and significant loss in
mechanical properties.
• The forces of attraction between
polymer chains can be overcome by
heating thereby allowing the chains to
slide over one another (polymer flow in
melted state).
• Most linear polymers and some
branched polymers are thermoplastics
• They support hot-forming methods
such as injection-moulding and FDM.
• Poor resistance to high temperature.
Low strength but ductile.
 Overview of Polymers
• Thermosets
• Harden the first time they are heated,
and do not soften after subsequent
heating.
• During the initial heat treatment,
covalent linkages are formed between
chains (i.e. the chains become cross-
linked).
• Thermoset polymers do not melt with
heating but will degrade at high
enough temperatures.
• Network/crosslinked polymers are
typically thermosets.
• High thermal stability. Strong, rigid,
hard, somewhat brittle.
 Topic 3 Polymers

3.1 Overview of Polymers

3.2 Molecular Structures and Properties of Polymers
3.3 Additives to Polymers
3.4 Common Polymers and Applications
3.5 Processing of polymers
Molecular Structures and Properties of Polymers

• Polymer: High molecular weight molecule made up of a small

repeat unit (monomer).
• Monomer: Low molecular weight compound that can be
connected together to form polymer.
• Polymer = many mers

• Homopolymer: polymer formed from one monomer (All

repeating units are the same)
• Copolymer: polymer made up of 2 or more monomers
Molecular Structures and Properties of Polymers

 Physical properties of polymers depend not only on their

molecular weight/shape, but also on the difference in the
chain structure.
• Four main structures
• Linear polymers (eg. HDPE, PVC, Nylon)
• Branched polymers (eg. LDPE)
• Crosslinked polymers (eg. Rubber)
• Network polymers (eg. Kevlar, Epoxy) Kevlar Cut-Resistant Gloves

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength
 Molecular Structures and Properties of Polymers

The polymer chain layout determines a lot of material properties.

 Amorphous:
 No ordered arrangement of molecular chain in
the solid state
 When it is heated, it shows no definite melting
temperature, but progressively becomes less
rigid

 Crystalline:
 Ordered arrangement of the molecules in the
solid state
 Distinct melting point; Higher melting point
 Molecular Structures and Properties of Polymers

• Polymer crystallinity:
• Polymers often are only partially crystalline
• Why? Molecules are very large -- Have crystalline regions dispersed
within the remaining amorphous materials
• Polymers are often referred to as semi-crystalline.

crystalline
region

amorphous
region

• % Crystallinity: % of material that is crystalline.

• Tensile strength and modulus of elasticity often increase with %
crystallinity.
• Annealing causes crystalline regions to grow. % crystallinity increases.
 Molecular Structures and Properties of Polymers
• Molecular Weight (M):
• Molecular weight (M) is defined as the mass of 1 mole of molecular
chains. (1 mole = 6.02 × 1023 )
• The molecular weight of a polymer is closely related to the length of the
chains. As chains in a polymer usually vary in lengths, value for M is
typically averaged.
• Commercial polymers usually have molecular weight between 10,000
and 10,000,000

low M high M

Eg. 1 mole of carbon weighs 12 grams.

1 mole of water (1 oxygen [16] and 2 hydrogen [1]) weighs 18 grams.
1 mole of polypropylene (3 carbons [12] and 6 hydrogen [1]) weighs
378,000 grams (assuming 9,000 mers have linked up).
 Molecular Structures and Properties of Polymers

• Molecular Weight (M):

• Effect of Molecular Weight on Properties
• When making polymers, the goal is to make a material with the ideal
properties.
• The longer the molecules (or the higher the molecular weight) the
higher the entanglement forces.
 Molecular Structures and Properties of Polymers

• Molecular Weight (M):

• Effect of Molecular Weight on Properties

• A higher molecular weight:

(1) Increases ductility: The higher degree of entanglement allows the
material to be pulled further before the chains break.
A candle and Polyethylene (PE) have basically the same molecular
structure. The chain length of the candle is just much shorter than that
of the PE. If you bend a bar of PE in half – it will bend, if you bend a
candle in half, it will fracture.

(2) Increases the tensile & impact strength of the material: The higher
degree of entanglement means that in order to rupture, more
polymer bonds need to be broken, this means that the polymer
can absorb more energy before failing.
 Molecular Structures and Properties of Polymers

• Molecular Weight (M):

• Effect of Molecular Weight on Properties

• A higher molecular weight

(3) Increases the viscosity of the material:
This makes it harder to process the material
using conventional methods. The longer the
chains, the harder it is to get them to flow
because they are more tangled.

(4) Increases the chemical resistance: It takes

more damage to the main chains of the
molecules before it will affect the strength of
the material.
 Molecular Structures and Properties of Polymers

• Molecular Weight (M):

• Effect of Molecular Weight on Properties

Many times it turns out to be a trade-off between the required properties and
processability of the material. Manufacturers want materials that will flow easily
in order to form complex geometries, but that can affect the properties of
material used to create the product.

Example: CD’s and DVD’s are made from the same material as most safety glasses, Polycarbonate.
Safety glasses require a higher molecular weight in order to provide the necessary property of impact
resistance. CD’s and DVD’s require a lower molecular weight material in order to fill out the thin walls.
CD’s and DVD’s can shatter, safety glasses don’t.
 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

 For most materials, we are concerned with the melting point and
boiling point. These are the temperatures at which the matter
experiences a ‘change of state’ (‘solid to liquid’ & liquid to gas)

 For thermoplastic materials, we are concerned with:

• Glass Transition Temperature (Tg)
• Melting Temperature (Tm)
 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

Glass Transition Temperature (Tg)
When an amorphous polymer is heated, the temperature at which it
changes from a glass to the rubbery form is called the glass transition
temperature (Tg). This is the temperature below which an amorphous
solid (such as glass, polymers, tire rubber, or cotton candy) goes from
being ductile to brittle.

For most common materials, this temperature is so high or so low that it is not easily observed –
the Tg of window glass is 564 degrees C, and that of tire rubber is -72 degrees C.
But many plastics exhibit their transition at everyday temperatures and can be “frozen” into
brittleness. One example: polypropylene, an inexpensive material often used in containers, toys,
outdoor furniture, and recycling bins has a Tg of between -20 and 0 degrees C, so it can easily lose
its molecular mobility and become shatter-prone on a winter day.
 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

Glass Transition Temperature (Tg)
The sample to the left experienced a brittle failure
• The material did not yield before failure
• The material broke like glass

The sample to the left broke in a ductile manner

• The material yielded (stretched) before failure
• The material behaved more like a rubber
 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

Melting Temperature (Tm)
For Crystalline or Semi-Crystalline materials, the melting temperature
(Tm) is the temperature at which the crystals melt.
Amorphous materials don’t truly have a Tm. They just continue to
soften more until they behave more like a liquid. When we refer to the
melt temperature for amorphous materials, it is usually the
temperature at which we can process it.
 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

Amorphous Thermoplastics -- Tg Semi-Crystalline Polymer -- Distinct Tm

 Molecular Structures and Properties of Polymers

• Effect of Temperature on Properties

 Topic 3 Polymers

3.1 Overview of Polymers

3.2 Molecular Structures and Properties of Polymers
3.3 Additives to Polymers
3.4 Common Polymers and Applications
3.5 Processing of polymers
 Additives to Polymers
• Foreign materials are added to change the mechanical,
chemical and physical properties of the polymers.
 (a) Filler  (d) Colorant
 Increase bulk & reduce cost  Organic dye or inorganic
 Improve properties eg. pigment to form color
heat and chemical  (e) Lubricant
resistance
 Reduce friction during
 (b) Plasticiser processing or prevent
 Lowers Tg to Improve sticking to molds
ductility & softness  (f) Flame retardant
 (c) Stabiliser  Reduces the flammability of
 Prevent degradation by plastic
heat and light
 Topic 3 Polymers

3.1 Overview of Polymers

3.2 Molecular Structures and Properties of Polymers
3.3 Additives to Polymers
3.4 Common Polymers and Applications
3.5 Processing of polymers
 Common Polymers and Applications

• Structures of Commonly used polymers:

Polymer Repeat Unit Polymer Repeat Unit

Polymethyl methacrylate
Polyethylene (PE)
(PMMA)

Polyvinyl chloride Phenol-formaldehyde

(PVC) (Bakelite)

Polytetrafluoroethylen Polyhexamethylene
e (PTFE) adipamide (Nylon 6.6)

Polyethylene terephthalate
Polypropylene (PP)
(PET)

Polystyrene (PS) Polycarbonate (PC)

 Common Polymers and Applications
Thermoplastic Materials:

(a) Polyethylene (PE)

• Cheap, tough, flexible
• Good chemical resistance
• Applications:
• LDPE: Bread bags, frozen food bags, grocery bags.
• HDPE: Milk, water and juice containers, toys, liquid detergent
bottles.
LDPE HDPE
 Common Polymers and Applications

(b) Polypropylene (PP)

• Strength similar to HDPE, but easier to
injection mold.

• Good fatigue properties.

• Excellent chemical resistance – no solvent

for PP at room temperature!

• Applications:
• Gasoline tanks, chemical tanks, luggage,
battery cases, ropes, fibers or filaments.
• Consumer products: Ketchup bottles,
yogurt containers and margarine tubs,
medicine bottles.
 Common Polymers and Applications

(c) Polyvinyl Chloride (PVC aka Vinyl)

• Plasticized (vinyl) – low strength.
• Applications: mostly used for decorative coatings (wallpaper),
wire coating, imitation leather, etc.

• Rigid (no plasticizer) – much stronger, tough, resistance to

grease/oil, resistance to chemicals, clarity, low cost.
• Applications: Chemical storage tank, piping, ducting
 Common Polymers and Applications

(d) Polystyrene (PS)

• Brittle, transparent, material
• Excellent electrical insulator
• Use in toys boxes, casing, radios

(e) Polyamide (Nylon)

• Strong and tough
• Relatively high melting point
• Low friction
• Use in gears, bearings, toothbrush bristles
 Common Polymers and Applications

(f) Acrylonitrile-butadiene-styrene (ABS)

• Tough, stiff and abrasion resistant.
• Moderate tensile and compressive strengths.
• Remarkable dimensional stability
• Use in instrument panels, safety helmets

(g) Acrylics
• Completely transparent thermoplastics
• Stiff strong with outstanding weather resistance
• Use in lenses for car lights, signs and nameplates
 Common Polymers and Applications
Thermoset Materials:

(a) Alkyds
• Hard and stiff
• Good mechanical and electrical properties,
dimensional stability
• Encapsulation of small electronic parts

(b) Phenolics (Bakelite)

• High stiffness, impact, and heat resistance
• Electrical plugs, sockets, switches

(c) Silicones
• Excellent chemical inertness.
• Low toxicity
• Water repellent properties
Thank You
Topic 3.5
Polymer Processing
Materials Technology
 Topic 3.5 Polymers Processing

3.5.1 Plastic Manufacturing Processes

3.5.2 Injection Moulding
3.5.3 Extrusion
3.5.4 Compression Moulding
3.5.5 Transfer Moulding
 3.5.1 Plastic Manufacturing Processes

Plastic manufacturing processes are used to convert plastic

raw materials into (semi-) finished products.
(a) Processing of Thermoplastic
• To produce thermoplastic
products, the raw polymeric
material are often in the form of
pellets, granules, flakes or
powders.
• Such forms can be easily re-melted
and formed to the desired shapes.
• E.g Injection Moulding, Plastic
Extrusion etc.
powder
pellets
(b) Processing of Thermoset
• Thermoset polymers are
permanently set, with heat and
catalysts, upon polymerization.
• Reheating of any thermoset
polymer will not change their shape
and heating at high temperatures
will only cause disintegration and
damage to the polymer.
• Raw material form monomer
solutions or rod and sheet stocks.
• E.g. Compression Moulding,
Transfer Moulding
 3.5.2 Injection Moulding
• The injection moulding process involves melting and injecting
thermoplastic polymers into a mould cavity that has pre-existing
features that need to be replicated. The injected plastic solidifies in
the mould upon cooling and can be released subsequently.

http://www.milacronindia.com/images-rev/omega-450w-s.jpg
 3.5.2 Injection Moulding

This Photo by Unknown Author is licensed under CC BY-SA

Polymer granules
feed via hopper, The plastic
Heated plastic
polymer melts Injects molten product is
fills barrel,
into molten state polymer at high allowed to cool
motorised screw
using heater pressure into and solidified
pushes molten
bands and mould via gates before being
polymer into a
friction action of and hot runners. ejected from the
mould.
a reciprocating opened mould.
screw barrel.
3.5.2 Injection Moulding
 3.5.2 Injection Moulding
Advantages
1. Fast – short cycle time.
2. Suitable for mass production.
3. Intricate shape can be achieved.
4. Repeatability within tolerances.
5. Design flexibility – by changing into different
mould design.
6. Large material choice - large selection of
thermoplastic resins to choose from.
7. Little to no finishing of parts.

Disadvantages
1. Expensive machinery – high initial tooling and machinery cost.
2. Part design restriction - plastic parts must be designed with injection
moulding consideration and must follow the basic rules of injection
moulding.
3. Less cost effective for producing low volume of parts.
 3.5.3 Extrusion
• Plastic Extrusion Process is an operation for transforming a polymer
using an extruder from the solid to the easily mouldable molten
state, then discharging it through an extrusion die in a pre-
determined cross-sectional shape and re-solidifying by cooling.
3.5.3 Extrusion
 3.5.3 Extrusion
Advantages
1. Suitable for mass production.
2. Relatively low cost as compared to other moulding
processes.
3. Shorter lead time vs. other moulding processes.
4. Long and continuous part can be produced.
5. Large material choice - large selection of thermoplastic
resins to choose from.

Disadvantages
1. Suitable to produce product with uniform cross sectional shape only.
2. Limited complexity of shape.
 3.5.4 Compression Moulding
Compression moulding is the simplest and most widely used process
for making thermoset polymer products.

Compound or blend is placed in mould and heated under pressure

within the platens of a steam-heated press. When reaction is
complete, product is cooled and ejected.

This Photo by Unknown Author is licensed under CC BY-SA

3.5.4 Compression Moulding
 3.5.4 Compression Moulding
Advantages
1. Relatively low capital and tooling cost.
2. Low mould maintenance.
3. Low residual stress.
4. Good surface finish of the moulded parts.

Disadvantages
1. Low production rate compared to injection moulding.
2. Challenging for complex part geometry.

This Photo by Unknown Author is

licensed under CC BY-SA
 3.5.5 Transfer Moulding
Transfer moulding is another process typically used for thermoset. This
process is capable of moulding part shapes that are more intricate than
compression moulding but not as intricate as injection moulding.

• A thermosetting charge (preform) is loaded and heated inside a chamber

immediately ahead of the mould cavity.
• Pressure applied on the heated material using a plunger to force the
softened polymer to flow into the heated mould.
• The polymer within the mould cavities are permitted to cure before the
final part is ejected from the mould.
 3.5.5 Transfer Moulding
Transfer moulding is another process typically used for thermoset. This
process is capable of moulding part shapes that are more intricate than
compression moulding but not as intricate as injection moulding.

• A thermosetting charge (preform) is loaded and heated inside a chamber

immediately ahead of the mould cavity.
• Pressure applied on the heated material using a plunger to force the
softened polymer to flow into the heated mould.
• The polymer within the mould cavities are permitted to cure before the
final part is ejected from the mould.
 3.5.5 Transfer Moulding
Advantages
1. Low moulding equipment cost compared to injection moulding.
2. Shorter cycle time compared to compression moulding.
3. Tighter dimensional tolerance which leads to more complex
shape can be moulded using transfer moulding as compared to
compression moulding.

Disadvantages
1. More expensive as compared to compression moulding.
2. Low production rate compared to injection moulding.
Thank You