RUBBER

Definitions

• Rubber is a polymer, which is a word that is derived from the Greek meaning “many parts”.
Some polymers are found in nature, such as cellulose in wood. Natural rubber is a naturally
occurring polymer obtained from the latex of rubber trees. If you could see a bunch of
polymers, they would look like a bowl of spaghetti.

Rubbers are described as materials which show “elastic” properties. Such materials are
generally long chain molecules known as “polymers” and the combination of elastic and
polymers has led to the alternative name of “elastomers”. Rubbers and elastomers are
synonym
• Highly amorphous
• Highly random orientation
• High elongation

Products made from rubber have a flexible and stable 3–dimensional chemical structure and
are able to withstand under force large deformations. For example the material can be
stretched repeatedly to at least twice its original length and, upon immediate release of the
stress, will return with force to approximately its original length.
Under load the product should not show creep or relaxation. Besides these properties the
modulus of rubber is from hundred to ten thousand times lower compared to other solid
materials like steel, plastics and ceramics. This combination of unique properties gives rubber
its specific applications like seals, shock absorbers and tyres.

Elastomers
Elastomers are rubbers E < 1 GPa

1. The material must be macromolecular.

2. Must be amorphous (at least at low strains).
3. Tg must be below the operating temperature.
4. Must have low secondary forces between molecules so as to obtain the requisite flexibility.
5. A moderate degree of crosslinking must exist to establish an elastomeric network.

Tg
There is a certain temperature (different for each polymer) called the glass transition
temperature, or Tg for short. When the polymer is cooled below this temperature, it becomes
hard and brittle, like glass. Some polymers are used above their glass transition
temperatures, and some are used below. Hard plastics like polystyrene and poly(methyl
methacrylate), are used below their glass transition temperatures; that is in their glassy state.
Their Tg's are well above room temperature, both at around 100 oC. Rubber elastomers like
polyisoprene and polyisobutylene, are used above their Tg's, that is, in the rubbery state,
where they are soft and flexible.

• World usage is 15 million metric tons (1000kg)

• Natural rubber is 35%

• Synthetic rubber is 65%, (SBR –18%, rest is other elastomers)
• Natural rubber
– 75% goes to tires,
– 5% automotive mechanical parts,
– 10% non-automotive mechanical parts,
– 10% miscellaneous parts (medical and health related).
– Available as technically specified rubbers, visually inspected rubbers, and
specialty rubbers.
Strain

Stress
Classification and types of material

• General Purpose
• Solvent Resistant
• Heat Resistant

General Purpose
1. Natural – low cost material with excellent physical properties.
2. Polyisoprene – man made natural rubber – this is cleaner than true natural rubber.
3. SBR – very similar to natural rubber. It is usually the lowest cost and highest volume of
any rubber made. It has slightly poorer physical properties than natural rubber, but is
tougher and slightly more resistant to heat and flex cracking.
4. Butadiene – similar to natural and SBR. It is very difficult to process, so it is usually
blended with other polymers
5. Butyl – This is chemically unlike the others we have talked about. It is very resistant to
ozone and some corrosive chemicals. It is impermeable to gases, so it is used in tires.
It is also very energy absorbing.
6. EPDM – This has excellent resistance to heat, ozone, and sunlight. It has a very
unique combination of physical properties. Other than applications requiring resistance
to oil, there is scarcely an application in which EPDM is totally unsuitable. It also
processes very well.

•Solvent resistant
1. Neoprene – polychloroprene – excellent all purpose elastomer with a nearly ideal
balance of properties and few practical limitations. It is used for wet suits.
2. Nitrile – nitrile and neoprene are the highest volume oil-resistant elastomers. Nitrile is
superior to neoprene in resistance to oil and gasoline. However, it does not perform as
well as neoprene in applications requiring exposure to weather, ozone, and sunlight.
Properties of nitrile vary considerably depending on the ratio of acrylonitrile and
butadiene. As the acrylonitrile level increases, oil and solvent resistance and abrasion
resistance improve. As the acrylonitrile level decreases, these properties decrease, but
low temp., flexibility and resilience improve.
When nitrile is modified with PVC, its resistance to weather, ozone, and sunlight
improves considerably without significant sacrifice in oil-resisting properties.
3. NBR/ PVC – resistant to gasoline & ozone
Carboxylated nitrile – this is tougher and more resistant to tear and abrasion, but is
less resilient and flexible at low temps.
4. Hypalon – this is a close match to neoprene, except is superior in resistance to acids,
solvents, ozone, and oxidation. It is used on a lot of roofs.
5. Epichlorohydrin – Excellent resistant to gasoline. It appears to have a combination of
desirable properties of nitrile and neoprene, but its superior impermeability to gases
often causes processing problems and produces processing problems due to air
entrapment.

Heat resistant
1. Silicone – outstanding ability to retain rubbery properties through extremes in
temperatures. It is the most heat resistant elastomer on the market. Service temps
from -150 to 500F. Silicone does not have very high tensile strength, but most of it
can be retained at very high temps.
2. Flouroelastomer (Viton, Flourel) – very expensive with outstanding resistance to
a wide variety of oils, fuels, acids, and solvents at elevated temperatures. Because
of its price, it is used only in applications requiring excellent stability under
extremely severe operating conditions.
Natural Rubber
• Raw material extracted from trees
• Poly-cis-isoprene (40%) in water (C5H8) n

CIS

cis polyisoprene Tm = 28°C, Tg = -70°C

trans polyisoprene Tm = 68°C, Tg = -70°C

Natural rubber is the prototype of all elastomers. It is extracted in the form of latex
from the bark of the Hevea tree.
The rubber is collected from the latex in a series of steps involving preservation,
concentration, coagulation, dewatering, drying, cleaning, and blending. Because of
its natural derivation, it is sold in a variety of grades based on purity (color and
presence of extraneous matter), viscosity, viscosity stability, oxidation resistance,
and rate of cure. Modified natural rubbers are also available, with treatment usually
performed at the latex stage.
The natural rubber polymer is nearly 100% cis-1,4 polyisoprene with Mw ranging
from 1 to 2.5 x 106. Due to its high structural regularity, natural rubber tends to
crystallize spontaneously at low temperatures or when it is stretched. Low
temperature crystallization causes stiffening, but is easily reversed by warming.
Crystallization gives natural rubber high tensile strength and resistance to cutting,
tearing, and abrasion.

Natural rubber in unfilled form

 very large elastic deformations
 very high resilience,
 resistance to cold flow
 resistance to abrasion, wear, and fatigue.
 Natural rubber does not have good intrinsic resistance to sunlight, oxygen, ozone,
heat aging, oils, or fuels (reactive double bond).
Production of Natural Rubber
EXTRACTION

•Natural rubber is tapped from rubber trees (Hevea brasiliensis) as latex

The trees are grown on plantations in Southeast Asia and other parts of the world
•Latex is a colloidal dispersion of solid particles of the polymer polyisoprene in water
Polyisoprene (C5H8) n is the chemical substance that comprises rubber, and its content
in the emulsion is about 30% to 40 %
•The latex is collected in large tanks, thus blending the yield of many trees together

RECOVERING THE RUBBER

•The preferred method of recovering rubber from latex involves coagulation by adding
an acid such as formic acid (HCOOH); coagulation takes about 12 hours
•The coagulum, now soft solid slabs, is then squeezed through a series of rolls which
drive out most of the water and reduce thickness to about 3 mm (1/8 in)
•The sheets are then draped over wooden frames and dried in smokehouses. Several
days are normally required to complete the drying process

The resulting rubber, now in a form called ribbed smoked sheet, is folded into large
bales for shipment to the processor. It has a characteristic dark brown color.

• In some cases, the sheets are dried in hot air rather than smokehouses, and the term
air-dried sheet is used; this is considered to be a better grade of rubber
•A still better grade, called pale crepe rubber, involves two coagulation steps, followed
by warm air drying. Its color is light tan

Rubber, at this stage, is soft, sticky and thermoplastic. It has low tensile strength,
prone to bacterial brake down and low elasticity. It is easy to understand the
molecular structural origin for these properties. The substance is a mixture of polymeric
chains with varying lengths. Most importantly, there is no crosslinking at all. As a result,
the material, although known for several centuries, did not find any significant
application. When natural rubber is stretched, the chains become elongated and slide
past each other until the material pulls apart.

The properties of rubber can be dramatically altered by cross linking the polymer
chains. This process, carried out with sulfur, is known as Vulcanization. In 1939,
Charles Goodyear discovered that mixing hot rubber with sulfur produced a stronger
more elastic material. This process is called vulcanization.

Vulcanization, curing and crosslinking are equivalent terms referring to the

process by which individual polymer chains are transformed into a network.

Vulcanization results in cross-linking of the hydrocarbon chains by disulfide

bonds. When the polymer is stretched, the chains no longer can slide past each
other, and tearing does not occur.

The key chemical modification is that sulfide bridges are created between adjacent
chains. The crosslinking makes rubber non-sticky and improves its tensile strength.
The material is no longer thermoplastic. These attractive physical properties of
vulcanized rubber have revolutionized its applications.

For the process of vulcanization to be useful and successful, it should be controlled. It

should begin when required, accelerate when needed and must stop at the right time.
In the jargon of rubber technologists, these are termed as

should begin when required Scorch resistance,

accelerate when needed Acceleration and
must stop at the right time Cure time, respectively.
Scorch resistance is the time elapsed before vulcanization starts. It is necessary to
have suitable scorch resistance so that there is enough time for mixing, storing and
moulding of the rubber mixture into the desired shape and size.

Premature vulcanization results in the development of cracks in rubber, making the

resulting products unusable. Once vulcanization begins, it should be completed as fast
as possible in order to have practical batch cycle.

Shorter cure times are preferred. Thus, we need to control the way molecules interact
with each other at different stages in order to achieve the desired physical property.

A typical recipe for vulcanization

Temperature 140 -180°C
Sulfur 2-3 parts per 100 parts of rubber (phr)
Accelerator 0.5-1.0 phr
ZnO 3-5 phr

Sulphur vulcanization systems can be divided into 3 systems depending on the relative
amount of sulphur & accelerator used.
The three systems can be differentiate through the types of crosslinking produced and
the main chain modification after vulcanization
A EFFICIENT VULCANIZATION B CONVENTIONAL VULCANIZATION
VULCANIZATION STEPS:

1. Compounding
Rubber is always compounded with additives. Compounding add chemicals for
vulcanization, such as sulfur. Vulcanization with sulfur alone is no longer used today,
due to the long curing times. Various other chemicals are combined with smaller doses
of sulfur to accelerate and strengthen the treatment.

Additives include fillers which act either

 To enhance the rubber's mechanical properties (reinforcing fillers) or
 To extend the rubber to reduce cost (non-reinforcing fillers)
It is through compounding that the specific rubber is designed to satisfy a given
application in terms of properties, cost, and processability.

The single most important reinforcing filler in rubber is carbon black, a colloidal form of
carbon, obtained by thermal decomposition of hydrocarbons (soot) its effect is to
increase tensile strength and resistance to abrasion and tearing of the final rubber
product. Carbon black also provides protection from ultraviolet radiation. Most rubber
parts are black in color because of their carbon black content.

China clays - hydrous aluminum silicates Al2Si2O5(OH)4 provide less reinforcing than
carbon black but are used when black is not acceptable
•Other polymers, such as styrene, PVC, and phenolics
•Recycled rubber added in some rubber products, but usually 10% or less
•Antioxidants; fatigue- and ozone-protective chemicals; coloring pigments; plasticizers
and softening oils; blowing agents in the production of foamed rubber; and mold
release compounds

To avoid premature vulcanization, a two-stage mixing process is usually employed

Stage 1 - carbon black and other non-vulcanizing additives are combined with the raw
rubber. The term masterbatch is used for this first-stage mixture

Stage 2 - after stage 1 mixing has been completed, and time for cooling has been
allowed, stage 2 mixing is carried out in which vulcanizing agents are added

2. Forming Process
After all compounding ingredients have been properly mixed the compounded green
stock is tacky and thermoplastics
In this plastic condition, the stock can be shaped by the applications of force.
This can be accomplished for example, by squeezing it betweens rolls (calendering) or
pushing through an orifice having the desired shape (tubing or extruding).

3. Vulcanization Process
After the green stock has been formed to the desired shape, it needs to be converted
to an elastic material. Vulcanization process usually under pressure at elevated
temperature using different techniques such as
i. Press vulcanization
ii. Open vulcanization
iii. Continuous vulcanization
Chemically the process involves insertation of crosslinks between the polymer
macromolecules through the actions of vulcanizing ingredients.

Press vulcanization takes place in press that supply heat and pressure.
A vulcanizing press consists essentially of two or more plates that can be bought
together and separated by hydraulic pressure heated by steam or electricity
The rubber articles are vulcanized in various moulds between the heated plates under
pressure. In its simplest form, a mould consists of two metal plates with cavities
conforming to the outside shape of the desired finished part.
 Most of rubber products produced using this method. Rubber compound is placed in
each cavity of the mold and closed and placed in hydraulic press.
Under the applied of hydraulic pressure (4-6 MPa) at elevated temperature (140-
200°C) using the cure time obtained from rheometer curve. After mould is closed, the
stock will flow and completely fill the mould cavity the mould is maintained closed
under pressure for a prescribed time at particular moulding temperature. The mould is
then removed from the press and opened to remove the moulded part.

4. Finishing Process
Many rubber articles require finishing operations after vulcanization.
For example,
 The flash attached to moulded parts must be removed before the parts are
ready for use is carried out by hand trimming using scissors or knives.
 Some rubber parts are painted to give them an attractive finish or more often to
protect against ozone, oils, acids, chemicals ant the like. The paints are usually
rubber based.
 Items such as seals and windshield wiper blades may require surface treatment
with chlorine, bromine or fluorine in water. The halogenated surface will have
lower friction than the untreated surface while the bulk will be unaffected.
 The finishing operations of extruded articles include coiling, cutting to specific
length and washing.

Materials Function
Elastomer/raw rubber Basic components in rubber compounding

Fillers Used for reinforced or modified the mechanical

properties and also to reduced the cost
Plasticier To ease the processing, to modify the specific
properties and also as extender’
Anti oxidant To protect the rubber from ageing

Accelerator To increase vulcanization process and reduced the

time of vulcanization
Activator To increased the accelerator efficiency

Vulcanization agent Needed during vulcanization process to produced a

crosslinking

Other ingredients Used for specified purpose such as for coloring, as

retarder etc