Polymeric Materials

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Per
2nd semester 2006
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Polymers
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 Outline: Polymeric Materials
 Definition
 Classification of Polymer
 Polymerization
 Structure-Property Relationship
 Effect of Temperature on Thermoplastics
 Polymer Processing
 Strain-induced Crystalline
 Additives

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 Polymeric Materials in Everyday Life

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 Polymer Applications
 Plastics: two types  Elastomers: consist
of plastic are of linear polymer
thermoplastic and chain that are lightly
thermosetting cross-linked & high
degree of elasticity

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 Polymer Applications
 Fibers: be capable of  Adhesives: used to
being drawn into long join together the
filament having at surfaces of two
least a 100:1 length-to solid materials
diameter ratio. Ex. PA
(nylon), PES (dacron),
and PAN (acrylic
fibers).

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 Polymer Applications
 Foams: containing  Films: having
volume percentage thicknesses
of small pores between 0.025 –
0.125 mm and used
as packaging
product

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 Definition

POLYMER (Greek root)

poly = many meros = part

“substance containing high-molecular-

weight molecules, consisting of repeating unit
which are bond to each other”

MONOMER
mono = one meros = part
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 Classification: Source
Natural polymers : Synthetic polymers :
wood, rubber, cotton, PE, PP, PVC, PS, and
wool, leather, and PET.
silk.

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 Classification: Structure &
Physical Property
 Thermoplastic
Linear or branched polymers in which
chains of molecules are not interconnected to
one another.
“Polymer can be soften or molten and
reformed into new shapes. Process can be
reheated.”

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 Classification: Structure &
Physical Property
Thermosetting

Polymers that are heavily cross-linked to

produce a strong three dimensional network
structure.
“Polymer cannot be soften or molten and
reshaped.”

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 Classification: Structure &
Physical Property
Elastomer

These are polymers that have an elastic

deformation > 200%
“Material resumes its original shape when
stretched or compressed and then released.”

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 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a
trademark used herein under license.

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Thermoplastic
Elastomer
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Differences between Thermoplastic & Elastomer
 Vulcanization
 Cross-linking elastomer chains by introducing
sulfur or other chemicals

Polyisoprene
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 Properties of Thermoplastic Polymers

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 Properties of Thermosetting Polymers

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 Properties of Elastomers

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 Design/Materials Selection
 Design the type of polymeric material
you might select for the following
applications:
A surgeon’s glove
 A beverage container
 A car bumper

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 Polymerization
Crude
Crude Oil
Oil or
or Natural
Natural Gas
Gas
 Polymerization:

The process that monomer

units are bonded by Petroleum
Petroleum Products
Products

covalent bonds to generate

giant molecules.
Monomer
Monomer

Polymerization Polymer
Polymer
Monomer Polymer
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 Addition Polymerization

 Process by which polymer chains are built

up by adding monomers together without
creating a byproduct.
 Unsaturated Bond: the double- or even
triple- covalent bond joining together in an
organic molecule
 Functionality: the average no. of reactive
functional groups (sites) per monomer
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 Addition Polymerization

1. Initiation

Note:-
Addition polymerization
2. Propagation is used in the synthesis
of PE, PP, PVC, and PS,
as well as many of the
copolymers.
3. Termination

Combination

or
Disproportionation
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 Addition Polymerization
Thomson Learning™ is a trademark used herein under license.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.

(a) producing free radicals from initiators such as benzoyl peroxide

(b) attachment of a polyethylene repeat unit to one of the initiator radicals

(c)ofattachment
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 Condensation Polymerization
 A polymerization mechanism in which a small
molecule (e.g., H2O, CH3OH, etc.) is
condensed out as a byproduct.
 The thermosetting polyesters and phenol-
formaldehyde,
nylons, and PC
are produced
by condensation
polymerization.

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 Condensation Polymerization

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

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 Condensation Polymerization
H H H H H H H H O H H H HO
N C C C C C C N + HO C C C C C C O H
H H H H H H H H H H H H

Hexamethylene diamine Adipic acid

H H H H H H H O H H H HO
N C C C C C C N C C C C C C O H + H2 O
H H H H H H H H H H H H
Water

H H H H H H H O H H H HO
N C C C C C C N C C C C C C
H H H H H H H H H H H n
6,6-Nylon
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 Degree of Polymerization

The degree of polymerization refers to the total

number of repeat units in the chain.
Average molecular weight of the polymer
Degree of Polymerization =
Molecular weight of the repeating unit

Ex. Calculate the degree of polymerization if polyethylene (PE)

has a molecular weight of 56,000 g/mol.

H H Mrepeatunit = 2(atomic wt. of C) + 4(atomic wt. of H)

C C
H H
= 2(12) + 4(1) = 28
n

Polyethylene (PE) Degree of Polymerization = 56,000/28 = 2,000

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 Ex. Structure-Property Relationship

Low Density High Density

Property
Polyethylene Polyethylene

Branches many few

Density 0.195 - 0.925 g/cm3 0.945 - 0.965 g / cm3

Crystallinity 55% - 75% 80% - 95%

Hardness, Flexibility soft, pliable harder, stiff

Glass transition temp. about 75 oC
Melting Point about 110 oC
food wrapping, film, flexible
Typical Uses
bottles, garbage bags
Solubility softens and swells in
hydrocarbon solvent
about 100 oC
about 130 oC
milk jugs, bleach bottles,
pipes, an excellent
electrical insulator
Insoluble in most organic
solvents

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Effect of Temperature on Thermoplastics

 Glass Temperature (Tg): the temp. range

below which the amorphous polymer assumes
a rigid glassy structure
 Melting Temperature (Tm): the temp. range
above which molecules transform form
ordered to disordered molecular states.
 Degradation Temperature: the temp. above
which a polymer burns, chars, or
decomposes.
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 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson
Learning™ is a trademark used herein under license.

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Effect of Temperature on Thermoplastics
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a
trademark used herein under license.

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Effect of Temperature on Thermoplastics
 Processing
 Thermoplastic  Elastomer
 Injection Molding  Extrusion
 Extrusion  Compression Molding
 Blow Molding
 Compression Molding
 Themosetting  Fiber
 Reaction Injection  Spinning
Molding (RIM)
 Compression Molding
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 Injection Molding

Injection molding is the most widely used

technique for fabricating thermoplastic
materials.
Probably the most outstanding feature of
this technique is the speed with which pieces
can be produce due to cycle times are short
(commonly within the range of 10 – 30 s)

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 Injection Molding Machine
 Injection Unit  Mold Unit
- Hopper - Stationary Mold
- Barrel, Heater - Movable Mold

- Nozzle
 Clamping Unit
- Screw

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 Reaction Injection Molding (RIM)
Thermosetting polymers may also be injection molded;
curing takes place while the material is under pressure in
a heated mold.
A process likes
injection molding. Two
or more kinds of fluid
plastics are mixed,
often without heating,
and injected into a
mould where the
mixture solidifies.
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 Extrusion
 The extrusion process is simply injection molding
of a viscous thermoplastic through an open-ended
die, similar to the extrusion of metals.
 The technique is especially adapted to producing
continuous lengths having constant cross-sectional
geometries.

Ancillary Equipment
i.e. Bonding, Cutting,
Printing,…
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 Extrusion
Major type of Extrusion Products
 Profile
 Pipe
 Sheet
 Film
 Wire Covering
 Filament

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 Blown Film Extrusion

This process related to the extruder is fitted with

an annular die, pointing (usually) upwards. The tube
produced is inflated with air and at the same time is
drawn upwards in a continuous process.

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 Fiber Forming

The process by
which fibers are
formed from bulk
polymer material is
termed spinning.
The strength of
fibers is improved by
a post forming
process called
drawing.
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 Blow Molding
 Injection Blow Molding  Extrusion Blow Molding

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 Compression Molding
 Compression molding is almost exclusively
used for thermosetting and elastomer.
Step
1. Place and preheat compound or preform
between male & female mold
2. The mold is closed, heat & pressure are applied
3. The mold is opening

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 Strain-induced Crystalline
 when a rubbery polymer is stretched, the
molecules become aligned, which leads to
crystallization (non-permanent)
 non-rubbery polymers can be stretched to
increase their crystalline proportion
permanently
 stretching in two directions simultaneously
induces biaxially oriented crystallization
 e.g. biaxially stretched PET, PVC, PP: good
strength with high clarity (no optical
interference)
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 Strain-induced Crystalline

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

This figure shows a schematic of the blow-

stretch process used for fabrication of a standard
two-liter PET (polyethylene terephthalate) bottle
from a preform. The stress induced crystallization
leads to formation of small crystals that help
reinforce the remaining amorphous matrix.
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 Strain-induced Crystalline

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 Additives
 Fillers: to improve mechanical properties
and reduce cost.
 Plasticizers: to improve flexibility,
ductility, and toughness of polymers. Their
presence also produces reductions in
hardness and stiffness.
 Stabilizers: to protect against
atmospheric oxidation or UV radiation.
 Colorants: to classify application of
materials.
 Flame retardants: may function by
interfering with the combustion process
through the gas phase, or by initiating a
chemical reaction that causes a cooling of
the combustion region.
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