Rubber

Compounding
Experiment No: 01,02,03

PSC 307 1.0 Polymer

Practical Level 1B
G.A.N.K.Gunawardhana
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Date: 31/10/2023

Experiment No: 01,02,03

Experiment Name: Rubber Compounding, Cure characteristics and Evaluation of properties of

rubber vulcanizates

Objectives:
• To familiarize with the mixing technologies related to rubbers
• To understand and explain the effect of type of filler, antioxidant and vulcanizing
agent/system on physical, mechanical and chemical properties of the vulcanizates
• To select the process operation conditions based on the cure characteristics of a rubber
compound.
• To prepare homogeneous rubber compound of different vulcanizing systems by using two-
roll mill.
• To familiarize with rheometers and rheographs to obtain cure characteristics, processing
characteristics and physical properties of rubber compunds.
• To study the properties of the rubber vulcanizates in terms of tensile, tear, hardness,
rebound resilience, abrasion.

Introduction:

In principle, the basic properties of the elastomers come from their nature. However, the
incorporation of other ingredients into the matrix can modify the properties. Rubber compounding
or formulation is the addition and mixing of several chemicals with raw rubber to obtain the
desired properties. There are several types of adding chemicals such as crosslinking agents,
reinforcements, anti-degradants, accelerators, fillers, and pigments. A good compounding needs
to consider many aspects such as environmental safety, good processability, satisfactory service
life, and minimum production cost.

Table 1:The rubber ingredients and their function in rubber compounds

Ingredients Function
Elastomer The main characteristics of rubber
compounds.
Vulcanizing agent To produce a chemical reaction with rubber
matrix to form crosslinking.
Accelerators Materials To increase the speed of the vulcanization.
Activator To increase the effect of accelerators.
Fillers To reinforce the rubbers.

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 The ingredients are mixed with rubber according to a proportion with the rubber material.
The recipe includes all the ingredients and proportions and is called “formulation”. To indicate
the quantities, the unit used is “phr” (parts per hundred parts of rubber). various aspects of the
end product are taken into consideration such as working environment or temperature, oxidation,
abrasion resistance, chemical resistance, physical properties and other properties in order to
determine the exact proportions at parts per hundred rubber (pphr). During the compounding
process, good distributive and dispersion mixing must be achieved to get a homogenous
compound. Dispersive mixing involves the generation of high shear stress in the rubber melt to
significantly reduce the size of any dispersed particles. It can be achieved by passing the mixture
through small regions of intense deformation. On the other hand, distributive mixing involves
stretching, dividing and reorienting the flow of the rubber melt in order to eliminate local
variations in material distribution.

Most rubbers require a vulcanization process to convert them into elastic and flexible
products. Crosslinks are introduced during the vulcanization process into the rubber matrix to
improve the tensile properties, hardness, abrasion resistance, and others. Generally, a vulcanizing
system consists of three components, which are vulcanizing agent, accelerator, and activator.
vulcanizing agent is normally added in the last mixing stage to avoid pre-mature vulcanization.
There are a few types of vulcanizing systems, which depend on the vulcanizing agent used in the
compounding. For example, sulfur vulcanization, peroxide vulcanization, and also urethane
vulcanization. Three types of sulfur vulcanization system depend on the ratio or Sulphur to
accelerator which are shown in Table 2 below.

Table 2: Different sulphur vulcanization

System Sulfur content, phr Accelerator, pphr

Conventional vulcanization 2.0 - 3.5 1.0 – 0.5
(CV)
Semi- efficient vulcanization 1.0-2.0 2.5-1.0
(semi-EV)
Efficient vulcanization (EV) 0-1.0 0- 2.0

This curing system does not require an unsaturation site as compared to sulphur vulcanizing
system. The types of crosslinks formed in sulphur vulcanizing system is sulphur-sulphur and
carbon-sulphur crosslinks while carbon-carbon crosslink is formed in the peroxide vulcanization
system. Different types of vulcanizing systems will produce rubber compounds with different
Mooney viscosity.

These additives should be mixed with raw rubber in required quantities is very important
to get a product with the desired qualities. Two types of mixing equipment can be used to mix the
additives and raw materials on a laboratory scale and industrial scale. They are an internal mixture
and a two-roll mill. Depending on the physical property requirements of the compound, it can be
prepared by either internal mixture or on mills.
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Internal mixer

A typical internal mixer has two counter-rotating rotors that are encased in a mixing
chamber. The compounding ingredients are added to the mixing chamber. The additives and other
raw components are dispersed by two rotors in the chamber that produce strong shear stresses. A
consistent, high-quality compound is produced as a result of the creation of these shear forces.
Modern mixers are able to consistently create high-quality compounds in massive quantities
because of computer monitoring of internal mixer factors including power usage, temperature
gradients across the mixing chamber, and mix durations.

Figure 01: Internal Mixture

Two-roll mill

Two-roll mill is an open mill with two rollers and they are rotated at different speeds
towards each other. The ratio of the speeds of two rollers called as friction ratio and due to the
friction ratio shear forces are generated on rubber. Also, it is operated under cooling conditions
to prevent scorching. The specific type of compound is what determines how to establish the
variable roll speed ratio. The resulting shear and mixing intensity increase with increasing friction
ratio.
Mill mixing results in lower batch weights takes longer, and uses more energy. However,
the compound's heat history is decreased, which might be useful for processing compounds using
high-performance rapid acceleration devices.

Figure 02: Two Roll Mill

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Mixing operation

The mixing of rubber compounds using an internal mixer usually consists of selectively
charging the mixer chamber with the material, in a series of controlled steps. The prime objective
is to ensure that each compounding ingredient is incorporated into the rubber, and then uniformly
distributed and dispersed throughout the batch. Poor dispersion can result in scorching, non-
reproducible processing in shaping and forming operations, and mechanical failure in service to
mention but a few end effects.

Here only two roll mill was used to form a homogeneous mixture. Then by using
compression molding, a thin rubber sheet was formed and tested by using moving die rheometer,
universal testing machine.

For performing the tensile test on the universal testing machine, one end of the specimen
is gripped in the upper cross-head of the machine, which is a fixed head. The other end of the
specimen is gripped in the adjustable (movable) cross-head. This set-up is schematically shown
in fig.4 Tensile load is gradually applied to the specimen by means of the loading unit of the
machine. In all modern machines a hydraulic drive is used to move the adjustable crosshead
downwards to apply the desired tensile load on the test piece. A separate load-measuring unit
incorporated in the machine shows the magnitude of the applied load.

Figure 3: Universal testing machine for tensile test

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 Figure 04: Diagram of Test piece & Universal testing machine

When developing a compound, the constituents' composition can

be changed until the required vulcanization properties are obtained. By using a rheometer the
curing characteristics of the rubber compound, the processing characteristics, the physical
properties of the material can be determined. The rubber industry uses two different types of
rheometers: moving die rheometers, or MDRs (moving disc rheometers), both of which serve the
same primary function.

Depending on the type of compound and the cross-linking method employed, a test piece
of raw rubber compound is inserted into the rheometer's cavity, and the rheometer is closed,
putting the rubber compound under positive pressure at a certain constant temperature. The test
piece is under shear strain as a result of this operation. The torque needed to cause the disc to
oscillate is determined by the rubber compound's stiffness, or shear modulus. The specimen
becomes more rigid and, thus, the torque on the rotor rises as the compound in the cavity cures
more quickly. Rubber is a non-Newtonian material. The shear modulus is directly proportional to
the cross-linking density. The rheometer thus measures a degree of cure, over time, at a given
temperature. A plot of measured torque value, over time,
produces a typical curing curve.

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 Figure 05: Moving die reometer

Figure 06: oscillating disc rheometer

Rheograph is a cure curve obtained by a “Oscillating Disc Rheometer”, it is one instrument

to determine the kinetic crosslinking. An oscillating rotor is surrounded by test compounds, which
is enclosed in a heated chamber. The torque required oscillating the rotor and it is monitored as a
function of time2. From the cure curve of torque against time, all the vulcanization characteristics
of the rubber compound can be determined directly. The rheograph is divided into 3 phases, which
are explained in Fig. 7:

1- Phase 1: It represents the processing behavior of the rubber compound.

2- Phase 2: It describes the curing characteristics of the rubber compound.
3- Phase 3: It gives an indication of the physical properties of the rubber compound.

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 As the compound gets heated under pressure, the viscosity decreases, and the torque fall.
The lowest value of torque recorded is called ML. It is a measure of the stiffness of an uncured
rubber compound at a given temperature. As the curing starts, the torque increases
proportionately. Depending upon the type of compound, the slope of rising torque varies. After a
while, the torque typically attains maximum value and it plateaus out, it is called the “plateau
curve”. If test is continued for sufficient time, the reversion of cure occurs and torque tends to
fall. This type of curve with reversion is called the “reverting curve”. At times the torque shows
a continuous rising trend during the period of record. Such type of curve is called a “rising or
marching curve”. MH (Max. torque) is the highest torque recorded in the plateau curve. In the
reverting curve, the Max. torque recorded is abbreviated as MHR. Maximum torque can be
expressed measure of stiffness of vulcanized rubber. The difference between maximum and
minimum torques can be expressed as a parameter of crosslink density.

After attaining minimum torque, during the curing phase, scorch time TS2 is recorded as
the torque rises 2 units above ML, scorch is premature vulcanization in which the rubber becomes
partly vulcanized before the product is in its final form and ready for vulcanization. It reduces the
plastic properties of the compound so that it can no longer be processed. Scorching is a result of
both the raising of temperature during processing and the amount of time that the compound is
exposed to elevated temperatures. This period before vulcanization starts is generally referred to
as “scorch time”. Since scorching ruins the rubber, it is important that vulcanization does not start
until this process is complete.

Optimum cure time Tc90 is the time at which 90% of the cure has taken place. The cure
rate is essentially a measure of the linear slope of the rising curve. The rate of cure is the rate at
which cross-linking and the development of stiffness (Modulus) of the compound occur after the
scorch point, when the compound is heated beyond the scorch point, the properties of the
compound change from a soft plastic to a tough elastic material required for use. During the
curing phase, crosslinks connect the long polymer chains of the rubber together. As more
crosslinks are formed, the polymer chains become more firmly connected, and the stiffness
(modulus) of the compound increases. The rate of cure is an important vulcanization parameter
since it determines the required time for the complete curing process. The cure rate index is a
simplified parameter that can be given by the following equation.

CRI = 100/(Tc90-TS2)

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 Fig. 7: Rheograph (cure curve)

Materials:

• Natural rubber
• Carbon black
• Antioxidant (6PPD)
• ZnO
• Stearic acid
• Sulphur
• TMTD
• TBBS
• PVI

Apparatus:

• Electronic balance
• Spatula
• Watch glasses
• Two roll mill
• Oscillating Disc Rheometer
• Universal Testing machine

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Methodology:

Compounding procedure

The formulation/s were referred to and assigned. The weights of each ingredient were
calculated for 300 g of rubber and recorded. The ingredients were weighed according to the
calculated weights and labeled. The rubber was mixed with compounding ingredients, using a
two-roll mill, as per the order given following the mixing cycle, and sheeted out. The compounds
were labeled.

The typical mixing cycle

The rubber was charged to the nip of the two roll mills and mixed until softened into a
uniform mass (3 min). Then activators, slow accelerators, antioxidants, and other ingredients
(other than the vulcanizing agent and fast accelerators) were added through the nip and mixed to
optimize the dispersion (2 min). Fillers and softeners/oils were added in two stages taking half of
each (4 min). The mixture was then dumped onto a metal tray and cooled. Finally, the vulcanizing
agent (and fast accelerators if any) was added using the two-roll mill.

Table 03: Formulations for each group

Group 01 Group 02 (Semi- Group 03 Group 04
(Conventional Efficient V.) (Efficient V.) (Efficient V.+
V.) pre vulcanizator
inhibitor)
NR 100 100 100 100
Carbon Black 50 50 50 50
Antioxidant 1 1 1 1
(6PPD)
ZnO 5 5 5 5
Stearic acid 2 2 2 2
Sulphur 2.5 1.5 0.5 0.5
TMTD 0.35 0.75 1.5 1.5
TBBS 0.43 0.75 1.5 1.5
PVI - - - 0.3

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Readings and Observations:

Group 1,
Time Compoun Shif Lot Batc Temp ML MH TS1 TS2 TC5 TC9 QC
d t No. h . 0 0
7:22:1 17phrgrss 1 A12 1 150 0.1 22.7 0.9 0.9 1.33 2.13 PAS
4 AM 1 3 5 3 0 7 S

Group 1
25

20

15
Torque

10

0
0 2 4 6 8 10 12
Time (min)

Curve 1

Trial 01

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Trial 2

Trial 3

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Trial 4

Group 2,

Date Time Compou Shif Lot Batc Tem ML MH TS1 TS2 TC5 TC9 QC
nd t No. h p. 0 0
6/9/20 8:12:1 17phrgrs 1 A12 1 150 0.1 21.4 1.2 1.3 1.6 2.7 PAS
23 0 AM s1 3 5 7 3 2 0 8 S

GROUP 2
Curve 1

25

20

15
TOQUE

10

0
0 2 4 6 8 10 12
TIME (MIN)

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Trial 1,

Trial 2

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Trial 3

Trial 4,

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Group 3,

Date Time Compou Shif Lot Batc Tem ML MH TS1 TS2 TC5 TC9 QC
nd t No. h p. 0 0
6/9/20 8:57:4 17phrgrs 1 A12 1 150 0.2 18.7 1.4 1.5 2.0 4.6 PAS
23 9 AM s1 3 7 2 2 7 7 7 S

GROUP 3
Curve 1

25

20

15
TOQUE

10

0
0 5 10 15 20 25
TIME (MIN)

Trial 1,

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Trial 2,

Trial 3

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Trial 4,

Group 4,

Date Time Compou Shif Lot Batc Tem ML MH TS1 TS2 TC5 TC9 QC
nd t No. h p. 0 0
6/9/20 9:42:2 17phrgrs 1 A12 1 150 0.2 15.4 1.5 1.7 2.2 5.0 PAS
23 1 AM s1 3 5 8 7 3 8 0 S

GROUP 4
Curve 1

25

20

15
TORQUE

10

0
0 2 4 6 8 10 12 14 16
TIME (MIN)

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Trial 1,

Trial 2,

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Trial 3

Trial 4,

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Calculations:

Group 01 Group 02 (Semi- Group 03 Group 04

(Conventional V.) Efficient V.) (Efficient V.) (Efficient V.+ pre
vulcanizator
inhibitor)
Tensile Tensile Tensile Tensile Tensile Tensile Tensile Tensile
Strength Modulus Strength Modulus Strength Modulus Strength Modulus
(MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa)

Trial 1 1.34 0.00185 1.9 0.0027 1.526 0.00245 1.66 0.00226

Trial 2 1.4 0.00192 2.33 0.0028 1.89 0.00255 1.74 0.00231
Trial 3 1.44 0.00203 1.79 0.002744 1.58 0.00248 1.58 0.00213
Average 1.393333 0.001933 2.00666 0.002748 1.665333 0.00249 1.66 0.00223

CRI = 100 / (𝑡90−𝑡𝑠2)

Group 01 Group 02 (Semi- Group 03 Group 04

(Conventional Efficient V.) (Efficient V.) (Efficient V.+
V.) pre vulcanizator
inhibitor)
T90 (min) 2.13 2.78 4.67 5
Ts2 (min) 0.97 1.32 1.57 1.73
CRI 86.2069 68.49315 32.25806 30.58104

Discussion:

In this experiment, four different formulations were used to compound the natural rubber
latex. By varying the ratio of accelerator-to-sulfur, the sulfidic linkages between the rubber chain
were formed with various sulfur atoms (C-S-C, mono-sulfidic; C-S2-C, di-sulfidic and C-Sx-C,
poly-sulfidic, where x can vary 3 to 6) resulting in the different end used properties of rubber
such as curing properties, mechanical properties, thermal stability, and aging properties.

Generally, the vulcanized rubbers with CV system have high crosslink density which
contains predominantly polysulfudic linkages resulting in good mechanical properties for
products. In contrast, semi-EV and EV systems give enhanced thermal properties due to forming
mono- and di-sulfidic linkages, but at the expense of reducing mechanical properties compared
to the vulcanized rubbers with CV system. This is caused by lower crosslink density. In here
TMTD is used as the accelerator.

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 The cure characteristics of the rubber compound were obtained from rheographs. The cure
characteristics, expressed in terms of ts2, t90, CRI, ML, MH, and MH–ML, for vulcanized NR
in each group are calculated and listed in the calculation part. The ts2 is the time that vulcanization
begins, while t90 is the optimum vulcanization time.

According to the obtained results, the greatest tensile strength value can be seen in the
semi-efficient system and the highest tensile modulus value can be seen in the efficient system.
Because the combination contained pre-vulcanizing inhibitors, sample 04 yielded the greatest
cure time value. It prolongs the time needed to vulcanize the rubber sample and stops the
vulcanization process before heating.

Among the three sulfur vulcanization systems, the EV system contained the highest
accelerator concentration. However, the EV system showed unexpected results when the ts2 and
t90 were the longest, while the CRI referred to the rate of vulcanization was the lowest. On the
other hand, the CV system exhibited shorter ts2 and t90 than the semi-EV system.

The types of sulfur vulcanization systems had no strong effect on the changes of ML
indicating to the similar uncured modulus and processing properties, while dependencies were
observed for MH and MH–ML.

References:

1) https://www.sciencedirect.com/topics/engineering/internal-mixer (25/11/2023)

2) COMPARISON AND TESTING OF TENSILE STRENGTH FOR LOW & MEDIUM

CARBON STEEL”
DEVENDRA YADAV& ABHISHEK GAIKWAD
International Journal of Mechanical Engineering (IJME)
ISSN(P): 2319-2240; ISSN(E): 2319-2259
Vol. 4, Issue 5, Aug - Sep 2015, 1-8 (26/11/2023)
3) https://www.researchgate.net/publication/299535637_COMPARISON_AND_TESTING
_OF_TENSILE_STRENGTH_FOR_LOW_MEDIUM_CARBON_STEEL (17/11/2023)

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