Rubber compounding

Rubber

compounding

is

the

complex,

multidisiplinary science of selecting and blending

the appropriate combination of elastomers and
other

ingredients

manufacturing,

to

meet

the

environmental,

performance,
and

cost

requirements for rubber goods made and used in

commerce. There is a wide variety of elastomers
and ingredients that are available in making rubber
goods, which include all of the following types of
products:
footwear,

tires,

innertubes,

rubber

weatherstripping,

rolls,

O-rings,

retreaded
hoses,

seals,

tires,
belts,

diaphragms,

tubing, rubber and latex gloves, ball bladders,

medical devices, bumpers, and numerous other
products.
Compounding is a term that has evolved within
the plastics and rubber industry and in many
respects is a misnomer for the material science of

modifying a polymer or polymer blend through

addition of other materials to achieve a set of
mechanical

properties

for

specific

service

application.
Raw materials for a compound are generally
selected in the following order:
(1) polymer (natural or synthetic rubber)
(2) fillers or reinforcing agent
(3) antioxidants and antiozonants
(4) plasticizers or oils
(5) bonding agent or adhesive (if needed)
(6) tackifer (if needed)
(7) vulcanization system [curing agent,
accelerator(s), or coagent]
Performance requirements of the final product
often dictate which specific type of elastomer can
be used. The expected usable life for the product is
controlled by many factors such as end-customer
needs, competitive situation in the marketplace,

safety, and reliability. Rubber products are almost

always used as a functional part of another system.
For example, tires, hoses, belts, O-rings, and
numerous

rubber

components

are

used

in

manufacturing automobiles and trucks. The overall

life of the vehicle as well as its performance level
often relates to the service life or quality level of
the rubber parts.

Equipment used for Compounding

The rubber technologists mixing department has
bags of powders, drums of liquids and bales or
granules or chips of raw gum elastomer. These are
weighed out precisely, to match both the batch
weight needed and the ratio of ingredients in the
formulation. Machines are necessary to mix these
chemicals, resulting in a finely blended, solid

homogeneous

mixture.

In

many

cases,

the

compounder and process operator expend their

energy reducing the elastic component of the
uncured rubber compound, to help it process, and
then

increase

that

component

again

during

vulcanization. Mixing is accomplished using mills

and/or internal mixing machines. The resulting
compound is then preshaped by mills, extruders or
calenders, to prepare it for vulcanization. The latter
is achieved using molds (which further shape the
product),
autoclaves, and sometimes ovens. That just leaves
finishing operations, such as removing flash (see
section 4.6.1 for an explanation of flash), or maybe
the

grinding

of

rubber

rollers

(cured

in

an

autoclave) to a finished dimension, and then

packaging the product.
Mills
These were used at the beginning of the rubber
industry and are still an essential piece of
rubber processing equipment.
A mill consists of two horizontally placed hollow
metal cylinders rotating towards each other (see
Figure ). The distance between the cylinders (mill
rolls) can be varied, typically between 0.25 to 2.0
cm. This gap between the rolls is called a nip.

Figure Conceptual view of rubber mill rolls

Operation
Raw gum elastomer is placed into the gap between
the two mill rolls, the mill nip. It then bands, as a
continuous sheet, onto one of the rolls. The speeds
of the two rolls are often different, the back roll
rotating faster than the front. The difference in
speed between the two rolls is called the friction
ratio and allows a shearing action (friction) at the

nip to disperse the ingredients and to force the

compound to stay on one roll, preferably the front
one. A friction ratio of 1.25:l is common. Powders,
liquids, etc., are then added to the nip in a specific
way. The process produces friction which creates
heat. This excess heat needs to be removed, either
by spraying or flooding the inside of the roll with
cooling water or by passing water through drilled
channels in the wall of the roll.
A device is necessary to prevent the rubber from
moving past the end of the rollers. This is
accomplished by a piece of metal called a guide,
positioned at each end of the roll, so as to
almost touch the surface. At the beginning of the
mixing process, pieces of material tend to

Mill processing
The

following

description

relates

primarily

to

compounds which use sulfur as the crosslinking

agent. The key to mixing (in a Banbury mixer or a
mill) is to maintain sufficient viscosity to ensure an
adequate shearing action, to distribute the nonrubber ingredients into the raw gum elastomer, or
to

force

the

raw

gum

elastomer

into

the

microscopic spaces of each filler particle. Both

mechanisms have been hypothesized and one
typical mixing sequence might be as follows: The
raw gum elastomer is placed into the nip and
allowed to band onto the front roll. In the case of
NR, it needs to move though the nip quite a few

times to reduce its nerve (elasticity) and to lower

its

high

viscosity

(low

viscosity

grades

are

available). It then forms a smooth, more plastic,

band on the roll. Normally most powders (other
than accelerators and sometimes sulfur) are then
added. If significant heat is produced, then crosslinking agents and accelerator addition will be
delayed to the last part of the mixing process. In
some cases, when excessive heat is produced, it
may be necessary to remove the compound from
the mill before the accelerator is added, to avoid
scorching (prevulcanization). The compound at this
point is known as a masterbatch.
Internal mixing machines

If the rolls of a mill are twisted to produce a

corkscrew effect (they would now be called rotors),
and then a block of steel is placed over the mill nip
with the block connected to a steel rod above it,
this would be called a ram. The ram would move
up, to allow addition of ingredients to the nip, and
it would move down to force the compound
ingredients into the nip. If the whole thing is
surrounded in a heavy metal jacket with a chute at
the top to put ingredients in and a door at the
bottom (underneath the rotors),
to let the mixed material out, the result will be an
internal mixing machine.
Operation

In 1916 Mr. Fernley H. Banbury, improved on an

internal mixing machine built by Werner &
Pfleiderer [ 11 by designing the Banbury mixer.
The Banbury mixer had modified rotors and the
addition of a floating weight. The internal mixer
rapidly became an essential part of the rubber
industry. At the present time, mixers are available
in sizes ranging from those capable of mixing a kg
or so, to those that can mix more than 500 kg per
load, equivalent to many large mills. The internal
mixer is faster, cleaner, (produces less dust from
powdery materials such as carbon black, silica and
clay), uses less floor space, and is probably less
operator sensitive. It has thus displaced the mill for
most

compounding

operations.

However,

the

variable nip opening on a mill, plus immediate

visual feedback of the state of the mix, allows a
good mill operator a high degree of control and
consequently dispersion. The internal mixer has a
fast mixing capability, from around two to ten
minutes, and thus requires an efficient cooling
system. This is provided by drilled channels in the
walls of the mixing chamber, through which water
passes to control the mix temperature. The rotors
and discharge door can also be water cooled. The
temperature of the compound being mixed is
measured by a thermocouple in the side of the
mixing chamber. Other
parameters which can be measured and controlled
during the mixing process are electrical

power (amperage or watts) and time.

Figure
)
Raw gum elastomer is dropped through the hopper
into the mixing chamber where it is mixed by the

rotors. The ram, pressing on to the rubber mixture,

is forced down by a pneumatically or hydraulically
controlled cylinder, whose pressure is adjusted to
give the best control of the mixing process. Oil may
be poured in from the hopper, or injected through a
valve in the hopper wall just above the mixing
chamber, Mixing can occur between the rotors
(intermeshing

rotors)

or

between

the

mixing

chamber walls and the

rotors

(tangential

rotors),

depending

on

the

machine. The rotor to rotor, or rotor to wall,

clearance is very important to correct mixing.
Recent modifications are the Banbury ST rotors
(synchronous

technology)

and

Pominis

VIC

(variable intermeshing clearance) design, where

the distance between the rotors can be varied.
Non-black fillers and other compounding
ingredients
Silica
There are two types of silica, natural and
precipitated. Natural silicas like diatomaceous
earth Impart stiffness and give a very dead
compound which will extrude without swelling.
These are not considered among reinforcing fillers.
Precipitated silicas are the best's non-black
reinforcing fillers so far developed and come
closets to carbonblack properties. They have a
particle size as fine that of carbon black and they
also have an extremely reactive surcease. These
are generally prepared from sodium silicate
solution by precipitation.
Precipitated silicas are easily mixed and excellent
dispersion is obtained. It is better to mix silica
batches in a Danbury than on a roll mill. No special
precautions need be taken for Danbury mixing,

procedures ordinarily used for other reinforcing

fillers should be followed. If mill mixing is following
for silica loaded NR compounds, some productions
should be taken to ensure good properties and
hence the complete batch should mixed and cut
from the mill as quickly are possible. It is also
preferable to mix rubber and silica alone and then
to complete the mixing after maturing for one or
two says. The probable reason for the
improvement in properties is that in the absence of
any other material, the rubber penetrates more
into the filler and thus causes better filler-rubber
interaction. Subsequent addition of other materials
does not interfere with any existing rubber-filler
bond.
Silicas stiffen rubber compounds to a considerable
extent. The stiffening can be reduced by the
addition of suitable plasticisers. Properties like
tensile strength, hardness, tear resistance and
abrasion resistance are improved very much.
Compression set, however, is increased.
Excessive milling may cause reduction in
properties Reinforcing silicas are highly adsorptive.
Hence in formulating NR Compounds containing
them, it is necessary to use more than the normal

quantity of accelerators or else to use certain

activators like DEG of triethanolamine. In silicafilled NR compounds thiaz 01- thiuram
combinations are not satisfactory as these are
scorchy and are not flat coming. Thiazol-guanidine
combinations are found to be more satisfactory.
However in silicas filled SBR compounds both these
combinations are satisfactory. Silicas are generally
used in white or light coloured stocks Hence it is
essential that non-staining and non-discoloring
anti-oxidants are used in such compounds.

In SBR compounds containing silica, use of CD

resin helps in realising the best tensile and year
properties. About 10 parts of resin in a 30 volume
loaded stock and proportionately smaller quantities
for lower loading should be used. It is not
necessary to observe any precautions white mixing
silica filled SBR compounds, as in the case of NR.
Precipitated silicas impart very good properties to
nitrile rubbers, giving good tensile strength and
tear resistant. They are also excellent reinforcing
fillers for neoprene's. Good tensile strength and
tear resistance can be attained sacrificing
elongation. It is also possible to get easily

prosecutable buty1 stocks with good physical

properties by using precipitated silica as filler.
Precipitated silicas are suitable as filler for
translucent compounds based on NR, SBR and
nitrile rubbers.
Fillers of minor importance:

The following fillers find use only to a limited

extent.
Slate flour : May the used in cheap acid resistant
stocks where whiting is not suitable
Barytes : This is naturally occurring Barium
sulphate. It is easily milled into rubber but is inert.
Used in acid resistant compound and where weight
is important.
Balance fixe : This is precipitated Barium Sulphate.
Finer than barytes. These also come under inert
fillers.
Magnesium : This gives very stiff compounds with
high permanent set. Used in
Carbonate : translucent compounds.

Organic fillers

1. Cork: Natural cork, ground to various degrees of

fineness gives compounds with
a high degree of resilience and compressibility and
is used in flooring, gaskets etc.
2. Glue: Animal or fish glue added as powder or in
hydrated form imparts a degree of oil and fuel
resistance to NR for suck items as hose linings and
gaskets, when cheapness and very moderate fluid
resistance are required.
3. Cyclised natural rubber: This usually blended
with NR, gives compounds of high modulus and
hardness with low specific gravity. A moderate
amount assists in giving a good surface finish to
moulded goods.
4. High styrene resins: Copolymers of butadiene
and styrene, with 50-80% bound styrene are
alternatives to Cyclised rubber for high modulus,
tear resistance and abrasion resistance. In
combination with silica or silicates their main use is
in hardwearing shoe soling.

Plasticisers and Extenders

Plasticisers are added in rubber compounds with
the following objectives.
1. Increase plasticity and workability of the
compound.
2. Aid in wetting and incorporation of fillers
3. Provide lubrication to improve extrusion,
moulding or other shaping operations.
4. Reduce batch temperature and power
consumption during mixing
5. Modify the properties of the vulcanised products.
Plasticisers are divided broadly into two classes:
chemical Plasticisers and physical Plasticisers. The
former types act by reducing the molecular weight
of the rubber, by chain scission. Physical platiciser
not as intermolecular lubricants.
Chemical Plasticisers are appropriate when:
a) The primary concern is for modifying the
properties of the uncured stock rather than those
of the vulcanisate.
b) The type of rubber being used is one which
responds to such agents.
c) The other compounding ingredients and mixing

conditions are right for maximum activity of the

plesticiser
d) The cost is favourable in comparison with other
methods of getting the same effect.
Physical plasticisers are used when:
a) Modification of the vulcanisate properties is also
desired
b) Processing required the lubricating, tackifying
and other special properties that can be obtained
with different physical softeners.
c) Cost is favourable in comparison with other
approaches.
Different chemical Plasticisers and are available
which are quite different from one another and are
effective under different conditions. Some are
listed below:
1. Certain accelerators (eg. MBT & DPG) have mild
Plasticising action on NR.
2. Aromatic mercaptans (eg. Thionaphthol & Xylyl
mereaptan) have strong softening effect on NR and
reclaim.
3. Phenyl hydrazine salts-strong in NR & SBR.
4. Thiuram disulphides - Strong in neoprenes.
5. Benzami dodipheny1 disulphide - effective only
at high temperature.

6. Certain petroleum sulophenol, especially its zinc

salt, is powerful in NR and at high temperature in
SBR.
It is important to note that in the absence of a
chemical plasticiser NR breaks down most rapidly
at low mill temperatures and that the chemical
plasticisers work most effectively at high
temperatures. For this reason, the compounded
should use a fully effective quantity of the
chemical plasticiser and masticate at high
temperatures or else leave it out altogether and
masticate at as low a temperature as possible.
Most of the important physical plasticisers come
from any one of the following sources.
1. petroleum (mineral oils, resins, waxes, asphalt)
2. pine tree (Pine tar, pitch, resins)
3. Coal tar (coal tar oil, pitch, resins)
4. Natural fats & Oils (Vegetable oil, blown Oils,
fatty acids, fictive)
5. Synthetic organic compounds (Ester Plasticiser,
liquid polymers etc.)
Petroleum oils are the most common among the
above. They range from highly aromatic to

aromatic, naphthenic and paraffin Oils. All these

are available in various grades of viscosity and
staining power. When softeners are used in small
dosages, merely to improve processing, the
aromatic oils are suitable. But for very high dosage
of softeners along with high quantities of carbon
black or mineral fillers, naphthenic oils are
preferred from the viewpoint of compatibility and
aging resistance. Paraffinic oils and petroleum jelly
should be used only when internal lubrication and
high gloss are required. Aromatic oils cause
staining and discolouration while naphthenic and
paraffinic types do not.
In general, the main factors considered for
selection of physical plasticisers are as follows:
1. Compatibility
2. Cost
3. Efficiency
4. Staining characteristics
5. Low temperature properties
6. Effect on vulcanization and ageing
characteristics of the rubber
Extenders
These are substances which are added to rubber

compounds in lage quantities so that the cost of

the compound can be reduced, without seriously
affecting the final properties. Important among the
commercially used extenders are the following.
1. Rubber reclaim
This is a product resulting from the treatment of
vulcanised scrap rubber tires, tubes etc. by the
application of heat and chemicals, whereby a
substantial degree of devulcanisation and
regeneration of the rubber compound to its original
plastic and state is affected, thus permitting the
product to be processed, compounded and
vulcvanised. Reclaiming is essentially
depolymerisation, the combined sulphur is not
removed. Different types are available, depending
upon the original type of waste rubber employed.
Whole tyre reclaim (WTR) contains about 50%
rubber hydrocarbon and 20-25% carbon black, the
rest being plasticisers and miscellaneous
ingredients. While using whole tyre reclaim for
every 1 part of rubber which is being replaced, 2
parts of reclaim is added. In addition to the
economic advantage, use of reclaim has other
beneficial affects such as short mixing time, low
power consumption, low heat development during

processing, reduced swelling and shrinkage, higher

cure rate, minimised reversion, good ageing etc.
Factice:
This is a class of elastic gums made by reacting
certain vegetable oils with sulphur. Most familiars
is the one used in erasers. Fictive can be blended
with NR and with some synthetic rubbers is a
rather high proportion and the blend will remain
highly elastic. It will also be soft and suffer much
loss of strength and abrasion resistance. Another
way in which it is used is to increase the tolerance
for liquid softeners in synthetic rubber compounds.
Mineral rubber
Airs blown petroleum asphalt are called mineral
rubber. Products of this sort wold hand only
moderate weakening effect on tensile and tear
strength. But would relatively be poor in respect of
resilience and heat build up and flexing.
White pigments and colours
White pigments are used in rubber compounds to
which them. Its use in coloured compounds mains

the colours brighter important among the common

white pigments are titanium dioxide and
lithophone.
Pure titanium is extracted from minerals,
precipitated as the hydroxide, calcined to the oxide
and ground. It is a semireinforcing filler
comparable on a volume basis with zinc oxide, but
is mainly used for its whitening power in tyre
sidewalks, hospital accessories, floor tiles etc. And
as an excellent heat resistant filler for silicone
rubber. The agnate form is preferred where
extreme wittiness is required. The retile form gives
a rather creamier colour, but is more state at high
temperatures.
Lithophone is a mixture of zinc suphide and barium
sulphate, usually coprecipitated in equimolecular
proportions it is used mainly in cheaper white or
coloured compounds as a whitening agent.
Colour
There are two types of colours: inorganic and
organic. The inorganic colours are noted for their
stability to curing conditions, and for their
complete freedom from staining or 'bleeding'.

Important inorganic colours are antimony

trisulphide (Crimson and Golden) (cadmium
sulphide) (deep red to orange to yellow), Cadmium
sulphoselenide (Colours similar to those of
sulphides), Chromium oxide (dull green), Iron oxide
(deep red yellow), mercuric sulphide (bright red),
Nickel titillate (Yellow and ultramerineblue). The
inorganic colouring agents in general give rather
dull colours. Hence for brightly coloured material is
desirable to use more expensive synthetic organic
pigments which are available in a very large range
of colours and shades. Pastel shades are generally
obtained by combining such materials with light
colourd inorganic pigments like titanium dioxide.
Many of these pigments are available as pastes or
as masterbatches in rubber, which greatly assists
in dispersion. If powders are used as such, these
shall be added early in the mixing cycle. Certain
dyestuffs soluble in rubber are also used to
produce dedicate shades in translucent materials.
Chemical blowing agents
In the manufacture of cellular rubbers from solid
rubbers, many types of chemicals are used. The
commonly used one in sponge is sodium
bicarbonate, though ammonium carbonate and

bicarbonate are also used. These materials liberate

carbon dioxide gas on heating. The blowing
operation is pressure dependent and hence these
are not favored in microcellular compounds.
Organic chemicals such as those based on
dinitrosopentamethylene tetramine, benzene
sulphony1 hydroxide and azodicarbonamide
liberate nitrogen gas on heating and find use either
alone or in combination with inorganic blowing
agents for applications where controlled cell
structure is important. Decomposition of
dinitrosopentamethylene treatment is accelerated
by fatty acids like stearic acid. Hence it is
customary to use a larger proportion of stearic acid
than what is usually used, in compounds
containing DNPT based blowing agent. The
unpleasant odour that is associated with the
stearic acid activated decomposition of DNPT can
be minimised by the use of urea.