Properties of SBR compounds filled with two kinds of filler, Epoxy-Polyester Hybrid resin(EPH) (10, 
20, 30, 40 phr) and Nanoclay (Closite 15 A) (1, 3, 5, 7 phr) were studied. Microcomposite samples and 
nanocomposite samples were prepared by Haake internal mixer. Curing agents and additives i.e. dicumylperoxide Properties of SBR compounds filled with two kinds of filler, Epoxy-Polyester Hybrid resin(EPH) (10, 
20, 30, 40 phr) and Nanoclay (Closite 15 A) (1, 3, 5, 7 phr) were studied. Microcomposite samples and 
nanocomposite samples were prepared by Haake internal mixer. Curing agents and additives i.e. containing 30 phr resin show higher value of modulus than sample containing 7 phr nanocaly. Rheological 
measurement showed that both fillers lead to an increase in viscosity and dynamic modulus of samples 
which is as a result of good interaction established between polymer/filler. Moreover, due to nanometer 
scale of nanoclay particles, reinforcing effect of Nanoclay was more noticeable and in micrometer scale of 
Epoxy-Polyester Hybrid particles, Epoxy resin cured by Polyester is used to improved wet ability of SBR 
compounds. SEM photomicrographs of cryogenically fractured samples confirmed the mentioned results.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3506

Alipour, A.

Haghnegahdar, M.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 1 No 1, 01NDLCN08(3pp) (2012) 
 
 
2304-1862/2012/1(1)01NDLCN08(3) 01NDLCN08-1  2012 Sumy State University 
Effects of Epoxy-Polyester Hybrid and Nanoclay on Morphology, Rheological and 
 Mechanical Properties of Styrene-Butadiene Rubber  
 
M. Haghnegahdar, A. Alipour 
 
Department of Polymer Engineering, Faculty of Graduate studies,  
Tehran South Branch, Islamic Azad University, Tehran, Iran 
 
(Received 19 June 2012; published online 24 August 2012) 
 
Properties of SBR compounds filled with two kinds of filler, Epoxy-Polyester Hybrid resin(EPH) (10, 
20, 30, 40 phr) and Nanoclay (Closite 15 A) (1, 3, 5, 7 phr) were studied. Microcomposite samples and 
nanocomposite samples were prepared by Haake internal mixer. Curing agents and additives i.e. di-
cumylperoxide (DCP), Carbon Black (CB) and oil were added to the compound on the two-roll mill. The 
modified silicate is analysed by X-ray which suggested intercalation of elastomer chains into silicate lay-
ers. Mechanical properties of the samples suggested that both fillers increase modulus, but sample con-
taining 30 phr resin show higher value of modulus than sample containing 7 phr nanocaly. Rheological 
measurement showed that both fillers lead to an increase in viscosity and dynamic modulus of samples 
which is as a result of good interaction established between polymer/filler. Moreover, due to nanometer 
scale of nanoclay particles, reinforcing effect of Nanoclay was more noticeable and in micrometer scale of 
Epoxy-Polyester Hybrid particles, Epoxy resin cured by Polyester is used to improved wet ability of SBR 
compounds. SEM photomicrographs of cryogenically fractured samples confirmed the mentioned results. 
 
Keywords: Rheological Properties, Epoxy-Polyester Hybrid, Nanoclay, XRD, SEM Photomicrograph, Me-
chanical Properties 
 
 PACS numbers: 61.05.cp, 62.25.–g 
 
 
1. INTRODUCTION 
 
Polymer–clay nanocomposites are of great interest 
for both scientific challenges and industrial applica-
tions [1–4]. In the open literatures, the polymer–clay 
nanocomposites are generally classified into three 
groups according to their structures, i.e., nanocompo-
sites with intercalated, exfoliated, or both of intercalat-
ed and exfoliated structures. To achieve a nano-scale 
dispersion of silicates in a polymer matrix, the silicates 
are generally pretreated with alkylammonium ions to 
produce an organoclay. This treatment is effective in 
opening up the gallery of silicate, and the organo-clays 
can then be easily dispersed in the polymer matrix and 
form nanocomposites with an intercalated or exfoliated 
structure. In the former case, the spacing between the 
silicate layers is increased by the incorporation of ex-
tended polymer chains into the layers. The tradition 
methods to prepare polymer nanocomposites are to 
intercalate monomers or polymers into swellable-layer 
silicate hosts, and especially for rubbers, there are 
mainly three kinds of methods for preparing the rubber 
matrix nanocomposites: latex, solution, and melt com-
pounding. Considering industrialization, melt interca-
lation is one of the feasible operations, in which poly-
mer is directly intercalated into modified silicate layers 
(organoclay) in the molten state to prepare nanocompo-
sites. The driving force of the intercalation is deter-
mined by physical and/or chemical interactions be-
tween polymers and modified silicate. Regarding to the 
low cost of the Epoxy-Polyester Hybrid resin(EPH) and 
improvement observed in rubber compounds, high ad-
vantages of using of EPH powders in polymer industry 
has been evidenced [5]. This study considers the effect 
of two kinds of fillers on the properties of SBR. 
 
 
2. EXPERIMENTAL 
 
2.1 Material 
 
SBR, Nanoclay (Closite 15A) , EPH and cure ingre-
dients were supplied from Bandar Imam petrochemical 
co, Southern clay company (U.S.A), Local company 
(Iran) and Bayer co respectively. 
 
2.2 Samples Preparation 
 
Samples were prepare by Haake internal mixer at 
temperature of 105 C and the rotor speed was 60 rpm 
for 7 min. Curing agents were mixed with compound on 
two-roll mill (Polymix 200 L) at 25 C and rotor speed 
of 70 rpm (see Table 1).  
 
2.3 Characterization 
 
X-ray diffraction patterns of the samples were record-
ed on a STANDI MP model X-ray Diffractometer “STOE”  
X’Pert (40 kV, 30 mA) by using Cu-Kα radiation 
(   1.540598 Å) with a scanning rate 2º/min at room tem-
perature. The basal spacing of silicates was estimated 
from the position of the plane peak in the WAXD intensity 
profile using the Bragg’s law, d  /(2sin max). The rheo-
logical measurements were performed using a RPA 2000 
oscillatory rheometer (Alpha Technology Company) at 
80 C  and frequency of 0.1-1000 (rad/sec). To study the 
morphology, the cryogenically tensile fractured of samples 
were coated with gold and viewed with a TESCAN scan-
ning electron microscope.  
 
3. RESULTS AND DISCUSSION 
 
XRD is a powerful technique to follow the intercala-
tion of elastomer chains into the silicate layers of clay 
and dispersion of organoclay in the polymer matrixn.  
 M. HAGHNEGAHDAR, A. ALIPOUR PROC. NAP 1, 01NDLCN08 (2012) 
 
 
 01NDLCN08-2  
Table 1 – Composition of Prepared Samples 
 
Sample Code SBR(phr) Cloisite15A(phr) EPH (phr) 
Carbon 
Black(phr) 
Oil(phr) DCP(phr) 
S 100 - - 30 5 0.5 
N1 100 1 - 30 5 0.5 
N3 100 3 - 30 5 0.5 
N5 100 5 - 30 5 0.5 
N7 100 7 - 30 5 0.5 
P10 100 - 10 30 5 0.5 
P20 100 - 20 30 5 0.5 
P30 100 - 30 30 5 0.5 
P40 100 - 40 30 5 0.5 
 
Fig. 1 shows the XRD patterns Prepared samples. 
The interlayer spacing of the original Cloisite 15A 
(2   2.97), (d  31.5Å). Shift of the organoclay diffrac-
tion peak to lower 2θ values indicated that elastomer  
chains intercalated between consequent silicate layers. 
This clearly indicates that inter lamellar spacing of the 
clay are enlarged after melt compounding.  As expected 
intensity increases with an increase in nanoclay. Fig. 2 
shows the comparison of complex viscosity and dynam-
ic moduli, G' of sample containing nanoclay and EPH. 
As seen, both fillers have a increasing effect in rheolog-
ical properties. In fact addition of nanoclay and EPH, 
lead to an increase in complex viscosity which can be 
attributed to the good interaction established in the 
interface of polymer/filler. It is noticeable that EPH 
causes a greater effect on the viscosity which means 
more reinforcing than nanoclay. Moreover the viscosity 
has a descending trend by frequency increase which is 
because of pseudoplastic nature of compounds. On the 
other hand, G' of samples have a ascending trend by 
filler loading. In comparison with pristine SBR, the 
filled samples show higher value of dynamic modui. It 
is because of this fact that both fillers form a network 
structure which increases interaction between poly-
mer/filler and as a consequence, G' increases. It is obvi-
ous that EPH filled samples show higher dynamic 
moduli[3, 6]. Insights on the morphology of prepared 
sample are illustrated in Fig. 3 where SEM images in 
the same magnification of cryogenically fractured of 
samples with and without  EPH and Nanoclay are re-
ported The harsh fracture surface of sample containing 
5% nanoclay and sample containing 30 phr EPH com-
pared to pristine SBR  is representative of good inter-
action between matrix and filler particles, implying the 
effective reinforcement of fillers. 
 
2 4 6 8 10
2θ ( degree )
In
te
n
si
ty
 (
 a
.u
 )
N7
N5
N3
N1
 
 
Fig. 1 –  XRD results of prepared samples 
1.00E+00
1.00E+02
1.00E+04
1.00E+06
1.00E+08
0.01 0.1 1 10 100 1000
Frequency ( Rad/Sec )
C
o
m
p
le
x
 V
is
c
o
s
it
y
 (
 P
a
.S
 )
1
10
100
1000
G
' 
( 
K
p
a
 )
S
N1
N3
N5
N7
 
 
Fig. 2 – Rheological properties of samples filled with a) EPH 
and b) Nanoclay 
 
 
 
 
 
 S 
P30 
P 
N5 P30 
 EFFECTS OF EPOXY-POLYESTER HYBRID … PROC. NAP 1, 01NDLCN08 (2012) 
 
 
01NDLCN08-3 
 
 
Fig. 3 – SEM Photomicrographs of samples 
 
 
4. CONCLUSION 
 
Rubber comounds based on SBR/nanoclay and 
SBR/EPH were prepared via vulcanization process and 
characterized by several techniques. In these materials 
rubber chains could penetrate into silicate layers re-
sulting an increase in d-spacing of layers which was 
confirmed by XRD results. On the other hand enhanced 
viscosity and dynamic modulus of samples suggested a 
good interaction between polymer matrix and filler 
particles that also was viewed by SEM photomicro-
graphs.  
 
REFRENCES 
 
1. A. Alipour et al., Proc of 3rd Conference on Nanostructres, 
(Kish Island: Iran: 2010). 
2. S. Varghese, K. Gatos, A. Apostolov, J. Karger-Kocsis, J. 
Appl. Polym. Sci. 92, 543 (2004). 
3. S. Varghese, J. Karger-Kocsis, K. Gatos, Polymer 44, 3977 
(2003). 
4. K. Urayama, T. Kawamura, S. Kohjiya, Macromol. 34, 
8261 (2001). 
5. Y. Jahani, M. Ehsani, Polym. Eng. Sci. 49, 619 (2009). 
6. Y. Wang, Zhang, H.-Z Wu, Y.-P, J. Appl. Polym. Sci. 96, 
318 (2005). 
 
N
5 


English

Effects of Epoxy-Polyester Hybrid and Nanoclay on Morphology, Rheological and   Mechanical Properties of Styrene-Butadiene Rubber

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 1 No 1, 01NDLCN08(3pp) (2012)   2304-1862/2012/1(1)01NDLCN08(3) 01NDLCN08-1  2012 Sumy State University Effects of Epoxy-Polyester Hybrid and Nanoclay on Morphology, Rheological and  Mechanical Properties of Styrene-Butadiene Rubber   M. Haghnegahdar, A. Alipour  Department of Polymer Engineering, Faculty of Graduate studies,  Tehran South Branch, Islamic Azad University, Tehran, Iran  (Received 19 June 2012; published online 24 August 2012)  Properties of SBR compounds filled with two kinds of filler, Epoxy-Polyester Hybrid resin(EPH) (10, 20, 30, 40 phr) and Nanoclay (Closite 15 A) (1, 3, 5, 7 phr) were studied. Microcomposite samples and nanocomposite samples were prepared by Haake internal mixer. Curing agents and additives i.e. di-cumylperoxide (DCP), Carbon Black (CB) and oil were added to the compound on the two-roll mill. The modified silicate is analysed by X-ray which suggested intercalation of elastomer chains into silicate lay-ers. Mechanical properties of the samples suggested that both fillers increase modulus, but sample con-taining 30 phr resin show higher value of modulus than sample containing 7 phr nanocaly. Rheological measurement showed that both fillers lead to an increase in viscosity and dynamic modulus of samples which is as a result of good interaction established between polymer/filler. Moreover, due to nanometer scale of nanoclay particles, reinforcing effect of Nanoclay was more noticeable and in micrometer scale of Epoxy-Polyester Hybrid particles, Epoxy resin cured by Polyester is used to improved wet ability of SBR compounds. SEM photomicrographs of cryogenically fractured samples confirmed the mentioned results.  Keywords: Rheological Properties, Epoxy-Polyester Hybrid, Nanoclay, XRD, SEM Photomicrograph, Me-chanical Properties   PACS numbers: 61.05.cp, 62.25.–g   1. INTRODUCTION  Polymer–clay nanocomposites are of great interest for both scientific challenges and industrial applica-tions [1–4]. In the open literatures, the polymer–clay nanocomposites are generally classified into three groups according to their structures, i.e., nanocompo-sites with intercalated, exfoliated, or both of intercalat-ed and exfoliated structures. To achieve a nano-scale dispersion of silicates in a polymer matrix, the silicates are generally pretreated with alkylammonium ions to produce an organoclay. This treatment is effective in opening up the gallery of silicate, and the organo-clays can then be easily dispersed in the polymer matrix and form nanocomposites with an intercalated or exfoliated structure. In the former case, the spacing between the silicate layers is increased by the incorporation of ex-tended polymer chains into the layers. The tradition methods to prepare polymer nanocomposites are to intercalate monomers or polymers into swellable-layer silicate hosts, and especially for rubbers, there are mainly three kinds of methods for preparing the rubber matrix nanocomposites: latex, solution, and melt com-pounding. Considering industrialization, melt interca-lation is one of the feasible operations, in which poly-mer is directly intercalated into modified silicate layers (organoclay) in the molten state to prepare nanocompo-sites. The driving force of the intercalation is deter-mined by physical and/or chemical interactions be-tween polymers and modified silicate. Regarding to the low cost of the Epoxy-Polyester Hybrid resin(EPH) and improvement observed in rubber compounds, high ad-vantages of using of EPH powders in polymer industry has been evidenced [5]. This study considers the effect of two kinds of fillers on the properties of SBR.   2. EXPERIMENTAL  2.1 Material  SBR, Nanoclay (Closite 15A) , EPH and cure ingre-dients were supplied from Bandar Imam petrochemical co, Southern clay company (U.S.A), Local company (Iran) and Bayer co respectively.  2.2 Samples Preparation  Samples were prepare by Haake internal mixer at temperature of 105 C and the rotor speed was 60 rpm for 7 min. Curing agents were mixed with compound on two-roll mill (Polymix 200 L) at 25 C and rotor speed of 70 rpm (see Table 1).   2.3 Characterization  X-ray diffraction patterns of the samples were record-ed on a STANDI MP model X-ray Diffractometer “STOE”  X’Pert (40 kV, 30 mA) by using Cu-Kα radiation (   1.540598 Å) with a scanning rate 2º/min at room tem-perature. The basal spacing of silicates was estimated from the position of the plane peak in the WAXD intensity profile using the Bragg’s law, d  /(2sin max). The rheo-logical measurements were performed using a RPA 2000 oscillatory rheometer (Alpha Technology Company) at 80 C  and frequency of 0.1-1000 (rad/sec). To study the morphology, the cryogenically tensile fractured of samples were coated with gold and viewed with a TESCAN scan-ning electron microscope.   3. RESULTS AND DISCUSSION  XRD is a powerful technique to follow the intercala-tion of elastomer chains into the silicate layers of clay and dispersion of organoclay in the polymer matrixn.   M. HAGHNEGAHDAR, A. ALIPOUR PROC. NAP 1, 01NDLCN08 (2012)    01NDLCN08-2  Table 1 – Composition of Prepared Samples  Sample Code SBR(phr) Cloisite15A(phr) EPH (phr) Carbon Black(phr) Oil(phr) DCP(phr) S 100 - - 30 5 0.5 N1 100 1 - 30 5 0.5 N3 100 3 - 30 5 0.5 N5 100 5 - 30 5 0.5 N7 100 7 - 30 5 0.5 P10 100 - 10 30 5 0.5 P20 100 - 20 30 5 0.5 P30 100 - 30 30 5 0.5 P40 100 - 40 30 5 0.5  Fig. 1 shows the XRD patterns Prepared samples. The interlayer spacing of the original Cloisite 15A (2   2.97), (d  31.5Å). Shift of the organoclay diffrac-tion peak to lower 2θ values indicated that elastomer  chains intercalated between consequent silicate layers. This clearly indicates that inter lamellar spacing of the clay are enlarged after melt compounding.  As expected intensity increases with an increase in nanoclay. Fig. 2 shows the comparison of complex viscosity and dynam-ic moduli, G' of sample containing nanoclay and EPH. As seen, both fillers have a increasing effect in rheolog-ical properties. In fact addition of nanoclay and EPH, lead to an increase in complex viscosity which can be attributed to the good interaction established in the interface of polymer/filler. It is noticeable that EPH causes a greater effect on the viscosity which means more reinforcing than nanoclay. Moreover the viscosity has a descending trend by frequency increase which is because of pseudoplastic nature of compounds. On the other hand, G' of samples have a ascending trend by filler loading. In comparison with pristine SBR, the filled samples show higher value of dynamic modui. It is because of this fact that both fillers form a network structure which increases interaction between poly-mer/filler and as a consequence, G' increases. It is obvi-ous that EPH filled samples show higher dynamic moduli[3, 6]. Insights on the morphology of prepared sample are illustrated in Fig. 3 where SEM images in the same magnification of cryogenically fractured of samples with and without  EPH and Nanoclay are re-ported The harsh fracture surface of sample containing 5% nanoclay and sample containing 30 phr EPH com-pared to pristine SBR  is representative of good inter-action between matrix and filler particles, implying the effective reinforcement of fillers.  2 4 6 8 102θ ( degree )Intensity ( a.u )N7N5N3N1  Fig. 1 –  XRD results of prepared samples 1.00E+001.00E+021.00E+041.00E+061.00E+080.01 0.1 1 10 100 1000Frequency ( Rad/Sec )Complex Viscosity ( Pa.S )1101001000G' ( Kpa )SN1N3N5N7  Fig. 2 – Rheological properties of samples filled with a) EPH and b) Nanoclay       S P30 P N5 P30  EFFECTS OF EPOXY-POLYESTER HYBRID … PROC. NAP 1, 01NDLCN08 (2012)   01NDLCN08-3   Fig. 3 – SEM Photomicrographs of samples   4. CONCLUSION  Rubber comounds based on SBR/nanoclay and SBR/EPH were prepared via vulcanization process and characterized by several techniques. In these materials rubber chains could penetrate into silicate layers re-sulting an increase in d-spacing of layers which was confirmed by XRD results. On the other hand enhanced viscosity and dynamic modulus of samples suggested a good interaction between polymer matrix and filler particles that also was viewed by SEM photomicro-graphs.   REFRENCES  1. A. Alipour et al., Proc of 3rd Conference on Nanostructres, (Kish Island: Iran: 2010). 2. S. Varghese, K. Gatos, A. Apostolov, J. Karger-Kocsis, J. Appl. Polym. Sci. 92, 543 (2004). 3. S. Varghese, J. Karger-Kocsis, K. Gatos, Polymer 44, 3977 (2003). 4. K. Urayama, T. Kawamura, S. Kohjiya, Macromol. 34, 8261 (2001). 5. Y. Jahani, M. Ehsani, Polym. Eng. Sci. 49, 619 (2009). 6. Y. Wang, Zhang, H.-Z Wu, Y.-P, J. Appl. Polym. Sci. 96, 318 (2005).  N5 

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Effects of Epoxy-Polyester Hybrid and Nanoclay on Morphology, Rheological and Mechanical Properties of Styrene-Butadiene Rubber

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