Polymers

Polymers
The word plastics is from the
Greek word Plastikos, meaning
able to be shaped and molded

Polymers
Polymers are long-chain molecules and are
formed by polymerization process, linking and
cross linking a particular building block
(monomer, a unit cell).
The term polymer means many units
repeated many times in a chainlike
structure.
Most monomers are organic materials, atoms
are joined in covalent bonds (electronsharing) with other atoms such as oxygen,
nitrogen, hydrogen, sulfur, chlorine,.
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Polymer
Poly

mer
many

repeat unit (building blocks)

repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Carbon chain
backbone
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Chemistry and Structure of

Polyethylene

Tetrahedral
arrangement
of C-H

Polyethylene is a long-chain hydrocarbon.

Top figure shows repeat unit and chain structures.
Other figure shows zigzag backbone structure.

Ancient Polymers
Naturally occurring polymers (those
derived from plants and animals)
have been used for centuries.
Wood
Cotton
Leather

Rubber
Wool
Silk

Cellulose

Cellulose is a highly abundant organic compound.

Cellulose serves as the principal structural
component of green plants and wood.
Cotton is one of the purest forms of cellulose and
has been cultivated since ancient times.
Cotton also serves (along with treated wood pulp)
as the source the industrial production of
cellulose-derived materials
which were the first "plastic" materials of
commercial importance.

Rubber

This milky fluid produce from plantsis especially

abundant in the rubber tree (Hevea)
After collection, the latex is coagulated to obtain the
solid rubber.
Natural rubber is thermoplastic, with a glass transition
temperature of 70C.
Raw natural rubber tends to be sticky when warm and
brittle when cold,
It did not become generally useful until the midnineteenth century
By heating it with sulfur
A process he called vulcanization could greatly
improve its properties.

cis-polyisoprene
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Monomer
Single repeating unit in polymer chain
is known as monomer. e.g
The monomer in polyethylene is
Monomer refers to the small molecule from
which a polymer is synthesized.

polyethylene
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Degree of polymerization

Number of repeating unit in polymer

molecular chain is known as degree of
polymerization.
Polymer molecular chains normally contains
large number of repeating units e.g
The average DP for polyethylene ranges
from about 3500 to 25000
Corresponding to average molecular mass
ranging from about 100,000 to 700,000
g/mol.
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Polymerization
Free radical polymerization: ethylene gas
reacts with the initiator (catalyst). (R. is the
unpaired electron)
R

H H
H H

H H

C C

R C C

H H
monomer
(ethylene)

free radical

R C C

H H

initiation

H H
Monomer refers to the small molecule from which a
polymer is synthesized.

H H

H H H H

C C

R C C C C

H H

H H H H

propagation

dimer

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Polymers
The wordpolymer means "many parts."
A polymeric solid material may be considered to
be one that,
Contains many chemically bonded parts or units
which themselves are bonded together to form a
solid. or
Large molecules that are composed of or made
of repeating units connected to each other by
chemical bonds.
Two industrially important polymeric materials
arei)plasticsand ii)elastomers.
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Polymeric materials
Two industrially important polymeric
materials are
Plastics . Plastics refer to a class of
materials which can be molded and formed
into shapes.
Elastomers Elastomers can be elastically
deformed a large amount
when a force is applied to them and can
return to their original shape when the
force is released.
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Types of Plastics
Plastics can be divided into two
classes,
i)Thermoplastics and
ii)Thermosetting plastics,
Depending on how they are
structurally and chemically bonded.

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Thermoplastics
Thermoplastics are those plastic
materials which are reversibly
softened by heat.
They require heat to make them
formable and after cooling, retain
their shape they were formed into.
Examples are Polyethylene, PVC,
Polypropylene, polystyrene etc.
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Thermoplastics and
The response ofThermosets
a polymer to mechanical forces at
elevated temperature is related to its dominant

molecular structure.
One classification of polymers is according to its
behavior and rising temperature. Thermoplastics and
Thermosets are the 2 categories.
A thermoplastic is a polymer that turns to a liquid
when heated and freezes to a very glassy state when
cooled sufficiently.
Most thermoplastics are high-molecular-weight
polymers whose chains associate through weak Van
der Waals forces (polyethylene); stronger dipoledipole interactions and hydrogen bonding (nylon).
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Thermoplastics and
Thermosets
Thermoplastic polymers differ from
thermosetting polymers (Bakelite, vulcanized
rubber) since thermoplastics can be remelted
and remolded.
Thermosetting plastics when heated, will
chemically decompose, so they can not be
recycled. Yet, once a thermoset is cured it tends
to be stronger than a thermoplastic.
Typically, linear polymers with minor branched
structures (and flexible chains) are
thermoplastics. The networked structures are
thermosets.
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Examples of Thermoplastics

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Thermosetting Plastics

Thermosetting plastics formed into a permanent

shape and cured or set by a chemical reaction
They cannot be remelted and reformed into
other shape
But degrade or decompose upon heating to high
temperature.
Thus, thermosetting plastics cannot be recycled.
Examples include Phenolics, Epoxy Resins,
polyesters etc.

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Elastomers,
Often referred to as rubber, can be a
thermoplastic or a thermoset depending on the
structure.
They are excellent for parts requiring flexiblity,
strength and durability:
Such as automotive and industrial seals, gaskets
and molded goods,
roofing and belting, aircraft and chemical
processing seals, food,
pharmaceutical and semiconductor seals, and
wire and cable coatings.
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Paper or Plastic?

We live in a plastic society.

Everything around us is plastic.
Could you go for a day without
plastic?
Toothbrush, clothing, food
containers, cooking spatulas,
pans, bottled water, automobile
parts, bicycle parts, eye glasses,
iPod, calculator, mouse,
computer parts, printer, stapler,
head phones, TV, clock, flash
memory housing, usb connector,
keyboard, shoes, backpack parts, 21

Why Design with Plastics?

Corrosion resistance
Low electrical and thermal
conductivity, insulator
Easily formed into complex shapes,
can be formed, casted and joined.
Wide choice of appearance, colors
and transparencies

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Disadvantages of using Plastics

Low strength
Low useful temperature range (up to 600 oF)
Less dimensional stability over period of
time (creep effect)
Aging effect, hardens and become brittle
over time
Sensitive to environment, moisture and
chemicals
Poor machinability
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Overview of
Rubber Processing and Products
Many of the production methods used for
plastics are also applicable to rubbers
However, rubber processing technology is
different in certain respects, and the
rubber industry is largely separate from
the plastics industry
The rubber industry and goods made of
rubber are dominated by one product: tires
Tires are used in large numbers on
automobiles, trucks, aircraft, and bicycles
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Rubber Processing and

Shaping
Production of rubber goods
consists of two basic steps:

1. Production of the rubber itself

Natural rubber is an agricultural crop

Synthetic rubbers are made from
petroleum

2. Processing into finished goods,

consisting of:
(a) Compounding
(b) Mixing
(c) Shaping
(d) Vulcanizing

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The Rubber Industries

Production of raw NR might be classified
as an agricultural industry because
latex, the starting ingredient, is grown
on plantations in tropical climates
By contrast, synthetic rubbers are
produced by the petrochemical industry
Finally, processing into tires and other
products occurs at processor (fabricator)
plants, commonly known as the rubber
industry
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Production of Natural
Rubber
Natural rubber is tapped from rubber trees
(Hevea brasiliensis) as latex
The trees are grown on plantations in Southeast
Asia and other parts of the world

Latex is a colloidal dispersion of solid

particles of the polymer polyisoprene in water
Polyisoprene (C5H8)n is the chemical substance
that comprises rubber, and its content in the
emulsion is about 30%

The latex is collected in large tanks, thus

blending the yield of many trees together
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Recovering the Rubber

The preferred method of recovering rubber from
latex involves coagulation - adding an acid such as
formic acid (HCOOH); coagulation takes about 12
hours
The coagulum, now soft solid slabs, is then
squeezed through a series of rolls which drive out
most of the water and reduce thickness to about 3
mm (1/8 in)
The sheets are then draped over wooden frames
and dried in smokehouses
Several days are normally required to complete the
drying process
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Synthetic Rubber
Most synthetic rubbers are produced from
petroleum by the same polymerization
techniques used to synthesize other
polymers
Unlike thermoplastic and thermosetting
polymers, which are normally supplied to
the fabricator as pellets or liquid resins,
synthetic rubbers are supplied to rubber
processors in the form of large bales
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Compounding
Rubber is always compounded with
additives
Compounding adds chemicals for vulcanization,
such as sulfur
Additives include fillers which act either to
enhance the rubber's mechanical properties
(reinforcing fillers) or to extend the rubber to
reduce cost (nonreinforcing fillers)
It is through compounding that the specific
rubber is designed to satisfy a given application
in terms of properties, cost, and processability
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Carbon Black in Rubber

The single most important reinforcing filler in
rubber is carbon black,
a colloidal form of carbon, obtained by
thermal decomposition of hydrocarbons (soot)
Its effect is to increase tensile strength and
resistance to abrasion and tearing of the final
rubber product
Carbon black also provides protection from
ultraviolet radiation
Most rubber parts are black in color because of
their carbon black content
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Other Fillers and Additives in Rubber

China clays hydrous aluminum silicates
(Al2Si2O5(OH)4) provide less reinforcing than carbon
black but are used when black is not acceptable
Other polymers, such as styrene, PVC, and
phenolics
Recycled rubber added in some rubber products,
but usually 10% or less
Antioxidants; fatigue and ozoneprotective
chemicals; coloring pigments; plasticizers and
softening oils; blowing agents in the production of
foamed rubber; and mold release compounds
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Mixing
The additives must be thoroughly mixed
with the base rubber to achieve uniform
dispersion of ingredients
Uncured rubbers have high viscosity so
mechanical working of the rubber can
increase its temperature up to 150C (300F)
If vulcanizing agents were present from the
start of mixing, premature vulcanization
would result the rubber processor's
nightmare
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Two-Stage Mixing
To avoid premature vulcanization, a
twostage mixing process is usually
employed
Stage 1 - carbon black and other nonvulcanizing
additives are combined with the raw rubber
The term masterbatch is used for this firststage
mixture

Stage 2 - after stage 1 mixing has been

completed, and time for cooling has been
allowed, stage 2 mixing is carried out in which
vulcanizing agents are added
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Filament Reinforcement in Rubber

Products
Many products require filament
reinforcement to reduce extensibility but
retain the other desirable properties of
rubber
Examples: tires, conveyor belts
Filaments used for this purpose include
cellulose, nylon, and polyester
Fiberglass and steel are also used (e.g.,
steelbelted radial tires)
Continuous fiber materials must be added
during shaping; they are not mixed like the
other additives
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Shaping and Related

Processes
Shaping processes for rubber
products can be divided into four
basic categories:
1.
2.
3.
4.

Extrusion
Calendering
Coating
Molding and casting

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Vulcanization
The treatment that accomplishes crosslinking of
elastomer molecules, so that the rubber
becomes stiffer and stronger but retains
extensibility
On a submicroscopic scale, the longchain
molecules of rubber become joined at certain
tie points, the effect of which is to reduce the
ability of the elastomer to flow
A typical soft rubber has 1 or 2 crosslinks per 1000
units (mers)
As the number of crosslinks increases, the polymer
becomes stiffer and behaves more and more like a
thermosetting plastic (hard rubber)
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Vulcanization Chemicals and

Times
As it was first invented by Goodyear in 1839,
vulcanization used sulfur (about 8 parts by
weight of S mixed with 100 parts of NR) at
140C (280F) for about 5 hours
Vulcanization with sulfur alone is no longer used
today, due to the long curing times

Various other chemicals are combined with

smaller doses of sulfur to accelerate and
strengthen the treatment
The resulting cure time is 1520 minutes

A variety of nonsulfur vulcanizing

treatments have also been developed
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Tires and Other Rubber

Products
Tires are the principal product of the rubber
industry
Tires are about 75% of total rubber tonnage

Other important products:

Footwear
Seals
Shockabsorbing parts
Conveyor belts
Hose
Foamed rubber products
Sports equipment
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Tires
Pneumatic tires are critical components of the
vehicles on which they are used
Functions of vehicle tires:
Support the weight of the vehicle, passengers, and
cargo
Transmit the motor torque to propel the vehicle
Absorb road vibrations and shock to provide a
comfortable ride

Tires are used on automobiles, trucks, buses,

farm tractors, earth moving equipment,
military vehicles, bicycles, motorcycles, and
aircraft
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Other Rubber Products - Rubber

Belts for Conveyors and Pulleys
Widely used in conveyors and mechanical power
transmission systems
As in tires, rubber is an ideal material for these
products but the belt must have little or no
extensibility in order to function
Accordingly, it is reinforced with fibers, commonly
polyester or nylon

Fabrics of these polymers are usually coated by

calendering, assembled together to obtain
required number of plies and thickness, and
subsequently vulcanized by continuous or batch
heating processes
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Other Rubber Products

Footwear
Rubber components in footwear include soles,
heels, rubber overshoes, and certain upper
parts
Molded parts are produced by injection molding,
compression molding, and certain special
molding techniques developed by the shoe
industry
The rubbers include both solid and foamed
For low volume production, manual methods are
sometimes used to cut rubber from flat stock
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Processing of Thermoplastic
Elastomers
A thermoplastic elastomer (TPE) is a
thermoplastic polymer that possesses the
properties of a rubber
TPEs are processed like thermoplastics, but
their applications are those of an elastomer
Most common shaping processes are
injection molding and extrusion, which are
generally more economical and faster than
the traditional processes used for rubbers
that must be vulcanized
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TPE Products
Molded products include shoe soles,
athletic footwear, and automotive
components such as fender
extensions and corner panels
Extruded items include insulation
coating for electrical wire, tubing for
medical applications, conveyor belts,
sheet and film stock
No tires of TPE
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