Composites Science and Technology 128 (2016) 176e184

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Composites Science and Technology

journal homepage: http://www.elsevier.com/locate/compscitech

Conductive thermoplastic vulcanizates (TPVs) based on polypropylene

(PP)/ethylene-propylene-diene rubber (EPDM) blend: From strain
sensor to highly stretchable conductor
Li-Feng Ma, Rui-Ying Bao**, Rui Dou, Shao-Di Zheng, Zheng-Ying Liu, Rui-Yan Zhang,
Ming-Bo Yang, Wei Yang*
College of Polymer Science and Engineering, Sichuan University, State Key Laboratory of Polymer Materials Engineering, Chengdu, 610065, Sichuan, China

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

Article history: Conductive elastomeric materials of multi-walled carbon nanotube (MWCNT) filled thermoplastic
Received 13 February 2016 vulcanizate (TPV) based on polypropylene (PP)/ethylene-propylene-diene rubber (EPDM) blends were
Received in revised form fabricated via different processing procedures, i.e., one-step and two-step methods, to control strain
30 March 2016
sensitivity aiming at applications from strain sensors to stretchable conductors. The phase size of cross-
Accepted 2 April 2016
Available online 4 April 2016
linked EPDM could be effectively tuned and the average diameter of EPDM particles was 550 nm for one-
step TPV and 230 mm for two-step TPV. Uniform dispersion of MWCNTs in two-step TPV and serious
aggregations of MWCNTs in one-step TPV were observed. Both TPVs showed excellent strain-resistance
Keywords:
Carbon nanotubes
repeatability for 50 tensile and recovery cycles. The one-step-TPV showed a potential to be used as strain
Polymer-matrix composites (PMCs) sensor due to a high gauge factor (GF) of 1004 at a strain of 100%, while the resistance for the two-step
Electrical properties TPV composite was independent with strain even at a strain of 200%, resulting in a stretchable conductor
Scanning/transmission electron microscopy with excellent resistance memory effect. The different strain sensitivity can be explained by the orien-
(STEM) tation of PP matrix. Moreover, the two-step TPV showed much lower electrical conductivity percolation
X-ray diffraction (XRD) threshold, 0.65 wt.%. This work provided a simple route to tune the strain sensitivity of MWCNTs filled
TPVs based on PP/EPDM blends for applications from strain sensors to highly stretchable conductor
through different processing procedures to control the morphologies and MWCNT dispersion.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction butylene-styrene (SEBS) [6e9], etc.

Compared with conventional rigid conductive polymer com-
posites, electrically conductive elastomers with good flexibility and
substantial elastic stretchability hold great potential for strain
sensors, stretchable conductors and actuators [1e3], which meet
increasing need for multi-functional conductive materials. One of
the most efficient strategies for the fabrication of conductive elas-
tomeric materials is integrating an elastomeric matrix with carbon-
based fillers, such as multi-walled carbon nanotube (MWCNT) [4,5],
and recently, much attention has been devoted to the fabrication of
conductive thermoplastic elastomers, such as thermoplastic poly-
urethane (TPU), thermoplastic polyolefin (TPO) and poly (styrene-
butadiene-styrene) block polymer (SBS) and styrene-ethylene/
* Corresponding author.
** Corresponding author.
E-mail addresses: rybao@scu.edu.cn (R.-Y. Bao), weiyang@scu.edu.cn (W. Yang).
In terms of strain sensors, the change of resistivity under strain
is monitored to be used as signals for environmental strain stimuli
[10,11], and such behaviors have found a wide range of applications
according to the strain sensitivities. For instance, conductive elas-
tomers with high strain sensitivity can be used for health moni-
toring and movement sensors, while those with low strain
sensitivity can be used for stretchable conductors [12e14]. There-
fore, to expand the applications for strain sensors or stretchable
conductors, the control of strain sensitivity of conductive elasto-
mers is considered as one of the most important issues. Mixing
methods (e.g. shearing or ultrasonic treatment, etc.), functionali-
zation of MWCNTs (e.g. purification or chemical functionalization,
etc.), selection of the polymer matrix (e.g. conjugated polymers,
etc.), utilization of a third component (e.g. surfactant, compatibil-
izer, etc.), and other means (e.g. in situ polymerization, mixing with
polymer latex, etc.) [15e17] have been utilized to tune the strain
sensitivity of conductive composites.

http://dx.doi.org/10.1016/j.compscitech.2016.04.001
0266-3538/© 2016 Elsevier Ltd. All rights reserved.
 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184
Thermoplastic vulcanizates (TPVs), a group of high performance
thermoplastic elastomers prepared by dynamic vulcanization,
which consist of a high content of crosslinked rubber as the
dispersed phase and a low content of thermoplastics as the
continuous phase. TPVs combine the excellent resilience of con-
ventional vulcanized elastomers and the good processability and
easy recyclability of thermoplastics [18,19]. Several studies have
been performed to understand the relationship between the phase
structure and mechanical behaviors of TPV. Tian and co-workers
[20] studied the relationship the cross-linking of the rubber
phase, formation and agglomeration of the rubber nanoparticles
network, and found the rubber nanodroplets gradually trans-
formed into nanoparticles because of the inhomogeneous cross-
linking of the rubber phase at the initial stage of vulcanization.
Phase inversion occurred when all the rubber nanodroplets have
transformed into rubber nanoparticles. Oderkerk et al. [21] studied
the deformation and recovery behaviors of TPVs during uniaxial
stretching and relaxation process, and found that during this pro-
cess, only the thinnest plastic layers at the equatorial region of the
rubber particles undergone plastic deformation, while the non-
deformed plastic matrix layers worked as adhesion points keep-
ing the rubber particles together. Due to the increasing concerns
regarding environmental problems and more excellent combined
mechanical performance and lower processing cost compared with
traditional elastomer SBS and SEBS, TPVs comprise the fastest
growing elastomer market in recent years. In order to expand
practical applications of TPVs, much effort has been paid to the
development of conductive TPV materials. However, to date, much
attention has been devoted to the effect of various conductive fillers
on the morphology and electrical properties of TPV composites
[22e24], while little attention has been paid to the preparation of
TPV functional materials with tunable strain sensitivity.
In the current work, inspired by the progresses in tunable strain
sensitivities and the fundamental studies on the structure and
mechanical behaviors of TPV, MWCNTs filled conductive TPV ma-
terials based on PP/EPDM blends were fabricated via different
processing procedures, i.e., one-step and two-step methods, to tune
the strain sensitivity of the elastomeric composites aiming at ap-
plications from strain sensor to stretchable conductors. For the
conductive TPV fabricated by one-step method potentially to be
used as a strain sensor, the GF for resistance is about 1000 at a strain
of 100%, while the resistance for the two-step TPV composite is
independent of the strain during tests of large cyclic strain of 200%,
showing a potential to be used as highly stretchable conductors.
The two-step TPV also shows a perfect combination of electrical
performance, with a very low conductivity percolation threshold of
0.65 wt.% compared with that for conductive TPV [25e27] and
excellent repeatability performance.
2. Experimental
2.1. Materials and sample preparation
A commercial isotactic PP (T30s, MFR ¼ 2.3 g/10 min at 230  C
and 2.16 kg load) was purchased from Lanzhou Petroleum chemical
Co, Ltd., China. The EPDM (Nordel IP 4725P) was produced by Dow
Elastomers Co, Ltd, Wilmington, DE, with 4.9% Ethylidene norbor-
nene (ENB). Phenolic resin (PF), used as curing agent, was obtained
from Yuantai biochemistry industry company, China. MWCNTs
(Nanocyl 7000, Nanocyl S.A.) were used as conductive fillers in the
composites. According to the supplier, the MWCNTs have an
average diameter of 10 nm, length of 1.5 mm and a specific surface
area of 250e300 m2/g.
The melt-reactive blending process for preparing TPV/MWCNT
composites was carried out in an XSS-300 internal mixer (Shanghai
177
Kechuang Rubber Plastics Machinery Set Ltd, China) with a rotor
speed of 75 rpm. TPV/MWCNT composite elastomers were melt-
blended with two different processing procedures, which were
designated as one-step method and two-step method, respectively.
For the one-step method, PP and EPDM were first mixed in the
mixer at 200  C; and after 3min, PF was incorporated into the
mixing chamber and melt-reactive mixing was continued for
5 min; at last MWCNTs was introduced and mixed for another
10 min, after which the mixture was taken out and cut up. For the
two-step method, PP/MWCNT and EPDM/PF master batches were
firstly prepared in the mixer at 200  C for 5min and 20  C for
10 min, respectively. Subsequently, the two premixed batches were
blended for 5 min at 200  C. The preparation procedures are
summarized in Fig. 1.
After compounding, the mixtures were compression-molded
into sheets with a thickness of about 1.0 mm at 200  C for 10 min
under a pressure of 10 MPa. For all the samples, the weight ratio of
PP to EPDM was kept at 30: 70. The content of PF was 2 wt.% (to the
weight of the blends). For convenience, the specimens were
denoted as one-step-TPVx (two-step-TPVx), where x presented the
content of MWCNTs. Also, the TPV samples without MWCNTs,
devoted as one-step-TPV0 (or two-step-TPV0), were prepared with
the same procedure and processing parameters for comparison.
2.2. Characterization
The tensile test was performed using an AGS-J universal mate-
rial test machine with a crosshead speed of 10 mm/min. At least five
samples were used for each measurement and the average results
were reported.
Electrical conductivity of the samples was measured by a two-
probe method using two multi-meters (6517B, Keithley In-
struments, Inc, Ohio, USA) and a voltage supply when the volume
resistivity was below 106 U cm. However, for the samples with the
volume resistivity beyond 106 U cm, a high resistivity meter (ZC36,
Shanghai Precision Instruments Co., Ltd. China) was employed.
Copper paste was used to ensure good contact between the sample
surfaces with the electrodes. The sample dimensions for high and
low volume resistivity measurements were 3  50  50 mm3 and
3  12  120 mm3, respectively.
The resistance-strain behaviors were performed on a home-
made apparatus. The uniaxial tension and release was carried out
by the Shimadzu universal testing machine (AGS-J) with a constant
rate of 10 mm/min. The strain (ε) and resistance (R) data were
recorded through a LabVIEW program in a real-time manner. Both
ends of the dumbbell samples were coated by silver paint prior to
test in order to reduce the contact resistance.
The phase morphology of the samples was characterized with a
JEOL JSM-5900LV scanning electron microscope (SEM, FEI) at an
accelerating voltage of 20 kV. The fractured surfaces of
compression-molded samples were sputtered with gold before
observation to avoid charge accumulation. Furthermore, polarizing
optical microscopy (POM, Olympus Co., BX51) and transmission
electron microscopy (TEM, Philips CM120) were also used to
characterize the morphologies and distribution of MWCNTs.
Quantitative analysis of the morphology was performed using im-
age analysis of Image-Pro Plus6. At least 500 dispersed domains
were measured by manually tracing the phase boundaries to esti-
mate the number-average diameter for each sample.
The rheological measurements were carried out on a stress-
controlled dynamic rheometer (AR2000ex TA Corporation, USA)
in a dynamic frequency sweep from 0.01 to 100 Hz at a strain of 1%
within the linear viscoelastic region at 200  C.
Two-dimensional wide-angle X-ray diffraction (2D-WAXD)
measurements were conducted on U7B Beamline station at the
178 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184

Fig. 1. Schematic illustration of the processing procedures.

Shanghai Synchrotron Radiation Facility (SSRF, Shanghai, China)
with a wavelength of 0.15418 nm. The sample-to-detector distance
was 420 mm, and the size of the X-ray beam was 0.4  0.4 mm. The
(110) plane of PP was analyzed by azimuthal scans (0e360 ).
The degree of crystal orientation of different regions could be
calculated by Hermans orientation function f [28], which is
described as follows:


3 cos2 ∅  1
f ¼
2 which will facilitate the formation of much denser EPDM particles
where (cos2f) was defined as:
Z p  
2
  Ið∅Þsin∅ cos2 ∅ d∅
cos2 ∅ ¼ 0 diameter statistics. Fig. 2(d) shows the frequency dependence of
Z p
2 tan d obtained from rheological tests for the two TPV0. Compared
Ið∅Þsin∅ d∅
0 with that for two-step-TPV0, the tan d peak for one-step-TPV0
where f is the angle between the orientation direction and the
normal vector of a given (hk0) lattice plane, and I(f) is the intensity
diffracted from the (hk0) planes, which are normal to the crystal-
lographic direction. The limiting values of the orientation function,
f, taking f ¼ 0 as the shear flow direction are 0.5 for a perfectly
perpendicular orientation and 1.0 for a perfectly parallel
orientation.
3. Results and discussion
3.1. Morphology of TPVs without MWCNTs
Fig. 2(a) shows the morphologies of PP/EPDM blend and TPVs
without MWCNTs. For the PP/EPDM blend with a weight ratio of
30:70, PP phase exists in the form of isolated rodlike particles after
selective etching of EPDM phase, indicating that PP phase is the
dispersed phase in EPDM matrix. However, from Fig. 2(b) and (c),
EPDM phase of TPV0 fabricated by both methods inverses to
dispersed phase after dynamic vulcanization process induced by
the curing agent, PF powders. Further observation shows that there
is a huge difference between the phase sizes of EPDM particles in
TPV0 prepared by the two methods: the phase size of EPDM par-
ticles for one-step-TPV0 is much smaller than that for two-step-
TPV0. Quantitative analyses of average particle diameter and par-
ticle size distribution showed that the average particle diameter for
EPDM phase in one-step TPV0 is just 550 nm, while that in two-
step TPV0 is approximately 230 mm. It indicates that when the
content of EPDM is constant for both TPV0, there will be a much
larger amount of EPDM particles in the one-step-TPV0 samples,
(1)
network in PP matrix in the one-step-TPV0 than that for two-step-
TPV0. Such a much denser EPDM particle network will lead to a
much thinner PP layer between EPDM particles for one-step-TPV0,
which is consistent with the morphology observations and particle
(2)
shifts to a higher frequency and the values of tan d in the whole
frequency range drops to smaller values, which demonstrates that
the EPDM particles network is much denser in one-step-TPV0 [27].
Such a much denser EPDM particle network will lead to a much
thinner PP layer between EPDM particles for one-step-TPV0, which
is consistent with the morphology observations and particle
diameter statistics [31]. According to the previous study [29], it is
known that due to dynamic vulcanization reaction, EPDM phase
undergoes a drastic shearing and breaking process. For the two-
step method, when the EPDM and PF master batch were blended
with PP matrix in the internal mixer under a high shear and
elevated temperature condition, the EPDM particles could not be
broken up during the same processing time because of a faster
dynamic vulcanization rate caused by a better mixing state be-
tween the EPDM phase and PF powders compared with the case for
one-step TPV0 sample.
3.2. Mechanical performance of TPVs without MWCNTs
The representative stressestrain curves of the TPVs are pre-
sented in Fig. 3(a). For both TPV0 samples, there is no obvious
 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184
Fig. 2. SEM micrographs of PP/EPDM blend (a); one-step-TPV0 (b), and POM images of two-step-TPV0 (c).
Fig. 3. Stressestrain curves (a) and the elasticity modulus, tensile stress and elongation at break of TPV for one-step and two-step method (b).
yielding in the strainstress curves, showing a rubber-like
behavior. However, the two-step-TPV0 shows lower tensile stress
at a certain stretching and tensile modulus and the details values of
the tensile strength and other mechanical properties are shown in
Fig. 3(b). For the two-step-TPV0, the tensile strength at break and
elasticity modulus are 11.8 MPa and 24.7 MPa, lower than those for
the one-step-TPV, 13.1 MPa and 31.5 MPa. Meanwhile, the elonga-
tion at break for the two-step-TPV is 610%, 30% higher than that for
one-step-TPV0. According to Boyce and co-workers [30], when the
plastic layer is thicker at the equatorial region of the EPDM parti-
cles, less plastic deformation occurs, resulting in a pseudo-
continuous rubber phase which provides a more rubber-like
behavior of TPVs during loading, such as a larger elongation at
break. Therefore, the main reason for the different mechanical
behaviors between the two TPV0 samples is the thickness for PP
layer between the contiguous EPDM particles. These results are all
in accordance with the morphological characteristics and it is
reasonable to conclude that the EPDM particles size for TPVs can be
successfully controlled by adopting different processing
procedures.
3.3. Dispersion of MWCNTs in TPVs
Fig. 4 shows the TEM and SEM images for the TPVs with
MWCNTs. To make sure that the volume resistivity is almost at the
same level and the effective conductive pathway is comparable, the
samples one-step-TPV12 and two-step-TPV3 were chosen to
discuss the selective distribution and dispersion of MWCNTs. Due
to the vapor staining of EPDM phase by the ruthenium tetroxide,
the dark region and white regions represent for EPDM phase and PP
phase, respectively. It can be seen that the size of EPDM phase is in
179
accordance with the SEM observation shown in Fig. 2, indicating
that there is little effect on the morphological structure after
loading of MWCNTs. Further observation shows that the MWCNTs
are almost completely located in PP phase for the both TPV com-
posites. These phenomena are consistent with our previous report
concerning the preferential location of CB in PP matrix for TPV
composites due to the high viscosity ratio of cured EPDM compared
with PP [29]. For one-step-TPV12 composite, as shown in Fig. 4 (a)
and (b), it can be seen that the MWCNTs are not well dispersed in PP
phase, and the sample holds a disordered network of MWCNT
cluster rich and sparse regions in PP matrix, especially in the zoom-
in image as shown in Fig. 4(b). This may be attributed to the thinner
PP layer between EPDM particles due to the existence of a large
number of EPDM particles in PP matrix, which is difficult for the
dispersion of MWCNT particles. However, as shown in Fig. 4(c) and
(d), the MWCNTs are well dispersed in almost all the region around
EPDM particles. Meanwhile, MWCNT particles exist in the form of
incompact floccule, not dense aggregates. Combined with the SEM
photo seen in Fig. 4(e), it can be observed that there is no obvious
MWCNTs aggregates in the whole scope and the MWCNTs are well-
dispersed, even it is visible that there are some single MWCNT.
3.4. Electrical properties of the MWCNTs filled TPVs
Fig. 5 shows the room-temperature resistivity of all the elasto-
meric composites as a function of MWCNT content. It can be seen
that with increasing loading of MWCNTs, the volume resistivity of
the composites decreased sharply at a critical concentration of
MWCNT particles, indicating that a conductive network was
formed [30]. The power law relationship was used to describe the
threshold of the electrical conductivity perocolation (3) [32]:
180 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184

Fig. 4. Typical TEM images of one-step-TPV12 (a) and two-step-TPV3 (c) composites; images (b) and (d) are the amplification, respectively; SEM micrographs of two-step-TPV3(e).

Fig. 5. Electrical conductivity as a function of the MWCNT content, the inset is the fitting of experimental results with percolation law.

experimentally obtained conductivity, as shown in inset of Fig. 5.

rfðu  uc Þt
where r is the electrical resistivity, u is the mass fraction of
MWCNTs, uc is the threshold of the electrical conductivity perco-
lation, and t is the critical exponent. The electrical conductivity
percolation threshold, uc, of conductive composites can be deter-
mined through fitting of the classical percolation theory to the
(3) The percolation threshold of two-step-TPV with MWCNTs is
observed to be 0.65 wt.%, much lower than that of one-step-TPV
with MWCNTs, uc ¼ 11.2 wt.%, which is the smallest value
compared with previous studies on conductive TPV based on PP/
EPDM blends [22e24]. According to Li et al. [33], the critical factors
determining the percolation threshold of polymer/CNT
 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184
nanocomposites include the aspect ratio of MWCNTs and the
dispersion of MWCNT agglomerates. Because of the same kind of
materials and blending ratio, as well as the similar processing
temperature, time and shear rate, the results clearly show a pre-
dominant contribution of the different processing procedures to
the electrical properties of the composites. Therefore, the distinctly
different percolation thresholds of these two series of elastomeric
composites are principally from the dispersion states of MWCNTs
caused by the different phase structures of TPV: the much thinner
PP layer between adjacent EPDM particles for one-step-TPV will
restrict the dispersion of MWCNTs particles, while the well-
dispersed MWCNTs for two-step-TPV appears resulting from a
premixed PP/MWCNTs master batch and thicker PP layer between
EPDM particles. The percolation threshold is lower than that for
SBS/MWCNTs and SEBS/MWCNTs composites using melting
method [34,35]. Obviously, two-step-TPV is more appropriate to
prepare conductive elastomeric materials with a relatively low
content of MWCNTs.
3.5. Strain-sensing behaviors of MWCNTs filled TPVs
To explore the sensing behavior of these elastomeric compos-
ites, one-step-TPV12 and two-step-TPV3 with comparable con-
ductivity were studied by measuring the electrical resistance as a
function of uniaxial strain, as shown in Fig. 6(a). It can be observed
that the two kinds of conductive TPVs show distinctly different
sensing behaviors. For two-step-TPV3 elastomer composite, the
resistance is independent of the increasing strain up to 100%, which
shows a potential to be used as highly stretchable conductor.
However, one-step-TPV12 elastomer composite demonstrates a
linearly increased resistance with increasing strain, which is highly
demanded for strain sensors. Moreover, after cyclic 50 tensile and
recovery process, both kinds of conductive TPVs show a perfect
resistance memory effects, indicating that a stable conductive
network has been formed in the composites.
The variation of resistance due to mechanical deformation can
be quantified through determination of gauge factor (GF) [36]. GF is
the instant ratio of relative change in electrical resistance to strain:
GF ¼ dðR=R0 Þ=ds
where R and R0 are the real-time resistance and initial resistance,
respectively, s represents the strain. Fig. 7 presents the change of GF
Fig. 6. Resistivityestrain sensing behavior: normalized resistivity versus time.
181
with strain for the two conductive TPVs. It can be seen that one-
step-TPV12 composite shows more drastic rise in GF ranging from
0.1 at the beginning of deformation to 1004 at a strain of 100% with
increasing strain. However, for two-step-TPV3 composite, even at a
large strain up to 200%, the GF only exhibits a tiny increase
compared with the original value, clearly showing that the two-
step-TPV3 demonstrates a very stable conductivity under strain.
According to Oderkerk and Boyce et al., [32,38], the relative
matrix ligament thickness between rubber particles for TPV is
important for the formation of a pseudo-continuous rubber phase
which provides the rubber-like behavior of TPVs during loading,
and the plastic deformation will be initiated and concentrated in
zones where the matrix ligaments are the thinnest, whereas the
thicker plastic ligaments will remain unyielded. So to further
illustrate the key factors induced the distinct strain sensitivity and
the plastic deformation of PP of these two series elastomeric ma-
terials caused by the different processing procedures, 2D-WAXD
was conducted to examine the crystalline structure of PP matrix
under strain for different composites. Fig. 8(a)e(c) shows 2D-
WAXD patterns for the two kinds of TPV composites with 50%
strain. Due to the non-crystalline nature of EPDM [39], diffraction
rings of PP matrix, (110), (040), (130), and (111)/(041), from inside
to outside, respectively, are seen clearly in the stretched samples.
The two clear diffractions in the WAXD patterns represent the (040)
crystal planes of PP matrix [40]. In order to reveal the orientation
degree of the molecular chains, the intensity distribution of (110)
plane along the azimuthal angle between 0 and 360 was inte-
grated and shown in Fig. 8(d). It can be observed that at the equal
strain loading, the PP matrix for one-step-TPV12 shows much
higher orientation degree than that for two-step-TPV3. To compare
the orientation behavior among different TPV samples quantita-
tively, the Hermans orientation factor f was calculated. For one-
step-TPV12, the orientation factor is 0.16, while f for two-step-
TPV3 is too small to be calculated. This is to say, compared with
two-step-TPV3, during the same tensile strain, greater amount of
PP phase for one-step-TPV12 underwent larger plastic deformation,
which resulted in a much higher destruction rate of the MWCNT
conductive network formed in PP matrix. This result will facilitate
higher strain sensitivity for one-step-TPV12. However, for the two-
step-TPV3 composite, the plastic deformation did not occur for
(4) most PP phase according to the Hermans orientation factor f. The
geometrical deformation of the sample was all supplied by the
deformation of EPDM phase, while the PP phase was just
182 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184

Fig. 7. (a)The change of GF with strain for these two composite systems; 2D-WAXD patterns for (b) one-step-TPV12 and (c) two-step-TPV3 under 50% strain; (d) scattering intensity
distribution of (110) plane along azimuthal angle for TPVs samples.

Fig. 8. (a) The relative resistance in correspondence of 100% strain (R 100%/R0) for each cycle plotted as a function of cycle number; cycles of the relative resistanceestrain
relationship, from 50% to 100% strain, of one-step- TPV12 composites (b) and two-step-TPV3(c).

translational with EPDM phase deformation, resulting in extremely
stable conductive network with increasing the strain. So it is
reasonable to conclude that the strain sensitivity can be easily
controlled by adopting different processing procedures, leading to
conductive TPVs with potential applications from strain sensors to
stretchable conductors.
Fig. 8(a) shows the relative resistances in correspondence of the
maximum strain (100%) for each cycle (R100%/R0), plotted as a
function of cycle number. It can be observed that for one-step-
TPV12 composite, the value of R100%/R0 reaches a plateau after a
sharp decrease for the inchoative several cycles, which may result
from the destruction of deficient conductive paths [37]. After that,
the relative resistance levels off, showing the stabilized resistance-
strain dependence with cyclic loading. However, for the two-step-
TPV3 composite, the relative resistive always shows stabilized
resistance-strain dependence with cyclic loading, indicating good
resistance repeatability with loading and unloading process even
after 50 cycle numbers, which is vital for the practical application.
Also, 2nd, 25th and 50th cycle of the relative resistance-strain
relationship for one-step-TPV12 composite and two-step-TPV3 is
presented in Fig. 8(b) and (c), respectively. It is noticed that for the
curves of one-step-TPV12, it is observed that upon unloading from
50% stretching, the relative resistance did not recover to the initial
resistance with the path of loading, which is much higher than the
relative resistance on loading process. It indicates that there is an
obvious electrical hysteresis effect and dissipated energy for one-
step-TPV materials. However, for two-step-TPV3 materials, the
relative resistance is changed little from loading to unloading
process, indicating an insensitive electrical performance to the
strain. Further observation shows that the recover path of resis-
tance is nearly coincided with that of stretching process, displaying
an excellent performance using as a stretchable conductor.
According to above results and discussion, a sketch of conduc-
tive network evolution during stretching for these two TPV com-
posite systems is drawn to illustrate the insight more clearly. As
shown in Fig. 9. Conductive networks of one-step-TPV materials are
generally destroyed during stretching process. Such damage could
in turn result in loss in local contacts between the networks, and
consequently, high electrical sensitivity to the strain are obtained.
While the plastic deformation did not occur for most PP phase in
two-step-TPV material, resulting in a stable conductive network
and independence resistance with strain. This work provided a
 L.-F. Ma et al. / Composites Science and Technology 128 (2016) 176e184
Fig. 9. The sketch of the network morphology evolution for the two TPVs composites fabricated by different fabricated processes.
simple route to tune the strain sensitivity of TPV/MWCNT com-
posites for applications from strain sensors to highly stretchable
conductor through different processing procedures.
4. Conclusion
We combined the excellent resilience of the curing EPDM phase
and the unique mechanical behavior of PP layer between EPDM
particles, and provided a simple and low-cost approach to tune the
strain sensitivity of TPVs based on PP/EPDM blends with potential
applications from strain sensors to stretchable conductors via
control of the phase dimension of rubber particles and MWCNT
dispersion by the means of different processing procedures. The
strain sensibility of one-step TPV shows a high GF for resistance
1000 at a strain of 100%. Meanwhile, a high performance stretch-
able conductor even at a high strain up to 200%from the two-step
TPV has been presented with a lower percolation threshold, i.e.
0.65 wt.%, good resistance-strain repeatability and resistance
memory effect.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (NNSFC Grants 51422305 and 51421061), the
Major State Basic Research Development Program of China (973
program) (2011CB606006), the Innovation Team Program of Sci-
ence & Technology Department of Sichuan Province (Grant
2014TD0002) and the Sichuan Provincial Science Fund for Distin-
guished Young Scholars (2015JQO003).
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