Basics of Polymer and Rubber

WHAT ARE POLYMERS?

COMPLEX GIANT MOLECULE-
DIFFERENT FROM LOW MOL. WT.
COMPOUNDS
Eg.1) Nacl - MOL.WT. 58.5
Eg. 2) BUTADINE- MOL.WT. 54

POLY BUTADIENE (* 4000 units)

- MOL. WT. 2,00, 000
POLYMER
CLASSIFICATION
a) NATURAL / SYNTHETIC
b)ORGANIC / INORGANIC
c) THERMOPLASTIC /
THERMOSETTING
NATURAL POLYMERS

WOOD, COTTON, CELLULOSE,

STARCH ETC.

CLOTHING

ANIMAL SKIN
NATURAL FIBRES
SYNTHETIC FIBRES
POLYMERIZATION
MECHANISMS
a) FREE RADICAL b) IONIC
FREE RADICAL INITIATORS
a) AZO COMPOUNDS
b) PEROXIDES
c) HYDROPEROXIDES
d) PERACIDS
IONIC POLYMERIZATION
a) CATIONIC b) ANIONIC
CATIONIC POLYMERIZATION CATALYST
BF3/HOH (F3BOH)- H+

ANIONIC POLYMERIZATION CATALYST

Eg. BUTYL LITHIUM
LIVING POLYMERIZATION
APPLICATION- MANUFACTURE OF BLOCK
COPOLYMERS
COORDINATION POLYMERIZATION
Eg. ORGANOMETALIC COMPOUND/DIENES
RCH2Mt+BUTADIENE
CATALYST- ZIEGLER NATTA- TRIALKYL
ALUMINIUM & TiCl3

STEP POLYMERIZATION
Eg.1) POLYHYDRIC ALCOHOL+ADIPIC
ACID- RESULTS IN POLYESTER
2) POLYHYDRIC ALCOHOLS- RESULTS IN
POLY ETHERS
3) DICARBOXYLIC ACID+ DIAMINES-
RESULTS IN POLYAMIDE
TYPES OF POLYMERS
a) RUBBERS
b) PLASTIC
c) FIBRES
CHRISTOPHER COLUMBUS- 15th
CENTURY OBSERVED – IN SOUTH
AMERICA CHILDREN PLAY WITH
BALLS MADE OF NATURAL RUBBER

21 st CENTURY- RUBBER IS A
MULTIBILLION DOLLAR INDUSTRY
„ NATURAL
RUBBER
NATURAL RUBBER
SALIENT FEATURES

Major source-Hevea brasiliensis

Total global production (2004) - 8.24 million
tonnes
Total consumption (2004) - 8.11 million
tonnes
Production in over 20 countries
 Major producing
countries :
Thailand,Indonesia
Malaysia,India,China,
Vietnam

Major consuming
countries :
China,USA,Japan,
India,Malaysia,Korea
 Special characteristics of NR
„ High strength
„ Low heat generation
„ High tack and green strength
„ Excellent processability
„ Excellent resistance to chipping, chunking and tear
„ Economy
… Relatively inferior resistance to ageing, weathering and
heat
… Swells in contact with petroleum oils
… High air permeability
… Relatively inferior traction and wet skid resistance
 RUBBER PLANTATION

CROP (RUBBER)

Latex Field coagulum

80 % 20 %

Marketable forms of raw rubber

ƒ Ribbed sheet rubber
ƒ Concentrated latex
ƒ Block rubber
ƒ Crepe rubber
 COMPOSITION OF FIELD NR LATEX

IT IS A COLLOIDAL DISPERSION OF RUBBER PARTICLES IN WATER.

RUBBER - 30 – 40%
PROTEIN - 1 – 1.5%
RESIN - 1- 2.5%
SUGAR - 1%
ASH - LESS THAN 1%
WATER - 55 – 60%

PARTICLE SIZE - 0.5 – 3 MICRONS

PARTICLES ALWAYS EXHIBIT BROWNIAN MOVEMENT

Typewise production of NR in India (2002-03)

Type Quantity (MT) % Share

RSS 450215 69.3
Latex concentrate (DRC) 74325 11.5
Solid block rubber 74940 11.5
Pale Latex Crepe 1750

Others 48205 7.7

Total 649435
NATURAL RUBBER

INDUSTRIAL RAW MATERIAL FROM NATURE

SYNTHESISED BY THE TREE
UNDEGRADED TILL IT COME IN CONTACT
WITH AIR
CIS-POLY-ISOPRENE
NATURAL RUBBER –
MARKETABLE FORMS

SHEET RUBBER (RSS)

CREPE RUBBER
TECHNICALLY SPECIFIED RUBBER (TSR)
LATEX CONCENTRATES
NATURAL RUBBER – SHEET
RUBBER

¾ LOWER PROCESSING COST

¾ SIMPLE MACHINERY
¾ ADOPTED BY SMALL GROWER SECTOR
STEPS INVOLVED IN SHEET RUBBER PROCESSING

Sieving
Bulking
Dilution
Coagulation
Sheeting
Drying
Grading
NR Quality Issues

¾ Consistency
¾ Contamination
¾ Undried rubber
¾ Packaging
Ribbed Smoked Sheet Grades
RSS IX Colour
RSS 1 Extent of dryness
RSS 2 Mould growth
RSS 3 Tackiness
RSS 4 Blisters
RSS 5 Dirt
SHEET RUBBER
 Grading is done as per
Green Book specification.

BIS STANDARD IS 15361 : 2003

RAW NATURAL RUBBER –
RIBBED SMOKED SHEETS (RSS) -
GUIDELINESS
 BLOCK RUBBER
CRUMB RUBBER

TECHNICALLY SPECIFIED RUBBER

[TSR]

INDIAN STANDARD NATURAL RUBBER

[ISNR]
 PRODUCTION OF
BLOCK RUBBER
LATEX FIELD
COAGULAM

RECEPTION and PREBREAKER

BULKING

PIT COAGULATION BLENDING

CRUSHER CREPER (4-6 passes)

CREPER
 (CONTD)

SHREDDER OR CREPER/HAMMER MILL

DRYER

WEIGHING

GRADING PRESS

PACKING
TECHNICALLY SPECIFIED RUBBER -
ADVANTAGES

The consumer has the choice

More consistent
Impurities can be assessed
Being marketed in compact polyethylene wrapped
bales, contamination on storage handling and
transportation is minimum.
Minimum storage space
Reduction in processing time
DIFFERENT GRADES OF
BLOCK RUBBER

¾ ISNR 3 CV
¾ ISNR 3 L
¾ ISNR 5
¾ ISNR 10
¾ ISNR 20
¾ ISNR 50
TECHNICALLY SPECIFIED RUBBER
ISNR 3CV Tyres, Engineering components,
extruded and calendared products
ISNR 3L Light coloured pharmaceutical
feeding bottle teats, Industrial
rollers for paper and printing
industry
ISNR 5 Conveyor belts, cycle tubes,
engine mountings, footwear
ISNR 10, 20 Tyre
ISNR 50 Handmade hose, footwear, mats,
moulded hose
 BIS SPECIFICATIONS OF ISNR
CHARACTERISTICS ISNR ISNR ISNR ISNR ISNR ISNR
3CV 3L 5 10 20 50
DIRT (45 Micron 0.0 0.0 0.0 0.10 0.2 0.5
sieve) (%max) 3 3 5 0 0
ASH (%max) 0.0 0.0 0.6 0.75 1.0 1.5
5 5 0 0
NITROGEN (%max) 0.6 0.6 0.6 0.60 0.6 0.6
0 0 0 0 0
VOLATILE MATTER 0.8 0.8 0.8 0.80 0.8 0.8
(% max) 0 0 0 0 0
INITIAL - 30 30 30 30 30
PLASTICITER, Po
(min)
PLASTICITY 60 60 60 50 40 30
RETENTION INDEX,
PRI (min)
COLOUR - 6.0 - - - -
(LOVIBOND SCALE,
max)
ACCELERTED 8 - - - - -
STORAGE
HARDENING (max)
MOONY VISCOSITY, 60 - - - - -
ML (144) 100OC +
COLOUR CODE blac blac gree brow red yello
k k n n w
ISNR 5

• PRODUCED FROM FIELD LATEX.

• USED FOR HIGH QUALITY PRODUCTS LIKE

CONVEYOR BETS, CYCLE TUBES, ENGINE
MOUNTINGS, FOOTWEAR etc.
 ISNR 10, 20 & 50
• PROCESSED FROM QUALITY FIELD COAGULUM

• ISNR 10 AND 20 GRADES ARE USED BY TYRE

MANUFACTURERS IN BULK

• ISNR 50 GRADES USED FOR PRODUCTION OF

CHEAP PRODUCTS LIKE HAND MADE HOSES,
FOOT WEARS, MATS AND MOULDED GOODS.
 ISNR 3L
• PRODUCED FROM GOOD QUALITY FIELD
LATEX
• MAINLY USED FOR LIGHT COLOURED
PRODUCTS
• USED FOR HIGH PURITY PRODUCTS LIKE
PHARMACEUTICAL PRODUCTS, FEEDING
BOTTLE, PRINTING ROLLERS etc.
 ISNR 3CV
• PRODUCED FROM GOOD QUALITY FIELD
LATEX

• VISCOSITY STEBILISED AT NARROW RANGE

(60 + 5)

• USED IN THE MANUFACTURE OF TYRES,

ENGINEERING COMPONENTS EXTRUDED AND
CALENDERED PRODUCTS.
 SYNTHETIC RUBBERS

General purpose Special purpose

Resistance to chemicals Oil resistance

Solvents Chemical resistance
Fire Extreme temperature service
Temperature
 General purpose

¾Styrene butadiene rubber (SBR)

¾Poly butadiene rubber (BR)
¾Ethylene propylene rubber (EPM)
¾Ethylene propylene diene rubber (EPDM)
¾Poly isoprene rubber (IR)
¾Iso butylene isoprene Rubber (IIR)
SBR
SBR elastomer is principally manufactured by the
emulsion-polymerization process or by the
solution-polymerization process. Although the
emulsion process is dominant worldwide, SBR
producers are moving toward the solution
technology because it yields an elastomer of
superior properties. In the emulsion processes,
a major portion of the SBR elastomer is
manufactured via the cold-emulsion
polymerization method; globally, cold emulsion
accounts for more than 90% of emulsion SBR.
Styrene - Butadiene Rubber (SBR)

SBR is the largest tonnage synthetic rubber being made all over the
world. It accounts for about 60% of the synthetic rubber production
and more than 30% of all the rubber consumed. It is a copolymer of
butadiene and styrene. The most common SBR is having
approximately 25% styrene and 75% butadiene with a random
distribution of monomers. There are about 500 grades of this rubber
including a large proportion of oil-extended forms and
masterbatches of SBR with carbon black. SBR exhibits good abrasion
resistance and hence its major application is in tyre sector,
especially in passenger car tyres. Other important applications
include soles and heels for the footwear, floorings, mats and other
domestic items, conveyor belting, hose, rollers, cycle tyres, buffers,
gaskets and a large number of other industrial components. About
90% of the SBR produced is by emulsion polymerisation and the
rest by solution polymerisation. In addition, about 10% of all the
SBR produced is marketed in latex form and is used for applications
such as carpet backing, paper coating and latex foam. There is also
a small but growing quantity used in adhesives such as butadiene
styrene vinyl pyridine for making tyre
Styrene Butadiene Rubber (SBR)

-CH=CH2 + CH2=CH–CH=CH2

Styrene (30%) Butadiene ( 70%)

0C 4 0C
40

- CH2-CH=CH-CH2-
CH2

CH

Hot SBR Cold SBR

n

Styrene butadiene rubber

Butadiene

Petroleum cracking
CH2=CH–CH=CH2
Dehydrogenation of butanes/butenes

Styrene

-CH=CH2 Dehydrogenation of ethyl benzene

Ingredient Hot polymer Cold polymer

Butadiene 75 72
Styrene 25 28
Water 180 180
Fatty acid 4.5 4.5
KCL electrolyte - 0.3
t-dodecyl mercaptan (modifier) 0.28 0.20
K2S2O8 (initiator) 0.30 -
P-methane hydroperoxide - 0.063
FeSO4. H2O (activator) - 0.010
EDTA - 0.05
Sodium formaldehyde sulphoxylate- 0.05

Temperature 42 4
Conversion 72 60
Short stop hydroquinone N-N, dimethyl
dithio carbanmate
 Different Grades of SBR

Number Type

SBR – 1000 Hot polymers

SBR – 1100 Hot balck filled SBR (14% oil)

SBR – 1500 Cold polymer

SBR – 1600 Cold black filled SBR (14% oil)
SBR – 1700 Cold oil master batch
SBR – 1800 Cold black filled SBR (>14% oil)
SBR – 1900 Miscellaneous dry polymer

SBR – 2000 Lattices hot

SBR – 2100 lattices cold
 Properties of SBR

Processing
Tensile strength
SBR is inferior to NR Tear strength
Tack
Heat build-up

Permeability
Ageing
Resistant to heat and wear
Reinforcement by carbon black
SBR is superior to NR Low viscosity
Premastication not required
Less scorch
 Compounding and Processing

SBR is slower curing than NR

Requires lower less sulphur & more accelerator
Scorch problems are less with SBR

ZnO 3 – 4
Diethylene glycol 1.5 – 2
(Triethanol amine)
Stearic acid 1.5 – 2
Process oil 5 –7
Filler 20 – 30
Antioxidant 1 - 3
Accelertor (sulphenamide) 1.5 – 2
Sulphur 1.5 - 2
Applications

Passenger car tyres

Wires
Cables
Shoe soles
Extruded goods
SBR lattices are used in carpet back coatings
Polybutadiene Rubber (BR)
Polybutadiene can be produced by both emulsion and solution
polymerisation. Emulsion polymers are of random nature in
stereospecificity. Solution polymers can be manufactured into
stereospecifically tailor-made forms. It is achieved with the
use of different catalysts such as anionic or ziegleratta type.
BR has excellent resilience, abrasion resistance, and low
temperature flexibility. BR can have higher filler loading and
oil extension without property deterioration. Tear strength
and resistance to cut growth are relatively poor for BR and
hence is used as a blend with other rubbers. About 90% of
BR is used in tyres, blended in various proportions with SBR,
NR etc. Other application of BR is as an additive in rigid
plastics such as polystyrene for impact modification. Other
engineering applications such as V-belts, conveyor belting,
solid rubber tyres, antivibration mounting roller covering and
flexible heavy duty suction and discharge hoses.
 Butadiene Rubber

n CH2=CH–CH=CH2 -CH2-CH=CH-CH2- n

Butadiene cis-Poly butadiene

Production Solution/emulsion polymerisation

Emulsion BR Low mol.wt and shows cold flow
Solution BR High mol.wt and difficult to process
Properties of BR

Very good low temperature properties

Low heat build-up
High resilience
Better flex resistance
Good heat stability

Very high air permeability

Poor tack
Poor road grip
Poor tear and tensile strength
 Processing

Highly resistant to break down and poor mill banding

Rough extrusion appearance
Tight nip and low mixing temperature preferred
Used along with NR or SBR

Applications

Truck tyre treads

Modifier to plastics
Ethylene Propylene Rubber (EPM / EPDM)

Raw materials
Ethylene
Propylene
Catalysts

Amount of unsaturation in EPDM is 0.6 to 1,0 %

 Properties
Resistance to ozone and weathering
Resistance to heat ageing and compression set
Chemical resistance
Low temperature flexibility
Low polymer specific gravity
Good physical properties in highly filled stocks
Fast mixing, moulding and extrusion characteristics
Excellent electrical properties

Applications
Electrical insulation and jacketing
Automotive seals
Automobile hoses
Polyisoprene Rubber (IR)
This rubber can be considered as a synthetic replica
of natural rubber (NR). Special catalysts that could
produce Cis-1, 4-Polyisoprene, the chemical
analogue of NR was invented by the middle of the
20th century. Synthetic material is purer than NR,
as the latter contains protein, wood resins and
other non-rubber constituents. Applications include
tyres, extruded gaskets, sheeting, footwear, sponge
rubber and springs. Gutta-percha, the trans isomer
of polyisoprene can also be made synthetically. It
finds application as insulating material in deep sea
cables and gall ball covers.
Poly Isoprene Rubber (IR)
Solution polymerisation techniques
Stereo isomeric purity
Molecular weight and molecular weight distribution
Presence of functional groups attached to the polymer chain
Impurities
Processing
Little tendency of storage hardening
Initial banding is rapid
Avoid over mastication
Care for good dispersion
Applications
Areas where NR is used
Production of Chlorinated and isomerised rubbers
Pharmaceutical industry
 CH3 CH3
CH2=C–CH=CH2 - CH2-C=CH- CH2 -
n
1soprene(C5H8)
Cis-1,4-poly 1soprene

CH3 H CH3 H CH3 H

C C C C C C
CH2 CH2 CH2 CH2 CH2 CH2

CH3 H CH2 CH2 CH3 H

C C C C C C
CH2 CH2 CH3 H CH2 CH2
 CH3 H CH3 H CH3 H
C C C C C C
CH2 CH2 CH2 CH2 CH2 CH2

Cis-1,4 Polyisoprene (Natural Rubber)

CH3 H CH2 CH2 CH3 H
C C C C C C
CH2 CH2 CH3 H CH2 CH2

trans-1,4 Polyisoprene (Guttapurcha)

Butyl Rubber (IIR)
Butyl Rubber is a solution copolymer of isobutylene with a small
proportion (from 1 to 4%) of isoprene. Polyisobutylene by itself is fully
saturated, and the isoprene is included to provide sufficient double
bonds to allow vulcanisation with sulphur. Its outstanding property is
the very low permeability to air and other gases. Low resilience, very
good resistance to sunlight, ozone and aging, and relatively good
resistance to high temperature are the other specialities. Butyl tends to
be incompatible with other rubbers, but this difficulty can be overcome
by modifying the polymer with chlorine and bromine to give chlorobutyl
and bromobutyl rubbers.
The main application for all forms of butyl rubber is to make inner tubes
for tyres, and more recently is being used as linings for tubeless
industries. Its high heat resistance has lead to its utilization for
applications such as steam hose and the curing bags used in tyre
vulcanisation. Sunlight and weather resistance of butyl is exploited in
roofing membranes and reservoir sheeting. Its chemical resistance is
made use of in anticorrosion linings.
 Iso Butylene Isoprene Rubber (IIR)

Co-polymerisation of isobutylene with isoprene

at very low temperature ( - 65oC)

Properties

Low rates of gas permeability

Thermal stability
Ozone and weathering resistance
Vibration damping and higher coefficients of friction
Chemical and moisture resistance
Butyl rubbers are characterized by

Mooney viscosity (ML=100oC(1+8) -- 41 to 49

Degree of unsaturation---- 0.7 to 2.2 mole %
Type of antioxidant---- non staining antioxidant

Production by Exxon Butyl (USA)

Polysar Butyl (Canada)
 Processing

Mastication – low level of unsaturation, difficult to degrade,

use of plasticizer is recommended (DCP)
Mixing - Low mooney grade, cold tight mill, high mooney higher
temperature is preferred
Extrusion --Extruded surfaces has smooth surfaces and finish, filler
is added to reduce the nerve, Extrusion temperature
200-270 oC
Building - good green strength, good for building purposes
Vulcanization: Free of scorch, reversion ec, accelerated sulphur
vulcanization, crosslnking with dioxime and related
nitroso compound and polymethylol-phenol resin

Softeners: Paraffinic oils

Synthetic Rubber Production in India

Sl Product Manufacturer Capacity

No.

1 SBR Synthetics & 41,000

Chemicals Ltd.
Apar Ltd. 5,000

2 BR IPCL 50,000

3 NBR Apar Ltd. 8,000

4 EPDM Herdillia Ltd. 10,000

5 VP Apcotex 1,000
Latex (D.WT)
ENPRO 1,000
(D.WT)
 Nitrile Rubber (NBR)
Copolymer of butadiene and acrylonitrile by emulsion
process

CH2=CH–CH=CH2 + CH2=CH

Butadiene ( 70%) CN

Acrylonitrile

-CH2-CH=CH-CH2 -CH2=CH-

CN n

Acrylonitrile butadiene rubber

Properties

Good resistance to a wide variety of

non-polar Oils, fats and solvents

Acrylonitrile content (20-50%)

Low ---25%
Medium —35-50%
High ---35-50
PRODUCT MANUFACTURING
PROCESS
 DRY RUBBER PRODUCTS MANUFACTURE

COMPOUNDIN
RUBBER CHEMICALS
G

MATURATION

PRE-
WARMING

TESTING& QC

MOULDED GOODS EXTRUDED GOODS CALENDERED GOODS

 MOULDED GOODS CALENDARED
EXTRUDED GOODS
GOODS

BLANK PREPARATION AUTO CLAVE

OR
OVEN

MOULDING
(HYDRAULIC
PRESS)
VULCANISATION

FINISIHING OPERATION AND QUALITY CONTROL

PACKING AND DESPATCH

COMPOUNDING
COMPOUNDING
The mixture of rubber and ingredients used for
manufacture of any rubber product is called compound and
the art of making such a compound is called compounding.
Ingredients for product manufacture
1. Polymer or rubber
2. Crosslinking agents
3. Accelerators for crosslinking reaction
4. Accelerator modifiers (Activator and retarders)
5. Aids to processing
6. Reinforcing fillers (Black, mineral and organic)
7. Antidegradants
8. Aids to volume cost (inert fillers)
9. Colouring materials
10. Specific additives
 COMPOUNDING OF RUBBER
Elastomers go through a number of
processing steps in their transformation from raw
elastomers to finished products.
The mixture of rubber and other ingredients
used in a particular rubber manufacture is known
as a compound or a mix and the process of
making such a compound is called compounding
of rubber.
The principal task of compounding is to
secure an acceptable balance between the final
vulcanizate properties, processability and price.
A technical vulcanizate will contain the following
ingredients
1. Base polymer or blend of polymers
2. Cross linking agents
3. Accelerators
4. Activators
5. Antidegradants
6. Fillers
7. Processing aids
8. Diluents
9. Colouring materials
10. Specific additives
COMPOUNDING INGREDIENTS

„ BASE POLYMER
„ CROSS LINKING AGENTS
„ ACCELERATORS FOR CROSS LINKING REACTION
„ ACCELERATOR MODIFIERS- ACTIVATORS AND RETARDERS
„ REINFORCING FILLERS
„ PROCESSING AIDS
„ ANTI DEGRADANTS
„ INERT FILLERS- Aids to volume cost reduction
„ COLOURING MATERIALS
„ SPECIAL ADDITIVES
COMPOUND DESIGN

DESIGN REQUIREMENTS
„ SERVICE REQUIREMENTS/VULCANISATE PROPERTIES
„ PROCESSABILITY
„ ECONOMICS

DESIGN BASED ON
„ CUSTOMER SPECIFICATION/REQUIREMENTS
„ COMPETITOR'S SAMPLE
„ DEVELOP A NEW PRODUCT
SELECTION OF INGREDIENTS
Contd.

CROSS LINKING AGENTS/ACCELERATORS/ ACCELERATOR

MODIFIERS
„ CROSS LINKING AGENTS- Sulphur, peroxides, metallic oxides, resins
etc.
„ ACCELERATORS- Organic-amines & its derivatives
„ ACTIVATORS-ZnO+ Stearic acid
„ RETARDERS
„ PROPERTY REQUIREMENTS- HEAT RESISTANCE, TENSILE
PROPERTIES, TEAR PROPERTIES, COMPRESSION SET ETC. (based
on the nature of cross link)
„ COMPATIBILITY
„ PROCESSABILITY
„ NATURE OF THE PRODUCT
„ SHELF LIFE
„ AVAILABILITY
„ COST FACTOR
FUNCTIONS OF INGREDIENTS
Basic Additives
Sl. Ingredients Functions Example Dose
No. pbw

1. Elastomer Base Plymer NR, SR,RR 100.00

2. Vulcanising Crosslinking of S, Peroxides, 1.0-3.0

agents elastomers Resins, Dioxims,
Urethanes
3. Accelerators To reduce the Thiazoles/Sulphena 0.5-3.0
vulcanising/curing time mides/Dithiocarba
and to enhance degree of mates/Guanidines
cure
4. Activators To activate curing system Metallic oxides- 2.0-6.0
& to narrow down the ZnO,MgO,Pbo
heat requirements Fatty acids, Zinc
salts, Amines
Sl. Ingredients Functions Example Dose
No. pbw

5. Retarders To reduce the scorch Cyclohexyl 0.1-1.0

tendencies thiophthalimide(CTP)
, Benzoic acid
6. Antidegradants To protect vulcanizates from Phenolic/Quinoline/ 1.0-4.0
degrading agents like PPD
heat,light,oxygen,ozone etc
7. Processing aids To reduce break down Oils/Plasticizers/Resi 1.0-10
time,plasticity, increase tack ns
and improve processability

8. Fillers Ability to design for a Carbon black, Silica, 10-100

specific hardness or stiffness Clay,CaCO3
COMPOUNDING
„ It is the operation required to obtain a thorough
and uniform dispersion of all ingredients called
for by the formulae in the rubber
„ Machinery
2-roll mixing mill
kneader
internal mixers
Continuous, automatic high speed mixing
2 –ROLL MIXING MILL
Property requirements
* resistance to service temperature and life
„ environmental and chemical resistance
„ stress – strain properties
„ dynamic properties
„ fatigue performance
„ friction and wear performance
„ electrical and thermal properties
„ permeability, adhesion, staining and corrosion
„ processability, density and price
The mix
phr
„ Rubber 100
„ Vulcanizing agent 2.5 - 3.5
„ Accelerator/s 0.5 – 1.5
„ Activator 2.5 – 5.0
„ Antidegradents 1-2
„ Fillers AR
„ Softener 5 - 10
„ Other materials when necessary AR
Vulcanization process
1.Induction region
•*Cross linking starts at this stage * Scorch time is taken as two units above minimum viscosity
•* All processing and shaping operations are done before scorch time
•2.Curing region
•* Permanent cross links are formed, Dependent upon-Amount of vulcanizing agent,Activity,Reaction time,
•Temperature,Nature of rubber,Presence of other ingredients
•* Optimum cure time – is the time for attaining 90% torque
•* Amount of cross links formed decide the physical properties of the vulcanizate
•*3. Overcure region – Desides the stability of the network towards heat
Vulcanization of thick articles

* Upto 6 mm thickness cure time from Rheometer is

sufficient

*For thick articles 5 min extra is added for every

additional 6mm

*For industrial products cure input requirement for

vulcanization is obtained using programmed
temperature – profile curometer
 Vulcanization – Different methods
„ Moulding Methods other than moulding
( Shaping and curing (Curing of previously shaped compound/composites)
within the mould) Batch curing Continuous curing
* Compression •Autoclave or steam pan • High pressure steam tube
moulding
* Transfer moulding •Hot air oven • Hot air tunnel
* Injection moulding •Water curing • Fluidized bed
* Blow moulding
* Vacuum moulding
•Lead curing • Liquid curing method
• Continuous drum cure
• Microwave vulcanization
Different stages of quality control

1. Raw material testing

2. In process testing

3. Product testing
PROCESSING PROPERTIES
 Process Control Parameters

• Viscosity (viscoelastic behaviour)

• Curing characteristics
• Specific gravity
• Tack
• Green strength
• Shrinkage
• Bloom
Viscosity or Plasticity

Plasticity ease of deformation of the rubber

compound under an applied stress

Viscosity : resistance to plastic deformation or flow

and hence the inverse of plasticity

All process of unvulcanised rubber compound involves flow of the

rubber

Mixing,
Calendaring,
Extrusion,
Moulding
 Shear rates

Shear rates encountered in rubber processing operations --104 /s

Plasticity tests operate ---0.0025 to 1 per second).

Filled rubbers undergo profound changes in plasticity

Plasticity can be used as a check on the uniformity
of repeat batches for the control of the manufacturing process.

Different types of plastimeters

• Compression
• Rotational
• Oscillation
• Extrusion
• Mixer type plastimeter
 Compression plastimeters Wallace Rapid Plastimeter

A small cylinder of the rubber is compressed between parallel plates under a

definite force for a definite time, normally at elevated temperature,
the compressed thickness being the plasticity number

Such tests are

simple and quick
shear rates are very low (usually below 0.1 per second)
scorch and cure rate cannot be assessed.

A high plasticity number stiff rubber

a low plasticity number denotes a soft rubber.
This test has been widely adopted for factory control of
unvulcanised mixes and for the determination of the
plasticity retention index (PRI) of raw rubbers.
 Plasticity Retention Index (PRI)

Aged plasticity number

x 100
PRI =
Unaged plasticity number

Assess the oxidative effects of storage on natural rubber.

 Mooney viscometer

Torque necessary to rotate a disc in a cylindrical chamber

filled with rubber.
Two rotor sizes are used
Larger one with 9.5 ± 0.001inch in diameter used for reading up to
200units
Small rotor 1.20±0.001 inch in diameter readings higher than 200 units

The result is expressed as ML(1+4) at 100oC,

M denotes viscosity in Mooney,

L-large rotor,
1- preheat time,
4-time of reading after pre-heating.
 Curing characteristics

The Mooney viscometer is used to measure scorch,

i.e.the onset of vulcanization.
Mooney viscometer offers a more convenient
way of measuring scorch and rate of cure
when theMooney viscometer is run continuously at 120oC,
and by plotting viscosity against time.

The resulting Mooney curve can be used to calculate

•scorch time,
•time of cure
•cure index.
 Curing characteristics

Scorch time
time in minutes for the viscosity to rise 5 Mooney points for the large rotor (t5)
3 Mooney points for the small rotor (t3)

Time of cure
Time from the start of the viscosity to rise 35 Mooney points
18 Mooney points for small rotor above the minimum viscosity

Time of cure = t35-t5 (large rotor)

= t18-t3 (small rotor)
Rheometer

There are basically two types of curemeter

Reciprocating paddle type

Oscillating disc rheometer (ODR).

The oscillatingdisc type

Comprises a biconical disc embedded in the rubber in a closed
cavity rather in the same manner of the Mooney. The disc is
oscillated throughconstant angular displacement and the torque
required monitored.
Rheometer

Oscillating disc

Upper die

Sample

Lower die
Theory

Monsanto oscillating disc Rheometer

designed to measure the complete curing characteristic of a single
rubber compound,
The force (torque) needed to oscillate the disc is directly
proportional to the stiffness (shear modulus) of the specimen.
As the modulus increases during vulcanization,
the torque is recorded against time to give a curve of stiffness versus time.
Rheograph

Torgue (dN)

Reversi
on time

ts2 t90

Cure rate
PHYSICAL TESTING
Organisations producing
standards
„ -International organization 1972
„ -National Organization
„ -Individual Organization
British-BS 1901
America-ASTM
French -NIFT
German-DIN 1971
Indian -IS
ISO -1972
1. Hardness Test
„ Hardness represents the elastic modulus
of material under conditions of small
strain. Hardness test involve the
measurement of the depth of penetration
of an indentor of specified dimensions
under the application of a load either by a
dead weight or by a spring.
„Shore 0=for sponge rubber in degree.
„ Shore A=for soft rubber in degree
„ Shore D=for hard rubber in degree
„ Shore A correspond to IRHD but
lower below 300
2. Tensile stress/strain
„ Tensile strength is defined as the force per unit
area of original cross section of the sample,
required to stretch a rubber test piece to its
breaking point.

„ Modulus is the tensile stress strain required to

stretch a rubber test piece to a predetermined
elongation.

„ Elongation at break is the maximum elongation,

expressed as the percentage of the Original
length, prior to the rupture of the sample.
3. Tear Tests
„ Tear Strength is defined as the force per
unit thickness required to cause a nick out
in a rubber test piece to extend by the
tearing of the rubber when it is stretched,
under constant rate, in a direction
perpendicular to the plane of the cut.
4. Set, Creep and Stress
Relaxation
„ The deformation that remains in an elastomer
after the removal of an applied stress or strain is
“Permanent Set”.
„ When a constant load is applied to an elastomer
the deformation is not constant but increases
gradually with time, this behaviour is known as
“strain relaxation” or “Creep”.
„ When an elastomer is subjected to a constant
strain, a decrease in stress takes place with
time, this behaviour is called “stress relaxation”
„ The phenomena of permanent set, creep and
stress relaxation are the result of physical and
chemical changes in elastomer, both of which
occur simultaneously
5. Set Properties
„ Recovery after removal of an applied
stress or strain is the set. It depends on
time for which test is conducted and time
allowed for recovery.
Set=To-Tr
-------X100
To-Ts

To-Original thickness
Ts-Compressed thickness
Tr-Recovered thickness
6. Accelerated ageing tests
„ The testing is done usually, by keeping the test
samples under the influence of temperature,
oxygen or ozone for a specified period and then
determining the physical properties like tensile
strength or noting the visual appeal.
„ The fall in properties from the initial value or the
change in appearance gives an indication of the
resistance of the rubber vulcanizates to that
particular factor.
„ Apparatus like hot air ovens, oxygen bomb,
ozone chamber etc. are used for performing the
accelerated ageing.
7. Abrasion Tests
„ Abrasion resistance may be defined as
the resistance of the rubber vulcanizate to
wearing away by rubbing or impact during
service. The principle involved in the test
is to rub the test sample against a
standard rough surface for a specified
time. The loss is expressed in weight or
volume per hour.
8. Flex-Cracking and Cut -Growth
Tests
„ Resistance to flex cracking consists of two
parts
„ ie 1)resistance to crack initiation and
2)resistance to crack growth.
„ In Crack growth testing, a crack is initiated
purposely by means of a specially shaped
tool and the rate of growth of the cut is
measured during flexing.
„ Products like tyres, conveyor belts; shoe soles etc.
are subjected to repeated flexing during service. This
repeated flexing may gradually lead to failure of the
product. This is because repeated flexing of a rubber
vulcanizate causes cracks to develop in that part of
the surface where tension stress is set up during
flexing or if that part contains a crack or cut, causes
the crack to extend in the direction perpendicular to
the stress. Various machines like De mattia Flexing
machine (used for evaluation of tyre tread and side
wall compounds) Du Pont Flex machine (used for
evaluation of conveyor and transmission belt
compounds) and Ross Flex machine (used for
evaluation of footwear compounds) are commonly
used for evaluating the flex resistance of rubber
compounds.
9. Heat Build Up
„ This is an important property for tyre tread where fatigue
is caused by repeated cyclic deformation. Subjecting a
rubber to repeated deformation cycles results in a
change in stiffness and a loss of mechanical strength.
„ ‘Heat build -up ‘type of fatigue test is carried out on an
apparatus generally called a Flexometer which operate
in compression, shear or a combination of the two.
„ In Goodrich Flexometer a cylindrical test piece is cycled
at 1800 cycles/min with a stroke of 4.45mm for 25 min
and the temperature rise is recorded.
„ Apart from measuring temperature rise ,the static
deflection of the test piece ,its dynamic deflection,
compression set, and indentation hardness are
recorded.
10. Rebound resilience test
„ In rubber, resiliency may be defined as
the ratio of the energy returned to the
impressed energy i.e. resilience is a
measure of the ability of the rubber
vulcanizate to return the energy used to
deform it Resilience=
Rebound (1-cosØ) x100
------------------
(1-cos 45)
11. Low Temperature Properties
„ The low temperature performance of the rubber vulcanizates is
usually estimated by determining the freeze point and brittleness
temperature of the vulcanizates.
„ The freeze point is defined as the temperature at which the modulus
is ten times its value at 200c. It is determined by measuring the
torque required to produce an angular deflection at various low
temperature and calculating the rigidity modulus.
„ Brittleness temperature is the temperature, estimated statistically at
which 50% of the specimens would fail in the specified test. This is
measured by giving impact blows to the sample at various low
temperatures and observing the samples for development of cracks.
„ Since rubber products become hard and loose their elasticity at very
low temperatures the evaluation of the freeze and brittleness
temperature of the vulcanizates gives an indication of the freeze and
brittleness temperature of the vulcanizates gives an indication of the
low temperature serviceability of the products.
12. Electrical Properties
„ Rubber vulcanizates can be used as a good insulator in applications like wires and
cables.
„ But in certain cases like antistatic mountings it is made conductive by proper
compound designs. In applications mentioned above, properties like electrical
resistivity, dielectric strength, power factor, dielectric constant etc. are very important.
„ Dielectric strength is a measure of the ability of insulation to withstand Voltage. It is
the voltage per unit thickness at which electrical breakdown occurs when a potential
difference is applied under specific conditions.
„ The dielectric constant or specific inductive capacity is a measure of the insulations
ability to store electrical energy. It is the ratio of the electrical capacity of a condenser
using the elastomer under the test, as the dielectric, to the capacity of a similar
condenser using air as the dielectric.
„ The power factor of an insulating material indicates its tendency to generate heat in
service. If a capacitor using an elastomer as the dielectric is charge and then
immediately discharges, there is an energy loss in the form of heat. If the frequency
of charging and discharging is high, the heat generated will be very high. The ratio of
this loss, to the energy required to charge the capacitor is known as the power
factor.
„ The surface resistivity of a test piece is determined by measuring the current passing
under an applied D.C.potential between two electrodes in intimate contact with the
surface under test and separated from one another by a standard distance.
Thank You