Rubber Compounding & Viscometry

By
Swapnil Ahire

1
 Rubber Technology

Overview of Rubber

Mastication
Tool: Two-roll mill or internal mixer

Compounding

Testing: Scorch & Cure Characteristic

Rubber compound
Testing: Viscosity/Plasticity

Shaping Tool: Calendaring, spreading,

extruding, compression moulding,
transfer moulding, injection
Vulcanization moulding
Testing: Tensile Test, Tear Strength,
Compression Set, Abrasion, Final product
Resilience, Hardness, Ageing etc

Testing & Inspection 2

What is compounding?

Definition: Compounding is art & science of selection of rubber/rubbers ,ingredients &

their dosages & mixing them to produce dough which can process easily & give desired
properties in minimum cost to satisfy customer needs.

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.

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Major Objectives of Compounding

PROCESS REQUIREMENT
• Proper mixing (Incorporation, dispersion, distribution and
plasticization)
-Viscosity/process safety (ML1+4, MS)
• Shaping (Calendaring, Extrusion, Assembling and Molding)
-Vulcanization-Curing time (tc90), Scorch safety (ts5) temperature

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
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Major Objectives of Compounding (Cont..)

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 –Polar/Non Polar solvent media
• Other specific requirements

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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.
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Classification of Compounding Ingredients

1. Elastomers
2. Curing System (curatives)-Vulcanising agents
& Acceleartors
3. Activators and Retarders
4. Anti-degradants (Anti-oxidants, Anti-
ozonants, Protective waxes )
5. Processing aids (Peptizers, Lubricants,
Release Agents)
6. Fillers (carbon black, non-black materials)
7. Plasticizers, Softeners and Tackifiers
8. Color pigments
9. Special Purpose Materials (Blowing Agents,
Deodorants, etc.)

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Typical Compounding formulation

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Compound Design

DESIGN REQUIREMENTS
• Service requirements/vulcanizate properties
• Processability
• Economics

DESIGN BASED ON
• Customer specification/requirements
• Competitor's sample
• Develop a new product

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Rubber Selection

• Should have thorough knowledge about polymer

properties.
• Refer Property 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.

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Rubbers & their basic Properties

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Curing System
Selection of curing system based on:
 Base Polymer
• Saturated Rubber-Peroxide: EPR with DCP
• Unsaturated Rubber-Peroxide, Sulphur/accelerator & resin
• Special Polymers-Metal Oxide, Dioxime Resin
 Processing Technique
• Type of processing equipment used
• Temperature build up during processing
• Extent of rework usage
• Rheological property requirement
 Curing Conditions
• Type of product
• Method of curing employed
• Curing Temperature
• Flow requirement during curing
 Service Requirements
• Service Temperature
• Duration of exposure
• Property Requirement
Rubber Curing system mainly consist of curing agents & accelerators (Ingredients
used to speed up curing reaction)
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Curing System (Cont..)

Curing Agent:
TYPE COMMON USE

Sulphur or Sulphur bearing Natural Rubber, Isoprene, SBR, Butyl, Poly

materials 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

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Curing System (Cont..)
1) Sulphur based curing System:
A typical sulfur vulcanization system consists of following
ingredients:
• Zinc oxide = 3.0 to 10 phr
Activator
• Stearic acid = 1.0 to 4 phr
• Accelerator = 0.5 to 4 phr
• Sulfur = 0.5 to 3 phr
Accelerators: An accelerator is defined as the chemical added into a rubber compound
to increase the speed of vulcanization and to permit vulcanization to proceed at lower
temperature and with greater efficiency.
Accelerator also Decreases the Quantity of Sulphur necessary for vulcanization and
thus improving 'aged' properties of the rubber vulcanizates.

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Curing System (Cont..)
Types of Accelerators

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Curing System (Cont..)

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Sulfur curing Systems

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Sulfur curing Systems (Cont..)

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Curing System (Cont..)

2. Peroxide Curing
• Most common organic peroxide: dicumyl peroxide
(DCP)
• Saturated elastomer
• Major curative for silicone rubber
• Note: not recommended for some elastomers such
as IIR or CIIR

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Retarders & PVI

• To avoid scorch with faster curing systems and / or

with higher processing temperatures and prolonged
storage; ‘Retarders' or ‘Pre Vulcanization Inhibitors
(PVI) ' are added during compounding.
• Eg.

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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.

• Filler-rubber interaction depends on:

– External factor: total surface area of the filler which are in
contact with rubber
– Internal factor: surface activities & chemical properties
– Geometry factor: filler’s structure & filler porosity (minor
factor)

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Fillers (Cont..)

Selection is based on:

• Reinforcement
• Cost
• Processing requirement
• Color requirement
• Service requirement
• Any other special requirement

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Fillers (Cont.)

• Function of fillers:
– Reinforcement effect, i.e. to increase mechanical properties
(eg, TS & resistance to tearing) in the vulcanizate & to increase
stiffness, abrasion resistance
– Compound cost reduction
– Might be for coloring purpose
• Types of filler
– Reinforcing filler (Carbon black & silica):
To improve the mechanical properties of the filled rubber
vulcanizate
– Non-reinforcing filler (Clay, Calcium carbonate etc)
Stiffer & harder filled rubber vulcanizate will be obtained

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Carbon Black

• Have various type with different physical & chemical

properties
• Multiple size, surface area, structure & surface
activities
• Its surface has functional groups like phenolic,
ketones, carboxylic, lactones etc. these functional
groups will be responsible in interacting with the
rubber

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Carbon Black Classification

• Following ASTM D 1765

• 1st alphabet refer to rate of vulcanization; N refer to
normal rate & S is slow rate
• 1st digit after the alphabet refers to particle size;
smaller the number, smaller size.
• 2nd & 3rd digit after the 1st digit don’t have special
meaning
• 5 major reinforcing CB are N110, N220, N330, N341 &
N550

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Selecting Carbon Black

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Selecting Carbon Black (Cont.)

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CB loading & effect on Properties

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Silica

• More expensive vs. CB but yet performance similar as CB

• Special performance: improvement in tear strength,
reduction in heat buildup, & increase in compound
adhesion in multicomponent products such as tires
• Preparation method of silica: fume silica & precipitate
silica
• Fume Silica: smallest filler size (7–15 nm); obtained from
high temp rxtn btwn silicon tetrachloride and water
vapor
• Precipitate silica: better reinforcing performance &
reinforcing factor determine via particle size.
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Physical Properties of Silica

• Surface silanol concentration (silanol groups —Si—

O—H) influence the degree of surface hydration
• Surface acidity is controlled by hydroxyl grps on the
surface & is intermediate btwn those of P—OH & B—
OH.
• This intrinsic acidity can influence peroxide
vulcanization, although in sulphur curing, there is no
significant effect
• Rubber–filler interaction is affected by these sites

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Chemical Properties of Silica

• Surface silanol concentration (silanol groups —Si—

O—H) influence the degree of surface hydration
• Surface acidity is controlled by hydroxyl grops on the
surface & is intermediate between those of P—OH &
B—OH.
• This intrinsic acidity can influence peroxide
vulcanization, although in sulphur curing, there is no
significant effect
• Rubber–filler interaction is affected by these sites

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Problems with Silica Filler

• Increase in viscosity during compounding; especially

high surface area one
• Deactivation of accelerator system  longer cure
time
• Need coupling agents to improve effectivity.

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Silane Coupling Agent

• Function: to improve the affinity between rubber

and silica
• Silane coupling agent: bi-functional compounds
which react with silica surface & Sulphur containing
groups in vulcanized rubber
• Results: increased in modulus, resilience, abrasion
resistance but decrement in tear strength

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Silane Coupling Agent

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Other Fillers – Clay

• Commonly used white filler, due to:

– Low cost
– Reinforcing efficiency is btwn low to medium
– Ease of processing especially for extrusion & calendering
• Grades of China clays:
– Soft clays
– Hard clays
– Calcined clays
– Treated clays

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China Clays (cont.)

• Calcined clays:
– Obtained from hard clays in which the combined water has
been removed
– Give higher hardness, TS & electrical resistivity vs. hard
clays
• Treated clays:
– Hard clays which have been chemically treated offer better
filler reinforcement than the untreated clays

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Other Fillers
• Calcium carbonate is used as a low-cost filler in
rubber products for static applications such as carpet
underlay.
• Calcium carbonates grades:
– Ground limestone
– Whiting
– Precipitated whiting
– Treated whiting
• Titanium dioxide finds extensive use in white
products such as white tire sidewalls where
appearance is important

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Processing aids (Peptisers, plasticizers, dispersing aids)

• Function: to aid (help) processing

• Types:
– Processing aids
– Plasticizer
– Factice
– Low molecular weight polyethylene/Wax
– Fatty acids

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Plasticizer
• Types of plasticizers:
– The chemical plasticizers (peptiser)
– The physical plasticizers (softeners & extenders)
• Peptiser is used to ease NR moleclues chain break down (Added to the
rubber at the start of mastication)

• Physical plasticizer don’t react chemically with the rubbers but function
by modifying the physical characteristics of either compounded
rubber/ finished vulcanizate
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Plasticizer –Softeners/Extenders

• Petroleum oils are the most commonly used

physical plasticizers for processing
• Types of petroleum oils used as processing
aids and extenders are classified under three
headings:
– Paraffinic
– Napthenic
– Aromatic

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Factice

• Types of factice: white factice & brown factice

• Factice is vulcanized unsaturated vegetable or animal oil.
• Longer chain fatty acid containing oils such as rapeseed produce
a harder, more desirable factice
• Function: to facilitate processing by improving the incorporation
& dispersion of powders & reduce power consumption
• Presence of 5-30 phr of factice may be used to control die swell,
improve surface quality & prevent distortion of shape during
open steam vulcanization
• Large loadings of factice e.g. 100 -150 phr are used in very soft
compounds such as pencil erasers

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Low MW PE/Wax

• Functions:
– As processing aid
– As release agent to prevent sticking together of rubber
compounds
– As lubricant to help could flow & extrusion & prevent
blocking in dies

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Fatty Acid

• Function:
– As a plasticizer
– Aids dispersion of CB and other fillers
– Minimizes any tendency for sticking to the mill rolls
• Eg: stearic acid & is commonly used btwn 1-2 phr for
sulfur vulcanization system

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Anti-degradants

• Function: to extend the service life of

vulcanized elastomer by protecting them from
oxygen, ozone, light, heat, and flex fatigue
• Why?...due to the unsaturated backbones
• Types:
– Staining antioxidant & antiozonant
– Non-staining antioxidant & antiozonant
– Antiozonant
– Waxes
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Antidegradant Selection 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

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Antioxidant

• A/O react with

– Oxygen to prevent oxidation of vulcanized rubber
– Free radicals that degrade vulcanized rubber
• 2 main classes of staining type : polymerized
dihydroquinolines & diphenylamines
• Non staining have 4 groups type: phosphites,
hindered phenols, hindered bisphenols &
hydroquinones

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Anti-ozonant

• 2 classes: staining & non-staining antiozonants

• Non-staining types are less powerful & less versatile vs
to the staining types
• Most common antiozonant: para-Phenylenediamines
(PPDs)
• Also improve resistance to fatigue, oxygen, heat, and
metal ions

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Waxes

• Used to improve rubber ozone protection primarily

under static conditions.
• Have 2 categories: Microcrystalline wax & paraffin wax
• Microcrystalline wax:
– Tm: in the region of 55 to 100°C
– Extracted from residual heavy lube stock of refined petroleum
• Paraffin wax:
– Tm: in the region 35 to 75°C
– Obtained from the light lube distillate of crude oil

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 Anti-Degradant examples

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
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Other Ingredients

• Flame retardants : Chemicals which can improve the flame

retardency of the compound
Eg.H ighly chlorinated paraffins and waxes, Antimony oxide,
Aluminium oxide and selenium
• Colors and pigments : They provide esthetic look and appearance
for the product
Eg. Organic /Inorganic pigment
• Tackifying agents: They are useful in providing tackiness to the
compound.
Eg.wood rosin, coumarone resins, pine tar.

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Other Ingredients
Blowing agents
• They are materials which provide either open or
closed cell structure by producing CO2 or nitrous gases
during vulcanization
• Dinitroso pentamethylene tetramine (DNPT)
• Azocarbonamide (ADC)

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 Mixing
• Unvulcanized/raw 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
• The success of subsequent processing & finished
product quality depends entirely on the quality &
batch-to-batch consistency of the mixed compounds.
• ‘Mixing Process’ 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.
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 Mixing Stages

• 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.

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Mixing Mechanism

• The mixing of rubber is a composite operation,

involving a number of different mechanisms and
stages. These can be separated into four basic
processes:
–Viscosity reduction
–Incorporation
–Distributive mixing
–Dispersive mixing

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Compound Quality

• 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).

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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 & 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]

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Mastication

• 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.
• Peptizer needed to improve mastication efficiency

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Peptizers

58
Mixing Problems

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.
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Mixing Equipment

• Machinery
1. Internal Mixers (Intermix, Kneader , Banbury)
2. Two roll mill
3. Continuous mixers

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Internal Mixers

Kneader Banbury Intermix

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Banbury Mixer

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Two Roll Mill with stock blender & individual roll drives

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Viscometry

• Viscosity: Mooney Viscosity (Mooney viscometer)

 For a raw polymer type, choice of correct viscosity level is important to ensure
acceptable mixing and processing characteristics.
 Mooney viscosity is the most commonly used for measurement of rubber viscosity.
 Viscosity of rubbers is measured using the shearing disk viscometer. The torque of the
rotor is taken after 1 minute pre-heating the rotor plus 4 minute after that.
 Mooney scorch time , delta Mooney, cure index of compounded rubber
 The result for viscosity measurements are reported in the form 50 ML, 1+4 (100°C)
• where 50 M is the Mooney viscosity number,
• L indicates the use of the large 1.5 in. rotor (S would indicate the small 1.25 in. rotor),
• 1 is preheat time in minutes
• 4 test time in minutes
• 100°C is the temperature of the test.

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Mooney viscosity

65
Rheological properties of Rubber

RHEOMETER: Is the instrument which predict total rheological

behavior of rubber compound when it is heated from uncured form
to total vulcanized form
Two Main types
1. Oscillating Disc Rheometer (ODR)
2. Moving Die Rheometer (MDR)

 Provide curing characteristics

 Processing characteristics
 Physical Properties
 Cure Curve obtained with a Rheometer is a finger print of the compound’s vulcanization
and processing character.

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Oscillating Disc Rheometer
 Uncured rubber sample is confined in a
die cavity located in electrically heated
platens.
 The die temperature 100 – 200 °C. The
cavity is formed by a fixed lower die and a
moveable upper die.
 The rotor consists of a bi-conical disc with
integral shaft.
 The rubber sample completely surrounds
the bi-conical disc.
 The disc is oscillated at 100 cpm through
an arc of 1°, 3° or 5° by a motor driven
eccentric.

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 Rheometer Principle

• Viscosity :

• Drag Flow type viscometer

Moving Disc

Stationary Disc

• t = m dg/dt Shear stress = Viscosity X Shear Rate

• t - Shear stress proportional to torque required for rotation / oscillation.

• Shear rate constant as constant rate of rotation / oscillation (disc is oscillated at 1°, 3° or 5°)
• m Viscosity will increase with time as degree of cure of rubber will increase
Torque will increase with time & ploted as rheograph
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Rheometer Result

Marching
Phase I Phase 2 Phase 3 physical
Processing Curing properties

Plateau
Torque(lb/in)
Rheometric

Reversio
n
MI MH

ML
ts2 ts5 tc50 tc90 RT
Time(min)
TYPICAL RHEOMETER CURVE 69
Practical applications of Rheometer:-

 Tocheck quality of raw materials

 To check quality of mixing
 To check rheological behavior of given compound
 To set processing parameters- Curing time , curing
temperature
 To study different curing systems with respect to time and
temperature.
 To predict properties of final product

Rheometer test is essential quality control

parameter in rubber industry.

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Rheometer Application:

71
Rheometer Application:

72
Rheometer Application:

73
Moving Die Rheometer
 Improvement over ODR
 Time lag between the test sample temperature and the die cavity temperature.
 The friction between the rotor and the test cavity by elimination of rotor itself.
 Uniform shear to a smaller sample ensuring very little work input into the sample
and orientation effects are eliminated
 Elastic and viscous responses can be separated and measured simultaneously
with the cure data throughout the test.
 The viscous response S” provides information on stock processing characteristics
to see if predictions can be made regarding finished product performance.
 The elastic response S’ is a measure of state of cure at any point of time on the
cure curve at the given temperature of cure.
 The tan delta (= S” / S’) also can be continuously plotted on the MDR

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Typical MDR rheograph

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