Natural Rubber

Natural rubber has been known to the inhabitants of South America for
centuries. Christopher Columbus is considered to be the first European to
discover it, during his second voyage in 1493-6. He found the natives in Haiti
playing with balls made from the exudate of a tree called "cau-uchu" or
"weeping wood." The term "rubber" was coined by John Priestly in 1770, when
he found that the material could erase pencil marks.
 Rubber, also called India rubber, latex, Amazonian rubber, as initially
produced, consists of polymers of the organic compound isoprene, with
minor impurities of other organic compounds. Thailand and Indonesia are
two of the leading rubber producers. Types of polyisoprene that are used as
natural rubbers are classified as elastomers.

 Currently, rubber is harvested mainly in the form of the latex from the
rubber tree (Hevea brasiliensis) or others. The latex is a sticky, milky and
white colloid drawn off by making incisions in the bark and collecting the
fluid in vessels in a process called "tapping". The latex then is refined into
rubber that is ready for commercial processing. In major areas, latex is
allowed to coagulate in the collection cup. The coagulated lumps are
collected and processed into dry forms for sale.
Natural rubber is used extensively in
many applications and products, either
alone or in combination with other
materials. In most of its useful forms, it
has a large stretch ratio and high
resilience, and also is water-proof.

Latex being collected from a tapped rubber tree,

Rubber latex
Rubber tree plantation in Thailand
Rubber latex elasticity
 Properties of Natural Rubber

 Rubber exhibits unique physical and chemical properties. Rubber's stress–strain

behavior exhibits the Mullins effect and the Payne effect and is often modeled
as hyperelastic.

 Rubber strain crystallizes. Due to the presence of weakened allylic C-H bonds in

each repeat unit, natural rubber is susceptible to vulcanisation as well as being
sensitive to ozone cracking.

 The two main solvents for rubber are turpentine and naphtha (petroleum).

Because rubber does not dissolve easily, the material is finely divided by
shredding prior to its immersion. An ammonia solution can be used to prevent
the coagulation of raw latex.

 Rubber begins to melt at approximately 180 °C (356 °F).

 Mullins effect ?

The Mullins effect is a particular aspect

of the mechanical response in
filled rubbers in which the stress–strain
curve depends on the maximum loading
previously encountered. The
phenomenon, named for rubber
scientist Leonard Mullins, working at
the Tun Abdul Razak Research
Centre in Hertford, can be idealized for
many purposes as an instantaneous
and irreversible softening of the stress–
strain curve that occurs whenever the
load increases beyond its prior all-time stress–strain curves for a filled rubber showing
maximum value. progressive cyclic softening, also known as the
Mullins effect
 Payne effect ?
 The Payne effect is a particular feature of the stress-strain behaviour of rubber, especially
rubber compounds containing fillers such as carbon black. It is named after the British rubber
scientist A. R. Payne, who made extensive studies of the effect (e.g. Payne 1962). The effect is
sometimes also known as the Fletcher-Gent effect, after the authors of the first study of the
phenomenon (Fletcher & Gent 1953).

 The effect is observed under cyclic loading conditions with small strain amplitudes, and is
manifest as a dependence of the viscoelastic storage modulus on the amplitude of the
applied strain. Above approximately 0.1% strain amplitude, the storage modulus decreases
rapidly with increasing amplitude. At sufficiently large strain amplitudes (roughly 20%), the
storage modulus approaches a lower bound. In that region where the storage modulus
decreases the loss modulus shows a maximum. The Payne effect depends on the filler content
of the material and vanishes for unfilled elastomers.
Physically, the Payne effect can be attributed to deformation-induced changes in the material's
microstructure, i.e. to breakage and recovery of weak physical bonds linking adjacent filler
clusters. Since the Payne effect is essential for the frequency and amplitude-dependent dynamic
stiffness and damping behaviour of rubber bushings, automotive tires and other products,
constitutive models to represent it have been developed in the past (e.g. Lion et al. 2003).
 PROCESSING OF LATEX
 About 3 to 4 hours after tapping, the latex is collected from the tree, treated to prevent premature
coagulation and brought to a factory or a smallholder processing center. Ammonia (about
0.05%) is the most common stabilizer added to the latex though others such as sodium sulfite
and formaldehyde are also still used.

 Mixed stabilizers such as boric acid-ammonia and hydroxylamine-ammonia are used to make
certain special grades of rubber for export or local processing. Where latex itself has to travel a
long distance, higher concentrations of ammonia are used.

 In the initial collection (3 to 4 hours), about 80- 85% of the latex produced by the tree is
collected as latex (field latex). The latex continues to exude very slowly for several hours after
the initial collection.

 This latex is left to coagulate spontaneously in the cup to form "field coagulum,'' or ''cuplump;''
a small amount of latex also coagulates as a thin sheet on the tapping cut to form ''tree lace.''
These are collected on the next tapping day and constitute about 15-20% of total yield.
 On arrival at the factory, the latex is sieved and blended. Field latex is either
concentrated by removing part of the water to give ''latex concentrate,'' or it is
deliberately coagulated and processed into solid dry rubber. All cuplumps are
processed into dry rubber.

 About 7-10% of the world's natural rubber is converted into latex concentrate; more
than 75% of this comes from Malaysia. Concentration is achieved by centrifugation
(most common), by creaming, or by evaporation. The centrifuged latex is shipped as
latex concentrate containing 60% dry-rubber content. The remainder of the latex and
field coagulum are processed into conventional types of rubber such as ribbed smoke
sheets (RSS), pale crepes, and brown crepes, or into the newer forms of technically
specified "block" rubbers(TSR).
 Tapping of Latex

 Rubber tapping is the process by which latex is collected from a rubber tree. The latex is
harvested by slicing a groove into the bark of the tree at a depth of one-quarter inch (6.4 mm)
with a hooked knife and peeling back the bark. Trees must be approximately six years old and
six inches (150 mm) in diameter in order to be tapped for latex.

 The cut is made at an angle of 25-30° to the horizontal to sever the maximum number of latex
vessels. Tapping is done before sunrise, when the turgor pressure in the tree is maximum and the
yield of latex highest. The latex flows from the cut along a metal spout and into a cup made of
glass or glazed earthenware. Tapping is continued at regular intervals by reopening the cut down
the tree.
Isoprene Polyisoprene(Natural Rubber)

Cis-1,4-Polyisoprene
 Properties of Natural Rubber

 Natural rubber has flexibility and strength, as well as impurities and vulnerability to

environmental conditions and hydrocarbons.

 Compared to other rubbers, natural rubber is one of the most flexible types, and it’s
resistant to water and certain chemicals.

 It’s also resistant to cutting, tearing, wear, fatigue, and abrasion, with a working range
between -58 to 212 degrees F.

 Additionally, it has a lot of tensile strength and adheres easily to other materials.

 However, natural rubber isn’t as effective at resisting heat, light and ozone as other
rubbers like neoprene. The material also varies with the tree it’s produced from, as well
as containing natural impurities. While natural rubber is resistant to water and some
chemicals, it’s still vulnerable to fuel, oil, and non-polar solvents.
 Applications of Natural Rubber

 Natural rubber is used in applications requiring a high level of wear and heat
resistance.

 Due to its strength and compressibility, natural rubber is used in engineering

applications, like anti-vibration mounts, drive couplings, springs, bearings, rubber
bands, and adhesives.

 Majority of 50% of natural rubber is used in high-performance tires for race cars,
buses, and aircraft thanks to its strength and heat resistance.

 It’s also used in hoses, automotive parts, foam mattresses, and battery boxes.
 Because of its adhesive properties, natural rubber is also found in rubber cement
and the soil stabilization materials used around new roads.

 Even raw rubber is sometimes used for adhesives and as part of shoe soles.

 Additionally, about 10% of latex harvested from trees is simply reduced down to
60% rubber solution to make products like latex gloves or to use as a coating.
 Synthetic Rubber

 A synthetic rubber is any artificial elastomer. They are polymers synthesized

from petroleum byproducts. About 32-million metric tons of rubbers are produced annually in
the United States, and of that amount two thirds are synthetic.

 Synthetic rubber, just like natural rubber, has many uses in the automotive industry for tires,
door and window profiles, seals such as O-rings and gaskets, hoses, belts, matting, and flooring.
They offer a different range of physical and chemical properties, so can improve the reliability of
a given product or application. Synthetic rubbers are superior to natural rubbers in two major
respects, thermal stability and resistance to oils and related compounds.
 Styrene-Butadiene rubber (SBR)

Styrene-butadiene rubbers (SBR) are the general-purpose synthetic rubbers today, and were
originally produced by government-owned plants as GR-S. They are copolymers, i.e., polymer
chains obtained by polymerizing a mixture of two monomers, butadiene and styrene.

In india, first SBR manufacture was started by “Synthetic and Chemicals”, Bareilly in 1963,
however, this unit has been closed presently.
 Preparation of Styrene-Butadiene rubber (SBR)

 Also known as Buna-S

 Buna-S name is derived  from Bu-butadiene and Na-sodium/ natrium and S-styrene.

 It is a replacement for natural rubber.

 It is a random co-polymer formed by the emulsion polymerization of a mixture of 1,3
butadiene and styrene in the presence of peroxide catalyst at 5 degree Celsius and therefore
the product is called as cold rubber. The rubber obtained is also called Styrene butadiene
rubber (SBR).

 It is vulcanized with sulfur. The rubber is slightly inferior to natural rubber in its physical
properties.

 It is derived from two monomers, styrene and butadiene. The mixture of these two
monomers is polymerized by two basically different processes: from solution (S-SBR) or as
an emulsion (E-SBR).

 The styrene/butadiene ratio influences the properties of the polymer: with high styrene
content, the rubbers are harder and less rubbery.
 Properties of Styrene-Butadiene rubber (SBR)
 Styrene butadiene rubber (SBR) is one of the cheaper synthetic general purpose elastomers that
is sometimes used as a substitute for natural rubber (NR).
 It can be produced by free-radical solution polymerization or by emulsion polymerization either
warm at 30 to 60°C (hot rubber) or cold at temperatures near 0°C (cold rubber).
 Emulsion SBR (ESBR) continues to lose ground to solution SBR (SSBR) which is better suited
for high-performance tires. Nevertheless, emulsion SBR grades still account for more than 75%
of the total world capacity as of 2015. However, more and more SBR is produced by solution
polymerization.
 The addition of styrene lowers the price and contributes to the good wear and bonding properties.
The addition of styrene also improves the strength, abrasion resistance, and blend properties of
polybutadiene.
 The fatigue resistance and low temperature properties of SBR are usually inferior to natural
rubber, whereas its heat-aging properties and abrasion resistance are better. Like natural
rubber, SBR is vulnerable to thermal and oxidative degradation due to the presence of
double bonds in the polydiene backbone.

 Degradation generally occurs through cross-linking, which leads to an increase in stiffness

(embrittlement).

 SBR also has poor chemical resistance, that is, its solvent resistance and weathering
properties are inferior to most other elastomers.

 It has good abrasion resistance and good aging stability when protected by additives.
 Applications of Styrene-Butadiene rubber (SBR)

 It is used for the manufacture of passenger car tyres and treads, motor cycle and
scooter tyres, cycle tyres, floortiles, cable insulation and tubes.

 They are also used for the manufacture of conveyor belts, foot-wares, shoe
soles, hoses and electrical insulation.

 Typical applications include drive couplings, haul-off pads, conveyor belts, and
heels, adhesives, roll coverings and various other molded rubber goods.

 The typical working temperature range is -25°C to +100°C for static sealing.
 Polybutadiene Rubber

 Polybutadiene [butadiene rubber BR] is a synthetic rubber.

 Polybutadiene rubber is a polymer formed from the polymerization of the monomer 1,3-
butadiene.

 The IUPAC refers to polybutadiene as poly (buta-1,3-diene).

 Polybutadiene was first prepared and studied by Lebedev, a Russian, in 1910 using alkali
metals as the initiator in diene polymerizations. His work eventually led to the first industrial
production facility for synthetic rubber.
 Polymerization of Butadiene

 Most commercial processes for the preparation of polybutadiene employ solution

polymerization.
 polymerizations are carried out using essentially pure dry monomer and solvent such as
aromatic, aliphatic, and alicyclic hydrocarbons.
 Catalysts are charged under some inert atmosphere, e.g., nitrogen or argon.
 The polymerization is then carried out at a preselected temperature and time with adequate
agitation of the reaction media. When the desired conversion of polymer is achieved, the
catalyst is deactivated and the polymer stabilized against oxidation.
 The polymer is then recovered from the unreacted monomer and solvent, washed to remove
the catalyst residues, and dried.
 1,3-Butadiene is an organic compound that is a simple conjugated diene hydrocarbon (dienes
have two carbon-carbon double bonds).
 Polybutadiene forms by linking many 1,3-butadiene monomers to make a much longer polymer
chain molecule.
 In terms of the connectivity of the polymer chain, butadiene can polymerize in three different
ways, called cis, trans and vinyl. The cis and trans forms arise by connecting the butadiene
molecules end-to-end, so-called 1,4-polymerisation. The properties of the resulting isomeric
forms of polybutadiene differ.
 For example, "high cis"-polybutadiene has a high elasticity and is very popular, whereas the so-
called "high trans" is a plastic crystal with few useful applications. The vinyl content of
polybutadiene is typically no more than a few percent. In addition to these three kinds of
connectivity, polybutadienes differ in terms of their branching and molecular weights.
 It has been found that a substantial percentage of cis double bond configurations in the
polymer will result in a material with flexible elastomer (rubber-like) qualities.
 In free radical polymerization, both cis and trans double bonds will form in percentages that
depend on temperature.
 The catalysts influence the cis vs trans ratio.
Polybutadiene structures
 Properties of Polybutadiene Rubber

 Polybutadiene rubber (BR, PBD) is one of the cheapest and largest-volume synthetic
general-purpose elastomers which is sometimes used as a substitute for natural rubber
(NR).
 It is produced either by anionic polymerization or by coordination polymerization of 1,3-
butadiene typically in a non-polar solvent.
 The latter is often the method of choice because it allows for both tight control of the
molecular weight (MW) and excellent stereoregularity.
 The 1,3-butadiene can enter the growing polymer chain in three different ways yielding
the three structural isomers cis-1,4, trans-1,4 and vinyl-1,2, as shown in the figure below.
 cis-1,4- and trans-1,4-polybutadiene have a similar low glass transition temperature (Tg) of
approximately -107°C whereas 1,2-vinyl has a much higher Tg of about 0°C and thus is not
suitable for most elastomer applications. Dispite similar Tg's, cis and trans PBD have very
different mechanical properties and uses.
 For example, cis-1,4 rich PBD has very low crystallinity, and the lowest melting point,
whereas polybutadiene with a high trans-1,4 content has much higher crystallinity and is
much harder and less flexible.
 Butadiene rubbers are typically cured by sulfur systems and are often compounded with
other polymers and additives such as oils, fillers, crosslinking agents, and antioxidants,
which allows for a versatile variation of the elastomeric properties.
 Butadiene rubbers are not resistant to oil, gasoline and hydrocarbon solvents. They also have
poor heat resistance and are susceptible to attack by ozone due to the presence of double
bonds in the polymer backbone which are prone to thermal-oxidative degradation.
 Applications of Polybutadiene Rubber

 The major use of cis polybutadiene rubber is in tires.

 To optimize performance such as traction, rolling and abrasion resistance, it is typically
compounded with other elastomers such as natural rubber and SBR.
 Other applications are golf ball cores, inner tubes of hoses for sandblasting, and covers for
pneumatic and water hoses.
 Polybutadiene is also used as a toughening agent in plastics, in particular in high-impact
polystyrene (HIPS) and acrylonitrile-butadiene-styrene (ABS).
 High vinyl and high trans polybutadiene are produced on a much smaller scale and are used
on a much smaller scale. For example, high-vinly PBD is sometimes used in high quality
tires to improve rebound resilience whereas high-trans PBD is used in the outer lay of golf
balls.
 Emulsion polymerization

 Emulsion polymerization is a type of radical polymerization that usually starts with

an emulsion incorporating water, monomer, and surfactant.
 The most common type of emulsion polymerization is an oil-in-water emulsion, in which
droplets of monomer (the oil) are emulsified (with surfactants) in a continuous phase of water.

 The name "emulsion polymerization" is a misnomer that arises from a historical

misconception. Rather than occurring in emulsion droplets, polymerization takes place in the
latex/colloid particles that form spontaneously in the first few minutes of the process.

 Radical initiators include potassium persulfate and hydroperoxides in combination with

ferrous salts. Emulsifying agents include various soaps.
 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 or initiator.
 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.
 Polymerization is initiated by alkyl lithium compounds.
 Water and oxygen are strictly excluded.
 The organolithium compound adds to one of the monomers , generating a carbanion that then
adds to another monomer, and so on.
 For tire manufacture, S-SBR is increasingly favored because it offers improved wet grip and
reduced rolling resistance, which translate to greater safety and better fuel economy,
respectively.