Elastomer

Rubber
• A compound is mixed of the polymer, fillers, softeners, curatives and other additives. The
compound used are: either preformed by calendering, coating on a fabric or by extrusion to
become a component in a final product; or by calendering or extrusion given the right shape
for the final product; or for filling the cavity in a mould.
• For many products like tyres, hoses and belts the preformed parts have to be assembled to
the shape of the final product. The product is then cured at a temperature of 140 - 200 °C to
receive its requested final properties. Through the curing which is the crosslinking process, the
rubber compound properties are changed from a plastic to an elastic state.
• In some cases the curing is done at the same time as the forming of the product i.e. for
extruded products like sealing profiles and cables.
• The cured product may in some cases pass a post-process e.g. post-curing or surface
treatment.
• Finally a quality control operation is done.
Thermoplastic elastomers
• The material is normally supplied ready mixed directly from the raw material supplier.
• The shaping of the products is done by heating the material to a temperature above the
melting point. After the forming process the product is cooled to room temperature. That is
when the material will receive its properties.
• The main processes used are:
o Calendering
o Extrusion
o Moulding by injection in a cavity
• The final product has to pass a quality control operation.
Rubber: Special features
• The processing properties are highly depended on the composition of the rubber compound.
• To achieve the expected properties of a product a proper mixing procedure is essential.
• The final properties for the rubber product is achieved when the curing process is taking place
at a temperature of normally 140 – 200 °C whereby the rubber is cross-linked and obtains its
elastic state.
• The elastomer and hence the compound is viscous, therefore processing (e.g. extrusion or
moulding) of the uncured compound is improved at elevated temperature. The processing
temperature often goes up to 100 - 110 °C and is thereby coming close to the curing
temperature. The compound must be compounded so that scorching (start of curing reaction)
will not start at the processing temperatures.
• At the same time the curing reaction – being depended on time and temperature - must be as
fast as possible to admit short curing time and contribute to a high productivity.
• It was the American, Charles Nelson Goodyear, who in 1839 after many years of unsuccessful
attempts and great personal sacrifice discovered that if you mixed a small amount of sulphur
into the rubber and heated it then it obtained the desired properties.
• This basic discovery, which Goodyear patented in 1844, is what is known today as
vulcanisation (also called curing).
• Vulcanisation is a process in which rubber, by a change of its chemical structure, Charles
Nelson Goodyear using cross-linking, is transformed to an elastic state.
• Vulcanisation improves and amplifies the elastic properties of rubber over a greater
temperature range.
• The discovery of vulcanisation is so vitally important that the rubber industry would never
have been able to develop to what it is today without it
• There are plenty of different rubber types available but still the largest single type used is
natural rubber (NR), produced of latex from the tree Hevea Brasiliensis.
• The synthetic types of polymers, mainly manufactured from oil, have been developed either
to replace or to be used together with NR or to make polymers with properties superior of NR
in special areas, typically with better high temperature resistance, better outdoor resistance
and/or resistance to fuels and oils.
• A common classification of different types of rubber is:
➢General purpose elastomers
➢Special purpose elastomers
➢Speciality elastomers
• General purpose elastomers comprise: Natural rubber (NR), Polyisoprene rubber (IR), Styrene
butadiene rubber (SBR), Butadiene rubber (BR)
• These types have good physical properties, good process ability and compatibility, are
generally economical and are typical polymers used in tyres and mechanical rubber goods
with demand for good abrasion resistance and tensile properties.
• General purpose types constitute the largest volume of polymer used.
Special purpose elastomers comprise:
• Ethylene-propylene rubber (EPM and EPDM)
• Butyl rubber (IIR)
• Chloroprene rubber (CR)
• Acrylonitrile-butadiene rubber or Nitrile rubber (NBR)
They have all unique properties which cannot be matched by the general purpose types and are
very important for manufacturing of industrial and automotive rubber products.
The Speciality elastomers are a great number of polymers with very special properties, in many
cases of great importance for the automotive, aircraft, space and offshore industries.
Some of these polymers are:
• Chlorosulfonated Polyethylene (CSM)
• Acrylic Rubber (ACM)
• Silicone Rubber (PMQ/PV/MQ/VMQ)
• Floursilicone Rubber (FPQ)
• Fluor elastomers (FPM/FFKM/FEPM)
• Urethane Rubber (AU/EU)
• Epichlorohydrine Rubber (CO/ECO/GECO)
Properties
Ageing resistance
All elastomeric materials age more or less with time. The ageing process can be divided into two
main reactions, thermal and oxidative degradation.
Cold stiffening
When an elastomer is cooled down its rigidity increases and when it reaches what is known as the
glass transition temperature, the elastomer becomes completely rigid and brittle. When heated
however the elastomer regains its original properties. There are several methods of determining
the elastomer’s cold stiffening properties like TR-test and Gehman test.The brittle point is the
temperature at which the rubber becomes as hard as glass, brittle and breaks when impacted.
Compression set
By compression set is meant the permanent set that is obtained when the load is removed from a
compressed test piece. The compression set is given as a percentage of the deformation. An
acceptable, low, compression set is important for products which are used for sealing purposes.
Creep
Creep is a slow accumulative deformation in the rubber when subjected to a constant load.
Classification can be done for both elongation and compression and it is given as a percentage of
the original unloaded dimension.
Damping
If a solid rubber ball is dropped onto a hard surface, it will not bounce back to the initial height
due to the damping effect of the rubber. Internal friction and the kinetic energy, which is
transformed to heat in the rubber, cause the damping. The damping is normally measured by
determining the rebound elasticity using an impact pendulum and it is expressed as a percentage
of the initial height of the drop.
Discolouration
An elastomeric material that comes in contact with a surface painted in a light colour can
discolour that material. The discolouration is caused by antioxidants and softeners migrating from
the rubber and entering adjacent surfaces, such as plastic materials or painted surfaces. The effect
can be accelerated by sunlight.
Fatigue resistance
Certain elastomeric products are subjected to dynamic elongation or bending fatigue. The fatigue
resistance is different for different types of elastomer, but can also be affected by the composition
of the compound. Fatigue can be tested using test pieces for elongation or bending. The result is
given as the number of cycles at break. The property is often tested using the products
themselves.
Hardness
The hardness of an elastomeric material is a measure of its rigidity or modulus. This property is
the one most often used in the classification of elastomers in specifications, etc. The
measurement of hardness is carried out by pressing a measuring probe in the form of a truncated
cone or a hemisphere into the rubber. A measurement is made of how far the measuring probe
can penetrate into the rubber and the result is given in Shore A degrees or IRHD (International
Rubber Hardness Degrees).
Ozone resistance
Certain rubber materials, i.e. those with double bonds in the main molecular chain, are prone to
reaction with ozone. That leads to formation of typical cracks which run perpendicular to the
material’s direction of extension. The ozone attack increases with increased elongation of the
elastomeric material.
Resistance to oils, solvents and chemicals
Different types of elastomers have different resistances to oils, solvents and chemicals. These
resistances can, to a certain extent, also be affected by the compound. The resistance is often
tested by immersing the test pieces in the particular medium in question, e.g. oil. After a certain
length of time, sometimes at an elevated temperature, the changes in weight and volume are
measured, and sometimes also changes in mechanical properties.
Stress relaxation
A deformed rubber test piece, whether elongated or compressed, resists the deformation. The
opposing force decreases however with time and that is called stress relaxation. The opposing
force decreases faster at first and thereafter at a decreasing rate, and then finally after a long time
it often decreases quickly again when the life cycle of the material is at its end. Stress relaxation
can be divided into two different processes, physical and chemical relaxation.
Tear strength
Tear strength is an elastomeric material’s resistance to continuous tearing and it is given in N per
mm test piece thickness and determined by the tensile testing of a test piece with a nick in it. A
good tear resistance is related to good abrasion resistance and is an important property for
products.
Tensile strength and elongation at break
The tensile strength at break is a measurement of the material’s strength and is given in MPa. The
elongation is the material’s elongation at breaking point in %. Both the properties are determined by
tensile testing of a dumbbell test piece. Rubber materials produce, as opposed to metals, a non-linear
load/deformation curve. Standard materials normally have a tensile strength of 7 - 20 MPa and an
elongation at break of 200 - 500 %
Tensile stress
The tensile stress of an elastomeric material is a measurement of the elastomers resistance to
extension. Tensile stress is normally given for a particular elongation, 100 or 300 % and is given in MPa.
Tension set
The tension set is the resulting permanent deformation after the removal of the load from an
extended test piece and it is given as a percentage of the elongation.
Wear resistance - abrasion
Wear resistance is, together with elasticity, the property that makes rubber so useful. With regard to
abrasion, rubber is superior to the majority of materials, even steel. This is due to the fact that rubber
is soft and has a damping effect. Testing of abrasion is difficult to carry out in the laboratory and it is
also difficult to achieve a correlation with what happens in real applications. This is why nearly all
abrasion resistance testing is carried out on finished products.
Processes
Curing or vulcanisation
Curing or vulcanisation is a process where the elastomer compound is transformed from a
yielding plastic material into an elastic material. This is done by a sparse network of bonds
being formed between the molecules of the elastomer material. Normally sulphur is used as a
curing agent.
Calendering
A process where you squeeze the elastomer compound into a film (< 0.25 mm), foil (0.25 - 2
mm) or sheeting (> 2 mm).
Compression moulding
A process where the elastomer compound is inserted into a mould cavity, the mould is closed
and the products are cured. Just like making waffles.
Extrusion
A process which shapes the elastomer compound into long strips, e.g. sealing strips.
Injection moulding
A process where an injection cylinder is used to inject the elastomer compound into a closed
mould, in which the product is cured.
Mixing
Mixing is the process whereby the elastomers are mixed with ingredients such as fillers,
softeners, activators, antidegrading agents, processing aids, accelerators and curing agents
Materials
• Accelerators: Compounding materials that facilitate and speed up the vulcanisation. The
accelerators consist of complex organic compounds.
• Activators: Compounding materials which facilitate (activate) the vulcanisation reaction.
• Antidegradant: Compounding materials which protect against oxidation, e.g. antioxidants,
antiozonants and waxes.
• Curing agents: Compounding materials which form cross-links during vulcanisation. The most
common are sulphur and peroxides, but also resins and metal oxides are used.
• Fillers: Compounding materials which dilute the polymer. There are normally two types of fillers:
reinforcing and non-reinforcing. Reinforcing fillers increase the strength of the rubber materials.
They consist of materials with small size particles as reinforcing fillers. The most common are
carbon black and silica. Non-reinforcing fillers are pure diluents which reduce the price and also
impair the mechanical properties. The most common filler is whiting.
• Plasticisers (Softeners): Compounding materials which reduce the hardness of a rubber material,
e.g. oil.
• Processing aids: Compounding materials which facilitate the process, e.g. dispersing agents,
peptizing agents, mould lubricant, etc.
Terms to understand
PHR Parts Per Hundred Rubber (PHR).
• This is used for the calculation of formulas. The compound ingredients are given as parts per
100 by weight of the rubber polymer.
 Crystallisation
• A phenomenon which takes place in certain types of elastomers with highly regular molecules.
• At lower temperatures, the molecular chains arrange themselves close together and the
material hardens.
• When the temperature is increased the material regains its previous properties. This applies
primarily to natural rubber and chloroprene rubber.
Glass transition temperature
• The middle point of the temperature interval where a rubber material is transformed from an
elastic material to a hard and brittle glass-like material.
Basics
• A thermoplastic is shaped in a mould while the molten compound is being subjected to
pressure at an elevated temperature. The shape of the product is then fixed as it cools down
in the mould.
• The thermoplastic article can be reshaped if it is reheated again. The Greek word thermos
means heat and the word plastic means mouldable.
• Thermoplastics are not modified chemically during shaping.
• A thermoset hardens during shaping through chemical reactions, which lead to molecule
enlargement and the forming of crosslinks into a three dimensional network.
• A thermoset cannot be reshaped by recycling the pressure and heat process. After the curing
reaction, the thermoset are in fact not remeltable or soluble in solvents.
• At sufficiently high temperatures the molecules are instead degraded by molecular scission.
Elastomers
• The elastomers include materials with considerable elastic elongation, that is to say materials
which at room temperature can normally be extended to at least double their original
lengths without rupturing and which when the load is removed return to almost their
original lengths.
• This property can be found in polymers with easily moveable chains of molecules.
• In order for the molecular chains, after straightening out, that is to say after deformation, to
be able to return to their original configuration after the load has been removed, they must be
attached to each other at certain points, which is why the structure can be described as a
three dimensional network.
• A hard elastomer which can be an elastomer with so much filler that it cannot be elongated to
twice its length is normally still considered to be an elastomer.
• Rubber with lots of sulphur so called ebonite, is normally considered to be rubber, but should
in fact belong to the thermosets.
• Ebonite has so many crosslinks that a rigid network is created.
Rubber production
Production of rubber goods consists of two basic steps:
1. Production of the rubber itself:
Natural rubber is an agricultural crop
Synthetic rubbers are made from petroleum
2. Processing into finished goods, consisting of:
(a) Compounding
(b) Mixing
(c) Shaping
(d) Vulcanizing
The Rubber Industries
• Production of raw NR might be classified as an agricultural industry because
latex, the starting ingredient, is grown on plantations in tropical climates.
• By contrast, synthetic rubbers are produced by the petrochemical industry.
• Finally, processing into tires and other products occurs at processor (fabricator)
plants, commonly known as the rubber industry.
• The company names include Goodyear, B. F. Goodrich, and Michelin, all
reflecting the importance of the tire.
Production of Natural Rubber
• Natural rubber is tapped from rubber trees (Hevea brasiliensis) as latex
• The trees are grown on plantations in Southeast Asia and other parts of the
world
• Latex is a colloidal dispersion of solid particles of the polymer polyisoprene in
water
• Polyisoprene (C5H8 )n is the chemical substance that comprises rubber, and its
content in the emulsion is about 30%
• The latex is collected in large tanks, thus blending the yield of many trees
together
Recovering the Rubber
• The preferred method of recovering rubber from latex involves coagulation -
adding an acid such as formic acid (HCOOH);
• coagulation takes about 12 hours
• The coagulum, now soft solid slabs, is then squeezed through a series of rolls
which drive out most of the water and reduce thickness to about 3 mm (1/8 in)
• The sheets are then draped over wooden frames and dried in smokehouses
• Several days are normally required to complete the drying process
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
Synthetic Rubber
• Most synthetic rubbers are produced from petroleum by the same
polymerization techniques used to synthesize other polymers
• Unlike thermoplastic and thermosetting polymers, which are normally supplied
to the fabricator as pellets or liquid resins, synthetic rubbers are supplied to
rubber processors in the form of large bales
• The rubber industry has a long tradition of handling NR in these unit loads
Compounding
• Rubber is always compounded with additives
• Compounding adds chemicals for vulcanization, such as sulfur
• Additives include fillers which act either to enhance the rubber's mechanical
properties (reinforcing fillers) or to extend the rubber to reduce cost (non-
reinforcing fillers)
• It is through compounding that the specific rubber is designed to satisfy a given
application in terms of properties, cost, and processability
Carbon Black in Rubber
• The single most important reinforcing filler in rubber is carbon black, a colloidal
form of carbon, obtained by thermal decomposition of hydrocarbons (soot)
• Its effect is to increase tensile strength and resistance to abrasion and tearing of
the final rubber product
• Carbon black also provides protection from ultraviolet radiation
• Most rubber parts are black in color because of their carbon black content
Other Fillers and Additives in Rubber
• China clays - hydrous aluminum silicates (Al2Si2O5 (OH)4 ) provide less
reinforcing than carbon black but are used when black is not acceptable
• Other polymers, such as styrene, PVC, and phenolics
• Recycled rubber added in some rubber products, but usually 10% or less
• Antioxidants; fatigue- and ozone-protective chemicals; coloring pigments;
plasticizers and softening oils; blowing agents in the production of foamed
rubber; and mold release compounds
Mixing
• The additives must be thoroughly mixed with the base rubber to achieve
uniform dispersion of ingredients
• Uncured rubbers have high viscosity so mechanical working of the rubber can
increase its temperature up to 150 C (300 F)
• If vulcanizing agents were present from the start of mixing, premature
vulcanization would result - the “rubber processor's nightmare
Two-Stage Mixing
• 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
Filament Reinforcement in Rubber Products
• Many products require filament reinforcement to reduce extensibility but retain
the other desirable properties of rubber
• Examples: tires, conveyor belts
• Filaments used for this purpose include cellulose, nylon, and polyester
• Fiber-glass and steel are also used (e.g., steel-belted radial tires)
• Continuous fiber materials must be added during shaping; they are not mixed
like the other additives
Shaping and Related Processes
• Shaping processes for rubber products can be divided into four basic categories:
1. Extrusion
2. Calendering
3. Coating
4. Molding and casting
• Some products require several basic processes plus assembly work
Example: tires
Extrusion
• Screw extruders are generally used for extrusion of rubber
• The L/D ratio of the extruder barrel is less than for thermoplastics, typically in
the range 10 to 15, to reduce the risk of premature cross-linking
• Die swell occurs in rubber extrudates, since the polymer is in a highly plastic
condition and exhibits the “memory”property
• The rubber has not yet been vulcanized
Calendering
• 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
Roller Die Process
• Combination of extrusion and calendering that results in better quality product
than either extrusion or calendering alone
Coating
• Impregnating Fabrics with Rubber
• An important industrial process for producing automobile tires, conveyor belts,
inflatable rafts, and waterproof cloth tents and rain coats
Molded Rubber Products
• Molded rubber products include shoe soles and heals, gaskets and seals, suction
cups, and bottle stops
• Also, many foamed rubber parts are produced by molding
• In addition, molding is an important process in tire production
Molding Processes for Rubber
• 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
• Curing (vulcanizing) is accomplished in the mold in all three processes, this
representing a departure from the previous shaping methods, all of which use a
separate vulcanizing step
Vulcanization
• The treatment that accomplishes cross-linking of elastomer molecules, so that
the rubber becomes stiffer and stronger but retains extensibility
• On a submicroscopic scale, the long-chain molecules of rubber become joined at
certain tie points, the effect of which is to reduce the ability of the elastomer to
flow
• A typical soft rubber has 1 or 2 cross-links per 1000 units (mers)
• As the number of cross-links increases, the polymer becomes stiffer and behaves
more and more like a thermosetting plastic (hard rubber)
Vulcanization Chemicals and Times
• As it was first invented by Goodyear in 1839, vulcanization used sulfur (about 8
parts by weight of S mixed with 100 parts of NR) at 140C (280F) for about 5
hours
• Vulcanization with sulfur alone is no longer used today, due to the long curing
times
• Various other chemicals are combined with smaller doses of sulfur to accelerate
and strengthen the treatment
• The resulting cure time is 15-20 minutes
• A variety of non-sulfur vulcanizing treatments have also been developed
Tires and Other Rubber Products
• Tires are the principal product of the rubber industry
• Tires are about 75% of total rubber tonnage
• Other important products:
➢Footwear
➢Seals
➢Shock-absorbing parts
➢Conveyor belts
➢Hose
➢Foamed rubber products
➢Sports equipment
Tires
• Pneumatic tires are critical components of the vehicles on which they are used
• Functions of vehicle tires:
➢Support the weight of the vehicle, passengers, and cargo
➢Transmit the motor torque to propel the vehicle
➢Absorb road vibrations and shock to provide a comfortable ride
• Tires are used on automobiles, trucks, buses, farm tractors, earth moving
equipment, military vehicles, bicycles, motorcycles, and aircraft
PolyChloroprene
• CR (chloroprene rubber, polychloroprene, poly[2-chloro-1,3 butadiene], also
known by the generic names of first ‘DuPrene’ and later ‘neoprene’, is composed
of mostly trans-1.4-polychloroprene with the formula [CH2–CCl = CH–CH2]n.
• It is an important diene-based elastomer produced from its monomer
chloroprene, 2-chloro-1.3-butadiene, by free-radical emulsion polymerization
• Polymerization appears to take place almost entirely in the trans-1,4 form with
some cis-structures, and CR is a crystallizable elastomer.
• Vulcanization of CR is different from conventional methods, because
electronegative chlorine interferes both with the double bond and with the α-
methylenic group by deactivation, so that the common vulcanizing agent sulfur
is ineffective and/or slow for the CR case.
• CR can be vulcanized by heating with zinc and magnesium oxides alone, by
rearrangement and chlorine removal.
• This is exactly the same strategy employed for some of the other chlorinated
polymers, i.e. CSPE.
• For rubbers or elastomers, low values for Tg are essential.
• Most such materials have the general formula −[CH2−CH = C(X)−CH2]n− ;
however, in the case of chloroprene rubber where X = Cl, the size of Cl is
relatively large and polar, hence the Tg value of CR is not expected to be too low.
• In fact it is −20°C, compared with two common rubbers – BR (butadiene rubber)
or poly(cis-1,4-butadiene), where X = H and Tg is −108°C; and NR (natural
rubber) or poly(cis-1,4-isoprene), where X = CH3 and Tg is −66°C.
• CR has perfect mechanical properties and fatigue and tear resistances which are
second only to those of NR, with excellent oil, chemical and heat resistances, low
flammability, high ozone and weather resistance.
• CRs are widely used in general engineering applications, such as in the
production of dipped articles (e.g. gloves), wraps and sheets, as improvers of
bitumen, as the base material for (solvent- or water-based) adhesives, in various
molded goods, in cable coatings, transmission/conveyor belts and profiles, and
primarily as the material for gaskets, tubing, O-rings, seals, weather stripping
and hose (for gasoline).
• The damping capacity of CR is fairly high. Its low permeability to water makes it
suitable for sealer-type finishes for masonry and concrete. Unlike many other
elastomers, CR vulcanizates already have high tensile strengths in the absence of
carbon black and no reinforcing effect is found with any filler.
• From the beginning until the 1960s, chloroprene was produced by the older
“acetylene process”. This process has the disadvantages of being very energy-
intensive and having high investment costs.
• The modern chloroprene process, which is now used by nearly all producers, is
based on butadiene, which is readily available.
• Butadiene is converted into the monomer2-chlorobutadiene-1,3 (chloroprene)
via 3,4-dichlorobutene-1.
• In principle it is possible to polymerize chloroprene by anionic, cationic and
Ziegler- Natta catalysis techniques.
• However, because of product properties and economic considerations, free
radical emulsion polymerization is used exclusively today.
• It is carried out in a commercial scale using both batch and continuous
processes.
• With the aid of radical initiators, chloroprene in the form of an aqueous
emulsion is converted into homopolymers or, in the presence of comonomers
into copolymers.
• The polymerization is stopped at the desired conversion by the addition of a
short stopping agent. The latex is freeze-coagulated on large, refrigerated
revolving drums, from which it is drawn as a thin sheet.
• After washing and drying, the sheet is formed into a rope and then chopped to
form the familiar chips or granules.
• The physical, chemical and rheological properties of the different grades of
commercial polychloroprene are dependent on the ability to change the
molecular structure by changing polymerization conditions, e.g. polymerization
temperature or monomer conversion, polymerization aids (comonomers, type
and amount of molecular weight modifier and emulsifier) and conditions during
finishing.
• The high amount of trans-1,4-units in the polymer (about 90 % at standard
polymerization conditions) leads to synthetic rubber, which has crystallization as
an inherent property.
• Although specifically known and used for its oil resistance, CR is also a very good
general-purpose rubber that can replace NR in most of its uses.
• Some 60% of CR produced is being used in the rubber industry for products such
as molded goods, cables, transmission and conveyor belts.
• CR has been shown to make excellent tires (but cannot compete with other
elastomers in price).
• CR is also a very important source as a raw material for adhesives (both solvent-
based and water-based as well as contact adhesives, ca. 33%).
• CR contact adhesives are used for bonding high-pressure laminates, automotive
trim, roofing-membrane attachment, furniture, kitchen cabinets, custom display
cabinets, interior and exterior panels, wall partitions, etc.
Types of Polychloroprene: Structure and
properties of elastomers
• Normal linear grades (general-purpose grades):
General-purpose grades are mostly produced with n-dodecyl mercaptan as the
chain transfer agent and occasionally with xanthogen disulfides. If xanthogen
disulfides are used, the elastomers are more readily processible and give
vulcanizates with improved mechanical properties.
• Precrosslinked grades:
Precrosslinked grades consist of a blend of soluble polychloroprene and
crosslinked polychloroprene. They show less swelling after extrusion (die swell)
and better calenderability. Precrosslinked grades are particularly suitable for the
extrusion of profiled parts.
• Sulfur-modified grades:
Sulfur-modified grades are copolymers of chloroprene and elemental sulfur. The
viscosity is adjusted – in contrast to general-purpose grades - mostly after
polymerization by “peptization” of the polysulfide bonds by e.g.
thiuramdisulfides as peptization agents.
Sulfur modification improves the breakdown of the rubber during mastication
(lowering of viscosity).
Sulfur-modified grades are used in particular for parts exposed to dynamic
stress, such as driving belts, timing belts or conveyor belts because of their
excellent mechanical properties. But the polymers are less stable during storage
and the vulcanizates less resistant to aging.
• Slow crystallizing grades:
Slow crystallizing grades are polymerized with 2,3-dichloro-1,3-butadiene as a
comonomer.
This comonomer reduces the degree of crystallization by introducing
irregularities into the polymer chain.
High polymerization temperatures also make structural irregularities, if this
comonomeris not available.
Crystallization resistant grades are used to produce rubber articles which have to
retain their rubbery properties at very low temperatures.
 Company name Country capacity (Metric Tons)
➢ DuPont Dow Elastomers USA 100 000
➢ Bayer AG Germany 65 000
➢ EniChem France 40 000
➢ Denki Kagaku Kogyo Japan 48 0
➢ TOSOH Japan 30 000
➢ Showa DDE Japan 20 0
SBR
• Styrene-Butadiene rubber (SBR or Styrene-butadiene) is a synthetic
rubber comprising of styrene and butadiene monomers. The random copolymer
has characteristics like natural rubber and contains: Styrene content in the range
of 10-25% contributing to good wearing and bonding characteristics, while
the butadiene unit is composed approximately 60 to 70% trans-1,4; 15 to 20%
cis-1,4; and 15 to 20% 1,2 configurations for the polymer at 50°C.
 Key benefits of SBR include:
➢ Abrasion resistance
➢ Perfect impact strength
➢ Good resilience
➢ High tensile strength

Main applications of styrene butadiene rubber include

➢ tires and tire products
➢ automotive parts
➢ mechanical rubber goods

Asahi Kasei, Lion Elastomers, Versalis (Eni Group), Kumho Petrochemical etc. are
some of the key producers of SBR.
Structure and Properties of SBR
• SBR manufacturing method was first developed in Germany in 1930s when IG
Farben's Walter Bock and Eduard Tschunkur polymerized a synthetic rubber
called Buna-S from butadiene and styrene in an aqueous emulsion.
• Then the first solution polymerized random SBR grades were produced
commercially by Firestone and Phillips during 1960s.

• Today, there are two major types of SBR with different properties based on their
manufacturing process: Emulsion SBR (e-SBR) - Hot SBR or Cold SBR & Solution
SBR (s-SBR)
Emulsion SBR (e-SBR)
• It can be produced by free-radical emulsion polymerization of styrene and
butadiene either at 50 to 60°C (hot emulsion SBR) or at about 5°C (cold emulsion
SBR).
• The hot emulsion SBR process, which was developed first, leads to a more
branched polymer than the cold emulsion process.
• SBR grades produced using this process have exceptional processing
characteristics such as low mill shrinkage, good dimensional stability, and good
extrusion characteristics
• Cold SBR has a better abrasion resistance and, consequently, provides better
tread wear and dynamic properties.
• It also exhibits superior mechanical properties such as tensile strength compared
to grades produced by the hot emulsion polymerization route.
 Key Features
• Green strength becomes low with increasing oil extension
• Low resilience and low tensile strength
• Outstanding resistance to abrasion
• Low resistance to oil, other hydrocarbon fluids and ozone
• Hot polymers are difficult to process with low green strength
• Poor tear strength
• High styrene resins have good low-temperature properties but stiffen
Solution SBR (s-SBR)
• Solution SBR is produced by termination-free*, anionic solution polymerization
of styrene and butadiene with alkyl lithium initiator (e.g., butyllithium) in a
hydrocarbon solvent, usually hexane or cyclohexane.
*It enables the synthesis of polymers with a very narrow molecular weight
distribution and less chain branching.
• Solution SBR has a narrower molecular weight distribution, higher molecular
weight, and higher cis-1,4-polybutadiene content than emulsion polymerization
SBR.
• s-SBR rarely has more than 2% non-rubber materials in its finished form while e-
SBR may have an emulsifier (soap) content of up to 5% and nonrubber materials
sometimes in excess of 10%.
 Key Features:
• Good resilience and tensile strength
• Outstanding resistance to abrasion and fatigue
• Low resistance to oil, other hydrocarbon fluids and ozone
Styrene Butadiene Rubber Vs Natural Rubber
• While most of the properties of SBR are comparable with NR, but in some respects like
disadvantages include:
➢ Low elongation at break
➢ Low hot tear strength
➢ Hysteresis, resilience
➢ Heat build-up
• But the addition of resins and reinforcing fillers adequately improve these properties.
• However, there are properties which makes it superior over natural rubber. These include:
➢ Better processability,
➢ Slightly Better heat aging
➢ Better abrasion resistance and resistance to degradation (under heat)
• Also, scorch problems are less likely to occur with SBR than with NR.
SBR
• Overall, the most important factors in the commercial viability of SBR making it
material of choice over other rubbers are:
• Wide availability
• Low cost compared with those of all other synthetic rubbers
• Ability to accept high filler levels
• Relatively stable price compared with that of NR
• Overall properties on a cost/performance basis
Processing and Compounding Synthetic Rubber - SBR
• Unlike several other thermoplastics or thermosets (which are supplied in pellets
or liquid resins form), SBR is available to rubber processors in the form of large
bales.
• The processing of rubbers starts by mixing elastomers and additives. After that
rubbers are shaped by using different kinds of processing methods.
• SBR is often compounded with additives such as:
➢ Sulfur for vulcanization
➢ Reinforcing or non-reinforcing fillers to enhance its mechanical properties or to
extend the rubber to reduce cost
• Thanks to compounding, the styrene butadiene rubber further enhanced to
satisfy a given application in terms of properties, cost, and processability.
Fillers
• Carbon Black – Reinforcing Filler - Carbon black is a colloidal form of carbon obtained by thermal
decomposition of hydrocarbons (Soot). It:
– Increases tensile strength and resistance to abrasion and tearing
– Provides protection from ultraviolet radiation
– These enhancements are especially important in tires
• China Clays (e.g. - hydrous aluminum silicates) - It is less reinforcing than carbon black, however, it
is used for non-black rubber applications
• Calcium carbonate is a non-reinforcing filler and mainly added to reduce cost. Due to large
particle size, it does not 'bond' to the polymer in the same way as reinforcing fillers.
• Silica can serve both reinforcing and non-reinforcing functions. It provides dimensional stability,
improved thermal conductivity, and good electrical insulation properties at a low cost.
• Reclaimed (Recycled) rubber is also added as a filler in some rubber product
• Fiberglass and steel are also used as reinforcements.
• Filament reinforcement – It is used to reduce extensibility but retains the other desirable
properties. For example, extensively used in tires and conveyor belts
SBR
• More key additive types very often used in SBR processing include fatigue- and
ozone-protective chemicals; blowing agents in the production of foamed rubber;
flame retardants; curatives; processing aids; mold release compounds etc.
• After compounding, the shaping of rubber is further done by extrusion,
calendaring, coatings, compression molding, injection molding or casting.
• The processing of rubbers is quite difficult. Rubber has high viscosity and that is
why high shear forces are needed in the processing. Vulcanization poses
restrictions too.
• The processing temperature of rubbers is typically 70-140°C.
Optimizing SBR Properties – Rubber Blending
• SBR often blended or copolymerized with other polymers or chemically modified
to further enhance its basic properties. The addition of small amounts of
suitable rubber may improve properties such as oil or ozone resistance or
improve processing behavior.
• However, at times there are certain properties which are adversely affected by
non-compatible rubber blends such as tensile strength, low-temperature
behavior and co vulcanizability.
• SBR is compatible with NR, BR, EPDM, NBR, and CR.
Major Applications of SBR
• The major use of SBR is in the production of tires, particularly car
and lightweight vehicles tires.
• Benefits offered by SBR such as low rolling resistance, high traction during
braking, low abrasion etc. makes it an ideal material for tire applications.
• Cold SBR is used for lighter duty tires and other mechanical goods. SBR is neither
suitable for truck tire treads nor for elastic thread for golf ball manufacture.
• Solution SBR is generally more expensive than the e-SBR and is used in Specialty
applications.
• s-SBR consists of rubber with different styrene and vinyl levels both of
which raise the Tg and hence the wet grip.
• This is particularly useful in high-performance radial car tires and motorcycle
treads.
• Other automotive applications where SBR is blended with other elastomers
include belts, hoses, seals, and various extruded and molded items.
• Non-tire and non-automotive uses of SBR are in industries that require hoses,
belts, gaskets, or seals.
• SBR fulfills the key requirements for these applications like end use and service,
trouble-free processability as well as volume cost & availability of raw material.
• SBR is also widely used in footwear (shoe soles). The main requirements for
rubber sole compounds are abrasion and flex resistance, hardness, traction,
shape retention etc.
• Other applications of SBR include various kinds of solid wheels; roll covers;
coated fabrics; and electrical (wire and cable) insulation.
• The rubber hose is used for lining, insulation or cover which protects from
deteriorating. Properties which make SBR suitable material for choice are its
abrasion and degradation resistance.