Polymer Composites - 2021 - Zhao - Strain Sensing Behavior of Flexible Polypropylene Poly Ethylene Co Octene Multiwalled

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Received: 9 July 2021 Revised: 1 September 2021 Accepted: 29 September 2021
DOI: 10.1002/pc.26353
RESEARCH ARTICLE
Strain-sensing behavior of flexible polypropylene/poly

(ethylene-co-octene)/multiwalled carbon nanotube
nanocomposites under cyclic tensile deformation
Zhongguo Zhao1 | Siyang Shen1 | Yapeng Li1 | Xin Zhang1 | Juqiao Su1,2 |
Huan Li1 | Taotao Ai1 | Dahang Tang3
1
National and Local Engineering
Laboratory for Slag Comprehensive
Abstract
Utilization and Environment Technology, In this study, the associations between the structural evolution and physical
School of Materials Science and properties of polypropylene/poly(ethylene-co-octene)/multiwalled carbon
Engineering, Shaanxi University of
Technology, Hanzhong, China nanotube (PP/POE/MWCNTs) composites were established. The MWCNTs
2
Tire Technology Research Center, particles preferentially migrating from PP matrix to disperse in POE phase,
Guizhou Tyre CO., LTD., Yunyan District, which contributed to a richer network structure, thus resulting in a significant
Guiyang, China
3
improvement for electrical conductivity, as well thermal stability, and tough-
Central Research Institute, Kingfa
Science and Technology Co., Ltd.,
ness property with the elongation at break from 300% to 800%. Furthermore,
Huangpu District, Guangzhou, the online strain-resistance analysis showed that introducing POE phase had a
Guangdong, China
big advantage in improving the recovering resilience and stability of the
Correspondence conductive network structure of PP/POE/MWCNTs composites under a multi-
Taotao Ai, National and Local time circular tensile test with a strain of 5%. It was highlighted that the maxi-
Engineering Laboratory for Slag
mum and minimum electrical conductivity levels of PP/POE composites
Comprehensive Utilization and
Environment Technology, School of remained almost constant and even the ratio of the real-time resistance to the
Materials Science and Engineering, initial one was negative just at the beginning of each circulation regarding the
Shaanxi University of Technology,
Hanzhong 723000, China.
strain stretching and recovery. This was attributed to the oriented conductive
Email: [email protected] network structure of PP/POE nanocomposites induced by the applied strain,
thereby increasing the electrical conductivity. Overall, this research provides a
Dahang Tang, Central Research Institute,
Kingfa Science and Technology Co., Ltd., basic guidance for preparing composites with ultrahigh flexibility and stability
Huangpu District, Guangdong Guangzhou under a circular deformation, which is an essential element taken into consid-
510663, China.
eration for smart sensors with high sensitivity.
Email: [email protected]
KEYWORDS
Funding information
Project of Science and Technology electrical properties, MWCNTs, stretchable conductive polymer composites
Department of Shaanxi Province, Grant/
Award Number: 2021JQ-761; China
Postdoctoral Science Foundation, Grant/
Award Number: 2020M673585XB; the
Industrial Field of Key Research and
Development Plan of Shaanxi Province,
Grant/Award Number: 2021GY-222
Polymer Composites. 2022;43:7–20. wileyonlinelibrary.com/journal/pc © 2021 Society of Plastics Engineers. 7

15480569, 2022, 1, Downloaded from https://4spepublications.onlinelibrary.wiley.com/doi/10.1002/pc.26353 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [18/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
8 ZHAO ET AL.
1 | INTRODUCTION conductivity and lower percolation threshold. Moreover,

the piezoresistive sensitivity of PDMS/MWCNTs compos-
Conductive polymer composites (CPCs) are attracting a ites was abruptly enhanced. It is worth mentioning that
large amount of scientific and industrial interests,1,2 most researchers seemed to mainly focus on designing
which have been widely used in many fields, such as versatile strain sensors by using different flexible poly-
electromagnetic interference (EMI) shielding,3,4 self- mers and conductive fillers, but ignoring the deep cause
regulated heating materials,5 and sensors.6,7 Based on a to the complicated behavior as a response to the strain
percolation theory,8 there is a transition for CPCs from applied or released to CPC-based strain sensors. This is
insulator to conductor with regulating the loading con- generally ascribed to the evolution of conductive net-
tent of conductive particles (carbon black [CB],9,10 carbon works under strain and relaxation.28–30
nanotubes [CNTs],11,12 and grapheme,13 etc.) due to the It is often put forward that the structural evolution of
formation of the conductive network. Moreover, the CPCs morphology has a significant effect on the electrical
external environment (temperature, strain, and vapor, or response of conductive networks. Elucidating its rele-
liquid) can also have significant effect on the conductive vance in electricity-mechanical properties for CPCs is of
network, thus causing changes of conductivity.14,15 Based great significance for effectively designing and expanding
on the special properties, CPCs were widely used to fabri- the application of these composites. An investigation was
cate the smart sensors,15 among which CPCs based on carried out with respect to the resistivity response of
strain sensing seem to be most widely applied, especially MWCNTs/TPU composite films,31 showing that the com-
in human motion detections, health diagnosis, wearable posites possessed good recoverability and reproducibility
electronics, and electronic skin.16–19 after a strain applied to composites was released. It
Due to the outstanding characteristics of CNTs such should be noted that a critical strain is important to be
as the extraordinary mechanical, electrical and thermal selected for performing an excellent electromechanical
properties, the strain sensing behavior of CPCs filled with performance. However, based on the knowledge of the
CNTs have attracted tremendous attentions.20–22 In authors, how the elements caused by introducing a sec-
recent years, conductive composites containing CNTs as ond dispersed phase into the CPCs composite that the
strain sensors have been largely investigated. For exam- interconnection effect of the phase structure and filler
ple, Pham et al.23 studied the strain-resistivity behavior of dispersion, thus leading to changes of the conductive net-
poly (methyl methacrylate)/CNTs composites and work, influence the behavior of conductivity-strain has
observed reversible resistivity response with strains less rarely been investigated. Moreover, the portrait in terms
than 1%. They pointed out that the strain-sensitivity of the destruction and reconstruction of the conductive
property was able to be tailored by changing the parame- networks constructed under the applied strain remains
ters including the processing conditions, loading content unclear.
of CNTs particles and their corresponding distributions PP, a widely used engineering thermoplastic material,
in matrix. Vertuccio et al.24 reported a response of the was selected as the matrix due to its excellent easily-
electrical resistance of epoxy (EP)/multi-walled CNTs processing ability in this study. The elastomer (poly
(MWCNTs) nanocomposites on the applied strain and (ethylene-co-octene) (POE) showing an incompatible
observed a decreasing gauge factor of CPCs upon increas- property with PP material as a dispersed phase was added
ing the MWCNTs content. Zhang et al.25 studied the into the PP matrix to control the location of the conduc-
strain-sensing behavior of MWCNTs/thermoplastic poly- tive MWCTs filler particle, so that the destruction and
urethane (TPU) under a dynamic strain. They found that reconstruction of the conductive networks can occur eas-
adding only 0.2 wt% CNTs can significantly increase the ily, which achieved the aim at establishing the associa-
reproducibility and recoverability properties when a tion between the morphology structure evolution and the
strain of 5% was applied. However, when the strain physical properties. In this research, a solution adoption
exceeded 30%, the conductive network was observed to melting method was provided to prepare the PP/POE/
be ruined and rebuilt. In addition, Wang et al.26,27 found MWCNTs composites to systematically investigate the
that a third additive also played an important role in effect of POE component as a dispersion phase on the
enhancing the sensitivity of polymer based conductive physical properties including the conductive properties,
composites. For example, they reported that adding sili- crystallization, melting behavior and strain-sensing
con dioxide micro-particles (μ-SiO2) into the flexible behavior of CPCs. Specially, a critical strain of 5% applied
PDMS/multi-walled CNTs (MWCNT) composites to the PP/MWCNTs composite with or without POE was
improved the electrical conductivity and piezoresistive selected based on a tensile test to figure out the relevance
sensitivity, in which the larger μ-SiO2 particles owning of the associated evolution of network structures and the
the volume exclusion effect could induce higher electrical electrical conductivity under multi-time circular strain
ZHAO ET AL. 9
FIGURE 1 Schemes for the fabrication of PP nanocomposites by solution coating method followed by the compression molding
technique
stretching and recovery. The corresponding mechanism MWCNTs with an average diameter of 8–15 nm was pur-
was provided as well. chased from Chengdu Organic Chemicals Co. Ltd., Chi-
nese Academy of Sciences. Actone was provided by
Chengdu Kelong Chemical Reagent Factory, China. All
2 | MATERIALS AND METHODS the chemicals were used as received without any
treatment.
2.1 | Materials
Polyplefin elastomer (POE 8150) with a melt flow index 2.2 | Sample preparation
(MFI) of 0.5 g/10 min (190 C, 2.16 kg) was purchased
from Dow Chemical Company (America). PPC 3650 as a The PP based CPCs were prepared by using a solution-
Polypropylene (PP) was provided by Total Compagnie melting method, shown in Figure 1. Firstly, a stable sus-
Francaise Des Petroles which has a melting temperature pension of MWCNTs in acetone was prepared using an
of 165 C and MFI of 2 g/10 min (230 C, 2.16 kg). The ultrasonic cell disruptor for 30 min with a power of
TABLE 1 Component contents of samples including PP and its nanocomposites
Samples PP(wt%) MWCNTs (wt%) Samples PP (wt%) MWCNTs (wt%) POE (wt%)
PP 100 0 PPCNTE5 91 4 5
PP + 1%MWCNTs 99 1 PPCNTE10 86 4 10
PP + 2.5%MWCNTs 97.5 2.5 PPCNTE30 66 4 30
PP + 3.5%MWCNTs 96.5 3.5 PPCNTE50 46 4 50
PP + 5%MWCNTs 95 5
PP + 5.5%MWCNTs 94.5 5.5
PP + 6%MWCNTs 94 6
10 ZHAO ET AL.
1000 W. Then a certain amount of PP or POE pellets Tecnai G2 F20 S-TWIN, operated with an acceleration
were added to the acetone solution under mechanical voltage of 200 kV.
stirring for another 30 min until the solvent was evapo-
rated to obtain MWCNTs cladding on the surface of PP
or POE pellets, in which the pre-blending 2.6 | Thermogravimetric analysis
PP/MWCNTs or PP/POE/MWCNTs was achieved. Sub-
sequently, the pre-blending composites were further The thermodynamic stability was investigated by Ther-
mixed in an internal mixer (XSS-300) at 200 C for 7 min mogravimetric analysis (TGA, TA Instruments, Q50)
with the rotation rate of 50 rpm, in which PP/POE/ from 40 to 600 C under a nitrogen atmosphere. The ther-
MWCNTs composites with different formulas were mal degradation temperature was defined as the tempera-
obtained. Finally, the PP/POE/MWCNTs specimen with ture with a weight loss of 5% (Td5).
25 mm 5 mm 2 mm (length width thickness)
was obtained using a standard molding compression with
10 MPa at 200 C for 5 min. The detailed formula is dis- 2.7 | Conductivity test
played in Table 1.
In this study, a digit precision multimeter (model
TH2684A, Changzhou Tonghui Electronics Co. Ltd.,
2.3 | Differential scanning calorimetry ~
China) with a range of (10kΩ100TΩ) is used to measure
the conductivity of samples. The dimension of the sample
Q20 differential scanning calorimetry (DSC) apparatus for resistivity measurements was 25 mm 5 mm 2 mm.
(TA Instruments, USA) was used to investigate non- The volume conductivity (σ) was calculated as follows:
isothermal crystallization and melting behavior. First, the
sample was weight about 5–10 mg and then was heated σ ¼ 1=ρ ¼ L=RS, ð2Þ
to 200 C with a heating rate of 10 C/min. To eliminate
the heat history, sample was put at this temperature for where ρ is the electrical resistivity, L the length between
5 min. Finally, the sample was cooled down to 40 C with the electrodes, R the volume resistance, and S the area
a cooling rate of 10 C/min to record the crystallization size of the cross-section of sample.33 Within Equation (2),
curves. it is pointed out that the conductivity range of this
The relative crystallinity can be calculated with fol- multimeter lies in 1013 S/m 101 S/m.
lowing Equation 1:
ΔHi 2.8 | Tensile test

Xi ¼ 100%, ð1Þ
ΔHθi
The testing machine (Instron 4302, Instron Corporation,
where ΔHi is the calibrated specific fusion heat of PP and UK) was employed to evaluate the mechanical properties
ΔHθi is the standard fusion heat of 178 J/g for PP.32 according to a GB/T-1040 test standard, in which the
crosshead is moving with a speed of 50 mm/min. The
2.4 | Scanning electron microscope
To observe the filler dispersion, scanning electronic

microscope (SEM, JEOL SJM-5900VL) was used. The
sample was cryo-fractured in liquid nitrogen and then
sprayed with gold before observed.
2.5 | Transmission electron microscopy
Ultrathin sections (approximately 100 nm thickness) of

nanocomposites were cut using an ultramicrotome. For
transmission electron microscopy (TEM) observation, the
dispersion of MWCNTs in the PP matrix were examined F I G U R E 2 The schematic of the house-made inline setup for a
directly with the transmission electron microscope FEI strain sensing test
ZHAO ET AL. 11
average values of five tests for each sample were applied of magnitude when the filler content exceeded 4 wt%.
to compare the mechanical properties. This sharp change in conductivity indicated the forma-
tion of a percolating network (i.e., percolation behav-
ior).34 When the MWCNTs content further grew up to
2.9 | Mechanical–electrical properties 5 wt%, no obvious change for electrical conductivity was
under cyclic tension noted. This indicates that the filler content plays a vital
role in constructing a conductive network path for con-
The house-made online recording device for measuring ductivity of composites. Only the filler content reached a
the resistance of composites was established by con- critical value was the conductive network path
necting a computer and a high resistivity meter (model established, significantly improving the conductivity of
TH2684A, supplied by Changzhou Tonghui Electronics composites by shortening the distance among the con-
Co. Ltd., China), as shown in Figure 2. A standard tensile ductive particles.35 As shown in Figure 3A, when the
test was applied to all materials to distinguish the strain filler content lies between 3.5 and 5 wt%, the conductivity
value at which the yield behavior occurred with a tress- increased sharply, which indicated a completed conduc-
train curve. To observe the strain-sensing behavior, tive network was gradually formed and the conductive
10 extension–retraction cycles were conducted at the percolation value of the composite material seemed to lie
loading and unloading speed of 5 mm/min within a in the vicinity of 4.5 wt%. For comparison, the classical
strain of 5% smaller than that of yield strain for compos- percolation theory shown in Equation 1 was cited to pre-
ites. Two copper electrodes separated by 10 mm were dict the conductive percolation value of the composite
bonded with silver paste to achieve good contact between material. The resulting value was 4%, consistent with a
the electrodes and samples. previous report36:
σ ¼ σ 0 ðp p c Þt , ð3Þ
3 | R ES U L T S A N D D I S C U S S I O N
where σ is the conductivity of the composite, σ 0 and t are
3.1 | Electrical performance of CPCs constants, φ is the filler content, and φc is the percolation
threshold.
The effects of adding MWCNTs on the electrical conduc- Based on the mentioned above discussion regarding
tivity of MWCNTs/PP composites was investigated, the conductivity of PP/MWCNTs composite, we
shown in Figure 3. Increasing gradually the MWCNTs maintained the MWCNTs filler at a content value of
content enhanced the conductivity of the samples. The 4 wt% for PP/MWCNTs composite showing a percola-
conductivity displayed a dramatic increase of five orders tion phenomenon. As for comparison, another polymer
F I G U R E 3 The conductivity of MWCNTs/PP composites (A) and PP/POE/MWCNTs composites (B): The solid circles represent
experiment data and the black curves mean the fitting result based on the percolation threshold theory
12 ZHAO ET AL.
phase was added into PP + 4%MWCNTs composite. It is filler content. As the content of MWCNTs gradually
shown in Figure 3B that the electrical conductivity of increased, the distance between MWCNTs particles was
the PP/POE/MWCNTs composite increased with shortened, contributing to the agglomerations due to
increasing the POE loading. The electrical conductivity strong van der Waals force and π-π bonds.37 This was in
of composite reached a plateau when the POE content favor of constituting a continuous conductive network
achieved 50 wt%, and further increasing POE content structure, thus resulting in good conductive properties
resulted in little change of the conductivity. Moreover, of MWCNTs/PP. Shown in Figure 4D, the composite
the images from the polarizing microscope inserted in with 5 wt% POE exhibited a weak “sea-island” structure,
Figure 3B showed that adding POE did not lead to obvi- and no obvious interface was found between PP and
ous phase separation behavior of the PP/POE blend. POE phases, indicating a partial compatibility for PP
Even when the content reached 50 wt%, the commonly and POE. However, when the POE content was
known “sea-island” structures were not observed, but increased to 40%, it was difficult to distinguish the exact
POE as a dispersed phase uniformly existed in the poly- POE phase from the PP matrix phase. This finding indi-
propylene matrix. This in return highly promoted to cates that upon increasing the content of POE, it con-
form a more integrated conductive network, thus largely tributed to better POE dispersions thus better interfacial
increasing the electrical conductivity of PP/POE/ compatibility with PP matrix. Moreover, MWCNTs
MWCNTs composite by four magnitude orders com- seemed to preferentially distribute in POE phase, in
pared to PP/MWCNTs composite. which the MWCNTs was slightly agglomerated, as
shown in Figure 4E, F. This morphology structure had
an advantage in fully utilizing the conductive particles
3.2 | Morphology analysis of CPCs to construct the conductive network, improving the elec-
trical conductivity.
A correlation regarding the morphology structure and The TEM characterization was conducted to have a
the conductivity is needed to figure out how the struc- further insight into the distributions of conductive parti-
ture evolved while largely enhancing the conductivity. cles of PP + 4%MWCNTs composite with or without 30%
Figure 4 compared the morphologies of the composites POE shown in Figure 5. Figure 5A, B showed random
with various MWCNTs or POE content. It is presented alignments of MWCNTs in PP + 4%MWCNTs composite.
that for PP/MWCNTs composite, MWCNTs seemed to The interconnected structure and large-sized aggrega-
uniformly disperse in the polypropylene matrix at low tions were clearly noticed, which might be attributed to
F I G U R E 4 SEM micrograph of the morphology of the MWCNTs/PP nanocomposites. Top (A)–(C): The MWCNT content was from 1%
to 4%; bottom (D)–(F): The POE content increased from 5% to 40% with a constant MWCNTs loading of 4%
ZHAO ET AL. 13
FIGURE 5 TEM images of composites: (A) and (B) PP + 4%MWCNTs, (C) and (D) PPCNTE30
the high-intermolecular forces among MWCNTs. How- a double-percolation conductivity network structure is
ever, MWCNTs particles mainly migrated from the PP exhibited in Figure 3C, D, which further again explained
matrix to the dispersed POE phase after introducing POE the sharp enhancement of the conductivity for PP/POE/
into the nanocomposites. Moreover, the MWCNTs aggre- MWCNTs composites as compared to its counterpart PP
gations phenomenon is decreased, due the high affinity composite with the same MWCNTs loading not including
between the two phases.7 Consequently, the formation of POE phase.
FIGURE 6 The crystalline curves of composites

14 ZHAO ET AL.
T A B L E 2 The relative parameters

Samples To ( C) TP ( C) Wf Samples To TP Wf
of composites for crystalline behavior
PP 117.73 112.64 4.66 PPCNTE5 123.77 119.65 4.12
PP + 1%MWCNTs 124.02 120.6 3.42 PPCNTE10 123.32 119.23 4.09
PP + 2%MWCNTs 124.63 120.63 4.0 PPCNTE20 122.13 118.06 4.07
PP + 2.5%MWCNTs 125.09 121.77 3.32 PPCNTE30 121.66 118.45 3.21
PP + 3%MWCNTs 125.15 121.78 3.37 PPCNTE40 121.41 117.98 3.43
PP + 3.5%MWCNTs 125.07 120.92 4.15 PPCNTE50 120.16 116.21 3.95
PP + 4%MWCNTs 125.33 121.16 4.17
PP + 5%MWCNTs 124.99 121.7 3.29
PP + 5.5%MWCNTs 124.86 120.8 4.06
PP + 6%MWCNTs 124.71 120.1 4.61
3.3 | The crystalline behavior of CPCs adding POE phase into composites caused a decrease for
both To and Tp and a slight decrease for Wf in Figure 6B
The distributions of conductive particles in composites and Table 2. For example, with 50% POE phase the To
would have a significant effect on the crystalline behav- for the PP/POE/MWCNTs composite declined to 120.16
ior. Hence, all the samples were tested by DSC with the from 125.33 C for PP/MWCNTs composite, with the Wf
cooling rate of 10 C/min to determine the influence of slightly decreasing from 4.17 to 3.85. This is attributed
the addition of MWCNTs and POE on the crystallization to the reason that MWCNTs preferentially distributed in
behavior of the composites (Figure 6 and Table 2). It is POE phase as confirmed by TEM and SEM images
seen in Figure 6A that the addition of 0.1% MWCNTs sig- above, thus reducing the nucleation effect of MWCNTs
nificantly enhanced the initial crystallization temperature to a certain extent, which consequently inhibited the
(To) from 117.73 to 124 C and the maximum peak crys- crystallization nucleation and accelerated the crystalli-
tallization temperature (Tp) from 112.64 to 120 C, respec- zation growth of the crystalline structure of PP mole-
tively, mainly due to the large surface area of MWCNTs cules. However, considering a decreased viscosity of the
acting as the heterogeneous nucleation points. However, composites by introducing POE phase, it promoted the
further increasing MWCNTs content marginally changed mobility of molecular chains thus increasing the nucle-
the crystallization behavior. Table 2 also compared the ation speed during crystallization.38
half-peak width of crystallization (Wf = ToTP) with
adding MWCNTs particles or not. The declining trend of
Wf values for PP/MWCNTs as compared to that of neat 3.4 | The thermal property analysis
PP indicated an accelerating effect on the crystallization
rate. In contrast, given a constant 4 wt% MWCNTs, Considering the application environment in terms of
high temperature and strain for CPCs composites, ther-
mal stability is a very important factor that should be
evaluated. TGA test was conducted to determine the
influence of the addition of MWCNTs and POE on the
thermal stability of the composites in Figure 7. We
defined the starting degradation temperature in the
TGA curve as a certain temperature at which the loss of
TABLE 3 The relative TGA parameters of composites
Samples Td5 ( C) Samples Td5 ( C)

PP 324.8 PPCNTE30 435.5
PP + 4%MWCNTs 425.7 PPCNTE40 434.4
PPCNTE5 437.2 PPCNTE50 429.1
PPCNTE10 438.3 POE 368.3
PPCNTE20 438.2
FIGURE 7 The TGA curves of composites
ZHAO ET AL. 15
5 wt% mass of the material was achieved (Table 3). In for the elongation at break from 750% to 50%. Back to
general, adding 4 wt% MWCNTs resulted in a slight Figure 4, it seemed that MWCNTs particles distributed
increase of the Td5 temperature from 422.9 C for neat to homogeneously with a low filler loading of 1 wt%,
425.7 C for PP composite. The possible reason is that improving simultaneously the tensile strength and tough-
introducing the MWCNTs can improve the thermo- ness due to the intrinsic property of MWCNTs.36 How-
oxidative stability of PP and impeding oxygen penetra- ever, filler particles easily formed aggregates with a
tion, especially in vicinity of the nanotube surface. Pro- higher loading in PP matrix (shown in SEM images),
vided a constant loading of 4 wt% MWCNTs, which acted as the so-called stress defects, thereby the
introducing 5% POE into PP composite led to a signifi- strengthening and toughening properties of PP compos-
cant Td5 improvement by 11.5 C, while a slight decrease ites significantly deteriorated.
of the Td5 temperature was noted as the POE content Figure 8B compared the changes of mechanical prop-
surpassed 30%. This can be ascribed to the synergistic erties caused by the introduction of POE phase into PP
effect of POE and MWCNTs. The unique morphology composite with again a constant 4 wt% MWCNTs. It was
structure that MWCNTs particles were preferentially found that almost no change in the mechanical proper-
located in POE phase shown in Figure 4 and Figure 5 ties of PP/POE/MWCNTs composite was noticed as the
made the interface structure between POE and POE content was less than 10 wt%. Further increasing
MWCNTs prohibit the infiltration of air.39 This finding the POE loading to 40 wt% tremendously improved the
indicates that the introduction of POE into polypropyl- toughness thus larger elongation at break from 350% to
ene are potentially able to improve the flame-retardant 800% for composites, although it deteriorated further the
performance of the material. tensile strength of the composites. The former phenome-
non might be resulted from the interaction effect between
MWCNTs and POE, which played a good bridging role to
3.5 | The mechanical properties of CPCs improve the interfacial force, and the latter could be
attributed to the incompatibility between the PP phase
The tensile test was carried out to further explore the and POE phase.40–42 Interestingly, as the POE content
influence of the addition of nanoparticles and elastomers grew up to 50 wt%, the elongation at break decreased to
on the mechanical properties of the composites 400% but increased again to nearly 800% with POE
(Figure 8). As shown in Figure 8A, adding a low-content increasing to 60 wt%. This phenomenon is due to the
MWCNTs (less than 1 wt%) led to a significant enhance- interface force between PP and POE, which drove the
ment in tensile strengthening from 31.2 MPa to phase transition behavior to take place. When the POE
33.6 MPa, while the elongation at break showed little content increased to 50 wt%, the PP and POE formed the
change. As expected, further increasing the MWCNTs co-continuous structure and possessed the weakest inter-
content sharply decreased the tensile strength of the com- face forces. However, when the POE content was over
posites from around 34.2 MPa to 24.3 MPa, and the value 50 wt%, the phase structures changed, in which the POE
F I G U R E 8 The mechanical properties of PP nanocomposites: PP composite with a varying MWCNTs content from 0% to 5% (A); PP
+ 4%MWCNTs composite with a varying POE loading from 0% to 60% (B)
16 ZHAO ET AL.
F I G U R E 9 The stress–strain curves of PP and its composites (A), the zoom-in image of the local curve displayed in red box of
Figure 9A (B), stress as a function of strain with a maximum value of 5% for PP + 4%MWCNTs (C) and PPCNTE30 nanocomposites during
10 extension–retraction cycles (D)
acted as the matrix and the PP was the dispersed phase. cycle due to the selected small displacement of 5%. Upon
Hence, when POE content grew up to 60 wt%, the the applied strain of composites reached 5%, the machine
mechanical properties increased in contrast, which cor- crosshead began to move back with the same speed rate
responded well to other reports.41–43 until the stress damped to zero, during which the strain
Analysis mentioned above showed that introducing decreased as well as the stress variable. However, when
POE phase can significantly improve the toughness of the stress was restored to zero, the strain of PP + 4%
CPCs, especially as the loading content of POE lied MWCNTs composites cannot move back to the beginning
between 30 wt% and 40 wt%, which seemed to be a state. Moreover, with the circular number of operations
potential material candidate for fabricating flexible sen- increasing, the unrecovered strain slightly increased
sors. Before we started a cyclic tensile test for composites, (Figure 9C), indicating an obvious hysteresis effect for the
the tensile yield behavior for each material should be dis- PP + 4%MWCNTs composites caused by the viscoelastic
tinguished. The stress–strain curves of composites in behavior of the polymer matrix as previously reported.46
Figure 9 showed that the composites exhibited the yield In contrast, the hysteresis effect thus the unrecovered
behavior at a strain smaller than 10%,44,45 before which strain damped significantly by introducing POE phase into
the deformation of composites could be restored in a cer- composites (Figure 9D), confirmed by almost a complete
tain way. Therefore, to better observe the strain–stress stress and strain recovery showing an excellent recover-
behaviors of CPCs, 10extension–retraction cycles with ability and repeatability in multiple cycle tests. Therefore,
the maximum strain of 5% was executed, as shown in these composites showed a high strain sensitivity and good
Figure 9C, D. Figure 9C displayed that the stress nearly recoverability, which was an essential element for the
linearly increased with increasing tensile strain in each preparation of materials for flexible sensors.
ZHAO ET AL. 17
F I G U R E 1 0 ΔR/R0 plotted as a function of time for nanocomposites during the 10 cycles: (A) PP + 4%MWCNTs and (B) PPCNTE30
nanocomposites; relationship of the max ΔR/R0 and min ΔR/R0 versus cycle number of (C) PP + 4%MWCNTs and (D) PPCNTE30
nanocomposites
3.6 | Mechanical–electrical properties materials gradually increased in the tensile process and
under cyclic tension gradually decreased in the recovery process. Figure 10C
compared the ratio value of ΔR/R0 as a function of the
The changes of ΔR/R0 (R0 is the original resistance, and circular number regarding the stretching and recovering
ΔR is the instantaneous or real-time change in resis- process. It is found that ΔR/R0 values of the MWCNTs/
tance) as a function of the strain were investigated in PP nanocomposites increased gradually as the times of
detail, as displayed in Figure 10, which was used to eval- circulation operations increased. This finding can be
uate the evolution of conductive networks of composites illustrated as follow: the conductive network can be ori-
with loading or unloading particles. It is thought that the ented in the drawn direction,47 leading to the increase of
breakdown and reconstruction of conductive networks the distance between neighbor conductive particles dur-
occurred simultaneously during the tensile process.39 As ing the extension process. Moreover, the conductive net-
shown in Figure 10A, C, the ΔR/R0 value in PP + 4% work was destroyed when the strain exceeded the
MWCNTs composite increased with increasing strain and maximum level confirmed by the unrecoverable strains
then decreased with strain recovering, mainly ascribed to shown in Figure 10C, inducing an increase in the tunnel-
the changes of the conductive network structure during ing resistance between adjacent conductive nanofillers
the process of stretching and recovery. It can be imagined during the extension process. As a result, when the stress
that the distance between nano-conductive particles was removed, the conductive network cannot recover
increased with increasing the strain applied to PP matrix exactly to its original topologic structure at beginning.
while decreased with decreasing the strain. Therefore, Consequently, a larger ratio value of ΔR/R0 was gradu-
the orbital resistance between adjacent nano-conductive ally obtained with increasing circulation times.
18 ZHAO ET AL.
Interestingly, introducing POE can undoubtedly the tensile direction induced by the applied strain, the
change the conductive network structure constructed conductive networks constructed with MWCNTs and
previously for PP/MWCNTs composite. During the single POE might be rearranged, resulting in a more highly effi-
tensile process, the conductivity was increased and then cient utilization of conductive particles, and forming bet-
decreased mainly because of the good ductility of the ter conductive networks along the tensile direction. This
two-dimensional conductive network structure composed explained the reason for the smaller resistance of
of PP, POE, and MWCNTs particles. In the tensile pro- PP/POE/MWCNTs composites during stretching and
cess with a low strain, the conductive network structure recovering process as compared to the original resistance
became slightly oriented, thereby promoting the bridging values of composites without strains.
effect of the conductive particles and increasing the elec- A schematic illustration was proposed to explain the
tron transport efficiency of the conductive particles. As a evolution of conductive network of PP/MWCNTs/POE
result, the ΔR/R0 of MWCNTs/PP/POE nanocomposites composites during the extension-retraction process
displayed a stepwise decrease and ultra-small change (Figure 11). Figure 11A and A' displayed the original con-
from 0.15 to 0.35 within the whole strain increasing or ductive network structures, in which the MWCNTs intri-
recovering operations. It is worth mentioning that the cately distributed in PP matrix and formed the
ratio value of the maximum ΔR/R0 decreased with the conductive path with each other. After applying the
circulation times for stretching and recovering opera- stretching with various strain, the conductive network
tions, while that of the minimum ΔR/R0 maintained can be oriented in the tensile direction, leading to the
almost a constant. It should be noted that the conductive increase of the distance among MWCNTs particles. The
particles preferentially distributed in POE phase shown number of effective conductive networks decreased due
in Figure 4, therefore the extremely stable network con- to the deformations of the composites under tension with
structed by MWCNTs and POE might stem from the flex- different strains (Figure 11B). Increasing further the
ible property of POE. When the stress was eliminated, strain would be able to damage the conductive networks
the conductive network can be reconstructed without with larger degree (Figure 11C), therefore the ΔR=R0
any obvious destructions. Overall, it indicated that the value undoubtedly increased. As the 5% strain was
addition of elastomer significantly increased the stability released, no evident reconstruction or destruction of the
of the conductive network structure of the composite dur- conductive networks were observed in Figure 11D. It is
ing circular stretching, so that the electrical conductivity expected that the number of the effective conductive
of the composite did not significantly change as the strain paths would gradually decrease with increasing the circu-
applied to the composite, shown in Figure 10D. Further- lation times, resulting in the increase of the ΔR=R0 ratio
more, when the conductive network was oriented along value.
F I G U R E 1 1 Schematic illustration of influence of MWCNTs structure on the strain sensing behavior of MWCNTs/PP/POE composites
with different tensile strains: (A and A') initial state; (B–C and B'-C') the loading state; (D and D') final unloading state
ZHAO ET AL. 19
For PP/POE/MWCNT composites, no evident an application of smart sensors. The ultra-small value
destruction of the conductive networks was found in ranges from 0.15 to 0.35 of the maximum and minimum
Figure 11B, C. MWCNTs particles chose to distribute in ΔR/R0 during the whole multi-time circulation of tensile
POE phase, forming the conductive networks. The stretching and recovering indicated that the PP/POE/
effective conductive paths did not reduce because this MWCNTs composites achieved a high strain sensitivity
small-applied strain lied in the linear elastic regime for and good repeatability within this critical strain as com-
composites. Instead, the intrinsic good elasticity of POE pared to its counterpart PP/MWCNTs composite. Overall,
ought to be in favor of promoting the formation of the this study highlighted a facile method to prepare a highly
orientation of the conductive network. Furthermore, the strain sensitive material by just regulating the morphol-
slight decrease of the max and min values of ΔR/R0 was ogy of composites via introducing a second disperse
presented indicating that the conductive networks did phase. We believe that this investigation of the micro-
not deteriorate seriously with applying larger strains. structure evolution of a conductive network provides a
When the load was removed, the reconstruction of the guideline for the design and fabrication of strain sensing
conductive networks was more predominant and recov- devices for a variety of applications, including artificial
ered to the initial condition. Moreover, some of the new skin, soft robotics, human motion monitoring, flexible
formed conductive paths were preserved owing to the vis- electronics, and so forth.
coelastic behavior of the polymer composites, and a
richer conductive network was obtained along the tensile ACKNOWLEDGMENT
direction at the end of each circular operation, leading to The authors gratefully acknowledge the financial support
the distinct decrease of the maximum ΔR/R0 values. from Funded by Project of Science and Technology
Department of Shaanxi Province (2021JQ-761), the
Industrial Field of Key Research and Development Plan
4 | C ON C L U S I ON S of Shaanxi Province (2021GY-222) and China Postdoc-
toral Science Foundation (2020M673585XB).
In this study, the correlation between the evolution of
the morphology and physical properties of PP compos- CONFLICT OF INTEREST
ites, including the crystallization behavior, thermal sta- The authors declare no competing financial interest.
bility and especially the electrical conductivity, was
comprehensively investigated. Focus was on the response ORCID
of the electric conductivity on the strain-sensing behavior Dahang Tang https://orcid.org/0000-0001-5006-3470
of PP-based stretchable composites filled with conductive
MWCNTs fillers and blended with a second thermoplas- RE FER EN CES
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Polymer Composites - 2021 - Zhao - Strain Sensing Behavior of Flexible Polypropylene Poly Ethylene Co Octene Multiwalled

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Strain-sensing behavior of flexible polypropylene/poly

Polymer Composites. 2022;43:7–20. wileyonlinelibrary.com/journal/pc © 2021 Society of Plastics Engineers. 7

1 | INTRODUCTION conductivity and lower percolation threshold. Moreover,

TABLE 1 Component contents of samples including PP and its nanocomposites

ΔHi 2.8 | Tensile test

2.4 | Scanning electron microscope

To observe the filler dispersion, scanning electronic

2.5 | Transmission electron microscopy

Ultrathin sections (approximately 100 nm thickness) of

FIGURE 6 The crystalline curves of composites

T A B L E 2 The relative parameters

TABLE 3 The relative TGA parameters of composites

Samples Td5 ( C) Samples Td5 ( C)

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