Introduction to Rubber Technology

Elastomeric Materials
High molar mass material which when deformed at room temperature
reverts quickly to nearly original size and form when the load causing
the deformation has been removed (ISO 1382:1996)
• Common characteristics

– Large elastic elongation (i.e.200%)

– Can be stretched and then immediately return to their
original length when the load was released

 The term elastomer is often used interchangeably with the

term rubber

 Elastomers are usually thermosets (requiring vulcanization)

but may also be thermoplastic .
An elastomer is a cross-linked or vulcanized
polymer. Cross-linking is a chemical way of
linking the long polymer chains. A way to think
of this would be to take the bowl of spaghetti
and tie them together with a piece of thread
where ever the pieces of spaghetti touch each
other

There are several ways to crosslink rubber, but the most common is through the
use of sulfur. Sulfur, with the addition of heat and pressure, will crosslink
rubber. They connect up the long individual polymer chains into what is literally
a single unit.
 IMPORTANCE OF RUBBER
 Rubber is a polymer with inherent thermoplastic and elastomeric qualities,
meaning it can be stretched to great lengths without permanent deformation
and can withstand both electric and thermal strain.
 Flexibility is another important property of rubber; thus rubber sheet is as
flexible as cloth.
 strength as well as toughness are notable properties of rubber due to which its
elastic property may be put to be used even under abnormal condition.
 Rubber is highly impermeable to water and air.
 highly resistant to cutting, tearing and abrasion over a wide range of
temperatures.
 Not attacked by atmospheric gases and chemicals have no corrosive effects on
it.
 Due to plasticity, rubber is pliable and amenable(easy to control) as required.
Plasticity increases with increase of temperature.
 CLASSIFICATION OF RUBBER
A. According to source rubbers are classified as
I. Natural rubber: latex, Gutta Purcha etc

II. Synthetic rubber: SBR, IR, NBR etc

B. According to initial raw materials used

I. Rubbers made from single monomer: Butadiene rubber (BR)
II. Rubbers made from two/more monomers: styrene-Isoprene rubber (SIR)

C. Depending on application, they are classified as

I. General purpose rubber:
II. Special purpose rubber:

D. General classification: 4 classes

2. Hard plastic 3. Reinforcing 4. Paint
1. Elastomers resins vehicle

i) vulcanisable ii) unvulcanisable

a) Diene rubber b) non-Diene
rubber
Classification of elastomers (based on similar properties)
Elastomers have been classified in groups according to similarity of
properties and applications

Rubber type 61 (rubbers for general use)

Type 61 rubbers are used when the product does not require special
properties, such as oil, heat or weather resistance. These rubbers have
good mechanical properties and processability. They also have low price.
Elastomers that belong to this group are natural rubber (NR),
polyisoprene rubber (IR) and styrene-butadiene rubbers (SBR) and the
blends of these elastomers.
Rubber type 62

Rubber type 62 is a rubber type that has not been standardized. Butyl
rubber (IIR), chlorobutyl rubbers (CIIR) and bromobutyl rubbers (BIIR) are
elastomers which belong to this group. They have good ozone and
weather resistance. In addition, the gas permeability is low and they are
resistant to vegetable oils , but not to mineral oils.

Rubber type 63

Rubbers in this group have good oil resistance, but their ozone and
weather resistance are weak. Applications are products that come in
contact with oils. Nitrile rubber (NBR) is of rubber type 63. Rubber type
631 is rubber that has developed from nitrile rubber. It has better ozone,
weather and heat resistance than nitrile rubber. Hydrogenated nitrile
rubber (HNBR) belongs to this group. Rubber type 632 is nitrile rubber
blended with polyvinylchloride (NBR/PVC). It has better oil, ozone and
weather resistance than NBR.
Rubber type 64
Chloroprene rubber (CR) is representative of rubber type 64. It has good
resistance to vegetable oils and fairly resistance to good aliphatic and
naphtenic oils. A disadvantage is their poor resistance to aromatic oil.

Rubber type 65
Rubbers in this group have good weather and heat resistance and quite
good oil resistance. Polyacrylic rubbers (ACM) are in this group.

Rubber type 66
Rubber type 66 is not standardized. Polyurethane rubbers (AU, EU)
belong to this group. These rubbers are tough and have good weather
and oil resistance. Their heat resistance is poor.
Rubber type 67

Rubbers in this group (fluorocarbon rubbers (FPM)) have good weather,

heat, oil and chemical resistance.

Rubber type 68

Silicone rubbers (Q) belong to this group. They have good weather, cold
and heat resistance. Their mechanical properties are weak.

Rubber type 69

Epichlorohydrin rubbers (CO, ECO, GECO) belong to this group. They

have medium weather, oil and heat resistance.

Rubber type 70

Rubber type 70 comprises ethylene-propylene rubbers (EPDM, EPM).

They have good ozone, weather and heat resistance and poor oil
resistance.
 CLASSIFICATION OF RUBBER (continue)
Rubbers in both dry and latex form shall be classified and coded
from the chemical composition of the polymer chain in the following
manner:
M—Rubbers having a saturated chain of the polymethylene type.
N—Rubbers having nitrogen, but not oxygen or phosphorus, in the
polymer chain.
O—Rubbers having oxygen in the polymer chain.
R—Rubbers having an unsaturated carbon chain, for example,
natural rubber and synthetic rubbers derived at least partly
from diolefins.
Q—Rubbers having silicon and oxygen in the polymer chain.
T—Rubbers having sulfur in the polymer chain.
U—Rubbers having carbon, oxygen, and nitrogen in the polymer
chain.
Z—Rubbers having phosphorus and nitrogen in the polymer chain.
The “M” class includes rubbers having a saturated chain of the
polymethylene type. The following classification shall be used:
ACM—Copolymers of ethyl or other acrylate and a small amount of
monomer which facilitates vulcanization.
AEM—Copolymers of ethyl or other acrylates and ethylene.
ANM—Copolymers of ethyl or other acrylate and acrylonitrile.
BIMSM—Brominated polymers derived from a copolymer of
isobutylene and p-methylstyrene.
CM—Chloro-polyethylene.
CFM—Polychloro-trifluoro-ethylene.
CSM—Chloro-sulfonyl-polyethylene.
EOM—Copolymers of ethylene and an octene
The “R” class shall be defined by inserting the name of the monomer
or monomers before the word “rubber” from which it was prepared
(except for natural rubber). The letter immediately preceding the
letter R shall signify the diolefin from which the rubber was prepared
(except for natural rubber).
Any letter or letters preceding this diolefin letter signifies the
comonomer or comonomers. A parenthetical letter (S), for solution,
or (E), for emulsion, is used to indicate whether the rubber or latex
was prepared by solution or emulsion polymerization. The following
classification shall be used for rubbers of the “R” class:
ABR—Acrylate-butadiene.
BIIR—Bromo-isobutene-isoprene.
BR—Butadiene.
CIIR—Chloro-isobutene-isoprene.
CR—Chloroprene.
ENR—Epoxidized natural rubber.
HNBR—Hydrogenated acrylonitrile-butadiene.
IIR—Isobutene-isoprene.
IR—Isoprene, synthetic.
NBR—Acrylonitrile-butadiene.
NIR—Acrylonitrile-isoprene.
NR—Natural rubber.
PBR—Vinylpyridine-butadiene.
PSBR—Vinylpyridine-styrene-butadiene.
SBR—Styrene-butadiene.
SIR—Styrene-isoprene rubbers.
Rubbers of the “R” class having substitute carboxylic acid (COOH)
groups on the polymer chain shall be identified by the prefix “X”:
XBR—Carboxylic-butadiene rubber.
XSBR—Carboxylic-styrene-butadiene.
XNBR—Carboxylic-acrylonitrile-butadiene
 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
• The more the latex is removed, the more the
plant regenerates it.
• Latex composition: water- 60%, rubber
polymer- 35%, protien,enzyme and nucleic
acid- 3%; fatty acid and ester- 1%; inorganic
salt- 0.5%
 • Natural rubber is highly elastomeric (elongation 1000% for vulcanized natural
rubber)

• Compared to other elastomeric materials, natural rubber shows higher

tensile strength, high tear strength, high resilience, resistance to wear, etc

• Crude natural rubber was chiefly composed of cis-polyisoprene (a polymer

chain with carbon carbon double bond with repeating unit)

• Cis means that two pendent group (H and CH3) that are attached to the two
carbons in the carbon carbon double bond
• The alternate configuration where the two groups are located on the
opposite side of the carbon carbon double bond is called trans
• The presence of methyl group interfere the movement in polyisoprene
polymer- restricted bending and twisting motion (increased stiffness, higher
strength, and higher temperature stability
 Polyisoprene structure

Cis-polyisoprene Trans-polyisoprene
(Hevea rubber) (Gutta percha)
 Recovering the Rubber
• The preferred method of recovering rubber from latex involves
coagulation - adding an acid such as acetic/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
• It is then treated for preparing different grade natural
rubbers.
 Grades of Natural Rubber
• The resulting rubber, now in a form called ribbed smoked
sheet, is folded into large bales for shipment to the processor
– It has a characteristic dark brown color
• In some cases, the sheets are dried in hot air rather than
smokehouses, and the term air‑dried sheet is used; this is
considered to be a better grade of rubber
• A still better grade, called pale crepe rubber, involves two
coagulation steps, followed by warm air drying
– Its color is light tan

ribbed smoked air‑dried sheet pale crepe

 REFINING OF CRUDE RUBBER

1) Breakdown: The polymeric chains of the rubber are broken by

masticating/kneading the raw rubber between the warm rollers. During
breakdown, the rubber loses its reversibility gradually and turns plastic.

Mastication is a mechanical shearing process using two roll mill or internal

mixer) for
Reduced the molecular weight,
Reduced the viscosity and
To soften the raw rubber.
Mastication is a preliminary stage of processing the raw rubber.
At low temperatures the process shreds(cut) the rubber molecules into
smaller units.
This improves the plasticity and reduces the viscosity.
After mastication  the processing will be much easier and increased the
effectiveness of dispersions of compounding ingredients.
The mastication is compulsory for natural rubber due to high molecular
weight in nature (around 105-106 ).
In processing natural rubber, the stocks first are physically and
chemically masticated (shredded) before being mixed with fillers
and other ingredients. Shortening the polyisoprene molecules makes
the rubber softer and more malleable. Most synthetic rubbers do not
need the mastication step because they are made of shorter
molecules.
RUBBER COMPOUNDING

Rubber compounding is the complex, multidisciplinary field of selecting

and blending the appropriate combination of elastomers and other
ingredients to meet the performance, manufacturing, environmental, and
cost requirements for rubber goods made and used in commerce.

The term compounding has evolved within the plastics and rubber
industry and refers to modifying a polymer or polymer blend through
addition of other materials to produce useful materials with superior
properties for specific service applications. Also, environmental concerns
create interest in utilizing recycled rubber products for new rubber
compounds.
A. FILLER

Fillers are particulate materials added to improve the physical properties

and optimize the cost of the rubber compound. All particulate fillers
increase the hardness and stiffness of rubber compounds. The chemical
composition and its effect on rubber compound physical properties
typically classify fillers into three broad categories:

1.Reinforcing filler
2.Semireinforcing or extending filler
3.Nonreinforcing filler
Reinforcing filler

Reinforcing fillers improve the physical/mechanical properties of the rubber

vulcanizate such as tensile strength, tear resistance, abrasion resistance
etc. Improvements in rubber compound physical properties are directly
related to the filler particle size, whereby the smaller particulate fillers
impart greater reinforcement.
Functional fillers transfer applied stress from the rubber matrix to the
strong and stiff mineral.
It seems reasonable then that this stress transfer will be better effected if
the mineral particles are smaller, because greater surface is thereby
exposed for a given mineral concentration. And if these particles are
needle-like, fibrous or platy in shape, they will better intercept the stress
propagation through the matrix.
If the size of the filler particle greatly exceeds the polymer interchain
distance, it introduces an area of localized stress. This can contribute to
elastomer chain rupture on flexing or stretching. Fillers with particle size
greater than 10,000 nm (10μm) are therefore generally avoided because
they can reduce performance rather than extend or reinforce. Fillers with
particle between 1,000 and 10,000 nm (1 to 10μm) are used primarily as
diluents and usually have no significant effect, positive or negative, on
rubber properties. Semi-reinforcing fillers range from 100 to 1000 nm (0.1
to 1μm). The truly reinforcing fillers, which range from 10 nm to 100 nm
(0.01 to 01 μm), can significantly improve rubber properties.
A filler must make intimate contact with the elastomer chains if it is going
to contribute to reinforcement of the rubber-filler composite. Fillers that
have a high surface area have more contact area available, and
therefore have a higher potential to reinforce the rubber chains.
Particle-size distribution and particle shape also have significant effects
on composite reinforcement. A particle with a high aspect ratio has higher
reinforcement than a more spherical one. Fillers having a broad particle-
size distribution have better packing in the rubber matrix and provide
lower viscosity than that provided by an equal volume of the filler with a
narrow particle-size distribution.
A wide variety of particulate fillers are used in the rubber industry. Carbon
black is the filler of choice. All grades, with the exceptions of N880 and
N990 thermal blacks, reinforce rubber with the finest particle size carbon
blacks imparting the highest degree of reinforcement based upon
improved abrasion resistance, tear strength, tensile strength, and
stiffness. A number of mineral fillers are used in the rubber industry to
extend and/or reinforce elastomers. They include carbonates, clays,
silicas, silicates, and talc. However, when compared to carbon black, the
use of nonblack fillers by the tire and rubber industry is limited.
Aspect ratio is not applied to carbon black and precipitated silica. The
primary particles of these fillers are essentially spherical, but these
spheres aggregate in such a way that the functional carbon black and
precipitated silica filler “particles” are aggregated chains or bundles. The
anisometry of these fillers is described in terms of “structure”, which
incorporates aggregate shape, density and size. The higher the
structure, the greater the reinforcement potential.

Non-reinforcing/inert filler: do not impart these properties but help in

processing, reduce cost, retention of shape, color and other desirable
properties. Soft clay, coal dust, talc etc are non-reinforcing filler.
Fillers should be very fine, uniform and shouldn’t be contaminated
with metal and moisture. It should be ground, well screened and dried
before use.
B. Antidegradants

Good aging properties of rubber compounds are essential for providing

required service life of rubber products.The type of elastomer used is the
principal factor in considering aging properties. In general, the more
saturated is the backbone of the elastomer, the better is the aging
properties. For example, EPDM and butyl rubbers are quite stable when
compared to more unsaturated polymers such as polyisoprene, sytrene–
butadiene rubber, and polybutadiene. Unsaturated polymers are
susceptible to oxidation thermally or by reaction with ozone, thus
antioxidants and antiozonants are needed to extend the useful service
lives of products made with these elastomers.
 The factors affecting the aging of general purpose rubber having
conventional sulfur and accelerator systems are as follows
Oxygen: Addition of only 1–2% of oxygen is sufficient to cause
deterioration of properties for most general-purpose elastomers. Oxidation
proceeds by free radical mechanisms and leads to chain scissioning and
cross-linking. In the chain scission reaction, free radicals attack the
unsaturated polymer backbone causing chain breaking that results in
softening and weakening.
Heat: As expected, heat accelerates oxidation. Therefore, the effects
described previously are observed earlier in product use and are more
severe as the service temperature of the product is increased. Because
oxidation is a chemical reaction, a temperature increase of 10°C almost
doubles the rate of oxidation.
Flexing: Flex cracking is a common mode of fatigue failure in rubber
compounds. Flex cracking involves not only a mechanical fatigue but also
oxidation that is accelerated by heat generated during the flexing cycle.
The higher the rate of flexing, the greater is the heat generation, and the
worse is the fatigue life of the compound or product.
Light. Ultraviolet (UV) light promotes free-radical oxidation at the rubber
surface causing discoloration and formation of a brittle film of oxidized
rubber.
Ozone. Although ozone concentration in the atmosphere is only a few
parts per hundred million (pphm), it rapidly reacts with an elastomer’s
carbon–carbon double bonds, particularly the backbone unsaturations,
causing cracking of the rubber products.
Sulfur. Low sulfur compounds and efficient vulcanized (EV) sulfur-
accelerated systems have better aging resistance. Normally, the oxidation
rate increases with the amount of sulfur used in the cure.
Metals. Transition-metal ions, such as iron, copper, manganese, and
cobalt, when present even in small amounts, catalyze rubber oxidative
reactions by affecting the breakdown of peroxides in such a way as to
accelerate further attack by oxygen
Thus the age-resistors used must be capable of reacting with the agents
causing aging (oxygen, ozone) to slow or prevent the polymer
breakdown, to improve the aging qualities, and to extend the service life
of the product involved. Antioxidants should mix easily with rubber as well
as should not interfere with vulcanization
Antioxidant Types: Commercially available antioxidants may be divided
into three general classes: secondary amines, phenolics,and phosphites.
In general, the amines are more active than the phenolics that are in turn
more active than the phosphites.
Many antioxidants in these classes are volatile to some extent at
elevated temperatures and almost all antioxidants are readily extracted
from their vulcanizates by the proper solvent. These disadvantages have
become more pronounced as performance requirements for rubber
products have been increased.
Higher operating temperatures and the need for improved oxidation
resistance under conditions of repeated extraction have accelerated the
search for new techniques for polymer stabilization. Seals, gaskets, and
hose are some examples where high temperatures and solvent
extraction can combine to deplete a rubber product of its antioxidant and
thus lead to its oxidative deterioration faster.

Techniques for providing increased protection against oxidation under

severe temperature and solvent extraction conditions include the use of
polymer-bound antioxidants. Chemical attachment of the antioxidant
molecule to the polymer backbone eliminates volatility and extraction by
making the antioxidant essentially infinite in molecular weight after curing.

Two general methods of accomplishing this attachment have been used:

1.functionalized macromolecules react with antioxidant molecules to

provide the bound antioxidant, and
2.antioxidant molecules containing polymerizable functional groups may
be copolymerized with conventional monomers during polymer
production
C. Processing Agents
Functions of processing additives
Classification of processing additives

According to
chemical
structure
According to effects
Lubricants
The largest group of modern processing additives contain lubricants. The
essential raw materials for this class of products are fatty acid, fatty acid
salts, fatty acid esters, fatty acid amides and fatty alcohols. Paraffin wax
and LMW polyethylene and polypropylene were also included due to their
wax like characters.
Among the fatty acids, stearic acid still finds widespread application as a
material which improves both the processibility and the curing
characteristics of the compound. It is further used as a constituent of the
emulsifier system for synthetic rubber.

The most important metal soap is zinc stearate. Apart from lubrication, it is
also used dusting agent for uncured rubber.
Functions of lubricants

A processing additive predominantly

acting as an internal lubricant will
mainly serve as bulk viscosity
modifier and improve filler dispersion
while slip performance is influenced
to a minor extent.

A lubricant with predominantly

external action will greatly improve
slip and reduce friction between the
elastomer and the metal surface of
the processing equipment. Filler
dispersion can be improved through
accumulation at the interface
between elastomer and filler.
Peptizing agents

Physical peptization denotes

the thermomechanical
breakdown of rubber at
relatively low temperature. The
term includes viscosity
reduction achieved by using
zinc soap (physical peptizer)
as intermolecular lubricant.

Chemical peptization describes

the thermooxidative, catalysed
break down of rubber (mostly)
at elevated temperatures.
Benefits of using peptizing agents
a)Accelerate peptization b) reduce power consumption
c) Promote batch to batch uniformity
d) Reduce mixing cost
e) Facilitate blending of elastomers
f) Improve dispersion.
Homogenizing agents

Homogenizing agents are products which improve the homogeneity of

difficult to blend elastomers. They also assist incorporation of other
compounding materials.

Resinous compounding materials

used as homogenizing agents
are:

1. Hydrocarbon resins: petroleum,

tarpene, bitumene etc

2. rosins: their salts, esters and

other derivatives

3. Phenolic resins: phenol

formaldehyde resin
Dispersing agents

Since dispersing agents are mostly fatty acid derivatives, they can be
looked as sub group of lubricants. The central property is, however,
dispersion. They reduce mixing time and have a positive influence on
subsequent processing stages. Dispersing agents have distinct wetting
properties. They are often less polar fatty acid esters.
tackifiers
As most synthetic rubbers are less tacky than NR, it is often necessary to
introduce tackifying substances. They should lead to improved uncured ply
adhesion (building tack) on assembling and improved knitting of contact
areas. Tackiness should not be reduced by compounding materials like
waxes.
Different resins (as discussed in homogenizing agent) are used as tackifier
in rubber compound.
Plasticizers
The ester plasticizers can be split into general purpose and specialty
plasticizers such as

1.General purpose plasticizers: phthalic acid esters

2.Cold flexibility : aliphatic diesters of glutaric, adipic acid etc
3.Flame retardant: alkyl, aryl and mixed esters
4.Antistatic: polyglycol esters and ethers
Mold release agents

These are another sub group of lubricants, however their prime function is
to easier product release from the mold as well as decrease mold
contamination.
Organosilicones, fatty acid esters, metal soap and fatty acid amides are
used in this purpose.

others
Different phenolic resins are used as stiffening agents (increase
hardness) during curing operation.
Mineral oils are used as softening agent during extrusion operation.
D. Vulcanizing Agents
Vulcanization is a chemical process where sulfur or other materials form
crosslinks in the elastomer and thereby improve the polymer’s
mechanical properties. Sulfur is the most common vulcanizing agent for
the widely used diene-containing elastomers, such as natural
rubber,SBR,and polybutadiene. sulfur compounds usually react with the
polymer to produce a cross-linked material in which the linkages are –C-
Sx-C. The cross links may be mono-,di- or polysulfidic. Because this
material is insoluble in rubber, it resists migration to the surface prior to
cure and this bloom-free attribute contributes to maintaining better
building tack and better component-to-component adhesion. Peroxides
are probably the most common materials used after sulfur because of
their ability to cross-link a variety of diene- and nondiene-containing
elastomers.
E. Rubber Vulcanization Chemicals
The vulcanization systems consist of the following components: the
vulcanizing agent such as sulfur, the accelerator to activate the sulfur, a
retarder to help control the rate of vulcanization, and an activator such
as zinc oxide and stearic acid. Each can be discussed in turn.
(a) Accelerators: During sulfur vulcanization of rubber, accelerators
serve to control time to onset of vulcanization, rate of vulcanization, and
number and type of sulfur cross-links that form. These factors in turn
play a significant role in determining the performance properties of the
vulcanizate. It reduces the time required for the vulcanization of rubber
from several hours to a few minutes. In addition, less sulfur is needed
and a more uniform product is obtained.
The mechanism presumably involves the formation of an active form of
sulfur which forms a “sulfur bridge” at reactive sites within the rubber
molecule, linking the large molecules into a tight network structure. Apart
from accelerating vulcanization, accelerator should have a high critical
temperature. Critical temperature is the lowest temp., at which the
accelerator makes it action felt. Many accelerators are so active that they
start vulcanization even during mixing or calendering operations. Such
premature vulcanization is known as scorching. Thus an accelerator
should have a high critical temperature to avoid scorching. (e.g. 2-
mercaptobenzothiazole, benzothiozolyl disulfide etc.)
 (B) Activators: Activators are chemicals that increase the rate of
vulcanization by reacting first with the accelerators to form rubber-soluble
complexes. These complexes then react with the sulfur to form sulfurating
agents. The most common activators are combinations of zinc oxide and
.
stearic acid. Other fatty acids used include lauric, oleic, and propionic
acids. Sulfenamide accelerators generally require lower levels of fatty acid
because they release an amine during the vulcanization process that acts
to solubilize the zinc. Guanidines and similar amine accelerators also
serve to both activate and accelerate vulcanization.
(c) Retarder: The purpose of vulcanization retarders is to delay the initial
onset of cure in order to allow sufficient time to process the unvulcanized
rubber. Several main classes of materials are used commercially such as
organic acids and anhydrides, cyclohexylthiophthalimide and sulfenamide
. Examples of organic acid retarders include phthalic anhydride, benzoic
acid, and salicylic acids. These materials will react with more basic
accelerator fragments, with other basic compounding ingredients,and with
impurities. These basic moieties, which would normally serve to
accelerate vulcanization and produce a higher state of cure, are thus
neutralized by the acid retarders. Therefore, they are effective in delaying
the initial onset of cure. However, some retarders also lower the rate of
vulcanization and, in many cases, detract from the final mechanical
properties. The thiophthalimide (CTP) and sulfenamide classes of
retarders differ from the organic acid types by their ability to retard scorch
(onset of vulcanization) without significantly affecting cure rate or
performance properties.
Thus in conclusion the following ingredients are generally used as rubber
compounder
A. Filler (both reinforcing and non reinforcing)
B. Antidegradants (include antioxidants, antiozonants etc.)
C. Processing agents/additives
i) lubricants
ii) peptizing agents (physical peptizer and chemical peptizer)
iii) homogenizing agent
iv) dispersing agent
v) releasing agents
vi) tackifiers
vii) softening and stiffening agents
D. Vulcanizing chemicals
i) vulcanizing agent
ii) accelerators
iii) activators
iv) retarders
RUBBER COMPOUND MIXING
DEFINITION OF MIXING

MIXING is defined as the way different types of Raw Materials are

combined together to get a Mass that is substantially different from the
characteristics of individual components and is Homogeneous as far as its
physical and chemical properties are concerned and the same is
achieved through dispersive and distributive operation.
The aim of the mixing process is to produce a product that has the
ingredients dispersed and distributed sufficiently thoroughly to permit it to
shape readily, cure efficiently and give the required properties for the
application, all with the minimum expenditure of machine, time and
energy.
Purpose of mixing

1. The basic purpose of mixing is to mechanically breakdown the

rubber in an attempt to obtain a uniformly homogeneous mass, which is
subsequently formed into slabs or sheets of rubber.

2. In other words the mixing process mixes or blends the rubber with
the various constituents uniformly.

3. The mixing plasticizes the base material, i.e raw rubber.

 What are the different types of mixing?

In principle, there are two types of mixing

1. Continuous mixing.
2. Discontinuous mixing or batch mixing.
Either of the above mentioned processes usually comprise of two
stages namely,
The distributive and the dispersive stages.
The distributive mixing stage yields the master batch after primary
mixing and plasticizing. To get a good mix with the additives, the
rubber has to be plastic. The first stage mainly deals with the
mastication of rubber i.e. making the elastic rubber plastic. Thus the
name distributive as it churns and tears and distributes the elastic
rubber to get a sticky plastic yielding compound.
The dispersive stage serves for the final dispersion of the vulcanizing
agents
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 150°C (300°F)
• If vulcanizing agents were present from the start of mixing,
premature vulcanization would result –the “ rubber processor's
nightmare”
To avoid premature vulcanization, a two -stage mixing process is
usually employed
Stage 1- carbon black and other non-vulcanizing additives are
combined with the raw rubber
 The term masterbatch is used for this first -stage 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
Four basic steps are involved in the mixing operations are 

1. Incorporation : is the first stage of mixing during which the previously

separate ingredients form a coherent mass.

2. Dispersion : is the process during which the carbon black

agglomerates are reduced to their ultimate size

3. Distribution : is simple homogenization, during which the various

ingredients are randomly distributed throughout the mass of the mix.

4. Plasticization : during this operation the mix reaches its final

viscosity as plasticizers effectively lubricate the mix.
Different types of mixing machines

The mixing machines are perhaps the heaviest, dirtiest and most energy
gobbling entities in the rubber industry.

There are three types of mixing machines.

1. Rolling mills or external mixers.

2. Continuous mixers.
3. Banbury – type or internal mixers.

Except for the second type, the other two types can either be continuous
or discontinuous type.
Two roll mills
Every mixer must provide two basic functions, both equally important;
Acceptable dispersion (intensive or dispersive mixing) and
High uniformity (extensive or distributive mixing)
Two roll mills are most often used by the rubber technologist to
produce small quantities of mixed compound.
A mill consists of two horizontally placed hollow metal cylinders (rolls)
rotating towards each other.  The distance/gap between the mill rolls
(nip) can be varied, typically between 2 to 20 mm.
The speeds of the two rolls are often different, one roll rotating faster
than the other. The difference in speed between the two rolls is called
the friction ratio. The friction ratio allows a shearing action (friction) at
the nip to disperse the ingredients and to force the compound to stay on
one roll, preferably the front one. A friction ratio of 1.25:1 is common.
The rolls are equipped with internal cooling and heating system.
The gap between the rolls is adjustable within a range related to roll
diameter.
The mixing procedure is relatively standard. The operator places
portion of elastomers on the mill, kneading the sample by multiple
passes through the gap until sufficient reduction in stiffness permits it to
wrap and adhere to one roll.
The gap is adjusted so that a reservoir of elastomer is always rotating
above the nip. This reservoir is called the rolling bank.
Powders are now added into the gap with frequent pan sweeping.
Process oil and/or plasticizers is also added, usually after part of the
filler content has been incorporated.
At the conclusion of the mix, after cross-blending the batch is cut
from the mill for cooling and storage.
Advantages of two roll mill
High shear developed at the mill nip; this breaks up agglomerates and
drives incorporation of ingredients efficiently.
The massive surface exposure impart good cooling, thereby
maintaining the required stiffness of the compound.
Due to the roll friction ratio, the rolling bank imparts further high shear.

Disadvantages of two roll mill

The length of mixing cycle (usually about 30 minutes or

more/100kg batch)
Dependence on operator skills
Dust and dirt levels that are typical
Difficulty in batch to batch uniformity
Difficulty in standardizing subjective procedure
Banbury mixer or internal mixer

Banbury – type mixer is the most common internal batch mixer. To

overcome the long mixing cycle of two-roll mill and other shortcomings,
banbury mixer was originally manufactured.
The Banbury mixer was initially developed by Fernley H. Banbury from
1916 onwards.
Named so as the mixing operation is typically a batch operation in
which around 200 kilograms of formulated compound can be mixed in
3-5 minutes.
A Banbury mixer is a heavy-duty
two arm/rotor mixer that contains a
figure eight chamber with a rotor in
each lobe. Two rotors are operated
at a slight speed differential. The
rotors are not interlocking.
Mixing or shearing action occurs
between the rotors and the sides of
the mixer, and between the rotors
themselves.
The mixer is top loaded through an
opening (hopper) large enough to
accommodate bales of elastomers.
a floating weight, or ram, drops on top of
the feed to confine the material to the
mixing space and exert extra pressure on
the material.
The ram pressure can be varied as well
as it can be repeatedly lifted and
reapplied during the mixing process.
The rotor design is such that material in
the chamber is constantly being
displaced.
The ram is lifted after the mixing time has
elapsed and a hydraulically actuated trap
door is opened at the bottom of the
mixing chamber.
The rotors, side doors and mixing
chamber sides are provided with
heating/cooling channels. The
heating channels carry hot water to
heat the apparatus to ensure
uniform
initial conditions for each batch.
Cooling is provided during the
mixing process to
dissipate the excess heat which if
not removed may result in scorching
of the “mass”.
Mode of action of banbury mixer

1. milling: is the action of the rotors wiping material through the

periphery of the bore of the sides. This milling is more effective than the
2-roll milling as the angle of incidence of rotor-to-side is much sharper
than the case of 2-roll mills. The mass of rubber in front of a rotor wing
is subject to rolling action which causes heavy molecular shear in the
layers of rubber. Material which has already passed between the side
and rotor is also subject to some rolling motion
2. kneading: is caused by the rotor tips when material which has
been deformed by milling is carried to the center of the chamber and
relaxed. In Banbury as the connecting gears are of uneven ratio,
there are at least ten variable tip phases which constantly change
the quantity of the mass and its conformation. At one moment both
rotor tips may be directly opposed, at the next revolution the tips are
no longer directly opposed but are pushing and working the material
in a slightly different combination. This kneading results in shear,
folding over and periodic relaxing of the stock.
Advantages of banbury mixer

Highly reproducible cycles

Minimum dependene upon operator skills
Large capacity and high output
Relatively short mixing cycle
Potentially clean factory operations

Disadvantages of banbury mixer

More rapid temperature rise in mixing

More time needed for cleaning equipment
Much higher initial investment
Forming Process (Shaping)

 After all compounding ingredients have been properly mixed the

compounded green stock is tacky and thermoplastics
 In this plastic condition, the stock can be shaped by the applications
of force.
 This can be accomplished by
(1) Calendering
(2) Coating
(3) Extruding
(4) Molding and casting
Calendering

Calendering is a process where rubber compound is formed to a

continuous sheet or coated on a fabric. This is done by feeding the
rubber compound to one or several on each other following roll gaps.

Two rolls built together in a frame,

forms one gap and is called a two-roll
calendar.
• Three rolls forms two gaps and is
called three-roll calendar.
• Four rolls forms three gaps and is
called four-roll calendar

Figure: Calendering
 Calendering

In the calendering process, rubber is passed through a three- to five-roll

calender either to produce a sheet of controlled thickness or to force the
rubber into close contact with a textile or metal cord.
Stock is passed through a series of gaps of decreasing size made by a
stand of rotating rolls.
Rubber sheet thickness determined by final roll gap.
Perfect sheets up to 2 mm thickness can be produced without air
inclusions.
Machinery
In a calender the rolls are mounted in a frame made of cast iron with
high tensile strength. The rolls have a diameter from around 200 to 750
mm and face length from 250 to 2 500 mm (the smallest are laboratory
calenders) and are manufactured for highest concentricity, resistance to
deformation and with high quality surface finish.

To allow a good temperature control the modern calenders have

peripherally drilled passages for heating or cooling, while older
machines often are heated or cold from steam/water in the central bore.

The drive of a calender is normally a direct current drive which can be

either a separate motor for each roll or one central motor with the torque
transmitted between the rolls via gears.
Roll deflextion and methods of correction

A main problem with calendering is that the rolls bend because of

deformation due to the pressure from the rubber between the gaps.
This means that thickness variations of the calendered material will
occur.
In order to compensate for this deflection, different methods have been
developed.

The most common methods are:

1.Roll camber (roll crown)
2.Cross axis (crossed roll)
3.Roll bending
Camber is when one or several
rolls are ground so that they have
different diameters in the centre
and at the ends to compensate
for the deflection. This functions
well if you run products which
use roughly the same material
and thickness.
The figure shows an exaggerated
example of roll camber. In the
upper figure the rolls are
unloaded and in the bottom
figure they are loaded with
rubber between the rolls.
Roller die calender

For certain types of

manufacturing a roller die are
used, where an extruder with a
wide die applied directly to the
nip of a two roll calender.
With that process, up to about 15
mm thick sheeting can be
calendered with the result of low Figure: Roller die pocess ‑ rubber
porosity due to trapped air as no extrusion followed by rolling
bank of rubber is built up by the
feeding to the calendar.
Coating or Impregnating Fabrics with Rubber
A great part of calendering operations concern coating of fabrics. The
dominating example is coating of cord fabrics for different types of
tyres, but many other rubber products like hose, conveyor belt, V-belts,
reinforced sheeting and shoes are built up with the use of coated
fabrics too.
In principle two different techniques are used.
• Frictioning
• Coating
When frictioning, the rubber is forced into the fabric and the operation is
mostly carried out in a 3-rolls calender.
The frictioning effect is reached by
having different rotation speed on the
rolls. The middle roll which is carrying
the rubber runs faster than the bottom
roll carrying the fabric. It is important
that the rubber sticks to the middle roll
and that effect is achieved by selecting a formula giving a very soft
compound, normally with high polymer content.
The temperature on the rolls differs from each other. The upper roll is
usually about 100 °C and the middle roll a little bit lower as the rubber
bank will stay there for some time. The bottom roll ought to be rather high
up to 125 - 130 °C, which increases the plasticity of the rubber and make
it easier to force the rubber into the fabric.
Coating of fabrics is preferable done in a 4-roll Z-type of calender, as it is
then possible to coat both side in one operation.
The fabric is very often a cord fabric, which is typical for tyres, but woven
fabrics are coated with rubber.
The thickness of the coating can be from
some tenths of a mm up to a couple of mm,
depending on the product it is intended for.
The setting of the bottom roll nip must be
done very careful with respect to thickness
of the fabric as well of the coating.
By doing so, the rubber compound is pressed between the cords in
the fabric and surrounding each cord.
The thickness is automatic controlled by thickness control instruments.
 Extruding
During the rubber extrusions process, rubber material is processed
through a screw extruding machine very similar to those used in
extruding plastic.
Rubber extruders consist of a heated shearing screw conveyor or twin
screw conveyor and a die through which the plasticized and pressurized
rubber is squeezed.
Pre-heating of the material is optional, depending on the precision of
the die and the desired qualities of strength.
Stock rubber material enters the screw conveyor channel, often by
way of an attached hopper.
It is softened through heating and shearing, and the stock material is
then pressurized through the rotation of a screw.
 Heaters around the extruder’s barrels heats the stock and liquefies
them
 The pressure pushes the rubber through the die, which is located at
the end of the extruder.
The rubber then emerges from the extruder in a profile resembling
the die shape
After being extruded, the material is cured and sometimes vulcanized
using various methods.
Basically an extruder screw has three different zones
• Feed zone: the function of this zone is to preheat the rubber compound
and convey it to the subsequent zones.
• Compression zone: in this zone the screw depth gradually decreases so
as to compact the rubber. This compaction has the dual role of removing
any trapped air pockets and improving the heat transfer through the
reduced thickness of material.
• Metering Zone: in this section the screw depth is again constant but
much less than the feed zone. In the metering zone, the melt is
homogenized so as to supply at a constant rate, material of a uniform
temperature and pressure to the die.
The screw is machined out of a solid rod.
Like a shaft with helical screw on it, each turn of the helix is
called a flight. 
Important parameter= L/D of the screw (length of the flighted
portion of the screw/ inside diameter of the barrel)
L/D measures the capability of the screw to mix materials and
ability of the screw to melt hard-to-melt material. Typical L/D ratios
are 16:1 to 32:1
Molding
Principal molding processes for rubber are:
(1) Compression molding
(2) Transfer molding, and
(3) Injection molding
Compression molding is the most important technique because
of its use in tire manufacture.
Compression molding

Compression molding is a process in which a compound is squeezed into

a preheated mould taking a shape of the mould cavity and performing
curing due to heat and pressure applied to the material. The method
uses a split mould mounted in a hydraulic press. Compression moulding
process involves the following steps:
1.A pre-weighed amount of the
compound is placed into the
lower half of the mould. The
compound may be in form of
putty-like masses or pre-formed
blanks.

2. The upper half of the mould

moves downwards, pressing on
the compound and forcing it to fill
the mould cavity. The mould,
equipped with a heating system,
provides curing (cross-linking) of
the compound.

3. The mould is opened and the

part is removed for necessary
secondary operations.
The advantages of compression moulding are primarily the
following:
1. The method is simple and only requires relatively simple presses and
moulds. It is an appropriate method for short runs.
3. Suitable for products with large surface or large spreading.
4. Can be used for rubber compounds with high viscosity and poor flow
properties.

The disadvantages of compression moulding are the following:

1. The preparation of blanks and the insertion of blanks into the mould
are time consuming.
2. Complicated cavities can be difficult to fill out completely.
4. The production rate is relatively low.
Injection moulding
Injection moulding is a process in which the
compound is forced under high pressure into a
mould cavity through an opening (sprue).
The rubber material in form of strips is fed into
an injection moulding machine. The material is
then conveyed forward by a feeding screw and
forced into a split mould, filling its cavity
through a feeding system with sprue gate and
runners.
An injection moulding machine is similar to an
extruder. The main difference between the two
machines is in screw operation. In the extruder
type the screw rotates continuously providing
output of continuous long product (pipe, rod,
sheet).The screw of the injection moulding
machine is called a reciprocating screw since it
not only rotates but also moves forward and
backward according to the steps of the
moulding cycle.
It acts as a ram in the filling step when the
compound is injected into the mould and
then it retracts backward in the moulding
step. The mould is equipped with a
heating system providing controlled
heating and vulcanization of the material.
The compound is held in the mould until
the vulcanization has completed and then
the mould opens and the part is removed
from the mould.
Injection moulding is a highly productive
method providing high accuracy and
control of shape of the manufactured
parts. The method is profitable in mass
production of large number of identical
parts
 Advantages of injection molding:
The complete elimination of pre-forms. The production and need for pre-forms is
a labor intensive step that can potentially affect the finished product through
variability in pre-form weight and shape.
Elimination of operator placement of pre-forms. Since pre-forms are eliminated,
the need for operators to place the pre-forms in a cavity (compression molding) or
pot (transfer molding) is removed.
Injection screw pre-heats material before forcing it into cavities. This process
decreases the viscosity of the material, allowing it to flow more easily into the mold
cavities. Pre-heating provides the potential for decreased cure times through more
rapid cavity filling due to lower viscosity.
Reduced cycle time
Economical process for high volumes of medium to high precision components
Minimal material waste
 Refining
Synthetic rubbers are complex chemical Crude oil
compounds formed through the
polymerization of monomers. Synthetic Refining
rubber production (fig.) starts with the
refining process of oil, coal or other Naphtha Natural Gas
hydrocarbons with naphtha as one of the
desired products. The naphtha is then
combined with natural gas to produce Rubber plant
monomers. Typical monomers used for
Monomers
production feed material include
butadiene, styrene, isoprene,
chloroprene, acrylonitrile, ethylene or Additives Steam
propylene. These monomers are then
polymerized using catalyst and process
steam to form chains of polymers which
results in rubber intermediaries. These Synthetic
substances are then processed to their Rubber
final rubber products by vulcanization

To end product
processing
SOME COMMON MONOMERS AND RUBBERS
 COMMON MONOMER PRODUCTION SCHEME

1. Styrene:

The predominant route to the production of styrene is via ethylbenzene, which is

made by alkylating benzene with ethylene and subssequent
dehydrogenating to styrene over an aluminium chloride, solid phosphoric
acid, or silica-alumina catalyst.

C6H6 + C2H4 C6H5CH=CH2 + H2

2. 1,3 Butadiene:

(a) From ethyl alcohol

Silica gel, Ta2O5
CH2=CH – CH =CH2 + H2O
CH3CH2OH + CH3CHO 325°C, 1at. pr
3 moles 1 mole
(b) From petroleum

Butene, is passed over calcium nickel phosphate catalyst stabilized with 2%

chromium oxide at 625-700°C and a low butene pressure. The overall conversion
is about 40-50%.
Ca8Ni(PO4)6
C4H8 CH2=CH – CH =CH2
625-700°C

3. Acrylonitrile:

Acrylonitrile is principally produced by the sohio process that treats propylene

with air and ammonia in a catalytic reactor.

CH3CH=CH2 + NH3 + air CH2=CHCN

4. Isobutylene:

Usually recovered from refinery light-end operations by distillation.

5. Chloroprene:

manufactured from acetylene and hudrogen chloride. Acetylene is dimerized to

monovinylacetylene, which in turn reacted with hydrogen chloride to form
chloroprene.
aq. Cu2Cl2.NH4Cl
CH≡ CH CH2=CH-C≡CH
18-24°C 35 KPag Vinyl acetylene

HCl

CH2=CCl.CH=CH2
6. Isoprene:

(a) From propylene

CH3
dimerization
CH3-CH=CH2 CH2=C-CH2CH2CH3
propylene 2-Methyl-1-pentene
isomerization

CH3
CH3
pyrolysis
CH2=C-CH=CH2 + CH4 CH3-C=CHCH2CH3
isoprene 2-Methyl-2-pentene

•Production cost is potentially low

•Raw material is cheap and plentiful.

(b) From isobutylene and aldehyde Shreve’s chemical process
Page: 696-697
(C) From Acetylene and acetone

7. Ethylene and propylene:

These are readily available from refinary light end cuts or may be produced by
the steam cracking of propane or heavier fractions.
Manufacture of SBR
MONOMER PRODUCTION SCHEME

1. Styrene:

The predominant route to the production of styrene is via ethylbenzene,

which is made by alkylating benzene with ethylene and subsequent
dehydrogenating to styrene over an aluminium chloride, solid
phosphoric acid, or silica-alumina catalyst.

C 6H 6 + C2H 4 C6H5CH=CH2 + H2

2. 1,3 Butadiene:

(a) From ethyl alcohol

Silica gel, Ta2O5
CH2=CH – CH =CH2 + H2O
CH3CH2OH + CH3CHO 325°C, 1at. pr
3 moles 1 mole
(b) From petroleum

Butene, is passed over calcium nickel phosphate catalyst stabilized with

2% chromium oxide at 625-700°C and a low butene pressure. The overall
conversion is about 40-50%.
Ca8Ni(PO4)6
C 4H 8 CH2=CH – CH =CH2
625-700°C
Figure: Schematic diagram of the emulsion-polymerization method. Monomer molecules
and free-radical initiators are added to a water-based emulsion bath along with soaplike
materials known as surfactants, or surface-acting agents. The surfactant molecules,
composed of a hydrophilic (water-attracting) and hydrophobic (water-repelling) end, form
a stabilizing emulsion before polymerization by coating the monomer droplets. Other
surfactant molecules clump together into smaller aggregates called micelles, which also
absorb monomer molecules. Polymerization occurs when initiators migrate into the
micelles, inducing the monomer molecules to form large molecules that make up the latex
particle.
Two types of polymerization reaction are used to produce styrene-
butadiene copolymers:
Emulsion type and
Solution type
The emulsion products can be sold in either a granular solid form,
known as crumb, or in a liquid form, known as latex.
 Solution crumb production involves mixing the raw materials in a
homogeneous solution, wherein polymerization takes place.
 Emulsion crumb production involves producing an emulsion of raw
materials, resulting in bulk polymerization of droplets of monomers
suspended in water.
 Copolymers containing less than 45 weight percent styrene are known
as styrene-butadiene rubber (SBR). As the styrene content is increased
over 45 weight percent, the product becomes increasingly more plastic.
Production of crumb rubber by emulsion polymerization has been
the traditional process for the production of synthetic rubber.

 It is still the most commonly used method, accounting for 90% of

the world’s production of SBR.
Emulsion Crumb Process

As illustrated in the figure, raw materials in the form of

monomers, produced by the petroleum industry, is delivered to the
tank farms.

 The monomers include styrene and butadiene.

 Because production facilities such as these operate 24 hours per

day, 365 days per year, the tank farm always maintains a constant
supply.
 Short stop soln

Fig.: simplified flow diagram for SBR production

Other materials delivered and stored in tank farms include soap (detergent),
activator, catalyst, modifier, extended oil, and carbon black.

 Butadiene, as well as certain other monomers, is delivered with polymerization

inhibitors mixed in to prevent premature polymerization during delivery and storage.

 Production process begins with removal of the polymerization inhibitors, by passing

the monomer through a caustic scrubber.

 The monomers to be polymerized are homogeniously mixed with soap solution,

deionized water, catalyst, activator, and modifiers prior to entering the first of a series
of reactors..

 The purpose of the soap solution (or detergent) is to hold the entire mixture in a
stable emulsion throughout the polymerization process.
Rosin acid soap1 [rosin acid (~90% Abietic Acid) soap is a potassium
soap of rosin acid, a sodium soap of rosin acid, or a lithium soap of rosin
acid] or fatty acid soap2 is typically used.

 The purpose of the catalyst is to generate free radicals to initiate and

maintain polymerization.

 Typical catalysts used are hydroperoxide or peroxysulfates.

 The function of the activator is to assist the catalyst in generating free

radicals, as well as to enable reaction at lower temperature.

 The modifier [Mercaptan (Thiol)-which terminates growing chain)

acts to control the length of polymerized chain and, consequently, the
size (and molecular weight) of the polymer].
The process is operated as either “cold” (400F to 450F at 0-15 psig)
or “hot” (1220F at 40-60 psig), to produce cold SBR or hot SBR
respectively.

 Cold SBR processes are stopped at 60% polymerization.

 Hot SBR processes, the older of the two, are allowed to proceed to
near completion of the polymerization process.

 “Cold rubbers” have improved properties, compared with hot

rubbers but require more extensive process management.

For Cold rubber, the emulsified mixture resulting from the initial
mixing of monomers and additives must be kept cool by means of an
ammonia refrigerant prior to entering the reactors.
Also, a “short-stop3” solution must be added to the solution
exiting the reactor, in order to halt the polymerization process at 60%
completion (The overall polymerization reaction ordinarily is not
carried out beyond a 60 percent conversion of monomers to polymer,
because the reaction rate falls off considerably beyond this point and
product quality begins to deteriorate).

 Then, the unreacted monomers, as well as the catalysts, activators,

modifiers, water, and emulsifiers, must be separated from the
polymerized material, reconditioned, and returned for continued use.

 The latex emulsion is introduced to flash tanks4 where, using

vacuum flashing, the unreacted butadiene is removed. The butadiene
is then compressed, condensed, and pumped back to the tank farm
storage area for subsequent reuse.
The condenser tail gases and noncondensables pass through a
butadiene adsorber/desorber unit, where more butadiene is recovered.
 Some noncondensables and VOC vapors pass to the atmosphere or,
at some plants, to a flare system.
The latex stream from the butadiene recovery area is then sent to
the styrene recovery process, usually taking place in perforated plate
steam stripping columns. From the styrene stripper, the latex is stored
in blend tanks.
 The stripped latex must be protected from oxidation by oxygen or
ozone. This is accomplished by addition of an antioxidant in a blend
tank.
 The latex is pumped from the blend tanks to coagulation vessels,
where dilute sulfuric acid (H2SO4 of pH 4 to 4.5) and sodium chloride
solution (brine) are added.
The acid and brine mixture causes the emulsion to break, releasing
the styrene-butadiene copolymer as crumb product. The coagulation
vessels are open to the atmosphere.
 At this point, the product is called “crumb”.
 Carbon black and various oils are added to the crumb to produce
desired properties, including color.
 Leaving the coagulation process, the crumb and brine acid slurry
is separated by screens (shaker screen) into solid and liquid. The
crumb product is processed in rotary presses that squeeze out most
of the entrained water. The liquid (brine/acid) from the screening
area and the rotary presses is cycled to the coagulation area for
reuse.
The partially dried crumb is then processed in a continuous belt
dryer that blows hot air at approximately 93°C (200°F) across the
crumb to complete the drying of the product.
 The finished product is then weighed, baled, stored for shipping.
Properties of E-SBR: E-SBR is commercially available in Mooney viscosities
ranging from 30 to about 120 (ML1+4@125C). Lower Mooney viscosity E-SBR
grades band more easily on the mill, incorporate fillers and oil more readily, show
less heat generation during mixing, are calendered more easily, shrink less, give
higher extrusion rates and have superior extrudate appearance than the higher
Mooney viscosity grades. On the other hand, the high Mooney viscosity SBR’s
have better green strength, less porosity in the vulcanizate, and accept higher filler
and oil loadings.
As the molecular weight of the SBR increases, the vulcanizate resilience and the
mechanical properties, particularly tensile strength and compression set, improve.
The processability of SBR improves as its molecular weight distribution broadens.
Formation of high molecular weight fractions with the increase in the average
molecular weight can however, prevent improvements in the processability. This is
due to the fact that the tendency for gel formation also increases at higher
molecular weights
In addition to the polymer viscosity, polymerization temperature also plays an
important role in shaping the processability. E-SBRs produced at low polymerization
temperatures have less chain branching than those produced at higher temperature.
At an equivalent viscosity, cold polymerized E-SBR is normally easier to process
than hot polymerized E-SBR, and this applies particularly to a better banding on
mills, less shrinkage after calendering, and a superior surface of green tire
compounds. Hot rubbers give better green strength because they have more chain
branching.

The styrene content of most emulsion SBR varies from 0% to 45%. The percent
styrene of most commercially available grades of E-SBR is 23.5%. In vulcanizates
of SBR, as styrene content increases, dynamic properties and abrasion resistance
decrease while traction and hardness increase.
Polymerization temperature also affects the microstructure of E-SBR. In the cold
polymerized E-SBRs, the butadiene component has, on average, about 9% cis-1.4,
54.5% trans-1.4, and 13% of vinyl-1.2 structure. At a 23.5% bound styrene level, the
glass transition temperature, Tg, of SBR is about –50°C. As the styrene content in
the SBR increases, the glass transition temperature also increases. Rubbers with
very low Tg values are characterized by a high resilience and good abrasion
resistance, but have poor wet traction. By contrast, those rubbers with high Tg, as,
for instance, SBR 1721, exhibit a low resilience and poor abrasion resistance with an
excellent wet traction.
The emulsifier remains in the rubber after coagulation can also have an influence on
the processability. Rosin acid emulsifiers impart better knitting, tack and adhesion to
the SBR polymer. Generally, polymers emulsified with rosin acid have better extrusion
rates, slower cure rates, poorer heat resistance and can cause mold fouling and
polymer discoloration. Fatty acid emulsified SBR polymers generally have less tack,
faster curing, and high tensile properties. A compromise of the above properties is
obtained by using a mixed rosin acid/fatty acid emulsifier system.
Mechanical Properties. Since SBR lacks the self-reinforcing qualities of natural
rubber due to stress induced crystallization, gum vulcanizates of SBR have lower
tensile properties. The tensile property of E-SBR vulcanizates depends in great
measure on the type and amount of filler in the compound. Cured gum stocks have
only 2.8 to 4.2 MPa tensile strength, while fine particle carbon black loadings can
produce tensile strength of 27.6 Mpa. Though the compression set of some of the
common E-SBR compounds is high, by proper compounding and blending, it is
possible to obtain E-SBR vulcanizates with a low compression set
Electrical Properties. SBR is a non-polar polymer and its vulcanizates are poor
conductors of electricity. The electrical properties of E-SBR depend to a large extent
on the amount and type of emulsifier and coagulating agent(s) used.

Resistance to Fluids. While E-SBR vulcanizates are resistant to many polar

solvents such as dilute acids and bases, they will swell considerably when in contact
with gasoline, oils, or fats. Due to this limitation, SBR cannot be used in applications
that require resistance to swelling in contact with hydrocarbon solvents.

Cure Properties. SBR can be cured with a variety of cure systems including sulfur
(accelerators and sulfur), peroxides and phenolic resins. Processing of SBR
compounds can be performed in a mill, internal mixers or mixing extruders. SBR
compounds are cured in a variety of ways by compression, injection molding, hot air
or steam autoclaves, hot air ovens, microwave ovens and combinations of these
techniques.
Silicone Rubber
What is silicone?
Silicone is a generic name for a wide variety of polymeric chains and
networks constructed around a backbone of Si-O-Si.

Technically known as “polysiloxanes,” silicones are the “missing link”

between organic and inorganic chemistry.

Combining the advantages of glass and plastics, silicones are unique

materials unlike anything else in the world.

Like glass (which is silicon-based), silicones are temperature- and

moisture-resistant, chemically inert, and dielectric.
Like plastics (which are carbon-based), silicones are strong and able to
assume many forms.
 Silicone Rubber
Silicone rubber’s special features such as “Organosiloxanes Polymer” has been
originated from its unique molecular structure that they carry both inorganic and
organic properties unlike other organic rubbers. In other words, due to the Si-O
bond of Silicone Rubber and its inorganic properties, Silicone Rubber is superior
to ordinary organic rubbers in terms of heat resistance, chemical stability,
electrical insulating, abrasion resistance, weatherability and ozone resistance
etc...

.
isoprene
Chemical structure of silicone

Uncured silicone rubber contains polymers of different chain lengths.

It always comprises a principal silicon- oxygen chain (the siloxane
backbone) and an organic moiety bound to the silicon.

The properties of silicone rubber vary greatly depending on the organic

groups and the chemical structure. The organic groups may be methyl,
vinyl, phenyl or other groups
A silicon atom has four valence electrons, which is why silicone is often abbreviated
with a Q for “quaternary group”.
.
MQ

MQ, or polydimethylsiloxane (PDMS),

denotes a polymer in which two methyl
groups are bound to the siloxane
backbone.

VMQ

VMQ stands for a polydimethylsiloxane in which a

small number of methyl groups have been
replaced by vinyl groups
PVMQ

PVMQ stands for an VMQ in which a small

number of methyl groups have been replaced
by phenyl groups.

FVMQ

FVMQ stands for an VMQ in which a small

number of methyl groups have been replaced
by trifluoropropyl substituents.
Classification of silicone rubber
Solid Silicone Rubber
Solid silicone rubber contains polymers with a high molecular weight
and relatively long polymer chains. It is referred to as HTV (= high-
temperature-vulcanizing). It has normally two grades depending on
curing process:

1.Peroxide curing grades and

2.Addition curing grades

Liquid Silicone Rubber

Liquid silicone rubber contains polymers of lower molecular weight and
hence shorter chains. It has better flow properties. Liquid silicone rubber
is always addition-curing grades.
General properties of silicone
High bonding energy
Silicone rubber has siloxane bond (Si-O) of molecular structure as the
main chains. While carbon bond, C-C, carries 84.9 Kcal/mol, siloxane
bond carries 106.0 Kcal/mol It shows that siloxane bond has greater
capacity and stability. As a result, silicone rubber has better heat
resistance, electric conductivity and chemical stability than any other
ordinary organic rubbers.
Low intermolecular force with spiral structure
With its coil shaped spiral structure and low intermolecular force, silicone
(dimethylpolysiloxane) is highly elastic and compressible. Furthermore as
methyl groups are located in the outside of coil structure, they are free to
rotate on its own. As a result silicone rubber has outstanding water
repellency and contact resistance.
Heat and cold resistance

Silicone rubber withstands high and low temperatures far better than
organic rubbers. Silicone rubber can be used indefinitely at 150°C with
almost no change in its properties. It withstands use even at 200°C for
10,000 hours or more, and some products can withstand heat of 350°C
for short periods. Silicone rubbers are thus suitable as a material for
rubber components used in high temperature environments.
Silicone rubber also has excellent resistance
to cold temperatures. The embrittlement point
of typical organic rubbers is between -20° to -
30°C, compared to -60° to -70°C for silicone
rubbers. Even at temperatures at which
organic rubbers turn brittle, silicone rubber
remains elastic. Some products withstand
extremely low temperatures of -100°C and
below.
Weatherability
Silicone rubbers have exceptional weatherability. Ozone created by corona
discharge rapidly deteriorates most organic rubbers, but has almost no
effect on silicone rubber. In addition, silicone rubber can be exposed to
wind, rain and UV rays for long periods with virtually no change in its
physical properties.
Moisture and steam resistance
Silicone rubber can be immersed in water (cold water, warm water, boiling
water) for long periods with water absorption of about 1%, and with
virtually no effect on mechanical strength or electrical properties. Typically,
under ordinary pressure, contact with steam causes almost no
deterioration of silicone rubbers. With pressurized steam, however, the
effects increase as steam pressure increases. High pressure steam at
temperatures over 150°C causes breakdown of the siloxane polymer and
a decline in the properties of the rubber.
Resistance to oils, solvents, and other chemicals
Silicone rubber has outstanding resistance to oil at high temperatures.
Among common organic rubbers, nitrile rubber and chloroprene rubber
have somewhat higher oil resistance at temperatures below 100°C, but at
higher temperatures silicone rubber is superior. Silicone rubber also has
excellent resistance to solvents and other chemicals. It is essentially
unaffected by polar organic compounds (aniline, alcohol, etc.) or dilute
acids or bases, with the increase in volume due to swelling in the range of
only 10%–15%. Silicone rubber does swell in non-polar organic
compounds like benzene, toluene and gasoline; but unlike most organic
rubbers, it does not decompose or dissolve, and will return to its former
state when the solvent is removed. Silicone rubber is, however, adversely
affected by strong acids and bases, so it should not be used where it will
come in contact with such chemicals.
Electrical insulation
Silicone rubber has high insulation resistance of 1T Ω m –100T Ω·m,
and its insulating properties are stable over a wide range of temperatures
and across a wide frequency spectrum. There is almost no decline in
performance even when immersed in water, making silicone rubber an
ideal insulating material.

Thermal conductivity

The thermal conductivity of silicone rubber is about 0.2 W/m2·K, a value

higher than that of common organic rubbers. Some silicone rubbers
contain a high proportion of special inorganic fillers to improve thermal
conductivity (about 1.3 W/m2·K), and these are used to make products
including thermal interface sheets and heating rollers.
Flame retardancy
If silicone rubber is brought close to a flame, it will not ignite easily; but
once ignited it will continue burning. It is possible to impart flame
retardancy and/or self-extinguishing properties by adding a small amount
of flame retardant. When they do burn, almost no black smoke or noxious
gas is produced during combustion because these products contain none
of the organic halogen compounds typically found in organic polymer
rubbers.
Compression set
When using rubber materials for gaskets that will be under compression in
heated conditions, the ability of these materials to recover from
compression deformation is a crucial consideration. The compression set
of silicone rubber is consistent over a wide temperature range, from -60°
to +250°C.
Why silicone rubber is the better choice

Longer service life in adverse environments, Virtually unaffected by weather -- rain,

snow, humidity, ozone, or the sun's damaging ultraviolet (UV) rays -- for many years
Organic elastomers may become brittle and crack under prolonged exposure to the
environment

Wider operating temperature range -- from -100 to 316ºC (-148 to 600ºF)Organic

elastomers soften and deform irreversibly at temperatures >100ºC (>212ºF); they
become brittle at temperatures <-25ºC (<-13ºF)

Inherently good electrical insulating qualities that do not change significantly under

exposure to severe environmental stress (heat, cold, moisture, oil, ozone, UV rays)

Retains its natural flexibility and resilience (resists compression set) across a wider

temperature range

Enhances the comfort and feel of consumer goods

Excellent sealing performance

Inert (no taste or smell); many food-contact options

 Heat Resistance Electric Properties Cold Resistance

widely used to widely used for

manufacture rubber
components and
parts used in high-
temperature places
silicone rubber
insulation purposes in maintains its elasticity
high voltage
between -55 and -70°C .
environments.

Radiation Resistance Flame Retardancy Non toxic

Phenyl containing Silicone rubber does not used for baby nipple and
rubber used for easily burn stoppers in medical
cables at nuclear power when in contact with a application. also very
plants and connectors. flame ideal elastomer for
making swimming caps
and goggles.
How silicones work
As Adhesive
When a silicone adhesive cures, it becomes
mechanically and chemically locked in place,
like a puzzle piece.

Mechanical and chemical adhesion

The first requirement of good adhesion is good spreading and wetting. With
its low surface tension and slightly higher critical surface tension of wetting,
polydimethylsiloxane is a master at spreading, wetting, and leveling. It
quickly and completely penetrates into small voids in the surface of the
substrate.

By adding reactive adhesion promoters (silanes) to the adhesive, it can be

designed to chemically bond with anything from metal and glass to paper,
fabric, plastics, and even human skin. This chemical bond further
strengthens the mechanical bond
As defoamers

Silicone antifoams prevent foam from forming. Silicone defoamers

cause existing foam to rapidly collapse. The generic term "antifoam" is
often used to describe both types of foam-control products.

Foam is difficult to break down because it is stabilized by the surface

elasticity and surface viscosity of its film. Silicones have low surface and
interfacial tensions. This enables them to flow easily over the film. They
seek out openings between the foam-stabilizing surfactants at the
liquid-air interface and occupy them. Silicones’ low surface tension and
interfacial properties combined with their lack of foam-stabilization
properties cause the foam wall to thin and collapse.
As lubricants

The purpose of lubrication is to:

1. Separate two moving surfaces with a softer and easier-to-shear liquid

material or lubricant located between the surfaces.

2. Use pressure to increase the liquid’s viscosity, enabling it to separate

the two moving surfaces and reduce the coefficient of friction or the force
needed to move them against one another under an applied load.

Silicone oils, pastes, and greases contain long, linear polymers that slip
easily over one another. This free movement gives them their lubricating
properties.
As water repellent

Silicones have low surface tension,

which enables them to spread and
soak easily into a substrate’s pores.
Their highly flexible and mobile
siloxane backbone enables the water-
repelling methyl groups to orient
themselves toward the surface,
creating a waterproof "umbrella."

What makes this "umbrella" unique is its ability to breathe. Because

silicones have a very open molecular structure, water vapor trapped in
the substrate can easily slip through. Water molecules, however, are
too large to enter.
1 5
3 4

2
6
 1. How silicon is produced

Silicon does not exist on its own in nature. Most of it is bound with oxygen in materials like
sand and quartzite and granite rock. The silicon-oxygen bond in quartz is so stable it can only
be broken by white heat! (usually more than 1300°C.)
Silicon producers reduce high-grade quartz sand to elemental silicon via a
carbo-thermic smelting process:

•This reaction occurs in an electric furnace at <1,400°C (<2,600°F).

•The carbon monoxide gas (g) leaves the furnace so the silicon cannot react
with the carbon to form silicon dioxide.
•The molten elemental silicon, which is about 99 percent pure, is then
cooled and broken into lumps.
When used in silicone production, the silicon is ground into a fine powder
to increase the surface area available for reactions.
 2. How methylchloride is produced

Methylchloride is produced by condensing methanol with hydrochloric acid:

Two methyl groups (CH3) must attach to each silicon atom to produce one molecule of
dimethyldichlorosilane – the basic silicone building block.

Methanol is a major ingredient in the manufacture of silicone.

 3. How chlorosilanes are synthesized
Chlorosilanes are synthesized in a fluid bed reactor at temperatures ranging from 250 to
300°C (482 to 572°F) and at pressures of 1 to 5 bars.

The methyl chloride (CH3Cl) flows through a fluidized bed of silicon metal powder.

The reaction, which is catalyzed by a copper-based catalyst, generates a complex mix of

methyl chlorosilanes

The methyl chlorosilane mix contains:

•A large amount of dimethyldichlorosilane (Me2SiCl2) – the primary building block (bp 70°C)
•A moderate amount of methyltrichlorosilane (MeSiCl3) (bp 66°C)
•Some trimethylchlorosilane (Me3SiCl) (bp 57°C)
•A small amount of methyldichlorosilane (MeHSiCl2) (bp 41°C)
•Plus smaller amounts of other silanes
The chlorosilanes are then separated from one another through the process of fractional
distillation.
 4. How chlorosilanes are distilled

Each of the chlorosilanes produced during the synthesis stage has a unique boiling point.
These boiling points are used to distill the chlorosilanes from one another based on the
number of chlorine atoms attached to the molecule.

Because the boiling points of the various chlorosilanes are so close together, very tall
distillation columns are required to separate them.

Once separated, the chlorosilanes are ready to be turned into useful siloxanes through the
process of hydrolysis and condensation.
 5. How chlorosilanes are hydrolyzed & condensed
When water is added to dimethyldichlorosilane (the principal chlorosilane), the two react
to form disilanol and hydrochloric acid. This occurs because oxygen “likes” silicon more
than chlorine; and chlorine “likes” hydrogen more than oxygen (Me = CH 3).

The disilanols are unstable and strongly attracted to one another. Catalyzed by the
hydrochloric acid, they condense into polydimethylsiloxanes – molecules containing a
backbone of silicon atoms bonded to oxygen atoms.

Hydrolysis and condensation occur spontaneously, simultaneously, and very quickly. These
reactions are a veritable “perpetual chemistry machine,” resulting in a mixture of:
1.Cyclic rings (with 3-6 repeating SiO units)
2.Linear chains (with 30-50 repeating SiO units)
The cyclic and linear oligomers (mini-polymers) are separated from one another and distilled
into cuts based on the number of SiO units in the chain. Some are used as they are
(cyclosiloxane and low-molecular-weight silicone fluids, for example). But the majority are
further polymerized and finished to create a wide array of materials with an amazing range
of performance capabilities.
 How silicones are polymerized & finished
This is the “design center” of silicone manufacturing. It is where silicone scientists engineer an
infinite array of problem-solving and innovation-enabling silicone materials.
Silicone polymerization
Polymerization is the process of linking smaller molecular building blocks to create true
silicone polymers – molecules with many repeating units.
Silicone polymers can be made reactive or non-reactive. They can also be given an array
of organic or inorganic functionalities.

A process called “end blocking” is used to control chain length, molecular weight, and
viscosity.
Because the end-blocker is non-reactive, it prevents further polymerization from occurring.
Most silicone polymer chain ends are terminated with Me 3SiO2.

Silicone polymers can be combined with other ingredients, like fillers, crosslinkers, catalysts,
and pigments to make a wide variety of non-curing (fluids, greases, compounds) and curing
(elastomers, resins, gels) materials.
 Silicone finishing
Finishing is the process of delivering silicone performance in easy-to-use forms that meet
specific manufacturing process, application, or performance requirements.
Silicone finishing processes

•Emulsification – creating stable silicone fluid and water blends; emulsifying simplifies
the formulation process and reduces volatile organic compound (VOC) content.
•Solvent dispersion – dispersing or diluting silicone polymers or resins in various
solvents; the solvent is used to control evaporation rate and achieve compatibility with
other formulation ingredients.
•Compounding – incorporating fillers (such as silica) and/or additives (such as plasticizers
or fire retardants); compounding overcomes dispersion difficulties and helps control flow
rate and film thickness; fillers can also provide reinforcement and extend performance
time.
•Blending – mixing different forms or viscosities of silicones together or mixing them with
other materials; blending creates materials with unique properties and performance
characteristics.
Cure systems for silicone polymers
Silicone fluids can be used "as supplied." In other words, their properties
are fully developed. Silicone gels, elastomers, and resins, however, may
need to be crosslinked (or cured) to achieve their final properties. This
requires the presence of a crosslinker – a silicone molecule with multiple
functional sites that can react or link with another silicone polymer

Under the right conditions (heat, humidity, or ultraviolet light) – and in the
presence of the crosslinker and a catalyst – the individual polymer chains
will link together to form a more complex materia
Crosslinking or cure reactions for silicones

There are three crosslinking reactions for reactive silicone polymers:

A peroxide-initiated free radical reaction, which is activated by heat

Peroxide cure

A condensation reaction, which takes place in the presence of a tin

salt or titanium alkoxide catalyst
Heat cure
RTV moisture cure

An addition reaction, which is generally catalyzed by a platinum or

rhodium complex
Temperature-activated
Photo-initiated
Tire Manufacturing process
 What is a tire

A tire is a ring-shaped vehicle component that covers the

wheel’s rim to protect it and enable better vehicle
performance.

Tire’s contribution in automobiles is the most important

features of its performance.
 Functions of tire

Tires are the only point of contact of the vehicle with the road. The
intensions of the driver are finally executed by the tires. Tires must
perform several functions for the smooth functioning of the vehicle.
Steering
Carrying load
Cushioning
Transmitting drive
Long lasting life

Most of the functions of tire can be achieved with proper maintenance of

air pressure. Hence ability to hold pressure without any diffuse is
important.
 Types of tire

Redial Tire
Radial tire has a ply that is at or near 90
degrees to the direction of travel and the
ply goes from bead to bead.

Bias Ply Tire

Bias ply tire has the ply(s) cut at an

angle and the plies are laid over each
other in a criss cross method
Tire Components
1 Tread

2 Jointless cap plies

3 Steel-cord belt plies

4 Textile cord ply

5 Inner liner

6 Side wall

7 Bead reinforcement

8 Bead apex

9 Bead core
 Tire Components
Tread
Tread is a thick extruded profile that surrounds the tire carcass this is the
layer which comes in contact directly with road. Tread is made of
synthetic/natural rubber with additives to impart wear resistance.

Functions:
Cap: provides grip on all road surfaces,
wear-resistance and directional stability

Base: reduces rolling resistance and

damage to the casing

Shoulder: forms an optimal transition

from the tread to the sidewall
 Tire Components

Jointless cap plies

Above the steel belts and towards the tread are the cap plies, which
are much like the steel belts, except that the sheets are composed
of woven fibers, usually nylon, Kevlar or other fabrics. These plies
are inelastic.

Functions:

Help to hold the tire’s shape

Enhances high speed suitability

 Tire Components
Steel-cord belt plies

Belts are calendered sheets consisting of a layer of rubber, a layer of

closely spaced steel cords and a second layer of rubber. The steel cords
are oriented radially in radial tire construction.

Functions:
Enhances shape retention and
directional stability
Reduces the rolling resistance

Increases the tire’s mileage

performance
 Tire Components
Textile cord ply (body ply)
The body ply is a calendered sheet (two or more sheets are rolled
together such that mechanically they are bonded) consisting of
consecutive layers of rubber and reinforcing fabric. The textile materials
used are rayon, nylon, kevlar, polyester etc. passenger tires usually have
one or two body plies.
Functions:

Give structural strength to the tire.

Controls internal pressure and

maintains the tire’s shape.
 Tire Components
Inner liner

It is an extruded halobutyl rubber sheet compounded with additives that

results in low air permeability.

Functions:

Seals the air-filled inner chamber

Acts as a tube in tubeless tire.

 Tire Components
Side wall
Sidewalls are non-reinforced extruded profiles with additives to give the
sides of the tire good abrasion resistance and environmental resistance.
Additives include anti aging agents to protect the tire from
decomposition when exposed to UV light.

Functions:

Protects the casing from external

damage and atmospheric conditions
 Tire Components
Bead reinforcement Material: nylon, aramid etc.
Functions:
Reinforces the beads and protects the cord
body-plies from damage from rim friction or
from damage when replacing the rim.
Enhances directional stability
Gives steering precision
Bead apex
A triangular piece of stiff rubber which is
fitted onto the bead core to taper the rigid
bead into the flexible body plies in the
sidewall.
 Tire Components
Bead core

Beads are bands of high tensile strength steel wire encased in a rubber
compound. Bead wire is coated with special alloy of bronze to protect
from steel corrosion. Beads are inflexible and inelastic.

Functions:

Ensures that the tire sits firmly on the rim.

Tire Composition
Tire manufacturing process
 Tire manufacturing process
Banbury mixing and milling
A banbury mixer combines rubber stock, carbon black and other
ingredients to create a homogeneous rubber compound. Time, heat and
raw materials are factors utilized to engineer material composition.
Hundreds of components are combined to form rubber utilized for tire
manufacturing. The standard temperature of mixing is about 120°C.
 Tire manufacturing process

Shaping of rubber begin in the milling process. Milling process shapes

the rubber into flat, long strips by forcing it through two set rolls rotating
in opposite direction at different speeds.

Components manufacturing
The compounds are used in rubberising various components, such as
steel cord, Bead wire, Tread, Side wall etc. A tyre is manufactured from
10–30 different components.
 Tire manufacturing process
Belt and Ply Calendering
To produce fabric or steel belts, the fabric or steel cord must go through a
calendering process—an operation in which the rubber compound is
pressed on and into cords. Because the bonding of fabric to rubber or
steel to rubber is critical to performance, the calendering process is an
important step.
 Tire manufacturing process
Belt and Ply Calendering (cont.)

First, a pre-set number of fabric or steel cords under proper tension are
continuously pressed through two steel rollers, and rubber compound is
added to the opening area between the rollers. Then the rubber
compound is pressed into, on top of and on the bottom of the fabric or
steel cords. A continuous sheet of cord-rubber composite goes through
several more rollers to ensure good penetration and bonding between the
rubber and cords. The composite sheet is then cut into appropriate sizes,
shapes, and angles depending on the desired contour of the tire. 
 Tire manufacturing process
Inner liner Calendering
The inner liner is a critical component of modern tires. Inner liners are
calendered into thin sheets of specified thicknesses and then cut to
appropriate widths for use in tire construction.
Bead Component Preparation
The bead component of the tire is a non-extensible composite loop that
anchors the body plies and locks the tire onto the wheel assembly so that
it will not slip or rock the rim.
 Tire manufacturing process

The bead wire loop is made from a continuous steel wire covered by
rubber and wound around with several continuous loops. The bead filler
is made from a very hard rubber compound, which is extruded so as to
form a wedge. The bead wire loop and bead filler are assembled on a
sophisticated machine.
 Tire manufacturing process
Tire Tread Extrusion
Tire tread, or the portion of the tire that comes in contact with the road, consists of
tread itself, tread shoulder, and tread base. Since there are at least three different
rubber compounds used in forming this complex tread profile, the extruder system
consists of three different extruders sharing an extruder head. Three rubber
compounds are extruded simultaneously from different extruders and are then
merged into a shared extruder head. The next move is to a die plate where the
shape and dimensions are formed, and then through a long cooling line—from 100
to 200 feet long—to further control and stabilize the dimensions. At the end of the
line, the tread is cut according to a specific length and weight for the tire being
built. 
 Tire manufacturing process
Tire Sidewall Extrusion
The tire sidewall is extruded in a way similar to the tire tread component;
however, its structure and the compound used are quite different from
tread. Sometimes the sidewall extrusion process can be more
complicated, and four extruders may be needed.

Tire Building
At the center of the machine is a collapsible rotating drum that holds the
tire parts. First the inner layer is wrapped in the drum. Then The tire
assembler starts building a tire by wrapping the rubber-covered fabric
plies of the body around the machine drum.
 Tire manufacturing process
After the ends of these plies are joined with glue, the beads are added
and locked into place with additional tire body plies laid over the beads.
Then sidewalls are placed and then the tire is shaped by inflating the
central section of the drum. Then two steel cord belt plies are applied on
the drum. Finally, the extruded rubber layer for tread is glued into place,
and the assembled tire—the green tire—is removed from the tire-building
mechine.
 Tire manufacturing process
Curing or vulcanizing
Green tires are vulcanized in curing presses. The high steam pressure
conducted into the curing pad inside the curing press presses the elastic
green tire against the tread pattern and side texts inside the moulds,
giving the tire its final appearance.
 Tire manufacturing process
Final Finish & Inspection
Tire inspection is the last step in the tire manufacturing process—an
important step in ensuring quality in both performance and safety. The
tire inspection includes:
Trimming of the mold flash and micro-vents
Visual inspection for appearance and to spot obvious defects
X-ray examination to check internal structure and to spot defects
Tire durability, uniformity, and weight balance inspection

Each tyre is inspected both visually and by a machine. Attention is paid

to any faults and defects with the appearance of the tire in the visual
inspection.

When a tire has been inspected, it will be tested, labelled and

transferred to the warehouse for delivery.
Nitrile Butadiene Rubber - NBR
 Nitrile Rubber (NBR) is commonly considered the
workhorse of the industrial and automotive rubber
products industries

This is usually a co-polymer of 75% butadiene and

25% acrylonitrile monomer.

This is prepared by emulsion polymerization same

as SBR.

 Nitrile rubber, also known as Buna-

N, Perbunan, acrylonitrile butadiene rubber, and NBR, is a
synthetic rubber copolymer of acrylonitrile (ACN)
and butadiene. Trade names
include Nipol, Krynac andEuroprene.
Physical properties of NBR

It is generally resistant to oil, fuel and other chemicals. Increase in

acrylonitrile content increase the resistance.

The freezing point also increase with the increase in nitrile content.

 NBR’s has the ability to withstand a range of temperatures from -40 °C

to +125 °C.

. It has inferior strength and flexibility, compared to natural rubber.

This rubber is also resistant to aliphatic hydrocarbons. It is less resistant

to ozone, aromatic hydrocarbons, ketones, esters and aldehydes.

 This is low in tensile strength as the chain structure of polymer is

irregular.
 cable jacketing
fuel and oil
handling hose hydraulic hoses
non-latex gloves

Temp. range: –40°C to +125°C

NBR O rings

water handling 368,000 metric tons annually (2005)

applications

conveyor belting
seals and
grommets synthetic leather
roll covers
Production process: Nitrile Rubber
•NBR is produced in an emulsion
polymerization system (similar as
SBR). The water, emulsifier/soap,
monomers (butadiene and
acrylonitrile), radical generating
activator, and other ingredients are
introduced into the polymerization
vessels.
•Water is the reaction medium
•Heating of tanks to 30°C-40°C
Fig.: Simplified flow diagram
(incase of hot NBR) for NBR production
•Polymerization proceeds.
•Before shortstop agent such as diethyl hydroxylamine is added to react
with rest of the radicals
•Recovery of unreacted monomers is close to 100%. After monomer
recovery, latex is sent through a series of filters to remove unwanted
solids.
•It is then stabilized with an antioxidant
•The yielded polymer latex is coagulated using calcium nitrate, aluminum
sulfate, and other coagulating agents in an aluminum tank
The coagulated substance is then washed and dried into crumb rubber.
The process for the production of cold NBR is very similar to that of hot
NBR. Polymerization tanks are heated to 5-15°C instead of 30-40°C.
Under lower temperature conditions, less branching will form on polymers
(the amount of branching distinguishes cold NBR from hot NBR). 
 Like most unsaturated thermoset elastomers, NBR requires formulating
with added ingredients, and further processing to make useful articles.
Additional ingredients typically include reinforcement fillers, plasticizers,
protectants, and vulcanization packages. Processing includes mixing,
pre-forming to required shape, extrusion, and vulcanization to make the
finished rubber article. Mixing and processing are typically performed on
open mills, internal mixers, extruders, and calenders. Finished products
are found in the marketplace as injection or transfer molded products
(seals and grommets), extruded hose or tubing, calendered sheet goods
(floor mats and industrial belting), or various sponge articles
Acrylonitrile (ACN) Content

The ACN content is one of two primary criteria defining each specific NBR
grade. The ACN level, by reason of polarity, determines several basic
properties, such as oil and solvent resistance, low-temperature
flexibility/glass transition temperature, and abrasion resistance. Higher ACN
content provides improved solvent, oil and abrasion resistance, along with
higher glass transition temperature. Table below summarizes most of the
common properties for conventional NBR polymers. The direction of the
arrows signifies an increase/improvement in the values.
General Types of NBR
Cold NBR
Acrylonitrile content: ranges from 15% to 51%.
Mooney values: range from a very tough 110, to pourable liquids, with
20-25 as the lowest practical limit for solid material.
temperature range: 5 to 15°C, depending on the balance of linear-to-
branched configuration desired. The lower polymerization temperatures
yield more-linear polymer chains.

Fig: chemical structure of NBR with three possible isomeric structures for
the butadiene segments.
They are made with a wide array of emulsifier systems, coagulants,
stabilizers, molecular weight modifiers, and chemical compositions. Third
monomers are added to the polymer backbone to provide advanced
performance. Each variation provides a specific function
Hot NBR
Hot NBR polymers are polymerized at the temperature range of 30 to
40°C
This process yields highly branched polymers. Branching supports good
tack and a strong bond in adhesive applications.
The physically entangled structure of this kind of polymer also provides a
significant improvement in tear strength compared with a cold-polymerized
counterpart.
The hot polymers' natural resistance to flow makes them excellent
candidates for compression molding and sponge. Other applications are
thin-walled or complex extrusions where shape retention is important.
Crosslinked Hot NBR
Crosslinked hot NBR’s are branched polymers that are further cross-
linked by the addition of a di-functional monomer.
These products are typically used in molded parts to provide sufficient
molding forces, or back pressure to eliminate trapped air.
Another use is to provide increased dimensional stability or shape
retention for extruded goods and calendered goods. This leads to more
efficient extruding and vulcanization of intricate shaped parts as well as
improved release from calender rolls.
Carboxylated Nitrile (XNBR)
Addition of carboxylic acid groups to the NBR polymer's backbone
significantly alters processing and cured properties.
The result is a polymer matrix with significantly increased strength,
measured by improved tensile, tear, modulus and abrasion resistance.
The negative effects include reduction in compression set, water
resistance, resilience and some low-temperature properties.
Bound Antioxidant NBR
Nitrile rubbers are available with an antioxidant polymerized into the
polymer chain.
The purpose is to provide additional protection for the NBR during
prolonged fluid service or in cyclic fluid and air exposure.
When compounding with highly reinforcing furnace carbon black the
chemical reactivity between the polymer and the pigment can limit hot air
aging capability.
Abrasion resistance is improved when compared with conventional
NBR, especially at elevated temperatures. They have also been found to
exhibit excellent dynamic properties
HYDROGENATED NITRILE BUTADIENE RUBBER (HNBR)
PROPERTIES AND APPLICATIONS
HNBR is widely known for its physical strength and retention of properties
after long-term exposure to heat, oil, and chemicals.
Depending on filler selection and loading, HNBR compounds typically have tensile
strengths of 20 – 31 MPa when measured at 23°C.
Compounding techniques allow for HNBR to be used over a broad temperature
range, -40° to 165°C, with minimal degradation over long periods of time. For low-
temperature performance, low ACN grades should be used; high-temperature
performance can be obtained by using highly saturated HNBR grades with white
fillers.
As a group, HNBR elastomers have excellent resistance to common automotive
fluids (e.g., engine oil, coolant, fuel, etc.) and many industrial chemicals. Like NBR,
fluid and chemical resistance improves as the ACN content is increased.
The unique properties attributed to HNBR have resulted in wide
adoption of HNBR in automotive, industrial, and assorted, performance-
demanding applications. On a volume basis, the automotive market is the
largest consumer, using HNBR for a host of dynamic and static seals,
hoses, and belts.
Automotive Industrial Specialized
A/C seals and hoses Blow‐out preventers Hi‐performance
shoe soles
Engine seals, grommets, and gaskets Chevron seals
Fuel system seals and hoses Heat exchanger gaskets
Serpentine (multi‐V) belts Oil field packers
Suspension seals Paper mill rolls
Synchronous (timing) belts Rotary shaft seals Steel
Transmission systembonded piston mill rolls
seals
CHEMISTRY AND MANUFACTURING PROCESS
The basic structure of an HNBR elastomer is provided in Figure 1. As outlined
below, the process begins with the production of an emulsion-polymerized NBR.
This polymer is then dissolved in an appropriate solvent.
After the dissolution process is complete, the addition of hydrogen gas, in
conjunction with a precious metal catalyst at a designated temperature and
pressure, brings about a selective hydrogenation to produce a “highly saturated
nitrile” (HSN) polymer.
 The solvent and catalyst are then recovered and the remaining crumb is dried.
The dried product is then baled and packaged.
Even today, HNBR is still sometimes referred to as “HSN”.

Figure 1: HNBR Structure

Figure 2: HNBR Production Process
 Environmental Deficiencies
• Nitrile should not be exposed to
– direct sunlight
– moderate to high levels of atmospheric ozone
– oxygen
• Must be used in a closed system
Neoprene CH2=CCl.CH=CH2

Chloroprene Rubber (CR), widely known as Neoprene, was one of the first oil
resistant synthetic rubbers. However, it has only moderate resistance to petroleum
based oils and fuels.
. The biggest novelty of neoprene was its inherent resistant benefit to water, as
well as resistance to oils, heat, solvents and even its outstanding resistance to
degradation (better than natural or synthetic rubber). Subsequently it was the
perfect material for several industrial uses such as wire insulation, gaskets, and
hose material for the automobile industry.
It has better chemical, oil, ozone and heat resistance than natural rubber but a
rather lower level of physical properties.
 Chloroprene tends to slowly absorb water and its electrical properties are poor.
 Its gas permeability is fairly low and flame resistance is excellent, chloroprene
being one of the few rubbers that are self-extinguishing.
Chloroprene is made from butadiene, by first reacting it with chlorine in
the gas phase at ca 500 K to form 3,4-dichlorobut-1-ene and 1,4-
dichlorobut-2-ene. The former, on reaction with sodium hydroxide, yields
chloroprene:

Following purification by fractionation, the chloroprene monomer

is emulsified in water and polymerized at about 1000F under
atmospheric pressure in the presence of sulfur, with potassium
persulfate as catalyst
Chloroprene is widely used because of its wide range of useful
properties and reasonable price.
Typical applications include belting, coated fabrics, cable jackets,
seals and gaiters.
Neoprene is a registered trademark of DuPont Performance
Elastomers.

Thiokol

First developed in the early 1920 and may be said to be the first
commercial synthetic rubber produce in USA.

It is a polymer of ethylene polysulphide. It can be prepared by the

condensation of 1,2-dichloroethane with sodium polysulphide.
Particularly useful for linings for petroleum tanks, for building and
caulking (a waterproof filler and sealant that is used in building and
repair to make watertight) putties, cements, and sealants.
Properties

The properties of the polymers depend on the length of the aliphatic

groups and the number of sulphur atoms present in it.
The polymer behaves like elastomer when four sulphur atoms are
present per monomer and it do not behave as elastomer if only two sulphur
atoms are present per monomer. Thus in case of thiokol four methylene
groups should be present in the dihalide to induce elastic properties.
Some of the important properties are:

(i)Thiokol is resistant to the action of oxygen and ozone.

(ii) It is also resistant to the action of petrol lubricants and organic solvents
(iii) Thiokols showed outstanding resistance to swelling by organic solvents
but benzene and its derivatives cause some swelling.
iv) Thiokol films are impermeable to gases to a large extent.
(v) Thiokols are vulcanized with metal oxides such as zinc oxide.
(vi) But Thiokol has poor heat resistance and low tensile strength. The odor of
thiokol is very bad. It tends to lose its shape under continuous pressure

Uses:

(ii) It is used to engine gaskets and other such products that come into contact

with oil.

(iii) Thiokols are used for hoses and tank lining for the handling and storage of

oils and solvents.

Butyl rubber is among the most widely used commercially available
synthetic elastomers in use today. The consumption of the various
grades of butyl rubber is estimated to be over 500,000 tons.
Approximately 80% of this volume is utilized in inner liners for
tubeless tires and in inner tubes. It is particularly useful in instances
where low rates of gas permeability and improved chemical
resistance are important. The Army uses this material extensively for
their chemical protective clothing.
BUTYL RUBBER
It is a copolymer of 98% isobutene and 2% butadinene or isoprene.
The isoprene is added to introduce the necessary ethylenic linkages
for vulcanization.
Properties
Very high tensile strength
Very impermeable to gases including air. (less than 1/10 permeability to air and
other gases of the natural rubber.
Excellent resistance to heat, abrasion, ageing and chemicals
Soluble in hydrocarbon solvents (benzene) but highly insoluble in polar solvents
(alcohol,acetone etc.)
High resistance to ozone/oxidative degradation
It can be vulcanised but cannot be hardened much because of very low
unsaturation.
Butyl rubber or butyl polymer is generally prepared in a slurry process
using methyl chloride as a vehicle and a Friedel-Crafts catalyst as part of
the polymerization initiator. The use of methyl chloride is advantageous
because AICl3, a relatively inexpensive Friedel-Crafts catalyst, is soluble in
methyl chloride, as are the isobutylene and isoprene comonomers.
Additionally, the butyl rubber polymer is insoluble in the methyl chloride and
precipitates out of solution as fine particles.
To achieve high molecular weight, the reaction must be controlled at low
temperatures (-90 to -100°C). The reaction is highly exothermic. The most
commonly used polymerization process uses methyl chloride as the
reaction diluent and boiling liquid ethylene to remove the heat of reaction
and maintain the needed temperature.
•A slurry of fine particles of butyl rubber (dispersed in methyl chloride) is
formed in the reactor.
•The methyl chloride and unreacted monomers are flashed and stripped
overhead by addition of steam and hot water, and then they are dried and
purified in preparation for recycle to the reactor.
•Water is replacing the organic solvent in flash drum. Slurry aid (zinc or
calcium stearate) and antioxidant are introduced to the hot water/polymer
slurry to stabilize the polymer and prevent agglomeration.
•Then the polymer is screened from the hot water slurry and dried in a
series of extrusion dewatering and drying steps. Fluid bed conveyors and/or
airvey systems are used to cool the product to acceptable packaging
temperature. The resultant dried product is in the form of small "crumbs",
which are subsequently weighed and compressed into 75 lb. bales for
wrapping in PE film and packaging.
Reclaimed Rubber

Reclaimed rubber is the product resulting from the treatment of ground

vulcanized scrap rubber tires, tubes and miscellaneous waste rubber
articles by the application of heat and chemical agents, followed by intense
mechanical working. The regenerated rubber has almost the original
plasticity, permitting the same to be compounded, processed and
revulcanised.
During reclamation, the molecular weight of the elastomeric component
is substantially reduced (partial devulcanization process), however the
chemical unsaturation of finished reclaim is essentially unchanged from
that of the original vulcanized scrap.
This partially de-vulcanized product is commonly called reclaimed or re-
generated rubber and can be compounded, processed and re-vulcanized
much like virgin rubber.
Advantages
Reclaimed rubber is widely used in varieties of rubber products -
extruded, calandered, moulded etc.  because of either price advantage
and / or technical advantage . Whole tire reclaim (WTR) contain about
50% of rubber hydrocarbon (RHC) by weight and obviously the price is
much less than the virgin rubber. Part replacement of such virgin
rubber by quality reclaimed rubber works out quite satisfactorily.
Reclaimed rubber having lower Mooney Viscosity compared to virgin
rubber are much easily processed i.e faster processing with respect to
mixing, extrusion, calendering etc.  resulting in better productivity and
lower energy consumption.
Incorporation of reclaimed rubber in the compound helps to reduce die
swelling and shrinkage in extruded and calendered items. Since reclaimed
rubber already contains sulfur it increases the rate of cure of the compound
but are generally free from scorching problem and are safe in processing.
Introduction of reclaimed rubber imparts excellent ageing properties.

Disadvantages:
lower abrasion resistance of the vulcanizate containing reclaimed
rubber thus restricting its usage in such compound which are subjected
to wear and tear. The Tear properties of  reclaimed rubber compound is
also unsatisfactory.
Different manufacturing of reclaimed rubber
Reclaimed rubber can be manufactured by different methods of which the
most important is the Digester process. The raw material for reclaiming is
scrap rubber in a wide variety of forms, mainly tires. The first stage, in all
processes, is the cracking and grinding of the scrap rubber to reduce it to
a crumb or powder passing through a 20-30 mesh screen.

1.         Digester process

2.         Pan process
3.         High pressure steam process
4.         Banbury process
5.         Reclaimator process
Manufacturing process (Digester process)

Processing of scrap tires to make rubber crumb is one of the most

common and useful disposal steps followed in the rubber industry.
Crumb rubber is the name given to material derived by reducing scrap
tyre or other rubber into uniform granules with the inherent reinforcing
materials such as steel and fiber removed along with any other type of
inert contaminants such as dust, glass, or rock.
The first step in the process involves removal or extraction of steel
bead wire from the whole scrap tire. The bead wire is a thick twisted
strand that can be removed from the tire by mechanical “debeading”
The next step is shredding of the whole scrap tire into smaller pieces
(say around 60 mm wide pieces).
The shredded pieces are then fed by means of a conveyor into a
Cracker Mill to reduce size of the pieces further (say around 20 or 30 mm
wide pieces). Typically, the material enters the cracker mill at "ambient" or
room temperature. The temperature of the rubber will rise significantly
during the process due to the friction generated as the material is being
"torn apart."
The cracked rubber pieces are fed by means of a conveyor into a
Breaker Mill or Granulator to produce rubber powder of 20 to 30 mesh
size.
Product size is controlled by a screen within the machine. Screens can
be changed to vary end product size.
Magnetic Metal & Nylon Fiber Separator

The permanent magnetic drum is major cost saving non-electric

separator. It is widely used for removing steel pieces etc. from the
powder material processed in bulk form. It consists of a stationery
permanent magnetic assembly
around which the drum shell
revolves. The assembly has a
uniform magnetic field across the
entire drum. It holds ferrous
particles to the revolving shell
and the non magnetic material

falls freely from the shell. Magnetic flow sweepers are used in
combination with magnetic drum to remove any particles on the flow.
The Nylon fiber separator uses high pressure air flow to separate
nylon fabric fluff from the powder rubber by inertial action. The
separated scrap nylon fluff is conveyed by high pressure air draft
though pipes and collected in bins.
the material is subjected to Vibratory Sieving separating finer mesh
crumb from larger granules. The higher size granules are fed back for
further grinding to finer mesh size.  
Such prepared crumb rubber is mixed thoroughly with water,
process oil(pine tar or aromatic oil) & reclaiming agent (like Diaryl
Disulphide / Di-Xylene Disulphide) and allowed to mature for a while.
This is then fed to Dynamic De -vulcanizer or Autoclave heated by
Steam / Thermic Fluid etc. to desired temperature (around 2000 C) and
pressure ( 20 to 22 Kg / cm²) for a definite period of time (around 4 - 5
hours) during which rubber becomes partially de-vulcanized. The
material inside the autoclave is continuously mechanically worked
upon by means of an agitator (rotating paddle).
This partially de-vulcanized mass is dumped and then fed onto a Two
Roll Mixing Mill followed by preliminary refining on a Kneading Mill
(another two roll mixing mill). At this stage often China clay and / or
Carbon Black may be added which aid in smoothing the dried stock.
Finally, this is then subjected to refining using a Refining Mill where the
rolls are set with very low nip gap. Any hard, improperly de-vuclanized
particles remaining on the rolls are periodically removed to be
designated as “tailings” which is used in low priced molded products.
Refiner produces paper thin layer which is then collected, multiplied to
a thicker sheet and finally made a bale (20-30 Kg), wrapped in
polyethylene sheet & put in paper bag. 
Polymerization techniques
In polymer chemistry, polymerization is a process of reacting monomer
molecules together in a chemical reaction to form polymer chains or
three-dimensional networks.

IUPAC Defination
The process of converting a monomer or a mixture of monomers into a
polymer.
METHODS OF POLYMERIZATION

Polymerization reaction may take place in any of the three states of

matter- solid, liquid, gas. The solid state reactions are usually slow,
they are not considered  practical for this reason. The gas-phase
reactions do take place but normally they require maintenance of high
temperatures, a condition in which almost all high molecular weight
polymers become unstable. Hence almost all commercial process of
polymerization are liquid phase reactions
LIQUID-PHASE REACTIONS:

Homogenous type
 
Bulk Polymerization/Mass Polymerization
 Solution Polymerization
 
Heterogeneous type
 
Emulsion Polymerization
 Suspension Polymerization/Pearl/Bead Polymerization

The homogenous or heterogeneous terms refers only to initial conditions

of the system and are not to the subsequent conditions. For example,
Polymerization of vinyl chloride by mass polymerization method is
considered a homogenous type of reaction, because initially the system
is homogenous. But the polymer being incompatible to the monomer
phase, the system subsequently becomes heterogeneous.
Bulk Polymerization/Mass Polymerization
Bulk polymerization or mass polymerization is carried out by adding
a soluble initiator to pure monomer in liquid state. The initiator should
dissolve in the monomer. The reaction is initiated by heating or
exposing to radiation. As the reaction proceeds the mixture becomes
more viscous. The reaction is exothermic and a wide range of
molecular masses are produced.
Bulk polymerization is carried out in the absence of any solvent or
dispersant and is thus the simplest in terms of formulation. It is used for
most step-growth polymers and many types of chain-growth polymers.
In the case of chain-growth reactions, which are generally exothermic,
the heat evolved may cause the reaction to become too vigorous and
difficult to control unless efficient cooling. Thus bulk polymerization is
always accompanied with good cooling system.
Though, bulk polymerization is commercially less used, polymerization
of ethylene, styrene and methyl methcrylate are carried out by this
method. The heat dissipation and viscosity problem are reduced by
carrying out polymerization at low conversion. Bulk polymerization can
be carried out in conventional stirred tank reactor, long tubular reactor
with high surface to volume ratio and screw extruder reactors.
Advantages of Bulk polymerization

The system is simple and requires thermal insulation.

The polymer obtained is pure as no solvent contamination is present.
Large castings may be prepared directly.
Molecular weight distribution can be easily changed with the use of a
chain transfer agent.
The product obtained has high optical clarity.
Longer polymerization time for high molecular weight polymers.
Disadvantages of Bulk polymerization
Heat transfer and mixing become difficult as the viscosity of reaction
mass increases.
The problem of heat transfer is compounded by the highly
exothermic nature of free radical addition polymerization.
The polymerization is obtained with a broad molecular weight
distribution due to the high viscosity and lack of good heat transfer.
Very low molecular weights are obtained.
Autoacceleration /Gel effect should be there
local hot spots may (runaway reactions) occur resulting in
degradation and discoloration of the polymer product.
Removal of last traces of monomers is difficult.
Solution Polymerization
Solution polymerization is a method of industrial polymerization. In this
procedure, a monomer is dissolved in a non-reactive solvent that
contains a catalyst.
The reaction results in a polymer
which is also soluble in the
chosen solvent. Heat released by
the reaction is absorbed by the
solvent, and so the reaction rate
is reduced. Moreover the

viscosity of the reaction mixture is reduced, not allowing auto

acceleration at high monomer concentrations.
Once the maximum or desired conversion is reached, excess solvent
has to be removed in order to obtain the pure polymer. Hence, solution
polymerization is mainly used for applications where the presence of a
solvent is desired anyway, as is the case for varnish and adhesives. It is
not useful for the production of dry polymers because of the difficulty of
complete solvent removal.
Notable polymers produced using this method are polyacrylonitrile
(PAN) and polyacrylic acid (PAA).
Solution polymerization is used to create polymers and copolymers
by dissolving a monomer and a catalyst in a non-reactive solvent.
 During this process, the solvent liquid absorbs the heat generated
by the chemical reaction which controls the reaction rate.
The liquid solvent used in the solution polymerization procedure
usually remains a solvent for the resulting polymer or copolymer.
This process is only suitable for the creation of wet polymer types, as
the removal of excess solvent is difficult. While removal of excess
solvent is possible using distillation, it is usually not considered
economically possible in an industrial situation.
Advantages of solution polymerization

precise control of the chemical reaction

Heat transfer easy due to presence of solvent
Stirring is easy because the solution is low viscous
control over auto acceleration of the process due to low monomer
concentration
The product obtained is in liquid form and can be directly used for
applications such as adhesives
Disadvantages of solution polymerization
High mol.wt polymers cannot be manufactured by this process
because addition of solvent lowers monomer concentration which
lowers rate of  polymerization.
Complete removal of solvent is more difficult
Polymer obtained is Impure
Requires drying to be used as solid
Solvent may cause chain transfer
The solvents used in the solution polymerization procedure must be
chosen carefully. A solvent that is non-reactive to the monomer is
essential to the process. If a reactive solvent is used, dangerous chain
reaction processes or other undesirable effects can occur as a result of
auto acceleration. Auto acceleration is a reaction that occurs when the
heat produced by polymerization does not dissipated quickly enough by
the solvent. As the heat builds up, the viscosity of the solution increases,
causing the polymerization process to accelerate beyond safe control.
Suspension Polymerization
This method is also used to solve the problem of heat transfer. It is
similar to bulk polymerization where the reaction mixture is suspended
as relatively large droplets (10-1000µm) in an inert medium. Monomer,
initiator and polymer must be insoluble in the suspension media such as
water.
The water to monomer weight
ratio varies from 1:1 to 4:1 in most
polymerization.
The monomer droplets are
prevented from coalescing by
agitation and presence of
stabilizers. The suspension
stabilizers are typically used in less than 0.1 wt% of the aqueous phase.
Two types of stabilizer are used:

Water soluble polymers such as poly vinyl alcohol, sodium poly

styrene sulfonate, hydroxypropyl cellulose etc.
 Water insoluble inorganic compounds such as talc, barium sulfate,
kaolin, calcium phosphate etc.

The rate of suspension polymerization is similar to the rate of bulk

polymerization, but the heat transfer is much better. For suspension
polymerization, initiation, propogation, and termination take place
inside the droplet.

Styrene, acrylic and methacrylic esters, vinyl chloride, vinyl acetate and
tetrafluoro ethylene are polymerized by suspension method.
Advantages of suspension polymerization
Low viscosity due to suspension
Easy heat removal due to high heat capacity of water
The product obtained is in granular form (beads) which is convenient
to handle, isolation is easy
Stirring is easy

Disadvantages of suspension polymerization

Only water insoluble monomers are used
Purity is less when compared to polymer that obtained by mass
polymerization
Yield is low when compared to mass  polymerization
Emulsion Polymerization
Emulsion polymerization is a complex process in which the radical
addition polymerization proceeds in a heterogeneous system. This
process involves emulsification of the relatively hydrophobic monomer in
water by an oil-in-water emulsifier, followed by the initiation reaction with
either a water-soluble or an oil-soluble free radical initiator. At the end of
the polymerization, a milky fluid called “latex”, “synthetic latex” or
“polymer dispersion” is obtained. Latex is defined as “colloidal dispersion
of polymer particles in an aqueous medium”. In general, latexes contain
40-60 % polymer solids and comprise a large population of polymer
particles dispersed in the continuous aqueous phase (about 1015
particles per mL of latex).
Main ingredients of emulsion polymerization

A typical emulsion polymerization formulation comprises four basic

ingredients:
1.Monomer (mostly water insoluble)
2.Dispersion medium (usually water)
3.Emulsifiers/Surfactants
4.Initiator
Further auxiliaries, such as chain transfer agents, buffers, acids, bases,
anti-aging agents, etc., can be used.
Mechanism of emulsion polymerization

A number of mechanisms have been proposed for latex particle

formation by emulsion polymerization. The most important qualitative
mechanism of emulsion polymerization was proposed by Harkins in
1945 and 1946. This theory has been applied only to the emulsion
polymerization of “hydrophobic monomers” (such as sytrene) in the
presence of water-soluble initiators and nonspecific, micelle-forming
emulsifiers at concentrations significantly exceeding the critical
micelle concentration (CMC). There are three stages present in the latex
formation process, namely
1.The initial stage (Interval I)
2.The particle growth stage (Interval II)
3.The completion stage (Interval III)
Figure 1(a): system prior to initial stage
Such a system contains the emulsified monomer droplets (ca. 1-10 μm in
diameter) dispersed in the continuous aqueous phase with the aid of an emulsifier
at the very beginning of polymerization. Monomer-swollen micelles (5-10 nm in
diameter) also exist in this system provided that the concentration of emulsifier in
the aqueous phase is above (CMC). Only a small fraction (approximately 1%) of
the total monomer is actually solubilized by the micelles and only an insignificant
amount of monomer (with hydrophobic monomers such as styrene; about 0.04%)
is dissolved by water. Most of the monomer molecules are in the monomer
droplets which act as a reservoir of monomers during polymerization. Thus, the
system prior to initiation contains mainly three parts: the water phase, large
monomer droplets dispersed throughout the water phase, and the emulsifier
micelles containing solubilized monomer. In addition, a very small amount of
molecularly dissolved emulsifier and monomer-free micelles may exist
Figure 1(b): system during initial stage
The initial stage (Interval I): This stage is also called as “particle formation” or
“nucleation”. With the addition of initiator to the reaction mixture, the free-radicals
which initiate the polymerization are generated in the aqueous phase and diffuse
into monomer-swollen micelles. These micelles are the principal locus for the
initiation of polymer particle nuclei. In other words, they act as a meeting place for
the hydrophobic monomer and the water soluble initiator. Since they exhibit an
extremely large oil-water interfacial area for diffusing of free-radicals and have
high monomer concentration. On the other hand, a small amount of particle
initiation can occur within the continuous aqueous phase. Monomer molecules
dissolved in this phase are first polymerized by waterborne free-radicals. This
would result in the increased hdrophobicity of oligomeric radicals. When a critical
chain length is achieved, these oligomeric radicals become so hydrophobic that
they show a strong tendency to enter the monomer-swollen micelles and then
continue to propagate by reacting with those monomer molecules.
The amount of polymerization occurring in the monomer droplets is regarded as
being a very minor proportion of the whole because of their small surface area for
diffusing of the free-radicals. As a result, monomer-swollen micelles are favored
as the sites of the nucleation of polymer particles. Therefore, this nucleation
mechanism, proposed by Harkins and Smith and Ewart and modified by Gardon,
is called as “micellar” or “heterogeneous” nucleation.
After nucleation, monomer-swollen micelles are transformed into polymer
particles swollen with monomer. The monomers are then acquired to the particles
continuously from monomer droplets by diffusion through the aqueous phase,
because monomer has been consumed with in the reaction loci by the
polymerization process. Thus, the micelles grow from tiny groups of emulsifier
and monomer molecules to larger groups of polymer molecules held in emulsion
by the action of the emulsifier molecules located on the exterior surfaces of the
particles.
This action of the emulsifiers for providing colloidal stability of the growing
particle nuclei occurs by emulsifiers supplied from the aqueous phase; this in
turn tends to leads to dissociation of micelles containing monomer in which
polymerization has not yet started. With the continued adsorption of micellar
emulsifiers on to growing particles, the micelles start to disappear (Figure 1.b).
The particle nucleation stage (Interval I) ends with this disappearance of the
micelles at relatively early in the reaction (e.g. between 10% and 20%
conversion). During Interval I, the rate of polymerization increases with the
increasing time of reaction and only one out of every 100-1000 micelles
becomes a polymer particle. After the particle nucleation process is completed,
this number remains relatively constant toward the end of polymerization.
Figure 1(c): system during particle growth stage
The particle growth stage (Interval II): After the particle nucleation process is
completed, polymerization proceeds homogeneously in the polymer particles as
the monomer concentration in the particles is maintained at a constant
concentration by diffusion of monomer from the monomer droplets. The rate of
polymerization in this stage is constant. In addition, during this stage, the number
of monomer-swollen polymer particles and the monomer/polymer ratio remain
constant. The monomer droplets decrease in size as the size of the polymeric
particles increase. When monomer droplets completely disappear in the
polymerization system (at 50-80% conversion), the particle growth stage (Interval
II) ends (Figure 1.d). In this situation, the polymer particles contain all the
unreacted monomer and essentially all of the emulsifier molecules are also
attached to the surface of polymer particles.
Figure 1(d): system at the end of particle growth stage
Figure 1(e): system at the completion stage
The completion stage (Interval III): This is the final stage of the reaction.
In this stage, polymerization continues within the monomer-swollen
polymer particles which were formed during Interval I, and persisted and
grew during Interval II (Figure 1.d). In the ideal case, the number of
reaction loci during this stage is essentially fixed at the number which
had become formed at the end of Interval I. Whereas, the concentration
of monomer in the reaction loci and the polymerization rate continues to
decrease toward the end of polymerization. Finally, the polymerization is
complete and the conversion of essentially 100% is usually achieved.
The system now comprises a dispersion of small polymer particles
stabilized with the molecules of the original emulsifiers (Figure 1.e).
Advantages of emulsion polymerization include:

High molecular weight polymers can be made at fast polymerization

rates. By contrast, in bulk and solution free radical polymerization, there
is a tradeoff between molecular weight and polymerization rate.

The continuous water phase is an excellent conductor of heat,

enabling fast polymerization rates without loss of temperature control.

Since polymer molecules are contained within the particles, the

viscosity of the reaction medium remains close to that of water and is
not dependent on molecular weight.

The final product can be used as is and does not generally need to be
altered or processed.
Disadvantages of emulsion polymerization include:

Surfactants and other polymerization adjuvant (auxiliary agent)

remain in the polymer or are difficult to remove.
For dry (isolated) polymers, water removal is an energy-intensive
process
Emulsion polymerizations are usually designed to operate at high
conversion of monomer to polymer. This can result in significant chain
transfer to polymer.
Can not be used for condensation, ionic or Ziegler-Natta
polymerization, although some exceptions are known.
 Blown Film
One of the most common methods of film manufacture is Blown Film
(also referred to as the Tubular Film) Extrusion. The process involves
extrusion of a plastic through a circular die, followed by "bubble-like"
expansion.
The principal advantages of manufacturing film by this process
include the ability to:
Produce tubing (both flat and gussetted) in a single operation
Regulation of film width and thichness by control of the volume of
air in the bubble, the output of the extruder and the speed of the haul-
off.
The Process
Plastic melt is extruded through an annular slit die, usually vertically,
to form a thin walled tube. Air is introduced via a hole in the centre of
the die to blow up the tube like a balloon. Mounted on top of the die,
a high-speed air ring blows onto the hot film to cool it. The tube of
film then continues upwards, continually cooling, until it passes
through nip rolls where the tube is flattened to create what is known
as a ' lay-flat' tube of film.
The lay-flat film is then either kept as such or the edges of the lay-flat
are slit off to produce two flat film sheets and wound up onto reels.
Extrusion Blow Molding
The Process
The blow molding machine is based on a standard extruder barrel
and screw assembly to plasticise the polymer. The molten polymer is
led through a right angle and through a die to emerge as a hollow
(usually circular) pipe section called a parison.
When the parison has reached a sufficient length a hollow mould is
closed around it. The mould mates closely at its bottom edge thus
forming a seal. The parison is cut at the top by a knife prior to the
mould being moved sideways to a second position where air is blown
into the parison to inflate it to the shape of the mould.
After a cooling period the mould is opened and the final article is
ejected.
Injection Blow Molding
Injection blow moulding is used for the Production of hollow objects
in large quantities. The main applications are bottles, jars and    other
containers. The Injection blow moulding process produces bottles of
superior visual and dimensional quality compared to    extrusion blow
moulding.
The process is divided in to three areas:

Injection

The injection blow moulding

machine is based on an
extruder barrel and screw
assembly which melts the
polymer. The molten polymer
is fed into a manifold where it
is injected through nozzles
into a hollow, heated preform
mould. The preform mould
forms the external shape and is clamped around a mandrel (the core rod) which
forms the internal shape of the preform.
Blowing
The preform mould opens and the core rod is rotated and clamped into the
hollow, chilled blow mould. The core rod opens and allows compressed air into
the preform, which inflates it to the finished article shape.
Ejection

After a cooling period the blow mould opens and the core rod is rotated
to the ejection position. The finished article is stripped off the core rod
and leak-tested prior to packing. The preform and blow mould can have
many cavities, typically three to sixteen depending on the article size
and the required output. There are three sets of core rods, which allow
concurrent preform injection, blow moulding and ejection.
Extrusion Profiles and Sheet
the extrusion process makes a continuous length of plastic who’s cross
section is constant. This cross section is called the profile. A couple of
examples to illustrate this are hosepipes and curtain tracks.
An electric motor coupled to a hydraulic drive continuously turns a screw,
which is contained in the machines barrel. Plastic granules are fed into
the hopper of the extruder and are drawn down into the screw. The barrel
and screw are heated by external heating elements. As the plastic
granules move along the screw they melt and are forced through a die
which is located at the end of the barrel. The die contains the cross
section of the profile of the extrusion required.
When the plastic profile exits the die, it is still molten. It is channelled into
a water bath which contains sizing formers and guides. During its
passage through this cooling bath, the plastic solidifies and takes on its
final shape.
The still molten plastic coming out of the profile die has no strength. To
ensure that the process has the correct process speed, Take Off Rollers,
adjustable in speed, pull the solidified plastic through the cooling bath

Injection molding

Injection Molding along with extrusion ranks as one of the prime

processes for producing plastics articles. It is a fast process and is used
to produce large numbers of identical items from high precision
engineering components to disposable consumer goods.
Injection molding is a process in which a polymer is heated to a highly
plastic state and forced to flow under high pressure into a mold cavity,
where it solidifies.
Typical Material Used
Most thermoplastics can be processed by Injection Moulding. The
table below lists some of the commonly used materials:

Acrylonitrile-Butadiene-Styrene ABS
Nylon PA
Polycarbonate PC
Polypropylene PP
Polystyrene GPPS
Typical Products Produced
Power-tool housing Disposable razors

Electrical Switches Crates/Recycling boxes

Automotive dash boards Television Cabinets

Drug Inhalation Units Automotive bumpers

Wheelie bins Syringes

Telephone handsets Washing-up bowls
As illustrated in the schematic in Figure , injection molding machines consist of
two principal components: (1) the plastic injection unit and (2) the mold
clamping unit. The injection unit is like an extruder. It is having a barrel with that
is fed from one end by a hopper containing a supply of plastic pellets. In the
interior of the barrel is a screw whose operation surpasses that of an extruder
screw in the following respect: in addition to turning for mixing and heating the
polymer, it also acts as a ram that rapidly moves forward to inject molten plastic
into the mold. A non return valve mounted near the tip of the screw prevents
the melt from flowing backward along the screw threads. Afterward in the
molding cycle the ram retracts to its former position
The clamp unit is concerned with the operation of the mold. Its
functions are to (1) hold the two halves of the mold in proper alignment
with each other; (2) keep the mold closed during injection by applying a
clamping force sufficient to resist the injection force; and (3) open and
close the mold at the appropriate times in the molding cycle. The clamp
unit consists of two platens, a fixed platen and a moveable platen, and
a mechanism for translating the latter. The mechanism is basically a
power press that is operated by hydraulic piston
Step (1) mold is closed and clamped Step (2) melt is injected into cavity.

Step (3) screw is retracted. Step (4) mold opens, and part is ejected.
 Rotational moulding

The rotational molding

process consists out of four
phases. It all starts with filling
the mould with powdered
resin. The inside of this mould
is the negative of the final
product.

When the mould is closed it will be heated in the next phase. In this heating
process, the mould will rotate around the horizontal as well as the vertical axis.
During this heating process the plastic melts and attaches itself to the walls of the
mould. When the powder has molten and it is formed around the walls of the
mould subsequent the cooling process can be started. The cooling happens in the
next phase in which large fans blows air through the mould walls. When the
product is sufficiently solidified, it will be removed from the mould and the
rotational molding process is completed
Structural Foam
Structural Foam is a term commonly used to describe thermoplastic
injection molding components made by the injection molding process
which have a cellular core.
cellular plastic is one in which the outer surface is denser than the inner
layers. The core of the molding is of a honeycomb nature and less dense
than the outer surface. The combination results in a molding of a high
stiffness ratio compared with non-structural foam (compact) moldings.
Illustration 1. Prior to resin injection
the mold is clamped with 1/4 ton per
square inch minimum clamping
pressure. The pre-blended material is
held in the machine in an accumulator
prior to injection. The machine injects
a precisely measured short shot of
material.

Illustration 2. Structural Foam’s

thicker wall section along with the
blowing agent boost allows rapid and
low pressure filling.
 Illustration 3. After resin injection the
cavity pressure is isolated and the
blowing agent pressure continues to fill
the mold cavity.

Illustration 4. The blowing agent

pressure continues to pack the mold
even after the mold cavity is
completely filled. This blowing agent
pressure compensates for volumetric
shrinkage as the plastic cools. The
blowing agent becomes an internal
“cushion”.
Vacuum Forming
1. First, a wooden mould is made. This is made in the shape to which
the plastic will form around. Often where possible, the mould
should have angled edges, in order to allow the tooling to pop out
of the plastic when made.
2. The mould is then placed into the vacuum former oven. A plastic
sheet is then clamped above, but not on the mould
3. In the oven, the heater is positioned above the plastic. This will
heat up, warming the plastic & allowing it to become flexible &
moldable.
4. After a few minutes, the plastic should be at a temperature to allow
molding.
5. The shelf on which the wooden mould is sat on, is moved upwards
& into the flexible plastic using a handle.
6. The vacuum is then switched on, removing all air from the oven.
This allows the plastic to form to the shape of the mould.
7. Once cooled, the sheet is then removed from the oven, the mould
is removed & any excess trimmed.