Composites: Part A 79 (2015) 103–115

Contents lists available at ScienceDirect

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

Electrostatic self-assembled carbon nanotube/nano carbon

black composite fillers reinforced cement-based materials
with multifunctionality
Baoguo Han a,⇑, Liqing Zhang a, Shengwei Sun b, Xun Yu c, Xufeng Dong d, Tianjiao Wu a, Jinping Ou a,b
a
School of Civil Engineering, Dalian University of Technology, Dalian 116024, China
b
School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
c
Department of Mechanical Engineering, New York Institute of Technology, New York, NY 11568, USA
d
School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

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

Article history: Electrostatic self-assembled carbon nanotube (CNT)/nano carbon black (NCB) composite fillers are added
Received 25 August 2015 into cement mortar to fabricate smart cement-based materials. The grape bunch structure of CNT/NCB
Received in revised form 21 September 2015 composite fillers is beneficial for dispersing CNT/NCB in cement mortar matrix and achieving cooperative
Accepted 24 September 2015
improvement effect. The mechanical, electrically conductive, and piezoresistive behaviors of the cement
Available online 1 October 2015
mortar are investigated. The CNT/NCB composite fillers can effectively enhance the flexural strength and
electrical conductivity of cement mortars, and endow stable and sensitive piezoresistivity to cement mor-
Keywords:
tar at a low filler content. However, they weaken the compressive strength of cement mortar to some
A. Smart materials
B. Electrical properties
extent. The percolation threshold zone of cement mortar with CNT/NCB composite fillers ranges in the
B. Mechanical properties amount of 0.39–1.52 vol.%. The optimal content of CNT/NCB composite fillers is 2.40 vol.% for piezoresis-
E. Assembly tivity and the stress and strain sensitivities can reach 2.69% MPa
1 and 704, respectively.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction NCMs reinforced cement-based composites themselves will have

Cement-based composites are the most commonly used con-
struction materials in the world. Meanwhile, concrete structure
is the most widely used structure type. Cement-based composite
is a kind of brittle material and susceptible to cracking which could
lead to catastrophic accidents. Therefore, effective monitoring on
cement-based composites and improving cement-based composite
performance become a world concern [1–3]. Traditional monitor-
ing methods are to set various sensors (e.g. resistivity strain
gauges, optic sensors, piezoelectric ceramic, shape memory alloy
and fiber reinforced polymer bar, etc.) into or onto the concrete
structures [4–8]. However, these sensors have some drawbacks
including low sensitivity, high cost, short lifespan and poor anti-
interference performance, which make it difficult to utilize moni-
toring technology to a large scale in the realistic projects [9,10].
Researches demonstrated that proper addition of nano carbon
materials (NCMs) can endure cement-based composites with not
only great mechanical properties and anti-crack abilities, but also
durability and functional properties [11–13]. Furthermore, the
⇑ Corresponding author.
E-mail addresses: hithanbaoguo@163.com, hanbaoguo@dlut.edu.cn (B. Han).
sensing properties, thus achieving smart monitoring. With these
characteristics, NCMs reinforced cement-based composites can
improve safety and reliability of concrete structures [14]. Among
NCMs, carbon nanotubes (CNT) and nano carbon black (NCB) are
both found to be able to modify the mechanical properties, durabil-
ity and functional properties of cement-based materials due to
their excellent intrinsic properties and composite effects.
A lot of researches have been done on electrical conductivity
and piezoresistivity of cement-based composites with CNT. For
example, Saafi observed that the resistance of cement-based com-
posites with 1.5 vol.% CNT was 6000 X which decreased 96.5%
compared with plain cement mortar [15]. Luo et al. found that
the resistivity of cement-based composites with 2.0 wt.% CNT
was 1.83 kX cm, which yielded a cut of 99.8% [16]. Ma et al. inves-
tigated the effect of different contents of CNT on the resistivity of
the cement-based composites. The results showed that addition
of 0.5% CNT in the percolation threshold zone was able to decrease
the resistivity of the composites to 150,000 X cm, which was
83.33% of cement-based composites without CNT. Yu et al. fabri-
cated cement-based composites with 0.1 wt.% CNT and found that
the stress sensitivity was 1.35% MPa
1 [17]. Luo et al. found the
stress and strain sensitivities of cement-based composites with

http://dx.doi.org/10.1016/j.compositesa.2015.09.016
1359-835X/Ó 2015 Elsevier Ltd. All rights reserved.
104 B. Han et al. / Composites: Part A 79 (2015) 103–115
0.5 vol.% CNT were 0.4% MPa
1 and 54.2, respectively [18].
Although cement-based composites with CNTs present good elec-
trical conductivity and piezoresistivity, the improvements to elec-
trical conductivity and stress/strain sensitivity are limited because
CNT is hard to fully disperse in the cement material matrix [19]. On
the other aspect, the impact of addition of NCB on the electrical
conductivity and piezoresistivity of cement-based composites has
been also well studied. For example, Li et al. studied the effect of
different contents of NCB on the resistivity and piezoresistivity of
the cement-based composites [20]. They observed that the resistiv-
ity of the cement-based composites with 7.22 vol.% and 8.79 vol.%
of NCB was 7000 X cm and 700 X cm, respectively. The cement-
based composites with 8.79 vol.% NCB showed piezoresistivity
and their strain sensitivity was 55.28. It can be seen that the
required content of NCB is as high as 8.79 vol.% to significantly
improve electrical conductivity and endow cement-based compos-
ites only 55.28 of piezoresistive sensitivity. Additionally, such high
content of NCB can lead to sharp decrease in the mechanical prop-
erties of cement-based materials [20,21].
Electrostatic self-assembled CNT/NCB composite fillers have
excellent electrical conductivity and can achieve cooperative
improvement effect. Additionally, CNT/NCB composite fillers may
address the dispersion issue of CNT in cement-based materials
[22]. In this paper, electrostatic self-assembled CNT/NCB compos-
ite fillers are added in cement mortar to develop multifunctional
materials. The flexural and compressive strengths, electrical con-
ductivity and piezoresistivity under different compressive loading
conditions of these composites are investigated. The improvement
mechanism of CNT/NCB composite fillers to the properties of
cement mortar is also analyzed.
2. Experimental methods
2.1. Raw materials and specimen preparation
2.1.1. Materials and experiments equipment
The materials used in the experiments mainly include CNT/NCB
composite fillers, cement, silica fume, water, sand and water
reducing agent. CNT/NCB composite fillers (as shown in Fig. 1)
are purchased from Chengdu institute of organic chemistry Co.,
Ltd. Their properties are listed in Table 1. CNT/NCB composite
fillers were prepared as follow: CNT self-assembled to the surface
of NCB by electrostatic adsorption; and CNT and NCB formed a
grape bunch structure together, i.e. fibrous CNT just likes stem
and spherical conductive NCB likes grape. PO 42.5R Portland
(b)
(a)
Fig. 1. SEM images of CNT/NCB composite fillers: (a) 50,000; (b) 100,000. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)
Table 1
Main properties of CNT/NCB composite fillers.
Ingredient Composition Resistivity SSA OD of APS of
(CNT:NCB) (X cm) (m2/g) CNT (nm) NCB (nm)
CNT/NCB 40:60 10
3 65–75 >50 23
Note: SSA: specific surface area; OD: out diameter; APS: average particle size.
cement, conforming to the requirement of Chinese standard, is
produced by Dalian Onoda Cement Co. Ltd., China. As anther binder
material, 920D silica fume (Shanghai Tian Kai Silicon Fume Co. Ltd.,
China) was applied. Standard sand (Xiamen Ai Si Ou Standard Sand
Co. Ltd., China) was used as the fine aggregate. The water reducer is
3310E polycarboxylate superplasticizer supplied by Dalian Xi Ka
whose solid content is 45% and can reduce water to an extent of
30%. Stainless steel gauzes with opening of 50 mm  50 mm were
used as electrodes whose length and width are 10 and 6 whole
grids respectively.
The testing machines used include a mortar stirrer SJ-160
provided by Shenyang Mine Mechanical Factory, China; a mortar
folding meter DKZ-5000 supplied by Wuxi Jian Yi Instrument
Mechanical Co. Ltd., China; a universal material testing machine
WDW-200E purchased from Jinan Time Assay Machine Co. Ltd.,
China; a digital multimeter Keithley 2100 produced by Keithley
Instruments Inc., USA; a dynamic strain indicator DC-204R
provided by Tokyo Sokki Kenkyujo Co. Ltd.; and a fully-high defini-
tion scanning electron microscope (SEM) NOVA NANOSEM450
purchased from FEI Inc., USA.
2.1.2. Specimen preparation
After mixing trials, it was found that the amount of water redu-
cer and water to binder ratios both need increase to get required
workability of the fresh composites when the content of CNT/CB
composite filler exceeds 1.52 vol.%. The amount of water reducer
and water to binder ratio got thought mixing trials. There are
totally 6 sets of specimens whose mixing proportions are illus-
trated in Table 2. The specimen fabrication process is as follow.
First, all the raw materials needed were weighed according to
the designed mixing proportions. Next, the mixture of silica fume
and CNT/NCB composite fillers were put into the stirring pot and
stirred for 30 s at a low speed. Then the solution consisting of
water and water reducing agent was plunged in and a 30 s low-
speed stir again. Then half of cement was poured in for a slow
60 s stir which was followed by a quick 30 s stir. Next, the other
half cement was put in for a slow 60 s stir and then a quick 30 s
Stem
Grapes
(b)
 B. Han et al. / Composites: Part A 79 (2015) 103–115 105

Table 2
Mixing proportion of all specimens.

Serial Binder CNT/NCB Water to Water Sand to

number composite binder reducer binder
fillers (vol.%) ratio (wt.%) ratio
B00 1 0.00 0.42 0 1.5
B01 1 0.39 0.42 0 1.5
B02 1 0.77 0.42 1.0 1.5
B03 1 1.52 0.42 2.0 1.5
B04 1 2.40 0.56 2.5 1.5
B05 1 3.12 0.70 2.5 1.5

Note: (1) Binder is composed of cement and silica fume. Here make the mass of
binder a unity 1 and mass of silica fume accounts for 10% of binder; (2) the volume
percent of CNT/NCB composite fillers is relative to the whole material; (3) the mass
percentage of water reducer is based on that of binder.

Electrode Electrode Fig. 4. Flexural and compressive strength of cement mortars with CNT/NCB
composite fillers. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)

Table 3
Improvement percent of different cement mortar with CNT/NCB composite fillers
after curing 80 d.

Terms B00 B01 B02 B03 B04 B05

Improvement of flexural 0
6.7 6.7 18.3
15.0
45.0
strength (%)
Improvement of 0
11.1
13.7
7.7
37.2
51.5
compressive strength (%)

Fig. 2. Electrode arrangement in the specimens (40 mm  40 mm  80 mm). (For

interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
stir. Standard sand was added in for a slow 60 s stir and then a
quick 30 s stir. At last, a slow 60 s stir and then a quick 30 s stir
were required.
The specimens after stirring were put into the corresponding
oiled molds (there were two sizes of molds: 40 mm 
40 mm  80 mm and 40 mm  40 mm  160 mm). Then they
were put onto the vibrating table until shaking to an extent of
oozing slurry on the surface of specimens. Next, for 40 mm 
40 mm  80 mm ones, two stainless steel gauze electrodes were
embedded in the corresponding positions (Fig. 2) (30 mm and
50 mm respectively measured from one side of specimens). It
should be noted that the electrodes do not include inside speci-
mens for the mechanical test. All specimens were demolded after
24 h. And then they were cured in water at 20 °C. Specimens were
sent for certain tests at planned curing ages. Three specimens in
each group were used to test the mechanical, electrically
conductive and piezoresistive properties of cement mortar with
CNT/NCB composite fillers.
2.2. Measurement
2.2.1. Mechanical measurement
The mechanical properties were measured at the curing age of
80 d to guarantee complete hydration of cement mortar with
CNT/NCB composite fillers. The flexural strength was measured
by the mortar folding meter DKZ-5000. The compressive strength
was measured by a universal material testing machine
WDW-200E. Specimens were loaded to failure at constant loading
rate of 1.2 mm/min to obtain the elastic range of the compressive

Digital multimeter Dynamic strain indicator

Fig. 3. Test equipments for cement mortar with/without CNT/NCB composite fillers. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
106 B. Han et al. / Composites: Part A 79 (2015) 103–115

Fig. 5. SEM images of cement mortars with CNT/NCB composite fillers: (a) crack bridging of CNT, (b) CNT pull out.

900
106 800

700
Electrical resistivity (Ω.cm)

600

105 500

400

300
4 200
10
1d 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
3d
7d
103 14d
28d
80d

102
0.0 0.5 1.0 1.5 2.0
Content of fillers (vol.%)
Fig. 6. Electrical resistivity of cement mortars with CNT/NCB composite fillers. (For
interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
stress, thus determining the loading amplitude in the test of
piezoresistivity.
2.2.2. Electrical and piezoresistivity measurement
When measuring the resistance without loading at the curing
age of 1 d, 3 d, 7 d, 14 d, 28 d and 80 d, specimens were taken from
the water and wiped off water with cloth and then dried in the air
for 3 h.
The resistance without loading is measured by direct-current
(DC) two electrodes method, using a multimeter (Keithley 2100).
The resistivity are calculated according q = RS/L (where q is resis-
tivity, R is the measured resistance, S is cross sectional area, L is
the distance between two electrodes). The tests of piezoresistivity
2.5 3.0 3.5
Fig. 7. The structure of CNT/NCB composite fillers in cement mortars.
were under repeated compressive loads by displacement control
and only tested on the 40 mm  40 mm  80 mm specimens.
Polarization phenomenon is obvious for the specimens without fil-
lers and with 0.39 vol.% of fillers. The resistance values of the two
kinds of composites were recorded until the resistance tends stable
in electrically conductive and piezoresistive measurements. When
the filler content exceeds 0.39 vol.%, the electronic conduction is
dominant for the conductivity of the composites. As a result, there
is no polarization inside these composites. Compressive loads were
applied using the material testing machine with a loading rate of
0.4 mm/min and 7 cycles of repeated compressive loading with
stress amplitude of 8 MPa. The strain was measured by usage of
two strain gauges attached to the middle of two opposite sides
along the longitudinal direction (Fig. 3), and strain data was
recorded by a dynamic strain recorder (DC-204R). During this

Table 4
Comparison among different researches regarding cement-based composites with CNT or/and NCB.

Type of fillers Percolation threshold zone (vol.%) Resistivity range (X cm) Reduction extent (%) Sources
CNT/NCB composite fillers 0.77–1.52 17,956–783 97.8–99.9 This paper
NCB 7.22–11.39 7000–100 – Ref. [20]
0.68–1.58 40,000–300 94.3–99.6 Ref. [23]
CNT 0.5–1.5 75,000–6000 62.5–96.5 Ref. [15]
1.53–3.00 125,270–6512 80.4–99.0 Ref. [18]
 B. Han et al. / Composites: Part A 79 (2015) 103–115
(a) B01
(c) B03 (d) B04
Fig. 8. Conductive network in (a) B01, (b) B02, (c) B03, (d) B04 and (e) B05 (Arrow: CNT; Circle: aggregate of CNT). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
process, the DC resistance measurement was carried out in the
meantime by using a Keithley 2100 multimeter. The fractional
change in electrical resistivity is calculated as Dq = 100%  (qmin

q0)/q0 (where q0 is the resistivity without loading, qmin is the
minimum resistivity under compressive loading). After tests of
piezoresistivity of all specimens were conducted, the optimum
addition set of CNT/NCB composite fillers can be obtained. The
optimum specimens were used for further investigation about
effect of different parameters such as loading amplitude and load-
ing rate on the piezoresistive properties. Then under the circum-
stance of unchanging loading rate 0.4 mm/min, loading
amplitude was changed to 6 MPa and 10 MPa respectively to test
the piezoresistivity of the optimum specimens. Further, under
the unchanging loading amplitude of 8 MPa, the loading rate was
set at 0.2 mm/min and 0.6 mm/min to test the effect of different
loading rates. The sampling frequencies for resistivity, strain and
compressive loading are all at 2 Hz.
3. Results and discussions
3.1. Mechanical properties of cement mortars with CNT/NCB composite
fillers
Flexural and compressive strengths and their increase rate of
cement mortars with CNT/NCB composite fillers are shown in
Fig. 4 and Table 3, respectively.
The general trend for flexural strength is first increase and then
decrease with the increase content of CNT/NCB composite fillers.
Compared with plain cement mortar B00, cement mortars with
CNT/NCB composite fillers display an increase of 6.7% for B02
and 18.3% for B03, a decrease of 15.0% for B04 and 45.0% for B05
respectively in term of flexural strength. However, the flexural
strength of B04 can still reach 5.1 MPa.
Compressive strengths of cement mortar with CNT/NCB com-
posite fillers are all lower than that of B00. Compressive strength
107
(b) B02
(e) B05
decreases substantially when the content of CNT/NCB composite
fillers is more than 2.40 vol.%. The decrease of B04 reaches 37.2%
whereas the compressive strength can still maintain 44.6 MPa.
As for enhancement mechanism, CNT can improve flexural
strength by crack bridging and fiber pull-out effect (as shown in
Fig. 5) and NCB can fill some capillaries so that flexural strength
enhances with the increasing content of CNT/NCB composite fillers
when water-to-binder ratio is fixed at 0.42. However, the increase
of water-to-binder ratio and adsorption of NCB on the surface of
cement which affects hydration [21] may lead to significant
decrease of the flexural and compressive strength. In addition,
when high CNT/NCB fillers are present, CNT bundles could form
due to inhomogeneous dispersion of CNTs. The sliding among CNTs
within the bundles can also reduce the strength of the composite.
3.2. Electrically conductive properties of cement mortars with
CNT/NCB composite fillers
As illustrated from Fig. 6, the electrical resistivity of cement
mortars with CNT/NCB composite fillers varies slightly when the
content of CNT/NCB composite fillers is less than 0.39 vol.%. As
the content of CNT/NCB composite fillers increases beyond
0.39 vol.%, the electrical resistivity of the composites decreases
obviously. However, the resistivity changes slightly when the con-
tent of CNT/NCB composite fillers is more than 1.52 vol.%. There-
fore, the content levels of CNT/NCB composite fillers range
between 0.39 vol.% and 1.52 vol.%, where the electrical resistivity
varies dramatically is called as the percolation threshold zone.
Moreover, the electrical resistivities of B00 and B01 increase signif-
icantly with curing age while the electrical resistivities of the other
specimens increase slightly. The detail figure in Fig. 6 shows that
electrical resistivities of B03, B04 and B05 increase with curing
age from 1 d to 3 d while the electrical resistivities of B03, B04
and B05 become stable after curing 3 d.
108 B. Han et al. / Composites: Part A 79 (2015) 103–115

12 5
(a) 18 (b) 0 vol.%

Compressive stress (MPa)

10 18

Compressive strain (10 2με)

0 vol.%

electrical resistivity (%)

4

electrical resistivity (%)

8 15 15

Fractional change in

Fractional change in
3
6 12 12
2
4 9 9
2 1
6 0 6
0 3
-2 3 -1
0 -2 0
-4
-3 -3
-6 -3
-8 -4 -6
-6
-10 -5 -9
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)

12 6
(c) (d)

Compressive strain (102με)

0.39 vol.% 18 0.39 vol.% 18
Compressive stress (MPa)

10 5

electrical resistivity (%)

electrical resistivity (%)
8 4 15

Fractional change in
15

Fractional change in
6 3
12 2 12
4
9 1 9
2
0
0 6 6
-1
-2 3 -2 3
-4 -3
0 0
-6 -4
-8 -3 -5 -3
-10 -6 -6 -6
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Time (s) Time(s)

9 Compressive strain (102με) 4

Compressive stress (MPa)

(e) (f) 0.77 vol.% 8

electrical resistivity (%)

0.77 vol.%
electrical resistivity (%)

Fractional change in
Fractional change in

3
6 6
6 2
4
3
3 1 2

0 0 0 0
-1 -2
-3 -3
-2
-4
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Time (s) Time (s)

12 12 4 8
(g) (h)
Compressive stress (MPa)

Compressive strain (102με)

1.52 vol.% 1.52 vol.%

electrical resistivity (%)

electrical resistivity (%)

9 9 3 6
Fractional change in
Fractional change in

6 6 2 4
1 2
3 3
0 0
0 0
-1 -2
-3 -3 -2 -4
-6 -6 -3 -6
-9 -9 -4 -8
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Time (s) Time (s)

15 15
(l) (j)
Compressive stress (MPa)

electrical resistivity (%)

Compressive strain (10 2με)

2.40 vol.% 5
electrical resistivity (%)

10 10 25
Fracrional change in

4 2.40 vol.%
Fractional change in

5 5
20
3 15
0 0 2 10
1 5
-5 -5
0 0
-10 -10 -1 -5
-2 -10
-15 -15 -15
-3
-20 -20 -4
-20
-25
-25 -25 -5
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Time (s) Time (s)

Fig. 9. Compressive stress/strain and fractional change in electrical resistivity of B00–B05 under repeated compressive loading with stress amplitude of 8 MPa: (a) stress and
fractional change in resistivity of B00; (b) strain and fractional change in resistivity of B00; (c) stress and fractional change in resistivity of B01; (d) strain and fractional
change in resistivity of B01, (e) stress and fractional change in resistivity of B02; (f) strain and fractional change in resistivity of B02; (g) stress and fractional change in
resistivity of B03; (h) strain and fractional change in resistivity of B03; (l) stress and fractional change in resistivity of B04; (j) strain and fractional change in resistivity of B04;
(k) stress and fractional change in resistivity of B05; (l) strain and fractional change in resistivity of B05; (m) the relationship between fractional change in resistivity and
content of fillers. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
 B. Han et al. / Composites: Part A 79 (2015) 103–115 109

(k) (l)

Compressive strength (MPa)

5

Compressive strain (102με)

15 15
3.12 vol.% 20

electrical resistivity (%)

4

electrical resistivity (%)

3.12 vol.%
10 10

Fractional change in
Fractional change in
3 15
5 5 10
2
0 0 1 5
-5 0 0
-5
-10 -1 -5
-10 -2 -10
-15
-15 -3 -15
-20 -4
-20 -20
-25 -5
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Time (s) Time (s)

-25
(m) -22%
electrical resistivity (%)
Fractional change in

-20

-15

-10

-5

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

Content of fillers (vol.%)

Fig. 9 (continued)

Distance of CNT and NCB

Distance of CNT and CNT
Distance of NCB and NCB

Fig. 10. The distance changes in cement mortars with CNT/NCB composite fillers. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)

In comparison with results of other researches (Table 4), it is 3.3. Piezoresistive properties of cement mortars with CNT/NCB
discovered that the content level of CNT/NCB composite fillers in composite fillers
percolation threshold zone is the lowest and addition of CNT/NCB
composite fillers in cement mortars has the best reduction ability 3.3.1. Effect of concentration of CNT/NCB composite fillers on
on the electrical resistivity. piezoresistivity
The conductive mechanisms of cement mortars with CNT/NCB The variation in resistance of piezoresistive cement-based com-
composite fillers mainly include: (1) contacting conduction; (2) posites is stable and reversible under repeated compressive load-
tunneling conduction; (3) field emission conduction. In addition, ings within an elastic regime [24,25]. It can be seen from Fig. 4
NCB and CNT play the roles of short-range and long-range that ultimate compressive strength of B05 is 34.4 MPa which is
conductors in the cement mortar, respectively. As a result, the the lowest among all the specimens. The loading amplitude was
CNT/NCB composite fillers can achieve cooperative improvement set as 8 MPa, which is less than 1/3 of 34.4 MPa so that the defor-
effect to electrical conductivity. Moreover, the CNT/NCB compos- mation of specimens is ensured within an elastic regime.
ite fillers can be uniformly dispersed in cement mortar due to the As shown in Fig. 9, the relationships between fractional change
structure of the grape bunches (as shown in Fig. 7). The in electrical resistivity and stress/strain of B00–B05 have different
conductive network gradually comes into being with increasing trends under 7 times of cyclic compressive stress with amplitude
content of CNT/NCB composite fillers (as shown in Fig. 8). The of 8 MPa. It can been seen from Fig. 9(a)–(d) that electrical resistiv-
cement mortar with 0.39 vol.% of CNT/NCB composite fillers ities of B00 and B01 have no synchronously change with compres-
cannot form a conductive network due to lack of conductive sive stress/strain levels, i.e. the fractional changes in electrical
fillers. It is demonstrated that conductive network works well resistivity are around 0%. It indicates that B00 and B01 have no
when the content of CNT/NCB composite fillers is over 1.52 vol.%. piezoresistivity under compressive loading. For the other speci-
Furthermore, the hydration of cement has little effect on mens in Fig. 9(e)–(l), the overall trend is that the fractional change
resistivity of B03, B04 and B05 due to good conductive network in electrical resistivities decreases as the compressive stress/strain
of CNT/NCB composite fillers. increases and increases as stress/strain decreases. When the
110 B. Han et al. / Composites: Part A 79 (2015) 103–115

(a) 10
0 vol.% y=bx (b) 10
0.39 vol.% y=bx
8 Linear Fit of Data Parameter Value Error

electrical resistivity (%)

8

electrical resistivity (%)

Linear Fit of Data Parameter Value Error
R2=0.003 b 0.097 0.055

Fractional change in
6 R2=0.07 b 0.30 0.040

Fractional change in
6
4 4
2 2
0 0
-2 -2
-4 -4
-6 -6
-8 -8
-10 -10
0 1 2 3 4 5 0 1 2 3 4 5
Compressive strain (10 2με) Compressive strain(102 με)

(c) 1 2
(d)
electrical resistivity (%)

electrcial resistivity (%)

y=bx y=bx
0
Fractional change in

Parameter Value Error

Fractional change in
Parameter Value Error 0 b -2.31 0.0259
b -1.16 0.010

-1
-2

-2
-4
-3
0.77 vol.%
Linear Fit of Data -6 1.52 vol.%
-4 R2=0.94 Linear Fit of Data
R2=0.92
-8
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2 2
Compressive strain (10 με) Compressive strain (10 με)

(e) (f)
0 0
electrical resistivity (%)
electrical resistivity (%)

y=b1x+b2x2
Fractional change in
Fractional change in

y=b1x+b2 x2
Parameter Value Error
-5 b1 -13.86 0.224 -5 Parameter Value Error
b2 2.26 0.099 b1 -9.27 0.1078
b2 1.12 0.039
-10
-10
-15
-15
-20 3.12 vol.%
2.40 vol.%
Linear Fit of Data Linear Fit of Data
-25 R2=0.95
-20 R2=0.98

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Compressive strain (10 2με) Compressive strain (10 2 με)

Fig. 11. Fractional change in electrical resistivity of cement mortars with (a) 0 vol.%, (b) 0.39 vol.%, (c) 0.77 vol.%, (d) 1.52 vol.%, (e) 2.40 vol.% and (f) 3.12 vol.% CNT/NCB
composite fillers under 7 times of cyclic compressive loading. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

3.0 800
(a) 2.69
stress sensitivity (%/MPa)

704
2.5 700 (b)
Strain sensitivity

600
2.0
500
1.5 400
1.0 300
200
0.5
100
0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Content of fillers (vol.%) Content of fillers (vol.%)

Fig. 12. Stress and strain sensitivity of B00–B05 under 7 times of cyclic compressive loading: (a) stress sensitivity; (b) strain sensitivity. (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of this article.)

compressive stress reaches 8 MPa, the absolute value of fractional CNT/NCB composite fillers increases. B04 has the highest fractional
change in electrical resistivity of B02, B03, B04 and B05 can get to change in electrical resistivity among all composites.
the maximum values of 3.36%, 6.9%, 22.1% and 19.0% correspond- The change of electrical resistivity under compressive loading is
ing to peak strain values of 320 le, 300 le, 314 le and 351 le, caused by three aspects [13]. Firstly, the intrinsic electrical resistiv-
respectively (as shown in Fig. 9). The fractional change in electrical ity of CNT/NCB composite fillers changes [26]. Secondly, the
resistivity first increases and then decreases as the content of change of distances of adjacent CNT and NCB, CNT and CNT, NCB
 B. Han et al. / Composites: Part A 79 (2015) 103–115 111

Table 5
Comparison about sensitivity of different piezoresistive cementitious composites.

Types of fillers Concentration Stress sensitivity (% MPa
1) Strain sensitivity Sources

CNT/NCB composite fillers 2.4 vol.% 2.69 704 This paper
NCB – 1.2 200 Ref. [24]
8.79 vol.% 0.6 60 Ref. [20]
CNT 0.5 vol.% 0.4 54 Ref. [18]
2.0 wt.% – 220 Ref. [28]
0.1 vol.% 1.35 – Ref. [17]

(b)

Compressive strain (102 με)

(a)
Compressive stress (MPa)

8 18

electrical resistivity (%)

electrical resistivity (%)
6MPa 16 3 6MPa 15

Fractional change in
Fractional change in
6
12 2 12
4 9
8
2 1 6
4 3
0 0 0 0
-2 -4 -1 -3
-6
-4 -8 -2 -9
-6 -12 -12
-3 -15
-8 -16 -18
-4
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)

(d)
Compressive stress (MPa)

(c)
Compressive strain (102 με)
25
electrical resistivity (%)

10 8MPa 4

electrical resistivity (%)

20 8MPa 25
Fractional change in

Fractional change in
8 3 20
6 15
2 15
4 10
10
2 5 1 5
0 0 0 0
-2 -5 -5
-4 -1 -10
-10
-6 -15 -2 -15
-8 -20 -3 -20
-10 -25
-25 -4
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Time (s) Time (s)

(e) (f)
Compressive strain (102 με)
Compressive stress (MPa)

30 5 30
electrical resistivity (%)

12

electrical resistivity (%)

10MPa 10MPa
25 25
Fractional change in

9 20
4
20 Fractional change in
15 3 15
6 2
10 10
3 5 1 5
0 0 0 0
-5 -1 -5
-3 -10
-10 -2
-6 -15 -15
-20 -3 -20
-9 -4
-25 -25
-12 -30 -5 -30
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Time (s) Time (s)

(g) -30
electrical resistivity (%)

-25.4%
Fractional change in

-25 -22.1%

-20
-16.0%
-15

-10

-5

0
6 8 10
Compressive stress (MPa)

Fig. 13. Fractional change in electrical resistivity of B04 under 7 times of cyclic loading with stress amplitudes of 6, 8 and 10 MPa: (a) stress and fractional change in
resistivity under cyclic loading with stress amplitudes of 6 MPa; (b) strain and fractional change in resistivity under cyclic loading with stress amplitudes of 6 MPa; (c) stress
and fractional change in resistivity under cyclic loading with stress amplitudes of 8 MPa; (d) strain and fractional change in resistivity under cyclic loading with stress
amplitudes of 8 MPa; (e) stress and fractional change in resistivity under cyclic loading with stress amplitudes of 10 MPa; (f) strain and fractional change in resistivity under
cyclic loading with stress amplitudes of 10 MPa; (g) the relationship between fractional change in resistivity and stress amplitudes. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
112 B. Han et al. / Composites: Part A 79 (2015) 103–115

electrical resistivity (%)

electrical resistivity (%)

electrical resistivity (%)
2 0 5
Fractional change in

Fractional change in

Fractional change in
y=b1 x+b2 x 2 y=b1 x+b2 x 2
0 Parameter Value Error 0 y=b1 x+b2 x 2
-2 Parameter Value Error
b1 -8.88 0.216 -5 b1 -13.86 0.224
Parameter Value Error
-4 b2 1.04 0.110
b2 2.26 0.099 -5 b1
b2
-12.55 0.159
1.67 0.050
-6 -10 -10
-8
-10 -15 -15
-12
-14 -20 -20
6MPa 8MPa
10MPa
-16 Linear Fit of Data Linear Fit of Data -25 Linear Fit of Data
-18 R2=0.95 -25 R2=0.95 R 2 =0.97
-30
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Compressive strain (102με) Compressive strain (10 με) 2
Compressive strain (102με)
(a) (b) (c)
Fig. 14. Response of fractional change in electrical resistivity to compressive strain of B04 under compressive stress amplitudes of (a) 6 MPa, (b) 8 MPa and (c) 10 MPa. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

(a) 3.0 (b) 800

2.57 2.69 704
Stress sensitivity (%/MPa)

2.48 700 652

2.5 631
600

Strain sensitivity
2.0
500
1.5 400
300
1.0
200
0.5
100
0.0 0
6 8 10 6 8 10
Compressive stress (MPa) Compressive stress (MPa)

Fig. 15. Stress and strain sensitivity of B04 under 7 times of cyclic loading with stress amplitudes of 6, 8 and 10 MPa: (a) stress sensitivity; (b) strain sensitivity. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

and NCB may lead to connecting or be easy to produce tunneling mortars with 0 vol.% and 0.39 vol.% have no piezoresistivity. As
effect. There are more conductive paths which can form due to shown in Fig. 11(c)–(d), the relationships between the fractional
the structure of CNT/NCB composite fillers (as shown in Fig. 10). change in electrical resistivity and compressive strain of B02 and
Thirdly, the change of interface electrical resistivity of CNT/NCB B03 have a good linearity. However, it can be seen in Fig. 11(e)–
composite fillers and cement mortars matrix is caused by fiber (f) that the relationships between the fractional change in electri-
pull-out and push-in [27]. It should be noted that the change of cal resistivity and compressive strain of B04 and B05 are closer to
distance of conductive filler may matter most to electrical resistiv- polynomial relation. When the content of filler additives is low, the
ity and piezoresistivity. When the content of CNT/NCB composite ionic conduction in matrix is dominant to piezoresistivity. There-
fillers is less than 0.77%, the CNT/NCB composite fillers in the fore, the relationship between fractional change in resistivity and
matrix doesn’t form conductive network (as shown in Fig. 8(a)) applied strain is linear. With increase of the filler content, the tun-
and most distances among CNT/NCB composite fillers are too far neling and field emission conductions become dominant, which
to produce tunneling effect even under compressive loading. As a results in the nonlinear relation between fractional change in resis-
result, the cement mortars with 0.39 vol.% have high electrical tivity and applied strain. It is convenient to use a relatively small
resistivity (2.5  105 X cm) and don’t present piezoresistivity. amount of particle additives so as to keep the resistivity-strain lin-
With the increase of the CNT/NCB composite fillers level to earity. The stress and strain sensitivity of cement mortars with
2.40 vol.%, the CNT/NCB composite fillers not only uniformly CNT/NCB composite fillers are calculated as follows:
dispersed in cement mortars, but also are separated by cement

Dqmax
mortars matrix while the distances between CNT/NCB composite SES ¼ ð1Þ
fillers are close (as shown in Fig. 8(d)). Therefore, the electrical r
resistivity of cement mortars with 2.40 vol.% sharply decreases to

Dqmax
117.55 X cm. In addition, the number of conductive pathways SAS ¼ ð2Þ
increases more easily by field induced tunneling when distances
e
of adjacent CNT/NCB composite fillers further decreases under where SES is stress sensitivity, Dqmax is the amplitude of the frac-
compressive loading. When the content of CNT/NCB composite fil- tional change in electrical resistivity. r is the amplitude of the mea-
lers is 3.12 vol.%, the average distance of CNT/NCB composite fillers sured compressive stress. Where SAS is strain sensitivity, e is the
becomes more closer and even some CNT/NCB composite fillers are amplitude of the measured compressive stain.
in the state of overlap (as shown in Fig. 8(e)) so that the electron Fig. 12 shows stress and strain sensitivities of B00–B05. Both
and hole move through touching conduction. Consequently, the stress and strain sensitivities of cement mortars with CNT/NCB
electrical resistivity and piezoresistivity of mortar with 3.12 vol.% composite fillers increase firstly then decrease with increasing of
are lower than that of cement mortars with 2.40 vol.%. CNT/NCB composite fillers. Among composites with different con-
The relationship between fractional change in electrical resis- tents of CNT/NCB composite fillers, B04 has the highest stress and
tivity and compressive strain are shown in Fig. 11. Fig. 11(a)–(b) strain sensitivities which are 2.69 % MP
1and 704, respectively.
shows bad consistency to cyclic compressive strain, i.e. the cement The strain sensitivity of B04 is higher about 352 times than that
 B. Han et al. / Composites: Part A 79 (2015) 103–115 113

(a) 25 (b) 4 25

Compressive strain (102με)

Compressive stress (MPa)
10 0.2 mm/min

electrical resistivity (%)

electrical resistivity (%)

0.2 mm/min 20 20
8 3

Fractional change in

Fractional change in
6 15 15
2
4 10 10
5 1 5
2
0 0 0 0
-2 -5 -1 -5
-4 -10 -10
-6 -2
-15 -15
-8 -20 -3 -20
-10
-25 -4 -25
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Time (s) Time (s)
Compressive stress (MPa)

(c) (d) 4

Compressive strain (102με)

10 0.4 mm/min 25

electrical resistivity (%)

electrical resistivity (%)

0.4 mm/min 25
8

Fractional change in

Fractional change in
20 3 20
6 15
2 15
4 10 10
2 5 1 5
0 0 0 0
-2 -5 -5
-4 -10 -1
-10
-6 -15 -2 -15
-8 -20 -3 -20
-10 -25 -25
-4
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Time (s) Time (s)

(e) 25 (f) Compressive strain (102με) 4 25

Compressive stress (MPa)

10 0.6 mm/min
electrical resistivity (%)

electrical resistivity (%)

20 0.6 mm/min
8 3 20
Fractional change in

Fractional change in
6 15 15
10 2
4 10
2 5 1 5
0 0 0 0
-2 -5 -1 -5
-4 -10 -10
-2
-6 -15 -15
-8 -3 -20
-20
-10 -4 -25
-25 0 50 100 150 200 250
0 50 100 150 200 250
Time (s) Time (s)

(g) -25
-21.6% -22.1%
-20.9%
electrical resistivity (%)

-20
Fractional chenge in

-15

-10

-5

0
0.2 0.4 0.6
Loading rate (mm/min)

Fig. 16. Fractional change in electrical resistivity of B04 under 7 times of cyclic loading at loading rate of 0.2, 0.4 and 0.6 mm/min: (a) stress and fractional change in
resistivity at loading rate of 0.2 mm/min; (b) strain and fractional change in resistivity at loading rate of 0.2 mm/min; (c) stress and fractional change in resistivity at loading
rate of 0.4 mm/min; (d) strain and fractional change in resistivity at loading rate of 0.4 mm/min; (e) stress and fractional change in resistivity at loading rate of 0.6 mm/min;
(f) strain and fractional change in resistivity at loading rate of 0.6 mm/min; (g) the relationship between fractional change in resistivity and loading rate. (For interpretation of
the references to color in this figure legend, the reader is referred to the web version of this article.)

of typical strain gauge (about 2). In addition, Table 5 gives a clear fixed loading rate of 0.4 mm/min and different compressive
comparison about sensitivity among different piezoresistive stress amplitudes. The ultimate compressive stress of B04 is
cementitious composites. As can be seen, cement mortars with 44.5 MPa. Therefore, the compressive stress amplitudes of 6, 8,
CNT/NCB composite fillers in this paper possess excellent 10 MPa, which are less 1/3 of ultimate compressive stress, are
piezoresistivity. within elastic regime.
Fig. 13 shows the relationship between fractional change in
3.3.2. Effect of loading amplitude on piezoresistivity electrical resistivity and compressive stress/strain of B04 under 7
The cement mortars with 2.40 vol.% of CNT/NCB composite fil- times of cyclic loading with stress amplitudes of 6, 8 and 10 MPa.
lers (B04) present the best piezoresistivity among all the speci- It can be seen from Fig. 13(a)–(f) that the relationship between
mens. Therefore, B04 is chosen to study the piezoresistivity with change of fractional resistivity and compressive stress/strain has
114 B. Han et al. / Composites: Part A 79 (2015) 103–115

electrical resistivity (%)

electrical resistivity (%)

electrical resistivity (%)

0

Fractional change in
Fractional change in

Fractional change in
0 y=b1x+b2 x 2 0
y=b1x+b2 x 2 y=b1x+b2 x 2
Parameter Value Error
-5 Parameter Value Error -5 b1 -13.86 0.224 -5 Parameter Value Error
b1 -13.61 0.122 b2 2.26 0.099 b1 -12.15 0.175
b2 2.21 0.054 b2 1.81 0.071
-10 -10
-10
-15
-15 -15
-20
-20 0.2mm/min
Linear Fit of Data
0.4mm/min
Linear Fit of Data
-20 0.6 mm/min
Linear Fit of Data
R 2 =0.98 -25 R 2 =0.95 R 2 =0.98
-25 -25
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Compressive stress (10 2με) Compressive stress (10 2με) Compressive stress (10 2με)
(a) (b) (c)
Fig. 17. Response of fractional change in electrical resistivity to compressive strain of B04 under 7 times of cyclic compressive loading at loading rate of (a) 0.2 mm/min, (b)
0.4 mm/min and (c) 0.6 mm/min. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

(a) (b) 800 727 704

3.0 688
2.66 2.69 700
Stress sensitivity (%/MPa)

2.49
2.5
600

Strain sensitivity
2.0 500

1.5 400
300
1.0
200
0.5
100
0.0 0
0.2 0.4 0.6 0.2 0.4 0.6
Loading rate (mm/min) Loading rate (mm/min)

Fig. 18. Stress and strain sensitivity of B04 under 7 times of cyclic compressive loading at loading rate of 0.2, 0.4 and 0.6 mm/min: (a) stress sensitivity; (b) strain sensitivity.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

good synchronism and repeatability. As shown in Fig. 13, under 3.3.3. Effect of loading rate on piezoresistivity
compressive loading with stress amplitude of 6 MPa, the fractional The optimal specimen B04 is taken for further investigation
change in electrical resistivity can reach the maximum 16.0% as the under 7 times of cyclic loading with stress amplitude of
strain is 246 le. Under compressive loading with stress amplitude 8 MPa and different loading rates of 0.2, 0.4 and 0.6 mm/min.
of 8 MPa, the fractional change in electrical resistivity can reach Fig. 16 shows the fractional change in electrical resistivity
the maximum 22.1% as the strain is 314 le. Under compressive at different loading rates. It can be seen from Fig. 16(a)–(f)
loading with stress amplitude of 10 MPa, the fractional change in that the B04 has good piezoresistivity at different loading
electrical resistivity can reach the maximum 25.4% as the strain rates of 0.2, 0.4 and 0.6 mm/min. The maximum fractional
is 403 le. In general, the fractional change in electrical resistivity change in electrical resistivity of B04 at loading rate of 0.2,
of B04 grows with increasing compressive stress/strain. 0.4 and 0.6 mm/min are 21.6%, 22.1% and 20.9%, respectively.
With increasing the compressive stress amplitudes, the average The loading rate increased from 0.2 to 0.4 mm/min has
distances of CNT/NCB composite fillers became smaller. Therefore, little effect on maximum fractional change in electrical
the field induced tunneling can more easily occur which can resistivity. However, the maximum fractional change in electri-
enhance the fractional change in electrical resistivity and make cal resistivity decreases by 1.2% when the loading rate is
the piezoresistivity of B04 more significant. 0.6 mm/min.
Fig. 14 shows the relationship between fractional change in The decrease of maximum fractional change in electrical resis-
electrical resistivity and compressive strain of B04 under 7 times tivity at rate of 0.6 mm/min may be caused by the following rea-
of cyclic loading with stress amplitudes of 6, 8 and 10 MPa. The son. The numbers of pull in and push out nanotubes may
fractional change in electrical resistivity of B04 increases with decrease due the increasing of loading rate, just like that the cracks
increasing compressive strain. In addition, the relationships will less at the same stress amplitude when the loading rate is
between fractional change of resistivity and the compressive strain higher.
in Fig. 14 present a good quadratic polynomial relation. However, Fig. 17 shows that the fractional change in electrical resistivity
the quadratic polynomials are different for different stress decreased with increasing of compressive strain at loading rate of
amplitudes. 0.2, 0.4 and 0.6 mm/min. In addition, the fractional change in
Fig. 15 shows the stress and strain sensitivities of B04 under 7 electrical resistivity and compressive strain all have good quadra-
times of cyclic loading with stress amplitudes of 6, 8 and 10 MPa. tic polynomial relation. It should be noted that the results of
The stress/strain sensitivities of B04 firstly increase then decrease. quadratic polynomial relation are diverse due to different loading
The stress sensitivity of B04 under 7 times of cyclic loading with rates.
stress amplitude of 6, 8 and 10 MPa is 2.57, 2.69 and 2.48% MPa
1, Fig. 18 shows the stress and strain sensitivities of B04 at differ-
respectively. The strain sensitivity of B04 under 7 times of cyclic ent loading rates. It can be seen from Fig. 18(a) that stress sensitiv-
loading with stress amplitudes of 6, 8 and 10 MPa is 625, 704 ities of B04 at loading rate of 0.2, 0.4 and 0.6 mm/min are 2.66, 2.69
and 631, respectively. and 2.49% MPa
1, respectively. In addition, the stress sensitivities
 B. Han et al. / Composites: Part A 79 (2015) 103–115
at 0.2 and 0.4 mm/min are basically the same while the stress
sensitivity at loading rate of 0.6 mm/min goes down. As shown
in Fig. 18(b), the strain sensitivities of cement mortars with
2.40 vol.% at loading rate of 0.2, 0.4 and 0.6 mm/min are 727, 704
and 688, respectively. The strain sensitivity decreases with increas-
ing of loading rate.
4. Conclusions
Electrostatic self-assembled CNT/NCB composite fillers were
used to fabricate cement mortar with piezoresistivity. The flexu-
ral and compressive strengths, electrical resistivity and piezore-
sistivity of cement mortars with 0 vol.%, 0.39 vol.%, 0.77 vol.%,
1.52 vol.%, 2.40 vol.% and 3.12 vol.% CNT/NCB composite fillers
were investigated under different compressive loading condi-
tions. The flexural strength of cement mortars increases with
increasing the content of CNT/NCB composite fillers when the
water to binder ratio is 0.42. When the water to binder ratio
increases to 0.56 or 0.70, the flexural strength decreases. The
compressive strengths of cement mortars with CNT/NCB com-
posite fillers were all less than that of cement mortars without
CNT/NCB composite fillers. The electrical resistivity decreases
as the content CNT/NCB composite fillers increases. The percola-
tion threshold zone of cement mortar with CNT/NCB composite
fillers ranges in the amount of 0.39–1.52 vol.%. In addition, the
electrical resistivity increases with the curing age. However,
the growth of electrical resistivity with curing age is not obvious
when the content of CNT/NCB composite fillers exceeds 0.39 vol.
%. The cement mortars with only 0.77 vol.% of CNT/NCB compos-
ite fillers present piezoresistivity. With increasing the content of
CNT/NCB composite fillers, the sensitivity of piezoresistivity
firstly increases and then decreases. The optimal content level
of CNT/NCB composite fillers is 2.40 vol.% for piezoresistivity.
The fractional change of electrical resistivity, stress sensitivity
and strain sensitivity of cement mortars with 2.40 vol.% CNT/
NCB composite fillers under compressive loading with stress
amplitude of 8 MPa and loading rate of 0.4 mm/min were
22.1%, 2.69% MPa
1 and 704, respectively. The fractional changes
of electrical resistivity under compressive loading amplitude of
6, 8 and 10 MPa were 16.0%, 22.1% and 25.4%, respectively. How-
ever, the stress and strain sensitivities reached the maximum
when the compressive loading amplitude is 8 MPa. The maxi-
mum fractional change in electrical resistivity at loading rate
of 0.2, 0.4 and 0.6 mm/min were 21.6%, 22.1% and 20.9%,
respectively. The strain sensitivity decreases with the increase
of loading rate.
To our best knowledge, this is the first study that uses self-
assembled CNT/NCB composite fillers as doping particle additives
in cement and concrete materials. Thanks to their grape bunch
structure, electrostatic self-assembled CNT/NCB composite fillers
can be well dispersed in cement mortar matrix and achieve coop-
erative improvement effect, thus effectively enhancing electrical
conductivity of cement mortar and endowing stable and sensitive
piezoresistivity to cement mortar even at a low content of CNT/
NCB composite fillers. The cement-based materials reinforced with
electrostatic self-assembled CNT/NCB composite fillers have a rel-
atively simple preparation method because the self-assembled of
CNT and NCB can be well dispersed in cement-based materials
without using the ultrasonic dispersing method for CNT. In addi-
tion, the price of self-assembled of CNT/NCB composite fillers is
about half of the price of CNT. Therefore, electrostatic self-
assembled CNT/NCB composite fillers are promising modification
materials to develop multifunctional and smart cement-based
composites.
115
Acknowledgment
The authors thank the funding supported from the National
Science Foundation of China (51578110, 51178148, 51428801).
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