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A R T I C L E I N F O
A B S T R A C T
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ride), CNT/PVDF, composites prepared with different CNT types with and without function-
alization, via in situ-generated diazonium compounds. The results show that for a CNT
concentration close to the percolation threshold, tunneling is the main mechanism responsible for the electrical response, leading also to a significant increase of the piezoresistance
of the composites. Interestingly, this fact is independent of the CNT type or functionalization, as well as of the percolation threshold concentration. In this way, a close relationship
between the percolation threshold and the piezoresistive response was demonstrated. The
electromechanical response, as characterized by the gauge factor, reach values up to 3.9,
being among the largest obtained for thermoplastic composites and demonstrating the
suitability of these materials for sensor applications.
2013 Elsevier Ltd. All rights reserved.
1.
Introduction
Carbon nanotubes (CNTs) are considered suitable nanostructures for the development of functional composites due to
their mechanical reinforcement effects and electrical conductivity [13]. The use of this kind of nanostructures allows to
develop smart materials and functional composites by the
production of conductive polymer composites, using small
amount of CNT dispersed in an insulating polymer. In particular, composite materials can be developed with the ability to
significantly change the electrical response when subjected to
strains, which is suitable for the development of polymerbased strain sensors [4,5]. The effective use of CNT in composite applications depends significantly on the ability to disperse them throughout the matrix and on the compatibility
with the polymer matrix, which can be tailored through suitable modification of the CNT surface [6]. In order to increase
their compatibility with organic polymers and to improve process ability, CNT are often functionalized with organic chemical groups [7]. This functionalization improves dispersion but
can, on the other hand, hinder some of the properties necessary for the development of applications, such as the electrical conductivity [8]. The materials most commonly used as
conductive fillers include carbon black [9,10], metal powder
[11] and carbon nanofibers [12], among others. In the field of
resistance type strain sensors based on carbon composites,
two main types of strain sensors have been developed: single-walled carbon nanotube (SWCNT) buckypaper sensors
[13,14]; and sensors based on various CNT/polymer composites, such as SWCNT or multi-walled carbon nanotubes
* Corresponding author.
E-mail address: lanceros@fisica.uminho.pt (S. Lanceros-Mendez).
0008-6223/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.05.038
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569
2.
Experimental
2.1.
Processing of the materials and composite samples
preparation
Single-walled carbon nanotubes (SWCNT, AP-SWNT grade)
were purchased from Carbon Solutions Inc., Riverside, California. This SWCNT powder material is synthesized by the
electric arc reactor method using Ni/Y catalyst and contains
30 wt.% metal residue. The average diameter and length of
the SWCNT is 1.89 nm and 509 nm, according to atomic force
microscopy measurements [40]. Multi-walled carbon nanotubes (MWCNT, NC 7000) were provided by Nanocyl, Sambreville, Belgium. The Nanocyl 7000 series is produced by the
chemical vapor deposition process and contains <10 wt.%
metal oxides. The average diameter and length of the NC
7000 MWCNT is 9.5 nm and 1.5 lm (Transmission electron
microscopy data supplied by Nanocyl). Poly(vinilydene fluoride)-PVDF, was purchased from Aldrich (Mw 5,34,000, as obtained by gas phase chromatography).
CNT functionalization with heptadecafluorooctyl phenyl
groups was accomplished by reaction with the corresponding
in situ generated diazonium compound. 250 mg of CNT were
tip sonicated in 50 mL of DMF for 60 min. Separately, 460 mg
of heptadecafluorooctyl aniline were dissolved in 50 mL of
acetonitrile and added to the CNT dispersion. The mixture
was heated to 60 C under constant magnetic stirring, and
then 2 mL of isoamyl nitrite was added. The reaction mixture
was left overnight at 60 C, then vacuum filtered through a
0.1 lm Teflon membrane and washed with DMF and methanol. A thorough characterization of fluoroalkyl-functionalized
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2.2.
2.3.
Electrical and electromechanical characterization of
the composite samples
The electrical resistivity of the samples was measured by the
two-wire method, where the voltage was applied and the current measured by a Keithley 487 picoammeter/voltage source.
All measurements were performed in direct current (DC)
mode, at room temperature. On each sample, two parallel
rectangular gold electrodes were deposited by magnetron
sputtering on one side of the sample. Copper wires were attached to the electrodes with silver paint to ensure good electrical contact. The sheet resistivity qX:sq was calculated by:
qR
D
;
L
where R is the surface resistance, D is the length of the electrode (6 mm) and L is the distance between the electrodes
(1 mm). The electrical conductivity is given by the inverse of
the electrical resistivity 1/q .
dR=R
;
dl=l
In Eq. (2), R is the steady-state material electrical resistance before deformation and dR is the resistance change
caused by the variation in length dl [42]. The quantity l represents the length of the sample. The resistance change under
strain results from the contribution of the dimensional
change geometrical effect DRD- and from the intrinsic piezoresistive effect DRl. For the surface mode measurements
(Fig. 1) the GF can be written as [42]:
GF
dR=R
dq=q
DRD DRl 1 t
el
el
3al 4a2
;
6z
and the strain of the composite along the longitudinal direction is:
e
3dz
;
3al 4a2
3dz
:
5a2
Fig. 1 Reaction route applied for the functionalization of single- and multi-walled carbon nanotubes.
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571
Fig. 2 Schematic representation of the four-point bending tests: z is the vertical displacement of the piston, d is the
thickness of the sample (1 mm) and a is the distance between the first and the second bending points (15 mm) and l the
distance between the lower supports (45 mm).
different measurements for each sample. The calculated values of the GF for the up and down mechanical cycles was the
same, unless otherwise stated.
The measurement of the surface resistance change (DR/R)
in each mechanical experiment was obtained from the measurement of the electrical resistance, with an Agilent
34401A digital multimeter. For this purpose, two parallel rectangular gold electrodes of 6 mm width and 1 mm distance between them were vacuum evaporated onto one of the sides
the samples, and a copper wire was attached to the electrodes
with silver paste.
The mechanical tests were performed in a Shimadzu-AGIS testing instrument and consisted in four loading and
unloading cycles at a velocity of deformation of 2 mm min1
and 1 mm in z-displacement.
3.
3.1.
Electrical conductivity
Representative IV plots and for the dependence of the electrical conductivity with CNT concentration for the different CNT/
PVDF composites is show in Fig. 3. In all cases, the electrical
conductivity of the composites increases with increasing
CNT content (Fig. 3b), existing, however, significant differences
between the different samples. SWCNT and MWCNT composites show an overall similar trend with small differences in the
Fig. 3 (a) Typical IV plots for the composite samples prepared with the different CNT at a concentration around the
percolation threshold; SWCNT: 1.5 wt.%, MWCNTs: 0.75 wt.%, SWCNT Func: 4.6 wt.%, MWCNT Func: 1 wt.%. (b)
Concentration dependence of the electrical conductivity for the different composites.
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centration, in contrast with the percolation theory that predicts the formation of a contact network [48], conducting
inclusions such as the CNT are sufficiently close to each other
to be within the tunneling distance to create a conducting
network [4951].
Numerical calculations on the electrical conductivity of
CNT/polymer composites, with and without including the
tunneling effect show that the inclusion of the tunneling allows increased conductivity of the composite [52]. Also an
eventual nonlinearity of the IV curves has been proposed
as a way for investigating the origin of the conduction mechanism in CNT/polymer composites [53], but this approach is
also inconclusive as composites with tunneling-type conductivity also obey Ohms law and, therefore, show linear IV
relationships as contact-type conductivity. Finally, different
model, such as the ones based on the formation of capacitor
networks have been developed to explain low percolations
thresholds [39]. In this respect and due to the difficulty of
understanding the conductivity mechanism from the conductivity curves, it is interesting to explore the nature of the electromechanical response both, to evaluate the performance of
the materials as piezoresistive sensors and to further study
the origin of the electrical conductivity as this mechanism
will be affected by the mechanical solicitation.
Fig. 4 SEM images of CNT/PVDF composites at 2 wt.%. (a) SWCNT, (b) SWCNT Func, (c) MWCNT, (d) MWCNT Func.
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wt.%
GF
Standard error
SWCNT
SWCNT Func
MWCNT
MWCNT Func
1.5
4.6
0.75
1
3.24
3.76
3.91
3.49
0.04
0.07
0.06
0.06
3.2.
Electromechanical response
Electromechanical tests were performed in samples with different percentages of CNT, close to the percolation threshold
(Table 1), where the GF is the largest [16] and therefore can
give important insights on the origin of the conductivity
mechanism [45,53,54].
It has been shown that the percolation threshold corresponds to the region with the largest GF in CNT/polymer composites [16] due to the fact that close to the percolation
threshold an applied deformation is able to induce strong
and reversible variations (Fig. 5) in the nanotube network configuration (e.g., variations of the nanotubes relative distance)
[55], which has a strong influence in the variation of the electrical conductivity. Far from the percolation threshold, network variations are smaller and therefore their effect in the
electrical response is also small [56].
Fig. 5 shows a typical example of the electromechanical
experiments performed with the different samples, where it
can be observed the electrical resistance variation to repeated
loadingunloading cycles.
Fig. 5 shows that the electrical resistance changes fairly
linearly with the applied strain and that the linearity is maintained for the different cycles and for the different samples.
Fig. 5 Cyclic piezoresistive response as a function of time for (a) SWCNT: 1.5 wt.%, (b) MWCNT: 0.75 wt.%, (c) SWCNT Func:
4.6 wt.%, (d) MWCNT Func: 1 wt.% for the following conditions: bending of 1 mm, deformation velocity of 2 mm min1 at
room temperature.
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Ea
Ea
RT Rm 1 exp
Rt exp
kB T
kB T
LT
LB
RT
RB
AT
AB
Ea
RT Rm 1 exp
kB T
Ea
RB Rt exp
kB T
where LT and AT are the effective length and effective crosssectional area of the CNT. RT represents the intrinsic resistance, RB the junction resistance, Rm and Rt are proportional
constants, Ea is the tunnel activation and Eg is the band gap
of CNT, kB is the Boltzmann constant, and T is temperature
[57,58]. Eq. (5) can be rewritten as
Re
exp2ad0 e
R0
2p p
2m/
h
10
Table 2 Distance between two CNT, results of Eq. (9) as function of stress.
Samples
SWCNT
SWCNT Func
MWCNT
MWCNT Func
wt.%
1.5
4.6
0.75
1
Slope
3.26
3.74
3.90
3.48
Standard error
0.04
0.07
0.06
0.06
ad0
1.63
1.87
1.95
1.74
0.75
d0 (nm)
d0 (nm)
d0 (nm)
d0 (nm)
d0 (nm)
0.45
0.52
0.54
0.48
0.37
0.42
0.44
0.39
0.32
0.37
0.38
0.34
0.22
0.26
0.27
0.24
0.16
0.18
0.19
0.17
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4.
Conclusions
The piezoresistive response of CNT/PVDF, composites prepared with both SWCNT and MWCNT with and without functionalization with heptadecafluorooctyl phenyl surface
groups is driven by variation of the distance between CNT.
The GF is nearly independent of the filler type and concentration, once it is measured close to the percolation threshold,
tunneling being in this way the mechanism responsible for
the electrical and electromechanical response of the composites. The GF reaches values above three, which indicates a
main contribution from intrinsic piezoresistive effect and
demonstrating the suitability of these materials for sensor
applications.
Acknowledgements
This work is funded by FEDER funds through the Programa
Operacional Factores de Competitividade COMPETE and
by national funds by FCT-Fundacao para a Ciencia e a Tecnologia, project references PTDC/CTM/69316/2006, PTDC/CTMNAN/112574/2009, and NANO/NMed-SD/0156/2007, as well
as by the Spanish Ministerio de Economa y Competividad
through the projects reference EUI2008-00153, TEC 201015736 and PRI-PIBAR-2011-1. AF thanks the FCT for grant
SFRH/BD/69796/2010. The authors also thank the COST Actions MP1003 (European Scientific Network for Artificial Muscles, ESNAM) and MP0902 (Composites of Inorganic
Nanotubes and Polymers, COINAPO).
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