Composites Science and Technology 70 (2010) 1571–1573

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Composites Science and Technology

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

Short Communication

Effects of carboxyl radical on electrical resistance of multi-walled carbon

nanotube filled silicone rubber composite under pressure
Peng Wang *, Shengnan Geng, Tianhuai Ding
State Key Laboratory of Precision Measurement Technology and Instruments, Department of Precision Instruments and Mechanology, Tsinghua University, Beijing 100084, PR China

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

Article history: The piezoresistance of a multi-walled carbon nanotube filled silicone rubber composite under uniaxial
Received 17 December 2009 pressure was studied. The experimental results show that the active carboxyl radical on multi-walled car-
Received in revised form 3 May 2010 bon nanotubes can effectively improve the homogeneous distribution and alignment of conductive paths
Accepted 6 May 2010
in the composite. As a result, the composite presented positive piezoresistance with improved sensitivity
Available online 12 May 2010
and sensing linearity for pressure, both of which are key parameters for sensor applications.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
A. Carbon nanotubes
A. Polymers
A. Nano composites
B. Electrical properties
D. Scanning electron microscopy

1. Introduction aggregation and improve the degree of homogeneous dispersion.

Some composites containing dispersed conductive fillers in an
insulating polymer matrix have been studied for flexible force sen-
sor applications [1–4]. For a composite near the critical threshold,
we would expect to see a piezoresistive effect below a critical pres-
sure [5,6]. Recently, composites using multi-walled carbon nano-
tubes (MWCNT) as conductive filler have been widely studied
due to their excellent electrical conductivity. Dharap et al. [7]
and Park et al. [8] both demonstrated that MWCNT filled polymer
films can exhibit a change in electrical resistance induced by pres-
sure, or piezoresistance. An equation was proposed for predicting
the piezoresistance of the MWCNT/polymer composite films by
Park et al. [8]:
 was used as solvent to mix the fillers with the rubber. Mechanical
DR ke ð0 6 e 6 ec Þ
 ð1Þ
R0 ke þ uðe  ec ÞN ðe > ec Þ
where DR is the change in resistance, R0 is the initial resistance, k is
the slope of the linear region, e is the strain of film, ec is the critical
strain at which the numbers of contacting MWCNTs begins to de-
crease significantly, and N is the tunneling resistance between
two adjacent MWCNTs.
In the process of investigation, we found that the carboxyl
radical (COOH) on MWCNT contributes to avoiding the second
* Corresponding author. Tel./fax: +86 10 62772007.
E-mail address: peng@mail.tsinghua.edu.cn (P. Wang).
As a result, the piezoresistive properties of the composite
film may be improved. This phenomenon is the focus of this
paper.
2. Experimental
Silicone rubber (SR, Beijing Hangping Chem. Plant, China) was
used as a polymer matrix. Pristine MWCNTs (U-MWCNTs) without
any chemical functional groups attached and MWCNTs with car-
boxyl functional group (C-MWCNTs, Chengdu Organic Chem. Corp.,
China) were dispersed as conductive fillers. For both MWCNTs, the
conductivity exceeds 100 S/cm, the outside diameters and lengths
range from 20 to 30 nm and 10–30 lm, respectively. Ethyl acetate
stirring along with sonication were also used for better dispersion.
The viscous mixture was molded onto the substrate with interdig-
ital electrodes as shown in Fig. 1 and the solvent was evaporated.
Several samples with 14.5 wt.% MWCNTs were prepared as sample
A (U-MWCNTs) and sample B (C-MWCNTs). The unreinforced SR
without MWCNTs was also molded onto the substrate as sample
C. After molding, the sample was placed between the lift platform
and the sensing element of the digital force gauge, respectively.
And the uniaxial pressure was applied by the upward movement
of the lift platform. The contact area between compression ma-
chine and sample is 5  7 mm2, which is a little bigger than the
area of an interdigital electrode. The resistance was measured
using a HP-3458A digital multimeter.

0266-3538/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2010.05.008
1572 P. Wang et al. / Composites Science and Technology 70 (2010) 1571–1573

Fig. 3. SEM micrograph of the fractured surface for the U-MWCNTs/SR composite.

Fig. 1. Schematic of experimental sample.

3. Results and discussion

The initial electrical resistances of samples A–C measured under

zero pressure were 1.2 KX, 4.7 KX and 11 MX. For the purpose of
comparison, the relative electrical resistance change (R/R0, R is the
current resistance, R0 is the initial resistance) is utilized to describe
the test results in this paper. Fig. 2 shows the change of electrical
resistance in the samples under 0–2.86 MPa uniaxial pressure. It
can be seen that electrical resistance of sample C keep almost con-
sistant, but electrical resistances of sample A and sample B both in-
creased with pressure, showing positive piezoresistance.
Dissimilarly, the sample B presented a sharper and more linear in-
crease than sample A.
Figs. 3 and 4 show the SEM micrograph of the fractured surface
for the U-MWCNTs/SR and C-MWCNTs/SR composites. As can be
seen, most of U-MWCNTs intertwine together to form aggregations Fig. 4. SEM micrograph of the fractured surface for the C-MWCNTs/SR composite.
like three-dimensional particles, but the C-MWCNTs contribute
homogeneously like parallel one-dimensional nano-scale fibers.
This is because C-MWCNTs can remain independent through the
repulsing force between carboxyl radicals.
For composites with homogeneous C-MWCNTs, as pressure is
applied the elastic polymer matrix deforms to the extent that the
MWCNTs are forced straight and aligned with the direction of
stretching, as shown in Fig. 5a. As a result, the number of contact-
ing MWCNTs is reduced and the tunneling resistance increases.

Fig. 5. The schematic of deformation for U-MWCNTs and C-MWCNTs filled

composites.

This is why the composites displayed positive piezoresistance

Fig. 2. Changes of electrical resistance under various pressures for the samples A–C.
quantified by Park’s equation [8].
For the composite with aggregating U-MWCNTs, the aggrega-
tions have to be treated as particles. The piezoresistivity of parti-
cles filled polymer is different from that of homogeneous
MWCNTs filled one. For this case, the simplified general medium
equation by Hussain [9] can explain the change of electrical resis-
tivity with pressure:
 P. Wang et al. / Composites Science and Technology 70 (2010) 1571–1573
 w
1  /c
q ¼ ql
/  /c
where q is the resistivity of composite, ql is the resistivity of parti-
cle, /c is the critical percolation fraction, / is the current particle
fraction, and w is an exponent. When the composite is subjected
to stress the volume is compressed and the particle’s fraction in-
creases, with a resulting decrease in resistivity. However, as shown
in Fig. 5b, the thickness of the sample was also decreased, that re-
sults the resistance between two electrodes still increased under
pressure. So, for the sample A, the trend of the resistivity change
is opposite to that of the resistance change, which may have a neg-
ative effect on sensitivity and sensing linearity.
4. Conclusion
The carboxyl radical on MWCNTs can effectively improve
homogeneous distribution and alignment of the MWCNTs in poly-
mer matrixes to form 1 to 3D complex doping structures. These
structures give composites a positive piezoresistance both parallel
and perpendicular to the direction pressure is applied. In addition,
we also found that the MWCNTs with carboxyl radicals can im-
prove the sensing range, sensitivity and sensing linearity of com-
posites for pressure. However, the piezoresistance of the MWCNT
filled polymer composites can also be influenced by the fraction
1573
of MWCNTs, the polymer properties and the fabrication process.
ð2Þ
Further, more in-depth research and results will be published soon.
Acknowledgements
This study was supported by the National Natural Science Foun-
dation of China (Grant 60702001) and the 863 Program of MOST of
China (No. 2009AA04Z308).
References
[1] Qu SY, Wong SC. Piezoresistive behavior of polymer reinforced by expanded
graphite. Compos Sci Technol 2007;67:231–7.
[2] Knite M, Teteris V, Kiploka A, et al. Polyisoprene-carbon black nanocomposites
as tensile strain and pressure sensor materials. Sensors Actuat A-Phys
2004;110:142–9.
[3] Lumelsky VJ, Shur MS, Wagner S. Sensitive skin. IEEE Sensors J 2001;1:41–51.
[4] Wang LH, Ding TH, Wang P. Thin flexible pressure sensor array based on carbon
black/silicone rubber nanocomposite. IEEE Sensors J 2009;9:1130–5.
[5] Carmona F, Canet R, Delhaes P. Piezoresistivity of heterogeneous solids. J Appl
Phys 1990;61:2550–7.
[6] Taya M, Kim WJ, Ono K. Piezoresistivity of short fiber/elastomer matrix
composites. Mech Mater 1998;28:53–9.
[7] Dharap P, Li Z, Nagarajaish S, Barrera EV. Nanotube film based on single-wall
carbon nanotubes for strain sensing. Nanotechnolgoy 2004;15:379–82.
[8] Park M, Kim H, Youngblood JP. Strain-dependent electrical resistance of multi-
walled carbon nanotube/polymer composite films. Nanotechnology
2008;19(5):055705.
[9] Hussain M, Choa Y, Niihara K. Fabrication process and electrical behavior of
novel pressure-sensitive composites. Composites: Part A 2001;32:1689–96.