INTRODUCTION TO ELASTOMER

MANUFACTURE, PROCESSING AND

APPLICATIONS
Dr. D.K. Setua
Additional Director

Defence Materials & Stores Research &
Development Establishment, Kanpur - 208013
Elastomer manufacturing is interdisciplinary subject covering
Polymer Science, Rubber technology and Engineering.
CAOUTCHOUC used as playing balls by native children
of South America.
Development of materials are structured to meet changing
needs from generation to generation for better performance
standard.


Materials



Natural (sometimes found deficient for special
applications)
Man-made (for mass consumption preceded by a
cycle encompassing R&D, prototype production,
evaluation and marketing
Elastomers have the ability to sustain large extensions
without rupture and return to original shape.
They are polymers consisting of macromolecules of various
length, their nature is dependent on building unit and
arrangement in space.
Macromolecular nature imparts various degrees of freedom,
radius of gyration and free volume.
Compact molecules are tough and have low degree of freedom.
While larger molecules add to strength, the smaller ones impart
lubricating effect to large molecules. Materials, therefore show
viscous and elastic or viscoelastic behaviour.

Structure of Natural Rubber
CH
3
H

C = C


Cis 1,4-Polyisoprene
CH
2

CH
2


(
)
n
Composition of Natural Rubber
Natural Rubber (Hevea) latex varies in its composition, but the
following may be considered as typical.
Composition
Total Solids Content 36%
Dry Rubber Content 33%
Proteinous Substances 1-1.5%
Resinous Substances 1-1.5%
Ash < 1%
Sugars 1%
Water 60%

Tapping
Process of collecting latex from rubber tree
Grades of Natural Rubber
(International Standards of Quality & Packing in Natural Rubber)
Estate Brown Crepes: (Prepared from cup lump, other high-
grade scraps and pre-cleaned tree bark scrap)
Grade Quality
1X Clean Light Brown Crepe
2X
Inferior Grades
3X

Compo Crepes: (Prepared from lumps, tree scraps and
smoked sheet cuttings)
Grades:1,2,3

Estate Brown Crepes: (Prepared from cup lump, other high-
grade scraps and pre-cleaned tree bark scrap)



Properties
Molecular weight of the natural polymer is very high, but varies
between lattices from different clones
The number average molecular weight (M
n
) ranges between 0.25
x 10
6
to 2.71 x 10
6

The weight average molecular weight (M
w
) ranges between 3.4 x
10
6
to 10.2 x 10
6

Poly Dispersity Index (PDI) I;e M
w/
M
n
ranges from 3.63 to 10.94
Very flexible chain back bone leads to a very low glass transition
temperature (T
g
) of -73C
Because of the regular structure, NR is capable of crystallization
and the unstretched raw polymer has a crystalline melting point
(T
m
) of +25C
Crystallization may also be induced by stretching or straining
samples as is done in tensile tests. This is referred to as strain-
induced crystallization.
Vulcanization
Vulcanization is the process
of crosslinking natural
rubber by the application of
heat in presence of sulphur
(crosslinking agent)
Typical accelerated sulphur
vulcanization of NR involves
four components: Sulphur,
Accelerator, Activator, Fatty
acid
Vulcanization system is so
chosen that premature
vulcanization doesnt take
place during shaping
operations
As a precautionary measure
prevulcanization inhibitors
are also used
Conventional
System
(pphr)
Efficient
Vulcanizing
System
(pphr)
NR 100 100
Sulphur 2.0-3.5 0.4-0.8
Accelerator 1.2-0.4 5.0-2.0
Activator
(ZnO)
3.0-5.0 3.0-5.0

Fatty Acid
(Stearic
acid)
1.0-1.5 1.0-1.5

Non-Sulphur Vulcanization

Sulphur Chloride Curing: Curing NR at room temperature and
popularly called as cold cure-----still continues for curing proofed &
solution-dipped goods
Peroxide Curing: Not so popular in NR
Radiation Curing: Potentially attractive due to the absence of toxic
chemicals, but suffer from major disadvantage that there is little scope
for changing properties as is possible in case of sulphur curing by
varying the sulphur/ accelerator ration.
Urethane Crosslinking: Developed by MRPRA for excellent reversion
resistance
Resin Curing: Rarely used
Speciality Natural Rubbers
Constant Viscosity (CV) Rubbers
Deproteinized Rubbers
Skim Rubber
Superior Processing (SP) Rubber
Oil-Extended Natural Rubber (OENR)

NR is obtained from latex of Hevea Brasiliensis. Rubber
obtained from Guayule is substantially different from NR in
respect of microstructure and green strength. Efforts are on
to find out new renewable from other nonlactiferious cells of
vegetable origin.
To meet stringent demand of high abrasion resistance, low
rolling resistance, low heat generation is flexing, higher age
resistance etc., synthetic elastomers are required.

Structure of Styrene Butadiene Rubber

----(CH
2
- CH)
m
----(CH
2
-CH = CH-CH
2
)
n
----
SBR is a copolymer of styrene and butadiene

Mostly commonly encountered SBR is with styrene content of 23%

Increasing styrene content reduces its rubbery characteristics
Compounding
Blends:
Being of low polarity, SBR can practically be blended with all
non-polar rubbers over the whole range of blend compositions.

Binary blends like NR/SBR, BR/SBR and ternary blend like
NR/SBR/BR are of practical interest.

Vulcanizing Agents:
In contrast to NR, SBR requires less sulphur and greater
amount of accelerator
SBR vulcanizates of high hardness can be produced using high
sulphur concentrations
Besides ordinary elemental sulphur, insoluble sulphur is also
used to reduce the tendency of blooming.
Sulphur donors also play an important role in Semi EV and EV
systems.
Most widely used accelerators are: Sulphenamide and
Mercapto accelerators.


















Fillers:
Poor gum strength of SBR necessiates the incorporation
of reinforcing fillers for achieving the desired set of
mechanical properties.
Degree of reinforcement imparted by reinforcing fillers is
higher in SBR than in crystallizing rubbers like NR,CR or
IR.
Silica and Silane coupling agent are commonly used in
tyre tread formulations for better abrasion & tear
resistance.
Non-reinforcing fillers are basically used for cost
reduction or dilution.







Applications
Emulsion SBR (E-SBR): Passenger car and LCV tyre
Belting
Molded Rubber Goods
Shoe Soling
Cable Insulation / Jacket
Hose
Roll Covering
Food Packaging
Surgical & Sanitary Products
Pharmaceutical
Applications
Random Solution SBR (Random L-SBR): Tyres
Belting
Hose
Extruded Articles


Blocky Solution SBR (Blocky L-SBR): Hard Shoe Soling
Roller Covering
Technical Rubber Goods

Thermoplastic SBR: Roofing Applications
Shoe Applications
Nipples for Baby Bottles
Salient Features
Ranked 3
rd
(after NR and SBR) in terms of
tonnage

Structure of Polybutadiene Rubber
------(CH
2
-CH = CH-CH
2
)
n
----
C=C
H H
CH
2
CH
2
(
)
x
C=C
CH
2
)
y
H
CH
2
H

(
Trans-1,4-Polybutadiene
Cis-1,4-Polybutadiene
(CH
2
-CH)
m

CH
CH
2
1,2-Polybutadiene
3,4-Polybutadiene
(CH-CH
2
)
n
CH
CH
2
Types of Polybutadiene Rubber
High-cis (97%)-1,4-Polybutadienes: Polymerized by a Zeigler-
Natta type catalyst system consisting of either a cobalt or a nickel
salt / organic compounds of these metals, with an alkyl aluminium
halide.

Medium-high-cis(92%)-1,4-Polybutadienes: Polymerized by a
Zeigler-Natta type catalyst system based on titanium.

Low-cis (around 40%)-1,4-Polybutadienes: Polymerized in
presence of an alkyl lithium initiator.

Properties
Advantages:
Abrasion Resistance
Groove Cracking Resistance
Low Temperature Flexibility
Heat Aging Resistance
High Resilience at low deformations
Ozone Resistance
Ability to accept higher levels of filler and plasticizer with less
deterioration in properties

Disadvantages:
Poor Tack
Poor Road Grip
Poor Tensile Strength
Poor Tear Strength
Properties
With the exception of Silicone, BR has the lowest glass
transition temperature and therefore the highest resilience of
known rubbers. The expected low heat generation under
dynamic condition is however not observed.
Another peculiarity of BR inherent in its structure is the
spontaneous crosslinking. BR therefore requires much less
sulphur than other diene rubbers.
High flexibility of chains allows the incorporation of high
dosage of black and oil. This justifies its supplementary role in
tyre tread formulations in which it provides improved tread
wear without sacrificing wet grip.
Like SBR, BR also resist breakdown under mechanical shear.
Applications
Tyre Tread:
As blends with SBR in passenger car radials & as blends
with NR in truck tyres
Technical Rubber Goods:
Shoe Soling
Conveyor Belts
Impact Modifiers:
As in high impact polystyrene

COMMON ELASTOMERS AND THEIR BASIC PROCESSES
S.no Elastomer Repeating unit Phase of polymerisation Catalyst system
1.
a) Styrene Butadiene
Rubber (ESBR)

b) Solution SBR


c) S-B-S
Butadiene Styrene






Emulsion polymerization
uses soft or demineralised
water

Solution polymerization



Free radical


Zeigler-Natta

Stereospecific Catalyst
2.
Polybutadiene Butadiene Solution polymerization





Emulsion
polymerization
Stereospecific multicomponent
catalyst system based on
Nickel/ Cobalt Vanadium / Al
Zirconium or recent one uses
Neodymium


Free radical
3.
Polyisoprene Isoprene Solution polymerization
Zeigler-Natta Trialkyl
aluminium and titanium
tetrachloride gives Cis 1,4
polyisoprene
4.
Butyl Rubber (IIR) Isobutene & Isoprene
Continuous
solution process
AlCl
3

5. Ethylene Propylene rubber (EPM
& EPDM)
Ethylene Propylene
Solution
polymerization
Zeigler-Natta / Ionic
catalyst based on
Aluminium. Present
improvements are on use
of Metallocene
6.
Polychloroprene 2-Chloro-1,3 Butadiene Emulsion
Potassium or
Ammonium. Present
improvements are on use
of Metallocene
7.
Nitrile Rubber (NBR) Butadiene Acrylonitrile Emulsion
polymerization
Paramenthane
hydroperoxide.
Potassium persulphate
8.
Nitrile carboxylated Rubber
(XNBR)
Acrylonitrile Butadiene carboxyl
Vinyl Monomer
Emulsion Free radical
9.
Epichloro-hydrin rubber
(ECO)
Ethythenoxide Propylene oxide
Ethylene Chlorohydrin
Solution
Red Lead 2-
Mercaptoimidazoline
10. Ethylene Acetate rubber (EAM)
Ethylene Vinyl Acetate Solution Ionic catalyst
11.
Silicone rubber Organochloro Silanes
Bulk / Solution
Ionic
12. Polyisobutylene rubber
Isobutylene Solution Ionic
13. Urethane rubber (AU & EU) Di-isocyanate and glycol Bulk
condensation
Catalyst used for
condensation
14.
Ethylene / acrylic elastomer Ethylene acrylic esters
Solution /
Emulsion
Free radical
15.
Fluorinated rubber (FKM)
Vinylidiene Fluoride
tetrafluoroethylene hexafluoroethylene
1-hudropentafluoro0ropylene perfluoro-
methyl vinyl ether
Emulsion
polymerization
Ammonium persulphate

The following synthetic elastomers are manufactured in India:-
Acrylonitrile Butadiene by Gujarat Apar Polymers Ltd.
Rubber (NBR)
Poly-butadiene by IPCL
E-SBR by Synthetic & Chemicals Ltd.
EPDM by Herdellia Unimers
EVA by NOCIL
SBS by ATV Projects Ltd.
Lattices of elastomers also find many diversified applications.
Synthetic latex business is regarded as a fast growing sector in rubber
industry. Growth of these products is predicted to be 3% annually
world over for the next five years.
Different types of Lattices
1. Styrene Butadiene SBR
2. Carboxylated SBR X-SBR
3. Vinyl pyridine / SBR P-SBR
4. Nitrile and Carboxylated NBR NBR & XNBR
5. Polychloroprene CR
6. Ethylene Vinyl Acetate EVA

Liquid elastomers are made using ionic and stereospecific catalysts.
Nitrile and Butyl, low molecular weight elastomers are commercially
manufactured by controlling their chain length and are available in
solid form of 60-70%.
The major uses are:--
Reactive binders for abrasives and friction material.
Rheology modifiers
Vehicle for dispersion
Elastomer processing aid
Asphalt modifier
Cold moulding, electrical potting and sealants etc.