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Polymers

Polymers
Introduction
Definition
Polymers Terminology
Development of Polymers
What are polymers?
Raw Materials
Additive Agents in Plastics & their
Purpose
General Properties
Applications

Polymers
Polymerization
Polymerization Reactions
Categories of Polymers
Polymer Microstructure
Comparison b/w Thermoplastic &
Thermosetting materials
Thermoplastic materials
Thermosetting plastics

Special applications
Major Polymer Processes
Recycling

All Materials
Simple
Liquids

Gases

Metals

Ceramics

Solids
Polymers
(polymeric molecules)
Thermoplastics
Heat Forming

Thermosets
Heat Setting
Elastomers

Many + Parts This name hints at


how polymers are
made

Latin: Plasticus, that


which can be molded

This name honors


plastics useful property
of being easily molded

The word, polymer, implies that polymers are


constructed from pieces (monomers) that can be
easily connected into long chains (polymer). When
you look at the above shapes, your mind should see
that they could easily fit together.

Terminology
A polymer is any substance made up of many of repeating
units, building blocks, called mers.
When in form ready for further working, they are called
resins.
Polymers - seldom used in their neat form,
most often compounded with various
material is referred as a plastic.

additives. The resulting

Plastic: a polymer that can be molded when hot and retains its
shape when cooled

Frequently, polymers,
interchangeably.

resins,

plastics

are

used

Development of
Polymers
First synthetic polymers:

Polyvinyl chloride
(PVC) in 1838

Polystyrene in 1839

Now, 250 billion pounds


produced annually,
worldwide.

Polyvinylchloride(PVC)

Polymers Categories
Two Categories:
Natural polymers:
Wood, rubber,
wool, cotton,
leather, silk
Synthetic polymers:
Fibers
Plastics
Elastomers

What are polymers?


Polymers are mostly made up of Carbon, Oxygen, Hydrogen &
Nitrogen. Some have Si, F, Cl, S.
Polymers are considered a bowl of spaghetti or a bag of worms in
constant motion.
Polymers Include:
various agricultural products & numerous minerals
organic materials,
including petroleum, coal, gas, limestone, silica, and sulfur.
additional ingredients are added (during manufacturing process)
such as
colour, pigments, solvents, lubricants, plasticizers, and filler
materials.

Additive Agents in Plastics & their Purpose


Type

Purpose

Fillers - wood flour, quartz,


limestone, cotton, rag fibers,
powdered metals, graphite, clays
etc.

Enhance mechanical properties,


reduce shrinkage, reduce weight,
or provide bulk.

Plasticizers - Vinyl is very brittle


unless phthalate is added

Increase flexibility, improve flow


during molding, reduce elastic
modulus.

Lubricant- waxes, zinc & calcium


stearates.

Improve mold ability and extraction


from molds

Coloring agentspigments)

Impart color

Flame
ester

retardants-

(dyes

and

phosphate

Antioxidants -Carbon black

Reduce flammability.
Retard degradation due to heat or

General Properties
include:
Light weight: Most polymers have specific gravities between 1.1
and 1.6, compared with about 1.75 for magnesium (the lightest
engineering metal).
Corrosion resistance: Many polymers perform well in hostile,
corrosive, or chemical environments. Some are notably resistant
to acid corrosion.
Electrical resistance: polymers are widely used as insulating
materials.
Low thermal conductivity: polymers are relatively good thermal
insulators.
Variety of optical properties: Many polymers have an almost
unlimited colour range, and the colour goes throughout, not just on
the surface. Both transparent and opaque materials are available.

General Properties
Formability or ease of fabrication:
Objects can frequently be produced in a single operation.
Raw material can be converted to final shape through such
processes as casting, extrusion, and molding.
Relatively low temperatures are required for the forming of plastics.

Surface finish: The same processes that produce the shape also
produce excellent surface finish. Additional surface finishing may not be
required.

Comparatively low cost: The low cost of plastics generally


applies to both the material itself and the manufacturing process.
Plastics frequently offer reduced tool costs; and high rates of
production.

Applications
In less than a century, use of plastic has increased
tremendously throughout the

world, and applications

are limitless.
The United States currently produces more plastic than steel,
aluminum, and copper combined.

Plastics are used to save lives in applications such as

artificial organs,

shatter-proof glass, and


bullet-proof vests.

Applications
Used in
packaging and container applications,
due to their light weight, attractive appearance, and
ease of fabrication

household appliance housings,


clock cases, and
exteriors of electronic products,
thermal insulation to our homes, and
encapsulate our medicines

Applications
insulation on electrical wires and handles for hot articles
Soft, pliable, foamed plastics used extensively as cushioning
material.
Rigid foams are used inside sheet metal structures to provide
compressive strength.
Nylon has been used for gears, acrylic for lenses, and
polycarbonate for safety helmets and unbreakable windows.

diverse use as:


shower curtains, contact lenses, and clothing, and

compose some of the primary components in televisions,


computers, cell phones, and furniture.

Even the Statue of Liberty has a plastic coating to protect it from


corrosion.

Polymerization
Polymerization is a
process of reacting
monomer molecules
together in a
chemical reaction to
form three
dimensional networks or polymer
chain.

Polymerization
Two methods are used to achieve polymerization:
Addition / Chain polymerization, where two or more
similar monomers directly react to form these long-chain
molecules; and

Polymerization
Two methods are used to achieve polymerization:
condensation polymerization (Step reaction),
where two or more dissimilar monomers react to form
long-chain molecules plus the by-product water.

Polymer Family Tree


Thermoplastics
Will reform when melted

Not Cross-Linked
90% of market

Thermosets/Elastomers
Will not reform

Cross-linked
10% of market

Polyethylene
33%
Vinyls
16%
Polypropylene
15%
PMMA
ABS
Nylon
Polycarbonate
Saturated Polyester
PEEK
Polyurethane
Some are thermosets as well.
PVC

Epoxy
Melamine Formaldehyde
Phenolic
Polyester (unsaturated)
Polyimide
Polyurethane
Some are thermoplastic as well.
Silicone
Urea Formaldehyde

Types of Polymers

Linear Polymers THERMOPLASTIC

Branched Polymers THERMOPLASTIC

Types of Polymers

Cross-linked Polymers THERMOSETS

Usually more rigid or stiff

Polymer Microstructure
Polymer = many mers
mer
H H H H H H
C C C C C C
H H H H H H

mer
H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

mer
H H H H H H
C C C C C C
H CH 3 H CH 3 H CH 3

Polyvinyl chloride (PVC)

Polypropylene (PP)

Covalent chain configurations and strength:


secondary
bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength


By controlling the length and the branching, you can control the final hardness or
flexibility of the polymer plus qualities like resistance to solvents, acids, or heat.

Comparison of Polymers

Thermoplastics
:
--little cross
linking
--ductile
--soften w/heating
--Easily molded
--easily recycled
e.g.,
--polyethylene
--polypropylene
polycarbonate

Thermosets:
--large cross linking
(10 to 50% of
mers)
--hard, rigid and brittle
--do NOT soften
w/heating, heat resistant
e.g.,
--vulcanized rubber,
epoxies,
polyester resin,
phenolic resin
7

Thermoplastic materials
Thermoplastics require heat to make them formable and
after cooling retain the shape they were formed into.
These materials can be reheated and reformed into new
shapes a number of times without significant change in
their properties, as in the melting of paraffin. Recyclable.
may be used as additive to improve Impact strength of
rigid thermoplastics.
processed

by

injection,

blow

molding,

thermoforming, calendering, and others.

extrusion,

Commonly used Thermoplastics


Polyethylene (PE) - HDPE, LDPE
Polypropylene (PP)
Polystyrene (PS)
Polyvinyl chloride (PVC)
Acetals
Acrylics
Acrylonitrile - Butadiene-Styrene - ABS
Celluloses
Fluoropolymers - PTFE , Teflon
Polyamides (PA) - Nylons, Kevlar
Polyesters - PET

Thermoplastics
Polyethylene
Cheapest ands simplest synthetic polymer
Invented shortly before World War II
Made from CH2=CH2

Thermoplastics
Polyethylene
Has two forms
High-density polyethylene
(HDPE)
Low-density polyethylene
(LDPE)

Thermoplastics
Polyethylenes
The most used polymer,
corrosion resistant,
low heat resistant (<100C),
weak mechanical properties
but
strengthenable at
high molecular weight.
Applications:

toys, bottles, bags,


containers, bullet proof vests,
synthetic skating surface.

PE Products

Low density polyethylene is used to make


plastic bags, plastic wrap, and squeeze bottles,
plus many other things.

Polypropylene
Change a H to CH3
Harder and has higher melting point than
polyethylene

Thermoplastics
Polypropylenes (PP):
low density, as plastics or as fibre,
injection mouldable,
heat resistant (up to 160 C),

PP Gloves

microwave-safe and dishwasher-safe,


easily coloured, non - absorbant to

water

Applications
food containers, synthetic carpets,

clothing, outdoor furniture.

PP Chair

Polystyrene
Change a H to benzene ring
Widely used
Disposable cups
Insulation

Thermoplastics

Polystyrenes (PS):
hard plastic,
cheap,

poor shock resistance,

Applications

3 different PS cups

computer casing,
kitchen appliances,
model cars and airplanes
hard plastic parts inside cars,
also in foam forms, for wrapping,
packing and as insulation
PS Foam

Vinyl Polymers
Change a H to Cl
Tough thermoplastic
Polyvinyl chloride (PVC)

Thermoplastics
Polyvinyl chlorides (PVC)

rigid or flexible,
corrosion resistant,
water resistant,
fire resistant,

Rigid PVC pipes

Applications

plumbing pipes,
rain coat and shower curtains,
chemical containers,
vinyl clothing.

Flexible PVC Gumboot

Polyamides: Nylon
Usually made from reaction of diacids with diamines, but
may also be made from a single monomer with an
amino group at one end and acid group at other.

Thermoplastics
Nylon (polyamides):
low coefficient of friction;
high strength in tension,
abrasion resistance and toughness;
excellent dimensional stability;
good heat resistance;

Uses
mostly used in fibre form,
as monofilaments for textiles
products
fishing line, and ropes
zip fasteners
used for small gears and bearings,
Nylon rain jacket

Polyesters
polymer of terephthalic acid and ethylene
glycol.
Made by the transesterification of the methyl
ester.

Polyester
Polyester is a
copolymer.
made from equal
amounts of two
different monomers.
Polyester is used to
make bottles and
fabrics.

Teflon
Change all H to F
CF very strong.
Resists heat and chemicals
Makes very unreactive polymer

Thermoplastics
Fluorocarbons (PTFE,
Teflon):
usable at high temperatures,
corrosion resistant,
low coefficient of friction,
Inert in most chemicals

PTFE coated fry pan

Applications
Corrosion coatings,
thread seal tape,
non-lubricated bearings
nonstick coatings for cooking
utensils and electrical irons.

PTFE thread seal tape

Polycarbonates
Esters of carbonic acid.
Carbonic acid is in equilibrium with CO2 and
water, but esters are stable.
React phosgene with bisphenol A to obtain
Lexan for bulletproof windows.
CH3

O
Cl

Cl

+ HO

heat, loss of 2 HCl

OH

CH3
O

CH3

C O

C
CH3

O
O C O
n

Thermoplastics
Polycarbonates
(PC):
transparent,
good toughness,

Applications
sun glasses,
windows and
sunroofs
PC roof sheet

Thermoplastics
ABS
has excellent electrical properties,
high impact and tensile strength, and
is resistant to heat and chemicals.
Uses
Monofilaments of polypropylene are used in making rope, nets,
and textiles.
Other products are
hospital and laboratory ware,
toys, luggage,
furniture,
film for food packaging,
television cabinets, and electrical insulation.

Polyurethanes
Esters of carbamic acid, R-NH-COOH.
Urethanes are prepared by reacting an alcohol
with isocyanate.
Polyurethanes are prepared by reacting a diol
with a disocyanate.
O C N

N C O
+ HO CH2CH2 OH
CH3

H O

O H

N C O CH2CH2 O C N

H O
N C O CH2CH2
CH3

Thermoplastics
Polyurethane
Thermoplastic PU (TPU) have some
crosslinking, but purely by physical
means.
These

bonds

can

be

broken

reversibly by raising the materials


temperature,
extrusion.

as

in

molding

or

Thermoplastics
Polyurethane
Uses
Rigid foams: Laminated board
insulation, sprayed foam, packaging

stock,

Moldings,

Semi-flexible foam: Moldings, Integral-skin moldings


Flexible foam: Moldings, integral skin molding, carpet
underlay
Packaging: Furniture cushioning
Microcellular foam: RIM parts, shoe soles
Non-foam cast elastomers
Coatings, binders, thermoplastic elastomers, sealants,
paints

Polyurethane applications

Other Polymers

Thermosetting plastics
Thermosets, also known as thermosetting
plastics, may also be formed upon heating.
The shape is permanently "set" on cooling by
a chemical reaction which cannot be reversed,
i.e. it is impossible to reshape by heating.
Heating to above a critical temperature will
only cause decomposition of the structure and
degradation of properties.
Not recyclable.

Thermosetting plastics
Thermosetting plastics usually have a highly cross-linked or
three-dimensional framework structure in which an atoms are
connected by strong, covalent bonds.
generally produced by condensation polymerization where
elevated temperature promotes an irreversible reaction, hence
the term thermosetting.
Once set, subsequent heating will not produce the softening
observed with the thermoplastics.
maintain their mechanical properties up to the temperature at
which they char or burn.

Thermosetting Plastics
Thermosetting polymers are significantly stronger and more
rigid than the thermoplastics.
can

resist

higher

temperatures

and

have

greater

dimensional stability,
but they also have lower ductility and poorer impact
properties.
are not heat reversible.
In a sense, curing a thermoset is like cooking an egg.
Once it is cooked, reheating does not cause re-melting, so it
cannot be remolded.

Commonly used Thermosets


Epoxies
Phenolics
Polyesters
Polyurethanes
Silicones
Amino resins

Thermosets
Phenolics:
good strength,
relatively fragile,
high temperature
applications
Applications
Pot and pan handles,
Bakelite (the original
plastic, substrates for
electronics.

Bakelite 1930s phone

Thermosets
Polyesters Resins:
Polyesters (can be thermoplastic or
thermoset):
Have strong and good resistance to
environmental influences,
good mechanical properties,
castable
Applications
uses include boat and car bodies,
pipes, vents and ducts,
textiles,
adhesives, coatings, and laminates
Fiberglass resin, automotive trims.

Fibreglass hull

Thermosets
Epoxies:
Epoxies are known for:
excellent adhesion
chemical and heat
resistance

high mechanical
resistance & high
corrosion resistance,
high resistivity,
very good electrical
insulating properties

Fiberglass/Epoxy
Epoxy based materials are
used for
coatings, adhesives and
composite materials
(resin for carbon fiber and
glass-reinforced plastic).
Adhesives (Araldite),
anti-corrosion paints,
over-moulding of ICs,

THERMOSETS
Melamines:
excellent resistance to heat, water, and
many chemicals;
full range of translucent and opaque colors;
excellent electric arc resistance; tableware
(but stained by coffee);
Uses
used extensively in treating paper and
cloth to impart water-repellent properties

THERMOSETS
Urea-formaldehyde:
properties similar to those of phenolics but
available in lighter colors;
useful in containers and housings, but not
outdoors;
used

in

lighting

fixtures

because

of

translucence in thin sections;


as a foam, may be used as household
insulation.

Special applications

Nano-Textiles: Military Applications


Nano-fabrics offer the following possibilities to the
- Instant camouflage to environment;
military:
- manipulate light to make soldiers
invisible;
- Change a shirt-sleeve into a splint or cast;
- Possess built-in sensors of soldiers
physical condition and location;
- Weave radio communications directly
into the uniform's fabric;
- Automatically administer medicines &
transmit vital signs to distant medics;
- Provide impact protection materials and
systems;
- Provide chemical and biological
protection.

Nano-textiles: Liquid Armour

Impact resistant: bullet proof, will also resist


pointed objects such as needles, icepicks, swords

Made from a ballistic fabric (eg Kevlar) filled with a


shear thickening fluid
- this is a water like liquid that contains silica nanoparticles

Under normal conditions, the armour is like water


but it stiffens on impact

Materials such as this are perfect for combat


- imagine Superman with a suit which allows
flexibility for crime fighting while at the same time
enabling him to protect vulnerable areas

Since the material is also very lightweight it will not


result in extra energy expenditure during movement
(eg Superman flying).

What if polymers could sense and


respond to your environment?

Nano-technology has been used to create conductive


polymers
- these polymers contain carbon nano-tubes or other
components
which
respond
to
the
environment
- examples include : ink jet-printed functional polymers
which can detect volatile compounds; polypyrole polymer
which expands and contracts (could be used for artificial

Properties and Applications - Summary


Low density, high corrosion resistance, electrical
insulation.
Ease of manufacturing into complex shapes.
Widely used for consumer products.
Emerging as structural polymers (T<150-250C).
Sales of plastics, on a volume basis, has grown
more than double the steel production in the
U.S.

Thanks

Major Polymer Processes

Extrusion
Injection Molding
Blow Molding
Thermoforming

Recycling

Polymer Processes

Extrusion

Extrusion Product Examples

Extrusion Characteristics
The extrusion machine forms the basis of
nearly all other polymer processes.
Basically involves melting polymer pellets
and extruding them out through a two
dimensional die.
Produces long, thin products
Coating for electrical wire
Fishing Line
Tubes, etc.

Injection Molding

Injection Molding Product Examples

Injection Molding Machine Basics

Injection Molding Process Control


Very similar to die
casting
Must control heat
transfer and fluid flow
Do that by controlling
temperature and
pressure

Gas Assist Injection Molding

Applicable to hollow parts without interior control.

Injection Molding of Thermosets


Plastics set when they cool
Mold temperature will be set to allow full cavity
fill, while increasing production rate
Thermosets undergo a chemical crosslinking that
produces the solid structure
Mold temperature will be hotter usually set to
allow full cavity fill, while accelerating the
chemical reaction to cure.
Often called Reaction Injection Molding (RIM)

Blow Molding Processes

Extrusion Blow Molding Injection Blow Molding

Stretch Blow Molding

Blow Molding Products Examples

Thermoforming

(a) Vacuum, (b) Pressure, (c) Drape-vacuum,


(d) Plug-assist, (e) Pressure-bubble plug assist

Thermoforming Products

Recycling

Recycling of Plastics
The favorite
properties of plastics
are that they are
inert and won't react
with what is stored in
them.
They also are
durable and won't
easily decay,
dissolve, decompose
or break apart.

Since they dont decompose, the answer is to recycle


the plastics so they can be remade into something
else. Here we see a bunch of CDs getting recycled.

Polymer Recycling
1998 Approximately 20% of plastic
waste is recycled (optimistic estimate)
1998 Polymers account for
approximately 18% by volume of material
to landfills

The decks, fence, stepping stones, house shingles, and the


sweat shirt, were all made from recycled plastic.

The mile long boardwalk at Yellowstone National


Park was made from recycled plastic.

Needs vs. Challenges


Needs for a viable
program:
Stable supply of
materials with reliable
collection and sorting
Economical, proven and
environmentally sound
recycling process
End use applications for
the recycled material

Challenges
10-12 main
polymer types
Thousands of
blends
Additives
Impurities in
supply (labels,
glass, dirt, etc)

Thanks

Engineering Materials

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