TUT Plastics and Elastomer Technology

MOL-5906 Elastomers (Autumn 2008)

Introduction to elastomeric materials

The natives of South America alighted on exploiting the latex of Hevea Brasiliensis
rubber tree to produce waterproof footwear, among others, by soaking their feet to
liquid, latex, tapped from tree. From the Indian word “caa-o-chu” (a weeping tree),
inherit the words like caoutchouc in English and French, Kautschuk in German
language, caucho in Spanish, caucciù in Italian. The word rubber originates from the
early applications of rubber, i.e. from the property of caoutchouc to rub out pencil
writing.
In the 18th century when rubber appeared in Europe it was used for the fabrication of
suspenders and straps. Different kinds of materials were impregnated to be waterproof
by rubber. However, the performance of the rubber articles was quite poor, because
rubber was at that time still gummy and the fluctuation of temperatures caused great
changes in products. It was only at year 1839 when Charles Goodyear conceived
nearly by accident the vulcanization of rubber, which made rubber as an elastic
material capable of preserving its characters in large temperature range.
The idea of this part of “Professional Development Learning program for Rubber
Industries” course is to give students an extensive view of the elastomeric materials.
The structure and characters of most typical rubber and thermoplastic elastomers will
be examined during this course. In addition, familiarizing with applications and testing
of different elastomers, design and construction, as well as recycling of elastomeric
products are to be handled.
Definitions of elastomeric materials and rubbers
Low molar mass molecules, which can react with same or different
Monomer
kind of monomers, thus composing a polymer.

Macromolecules built up by the repetition of primary monomer units

Polymer in a way that properties of the material do not alter significantly in
consequence of insertion or removing of some primary units.

Homopolymer Polymer, which has been made up of only one kind of monomer.

Copolymer Polymer, which has been made up of two or more monomers.

High molar mass material, which, when deformed at room

Elastomer temperature, reverts quickly to nearly original size and form, when
the load causing the deformation has been removed (ISO 1382:1996)

Cross-linked, vulcanized, free of solvent elastomer, which contracts

to its 1,5 -fold original length in one minute, after the tension which
Rubber
has stretched the rubber to its double length in the room temperature,
has been released.

Cis-1,4-polyisoprene achieved from the latex of the rubber tree, most

Natural rubber
frequently from Hevea Brasiliensis plants.

Rubber, which has been produced by polymerizing one or more

Synthetic rubber
monomers.

Irreversible process, in which the rubber compound is transformed in

a chemical reaction (e.g. cross-linking) to a three dimensional
Vulcanization, network, which preserves its elastic characteristics at wide
cross-linking temperature range. The term vulcanization is connected to the use of
sulphur and its derivatives, whereas the term cross-linking is usually
connected with sulfur-free processes.

Thermoplastic elastomers are in many respects rubber like material,

Thermoplastic which need not to be vulcanized. Rubbery character disappears at the
elastomer processing temperature but revert when material has reached the
operating temperature.

Group of rubber elastomers, which produce same kind of characters

Rubber type
and applications to products made of that group of elastomers.

Vulcanized mixture of rubber fulfilling certain set of quality

Rubber quality
requirements.

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Manufacturing process of rubbers

The manufacturing process of synthetic rubber starts by manufacturing raw rubber.

The first step in this process is polymerization. This is a chemical reaction, where
small molecules (monomers) are joined together to form large molecules (polymers).
Natural rubber is collected ready polymerized form. So the manufacturing process of
natural rubber starts by mastication. Mastication is a process where molecules are
physically or chemically shredded so that mixing and processing would be easier. This
makes the rubber softer. Most synthetic rubbers do not need the mastication because
they are made of shorter molecules. Peptizing agent prevents reactions between the
broken chains.
Rubbers consist of elastomer and additives. Additives may be for instance fillers and
vulcanisation agents. The purpose of additives is e.g. to improve properties or
processability. Rubbers can be processed in many ways (e.g. compression moulding,
injection moulding and extrusion). During the process or after that the rubber is
vulcanised (cross-linked) when rubber elasticity and dimensional stability will appear.
After the process and vulcanisation rubber product often has to finish by e.g. cutting.

Behaviour of elastomers
The predominant property of elastomers is the elastic recovery after deformation in
compression or tension. Even after stretching of an elastomer many times its original
length, it will return after removal of the tension under ideal circumstances to its
original shape and length. In addition to this, elastomers are characterized by a great
toughness under static or dynamic stresses, a better abrasion resistance than that of

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steel, by an impermeability to air and water, and in many cases, by a high resistance to
swelling in solvents, and to attack by chemicals. Elastomers, like many other
polymers, show viscoelastic properties, which nowadays can be tailored for numerous
special applications, like e.g. tyres, vibration and shock isolation and damping. These
properties are exhibited at wide temperature range, and are retained under various
climatic conditions and in ozone-rich atmospheres.
Rubbers are also capable of adhering to most other materials, enabling different hybrid
constructions. In combination with fibers, such as rayon, polyamide, polyester, glass,
or steel-cord, the tensile strength is increased considerably with a reduction in
extendibility. By joining elastomers with metals, components, which combine the
elasticity of elastomers with the rigidity of metals, can be achieved.
The property profile, which can be obtained with elastomers depends mainly on the
choice of the particular rubber, the compound composition, the production process,
and the shape and design of the product. Depending on the type and amount of rubber
chemicals and additives in a com- pound, vulcanizates with considerably different
properties with respect to hardness, elasticity, or strength are yielded.
The viscoelasticity of elastomers and rubbers is easy to detect in practice. When
stretching a cross-linked elastomeric band, rubber band, a temperature rise of the band
can be observed as a consequence of emerging heat due to friction of viscous
deformation. The force that induces the recovery of deformed rubber, is dependent on
the entropy of rubber material.

The structure of elastomers at strain and dependence of elastic force on temperature T

and entropy S (Gedde).
The temperature range of elastic behavior of elastomers is limited by glass transition
temperature. At the temperatures lower than glass transition temperature the movement
of molecule chains is very restricted, and the large elastic deformations are not
possible. Elastomers are rigid and fragile materials under the glass transition
temperature. The physical background of elastomeric behavior is described in more
detail in the PDLRI section rubber physics.

General properties of elastomers

The property profiles of elastomers depend mainly on the choice of the particular
rubber, the compound composition, the production process, and the shape and design
of the product. Moreover, the character of loading e.g. whether it is static or dynamic,

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influences strongly in elastomer properties. Satisfactory properties can only be
obtained by proper compounding of elastomers with chemicals and additives, and
subsequent vulcanisation at adequate circumstances. Depending on the type and
amount of rubber chemicals and additives in a compound, and depending on the
degree of vulcanization, a given rubber can yield vulcanizates with considerably
different properties with respect to hardness, elasticity, or strength.
In the following chapters, the most frequently specified properties of rubbers will be
handled, with reference to ASTM 2000, SFS 3552 and SIS 162602 standards. Many of
the properties are presented in more detail in the PDLRI section testing and properties.
The comparison of the properties of different rubber types and also thermoplastic
elastomers is shown in the attached table, in context with handling of rubber types.
Thermal expansion
The amounts of thermal expansion of different rubbers vary remarkably, depending
e.g. on elastomers, fillers and their shares in the rubber compound. Generally speaking,
the linear thermal expansion coefficient of elastomeric materials is five 5 ... 20 -fold
compared with e.g. that of steels. Consequently, the heat shrinkage of molded
elastomer products can be several percent.
Hardness
The hardness of rubber is determined and measured based on a protrusion depth of a
standardized body under well-defined conditions. Hardness is one of the most
frequently measured property of rubbers. Hardness is commonly quantified with IRHD
or Shore 0 ... 100 scale. The hardness of conventional elastomeric product is around 50
... 70 IRHD.
Tensile properties
In order to obtain tensile material properties, it is customary to define the stress, which
is required to certain deformation, strain (see figure). Frequently, the stress values
corresponding 100 or 300 % deformation are chosen to describe tensile stiffness ( s
100 or s 300 module). The modulus at the early stage of tensile test is called Young's
modulus. The stress at the break of the sample is defined as tensile strength (MPa) and
the breaking deformation compared to the original length as elongation at break (%).
The values of tensile strength of rubbers and thermoplastic elastomers are taken as
satisfactory/good on the range 7 ... 15 MPa and excellent when the values are over 15
MPa. The values of elongation at break vary on the range 300 – 1000 %.

Typical tensile curves of different plastics (A, B and C) and rubber (D).

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Modulus of elasticity
As described earlier, aside from the tensile strength, the force is measured which
corresponds to a certain strain and is calculated to correspond to the original cross-
sectional area. This stress value is a measure for the stiffness of a rubber sample and
one of the most important measures for the evaluation of vulcanizates. The stress value
is often called a modulus. The use of the word modulus is incorrect, however, since the
stress value is always taken in an area where Hooke's law (Young's modulus with low
strains) does not apply any more.
The statistical mechanical theory of rubber elasticity gives the following equation for
the force and stress:

Here R is general gas constant, T is absolute temperature, Mc is the number average

molar mass of the chain segments between the cross-links of rubber, λ is relative
elongation (L/Lo) and ρ is the density. The equation contains in the form of “modulus”

the facts that tension increases with raising temperature and increasing degree of cross-
linking (decreasing Mc ). In addition, the stress depends on deformation speed and the
form of deformed body. The shape of the body is typically described by shape factor S.
Tear strength
Tear strength is defined as the resistance force, which a rubber sample, modified by
cut ting or slitting, offers to the propagation of the tear. Multitude of test specimen
configurations has been presented for tear test.
The force (kN) to tear the sample, divided by the thickness (m) of the sample is
defined as the value of tear strength. Also the tear energy - which is largely
independent of sample geometry, has gained importance in material evaluation.
The values for tear strength of elastomeric materials with good tear properties are on
the range 50-100 kN/m and values over 100 kN/m are excellent. Natural rubber is one
of the best elastomers in this respect.
Permanent set, relaxation and creep
Permanent set is a measure for the viscous behaviour of the elastomers. It can be either
compression or tension type of set. Permanent set is a measure for the viscous
behaviour of the elastomers.
The compression set CS, and also tensile set, is given at constant deformation by the
relation:

where h0 is the initial height of the sample before deformation, h1 is the height during
deformation and h2 the height after a certain amount of time after deformation, for

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example 50%. Frequently, the samples are stored in the compressed state at an
elevated temperature in order to simulate the requirements of gasket materials where
changes due to aging effects play a role.
Relaxation and creep express the time dependence of the stress or the deformation.
During the relaxation test the strain is kept constant and the change in stress is
monitored, during the creep test the stress is kept constant and the time dependent
strain is measured. The stronger the viscous component, the more pronounced
relaxation or creep is.

Abrasion resistance
Abrasion resistance describes the materials durability under wearing conditions. Most
rubbers have exceptionally good abrasion resistance, which is a consequence of
rubbers' ability to creep over the irregularities of wearing counterpart in sliding. A
good wearing resistance is typically achieved with vulcanized general-purpose
rubbers, NR, IR, SBR and BR. In an environment with oil exposure, polychloroprene
(CR) and nitrile rubber (NBR) are the rubbers with best abrasion resistance. Buthyl
and ethylene-propylene rubbers on the other hand, have the best abrasion resistance at
elevated temperatures.
Resilience and hysteresis
The ratio of stored, reversible energy in deformation and the dissipated energy is
described with the term resilience. The resilience can be easily evaluated by using
modern dynamic mechanical analyzers. Since the dissipated mechanical energy during
the dynamic loading is transformed into heat because of molecular friction, the viscous
component may be measured directly by monitoring the increase in heat of the sample
(heat build- up).
The energy dissipation property of rubbers is often called also internal dampening or
hysteresis loss. The hysteresis losses of rubbers depend quite strongly on temperatures
and loading amplitudes, and are typically of the order of 5 ... 40 %.
Electrical properties
Most general-purpose elastomers, like natural rubber (NR) and variety of synthetic
elastomers (e.g. SBR, IR, BR, EPDM, IIR, MQ ) exhibit a very low electrical
conductivity and are, therefore, suitable as electrical insulating materials. However,
some other types like CR and NBR contain electrically polarizable groups or dipoles
and are, therefore, less suitable as electrical insulators.
The range of electrical conductivity of all elastomers can be affected over a wide range
by the composition of the compound or by the addition of insulating (e.g. light) fillers
or of conducting substances, especially carbon blacks or antistatic plasticizers.
Rubber articles with such a high electric conductivity can be produced, too, e.g. for the
prevention of static electricity build-up.

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Chemical endurance
Some fluids can cause big volume changes of rubbers, which derive from the
impregnation of the fluid among the macromolecules (swell), or from the solution of
rubber ingredients into the fluid (shrinkage). Water, acids and bases may also bring
about some hydrolysis for certain rubbers, leading to impair of tensile properties.
Nitric acid and concentrated hydrochloric acid react with most rubbers and deteriorate
them.
Ozone and weathering resistance
A deformed rubber with strained parts, gets often cracks outdoors, because the double
bonds of macromolecules are broken by the oxygen, ozone or electromagnetic
radiation. Adding anti-aging agents, like waxes, antioxidants and antiozonants, can at
least partially, prevent the damages.

Dynamic properties
Elastomers are viscoelastic materials. It means that part of the deformation is
recovered after the load is removed and part of the deformation is permanent. Dynamic
properties of elastomers depend on temperature, type frequency of loading and
amplitude of deformation. Also shape of the product affects on dynamic properties.
Values describing dynamic properties:

• Dynamic modulus E*
o E* = E' + iE''
• Elastic modulus = storage modulus E'
o Represents the stiffness of the material
• Viscous modulus = loss modulus E''
o Represents the amount of energy dissipated into heat under load
• Tan delta, loss factor
o The ratio of loss and storage modulus
o The smaller the value of tan delta, the more elastic the material
o tan delta = E''/E'

Classification of elastomers
Elastomers have been classified to groups according to similar properties and
applications. Rubber types that have been standardized (ASTM D 2000, SFS 3551,
SIS 162602) are suitable for several industrial applications (e.g. tyres, belts, tubes and
seals).

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Rubber type 61 (rubbers for general use)
Type 61 rubbers are used when the product does not require special properties, like 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 rubber type that has not standard. Butyl rubber (IIR), chlorobutyl
rubbers (CIIR) and bromobutyl rubbers (BIIR) are elastomers in 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 mineral oils.
Rubber type 63
Rubbers in this group have good oil resistance, but ozone and weather resistance are
weak. Applications are products that are touched with oils. Nitrile rubber (NBR) is
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 poly-vinyl-
chloride (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 pretty good aliphatic and naphtenic oils. Disadvantage is poor
aromatic oil resistance.
Rubber type 65
Rubbers in this group have good weather and heat resistance and quite good oil
resistance. Poly-acrylic 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 they have good weather and oil resistance. Heat
resistance is poor.
Rubber type 67
In this group, rubbers (fluorocarbon rubbers (FPM)) have good weather, heat, oil and
chemical resistance.
Rubber type 68
Silicone rubbers (Q) are in this group. They have good weather, cold and heat
resistance. Mechanical properties are weak.

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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.
Other rubbers
These rubbers are not standardized:
ƒ CM, chlorinated polyethylene (medium weather and heat resistance)
ƒ CSM, chlorosulphonated polyethylene (good weather and acid resistance)
ƒ EVA, ethylene-vinyl acetate copolymer (resistant to aliphatic oils)
ƒ BR, butadiene rubber (good elasticity)
ƒ XNBR, carboksylated nitrile-butadiene rubber (tough and oil resistant)

Natural Rubber (NR)

Natural rubber can be isolated from more than 200 different species of plants.
Commercially significant natural rubber source is Hevea Brasiliensis. The natural
rubber is obtained from latex, which is the emulsion of cis-1,4-polyisoprene and water.
The latex is obtained from the tree by tapping into inner bark and collecting the latex
in cups. Increasing stabilizing agent such as ammonia can prevent too early
coagulation.

Cis-1,4-polyisoprene.

Collation of the latex from rubber tree.

The latex can be concentrated by centrifuging or creaming and sold as concentrated
latex. The latex can be coagulated with hydrogen carboxylic acid or acetic acid, form
in sheets or granulate and then dry it to a solid raw rubber. The raw rubber types are
for example ribbed smoked sheets (RSS), air-dried sheets (ADS) and pale crepes.

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The natural rubber also contains few percent s non-rubber constituents such as resins,
proteins, sugars and fatty acids that may function as weak antioxidants and
accelerators in the natural rubber. The natural rubber is usually vulcanized by using
sulphur, but also peroxides and isocyanates can be used.
The biggest producer countries of the natural rubber are Thailand, Indonesia, Malaysia
and India. Some classification systems that define the maximum content of dirt, cinder,
nitrogen and volatile elements, has been developed in these countries. One well-known
system is Standard Malaysian Rubber, which has been used since 1965.
There are numerous methods of processing latex into commercial grades of dry natural
rubber and latex, as shown in the enclosed picture below (Rubber Engineering, Indian
Rubber Institute, McGraw-Hill, 2000).

Methods of processing latex into commercial grades of dry natural rubber and into
concentrated latex.
Operating temperature range of NR is -55...+70 °C.

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Advantages of NR:
ƒ good processability
ƒ excellent elastic properties
ƒ good tensile strength
ƒ high elongation
ƒ good tear resistance
ƒ good wear resistance
ƒ little dissipation factor - low heat build up in dynamic stress
ƒ excellent cold resistance
ƒ good electrical insulator
ƒ high resistance to water and acids (not to oxidizing acids)
Disadvantages of NR:
ƒ poor weather and ozone resistance
ƒ restricted high temperature resistance (short-time maximum temperature
100°C)
ƒ swelling in oils and fuels: low oil and fuel resistance
ƒ unsuitable for use with organic liquids in general (even though the
vulcanisation remarkably improves the swelling resistance), the major
exception being low molecular weight alcohols
Applications:
ƒ tyres (60 - 70%)
ƒ tubes, conveyor belts and V-belts
ƒ coatings
ƒ gaskets
ƒ latex products
ƒ footwear
ƒ adhesives

Balloons. /1/ Rubber boots /6/

Natural rubber has also many modified types. There is e.g. oil-extended natural rubber
(OENR), which contains 20-30 % oil, epoxidized NR, and methacrylate grafted NR
(Heveaplus MG). The purpose of the modifying has been the improvement of NR
properties to meet the special needs of rubber manufacturers.

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Isoprene Rubber, Polyisoprene (IR)
Poly-isoprene rubber has the same basic chemical formula as the natural rubber (NR),
so it is a synthetic version of NR. The study of materials, which would be comparable
with NR started in the beginning of 20th century, but because of the high price of raw
materials and the weak quality of polymers, industrial production was not started.
Significant production was started in 1970s, when cheaper monomers and catalysts,
which produce stereo-specific polymers in solution polymerization, were available.
It is possible to create different kinds of isomeric structures by using different catalysts
and polymerization conditions in polymerization of isoprene monomers. The
structures, which are exploitable, are 3,4-, cis-1,4- and trans-1,4-polyisoprenes. Cis-1,4
-polyisoprene is a synthetic substitute for natural rubber and trans-1,4-polyisoprene is
a hard thermoplastic material (Gutta-percha or Balata).

Cis-1,4-addition Trans-1,4-addition

1,2-addition 3,4- addition

The isomeric structures of polyisoprene.

The properties of polyisoprene depend on the amount of its cis-1,4-units. The
commercial synthetic isoprene rubbers can be divided in different groups according to
the catalyst used.
• Li-IR group, whose catalyst in polymerisation, is alkyl lithium. The amount of
cis-1,4-units in Li-IR is about 90 % (10% 1,2- type IR).
• Ti-IR group. In these polymerizations, the catalysts are different kinds of
Ziegler-Natta catalysts. The typical content of cis-1,4-cis-units in Ti-IR is at
level 96 - 98 %.
• Lanthanide polyisoprenes have been developed in the recent years, which
approximates very well natural rubber. The share of 1,4-cis-units in lanthanide
IR can be 99.5 %.
The amount of cis-1,4-units influences on crystallization and regularity of molecule
structure. When cis-1,4-content arises, crystallization will facilitate, glass transition
temperature will decrease and strength properties will get better. Consequently, the
strength properties like modules, tensile strength and tear resistance of synthetic

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polyisoprenes are slightly worse than those of NR, whose cis-1,4- content is almost
100 %. Also, the building tack of IR is somewhat inferior to NR, and the green
strength is poorer. Otherwise, the properties of synthetic isoprene rubbers are similar
to NR. The most significant advantages of synthetic polyisoprenes compared to natural
rubber are their purity, good processibility and homogeneity of polymer structure.
Advantages of synthetic IR:
ƒ toughness
ƒ good abrasion resistance
ƒ cold resistance
ƒ competitive price
ƒ processability and adherence
ƒ good uncured tack
ƒ high tensile strength
ƒ high resilience
ƒ good hot tear strength
ƒ resistant to many inorganic chemicals
Disadvantages of IR:
ƒ restricted life time in high temperatures and oxidative circumstance
ƒ poor oil resistance
ƒ needs protection against oxygen, ozone and light
ƒ is not resistant to hydrocarbons
ƒ unsuitable for use with organic liquids
IR is often used with other rubbers. By blending other rubbers with isoprene, tensile
and tear strength and flexibility improve.
Applications of IR are similar to natural rubber:
ƒ tyres
ƒ conveyor lines and transmission straps
ƒ gaskets, tubes, paddings
ƒ footwear, sports equipment
ƒ protective gloves
ƒ sealants and sealing materials
Trans-1,4-polyisoprene (gutta-percha) resembles plastic and is used e.g. in golf balls,
deep sea cables, orthopedic applications and adhesives. Gutta-percha can also be
obtained from pruning of special trees, which are native in Malaysia.

Butadiene Rubber, Polybutadiene (BR)

The forerunner of poly-butadiene rubbers was Buna, which was prepared first time in
Germany in 1920s. Buna was a compound of butadiene and sodium. During World
War I it was noticed that the cold resistance of Buna was not good enough. In
consequence of that, American rubber scientists polymerized poly-butadiene (BR) in
1954. The BR rubbers have much better weather resistance than Buna.
Using solution polymerization in hydrocarbon solvent typically performs the
polymerization of the BR. Suitable catalysts are Ziegler-Natta -combinations, lithium
and its compounds. The elastomer is often named according to its catalyst or according
to metal inside it. Abbreviations used are among others Li-BR (lithium), Co-BR
(cobalt) and Ni-BR (nickel).

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Three different kinds of basic construction units can be formed in polymerization. The
catalyst and polymerization conditions affect on development of these units.

Cis-1,4-form Trans-1,4-form

1,2-form
The isomeric structures of BR.
The isomeric construction structures, which appear most, determine the properties of
polymer. The butadiene rubbers can be divided in three groups according to the
amount of cis-units.
Polybutadiene rubbers according to catalyst used.
Co-BR Ti-BR Li-BR
Cis-1,4-content, % 96 93 38
Trans-1,4-content, % 3 3 52
1,2-content, % 1 4 10
Glass transition temperature Tg ,
-108 -106 -93
°C
Melting temperature Tm , °C -11 -22 amorphous
Molar mass distribution medium board thin very thin
Branching degree medium low very low

Polybutadiene rubbers can be vulcanized with sulphur, sulphur compounds and

peroxides. The peroxide vulcanization is really effective and it produces highly cross-
linked poly-butadiene rubbers.
Advantages of BR:
ƒ excellent cold resistance and heat resistance
ƒ elasticity
ƒ excellent low temperature flexibility and resilience
ƒ abrasion resistance
Disadvantages of BR:

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 ƒ poor processability
ƒ weak mechanical properties
The processing of BR is really difficult. That's why it is usually blended with some
other rubbers, such as NR and SBR. In those blends, the purpose of BR is to reduce
heat build-up and improve the abrasion resistance of the blend. It also improves
flexibility.
Applications:
ƒ tyres (BR content typically 30-50%, blended with SBR and NR)
ƒ shoe soles
ƒ coatings of cylinders, V belts
ƒ gaskets, tubes
ƒ coatings
ƒ toys
ƒ transmission belts
ƒ conveyor belts

Styrene-Butadiene Rubber (SBR)

Styrene-butadiene rubber is the most important sort of synthetic rubber. It was initially
developed to replace natural rubber. The manufacturing method of SBR co-polymer
was developed in Germany in 1929 when the emulsion polymerization method at
about 50°C became mastered. In that method, macromolecular amorphous copolymer
was polymerized with styrene and butadiene.
There exist four different basic construction units in SBR. Three of them originate
from butadiene

Cis-1,4-form Trans-1,4-form

1,2-form Styrene
Isomeric structures of polybutadiene and the structure of styrene.
At present, styrene-butadiene elastomers can be produced by emulsion or solution
polymerization techniques. The “cold” emulsion polymerization, at about 5°C, is the
most widely used polymerization technique, even though the solution method has
steadily conquered the market share.

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In solution polymerization the polymerization typically occurs in dry hydrocarbon
solvent with anionic methyl-lithium catalyst. Depending on the specific
polymerization process, two different elastomer types can be formed. Another type
contains segmented styrene and butadiene blocks (TPE), the other type is rubber
elastomer with random distribution of co-monomers in polymer.
The styrene-butadiene rubber can be vulcanized by the use of sulphur, sulphur donor
systems and peroxides.
Processing method can affect on SBRs properties considerably. Molar mass, styrene
content and the amount of units vary depending on manufacturing technique.
Examples are shown in the attached table.
Properties of emulsion polymerization and solvent polymerization.
Emulsion - SBR Solvent-SBR
Molar mass Mn, g/mol 145000 200000
Molar mass Mw, g/mol 651000 420000
Mw / Mn 4,5 2,1
Styrene content, % 23,5 18
Cis-1,4-content, % 18 35
Trans-1,4-content, % 65 54
1,2-content, % 17 11
Glass transition temperature Tg,
- 50.6 - 69.7
°C
Commercial products of SBR: Buna EM, Krylene, Cariflex S a.o.
Type designation according to numeric code:
ƒ 10xx hot polymer without filler
ƒ 12xx solution - SBR
ƒ 15xx cold polymer without filler
ƒ 16xx cold polymer, carbon black master-batch
ƒ 17xx hot polymer, oil extended
ƒ 18xx cold polymer, carbon black/oil master batch
ƒ 19xx emulsion- resin- master batch
ƒ 'xx' indicates viscosity, coagulant, content of styrene
Advantages of SBR rubbers:
ƒ good abrasion and ageing resistance
ƒ good elasticity
ƒ low price
Disadvantages:
ƒ inferior mechanical properties (require reinforcements)
ƒ adhesion properties
ƒ poor oil resistance
ƒ poor ozone resistance
ƒ do not resist aromatic, aliphatic or halogenated solvents
ƒ low elongation at break

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Comparison between the properties of SBR and NR. 5 = excellent, 4 = very good, 3 =
good, 2 = fair, l = poor
Styrenebutadiene- Natural rubber
rubber SBR NR
Hardness, °IRH 40....90 30...90
Tensile strength at break,
7....25 7...28
N/mm2
Elongation at break, % 100...600 100...700
Operating temperature range
- maximum, °C 100 80
- minimum, °C - 45 - 55
Elasticity 5 5
Resistance:
- weather and ozone 1...2 1...2
- abrasion 4 4...5
- radiation 2...3 2...3

SBR needs more reinforcement to achieve good tensile and tear strength and durability
than natural rubber. SBR also has lower resilience than NR.
Applications:
ƒ car tyres (blended with BR, IR and NR)
ƒ footwear
ƒ conveyor belts
ƒ hoses
ƒ toys
ƒ moulded rubber goods
ƒ sponge and foamed products
ƒ waterproof materials
ƒ belting
ƒ adhesives

Tyre /10/

18
The use of SBR in tyres
Varying SBR content in copolymer like in tyre tread blends can modify the properties
of tyres.
Monomer contents that are typical of tyre tread blends.

The properties of polymer Low road resistance Good wet grip General use

Vinyl content (%) 10 50 35

Styrene content (%) 15 23 20
The effect of monomer content and Tg on the properties of tyres
Growing styrene Growing vinyl
The properties of tyres Higher Tg
content content
Wet grip Increasing Increasing Increasing
Wet steerability Increasing Increasing Increasing
Dry grip Increasing Increasing Increasing
Dry steerability Increasing Increasing Increasing
Fuel consumption Increasing Increasing Increasing
Ice grip Decrease Decrease Decrease
Snow grip Decrease Decrease Decrease
Life time Decrease Decrease Decrease

Butyl Rubbers
Isobutylene-Isoprene Rubber (IIR), Chlorobutyl Rubber (CIIR), Bromobutyl
Rubber (BIIR)
Butyl rubbers are prepared by copolymerizing small amounts of isoprene with
isobutylene. Isoprene units are placed randomly to the isobutylene chain as trans-1,4
form. Adjusting the polymerization temperature and the share of monomers can vary
the composition of the polymer. A typical butyl rubber contains 0.5 ... 3 mole percent
isoprene.
The properties of butyl rubbers depend on the length of the molecule chains and
saturation degree. When the amount of the double bonds is low, rubber has good
oxygen and ozone resistance. The bigger amount of double bonds accelerates the
vulcanisation process and increases the amount of cross-links.

19
 Isobutylene and isoprene units.
The properties of butyl rubbers can be improved by increasing 1 ... 2 weight percent
halogens, forming chlorobutyl (CIIR) and bromobutyl (BIIR) rubbers. Halogens are
mostly joined to the double bonded carbon without methyl group in the isoprene unit.
Addition of the halogens increases chain flexibility and enhances cure compatibility in
blends with other diene rubbers.
The butyl rubber can be cured with sulphur, but it does need accelerator. Dioxime
compounds together with the oxidizing agent can also be used. In that case cross-links
stand heat better than sulphur bonds. CIIR and BIIR have more reactive points to the
crosslinking, if the curing agent (sulphur or metal oxides) has been used in curing.
Peroxides cannot be used, because they may break down the elastomer chains.
Advantages of butyl rubbers:
ƒ stabile in long-term-use and high temperatures
ƒ low gas permeability
ƒ good ozone resistance
ƒ good weather resistance
ƒ elasticity in wide temperature range -73...100°C
ƒ low water absorption
ƒ resistant to oxidizing agent, vegetable and animal fats and polar solvents
ƒ heat stability
Disadvantages:
ƒ poor wear resistance
ƒ not resistant to hydrocarbon solvent and oil
ƒ relatively low elasticity
The properties of the halogenated butyl rubbers are similar with basic butyl rubber.
However, they have lower gas permeability and better thermal, ozone, weather and
chemical resistance. The halogenated butyl rubbers are used in applications that
demand rubber with a high vulcanization rate.
Applications:
ƒ inner tyres of cars and bicycles
ƒ steam hoses
ƒ coatings of fabrics and cables
ƒ base element of chewing gum
ƒ waterproof films
ƒ gutter gasket
ƒ inner tubes
ƒ pharmaceutical closures and membranes
ƒ vibration isolation

20
Diving suit /11/

Nitrile Rubber, Nitrile-Butadiene Rubber, Acrylonitrile Rubber (NBR)

Poly-acrylonitrile-butadiene rubber is a copolymer of butadiene and acrylonitrile. It
was synthesized first time in 1930. It is used because of good oil, fuel and fat
resistance. Acrylonitrile rubbers are also called just nitrile rubber.
The NBR is produced by emulsion polymerization. Polymerization rates of
acrylonitrile and butadiene are different. Because of that, the content of monomers in
copolymer is not same than the content of monomers in reaction mixture. The polymer
formed is random copolymer, where the acrylonitrile content varies between 18 ... 50
%. Changing temperature or a feeding of monomers can modify the composition of the
polymer.

Butadiene and acrylonitrile units.

Increasing of the acrylonitrile content improves oil resistance, hardness, abrasion
resistance and heat resistance, but raises the glass transition temperature.
Unlike most other synthetic rubbers, nitrile rubbers can be vulcanized with several
cross-linking systems. The vulcanization can take place in room temperature or in high
temperatures to accelerate the reactions.
The nitrile rubbers are used in applications, which demand good mechanical properties
and oil and fuel resistance. The NBR can be used blended with other rubbers. For

21
instance, the increasing of IIR to NBR improves weather properties and thermal
stability and decreases gas permeability of NBR.
Properties of NBR:
ƒ high oil and heat resistance
ƒ low ozone resistance
ƒ high swelling with some solvents (ketones and esters) and some oils
ƒ good resistance to oil, aliphatic and aromatic hydrocarbons and vegetable oils
ƒ good abrasion and water resistance
Applications of NBR:
ƒ seals, hoses, joints
ƒ roll coverings
ƒ conveyor belts
ƒ containers
ƒ protective clothes and shoes

Boots /6/ Gloves /9/

Modified nitrile rubbers:
Carboxylated nitrile rubbers (XNBR) and hydrogenated nitrile rubbers (HNBR) are
special modifications of NBR. The XNBR rubbers contain randomly placed carboxyl
groups that are derived from metacrylate acid or acrylate acid. The XNBR has better
abrasion resistance, hardness and tensile strength. It also has better low temperature
brittleness and better retention of physical properties after hot-oil and air ageing
compared to NBR.
Hydrogenated nitrile butadiene rubber (HNBR)
The nitrile rubber can also be improved by (partial) saturating the double bonds in
main chain butadiene by catalytic hydrogenation. This kind of NBR, HNBR, has been
developed to stand better ageing in oil and hot air.
Properties of HNBR:
ƒ oil- and gasoline swelling as NBR
ƒ application temperature up to 150°C
ƒ high tensile strength, weather resistant
ƒ peroxide curable types (double bond content < 1 %) and

22
 ƒ sulphur curable (double bond content < 4 – 6 %)
Main applications: vehicle tubing, seals, cables and profiles

Epichlorohydrin Rubbers
Epichlorohydrin Homopolymer (CO), Epichlorohydrin/Ethylene-Oxide
Copolymer (ECO), Epichlorohydrin Terpolymer (ETER)
There are three different types of epichlorohydrin elastomers: epichlorohydrin
homopolymer (CO), epichlorohydrin/ethylene-oxide copolymer (ECO) and
epichlorohydrin terpolymer (ETER), which form from epiclorohydrin, ethyleneoxide
and some other monomer (typically diene).

The structures of CO and ECO.

In polymerization of epochlorohydrin coordinate catalyst is used. Catalyst can be for
example a compound of aluminium alkyl, water and acetyl acetone. The
polymerization method used is solution polymerization in hydrocarbon solution. When
vulcanizing homo- and copolymer, chloromethyl group react with di-functional curing
agent, such as diamine, ethylenethiourea or urea. Terpolymers can be vulcanized with
sulphur or peroxide.
The biggest differences between epiclorohydrin homopolymer (CO) and copolymer
(ECO) are in elasticity and cold resistance. ECO is very elastic in wide temperature
range whereas CO is elastic only in elevated temperatures. That's why the
epichlorohydrine copolymers are used more than the homopolymers.
Properties of epichlorohydrin rubbers:
• resistant to oils, fuels and chemicals
• good fire resistance
• high cold and heat resistance
• good weather, ozone and thermal resistance
• good damping properties
• good processability
• low gas permeability
• weak tensile strength (fillers reinforce)
• high price
• risk of causing corrosion with metal
• very good dynamic properties
The use of epichlorohydrin rubbers is similar with nitrile rubbers. However, ECO
offers better oil resistance, elasticity and processability.

23
Applications:
• gaskets
• oil and petrol tanks and hoses
• belts, rolls
• coatings of wires and cables
• coatings of textiles
• vibration isolator
• membranes
• resilient mountings

Ethylene-Propylene Rubber (EPM), Ethylene-Propylene-Diene Rubber

(EPDM)
Ethylene-propylene rubbers can be divided in two groups: ethylene-propylene rubbers
(EPM) and ethylene-propylene-diene rubber (EPDM). EPM is a copolymer of ethylene
and propylene and EPDM is a terpolymer of ethylene, propylene and diene. The most
frequently used dienes, which offer the cross-linking sites for the elastomer, are
dicyclopentadiene, ethyldienenorborne and 1,4-hexadiene (see formulas below).
Rubbers usually contain 45 ... 60 wt.-% of ethylene monomer. Material with low
ethylene content is easier to process than the high ethylene content material. Especially
the green strength and extrudability improve as the ethylene content increases. Diene
content is usually 4-5 %, but sometimes it can be even 10 %.

The structure of EPM.

The ethylene-propylene rubbers are produced mostly by solution polymerization with
Ziegler-Natta type catalysts. The EPM rubbers cannot be vulcanized with sulphur
because of the absence of unsaturation in the main chain. The EPM can be cured with
peroxides or radiation. The EPDM can be vulcanized with sulphur, peroxide, resin
cures and radiation. Polymerization and catalyst technologies in use today provide the
ability to design polymers to meet specific and demanding application and processing
needs
Typical Properties
Ethylene-propylene rubbers are valuable for their excellent resistance to heat,
oxidation, ozone and weathering resistance due to their stable, saturated polymer
backbone structure. Properly pigmented black and non-black compounds are colouring
stable.
As non-polar elastomers, they have good electrical resistivity, as well as resistance to
polar solvents, such as water, acids, alkalies, phosphate esters and many ketones and
alcohols.
Amorphous or low crystalline grades have excellent low temperature flexibility with
glass transition points of about -60°C.
Heat aging resistance up to 130°C can be obtained with properly selected sulphur
acceleration systems and heat resistance at 160°C can be obtained with peroxide cured

24
compounds. Compression set resistance is good, particularly at high temperatures, if
sulphur donor or peroxide cure systems are used.
These polymers respond well to high filler and plasticiser loading, providing
economical (obs. low density too), easily processible compounds. They can develop
high tensile and tear properties, excellent abrasion resistance, as well as improved
flame retardance.
As the disadvantages of EP rubbers, bad oil and hydrocarbon resistance and poor tack
can be mentioned.
A general summary of properties (property ranges).
Property Value range
Mooney Viscosity, ML 1+4 @ 125 5-200+
°C
Ethylene Content, wt. % 45 to 80 wt. %
Diene Content, wt. % 0 to 15 wt. %
Specific Gravity, gm/ml 0.855-0.88 (depending on polymer composition)
Hardness, Shore A Durometer 30A to 95A
Tensile Strength, MPa 7 to 21
Elongation, % 100 to 600
Compression Set B, % 20 to 60
Useful Temperature Range, °C -50 ° to +160 °
Tear Resistance Fair to Good
Abrasion Resistance Good to Excellent
Resilience Fair to Good (stable over wide temp. ranges)
Electrical Properties Excellent
* Range can be extended by proper compounding. Not all of these properties can be
obtained in one compound.
Source: International Institute of Synthetic Rubber Producers.
Applications:
• products of automotive industry: seals and hoses, isolators
• gaskets and hosepipes, liners in building industry
• roll covers
• agricultural equipment: hoses, seed tubes, cushioning, silos
• wire and cable

25
Chloroprene Rubber, Polychloroprene (CR)
Polychloroprene was one of the first synthetic rubbers. The first chloroprene
monomers were prepared from acetylene. Nowadays they are synthesized from
butadiene, because it is easier and safer route. Chloroprene is polymerized by emulsion
polymerization by using potassium persulphate as free radical initiator. The main
component of the polymer usually is trans-1,4-units. In vulcanizing of CR, zinc oxide
and magnesium oxide blend is usually used.

Trans-1,4-form Cis-1,4-form

1,2-form 3,4-form
Isomeric structures of CR.
The chloroprene rubbers can be divided in G and W types according to their
mechanism to control the molecular weight of the polymer during the polymerization.
In G types, sulphur is copolymerized with the chloroprene, when it does not require
acceleration during curing. The G type rubbers have slightly inferior ageing resistance,
but resilience and tack are better than the W types. The W types chloroprene rubbers
require accelerator. The vulcanization doesn't manage with sulphur. Suitable
accelerators are metal oxides. The W type rubbers have better ageing properties and
thermal resistance than G type rubbers. Different grades of CR rubber and their typical
properties have been presented in the figure below.

26
 Different grades of CR / http://www.dupont-dow.com/ /
Polychloroprene is a versatile elastomer. It is used especially in demanding
circumstances.
Advantages of chloroprene rubber:
• good abrasion resistance
• good ozone resistance
• good tear strength
• good oil and solvent resistance
• inflammability
• good adhesion to metals
• increased hardness in high temperature environments
Disadvantages of CR:
• High swelling in some oils, hot water, acids and some organic solvents
Applications of chloroprene rubbers:
• conveyor belts and V belts
• hoses
• wire and cable coverings
• vibration isolators
• adhesives
• gaskets
• footwear
• coated fabrics
• wear suit applications, inflatables

27
Mask /2/ Gloves /9/ Rescue suit /7/

Polyacrylate Rubbers (ACM)

Polyacrylate rubbers are elastomers that are prepared from acrylic esters (typically
ethyl and methyl acrylate) and reactive cure site monomer (carboxylic acid or
chloroethyl vinyl ether).

The basic structure of acrylates.

The basic monomers of acrylate rubbers.
Monomer Structure, X
ethyl acrylate C2H5
butyl acrylate C4H9
methoxy ethyl acrylate C2H4OCH3
ethoxy ethyl acrylate C2H4OC2H5

28
 Examples of the structure of acrylate rubbers. Monomers are ethyl acrylate and
chloroethyl vinyl ether or carboxylic group.
The preparing of the polyacrylate rubbers is based on polymerization of acrylate and
metacrylate acids. Polymerization technique can be emulsion or precipitation
polymerization. In emulsion polymerization, catalyst can be persulphate-salt or redox-
system. In precipitation polymerization, the catalyst can be peroxide. The peroxides
are solvents to monomer, or atso-bis-isobutyro-nitrile, which degrade easily.
To make reactive sites for vulcanization, polyacrylate elastomers are copolymerized
with 1 ... 5 weight percent reactive component, such as carboxylic acid or
chloroethylene vinyl ether or epoxy compounds. Common vulcanization agents are
methylene dianiline or hexamethylene diamine carbamate, or metalcarboxyl soaps,
such as sodium- or kaliumstearate. Sulphur acts as a catalyst.
Properties of ACM:
• excellent ozone and weathering resistance
• very good heat resistance
• good oil resistance
• good elasticity
• excellent flexing properties
• resistant to oil and aliphatic solvents
• low gas permeability
• poor water, alkali and acids resistance
• good heat aging resistance
• low resistance to hot water
• not highly corrosive to steel
Applications:
• applications in automotive industry (e.g. boots, grommets and seals)
• seals, hoses, wire coverings
• adhesive formulations

Polyurethane rubbers (AU, EU, PUR)

Polyurethanes are named after urethane group, which forms when isocyanate group
reacts with the hydroxyl group of the alcohol. Depending on the type and amount of
feeding stocks and additives, polyurethanes can be thermosets or thermoplastics.

29
 Forming of urethane group.
Polyurethanes are the single most versatile family of polymers there is. Polyurethanes
can be solid or microcellular elastomers (both cross-linked rubbers and thermoplastic
elastomers), foams, paints, fibers or adhesives. They can also be processed with most
processing methods known at present (see figure).

Polyurethane rubbers (PUR) and also urethane thermoplastic elastomers (TPE-U) are
built up of long soft segments and short hard segments. The soft segments are formed
by the reactions between polyesterdiol or polyetherdiol with hydroxyl group ends. The
hard segments are formed by the reactions between isocyanates and chain extenders.
The polyurethane rubbers can be divided in polyesterurethane rubber (AU) and
polyetherurethane rubber (EU) according to polyol used.
The polyurethane rubbers can be divided in castable and kneaded (millable)
polyurethanes according to their process method.
Castable polyurethane rubbers are obtained in one-step process or two-step process. In
the one-step casting method polyol, di-isocyanate and chain extender react and the
product is formed in the same step. In the two-step casting method a prepolymer is
prepared first by the reaction between diisocyanate and polyol. In second step the
molar mass and the length of the chains of the prepolymer is raised and the structure is
cross-linked with chain extenders. The second step is often carried out in mould in
elevated temperatures. Extenders may be diols or triols. The two-step casting is more
used than the one-step casting.

30
The cross-linking, which forms the three-dimensional network in PUR, can be brought
out, as described above, by multifunctional chain extenders or isocyanates, but also
with sulphur and peroxides (especially the kneaded PUR grades).
The properties of polyurethane rubbers depend on structure of their chains. Polyester
based polyurethane rubbers have usually better mechanical properties and chemical
resistance than polyether based polyurethane rubbers. Polyether based polyurethane
rubbers have better properties in low temperatures and better hydrolysis resistance.
Properties of polyurethane rubbers:
• good abrasion and tear resistance
• good tensile strength
• hardness
• good oxygen and ozone resistance
• resistant to aliphatic hydrocarbons and oils
• low friction coefficient
• good insulator
Applications:
• wearing surfaces of wheels and rollers
• power transmission elements
• seals
• soles

Slit rings /5/ Injection molded boots /7/

Fluorocarbon Rubbers (FKM, FPM)

Fluorocarbon rubbers are very stable materials because of the strength of the bond
between fluorine and carbon. The most typical grades of fluorocarbon rubbers are
based on vinyl diene fluoride and hexafluoropropylene HFP monomers (see table
below), which have been denominated as FKM in ASTM standards and FPM in ISO
standards. There are also fluorocarbon rubbers containing chlorine in vinylidene
monomers (e.g. CFCl = CF2), denominated as CFM rubbers. The fluorocarbon rubbers
are usually produced by emulsion radical polymerization. Peroxy compounds act as
initiators.
Monomers used in fluorocarbon rubbers.

Monomer Structure
vinylidene fluoride
VF2
tetrafluoroethylene
TFE

31
chlorotrifluoroethylene
CTFE

hexafluoropropylene
HFP

1-hydropentafluoropropylene
HPTFP

perfluoromethylvinylether
FMVE

Structures of fluorocarbon rubbers

Monomers Structural unit Type Commercial types
designation
VF 2 + HFP FKM Viton A, AHV, A-
35, E-60,
Fluorel 2140, 2141,
2143, 2146
SFF-26
VF 2 + HPFP FKM Tecnoflon SL, SH

VF 2 + HFP + FKM Viton B, B-50

TFE

VF 2 + HPFP + FKM Tecnoflon T

TFE

VF 2 + TFCIE CFM KEL-F 3700, 5500,

SKF-32
PFMVE + TFE FKM ECD 006
+X

Most commonly used FKM rubbers can be vulcanized with diamines, polyhydroxide
compounds and bisphenols. The vulcanization system has a metal oxide as acid
acceptors.

32
Advantages of fluorocarbon rubbers:
• excellent heat resistance (even 200°C, temporarily 315°C)
• good chemicals and solvent resistance
• excellent oxygen, ozone and weather resistance
• incombustible
• good abrasion resistance
• good high temperature compression-set resistance
Disadvantages:
• low alkali resistance
• relatively poor mechanical properties
• limited elasticity in low temperatures
• the tensile strength decreases substantially at elevated temperatures
• high price
The fluorocarbon rubbers are used to special applications that require good heat,
oxygen or corrosion resistance and hot solvent and oil resistance.
Applications:
• car and airplane seals and hoses
• fire resistance coverings
• heat resistance insulators
• o-rings, shaft seals
• gaskets, fuel hose, valve-stem seals

Silicone Rubbers (Q)

The silicone rubbers are inorganic polymers, because their main chain structure does
not include carbon atoms. As shown in the picture, silicone and oxygen atoms –
siloxane groups - form the polymer main chain. There are typically also some pendant
groups, usually methyl groups, attached to the polymer chain. The molar mass of
silicone rubbers can vary at wide range, and consequently there are liquid materials as
well as traditionally resinous rubbers available.

The structure of silicone.

The silicone rubbers are usually polymerized from cyclic oligomers to linear
macromolecules. The vulcanization can be carried out at room temperature or elevated
temperature. Vulcanisation at room temperature occurs with crosslinking agent (e.g.
orthosilicon acid ether) or air. For the high temperature vulcanization peroxides are
used. The molar mass of silicon rubber vulcanized at elevated temperatures is higher
(300 000 - 1 000 000 g/mol) than in room temperature vulcanization (10 000 - 100 000
g/mol).

33
The silicone rubbers can be divided according to their pendant group structure.
Pendant group Rubber type
methyl CH3 MQ
phenyl C6H5 PMQ
vinyl CH2 = CH VMQ
vinyl CH2 = CH
PVMQ
phenyl C6H5
trifluoropropyl CF3CH2CH2 FMQ
vinyl CH2 = CH
FMVQ
trifluoropropyl CF3CH2CH2
In VMQ rubbers, a part of the methyl groups (< 0.5 %) is replaced with vinyl groups.
This facilitates vulcanization and reduces deformation set of the rubber. PMQ and
PVMQ rubbers have phenyl groups (5...10 %) instead of methyl groups. This improves
the properties of the silicone rubbers in low temperatures. Fluorosilicones (FMQ and
FMVQ) have better solvent resistance than other silicone rubbers.
Reinforcement fillers, such as silica, have to be used, because the mechanical
properties of pure silicone rubber are rather weak. For example, the tensile strength of
pure silicone rubber is the worst of rubbers. However, the mechanical properties of
silicone rubber do not weaken at high temperatures as much as in the case of other
rubbers.
Advantages of silicone rubbers:
• high temperature resistance, wide operating temperature range (even -100 ...
+300 °C)
• UV-light, oxygen and ozone resistance (peroxides have to be used for
vulcanisation)
• elasticity
• non-toxic, odourless, tasteless
• good release properties
• good electrical insulation
• good ageing resistance in high temperatures
• good resistance to low concentrations of acids, bases and salts
Disadvantages of silicones:
• weak oil resistance (exception aliphatic oils)
• low resistance to steam, acids and alkalis
• weak mechanical properties without additives
• high shrinkage in moulded articles
• the vulcanisation to obtain good mechanical properties has to be carried out
with peroxides
• price
Applications:
• electrical equipment and technical products at high temperatures
• medical devices and hospital supplies
• roll coverings
• cable coverings and insulators

34
 • lining compounds
• moulds
• o-rings
• seals for the aeronautics industry

Polysulfide Rubbers (T)

Polysulfide rubbers build up when dihalide react with sodiumpolysulfide. Polysulfide
rubbers have only one manufacturer Morton International. Polysulfide rubbers can be
divided to four different groups: Thiokol A, FA, ST and LP rubbers. A-types
polysulfide rubbers have ethylene-dichloride as a dihalide, FA-rubbers are produced
from the blend of ethylene dichloride and dichloroethylene formal. ST-rubbers are
produced from dichloroethyenel formal and trichloropropane. LP-types are liquid
polymers. They are built up by breaking down a high molecular weight polymer in a
controlled manner. The sulphur content of A-type is high (84 %), FA-types’ sulphur
content is 49 %, and ST-types' 37 %.

The polymerization of polysulfide. Reactants are ethylchloride and sodiumsulfide.

The A and FA types are usually vulcanized with the addition of zinc oxide. The ST
and LP types are vulcanized with oxidizing agent, like metal oxides or metal
peroxides.
Properties of polysulfide rubbers:
• excellent oil and solvent resistance
• good weather and ozone resistance
• bad smell
• difficult to machine
• narrow operating temperature range
• corrode copper
• very good low-temperature properties
Applications:
• paint, oil and fuel hoses
• seals
• paint and varnish rolls
• roller coverings

35
Ethylene-Vinyl Acetate Copolymer (EVA)
Ethylene-Vinyl Acetate elastomer is a copolymer of ethylene and vinyl acetate. The
properties of the rubber depend on the vinyl acetate content. EVA polymer has rubbery
properties when the vinyl acetate content is 40...60 wt%.

Ethyl-vinyl acetate rubber.

Preparing method of ethyl-vinyl acetate depends on desired vinyl-acetate content.
Mass polymerization gives 45 weight percent content at most; emulsion
polymerization gives over 50 weight percent content and solution polymerization 30 ...
90 weight percent content. EVA can be vulcanized with peroxides or ionizing
radiation. Sulphur cannot be used, because of the saturated main chain.
EVA is often blended with NR and SBR to improve the ozone resistance.
Properties of EVA:
• excellent oxygen, ozone and light resistance
• extremely good water and oil resistance
• good heat resistance
• do not resist organic solvents
• fire resistance
• good tack to other materials
• low price
• poor tear resistance
• low abrasion resistance
• low elasticity due to the thermoplastic character
• with reinforcements, high tensile strength can be obtained
Applications:
• cable and wire coverings
• seals
• floor materials
• some medical extrusions
• hoses

Polypropylene-Oxide Rubbers, Polypropylene Oxide-Allyl Glycidyl Ether

Copolymer (GPO)
Polypropylene-oxide rubbers are copolymers of propylene oxide and allyl glycidyl
ether. The typical allyl glycidyl ether content is about 5 %. Polymerization method is
solution polymerization in hydrocarbon. Vulcanisation can be made with sulphur.

36
 Polypropylene-oxide rubber.
Properties of polypropylene-oxide rubbers:
• good properties in low temperatures
• good elasticity
• good heat and cold resistance
• excellent oxygen, ozone and UV-light resistance
• weak oil resistance
• low internal damping
• high price
• broad temperature range
Applications:
• vibration absorbers
• engine mounts
• body mounts
• suspension bushing
• seals

Chlorinated Polyethylene (CM, CPE), Chlorosulphonated Polyethylene

(CSM, CSPE)
Polyethylene is normally a semi crystalline thermoplastic. However, chlorine can be
added to polymer chain to prevent crystallization. The amount of chlorine in
chlorinated PE determines the properties of the polymer. When using small contents
(25 %), the material is still crystalline. Incorporation of higher chlorine content (> 40
%) will make the material too brittle. The best rubbery properties are attained when
chlorine content is about 35 %. The chlorosulphonated polyethylene is similar to the
chlorinated polyethylene, but it is easier to cure because of the chlorosulphone group.
That is why the chlorosulphonated polyethylene is more used than the chlorinated
polyethylene. Typical chlorosulphone content in elastomer is less than 1.5 %.

Chlorinated polyethylene.

Chlorosulphonated polyethylene.

37
The chlorinated polyethylene can be cured with peroxides or radiation. The
chlorosulphonated polyethylene can be vulcanized with peroxides, metal oxides and
amines. Increasing chlorine content increases oil, fuel and solvent resistance, but
decreases low-temperature flexibility.
Properties of CM:
• really good UV light resistance
• good oil resistance
• really good oxygen, ozone and light resistance
• good tensile and breaking strength
• low compression set (up to 150 °C )
• very good dynamic fatigue
• excellent ageing resistance
• very good chemical resistance
• good flame resistance
• very good colour stability
Properties of CSM:
• oxidation and ozone resistance
• chemical resistance good
• relatively difficult to process
• high swelling in some type of oils
• high compression set at high temperatures
• good cold, heat and flame resistance
Applications:
• cable and wire coverings
• electrical insulator
• floor materials
• coated fabrics
• hoses
• pond liners
• moulded goods
• automotive tubes
• boots
• dust covers

Rubber blends
Rubber materials in applications are always rubber blends. They contain basic
elastomer or masterbatch and additives. This way the properties of material are
improved or changed.
Compositions of rubber blends are described in recipes. The basic recipes are simple
and they are standardized. These recipes can be modified when new blends are
developed. Recipes inform the materials and amounts used in rubber blend. The
amounts of constituents are usually represented parts per hundred parts of rubber (phr).

38
The basic recipe for rubber vulcanized with sulphur.
Material phr
Raw rubber 100
Sulphur 0-4
Zinc oxide 5
Stearic acid 2
Accelerator 0.5-3
Antioxidant 1-3
Filler 0-150
Plasticizer 0-150
Other additives 0-

Thermoplastic elastomers (TPE)

Thermoplastic elastomers are a polymer group, whose main properties are elasticity
and easy processability. The use of thermoplastic elastomers has grown noticeably
during a couple of last decades.
Thermoplastic elastomers are a wide material group. These materials have many
advantages of which the most important ones are
• good properties in low temperatures
• excellent abrasion resistance
• damping properties
• good chemical resistance
• easy processability (compared to rubber)
• recyclable material
A restrictive features of thermoplastic elastomers compared to rubbers are the
relatively low highest operating temperature (< 130 - 160°C), small selection of soft
grades and high price of TPE's.
Thermoplastic elastomers are used in areas where elasticity in vast temperature range
is required. The main applications are in automotive industry and sport accessories.
Thermoplastics elastomers can be divided in the following groups:
1. Styrene-diene block copolymer
2. Elastomeric alloys
3. Thermoplastic urethane elastomers
4. Thermoplastic ester-ether copolymers, TPE-E
5. Thermoplastic amide copolymer, TPE-A

39
Styrenic thermoplastic elastomers (TPE-S)
SBS (Styrene/Butadiene Copolymer), SIS (Styrene/Isoprene Copolymer), SEBS
(Styrene/Ethylene-Butylene Copolymer), SEPS (Styrene/Ethylene-Propylene
Copolymer)
Thermoplastic elastomers that base on styrene are block copolymers, where polydiene
unit divide polystyrene blocks. Polydiene may be for example butadiene (SBS),
isoprene (SIS), ethylene-butylene (SEBS) or ethylene-propylene (SEPS). Styrene
content varies with different materials, but usually it is 20-40 %.

The linear and the radial structure of styrenic TPEs.

Advantages of styrenic TPEs:
• high tensile strength and modulus
• good miscibility
• good abrasion resistance
• good electrical properties
• large variety in hardness
• high friction coefficient (correspond to NR)
• colourless, good transparency
Disadvantages:
• poor high temperature resistance (highest operation temperature, SBS 65 °C,
SEBS 135°C)
• weak oxygen, ozone and light resistance of SBS (exception SEBS)
• poor oil and solvent resistance

40
Applications:
• rubber products in car industry
• cables and wires
• shoe soles
• adhesives
• with thermoplastics in multi-component injection moulding and co-extrusion

Elastomeric alloys
Elastomeric alloys are blends of elastomers and thermoplastics that can be processed
by processing methods of thermoplastics. Elastomeric alloys are:
• Thermoplastic Olefin Elastomers (TPO)
• Thermoplastic vulcanizates (TPV)
• Melt Processible Rubbers (MPR)
Thermoplastic Olefin Elastomers (TPO, TOE)
Thermoplastic olefin elastomers are most commonly blends of PP and EPM or PP and
EPDM. Natural rubber and butyl rubber have also been used. Blend can be made in
mechanical mixing unit like twin-screw extruder or in polymerization reactors.
Properties of thermoplastic olefin elastomers vary according to components, mixture
ratio and conditions of alloying. Properties typical of thermoplastic olefin elastomers:
• good chemical resistance
• excellent weathering resistance
• low density
• good processibility
• low price
Applications:
• buffers and outside profiles in car industry
• wire and cable coatings
• hoses
Thermoplastic Vulcanizates (TPE-V, TPV, DVR)
Thermoplastic vulcanizates are blends of thermoplastics and elastomers that have been
dynamically vulcanized during their mixing (see picture). That kinds of materials are
for example dynamically vulcanized blends of PP and EPDM and PP and NBR.
Properties of material depend powerfully on structure and content of elastomer.

The properties of thermoplastic vulcanizates:

• small permanent deformation
• good mechanical properties
• good properties in low temperatures
• fatigue durability
• good liquid and oil resistance

41
Applications:
• car components
• tubes
• electrical insulators

Melt Processible Rubbers (MPR)

Melt processible rubbers are very rubbery materials that look and feel like traditional
rubbers. However, they can be processed like thermoplastics. Melt processible rubbers
have one phase structure, so they differ from other thermoplastic elastomers that have
two-phase structure.
Properties of melt processible rubbers:
• excellent elasticity
• stress-tensile behaviour correspond to vulcanised rubbers
• softness and flexibility

Thermoplastic Urethane Elastomers (TPU, TPE-U)

Polyurethanes are named after the urethane group, which is formed when isocyanate
group reacts with the hydroxyl group of the alcohol. Depending on the type and
amount of feeding stocks and additives, polyurethanes can be thermoplastics, rubbers (
PUR ) or thermoplastic elastomers.

Forming of urethane group.

Thermoplastic polyurethane elastomers form from long (MW around 600 – 3000
g/mol) soft segments of linear polyester (TPE-AU) or polyethers (TPE-EU) and short,
hard urethane segments that are formed of di-isocyanate and small alcohol molecule
chain extender, e.g. butane diol.

42
The structure of thermoplastic urethane elastomers: long ester or ether diol chains
and hard urethane segments
The properties of thermoplastic urethane elastomers vary strongly according to
feedstocks and the ratio of hard and soft segments in the material. The soft segment
component influences in the low temperature properties of TPE-U especially, but also
to many other characteristics. Depending whether the soft segment is formed of
polyester or polyether, the properties can be compared according to the table below.

The properties of TPAU and TPEU.

Property TPAU TPEU

Tensile strength ++ 0

Abrasion resistance ++ 0

Tear resistance ++ 0

Radiant energy resistance + 0

Hydrolysis resistance -/0 +

Low swelling in oil, fat and petrol + 0

Weather resistance + 0

Oxidation resistance + -/0

Microbes resistance -/0 ++

Water absorption 0 +

Impact resistance in low temperatures 0 ++/0

++ excellent, +good, 0 fair, -poor

Advantages of thermoplastic urethane elastomers:
• good abrasion resistance
• good tear strength
• good strength and stiffness properties
• low friction coefficient (depends on hardness)

43
 • good oxygen, ozone and weather resistance
Disadvantages of thermoplastic urethane elastomers:
• poor hydrolysis resistance
• poor resistance to chlorinated and aromatic solvents
• relatively poor UV-light resistance
Applications:
• conveyor belts
• footwear
• cable and wire coatings
• hoses
• components of car industry

Thermoplastics Polyester-Ether Elastomer (TPE-E)

Polyetherglycols, such as polyethylene, polypropylene or polybutylene ether glycols
are soft segments in thermoplastics polyester-ether elastomers. Hard segments are
dimethylterephtalate or 1,4-butanediol.
Advantages:
• good oxygen and ozone resistance
• good oil resistance
• good strength properties
Disadvantages:
• small variety in hardness
• low elongation at break (requires own design principles of products)
• poor hydrolysis resistance
• poor UV-light resistance
• high price
Applications:
• cable and wire coatings
• gaskets
• hoses, tubes

Thermoplastic Polyamide Elastomers (TPE-A)

Soft segments of polyesters or polyethers and rigid block of polyamide form
thermoplastic polyamide elastomers. Polyamide can be for example polyesteramide
(PEA), polyetheresteramide (PEEA), polycarbonate-esteramide (PCEA) or polyether-
block-amide (PE-b-A). Properties of thermoplastic polyamide elastomers depend
strongly on type of polyamide block, type of polyol block, length and amount of
blocks.

44
 The structure of thermoplastic polyamide elastomers.
Properties of thermoplastic polyamide elastomers:
• good heat resistance (up to 170 °C)
• good chemical resistance
• good abrasion resistance
Applications:
• components in car motors and under the hood
• wire and cable coatings
• hoses
• footballs, ski boots
• films that penetrate water vapour

Comparison of different TPEs

Some values for the comparison of different TPEs are given in the table below.
TPE-S TPE-V TPE-U TPE-E TPE-A
3
Density [g/cm ] 0,9-1,1 0,89-1 1,1-1,3 1,1-1,2
Hardness Shore A/D 30A-75D 60A-75D 60A-55D 40-72D 75-63A
o
Lowest use temperature [ C] -70 -60 -50 -65 -40
o
Highest use temperature [ C] 70, 135 135 140 150 170
P(SBS)
Compression set at 100oC P F/G F/G F/G
F/G(SEBS)
Hydrocarbon resistance F/E G/E F/E G/E G/E
Hydrolysis resistance G/E G/E F/G P/G F/G
Price order [€/kg] 2...5 3...6 4...7 6...8 7...10

New development trends occurring in the field of TPEs

• Material innovations
• New polymerization techniques, metallocene techniques
• Foamed materials, e.g. supercritical gases
• Electrical properties, conductivities
• Paintability
• Blends including nanofillers
• Processing
• Coextrusion, coinjection, overmoulding
• Adhesion & joining

45
 • Milling, thermoforming, extrusion, injection & blow moulding (all processing
alternatives)
• Recycling
• Product innovations/development, hybrid products
• Product design to maximize the benefits of TPEs
• Smart products, functionality
• Design
• Food and health applications, bioapplications

Processing
Processing of rubbers
The processing of rubbers starts by blending elastomers and additives. After that
rubbers are processed with different kinds of processing methods. The possible
methods are calandering, extrusion, moulding techniques (e.g. compression moulding
and injection moulding) and dipping. After shaping the rubber product is vulcanized so
that the mechanical properties and the dimensional stability will appear. Vulcanisation
may occur during the processing or after that in many techniques.
The processing of rubbers is quite difficult. Rubber has high viscosity and that's why
high shear forces are needed in the processing. Vulcanisation poses restrictions too.

Shear rates in rubber processing.

Processing of thermoplastic elastomers
The general characteristics of the processing methods of thermoplastic elastomer and
thermoplastic elastomers are much the same. The most significant differences between
TPs and TPEs lie in the values of processing temperatures and viscosity. In the case of
thermoplastics the processing temperatures are usually higher and viscosity values are
slightly lower than those of TPEs. But as the first approximation, the processing
equipment of thermoplastics is mostly suitable also for processing thermoplastic
elastomers. The most common processing methods of thermoplastic elastomers are
injection molding, extrusion and blow molding techniques. The viscosity of TPEs is
significantly lower than the viscosities of traditional rubber elastomers, which offers
many processing advantage for TPEs compared with rubbers.
More detailed handling, see processing of elastomers.

46
Benefits of TPE processing (comparison with rubbers):
• No compounding
• No vulcanisation
• Faster processing properties (short cycle times)
• Standard thermoplastic processing equipment
• Thermally stable
• Recyclable
• Colourable in a broad range of intensities
• Clear grades available
• Paintable
• Printable
• Weldable
• Overmouldable onto a variety of different substrates
• Foamable

Design of elastomeric products

The purpose of design is to assist in converting inventions into successful innovations.

The target can also be to prolong the life of a product by giving it a new outlook or
shape (see also orienting studies product development and design)
The purpose of design is also to influence the attitude of consumer towards the
product, at various stage of the product life. Advertising, test results, outlook,
company image and price are factors that are used for attracting customers.
The important factors influencing the consumer:
• Before buying decision: shop display, total interior of the shop, colours,
materials, functions, fashion content and price
• When product is in use: products functions, ease of use and care
Impact of design for consumer.
Marketing mix Impact of Design
Price Production cost
Running cost Running and service costs
Quality Durability and quality level
Company image Package, display, promotion
Delivery performance On-time deliveries
After-sale service Service, repairs
Requirements for the development project may be defined on basis of customer
interviews. However, it is important to review these requirements, as often customers
do not really know what they want. Or their wishes are based on history rather than the
expectation of the market will be. Feasibility of various solutions is evaluated by a
feasibility study. The impact of each solution is tested in terms of profitability.
The manufacturer of elastomer products can design the product at customer's specific
request or develop new product and supply it for several customers. Technical rubber

47
products are often developed accordingly the request of the customer. Tyre is a good
example of the product that is designed by manufacturer and then marketed for
customers. The product design is often made in co-ordination with customer.
Elastomer component is often part of bigger unit, which may include metal mountings,
restrictions for size and form.
It is important that product meets requirements of customers better than products of
competitors. It is also useful if product is suited to further development.
Aspects cater to design
• Elastomer type
• Dimensioning
• Shaping
• Economic efficiency of materials and processing
• Processing method
• Reinforcement
Design process
Theoretically the phases of design process are:
1. Defining the problem and needs for product development and outlining the
project
2. Product development phase: Search for ideas and pulling them together to a
concentrated solution, developing a prototype and freezing the design
3. Before deliveries, product sketches and data, modification of operating system,
testing, full-scale production
And after product launching:
• Customer research (consumer research)
• After sale service
• Define problems and study them

Elastomer selection
The most important criteria of choosing elastomer:
• Flexibility
• Vibration damping
• Heat insulation
• Oil and chemical resistance
• Mechanical resistance (including abrasion resistance)
• Functionality in low and elevated temperatures
• Weather and ozone resistance
• Impermeability for gases and fluids
• Elasticity and vibration damping properties
• Long-term creep
• Processability
Many methods that may facilitate elastomer selection have been developed. One
example is the selecting tree. By means of the selecting tree, it is easy to make some

48
basic choices. One way is to feed the criteria to computer program and get a
recommendation of suitable material.

Selection tree of rubbers

Rubber factories have several basic rubber blends for different uses. When new blend
is needed, a suitable basic blend can be selected and modified to conform to the
requirements of the new product. Thus new rubber blend is obtained relatively easy,
because good basic data about the properties and processing already exist.

Dimensioning of elastomer products

In dimensioning the most important starting points to be taken into account in early
stage of design are
• Functionality
• Prediction and ensuring the risks of damage
• Prediction of lifetime
Product may be damaged in many ways. It can for example:
• Creep
• Fracture
• Change stiffness because of chemical changes caused by temperature

49
 • Change stiffness because the chemicals from environment diffuse to the
material
To predict the damages, it is important to know models of behaviour and parameters of
materials. Models of planning are not very advanced for elastomers. Exploitation of
those is complicated because of non-linear loading-deformation phenomena that make
the theoretical prediction of practical structures difficult.
Mechanical dimensioning
The purpose of product design is to assure the functionality of product. One of the
most important stages is to ensure that load capacity correspond to demands.
The influence of hardness
The most important property that characterizes rubber is hardness (stiffness). Hardness
has an approximate connection to compression modulus and shear deformation
modulus. The approximate relations can be presented according the equation
E ≈ 1,045 h (MPa) = 2(1 + ν ) ≈ 3 G,
where h = hardness, E = compression module, G = module for shear deformation, ν =
Poisson number (indicates the cross-section change in compression or tension).
Elastomers are practically incompressible (E = 1.0…3.5 GPa) and therefore their ν ~
0.5. The equation above is best valid when the hardness of rubber is 30…80 ShA
(corresponding G = 0.3…3 MPa).
Shape factor
The deformation of almost incompressible elastomeric materials is drastically
influenced by the shape of the loaded piece. The shape of rubber piece is described
with shape factor S (see figure below).

Stiffness in different loading situations

Taking the shape factor S into account, dependences between compression stress σ ,
compression modulus Ec, and shear modulus G (see picture below) can be written in
the form

50
σ = F/A = Ec (1 + 2 k S2) x/h and Ec = G (3 + CS2)
F = Pressing force
A = Cross-sectional area
E = Compression module
G = Shear module
k = Parameter that depends on hardness of rubber (assumption k = 1)
x = Compression deformation
h = Height in stress direction
C= Constant (form factor)
S = Shape factor
The equations above are best valid with the shape factor values 1 - 10. The factor C
depends also on the form of the sample, being typically between 4 (long stripe) ... 6
(round plate). Principal dependence of Ec on shape factor is shown in the picture
below.

Stiffness of rubber constructions can be controlled with the help of equations above.
The construction is shared with rubber plates that have shape factor greater than
single-layer structure. The method is, for example, used with bridge bearings where
the load capacity has to be considerable.

Compression modulus of natural rubber as a function of shape factor and hardness.

Allowed loadings for different rubbers
Stiffness dependencies on deformation were described by the equations on preceding
page. Using the equations the deformations caused by real loadings situations can be

51
estimated. Highest allowed values for different kinds of loading situations are often
presented. The values are empirically confirmed.
As an example, a series graphs are presented below (next page). It gives information
about the allowed compression loadings. In each graph the transversal lines outline the
following areas:
• Under the lower line is the area of allowed loadings
• Under the upper line is the area of allowed loadings but to be regarded with
reservation
It can be seen in the graph that in practice, allowed deformations is for
• Harder rubbers about 15 %
• Softer rubbers 20 – 25 %
Again, the loading stress has to be < 1MPa in compression and 0.3 MPa in shear.

52
 Loading estimation graphs for rubber products having different hardness and shape
factor.
The greatest values allowed in mechanical loading depend on the rubber and also on
other stress factors (including chemical loadings).

53
For example, if there is an application where the long-term creep is a critical factor, the
dynamical loadings have to be estimated separately. That is because they can generate
greater permanent deformations than static loadings.

Creeping values to filled and non-filled natural with static and dynamical loading.
Loading in stretching has also to be taken into account. Stretching deformations should
be minimized, because rubber molecules are susceptible to ageing reactions caused by
radiation, ozone and oxygen.
Creeping depends on the composition of elastomer. So it is not possible to draw far-
reaching conclusions on the grounds of theoretical modeling that base on typical
rubber type properties.
Rubber blends can contain 5 ... 20 components, so it is obvious that the properties vary
significantly. Thus the properties of new rubber blend are to be measured first and only
then the behaviour of the rubber can be evaluated.

Product shaping
As a result of dimensioning, certain limitations for products' dimensions have been
achieved. Before the mould design the structure of the elastomer product has to be
shaped so that the local stresses are avoided in loading situations. The weather
sensitive surfaces should not be exposed to stretch loadings.
The examples of designing for even loading are shown in the figures below.

54
Examples of applications used to get even distribution of loading stress and avoiding
tension in rubber product.

Recycling and reuse of elastomeric materials

The global consumption of vulcanized elastomers is about 17,2 million tons/year.
Approximately 40 % of that is natural rubber. Goodyear developed the first recycling
method. According to this patented method rubber waste was grinded and used as
filler.
The main problem with vulcanized rubber products is their use after their useful life
has expired. Rubber waste is usually generated from both the products of the
manufacturing process and post-consumer products, mainly consisting of scrap tires.
The environmental problems created by waste rubbers and legislative restriction
demands search for economical and ecological methods of recycling.
Why reclaim or recycle rubber?
Rubber recovery can be a difficult process. However, there are many reasons, why
rubber should be reclaimed or recovered;
• The price can be reduced to half compared to synthetic material.
• Recovered rubber has some properties that are better than those of virgin
rubber.
• Producing rubber from reclaim requires less energy in the total production
process than virgin material.
• It is an excellent way to dispose unwanted rubber products, which is often
difficult.
• It conserves non-renewable petroleum products that are used to produce
synthetic rubbers.
• Recycling activities can generate work in developing countries.
• Many useful products are derived from reused tyres and other rubber products.

55
 • If tyres are incinerated to reclaim embodied energy, they can yield substantial
quantities of useful power. In Australia, some cement factories use waste tyres
as a fuel source.

Recycling methods
Basically waste rubber can be recycled in three ways: It can be used for energy by
combustion, in its original form through devulcanization and as ground powder.
Recovery Alternatives
Kind of recovery Recovery process
Product reuse Repair Retreading
Regrooving
Physical reuse Use as weight
Use of form
Use of properties
Use of volume
Material reuse Physical Tearing apart
Cutting
Processing to crumb
Chemical Reclamation
Thermal Pyrolysis
Combustion
Energy reuse Incineration

Waste management hierarchy

Incineration

56
Incineration is a good and economic method of disposing of rubber. The energy
content of rubber is about 32,6 MJ/kg, which is about 10 % less than heavy oil (37,7
MJ/kg) and 1,3 times the energy content of coal (25.1 MJ/kg) Rubber is burned in
special incinerator. The purpose is to recover energy as much and as ecological as
possible.
Incineration produces oxygen, carbon dioxide, water and some toxic gases. Using
sufficiently high temperatures can prevent formation of toxic components, such as
dioxin.
Pyrolysis
Pyrolysis involves heating the rubber waste in the absence of oxygen. The
temperatures used in this process are typically 400-800 ° C. Pyrolysis process
produces three principal products: pyrolytic gas (10-20%), oil (40-50%), and char (30-
40%). Char is a fine particulate composition of carbon black, ash, and other inorganic
materials, such as zinc oxide, carbonates, and silicates. Other by-products of pyrolysis
may include steel, rayon, cotton, or nylon fibers from tire cords. Each product and by-
product is marketable:
• The gas has a high heat value.
• The light oils can be sold for gasoline additives to enhance octane, and the
heavy oils can be used as a replacement for number six fuel oil.
• The char can substitute for carbon black in some applications, although quality
and consistency is a significant impediment.
The quality and quantity of pyrolytic products depend on the reactor temperature and
reactor design. Heating rate, reaction time and pressure are also important process
variables.
Pyrolysis does not pollute air significantly because most of the pyro-gas generated is
burned as fuel in the process. During burning, the organic compounds are destroyed.
The decomposition products are water, carbon dioxide, carbon monoxide, sulphur
dioxide and nitrogen oxides.
Grinding of vulcanized rubber waste
Sometimes it is good to reduce the size of the rubber. For example landfill of whole
tyres may be prohibited, while it is permissible to dump granulated tyre chips. The size
reduction of rubber waste enables the burning process too. In most other cases the
grinding of rubber articles is required to remove the rubber from reinforcing textiles or
metals and prepare the rubber for the next processing step, such as adding in virgin
rubber or other polymeric compounds, surface activation or devulcanization.
Size reduction can be caused by impact, cutting or tearing, or by degradation of the
rubber. There are three ways to break down tyres into crumb rubber. All three begin by
shredding or cutting the tyres into relatively large pieces (average size 20 x 20 mm).
There are three processes steps:
1. milling and grinding of dry material at ambient temperature (ambient grinding)

57
 Typical ambient grinding system
2. milling of frozen material cooled to liquid nitrogen temperatures (cryogenic
grinding)

Typical cryogenic grinding system

3. milling of swollen material with subsequent solvent recovery (wet grinding).
Crumb rubber is measured by mesh or inch and it is generally defined as rubber that is
reduced to a particle size of 3/8-inch or less. Crumb sizes can be classified into four
groups that are:

58
 ƒ large or coarse (9-5 mm or 3/8” and 1/4”) (ambient grinding)
ƒ mid-range (10-30 mesh or 2-0.6 mm or 0.079”-0.039”) (ambient grinding)
ƒ fine (40-80 mesh or 0.425-0.180 mm or 0.016”-0.007”) (cryogenic and wet
grinding)
ƒ superfine (100-200 mesh or 0.149-0.074 mm or 0.006”-0.003”) (cryogenic and
wet grinding)
The chemical composition, the duration of breakdown and the ratio of thermal to
mechanical breakdown influence the physical properties of reclaim. Varying the
duration and ratio of the different breakdown steps allows the production of custom
reclaims differing in viscosity, tensile strength and other related properties. An
explanation of this effect is found in the selectiveness of the mechanical breakdown
step: it is primarily the carbon – carbon backbones of the network, which are broken
down, and preferably the longer chains will be broken. This leads to a more narrow
molar mass distribution. The thermo-chemical breakdown step is random. As a result,
the percentage of low molar mass-polymer, acting as a peptizer and having no
reinforcing effect on the network, increases and the tensile strength of the cured
reclaim decreases. These differences in reclaim quality influence the properties of a
compound containing the different reclaims.
Recycled rubber powder obtained from ambient or cryogenically ground tyres can be
utilized as filler in rubber and other polymeric compound. In cryogenically and wet
ground rubbers, smaller particle size allows recycled rubber to be used at moderately
high levels and still maintain the processability. The incorporation of GRP into
polymeric matrix typically impairs the mechanical properties of the resulting
composites. This is because of poor matrix-filler adhesion and the lack of reactive sites
on the particle surface. Thus the related end products generally find applications with
low performances. To overcome this problem various surface treatments of GRP have
been proposed:
ƒ Coating of the GRP
ƒ Interfacial compatibilizing
ƒ High-energy radiation such as plasma, corona and electron beam radiation
ƒ Reactive gas treatment
ƒ Chlorination
ƒ Surface grafting
ƒ Use of coupling agents
Devulcanization
Devulcanization is one of the new methods of recycling waste rubber products.
Devulcanization means the cleavage of cross-linking sulphur bonds in rubber
vulcanizates, without cleavage of the polymer chain bonds. Devulcanization is a good
way of utilizing rubber waste because it assumes renewal of the original chemical
formula of elastomers and provides a possibility of recovering elastomers from rubber
vulcanizate waste. It can also be incorporated into the compound in a considerably
larger amount than surface modified or non-modified rubber scrap. In general, instead
of adding one part of unmodified rubber scrap, about three parts of surface modified or
about seven parts of devulcanized rubber can be added.
However, in practice a total devulcanization process is very difficult to achieve since
many problems are caused by accompanying chemical transitions such as
depolymerization, thermal destruction and oxidation that worsen the properties of the
recovered elastomers. The main problem is the very low thermal conductivity of

59
rubber and the extremely difficult selective regulation of the quantity of energy carried
to the cross-linking bonds. In practice, it is virtually impossible to achieve such levels
of energy evenly distributed in all materials. It is necessary to find experimentally the
optimal devulcanization conditions that lead to devulcanized products with good
properties can be obtained.
At the initial stage of devulcanization reaction, the polysulphide and disulphide bonds
are changed to monosulphide bonds by heat. Furthermore, the monosulphide bond is
broken by addition of shear stress and finally recycled uncured rubber is achieved.

Mechanism of cross-linking bond breakage reaction

Both physical and chemical processes are used to carry out the devulcanization or
reclaiming of GRP. The powder is either subjected to shear action in suitable
equipment like extruder or two-roll mill and partially decrosslinked or to chemical
action to achieve reclaimed material. In addition e.g. devulcanization by
microorganism has been examined. There is also a commercially produced
devulcanization agent on the market (De-Link R). Physical processes involve
applications of mechanical, thermo-mechanical, microwave or ultrasound energy to
partially devulcanize the rubber. In the chemical reclaiming process, different
chemical reactants like diphenyldisulphide, dibenzyldisulphide, diamyldisulphide,
mercaptan, xylenethiol, iron oxide/phenyl hydrazine mixture etc. have been used for
the treatment of scrap ground rubber powders at elevated temperature. In chemical
treatment done by Kim and Park the chemical reagent used was di(benzanidopheny)-
disulfide. It enables the polysulfide bond from polymer chain to be destroyed. The use
of the treated crumb rubber enhanced the mechanical performance of the rubber
compounds produced.

Utilization of unvulcanized rubber waste

Unvulcanized rubber waste is mainly generated from the manufacturing process. It is
also very useful to recycle. Reinforced rubbers that contain a steel wire and textile
fiber are difficult to recycle. However, all these include valuable raw materials. The
utilization of unvulcanized rubber waste provides a variety of processing advantages.
It also has the positive effect on energy consumption because much less energy is
consumed through the production and utilization of products including waste rubber
than through the manufacture of virgin raw materials. One option of course is a
vulcanization of an unvulcanized rubber waste. After that the grinding is possible.

60
Processing of recycled rubber
Unvulcanized rubber waste
Temperature has a big role in processing of unvulcanized rubber. In order to maintain
the temperature rise within an acceptable limit, the mixing equipment has to be
coolable. The temperature must be controlled to ensure that excessive plasticization or
to prevent early scorching. Every elastomer has an optimum temperature for efficient
heat exchange.
When mixing unvulcanized rubber waste with virgin rubber and ingredient in internal
mixer, the mixers have to be cooled very well in order to remove the heat generated
during the mixing cycle. Unvulcanized rubber waste has to be filled into the mixer in
the shortest possible time and also the whole mixture has to be discharged very
rapidly. After the discharge from the internal mixer, the compound is in the form of
lumps and has to be homogenized, cooled and sheeted out on follow-up equipment
such as sheeting mill or forming extruder.
In mill mixing a temperature control is easier. The rolls are cooled down to remove
excessive heat, which is built up during mixing. That is why the processing of
unvulcanized rubber waste with two roll mill is the most safe process, concerning the
risk of scorching.
To prevent the risk of scorching, also some retarders can be used. The advantage of
using unvulcanized crumb rubber is that it can be bonded directly to the elastomer
matrix.
Vulcanised rubber waste
One of the most effective ways of reusing rubber waste is to load it into new rubber
products in the form of fine ground powder (rubber scrap). Rubber scrap is easy to
apply with simple equipment and has positive influences on the processing behaviour
of a compound.
The main advantages derived from the use of reclaim concern the processing
behaviour of the compound. These include:
ƒ Shorter mixing cycles resulting in reduced processing costs
ƒ Lower mixing, calendering and extrusion temperatures resulting in fast and
uniform calendering and extrusion
ƒ Improved penetration of fabric and cord
ƒ Lower swelling and shrinking during extrusion and calendering
Other important advantages are:
ƒ Lower raw material costs
ƒ Better air venting properties
ƒ Improved stability during curing in hot air or open steam
ƒ Improved reversion and aging performance of natural rubber compounds
(ozone, UV)
In the processing of cryogenically ground rubber certain particle sizes are more
suitable in specific applications:
• Extrusion: 80-100 mesh cryogenically ground rubber is needed to avoid
fracturing and rough edges. In extrusion of thick section 50-60 mesh

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 cryogenically ground rubber can be used depending on the surface smoothness
of the final product. The optimum level of cryogenically ground rubber to be
added to virgin rubber is 5%.
• Calendering: for optimum surface smoothness of products, whose thickness are
1,5 mm or less, the compound requires 80-100 mesh cryogenically ground
rubber. Where smoothness is not so important/critical 30-60 mesh can be used.
The optimum level of cryogenically ground rubber in calendering is 10%.
• Moulding: the cryogenically ground rubber in all mesh sizes can be used
because all mesh sizes help in removing trapped air during moulding. The
cured rubber particles provide a path for the air to escape by bleeding air from
the part.
• Mould flow: cryogenically ground rubber generally improves mould flow.
Shrinkage is usually less for compounds containing cryogenically ground
rubber. The shrinkage reduction is proportional to the amount of cryogenically
ground rubber in the compound. So less mould flashing was found with
increase in the percentage of cryogenically ground rubber.
Devulcanized rubber waste
The devulcanized rubber can be processed, shaped and vulcanized in the same way as
the virgin rubber. There are also many benefits derived from the use of devulcanized
rubber in rubber compounds:
ƒ Shorter mixing cycles – lower power consumption
ƒ Low calendering, mixing and extrusion temperatures – greater uniformity
ƒ Improved penetration of fabric and cord
ƒ Increased tack with minimal effect on temperature variation
ƒ Low swelling and shrinkage during extrusion or calendering
ƒ Improved stability during curing in hot air or open steam
ƒ Better air venting
ƒ Improved reversion and ageing performance on natural rubber
ƒ Lower raw material costs
One shortcoming of reclaim is that it lowers the green strength of the compounds.

Applications of waste rubber

ƒ Pavements
ƒ Sound barriers
ƒ Polymer mortars and concretes
ƒ Recycled rubber can be applied to the entire range of rubber products including
tyres, technical rubber goods, conveyor belts, shoe soles and industrial
coatings.
ƒ Rubber powder can be applied to sport surfaces as a rubber mat when bounded
with a polymer binder e.g. polyurethane or only just as such mixed with sand.
ƒ Whole tyres can be used for artificial reefs, breakwaters, erosion control,
playground equipment and highway crash barriers.

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Recycling of tyres
The recycling methods of rubbers are: product reuse, material reuse and energy
recovery. Most tyres of cars and vans can be retreaded. Tyre of cat can be retreated
once and tyres of vans 2 to 3 times. Retreated tyres should only be mounted on low-
speed rated cars. There must be an age-restriction for the acceptance of worn tyres
(e.g. 6 years) and careful inspection is required prior to start buffing and afterwards
during the process. In addition lower weight or longer running tyres are becoming less
suitable for retreading operations. Lifetime and driving distance expectations for truck
tyres have increased and retreading is common.
If product can not be reused, it can be used in secondary purposes. The biggest
secondary reuse applications of tyres are road building, noise barriers and landfills. In
those applications the tyre powder may be act as insulator or lightening material
between different bearing courses. Blasting mat and buffers in piers are used too.
Examples of the amount of tyres in different secondary reuse applications.
Application The amount of The largeness of the product
tyres [piece]
Bitumen asphalt 2500 Per road km
Noise barrier 20000 Per road km (3m high)
Playground 1400 about 500 m2
Playground safety ground 300 about. 50 m2
Sports field 6000 6000 m2
Sport hall 1300 1000 m2
Electricity production 150-675 tons Per month

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