Elastomeric Materials

CHRISTOPHER COLUMBUS- 15th

CENTURY OBSERVED IN SOUTH

AMERICA CHILDREN PLAY WITH
BALLS MADE OF NATURAL RUBBER
21 st CENTURY- RUBBER IS A
MULTIBILLION DOLLAR INDUSTRY

Elastomeric Materials
Common characteristics;
Large elastic elongation (i.e.200%)
Can be stretched and then immediately return to their
original length when the load was released
Elastomers are sometimes called rubber or

rubbery materials
The term elastomer is often used
interchangeably with the term rubber
Elastomers are usually thermosets (requiring
vulcanization) but may also be thermoplastic (see
thermoplastic elastomer).

 All materials have some elastic elongation

elastic elongation = elongation of any material when

that material is at its yield point

Ceramic & metal- small elastic elongation; 2%
PE, elastic elongation; 50%

Stress-strain diagram

Idealized stress-strain curves for

metals, conventional plastics and
elastomer

Diagram showing the random, natural

state of elastomer when under no stress
and when stressed

 A material may be elastomeric at room temp,

however rigid at lower temp (why???)

They are amorphous polymers existing above their
glass transition temperature, so that considerable
segmental motion is possible.
At ambient temperatures rubbers are thus
relatively soft (E~3MPa) and deformable

 Most elastomers are crosslink. Atoms between

crosslink can still move, uncoil and coil.

The long polymer chains cross-link during curing
and account for the flexible nature of the
material.
Without crosslink, an elastomer may be
elongated beyond elastic limit, with crosslink,
max. elongation is set safely within the elastic
region
Crosslink density- total number of crosslink in
the system (less elongation is desired, number of
crosslink can be increased)

Natural Rubber
Rubber tree (Hevea Braziliensis)
Natural rubber is obtained by drying a latex rubber (milk

in which the butter fat component is suspended in water

salution)
High temperature stability cooking the crude natural
rubber with sulphur (vulcanization)
Vulcanization creates crosslinking between rubber
molecules
Natural rubber is highly elastomeric (elongation 1000%
for vulcanized natural rubber)
Compared to other elastomeric materials, natural rubber
shows higher tensile strength, high tear strength, high
resilience, resistance to wear, etc

Polymer repeating groups

Crude natural rubber was chiefly composed of cis-

polyisoprena (a polymer chain with carbon carbon double

bond with repeating unit)
Cis means that two pendent group (H and CH3) that are
attached to the two carbons in the carbon carbon double
bond
The alternate configuration where the two groups are
located on the opposite side of the carbon carbon double
bond is called trans
The presence of methyl group interfere the movement in
polyisoprene polymer- restricted bending and twisting
motion (increased stiffness, higher strength, and higher
temperature stability

Polyisoprene structure

Cis-poliisoprena

Trans-poliisoprena

(Hevea rubber)

(Gutta percha)

Natural Rubber
H H
C H
H

C
H

Gutta percha or Balatta

(trans-polyisoprene)

H C

H
C

Hevea Rubber
(cis-polyisoprenene)

C
C H

H C
H

 Properties of cis and trans are quire different

Cis is highly elastomeric & sensitive to heat

softening
Trans materials is called gutta percha, much
harder than cis isoprena-used for golf balls
During vulcanization process, sulphur will react
with carbon carbon double bond

Natural Rubber
Material is processed

Natural Rubber
Latex is then dried, sorted and smoked

Synthetic Polyisoprene or Isoprene

Rubber
Disruption of supplies of natural rubber during world war I

and II & increase needs for elastomeric materials- needs for

synthetic rubber
Synthetic polyisoprena made in early 1900s, used for tires
for lightweight vehicles
Combination of cis and trans molecular forms- mixture of
properties
Ziegler-Natta catalyst system was developed in 1950s, it
was found that 90% pure cis-isoprena could be produced by
this catalyst system
However, natural rubber is used more extensively because
of its low cost

Butadiene Rubber (BR)

Synthetic rubber
Repeating units of both have a backbone of four
carbon atoms including carbon carbon double bond
Polybutadiene has just two hidrogen attached to the
carbon carbon double bond
Absence of methyl group in polybutadiene results in
poorer strength & tear strength than would
polyisoprena. Resilient is about the same.
Polybutadiene has poor resistance to solvents

Butadiene Rubber (BR)

H
C

H
H

C
C

H
H

How is this polymer different from natural rubber?

Butadiene Rubber (BR)

Lower mechanical strength because of no of pendant

methyl group but also more flexibility

Lower cost (all synthetic from cheap monomer)
Improvement of low-temp flexibility
Compatibility with other polymer materials

 Advantages of Polybutadiene; low cost, improvement in low

temp. flexibility, compatibility with many other polymeric

materials, good adhesion to metal
Butadiene monomer is added to the monomer of the other
plastic copolymer is created
Butadiene monomer + polystyrene = styrene butadiene
rubber (SBR)
Bulky Styrene molecules add stiffness and intermolecular
interference to butadiene while butadiene adds flexibility
and toughness to styrene

SBR

BR

Styrene Butadiene Rubber (SBR)

Oil-Resistant Elastomers
NBRNitrile Butadiene Rubber
Copolymerization of butadiene and acrylonitrile
More expensive than SBR or BR
CRChloroprene rubber (neoprene)
Thermal stability
Non-flammable

Thermoplastic Elastomer (TPE)

These materials are not crosslinked, have some distinct

processing advantages over traditional thermoset

elastomers and physical properties of vulcanised
elastomers
TPEs are able to be molded like thermoplastic (injection
molding, extrusion, etc)
Thermoplastic elastomers are more temperature sensitive
Scrap and reject of these materials can be recycledenvironmetal friendly behavior
Normal crosslinked polymers cannot be recycled because
they don't melt. They don't melt because the crosslinks tie
all the polymer chains together, making it impossible for
the material to flow.

Thermoplastic Elastomers (TPE)

Many of the properties of thermoset elastomers
Resiliency
Elasticity
More easily processed
Injection molding, extrusion and other standard
thermoplastic processes
Highly compatible with polyolefins
EPDM is crosslinked very lightly and may not be capable
of being melted

Thermoplastic Elastomer (TPE)

The capability to repeatedly process thermoplastic elastomers
provides the major benefit of TPEs over elastomer.

Variable

TPE

Elastomer

Fabrication

Rapid (seconds)

Slow (minutes)

Scrap

Reusable

High Percentage waste

Curing Agents

None

Required

Machinery

Conventional
Special Vulcanizing
Thermoplastic Equipment Equipment

Additives

Minimal or None

Numerous Processing Aids

Design Optimization

Unlimited

Limited

Remold Parts

Yes

Unlikely

Heat Seal

Yes

No

Thermoplastic Elastomer (TPE)

Benefits of TPEs compared to

Elastomer
Design flexibility
Lower fabrication costs
Shorter processing times
Little or no compounding required
Scrap is fully recyclable
Consistency of product
Can be blow molded
Can be thermoformed
Lower consumption of energy
Simpler processing
Better control of product quality
Broader range in product density
Lower per-piece finished part cost
More environmentally friendly

Silicones, or polysiloxanes
Silicones, or polysiloxanes, are inorganic-organic

polymers with the chemical formula [R2SiO]n, where

R = organic groups such as methyl, ethyl, and
phenyl.

These materials consist of an inorganic silicon-

oxygen backbone (...-Si-O-Si-O-Si-O-...) with organic

side groups attached to the silicon atoms, which are
four-coordinate.

Silicones

H
H

H
H

)n

)n

Silicones, or polysiloxanes
In some cases organic side groups can be used to link

two or more of these -Si-O- backbones together. By

varying the -Si-O- chain lengths, side groups, and
crosslinking, silicones can be synthesized with a wide
variety of properties and compositions.
They can vary in consistency from liquid to gel to
rubber to hard plastic. The most common type is
linear polydimethylsiloxane or PDMS

Silicones, or polysiloxanes
Service temperature to about 260C
Good chemical resistance, low water absorption,

good electrical properties, & available in flame

retardant grade
In the plumbing and automotive fields, silicone
grease is often used as a lubricant. In plumbing, the
grease is typically applied to O-rings in faucets and
valves.
In the automotive field, silicone grease is typically
used as a lubricant for brake components since it is
stable at high temperatures, is not water-soluble

Silicones

PROCESSING OF ELASTOMER
Common machine used for
rubber compounding:1.
2.

Banbury mixer
2-roll mill

Overall processing route for rubber

1st Stage mix

2st Stage mix

Rubber, filler,
oils, etc
Active
vulcanizing
agent

Preform:
calendering,
extruder, etc
Cure: Vulcanizing by heat and
temperature; compression molding,
oven steam cure, etc
150C

Testing;
compound
plasticityviscosity
testing, curing,
propertiestensile,
hardness, etc

RUBBER CURING/ CROSSLINK

DENSITY

INTRODUCTION

Common instrument used to determine the

kinetics of crosslinking
1.

2.

Oscillating disc rheometer (ODR)

An oscillating rotor is surrounded by a test
compound, which is enclosed in a heated chamber.
The torque required to oscillate the rotor is
monitored as a function of time at the temperature
chosen for vulcanisation.

Moving-die rheometer (MDR)

Use thinner samples and has a faster thermal
response than ODR

Oscillating disc rheometer (ODR)

In order to predict the cure behavior of rubber compounds,

torque rheometers or curemeters are used.

Cure Behavior

These instruments measure the torque required to oscillate a

biconical disk within the rubber compound. The result is a

torque-time trace:

Tmin is the minimum torque.

ts is the scorch time

Tplat, is the plateu torque at tp

The thermal stability of the

network at curing temperature is
indicated by the stability of the
plateu torque.

3 Stages of curing/vulcanization
characteristics

The vulcanization process can be described by

rheometer curve.

The curve has three stages:

1.

Induction and scorch

2.

Curing : This region can sub-divided into

1. Under vulcanization / undercured
2. Optimum vulcanization

3.

Overcure : this region may show

1.
2.
3.

Plateau cured
Reversion cured
Marching cured

1.

INDUCTION / SCORCH
Initially a sudden increase in torque as the chamber closed.

As the rubber is heated its viscosity decreases, resulting in a net decrease in

torque.

2.

CURING
Eventually, the rubber compound begins to vulcanise and transform into an
elastic solid (known as an elastomer) the torque rises.

Molecular chain scission may also be occurring an increasing torque

indicates that an increase in crosslinks is dominant.

3.

OVER CURED
If the torque reaches a plateau this indicates a completion of curing and
the formation of a stable network.

If chain scission and/or crosslink breakage become dominant during

prolonged heating the torque passes through a maximum and then
decreases, a phenomenon termed reversion.
Some NR compounds, particularly at high curing temperatures, exhibit
reversion.

Some compounds show a slowly increasing torque at long cure times

creeping/marching cure.

This behaviour often occurs in compounds that initially form many polysulphidic
linkages.
With extended cure times, these linkages may break down and re-form into
linkages of lower sulphur rank, thereby increasing the total number of crosslinks.

A typical torque-time curve along with characteristic terms

to describe the different behaviours.

Creeping

Tmax

0.9(Tmax Tmin)

The

Plateau

Reversion

scorch time, ts1 is the time at which the torque is 0.1 Nm above
minimum torque gives an indication of the safe period before the mix
becomes un-processable due to the formation of crosslinks

Kinetics of Crosslinking
To avoid premature crosslinking (scorch), the mold

cavity during processing should be filled during the

induction period, therefore the determination of the
induction time, ti, is important.

Important Definitions
Scorch: Scorch is premature vulcanization, in which the

stock becomes partly vulcanized before the product is in

its final form and ready for vulcanization.
Rate of cure: Is the rate at which crosslinking and the

development of the stiffness (modulus) of the compound

occur after the scorch point.
State of cure: A term to indicate the development of a

property of the rubber as cure progresses.

Cure time: is the time required during the vulcanization

step for the compounded rubber to reach the desired state

of cure
Overcure: A cure which is longer than the optimum.

Determination of crosslink density after

curing/ vulcanization
The crosslink density of an elastomer can be determined from

swelling or mechanical measurements.

The determination of crosslink density by equilibrium

measurement is a practical method for

swelling

estimating the state of cure of a rubber product, and also

for monitoring the degradation process including scission and
crosslinking reactions.

In a crosslinked elastomer the presence of an interconnected

network precludes the possibility of solution but immersions in a

solvent results in swelling.

Swelling will continue until the retractive forces in the extended

chains balance the forces tending to swell the network.

This equilibrium swelling in a solvent like toluene or n-decane

can be used to determine the crosslink density.

The

mass uptake of the solvent is plotted against

the square root of time until saturation.

Swelling measurements
Weigh the initial mass of each 2-3 mm cube test

piece using a laboratory balance capable of reading

to 0.0001gm.
Then immersed the test pieces in toluene at room

temperature at least 6 hours until a state of

equilibrium swelling is obtained.
On attainment of equilibrium, take out the test

pieces from swelling solvent, wipes the surfaces

and weigh.

Flory-Rehner equation
One expression widely used to relate the amount of

swelling to the crosslink density is the

ln1 v r v r

2
v r

1 1/ 3
pVo Mc v r

where
Vo is defined as molecular volume of the swelling liquid,

vr is the volume fraction of the original rubber network in

the swollen gel and

is the polymer-

Mc is crosslink density..

solvent interaction parameter

(often depending on vr for a particular rubber-solvent
system and normally given as 4.2 for n-decane)

Mooney-Rivlin equation
Another way of to determine crosslink density are from

equilibrium stress-strain
equation :

2 2

measurement using

C1

C2

where
is engineering stress (force per unit original cross sectional area),
is an
extension ratio and
C1 , C2 is a constant.

 According to equation, a graph of reduced stress,

versus

should give

a slope of C2 and an intercept of C1 on the ordinate.

It is known that the C1 value relates to the number of chemical

and physical crosslinks which gives the stiffness of the rubber
material and

the C2 value is believed to relate to the number of chain

entanglements

Stress-Strain measurements
Stress-strain measurements are determined by

stretching strip test pieces at a constant rate using

tensile machine (Instron).
The test pieces are cut from molded sheets.
The measurements are similar as tensile strength

measurements except that it should be carried out

at a lower strain rate.
Normally it was carried out at speed 30mm/min

Mooney viscosity
For a raw polymer type, choice of correct viscosity level is important to

ensure acceptable mixing and processing characteristics.

Viscosity levels for polymers are commonly expressed in terms of

Mooney viscometer readings.

Mooney viscosity is the most commonly used for measurement of mix

viscosity.

Viscosity of rubbers is measured using the shearing disk viscometer.

The torque of the rotor is taken after 1 minute pre-heating the rotor plus
4 minute after that.

The result for viscosity measurements are reported in the form 50 ML,

1+4 (100C)

where 50 M is the Mooney viscosity number,

L indicates the use of the large 1.5 in. rotor (S would indicate the small 1.25
in. rotor),
1 is the time in minutes that the specimen was permitted to warm in the
machine before starting the motor at which the reading is taken,
100C is the temperature of the test.

Mooney viscosity
For a raw polymer type, choice of correct viscosity level is important to

ensure acceptable mixing and processing characteristics.

Viscosity levels for polymers are commonly expressed in terms of

Mooney viscometer readings.

Mooney viscosity is the most commonly used for measurement of mix

viscosity.

Viscosity of rubbers is measured using the shearing disk viscometer.

The torque of the rotor is taken after 1 minute pre-heating the rotor plus
4 minute after that.

The result for viscosity measurements are reported in the form 50 ML,

1+4 (100C)

where 50 M is the Mooney viscosity number,

L indicates the use of the large 1.5 in. rotor (S would indicate the small 1.25
in. rotor),
1 is the time in minutes that the specimen was permitted to warm in the
machine before starting the motor at which the reading is taken,
100C is the temperature of the test.

Mooney schorch
For a raw polymer type, choice of correct viscosity level is important to

ensure acceptable mixing and processing characteristics.

Viscosity levels for polymers are commonly expressed in terms of

Mooney viscometer readings.

Mooney viscosity is the most commonly used for measurement of mix

viscosity.

Viscosity of rubbers is measured using the shearing disk viscometer.

The torque of the rotor is taken after 1 minute pre-heating the rotor plus
4 minute after that.

The result for viscosity measurements are reported in the form 50 ML,

1+4 (100C)

where 50 M is the Mooney viscosity number,

L indicates the use of the large 1.5 in. rotor (S would indicate the small 1.25
in. rotor),
1 is the time in minutes that the specimen was permitted to warm in the
machine before starting the motor at which the reading is taken,
100C is the temperature of the test.

Compound costing & Specific gravity

calculations
In the rubber industries it is customary to buy by

weight and sell by volume

The density of the mix thus plays a vital part in
material costing calculations.
Only a volume vs volume cost comparison is
meaningful when costing a product
For a raw polymer type, choice of correct viscosity
level is important to ensure

Density of the Mixture & Specific

gravity
1. Density of the mixture

Mass
Density

Volume

The normal units are g/ml3

2. Specific gravity (S.G)

Weight of a given volume of material

S.G
weight of the same volume of water

Specific gravity = weight of a given volume of material

1.0 Introduction

APPLICATION OF ELASTOMER
BEARINGS - STRUCTURAL

JOINTS THAT ARE

INSTALLED BETWEEN A
STRUCTURE AND ITS
FOUNDATION.
THE BEARING IS VERY

STIFF AND STRONG IN THE

VERTICAL DIRECTION, BUT
FLEXIBLE IN THE
HORIZONTAL DIRECTION.

HOW THE BEARING WORKS

Figure: Base-Isolated and Fixed-Base Buildings

A

base isolated structure is supported by a

series of bearing pads which are placed
between the building and the building's
foundation

2.0 How The Bearing work?

AS A RESULT OF AN EARTHQUAKE,

THE GROUND BENEATH EACH

BUILDING BEGINS TO MOVE.
EACH BUILDING RESPONDS WITH
MOVEMENT WHICH TENDS
TOWARD THE RIGHT.
THE BUILDING'S DISPLACEMENT
IN THE DIRECTION OPPOSITE THE
GROUND MOTION IS ACTUALLY DUE
TO INERTIA.

2.0 How The Bearing work?

I N A D D I T I O N T O D I S P L A C I N G T O W A R D

THE RIGHT, THE UN-ISOLATED

BUILDING IS ALSO SHOWN TO BE
CHANGING ITS SHAPE-FROM A
RECTANGLE TO A PARALLELOGRAM.
DEFORMING
T H E P R I M A R Y C A U S E O F E A R T H Q U A K E
DAMAGE TO BUILDINGS IS THE
DEFORMATION WHICH THE BUILDING
UNDERGOES AS A RESULT OF THE
INERTIAL FORCES ACTING UPON IT.

2.0 How The Bearing work?

T H E B A S E - I S O L A T E D B U I L D I N G

RETAINS ITS ORIGINAL,

RECTANGULAR SHAPE.
I T I S T H E E L A S T O M E R I C B E A R I N G S
SUPPORTING THE BUILDING THAT
ARE DEFORMED.
I T I M P L I E S T H E I N E R T I A L F O R C E S
ACTING ON THE BASE-ISOLATED
BUILDING HAVE BEEN REDUCED.

3.0 Elastomeric Bearings

ELASTOMERIC BEARINGS

Fig: Basic structure of

rubber bearing

CONSIST OF THIN RUBBER SHEETS BONDED

ONTO THIN STEEL PLATES AND COMBINED
WITH AN ENERGY DISSIPATION MECHANISM.
THE RUBBER SHEETS ARE VULCANIZED AND
BONDED TO THE THIN STEEL PLATES UNDER
PRESSURE AND HEAT.
IT IS DESIGNED IN SUCH A WAY THAT
BEARING IS VERY STIFF AND STRONG IN
VERTICAL DIRECTION, BUT FLEXIBLE IN
HORIZONTAL DIRECTION.
THICK MOUNTING STEEL PLATES ARE
BONDED TO THE BOTTOM AND TOP
SURFACES ALLOWING THE ISOLATOR TO BE
FIRMLY CONNECTED TO THE FOUNDATION
BELOW AND THE SUPERSTRUCTURE ABOVE.

Processing
Flow Chart Seismic
Rubber
Bearings