RUBBER COMPOUNDING

TECHNOLOGY

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

[email protected]
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.
2.
3.
4.
5.

6.
7.
8.
9.
10.

Elastomers
Vulcanizing Agents (curatives)
Accelerators
Activators and Retarders
Antidegradants (Anti-oxidants, Antiozonants, Protective
waxes )
Processing aids (Peptisers, Lubricants, Release Agents)
Fillers (carbon black, non-black materials)
Plasticizers, Softeners and Tackifiers
Colour pigments
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

materials

Natural Rubber, Isoprene, SBR,

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

Extending Type

Carbon Black (listed in

order of increasing
particle size)

N220 (ISAF)
N330(HAF)
N550 (FEF)
N762 (SRF-LM)
N990 (MT)

Non-black

Silica
Zinc Oxide
Magnesium Carbonate
Aluminium Silicate
Sodium Aluminosilicate
Magnesium Silicate
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
for 1 unit
increase in
Hardness

Polymer Hardness

NR

SBR

CR

NBR

37-40

39-41

41-43

42-44

1.6

1.5

Ppt. Silica

3.3

2.2

Calcium silicate

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
Dsgn

DBP

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

HAFLS

N326

72

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 Dithiobisbenzaldihide

Pepton 44

Peptizer for NR

Xylyl Mercaptans

RPA-3

Peptizer for NR,IR,SBR and

NBR.

Low-molecular-weight
polyethylene

A-C Polyethylene
617A

Release agent, Lubricant

Calcium Oxide

Desical P

Desiccant

Aliphatic-naphthenicaromatic resins

Strucktol 60NS

Homogenizing agent for all

elastomers.

Paraffin wax

Release agent, lubricant

Polyethylene glycol

Carbowax
PEG3350

Activator for silica, lubricant

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-nonylphenyl) phosphite

None to slight

Diphenylamines

Octylated diphenylamine

Slight to moderate

Naphthylamines

Phenyl-alpha-naphthylamine

Moderate

Quinolines

Polymerized 2,2,4, tri-methyl

1,2-dihydroquinoline

Slight to moderate

Carbonyl-amines
condensation product

Reaction product of
diphenylamine and acetone

Considerable

Para-phenylene diamines

Mixed Diaryl-p-phenylene
diamines

Considerable to severe

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
Vulcanizing agent
Accelerator/s
Activator
Antidegradents
Fillers
Softner
Other materials when necessary

100
0.3 - 3.5
0.5 1.5
2.5 5.0
1-2
As required

5 - 10
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 160C 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 100C > 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, 60-70C).

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
TIME, MIN

MOONEY VISCOSITY (ML1+4 @ 100C, UNITS)

WITHOUT PEPTIZER

WITH PEPTIZER (DBD=0.5 PHR)

@ 70C

@ 100C

@ 70C

@ 100C

95

95

95

95

76

85

58

56

57

83

40

40

47

68

33

28

12
45
START TEMPERATURE,
OPEN MILL (TIME = 8 MIN)
70 C
100 C
INTERNAL MIXER (TIME 4
MIN)
150 C
160 C

65
30
24
MOONEY VISCOSITY (ML1+4 AT 100C), UNITS
PEPTIZER = 0
55
75

PEPTIZER = 0.25
42
42

PEPTIZER = 0.5
36
37

90
88

54
48

42
36
45

Mixing
Time,
Min

Mixer Speed 25 rpm

Mixer Speed 50 rpm

No Peptizer

0.1 Phr PCTP

No Peptizer

0.1 Phr PCTP

ML1+4@100C

ML1+4@100C

ML1+4@100C

ML1+4@100C

90

90

90

90

74

69

69

52

68.5

60

50

37

67

56

42

29

65

53

34

Note
of Mooney
viscosity at
10the rapid reduction
61
50
- 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

Poor
Dispersion

REASONS
Batch size not optimized, mixing time is
lower, filler addition time not proper,
insufficient ram pressure, poor 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 temp. , poor dispersion,
Batch to Batch
variation in ram pressure, variation in
Variations
polymer / filler/ oil quality / rework quality,
under / over mastication of NR
Poor
Processability

Compound viscosity not within controlled

limits, under / over mastication of NR,
Processing temp. not under control, poor

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

Torque rating
kW / RPM

Banbury
Mixer

Mixer
Chamber
Net Volume,
ltr

Approx.
Batch Wt *
kg

Mixing
Speed
Range,
RPM

Compact
Drive

Uni
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

Approx.
Machine
Weight, MT

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

55

Capacities: Intermix
Mixer
Chamber
Net Volume,
ltr

Approx.
Batch Wt
kg

Single Speed

Two Speed

K0

1.8

1.26

76

75 / 150

5,

K1

5.5

3.9

40 / 145

Variable drive

50

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

Intermix

Mixing Speed, RPM

Motor HP
1-Speed , 2-Speed

5 / 10

Machine
Weight,
MT
5.6
20

( * 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

RUBBER

COMPOUNDIN
G

CHEMICALS

MATURATION

PREWARMING
TESTING& QC

MOULDED GOODS

EXTRUDED GOODS

CALENDERED GOODS

MOULDED GOODS

EXTRUDED GOODS

AUTO CLAVE
OR
OVEN

BLANK PREPARATION

MOULDING
(HYDRAULIC
PRESS)

CALENDARED
GOODS

VULCANISATION

FINISIHING OPERATION AND QUALITY CONTROL

PACKING AND DESPATCH