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Determination of the most efficient form of sulfur for use as a natural rubber
curing agent by comparison of physical and thermal attributes of cured rubber

Article  in  Petroleum Chemistry · January 2018

DOI: 10.1134/S0965544118010048

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ISSN 0965-5441, Petroleum Chemistry, 2018, Vol. 58, No. 1, pp. 89–93. © Pleiades Publishing, Ltd., 2018.

Determination of the Most Efficient Form of Sulfur

for Use as a Natural Rubber Curing Agent by Comparison
of Physical and Thermal Attributes of Cured Rubber1
Alireza Motavalizadehkakhky and Hedieh Shahrampour*
Department of Chemistry, Faculty of Science, Islamic Azad University, Neyshabur Branch, Neyshabur, Iran
*e-mail: Hediehshahrampoor@yahoo.com
Received January 30, 2017

Abstract⎯Vulcanization, by creating a three-dimensional cross-linked network, improves the physical-

mechanical and thermal properties of elastomers. A popular agent for curing natural rubber (NR) is sulfur.
Insoluble sulfur (IS) and rhombic sulfur (RS) are common allotropes of elemental sulfur. In this research, it
was observed that the use of the two types of sulfur (IS and RS) gives different results. In terms of cure behav-
ior, tear resistance and hardness, RS-vulcanized NR performed better, whereas in viscosity, tensile strength,
aging and compression set, IS-vulcanized NR was better; because of the lack of blooming, IS could replace
of rhombic sulfur as the curing agent in certain applications.

Keywords: cross-linking, sulfur, cure behavior, thermal properties, rubber

DOI: 10.1134/S0965544118010048

INTRODUCTION vulcanization of natural rubber the cross-links may

Rubber, in its natural state, is not durable, is very
sticky, and will begin to deteriorate in a matter of days.
The rubber industry essentially started in 1839 when
Charles Goodyear discovered vulcanization (the cur-
ing process). In fact, rubber is essential for a modern
industrialized economy. Natural rubber obtained from
the Hevea brasiliensis tree is currently the only natural
rubber resource commercially available. It is an
important material in the rubber industry, particularly
for the manufacture of rubber tires [1–3].
Vulcanization (curing) of rubber is a chemical pro-
cess whereby polymer molecules are linked to other
polymer molecules by atomic bridges. In general, the
process is brought about by heating rubber in the pres-
ence of sulfur cross-linking agents, which are used to
form chemical links between molecular chains, result-
ing in a three-dimensional network of connected mol-
ecules. The degree of cross-linking can have a pro-
found impact on the swelling characteristics of the
cross-linked system [4].
The vulcanizing agent reacts with unsaturated
polyisoprene chains in NR, forming cross-links that
tie the molecules together chemically at certain points
throughout the solid material. This is an essential step
in developing full elastomeric properties, as the pres-
ence of cross-inks ensures the largely elastic recovery
of the material after gross deformation. In the sulfur
1 The article is published in the original.
involve one, two or several S atoms, depending on the
cross-linking conditions and other agents. Unvulca-
nized natural rubber, although somewhat soft, mani-
fests definite elastomeric properties, despite its lack of
chemical crosslinks [5].
Sulfur is the most commonly used cross-linking
agent for all general-purpose rubber. This is because of
sulfur is inexpensive and widely available, and has
good mechanical properties. Insoluble sulfur is the
amorphous form of elemental sulfur; it is insoluble in
CS2 and is polymeric in nature with a molecular
weight of 100000 to 300000. This form of sulfur is
insoluble in the most solvents and rubbers; hence the
name, insoluble sulfur. Because of its persistence it
resists migration to the surface prior to curing, hence
blooming of sulfur does not take place. It is use in
compounds where blooming will not occur go deteri-
orate building tack [6].
Sulfur blooming may be prevented by the use of
insoluble sulfur and the controlling mixing tempera-
ture as insoluble sulfur gets converted to the soluble
form at about 90°C [7].
The only stable form of sulfur at STP conditions is
the well-known orthorhombic α-S8 modification,
which was known even in antiquity. It is no wonder
that this allotrope has been by far the best studied.
Although there is a considerable amount of knowledge
on the structural, physical and chemical properties of
α-S8, there are also still experimental and theoretical

89
90 ALIREZA MOTAVALIZADEHKAKHKY, HEDIEH SHAHRAMPOUR

Table 1. Compounding recipes used in this work TESTING

a
Amount, phr
Chemical ingredients
IS RS
Natural rubber (NR) 100 100
Stearic acid 1 1
ZnO 3 3
TBBS 1 1
Insoluble sulfur (IS) 2 –
Rhombic sulfur (RS) – 2
a
phr = part per hundred of rubber.
ambiguities. For example, there are contradictory
reports on the thermal volume expansion below 300 K
[8, 9].
The purpose of this work was to study of the poten-
tial utilization of insoluble sulfur as vulcanizing agent
in the rubber industry rather than rhombic sulfur usu-
ally used for vulcanization of natural rubber (NR).
EXPERIMENTAL
Materials. NR (SCR 5) was purchased from the
Yunnan Natural Rubber Industry Co., Ltd, Kunming,
China. Rhombic sulfur was supplied by Chemmin Co.
Ltd. Insoluble sulfur was supplied by Eastman Chem-
ical Co. Ltd. Stearic acid and zinc oxide (ZnO) were
purchased from Chemmin Co. Ltd. N-tert-butyl-2-
benzothiazole sulfenamide (Santocure-TBBS) was
from Reliance Technochem Co.
Compound preparation. The test materials (vulca-
nized rubber) were formulated as shown in Table 1.
According to ASTM method D-3182. The raw rubbers
were first masticated in the laboratory-scale, open,
two-roll mill (LabTech, Model LRM 150, Thailand)
for ten minutes. Zinc oxide, stearic acid and the other
additives were added sequentially to the masticating
natural rubber. Finally, the different forms of sulfur
were added to separate batches of NR-additives mix-
ture, and these were mixed for another ten minutes of
curing. The rubber samples thus prepared were kept at
ambient temperature for at least 24 h before measure-
ment of their physical and thermal properties.
The cure characteristics of the mixes were deter-
mined at 180°C using a Moving Die Rheometer
(MDR) (SANTAM, Model SRT-200B, Iran),
according to ASTM-D-5289, ISO-6502. The opti-
mum cure time (T90), scorch time (Ts2), minimum
torque (ML), maximum torque (MH), and cure-rate
index (CRI) was calculated as Eq. (1) [1].
CRI = 100 ( T90 −  Ts 2 ) . (1)
The viscosity of the rubber compounds was mea-
sured at 121°C in a single-speed rotational Mooney
viscometer (model ML (1 + 4) SMV-200) according
to DIN-53525, ISO-289, and ASTM-D-1646 Stan-
dard. The results were expressed in Mooney Units
(MU). The tensile strength, Young’s modulus
and elongation at break were done according to
ASTM-D-412. The rubber vulcanizates were analyzed
on Universal testing machine H10KS with dumbbell-
shaped test-pieces 20 mm long, 4 mm wide and 2 mm
thick. For each type of rubber, three test pieces were
fractured, and the median of the three values was sub-
sequently noted.
Aging resistance was determined at 70°C for 7 days
as per ASTM-D-573. The values for the tensile prop-
erties, elongation at break and hardness (both before
and after aging) were determined. The percentage of
retention was calculated as Eq. (2) [10].
Value after aging
Retention =   × 100 . (2)
Value before aging
Compression testing of the rubber specimens was
done according to ASTM-D-395. Samples com-
pressed to a particular thickness were heated in an air
oven at 70°C for 22 h. The hardness of the cured mate-
rial was measured according to ASTM-D-2240-97
using a Shore A type durometer hardness tester,
Yingkou Testing Machine Co. Reported hardness val-
ues are the average of readings taken at three different
locations on each sample at room temperature.
Tear resistance of the materials was measured on an
Instron Universal Testing Machine at a crosshead
speed of 500 mm/min according to ASTM-D-624.
Resistances to ozone for the vulcanized rubber
specimens were determined in a Dongguan Yuanyao
Electronics Technology Co. Ltd. Ozone resistance
test chamber, according to ASTM-D-1149.

Table 2. Cure characteristics of vulcanizates

Specimens T90, MM:SSa Ts2, MM:SS T50, MM:SS ML, dN.mb MH, dN.m CRI, min–1
IS-NR 00:46 00:26 00:33 2.00 21.53 500
RS-NR 00:43 00:25 00:31 1.12 24.47 555.5
a MM:SS = Minutes:Seconds.
b dN.m = Desi Newton. Meter.

PETROLEUM CHEMISTRY Vol. 58 No. 1 2018

 DETERMINATION OF THE MOST EFFICIENT FORM OF SULFUR 91

RESULTS AND DISCUSSION Table 3. Rheological behavior of vulcanizates

Curing characterization. The cure behaviors of the
vulcanized rubber specimens are compared in Table 2.
Obviously, the scorch times TS2, the times before the
onset of vulcanization, and indication of scorch safety
time show similar results. The optimum cure times
T90, measures of cure rates or an estimate of cure times
at the test temperature, were somewhat less for RS-
vulcanized NR, which is consistent with the increased
cure rate index (CRI). The minimum torque (ML)
relates crudely to the processability of the rubber com-
pound and was lower for RS-vulcanized NR. On the
other hand, the maximum torque (MH), which relates
to the ultimate crosslink density resulting from the vul-
canization process, was higher for RS-vulcanized NR.
Rheological behavior. The rheological behaviors of
the vulcanized rubber specimens are shown in Table 3.
The minimum viscosity (MV) as measured with
Mooney viscometer was higher for IS-vulcanized NR
than for RS-vulcanized NR, presumably because of
the long polymeric sulfur chains IS-vulcanized NR.
Hardness. The results of the hardness tests of the
vulcanized rubbers are illustrated in Fig. 1. The pri-
mary use of hardness testing, using the Barcol hard-
ness test, of materials is to assess cure. This test
showed that RS-vulcanized NR is harder than IS-vul-
canized NR.
Tensile strength. The results of the tensile strengths
of vulcanized rubber specimens are shown in Tables 4
and 5. Results of measurements of tensile strength,
Young’s modulus and elongation at break point are
illustrated in Figs. 2, 3, and 4, respectively. The tensile
strength can be used to assess the ultimate state of cure
as well as to crudely assess the cure rate. The tensile
strength is an indication of how strong a compound is,
and in this study showed that IS-vulcanized NR was
higher, presumably because of self-reinforcement.
The elastic modulus (Young’s modulus) is a measure
of the stiffness of the material, and in this study it can
be seen that it is a bit higher for RS-vulcanized NR
than for IS-vulcanized NR. Elongation is the measure
of how much a specimen stretches before it breaks; in
this study the IS vulcanized NR showed more elonga-
tion before breaking.
Rheological behavior
Specimens
Mia, MUb MVc, MU ML, MU
IS-NR 66.5 50.96 56.15
RS-NR 42.3 34.69 35.32
a
Mi = moony initial.
b
MU = Moony Unite.
c
MV = minimum viscosity.
Aging. The results of aging tests on vulcanized rub-
ber specimens and the percentage of retention are
shown in Tables 6 and 7, respectively; aging parame-
ters are illustrated in Fig. 5. Aging is an important test
that relates to the longevity of rubber compounds. The
tests made before and after ageing show greater
changes for IS-vulcanized NR than for, RS-vulca-
nized NR.
Tear. The results of tear test on vulcanized rubber
specimens are shown in Fig. 6. Usually tear properties
are reported as the force required to pull a rubber test
piece apart using a tensile testing instrument under
controlled conditions. In this study it can be seen that
the amount of force for the IS-vulcanized NR was
high, indicating that it has more flexibility.
Compression set. Compression set test for vulca-
nized rubber specimens illustrated in Fig. 7. The pur-
pose of the compression set test is to measure the abil-
ity of the rubber specimen to retain its elastic proper-
ties after compressive forces have been applied for a
prolonged period of time at elevated temperatures.
The results of this test show that RS-vulcanized NR is
less compressible than is, IS-vulcanized NR, which is
indicative of high resistance to deformation; this
makes it a good option for sealing.
Resistance to ozone. Ozone (O3), resistance is used
to test the relative ability of the rubber compound to
resist outdoor weathering or ozone chamber testing. In
this study, both vulcanized rubber specimens cracked

71.6 71.5 155 152.9

71.4 150 IS-NR
IS-NR
71.2 RS-NR
RS-NR 145
kg/cm2
Shore A

71.0 140
70.8 134.6
135
70.6 70.5
70.4 130
70.2 125
70.0

Fig. 1. Hardness of vulcanizates. Fig. 2. Tensile strength for vulcanizates.

PETROLEUM CHEMISTRY Vol. 58 No. 1 2018

92 ALIREZA MOTAVALIZADEHKAKHKY, HEDIEH SHAHRAMPOUR

14 12.81
12 IS-NR
11.47

10 RS-NR
8.81
8.03
8

mPa 6 4.96 5.29

4
2.35 2.57
2
0
Modulus 50% Modulus 100% Modulus 150% Modulus 200%

Fig. 3. Elastic modulus for vulcanizates.

%
300
258.6 IS-NR
250 RS-NR
205.15
200
150
100
50
0

Fig. 4. Elongation at the breaking point for vulcanizates.

90 84.6
80 IS-NR
70 RS-NR
60 54.1
50
40 38.8

30 27.5
20
10
1.8 0.65
0
the changes of elongation the changes the changes of hardness
of tensile strength

Fig. 5. The changes of properties both before and after aging.

%
14 12.8
35 32.2 12 IS-NR
30 IS-NR 9.7 RS-NR
25.2 10
25 RS-NR
N/mm

20 8
15 6
10 4
5 2
0 0

Fig. 6. Force required to tear specimens. Fig. 7. The results of the compression set.

PETROLEUM CHEMISTRY Vol. 58 No. 1 2018

 DETERMINATION OF THE MOST EFFICIENT FORM OF SULFUR 93

Table 4. Modulus results of the IS-vulcanized NR

Results Force, kg/f Extension, mm Stress, kg/mm2 Elongation, %
Peak 13.63 51.72 1.53 258.6
Modulus 50% 2.14 10 0.24 50
Modulus 100% 4.51 20 0.50 100
Modulus 150% 7.31 30 0.82 150
Modulus 200% 10.43 40 1.17 200

Table 5. Modulus results of the RS-vulcanized NR

Results Force, kg/f Extension, mm Stress, kg/mm2 Elongation, %
Peak 11.53 41.03 1.35 205.15
Modulus 50% 2.25 10 0.26 50
Modulus 100% 4.62 20 0.53 100
Modulus 150% 7.70 30 0.90 150
Modulus 200% 11.2 40 1.31 200

Table 6. Aging of vulcanized NR specimens

Specimen Force, kg/f Extension, mm Stress, kg/mm2 Elongation, % Hardness, Shore A
IS-NR 8.82 34.8 1.00 174 71.5
RS-NR 9.38 33.27 1.07 166.3 70.5

Table 7. Percentage of retention 2. P. Phinyocheep, Chemistry, Manufacture and Applica-

tions of Natural Rubber (Elsevier, New York, 2014).
Specimens Elongation, % Tensile strength, %
3. M. P. Groover, Fundamentals of Modern Manufactur-
IS-NR 67 65 ing: Materials Processes, and Systems (John Wiley &
Sons, US, 2002).
RS-NR 81 80
4. M. Bolgar, J. Hubball, J. Groeger, and S. Meronek,
Handbook for the Chemical Analysis of Plastic and Poly-
at 200 pphm within 24 h, making it impossible, in this mer Additives (CRC Press Inc. Publishing, USA, 2008).
case, to compare them. 5. C. Hall, Polymer Materials (2nd Ed., Macmillan Educa-
tion Publishing, London, 1989).
CONCLUSIONS 6. R. Mukhopadhyay, S. Gupta, K. C. Baranwal, and
A. K. Bhowmick, Reverse Engineering of Rubber Prod-
Comparison of the properties of NR cured using ucts: Concepts, Tools, and Techniques (CRC Press Inc.
two types of sulfur indicated that the use of insoluble Publishing, USA, 2013).
sulfur has high potential for vulcanization for prepara- 7. B. G. Crowthe, Handbook of Rubber Bonding (Rapra
tion of certain types of elastomer. The property of self- Technology Ltd., England, 2001).
reinforcement of natural rubber gives the vulcanized
product improved physical properties and thermal 8. P. Coppens, Y. W. Yang, R. H. Blessing, W. F. Cooper,
and F. K. Larsen, J. Am. Chem. Soc. 99 (3), 760 (1977).
resistance that may make it more suitable for certain
applications. 9. R. Steudel, Elemental Sulfur and Sulfur-Rich Com-
pounds I (Springer Heidelberg Publishing, New York,
1965).
REFERENCES 10. L. C. Hollaway, M. K. Chryssanthopoulos,
1. J. S Dick., Basic Rubber Testing: Selecting Methods for a S. S. J. Moy, Advanced Polymer Composites for Struc-
Rubber Test Programme (ASTM International Publish- tural Applications in Construction (Woodhead Publish-
ing, USA, 2003). ing Ltd., England, 2004).

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