RUBBER COMPOUNDING

TECHNOLOGY

SUDHA.P
DEPUTY DIRECTOR(RIDT)
RUBBER TRAINING INSTITUTE
DEPARTMENT OF TRAINING
RUBBER BOARD
KOTTAYAM-686 009

sudha@rubberboard.org.in
Mob: 94964 13731
 RUBBER COMPOUNDING

COMPOUND
It is a homogenous mixture of ingredients used in a
particular product manufacture such that the properties
of most of the ingredients are unchanged in the final
product whereby providing a defined set of
mechanical properties.

COMPOUNDING
It is the science of selecting and combining elastomers
and additives to obtain physical and chemical
properties for a finished product.
 RUBBER COMPOUNDING
OBJECTIVE
1. To secure certain properties in the finished product to satisfy
the service requirements.
2. To attain processing characteristics necessary for efficient
utilization of available equipment.
3. To achieve desirable properties and processability at the
lowest cost.

The most important factor in compounding is to secure an

acceptable balance among demands arising from the above
three criteria.
 MAJOR OBJECTIVES OF COMPOUND
DEVELOPMENT
PROCESS REQUIREMENT
 Proper mixing (Incorporation, dispersion, distribution and
plasticization)
 Viscosity/process safety (ML1+4, MS)

 Stickiness and tackiness

 Shaping (Calendering, Extrusion, Assembling and Moulding)

COMPOUND PROPERTY REQUIREMENT

 Hardness

 Stress-Strain properties (TS, EB, M-100, M-300, tear)

 Abrasion resistance

 Hysteresis & set properties

 Resistance to cut growth, fatigue, flex cracking

 MAJOR OBJECTIVES OF COMPOUND
DEVELOPMENT
RESISTANCE TO DEGRADATION

 Heat, Oxygen, Ozone

 Flame
 Liquids
 Light

MISCELLANEOUS PROPERTY REQUIREMENTS

 Low temperature flexibility
 Electrical properties
 Permeability
 Contact with food stuff and drugs
 Bonding to metal & textiles
 Swelling
 Other specific requirements
 CLASSIFICATION OF COMPOUNDING
INGREDIENTS
1. Elastomers
2. Vulcanizing Agents (curatives)
3. Accelerators
4. Activators and Retarders
5. Antidegradants (Anti-oxidants, Antiozonants, Protective
waxes )
6. Processing aids (Peptisers, Lubricants, Release Agents)
7. Fillers (carbon black, non-black materials)
8. Plasticizers, Softeners and Tackifiers
9. Colour pigments
10. Special Purpose Materials (Blowing Agents, Deodorants,
etc.)
 COMPOUND DESIGN

DESIGN REQUIREMENTS
 SERVICE REQUIREMENTS/VULCANISATE PROPERTIES

 PROCESSABILITY
 ECONOMICS

DESIGN BASED ON
 CUSTOMER SPECIFICATION/REQUIREMENTS
 COMPETITOR'S SAMPLE
 DEVELOP A NEW PRODUCT
POLYMER SELECTION CRITERIA
 Cost
 Ease of mixing
 Strength requirements
 Modulus or stiffness requirement
 Abrasion resistance requirement
 Elongation requirement
 Oil resistance requirement
 Low temperature requirement
 Fatigue requirement
 Tack
 Set of stress relaxation
 Service temperature
 Dynamic properties (hysteresis, damping resistance)
 Flammability
 Chemical resistance
 POLYMER SELECTION

 SHOULD HAVE THOROUGH KNOWLEDGE ABOUT POLYMER

PROPERTIES
 REFER STANDARD SELECTION CHARTS/COMPARATIVE CHARTS
 BLENDS OF POLYMERS
 PROCESSABILITY FACTOR-suitability for the processes and methods
adopted
 COST FACTOR
 AVAILABILITY OF DATA ON POLYMER GRADES, PROPERTIES,
START UP FORMULATIONS ETC.
 VULCANIZING AGENTS
TYPE COMMON USE
Sulphur or Sulphur bearing Natural Rubber, Isoprene, SBR,
materials Butyl, Poly Butadiene, EPDM,
Nitrile
Organic Peroxides Urethane, Silicone, Chlorinated
Polyethylene, PVC/Nitrile

Metallic Oxide Polychloroprene, Chlorosulphonated

Polyethylene, Polysulphide
Organic Amines Acrylic, Fluorocarbon,
Epichlorohydrin
Phenolic Resins Butyl
 CURING SYSTEM

Selection of curing system is based on:

 Base polymer
 Processing conditions
 Curing conditions
 Service requirement

Base polymer
 Saturated rubber – peroxide e.g. EPR with DCP
 Unsaturated rubber-peroxide, sulphur/accelerator & resins, e.g. EPDM with
DCP, NR with sulphur accelerator, IIR with Resin
 Special Polymers – Metal oxide, Dioxime, Resin e.g. CR with ZnO/MgO
 ACCELERATORS

An accelerator is usually a complex organic chemical which takes part in the

vulcanization, thereby reducing the vulcanization time considerably- Organic
amines & its derivatives . It also improves the properties. Its action may be:

slow- eg. Guanidines, Diphenyl guanidine (DPG)

Di ortho tolyl guanidine(DOTG)

medium- eg. Thiazoles, Mercapto benzo thiazole (MBT)

Di benzthiazyl di sulphide) (MBTS)

fast ( ultra)- eg. Thiurams, Tetramethyl thiuram monosulphide (TMTM)

Tetramethyl thiuram di sulphide (TMT)

Dithiocarbamates, Zinc diethyl dithiocarbamate (ZDC)

Zinc dibutyl dithiocarbomate(ZDBC)

Delayed-action fast- eg. Sulfenamides

Cyclohexyl benzthiazyl sulfenamide (CBS)
Dicyclohexyl benzthiazyl sulfenamide (DCBS)
Morpholino thio benzthiazylsulfenamide (MOR)
Tertiary butyl benzthiazyl sulfenamide (TBBS)
 CURING SYSTEM (Contd..)
Accelerator Activator
 ZnO and Stearic acid for sulphur cure system
 TAC for peroxide cure system
Processing condition
 Type of processing equipment used
 Temperature build up during processing
 Extent of rework usage
 Rheological property requirement
Curing conditions
 Type of the product
 Method of curing employed
 Temperature of curing
 Flow requirement during curing
 CURING SYSTEM (Contd..)

Service Requirements
 Service temperature
 Duration of exposure
 Mechanical property requirement.
 Dynamic property requirement
 Ageing behaviour and permanent set requirements.
 Special property requirement.
 FILLERS

• Fillers are materials used to extent the range of

physical properties, to reduce compound cost,
modify the processing properties and to influence
the chemical resistance of the compound.

The effect of a filler on rubber depends on-

• structure

• particle size

• surface area

• geometrical characteristics
 FILLERS
Reinforcing Type Carbon Black (listed in N220 (ISAF)
order of increasing N330(HAF)
particle size) N550 (FEF)
N762 (SRF-LM)
N990 (MT)
Non-black Silica
Zinc Oxide
Magnesium Carbonate
Aluminium Silicate
Sodium Aluminosilicate
Magnesium Silicate
Extending Type Calcium Carbonate
Barium Sulfate
Aluminium Trihydrate
Talc and Soapstone
• reinforcing carbon blacks
• non- reinforcing carbon blacks
• reinforcing non- black
• semi reinforcing non- black
• non- reinforcing non- black

• Reinforcing carbon blacks

 Furnace black
 SAF – Super Abrasion Furnace
 ISAF – Intermediate Super Abrasion Furnace
 CF - Conductive Furnace
 SCF - Super Conductive Furnace
 HAF - High Abrasion Furnace (Low
structure and high structure)

 FF - Fine Furnace

 FEF - Fine Extrusion Furnace

 GPF- General Purpose Furnace

 SRF- Semi Reinforcing Furnace

 Thermal Black
MT - Medium Thermal
• Channel black

• EPC Easy Processing Channel

• Reinforcing Non- black

Precipitated silica and fumed silica

• Semi Reinforcing Non-black
aluminium and calcium silicates
high styrene resins
phenolic resins
 Fillers

Selection is based on
• Reinforcement
• Cost
• Processing requirement
• Colour requirement
• Service requirement
• Any other special requirement
 Compound Designing –
Hardness

phr required
Polymer Hardness for 1 unit
increase in
Hardness
NR SBR CR NBR
37-40 39-41 41-43 42-44

2 1.6 1.5 Ppt. Silica

3 3.3 2.2 Calcium silicate
5 4.1 4.5 Hard clay
7.9 5.6 5.0 Soft clay
6.6 8.4 5.0 Whiting
 Compound Designing – Hardness
Contd.

NR SBR IIR CR PBR NBR EPDM Black ASTM DBP

Dsgn

1.5 1.8 1.3 1.2 2.2 1.7 2.4 SAF N110 113

1.7 2.0 1.5 1.3 2.5 1.9 2.7 ISAF N220 114

1.9 2.3 1.7 1.5 2.8 2.1 3.0 HAF N330 102

2.3 2.8 2.1 1.8 3.4 2.6 3.7 FEF N550 119

2.5 3.1 2.3 2.0 3.8 2.9 4.1 GPF N660 90

2.8 3.4 2.5 2.2 4.2 3.2 4.5 SRF N774 70

2.1 2.6 1.9 1.7 3.2 2.4 3.4 HAF- N326 72

LS
 SOFTENERS

 Processing aids
A softener is an ingredient that :
1. speeds up the rate of polymer breakdown
2. helps to disperse the other compounding
ingredients
3. helps to reduce nerve within the compound
4 can impart building tack
5. improves the processing properties and
modify the final compound properties
6. adjusts the compound cost and reduce power
consumption during processing
 Mineral petroleum oils
 They are available from petroleum industry.

paraffinic
naphthenic
aromatic
 Plasticizers

They are of the synthetic type , used where mineral oils

are not compatible with the rubber
dibutyl phthalate -DBP
di isobutyl phthalate-DIB
di octyl phthalate - DOP
*Factices
They are vulcanized vegetable oils used as plasticizers to
get smooth compound in extrusion (brown) & to reduce
abrasion resistance in products like erasers (white)
 PROCESSING AIDS
COMPOSITION EXAMPLE FUNCTION
Activated Dithio- Pepton 44 Peptizer for NR
bisbenzaldihide
Xylyl Mercaptans RPA-3 Peptizer for NR,IR,SBR and
NBR.
Low-molecular-weight A-C Polyethylene Release agent, Lubricant
polyethylene 617A
Calcium Oxide Desical P Desiccant
Aliphatic-naphthenic- Strucktol 60NS Homogenizing agent for all
aromatic resins elastomers.
Paraffin wax Release agent, lubricant
Polyethylene glycol Carbowax Activator for silica, lubricant
PEG3350
Petroleum hydrocarbon Petrolatum Release agent, lubricant
 PROCESSING AIDS

Selection is based on

 Nature of polymer
 Solubility parameter
 Viscosity requirement
 Filler dispersion
 Processing requirement
 Any other special requirement
 ANTI-DEGRADANTS- They are agents added to rubber to improve
ageing properties, resistance to oxygen, ozone, alkali, acid, chemicals etc

TYPE EXAMPLE STAINING

Hindered Phenol 2,6 Di-t butyl p-cresol None to slight
Hindered Bis-phenols Anti-oxidant 2246 None to slight
Hindered Thiobisphenols Santowhite Crystals Slight
Hydroquinones 2,5 di(tert-amyl) hydroquinone None to slight
Phosphites Tri(mixed mono and di-nonyl- None to slight
phenyl) phosphite
Diphenylamines Octylated diphenylamine Slight to moderate

Naphthylamines Phenyl-alpha-naphthylamine Moderate

Quinolines Polymerized 2,2,4, tri-methyl Slight to moderate
1,2-dihydroquinoline
Carbonyl-amines Reaction product of Considerable
condensation product diphenylamine and acetone
Para-phenylene diamines Mixed Diaryl-p-phenylene Considerable to severe
diamines
 ANTI-DEGRADANTS

Selection is based on

 Type of protection desired

 Environment in which the product is exposed.
 Chemical activity
 Persistence (volatility and extractability)
 Nature of end use
 Discolouration and staining
 Toxicology
 Cost
 OTHER MATERIALS

 Peptizers : They speed up the rate of polymer break down and

also control the speed of breakdown, decreasing nerve within
the compound and shrinkage during subsequent processing.
penta chloro thiophenol Renacit VII

 Retarders : They help to increase the scorch time (premature

vulcanization) but do not interfere with the vulcanization

 cyclohexyl thiophthalimide (CTP) Santogard PVI

 Stiffeners : Stiffeners are used to improve the plasticity of the

compound in very small quantities.
dihydrazine sulfate
 Flame retardants
Chemicals which can improve the flame retardency of
the compound
highly chlorinated paraffins and waxes, antimony oxide,
aluminium oxide and selenium

 Colors and pigments

 They provide esthetic look and appearance for the product
[organic and inorganic]
 Tackifying agents
They are useful in providing tackiness to the compound.
wood rosin, coumarone resins, pine tar.
Blowing agents
 They are materials which provide either open or

closed cell structure by producing CO2 or nitrous

gases during vulcanization
 dinitroso pentamethylene tetramene (DNPT)

 azocarbonamide (ADC)

 baking soda (sod.bicarbonate)

 Bonding agents
 They facilitate adhesion between rubbers, fibers, fabrics,
metals
 chemlok, resorcinol – formaldehyde- latex for dipping of
nylon cords in tyre manufacture
 Reordants
 They are basically perfumes added to mask odors of rubber
during processing and service life of rubber.
 Bactericides / fungicides to resist microbial agents
 STEPS OF COMPOUND DEVELOPMENT
Modification of existing compound with respect to

 Cost/price
 Processing
 Performance

New compound development

 Set specific objectives (properties, processing, price etc)

 Select best polymer
 Study test data of existing compounds
 Survey compound formulations.
 Choose starting formulation.
 Develop compound in the laboratory to meet objectives.
 Estimate cost of the compound.
 Evaluate processability in factory
 Use compound to make a product sample.
 Test product sample against performance specification.
 The mix
 Rubber 100
 Vulcanizing agent 0.3 - 3.5
 Accelerator/s 0.5 – 1.5
 Activator 2.5 – 5.0
 Antidegradents 1-2
 Fillers As required
 Softner 5 - 10
 Other materials when necessary As required
STAGES OF PRODUCT DEVELOPMENT :
Compound Design,

Lab Evaluation,

Shop floor processing trials

(mixing, moulding,extrusion,
calendaring, fabrication of product,
curing, etc ),

Analysis of feedback ,

Compound Modification (if reqd.),

Testing of processing properties

and of finished product,

Field trials,

Validation of manufacturing
process.
 MIXING

 Compound properties & batch to batch consistency depends on

:
 Compounding formulation design,
 Raw materials Quality,
 Effects of Further Processing,
 Rework blending (Rework Quality & Quantity)
 Rubber processing equipments available & their
condition.
 The knowledge of Raw Materials used & their behavior during
mixing and further processing is essential
 MIXING

 Mixing Process is the base of Rubber Product Manufacturing

Technology.
 The success of subsequent processing & finished product
quality depends entirely on the quality & batch-to-batch
consistency of the mixed compounds.
 ‘Mixing’ deals in deciding:
 What equipment to use (speeds, pressures, temperature, time
cycles, procedures, etc. to blend the selected compounding
ingredients into a properly mixed compound.
 How to achieve High Degree of Dispersion and batch to
batch consistency.
MIXING
• Mixing process can be sub-divided into three stages :

1) Feeding ingredients to mixer (correct quantities at

correct times at correct temperature.),

2) Actual Mixing of the ingredients,

3) Discharge of mixed compound and its shaping,

cooling, packaging and storage for the next process.

38
MIXING Five main steps involved in the Mixing Operations :

1. Sub Division
Of larger lumps & aggregates,

2. Incorporation
Of powders or liquids

3. Dispersion
Involves reduction of the size of agglomerates,

4. Simple Mixing
Involves moving particles from one point to another.

5. Viscosity Reduction By breakdown of the polymer and transforming it to

desired viscosity.

39
MIXING
• A good Dispersion rating requires :
 High Shear Stress (i.e. High mix viscosity),
 High Filler Loading,
 Polymers of not too low viscosity,
 Low Mixing temperatures,
 Charging oils at the end of mixing cycle.

• During Dispersive mixing, the carbon black agglomerates are

broken down to less than 1 micron size.
• Dispersion largely depends on shear stress ( a critical value of
shear stress is necessary to breakdown the agglomerates
below which no dispersion action will take place).
40
Two-Stage Mixing in Internal Mixers
• To avoid scorching of compound; a two stage mixing procedure
is used.
• Stage 1 - carbon black and other non vulcanizing
additives are combined with the raw rubber and
Higher mixing temperatures up to 160°C are used.
[The term Master Batch is used for 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. Lower mixing temperatures 90-
100 °C are used.
[The term Final Batch is used for second stage
mixture] 41
MIXING

42
NR Mastication & Blending NR+SR

• Mastication of NR to Optimum Degree and proper blending

of Synthetic Rubbers with NR is Very Important .
• Ingredients which are difficult to disperse (e.g. hard carbon
blacks, Ppt. silica, ZnO, etc) require Higher stock viscosity
to disperse well.
 Stock Viscosity Control is achieved through:
 Compounding formulation design,
 Close temperature control during mixing operations,
 Use of specific sequence for addition of ingredients ,
 Remixing of the stock after cooling.
43
• Raw NR is dry & tough (Mooney Viscosity at 100°C > 80)
and has to be masticated to a Workable Level of Mooney
Viscosity of 50 to 60.
• Most Synthetic Rubbers are produced to a tailored Mooney
viscosity (range 50 – 60) and hence ‘Mastication’ is not
necessary.
• Keep Lower Mastication Temperatures when a Two-Roll
mill is used (say, 60-70°C).
• Viscosity of Masticated NR should be closer to the
Synthetic Rubber to be blended with it.
• NR-BR blends require higher shear rates for proper
blending and hence Banbury / Intermix are more suitable
than a mixing mill.
44
EFFECT OF MASTICATION TEMPERATURE ON MOONEY VISCOSITY OF NR
MILLING MOONEY VISCOSITY (ML1+4 @ 100°C, UNITS)
TIME, MIN WITHOUT PEPTIZER WITH PEPTIZER (DBD=0.5 PHR)
@ 70°C @ 100°C @ 70°C @ 100°C
0 95 95 95 95
3 76 85 58 56
6 57 83 40 40
9 47 68 33 28
12 45 65 30 24

START TEMPERATURE, MOONEY VISCOSITY (ML1+4 AT 100°C), UNITS

OPEN MILL (TIME = 8 MIN) PEPTIZER = 0 PEPTIZER = 0.25 PEPTIZER = 0.5
70 °C 55 42 36
100 °C 75 42 37
INTERNAL MIXER (TIME 4
MIN)
90 54 42
150 °C
88 48 36
160 °C
45
 Mixing Mixer Speed 25 rpm Mixer Speed 50 rpm
Time, No Peptizer 0.1 Phr PCTP No Peptizer 0.1 Phr PCTP
Min
ML1+4@100°C ML1+4@100°C ML1+4@100°C ML1+4@100°C
0 90 90 90 90
2 74 69 69 52
4 68.5 60 50 37
6 67 56 42 29
8 65 53 34 -
10 61 50 - -
Note the rapid reduction of Mooney viscosity at higher rotor speeds
in the presence of chemical Peptizer at a very small dosage.

46
Effects of “Under Mastication” of NR

• Lower Mixing Cycles,

• High heat build up during mixing and subsequent steps,
• Poor extrudability / calendaring properties of the stock,
• Excessive shrinkage & dimensional control problems with
extrudates / calendared stocks.
• Scorchy compounds.
• Excessive porosity in extrudates,
• Difficulties with ‘Rework’ blending,

47
Effects of “Over Mastication” of NR
 Lower shrinkage of extrudates / calendared sheets,
• Lower die swell & loss of dimensional control,
• Increased curing defects in finished products due to excessive
flow and air entrapment,
• Compounded sheets stick to each other during storage and
sagging of sheets,
• Excessive surface tack due to poor green compound strength,
• Loss of dynamic, tensile & tear strength properties of the
vulcanizate,
• Changes in the viscosity of solvent based solutions & loss of
surface tack.
48
MIXING PROBLEMS & REASONS

PROBLEMS REASONS
Batch size not optimized, mixing time is lower, filler
addition time not proper, insufficient ram pressure, poor
Poor Dispersion temp. control, poor / inconsistent raw material quality,
excessive moisture content in polymer and fillers, under /
over mastication of NR.

Variation of start temp., variation in dump time and / or

Batch to Batch temp. , poor dispersion, variation in ram pressure, variation
Variations in polymer / filler/ oil quality / rework quality, under / over
mastication of NR
Compound viscosity not within controlled limits, under /
over mastication of NR, Processing temp. not under
Poor Processability
control, poor dispersion, higher loading of plasticizer /
tackifiers / fillers/rework.
49
 Manufacturing process
 Unvulcanized rubber, whether natural or synthetic
behaves as a viscoelastic fluid during mixing. 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
KNEADER
Two Roll Mill with stock blender & individual roll drives

53
F 270 Banbury Mixer K 6A INTERMIX

54
 Capacities: Banbury Mixers
Mixer Mixing Torque rating
Approx. kW / RPM Approx.
Banbury Chamber Speed
Batch Wt * Machine
Mixer Net Volume, Range, Compact Uni
kg Weight, MT
ltr RPM Drive Drive
F 50 50 50 40 - 120 2.2 4.6 13.2
F 80 80 60 30 - 105 3.7 6.3 16.1
F 120 120 90 30 - 90 5.6 9.0 19.5
F 160 160 120 20 - 80 7.5 12.0 30.2
F 200 200 165 20 - 60 8.9 12.7 30.5
F 270 270 202 20 - 60 13.1 24.6 43.0
F 370 414 310 20 - 60 - 37.3 54.0
F 440 438 330 20 - 60 - - -
F 620 672 500 20 - 50 - 52.2 110.5

( * Fill factor = 75% , S.G. = 1.0 )

55
 Capacities: Intermix
Mixer
Approx. Mixing Speed, RPM Motor HP Machine
Chamber
Intermix Batch Wt Weight,
Net Volume,
kg Single Speed Two Speed 1-Speed , 2-Speed MT
ltr
K0 1.8 1.26 76 75 / 150 5, 5 / 10 5.6
K1 5.5 3.9 40 / 145 Variable drive 50 20
K 2 20 14 30 22 / 44 50. 50 / 100 50
K 2A 49 34 33 22 / 44 150 , 75 / 150 60
K4 91 64 33 22 / 44 220, 50 / 300 98
K5 143 100 33 22 / 443 300, 200 / 400 140
K6 206 144 33 22 / 44 475, 320 / 640 235
K 6A 257 180 33 22 / 44 500, 350 / 700 280
K7 310 217 33 22 / 44 750, 500/1000 310
K8 498 349 33 22 / 44 - -

( * Fill factor = 70% , S.G. = 1.0 )

56
 Dry rubber based products

Mix and Compound Design

For manufacture of dry rubber products, the
following minimum process steps are essential
 compounding

 shaping

 vulcanization
MIXING PROCEDURE
Weighing compounding ingrediants as per
formulation

Mastication

Compounding And Homogenisation

Maturation
 Prewarming

Blank preparation
 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