J Mater Sci (2022) 57:12416–12437

Composites
C O M P O S I T E S & N&
A Nnanocomposites
OC O M P O S I T E S

Experimental study and piezoresistive mechanism

of electrostatic self-assembly of carbon nanotubes–
carbon black/epoxy nanocomposites for structural
health monitoring
Yanlei Wang1 , Yao Fu1, Ziping Meng1, Baolin Wan2,* , and Baoguo Han1

1
State Key Laboratory of Coastal and Offshore Engineering, School of Civil Engineering, Dalian University of Technology,
Dalian 116024, Liaoning, China
2
Department of Civil, Construction and Environmental Engineering, Marquette University, Milwaukee, WI 53201, USA

Received: 3 January 2022 ABSTRACT

Accepted: 6 May 2022 Since electrostatic self-assembly carbon nanotubes–carbon black (CNTs–CB)
Published online: composite fillers have good electrical conductivity and an easy dispersion
30 June 2022 process, they were incorporated into epoxy matrix to fabricate the CNTs–CB/
epoxy nanocomposites. The mechanical properties, electrical conductivity,
 The Author(s), under piezoresistivity, as well as microstructure characterization of the CNTs–CB/
exclusive licence to Springer epoxy nanocomposites were experimentally investigated. The piezoresistive
Science+Business Media, LLC, mechanisms of the CNTs–CB/epoxy nanocomposites were also established
part of Springer Nature 2022 based on tunneling conduction and contacting conduction. The significant
improvements in compressive yielding strength and elastic modulus of the
nanocomposites could be attributed to the stable interfacial interaction. A
moderate percolation threshold was obtained at 0.41 vol% for the CNTs–CB/
epoxy nanocomposites in comparison with that of the nanocomposites filled
with only CNTs or CB particles. In monotonic compressive loading, the CNTs-
CB/epoxy nanocomposites exhibited highly sensitive and remarkably non-
monotonic piezoresistive responses, which could be divided into three stages
and showed dependence on the distinct evolution of hybrid conductive net-
works under compression. Moreover, the experimental results of cyclic loadings
confirmed the stability, repeatability, and recoverability in piezoresistive
responses of the nanocomposites. Overall, the highly sensitive and steadily
piezoresistive responses demonstrate that the CNTs–CB/epoxy nanocomposites
are attractive to be used as compressive strain sensors for structural health
monitoring in civil infrastructures.

Handling Editor: Annela M. Seddon.

Address correspondence to E-mail: baolin.wan@marquette.edu

https://doi.org/10.1007/s10853-022-07402-6
J Mater Sci (2022) 57:12416–12437
Introduction
Civil infrastructures (e.g., buildings, bridges, and
highways) often suffer from fatigue load, impact
load, and various extreme natural disasters (e.g.,
earthquakes and hurricanes), which threaten the
safety and service life of these infrastructures [1].
Therefore, it is extremely important to install strain
sensors at critical locations of structures for accu-
rately diagnosing their real-time status [2–4]. Cur-
rently, commonly used strain sensors for structural
health monitoring (SHM) include metal foil resis-
tance strain gauge, piezoelectric ceramic, optical
fiber, and piezoresistive strain sensors [4–6].
Due to their characteristics of easy fabrication,
excellent durability, low cost, and remarkable
piezoresistive properties, electrically conductive
composites have attracted great interest from
researchers in the past few decades [7–9]. Electrically
conductive composites, which are used as piezore-
sistive strain sensors, are generally consisted of
insulating or semiconducting matrix materials (e.g.,
polymer [8, 10–14], cement [4, 9, 15, 16], and ceramic
[17, 18]) and conductive reinforcements (e.g., carbon
black [10, 12], nickel powder [15, 16], carbon nan-
otubes [5, 11, 13], carbon nanofibers [19–22], and
graphene platelet [23, 24]). The piezoresistive
responses of these piezoresistive strain sensors gen-
erally stem from the relative change in electrical
resistivity when they are subjected to external effects
(e.g., stress, strain, and temperature). This variation
in electrical resistivity is considered to be related to
the change in the number of the contact point and the
distance between conductive particles. Therefore,
they have great potential applications for SHM in
civil infrastructures. The cement-based conductive
composites have attracted tremendous attention in
the applications of piezoresistive strain sensors
embedded in concrete due to their similar composi-
tion and natural compatibility with concrete struc-
tures [4, 6, 9, 25, 26]. Dong et al. [25] investigated the
piezoresistive sensitivity and repeatability of cemen-
titious composites reinforced with carbon nanotubes
(CNTs) exposed to cyclic compression and impact.
The results showed that the cementitious composites
filled with CNTs could obtain stable and uniform
12417
fractional changes of resistivity during cyclic com-
pression. Sun et al. [26] investigated the piezoresis-
tive cementitious composites with nanographite
platelets (NGPs) under different cyclic compressive
loading conditions and their capability in measuring
dynamic loading rate. They concluded that the
cement-based composites with NGPs not only pos-
sessed sensitive piezoresistive behavior but also
showed stable repeatability to different loading con-
ditions. However, cement-based conductive com-
posites exhibit a strong moisture dependence, thus
causing a serious adverse impact on the precision of
such sensors, especially when exposed to harsh
environments [27–29]. Moreover, the ultimate com-
pressive strain of confined concrete structures (e.g.,
steel tube or fiber-reinforced polymers confined
concrete structures [30–34]) is generally up to 1–3%,
which is much higher than the strain sensing range of
cement-based sensors which is limited to less than
0.5% [19]. Therefore, it is necessary to fabricate
piezoresistive strain sensors with excellent water-
proofness and broad strain monitoring range for
SHM in civil engineering.
Epoxy resins, which have dense and stable cross-
linked structure and large deformation range, have
been studied as the substitute for cement materials
for the matrix in manufacturing piezoresistive strain
sensors with favorable mechanical properties and
wide strain sensing range, as well as excellent water
resistance. Shen et al. [35] explored the changes in
electrical resistance of epoxy composites filled with
CNTs under compression. It was revealed that the
CNTs/epoxy composites showed a significant
decrease in electrical resistance under compression.
The test results reported by Tian et al. [13] also
showed that the CNTs/epoxy composites had good
piezoresistive properties when exposed to different
loading levels. The aforementioned studies have
confirmed that epoxy-based composites with low
CNTs concentrations could exhibit excellent electrical
conductivity and piezoresistivity. Nevertheless, the
piezoresistive sensitivity of most nanocomposites
with CNTs is usually limited between 0.5 and 5 at the
bulk scale, especially under compression
[2, 5, 7, 11, 36–39]. In addition, the composites filled
with CNTs are prone to exhibit poor repeatability
under cyclic loading due to the large aspect ratio
12418
[40–42]. Research has shown that carbon black (CB)
nanoparticles could also endow composites with
good electrical and piezoresistive properties [10, 12].
For instance, Wichmann et al. [10] demonstrated that
the epoxy-based nanocomposites with CB exhibited
pronounced piezoresistive responses with higher
strain sensitivity and good repeatability. However,
the percolation threshold of nanocomposites filled
with CB is generally much higher than that in
nanocomposites containing CNTs [10, 43–45]. This
leads to the large filler dosage of CB in the matrix,
which may introduce local defects in the nanocom-
posites and significantly impair their mechanical
properties [19, 46]. Synthetically considering these
factors, blending CNTs and CB conductive nanopar-
ticles into a polymer matrix might be a new alteration
to balance the requirements of high strain sensitivity,
good constancy, and appropriate filler concentration
[41, 47–51].
At present, there are many researches on con-
ducting nanocomposites by simply mixing CNTs and
CB nanoparticles into the polymer matrix
[41, 44, 45, 47–49]. The researchers verified that the
combination of CNTs and CB conductive fillers into a
polymer matrix could effectively improve the elec-
trical conductivity and piezoresistivity of nanocom-
posites via constructing the distinct conductive
network in the matrix on account of the synergistic
effect. However, the characteristics of easy agglom-
eration make it difficult to realize the uniform dis-
persion of CNTs and CB nanoparticles into a polymer
matrix. Generally, ultrasonic treatment is often used
to assist in dispersing CNTs and CB hybrid
nanoparticles during the simple mix process
[5, 8, 10–12]. This dispersion process with ultrasonic
treatment is usually sophisticated and time-consum-
ing, which will increase the difficulty in fabricating
nanocomposites. What is more, the synergistic effect
between CNTs and CB relies heavily on their dis-
persion states in the polymer matrix [49]. Electrostatic
self-assembly CNTs–CB composite fillers with special
grape clusters structures can be prefabricated before
they are incorporated into the polymer matrix.
Specifically, the surfaces of CNTs and CB are modi-
fied by cationic and anionic surfactants, respectively;
and then, the CB particles are attached to the sur-
rounding of CNTs by electrostatic force [50]. This
assembly process enables the CNTs–CB composite
fillers to have a larger volume compared to the
individual CNTs or CB particles, which not only
J Mater Sci (2022) 57:12416–12437
simplifies the dispersion process without additional
ultrasonic treatment, but also ensures the realization
of a good synergistic effect between the hybrid
nanoparticles [4]. A few studies showed that the
electrostatic self-assembly CNTs–CB composite fil-
lers-reinforced silicon rubber (SR) matrix [50] and
cement matrix [4] could achieve not only the
enhancement in electrical conductivity and piezore-
sistivity with low filler concentration, but also the
simplification in the filler dispersion method. How-
ever, there is no investigation of the effects of elec-
trostatic self-assembly CNTs–CB composite fillers on
the piezoresistive behavior of epoxy-based
nanocomposites under compression. Simultaneously,
the epoxy resin possesses the features of easy fabri-
cation, good creep resistance, excellent water resis-
tance, and broad strain sensing range, compared to
silicon rubber matrix and cement matrix [8, 19].
Therefore, it is very meaningful to investigate the
various properties (i.e., mechanical properties, elec-
trical conductivity, and piezoresistivity) of epoxy-
based nanocomposites integrated with electrostatic
self-assembly CNTs–CB composite fillers, and to
explore their potential applications as a piezoresistive
strain sensor.
The objectives of this study include two aspects: (1)
analyzing the influence of the concentrations of elec-
trostatic self-assembly CNTs–CB composite fillers on
the mechanical properties, electrical conductivity, and
piezoresistivity of epoxy-based nanocomposites
under compression; and (2) verifying the piezoresis-
tive mechanisms of electrostatic self-assembly CNTs–
CB composite fillers-reinforced epoxy-based
nanocomposites subjected to different levels of com-
pressive load. To achieve these goals, epoxy-based
nanocomposites filled with different volume percent-
ages of electrostatic self-assembly CNTs–CB compos-
ite fillers ranging from 0.5 to 2.0 vol% were fabricated
by a simple and facile mechanical stirring method. The
mechanical and electrical properties of CNTs–CB/
epoxy nanocomposites embedded with different
electrostatic self-assembly CNTs–CB composite fillers’
concentrations were investigated. The mechanisms of
the piezoresistive response of the CNTs–CB/epoxy
nanocomposites corresponding to different strain
levels were then theoretically demonstrated. Further-
more, the piezoresistive responses of the nanocom-
posites at different loading conditions were
experimentally studied to reveal their stability,
repeatability, and feasible strain sensing range.
J Mater Sci (2022) 57:12416–12437
Experimental program
Raw materials and specimen fabrications
A commercially available epoxy resin (produced by
Tianjin Swancor Wind Power Materials Co., Ltd.,
China), which is composed of base component
(model 2511-1A) and hardener (model 2511-1BS) with
a weight ratio of 100:30, was selected for the fabri-
cation of the specimens in this study, because it
exhibits the characteristics of low viscosity, moderate
gel time, and good infiltration to carbon nanoparti-
cles. The electrostatic self-assembly CNTs–CB com-
posite fillers were acquired from the Chengdu
Institute of Organic Chemistry Co., Ltd, China. Their
resistivity is less than 0.01 X•cm and their specific
surface area is 540–560 m2/g. They are composed of
CNTs and CB with a weight ratio of 40:60. The
average diameter of CB particles is 35 nm, and the
specific surface area is 934 m2/g. The primary out-
side diameter of CNTs particles is 10–30 nm, and the
average length is 10–30 lm. Figure 1 shows their
specific grape clusters structure microscopically.
Stainless steel mesh was used in specimens as the
conductive electrodes with a size of
20 mm 9 30 mm.
A simple and facile mechanical stirring method
without additional ultrasonic treatments was used to
fabricate the epoxy-based nanocomposites containing
different concentrations of electrostatic self-assembly
CNTs–CB composite fillers in this study. The detailed
fabrication and molding procedures of CNTs–CB/
epoxy nanocomposites are exhibited schematically in
Fig. 2. Firstly, all different volume fractions of CNTs–
CB composite fillers were weighed by a high-preci-
sion electronic balance and dried in a vacuum oven at
Figure 1 SEM photographs
of CNTs-CB composite fillers:
a 50000X and b 100000X.
12419
60 C for 30 min before the dispersion process to
eliminate possible absorbed moisture during storage.
Then, the specific quantity of dry CNTs–CB com-
posite fillers was incorporated into the preheated
epoxy base component, which was heated in a water
bath at 60 C to further lower the viscosity [52, 53].
The mixture was first stirred at low speed (500 rpm)
at 60 C for 5 min and then at high speed (2000 rpm)
at 60 C for 25 min. Subsequently, the uniformly
dispersed mixture was placed in a vacuum oven at
60 C for 30 min to eliminate the entrapped air bub-
bles. After that, the mixture was cooled to room
temperature and the required quantity of the hard-
ener was added into the mixture with a gentle stir-
ring process at room temperature to reduce the
introduction of extra air bubbles. Next, the CNTs–
CB/epoxy mixture was vacuumed at room temper-
ature again to remove entrapped air bubbles and then
poured into the silicone rubber molds with the
dimension of 20 mm 9 20 mm 9 40 mm, which was
pre-coated with silicone oil release agent (model BD-
TM001, produced by Xi’an Beiduo Environmental
Protection Technology Co., Ltd., China) to easily
remove the specimens out of the molds after they
were cured. Two stainless steel mesh electrodes with
10 mm of separation were embedded in the molds in
advance. The specimens for mechanical property
tests had no embedded electrodes. The casted speci-
mens were first cured at room temperature for 24 h
and then cured at 60 C for another 24 h. It should be
noted that after adding the hardener component, the
operations such as the stirring and the vacuuming
should be performed quickly to prevent the epoxy
resin from the curing before the pouring, which could
tremendously damage the mechanical properties of
the nanocomposites. For the epoxy-based
12420
Figure 2 Fabrication and
molding procedures of CNTs–
CB/epoxy nanocomposite
specimens.
nanocomposites, the selected CNTs-CB composite
fillers concentrations in volume were fixed at 0.5
vol%, 0.75 vol%, 1.0 vol%, 1.25 vol%, 1.5 vol%, and
2.0 vol%, respectively.
Measurements
Microstructure characterization
The morphology and distribution of electrostatic self-
assembly CNTs–CB composite fillers in the epoxy
matrix were observed by a field emission scanning
electron microscopy (FESEM). The samples used for
inspection were cut from the fractured CNTs–CB/
epoxy nanocomposites after their mechanical tests.
Before the FESEM observation, a thin layer of plat-
inum was sputtered on the samples’ surface to
enhance the electroconductibility of the samples for
better imaging.
Mechanical measurement
The uniaxial compression test was conducted using
an electronic universal testing machine (model WDE-
200E, produced by Jinan Gold Testing Machines Inc.,
China). A displacement-controlled loading method
was applied to the specimens with a fixed loading
rate of 0.4 mm/min. The axial compression strain
was measured by a pair of strain gauges symmetri-
cally bonded to the center of both sides of the speci-
men along the length direction, as shown in Fig. 3. A
static strain acquisition system (model DH3820, pro-
duced by Donghua Testing Technology Co., Ltd.,
China) was used to record real-time compressive
J Mater Sci (2022) 57:12416–12437
Compression
Electrodes Strain gauges
Compression
Figure 3 Arrangement of strain gauges on the specimen.
strain data, and the sampling frequency was fixed at
1 Hz during the entire test process. Three specimens
for each composite filler concentration were tested.
Electrical measurement
Three specimens of each type of CNTs–CB/epoxy
nanocomposites with different electrostatic self-
assembly CNTs-CB concentrations (0 vol%, 0.5 vol%,
0.75 vol%, 1.0 vol%, 1.25 vol%, 1.5 vol%, and 2.0
vol%) were tested for the electrical properties. Com-
pared with four-electrode measurement method,
two-electrode measurement method has the advan-
tages of easy operation and stable electrical signal
[17, 18]. Therefore, the two-electrode measurement
method was adopted in the study to obtain the
electrical resistance. A Keithley 2100 digital multi-
meter was used to measure direct current (DC) elec-
trical resistance. The volumetric electrical resistivity
of specimens, q, was calculated by [20]:
J Mater Sci (2022) 57:12416–12437
RS
q¼
L ing, every specimen was subjected to six loading–
where R, S, and L are the bulk resistance of speci-
mens, the cross-sectional area of specimens, and the
distance between the two embedded electrodes,
respectively.
Piezoresistive measurement
A synthetical data collection system, combining
WDE-200E electronic universal testing machine,
Keithley 2100 digital multimeter, and DH3820 static
strain acquisition system, was used for inspecting the
piezoresistive properties. The three devices were all
connected with a computer to synchronously record
the real-time force data, bulk electrical resistance, and
compressive strain during the compression, respec-
tively. It should be noted that the piezoresistivity is
highly dependent on the electrical conductivity of the
nanocomposites [41, 54]. The nanocomposites con-
taining 0.5 vol% and 0.75 vol% electrostatic self-
assembly CNTs–CB composite fillers were unable to
output stable electrical signals due to their poor
electrical conductivity. Moreover, the nanocompos-
ites containing 2.0 vol% electrostatic self-assembled
CNTs–CB composite fillers lead to obvious agglom-
eration of the fillers due to excessive filler concen-
tration. Therefore, its economy, long-term working
life, and strain sensitivity are inevitably reduced.
Thus, the nanocomposites with volume fractions of
CNTs–CB composite fillers of 1.0 vol%, 1.25 vol%,
and 1.5 vol%, respectively, were selected to investi-
gate the piezoresistive responses of CNTs–CB/epoxy
nanocomposites under monotonic and cyclic loading.
As shown in Fig. 4, two different cyclic compressive
loading modes were adopted including a constant
amplitude cyclic and an incremental amplitude cyclic
Figure 4 Cyclic compressive 25
loading modes: a constant
amplitude; b incremental 20
Stress (MPa)
amplitude.
15
10
5 10
0 0
0 100
12421
loading. During the constant amplitude cyclic load-
ð1Þ
unloading cycles with the maximum compressive
stress level at 20 MPa, which kept the nanocompos-
ites in the linear elastic stage. A stepwise increase
compressive loading was applied from 5 to 45 MPa
with the incremental amplitude of 5 MPa, and every
level of compressive stress was conducted for three
cycles. Both monotonic and cyclic loadings were
performed at a constant speed of 0.4 mm/min. To
obtain the stable conductive network before the
piezoresistive properties testing, each specimen was
pre-compressed by applying several cyclic compres-
sive loading under a low-stress level (5 MPa). The
test setup is shown in Fig. 5.
The fractional change in volumetric resistivity
(FCR), f (unit:%), was approximately determined
according to Eq. (2) by ignoring the small deforma-
tion between two electrodes under small deformation
of the entire specimen [20].
R  R0 DR
f¼ ¼ ð2Þ
R0 R0
where R (unit:X) is the isochronous electrical resis-
tance during the compression; R0 (unit:X) is the initial
electrical resistance of the specimens without com-
pression; and DR (unit:X) is the relative change in
bulk electrical resistance during the compression.
Results and discussions
Morphology
Figures 6 and 7 exhibit the morphology and distri-
bution of electrostatic self-assembly CNTs-CB com-
posite fillers in the epoxy matrix. As shown in Fig. 6,
the CNTs–CB composite fillers were completely
(a) 50 (b)
40
Stress (MPa)
30
20
200 300 400 500 600 700 0 500 1000 1500 2000 2500 3000 3500
Time (s) Time (s)
12422 J Mater Sci (2022) 57:12416–12437

Figure 5 Experimental
devices of the piezoresistive
measurement.

Figure 6 Morphology of
grape clusters structure in
CNTs–CB composite fillers in
the epoxy resin matrix:
a 100,000 9 and b 200,000 9.

Figure 7 SEM images of CNTs-CB/epoxy nanocomposite fracture surface reinforced with a 0 vol%; b 0.5 vol%; c 1.0 vol%; d 1.25
vol%; e 1.5 vol%; and f 2.0 vol% of CNTs–CB composite fillers (yellow arrows: CNTs; yellow ellipse: CNTs agglomerations).

incorporated in the epoxy matrix and could remain addition, Fig. 7 demonstrates the distribution of
their original grape clusters structure in the matrix, CNTs–CB composite fillers with different filler vol-
which was essential to realize the synergetic effect. In ume fractions. From the SEM images of the fracture
J Mater Sci (2022) 57:12416–12437 12423

surfaces from the failed specimens in mechanical compressive mechanical properties of nanocompos-
tests, it can be concluded that the CNTs–CB com- ites with different concentrations of electrostatic self-
posite fillers could achieve a relatively well-dis- assembly CNTs-CB composite fillers. Figure 8a
tributed state in the epoxy matrix via the facile and shows the representative compressive stress–strain
simple direct mixing method used in this study due curves for the pure epoxy and its nanocomposites, in
to their special grape clusters structure. However, the which all typical stress–strain curves exhibited a
agglomeration of CNTs began to occur when the filler similar initial linear variation trend and then fol-
concentration reached 2.0 vol% as shown in Fig. 7f. lowed with a large scale of plasticity [14]. Addition-
This behavior is believed to associate with the rela- ally, Fig. 8a shows that the linear elastic limits of
tively high viscosity of the mixture with high CNTs– CNTs–CB/epoxy nanocomposites were around
CB composite fillers concentration. The uniform dis- 35–40 MPa. It is well recognized that the nanocom-
tribution of the conductive fillers within a certain posites should stay within the range of linear elastic
concentration range contributes to the favorable limit when they are used as piezoresistive strain
establishment of conductive networks in the epoxy sensors to avoid permanent deformation that has
matrix, which conduces to the considerable adverse effects on the precision of the compressive
enhancements in the mechanical properties, electrical sensors [55]. Figure 8b and c indicate that the intro-
properties as well as piezoresistivity of the epoxy- duction of CNTs–CB composite fillers into epoxy
based nanocomposites as described in the following resin had significant improvements in the mechanical
sections. properties of the nanocomposites in comparison with
those of pure epoxy resin. Compared with that of
Mechanical properties pure epoxy resin (i.e., compressive yield strength:
66.2 MPa), the compressive yield strengthes of the
The uniaxial compressive loading was conducted to nanocomposites filled with 0.5 vol%, 1.0 vol%, 1.25
investigate the mechanical properties of the CNTs– vol%, 1.5 vol%, and 2.0 vol% CNTs-CB composite
CB/epoxy nanocomposites. Figure 8 illustrates the fillers were increased by 11.5%, 19.2%, 23.1%, 25.5%,

Figure 8 Compressive 100

(a)
Compressive Stress (MPa)

mechanical properties of
CNTs-CB/epoxy 80
nanocomposites with different
concentrations of CNTs–CB 60
composite fillers: a typical 0 vol%
40 0.5 vol%
stress–strain curves; 1.0 vol%
b compressive yield strength; 20 1.25 vol%
and c elastic modulus. 1.5 vol%
2.0 vol%
0
0 3 6 9 12 15
Strain (%)
Compressive yield Strength (MPa)

120 4
(b) (c)
3.19
Elastic Modulus (GPa)

100 3.08
86.6 2.85 2.91
78.9 81.5 83.1 3 2.61
73.8 2.46
80 66.2

60 2

40
1
20

0 0
0 0.5 1.0 1.25 1.5 2.0 0 0.5 1.0 1.25 1.5 2.0
CNTs-CB Concentration (vol%) CNTs-CB Concentration (vol%)
12424
and 30.8%, respectively. At the same time, the cor-
responding elastic moduli of the nanocomposites
filled with 0.5 vol%, 1.0 vol%, 1.25 vol%, 1.5 vol%,
and 2.0 vol% CNTs–CB composite fillers were also
increased by 6.1%, 15.7%, 18.3%, 25.4%, and 30.0%,
respectively, compared with that of pure epoxy resin
(i.e., elastic modulus: 2.46 GPa).
These improvements in mechanical properties
could be ascribed to the reinforcing effect of the
CNTs–CB composite fillers. Generally, favorable
interfacial interaction is the foundation of this rein-
forcing effect on mechanical properties. When the
CNTs–CB composite fillers are evenly distributed
into the epoxy, excellent interfacial interaction will be
generated between the CNTs–CB composite fillers
and the epoxy matrix, thereby effectively transferring
stresses from the epoxy matrix to the composite fillers
[19, 20, 24]. Thus, CNTs–CB composite fillers pos-
sessing excellent mechanical properties can support a
portion of the compressive loading, and also signifi-
cantly enhance the compressive yield strength and
the elastic modulus of the composites. When the
CNTs–CB composite fillers concentration is
increased, the number of solid interfaces used for
stress transfer will also be increased, resulting in
better stress transfer efficiency and thus sustaining
more stress [24]. Meanwhile, due to the constraint of
CNTs–CB composite fillers (e.g., bridging effect), the
lateral deformation of epoxy is restricted and the
extension of microcracks in the matrix is subse-
quently limited, thus improving the compressive
yield strength and elastic modulus of nanocompos-
ites [19]. The fractured CNTs under high-stress level
and the bridging effect are shown in Fig. 9.
Electrically conductive properties
The relationship between the DC electrical resistivity
and the concentration of electrostatic self-assembly
CNTs–CB composite fillers without applying external
compressive stress is shown in Fig. 10. It can be seen
that the concentration of CNTs–CB composite fillers
had a prominent effect on the DC electrical resistivity.
It is obvious that increasing the concentration of
CNTs–CB composite fillers significantly decreased
the DC electrical resistivity of CNTs–CB/epoxy
nanocomposites. The electrical resistivity of the
specimens with 1.0 vol% CNTs–CB composite fillers
was around 6 orders of magnitude lower than that of
pure epoxy resin. This sudden decrease in electrical
J Mater Sci (2022) 57:12416–12437
resistivity implies the occurrence of a significant
percolation phenomenon (i.e., the conductive paths
begin to form in the epoxy matrix).
To better understand the percolation characteristic
of CNTs–CB/epoxy nanocomposites, the general
effective media (GEM) theory [19] was applied to
estimate their percolation threshold and critical
coefficient:
q ¼ q0 ðu  uc Þt ð3Þ
where q0 is a constant value; u is the volume fraction
of CNTs–CB composite fillers; uc is the critical vol-
ume fraction of CNTs–CB composite fillers (i.e., per-
colation threshold); and t is the critical coefficient
(which is used to judge the dimensionality of the
conductive networks in the nanocomposites). The
resistance of conductive composite fillers is negligible
compared to the extremely high resistance of the
epoxy matrix. The values of uc and t of nanocom-
posites were obtained by fitting the experimental
data. And the estimated results according to GEM
were shown in the insert in Fig. 10. According to the
fitting result, the percolation threshold value of
CNTs–CB/epoxy nanocomposites was estimated as
0.41 vol%, which was between the value of
nanocomposites comprising only CNTs and that of
nanocomposites with only CB particles. Based on the
researches on epoxy-based nanocomposites contain-
ing only CNTs [36, 39] or CB [43], the filler dimension
has significant effects on the electrical percolation
threshold. For example, Cao et al. [39] demonstrated
that the ultralow percolation threshold of 0.0125 vol%
for CNTs/epoxy composites was obtained due to
their large aspect ratio. However, Buketov et al. [43]
found that the composites filled with CB particles
possessed a much higher percolation threshold
around 8 wt%. Thus, the moderate percolation
threshold of nanocomposites containing CNTs–CB
composite fillers in this study indicates that blending
CNTs and CB particles into polymer matrix could
well tune the percolation threshold of nanocompos-
ites. This phenomenon could be ascribed to the
unique hybrid conductive networks due to the
unique synergistic effect between CNTs and CB
particles. Chen et al. [41] also confirmed that intro-
ducing a certain amount of CNTs into CB/isoprene
rubber composite could significantly reduce the per-
colation threshold due to the construction of hybrid
CNTs–CB networks. Moreover, the value of t fitted
with experimental data according to GEM was
J Mater Sci (2022) 57:12416–12437 12425

Figure 9 SEM images of

CNTs–CB/epoxy
nanocomposites: fractured
CNTs in a and b; and bridging
effect in c and d.

1014 -6
13 φc=0.41 t=2.88
Electrical resistivity (Ω.cm)

10 -7 R2=0.972
log(1/ρ)

1012 -8

1011
-9
Experimental data
1010 Linear fit
-10
109 -0.8 -0.4 0.0 0.4 0.8
log(φ凟φc)
108

107 Figure 11 Three different potential inner gaps in CNTs–CB

0.0 0.5
CNTs-CB content (vol%)
Figure 10 Electrical resistivity of CNTs–CB/epoxy
nanocomposites as a function of CNTs–CB concentration. (The
inset is the plot of the logarithm of conductivity vs. the logarithm
of reduced volume fraction.).
estimated as 2.88, which was higher than the theo-
retical numerical value for a three-dimensional ran-
dom network ðt  2Þ [42]. This much higher t value
may be attributed to a three-dimensional electrically
conductive network accompanied by a relatively
wide distribution of inner conductive particles
1.0 1.5 2.0 2.5 composite fillers in the nanocomposites.
distance (i.e., tunneling resistance) around the per-
colation thresholds [42, 47, 56–58]. Such hybrid three-
dimensional conductive networks were derived from
the numerous inner gaps between CNTs and CB
particles, e.g., CNTs–CNTs, CNTs–CB, CB–CB, as
shown in Fig. 11.
Generally, tunneling conduction and contacting
conduction are the mainly conductive mechanisms in
the aforementioned hybrid conductive networks.
Furthermore, the sophisticated inner gaps (Fig. 11)
generated different electron conduction modes in the
12426 J Mater Sci (2022) 57:12416–12437

epoxy matrix, including short-range conduction
between CB and remote-range conduction between
CNTs [44, 59]. These multiple modes of electron
conduction produce the complex hybrid conductive
networks and the moderate percolation threshold
based on the synergistic effect between CNTs and CB
particles. As shown in Fig. 7, adding more CNTs–CB
composite fillers led to a more noticeable reduction in
the inner distance between fillers. In this case, the
composite fillers gradually transform from the iso-
lated state to partial mutual overlap with the increase
in the filler concentration [13]. Thus, the dominant
conduction mechanism transforms from tunneling
conduction to contacting conduction with the
increase in the CNTs–CB concentrations. This is very
beneficial for the construction of continuous and
abundant conductive networks, increasing the elec-
trical conductivity of nanocomposites.
Piezoresistive properties
Piezoresistive properties under monotonic loading
To investigate the piezoresistive properties of CNTs–
CB/epoxy nanocomposites and explore their poten-
tial application as piezoresistive sensors, both strain
and electrical resistivity variations of specimens were
tested simultaneously when they were subjected to
monotonic compressive loading. Figure 12 shows the
changes of FCR of specimens filled with 1.0 vol%,
1.25 vol%, and 1.5 vol% electrostatic self-assembly
CNTs–CB composite fillers, respectively, under
compression. The FCR values of CNTs–CB/epoxy
nanocomposites changed synchronously with the
external compressive strain, manifesting a timely
resistance response. In addition, the FCR–strain
curves of all nanocomposites filled with different
CNTs–CB composite filler concentrations had obvi-
ous non-monotonic changes during the entire com-
pression process. The FCR vs. strain curves of CNTs–
CB/epoxy nanocomposites started with a linear
decline initially, followed by an abrupt decline, and
then reversed the trend to increase. This phe-
nomenon is highly dependent on the evolution of the
conductive networks in the matrix, which is related
to the construction and breakdown of electrically
conductive pathways with the increasing compres-
sive strain, causing the decrease and increase in the
electrical resistivity. The FCR–strain curves of CNTs-
CB/epoxy nanocomposites can be segmented into
three different stages: (1) linear elastic stage, (2) vis-
coelastic stage, and (3) plastic stage. In the first two
stages, all FCR values decreased linearly with the
increasing compressive strain until the electrical
resistivity plateau was reached as shown in Fig. 12.
This result is related to the decreasing tunneling
resistivity and the optimization of the conductive
network. The transition point denoted as e2 in Fig. 12
is closely corresponding to the yielding points of

Figure 12 FCR and 100 (a) 1.0 vol% 100

compressive stress vs. strain 80 80
for nanocomposites loaded 60 60
Stress (MPa)
FCR (%)

with a 1.0 vol%; b 1.25 vol%; 40

I II III
40
and c 1.5 vol% of CNTs–CB 20 20
composite fillers. 0 0
-20 -20
GF1
-40 GF2 -40
-60 ε1 ε2 -60
0 1 2 3 4 5 6 7 8
Strain (%)

100 (b) 1.25 vol% 100 100 (c) 1.5 vol% 100
80 80 80 80
60 60 60 60
Stress (MPa)
Stress (MPa)
FCR (%)

FCR (%)

40 40 40 I II III 40
I II III
20 20 20 20
0 0 0 0
-20 GF1 -20 -20 -20
GF1
-40 GF2 -40 -40 GF2 -40
-60 ε1 ε2 -60 -60 ε1 ε2 -60
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8
Strain (%) Strain (%)
J Mater Sci (2022) 57:12416–12437
nanocomposites in stress–strain curves according to
the 0.2% offset rule [11, 14]. In the third stage (i.e.,
beyond the yielding points), the FCR values exhibited
an increasing trend until the nanocomposites failed.
This is mainly due to the generation of microcracks
and the destruction of conductive pathways, which
leads to the violent separation between CNTs–CB
composite fillers and then hinders electron conduc-
tion [19]. In summary, the evolution of the conductive
network structures governs the piezoresistivity of
CNTs–CB/epoxy nanocomposites.
The gauge factor (GF) of strain sensors, which is
defined as the ratio of DR/R0 to concurrent com-
pressive strain e (i.e., FCR/e), is generally used to
evaluate the strain sensitivity of nanocomposites and
provides a more accurate description of the piezore-
sistive response. The linear regression analysis results
for the first two stages of FCR–strain curves are listed
in Table 1. The GFs in stage I of the CNTs–CB/epoxy
nanocomposites with the filler concentrations of 1.0
vol%, 1.25 vol%, and 1.5 vol% were calculated as 6.94,
4.66, and 4.60, respectively, and the GF values in
stage II were fitted as 30.10, 26.39, and 18.53,
respectively. A larger compressive strain amplitude
led to a higher strain sensitivity. This increasing
strain sensitivity could be ascribed to that denser
conductive networks were established when speci-
mens were exposed to higher strain levels, leading to
more decrease in the electrical resistivity. In addition,
the GF values in Table 1 for CNTs–CB/epoxy
nanocomposites are markedly higher than those in
many other researches studying thermosetting matrix
nanocomposites [36–39]. For example, Ku-Herrera
et al. [38] investigated the piezoresistivity of the
CNTs/vinyl ester composites filled with 0.3, 0.5, and
1.0 wt% CNTs in compression and found that the
strain sensitivities of them before matrix yielding
were 0.91, 2.39, and 4.55, respectively, which are
much lower than those in CNTs–CB/epoxy
Table 1 Gauge factors of CNTs–CB/epoxy nanocomposites
CNTs–CB concentrations Gauge factors in stage I Coefficient of
(vol%) (GF1) determination
(R2)
1.0 6.94 0.993
1.25 4.66 0.994
1.5 4.60 0.995
12427
nanocomposites (i.e., 30.10 for the nanocomposites
with 1.0 vol% CNTs–CB composite fillers before
yielding). This distinct phenomenon indicates that
the introduction of CB particles makes the conductive
network more susceptible to external forces, resulting
in higher strain sensitivities. However, these GF
values are lower than those of thermoplastic [12, 54]
and elastomeric matrix composites [41, 60]. This
manifests that the strain sensitivity of the nanocom-
posites is also relevant to the flexibility of matrix
materials [12]. In addition, the research of Yang et al.
[61] showed that when the concentration of graphite
nanoplatelets(GNP) reached 50 wt%, the GF value for
strain sensing of freestanding CNT/GNP buckypa-
pers was up to 8.18, and the corresponding R2 was
0.999. Another research of Yang et al. [62] showed
that hybrid CNT/Graphene (GN) film sensors were
highly sensitive to the initiation and evolution of
shear damages. This manifested that the film sensors
fabricated by composite fillers free from flexible
substrates might have unique advantages in the
sensitivity and the linearity. Furthermore, Table 1
shows that the GF values also show high dependency
on the CNTs–CB composite fillers concentrations.
There is a gradually decreasing strain sensitivity for
the nanocomposites with the increase in the CNTs–
CB composite filler concentration. The reduction in
the inter-particle gaps and the increase in the con-
ductive network compactness account for this
decreasing sensitivity. Considering that the linearity
of the FCR–strain curves of the nanocomposites with
three different filler concentrations in this paper is
not much different, the nanocomposite with 1.0 vol%
CNTs–CB composite fillers, due to its high strain
sensitivity and the minimum filler concentration,
show greater potential in making compressive strain
sensor. Other researches [40, 51] showed that higher
electrical resistivity manifests higher strain sensitivity
at lower conductive filler concentration, and the
Gauge factors in stage II Coefficient of
(GF2) determination
(R2)
30.10 0.994
26.39 0.996
18.53 0.996
12428
dominance of tunneling effects could be used to
explain this phenomenon. The CNTs–CB concentra-
tions of specimens in this research were beyond the
percolation threshold. Therefore, the dominance of
tunneling effects on piezoresistive responses gradu-
ally reduced and the contact conduction became
dominant, leading to a more compact conductive
network and lower strain sensitivity.
Piezoresistive mechanisms under monotonic loading
According to the previous discussion, the evolution
of the conductive networks in the matrix may result
in different piezoresistive mechanisms under differ-
ent compressive strain amplitudes. The evolution of
conductive networks in schematic form and the
expansion of microcracks in SEM images of
nanocomposite with 1.0 vol% electrostatic self-
assembly CNTs–CB composite fillers are illustrated
in Figs. 13 and 14, respectively.
As shown in Fig. 13a, the CNTs-CB composite fil-
lers were uniformly distributed and there was no
damage in the matrix in the original state without
applied compressive strain. In the initial state, the
distribution of conductive junctions (red circle
in Fig. 13a) was limited, resulting in less conductive
paths and showing high electrical resistivity. As the
compressive strain was in stage I (i.e., linear elastic
stage in Fig. 12), the nanocomposites generated only
a minor volumetric deformation in the direction of
compression, and the morphology of conductive
networks could hold their original structure form.
When the larger compressive strain was applied to
the nanocomposites, the inter-particle gaps decreased
and the partial contacts between neighboring fillers
increased, leading to the reduction in electrical
Figure 13 Schematic
illustration of the evolution of
conductive networks at
different compressive strains.
J Mater Sci (2022) 57:12416–12437
resistivity. Under this circumstance, the number of
conductive junctions increased (Fig. 13b). Therefore,
more conductive paths could be formed and the
electrical resistivity gradually decreased. In this
stage, tunneling conduction plays a dominant role
and accounts for the decreasing electrical resistivity.
Moreover, Fig. 14a shows that the structure of the
epoxy matrix also could remain unchanged without
any microcracks in the linear elastic stage. This phe-
nomenon indicates that such a low strain level cor-
responding to the linear elastic deformation would
not damage the matrix structure. Therefore, more
conductive networks could be generated in this stage,
mainly owing to the reduction in the distance
between neighboring CNTs–CB composite fillers.
For the larger compressive strains in stage II (i.e.,
viscoelastic stage in Fig. 12), more conductive paths
were generated, and thus, the electrical resistivity of
nanocomposites decreased along with the compres-
sion. Therefore, a higher strain sensitivity was
obtained. In addition, under larger strain amplitudes,
the deformation of nanocomposites gradually
increased and gave rise to the generation of damage
in the epoxy matrix. These microcracks in the matrix
shown in SEM images (Fig. 14b) demonstrate that the
higher strain level caused the formation of localized
microcracks. However, the number of microcracks
was still limited due to the excellent mechanical
properties of the epoxy matrix. Therefore, the con-
struction of new conductive paths is much faster than
the destruction within a certain high strain range, and
the decline in electrical resistivity still dominates.
According to ‘Piezoresistive properties under mono-
tonic loading’ section, all FCR versus strain curves
had an abrupt decreasing trend and the correspond-
ing GF values showed a significant increase in this
J Mater Sci (2022) 57:12416–12437
Figure 14 SEM photographs of the damage initiation and accumulation in CNTs–CB/epoxy nanocomposite under different loading
conditions: a linear elastic stage; b viscoelastic stage; and c plastic stage.
stage. The dramatic improvements in strain sensi-
tivity are considered to be associated with not only
the further reduction in the adjacent gaps between
composite fillers, but also the rearrangements of
CNTs–CB nanoparticles along with the deformation
of the epoxy matrix under larger strains. On the one
hand, the gaps between adjacent CNTs-CB composite
fillers further decrease and the number of conductive
junctions also continuously increases (Fig. 13c),
which significantly reduces the electrical resistivity of
the nanocomposites. On the other hand, the spherical
CB aggregates attached around CNTs in the CNTs–
CB composite fillers are more prone to move and slip
along with the motion of epoxy molecular segments.
Thus, the gaps between CNTs are effectively bridged
and the mutual contacts are further strengthened,
contributing to the formation of new conductive
paths and the enhancement of existing conductive
networks in the nanocomposites [47, 49]. Under these
circumstances, contact conduction gradually becomes
dominant. Therefore, the aforementioned two
superposed positive effects generate denser and more
thorough conductive networks, resulting in the lower
electrical resistivity and the higher strain sensitivity
of nanocomposites.
When the strain entered into stage III (i.e., plastic
stage in Fig. 12), all FCR curves firstly experienced a
platform and then followed by an increase. This
platform could be attributed to the coexistence of the
establishment and destruction of conductive net-
works. During this stage, the nanocomposites were
further compressed, leading to the occurrence and
progress of large deformation in nanocomposites as
well as the rapid accumulation and development of
microcracks in the matrix (Fig. 13c). These expanding
microcracks intensify the enlargement of gaps and
the reduction in contacts between CNTs–CB
12429
composite fillers, which excessively destroy the
electrically conductive paths and seriously block the
transmission of electrons. Given this dominance, the
electrical resistivities of nanocomposites continu-
ously increase. Thus, the establishment and destruc-
tion of conductive paths gradually begin to reach a
balance along with the increase in the strain ampli-
tude. With further increasing the applied strain, this
balance is gradually destroyed, and the destructive
process of conductive networks increasingly plays a
key role. In addition, the Poisson’s effect also could
enhance the transverse expansion along with the
compression deformation of nanocomposites, leading
to the transformation from microcracks to macroc-
racks and the further increase in electrical resistivity.
Hence, both of these two factors contribute to the
increase in the electrical resistivity of nanocomposites
in stage III.
Piezoresistive properties under constant amplitude cyclic
loading
The aforementioned investigations have shown that
the CNTs–CB/epoxy nanocomposites had obvious
piezoresistive responses and broad strain sensing
ranges. In addition to the strain sensitivity, the sta-
bility and repeatability of the nanocomposites also
play essential roles in the application of piezoresis-
tivity strain sensors [47]. To study their stability and
repeatability, the CNTs–CB/epoxy nanocomposites
were subjected to six constant amplitude loading–
unloading compressive cycles within the linear elas-
tic stage of the nanocomposites to verify their
remarkable piezoresistivity in real service conditions.
The values of stress, strain, and FCR as a function
of time during the loading–unloading cyclic process
are shown in Fig. 15. It is obvious that the FCR value
12430 J Mater Sci (2022) 57:12416–12437

Figure 15 Conpressive stress, 25 -1.2 -9

(a) Stress Strain FCR 1.0 vol%
-8
strain, and FCR value vs. time -1.0
20 -7

Stress (MPa)
under constant cyclic

Strain (%)

FCR (%)
-0.8 -6
compressive loading for 15 -5
nanocomposites loaded with: -0.6 -4
10
a 1.0 vol%; b 1.25 vol%; and -0.4 -3
-2
c 1.5 vol% CNTs–CB 5
-0.2 -1
composite fillers. 0
0 200 400 600 800
Time (s)

25 -9 25 -1.2 -9
(b) Stress Strain FCR 1.25 vol% -1.2 -8 (c) Stress Strain FCR 1.5 vol%
-8
20 20 -1.0
-1.0 -7 -7

Strain (%)
Stress (MPa)

Stress (MPa)

FCR (%)
Strain (%)

FCR (%)
-6 -0.8 -6
15 -0.8 -5 15 -5
-0.6
-0.6 -4 -4
10 10
-3 -0.4 -3
-0.4
-2 -2
5 5 -0.2
-0.2 -1 -1
0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
Time (s) Time (s)

closely followed the variation of the external com- nanocomposites. In general, all aforementioned
pressive stress/strain, indicating the instantaneous results exhibit that CNTs-CB/epoxy nanocomposites
piezoresistive response. When the specimen was have good stability, and repeatability without hys-
compressed, the movement of the molecular network teresis effect, which is quite beneficial for the appli-
dragged the bound CNTs–CB composite fillers cations of piezoresistive sensors in SHM.
through a strong interface bond, resulting in the
decline in the inter-particle gaps, therefore decreasing Piezoresistive properties under incremental amplitude
the electrical resistivity of the nanocomposites. On cyclic loading
the contrary, when the compression was released, the
electrical resistivity of the nanocomposites gradually Piezoresistive strain sensors will be inevitably used
increased due to the increase in the inter-particle for the entire service life monitoring of infrastruc-
gaps. Additionally, the minimum FCR value did not tures under different loading conditions. Therefore,
change significantly after each loading–unloading the strain sensing properties of CNTs–CB/epoxy
cycle compared with the initial state, indicating that nanocomposites under incremental amplitude cyclic
the electrically conductive network could be basically compressive testing were investigated in this study to
reset. In addition, the maximum value of FCR simulate the real service circumstance.
remained almost unchanged without slight fluctua- The typical piezoresistive responses of CNTs–CB/
tions during the six compression loading and epoxy nanocomposites as a function of loading time
unloading cycles, which indicates that the nanocom- and interrelated compressive strain and stress during
posites possess considerable repeatability. Figure 16 the loading–unloading compressive cycles are shown
shows the FCR–strain curves of composites subjected in Fig. 17. It is observed that FCR values mono-
to compressive cycles. As illustrated in the figure, the tonously increased and decreased as the variation of
fitting results of the three sets of data showed a applied stress/strain regardless of the composite fil-
strong linear relationship without fluctuation which ler concentration, which verifies their excellent
was consistent with the results under monotonic piezoresistive response under different loading
compression loading. Among them, the nanocom- amplitudes. Moreover, the absolute value of the FCR
posites containing 1.0 vol% CNTs–CB composite fil- displayed an increasing trend with the increase in the
lers still showed the greatest strain sensitivity, which compressive strain. This phenomenon could be
was 36.8% higher than that of 1.5 vol% fillers. This ascribed to the decrease in distance between the
phenomenon further verifies the significantly adjacent CNTs–CB particles and the compact distri-
stable and repeatable piezoresistive response of the bution of the conductive networks under high strain
J Mater Sci (2022) 57:12416–12437 12431

Figure 16 FCR value of 0

CNTs–CB/epoxy 1.0 vol% Linear fit (a)
nanocomposites as a function -1
of strain under constant cyclic

FCR (%)
compressive loading for -2
nanocomposites loaded with:
-3
a 1.0 vol%; b 1.25 vol%; and
c 1.5 vol% CNTs–CB
-4 R2 0.997
composite fillers.
Slope 6.075
-5
0.0 -0.2 -0.4 -0.6 -0.8
Strain (%)

0 0
1.25 vol% Linear fit (b) 1.5 vol% Linear fit (c)

-1 -1

FCR (%)
FCR (%)

-2 -2

R2 0.998 R2 0.998
-3 -3
Slope 4.776 Slope 4.441

0.0 -0.2 -0.4 -0.6 -0.8 0.0 -0.2 -0.4 -0.6 -0.8
Strain (%) Strain (%)

Figure 17 Relationships of 50 -2.0 -50

(a) Stress 1.0 vol%
incremental cyclic 40 Strain -40
Stress (MPa)

FCR -1.5
compressive stress/strain and
Strain (%)

FCR (%)
30 -30
FCR versus time of -1.0
nanocomposites filled with 20 -20
a 1.0 vol%; b 1.25 vol%; and 10
-0.5
-10
c 1.5 vol% CNTs–CB
0 0.0 0
composite fillers. 0 500 1000 1500 2000 2500 3000
Time (s)
50 -2.0 -50 50 -2.0 -50
(b) Stress
1.25 vol%
(c) Stress
40 Strain -40 40 Strain 1.5 vol% -40
-1.5 -1.5
Stress (MPa)

FCR FCR Strain (%)

Stress (MPa)

Strain (%)

FCR (%)
FCR (%)

30 -30 30 -30
-1.0 -1.0
20 -20 20 -20
-0.5 -0.5
10 -10 10 -10

0 0.0 0 0 0.0 0
0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000
Time (s) Time (s)

amplitudes. In other words, the increasing stress/ increased with the increase in the compressive
strain amplitude gradually reduces the gaps of strain/stress amplitude [20].
adjacent fillers and increases the number of conduc- Figure 17 shows that the maximum FCR values for
tive paths in composites, resulting in a more compact the strain amplitudes below 1.2%, which was in the
conductive network and a significant increase in linear elastic stage of the nanocomposites, remained
piezoresistive responses. Therefore, the piezoresistive unchanged within each strain level. In this stage, the
properties of the nanocomposite are significantly conductive networks deformed with the compression
of the nanocomposites and reverted to the original
12432
Figure 18 Peak shifts of the
(a)
CNTs–CB/epoxy
Compressive strain (%)
nanocomposites: a the
definition of the peak shift, and
Δt
b the calculated peak shifts of
t 3
the nanocomposites with
different CNTs–CB under
different compressive strain
levels.
morphology without residual deformation or irre-
versible damage after compression was removed. For
the strain amplitudes beyond 1.2%, the maximum
FCR values not only showed a clear increase but also
exhibited a continuous upward tendency in the next
two cycles. The distinct conductive networks gener-
ated by the synergistic effect in CNTs–CB composite
fillers govern this particular phenomenon. This might
presumably stem from the construction of some
additional conductive pathways due to the rear-
rangement of the CNTs–CB composite fillers (mainly
the movement and slippage of CB particles) at a
higher strain level, thus causing the higher sensitivity
[41, 47–49]. Moreover, the FCR values can not return
to their initial values and obtain small positive values
at the end of releasing, showing that irreversible
destruction is formed in the conductive networks.
The accumulation and expansion of microcracks in
the matrix account for this phenomenon. Therefore,
this result reveals that electrical resistivities of the
CNTs–CB/epoxy nanocomposites are very sensitive
to the irreversible damage occurring within the
matrix, which could be used to distinguish the linear
elastic and the viscoelastic deformations.
The response time to applied stress/strain is also a
crucial element in evaluating the piezoresistivity of
nanocomposites for the applications of strain sensors
[59, 63]. Currently, the peak shift is used to evaluate
the response time of sensors, and the lower peak shift
indicates the smaller hysteresis, implying the accu-
rately synchronous response between the variation of
electrical resistivity and applied load [63]. The sche-
matic of the peak shift is shown in Fig. 18a and its
definition is determined as follows:
Dt
Peak shift ¼  100%
t sions could be obtained from this study:
J Mater Sci (2022) 57:12416–12437
6
(b)
1.0 vol%
5
1.25 vol%
1.5 vol%
Peak shift (%)
4
FCR (%)
2
1
0
Time (s) 0 10 20 30 40 50
Stress (MPa)
where Dt is the difference in time between peak stress
and corresponding peak FCR value (Fig. 18a); and
t represents the time interval in one loading–un-
loading compression cycle (Fig. 18a).
In Fig. 18b, the peak shift values of CNTs–CB/
epoxy nanocomposites with different concentrations
of composite filler under different stress are dis-
played. Figure 18b shows that the peak shift values of
nanocomposites maintained a relatively low level
compared to some other research [59, 63]. It should be
noted that the testing equipment might have an
unknown delay to catch and record data. If this was
taken into account, the actual peak shift values for the
nanocomposites would be lower. The result showed
that the increasing CNTs–CB amount and compres-
sive loading amplitudes could both reduce the peak
shift values. The reduced distance between the adja-
cent CNTs–CB particles could be used to illustrate
this phenomenon. In this case, the electron mobility
between the composite fillers is highly strengthened
based on the tunneling effect, thus improving the
response time [19, 59].
Conclusions
The epoxy-based nanocomposites containing differ-
ent concentrations of electrostatic self-assembly
CNTs–CB composite fillers were fabricated in this
study. The mechanical and electrical properties as
well as the piezoresistive response of the CNTs–CB/
epoxy nanocomposites were experimentally investi-
gated. The mechanisms of the piezoresistive response
of the CNTs–CB/epoxy nanocomposites at different
strain levels were also explored. The main conclu-
ð4Þ
J Mater Sci (2022) 57:12416–12437
(1) FESEM images displayed that the electrostatic
self-assembly CNTs–CB composite fillers could
achieve relatively uniform distribution in the
epoxy matrix via a facile and simple mechanical
stirring method without ultrasonic treatment
on account of the synergistic effects. This is
because the grape clusters structure of the
electrostatic self-assembly CNTs–CB composite
fillers can prevent CNTs from approaching
each other and forming agglomeration.
(2) Compared with epoxy-based nanocomposites
filled with only CNTs or CB particles, a mod-
erate percolation threshold was obtained at 0.41
vol% for CNTs–CB/epoxy nanocomposites.
This is because a more significant hybrid
conductive network including short-range con-
duction and remote-range conduction was
constituted by CNTs and CB particles due to
the synergistic effect between CNTs and CB
particles.
(3) A highly sensitive and remarkably non-mono-
tonic piezoresistive response of CNTs-CB/
epoxy nanocomposites under monotonic com-
pressive loading was achieved, which could be
divided into three stages corresponding to
different mechanisms. The strain sensitivities
of the CNTs-CB/epoxy nanocomposites were
much higher than that of the nanocomposites
comprising CNT only, especially when they
were subjected to larger strains. This is because
the conductive networks tuned by CB particles
were more vulnerable, leading to higher
sensitivity.
(4) Schematic models were proposed to illustrate
the different mechanisms of the piezoresistive
responses induced by the tunneling conduction
and contacting conduction. The strain sensitiv-
ities of nanocomposites exhibited a linear
increase followed by an abrupt rise and then a
decrease. This could be interpreted by the
distinct evolution of hybrid conductive net-
works constituted by the electrostatic self-
assembly CNTs–CB composite fillers. The
reduction in tunneling resistance dominated at
the beginning; then, the CB particles could
move into the gaps to strengthen the conduc-
tive networks, and ultimately, the conductive
networks were gradually destroyed.
12433
(5) The electrical resistivities of CNTs–CB/epoxy
nanocomposites synchronously and closely
varied with the applied compressive strain
(around 0.70%) under constant amplitude cycle
loading, demonstrating excellent stability,
recoverability, and repeatability in piezoresis-
tive responses. These regular changes in elec-
trical resistivities are attributed to the variation
of nanoscale conductive networks structure in
the matrix, i.e., the stochastic approaching and
separation of inter-particle gaps induced by the
compressive strains.
(6) The piezoresistive responses of CNTs–CB/
epoxy nanocomposites under incremental
amplitude cyclic compressive loading also
demonstrated their stable recoverability within
a relatively broad strain range (around 1.20%).
Beyond this strain range, slight irreversible
resistivities were observed under high com-
pressive strains. This phenomenon demon-
strates that electrical resistivities are very
sensitive to the irreversible damage in the
matrix. This result could be used to distinguish
the linear elastic and the viscoelastic deforma-
tions of nanocomposites and qualitatively iden-
tify the occurrence of irreversible deformation
in the nanocomposites.
Due to the special grape cluster structure of elec-
trostatic self-assembly CNTs–CB composite fillers,
the distribution process of composite fillers could be
greatly simplified. The introduction of electrostatic
self-assembly CNTs–CB composite fillers into epoxy
could generate complicated conductive networks and
endow the CNTs–CB/epoxy nanocomposites with
excellent mechanical properties, moderate percola-
tion threshold, highly sensitive and repeat-
able piezoresistive response, which well balance the
shortcomings of nanocomposites filled with only
CNTs or CB particles. Among them, the nanocom-
posites containing 1.0 vol% CNTs-CB composite fil-
lers had significantly higher strain sensitivity and the
minimum filler concentration, which showed attrac-
tive potentials for the fabrication of compressive
strain sensors for structural health monitoring in civil
infrastructures.
12434
Acknowledgements
The authors are grateful for the financial support
from the National Natural Science Foundation of
China (Nos. 51978126 and 51778102).
Funding
National Natural Science Foundation of China,
51978126, Yanlei Wang, 51778102, Yanlei Wang
Declarations
Conflict of interest The authors declare that they
have no conflict of interest.
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