POLYMERS

Group Members

Seda KOCA
Bengi AYDİLEK
Didem Büşra KABAKÇI
Gözde ERGİN

11.11.2009
Hacettepe University
 Physical Characteristics of Polymers
 The melting or softening temperature ↑ molecular weight ↑

 The molecular shape of the polymer has influence on the elastic

properties. ↑ coils the ↑ elasticity of the polymer

 The structure of the molecular chains has an effect on the strength

and thermal stability. ↑ crosslink and network structure within the
molecule ↑ the strength and thermal stability.
 Polymer Crystallinity

 Crystallinity is indication of amount of crystalline region in polymer

with respect to amorphous content

 X-ray scattering and electron microscopy have shown that the

crystallites are made up of lamellae which,in turn, are built-up of
folded polymer chains

 Figure.6 Schematic representation of (a) fold plane showing regular chain folding, (b) ideal stacking oflamellar
crystals, (c) interlamellar amorphous model, and (d) fringed micelle model of randomly distributed crystallites
 (Plastic Technology Handbook)
 Polymer crystallinity

 Crystallinity occurs when linear polymer chains are structurally

oriented in a uniform three dimensional matrix. Three factors that
influence the degree of crystallinity are:

 i) Chain length
 ii) Chain branching
 iii) Interchain bonding

Figure 7: Crystalline chain

http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/orient/Orient.htm
 Polymer cristallinity
Crystallinity influences:
Hardness,modulus tensile, stiffness, crease, melting point of polymers.
 Most crystalline polymers are not entirely crystalline. The chains, or
parts of chains, that aren't in the crystals have no order to the
arrangement of their chains
 Crystallinity makes a polymers strong, but also lowers their impact
resistance
 Crystalline polymers are denser than amorphous polymers, so the
degree of crystallinity can be obtained from the measurement of
density  Wc=Φcρc/ ρ
ρ  density of entire sample
ρc  density of the crystalline fraction.
Φc volume fraction
Wc mass fraction
 Determinants of Polymer Crystallinity

 The degree of crystallinity of a polymer depends on the rate of cooling

during solidification as well as on the chain configuration.

 In most polymers, the combination of crystalline and amorphous

structures forms a material with advantageous properties of strength
and stiffness.

Figure 8: Mixed amorphous crystalline macromolecular polymer structure

(http://web.utk.edu/~mse/Textiles/Polymer%20Crystallinity.htm)
 Polymer cristallinity
 Polymer molecules are very large so it might seem that they could not
pack together regularly and form a crystal. Regular polymers may form
lamellar crystals with parallel chains that are perpendicular to the face
of the crystals.

 A crystalline polymer consists of the crystalline portion and the

amorphous portion. The crystalline portion is in the lamellae, and the
amorphous portion is outside the lamellae .

Figure 9. Arrangement of crystalline and amorphous portions

http://pslc.ws/mactest/crystal.htm#structure
 Cristillanity and amorphousness
 An amorphous solid is formed when the chains have little orientation
throughout the bulk polymer. The glass transition temperature is the point
at which the polymer hardens into an amorphous solid.
 In between the crystalline lamellae,regions with no order to the
arrangement of the polymer chains  amorphous regions
 Polyethylene can be crystalline or amorphous. Linear polyethylene is nearly
100% crystalline. But the branched polyethylene is highly amorphous.

Figure 10.Linear and Branched Polyethylene

(http://pslc.ws/macrog/kidsmac/images/pe03.gif )
Examples...
 Highly crystalline polymers:
Polypropylene, Nylon, Syndiotactic polystyrene..
 Highly amorphous polymers:
Polycarbonate, polyisoprene, polybutadiene
 Polymer structure and intermolecular forces has a major role of a
polymer’s crystallinity.
Classification of Polymers
…with regard to their thermal processing behavior ;

Thermoplastic Polymers (Thermoplastics)

soften when heated and harden when cooled

Thermosetting Polymers (Thermosets)

once having formed won’t soften upon heating
Thermoplastics
have linear or branched structure
chains are flexible and can slide past each other
have strong covalent bonds and weak intermolecular van
der Waals bonds

elastic and flexible above glass transition temperature

can be heat softened, remolded into different forms

reversible physical changes without a change in the

chemical structure
Thermosets
chains chemically linked by covalent bonds
hardening involves a chemical reaction which
connects the linear molecules together to form a
single macromolecule.
Thermosets
once polymerization is complete, cannot be softened, melted
or molded non-destructively.

have higher thermal, chemical and creep resistance than

thermoplastics

Thermosets suitable materials for

Composites
Coatings
Adhesive applications
Common thermoplastics
Commodity Polymers
POLYETHYLENES
POLYPROPYLENE
POLYSTYRENE
POLYVINYLCHLORIDE-PVC
POLYMETHYLMETHACRYLATE-PMMA
Engineering Polymers(have a thermal resistance 100-150°C)
POLYCARBONATE
NYLON(POLYAMIDE)
POLYETHYLEN TEREPHATALATE-PET
High Performance Polymers (have a thermal resistance >150°C)
POLYTETRAFLUOROETHYLENE-teflon
POLYARYLETHERKETONES-PEEK
POLYETHYLENE
prepared directly from the polymerization of ethylene (C2H4).

two main types are; low-density (LDPE) and high-density

polyethylene (HDPE)

Advantages
cheap
good chemical resistance
high impact strength
Limitations
low heat resistance (upper temperature limit is 60°)
degrade under UV irradiation. 
high gas permeability, particularly CO2

Applications
extensively for piping and packaging
chemically resistant fittings, garbage bags
containers, cable covering
POLYPROPLYLENE
improved mechanical properties compared to polyethylene;
has a low density (900–915 kg/m3), harder, and has a higher
strength
Good chemical and fatigue resistance

Disadvantages
Oxidative degradation, high thermal expansion, high creep
poor UV resistance
Applications
medical components, films for packaging (e.g. cigarette
packets)reusable containers, laboratory equipment
POLYSTYRENE
a light amorphous thermoplastic
Advantages
low cost, easy to mould, rigid, transparent
no taste, odor, or toxicity, good electrical insulation
Disadvantages
sensitive to UV irradiation (e.g. sunlight exposure)
chemical resistance is poor, brittle
Applications
CD-DVD cases, electronic housings, food packaging, foam
drink cups and egg boxes
POLYVINYLCHLORIDE-PVC

was the first thermoplastic used in industrial applications

very resistant to strong mineral acid and bases, good electrical

insulators, flame-retardant

Two grades of the PVC material are available:

rigid PVC is used in the construction industry for piping
cold water and chemicals
flexible PVC is used in wire and cable coating, paints, signs
Common thermosets

EPOXIES
UNSATURATED POLYESTERS
PHENOL FORMALDEHYDE (PHENOLIC)
POLYURETHANES
EPOXIES
Advantage
mechanically strong, highly adhesive
good chemical and heat resistance
electrical insulators
Disadvantage
expensive
Applications
as industrial adhesives, coatings or as matrices in advanced
reinforced plastics and also as encapsulation media
UNSATURATED POLYSTERS
Advantage
hard, high strength
cheap compared to Epoxy 
good electrical insulator
high heat resistance
Disadvantage
poor solvent resistance compared to other thermosets
Applications
molding or casting materials for a variety of electrical
applications, matrix for composites such as fiberglass
boats, fences, helmets, auto body components
PHENOLICS
most commonly used thermosets

high hardness, excellent thermal stability; low

tendency to creep

Applications
wiring devices, bottle caps, automotive parts, plugs
and switches, as adhesives coatings and molded
components for electrical applications
POLYURETHANES
depending on the degree of cross-linking they behave as
thermosets or thermoplastics

low cost, high impact strength, high adhesion properties

be processed into coatings, adhesives, binders, fibers and

foams
Methods of polymer fabrication

 Extrusion of polymers
 Injection Molding
 Blow Molding
 Thermoforming
 Compression Molding
 Casting
Extrusion of polymers
method used mainly for thermoplastics

is a continuous process as long as raw pellets are supplied

is a process of manufacturing mostly long products of

constant cross-section;
i.e.. rods, sheets, pipes, films, wire insulation coating
… extrusion

pelletized material is successively compacted, melted and

formed into a continuous charge of viscous fluid
temperature of the material is controlled by
thermocouples

forcing soften polymer through a die with an opening

the product going out of the die is cooled by blown air or in

water bath
extruder
Injection Molding
most widely used technique for thermoplastics
highly productive method, profitable in mass production of
large number of identical parts

polymer in form of pellets is fed into machine and is pushed

forward into a heating chamber then the molten plastic is
forced through a nozzle into the enclosed mold cavity
pressure is maintained until solidification and then the mold
opens and the part is removed
Blow Molding
is a process in which a heated hollow thermoplastic tube
(parison) is inflated into a closed mold
disposable containers, recyclable bottles, automotive fuel
tanks, tubs are produced
involves manufacture of parison by extrusion, injection or
stretching
parison in a semi molten state is placed in a two piece mold
having the desired shape

parison is inflated by air blown, taking a shape conforming

that of the mold cavity

parison is then cut on the top, mold cools down, its halves
open, and the final part is removed
Thermoforming
is a process of shaping flat thermoplastic sheet
softening the sheet by heat, followed by forming it in the mold
cavity
Thermosets can not be formed by the thermoforming because
of their cross linked structure
widely used in the food packaging industry; manufacturing of
ice cream and margarine tubs, meat trays, microwave
containers, sandwich packs etc.
Thermoforming methods
three thermoforming methods, differing in the forming stage:

1. Vacuum Thermoforming; shaping a preheated thermoplastic

sheet by means of vacuum produced in the mold cavity

2. Pressure Thermoforming;... by means of air pressure.

3. Mechanical Thermoforming;... by direct mechanical force

Thermoforming by vacuum and mechanical force
Compression Molding
used mostly for molding thermoset resins

pre-weighed amount of a polymer mixed with additives is

placed into the lower half of the mold
polymer is preheated prior to placement into heated mold
cavity ,half of the mold moves down, pressing on the polymer
charge and forcing it to fill the mold cavity

suitable for molding large flat or moderately curved parts; side

panels for automotive, electric housings etc.
Casting
both thermosets and thermoplastics may be cast.

molten polymer is poured into a mold and allowed to solidify

for thermoplastics solidification occurs upon cooling

while thermoset’s hardening is a consequence of
polymerization reaction
REFERENCES
 François Carderelli, Materials Handbook: A Concise Desktop
Reference,2nded.,Springer
 Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis
Group
 J. A.Brydson, Plastics Materials, 7thed., Heinemann
 William D. Callister ,Materials Science and Engineering,7th ed., Wiley
 http://www.substech.com
 http://www.azom.com
 http://en.wikipedia.org
 Recycling:
A Sector of Solid
Waste Management

http://environment.utk.edu/policy.html
What is Recycling?

Recycling refers to the process of collecting used materials

which is usually considered as ‘waste’ and reprocessing
them. Recycling varies from ‘re-use’ in the sense that while
re-use just means using old products repeatedly, recycling
means using the core elements of an old product as raw
material to manufacture new goods.
Why Recycling is Important?
 Recycling Saves Energy

 Recycling Saves Environmental Conditions and Reduces

Pollution

Recycling Saves Natural Resources

Economic Benefits

Recycling Saves Space for Waste Disposal

Benefits

• Conserves Resources
• Prevents emissions of greenhouse gasses &
water pollutants
• Supplies valuable raw materials to industry
• Saves tax-payer dollars
• Creates jobs
• Stimulates development of greener technologies
• Reduces the need for new landfills and
incinerators
Recycling of polymers
Recycling of Polymers

Chemical recycling
Mechanical recycling Energy recycling

Chemolysis
Thermolysis
Glycolysis
Pyrolysis
Methanolysis
Hydrogenation
Hydrolysis
 Why do we use mechanical, chemical and
energy recycling?
Hence mechanical recycling is realy best suited to clean plastic
waste,such as packaging material.
•Chemical recycling of waste plastics is important issue.

We have applied reaction in water or organic solvent in

sub- or supercritical condition to convert polymers into its
monomers.
Condensed polymers such as polyethylene terephthalate or
nylon 6 were depolymerized to its monomers by hydrolysis of
alcoholysis in supercritical water or alcohol.
Conclusive Facts
1 t = 20,000 plastic bottles

 25,000 t of bottles recycled in the UK in 2003 saved approximately

25 million kWh of energy

 25 recycled PET bottles can be used to make an adult’s fleece jacket

Recycling a single plastic bottle can conserve enough energy to light

a 60 W lightbulb for up to 6 h
SOME PHOTOS
We have done it!!!

Ref: http://www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt

 Look at the changes you could
make with recycling...

http://environment.utk.edu/policy.html
 REFERENCES
 http://www.buzzle.com/articles/why-is-recycling-important.html

 http://www.chevroncars.com/learn/wondrous-world/recycling-process

 www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt

 François Carderelli, Materials Handbook: A Concise Desktop

Reference,2nded.,Springer

 Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis
Group
 REFERENCES

 J. A.Brydson, Plastics Materials, 7thed., Heinemann

 William D. Callister ,Materials Science and Engineering,7th ed., Wiley

 http://www.substech.com

 http://www.azom.com

 http://en.wikipedia.org
 REFERANCES
 Plastic Technology Handbook, 4th Edition, Authors: Manas Chanda,Salil K.
Roy

 http://pslc.ws/mactest/crystal.htm#structure

 http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/struct/struct.htm