COVENANT UNIVERSITY

COLLEGE OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY

COURSE TITLE: Polymer Technology

COURSE CODE: CHM423 UNIT: 2
SESSION: 2019/2020 LOCATION: Hall 112
LECTURER: A. A. Akinsiku (PhD)

STUDIES OF ELASTOMERS

Elastomers are amorphous polymers which possess both viscous and elastic properties. The
term elastic refers to the tendency of an object to return to its original shape after being
stretched or compressed. All polymers above the glass transition temperature (Tg), act as
rubbers due to entanglements. However, when the entanglements break, the polymer will
begin to flow. The glass transition temperatures of all rubber are quite low, usually below
room temperature; therefore, many polymers at room temperatures act as rubbers
(elastomers) with many useful properties. The elastomers are used in many applications
because of their unusual properties, which are unmatched by other types of materials.

Differences exist between elastomers and rubber, in the sense that the former are processed
from natural gas and petroleum bye products to synthetic rubber. In contrast, rubber is
derived from organic materials from nature. The elastomeric materials can be modified after
curing by heat, irradiation, and vulcanisation by chemical reaction. However, the
vulcanisation reduces the viscosity; increase the elasticity, also elastomer would be insoluble
in boiling solvent and becomes more resilience. Under normal conditions, the long molecules
chains making up an elastomeric material are randomly distributed and are irregularly coiled.
But when a force is applied to it, the molecular chains straighten out in the direction of the
force; when these external forces are removed, the chains spontaneously return to their
standard configuration and original shape.

Elastomers display characteristics of rubber in terms of flexibility and elasticity; they possess
notably low Young’s modulus and high yield strain compared with other materials. They are
also cross-linked amorphous polymer above its Tg; form covalent links between different
polymer chains and joining them all into a single networked molecule. A large number of
cross-links make the material rigid, hard, and closer in properties to a thermoset. The
elastomers are differentiated from other polymers by their mechanical properties, and the
cross-links lead to polymers having excellent mechanical properties, such as tensile strength,
dimension stability, excellent thermal resistance, and easy processing. The uniqueness of
elastomers is that they can be stretched to many times their original length, and can return
to their original shape without permanent deformation. Elastomers can also be grouped as
thermosets and thermoplastics.

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Thermosetting elastomers are further classified as general-purpose elastomers and specialty
elastomers. General-purpose elastomers are used in some applications, such as styrene
butadiene rubber (SBR), butadiene rubber (BR) and natural rubber. General elastomers are
unsuitable in many applications, and so require higher performance. Specialty elastomers are
more costly and hence are produced in smaller volumes, such as silicon rubber, polyacrylic
rubber (PAR), etc. The cross-links in polymer chains similarly affect the morphology,
miscibility, and composition of thermosetting polymers. Some common thermosetting
elastomers include natural rubber (NR), silicone, butadiene rubber (BR), styrene butadiene
(SBR), chloroprene, fluorocarbon, ethylene-propylene, polyurethane, etc. Still, their low
toughness, resistance to temperature and crack initiation restrict their extensive applicability.

Thermoplastic elastomers display a combination of thermoplastic and elastomeric properties.

They are modified to behave as thermoplastics during processing (melting), and as elastomers
during use. Their molecules are tied together when the rubber is being used but allows the
chains to separate when being processed. Examples are thermoplastic urethane, styrenic
block copolymers, copolyether ester elastomers, polyester amide, etc. These materials
facilitate different noble electrical properties, such as excellent water, ozone, weather, heat,
and steam resistance and have smaller temperature flexibility. The main advantages of
thermoplastic elastomers over rubber are easy processing and the ability to change
properties due to recycling and reuse. These elastomers have a strong ability to retain their
shape after being deformed and have a high melting temperature and zero-creep
phenomenon.

Primarily, elastomers are used for seals, adhesives, moulded flexible parts, gaskets, rubber
and septum. Further applications of elastomers are in the automobile industry to make tires,
braking systems, chassis, interior components, etc. In many cases, improvements in
mechanical properties of elastomers are required to extend their lifetime and further broaden
their applications. Most elastomers are thermosets which require curing, and in the curing
process, the long molecules chains held together by chemical bonds (covalent bonds). The
material becomes stronger, and it cannot be remelted, remoulded, recycled, and
reprocessed.

Features of Elastomers

Elastomeric behaviour was first realised in a natural rubber (NR) vulcanised by reaction with
sulphur. All synthetic materials are closely modelled on natural rubber, being linear chain
polydiene and random copolymers, with C=C double bond unsaturation in the chain to permit
irreversible cross-linking, mostly as in natural rubber itself. Some elastomers have close
structural relations of thermoplastics and thermosets.

For rubberiness, the polymers must be far above their Tg, and for practical advantage and
common use, Tg for elastomers or rubbers should be in the range -40 to -800C (Figure 2). This
is commonly attained in systems of low cohesive energy density and poor molecular
symmetry resulting in amorphousness. Although these requirements and features for
elastomers imply high local or segmental mobility, the gross or full-scale movement as in the
flow region must be low in practical elastomers.

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Figure 2: Temperature dependence of log modulus in a polymer system

Special properties of elastomers

The most important properties of elastomer materials are elasticity and resiliency.

1. Elasticity

Elasticity is the property that allows elastomers to return to their original shape after the force
which stretch, compress or bend them is removed. The covalent bonds (cross-linkages) help
and ensure the elastomer to return to its original configuration when the stress is removed,
but without cross-link or with short cross-link, uneasily reconfigured chains. Therefore, when
the elastomer structure contains no cross-links, and a force applied on it causes both elastic
and plastic deformation; after the load is removed, the elastomer is permanently deformed,
because of uneasily reconfigured chains. But when cross-linking occurs in elastomer, the
elastomers still undergo large elastic deformation; however, when the load is removed, the
elastomer returns to its original shape, these behaviours as shown in Figure (2). As a result of
this, materials have extreme flexibility and extend from (5-10) times, depending on the
specific material.

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Figure 2: (a) Elastomers without cross-linking (b) Elastomers with cross-linking

2. Resiliency

The resilience of a material is the ratio of the returned energy to the input energy. It points
out to the speed of return (recovery) of elastomers to its original shape after a deforming
force (external force) is removed. The deforming force is applied as input energy to the
elastomer, when the elastomer returns to its original shape, part of these input energy is not
returned but is dissipated as heat energy within the elastomer.

The chart below provides general information and features for various common elastomeric
compounds. Rubber compounding is a broad field. Basic elastomers are mixed with a variety
of chemicals and ingredients to obtain desired physical properties. Many basic polymers are
available that can yield compounds with unique physical properties.

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 Common elastomeric compounds

Common Designation Composition General General Chemical Resistance

Name(s) Properties
Resistant to: Attacked by:

Neoprene CR Chloroprene Good weathering Moderate chemicals Strong

resistance. and acids, ozone, oils, oxidising
Flame retarding. fats, greases, many acids, esters,
Moderate resistance oils, and solvents. ketones,
to petroleum-based chlorinated,
fluids. aromatic, and
nitro
hydrocarbon.

EPDM EPDM, EPM Ethylene- Excellent ozone, Animal and vegetable Mineral oils
propylene-diene; chemical, and ageing oils, ozone, strong and and solvents,
Ethylene-propylene resistance. oxidising chemicals. aromatic
Weak resistance to hydrocarbons
petroleum-based
fluids.

Buna-N NBR Nitrile-butadiene Excellent resistance Many hydrocarbons, Ozone (except

to petroleum-based fats, oils, greases, PVC blends),
fluids. hydraulic fluids, ketones,
Good physical chemicals. esters,
properties aldehydes,
chlorinated
and nitro
hydrocarbons.

Silicone Q, Si Polysiloxane Excellent high and Moderate or oxidising Many

low-temperature chemicals, ozone, solvents, oils,
properties concentrated sodium concentrated
Fair physical hydroxide. acids, dilute
properties. sodium
hydroxide.

SBR SBR Styrene-butadiene Good physical Most moderate Ozone, strong

properties and chemicals, wet or dry, acids, fats,
Abrasion resistance organic acids, oils, greases,

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 to petroleum-based alcohols, ketones, most
fluids. aldehydes. hydrocarbons.

Butyl IIR Isobutene-isoprene Excellent weathering Animal and vegetable Petroleum,

resistance fats, oils, greases, solvents, coal
Excellent dielectric ozone, strong and tar solvents,
properties oxidising chemicals. aromatic
Low permeability to hydrocarbons.
air
Good physical
properties
Weak resistance to
petroleum-based
fluids.

Natural, NR Isoprene, natural Excellent physical Most moderate Ozone, strong

gum properties including chemicals, wet or dry, acids, fats,
rubber abrasion and low- organic acids, oils, greases,
temperature alcohols, ketones, most
resistance. aldehydes. hydrocarbons.
Weak resistance to
petroleum-based
fluids.

Urethane AU, EU Polyethylene, Poly Good ageing and Ozone, hydrocarbons, Concentrated
oxy-1,4, butylene excellent abrasion, moderate chemicals, acids,
ether tear, and solvent fats, oils, greases, etc. ketones,
resistance. esters,
Poor high- chlorinated
temperature and nitro-
properties. hydrocarbons.

Viton, FPM Hexaflouroprop- Excellent oil and air All aliphatic, aromatic Ketones, low
Fluoro- ylenevinylidene resistance both at and halogenated molecular
elastomer fluoride. low and high hydrocarbons, acids, weight esters
temperatures. animal and vegetable and nitro-
Very good chemical oils. containing
resistance. compounds.

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ECH, ECO Ethylene-oxide Good low Similar to nitrile with Ketones,
Hydrin, temperature ozone resistance esters,
Herchlor chloromethyl- properties aldehydes,
oxirane chlorinated
Excellent oil and and nitro-
ozone resistance hydrocarbons

Fair flame resistance

Low permeability to
gases

Bibliography

The Effect of Sterilisation on Plastics and Elastomers (Third Edition), 2012

Liesl K. Massey, in Permeability Properties of Plastics and Elastomers (Second Edition), 2003

Vinny R. Sastri, in Plastics in Medical Devices, 2010

K. Pal, ... J. Bahadur, in Progress in Rubber Nanocomposites, 2017

Q. Adnan, Rubber technology lecture.