Composites Part A 121 (2019) 254–264

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Composites Part A
journal homepage: www.elsevier.com/locate/compositesa

Construction of multiple crosslinking networks in EPDM rubber: Synergistic T

reinforcing effect of graphene-zinc dimethacrylate on EPDM and
improvement mechanism of sealing resilience
⁎
Zun Yuana, Weihang Lib, Chengjie Lia, Lin Yea,
a
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065, China
b
School of Electronic and Engineering, University of Electronic Science and Technology of China, Chengdu 611731, China

A R T I C LE I N FO A B S T R A C T

Keywords: EPDM/Graphene (GN) - Zinc dimethacrylate (ZDMA) nano-composite was prepared by in situ formation of
Polymer-matrix composites ZDMA in GN layers. Both EPDM and ZDMA molecules were confirmed to intercalate into GN layers with strong
Interface/interphase interfacial interactions and high efficiency. Compared with neat EPDM, addition of GN-ZDMA resulted in 291%
Microstructural analysis increase of tensile strength and 48% increase of elongation at break, superior to that of EPDN/GN and EPDM/
Compression molding
ZDMA. Furthermore, the increase in compression set and decrease in contact stress relaxation coefficient can be
retarded during aging, resulting in enhancing durable sealing resilience. GN sheets were homogeneously em-
bedded in matrix, which helped uniform distribution of ZDMA itself. During vulcanization process, multiple
crosslinking networks was constructed, including covalent crosslinking from EPDM, ZDMA and aid of GN, and
ionic crosslinking from poly-ZDMA, resulting in significant increase in crosslinking density and retention ratio
during aging, and thus exhibiting synergistic reinforcing and stabilizing effect of GN-ZDMA on EPDM.

1. Introduction
Ethylene-propylene-diene monomer (EPDM) rubber with saturated
and nonpolar main chain, is copolymerized by ethylene, propylene and
unsaturated diene [1,2]. It exhibits high elasticity at low temperature,
excellent heat and ozone resistance, and superior electrical insulation
property, and is extensively applied in seals, conveyor belts, waterproof
materials, cables, and so on [3,4]. Especially, EPDM is one of the most
widely used sealing materials. Under constant strain or deformation in
sealing applications, the retained stress in such deformed EPDM seals
declines during use and eventually loses its sealing function. The resi-
lience performance of EPDM characterizes the capability of retaining
stress during use as a sealing material, while compression set and
contact stress relaxation behavior are important indicators reflecting
the resilience performance of EPDM. In general, EPDM is usually re-
inforced with inorganic fillers, like carbon black (CB), carbon white
(SiO2), montmorillonite, etc. Valentini et al. [5] prepared EPDM/CB
composite by using a two-roll milling. It was observed that addition of
48 wt% carbon black (CB) resulted in a roughly 35% increase in tensile
strength. Mokhothu et al. [6] prepared EPDM/silica nano-composites
via solution-blending, while addition of 10 wt% SiO2 resulted in a
roughly 157% increase in tensile strength. Usuki et al. [7] prepared
EPDM-clay hybrid materials via the method of melt-blending and two-
roll milling, and addition of 15 wt% montmorillonite (OMMT) resulted
in a roughly 44% increase in tensile strength, and 23% increase in
elongation at break. Although these solid fillers have been proven to be
beneficial for improving mechanical properties for EPDM, their dosage
is usually in great demand and their efficiency needs to be improved.
Moreover, the sealing resilience performance of the composites was far
less investigated.
Graphene nanosheets (GNs), as a two-dimensional material with
one-atom-thick planar sheet, have received worldwide attention due to
unique properties, like excellent mechanical strength, high electrical
and thermal conductivities, and superior load-bearing capacity [8,9]. In
addition, GN with extremely large specific surface area can prevent the
diffusion of oxygen in polymer matrix and the outward diffusion of
degradation products. In the meantime, GNs has a high electronic af-
finity to capture the free radicals produced by molecular degradation,
which has a significant stabilization effect on polymer materials
[10,11]. The incorporation of small amount of GNs to EPDM matrix can
achieve remarkable enhancement in mechanical and thermal con-
ductive properties. Tang et al. [12] prepared EPDM/GO nano-compo-
site via the method of solution-blending and two-roll milling. It was
observed that by addition of 0.5 wt% GO, the tensile modulus and

⁎
Corresponding author.
E-mail address: yelinwh@126.com (L. Ye).

https://doi.org/10.1016/j.compositesa.2019.03.039
Received 29 January 2019; Received in revised form 22 March 2019; Accepted 25 March 2019
Available online 26 March 2019
1359-835X/ © 2019 Published by Elsevier Ltd.
Z. Yuan, et al.
strength, and elongation at the break of EPDM increased by 130%, 50%
and 30%, respectively. Allahbakhsh A et al. [13] prepared EPDM/GO-
sodium dodecyl sulfate (SDS) nano-composite by using a modified
technique based on Hummers' method and two-roll milling. Rheometry
analysis showed that the physical interactions between EPDM and GO
molecules were improved in presence of SDS, while the maximum
tensile strength of the composite increased by 137%. Lei et al. [14]
prepared EPDM/GN composite by using a Haake internal mixer. It was
found that the thermal conductivity of the composite increased with GN
fraction, fitting well with Geometric Mean Model, reaching
0.910 W·m−1·K−1 at 2 wt% GN content, being 4.5 times that of neat
EPDM. Although plenty of researches have been dedicated to various
EPDM/GN composites [15–17], researches on the structure, sealing
resilience property of EPDM/GN nano-composites as sealing materials
were rarely reported.
As one kind of unsaturated carboxylic acid salt, zinc dimethacrylate
(ZDMA) is usually used as active crosslinking agent of rubber, which
can be polymerized under the initiation of peroxide, and dispersed in
the matrix by nanoparticles to improve the crosslinking density and
mechanical strength of EPDM matrix [18,19]. Meanwhile, ionic groups
of ZDMA were introduced into rubber molecular chains, which ag-
gregated to further form ionic crosslinking network. In this work, based
on the industrial product of GN, on its surface with a small amount of
oxygen groups as the reactive sites, α-methacrylic acid (MAA) was first
intercalated into GN layers during two-roll milling of EPDM, then zinc
oxide (ZnO) particles was added, and thus zinc dimethacrylate (ZDMA)
can be expected to in situ form in GN layers. Meanwhile, the formed
ZDMA acted as a bridge to improve the compatibility of GN and EPDM.
Therefore, during the process of vulcanization, a multiple network
structure composed of covalent crosslinking bond of EPDM/ZDMA,
ionic crosslinking bond of ZDMA, and GN centered crosslinking net-
work can be constructed in EPDM rubber. The intercalation behavior
and structure, the synergistic reinforcing and stabilizing effects of GN-
ZDMA on EPDM were investigated. In addition, the improvement me-
chanism of sealing resilience was explored.
2. Experimental section
2.1. Materials
EPDM (Keltan8550 with 55 wt% ethylene and 5.5 wt% 5-ethyli-
dene-2-norbornene (ENB)) was purchased from Lanxess Co. Ltd
(Germany). α-methacrylic acid (MAA) and Zinc oxide (ZnO) with
analytical grade was purchased from Kelong Chemical Reagents Co.
Ltd. (Chengdu, China). GNs with micron grade size particles were ob-
tained from Sixth Element Materials Technology Co. Ltd. (Changzhou,
China). Other rubber ingredients were industrially available products
and used as received.
2.2. In situ preparation of EPDM/GN-ZDMA nano-composite
The preparation of EPDM/GN-ZDMA (10.5 wt% based on EPDM)
nano-composite was carried out by two-roll milling and hot pressing
process. Under the strong shear force of two roll, GN powders (6 wt%
based on EPDM) was first added into EPDM to be mixed thoroughly,
and then MAA was dripped slowly into the mixture. Afterward, Zinc
oxide (ZnO) was added to in situ form ZDMA (4.5 wt% based on EPDM).
Furthermore, other rubber ingredients and curing agents were se-
quentially added. The rubber mixture were finally were subjected to
curing at 170 °C and 15 MPa by compression molding. The resulted
vulcanized rubber was denoted as EPDM/GN-ZDMA. For comparison,
the samples of neat EPDM, EPDM/GN (10.5 wt% based on EPDM)
composite and EPDM/ZDMA (10.5 wt% based on EPDM) composite
were also prepared via the same procedure.
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Composites Part A 121 (2019) 254–264
2.3. Measurements
2.3.1. FT-IR analysis
The structure of GN samples was analyzed with a Nicolet-560
Fourier-transform infrared (FT-IR) spectrometer (U.S.A). The scanning
rate was 20 min−1, and the resolution was 4 cm−1.
2.3.2. X-ray photoelectron spectroscopy (XPS) analysis
The XPS analysis of GN samples was performed on a XSAM 800
spectrometer (KRATOS Co., UK), using AlKa radiation (1486.6 eV) at a
pressure of 2.0 × 10−7 Pa.
2.3.3. Thermo-gravimetric (TGA) analysis
The intercalation ratio of GN samples was investigated with TA2950
thermo-balance from TA Co. (USA) under nitrogen atmosphere. The
samples (10 mg) were heated from room temperature to 800 °C under a
heating rate of 10 °C/min.
2.3.4. X-ray diffraction (XRD) analysis
The interlayer spacing of GN samples were measured with RigakuD/
max III B X-ray diffraction equipment (Japan). Cu Kα radiation
(λ = 0.154 nm) was used at a generator voltage of 40 kV and current of
35 mA. The d-spacing of the GN samples were calculated with Bragg
equation:
2dsinθ = n λ (1)
where θ is the diffraction angle; n is the order of diffraction and λ is the
incident wave length.
2.3.5. Scanning electron microscopy (SEM) analysis
The morphology of the cryogenically fractured and tensile fractured
surfaces of EPDM composites was observed with a JEOL JSM-5900LV
SEM (Japan). The operating voltage was 15 kV. The samples were ion
beam sputter-coated with gold with sheet thickness of 1–20 nm.
2.3.6. Transmission electron microscopy (TEM) analysis
The micro-structure of EPDM composites was observed on JEOL
JEM 100CX II TEM equipment (Japan), and the acceleration voltage of
200 kV was applied.
2.3.7. Mechanical properties
The tensile performance of EPDM composites was measured with a
4302 material testing machine from Instron Co. (U.S.A), according to
ISO 37-2005. The tensile speed was 500 mm/min, the standard sample
was dumbbell-shaped section with a thickness of 2 mm, a length of
75 mm and a width of 4 mm.
2.3.8. Dynamic mechanical analysis (DMA)
Dynamic mechanical properties of EPDM composites were tested on
a DMA Q800 apparatus (TA instruments) with a tension mode at a
frequency of 1 Hz. The linear viscoelastic properties were investigated
under maximum amplitude of 20 µm and heating rate of 3 °C min−1 in
the range of −80 to 30 °C.
2.3.9. Compression set
The compression set of EPDM composites was measured with rubber
compression deformation tester (Model A) at 150 °C after prolonged
compression at constant strain (25%), according to ISO 815-1:2014.
The standard cylinder specimen was prepared with a diameter of
29.0 ± 0.5 mm and a height of 12.5 ± 0.5 mm. The compression set
of EPDM nano-composites was calculated with Eq. (2).
h 0 − h1
c(%) = × 100%
h 0 − hs (2)
where h0 and h1 are sample height of EPDM nano-composites before
and after aging, respectively; hs is the height of the limiter.
Z. Yuan, et al. Composites Part A 121 (2019) 254–264

Scheme 1. Schematic illustration of preparation process of EPDM/GN-ZDMA. (For interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)

2.3.10. Contact stress relaxation coefficient (Kc)

The contact stress of EPDM composites was measured with a 4302
material testing machine from Instron Co. (U.S.A), according to ISO
7743-2007. The sample was compressed at a speed of 1 mm/min until
reaching the compressive height, and the contact stress value was re-
corded. The contact stress relaxation coefficient Kc of EPDM samples
was then calculated as follows:
σ
Kc =
σ0 (3)

where σ0 and σ were the contact stress of EPDM sample before and after
aging (MPa), respectively.

3. Results and discussion

The EPDM/GN-ZDMA nano-composite was prepared through con-

ventional two-roll milling and hot pressing process. As described in
Scheme 1, GN was first added into EPDM to mix uniformly, and then
MAA was added and intercalated into GN layers during two-roll milling
of EPDM. Next zinc oxide (ZnO) particles was added, and thus zinc
dimethacrylate (ZDMA) can in situ form in GN layers through the
neutralization reaction of MAA and ZnO. During further vulcanization,
a multiple network structure can be expected to be constructed in
EPDM rubber.
3.1. Intercalation structure of EPDM/GN-ZDMA nano-composite
For studying intercalation structure of EPDM/GN-ZDMA nano-
composite, the composite sample was dissolved in cyclohexane, cen-
trifugated and washed repeatedly with cyclohexane to remove free
EPDM molecules, and the resultant hybrid GN sample was denoted as
GN-EPDM-ZDMA. For comparison, the hybrid sample prepared in ab-
sence of ZnO or ZnO/MAA was denoted as GN-EPDM-MAA and GN-
EPDM, respectively.
The structural features of GN, GN-EPDM, GN-EPDM-MAA and GN-
EPDM-ZDMA were characterized by FT-IR, as shown in Fig. 1. For GN,
the absorption peak at 3438.6 cm−1 was attributed to OeH stretching
vibration, the band at 1634 cm−1 was related to eOH bending vibra-
tion or C]C skeletal ring vibration, and the absorption peaks at
Fig. 1. FT-IR spectra of GN, GN-EPDM, GN-EPDM-MAA and GN-EPDM-ZDMA.
(For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
1121.5 cm−1 and 860.3 cm−1 were attributed to CeOeC asymmetric
and symmetric stretching vibrations, respectively [20]. These vibra-
tions revealed the existence of hydroxyl (OeH) and epoxy (CeOeC)
groups on GN surface. For GN-EPDM, besides the above characteristic
peaks attributed to GN, the new peaks at 2920.0 cm−1 and
2851.5 cm−1 were observed, related to asymmetric and symmetric
stretching vibrations of methylene (eCH2e) groups on EPDM molecules
[21], respectively, indicating that EPDM molecules were intercalated
into GN layers. For GN-EPDM-MAA, the spectrum resembled that of
GN-EPDM sample, and the red-shift of hydroxyl (OeH) suggested the
hydrogen-bonding interactions between oxygen group of GN and car-
boxyl group of MAA molecules. Furthermore, the new peaks at
1775.3 cm−1 and 1635.5 cm−1 can be observed, which were attributed
to C]O stretching vibration and C]C stretching vibration of MAA
[22]. These results indicated that EPDM and MAA molecules were ef-
fectively intercalated into GN layers. For GN-EPDM-ZDMA, the red-shift

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Fig. 2. XPS results for all samples (a) and the related C1s and Zn2p spectra of GN (b), GN-EPDM, GN-EPDM-MAA (c) and GN-EPDM-ZDMA (d, e, f). (For interpretation
of the references to color in this figure legend, the reader is referred to the web version of this article.)

of hydroxyl (OeH) suggested the hydrogen-bonding interactions be-

tween oxygen group of GN and carbonyl group of ZDMA molecules. In
addition, the broad peaks at 1560.3–1521.9 cm−1 corresponded to
stretching vibration of C]O groups of ZDMA, which shifted to low
frequency because C]O bond and CeO bond were homogenized. Due
to conjugation of C]O and C]C double bonds in ZDMA, the stretching
vibration of C]C double bonds shifted to high frequency of
1640.6 cm−1. Moreover, the new peaks at 985.1 cm−1 and 875.1 cm−1
were ascribed to C-H external bending vibration of C]C double bond
on ZDMA molecules [23]. The above analysis indicated in situ forma-
tion of ZDMA in GN layers by reaction of MAA with ZnO.
The elemental composition of GN, GN-EPDM, GN-EPDM-MAA and
GN-EPDM-ZDMA was analyzed with XPS analysis (Fig. 2(a)), and the
corresponding elements percentages were listed in Table 1. For GN, two
peaks at 285.5 eV (C1s) and 533.8 eV (O1s) were detected. For GN-
EPDM, the spectrum resembled that of GN sample, but the content of C
element was higher than that of GN due to intercalation of EPDM
Fig. 3. TGA curves of GN, GN-EPDM, GN-EPDM-MAA and GN-EPDM-ZDMA.
molecules into GN layers. For GN-EPDM-MAA, besides signals of C1s (For interpretation of the references to color in this figure legend, the reader is
and O1s, no new peak of other element was found. However, the content referred to the web version of this article.)
of O element was higher than that of GN due to intercalation of MAA
molecules into GN layers. For GN-EPDM-ZDMA, besides strong signals
CeOH at 285.9 eV and CeOeC at 287.4 eV. However, for GN-EPDM-
of C1s and O1s, the new peaks at 1022.7 eV (Zn2P3/2) and 1045.9 eV
MAA and GN-EPDM-ZDMA, the new appearance of O]CeO at
(Zn2P1/2) were observed, revealing that ZDMA molecules were inter-
289.3 eV in Fig. 3(c, d) indicated presence of MAA and ZDMA mole-
calated into GN layers [24].
cules in GN layers. Meanwhile, Zn2P3/2 and Zn2P1/2 peak ascribed to
The C1s core level spectrum of GN with peak-fitting curves in
the ZDMA were observed in Zn spectrum for GN-EPDM-ZDMA [25],
Fig. 2(b) showed three components: sp2 C]C and sp3 CeC at 284.6 eV,
further demonstrating intercalation of EPDM and ZDMA molecules into
GN layers.
Table 1 TGA was conducted to quantify the intercalation ratio of EPDM,
Percentage of atomic composition of GN, GN-EPDM, GN-EPDM-MAA and GN- MAA and ZDMA molecules into GN layers, as shown in Fig. 3. The
EPDM-ZDMA. sample of GN showed a weight loss of 4.78% in range of 30–800 °C due
Samples C (%) O (%) Zn (%)
to removal of water held on its surface and decomposition of oxygen
groups on surface. In contrast, for GN-EPDM and GN-EPDM-MAA, be-
GN 90.30 9.70 – sides the weight loss related to GN, the obvious degradation in range of
GN-EPDM 92.08 7.92 – 400–500 °C was caused by decomposition of EPDM [26]. Especially, the
GN-EPDM-MAA 89.46 10.54 –
GN-EPDM-ZDMA 79.44 15.87 4.69
weight loss of GN-EPDM-MAA was higher than that of GN-EPDM due to
decomposition of MAA molecules.

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For GN-EPDM-ZDMA sample, the degradation process had two

stages. In the first stage, the weight loss in the range of 30–400 °C was
attributed to ZDMA decomposition. In the second degradation stage in
range of 400–500 °C, an obvious weight loss was observed, attributed to
decomposition of EPDM molecules in GN layers. Compared with GN,
the thermal weight loss for GN-EPDM increased by 17.71%, and a
further weight loss of 5.52% and 11.94% for GN-EPDM-MAA and GN-
EPDM-ZDMA were observed, respectively.
According to the above TGA data, the intercalation ratio of EPDM,
MAA and ZDMA molecules can be estimated. For GN-EPDM, the in-
tercalation ratio (D) of EPDM molecules per unit mass of GN was cal-
culated with follows: [27]
M1 = M0 × W1 − (M0 − M1) × W2 (4)
that is,
W1 − W2
M1 = × M0
1 − W2 (5)

M1
D= × 100%
M0 − M1 (6)
where W1 and W2 are the thermal weight loss ratio (%) of GN-EPDM
and GN, respectively; M0 is the weight (mg) of the added GN-EPDM; M1
is the weight (mg) of EPDM intercalated into GN layers. The inter-
calation ratio of GN-EPDM-MAA and GN-EPDM-ZDMA was calculated
in the same way.
As shown in Table 2, the intercalation ratio of GN-EPDM-MAA and
GN-EPDM-ZDMA were much higher than that of GN-EPDM due to an-
choring effect of MAA and ZDMA between EPDM and GN layers.
The XRD patterns of GN, GN-EPDM, GN-EPDM-MAA and GN-EPDM-
ZDMA samples were illustrated in Fig. 4, and the characteristic para-
meters were listed in Table 3. For GN sample, the broad peak for (0 0 2)
plane was observed at 2θ = 25–28°, corresponding to interlayer spacing
of 0.1750 nm. For GN-EPDM, the diffraction peak at 2θ = 25.94°, cor-
responding to interlayer spacing of 0.1760 nm, was similar to GN
sample. However, for GN-EPDM-MAA sample, the characteristic peak at
2θ = 25.86° broadened, corresponding to interlayer spacing of
0.1765 nm. Meanwhile, compared with GN and GN-EPDM sample, the
relative peak intensity of (0 0 2) plane of GN decreased significantly,
resulting from destruction of orderly structure of GN intercalated with
EPDM and MAA molecules [28]. For GN-EPDM-ZDMA, the diffraction
peak for (0 0 2) plane of GN shifted to lower angle at 2θ = 18.26°,
corresponding to the interlayer spacing of 0.2458 nm, significantly
larger than that of GN-EPDM and GN-EPDM-MAA. Moreover, the new
diffraction peaks at 2θ = 9.92° and 10.98° corresponding to ZDMA
were observed, indicating a more efficient intercalation of EPDM and
ZDMA molecules into GN layers [29].
Based on the above analysis, compared with GN-EPDM sample, for
the sample of GN-EPDM-ZDMA, ZDMA in situ formed in GN layers with
strong hydrogen-bonding interaction between oxygen group of GN and
carbonyl group of ZDMA molecules, resulting in a more efficient in-
tercalation of EPDM-ZDMA molecules into GN layers. On the other
hand, ZDMA with double bonds can be chemically grafted onto EPDM
rubber macromolecular chains under initiation of peroxide [30,31].
And thus the in situ formation of ZDMA in GN layers can act as a bridge
to improve the interaction and compatibility between GN and EPDM. A
proposed model provided an illustration for the formation of bridging
effect of ZDMA in the EPDM/GN-ZDMA nano-composite, as illustrated
Table 2
The intercalation ratio of of GN-EPDM, GN-EPDM-MAA and GN-EPDM-ZDMA.
Samples GN GN-EPDM GN-EPDM-MAA GN-EPDM-ZDMA
W (%) 4.78 22.49 28.01 34.43
D (%) – 22.85 32.27 45.12
Note: W is the thermal weight loss ratio of the samples.
Fig. 4. XRD patterns of GN, GN-EPDM, GN-EPDM-MAA and GN-EPDM-ZDMA.
(For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
Table 3
XRD parameters of GN-EPDM, GN-EPDM-MAA and GN-EPDM-ZDMA.
Samples Angle (2θ/o) Interlayer spacing (d/nm−1) Intensity (a.u.)
GN 26.10 0.1750 371,100
GN-EPDM 25.94 0.1760 359,300
GN-EPDM-MAA 25.86 0.1765 297,942
GN-EPDM-ZDMA 18.26 0.2458 301,917
in Scheme 2.
3.2. Mechanical properties and sealing resilience performance of EPDM/
GN-ZDMA nano-composite
The mechanical properties and sealing resilience performance of
EPDM/GN-ZDMA nano-composite were investigated by comparison
with neat EPDM, EPDM/GN and EPDM/ZDMA composites. Fig. 5a
showed the stress-strain curves of neat EPDM and EPDM composites.
Obviously, the stress-strain curves of the samples presented an un-
typical yield point and strain hardening behavior [32]. Compared with
neat EPDM, the area under stress-strain curves of EPDM composites had
a significant increase.
Fig. 5b showed the mechanical performance of neat EPDM and
EPDM composites. Compared with neat EPDM, addition of 10.5 wt%
GN resulted in a roughly 453% increase in tensile strength, from 1.59 to
8.80 MPa, and the elongation at break increased by 185%; while for
EPDM/ZDMA composite, addition of 10.5 wt% ZDMA resulted in a
nearly 325% increase in the tensile strength from 1.59 to 6.76 MPa and
the elongation at break increased by 149%, indicating of reinforcing
and toughening effects of GN or ZDMA on EPDM matrix. However, for
EPDM/GN-ZDMA composite, addition of 10.5 wt% GN-ZDMA resulted
in a nearly 508% increase in the tensile strength from 1.59 to 9.67 MPa
and the elongation at break increased by 235%, much higher than that
with 10.5 wt% ZDMA addition or 10.5 wt% GN addition, indicating
synergistic reinforcing and toughening effects of GN-ZDMA on EPDM
matrix.
The temperature-dependent curves of the storage modulus (E′) and
loss factor (tan δ) of EPDM composites were shown in Fig. 6, and the
DMA parameters were listed in Table 4. Taking the temperature cor-
responding to tan δ peak as the glass transition temperature (Tg), In
Fig. 6a, below Tg, the storage modulus decreased with increasing
temperature, and at Tg, it decreased sharply owing to the free

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Z. Yuan, et al.
Scheme 2. Schematic illustration of interfacial interactions in EPDM/GN-ZDMA. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
movement of EPDM molecular segments in high elastic state. Compared
with neat EPDM, E′ of EPDM composites had a significant increase. For
EPDM/GN and EPDM/ZDMA, E′ was not significantly different. How-
ever, E′ of EPDM/GN-ZDMA was higher than that of the composites
with addition of GN or ZDMA, indicating an improvement in stiffness
and load-bearing capacity of the composite, indicating synergistic re-
inforcing effect of GN-ZDMA on EPDM.
Another important feature was the shift of tan δ peak (Tg) for
EPDM/GN-ZDMA nano-composite toward a higher temperature, as
shown in Fig. 6b. Compared with neat EPDM, Tg of EPDM composites
shifted to a higher temperature, while EPDM/GN-ZDMA nano-compo-
site presented the highest Tg, reflecting an enhancement of interfacial
interaction between GN-ZDMA and EPDM matrix [33]. The value of tan
δ of EPDM/GN-ZDMA was slightly suppressed, indicating that the
movement of molecular chains of EPDM became much more difficult.
The compression set of the neat EPDM and EPDM nano-composites
measured at 150 °C for 24 h was shown in Fig. 7a. Compared with neat
EPDM, with the addition of GN or ZDMA, the compression set of the
EPDM nano-composites decreased, while EPDM/GN-ZDMA nano-com-
posite had a minimum compression set. Furthermore, the samples of
neat EPDM and EPDM composites were aged under compression stress
at 150 °C for 15 days. Fig. 7b summarized the variation of the com-
pression set of all EPDM samples with increasing aging time. The var-
iation of compression set with time presented three stages: In the first
stage (I: 0 < t ≦ 3 d), all samples had an obvious increase in com-
pression set. In the second stage (II: 3 < t ≦ 13 d), the compression set
Fig. 5. Stress-strain curves (a) and mechanical properties (b) of neat EPDM, EPDM/GN, EPDM/ZDMA, and EPDM/GN-ZDMA. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
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Composites Part A 121 (2019) 254–264
of all samples increased relatively slowly with some fluctuations. In the
last stage (III: t > 13 d), the compression set of all samples, except
EPDM/GN-ZDMA, showed a drastic increase. After aging for 15 days,
the compression set of neat EPDM, EPDM/GN, EPDM/ZDMA and
EPDM/GN-ZDMA nano-composites were 81.27%, 74.41%, 77.59% and
61.69%, respectively.
The variation of the contact stress relaxation coefficient (Kc) of all
EPDM samples as a function of aging time at 150 °C was shown in
Fig. 7c. It is generally considered that the smaller the value of Kc, the
more serious the attenuation of contact stress and the worse the sealing
performance of materials [34]. The variation of Kc with time also
showed three stages: In the first stage (I: 0 < t ≦ 3 d), the Kc value of all
samples decreased sharply, indicating that an extremely apparent
contact stress relaxation occurred at an early stage. During the second
stage (II: 3 < t ≦ 13 d), the Kc value decreased relatively slowly. In the
last stage (III: t > 10 d), the Kc value of all samples, except neat EPDM,
eventually levelled off. After aging for 15 days, the Kc value of neat
EPDM, EPDM/GN, EPDM/ZDMA and EPDM/GN-ZDMA nano-compo-
sites were 0.11, 0.24, 0.21 and 0.35, respectively. The above results
indicated that addition of GN or ZDMA can retard an increase in
compression set and a decrease in Kc, resulting in an enhancement of
durable sealing resilience performance. Moreover, the GN-ZDMA
showed a synergistic effect on improving sealing resilience performance
and thermal-stability of EPDM.
Z. Yuan, et al. Composites Part A 121 (2019) 254–264

Fig. 6. Dynamic mechanical properties of neat EPDM, EPDM/GN, EPDM/ZDMA and EPDM/GN-ZDMA. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

Table 4 3.3. Improvement mechanism of mechanical properties and sealing

The numerical DMA data for neat EPDM, EPDM/GN, EPDM/ZDMA and EPDM/ resilience of EPDM/GN-ZDMA nano-composite
GN-ZDMA.
Samples Storage modulus α relaxation temperature Tanδmax SEM and TEM analysis were used to observe the micro-morphology
(MPa) (°C) of GN and ZDMA in EPDM matrix, as shown in Fig. 8. For EPDM/GN
composite, GN was poorly distributed in EPDM matrix, and apparent
neat EPDM 752.8 −48.86 1.676
GN aggregates can be observed, as shown in Fig. 8(a and a’) (marked by
EPDM/GN 807.7 −47.37 1.578
EPDM/ZDMA 808.7 −46.35 1.556 red arrows). For EPDM/GN-ZDMA composite, GN sheets were homo-
EPDM/GN-ZDMA 895.2 −44.59 1.529 geneously embedded in matrix (Fig. 8(b and b’), marked by red arrows),
demonstrating relatively better compatibility between GN sheets and

Fig. 7. Compression set (a, b) and contact stress relaxation coefficient Kc (c) of neat EPDM, EPDM/GN, EPDM/ZDMA and EPDM/GN-ZDMA. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

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Fig. 8. SEM images of cryogenically fractured surface of EPDM/GN (a), EPDM/GN-ZDMA (b) and EPDM/ZDMA (c) (magnification: ×5000); TEM images of EPDM/
GN (a’), EPDM/GN-ZDMA (b’) and EPDM/ZDMA (c’). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)
EPDM chains contributed to exfoliation of GN sheets in matrix via
bridging effect of ZDMA molecules. In addition, it can be seen that a few
ZDMA blocky particles and poly-ZDMA were evenly embedded and
dispersed in the EPDM matrix without obvious agglomeration (Fig. 8(b
and b’), marked by blue arrows and ellipses). For EPDM/ZDMA com-
posite, only ZDMA particles and the darker phase of poly-ZDMA can be
observed (Fig. 8(c and c’), marked by blue arrows and ellipses), where
the poly-ZDMA phase tended to self-aggregate [35,36]. Based on the
above analysis, the in situ formation of ZDMA not only facilitates the
better dispersion of GN in EPDM matrix, but also helps the uniform
distribution of ZDMA itself in matrix.
The morphologies of the tensile fractured surface of neat EPDM and
EPDM composites were shown in Fig. 9. The tensile fractured surfaces
of neat EPDM were relatively flat and smooth (Fig. 9a), showing brittle
fracture characteristic. For EPDM/ZDMA composite, the fractured sur-
faces exhibited obvious voids attributed to the easy detachment of ag-
glomerated ZDMA from the EPDM matrix (Fig. 9b). For EPDM/GN
composite, the fractured surface was relatively rough, showing obvious
characteristics of ductile fracture (Fig. 9c and c’). Moreover, GN was
debonded from the matrix under tensile stress due to the weak inter-
facial interaction. For EPDM/GN-ZDMA composite, many folds and
large deformation can be observed on the fractured surface (Fig. 9d and
d’), which absorbed energy and endowed the composites with obvious
ductile fracture characteristic. Meanwhile, GN was tightly embedded in
EPDM matrix with strong interfacial interaction, which can transfer and
relax interfacial stress, and hinder matrix crack growth [37].
Crosslinking density has a pronounced effect on the mechanical
properties and the sealing resilience of materials [38]. The crosslinking
density of EPDM, EPDM/GN, EPDM/ZDMA and EPDM/GN-ZDMA
samples were further investigated, as depicted in Fig. 10a. Compared
with neat EPDM, addition of GN resulted in a significant increase of
total crosslinking density (Vr) and covalent crosslinking density (Vr1),
indicating an abundant chemical crosslinking network of EPDM chains
formed with the aid of GN in the composite system, leading to im-
provement of the crosslinking density of the nano-composite [39]. For
EPDM/ZDMA, addition of ZDMA resulted in an increase in covalent
crosslinking density (Vr1), indicating ZDMA can be chemically grafted
onto EPDM rubber macromolecular chains. Moreover, the ionic
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crosslinking network formed by poly-ZDMA, resulting in an apparent
increase of ionic crosslinking density (Vr2) [40]. For EPDM/GN-ZDMA,
a notable improvement in total crosslinking density (Vr) was due to
formation of abundant covalent crosslinking network contributed by
EPDM molecular chains, ZDMA and the aid of GN, and ionic cross-
linking network formed by poly-ZDMA. Therefore, a multiple cross-
linking network structure was constructed in the EPDM/GN-ZDMA
nano-composite, which was beneficial for significant improvement of
sealing resilience of EPDM composite.
A proposed model provided an illustration for the formation of a
multiple crosslinking network structure for the sample of EPDM/GN-
ZDMA, as illustrated in Scheme 3.
The crosslinking density of EPDM samples aged under compression
at 150 °C for 15 days was measured, and the retention ratio of different
crosslinking densities was calculated, as shown in Fig. 10b. It can be
seen that the retention ratio of total crosslinking density (Vr) increased
in the order of neat EPDM (39.6%) < EPDM/ZDMA
(45.4%) < EPDM/GN (63.6%) < EPDM/GN-ZDMA (68.2%), re-
sulting in a remarkable improvement of durable sealing resilience for
the sample of EPDM/GN-ZDMA. By comparison with the samples of
neat EPDM and EPDM/ZDMA, EPDM/GN presented the highest reten-
tion ratio of covalent crosslinking density formed with the aid of GN,
indicating that GN had a superior stabilizing effect on EPDM matrix.
Moreover, the retention ratio of ionic crosslinking density was ob-
viously lower than that of covalent crosslinking density, indicating the
ionic crosslinking network was more inclined to be destroyed under
high temperature and compression stress.
In summary, the improvement mechanism of mechanical properties
and sealing resilience of EPDM/GN-ZDMA nano-composite can be de-
duced as follows: for EPDM/GN-ZDMA nano-composite, GN sheets were
homogeneously embedded in EPDM matrix with strong interfacial in-
teraction via bridging effect of ZDMA molecules, which also helped the
uniform distribution of ZDMA itself in matrix. During the process of
vulcanization, a multiple crosslinking network structure, including
covalent crosslinking network contributed by EPDM molecular chains,
ZDMA and the aid of GN, and ionic crosslinking network contributed by
poly-ZDMA formed, resulting in a significant increase in total cross-
linking density (Vr), which can transfer and relax interfacial stress, and
Z. Yuan, et al. Composites Part A 121 (2019) 254–264

Fig. 9. SEM images of the tensile fractured surfaces of neat EPDM (a), EPDM/ZDMA (b), EPDM/GN (c, c’), and EPDM/GN-ZDMA (d, d’) (a, b, c, d: magnification
×1000; c’, d’: magnification ×10,000). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 10. Crosslinking density (a) and retention ratio of crosslinking density (b) of neat EPDM, EPDM/GN, EPDM/ZDMA and EPDM/GN-ZDMA.

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Scheme 3. Proposed model of crosslinking network structure of EPDM/GN-ZDMA. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
hinder matrix crack growth, thus improving the glass transition tem-
perature (Tg), mechanical strength and toughness and sealing resilience
performance of composite. In addition, compared with neat EPDM, the
retention ratio of total crosslinking density of the composite also in-
creased during aging, resulting in an enhancement of durable sealing
resilience performance.
4. Conclusions
In this work, the EPDM/GN-ZDMA nano-composite was prepared
through two-roll milling and hot pressing process. EPDM and ZDMA
molecules were confirmed to intercalate into GN layers with high in-
tercalation ratio through strong interfacial interactions. Compared with
neat EPDM, addition of GN-ZDMA resulted in 291% increase in tensile
strength and 48% increase in elongation at break, superior to that of
EPDN/GN and EPDM/ZDMA, and E′ and Tg of EPDM/GN-ZDMA nano-
composite also increased, indicating synergistic reinforcing effect of
GN-ZDMA on EPDM. Furthermore, addition of GN or ZDMA can retard
an increase in compression set and a decrease in Kc, resulting in an
enhancement of durable sealing resilience performance. GN sheets were
homogeneously embedded in EPDM matrix via bridging effect of ZDMA
molecules, which also helped the uniform distribution of ZDMA itself in
matrix. In addition, a notable improvement in total crosslinking density
(Vr) by formation of a multiple crosslinking network including covalent
and ionic crosslinking network, was beneficial for significant im-
provement of mechanical properties and sealing resilience of EPDM
composite. Moreover, EPDM/GN-ZDMA had an obvious increase in the
retention ratio of Vr, indicating stabilizing effect of GN-ZDMA on EPDM
matrix. The present work shows a promising perspective in developing
EPDM nano-composites with excellent mechanical and sealing resi-
lience performance applied as sealing materials.
Acknowledgment
This work was supported by Science and Technology Project of
Sichuan Province of China (2019YFG0240).
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