Polymer Testing 56 (2016) 1e9

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

Mechanical and rheometric properties of gilsonite/carbon black/

natural rubber compounds cured using conventional and efficient
vulcanization systems
Juan Sebastia
lez a, *, Sandra Vela

n Ve
squez a, Diego Giraldo b
a
Grupo BIOMATIC - Biomeca
nica, Materiales, TIC, Disen
stico, caucho y sus cadenas productivas, Centro de Disen
~ o y Calidad para el Sector cuero, pla ~o y
Manufactura del Cuero del SENA, Itagüí, Antioquia, Colombia
b
Grupo de Materiales Polim
ericos, Departamento de Ingeniería Metalúrgica y de Materiales, Facultad de Ingeniería, Universidad de Antioquia UdeA, Calle
70 No. 52-21, Medellín, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: The effect of adding gilsonite micrometric particles on the properties of N330 carbon black (CB) rein-
Received 12 May 2016 forced natural rubber (NR) compounds was investigated. Formulations with 30/0, 22.5/7.5, 15/15, 7.5/22.5
Received in revised form and 0/30 parts per hundred of rubber (phr) of CB/gilsonite were used, comparing the effect of conven-
16 August 2016
tional and efficient vulcanization systems. Gilsonite was characterized by X-ray fluorescence (XRF),
Accepted 4 September 2016
Available online 8 September 2016
thermogravimetric analysis (TGA), elemental analysis, X-ray diffraction (XRD) and scanning electron
microscopy (SEM). Tension, uniaxial compression, compression-set, abrasion resistance and dielectric
strength tests were carried out on specimens that were moulded using the optimal curing time
Keywords:
Vulcanization systems
measured by oscillating disc rheometry (ODR). Abrasion wear resistance, and mechanical and rheometric
Gilsonite properties varied with the CB/gilsonite content and on the vulcanization system. It was found that
Natural rubber gilsonite facilitated the incorporation of carbon black during mixing, diminished the reversion during
Rubber-filler interaction rheometric tests of compounds with efficient vulcanization cure systems and increased the dielectric
strength. Some gilsonite/CB/NR compounds showed similar rheometric properties, compressive modulus
and wear resistance to CB/NR compounds, which evidenced the use of gilsonite as an available filler for
NR-based materials.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction other mechanical properties [1,2]. NR-based compounds employ

Natural rubber (NR) reaches 40% of rubbers worldwide con-
sumption. NR is a widely used elastomer obtained from the latex of
some plant species, among which the Heveas brasiliensis tree is the
most commonly used in the industry [1]. An NR article
manufacturing begins with the mixing of NR with organic and
mineral additives; then the mixture is cured by the vulcanization
process at temperatures usually between 140 and 180
C. As a result,
the compound acquires high elasticity that distinguishes elasto-
meric materials from any other type of polymer. In the NR vulcani-
zation process, a cross-linked structure is obtained with improved
environment and solvent resistance, tensile strength, elongation at
break, tear strength, abrasion resistance, compressive stiffness and
* Corresponding author.

lez).
E-mail address: jsebastian.velez@udea.edu.co (J.S. Ve
vulcanization systems that are formed by: activators, curing agents
and reaction accelerators or retardants [3,4]. It was found that from a
greater accelerator/sulphur ratio, a faster reaction is obtained, and
promotes the formation of monosulphide and disulphide crosslinks
over polysulfide crosslinks. Quantity and type of crosslinks affects
the rheological, mechanical and thermal properties of cured rubbers
[3e5]. Hence, properties of vulcanized rubber compounds depend
on the vulcanization process, the type and structure of the elas-
tomer, and on the type and concentration of the ingredients of the
vulcanization system [6]. Based on the sulphur content and accel-
erator/sulphur ratio, vulcanization is classified into efficient (EV),
semi-efficient (SEV) and conventional (CONV) vulcanization sys-
tems; each exhibits a different performance with regard to thermal,
mechanical and chemical behaviour [7].
Rubber industry uses fillers to improve properties and/or reduce
costs [5,8]. Some fillers result in a reinforcing effect, therefore an
improving of mechanical properties is achieved, but other fillers do

http://dx.doi.org/10.1016/j.polymertesting.2016.09.005
0142-9418/© 2016 Elsevier Ltd. All rights reserved.
2 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9
not alter the mechanical properties or can even reduce it [9e11].
The most used reinforcement filler in the rubber industry is carbon
black [5,12], whose morphology, size and affinity with the elasto-
meric matrix have not been surpassed by any other reinforcing
filler [13,14]. However, one of the main disadvantages of carbon
black is its volatility that difficult its incorporation to the compound
during mixing. In the case of rubber articles where electrical
insulation is needed, reinforcement with carbon black could be a
problem due to its low dielectric strength when compared with
other mineral fillers [15]. For this reason the rubber industry is
constantly in search of alternatives to improve rubber processing
and properties, and/or reduce costs. Gilsonite could be an inter-
esting additive for rubber compounds owing to its bituminous
composition, availability and relative low price. It is a bitumen-
impregnated rock known for its high content of asphaltene,
commonly added to asphalts to improve the performance of
asphalt binder at high temperatures [16,17]. Savage and Hitchcock
have studied gilsonite in rubber formulations for electrical wiring
[18], but no other studies have been reported on mechanical,
thermal or processing properties of gilsonite/rubber compounds.
As stated by Roland [19], the interest in the electrical properties of
rubber compounds is primarily due to the strong effect of fillers,
hence the relevance of assessment non-conventional fillers for
rubber industry.
This study is aimed at the characterization of gilsonite available
in Colombia, and to evaluate its processability, mechanical prop-
erties and abrasion resistance in NR compounds using different
gilsonite and carbon black contents and comparing conventional
and efficient vulcanization system behaviour. The effect of the
addition of gilsonite on dielectric strength is also evaluated, since it
is a subject of interest for some rubber articles as shoe soles and
vibration isolators.
2. Experimental
2.1. Materials
NR grade TSR-10 from Guatemala, N330-grade CB from Cabot Cor-
poration, zinc oxide (ZnO), stearic acid, N-butylbenzothiazole-2-sul-
fenamide (TBBS) and sulphur (S) from Bayer Co. were purchased from
IndustriasdelCaucho,inMedellín,Colombia.Groundedandpulverized
gilsonitewasprovidedbyGilsontech,inCúcuta,Colombia.
2.2. Gilsonite preparation and characterization
Grounded and pulverized gilsonite was sieved by using a
200 mesh sieve. The particle-size distribution (PSD) was measured
at a Malvern equipment reference Mastersizer 2000.
Elemental analysis was carried out to determine carbon,
sulphur, nitrogen, hydrogen and oxygen content in gilsonite and CB,
by using a LECO elemental analyser. Carbon, hydrogen and nitrogen
Table 1
Formulations studied in this work.
Material CONV system
a
phr
Natural rubber (NR) 100
Zinc oxide (ZnO) 5 5
Stearic acid 2 2
TBBS 0.8
Sulphur (S) 2.75
Accelerant/sulphur ratio 0.3
Carbon black N330/gilsonite 30/0, 7.5/22.5, 15/15, 22.5/7.5, 0/30
a
Parts per hundred parts of rubber.
contents were determined at 1050
C, while oxygen content was
measured at 1250
C in helium atmosphere. Sulphur content was
measured at 1350
C with oxygen flow and an IR detector. The main
elemental composition was analyzed by X-ray fluorescence (XRF) in
a spectrometer model Optim'x Thermo.
Thermogravimetric analysis (TGA) was carried out on a TA In-
struments Q500 equipment between 25 and 900
C under nitrogen
atmosphere with a heating rate of 20
C/min. A following TGA
analysis was carried out using a temperature interval of 25e550
C
with a heating rate of 20
C/min under a nitrogen atmosphere. Once
a temperature of 550
C was reached, the atmosphere was changed
to oxygen. At this state an isotherm for 5 min was applied. Finally
the temperature was increased up until 900
C at 20
C/min.
X-ray diffraction (XRD) analysis was carried out by using a
Rigaku Miniflex diffractometer. The samples were scanned from 10

to 90
diffraction angle (2q) in scanning steps of 2
. Particle
morphology was analyzed in a scanning electron microscope (SEM)
JSM-590LV (JEOL).
2.3. Compounding, rheometric tests and specimens fabrication
Table 1 displays the compound formulation of gilsonite/CB/NR
compounds with conventional (CONV) and efficient (EV) vulcani-
zation systems. As showed in Table 1, five compounds for each
vulcanization system were evaluated varying the gilsonite and
carbon black content. In all the compounds the total content of CB
and/or gilsonite was 30 phr.
ThecompoundingprocesswascarriedoutonaBollingtwo-rollmill
with 600 diameter  1200 length rolls. Rheometric properties of three
samplesrandomlycutfromeachcompoundweremeasuredat160
Cby
using a Monsanto Oscillating Disc Rheometer (ODR). Specimens for
mechanicaltestswerevulcanizedintoahotpressmouldingmachineat
160
C, using the t100 time determined by rheometric tests. Tensile
specimenswereobtainedfroma2mmthicknesssheetmouldedforeach
compound,andthreedumbbell-shapedspecimenswerepunchedout
from each sheet. For uniaxial compression and compression-set tests,
three cylinders according to ASTM D575 standard were moulded for
eachcompound.Cylindersof6mmindiameter12mmoflengthwere
mouldedtoobtainsamplesforweartests.
2.4. Tensile and compressive properties
Tensile modulus values at 100% (M100) and 300% (M300) of
elongation were evaluated from the stress-strain curves of dumb
bell samples according the ASTM D412 standard. The grip separation
speed was set to 500 mm/min and initial gauge length to 25 mm.
Tensile forces were applied by using a Digimess universal testing
machine and a maximum elongation of 550% was applied during
tests.
Compressive modulus values were measured from uniaxial
compressionteststhatwerecarriedoutinaShimadzuInstronuniversal
EV system
phra
100
3.5
0.6
5.8
30/0, 7.5/22.5, 15/15, 22.5/7.5, 0/30
 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9 3

Fig. 1. Particle-size distribution of gilsonite.

Fig. 2. SEM micrographs of gilsonite particles added to the rubber compounds.

testing machine at a crosshead speed of 20 mm/min, compressing the Table 2

specimens up to 25% of strain. Compression-set tests were carried out Gilsonite and CB composition detected by elemental analysis.

accordingtomethodBspecifiedinASTMD395standard,at70
Cduring Filler Element (%w/w)

22 h, using the device recommended by the standard. Hardness of C H N O S Others
dumbbell-shaped specimens was measured using a Shore A-type
Gilsonite 75.2 7.0 1.5 8.4 1.5 6.4
durometeraccordingtheASTMD2240standard.
Carbon black 86.3 12.8 0.1 0 0.8 0

2.5. Abrasion wear tests

Table 3
Abrasion wear resistance of cylindrical specimens was carried Gilsonite composition detected by X-ray fluorescence (XRF) spectrometer.
out by using a Maqtest apparatus according to ASTM D5963,
Element S Fe V Si Ti Al Ni K Pb Ca Zn
applying 10 N as normal load.
% w/w 72.1 7.5 5.4 4.6 3.6 1.6 1.5 1.1 0.9 0.6 0.5

2.6. Dielectric strength

100
Dielectric strength of 7 cm diameter  2 mm thickness speci- N itro g e n
N itro g e n - a ir
mens was measured in a Baur equipment reference DPA. Cylin- 1
1.5
drical electrodes were used, and 1 KV/s was applied during the 80
Derivat. weigth
change (%/°C)

tests. The maximum applied voltage was 75 KV. Tests were carried 1
1.0
out at room temperature.
Weigth (%)

60
0
0.5

3. Results and discussions

40
0
0.0
0 200 400 600 800 1000
3.1. Gilsonite characterization Tem
mperature (°C))
20
N itro g e n A ir
Figs. 1 and 2 show the particle-size distribution and SEM mi-
crographs respectively of gilsonite added to rubber compounds. It 0
0 100 200 300 400 500 600 700 800 900
can be observed that gilsonite particles presented sizes between 0.4 T e m p e ra tu
u re (°C )
and 40 mm, with approximately 80% with sizes between 2 and
15 mm. Particles appeared to be polyhedral with smooth and flat Fig. 3. TGA and DTGA thermograms of gilsonite in nitrogen and air atmospheres.
4 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9

Fig. 4. Diffractogram of gilsonite.

surfaces, which do not favour the mechanical interlocking with the
rubber matrix, since it is well known that irregular shapes and high
surface area are preferred to increase the reinforcing effect of fillers.
Table 2 indicates the results of gilsonite and CB elemental
analysis, and Table 3 shows the gilsonite composition detected by
XRF, regarding the latter is a semiquantitative technique. The
elemental composition of gilsonite showed lower percentages of
carbon and hydrogen when compared to CB, but higher percent-
ages of oxygen, sulphur and other elements. Sulphur content in
gilsonite could alter the vulcanization kinetics, but it must be
evaluated at rheometric tests. Zinc and iron could also influence the
vulcanization, but they are present in low contents.
Fig. 3 shows the thermogram obtained by TGA for gilsonite. Un-
der nitrogen atmosphere, one single weight loss of 49.73% was
observed; this decomposition started at 380
C and ended at 470
C,
and it is attributed to the hydrocarbon decomposition. The residue
mass at the end of the test was 43.69% w/w. Under nitrogen-air at-
mosphere, the weight loss occurred in two-step losses. In the first
step, the weight loss was of 42.75%, at the same temperature in-
tervals observed in the nitrogen atmosphere test. In the second step,
53.86% weight loss is attributed to the hydrocarbon decomposition
when gilsonite was exposed to oxygen in at 550
C when the
isothermal process was applied. At 900
C 3.2% of the specimen
remained as residue.

30
30 CB
25 7.5 Gils - 22.5 CB
15 Gils - 15 CB
22.5 Gils - 7.5 CB
20 30 Gils
Torque (dN.m)

15

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Time (min)

a. Conventional vulcanization system

30

30 CB
25 7.5 Gils - 22.5 CB
15 Gils - 15 CB
20 22.5 Gils - 7.5 CB
Torque (dN.m)

30 Gils
15

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Time (min)

b. Efficient vulcanization system

Fig. 5. Rheometric curves at 160
C using (a) conventional and (b) efficient vulcanization systems.
 J.S. V
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Table 4
Rheometric properties of the compounds studied in this work.

System Parameter Gilsonite/CB content (phr)

0/30 7.5/22.5 15/15 22.5/7.5 30/0

CONV ML (dN.m) 1.22 ± 0.05 2.07 ± 0.52 1.16 ± 0.09 0.97 ± 0.37 1.64 ± 0.92
MH (dN.m) 27.81 ± 0.54 29.15 ± 2.02 27.33 ± 1.51 25.73 ± 1.07 21.33 ± 1.50
MH e ML (dN.m) 26.59 ± 0.49 27.08 ± 1.70 26.17 ± 1.42 24.76 ± 0.70 19.69 ± 0.68
ts2 (min) 3.54 ± 0.22 3.57 ± 0.21 3.54 ± 0.13 3.15 ± 0.13 3.79 ± 0.36
t100 (min) 9.25 ± 1.35 8.67 ± 1.14 9.54 ± 0.69 7.11 ± 0.91 12.06 ± 2.09
CRI (min1) 0.18 ± 0.04 0.20 ± 0.03 0.17 ± 0.02 0.25 ± 0.03 0.12 ± 0.05
EV ML (dN.m) 1.25 ± 0.00 1.27 ± 0.21 0.88 ± 0.11 0.74 ± 0.05 1.17 ± 0.10
MH (dN.m) 26.00 ± 0.72 24.88 ± 1.25 21.97 ± 0.31 19.33 ± 0.27 24.10 ± 0.54
MH e ML (dN.m) 24.75 ± 0.72 23.61 ± 0.94 27.09 ± 0.20 18.59 ± 0.22 22.93 ± 0.44
ts2 (min) 5.02 ± 0.10 4.61 ± 0.42 4.50 ± 0.17 4.58 ± 0.10 3.34 ± 0.18
t100 (min) 13.65 ± 0.61 11.42 ± 4.78 13.73 ± 0.69 14.24 ± 0.90 8.58 ± 0.46
CRI (min1) 0.12 ± 0.02 0.15 ± 0.06 0.11 ± 0.02 0.10 ± 0.03 0.19 ± 0.01

Fig. 4 shows the diffractogram obtained from DRX analysis. Ac- peaks at diffraction angles 2q of 20.827
, 26.593
, 50.046
, 59.857

cording to the Inorganic Crystal Structure Database for quartz (ICSD and 68.193
correspond to the hexagonal SiO2, whereas the peaks at
01-083-0539) and for aluminium oxide (ICSD 00-031-0026), the 20.935
, 24.921
, 25.652
, 40.472
and 50.167
were identified as

20

30 CB
15
Stress (MPa)

7.5 Gils - 22.5 CB

10
15 Gils - 15 CB

22.5 Gils - 7..5 CB

5
30 Gils

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
Strain (mm/mm)

a. Conventional vulcanization system

20 30 CB

15
7.5 Gils - 22.5 CB
Stress (MPa)

10
15 Gils - 15 CB
22.5 Gils - 7..5 CB
5
30 Gils

0
0 1 2 3 4 5
Strain (mm/mm)
b. Efficient vulcanization system
Fig. 6. Stress-strain curves of CB, gilsonite and CB/gilsonite NR compounds with (a) conventional and (b) efficient vulcanization systems.
6 J.S. V
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Carbo
on black conttent (phr)
30,0 22,5 15,0 7,5 0,0
3.5 9
M100
M CONV
M100
M EV 8
3.0 M300
M CONV
M300
M EV 7
100% Modulus (MPa)

300% Modulus (MPa)

2.5 6

5
2.0
4

1.5 3

2
1.0
1

0.5 0
0.0 7.5 15.0 22.5 30.0
Gils
sonite conten
nt (phr)

Fig. 7. Tensile modulus M100 and M300 of CB, gilsonite and CB/gilsonite NR com-
pounds using conventional and efficient vulcanization systems. Lines between data are Fig. 9. Compressive modulus of CB, gilsonite and CB/gilsonite NR compounds using
presented only to facilitate the visualization. conventional and efficient vulcanization systems. Lines between data are presented
only to facilitate the visualization.

22.5 gilsonite/7.5 CB/NR compounds presented lower vulcanization

Fig. 8. Hardness of CB, gilsonite and CB/gilsonite NR compounds using conventional
and efficient vulcanization systems. Lines between data are presented only to facilitate
the visualization.
aluminium oxide (Al2O3).
3.2. Rheometric characteristics
Fig. 5 shows the rheometric cure curves at 160
C using con-
ventional and efficient vulcanization systems. Rheometric proper-
ties of the compounds studied in this work are presented in Table 4.
The rheometric properties considered in this work were the min-
imum torque ML, maximum torque MH, difference between MH
and ML, the scorch time ts2, the time for reaching the 100% of the
curing t100 and the curing rate index CRI.
It can be observed that curves for CB/NR and 7.5 gilsonite/
22.5 CB/NR compounds are very similar, for both CONV and EV
systems. Increase of gilsonite up to 15 and 22.5 phr at the same time
that CB content was decreased at 15 and 7.5 phr, respectively,
diminished the stiffness of the cured compounds, which indicates a
lower reinforcing effect of fillers at those levels; this behaviour was
observed for both vulcanization systems. 15 gilsonite/15 CB/NR and
times than CB/NR and 7.5 gilsonite/22.5 CB/NR compounds,
because of the reactivity of hydrocarbon chains and sulphur at
gilsonite.
As expected, CB reinforced NR cured with a conventional
vulcanization system showed reversion i.e. decreasing of torque
with increasing testing time after the end of the curing. A plateau
curing curves after the end of the vulcanization was observed for
efficient vulcanization system. For compounds exhibiting reversion
behaviour, t100 was taken at the time where maximum torque was
presented; exhibiting a plateau after ending the curing reaction,
t100 was taken at the time where torque values reached a steady
behaviour. It is remarkable that addition of gilsonite to CB/NR
compounds did not affect the reversion of compounds cured using
conventional vulcanization systems or the plateau of compounds
cured using efficient vulcanization systems. However, compounds
only with gilsonite showed rheometric curves with different
behaviour to compounds with some content of CB. Gilsonite/NR
compound cured with conventional vulcanization system showed
the highest reaction time and did not exhibit reversion; the com-
pound only with gilsonite and an efficient vulcanization system
showed the lowest reaction time and presented reversion. This
indicates the synergic effect of CB and gilsonite, and influence of
gilsonite on the vulcanization kinetics. It is well known that
reversion in NR sulphur-based vulcanization is related to accel-
erant/sulphur ratio [3,4,6,7], therefore, differences in the behaviour
after the end of the vulcanization process could be associated to
gilsonite interaction with the ingredients of the vulcanization
systems.
3.3. Tensile and compressive properties
Tensile curves until 550% of elongation are shown in Fig. 6. One
representative curve is showed for each material seeking to facili-
tate the visualization of the curves. 100% and 300% modulus,
hardness and compressive modulus are shown in Figs. 7e9,
respectively. It is important to note that lines between data are
presented in Figs. 7e9, 11 and 12 only to facilitate the visualization,
but it was observed that CB/NR compounds exhibited a behaviour
with some remarkable differences when compared with CB/
 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9 7

Fig. 10. SEM micrographs of the fracture surfaces during tensile tests of CB, CB/gilsonite and gilsonite filled NR compounds using conventional and efficient vulcanization systems.

gilsonite/NR compounds or gilsonite/NR compounds as will be
discussed in the next sections.
It can be observed that CB presented a reinforcing effect as ex-
pected; however, stiffness decreased with increasing the gilsonite
content and decreasing the CB content.
It is observed that all the compounds using conventional
vulcanization system showed higher stiffness than those with
efficient vulcanization (EV) system. This behaviour is attributed to
the formation of polysulfide crosslinks which enhances stiffness
more than monosulfide or disulfide crosslinks, regarding that using
conventional vulcanization systems promotes more polysulfide
crosslinks than EV systems in sulphur-based vulcanization of NR
[6,7].
The setback in hardness, tensile and compressive modulus is
attributed to the combined effects of the decreasing content of CB
and a poor rubberegilsonite interaction. Urrego [6] studied the
same vulcanization systems used in this work, in NR compounds
without the addition of any filler. He found the same tensile
modulus and hardness obtained in this work for gilsonite/NR cured
with the conventional vulcanization system. Cured gilsonite/NR
compounds using the efficient system show increased hardness,
tensile and compressive modulus compared to the same formula-
tion cured with conventional system, an opposite behaviour than
materials with some CB content. This could suggest that gilsonite
affect the structure of the cross-linked network as described in the
rheometric properties presented previously in this work.
SEM micrographs of the failed fracture during tensile tests of
some compounds at various curing systems are shown in Fig. 10.
Decrease of CB content and increase of gilsonite content result in
less tearing lines and surface roughness of the rubber matrix. This
indicates a reduction of rubber-filler interaction when gilsonite
content is increased, which altered the crack paths in rubber
decreasing resistance to crack propagation. Some isolated particles
of gilsonite appeared in the gilsonite/NR and CB/gilsonite/NR
8 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9
Fig. 11. Variation of compression-set values of the CB, CB/gilsonite and gilsonite NR
compounds using conventional and efficient vulcanization systems. Lines between
data are presented only to facilitate the visualization.
Carbon black content (phr)
30.0 22.5 15.0 7.5 0.0
CONV
EV
600
Volumetric loss (mm )
3
400
200
0.0 7.5 15.0 22.5 30.0
Gilsonite content (phr)
Fig. 12. Volumetric loss in abrasion tests of CB, CB/gilsonite and gilsonite filled NR
compounds using conventional and efficient vulcanization systems. Lines between
data are presented only to facilitate the visualization.
compounds, which is another evidence of low rubberegilsonite
interaction when mechanical stresses are applied.
Since no differences between tensile modulus were observed for
gilsonite/NR compounds cured using conventional and efficient
vulcanization systems, gilsonite appeared to be responsible for
setback in rigidity instead of the type of crosslinking related to the
vulcanization system. Additionally, the sulphur at gilsonite reacted
with the rubber chains and the vulcanization system for producing
additional crosslinks. The formation of new links between the
rubber chains and the sulphur of the gilsonite reduced chain
mobility and slippage when a load was applied to the rubber.
Compression-set results are shown in Fig. 11. It was found that
compounds only with CB or only with gilsonite showed no
dependance of the vulcanization system, but CB/gilsonite/NR
compounds cured with conventional systems presented higher
Carbon black content (phr)
30.0 22.5 15.0 7.5 0.0
40
35
Dielectric strength (KV/mm)
30
25
20
15
10
0.0 7.5 15.0 22.5 30.0
Gilsonite content (phr)
Fig. 13. Dielectric strength of CB, CB/gilsonite and gilsonite filled NR compounds. Lines
between data are presented only to facilitate the visualization.
values of compression-set than those cured with efficient systems.
Compounds cured with efficient vulcanization system showed a
continuous increase in compression-set with the increase in
gilsonite content. This behaviour is explained by the decrease in the
reinforcing effect of CB when gilsonite was added, which allows the
relaxation of NR chains. Same behaviour is observed in compounds
cured with conventional vulcanization system, with the noticeable
exception of gilsonite/NR specimens. Low compression-set of
gilsonite/NR compound vulcanized with conventional system is
due to interaction between gilsonite particles and NR matrix, which
was not affected by the effect of CB.
Results of abrasion tests are shown in Fig. 12. It is observed that
CB/gilsonite/NR compounds with efficient vulcanization systems
showed lower abrasion resistance than the same compounds cured
with conventional vulcanization system. This difference is attrib-
uted to the prevalence of polysulphide crosslinks in latter, which
are more resistant to abrasion wear than mono or disulphide
crosslinks that are prevalent on compounds cured with efficient
system. CB/NR and gilsonite/NR compounds showed different
behaviour to CB/gilsonite/NR compounds, indicating a synergic
effect on the abrasion resistance when CB and gilsonite were added.
No difference was observed between the wear resistance of
30 phr CB/NR and 22.5 phr CB/7.5 phr gilsonite/NR compounds
cured with a conventional vulcanization system. A slightly increase
in volumetric loss was found with the conventional vulcanization
system for 15 phr CB/15 gilsonite/NR and 7.5 phr CB/22.5 gilsonite/
NR compounds. A remarkable increase in volumetric loss was
observed for gilsonite/NR compound using a conventional vulca-
nization system, which is related to the poor interaction between
gilsonite particles and NR matrix when CB is not present as rein-
forcing filler.
CB reinforced compounds cured with efficient vulcanization
systems exhibit increased volumetric loss with increasing gilsonite
content. However, gilsonite/NR without CB compound show an
improved abrasion resistance than 7.5 phr CB/22.5 phr gilsonite/NR.
This is attributed to the synergic effect of CB and gilsonite on the
volumetric loss setback.
As presented in Fig. 13, addition of gilsonite improved the
dielectric strength of the compounds, because of the wellknown
dielectric behaviour of asphaltites, as the gilsonite used in this
study. Since CB has low dielectric strength when compared to
 J.S. V
elez et al. / Polymer Testing 56 (2016) 1e9
gilsonite, no synergic CB/gilsonite effect was observed. Regarding
NR is a non-polar polymer, gilsonite appeared to be responsible for
the improvement on dielectric strength of the compound.
4. Conclusions
Micrometric gilsonite acts as filler in NR and CB/NR compounds,
and low mechanical interlocking with the rubber matrix is
observed. Rheometric tests and mechanical properties indicate a
synergic effect of gilsonite and CB in some composites. This
behaviour could be related to sulphur and zinc found in gilsonite
which modifies the kinetics of the vulcanization reaction and the
structure of the cross-linked network, because of the wellknown
effect of sulphur and zinc in natural rubber curing process. The
effect of gilsonite on mechanical properties depended of the
vulcanization system, especially the modulus under compressive
loads and abrasion resistance. Gilsonite increases the dielectric
strength of carbon black reinforced natural rubber and facilitates
the incorporation of carbon black during mixing. These results
suggest that gilsonite could be used as a filler in natural rubber
compounds regarding the low cost and availability of gilsonite.
Acknowledgments
The authors would like to thank the SENNOVA at SENA (the
Spanish acronym for the National Training Service of Colombia), by
its support through the SENNOVA Leaders program for making this
research possible.
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