L. D.

COLLEGE OF ENGINEERING
AHMEDABAD – 380 015

Name: Maulik Maheshbhai Chauhan

Semester: M.E.-II Enrollment No.: 230280788001

Subject: Rubber Blends (3724002) Year: 2023-24

 Certificate

This is to certify that Maulik Maheshbhai Chauhan

Enrollment No. 230280788001 of M.E. Semester-II of Rubber

Technology Department has satisfactorily completed the course

in the subject of Rubber Blends (3724002) within four walls

of L. D. College of Engineering, Ahmedabad -380015.

Date of Submission : ______________________________________

Staff in-Charge : ______________________________________

Head of Department : ______________________________________

i
 Certificate

This is to certify that the above term work of Maulik Maheshbhai

Chauhan University Exam No. 230280788001 of M.E. Semester-II of

Rubber Technology Department is assessed for University

examination on ___________________.

Int. Examiner ______________________________________

Ext. Examiner ______________________________________

ii
3724008 Index

Index
Sr. Page Number Date of Date of Initial
Title From To
No Start Completion of Staff

To study about the Rubber-

1 01 07 21-02-2024 28-02-2024
Rubber blends methods.

To study about the analytical

2 methods for rubber-rubber 08 15 28-02-2024 06-03-2024
blend characterization.

To measure the crosslink density

3 16 21 06-03-2024 13-03-2024
of given rubber sample.

4
To study about the rubber blend 22 24 13-03-2024 19-03-2024
with graft co-polymer.

To study about Rubber – Rubber

5 Blend for Food Contact 25 28 27-03-2024 03-04-2024
Application.

To study about NR / EPM rubber

6 29 32 03-04-2024 09-04-2024
blend.

To study about Blending of

NR/EPDM Rubber for weather
7 33 36 24-04-2024 01-05-2024
profile by curing with sulfur or
peroxide system.

To study about NR/EPDM

8 Vulcanization Mixing Process 37 39 01-05-2024 15-05-2024
with their Properties.

To study about the vulcanization

9 of Carboxylated rubber and it’s 40 46 15-05-2024 22-05-2024
blends with other polymer.

To study about compounding of

10 NR / EPDM Blend for tire 47 51 22-05-2024 29-05-2024
sidewalls.

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3724008 Practical - 01

Practical - 01

AIM: To study about the Rubber- Rubber blends methods.

1.1 Miscibility of Rubber-Rubber Blends

Examples of Miscible Rubber-Rubber Blends:
❖ Stirene-butadiene rubbers (SBRs) with varying stirene levels.
❖ Nitrile-butadiene rubbers (NBRs) with different acrylonitrile contents.
❖ SBR and butadiene rubber (BR).
❖ Natural rubber (NR) with vinyl BR.
❖ High vinyl BR and isoprene rubber (IR) are also miscible.
Factors Affecting Miscibility:
❖ Copolymers with slightly different compositions can sometimes be miscible.
❖ Differences in microstructure of materials used can result in seemingly contradictory
findings about blend homogeneity.
❖ Example: NR with BR can be heterogeneous or miscible depending on the type of BR used.
Advantages of Miscible Blends:
❖ Greater mechanical integrity compared to multiphase systems.
❖ Enhanced tensile properties due to volume contraction and increased number of chains
per unit cross-sectional area.
❖ Thermodynamic equilibrium morphology minimizes dependence on mixing conditions
and reduces likelihood of morphological changes during postmixing operations.
Non-Equilibrium Morphology Considerations:
❖ Slow diffusion of macromolecules can result in blend vulcanizates with non-equilibrium
morphologies.

1.2 Possibilities for Rubber Blend Morphology

Insufficient Mixing Duration:
❖ Miscible polymers exhibit heterogeneity if the mixing duration is insufficient to achieve
equilibrium before crosslinking.
❖ Mostly of academic interest due to the rarity of miscible elastomer blends.

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3724008 Practical - 01
Mechanical Mixing:
❖ Vigorous mechanical mixing can overcome small potential barriers to unlike segmental
interactions, resulting in homogeneous morphology detectable by standard analytical
techniques.
❖ Inhibition of demixing due to bonding with adjacent filler particles or presence of long-
chain branching may lead to a stable, non-equilibrium morphology.
Temperature Effects:
❖ Blending or curing at temperatures above the lower critical solution temperature (LCST)
can cause phase separation of miscible polymers.
❖ The phase separation is mainly due to increased entropy loss associated with volume
changes during mixing.
LCST and UCST Behavior:
❖ Miscible polymer blends generally exhibit LCST behavior.
❖ Upper critical solution temperatures (UCST) are rare in high molecular weight materials
without specific attractive interactions.
❖ Example: Observed UCST behavior in SBR-BR blends has been debated in the literature.

1.3 Multiphase Rubber Blends

Definition of Compatibility:
❖ Elastomer blends are often not molecularly dispersed.
❖ Blends are considered compatible if they offer a technically advantageous combination of
properties.
❖ True compatibility implies no spontaneous macroscopic demixing, though this is rare due
to the slow diffusion of macromolecules.
Morphology of Rubber Blends:
❖ Dependent on mixing procedures, rheological properties, and thermodynamic
considerations.
❖ Can result in a dispersion of one component in a continuous matrix or co-continuous
phases (Interpenetrating Polymer Network, IPN).
Interpenetrating Polymer Network (IPN):
❖ Can be created intentionally during synthesis or by controlled mixing techniques.
❖ Equal-volume fractions and viscosities favor co-continuity.
❖ Properties such as modulus are expected to be additive due to the unique morphology.

2
3724008 Practical - 01
❖ Limited commercial IPN materials involve rubber-rubber mixtures.

Continuous Phase and Viscosity:

❖ The continuous phase is usually the rubber with lower viscosity if present at a high
concentration.
❖ The more fluid component can encapsulate the more viscous phase.
❖ The component that can be highly extended without fracturing is likely to form the
continuous phase.
Dispersed Phase and Normal Stress:
❖ Phase with larger normal stress function forms dispersed particles.
❖ Measurement of normal stresses is challenging, especially at high shear rates.
Mixing and Particle Dynamics:
❖ Dispersed domains deform and fracture in high-shear regions of the mixing vessel.
❖ Particles collide and coalesce to form larger domains.
❖ Morphology represents a balance between dispersion and flow-induced coalescence.
❖ Predicting morphology involves considering the stress exerted on particles and their
relative viscosities.
Experimental and Theoretical Studies:
❖ Focus on dispersion of fluid particles in a medium.
❖ Minimum stress for droplet breakup is lowest when viscosities of both phases are similar.
❖ Extensional flow fields are more effective than shear flow for particle dispersion due to
continual stretching.
Flow-Induced Coalescence:
❖ Requires collision, drainage and fracture of the intervening film, and molecular
interdiffusion.
❖ Extensive when the viscosity of particles is lower or comparable to the continuous phase.
❖ More viscous continuous phase reduces coalescence rate, but increased shearing can
increase collision and coalescence rates.
❖ Ultimate particle size is limited by a steady-state competition between breakup and
coalescence.
❖ Prolonged mixing does not result in finer dispersion after a certain point due to the
balance between these processes.

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1.4 Properties of Rubber Blends

Rheology
❖ Blending rubbers can improve processing behavior, including viscosity reduction and
resistance to fracture.
❖ Viscosity of blends can show anomalous behaviors, such as non-linear relationships with
composition.
❖ Factors influencing viscosity include free volume changes and dispersed particle effects.
❖ Morphology rearrangement in blends can accommodate applied stresses, affecting
viscosity.
❖ Filler distribution, such as carbon black, significantly impacts rheological properties.
Modulus
❖ Blend modulus is influenced by individual component moduli and blend morphology.
❖ Stress-strain response can be affected by curatives distribution and glass transition
temperatures.
❖ Modulus behavior may range from upper to lower bounds, influenced by blend models
and crosslinking methods.
❖ Filler distribution, especially carbon black, can alter the dynamic shear modulus of
blends.
Transport Properties
❖ Transport properties like permeability depend on blend morphology and component
miscibility.
❖ Permeability can exhibit synergistic behavior in some blends.
❖ Transport models often use parallel and series configurations based on continuous and
dispersed phases.
❖ Electrical conductivity in rubbers is influenced by carbon black distribution and phase
affinities.
Adhesion and Tack
❖ Blending can improve both cocure adhesion and autoadhesion of rubber stocks.
❖ Autoadhesion depends on surface composition and rheological characteristics of the
blend constituents.
❖ Blends of natural rubber with synthetic rubbers can achieve high tack due to surface
composition effects.
❖ Cocure adhesion is influenced by blend composition and cure systems, with surface
composition playing a crucial role.
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Hysteresis
❖ Blending elastomers can achieve lower hysteresis with acceptable trade-offs in other
properties.
❖ Nonuniform filler distribution in blends can reduce hysteresis, particularly with carbon
black.
❖ Specific blend ratios and configurations can optimize hysteresis for specific applications,
such as tire treads.
Failure Properties
❖ Blending can enhance tear strength, cut growth resistance, fatigue life, and ozone
cracking resistance.
❖ Interphase bonding and crosslinking significantly impact the ultimate properties of
blends.
❖ The continuous phase's properties heavily influence the overall blend performance.
❖ Filler distribution in the continuous phase can improve properties like tear resistance
and fatigue life.

1.5 Preparation of Rubber Blends

Introduction
❖ Industrial mixing aims to produce materials with desired properties.
❖ Multiphase polymer systems often do not correspond to equilibrium or steady-state
morphology.
❖ Rubber blends can be prepared via synthesis, latex/solution blending, or mechanical
mixing.
❖ Mechanical mixing is the most common method.

1.6 Mixing Equipment

Mixing Operation Functions:
❖ Distributive mixing: Uniform composition throughout the batch.
❖ Dispersive mixing: Breaking up macroscopic components into finer domains.
Batch Mixing:
❖ Preferred in commercial operations due to handling large bales of rubber.
❖ Extruders are used to improve distributive mixing and shape rubber.

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3724008 Practical - 01
❖ Dispersive mixing in internal mixers (e.g., Farrel Banbury) or open-roll mills for small
batches.
Internal Mixers:
❖ Developments to improve mixing:
❖ Increased number of wings on rotors for more high-shear areas.
❖ Intermeshing rotors for enhanced shearing between rotor tip and walls.
Cooling Systems:
❖ Efficient cooling in internal mixers to maintain high viscosity.
❖ Cooling systems involve drilling passages for water flow close to the mixing chamber
surfaces.
Extruders:
❖ Assist in distributive mixing.
❖ Modified screw designs (e.g., pins, cavity transfer mixers) to enhance mixing efficiency.
❖ Twin-screw extruders for shearing forces and intensive mixing.
Continuous Mixing Methods:
❖ Ongoing interest in continuous mixing due to efficiency.
❖ Challenges include feeding continuous mixers and obtaining acceptable dispersion.
❖ Various mixers (e.g., Farrel continuous mixer, Berstorff planetary gear extruder) utilize
different mechanisms for intensive mixing.
Flow Fields:
❖ Mixing relies predominantly on shearing flows.
❖ Effective dispersion requires pure straining flow fields.
❖ Commercial mixing typically involves shearing stresses.

1.7 Distribution of Compounding Ingredients

Vulcanizate Properties:
❖ Challenges in developing satisfactory network structures in rubber phases.
❖ Different solubility and affinity of sulfur and accelerators for rubbers cause crosslink
density variations.
Curative Distribution:
❖ Curatives locate in the continuous or lower-viscosity phase first.
❖ Mixing scheme affects initial curative distribution.
❖ Curative migration can cause cure imbalance.

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Improving Blend Properties:
❖ Preblending curatives into elastomers can improve crosslink distribution.
❖ Short, high-temperature cure cycles can alter blend properties.
❖ Chemical modification of accelerators and direct attachment of curatives to elastomers
can address curative imbalance.
Interfacial Crosslinking:
❖ Essential for mechanical integrity.
❖ Sensitivity to vulcanization rate and cure systems.
❖ Polysulfidic linkages and monosulfidic linkages influence interfacial bonding.
❖ Presence of third, small-molecule components can promote curative accumulation at
interfaces.
Polymeric Compatibilizers:
❖ Block or graft copolymers can improve interfacial connectivity.
❖ Block copolymers are superior to grafts due to better configuration ability.
❖ Used primarily in rubber-glassy/crystalline material blends but applicable to rubber-
rubber blends.

1.8 Distribution of Fillers and Processing Aids

Nonuniform Distribution:
❖ Influences properties of multicomponent rubber stock.
❖ Preferential uptake of carbon black by certain rubbers.
❖ Carbon black affinity decreases in the order: BR > SBR > NR > EPDM > IIR.
Mixing Methods:
❖ Vigorous mechanical mixing prevents carbon black transfer.
❖ Less vigorous methods (e.g., solution blending) may allow carbon black transfer to
compatible phases.
Other Components:
❖ Oils, resins, and rubber chemicals can have differing affinities for blend phases.
❖ Nonuniform distribution and postmixing migration observed.

7
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Practical - 02

AIM: To study about the analytical methods for rubber-rubber blend characterization.

2.1 Nuclear magnetic resonance (NMR) spectroscopy

NMR spectroscopy is used in research laboratories to determine the structures of materials

such as new drugs and polymers. Magnetic resonance imaging is also used increasingly in
body scanning to obtain images of arms and legs, the head, or the whole body.
NMR spectroscopy gives information about the environment in which the nuclei of atoms are
found in molecules. If a nucleus is in the presence of an external magnetic field it can align
itself either with the external field (+) or against it (–). The nuclei of many elements (eg.
hydrogen) spin about an axis.
Nuclei with spin have what is called a magnetic moment, rather like the magnet of a compass
needle. So, in the presence of an external magnetic field these nuclei tend to turn to a preferred
orientation – just like a compass needle in the Earth’s magnetic field.
Nuclei obey quantum laws and for nuclei with a spin quantum number of 1/2 only two
orientations can be adopted – i.e the more favoured orientation +1/2 and the less favoured
orientation -1/2.

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When a molecule is placed in a magnetic field, weak electric currents are induced in the
electrons surrounding the nuclei. These currents flow in such a way as to produce a local
magnetic field which opposes the applied field. The nuclei therefore experience a fractionally
smaller total field than the applied external field. This means that each nucleus can have a
different magnetic environment and this gives rise to differences recorded in the spectra.

2.1.1 The spectrometer

Fourier transform (FT) NMR machines are the most common instruments in modern
laboratories. The field in FT machines is provided by a superconducting magnet – maintained
at liquid helium temperature (4 K). Fourier transform machines have a constant magnetic
field and excite all the nuclei – e.g protons – simultaneously by generating a range of
frequencies in a pulse for several microseconds.
When all the protons are excited simultaneously, each sends out Radio frequencies of the type
as they return to equilibrium with their surroundings. This is analogous to what happens
when a bell is hit. A sound characteristic of the bell is given out and then dies away.
The detected signal is a combination of the frequencies of each chemically distinct nucleus.
This is digitised and stored on a computer.

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2.1.2 The spectrum

The high resolving power of modern spectrometers enables spectra to be produced which
display a wealth of information. Each set of peaks is centered on a d value (the chemical shift).
The d values vary according to the chemical environment and the d value gives an indication
of the degree of shielding – by the surrounding electrons – experienced by the proton (s). In
most spectra trime thylsilane (TMS) is used to reference the signal to a zero and all other
signals are relative to this standard.

2.1.3 Shielding

Chemical shift depends on the electronegativity of the atoms in molecules. For example,
protons on carbon atoms adjacent to Cl, Br or I (ie CH–Cl, CH–Br, CH–I) resonate at a higher d
value than protons on carbon atoms adjacent to other carbon atoms (eg CH–R)

2.1.4 Spin-spin coupling

The signal arising from a particular proton within the molecule may be split into a doublet, a
triplet or a multiplet. This occurs through interaction with the magnetic moments of other
protons separated by two or three chemical bonds. This effect – spinspin coupling – occurs
through the disturbance, by the magnetic nuclei, of electron motions in the intervening bonds.

2.1.5 Integration of peaks

The amount of energy absorbed at each frequency is proportional to the number of protons
absorbing.
By measuring the height of the integration curve at each set of peaks the ratio of protons
absorbing can be determined.

2.1.6 Application

NMR spectroscopy is use to determine cross link density of a given compound.

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2.2 Differential Scanning Calorimetric

2.2.1 Instrumentation:

The concept of operation of this instrument is based on keeping the temperature of Reference
and Sample are the same? This is achieved by placing the temperature sensors (platinum
resistance thermometers) in a bridge circuit.
Any change in temperature in either the sample or in the reference (by virtue of any exo- or
endothermic event) is immediately compensated for by an equivalent amount of current flow
required to drive a heater to keep them at the same temperature.

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2.2.2 Operating Parameters for DSC

Sample Size: In order to avoid temperature gradients inside a sample, a small sample size is
preferred. A small sample size also gives better resolution.
Thermal Transport: Heat transfer to the sample can be affected by the following factors: (1)
physical arrangement of the sample and reference relative to the furnace; (2) the choice of
sensor, its size and position; and (3) the type of construction materials.
Effect of Heating Rate: The thermal lag between the sample and the sensor increases as the
heating rate increases and, generally, the resolution of a transition (or other thermal event)
decreases.

2.2.3 Application

The numerous applications of DSC are helpful in characterizing polymeric materials.

In Rubber –Rubber Blend DSC curve the midpoint of the transition is recorded as the glass
transition temperature (Tg). The Tgs of the raw polymers, SBR and EPDM are found to be –
50.47 and -45.70°C respectively and that of E80 blend is –46.75°C.

2.3 SEM (Scanning Electron Microscopy)

The process of image formation in a scanning electron microscope (SEM) can be described in
terms of a focused electron probe being scanned across the specimen surface, under high
vacuum, while synchronized to the raster scan on a TV type display.
In simplified terms secondary electrons are low energy electrons which have been in
elastically scattered by atomic electrons in the sample, and backscattered electrons are high
energy electrons which have been elastically scattered by atomic nuclei.
Secondary electrons are largely responsible for contrast dependent on variations in the
surface topography and backscattered electrons are largely responsible for contrast
dependent on variations in elemental composition.
There is very little variation in topography and hence very little contrast due to the secondary
electron signal.

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SEM idealized sample

2.3.1 Chemical Staining

Where a region has been stained by osmium tetroxide it will yield a greater proportion of
backscattered electrons than a region which contains less, or no, osmium tetroxide. Therefore,
the stained region will appear brighter.
The NR contains a greater degree of unsaturation and is consequently stained to a greater
degree and appears brighter than the NBR phase.

2.3.2 Chemical Etching

For a predetermined time a chemical is introduced to the surface and chemically etches out
one of the phases.
The specimen has been etched with phosphotungstic acid which has etched away the NR
phase whilst leaving the ENR-25 phase intact.

2.3.3 TEM (Transmission Electron Microscopy)

Transmission electron microscopy (TEM) provides the highest resolution, hence the sharpest
images, of the conventional electron microscope techniques.
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Images are formed in a TEM by focusing an electron beam onto an -thin section (typically 150
nm thick or less) of the specimen. Electrons travel through the specimen, either deflected or
undeflected, and are focused and enlarged by a series of electromagnetic lenses onto either a
fluorescent viewing screen or a piece of electronsensitive film.

The beam is focused on to the region of interest, rather than scanned across it. A phase that
has been preferentially stained with osmium tetroxide will scatter electrons further on
average than an unstained region. With the use of a contrast limiting aperture, these scattered
electrons are prevented from travelling further down the microscope and consequently the
stained area appears to be dark rather than light as in the case of SEM.
In NR-EPDM blend by working at higher magnification it was possible to show that the filler
appeared to be wholly located within the NR phase.

2.3.4 Limitations

The most significant of these is that it is an extremely time-consuming technique.

It requires ultra-thin sections, less than 150 nm thick, and preparation of sections of this type
can take from two hours to several days depending upon the nature of the sample.

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2.4 STEM (Scanning based transmission electron microscopy)

It is described as the "missing link" between TEM and LM.

The STEM mount consists of several copper components. The top part of the mount consists
of a hollow tube of 2.7 mm internal diameter incorporating a locking cylinder in which the
prepared specimen, placed on a standard TEM examination grid, is held.
The principle is thus: the focused electron beam is scanned across the section and electrons
strike the sample. The thickness of the section usually precludes any signal due to transmitted
secondary electrons. The important portion of the signal is therefore due to forward-scattered
as opposed to backscattered electrons which produce an image determined by mass and
thickness of the regions being examined, as in the case of TEM. After transmission, these
electrons strike the angled plate producing a secondary electron signal which is detected by
the secondary electron.

Detector.

STEM has several advantages over conventional TEM, SEM and LM. The added versatility
imparted to the SEM by virtue of its digital electronics means that it is capable of imaging
thicker sections than the TEM, although resolution is obviously improved with thinner
sections, and since it can use Polaroid instant film.

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Practical - 03

AIM: To measure the crosslink density of given rubber samples.

3.1 Cross-Link Density

The cross-link density is defined by the density of chains or segments that connect two infinite
parts of the polymer network, rather than the density of cross-link junctures.
Three methods for detection crosslink density:
Chemical method: - Analytical method
Physical method: - Mooney-rivlin equation
Continuous method: - ODR

3.2 Type of Measurement

The degree of cross linking in elastomers depend on the measurement of either equilibrium
volume swell or equilibrium moduli.
Determination of cross linking using mooney-rivlin equation.
Determination of crosslink density using swelling data.

3.3 The degree of cross linking in elastomers depend on the measurement of

either equilibrium volume swell or equilibrium moduli

Presently available physical methods for determining the degree of cross linking in elastomers
depend on the measurement of either equilibrium volume swell or equilibrium moduli.
Usually, equilibrium moduli are determined in extension on solvent-swollen samples, and the
effective network chain concentration is calculated from

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Where;
Ve/V: the effective network chain concentration
ɸ: the volume fraction of elastomers in the swollen sample,
T: the force per unit area of unswollen sample required to elongate the swollen sample to
the extension ratio a,
R: the gas constant,
T: the absolute temperature
Measurements of equilibrium moduli in extension are either time-consuming or require
relatively elaborate equipment.

3.4 Determination of cross linking using mooney-rivlin equation:

The stress-strain behavior of rubber vulcanizates can be described by the Mooney-Rivlin

relation which in simple extension, gives:

s =2(C1 + C2/ a) (a – 1/ a2)

Where s is the true stress, which produce an extension ratio in the sample, a is the strain ratio
and C1 and C2 are parameters characteristics of the rubber vulcanizates. It has been shown
that, C1 is a quantity pertaining the ideal elastic behavior, while C2 express the departure from
the ideal elastic behavior tensile results are displayed in the from of the Mooney-Rivlin simple
were evaluated Constants C1 and C2 have been obtained with the use of the strain
amplification factor X, which is defined as:

X = s / e E0 = E / E0

Where e is the strain produced by a stress s, and E0 is the modulus of the matrix, which means
that the local strains are on the average X times is greater than the overall strains. The constant
C1 and C2 are readily determined, and their dependence on the concentration of the blends
and kinetic theory of rubber elasticity is given by:

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2 C1 = υ KT

where, K is the Boltzmann`s constant and T is the absolute temperature. The constant C 1 is
related to the network-chain density υ.

3.5 Determination of crosslink density using swelling data:

Linear polymers often will completely dissolve in their own monomers or in another good
solvent. A good solvent for a polymer is one that is either similar in chemical structure to the
polymer or one, which can interact with the polymer main-chain or side groups.
One way for determining the solubility of polymers in solvent is through the estimation of
solubility parameter (d). The following relationship can often be used to estimate the
solubility of a polymer in a solvent,

(d1- d2)½ < 1

Then the polymer will dissolve in the solvent. Using a group contribution analysis approach,
the solubility parameter of a material can be estimated by the following equation.

d = (ρ ∑ Fi) / M

Where d = the solubility parameter, ρ= the density of the material; Fi = the group molar
attraction constant; M= the molecular weight of the material. We find the square-root of the
difference between rubber and solvent (Toluene) as shown in Table

➢ From the previous results, it can be concluded that toluene is a good solvent for the three
rubbers (NR, SBR & NBR).Therefore; toluene is the most suitable solvent. The swelling of a
rubber by a liquid is a mixing process; two substances mix when the free energy of mixing
(ΔG) is negative, if the change in enthalpy (ΔH) is less than the product of absolute
temperature (T) and the change in entropy ΔS as given by the Gibbs equation:

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ΔG = ΔH -T ΔS

Table : The values of solubility parameter of the rubber under investigation

(δ1 ) (cal/cc) ½ for (δ2 ) (cal/cc) ½ for (δ1 - δ2) ½ (cal/cc) ½

rubber solvent

NR 8.1 8.9 0.89

SBR 8.04 8.9 0.927

NBR 9.25 8.9 0.59

In simple terms, mixing is favored by minimum or negative enthalpy change and mixing
entropy change. Equilibrium swelling in toluene was used to determine the crosslink density
of the different blend ratios. Consequently, it was possible to make use of the swelling data to
calculate the molecular weight between two successive crosslink (Mc) by the application of
the well-known Flory Rehner equation.

1/Mc = -1/2ρV0 [(ln (1 – VR) + VR + µ VR 2) / (VR ⅓ - ½ VR)]

Hence the crosslink density can be calculated from the equation,

Crosslink density (υ) = 1/2Mc

Where ρ is the density of rubber; V0 is the molar volume of solvent absorbed (toluene
V0=106.3cm3 /mole); VR is the volume fraction of the rubber in the swollen material.
The equilibrium swelling measurements, soluble fractions, molecular mass (M c) and the
crosslink density υ. One can notice that, equilibrium swelling and Mc were decreased, while
the soluble fraction and crosslink density υ increased by increasing either SBR or NBR content
in the blends.

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3.6 Calculation

CROSS LINK DENSITY / SWELLING %

Sample Units Values
POLYMER NR/NBR
SOLVENT Toluene
Original wt of specimen m1 gm 4.6
Swelled wt.(Gained wt) m2 gm 4.95
S. G. of Solvent/DENSITY ds gm/cc 0.866
S. G. of Specimen dr gm/cc 1.2
Density of polymer dp gm/cc 0.95

% SWELLING BY VOLUME 149.1114

FLORY REHNER EQUATION

Molecular wt. of solvent M gm/mole 92.14
Molar Volume Solvent Vs cc/mole 106.397
Volume Fraction of Polymer Vr 0.90462349

Polymer lattice constant B1 0.34

Universal Gas constant R cal/ K mol 1.986
Temperature T degree K 298.15
Solubility parameter of solvent Delta s cal/ cc 8.9
Solubility parameter of polymer Delta p cal/ cc 9.2

Bristow and Watson semi equilibrium eqn.

Polymer - Solvent Interaction X 0.356

1-Vr 0.09537651
ln(1-Vr) 2.349922956
X* Vr^2 0.291470946
(Vr^0.33)-
0.51515132
(Vr/2)
dp * Vs 101.0773672

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No. avg. molecular wt. between crosslinks Mc 14.684

Crosslink density 1/2Mc 0.034

Modulus G 48.389

3.7 STRESS – STRAIN METHOD

The Mooney-Rivlin equation can be used to calculate the crosslink density of vulcanised
rubber without filler using the stress-strain data:

F = load in newton;
Ao= Initial cross-sectional area
λ = extension ratio
ρ = sample density
R = gas constant
T = absolute temperature
Mc = Average molecular weight of rubber segment between crosslinks (g/mol)
C1= Mooney-Rivlin elastic constant

A plot of F/[2Ao/(λ - λ-2 )] versus λ-1 yields C1 at the intercept, which can be used to calculate
Mc using equation (1) and hence crosslink density can be determined.

F = 2Ao (λ - λ-2 )(C1 + C2/ λ)

F 2Ao (λ-λ-2 ) = C1+C2/λ

2C1 = ρRT/Mc (1)

3.9 Conclusion

The best method among the three used methods for obtaining these results is the Mooney-
Rivlin equation, due to its simple and reliable method for determination of crosslink density
for cured rubber for 0.010 and s-39 MOR is 0.012 and modulus are respectively 13.885 and
17.002 N/m2.
21
3724008 Practical - 04

Practical - 04

AIM: To study about the rubber blend with graft co-polymer.

4.1 Introduction

Blends of highly incompatible elastomers may sometimes be improved by the addition of

small amounts of another polymer. The presence of block or graft copolymers can also
alleviate blending of incompatible elastomers as they can alter interfacial properties.
In NR/NBR blend the basic problem is in the difference of polarity between two polymers. As
NR is highly non polar and NBR is highly polar in nature so blend formed will be incompatible
and desired level of properties cannot be achieved. To overcome this problem we can graft
NR/PMMA so that difference in polarity between two polymers will be reduced and optimum
blend will be obtained.
MG30 is a mixture of graft copolymer with ungrafted NR and poly (methyl methacrylate),
PMMA, present as a homopolymer. It was considered that there would be sufficient interaction
between the PMMA graft chains and the acrylonitrile repeat units of the NBR for the graft
copolymer to locate at the NR/NBR interface and thus reduce interfacial tension and hence
phase size.

4.2 Mixing

Mixing of this blend can be done in three ways:

Separate master batches of NR, MG30 and NBR, containing 5 phr zinc oxide, 2 phr stearic acid
and 1.5 phr TMQ, were prepared in a BR Banbury internal mixer and the master batches were
cross-blended and finalized with curatives on a two-roll mill.
NR and MG30 were cross-blended and master batched with zinc oxide, stearic acid and TMQ
in a BR Banbury internal mixer and cross blended with the NBR master batch and finalized
with curatives on a two-roll mill.
NR, MG30 and NBR were cross-blended in a Bra bender PL2000 Plastic order fitted with a
350S mixing head and Banbury rotors at a rotor speed of 100 rpm for 3 minutes. Zinc oxide,
stearic acid, TMQ and curatives were added in a second stage mixing for 2.5 minutes at a

22
3724008 Practical - 04
circulating oil temperature of 40°C and a rotor speed of 80 rpm. The oil temperature in the
first mixing stage was 50 DC, 100°C or 110°C.

4.3 Phase Morphology

In the absence of PMMA large phase size is observed in between NR and NBR because of which
interfacial tension is very high and non-uniform blend is obtained.

Fig 4.1 Large phase size between NR/NBR

If interfacial adhesion is poor wherein a region of the two phases appears to have been pulled
apart from each other during sectioning. This may be a significant factor in the low tensile
strength observed for this blend.
When we blend NR/NBR with NR/PMMA grafted copolymer phase size is reduces hence
lowers the interfacial tension due to which uniform blend with optimum level of properties is
obtained.

4.4 Physical Properties

Higher tensile strengths are observed in the presence of MG30 rubber than for comparable
binary blends. Whilst part of the improvement may be attributed to a reinforcing effect of the
substantial amounts of MG30, a reduction in phase size will also play a role.
Tensile strength increases with increasing MG30 content.

23
3724008 Practical - 04

4.5 Crosslinking Density Distribution in the blends

The addition of MG30 appears to reduce the mal distribution in crosslink density, presumably
as a result of reduced phase sizes and the greater role of migration of intermediates during
vulcanization.
Blends with part substitution of either NR or NBR with MG30 consistently show a significant
bias of crosslinks in favour of the NR phase. This may be due to the reduction in phase size in
the presence of MG30.
The crosslink distribution in blends with such large phase sizes as are encountered in blends
with NBR containing 41 % acrylonitrile is largely determined by the distribution of curatives
prior to vulcanization.

24
3724008 Practical - 05

Practical - 05

AIM: To study about Rubber – Rubber Blend for Food Contact Application.

5.1 Introduction

The initial work into preferred formulations for NR/NBR blends produced a series of cure
systems suitable for use in blends of NR with NBR containing either 41% or 34% acrylonitrile.
The blends may be further improved by the use of low levels of compatibilizer, either
polychloroprene (CR) or a graft copolymer of natural rubber with poly- (methyl ethacrylate)
(Heveaplus MG30).
Milking inflations are used in the dairy industry and, as they are the part of the milking
machine which fits on the teat of a cow, they come into direct contact with milk.
Therefore, all ingredients must conform to regulations governing food contact.

Food and Drugs Administration (FDA)

Federal Health Authority or BGA

These differ from country to country, but those set by the US Food and Drugs Administration
(FDA) are particularly pertinent because of both the size of the US market and the use of these
regulations elsewhere.
A wide range of fillers is allowed, but a limit of 10% by weight of the total formulation is
imposed on furnace carbon black. This limitation can prove very difficult for NBR, which lacks
the inherent high strength of NR, because it is difficult to obtain adequate physical properties
for certain designs of milking inflation.
A wide range of plasticizers is also tolerated, but the total must not exceed 30% w/w. The
selection of N660 black and dioctyl phthalate (DOP) as plasticizer in the work considered here
is consistent with common practice for milking inflations.
Two white fillers were used; silica was initially selected but, as this is relatively expensive,
cheaper calcium carbonate was also investigated.

25
3724008 Practical - 05

5.2 Formulations for Milking Inflations to Meet FDA Regulations:

5.2.1 Compounding to meet a specification:

Milking inflations have to meet certain specifications set by suppliers to the dairy industry.
One particular specification is presented in Table In addition to the specification; practical
considerations dictate that a higher tear strength would be desirable, if not necessary.
Substantial hot tear resistance is required in order to ensure de-moulding from the injection-
mould cavity without tearing of the inflation.
Resistance to swelling by butter oil is a key requirement of milking inflations. For a range of
nitrile rubbers differing in acrylonitrile content, it is seen that those containing either 41 wt%
acrylonitrile, NBR41, as typified 34 wt% acrylonitrile, NBR34, swell very little in butter oil
while NR is known to have very poor resistance to swelling in oils.

5.2.2 Typical milking inflation specification (USA).

Unaged properties

❖ Tensile strength 10.5 MPa (min)

❖ Elongation at break 350% (min)
❖ Crescent tear strength 15 N/mm (min)
❖ Hardness 50 Shores A° (+/-3)
❖ Elongation after 90 min 60 to100% at 1 N/mm
❖ Subsequent tension set 2.5% (max)

After heat ageing (72 hours at 100 0C):-

❖ Change in tensile strength 20% (max)

❖ Change in elongation at break 50% (max)
❖ Change in hardness 20 Shore A° (max)
❖ Change in elongation at 1 N /mm2 35% (max)

The carbon black was placed wholly within the NR masterbatch at a loading of 25 phr in order
to make best use of restriction of swelling arising from rubber-filler interaction.
26
3724008 Practical - 05
The carbon black is not required to reinforce the NBR phase - the NR phase will impart the
necessary strength properties to the blend.
Initially, the NBR masterbatch was filled with a low level of white filler, silica (10 phr).
The plasticizer was distributed between the two masterbatches to ensure that the fillers
mixed effectively.
In addition to filler and plasticizer, both masterbatches contained 5 phr zinc oxide, 2 phr
stearic acid and 3 phr of the antidegradant IPPD.
A number of promising cure systems identified in investigations of crosslink distribution in
Gum vulcanizates were used; all contained 1.3 phr sulphur.
Separate masterbatches of the NR and the NBR were each prepared in an internal mixer, and
then cross-blended to give a 50:50 polymer ratio and finalized with curatives on a two-roll
mill.
The blends were compression moulded to the optimum cure time at 180 0C.

5.3 Testing

Limited physical testing on both blends demonstrated that whilst tensile strengths were high,
Resistance to swelling in butter oil was poor.
Unaged physical properties of 50:50 NR: NBR41 blends cured using the preferred accelerator
systems are shown in Table 50:50 NR: NBR34 blends had very similar properties.
Crescent tear strengths are very good, hardness values are slightly low but butter oil swellings
exceed the permitted FDA maximum by about six times.
The crosslink density distribution between the two rubber phases was undesirable for both
the NBR41 and NBR34 blends, with both systems showing a marked bias in favour of the NBR
phase.
Despite the level of crosslinking in the NR phase of the NR/NBR41 blends being very low, the
blends had fairly high tensile strengths.
However, the major problem remained the very high swelling in butter oil.
Replacement of the 10 phr silica used in the NBR masterbatch with 60 phr of alternative and
cheaper - white filler, calcium carbonate, was investigated as an indirect means of reducing
the level of swelling in butter oil.
Addition of a relatively high level of inert white filler to the NBR phase, and the corresponding
increase in DOP plasticizer (20 phr) to maintain hardness, serves to increase the formula
weight of the blend compound.
27
3724008 Practical - 05
This enables the level of carbon black in the NR phase to be increased from 25 to 35 phr, whilst
still remaining within the FDA permitted limit of 10 wt% carbon black overall.

Fig 5.1 Dependence of volume swelling of NBR vulcanizates in butter oil

on acrylonitrile content.

Addition of a high level of inert filler, albeit only to the NBR phase, does reduce the tensile
strength of the blend, although it remains above the minimum specification.
A significant reduction of swelling in butter oil is also achieved, although the levels shown in
Table remain too high.
Some different distributions of filler addition were explored; for instance, adding all the
calcium carbonate to the NBR masterbatch in one blend, and distributing it between the NR
and the NBR in another blend.
In most cases, the differences in properties was minimal, therefore it was decided to leave the
filler in the NBR masterbatch.
Swelling in butter oil could only be reduced to acceptable levels by reducing the quantity of
the highly swelling component in the blend, the NR.
Thus, 35:65 and 25:75 NR: NBR blends were investigated.
A major consequence was that the amount of carbon black in the NR master batch could be
greatly increased, whilst remaining within the overall limit set for carbon black in the blend.
This would assist in lowering the swelling. Given the reduction in NR content of the blend, it
was necessary to revert to silica as filler in order to ensure adequate strength properties.

28
3724008 Practical - 06

Practical - 06

AIM: To study about NR / EPM rubber blend.

6.1 Introduction

Blend of NR with EPM is made to combine the properties of both Natural rubber and Ethylene
propylene monomer and to make it economical because EPM is very expensive.
The main problem with this blend is distinguished phase size. NR and EPM exhibits high
interfacial tension due to their difference in structures and because of this higher phase size
is observed so blend will not be uniform in nature.

6.2 Morphology

Morphology of this blend depends on the properties required in the final application. If
maximum ozone resistance is required then EPM should be in continuous phase while the NR
component may form a disperse or continuous phase.
Difference in the solubility parameter of EPM and NR is very high so interfacial tension is also
high and due to this large phase size is observed within the blend. And when we analyse the
blend by magnification different phase of NR and EPM is detectable it shows that improper
blending is carried out.
But this morphology can be rectified by modification in the compounding, vulcanizing and
mixing technique. And by adding compatibilizer. It will help in reducing the interfacial tension
so ultimately phase size will be reduced and improved blending will be obtained.
In this blend NR appears darker than EPM and it is evident that NR forms the matrix phase.
The lighter EPM is present as a disperse phase within this matrix. The EPM domains are
elongated, roughly 20 x 5 µm in size, and separated by relatively narrow (210 µm) regions of
NR. The interphase boundary appears to be smooth. Therefore, the blends do not naturally
possess the desired morphology.

29
3724008 Practical - 06

Phase contrast micrograph of a conventional NR/EPM blend

6.3 Dynamic Vulcanization of NR/EPM Blend

Dynamic vulcanization has been used to improve the properties of thermoplastic elastomer
blends and to control the dispersion and distribution of carbon black in polymer blends.
Dynamic vulcanization is a procedure whereby one of the components of the blend is
vulcanized or partly vulcanized, during the mixing process, whilst the other component
remains completely uncured. The introduction of cross links into one of the phases increases
the viscosity of this phase, leading to a change in blend rheology, and hence in the morphology
of the blend.
In case of gum blends the only ingredients in the mix were the two polymers, zinc oxide,
stearic acid and the cure system. The insertion of crosslinks into the NR phase could be
monitored by its effect on the mix viscosity and hence the mixing torque.
Dynamic vulcanization began once the mix reached a temperature of 125-135°C and then the
mixing torque rose as dynamic vulcanization proceeded. The mix has to be dumped below
165 °C to avoid polymer degradation.
The micrograph shows a finer structure than found earlier. In addition, the phases appear to
be co-continuous and the phase boundaries appear to be much rougher than in the
conventional blend.

30
3724008 Practical - 06

Phase contrast micrograph of a dynamically vulcanized NR/EPR blend

In clay filled blends powders, curatives and some of the clay were added after an initial period
of polymer blending, the rest of the ingredients being added after a total mixing time of two
minutes. This was before dynamic vulcanization had occurred.
Adding these cold ingredients to the hot mix causes the mix temperature to fall, resulting in a
delay in the onset of dynamic vulcanization. This mix cycle was, therefore, much too long. The
addition of the cold ingredients lowers the mix temperature by about 20°C, whilst the
presence of oil lowers the mix viscosity, hence reducing mixing torque and the rate at which
the temperature subsequently increases.
Mixing is thus able to continue for a sufficient time after the second addition to ensure that
the materials are properly dispersed. The total mix cycle is about six minutes in length.

6.4 Vulcanisation of DV blends:

Peroxide:

Peroxide curing is required to get the final shape of the product. The peroxide was used at 2.5
phr and the sheets were vulcanized for one hour at 160°C. Co-agents are used in peroxide
curing for achieving optimum level of properties.

31
3724008 Practical - 06
Radical Co-agents

The presence of HVA-2 gave an increased modulus, but at the expense of a significant
reduction in tensile strength. Of the two allyl silanes investigated, Silquest RC 1 is to be
preferred for reasons of health and safety: the by-product of its coupling reaction with clay is
ethanol whilst that of Silquest A 172 is a more toxic alcohol.

6.5 Radiation

Based on the observed modulus, the optimum dosage was found to be about 300 kGy, but this
may have been influenced by the degree of porosity. Comparing moduli of irradiated and
Dicup cured sheet suggests that electron beam irradiation is giving considerable crosslinking.
Despite its use as a coagent in electron beam irradiation of EPM compounds, tri-allyl
cyanurate (TAC) was found to reduce the crosslinking efficiency when used in these DV
blends; Silquest RC 1 and the Sartomer resin are the preferred agents. Thus irradiation is a
feasible method of vulcanization of the DV blends, although the process has not been
optimized.

6.6 Application

The main application of this blend is in high tension cable industry. The cable insulation
industry the materials should be capable of being crosslinked by high energy radiation, such
as electron beam irradiation.
It is also used in automotive and construction industries.
32
3724008 Practical - 07

Practical – 07

AIM: To study about Blending of NR/EPDM Rubber for weather profile by curing with
sulfur or peroxide system.

7.1 Introduction

The development of blends of natural rubber (NR) with ethylene-propylene-diene monomer

(EPDM) with the aim of combining the excellent physical properties of NR with the ozone
resistance of EPDM has received much attention over the past three decades.
The principal target application for such blends has for many years been tire sidewalls where
ozone cracking was seen as a limiting factor on the service life of a tire. However, extruded
weather seal profiles for vehicles and light coloured injection-moulded goods for domestic
appliances, markets once dominated by NR, but now almost entirely superseded by EPDM,
are also attractive areas for NR/EPDM blends.
Whilst ozone resistance has been comparatively easy to achieve in NR/EPDM blends the
general physical properties of NR/EPDM blends have been less than satisfactory.
The main problems associated with the generally poor properties of NR/EPDM blends are a
direct result of the relative chemical reactivities of NR and EPDM. NR is a highly unsaturated
and hence reactive polymer, making it very susceptible to attack by ozone; conversely EPDM
has a very low level of unsaturation, typically less than 3 mol%, and hence has a low reactivity
towards ozone. In a blend, such a disparity in reactivity is reflected in the relative rates of
crosslinking during vulcanization.
Both within and between the two phases, diffusion of curatives towards the faster curing NR
phase occurring readily during mixing and curing
The lower solubility of many curatives in EPDM as compared with NR further reduces the
propensity towards crosslink formation in the EPDM phase. Overall, these factors combine to
give a blend having a highly cross-linked NR phase and a very poorly crosslinked EPDM phase.

33
3724008 Practical - 07

7.2 Approaches to Improving NR/EPDM Blend Properties

There have been several notable approaches to improving the properties of NR/EPDM blends
attempted over the past 25 years or so. Generally, these approaches have sought to increase
the cure rate of EPDM, either by means of modifying the EPDM to make it more reactive
towards
Curatives, or by using curatives that have an increased reactivity towards EPDM. Morrissey
reported the halogenation of EPDM in solution to be effective in improving cure compatibility
in blends with highly unsaturated elastomers such as NR and SBR. Baranwal and Son modified
EPDM in solution with accelerator species, including the sulphur donor dithiodimorpholine
(DTDM), using UV irradiation in the presence of a photosensitizer.
Similar work was reported by Hashimoto et al. Whereby pendant accelerator groups were
introduced to the EPDM polymer chain prior to cross-blending with NR. Hopper modified
EPDM with N-chlorothioamides, again in solution, to introduce reactive pendant groups which
could behave as a crosslink precursor during normal vulcanization of the blend.
More recently, Coran has reported the modification of EPDM with maleic anhydride in the
internal mixer at high temperatures which, through the introduction of carboxylate pendant
groups, was suggested to form reversible ionomeric crosslinks with zinc oxide added as part
of the normal sulphur cure system.
The increasing commercial availability of EPDM grades with higher levels of unsaturation,
aimed specifically at increasing the rate of cure in EPDM compounds with sulphur-based cure
systems, has also led to improved levels of cure being achieved in the EPDM phase of a blend
with NR. However, even the so-called Very highly' unsaturated EPDM grades still have less
than 10% of the unsaturation of NR on a molar basis.
As an alternative to modifying EPDM to redress the imbalance in reactivity of curatives
towards NR, the use of accelerators with greater solubility in the EPDM phase of a blend has
been investigated Although the use of accelerators containing higher alkyl substitution was
shown to greatly enhance the properties of blends containing EPDM, few if any of these
accelerators with long alkyl substituents have been commercialized.
The mobility of curatives between phases of a blend of elastomers which differ in polarity can
be restricted by the use of lead oxide activator.
The resulting insoluble lead accelerator salt effectively removes the thermodynamic driving
force for curative diffusion between the elastomer phases and gives a blend with a good level
of covulcanization.

34
3724008 Practical - 07
Manipulation of curative type, whilst not requiring an additional mixing stage, does however
preclude the means for imparting other useful properties on the blend that EPDM
modification can produce. All of the EPDM modification methods described above achieves a
significant improvement in the physical properties of NR/EPDM blends.
This result directly from the introduction of reactive sites able to participate in the cure
process and speed up vulcanization in the EPDM phase, so improving the level of crosslinking
achieved.
It should be noted, however, that only one of the EPDM modification procedures recorded
above was achieved in an internal mixer, although the reagents and conditions required for
modification are hardly suitable for large scale mixing in a factory environment.
Three commercially available sulphur donors, bisalkylphenoldisulphide (BAPD),
dithiodicaprolactam (DTDC) and dithiodimorpholine (DTDM), have been used to modify
EPDM by mixing at elevated temperatures in an internal mixer as part of a normal
masterbatch mixing cycle.
This procedure has been termed 'reactive mixing7. As has been the case in work reported by
others in this field, the choice of EPDM grades used has been restricted to commercially
available grades with a very high level of unsaturation.
The modification is believed to be similar in nature to that described by Hopper in which a
functionality (alkylphenol monosulphide, caprolactam or morpholino) derived from the
sulphur donor is bound to the EPDM via a sulphur linkage. A simplified representation of what
is thought to occur is shown in Figure. During vulcanization, either part, or all, of the bound
sulphur donor moiety can act as a leaving group, being displaced by 2mercaptobenzothiazole
(MBT), a vulcanization intermediate, to form a crosslink precursor site on the EPDM polymer
chain.
Applications of NR/EPDM blends, a 60:40 NR/EPDM blend ratio were used. This blend ratio
has been shown to exhibit good ozone resistance in both static and dynamic ozone tests. It is
desirable both in terms of performance and cost to maximize the NR content of such blends
whilst maintaining adequate ozone protection without added antiozonants. Whilst lower
volume ratios of EPDM have been investigated, indications.
Were that insufficient ozone protection was afforded.
These findings are in accord with previously published work. The work described here
demonstrates that modification of EPDM with sulphur donors using a 'reactive mixing'
procedure leads to an improved level of crosslinking in the EPDM phase of an N R/EPDM
blend.

35
3724008 Practical - 07
For one of the modifiers (BAPD), a reduction in phase size in the blend is also observed. In
addition, all three of the modifiers act so as to increase the level of interaction between the
EPDM and carbon black.

General approach to EPDM modification

Formation of vulcanization precursor.

36
3724008 Practical - 08

Practical - 08
AIM: To study about NR/EPDM Vulcanization Mixing Process with their Properties.

8.1 Mixing Procedures

For the compounds described in this chapter, mixing was performed in a variety of laboratory
scale internal mixers ranging in size from a Brabender PL2000E fitted with a 35OS mixing
head and Banbury style rotors (300 ml capacity, 0.75 fill factor) to a 0OC Banbury (3 litre
capacity, 0.75fill factor).
In order for modification of EPDM to be achieved, separate NR and EPDM master batch mixing
procedures have been adopted. Cross-blending of the modified EPDM master batch with a NR
master batch is achieved in a second mixing stage and a third mixing stage is required for the
addition of curatives.
The EPDM modification procedure is carried out using~1phr modifier in an internal mixer
under conditions which will result in a batch temperature of at least 1500C being achieved
and then maintained for between 1 and 2minutes.
The batch temperature on dumping is typically170°±5° which is not unusual for factory
processing.
The requirements of the procedure are consistent with the modification reaction being free
radical in nature, in that high temperatures facilitate cleavage of the sulphur donor SS bond
and the formation of polymer radical species.
The admittance of air at such a stage of the mixing procedure has been found to effectively
quench the modification reaction, oxygen being an extremely efficient radical trap.
Nonetheless, the necessary conditions can be attained in a factory environment – as
demonstrated by mixing in a Banbury.
Analysis of the modified EPDM has been carried out by gel permeation chromatography (GPC)
followed by ultraviolet (UV) spectroscopy at 240nm.
This has confirmed that UV active groups have become bound to the EPDM polymer chain.
Quantification of the bound modifier is possible if the extinction coefficient of the bound
moiety is taken to be that of the sulphur donor.
Typically, the level of modification has been estimated by the GPC/UV technique to be in the
range 0.1-0.5 wt%. However, at such a low level of modification, conclusive structural
identification of the polymer bound groups has not been possible.

37
3724008 Practical - 08

8.2 Physical Properties

The combined effects of the different sulphur donor modifying agents can be seen in the
physical properties of black-filled (50 phr N660) 60:40

Interaction between EPDM and carbon black (50 phr N660)

Tensile properties of black-filled (50 phr N660) NR/EPDM

blends(2.0 phr S/0.6 phr CBS, fmax/150 0C).

NR/EPDM blends cured with 2.0 phr sulphur/0.6 phr CBS to optimum cure level (fmax) at
150 0C. As seen in Figure 14.7, all of the modifiers produce an increase in modulus and tensile
strength when compared with the unmodified EPDM blend. The high modulus of the
DTDMmodified EPDM blend is likely to be a result of the very high level of interaction
developed between the modified EPDM and carbon black.

38
3724008 Practical - 08
The effect of the BAPD modification on the more 'dynamic' of physical properties such as
Goodrich heat build-up (ISO 4666/3,1982) can be seen in Figure At three different loadings
of N660 carbon black in the EPDM masterbatch, (NR masterbatch loading constant at 50 phr
N660), the effect of the modification is to reduce heat build-up significantly.
As expected, this effect is most noticeable at the higher black loadings in the EPDM
masterbatch, where a greater level of interaction between the modified EPDM and carbon
black would exist.
Although not demonstrated here, similar behaviour would be anticipated for the other two
modifying agents.

39
3724008 Practical - 09

Practical - 09
AIM: To study about the vulcanization of Carboxylated rubber and it’s blends with
other polymer.

9.1 Introduction
Carboxylated elastomers are construed as rubbers and lattices containing pendent carboxyl
groups at random sites along the chain.
Liquid polymer with terminal carboxyl groups and thermoplastic ionomers are not included.
The introduction of pendent carboxyl groups and subsequent formation of ion reach
aggregates at these sites profoundly affect vulcanization properties.
The methods of production polymer composition vulcanization and properties of carboxyled
elastomers will review.

9.2 Preparation of Carboxylic Rubbers (Emulsion Polymerization)

The majority of Carboxylated elastomers are produced by emulsion polymerization at
temperatures ranging from about 50 to 60°C.
Coagulation must also be carried out using reagents that ensure that the carboxyl group
remains acidic, and acids, or blends of salts and acids, fulfill this function satisfactorily.
Emulsion copolymerization of half-esters of carboxylic acids may be carried out in basic
media.
The half ester moiety is said to render the carboxyl compound hydrophobic. The ability to
produce Carboxylated elastomers in a basic medium would indeed offer an advantage, since
polymerization in an acidic medium requires the use of stainless-steel vessels and piping.

Ingredients Phr
Monomers 100.0
Dodecylamine (90%
5.0
neutralized with HCL)
Aluminium chloride 0.2
Potassium persulfate 0.2
Sulfone B-8 0.4
Water 200.0

40
3724008 Practical - 09
As in many emulsion polymerization recipes, tertiary dodecyl mercaptan is recommended as
a modifier to control molecular weight. HCI (or methanolic HCI) is suggested as coagulant.
The recommended polymerization conditions were 6-25 hours at 30-50°C for 75-90%
conversion.
This is a somewhat lower temperature than the 60°C quoted in earlier patents Polymer
process ability and properties are affected to some extent by polymerization temperature.
The number of carboxylic acids in the polymer and their distribution depend on the type of
acid, the ratio of monomers charged, whether or not they are charged incrementally. And the
degree of conversion to polymer.
The efficiency of incorporating the acid has been said to depend on its relative solubility in
the hydrocarbon and water phases. Acrylic acid is more soluble in the aqueous phase, and only
half of that charged is polymerized.
Meth acrylic acid is about five times more soluble in the hydrocarbon than in the water phase.
Hence it is efficiently incorporated into the polymer.

9.3 Blends of Carboxylated Elastomers with other Polymers

9.3.1 Blends of Carboxylated and Regular NBR
The blending of NBR with XNBR as a route to improving tensile strength and abrasion
resistance without loss of oil resistance.
They sought minimal increase in cost and compression set and minimal loss of scorch
resistance and low-temperature flexibility.
Using sulfur-zinc peroxide or sulfur-zinc oxide systems resulted in poor properties because
of differing cure rates in the two rubbers.
When sulfur donor-low sulfur or peroxide cures were used. Cure rates were comparable in
NBR and XNBR.
The cure rates of the blends were also comparable and physical properties of the blends, as
well as abrasion resistance and compression set. were intermediate between those of the
parent properties as expected.
The effect of replacing 10 and 20 phr of regular NBR with XNBR in a lowsulfur/accelerator
recipe. The minor quantities of XNBR increased 300% modulus but decreased tensile strength
and abrasion resistance and increased compression set markedly.
This might be because the vulcanization characteristics of XNBR were not identical with those
of the NBR in the recipe used.
41
3724008 Practical - 09

9.3.2 Blends of Carboxylated NBR with Polybutadiene

The blending of 75 parts XNBR with 20 parts polybutadiene and using 10 parts zinc oxide
master batch as curative improved the low-temperature flexibility of XNBR.
The brittle point fell from - 40 to - 48°C in the presence of the polybutadiene.
There was some loss in tensile and tear strength and. not surprisingly. An increase in swell in
ASTM No. 3 oil from 11 to 37%.

9.3.3 Blends of Carboxylated NBR with Epichlorohydrin Rubber

The Carboxylated nitrile rubber and Epichlorohydrin rubber were cross linked directly in the
presence of DBU (1,8-diazabicyclo, undec-7-ene). This is produced an ester linkage, and the
resulting vulcanizate had much lower Compression set than conventional blend vulcanizates.

9.3.4 Blends of Carboxylated NBR with PVC

The blends of Carboxylated NBR with PVC were more easily prepared than those with regular
NBR.
The XNBR-PVC blends extruded more smoothly, remained non brittle down to lower
temperatures, and exhibited greater abrasion resistance and thermo plasticity.
The tendency for XNBR to crosslink during fluxing with PVC had been an obstacle to the
production of XNBR-PVC.
The proprietary blends containing none staining. Non discoloring stabilizers were on the
market.
The XNBR-PVC compounds whether black- or white-filled, extruded faster and swelled less
than their NBR-PVC counterparts.
Although at low PVC levels the NBR-based extrudates were slightly smoother.
Tear and tensile strength and especially abrasion resistance were increased when XNBR
replaced NBR.
XNBR blends were stiffer then NBR vulcanizates at low temperatures, and, as expected,
increasing PVC decreased low-temperature flexibility.
Some complex compression set results were noted including lower set for black-filled XNBR-
PVC counterparts.
Up to a 70/30 XNBR/PVC ratio, dynamic ozone resistance was better than for NBRPVC.

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At higher XNBR levels, dynamic ozone resistance was poorer because of the high modulus of
the blend.
XNBR-PVC blends for use in light-colored extra heavy-duty cable jackets. He noted a
substantial increase in tensile and tear strength and an appreciably lower brittle point for the
XNBR-PVC blends compared to those of regular NBR-PVC.
At low temperatures the XNBR-PVC compounds are very stiff, but they are not brittle.
Replacing dioctylphthalate plasticizer by dioctylsebacate resulted in improved tensile
strength and abrasion resistance, better low-temperature flexibility, and better aging
resistance.
Many of these attributes are consistent with lower plasticizer volatility. The presence of 0.25
part sulfur as coagent in a peroxide cured system increased scorch safety and raised ultimate
elongation before and after aging.
Sulfur cannot be included in light-colored lead press-cured compounds, since lead sulfide.
Which is black, would rapidly be formed. It was noted that these compounds (XNBR-PVC
blends) could be readily vulcanized in the electron beam.
The care that must be taken in fluxing XNBR-PVC blends. They warned against using
stabilizers that contain zinc ions and suggested calcium stearate at 2 phr.
They stated that stabilizers containing zinc would promote scorch by formation of zinc salts
with carboxyl groups. One part of stearic acid added during fluxing was said to improve flow
properties.

9.3.5 Blends of Carboxylated NBR with Regular NBR and PVC

The substitution of some PVC and/or NBR in regular NBR-PVC blends with XNBR increased
stiffness, tensile strength; tear strength, and abrasion resistance.

9.3.6 Blends of Carboxylated NBR with Chlorosulfonated Polyethylene

Since both chlorosulfonated polyethylenes (CSM) and XNBR can be cross linked with
magnesium oxide.
Magnesium oxide would covulcanize blends of these polymers. He found that modulus and
tensile strength of CSM increase when blended with XNBR and cured with magnesium oxide
at room temperature.

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XNBR greatly increased oil and fuel resistance of CSM membrane compounds, which was
foreseen as an advantage of the blend.
Unfortunately, blending reduced the tear resistance and aging resistance of the compounds.

9.3.7 Blends of Carboxylated NBR with Chlorobutyl Rubber

An unfilled mill-mixed blend of XNBR and CIIR, without added curatives, was rendered
insoluble in chloroform after molding 60 minutes at 180°C.
The physical properties of this “self-vulcanized” unfilled system were not spectacular, and no
data were presented for blends containing fillers.
The rubbers in this blend were shown to be immiscible.

9.3.8 Blends of Carboxylated NBR with Polychloroprene

A mill mixed blend of XNBR and CR. After molding 60 minutes at 180”C, the blend was shown
to be covulcanized.
The covulcanization was confirmed by Monsanto Rheometry. Solvent swelling and FTIR
analysis.
The extent of cross linking increased with increasing CR content.
The properties of unfilled and ISAF black-filled mill-mixed 5050 blends of XNBR and CR,
molded 60 minutes at 190°C.
The products were insoluble in chloroform. DSC and dynamic mechanical analysis indicated
that the rubbers were immiscible.
The authors claimed that their system required less energy for processing since it contained
no rubber chemicals.

9.3.9 Blends of Carboxylated NBR with Modified Natural Rubber

A mill-mixed blend of XNBR and carboxylated NR were cross linked during molding for 60
minutes at 160°C.
Dynamic mechanical measurements indicated that the components of these blends were
compatible.

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The blends were said to have excellent processing safety, good abrasion resistance, and
excellent oil resistant but the balance of physical properties as reported does not appear to
provide useful practical vulcanizates at any blend ratio.
XNBR as a compatibilized for chlorinated NR and epoxidized NR, which are partially miscible.
The quantity of XNBR required was found to depend on the blend composition. The physical
properties of the blend were not discussed.

9.3.10 Blends of Carboxylated NBR with Polyacrylic Rubber

Processability of the ACM was improved by blending and physical properties were also
improved.
IR spectra indicated that covulcanization had taken place on heating the blend. Preheating the
blend of virgin polymers improved vulcanizate properties and delayed hightemperature
degradation.
The covulcanization of 5050 blends of XNBR and ACM in presence of lead oxide and2
mercaptobenzothiazole (MBT) or ethylentehiourea (ETU).
They concluded that lead oxide enhanced the effectiveness of MBT or ETU as curatives,
through the formation of lead sulfide and metal ion bridges. MBT produced a greater degree
of cure than ETU, probably through the formation of monosulfide crosslink.

9.3.11 Blends of Carboxylated NBR with Polyolefin’s

Carboxylated NBR in a study of compatibilized blends of NBR and polyolefin’s.
The polyolefin used was triethylene tetra mine-modified, malefic acid-modified propylene
masterbatch blended 50/50 with XNBR.
Unfortunately, no other rubber in the study appeared to have been blended with the same
modified polypropylene.
In any event, as might be expected. The blend containing XNBR had high tensile strength (19.2
MPa) and high modulus at 100% extension. It also had relatively high ultimate elongation
(250%).

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9.3.12 Blends of Carboxylated EPDM with Polyethylene Terephthalate

The notched Izod impact strength of polyethylene terephthalate tripled when it was blended
in 70/30 ratio with carboxylated EPDM.
The latter was produced by blending an ethylene propylene rubber containing 72% ethylene
together with endobicyclo 5-heptene-2.3-dicarboxylic acid anhydride and t-butyl peroxide in
an extruder at 200°C in the ratio 1000/3/1.

9.4 Applications of Carboxylated Elastomers

9.4.1 Uses of Carboxylated Latices
Dipped Goods
Leather Finishing
Paper Coating
Textile Applications
Adhesives

9.4.2 Uses of Solid Carboxylated Elastomers

Adhesives
Tires
Seals
O-Rings
Oil-Field Applications
Footwear
Hose tubes and covers
Miscellaneous Application

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Practical - 10
AIM: To study about compounding of NR / EPDM Blend for tire sidewalls.

10.1 Introduction
A tire sidewall provides the physical connection between a vehicle's wheel and the tire tread:
it transmits power and braking force to the tire tread which is itself in contact with the road
surface.
The sidewall also provides a significant part of a vehicle's suspension and plays an important
role in the general handling of the vehicle on the road. As can be seen in Figure, the sidewall
is a remarkably thin and seemingly fragile part of the tire considering its function.
The trend today is for passenger vehicles to be fitted with radial ply tires with the requirement
that they continue to meet ever-increasing performance criteria necessary to match the rising
capabilities of modern cars.
This has led to tires which are lighter in weight, have lower profiles and a wider tread to give
improved grip and better high-speed handling.
These requirements have put an even greater demand on the sidewall compound as the flex
area is concentrated into an even smaller region of the tire.
In addition, the expected lifetime of a modern tire is greater than ever before at around 80,000
kilometers.
Current tire black sidewall compounds are generally based on blends of natural rubber (NR)
with polybutadiene (BR) and contain antioxidants, antiozonants and waxes to protect against
cracking and environmental weathering.
During the lifetime of the tire the antiozonants and waxes present are brought to the surface
which discolours the sidewalls and, as the protectants become depleted, the sidewalls harden
and crack.
The appearance of the tire sidewall deteriorates quite noticeably long before cracking occurs
and continues to do so throughout the lifetime of the tire.
For a car, the appearance of the tire contributes to the overall appearance of the vehicle and
so is of some importance to the manufacturer.
A tire sidewall built using a blend of NR with ethylene-propylene-diene monomer (EPDM)
would be protected against attack by ozone (Chapter 14) and, having no need for antiozonant,
would maintain its initial 'new' appearance and would thus be advantageous.

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Truck tires usually undergo more than one retread in their lifetime and so it is important that
the sidewall should be able to perform adequately for the entire life of the tire.
Depletion of anti-degradants in the sidewall can become a serious problem even after only the
first or second retread.
Thus, if the ultimate mileage target for a truck tire of one million miles is ever to be realized,
the tire would be expected to undergo three or four retreads and would be dependent upon
the sidewall.

10.2 Properties of Comparable NR/BR and NR/EPDM Blend Formulations

A typical tire sidewall compound is a 50:50 NR:BR blend containing carbon black (50 phr
N660) and oil (10 phr) and a variety of other ad ditives, including antiozonants. Such a
compound would be expected to have a tensile strength of over 20 MPa and a modulus at
100% strain (M100) value of about 1.5 MPa (Figure 15.2) when cured at 150 °C to optimum
cure (max). In comparison, a 60:40 NR-EPDM (Vistalon 6505) blend having the same black
and oil loading but no antiozonants, cured under similar conditions, has a slightly reduced
tensile strength but a significantly increased modulus (M100).
Use of EPDM modified with 1 phr of the sulphur donor bis-alkylphenoldisulphide (BAPD) in
a blend with NR, although improving the tensile strength of the blend, produces a further
increase in compound modulus.
Using cure conditions more usual for car tire production, a cure temperature of 170 °C for a
duration of twice optimum cure (2 x max), the tensile strength of the modified-EPDM blend

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compares more favorably with that of the NR/BR control compound but a greater differential
in moduli values is apparent.
The higher modulus of the NR/ modified-EPDM blend is believed to result in part from the
high cross-link density of the dominant NR phase in the NR/EPDM blend, the higher T, of
EPDM compared with BR and from the higher level of interaction developed between
modified-EPDM and carbon black.
A significantly higher modulus in a sidewall compound is undesirable as it might be expected
to produce a greater stress concentration in the shoulder region of the tire, thus increasing
the risk of failure at this point.

Tensile properties of black-filled blends (50 phr N660, 10 phr oil, 2 X tmax/170 °C).

Tensile properties of black-filled blends (50 phr N660, 10 phr oil, tmax/150 °C).

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It is clear from the above that a formulation suitable for NR/BR tire sidewalls is inappropriate
for a 60:40 NR modified-EPDM blend.
Although there are a large number of possible variables to consider in the development of a
NR/ modified-EPDM blend appropriate for tire side-walls, some simplifications may be made.
The polymer blend ratio can be set at 60:40 NR-EPDM to ensure adequate ozone resistance of
the compound (71. A particular EPDM grade (Polysar 585) had been adopted initially as it has
a very high level (~11%) of ethylidene norborneny1 (ENB) unsaturation, it is readily available
and has given particularly good performance in the more basic studies of NR/modified EPDM
blends.
Although modification of EPDM with 4, 4-dithiodimorpholine (DTDM) has made possible high
levels of interaction between the polymer and carbon black and provided good reversion
resistance and in a blend with NR, current concern in the rubber industry regarding the
possible formation of nitrosamines during vulcanization would appear to exclude the
commercial use of TDM as a modifying agent.
Initial work on the level of modifier to use suggested overall levels up to about 2 phr, with
there being no benefits to using higher levels of modifier. Subsequent work showed that a
com-bination of 0.8 phr BAPD with 0.4 phr DID was the most appropriate for a range of
properties.
A reinforcing grade of carbon black (N339) was selected for use in NR/modified-EPDM
sidewalls in order to match the abrasion resistance of current NR/BR sidewalls containing
N660 carbon black.
The EPDM modification procedure requires a separate masterbatch then cross-blend mixing
stages which permit different black loadings to be used in the two phases of the blend. This
possibility may bring additional benefits not available from a single-stage mixing procedure,
although identification of appropriate black loadings for each masterbatch would be a
complex matter involving considerable experimentation.
A suitable cure system based on sulphur and CBS has been identified after comparisons with
a typical NR/BR sidewall compound and by using crosslink density measurements obtained
by the swollen-state NMR spectroscopy of gum blend vulcanizates.
Of the variables identified above, perhaps the three most difficult to assess without further
experimentation are black loading in each of the separate masterbatches and the overall oil
level in the blend. The most efficient way of assessing three such variables is to use an
experimental design approach.

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Table: Design compound formulations

10.3 DESIGN COMPOUND FORMULATIONS

Blends having the preferred formulation were prepared in mixers fitted with tangential
(Banbury) type and intermeshing (Intermix) type rotors up to relatively large laboratory scale
(~33 kg), thus demonstrating that the reactive mixing EPDM modification technology can be
successfully applied to larger-scale mixing.
Although satisfactory levels of EPDM modification were achieved in all cases, it was apparent
that 'over-modification' could occur if the modified-EPDM masterbatch is allowed to remain
at temperatures in excess of 150 °C for more than about eight minutes.
The manifestation of such 'over-modification' is the development of a very high level of
interaction between the EPDM and carbon black which renders the compound crumbly and
very difficult to process.
Such problems are likely only to be encountered in large-scale mixing in a factory where
delays in production processes downstream of the dump mill can sometimes occur and lead
to freshly mixed compound having to be held back for a period of time.
In a factory operation the time taken to process and cool a large batch on a mill is usually
dictated by the mix cycle time and is usually much less than eight minutes, al though for a
dump extruder processing several consecutive batches, the compound may remain at a
relatively high temperature for longer than on a mill.

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