Basic Principal of rubber processing technology

Molding and vulcanization

Raw rubber Mastication Mixing Extrusion Vulcanization

Compounding Calendering
ingredients
Building

1. Vulcanizing ingredients or curatives

2. Fillers
3. Softeners, Plasticizers, Process aids
4. Antioxidants and other anti-degradants
5. Retardars
6. Pigments and colours
7. Others e.g. fungicides, re-odourants, tackifiers etc.
 3 and 4 roll calenders

3 roll calender 4 roll calender

 Calendering Technology
A rubber calender consists of number of rolls, also called bowls held in a framework.

It consists of 2/3/4 rolls and is used to produce sheets of various thicknesses, coating textiles
or other supporting materials with thin rubber sheets or frictioning fabrics with rubber
compounds. Heating and cooling arrangements are associated with the calender rolls to take
care of the rubber viscosity.

The gap between two subsequent rolls is called ‘nip’ gap. The calender rolls are
solid cast iron for to combat the high separating force generated by highly viscous rubber
compound.

Three-roll calenders are most popularly used. The central roll is driven and the upper and
lower rolls are driven with the help of the central roll using gears. Gears are also provided for
operating the rolls at uneven speeds for ‘frictioning’ operations.

The softened compounded rubber mass, called ‘dough’ is fed into the calender for
sheeting/topping/frictioning operations.
During the calendering process a rolling bank is formed in the nip, the
surface of which continually tears open, leading to the inclusion of air.
This air should be removed by heavy compression and this lead to
the production of a rubber sheet of maximum thickness of 2 mm in a
standard calender machine.

Much thicker sheets can only be produced by overlapping thin sheets or

by using extruder/calender combination.

Control of viscosity of the rubber compound is absolutely important to

produce frictioning and topping operations of fabric linings.

The previously stored rubber compound is first passed through “cracker

mill” then through “warming mill” and then finally fed into the calender
through conveyor system.
 Types of calenders

Other than these, we can have L, F type “offset I” and “S” or Inclined Z type
calenders, specifically designed for easy feeding of the rubber compounds
Calender rolls typically have face lengths of 225 mm (lab models), 1700
mm (steel cord calenders), 2100 mm (textile cord calenders), and up to
3500 mm (special sizes e.g. for roof covering industry). Most calenders
Used in the rubber industry, however, have face lengths ranging between
1200-1700 mm.
Rubber Calendering Methodology:

Operations:
1.Sheeting: Two roll calenders; seldom three roll calenders
2.Skim Coating/ Frictioning: Three roll calenders (single side); Four roll
calenders (either sides)
3.Thickness: 2 mm in single run; 18 mm using plying technique

Constructional Components of Rubber Calender

1. Calender rolls: Highest concentricity and shape-accuracy at process temp. High

quality surface finish and surface hardness
Resistance to deflection/deformation against the rubber compounds to be processed
Impermeability to heating/cooling agents
Calender rolls are made of chilled cast iron for resisting separating forces up to
6000 N/cm. For greater separating forces, composite cast rolls with a core of
graphite cast iron and a shell of chilled cast iron is generally used.
 Formation of plies
Calendering – four roll calender
•Frictioning Final reinforcement is decided by
fibre, cord, fabric
•Topping
and arrangement of plies
In topping both the rubber films and textile moves at
same speeds, whereas in frictioning rubber moves at a
faster speed.
Now the plies are build as per the design requirement,
build them up and vulcanize.

Rubber

Fabric
Rubber
The calender rolls are given positive or negative roll crown, with the
diameter in the middle being between 0.05 and 0.1 mm larger or smaller
than at the ends.

Roll cambering: Rolls are not parallel to compensate for variation in thickness across
the sheet for various crowning.
2. Calender frame: It is made of gray cast iron. This is so designed
that the rolls do not deviate from the operating
axis. Provisions are also there to install edge
cutting/ measuring devices.

3. Roll-gap adjusting device: The design is based on roll-separating

forces produced during production.
Worm gear units with spindle adjusting
gears are driven by d.c. motors are
generally used.

4. Roll heating/cooling devices: Two types: Central bore system

and peripheral drilled system.
For rough operations, mixture of
steam and water is used. For
better control especially above
1000 C, saturated steam is used.

5. Edge trimming device: The irregular edges of the rubber mass

is trimmed off with the help of a separately
driven circular knives fitted over the rolls.
Generally a reduction of 200-300 mm from the face length of the calender
is maintained to erase the edge effect. This cut out materials is again
fed to the calender by suitable automated/ manual processes.

6.Calender drive: D.C. motor drives are used to run calender rolls.
For evenly moving calender rolls, single
motor drives are used. For variable roll speed calenders, either multi-motor
drives/ single motor drives and special gear units with switching step facility
is used.

7.Other attachments include: thickness gauge, prickling unit etc.

Problems during calendering and remedies:

1. Uneven sheet surface: Raise temperature of the calender rolls/feed

2. Crows feet defect (forming acute angle along the rolling direction):
Raise the temperature of the roll in contact with
the compound surface
3. Blister on the surface: The roll temperature is too high; reduce the
roll temperature forming the surface/ feed
temperature.
Extrusion of Rubber Compounds
Extrusion is the process of forcing the polymer/ rubber material through
an orifice or dies so as to obtain the material in continuous length.

The extruded material subsequently cut to required lengths and the

vulcanization is carried out by a continuous or batch process.

In rubber industry, extrusion is used in various applications like making

of tyre treads, tubes, rubberizing bead wire, cable sheathing etc. Tubes,
rods etc. both solid and hollow types can be prepared using extrusion
process.
The plasticizing component in an extruder is the metal ‘screw’ placed inside a
barrel in the front end of which fitted a die and at the other end a hopper for
compound feeding.

The screw is driven at a slow speed with the help of an electric motor through a
reduction gear.

The compound is fed through the hopper; the feed may be hot or cold and in the
form of pellets, cut strips or continuous strip.

The screw is usually bored to facilitate water cooling. The barrel is also water
jacketed for cooling.

The feed hopper should preferably have both steam and water connections for
heating and cooling the feed.
Design of an extruder screw
Flighted length/Diameter (L/D) ratio: The ratio produced by dividing the effective
length of the screw by its diameter. The L/D ratio of plastics extruder is generally
Greater than that of a rubber extruder mainly due to scorching.
Rubbers: 10:1 to 20:1; For plastics even 40:1 is possible.
L/D = 3:1 to 8:1 are cold feed extruder
Lead: The horizontal distance the flight progresses in one revolution of the screw.

Pitch: The axial distance between two adjacent flights.

Starts: The number of flights in one revolution of the screw.

Compression ratio: It is the relative depth of the channel at the feed section of
the screw vis a vis the channel depth at the delivery end.

Potential output of an extruder per minute:

Output= A.(L/2).R.d.; A= Cross sectional area; L= lead length; R= Screw r.p.m.;

d= Density of the rubber compound

Q = Qdrag-Qpessure-Qleakage
 Assignment # 2

A polymer is extruded with a screw extruder, whose single

metering section has the dimensions: barrel internal diameter
D=150mm. Screw pitch = 150mm; depth of screw flights H =
9mm; width of the screw flights e = 15mm and length of
metering section =1m. (the screw is a single start helix). If the
screw turns at 100rev/min, find the volume throughput of the
polymer when no die is attached (Open discharge case).
Effects of the screw and barrel temperatures:

The output is dependent on the relative grip on the rubber between the
screw and the barrel- the higher the grip of the barrel, the higher the
output.

The grip in the feed zone is influenced by friction until the rubber
reaches a temperature of 60-700 C; above this temperature the viscosity
drops rapidly up to 100-1100 C. Thus for maximum output, a hot feed
pocket needed to establish the grip; the screw temperature should high
and the barrel kept cool.

To achieve high degree of processing efficiency, the polymer/rubber

must be encouraged to flow and cross blend as it progresses down
the length of the screw. This in turn requires that the polymer should
gain heat at the earliest possible stage to ensure that the mixing and
blending action of the screw can be carried out on a material that starts
to flow at around 700 C.
Extruder Die

Two basic concepts of die design:

1.Straight way die: polymer’s axial flow path remains unchanged
2.Right angle die: Polymer’s axial flow path is converted to a 900 change in
direction

Design Criteria
1. Compactness of design
2. Uniformity of heating/cooling arrangements for total all round temperature
control
3. Evenly balanced flow path for the polymer
4. Streamlined flow paths to ensure that no dead areas are present
5. Should have quick locking and hinging facility to locate it in position with
respect to extruder barrel
6. Quick cleaning and die changing with minimum loss in production

Volumetric output vs. Head pressure (Die resistance)

 Deep channel

Large die orifice

Q Small die orifice

Shallow
Channel

P
Die swell

Die swell (%)= (Diameter of the extruded)/ (Die diameter) x 100

For majority of extrusion systems the die area is considerably smaller

than the annular area of the polymer emerging from the screw delivery
point.

After emerging from the die, the rubber tries to release the inbuilt stress
due to this compression and swells in diameter. This also reflects the
elastic response characteristics of this material.

Rubber is incompressible and hence increases in diameter decreases

length of the extrudate. The conveyor speed that pulls of the rubber
extrudate should be so adjusted to take care of this shrinkage.

Negative die swell is observed if the area of the screw delivery point
is larger than the die area.
No theories are yet capable of calculating adequately the correlation
between the die shapes and corresponding extruded shapes

In practice it has been found that rubber formulations that induce wall
slip produce lesser die swell and greater length recovery

Addition of fillers to rubbers reduces die swell mainly due to: increase
in viscous characteristics and reduction in volume fraction of the rubber
Trouble shooting in Extrusion

1. Porosity: Due to retention of moisture in the mineral fillers; Increase

the temperature in the feed zone; dry the mineral fillers for
longer period.

2. Sticking to the screw: Due to green tack property; Dusting of the

compound with talc.

3. Torn extruded edges: Insufficient loading of reinforcing fillers; Load

higher proportion of fillers, Incorporate some
proportions of PF or CI resins.

4. Rough surfaces: Due to improper mastication of the rubber; poor

rubber blending, presence of agglomerates of
poorly dispersed ingredients, presence of “dead
spots” or due to too low die temperature; Increase
the die temperature or take precautions accordingly.
Moulding of rubber compounds

Moulding is an operation of shaping and vulcanization of rubber

compounds by means of heat and pressure in a mould of
appropriate form.

These moulded goods are used in day to day life in household,

electrical, surgical, automotive and other applications.

There are various molding processes but all of them are basically
similar. The difference lies in introduction of the rubber compound
into the mould.

Three different techniques of moulding: Compression, Transfer and

Injection
Moulds

In any of the moulding processes the most important equipment

is the mould.

Moulds are generally made of steel and usually consist of two or

more flat metal plates of varying thickness which are so shaped that
when kept together they form one or more closed mould cavities.

Single moulds having more than even one thousand cavities are in
use.

Apart from steel, moulds are also made of aluminum alloy and
white metal (80% lead, 10% tin and 10% antimony).

Multiple moulds are sometimes necessary to increase the production

rate. The moulds are carefully designed and finished to get products
of correct dimension and smooth surface finish.
Shrinkage of the rubber compounds and the moulds are to be kept
in mind to obtain correct dimension of the rubber products.

Shrinkage is the term used to describe the difference in the

dimensions of the mould and the article produced from it.

This shrinkage takes place because the coefficient of thermal

expansion (volume) of steel is 0.3 x 10-4 /0C while that of rubber
lies between 4-7 x 10-4 /0C. The linear shrinkage of rubber compounds
vary between 1.5 to 3% and so the molds are made larger by this
factor than the size of the moulding to be produced in order to keep
the recommended linear dimension.
Mould lubrication is an important factor during moulding of rubber
compounds for smooth flow inside the mould and easy ejection
of the compounds.

Detergents, soaps, wetting agents, silicone emulsions, aqueous

dispersions of mica, talc, fatty acids are used for this purpose and
are known as mould lubricants or mould release agents.

Dry lubricants are also available based on teflon, polyethylene.

The lubricants should be applied in minimum quantities depending

upon the mould complexities and the rubber to be processed.

The excess lubricants deposit over the surface of the rubber

products and cause defective surface. If not carefully used it also
hampers the rubber-to-metal bonding which is also necessary.
In order to have good surface finish, the moulds are to be cleaned
regularly.

Abrasives are suitable for cleaning of simple moulds while the

complicated moulds are cleaned by grit blasting, vapour blasting
and electrolytic oxidation in salt baths and ultrasonic cleaning.

In grit blasting, ground nut shells of 10-30 mesh are used. Vapour
blasting consists of high pressure application of detergent
solutions. Salt baths are used in bigger plants; they are efficient
but hazardous. Ultrasonic cleaning is applied to the moulds
immersed in hot detergent solutions kept at around 800 C.
Compression Molding

The oldest and the most popular technique of making rubber

molded goods

Presses are used as the main equipment in compression

molding

The main function of the press is to apply pressure and to

maintain it

Hand operated molding presses are used for small scale

production; Mechanical presses are also available especially
used for large and complicated designed articles
Hydraulic press

Single day-light multi-cavity hydraulic press

Hydraulic press

Multi day light multi-cavity hydraulic press

The total pressure on the molds depends upon ram cross-
sectional area and the pressure in the hydraulic system and
is independent of stroke, material and time of molding cycle

Most popular type of hydraulic press is that with up-stroke; In

this case the lower platen moves upward to close the mold

In the down-stroke type presses, the upper half moves and

the lower half remains static

Steam is the usual means employed for attaining the operation

Temperatures; electrical heating is also used especially for larger
presses

45 Kg/cm2 platen pressure is considered to be adequate

To avoid distortion of the platen, ram diameter should be 75%
Or more than the average platen dimensions

Each platen should have minimum thickness of 5 cm

Approximate steam consumption of the press can be taken as

1 Kg/hr per 900 sq. cm of exposed surface of platen

For electrically heated press 2KW/1000 sq. cm of platen area

should be provided to avoid wide temperature fluctuations

Molding temperature usually varies from 100-1700 C; After

the curing time the molds are open and the rubber article is
taken out after slow releasing of the molding pressure
It is sometimes advisable to provide suitable support during
cooling especially for large and complex articles

The compounds for molding are preformed to the approximate

shape of the mold cavity and is known as ‘blanks’.

The ‘blanks’ are pre-weighed to avoid non-fills and rejects

Always the material is weighed 5-10% excess of actual cavity

weight in order to avoid mold starving

Dusting with talc can be done to avoid mold sticking especially

for high tack green rubber compounds
Limitations of compression molding process:

Slow process; High cycle time. This is overcome by increasing the

molding temperature which increases the chances of scorch due
to poor heat transfer. This is overcome by using transfer molding
process.

Transfer Molding
The rubber is contained in a chamber above the
closed mold cavity.

It is forced into the cavity through connecting holes

by a ram which operates when the press is closed.

The blank is preheated in the chamber above the

cavities.

Due to forcing of the compound through the holes

under pressure the temperature of the compound
further increases and thus the cure time is reduced

This method of molding is preferred for rubber-to-metal

bonded goods, large and complex components
Essentials of transfer molding:

This gives shorter cure times with lesser number of

rejects

The compound to be either in pad form or as pellets

in sufficient quantity to fill the mold cavities.

Gives better rubber-to-metal bonds due to easy

location of metal parts

Limitations

High cost

Fewer mold cavities

Longer changeover time

Injection molding
Considered as a modification of transfer molding
technique

The compound is fed into the mold cavity near its

molding temperature which reduces the cure time

This is used for mass production of small components

free from flash lines

Generally two types: Ram type and Reciprocating

Screw type
Screw injection molding machine

The rubber compound is fed in the form of strips

The screw plasticizes the compound by frictional

Heat; the temperature rises from 30 to 700 C

The mold is maintained at a temperature 50- 750 C

higher than the screw chamber temperature

The vulcanization takes place by virtue of heat the

rubber gained before entering the mold. Extra heat
is supplied in the form of electrical or oil heating
systems.

After stipulated plasticization, the screw pushes the

rubber inside the mold via runner and gate.
The screw holds the pressure till the curing is
over. After, curing it comes back and thus called
reciprocating screw type machine.

This process generates molded articles with very

good physical properties; flex resistance is also
several times higher compared to compression
molded articles.

This technique is used to mold articles like footwear

sole and heals, O rings, gaskets, window seals etc.

Multi-cavity injection molding machines are also

available in the market.
Ram injection molding machine

The operation principle is same, only difference

is the presence of a ram instead of a screw which
forces the rubber inside the mold after preheating
in the chamber.

Essentials

Shorter cure cycle

Products with superior physical properties especially

for thermoplastics

Products with superior finish and no flash marks

Limitations: High cost of the machine

Rubber Coated Textiles

Rubber coated or rubberised fabrics means the fabric

impregnated or surface coated with rubber. An alternative
name to rubberised fabric is proofed fabric; e.g. water-proof
cloth.

The textiles contribute a very high tensile strength, modulus

and overall strength which complements the elasticity and
flexibility of the rubber.

The fabrics used for making rubber coated textiles are

cotton, rayon, nylon and terylene.
Cotton is relatively easy to coat with rubber as it is
a short length stapled fibre having free ends which
provides mechanical adhesion with rubber.

Other continuous length synthetic fibres are difficult

to coat as they do not have frequent free ends like
cotton and thus mechanical adhesion is also relatively
poor.

Synthetic fabrics are therefore treated chemically before

coating with rubber to achieve good bond between them
and the rubber.

The important synthetic fabrics used for coating are rayon,

nylon and polyester of which rayon is easiest to bond
while polyester is most difficult to bond.
Rayon is hydrophilic and an aqueous based dip can
penetrate the surface of the filaments and form a
good between dip and textiles.

Polyester is an inert fibre requires more exotic bonding

system.

Bonding adhesives generally used:

1. Resorcinol-formaldehyde resin with NR
2. Resorcinol-formaldehyde resin with SBR
3. Resoncinol-formaldehyde resin with vinyl pyridine

The fabric which has to coated with rubber first is dipped

into these latex adhesives for pretreatment.
RF-NR Adhesive:

For treatment of rayon subsequently coated with NR

A. Resorcinol: 11.3 parts

Formaldehyde (37%) 24.5
Sodium hydroxide (10%) 10
Water 278

B. Natural rubber latex (60%) 167

Sodium hydroxide (10%) 10
Water 157
RF-SBR Adhesives:
Formula 1 Formula 2
A.Resorcinol: 13 13
Formaldehyde (37%) 19 19
Sodium hydroxide (10%) 8 19
Water 305 305

B.SBR Latex (29/71; 40%) 200 50

Styrene butadiene
vinyl pyridine latex (40%) 50 200
Water 380 19

Formula 1 is suitable for treatment of rayon fabric

while formula 2 is suitable for nylon fabric. Both these
fabrics are to be subsequently coated with SBR.
RF-VP Adhesives:
Formula 1 Formula 2

A.Resorcinol 13 ---
Formaldehyde (37%) 19 20
Stopped RF condensate
(75%) --- 27
Sodium hydroxide (10%) 9 8
Water 240 410

B.Styrene-vinyl pyridine
butadiene polymer
(15/15/70; 40%) 250 250
Water 44 ---

These formulations are suitable for nylon to be coated with

SBR and NR compounds respectively
The adhesion improvement between the treated
synthetic fabrics and the rubber is through mechanical
action by spreading the stress over a greater surface
area.

Crosslinks can form between the rubber in the

resin and the rubber coating thus giving a bond between
the rubber and the fabric.

Self-bonding rubber mixes:

Based on resorcinol, formaldehyde donor e.g. hexa and

silica. Formulation is based on NR and contains carbon
black (25 phr) and a 50:50 blend of reinforcing silica and
resorcinol (phr) and 1.5 phr hexa. This composition promotes
Bonding in untreated, clean nylon and rayon fabrics.
Cord dipping
Rubber coating machines

1. Spreading
2. Calendering
Rubber to metal bonding

For certain applications like rubber roll coverings,

Tanks, pipe and pump linings, trolley wheels, engine
Mounts etc. need rubber to be bonded to metals.

Four main methods of bonding:

1. Ebonite bonding
2. Brass plating
3. Isocyanate bonding
4. Use of rubber derivatives like cyclised rubber,
Rubber hydrochlorides and proprietary bonding
agents
Metal surface cleaning:

Clean surface is of vital importance in getting

good bonds

The first treatment given to the metal part is

degreasing to remove oil and grease

Afterwards, the metal parts are cleaned free of

rust, scale, dust and other foreign matter by
scouring sand blasting, vapour blasting, or simply
by wire brushing, polishing with abrasives or by
machining
Removal of metal oxides is achieved by
Means of dilute acids

Stainless steel, nickel and monel parts

Should be pickled in chromate liquors

Preparation of chromate pickling solution:

Sodium dichromate: 5 parts

Concentrated nitric acid: 9 parts
Preparation of concentrated acid pickling
Solution:

Concentrated nitric acid: 100 c.c.

Concentrated sulphuric acid: 100 c.c.
Zinc oxide: 8g
Summary of pre-treatments given to different
Metals and alloys:

Metal Treatment

Mild steel Pickle in HCl or 15% phosphoric

and chromic acid prickle

Brass Chromate conc. acid pickle or

Ammonium persulphate pickle

Galvanised iron 45% phosphoric acid at 700 C for 2 min

Magnesium Chromate pickling for 1-2 min

Chrome plated nickel,

Monel, Stainless steel Chromate pickle

Copper and bronze Brass plated

Zinc Etch with conc. HCl and carefully neutralize

 Vulcanization / curing
1. Rubber is converted
Oscillating Die Rheometer (ODR) from low strength plastic
to highly resilient to
and Moving Die Rheometer (MDR) strong elastic material
2. Crosslinked rubber does
not dissolve in solvent
3. Physical properties and
temperature range of
application increases
4. Rubber looses its
tackiness and becomes
more resistant to
weathering

MDR –easier
sample loading and
better heat transfer
Cure curve
 Factors

Temperature
Thickness
Thermal stability
 Temperature

140

Crosslink
Density

160

180

200 oC

Cure Time (Minutes)

 Thickness

Rubbers – bad conductor of heat

1. Heat in a stepwise manner
2. Building articles from different
compounds
3. Preheating and rapid post-heating
4. Post-cure
5. Use fillers of high thermal conductivity
6. Use transfer or injection molding
Vulcanization Methods

•Batch
•Continuous
1. Pressurized Steam
2. Hot Air
3. Hot Air Fluidized bed
4. Liquid Salt Bath
5. Rotocure vulcanization
6. Moulding
7. Radiation Vulcanization –microwave dielectric
heating
 References
• Handbook of rubber technology – Steven Blow
• Textbook of polymer science –F.W. Billmeyer
• Rubber technology and manufacture – C.M. Blow and
C. Hepburn
• Rubber engineering – Indian Rubber Institute
• Science and Technology of rubber – F.R. Eirich
• Science and Practice of Rubber Mixing-Nobuyuki Nakajim
• Rubber Processing – Peter S. Johnson
• Polymer Mixing – Chris Rauwendaal
• Rubber Processing on a Two-roll Mill - B.R. Gupta
• Rubber Technology – Maurice Morton