Elastomeric materials

Dr. Farhan Saeed

Rubber compounding ingredients
 Fillers
 Curing agents
 Accelerators
 Activators
 Antidegradants
 Processing aids
 Blowing agents
 Retarders
 Colourants
Vulcanization of rubber
Vulcanization
 Unvulcanized rubber products are not very
strong and have the consistency of chewing
gum.
 Charles Goodyear invented the first

recognizable method of vulcanization.

◦ Heating natural rubber with sulfur
◦ Both natural and synthetic rubber are vulcanized
today
◦ 90% of all vulcanization occurs with sulfur of
natural rubber, ethylene-propylene-diene (EPDM),
butyl rubbers, and nitrile rubber.
Effects of Vulcanization on Rubber
Effects of Vulcanization on Rubber
 Vulcanization causes Mechanical property changes
◦ Tensile strength, Tear strength, hysteresis, elastic recovery
stiffness.
 Increases tensile modulus and Dynamic modulus
 Hysteresis is reduced with increased crosslink formation
 Hysteresis the amount of plastic stretch that does not recover to final
state. It is a measure of the deformation energy which is not stored but
converted to heat.
 Vulcanization causes a trade-off between elastic and plastic
deformations.
 Increases Tear strength, Fatigue life, and Toughness with small
amounts of crosslinking, but are reduced with additional links.
◦ Reversion is a loss of network structures by thermal aging
 Result to isoprene rubbers vulcanized by sulfur that is vulcanized too
long
 Most severe at temperatures above 155°C.
Effects of Vulcanization on Rubber
 Vulcanization causes profound chemical changes
◦ Long rubber molecules (MW between 100,000 and
500,000) become linked together with junctures
(crosslinks) spaced along the polymer chains
◦ Rubber becomes essentially insoluable in any solvent and
can not be processes by means which requires it to flow.
 E.g., mixer, extruder, mill, calender, forming, or shaping
 Usually the crosslinked rubber is die cut to final part shape.
◦ Mechanical property changes
 Increases tensile modulus (static or standard tensile test
pulling)
 Increases slightly the Dynamic modulus (found from
sinusoidal pulling and pushing on sample) since it is a
measure of the viscous and elastic behavior of rubber.
Vulcanization Process
 Vulcanization Process
◦ Mixing: Raw rubber, sulfur, accelerators, fillers,
preservatives, etc. according to a recipe.
◦ Important process characteristics
 Time elapsed before crosslinking starts
 Need sufficient delay (scorch resistance or resistance to
vulcanization) before crosslinking starts to permit mixing,
shaping, and forming of product.
 Rate of crosslinking formation once it starts
 Need to have rapid crosslinking to minimize cycle time
 Extent of crosslinking at end of process
 Need to be controlled to get the proper amount of crosslinking.
Curemeters
 Rotor based curemeters
◦ Oscilating Disc Rheometer (ODR)

 Rotorless curemeter
◦ Moving Die Rheometer (MDR)

Torque

Rubber
Curemeters
Curemeter results
Cure Properties
 Scorch time (ts)
 Optimum cure time (t90/t95)
 Cure rate index
 Time for x% curing
 Cure Properties
Torque (dN.m )

80
70
60
50
40
30
20
10
0
0 5 10 15 20 25 30

Time (min)
Curing Agent
 Material used to form crosslinks between the
chain of the polymers is known as curing or
vulcanising agent

 Sulphur is most widely used curing agent

 Sulphur donors can also be used as curing

agent
 Metal oxides
 Peroxides
 Resins
Accelerators
 Increase the rate of sulfur crosslinking and the crosslink
density.
 Classified by two techniques-
 Rate of vulcanization- Rated as ultra accelerators, Semiultra-
accelerators, fast accelerators, medium-rate system, and slow
accelerators
 Chemical classifications- Fall into eight groups:
 Aldehydemines
 Dithiocarbamates
 Guanidines
 Thioureas
 Sulfenamides
 Thiazoles
 Thiurams
 Xanthates
Accelerators
 Sulphur based curing
 Curing time:5-6 hr

 ZnO and MgO

 Reduced curing time to 2-3 hr

 1906 Aniline used as accelerator

 Organic nitrogenous based accelerators
Comparison of different classes of accelerators

Class Rate of curing

Aldehyde-amine Slow

Guanidines Medium

Thiazoles Semi-fast

Sulphenamides Fast-delayed action

Sulphenimides Fast-delayed action

Dithiophosphates Fast

Thiurams Fast

Dithiocarbamates Very fast

Primary accelerators
Secondary accelerators
Comparison of different accelerators
Comparison of different accelerators
The most common accelerators
Crosslink types and chain
modification
Type of cure systems

Sulphur (S) Accelerators (A)

Type A/S ratio
(phr) (phr)

Conventional curing
2 - 3.5 0.4 - 1.2 0.1 - 0.6
system

Semi-efficient curing
1 - 1.7 1.2 - 2.4 0.7 - 2.5
system

Efficient curing system 0.4 - 0.8 2-5 2.2 - 12

Activators
 Activators are used to improve efficiency of
the accelerators in the sulphur cure systems.

 Inorganic activators comprise mainly metal

oxides such as zinc oxide, magnesium oxide,
lead oxide and litharge.

 Organic activators are fatty acids such as

guanidine, ureas, weak amines, amides, poly
alcohol and amino alcohol.
Activators