Iranian Polymer Journal (2018) 27:287–296

https://doi.org/10.1007/s13726-018-0609-6

ORIGINAL RESEARCH

Tensile, thermal, flammability and morphological properties

of sepiolite filled ethylene propylene diene monomer (EDPM) rubber
composites
Nurul Aizan Mohd Zaini1,2 · Hanafi Ismail1 · Arjulizan Rusli1

Received: 22 August 2017 / Accepted: 20 January 2018 / Published online: 20 March 2018
© Iran Polymer and Petrochemical Institute 2018

Abstract
The effect of sepiolite loading content on the curing characteristics, tensile mechanical, thermal, swelling, flammability and
morphological properties of sepiolite-filled ethylene propylene diene monomer (EPDM) composites was investigated. The
composites were prepared with sepiolite loadings of 0–70 part per hundred (phr) of rubber using a two-roll mill. The results
highlighted the improvement in the tensile properties and cross-link density values peaked at 60 phr of sepiolite loading.
The scorch time, curing time, swelling percentage, and linear burning rate of the composites decreased with an increase in
sepiolite loading. Thermogravimetric analysis showed an increasing trend with increase in sepiolite loading. The tempera-
tures corresponding to 5, 25 and 50% weight loss (T5wt%, T25wt% and T50wt%) and the percentage of char residue gradually
increased with increase in sepiolite loading. The homogenous dispersion of the sepiolite particles in the EPDM matrix and
the formation of zigzag structures, especially at 60 phr, were the main reasons of the improvement of mechanical properties
which were confirmed by the morphological studies. The formation of a protective layer, which acted as a barrier against
heat transfer into the deeper layers, enhanced the flammability resistance of the composites. Notably, the EPDM filled with
60 phr sepiolite exhibited excellent performance in the aspects of mechanical, thermal stability and flammability properties
and resistance towards swelling.

Keywords Sepiolite · Cure characteristics · Tensile properties · Swelling behaviour · Thermal stability · Flammability

Introduction out to obtain alternatives for carbon black due to limited

petroleum feedstock, dark colour and environmental harm.
It is impossible to utilize most elastomers in the absence Among all the potential alternatives, those with clay
of commercial fillers in the rubber industry. Most commer- materials have been widely investigated, possibly due to the
cial fillers such as carbon black, precipitate silica and cal- fact that these materials are abundant and their intercalation
cium carbonate are incorporated into rubber compounds to chemistry has been studied for a long time [6]. Most recent
improve the mechanical properties, reduce cost and provide studies have emphasized the use of layered silicates based
a colour base for rubber [1, 2]. In fact, carbon black is a on the smectite class of aluminium silicate clays, particularly
prominent commercial filler because of its strong reinforcing montmorillonites (MMT) as the reinforcing phase [7–9] in
ability. Extensive research works [3–5] have been carried various polymer matrices. Besides these nanofillers, there
are other alternative nanoclays that can be included in poly-
mer matrices. To date, only a handful of studies have con-
sidered the use of sepiolite, with a needle-like morphology
* Hanafi Ismail to strengthen various polymers [10].
[email protected] Sepiolite can be expressed as ­ S i 12 O 3 0 Mg 8
1 (OH)4(OH2)4·(H2O)8 [11, 12]. It is chemically known as a
School of Materials and Mineral Resources Engineering,
Engineering Campus, Universiti Sains Malaysia, hydrated magnesium silicate [13]. The compound belongs
14300 Nibong Tebal, Penang, Malaysia to a 2:1 phyllosilicate structure, where one octahedral
2
Faculty of Applied Sciences, Universiti Teknologi Mara sheet is sandwiched between two tetrahedral sheets. It is
Perlis, 02600 Arau, Perlis, Malaysia microfibrous in nature with 2–10 mm particles and exhibits

13
Vol.:(0123456789)
288 Iranian Polymer Journal (2018) 27:287–296

nanosized tunnel structures [14, 15]. The fibrous-like struc- Table 1  Elemental Analyte Amount (wt %)
ture of sepiolite is dispersed into the polymer matrix easier compositions of sepiolite
obtained by XRF CaO 47.49
than platelet-like minerals such as MMT [16]. Moreover,
sepiolite can prevent flocculation when it is distributed SiO2 41.53
within the network of a polymer, which would reduce MgO 10.09
filler agglomeration [11] and result in higher mechanical K 2O 0.25
reinforcement. Interestingly, sepiolite has the potential to Fe2O3 0.19
strengthen the fire retardant properties, since it can form a Al2O3 0.18
char layer at the silicate surface. It can act as a barrier that Na2O 0.11
lessens the oxygen transmission rate, impedes flame spread SrO 0.09
and keeps the structural integrity of the burnt samples [17, NiO 0.03
18]. With promising characteristics, sepiolite becomes a ZrO2 0.02
potential filler to improve the properties of polymer com- CuO 0.02
posites such as mechanical, thermal and flame retardancy
properties. Sepiolite clay has an interesting mechanical rein-
forcing capability in various polymeric matrices [19–21]. Table 2  Compounding formulations for EPDM/sepiolite composites
However, little research has paid attention to the applicabil- (phr)
ity of sepiolite as a reinforcing filler in EPDM. Materials Content (phr)
EPDM is a synthetic elastomer which can be used as
EPDM 100
electrical insulating materials, building profiles, electrical
Zinc oxide 5
sheathings, roofing materials, cover stripes and cables [22].
Stearic acid 1.5
Wang et al. [23] conducted a preliminary study on surface
TMTDa 1.5
free energy and tensile properties of EPDM filled with a
MBTb 0.8
fixed amount of sepiolite treated with various coupling
Sulphur 1.5
agents. They observed a good dispersion of the sepiolite
Sepiolite 0, 4, 10, 20, 30, 60, 70
with the presence of coupling agent that improved the ten-
sile properties of the composites. However, the researchers a
Tetramethyl thiuram disulphide
focused on a limited number of properties (i.e. tensile prop- b
Mercaptobenzothiazole
erties and surface energy) of the EPDM/sepiolite compos-
ites. In response to this issue, additional studies are needed
to generate positive outcomes from the various properties of sepiolite clay was obtained from Hebei DFL Minmet Refrac-
the sepiolite-filled EPDM composites. tories Corp., China.
In this study, the potential of sepiolite as a filler in EPDM Table 1 shows the elemental compositions of sepiolite
was studied based on the cure characteristics, mechanical, clay obtained using an X-ray fluorescence (XRF) spectrom-
swelling, thermal and flammability properties of EPDM/ eter (RIX 3000, Rigaku Industrial Corp., Osaka, Japan).
sepiolite composites at various sepiolite loadings that to the The sepiolite was pre-dried in an oven at 80 °C for 24 h
best of our knowledge [24] has not been reported before. before density measurement which was developed using a
The morphology of the tensile fracture surface and the char gas pycnometer (AccuPyc II 1330, Micromeritics Instru-
residue of the composites was examined to associate with ment Corp., USA). The density of sepiolite was found to be
their tensile and flammability properties. 2.9461 g/cm3. This material had an average particle size of
4.08 µm, obtained using a particle size analyser (Sympatec
GmbH, Clausthal-Zellerfeld, Germany). Other compound-
Experimental ing ingredients, such as zinc oxide, stearic acid, tetramethyl
thiuram disulphide (TMTD), mercaptobenzothiazole (MBT)
Materials and sulphur, were purchased from Bayer (M) Ltd.

EPDM in the form of Vistalon 2504N was used in this Sample preparation
research and purchased from Exxon Mobil Chemical. It con-
tained 54% ethylene with 3.6% of ethylidene norbornene Just prior to preparation of compounds, any existing mois-
(ENB) and Mooney viscosity [ML (1 + 4) at 125 °C]of 26.8 ture was removed by placing the sepiolite in an oven for
(Mooney Unit). The density of the EPDM was 0.818 g/ 24 h at 80 °C. Table 2 illustrates the compounding for-
cm3 measured using an analytical weighing balance (XB mulations for EPDM/sepiolite composites prepared on a
220A, Precisa Gravimetrics Ag, Dietikon, Switzerland). The two-roll mill (XK-160, Shanghai Rubber Machine Works,

13
Iranian Polymer Journal (2018) 27:287–296 289

Shanghai, China). All composites were mixed for 21 min calculated based on Eq. (3) where δs, δr, R and T are the
according to ASTM D3568. Utilizing a moving die rheom- solubility parameters of the solvent and rubber network, the
eter (MDR2000, Alpha Technologies, Ohio, USA) at universal gas constant (8.314 J/mol K) and absolute tem-
160 °C, the optimum cure time (t90) and scorch time (ts2) perature, respectively. The χ value of 0.49 was obtained
were obtained according to ASTM D2240. Based on their using Eq. (3):
respective t90 values, the compounds were moulded into
(3)
( )
𝜒 = 𝛿s − 𝛿r V0 ∕RT.
2 or 3 mm rectangular sheets with a dimension of either
150 mm × 122 mm × 2 mm or 145 mm × 110 mm × 3 mm The degree of cross-link density (V) is given by Eq. (4):
using an electrically heated hydraulic press (GT-7014-A30C, 1
GoTech Testing Machine Inc., Taichung City, Taiwan) at V=
2Mc
. (4)
160 °C with a pressure of 10 MPa.
Thermal analysis
Tensile properties
Thermogravimetric analysis (TGA) using an analyser
To prepare the dumbbell shaped specimens, 2 mm compres- (Pyris™ 6 TGA, Perkin Elmer, USA) was performed on
sion moulded sheets were punched after storing in a desicca- 10 mg samples that were heated from 30 to 600 °C at 20 °C/
tor for 24 h. According to ASTM D412, a universal testing min under nitrogen flow (50 mL/min). TGA measured the
machine (Instron 3366, Instron, Singapore) was adopted to weight loss as a function of temperature.
measure the tensile strength, elongation at break and tensile
stress at 100% elongation. The measurements were con- Flammability test
ducted at a crosshead speed of 500 m/min with 10 kN load.
According to ASTM D635, the horizontal burning test was
Swelling behaviour performed to test the flammability. The samples were cut
into a dimension of 125 mm × 13 mm × 3 mm. The flame
Swelling tests for the EPDM/sepiolite composites were was ignited at one end of the sample using natural gas. The
performed in toluene according to ASTM D471-12a. An burnt length and time for the flame front to reach the 25 mm
electrical balance was used to weigh the vulcanized samples reference mark and travel to the 100 mm reference mark
after they were cut into 30 mm × 5 mm × 2 mm strips. The were noted. Equation (5) was used to calculate the linear
compounds took 72 h to achieve swelling equilibrium. The burning rates of the burnt samples, where V denotes the lin-
three samples for each compound were immersed in toluene. ear burning rate, L is the burnt length and t denotes the time
Once the samples reached the swelling equilibrium, they in minutes [26]:
were wiped, weighed and recorded after removing from the V = 60L∕t. (5)
liquid. The formula to determine the swelling ratio is accord-
ing to Eq. (1): Morphological study

FESEM was used to examine the morphology of the sepio-

( )
W 1 − W0
Swelling percentage (%) = × 100, (1)
W0 lite particles, tensile fracture surfaces and charred surfaces
of the EPDM/sepiolite composites (Zeiss Supra 35-VP, Carl
where W1 denotes the mass of the swollen sample, and W0 Zeiss NTS GmbH, Oberkochen, Germany). The specimens
denotes the initial mass of the sample prior to immersion. were coated with a thin layer of gold–palladium. The coat-
The results of the swelling ratio were used to calculate the ing is important to eliminate electrostatic charges which are
molecular weight between two cross-links by applying the generated during the examination.
Flory–Rehner equation [25] as stated in Eq. (2):
1∕3
Mc =
[−𝜌p Vs Vr ]
, (2)
Results and discussion
[ln(1 − Vr ) + Vr + 𝜒Vr2 ]
Microstructure of sepiolite particles
where Mc denotes the mean molecular weight between the
cross-links, ρp the density of the rubber (EPDM = 0.808 g/ Figure 1 shows the FESEM micrograph of the sepiolite’s
cm3), Vs the molar volume of the solvent (107.0 mL/mol microstructures. Most structures appeared in bundles of
for toluene) and Vr the volume fraction of the swollen rub- aggregate, fibrous-like structures [27] of various sizes and
ber. The interaction parameter of the rubber network, χ was nearly individualized fibrous structures. At the same time,

13
290 Iranian Polymer Journal (2018) 27:287–296

when the sepiolite loading reached 70 phr. This was due to

excess sepiolite, which tended to form agglomerates which
were able to slip, and therefore to cause a lubricating effect
upon shearing.
Figure 3 shows the effects of sepiolite loading on t90 and
ts2 of the EPDM/sepiolite composites, which were obtained
by using a rheometer. In the present study, ts2 is the scorch
time and its two units above the minimum torque of the
rheogram. On the contrary, t90 was directly associated with
the optimum time of cross-links formation [31]. The ts2 for
the EPDM/sepiolite composites decreased gradually when
sepiolite loading increased. Good dispersion of sepiolite in
the EPDM matrix could reduce the ts2 value and encour-
Fig. 1  FESEM micrograph of sepiolite particles at 3000× magnifica- age the initiation of cross-link and shorten the scorch time.
tion Furthermore, the high content of the metal oxides present
in sepiolite causes it to act as a passive activator (Table 1).
In Fig. 3, when the filler loading increases from 60 to
needle-like shapes and rods can be observed in the FESEM 70 phr, the cure times for the EPDM/sepiolite composites
image. This observation is congruent with those reported increase. This happens possibly due to the good disper-
by Suarez and Garcia-Romero [28] who found that sepiolite sion of sepiolite in the EPDM matrix and the increase in
is a mineral with fibrous morphology due to its crystalline the metal oxide content as the concentration of the sepiolite
structure. filler increases from 0 to 60 phr. At sepiolite loading of 70
phr, the filler becomes the dominant component of the com-
Curing characteristics posite system. At high loading of filler, the improvement in
t90 does not compensate the inhibition of cross-link forma-
Figure 2 illustrates the effects of different sepiolite loadings tion by the presence of agglomerated fillers. Consequently,
on the maximum torques (MH) of the EPDM/sepiolite com- it extends the vulcanization process.
posites, which were obtained from the cure characterization
test. The MH can be related to the modulus of the composites Tensile properties
[29, 30], whereas high MH indicates that the composites have
high stiffness. When the sepiolite concentration increases Figure 4 presents the tensile strength of EPDM/sepiolite
from 0 to 70 phr, it encourages a linear increment in the MH composites as a function of the filler loadings. The results
values. In other words, sepiolite fillers could affect the stiff- show that the sepiolite can increase the tensile properties of
ness of rubber, whereby the mobility of the rubber chain at EPDM up to the optimum loading of 60 phr. This is because
the surface of filler decreased at a higher filler loading. This the high ratio of fibrous-like structure allows the sepiolite
condition could be linked to the high shear value of rub- to disperse effectively in the EPDM matrix, thereby facili-
ber compound which increased the torque value at a higher tating the stress transfer within the composites. The tensile
sepiolite loading. However, the modulus decreased gradually

Fig. 2  Variation of MH of EPDM/sepioite composites as a function Fig. 3  Effects of sepiolite loading on scorch time and cure time of
of sepiolite loading EPDM/sepiolite composites

13
Iranian Polymer Journal (2018) 27:287–296 291

Fig. 5  Effect of different sepiolite loadings on the tensile modulus of

Fig. 4  Effect of different sepiolite loadings on the tensile strength and EPDM/sepiolite composites
elongation at break of EPDM/Sepiolite composites

strength slightly declines at 70 phr of sepiolite, even though solvent penetration into the composites, which was related
it is higher than that of unfilled EPDM composite. When to a lower cross-link density. Figure 6 demonstrates that the
the loading of filler is more than 60 phr, the filler–filler swelling percentage of sepiolite-filled EPDM composites
interactions become stronger than the rubber–filler inter- decreases with an increase of filler content up to 60 phr.
action. Therefore, a slight reduction in tensile strength is The penetration of toluene into the sepiolite/EPDM network
observed. This observation can confirm by Payne effect (log is restricted by the cross-links through reducing the solvent
G′ − strain %) [32, 33]. diffusion path that, in turn, precludes further swelling of the
Figure 4 also displays the elongation at break of EPDM/ sepiolite/EPDM composites. Nevertheless, the swelling level
sepiolite composites, which follows a trend similar to that for increases when the sepiolite loading reaches 70 phr due to a
tensile strength. With sepiolite up to 60 phr, the good adhe- poor dispersion of sepiolite at high filler loading that causes
sion among well-dispersed sepiolite particles enables the inadequate wetting of sepiolite by EPDM. Subsequently, it
EPDM matrix distributes the force evenly to the filler and increases the solvent diffusion path that enables direct diffu-
reduces the potential for propagation of crack. This enhances sion of solvent. Hence, both higher swelling percentage and
the elastic properties of the composite to gain a higher strain lower swelling resistance take place concurrently.
tolerance. In elastomer composites, the agglomeration of The Flory–Rehner equation is applicable to determine the
filler particles decreases the elongation at break to limit the number of cross-link points per unit volume [25]. Figure 6
movement of the rubber chain in the presence of stress. Con- also demonstrates that the cross-link density is inversely pro-
sequently, it caused a slight reduction of elongation at break portional to the swelling percentage. At 60 phr filler load-
at 70 phr. A similar finding was also reported by Ismail et al. ing, the efficient distribution and good interaction between
[34], stating that the incorporation of clay into the EPDM sepiolite and EPDM matrix could produce more cross-links.
matrix increased the elongation at break of the composites
up to an optimum loading.
Figure 5 presents the tensile modulus of EPDM/sepiolite
composites. The results show that the modulus of the com-
posites increases when the sepiolite loading increases up to
the optimum loading of 60 phr. This means that the filler can
influence the stiffness of the composites [35] at higher load-
ing levels. However, the modulus decreases gradually when
the sepiolite loading reaches 70 phr. This may be due to
excess sepiolite which tends to form agglomerates, which are
able to slip and therefore cause lubrication effect upon shear.

Swelling behaviour

Swelling test can measure the cross-link density of the rub-

ber network [34]. In this study, higher swelling percentage Fig. 6  Effect of sepiolite loading on the swelling percentage and
of the composites in toluene indicated a greater degree of cross-link density of EPDM/sepiolite composites

13
292 Iranian Polymer Journal (2018) 27:287–296

Due to the high filler–filler interaction, a further increase in

filler content to 70 phr could reduce the cross-link density
of composite.

Thermal stability analysis

Table 3 summarizes the thermal degradation properties of

EPDM/sepiolite composites as compared to those of EPDM
compounds. In general, the thermal stability of polymer
composites can be evaluated quantitatively by measuring
the weight loss by decomposition of polymer structure. The
heating process stimulates the production of volatile prod-
ucts, and it leads to weight loss [36]. Fig. 7  Effect of sepiolite loading on the flammability of EPDM/sepi-
All sepiolite-filled EPDM composites exhibited a bet- olite composites
ter thermal stability than unfilled EDPM. Since sepiolite
can act as a mass transport barrier thermal insulator, the
incorporation of sepiolite into the EPDM matrix has a large rate of burning. The linear rate of burning is consistent with
contribution to the improvement of overall thermal stability the thermal properties of the composites. During the burning
of the composites [37]. The temperature corresponding to process, the structure of the clay minerals and the formation
5, 25 and 50% weight loss increased with a rise in sepiolite of carbonaceous char layers contribute to the fire resistance
content. For instance, the temperature at 5% weight loss for nature of these composites [39]. The oxygen diffusion was
unfilled EPDM compound was 432 °C. In the presence of inhibited by the sepiolite structure during the combustion
70 phr sepiolite, the temperature increased up to 458 °C. process, and reduced the amount of thermally decomposed
Besides, the fibrous structure of the sepiolite provides an volatiles escaping from the interior polymer matrix. The
insulation effect [38]. The entrapment of volatile products process was further inhibited by the char formed at higher
reduced the heat transfer and prevented the thermal degra- filler loading and the char shielded the underlying EPDM
dation and decomposition processes. Table 3 depicts that matrix from the heat.
the char residues of the composites increase as the sepiolite
loading increases. For example, the char residue at 600 °C Morphology of tensile fractured surfaces
increases from 5 to 41%, with clay loadings from 0 to 70
phr. Well-dispersed sepiolite may restrict the mobility of the Figure 8a–e presents the tensile fracture surfaces at differ-
polymer chains and delay the heat transfer. ent sepiolite loadings at 2000× magnification. Excellent
distribution of sepiolite particles in EPDM is observed in
Flammability analysis Fig. 8b–d at different sepiolite loadings. Due to the fibrous
structure of filler, Bidsorkhi et al. [20] suggested that the
As determined by the linear rate of burning, Fig. 7 displays sepiolite could disperse well in the polymer matrix. Fig-
the effect of different sepiolite loadings on the flammability ure 8d shows the individual needle-like particles of sepiolite
of EPDM/sepiolite composites. As seen, the linear rate of which are distributed into the matrix. Meanwhile, the zigzag
burning reduces when the sepiolite concentration increases. structure, schematically shown in Fig. 9, supports the highest
The EPDM/sepiolite composite with 70 phr sepiolite exhib- tensile strength which was obtained at 60 phr clay loading.
its the longest time to burn, and it shows the lowest linear With the incorporation of 70 phr sepiolite, Fig. 8e indicates

Table 3  TGA results of unfilled Sepiolite Temp at 5% wt Temp at 25% wt Temp at 50% wt Max wt loss (%) Char residue
EPDM and sepiolite-filled content (phr) loss, T5 (°C) loss, T25 (°C) loss, T50 (°C) at 600 °C (%)
EPDM composites
0 432 477 489 56.4 5.7
4 434 478 491 54.8 8.2
10 438 478 491 52.3 13.2
20 440 479 492 44.1 20.2
30 446 481 494 42.3 25.4
60 449 483 498 38.6 37.9
70 458 485 500 34.5 41.9

13
Iranian Polymer Journal (2018) 27:287–296 293

Fig. 8  Tensile fracture surfaces of the EPDM/sepiolite composites with sepiolite loadings of a 0 phr, b 10 phr, c 20 phr, d 60 phr, and e 70 phr at
2000× magnification

the invisible detachments in the composites with a lower

amount of fillers. Also, the formation of many microcracks
observed on the fractured surface of the composite contain-
ing 70 phr sepiolite may be due to the filler–filler interaction
that is more dominant than the rubber–filler interaction. The
formation of microcracks results in lower tensile strength.
Both factors contribute to the reduction of both tensile prop-
erties and formation of cross-links at sepiolite loadings of 70
phr as can be seen in Figs. 4 and 6, respectively.

Morphology of charred residues

Figure 10a–c presents the morphologies of charred resi-

dues of EPDM/sepiolite composites at 30, 60 and 70 phr of
Fig. 9  Schematic representation of zigzag structure sepiolite loadings after the flammability test. The burned

13
294 Iranian Polymer Journal (2018) 27:287–296

Fig. 10  Charred surfaces of EPDM/sepiolite composites with sepiolite loadings of a 30 phr, b 60 phr, and c 70 phr at 1000× magnification

composite samples at 0–20 phr sepiolite loadings extin- Conclusion

guished quickly after the fire source was removed. The
FESEM micrographs for those samples without formation Incorporation of sepiolite particles into the EPDM matrix
of char were not taken. The char protective layers dur- decreased the optimum curing times and scorch times,
ing combustion proved an effective method for improv- while it maximized the torque values of the EPDM/
ing flame retardancy. They become insulating barriers to sepiolite composites due to the formation of more cross-
forbid the oxygen and discard the heat from reaching the links. The tensile strength, elongations at break, and ten-
underlying matrix [40, 41]. sile modulus of the composites increased with a rise in
The char formed on the top of the burning compos- filler loading up to 60 phr. These increments in mechani-
ites, as seen in Fig. 10a, creates a protective barrier layer cal properties were attributed to the good dispersion of
impeding the transport of flammable vapour and trans- sepiolite particles within the EPDM matrix. In contrast,
mission of oxygen gas as well as delaying the spread of at 70 phr filler loading, the filler–filler interaction was
flame. This improves the flammability resistance of the stronger than the rubber–filler interaction, so it resulted
composites, thereby reducing the linear rate of burning. in lower mechanical properties. The cross-link density val-
The microcrack induces lower flammability resistance and ues increased as the sepiolite loading was increased to 60
a higher linear rate of burning. The formation of cracks phr. In fact, the sepiolite could act as a thermal insulator
on the surface permits the transmission of oxygen, further by reducing the heat transfer through the composites. This
aids the flame spread, and destroys the structural integrity remarkably improved the thermal stability of the EPDM/
of the composites [17]. sepiolite composites when there was an increase in clay
As the amount of sepiolite within the rubber matrix loadings.
increased from 30 to 70 phr, the area of the protective layer Apart from that, the FESEM micrographs showed nee-
increased (Fig. 10c) and covered the entire area of EPDM dle-like structures for the sepiolite particles and confirmed
without formation of openings or cracks. Hence, this fur- a homogeneous dispersion for the filler particles incorpo-
ther confirmed the reduction of linear burning rate as well rated within the composite up to 60 phr. They also showed
as the increment of char residues in the EPDM/sepiolite that the detachment was the highest at 70 phr sepiolite
composites as shown by TGA results.

13
Iranian Polymer Journal (2018) 27:287–296 295

loading. The flammability resistance of the composites 13. Tartaglione G, Tabuani D, Camino G, Moisio M (2008) PP and
improved due to the formation of protective barrier layers PBT composites filled with sepiolite: morphology and thermal
behaviour. Compos Sci Technol 68:451–460
demonstrated by lower linear burning rate of composite 14. Kotal M, Bhowmick AK (2015) Polymer nanocomposites from
samples. The EPDM composites containing 60 phr sepio- modified clays: recent advances and challenges. Prog Polym Sci
lite demonstrated the best performance of tensile proper- 51:127–187
ties (i.e. strength, elongation-at-break, modulus), swell- 15. Chen H, Lu H, Zhou Y, Zheng M, Ke C, Zeng D (2012) Study
on thermal properties of polyurethane nanocomposites based on
ing, thermal stability and flame resistance, which are key organo-sepiolite. Polym Degrad Stab 97:242–247
characteristics for use of EPDM as insulating materials in 16. Bilotti E, Zhang R, Deng H, Quero F, Fischer HR, Peijs T (2009)
the construction and transport sectors. Sepiolite needle-like clay for PA6 nanocomposites: an alternative
to layered silicates? Compos Sci Technol 69:2587–2595
Acknowledgements The authors would like to thank all levels of 17. Darder M, Matos CRS, Aranda P, Gouveia RF, Ruiz-Hitzky
staff in the Department of Materials and Mineral Resources Engineer- E (2016) Bionanocomposite foams based on the assembly of
ing, Universiti Sains Malaysia (USM). They provided a wide variety starch and alginate with sepiolite fibrous clay. Carbohydr Polym
of unconditional facilities to make this research success. One of the 157:1933–1939
authors is also deeply indebted to the Ministry of Higher Education 18. Hapuarachchi TD, Peijs T (2010) Multiwalled carbon nanotubes
of Malaysia (KPT(BS)821115065540) and Universiti Teknologi Mara and sepiolite nanoclays as flame retardants for polylactide and its
(UiTM) (600-BPD (PKH.1/2/9946) for providing funding to conduct natural fibre reinforced composites. Compos A 41:954–963
this research. 19. Lowe DJ, Chapman AV, Cook S, Busfield JJC (2011) Natural
rubber nanocomposites by in situ modification of clay. Macromol
Mater Eng 296:693–702
20. Bidsorkhi HC, Soheilmoghaddam M, Heidar Pour R, Adelnia H,
Mohamad Z (2014) Mechanical, thermal and flammability prop-
References erties of ethylene-vinyl acetate (EVA)/sepiolite nanocomposites.
Polym Test 37:117–122
1. Rattanasom N, Saowapark T, Deeprasertkul C (2007) Reinforce- 21. Takei T, Oda R, Miura A, Kumada N, Kinomura N, Ohki R,
ment of natural rubber with silica/carbon black hybrid filler. Koshiyama H (2013) Effect of dispersion of sepiolite in sepi-
Polym Test 26:369–377 olite-NBR composite on the tensile strength. Compos Part B
2. Razzaghi-Kashani M, Hasankhani H, Kokabi M (2007) Improve- 44:260–265
ment in physical and mechanical properties of butyl rubber with 22. Shokrzadeh A, Naderi G, Esmizadeh E (2014) Mechanical and
montmorillonite organo-clay. Iran Polym J 16:671–679 rheological properties of calcium carbonate-filled ethylene pro-
3. Datta J, Kosiorek P, Wloch M (2016) Effect of high loading of pylene diene elastomer reinforced by metallic acrylate salt. Fibers
titanium dioxide particles on the morphology, mechanical and Polym 15:1694–1700
thermo-mechanical properties of the natural rubber-based com- 23. Wang F, Tang QG, Chen C, Chen YL, Liu HM, Liu HF (2013)
posites. Iran Polym J 25:1021–1035 Effect of sepiolite nanofibers on properties of EPDM nanocom-
4. Rooj S, Das A, Heinrich G (2011) Tube-like natural halloysite/ posites. Appl Mech Mater 320:595–598
fluoroelastomer nanocomposites with simultaneous enhanced 24. Mohd Zaini NA, Ismail H, Rusli A (2017) Short review on sepi-
mechanical, dynamic mechanical and thermal properties. Eur olite-filled polymer nanocomposites. Polym Plast Technol Eng
Polym J 47:1746–1755 56:1665–1679
5. Praveen S, Chattopadhyay PK, Albert P, Dalvi VG, Chakraborty 25. Flory PJ, Rehner J (1943) Statistical mechanics of cross-linked
BC, Chattopadhyay S (2009) Synergistic effect of carbon black polymer networks II. swelling. J Chem Phys 11:521
and nanoclay fillers in styrene butadiene rubber matrix: develop- 26. America Society for Testing and Materials: ASTM D635-14.
ment of dual structure. Compos A 40:309–316 Standard test method for rate of burning and/or extent and time
6. Pavlidou S, Papaspyrides CD (2008) A review on polymer-layered of burning of plastics in horizontal position
silicate nanocomposites. Prog Polym Sci 33:1119–1198 27. Chikh A, Benhamida A, Kaci M, Pillin I, Bruzaud S (2016) Syn-
7. Nguyen QT, Baird DG (2006) Preparation of polymer–clay nano- ergistic effect of compatibilizer and sepiolite on the morphology
composites and their properties. Adv Polym Technol 25:270–285 of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene
8. Pojanavaraphan T, Schiraldi DA, Magaraphan R (2010) Mechani- succinate) blends. Polym Test 53:19–28
cal, rheological, and swelling behavior of natural rubber/mont- 28. Suárez M, García-Romero E (2012) Variability of the surface
morillonite aerogels prepared by freeze-drying. Appl Clay Sci properties of sepiolite. Appl Clay Sci 67–68:72–82
50:271–279 29. Malas A, Das CK (2011) Carbon black–clay hybrid nanocompos-
9. Razavi-Nouri M, Karami M, Naderi G (2017) Rheological ites based upon EPDM elastomer. J Mater Sci 47:2016–2024
behavior and morphology of acrylonitrile-butadiene rubber/ 30. Teh PL, Ishak ZAM, Hashim AS, Karger-Kocsis J, Ishiaku US
poly(ethylene-co-vinyl acetate) blends filled by various organo- (2004) Effects of epoxidized natural rubber as a compatibilizer
clay contents. Appl Clay Sci 145:1–10 in melt compounded natural rubber-organoclay nanocomposites.
10. Chivrac F, Pollet E, Schmutz M, Avérous L (2010) Starch nano- Eur Polym J 40:2513–2521
biocomposites based on needle-like sepiolite clays. Carbohydr 31. Khimi SR, Pickering KL (2014) A new method to predict opti-
Polym 80:145–153 mum cure time of rubber compound using dynamic mechanical
11. Olivato JB, Marini J, Yamashita F, Pollet E, Grossmann MVE, analysis. J Appl Polym Sci 131:1–6
Avérous L (2017) Sepiolite as a promising nanoclay for nano- 32. Fröhlich J, Niedermeier W, Luginsland HD (2005) The effect of
biocomposites based on starch and biodegradable polyester. Mater filler-filler and filler-elastomer interaction on rubber reinforce-
Sci Eng C 70:296–302 ment. Compos A 36:449–460
12. Zotti A, Borriello A, Ricciardi M, Antonucci V, Giordano M, 33. Kamal MM, Clarke J, Ahmad A (2009) Comparison of properties
Zarrelli M (2015) Effects of sepiolite clay on degradation and fire of natural rubber compounds with various fillers. J Rubber Res
behaviour of a bisphenol A-based epoxy. Compos B 73:139–148 12:27–44

13
296 Iranian Polymer Journal (2018) 27:287–296

34. Nabil H, Ismail H, Azura AR (2013) Compounding, mechanical 38. Chen H, Zheng M, Sun H, Jia Q (2007) Characterization and
and morphological properties of carbon-black-filled natural rub- properties of sepiolite/polyurethane nanocomposites. Mater Sci
ber/recycled ethylene-propylene-diene-monomer (NR/R-EPDM) Eng A 445–446:725–730
blends. Polym Test 32:385–393 39. Khobragade PS, Hansora DP, Naik JB, Chatterjee A (2016) Flame
35. Sombatsompop N, Kumnuantip C (2003) Rheology, cure char- retarding performance of elastomeric nanocomposites: a review.
acteristics, physical and mechanical properties of tire tread Polym Degrad Stab 130:194–244
reclaimed rubber/natural rubber compounds. J Appl Polym Sci 40. Gong J, Tian N, Wen X, Chen X, Liu J, Jiang Z, Mijowska E,
87:1723–1731 Tang T (2014) Synergistic effect of fumed silica with N
­ i2O3 on
36. Bidsorkhi HC, Adelnia H, Naderi N, Moazeni N, Mohamad Z improving flame retardancy of poly(lactic acid). Polym Degrad
(2017) Ethylene vinyl acetate copolymer nanocomposites based Stab 104:18–27
on (un)modified sepiolite: flame retardancy, thermal, and mechan- 41. Dittrich B, Wartig KA, Hofmann D, Mülhaupt R, Schartel B
ical properties. Polym Compos 38:1302–1310 (2013) Flame retardancy through carbon nanomaterials: car-
37. Roy N, Bhowmick AK (2010) Novel in situ polydimethylsiloxane- bon black, multiwall nanotubes, expanded graphite, multi-layer
sepiolite nanocomposites: structure-property relationship. Poly- graphene and graphene in polypropylene. Polym Degrad Stab
mer 51:5172–5185 98:1495–1505

13