Contents

1. Introduction
1.1 Aim of Work

2. Theoritical Learnings
2.1 Types of Polymer Blends
2.1.1 Elastomer/Elastomer Compounds
2.1.2 Thermoplastic /Elastomer Compounds
2.1.3 Thermoplastic / Thermoplastic compounds

3. Experimental
3.1 Materials
3.2 Techniques
3.3 Measurements
3.3.1.1. Tensile Strength (TS)
3.3.1.2. Tensile Modulus at 100 %( M 100)
3.3.1.3. Elongation at break %(Eb%)
3.3.1.4. Hardness
3.3.2. Physical Measurement
3.3.2.1. Detremination of Gel fraction %( GF %)
3.3.2.2. Detremination of swelling number (SN)

4. Analysis and Conclusion

 INTRODUCTION
In the present investigation, mixtures of natural rubber (NR) and styrene-
butadiene rubber (SBR) were created, and each component's characteristics
were investigated. These attributes consisted of the blend's morphology, which
refers to its physical structure, as well as its transport behaviour, which refers to
the method in which substances flow through the blend, as well as its dynamic
mechanical and mechanical properties. Certain transport characteristics such as
diffusivity, captivity, and permeability were computed after the transport
behaviour of the SBR/NR mix was tested under the impact of n-alkanes, also
known as hydrocarbons, in the temperature range of 25-60 degrees Celsius. The
study was conducted. In addition, phantom and affine models were used to
conduct an analysis of the network structure of the mix. The researchers also
investigated the effect that the blend ratio had on the dynamic mechanical
characteristics of the SBR/NR mix at various temperatures. They discovered that
the storage modulus of the blend dropped as the temperature increased. In the
end, the researchers attempted to establish a correlation between the blend's
properties and its morphology. Furthermore, they carried out mechanical tests
on unswollen, swollen, and reswollen samples in order to gain an understanding
of the stability of the membranes that were produced using the blend.

AIM OF THESIS

The integration of chemical compound substances has proved to be AN

efficacious suggests that of making novel chemical compound materials that
possess not solely the basic attributes of the mix elements, however conjointly
new and specific modifications. As a result, the mixing technique has become a
fascinating and commercially viable one. Rubbers, being solid chemical
compound materials, square measure usually homogenized through mechanical
suggests that.
The current investigation involves the creation of blends from 2 forms of rubber:
natural rubber (NR) and artificial vinyl polymer hydrocarbon rubber (SBR). each
NR and SBR square measure organic compound amorphous rubbers that serve a
general purpose, though' NR could be a homopolymer with a daily structure that
crystallizes upon stretching, while SBR, consisting of 2 monomers, exhibits a
random structure that doesn't crystallize beneath constant circumstances. in
addition, the properties of SBR will vary supported the quantitative relation of
its monomers, vinyl polymer and hydrocarbon. the precise form of SBR utilised
during this study contains twenty three.6 wt.% styrene. it's anticipated that the
mixing of NR and SBR can end in complementary properties.
Rubber and rubber compounds square measure typically utilised during a
processed state, characterised by a network structure, so as to resist numerous
styles of stress. vulcanisation is usually achieved through the formation of
chemical crosslinks between rubber macromolecules and vulcanizing agents, like
sulfur. during this regard, radiation, like gamma rays, has been found to be
effective in causing chemical crosslinking between rubber molecules within the
absence of additives like sulfur. In fact, the radiation vulcanisation method has
been shown to be economically viable and offers various benefits not gettable
through alternative thermo-chemical ways, as well as the flexibility to use the
next proportion of artificial SBR rubber in NR blends while not a decrease in
cohesive strength. Therefore, this investigation aims to utilize numerous doses
of gamma rays to induce vulcanisation and examine the mechanical, physical,
and thermal properties of the ensuing blends.
Fillers square measure oftentimes additional to rubber compounds for
numerous functions, like rising mechanical properties or increasing volume. As
such, this study aims to include differing types of fillers, as well as Hisil, HAF,
atomic number 6, clay, and oxide (TiO2), into NR/SBR blends during a mounted
quantity of forty phr (parts per hundred elements of rubber). Again, the impact
of irradiation on the properties of the ensuing rubber mix composites are
evaluated.
In radiation vulcanisation, it's fascinating to realize the best properties of rubber
compounds at the bottom doable dose of irradiation so as to forestall
degradation processes from occurring at higher doses. This goal is achieved by
victimization organic molecules with giant molecular weights and double bonds
in their structure, referred to as coagents, that participate within the formation
of chemical bonds with rubber macromolecules upon irradiation and enhance
the degree of crosslinking. Therefore, this investigation aims to utilize 3
coagents with varied numbers of double bonds: N, N-methylene diacrylamide
(MDA), trimethyl gas TriMet salt (TMPTMA), and characid methyl gas tetra salt
(TMMT). The impact of irradiation on the properties of increased NR/SBR
composites will be examined.

Theoretical Pre-requisites
the process of blending two or more polymeric components together is often
regarded as an inefficient and unpopular way to modify the final product's
qualities. Because of their distinct chemical make-ups and structural
arrangements, the various types of rubber each have their own set of drawbacks
and applications that cannot be used with them. Because of this, rather than
generating a new elastomer by chemical means, it is more cost-effective to
combine the shortcomings of two or more different forms of rubber by blending
together numerous types of rubber, each of which has the undesirable property in
question.

Types of polymer blends:

1. Elastomer /elastomer compound:
2. Thermoplastic-thermoplastic compounds:
3. Elastomer /thermoplastic compounds:

Elastomer /elastomer compound:

Polymers in the colloidal size range have a large aspect ratio, leading to a complex, entangled
structure that resembles spaghetti. This interwoven quality causes these polymers to have a high
level of viscosity, requiring a lot of energy to flow. It can be difficult to extract a single strand
from the tangled mass, often resulting in the formation of knots. Elastomers, also known as
rubber, are macromolecular materials that quickly return to their original dimensions and shape
after being subjected to significant deformation by a small stress and the release of that stress.
Thermoplastic-thermoplastic compounds:
We looked into the effects of three commercial accelerators on the processability
and mechanical properties of a blend of 60% natural rubber and 40% ethylene
propylene diene monomer (NR/EPDM). These accelerators belonged to the
sulfonamides group (Santo cure-TBBS), the thiuram group (Perkasie-TMTD),
and the mercaptide group (Perkasie-MBT, Perkasie-MBTS). Our results showed
that the accelerator type had a major impact on the compound's viscosity as well
as the curing properties. Particularly, we discovered that TBBS offered high cure
compatibility between the NR and EPDM phases, leading to improved
mechanical characteristics. However, TMTD led to substantial cure
incompatibility and low tensile strength despite its high cure state attainment. The
reduced reactivity of the two mercaptide accelerators led to vulcanizates with low
modulus, hardness, and degree of elasticity, whereas the tensile strength of the
mix cured with MBTS was rather high.

Elastomer /thermoplastic compounds:

These materials which behave like thermoplastic elastomers. Models accurately

anticipated the phase inversion composition. Mix proportions affect tensile strength,
elongation at break, tension set, and hardness. Carvalho et al. produced thermoplastic
starch/natural rubber polymers in 2003. Blends containing 2.5% to 20% natural rubber
were made in a high-output batch mixer at 150°C. The blends were analysed using
stress-strain and SEM. As expected, modulus and tensile strength dropped. Some mixes
displayed phase separation, depending on the rubber and plasticizer (glycerol). Increased
plasticizer allowed for more rubber. SEM demonstrated a homogeneous distribution of
natural rubber in the thermoplastic starch matrix's continuous phase. Pathum et al. (2007)
researched radiation cross-linking of an insulator for thin electrical wires manufactured
from phthalic anhydride and nonylphenol. The gel content of NR/LDPE blends with
50/50 and 60/40 ratios increased with radiation dosage.

Filler on Rubber compounds

The Compounding of Rubber (RT60003) discusses the manufacturing of

vulcanizing agents, accelerators, antioxidants, blowing agents, flame retardants,
and other additives that are used in the compounding of rubber, as well as their
purposes.
The course titled "Rheology and the Processing of Materials" (RT60015)
discusses the physics and technology of mixing, including the use of internal and
two-roll mixers, as well as the rheological principles and processing methods,
such as calendaring and extrusion.

Evaluation of Rubbers Using Physical Methods (RT60013) involves determining

the resistance of the material to liquids by conducting swelling tests, dynamic
tests, tests of rebound resilience, and low temperature tests. Additionally, the
dynamic stress-strain characteristics of the material are analysed. This also
involves establishing the material's permeability, electrical properties, and
resistance to ageing, in addition to determining the adhesion and binding strength
of rubber to fabric and rubber to metal with the use of applicable testing standards
such as ISO, ASTM, and ISI.

Effect of coagent on rubber compounds

Exposing certain polymers, called crosslinking polymers, to radiation can
improve their dimensional stability and mechanical properties. However,
some types of rubber require large amounts of radiation to achieve the
desired level of crosslinking. Unfortunately, exposing these materials to
high doses of radiation can also damage their mechanical properties due to
radiation deterioration. In a study, the process of radiation vulcanization of
natural rubber latex was accelerated using phenoxy ethyl acrylate (PEA)
and another chemical called TMPTMA. The results showed that PEA is a
more effective accelerator for this process because it gives the rubber
similar physical properties to n-butyl acrylate, which is commonly used as
an accelerator. However, PEA has a slightly weaker sensitizer effect
compared to n-butyl acrylate, so slightly higher doses may be needed to
achieve the same physical properties. The experimental data on the
permeation of the SBR/NR blend was fit using several different composite
models, and it was found that the Robeson model matched the
experimental data for the N50 component exactly. The enthalpy of sorption
shows that Henry's law type sorption occurs in SBR, but as the volume
fraction of NR increases, this type of sorption changes to Langmuir-type
sorption. The network characterization results showed that the crosslinks in
the SBR/NR blend deform in an affine manner, and the degree of
crosslinking has a significant impact on the measured properties. It was
found that the order in which the degree of crosslinking is determined by
swelling, tensile stress-strain, and dynamic mechanical analysis is the
same, but the degree of crosslinking calculated using dynamic mechanical
analysis is significantly lower than the others.

EXPERIMENT
The following procedures were taken into account before, during, and after
the mixing process:

• After going through the rollers without being banded the first two times
at a roll opening of about 0.2 mm, the rubber was then banded using a
mill opening of approximately 1.5 mm. There was a cut made every thirty
seconds, alternating between the two sides.
• The temperature of the roller was maintained at 70 degrees Celsius at all
times.
• The amount of time spent grinding (mastication) was regulated and
hovered around ten minutes on average. During the process of
masticating rubber blends on the rubber mill, all of the elements that
were measured out were completely integrated.
• After mixing, the weight of the blends was measured again to confirm
that there was not a significant loss of weight (more than 0.5%).
• Using a hot press set to 110 degrees Celsius for twenty minutes and with
16 megapascals of pressure, the compound was crushed into a sheet one
millimetre thick.

Morphology
For the SEM research, cryogenically fractured samples were used, and the process was
conducted in liquid nitrogen. By soaking the broken edge of the samples in petroleum ether for
72 hours at room temperature, it was possible to preferentially extract the NR phase from the
cryogenically fractured samples. The samples from which the NR had been removed were then
dried in an air oven. After this, the samples were coated with gold using sputter coating, and the
scanning electron microscope used to take pictures was a Phillip's model.

M M t
L H ts1 ts2 90 CRI
Blend Ratio (den m) (den m) (m : s) (m : s) (m : s) (min21)

N0 (SBR1000) 1.16 17.13 72.48 82.48 17.022 11.271

N
30 (SBR770/NR300) 0.749 71.23 5.459 6.453 13.029 15.224
N
50 (SBR560/NR506) 02.654 6.712 4.459 5.254 112.40 17.026
N
70 (SBR630/NR760) 10.53 6.091 43.06 5.2105 102.23 19.320
N100 (NR1600) 02.61 4.852 33.12 4.416 120.05 17.829

Morphology of Blends

The microstructure of a mix of SBR and NR polymers may be affected by the relative
quantities of each component, the viscosity of the individual components, as well as the
processing history of the blend. Other factors that can have an effect on the
microstructure include temperature and time. In many types of mixtures, the component
that has a lower viscosity has a greater tendency to form the continuous phase throughout
a broad range of different concentrations. In the instance of the SBR/NR blends that were
investigated in this article, the morphology may take on a variety of forms, ranging from
the NR existing as tiny domains spread across an SBR matrix to the NR forming a
continuous phase with SBR present as dispersed domains. The permeation qualities of
the mix may be significantly influenced, both directly and indirectly, by the size and
location of the scattered domains. These mixes seem to have a heterogeneous
composition, as seen by the SEM photos.

Rubber Sample Preparation

Two processes, mastication and compounding, were used to make the rubber samples. In
the mastication phase, the rubber was combined for 5 minutes on a laboratory two-roll
mill before a measured quantity of filler (Posi or Fasi) was added and the mixture was
processed for a further 20 minutes. At the compounding stage, vulcanization chemicals
were added to the rubber and filler while being blended for an extra 20 minutes on a two-
roll mill. The resultant compounds were kept in storage at 25 degrees Celsius and 50
percent humidity until further evaluation. There were 100 parts rubber to 5 parts zinc
oxide to 2 parts stearic acid to 0.5 parts mercaptobenzthiazole to 0.2 parts diphenyl
guanidine to 3.0 parts sulphur in the rubber utilised in the investigation.

Measurements

1. Specimens

4 millimetres in terms of the width

length: 50 millimetres

2. Tensile Strength

The formula takes into consideration factors such as load, breadth, and thickness.

Tensile Modulus at 100% force required per unit area to stretch specimen to a
certain elongation (in megapascals)

"Tensile Strength" (TS) = "Length over Weight" (101 MPa)

Where:

L = Breaking Load Necessary

Dimensional data in centimetres for the specimen's width, W

T = sample thickness in centimetres.

3. Elongation at Break

A measurement of how far a piece of rubber can stretch before snapping

(expressed as percentage of distance between benchmark measurements)

Eb (%) = (L-L0/L0) ×100

4.Hardness

Evaluated using a durometer, with findings given on the Shore A scale

5.Swelling Number

Shows the amount by which the specimens expanded after being immersed in the
solvent Gel Fraction Percentage the proportion of the total sample weight that is
insoluble upon extraction

Gel fraction % = (W1/W0) x100

6.Thermal Readings and Temperatures

Performed with the help of a Shimadzu TGA-50 Examination of Rubber and

Rubber Mixtures a scanning electron microscope was used investigate the
structure and morphology.
 ANALYSIS AND
CONCLUSION
Dynamic Mechanical Analysis:

The dynamic mechanical characteristics (such as storage modulus, loss modulus,

and damping) of three different kinds of rubber (SBR, NR, and their mixes) were
examined at a variety of temperatures. These qualities include storage modulus,
loss modulus, and damping. In order to evaluate whether or not the system was
compatible, a dynamic mechanical examination was carried out. This research
looked at how the damping varied as a function of temperature. In most cases, the
damping curve for incompatible blends will have two peaks that correspond to
the temperatures at which the glass transition occurs in the different polymers. In
the case of blends that are very compatible, there will be a single peak between
the transition temperatures; however, in the case of mixes that are only partly
compatible, the transition will be widened. The glass transition temperature, or
Tg, of the blends may also be altered to higher or lower temperatures depending
on how well they are compatible with one another and the components that make
them up. It was discovered that NR had a damping that was much greater than
that of SBR. The mixtures displayed two peaks at around 254 and 235 degrees
Celsius, which is evidence that they cannot be used together. Temperature and
NR concentration also had an effect on the blends' storage modulus and loss
modulus values, respectively. The two-phase structure of the SBR/NR blends was
verified by the use of dynamic mechanical analysis. The storage modulus grew as
the frequency of the measurement increased, but it reduced as the temperature
increased. At first, a rise in frequency resulted in a reduction in the loss modulus,
but this effect was reversed after the system passed through the transition area.
When the temperatures were low, the tan values went down as the frequency
went up, while the opposite was true when the temperatures were high. The tan
max moved to higher temperatures at greater frequencies as the temperature
increased. The viscoelastic properties of the mixes were sensitive to changes in
temperature as well as frequency.
Variation of tan _ with temperature of SBR/NR blends.

Cross links after 60-100 units

No crystallization at room
temperature.
Mechanical Properties
In order to get a better understanding of how rubber samples deform when a load
is applied to them, the stress-strain curves of the samples in their various states
(unswollen, swollen, and reswollen) were studied. The curves of deformation for
the homopolymers and their blends were very comparable to one another. At low
strain levels, the blend that had the greatest concentration of SBR displayed the
most stress, while the blend that contained the highest concentration of NR
displayed the lowest stress. The amount of tension needed to shatter the samples
rose as the percentage of NR in the samples increased. After the samples had
reached equilibrium saturation in n-hexane, there was a shift in the stress-strain
behaviour of the enlarged samples. The stress levels at low strain levels followed
the same pattern as the unswollen samples, but the maximum stress rose with
increasing NR content up to 50%, after which it declined. The unswollen
samples' stress levels at low strain levels followed the same pattern as the
unswollen samples. This was because the swelled samples, especially those with
a high NR concentration, did not exhibit any behaviour consistent with strain-
induced crystallisation. As a result of the presence of solvents in the swelled
samples, the mobility of the polymeric chains was reduced, which made orienting
challenging. There was an overall increase in the magnitude of the maximum
stress value, but the stress-strain behaviour of the reswollen samples was
comparable to that of the unswollen samples. After going through the sorption-
desorption process, it was determined that the increase in characteristics was due
to enhanced interchain interaction. The homopolymers and blends both exhibited
an improvement in their mechanical characteristics (such as tensile strength and
elongation at break) as they progressed from N0 to N100. Because the value of
Young's modulus increased from N0 to N100, it can be deduced that initial
stretching of SBR and blends with a larger percentage of SBR need a greater
amount of stress. There was an overall decrease in the magnitude of all
mechanical characteristics when the material was in the swelled condition. The
glass transition temperature of the swelled specimens and the interchain
interaction were the two elements that determined how the tensile behaviour of
the swollen specimens was affected. The Young's modulus and tensile strength of
the reswollen specimens both rose, however the elongation at break went in the
other direction. Frequency had an effect not only on the mechanical qualities of
the rubber samples but also on their chemical composition. The loss modulus and
tan values altered in different directions at low and high temperatures, whereas
the storage modulus changed in the other direction as the frequency rose. The
viscoelastic properties of the mixes were sensitive to changes in temperature as
well as frequency.
 Tensile Elongation Young's Secant Modulus (MPa)
Strength at Break Modulus
M M M
Sample System (MPa) (%) (MPa) 100 200 300

Unswollened N 11.82 371 11.36 01.43 11.05 01.24

N
20 24.59 862 12.22 03.62 11.01 91.35
N
z0 15.24 869 05.80 03.66 20.98 81.34
N
70 63.09 1057 07.62 09.64 30.96 61.27
N
900 64.63 1059 07.35 09.37 50.58 30.79
Swollened N0 05.70 225 70.68 0.493
N
37 40.90 2911 07.49 09.38 70.66
N
55 13.04 3422 07.59 0.936 70.63 40.90
N
74 02.64 3622 90.43 08.27 70.42
N
900 01.54 3940 09.32 07.20 70.32 20.42
Deswollened N0 12.89 348 17.72 03.883
11.52
N
80 42.62 8740 18.545 02.749 81.119 4
N
70 52.40 842 61.69 120.814 81.159 21.60
N
50 62.25 1022 07.603 01.959 81.343
N
100 61.81 1040 08.976 04.625 81.04 21.40

Stress-Strain Curve for reswollen SBR/NR Blends

 Summary
In this work, we investigated how the transport behaviour, as well as the
mechanical and dynamic mechanical characteristics of SBR/NR blends, are
affected by the blend content. According to the findings of the SEM study,
the compositions of the 50/50 and 30/70 SBR/NR blends showed a
continuous structure. The findings of the DMA experiment proved that
SBR and NR blends are incompatible. This was shown by the appearance
of two relaxation peaks that corresponded to the Tg values of SBR and NR.
When there is a higher concentration of NR, there is a corresponding
reduction in the blend's storage modulus, which is accompanied by an
increase in the blend's loss modulus and tan delta. Blends have mechanical
characteristics that are midway between those of homopolymers and those
of the blends themselves. Because of the intense contact that occurs
between the rubber and the solvent during the swelling process, the
characteristics of the swollen samples are drastically diminished. In
addition, a number of transport characteristics demonstrated that the mix
has a heterophase character. The diffusion coefficient, the permeation
coefficient, and the sorption coefficient are all somewhere in the middle of
what the separate components have. After attempting to match the
experimental permeation data with a variety of composite models, it was
determined that the Robeson model provided the best fit to the
experimental values for the N50 composition. Based on the enthalpy of
sorption, it can be deduced that Henry's law-type sorption occurs in SBR.
However, when the volume fraction of NR increases, this kind of sorption
transitions into Langmuir-type sorption. According to the findings of the
network characterisation, the crosslinks in the SBR/NR blends deform in
an affine fashion. It was discovered that the degree of crosslinking that was
determined via swelling, tensile stress-strain, and dynamic mechanical
analysis is in the same order. This is noteworthy since the degree of
crosslinking has a substantial impact on a variety of characteristics. The
degree of crosslinking that can be detected by dynamic mechanical analysis
is, however, much lower than the degree that can be established through
the other approaches.