Morphology and Characterization of

Clay-reinforced EPDM Nanocomposites

SEYED JAVAD AHMADI, YU DONG HUANG* AND WEI LI

Department of Applied Chemistry, Faculty of Science
Polymer Materials and Engineering Division
Harbin Institute of Technology
Harbin 150001, People’s Republic of China

(Received January 12, 2003)

(Accepted July 17, 2004)

ABSTRACT: The clay-reinforced ethylene propylene diene terpolymer (EPDM)

nanocomposites with organo-montmorillonite (OMMT) and EPDM–clay conven-
tional composites with pristine MMT are compared in terms of their morphology,
mechanical properties, and solvent resistance. The maleic anhydride grafted EPDM
(MAH-g-EPDM) is used as the compatiblizer for preparing clay-reinforced EPDM
nanocomposites via a melt intercalation process. The formation of exfoliated nano-
composites is confirmed by X-ray diffraction (XRD) and transmission electron
microscopy (TEM). Furthermore, the morphological change during the mixing times
of vulcanization process through exerting shearing force on clay particles is
discussed. The mechanical properties and solvent resistance of clay-reinforced
EPDM nanocomposites are examined as a function of the organoclay content in the
matrix of the polymer, the result shows remarkable improvement relative to that of
conventional composites.

KEY WORDS: clay-reinforced EPDM nanocomposites, exfoliation, organoclay,

melt intercalation, morphology.

INTRODUCTION

DDITION OF INORGANIC fillers to a polymer matrix has been demonstrated to be an

A effective method to achieve reinforcement of the polymer hybrid materials consisting
of organic and inorganic components. Nanocomposites are formed when phase mixing
occurs on a nanometer length scale. Due to the improved phase morphology and
interfacial properties, nanocomposites exhibit mechanical, thermal, barrier, and chemical
properties superior to conventional composites [1–7]. Montmorillonite is the most
commonly used clay to prepare nanocomposites, but the lack of affinity between
hydrophilic layered silicates and hydrophobic polymer makes them difficult to be miscible

*Author to whom correspondence should be addressed. E-mail: huangyd@hope.hit.edu.cn

Journal of COMPOSITE MATERIALS, Vol. 39, No. 8/2005 745

0021-9983/05/08 0745–10 $10.00/0 DOI: 10.1177/0021998305048154
ß 2005 Sage Publications
746 S. J. AHMADI ET AL.

at the nanoscale level. Thus, chemical modification of layered silicates is important in the
preparation of nanocomposites. This can be done by an ion-exchange reaction through
ions that already exist in clay such as Kþ, Naþ, Caþ, Mgþ, and organic cations such as
alkyl ammonium ions to form the organosilicate [8]. The organosilicate can be broken
down into their nanoscale building blocks and uniformly dispersed in the polymer matrix.
When the clay platelets are thoroughly dispersed in the polymer matrix, the nano-
composites are ‘exfoliated.’
EPDM is an unsaturated polyolefin rubber with a wide range of applications. However,
it is incompatible with polar organophilic clay to prepare products having desired
properties because it does not include any polar group in its backbone. Recently, Kato et
al. [9–12] have reported a new approach to prepare nonpolar polymer clay hybrids by
using a functional oligomer. Till now, there are few studies on the formation, morphology,
and properties of EPDM–clay nanocomposites. Usuki et al. [13] and Chang et al. [14] have
reported the preparation and mechanical properties of EPDM–clay nanocomposites,
prepared via the vulcanization process by using some special vulcanization accelerators
and the melt compounding process with a liquid low molecular weight EPDM, respectively.
In this paper, we compare the clay-reinforced EPDM nanocomposites with EPDM–
clay conventional composites prepared through the melt blending method by using
maleic anhydride grafted EPDM (MAH-g-EPDM) as a compatibilizer, in terms of their
morphology, mechanical properties, and solvent resistance. The morphological change
caused by shearing force during the mixing times of vulcanization process is also discussed.

EXPERIMENTAL

Materials

Pure sodium montmorillonite (Kunipia-F) with a cation-exchange capacity (CEC)

of 119 meq/100 g was supplied by Kunimine Mining Ind. Co. (Tokyo, Japan).
Octadecylamine purchased from Fluka was used as the organic modifier for MMT.
MAH-g-EPDM (0.8 wt%) oligomer from Huzhou Genius Engineering Plastics Co. Ltd
(Huzhou, China) was used. The EPDM (J-3062E) ENB type was obtained from Jilin
Chemical Ind. Co., Ltd (Jilin, China). All chemicals were used without further
purification.

Preparation of Organophilic Clay and Clay-reinforced EPDM Nanocomposites

The organophilic clay was prepared via ion-exchange reaction in water by using
octadecylamine as the reference [11]. In order to prepare clay-reinforced EPDM nano-
composites, different amounts of organoclay powder were premixed by shaking with
100 phr (part per hundred of rubber by weight) of EPDM and 20 phr of MAH-g-EPDM in
a bag. This mixture was melt blended together in a twin-screw blender, model RM-200,
with a chamber size of about 40 cm3 at 150
C. The rotational speed of the screw was
90 rpm and mixing time was 15 min for all cases. To compare the properties of nano-
composites with that of the conventional composites, the EPDM–clay composites with
pristine MMT were prepared under the above-mentioned conditions. Then, the EPDM
hybrids (100 phr) were sequentially mixed with zinc oxide (5 phr), stearic acid (1 phr),
Morphology and Characterization of EPDM Nanocomposites 747

vulcanization accelerator [M (2-Mercapto benzothiazole, 0.5 phr) and TMTD (tetramethyl

thiuram disulfide, 1.5 phr)] and sulfur (1.5 phr) by using a roll mill, model SK-160B, at a
temperature about 60
C. The vulcanization was carried out in standard hot press at 150
C
for 30 min to yield rubber sheets (340  150  2 mm3).
To study the effect of MAH-g-EPDM as a compatibilizer, the composites of EPDM and
organoclay without MAH-g-EPDM were also prepared.

Measurement

The Fourier transform infrared (FT-IR) spectra were recorded on a Nicolet spectro-
photometer model Nexus-670 in the range of 400–4000 cm1. The KBr discs were used
for powder samples. Dispersibility of the organoclay in the polymer matrix was evaluated
by XRD and TEM. XRD patterns were recorded by a Phillips X’Pert X-ray generator
with Cu K
radiation at 40 kV and 40 mA. The diffractograms were scanned in 2 ranges
from 1 to 9
at a rate of 2.4
/min. The basal spacing of the silicate layers, d, was calcu-
lated according to Bragg’s equation,  ¼ 2dsin. A transmission electron micrograph was
obtained with a transmission electron microscope (H-800, Hitachi Co.) using an
acceleration voltage of 200 kV. The tensile measuring test was carried out with universal
tensile tester (Model DSC-5000, Shimadzu Co.) at 25
C with a head speed of 500 mm/min.
The shore hardness was measured by using a Shore-A hardness instrument (LX-A,
Shanghai Liuling Instrument Factory, China). All measurements were taken three times
and the result values were averaged. The solvent resistance of EPDM–clay hybrids was
measured as follows: The samples with similar shape (20  10  2 mm3) were entirely
immersed in a container of pure xylene (xylene is a good solvent for EPDM) maintained at
about 25
C for 24 h. The percentage of the change in mass was calculated by using the
formula:

M  M0
Change in mass% ¼  100
M0

where, M0 represents the dried weight of the specimen and M the weight of the specimen
after immersion.

RESULTS AND DISCUSSION

Morphology of Clay-reinforced EPDM Nanocomposites

IR, XRD, and TEM were used to investigate the morphology of clay-reinforced EPDM
nanocomposites. Figure 1 is the IR spectra of pristine MMT and organo-MMT. The
absorption band at 1090 cm1 was characteristic of Naþ-MMT (Figure 1(a)).
After the treatment, organo-MMT exhibited the characteristic bands of C–H stretching
at 2921 cm1 and 2850 cm1 as well as the peak at 1469 and 724 cm1 related to CH2
(Figure 1(b)). So it can be concluded that the alkyl ammonium has been exchanged
with cations of the MMT interlayer. Further evidence of ion-exchange reaction and
intercalation of alkyl ammonium chains between the nanolayers was supported by XRD
patterns. The X-ray diffraction patterns are shown in Figure 2. The peak of organo-MMT
748 S. J. AHMADI ET AL.

Figure 1. IR spectra of MMT and OMMT.

Figure 2. XRD patterns of (a) pure clay (MMT); (b) organoclay (OMMT); (c) EPDM þ MMT; and
(d) OMMT þ MAH-g-EPDM.

(Figure 2(b)) is shifted to lower angles compared with Naþ-MMT (Figure 2(a)). Thus,
the interlayer distance of Naþ-MMT was extended after organic modification with
the octadecylamine. This clearly indicates the intercalation of alkyl ammonium chains
between the silicate layers.
Figure 2(c) shows the XRD pattern of melt mixing of organoclay with EPDM (EPDM–
OMMT). It is clear that, the d-spacing of EPDM–OMMT is nearly the same as that
of OMMT (Figure 2(b)). It indicates that the EPDM–OMMT has deintercalated the
morphology, which may result from immiscibility between EPDM and organoclay
because EPDM does not include any polar group in its backbone.
Figure 2(d) shows the XRD patterns of composites of MAH-g-EPDM with organo-
MMT (MAH-g-EPDM–OMMT). After melt compounding, in the case of MAH-g-
EPDM–OMMT, the characteristic peak is widening and shifting to angles smaller than
that of organoclay. This indicates that the molecules of MAH-g-EPDM are intercalated
into the layered silicate of clay, expanding the basal spacing of organoclay. The strong
hydrogen bonding between the maleic anhydride group and the oxygen group of the
Morphology and Characterization of EPDM Nanocomposites 749

Figure 3. XRD patterns of EPDM–organoclay nanocomposites with different clay content: (a) before and
(b) after vulcanization process.

silicate as well as the shear force exerted on OMMT during melting compound can
produce the driving force necessary for the intercalation [9]. The interlayer spacing of the
clay as well as its compatibility with polymer are increased, so the clay galleries could
easily be intercalated with the EPDM.
The XRD results of EPDM–clay nanocomposites with different clay contents, (a)
before and (b) after vulcanization process, are shown in Figure 3. Before the vulcanization
process for some nanocomposites with low clay content (2–10 phr), an exfoliated structure
was obtained as verified by the absence of any distinct diffraction peak, as well as by TEM
observations. For some composites with high clay content (15 phr), there is a weak peak
around 2.5
, suggesting that some portion of the organoclay is aggregated, but it can
be seen that after the vulcanization process, the weak peak of the high clay content has
disappeared, which means the dispersion of organo-MMT in the EPDM matrix is
significantly improved and the basal spacing of clay layers has increased. A homogenized
dispersion of MMT in the EPDM matrix was obtained by applying high shear stress
during compounding by roll mill, which causes the agglomerates of organoclay to become
smaller and the intercalated structure to be transferred into an exfoliated structure. This
is caused by the shear-induced diffusion of polymer chains into the agglomerates and
the diffusion of polymer chains within the silicate galleries.
In general, the organophilic modification is accompanied by increasing interlayer
distances. Then, the energy gained through favorable interaction between the com-
patiblizer (MAH-g-EPDM) and the organo-silicate layer, while exerting a shearing force,
leads to obtaining exfoliation structure. It is to be emphasized that the coexistence of the
three parameters, clay modification, use of a suitable compatiblizer, and exerting a
shearing force were necessary for achieving a high degree of exfoliation structure in
EPDM–clay nanocomposites.
Figure 4 shows the XRD patterns of a vulcanized EPDM–clay conventional composite.
It contains two peaks at 7.1
corresponding to a basal spacing of 1.24 nm and 6.6

corresponding to a basal spacing of 1.33 nm. The peak at 7.1
(1.24 nm) is related to
silicate layers of MMT in EPDM clay composites (Figure 2(a)) and indicates that the
gallery distance of clay is not changed. Thus, the EPDM chains does not intercalate into
the gallery of MMT. The second peak that appears at 2 ¼ 6.6
(1.33 nm) which can also
be seen in the vulcanized EPDM and vulcanized mixture of EPDM þ MAH-g-EPDM
(Figure 5), maybe caused by a high content of ethylene in the EPDM that we used in this
750 S. J. AHMADI ET AL.

Figure 4. XRD patterns of vulcanized EPDM–clay composites with different clay content.

Figure 5. XRD patterns of: (a) vulcanized EPDM and (b) vulcanized EPDM þ MAH-g-EPDM.

study (about 68.5–74.5%). However, in the EPDM nanocomposites, this peak does not
exist (Figure 3). The strong interaction between the organoclay and the molecules of
polymer can change the morphology of nanocomposites.
Transmission electron microscopy was also used to visually evaluate the morphology
and dispersion of organoclay in the polymer matrix. Figure 6(a) determines that every
layer of silicate is well dispersed in the EPDM matrix and a high degree of exfoliation of
nanometer-size clay particles is obtained; the dark lines represent a cross section of the
clay layers. But in Figure 6(b), for EPDM composites prepared by pristine MMT, the
agglomerated particles are detected. From the above result, it can be concluded that
the modification of MMT with an organic modifier and MAH-g-EPDM as compatiblizer,
as well as the high shear stress are all important factors influencing the morphology
development of EPDM–organoclay nanocomposites.

Influence of Clay Dispersion on Mechanical Properties

The mechanical properties tests were performed on EPDM–clay hybrids under different
MMT loadings and the results are shown in Figures 7–9. Figure 7 shows that below 5 phr
OMMT, the tensile strength increases with increasing clay content but decreases a little bit
above 5 phr.
The EPDM–organoclay nanocomposites have higher values of tensile strength
when compared to the macrocomposites with the pristine clay and unfilled EPDM.
Morphology and Characterization of EPDM Nanocomposites 751

Figure 6. Transmission electron micrographs of: (a) EPDM–organoclay nanocomposites and (b) EPDM–clay
composites.

For example, the tensile strength of nanocomposites with 5 phr organoclay is about 175%
higher than that of the conventional composites with the same value of clay content
and also 158% bigger than that of unfilled EPDM.
The tensile modulus of EPDM nanocomposites also is higher than that of EPDM
composites and unfilled EPDM (Figure 8). For instance, by the addition of 15 phr clay
content, the tensile modulus of nanocomposites is increased to about 60% higher than
that of EPDM macrocomposites and 97% higher than that of EPDM without clay. The
enhancement in tensile strength and tensile modulus is directly attributed to the dispersion
of nanosilicate layers in the EPDM matrix and strong interaction between EPDM and
organoclay. The lower tensile strength above 5 phr OMMT can be attributed to the
inevitable aggregation of the silicate layers in high clay content.
A similar result is observed for the shore hardness of EPDM–clay hybrids (Figure 9).
The shore hardness of EPDM–organoclay nanocomposites increases with increase
in clay content. Improvement in hardness with increase in clay content for EPDM
752 S. J. AHMADI ET AL.

Figure 7. Effect of filler loading on tensile strength of: (a) EPDM–organoclay nanocomposites and (b) EPDM–
clay composites.

Figure 8. Effect of filler loading on tensile modulus of: (a) EPDM–organoclay nanocomposites and (b) EPDM–
clay composites.

Figure 9. Effect of filler loading on shore hardness for: (a) EPDM–organoclay nanocomposites, and
(b) EPDM–clay composites.
Morphology and Characterization of EPDM Nanocomposites 753

Figure 10. Solvent resistance of unfilled-EPDM, EPDM–organoclay nanocomposites, and EPDM–clay

composites with different clay content in pure xylene after 24 h at 25
C.

nanocomposites is observed to be greater than that of the conventional EPDM. The

uniformly distributed exfoliation platelets improved the stiffness of EPDM. The presence
of these stiff clay platelets and entanglement of polymer chains made the EPDM
nanocomposites harder.

Solvent Resistance Property of Clay-reinforced EPDM Nanocomposites

Figure 10 shows the results of the solvent uptake measurements of unfilled-EPDM,

EPDM–organoclay nanocomposites, and EPDM–clay composites. The nanocomposites
exhibited not only superior mechanical properties but also exceptional solvent resistance;
the solvent uptake ratio of the EPDM nanocomposites was lower than that of the unfilled-
EPDM and the conventional EPDM composites. For example, the solvent uptake ratio
was decreased from 358.8% for unfilled-EPDM and 351.2% for EPDM composites (clay
content of 5 phr clay) to 180.6% for EPDM nanocomposites (clay content same as that
of EPDM composites). This phenomenon can be explained by the fact that the large
aspect ratio of organo-MMT layers possesses excellent barrier properties, and especially
the exfoliated structure of MMT layers can maximize the available surface area of the
reinforcing phase [15].

CONCLUSIONS

EPDM nanocomposites and EPDM conventional composites were prepared through

the melt blending method. Their morphologies were demonstrated by XRD, IR and TEM,
the results show that the silicate layers of nanocomposites were exfoliated and dispersed
uniformly in the polymer matrix. The nanocomposites had superior mechanical properties
and solvent resistance when compared to that of the conventional composites. These
enhancements are attributed to the more uniformly dispersed nanoparticles of organoclay
in the polymer matrix.
754 S. J. AHMADI ET AL.

ACKNOWLEDGMENTS

The authors wish to thank the Harbin University of Science and Technology for
providing the twin-screw blender instrument and also to thank Heilongjiang Plastics
Engineering Institute of Technology for their technical help in the tensile properties
measurements.

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