RUBBER TECHNOLOGY

CÔNG NGHỆ CAO SU

CAO XUAN VIET (Ph.D)

DEPARTMENT OF POLYMER MATERIALS
FACULTY OF MATERIALS TECHNOLOGY, HCMUT
 Contents
v Rubber Elasticity
v General Properties of Rubber
v Structure- Properties Relationship
 Rubber Elasticity
• There's one thing that all rubber, natural
and synthetic, has in common. All
rubber is stretchy.
 Rubber Elasticity
• There's one thing that all rubber, natural
and synthetic, has in common. All rubber is
stretchy.
 Rubber Elasticity
• What makes rubber stretchy? The answer
has to with entropy.
• What is entropy? Entropy is disorder.
• There is an important law of physics,
called the Second Law of
Thermodynamics which that a system will
move from a state of order to a state of
disorder.
 Rubber Elasticity
• This entropy business is often
inconvenient, but entropy is also what
makes rubber work. Rubber molecules
are polymers, that is they are shaped
like very long chains.
• When the piece of rubber is just sitting
there, the molecules are just tangled
up in a random mess.
 Rubber Elasticity

When the molecules are like this we say they have a high degree
of entropy.
 Rubber Elasticity

But when the rubber is stretched, the chains become aligned in one
direction
 Rubber Elasticity
• When the chains are aligned, they are ordered.
That is, they don't have as much entropy as
they did before the rubber was stretched.
• As soon as one lets go of the stretched
rubber, those chains are going to try to
become disordered again.
• This means the return to their original
tangled mess. This makes the piece of rubber
snap back to its original size and shape.
 Rubber Elasticity
• When you pull on the rubber band, the
polymer chains become aligned.
• When the chains align, something can
happen. The chains can line up and pack
together into extremely ordered
arrangements called crystals.
• Stress induced crystallization

rubber molecules in a crystal

 Rubber Elasticity
• When molecules, not just rubber
molecules, but any molecules, form
crystals, they give off heat.
• This is why the rubber band feels hot when its
stretched. When you let go of the rubber
band, the polymer molecules break out of
those crystals.
• Whenever molecules break out of crystals,
they absorb heat. That's why the rubber band
feels cold when you let go of it.
 Rubber Elasticity
• There's something else that makes
rubber stretchy. That is crosslinking.
• Most rubber objects are made of some
kind of cross-linked rubber.
• Crosslinking is a way of chemically
joining all the polymer chains of a
piece of rubber into one giant molecule
Model of long elastomer molecules, with low degree of crosslinking:
(a) Unstretched
(b) Under tensile stress
 Crosslinking
• This process for making rubber more
useable became known as vulcanization.
• The sulfur molecules each contain eight sulfur
atoms, arranged in a ring. When these sulfur
molecules are heated with polyisoprene
molecules, something nifty happens.
• The sulfur rings open, and fall apart.
Fragments of the sulfur rings will join with
the polyisoprene, joining the chains together.
 Crosslinking
• Bridges made by short chains of sulfur
atoms tie one chain of polyisoprene to
another, until all the chains are joined into
one giant supermolecule.
• These crosslinks tie all the polymer
molecules together. Because they're tied
together, when the rubber gets hot, they can't
flow past each other, or around each other.
• This is why it doesn't melt. Also, because
all the polymer molecules are tied together,
they aren't easily broken apart from each
other.
 Crosslinking
• The more sulfur crosslinks you put
into the polyisoprene, the stiffer it
gets.
Ø Lightly crosslinked, it's a flexible rubber.
Ø Heavily crosslinked, it's a hard thermoset.
• This crosslinking makes the rubber stronger.
It also allows the rubber to keep its shape
better when it is stretched over and over
again.
• Crosslinking also makes rubber difficult to
recycle.
Increase in stiffness as a function of strain for
three grades of rubber: crude natural rubber, hard
vulcanized rubber and soft vulcanized rubber.
Differences between linear polymers and
elastomers

Linear Polymers Elastomers

Physical properties Physical properties
determined by chain determined by degree of
length crosslinking
Linear polymers are Elastomers are solids
liquids when is heated; with indefinite molecular
viscosity increases with weight
molecular weight
Soluble in solvents Swell in solvents
General Properties of Rubber
 General Properties
• Elastomers are complex materials that exhibit
unique combinations of useful properties. The
first and foremost property is elasticity.

• Besides elastic recovery, the majority of

elastomers possess other useful properties,
including:
– Excellent abrasion resistance.
– Good mechanical properties: tensile, tear,
creep, hardness, stiffness.
 Resilience
• Resilience (%) is essentially a measure of
rubber elasticity.
• When a rubber is deformed, energy is stored by
the rubber
• When it is allowed to recover, work is done by
the rubber
• However, the work recovered is always less than
the work required to deform the rubber
• This difference in energy appears as heat in
rubber (heat build-up)
• Resilience is the ratio of energy given up on
recovery from deformation to the energy required
to produce the deformation.
 Resilience
• Low resilience could due to:
– Over or under vulcanized.
– Higher reinforcing properties of the fillers.
• NR and BR are the most resilient
rubbers.
– Rebound resilience = 80% at 298 K.
• NBR and IIR are the lowest resilient
rubbers.
 Resilience
• The simplest form of resilience test
involves the dropping of a steel ball onto
a rubber specimen and noting the height
of rebound.
• Various rebound pendulums are
available:
– Schob
– Dunlop,
– Goodyear-Healey
Resilience

The rebound resilience, R, as a

percentage, is given by the
following equation:

h’
R= X 100
h

Where
h’ is the rebound height;
h is the height of fall
 Schob pendulums

The rebound resilience, R, as a percentage,

is given by the following equation:

R = (1 – cos α ) X 100
 Hysteresis

• Hysteresis is a measure of deformation energy

that is not stored by the elastic network, but the
energy is converted to heat.

• It is the difference between the deformation

energy and recovery energy.

• Hysteresis is equal to 100% minus %resilience:

Hysteresis (%) = 100 - Resilience

 Hysteresis
• Rubber gum will convert most of the
deformation energy into the mechanical
energy used in returning to the original shape.

• However, filled rubbers tend to increase the

hysteresis of rubbers. This is due to the energy
consumed;
• Hysteresis is equal to 100% minus %resilience:
– in polymer-filler friction, and
– in dislocating polymer segments from active
filler surfaces.
Hysteresis
 Hysteresis
• Automobile tires are made out of two kinds of
rubber due to hysteresis.
• High hysteresis rubber - heats up, does not
release heat i.e. high heat build-up.
– SBR; suitable to make tire treads.
– does not release heat, high hysteresis-
prevents slipping on wet surfaces.
 Hysteresis
• Low hysteresis rubber – releases
heat i.e. low heat build-up.
– NR; suitable to make tire sidewalls.
– releases heat, low hysteresis.
 Hysteresis

Ø Low-hysteresis rubber rebounds quickly;

Ø high-hysteresis rubber lags in rebound after
deformation.
 Heat Build-Up
• Is the temperature rise in a rubber component
due to hysteresis.
• Occurs as a result of rapid cyclic deformations.
• It depends on:
– hysteresis, thermal conductivity, and
thickness of rubber vulcanizates.
 Heat Build-Up
• The heat (generated by hysteresis
under cyclic deformation) leads to;
– a temperature rise which can be very high in
the interior of relatively thick rubber
components due to the low thermal
conductivity of rubbers.
• Heat build-up can be reduced by;
– Using a more resilient compound (rubber
+ ingredients),
– Altering the shape of the component.
 Heat Resistance
• Heat resistance of a rubber is the effect of
elevated temperatures on rubber for
prolonged periods.
• It depends on 3 factors:
– Bond dissociation energies of the main chain.
o C—C crosslink has bond energy of 350 kJ/mol,
C which is higher than C—S (285 kJ/mol) or
S—S (267 kJ/mol).
– Vulcanizates produced by peroxides exhibit
far better heat resistance than by sulphur.
 Heat Resistance
• CR (chloroprene rubber), CSM
(chlorosulphonated rubber) and
FKM (fluorocarbon rubber);
– contain halogens which helps to make
them flame resistant.
– The carbon-fluorine (C-F) & carbon-chlorine
(C- Cl) bonds; are stronger than the carbon-
carbon (C-C) bonds, contribute towards
providing thermal stability and chemical
resistance.
 Heat Resistance
Service temperatures for some rubbers
 Set
• Rubbers are not perfectly elastic.
• They are _____ materials which behave
partially as a viscous liquid & partially as
an elastic solid.
• Therefore, prolonged deformation leads
to some degree of permanent
deformation.
– Part of the deformation may recover
completely.
– Other part remains permanently.
 Set

• Set is the amount of deformation remaining

after removing the deforming (distorting)
force irrespective of whether the load was
in tension, compression, or shear.
• Generally, the lower the set, the better the
rubber performance.
 Set
• If a rubber is stretched under specified
conditions and allowed to retract, the
extension remaining after retraction,
expressed as a percentage of the
original length is called tension set.
• If the rubber is compressed under
specified conditions and allowed to
restore, the compression remaining after
restoration, expressed as a percentage
of the initial thickness, is called
compression set.
 Creep and stress relaxation
• Stress-strain tests are considered
short- term tests, which means that
the mechanical loading is applied
within a relatively short period of
time.
• This serious limitation can be
overcome with the use of creep
and stress relaxation data while
designing a part.
 Creepand stress relaxation effect
• Creep is an increase in plastic strain under constant stress.
• Stress relaxation is a decrease in stress under constant
strain.

Creep effect Stress relaxation effect

 Creepand stress relaxation effect
1. Creep
• Occur when an elastomeric component is subjected to a
static preload, then this load causes a progressive
increase in deformation as a function of time.
• important in a wide variety of applications, eg:
building
mounts, automotive suspensions, etc.
• expressed as a percentage of the initial deflection:

Where:
xo is the initial deflection, and
xt is the deflection at time t.
• Creep in rubber consists of both:
Ø physical creep (due to molecular chain slippage) and
Ø chemical creep (due to molecular chain breaking)

• thus the total creep is given by:

Where:
A = physical creep rate (%)
B = chemical creep rate (%)
to = initial time
• The initial deflection must be measured at a defined
initial time t0, which should be about 10 times longer
than the time taken to apply the deformation.
 2. Stress relaxation

• Occur when an elastomer is held at a constant deformation,

there is a decrease in stress as a function of time.
• Important in sealing application
• Stress relaxation is usually defined as the loss in stress
expressed as a percentage of the initial stress:

Where:
so is the initial stress, and
st is the stress at time t.
A total relaxation rate can be determined by combining
physical and chemical rates. Thus:

Where:
A = physical relaxation rate (%)
B = chemical relaxation rate (%)
to = initial time
 Fatigue
• Fatigue is the maximum ____ level that a
rubber can sustain without _____.
• It is defined as the in _____ properties &
eventually rupture (failure) of rubber when
subjected to stress well below its ultimate
tensile stress.
• The onset of fatigue in rubber is characterized
by the appearance of a series of _____ on the
surface, which enlarge on repeated
deformation & ultimately cause failure.
Structure - Property
Relationships
 Effect of Macrostructure
1. Molecular Weights (MW) will determine
properties of rubber grades:

• Low MW
– Low viscosity
– Good processibility
– Difficult to vulcanize (because few crosslinks
not sufficient to form networks)
– Poor mechanical properties; Low tensile
strength
 Effect of Macrostructure
• High MW
– High viscosity
– Facing processing problems
– Easier to vulcanize compared to low MW (Few
crosslinks already suffice to form networks.)
– Good mechanical properties; High tensile
strength, creep resistance, and melting
temperature increases (↑) and impact toughness
increases (↑)
 Effect of Macrostructure

2. Molecular Weight Distribution

• Narrow MWD:
– Soften in a limited temperature range.
– Poor processing characteristics.
– Poor mixing process: poor fillers/ingredients
distribution.
 Effect of Macrostructure
• Broad MWD:
– Soften in a wider temperature range.
– Better processing characteristics
– Good mixing process (e.g.; better fillers/
ingredients distribution)
– Tensile strength decreases ( ↓ ) and Impact
strength decreases ( ↓ )