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Polyaniline nanoparticlecarbon nanotube hybrid network vapour sensors with switchable

chemo-electrical polarity

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2010 Nanotechnology 21 255501
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IOP PUBLISHING

NANOTECHNOLOGY

Nanotechnology 21 (2010) 255501 (10pp)

doi:10.1088/0957-4484/21/25/255501

Polyaniline nanoparticlecarbon nanotube

hybrid network vapour sensors with
switchable chemo-electrical polarity
Jianbo Lu1 , Bong Jun Park2 , Bijandra Kumar1, Mickael Castro1 ,
Hyoung Jin Choi2 and Jean-Francois Feller1
1

Smart Plastics Group, European University of Brittany (UEB), LIMATB -UBS,

Lorient 56321, France
2
Department of Polymer Science and Engineering, Inha University, Incheon 402-751, Korea
E-mail: jean-francois.feller@univ-ubs.fr

Received 30 November 2009, in final form 29 April 2010

Published 28 May 2010
Online at stacks.iop.org/Nano/21/255501
Abstract
Chemo-resistive sensors were prepared from monodisperse poly(aniline) nanoparticles
(PaniNP) synthesized via oxidative dispersion polymerization. Poly(styrene sulfonic acid)
(PSSA) was used as the stabilizer and dopant agent. PaniNP transducers were assembled by
spraying layer by layer a solution containing different concentrations of PaniNP and multi-wall
carbon nanotubes (MWNT) onto interdigitated electrodes. This process led to stable sensors
with reproducible responses upon chemical cycling. Chemo-electrical properties of these
sensors have been investigated in sequential flows of pure nitrogen and nitrogen saturated with a
set of volatile organic compounds (VOC). Interestingly the sensing mode of PaniNP transducers
(the NVC or PVC effect) can be switched simply by increasing PaniNP content or by the
addition of only 0.5% of MWNT to reach a resistance lower than 150 . Due to their original
conducting architecture well imaged by atomic force microscopy (AFM), i.e. a double
percolated conductive network, PaniNPMWNT hybrids present both higher sensitivity and
selectivity than other formulations, demonstrating a positive synergy. Mechanisms are proposed
to describe the original chemo-electrical behaviours of PaniNP-based sensors and explain the
origin of their selectivity and sensing principle. These features make them attractive to be
integrated in e-noses.
S Online supplementary data available from stacks.iop.org/Nano/21/255501/mmedia
(Some figures in this article are in colour only in the electronic version)

electronic properties such as electrical conductivity, low

energy optical transitions, low ionization potential and high
electron affinity. This extended -conjugated system of the
conducting polymers has single and double bonds alternating
along the polymer chain. The higher values of the electrical
conductivity obtained in such organic polymers have led
to the name synthetic metals [3]. Due to their unique
electrical properties, interaction of conjugated polymers with
gas or vapour molecules (electron acceptors or donors) causes
changes in both carrier density and mobility, leading to
significant changes in conductivity. Besides, the conformation
of the conducting polymer chain can be modified due to
strong interaction with certain organic solvents, which is

1. Introduction
Over the last decade, the development and design of smart
materials from conductive polymer composites (CPC) have
drawn increasing interest, especially for sensing applications.
CPC sensitivity to elongation, temperature or organic vapours
has made them very attractive in designing transducers to
monitor accidental events like air pollution, overheating
or overloading.
Compared to conventional insulating
polymers, intrinsically conducting polymers have physical
and chemical properties that can be tailored over a wide
range of characteristics [1, 2].
Conducting polymers
contain a -electron backbone responsible for their unusual
0957-4484/10/255501+10$30.00

2010 IOP Publishing Ltd Printed in the UK & the USA

Nanotechnology 21 (2010) 255501

J Lu et al

microelectrodes in order to control finely the conductive

architecture building. The transducers structure has been
imaged by atomic force microscopy (AFM) to determine
the nature of PaniNP/MWNT association at the nanoscale.
The validation of sensor performance by sequential exposure
to a set of standard VOC showed that chemo-electrical
properties could be tuned by varying PaniNP concentration
and that, interestingly, only a small amount of MWNT
added to poly(aniline) nanoparticles could enhance not only
the transducers conductivity, but also switches the vapour
response from negative to positive.

called a secondary doping process. Consequently there

occurs a change in conductivity [4, 5]. The p-type and
n-type sensing response, i.e. an increase or decrease in
resistivity, can both be observed for conducting polymers
towards different organic solvents. The vapour response
depends on the nature of the dopant anion in the polymer
whereas the same sensor has p-type and n-type sensing
responses to different vapours [6]. Thus by simply following
their electrical resistivity variation, environmental monitoring
can be done, which makes conducting polymers promising
materials for sensing applications [711].
Poly(aniline)
(Pani) is one of the conducting polymers having the highest
mechanical flexibility, environmental stability and controllable
conductivity with acid/base (doping/undoping) [12, 13]. The
synthesis of poly(aniline) can be carried out by dispersion
polymerization in the presence of a polymeric stabilizer, which
prevents PaniNP from aggregating during polymerization; at
the end of the process uniform and spherical monodisperse
PaniNP are obtained [1416]. A lot of applications can
be found for poly(aniline)-based composites such as food
quality control [10]. Pani can be used to sense alcohols [17],
since n-type responses are obtained due to interactions with
methanol and short-chain alcohols that generate a secondary
doping effect. Conversely long-chain alcohols can hardly
diffuse into poly(aniline), which causes strong barrier effects,
affecting charge transfer and leading to a p-type sensing
response [1719]. Nevertheless, increasing the poly(aniline)
specific surface by processing it in the form of nanofibres is
found to enhance its sensitivity to acid vapours due to better
vapour diffusion [20].
Nevertheless, although poly(aniline)-based smart materials have demonstrated a good sensitivity and reproducibility,
their lack of stability to humidity and irradiation still affects
their development for applications. To this extent, carbon
nanotubes (MWNT), which have recently attracted a lot of
attention due to their exceptional properties [2124], could
provide Pani with a high level of stability [25]. Some examples
of the association of MWNT with conducting polymers has
already led to a positive synergy [2628]. Therefore it is
expected that the addition of only a small amount of MWNT to
Pani will significantly improve the mechanical, electronic and
chemo-electrical properties of poly(aniline)-based hybrids, as
shown by some authors in the literature [2932]. Moreover,
PaniNPMWNT hybrids have already been used successfully
for some smart applications like electro-rheological fluids
(ER) whose viscosity can be tuned with DC electric field
strength [33, 34], electro-chemical biosensing [35] or gas
sensing [36, 37]. However, reviewing the literature, the effect
of poly(aniline) concentration on vapour sensing behaviour is
still not fully elucidated. Thus, developing a chemo-resistive
hybrid material for vapour sensing by building a conducting
architecture through the association of PaniNP with carbon
nanotubes has been a promising perspective.
In this paper we have investigated PaniNPMWNT hybrid
chemo-electrical properties and compared their characteristics
as vapour sensors with neat PaniNP or MWNT alone. A spray
layer by layer (LbL) assembly has been chosen to structure
PaniNPMWNT hybrid films straight onto interdigitated

2. Experimental details
2.1. Materials
Poly(styrene sulfonic acid) (PSSA) ( Mw = 80 000 g mol1 )
obtained from Sigma-Aldrich (USA) is used as the polymeric
steric stabilizer and the pendant aromatic ring of PSSA acts
as a dopant agent due to its acidity; PSSA is formed by ion
exchange of poly(sodium 4-styrene sulfonate) (PSSS) VERSA
TL-502 from Alco Chemical (USA) with HCl. Multi-wall
carbon nanotubes modified on their surface by carboxylic
acid (MWNTCOOH) NC 3101 kindly provided by Nanocyl
(Belgium) had a carbon purity higher than 95%. This grade
was chosen to increase MWNT dispersibility in water and thus
improve interactions with PaniNP. Methanol and toluene were
received from Aldrich (France) and chloroform was obtained
from Acros (France). All solvents were used without any
further purification.
2.1.1.
Synthesis of Pani nanoparticles.
Poly(aniline)
nanoparticles (PAPSSA) were synthesized by oxidative
dispersion polymerization using the PSSA long chain as a
stabilizer with acidity and as a dopant agent. 37.5 g of
PSSA was slowly dissolved in 350 ml of deionized water (Dwater) and then used for nanoparticle preparation. 41.67 g
of aqueous hydrochloric acid (HCl, 35.5 wt% in H2 O) and
0.2 mol of aniline were added to the solution and the
reaction mixture was continuously stirred at 0 C. Then
150 ml of aqueous solution containing 0.1 mol of an oxidant,
ammonium peroxydisulfate (NH4 )2 S2 O8 (APS), was added
through dropping by 5 ml min1 and stirred for 24 h at 0 C.
The light yellow solution gradually darkened and acquired an
emerald colour over a period of 40 min and eventually turned
dark green, which is a characteristic of the doped poly(aniline).
The resulting dark green dispersions were purified three times
by centrifugation, filtered and washed in order to remove
oligomers and monomers in excess.
2.1.2. PaniNP solution preparation. The poly(aniline)
nanoparticle suspension concentration was varied through a
dilution process; the required amount of PaniNP is achieved
by controlling the ratio of solute and solvent. D-water was
used as the solvent to lower the concentration of the PaniNP
mother suspension (MS) (0.05 g cm3 ). PaniNP dispersion
was ensured by sonication at 25 C for 2 h prior to film
deposition.
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Nanotechnology 21 (2010) 255501

J Lu et al

Table 1. Dilution process and electrical properties of PaniNP composite-based thin film.
Sample

Total mass (g) PaniNP MS/D-water (g/g) [PaniNP] (wt%MS) [PaniNP] (wt%)a Layer nb Resistance ()

1%PaniNP
1%PaniNP0.005%MWNT
2%PaniNP
3%PaniNP
4%PaniNP
5%PaniNP

20
20
20
20
20
20

4/16
4/16
8/12
12/8
16/4
20/0

20
20
40
60
80
100

1
1
2
3
4
5

10
10
10
10
10
10

7000
110
4000
700
110
80

For volume % use dPani = 1.40 g cm3 [46] and dMWNT # 1.75 g cm3 [50].

2.1.3. PaniNPMWNT hybrid sensor preparation. PaniNP

transducers were then processed by spray layer by layer (LbL)
assembly onto interdigitated electrodes (figure 1) obtained by
capacitor cleavage [38]. A home-made device allows the
precise control of spraying conditions like nozzle flow rate
(index 2), air pressure ( ps = 0.20 MPa), sweep speed ( ps =
0.20 MPa) and target to nozzle distance (dtn = 8 cm) [39].
In order to obtain reproducible transducers with relatively
low resistance the LbL process was monitored by following
the evolution of electrical resistance as a function of layer
deposition. A two-step method was used to prepare PaniNP
MWNT hybrids. Firstly 1 mg of MWNT was added to
16 g of D-water to obtain a homogeneous solution (6.25
105 g cm3 ) by 6 h sonication at 25 C. In the second step
4 g of 100% PaniNP MS (0.05 g cm3 ) was introduced into
the MWNT solution. A uniform mixture of MWNT (5
105 g cm3 ) and PaniNP (0.01 g cm3 ) was obtained after 2 h
of sonication at 25 C. PaniNPMWNT (1/0.005) transducers
were then processed by spray LbL in the same conditions as
for PaniNP alone to lead to a final MWNT/PaniNP ratio in the
solid state of 0.5%. After spray deposition, all samples were
vacuum dried at 25 C for one day prior to chemical sensing
investigation. Sample characteristics are listed in table 1.

Figure 1. SEM picture of the interdigitated electrode obtained from a

cleaved capacitance.

set point amplitude to the free amplitude was maintained at

approximately 0.9. RTESP. AFM tips (Veeco), with typical
resonance frequency between 300 and 400 kHz and with tip
radii between 5 and 15 nm, were used. Diameters of PaniNP
were measured using the section analysis software of the
microscope (V6.13r1 by Digital instruments).

2.2. Techniques

2.2.4. Dynamical vapour sensing measurement. Chemoelectrical properties of PaniNP-based sensors were investigated
by recording their electrical signals when exposed to 10 min
periodic cycles of dry nitrogen and vapour streams. The
dynamic system consists in mass flow controllers, solvent
bubblers and electrical valves controlled by LabView software.
Bubbling dry nitrogen in liquid solvent provides a saturated
vapour stream, which was in turn diluted by nitrogen flow to
the desired concentration at room temperature. The sensing
device is presented in figure 2 where samples are placed in
a 9 cm 3 cm 3.5 cm chamber. The design of the
device allows us to keep constant the total flow rate at Q v =
100 cm3 min1 . Electrical characteristics of the transducers
were recorded with a Keithley 6517A multimeter [40]. In this
paper all experiments were done in nitrogen flows saturated
with the vapour to be analysed.

2.2.1. FT-IR and UVvis characterization. Successful

polymerization of PaniNPPSSA was confirmed by Fourier
transform infrared (FT-IR) using KBr pellets. In addition, UV
vis absorption spectra were tested to get the optical absorbance
of aqueous dispersions containing 1 wt% of PaniNP in the
wavelength range of 200800 nm. Additional figures showing
spectra and the attribution of peaks can be found in the
supporting information (available at stacks.iop.org/Nano/21/
255501/mmedia) document.
2.2.2. Transmittance electron microscopy (TEM) characterization. PaniNP dispersion was diluted in order to observe
single particles by TEM. The diluted dispersion was dropped
onto the TEM grid. The mesomorphology of PaniNP was
observed using a transmittance electron microscope (TEM,
Philips CM200) operated at an acceleration voltage of 120 kV.

3. Results
2.2.3. Atomic force microscopy characterization (AFM).
AFM images were obtained under ambient conditions using
light tapping mode AFM (TM-AFM) on a multimode scanning
probe microscope (Nanoscope IIIa, Veeco). The ratio of the

3.1. Structure and morphology of materials

3.1.1.
Characterization of PaniNP by TEM.
Pani
nanoparticle size distribution was determined by TEM. In
3

Nanotechnology 21 (2010) 255501

J Lu et al

Figure 2. Schematic of vapour sensing device.

Figure 3. TEM images of PaniNP. (a) Necklace structure of nanoparticles at low magnification, scale bar 0.8 m. (b) Individual nanoparticle
at high magnification, scale bar 100 nm.

figure 3(a), PaniNP shows a spherical and uniform shape

resulting from PSSA stabilization and a well-controlled
polymerization rate [14]. However, an aggregation of PaniNP
was observed, which is induced by strong interactions between
PaniNP. From figure 3(b), it is possible to estimate the diameter
of a single poly(aniline) nanoparticle as about 120 nm with a
distribution of 20 nm.

3.2. Electrical properties of PaniNP and PaniNPMWNT

hybrids
3.2.1. Electrical properties of PaniNP and PaniNPMWNT
hybrids in air. Figures 5 and 7 shows that the initial
resistance of sprayed LbL PaniNP transducers (measured at
room temperature in air) decreases regularly with increasing
PaniNP concentration in the suspension. Since PaniNP content
is easily adjusted, dilution is also a very convenient way to
adjust the samples conductivity. Interestingly only adding
0.005 wt% of MWNT to the 1 wt% PaniNP suspension allows
reducing the transducers initial resistance by about two orders
of magnitude. This behaviour can be understood by observing
again in figure 4 how MWNT can very well interconnect
PaniNP aggregates to build the hybrid network.

3.1.2. Characterization of PaniMWNT hybrids. Pani

MWNT solutions were sprayed onto a freshly cleaved
mica substrate to observe the surface morphology. The
PaniNPMWNT microstructure was characterized by TMAFM. Figure 4(a) reveals at first sight a uniform dispersion of
spherical PaniNP. It is also interesting to discover how MWNT
can interconnect PaniNP to form a hybrid conductive network.
Figure 4(b) represents the PaniNPMWNT architecture at
higher magnification. Unlike what is classically observed
when polymers homogeneously coat a nanotubes surface,
spherical PaniNP are decorating carbon nanotubes featuring
a necklace-like microstructure leading to original hybrid
architecture.

3.2.2. Sensitivity of PaniNP and PaniNPMWNT hybrid to

organic vapour. Chemo-electrical properties of PaniNP and
PaniNPMWNT sensors were compared when exposed to
sequential pure nitrogen/saturated vapour flows. Signals were
recorded and normalized by expressing the relative amplitude
4

Nanotechnology 21 (2010) 255501

J Lu et al

Figure 4. AFM images of PaniNPMWNT hybrids showing the

MWNT network built within PaniNP: (a) 2 m 2 m and
(b) 1 m 1 m.

Figure 6. Evolution of relative amplitudes A r with PaniNP content

(1, 2, 3, 4 and 5%) exposed to saturated vapours of (a) chloroform
and (b) water.

Chemical sensing experiments were done with two

different categories of solvents: polar solvents, like water
and methanol, and more dispersive solvents, like toluene and
chloroform, to investigate PaniNP selectivity. Figure 6(a)
summarizes the electrical responses of different PaniNP
transducers (made from suspension concentrations varying
from 1 to 5 wt% PaniNP) exposed to a water vapour stream.
Surprisingly Ar is found to be negative for 1, 2 and 3%
PAniNP while for 4% PaniNP it becomes positive. Similarly
in figure 6(b), upon exposure to chloroform vapour, exactly the
same phenomenon is observed. It seems that at low PaniNP
content (1, 2 and 3% PaniNP) sensors exhibit a negative
vapour coefficient effect (NVC) while at high concentrations
(4 and 5% PaniNP) a positive vapour coefficient effect
(PVC) is obtained. In figure 7 all PaniNP sensor responses
(from 1 to 5% PaniNP) towards methanol, water, toluene and
chloroform vapour are summarized and compared to that of
100% MWNT and 1%PaniNP0.005%MWNT. It is clear
from this graph that, whatever the vapour, an NVC/PVC
switching transition occurs when PaniNP content increases
from 3 to 4% PaniNP. Therefore PaniNP content appears
to be a very effective way of tuning the electrical response
polarity. Moreover, comparing more precisely the dynamic

Figure 5. Initial resistance of 1, 2, 3, 4 and 5% PaniNP and 1%

PaniNP0.005% MWNT dry films.

of responses Ar , defined in equation (1), in order to allow their

direct comparison:

Ar =

Rv Rinit
Rinit

(1)

where Rv is the resistance of the sensor when exposed to the

vapour and Rinit is the initial resistance in nitrogen.
5

Nanotechnology 21 (2010) 255501

J Lu et al

Figure 7. Selectivity of CPC (MWNT, 1% PaniNP0.005% MWNT

and 1, 2, 3, 4 and 5% PaniNP) towards methanol, water, toluene and
chloroform vapour, influence of MWNT presence and Pani content.

Figure 9. Vapour response of 1%PaniNP0.005%MWNT exposed to

methanol, water, toluene and chloroform.

4. Discussion
4.1. NVC/PVC switching mechanism
On the basis of previous observations of NVC/PVC polarity
switching it is interesting to propose a mechanism able to
describe this original effect. At first if can be stated that,
whatever the route used to generate this phenomenon, it must
be intimately related to the initial resistance of transducers
and thus to the conductive network architecture. In fact,
figure 5 shows that all sensors with an initial resistance
higher than 150  will lead to an NVC effect, whereas
below this value all sensors give rise to a PVC effect.
Nevertheless, It is likely that the origin of NVC/PCV switching
will be different whether conductivity increase has been
obtained through PaniNP or MWNT addition. But before
trying to explain the origin of this chemo-electrical transition
it is necessary to better understand independently which
mechanisms can be responsible for NVC and PVC. Classically,
the sensing principle of most conductive polymer composite
transducers (obtained by dispersing conducting nanofillers
into an insulating polymer matrix) finds its origin in the
PVC effect (p-type sensing). When subjected to vapour
molecules, the dense percolated network (carbon or metal) will
be sensitive to the weakest degradation of its connectivity by
conversion of close internanofiller contacts into less conductive
tunnel junctions. Thus, adsorption of solvent molecules
onto polymer chains and conductive nanofillers will tend to
increase the internanofiller gap and decrease the transducers
conductivity [4245]. This behaviour is characteristic of a
network built from hard fillers in close contact.

Figure 8. Vapour response of 1%PaniNP exposed to methanol,

water, toluene and chloroform.

chemo-electrical behaviour of 1%PaniNP and 1%PaniNP

0.005%MWNT responses in figures 8 and 9, respectively,
shows that just adding a small amount of SWNT can also
switch the sensors response polarity. Additionally almost
mirror responses are obtained, i.e. selectivity is quite the same,
whatever the sensing mode (PVC or NVC). Consequently, the
addition of a small amount of MWNT to PaniNP formulations
gives a second route to switch the sensors chemo-electrical
response polarity and also allows enhancing the response
amplitude. Moreover, in the presence of vapour molecules the
resistance increase is immediate and, after removal of vapour
molecules in a pure nitrogen flow, the initial resistance is
quickly recovered within seconds. Additionally all electrical
signals are reversible and reproducible. In almost all cases
signals reached saturation within the cycle time, but for
methanol in figure 9 Ar is still slightly increasing after 600 s,
suggesting that equilibrium conditions are not completely
reached. This phenomenon is often observed when the
affinity of solvent molecules for the transducer is too high or
when the number of diffusing molecules is important. Thus
the diffusing mode tends to be clustering, as discussed in
previous works [24, 25].

4.1.1. Case 1: PaniNP PVC response. In the case of a

PaniNP conducting network, as schematized in figure 10(a)
Case 1, a single polymer phase is responsible for both
electronic conduction and interaction with analytes. Thus the
PVC effect must result from PaniNP disconnection due to
solvent molecule adsorption on their surface and interaction
with the PASSA coating, increasing the gap between them.
6

Nanotechnology 21 (2010) 255501

J Lu et al

polymer transducer films subjected to polar organic vapour

molecules could be partially swollen on their surface (due to
molecular interactions like hydrogen bonding between solvent
and dopant (PSSA) or poly(aniline) macromolecules) and lead
to an increase in conductivity [6, 17, 41]. Moreover, according
to percolation theory, in the vicinity of the threshold, the
connectivity level is so weak that the PaniNP network is only
made of a couple of ohmic conductive pathways, the majority
of PaniNP not being in close contact. In such conditions only
some of the electrons can have enough energy to jump through
this gap by tunnelling. Thus, volume expansion resulting from
PaniNP surface swelling can decrease average interparticle
distance, increasing transducer conductivity and resulting in an
NVC effect. In Case 2 PaniNP are considered as smooth
spheres able to coalesce under expansion; not only their PSSA
shell has been swollen but part of their poly(aniline) core,
allowing interdiffusion of conducting chains. But in fact how
can the swelling contribution be either positive or negative?
It depends on the swelling depth of PaniNP, which in turn
is a function of the amount of VOC molecules relative to
the number of macromolecules available for swelling on the
PaniNP surface. In other words, for a given amount of analyte
molecules, swelling depth will be inversely proportional to
the number of PaniNP. Thus in transducers with a high
concentration of PaniNP (4 and 5%) VOC molecules will
simply adsorb on the surface, whereas for lower amounts of
PaniNP (13%) molecular relaxation or complete swelling will
take place [23, 24, 40]. Finally the NVC/PVC switching
effect can be understood as a transition in the sensing mode,
controlled by swelling thickness of PaniNP.
4.1.3.
Case 3: PaniNPMWNT PVC response.
The
representation of figure 10(c) Case 3 inspired from the
morphology revealed by AFM in figure 4 describes the
sensing mode assumed for the PaniNPMWNT hybrid. The
conducting architecture corresponds to a double percolated
network of PaniNP and MWNT. The light PaniNP network
interconnected by a few MWNT is being expanded upon
analyte diffusion, disconnecting the MWNT network and
thus resulting in a PVC effect.
Such a PVC effect
resulting from poly(aniline) expansion was clearly shown with
other transducers of the same chemical nature but different
architecture, i.e. MWNT coated by poly(aniline) [47].

Figure 10. Different cases explaining (a) Case 1: PVC in PaniNP,

(b) Case 2: NVC in PaniNP and (c) Case 3: PVC in PaniNPMWNT
hybrids.

This is only possible assuming that VOC molecules will not

penetrate too deeply in PaniNP and generate plasticization
and relaxation of macromolecules but only degrade interfacial
conduction. In Case 1 sensing PaniNP are considered as
hard spheres only swollen in their PSSA shell.

4.2. A route to design tuneable chemo-resistive sensors

PaniNP and PaniNPMWNT transducers have demonstrated
their versatility in designing tuneable chemo-resistive sensors.
4.2.1. Tailoring sensing mode. Depending on initial resistance, transducer composition and analyte uconcentration/
PaniNP-specific surface ratio, it is possible to obtain both
NVC/PVC effect sensing modes. Chemo-electrical properties
of sensors can be tailored by varying PaniNP concentration
or by adding a small amount of MWNT to the formulations.
In transducers with resistivities higher than 150 , no
effective conductive network is obtained due to insufficient
interconnection of aggregates; the conduction mechanism is

4.1.2. Case 2: PaniNP NVC response. Conversely, if

VOC molecules can swell PaniNP as depicted in figure 10(b)
Case 2, this will result in volume expansion and interdiffusion
of poly(aniline) macromolecules at the interface between
nanoparticles, leading to an increase in transducer conductivity,
i.e. negative vapour coefficient effect. The NVC effect
(also called n-type sensing) of Case 2 is in agreement with
the literature where it has been observed that conducting
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Nanotechnology 21 (2010) 255501

J Lu et al

Table 2. Solubility parameters of solvent vapours and PaniNP.

Toluene
MeOH
Water
Chloroform
PaniNPa
a

T (J cm3 )1/2

d (J cm3 )1/2

p (J cm3 )1/2

H (J cm3 )1/2

Vmolar volume (cm3 mol1 )

18.16
29.61
47.90
18.95
21.97

18.00
15.10
15.50
17.80
17.40

1.40
12.30
16.00
3.10
8.10

2.00
22.30
42.40
5.70
10.70

106.30
40.70
18.10
79.70

From [48, 49].

mainly governed by a decrease in the tunnelling effect and the

sensing mode will be the NVC effect. In transducers with
resistivities lower than 150 , electronic conduction in the
percolated network being initially ohmic will be degraded by
increasing tunnelling junction number and consequently the
sensing mode will be the PVC effect. Interestingly the best
combination of sensing effects is achieved with an appropriate
double percolated architecture of PaniNPMWNT hybrids that
maximizes sensitivity, reproducibility and selectivity leading
to a positive synergetic effect.
4.2.2. Tailoring selectivity. Whatever the sensing mode
chosen, NVC or PVC, PaniNP-based sensors are selective
towards the nature of the vapour, as can be noticed from
figure 7. As expected from previous works on MWNTfilled polymer nanocomposite sensors [23, 24], the selectivity
of PaniNPMWNT hybrids will be closely related to the
respective interactions of the two constituents with solvent
molecules. Classically this correlation is well expressed by the
FloryHuggins parameter 12 which can be calculated from
equations (2) and (3):

12 =

V
(T
RT

pol

sol )

Figure 11. Correlation between A r and 12 for all PaniNP

transducers plotted from table 3 data.

consequently (according to equation (5)) the higher the

resistivity increase, i.e. relative amplitude of Ar :

(2)

= a ebZ

with V the molar volume of the solvent (cm3 mol1 ); T is

the temperature (K), R = 8.314 J mol1 ; T sol is the solvent
global solubility parameter (J1/2 cm3/2 ); T pol is the polymer
global solubility parameter (J 1/2 cm3/2 ); T is derived from
equation (3) and table 2:

T2 = d2 + p2 + H2

(5)

where is the tunnel resistivity, a and b are positive constants,

and Z is the gap between two vicinal CNTs [51].
Nevertheless surprisingly as shown in figure 11, with
PaniNP transducers, experimental values of Ar are better fitted
with a logarithmic law like equation (6):


1
Ar = C log
(6)
+d
12

(3)

T is the global solubility parameter from dispersion bonds

between molecules (J1/2 cm3/2 ); d is the solubility parameter
from dispersion bonds between molecules (J 1/2 cm3/2 ); p is
the solubility parameter from polar bonds between molecules
(J1/2 cm3/2 ); H is the solubility parameter from hydrogen
bonds between molecules (J1/2 cm3/2 ).
Normally the selectivity brought by the polymer follows
quite well equation (4), expressing the fact that the relative
amplitude will increase if 12 tends to zero, i.e. similar
solubility parameters of both solvent and polymer (see
equation (2)):
b
Ar = a e 12
(4)

where Ar is the relative amplitude, c and d are positive

constants, and 12 is the interaction parameter.
All data (extracted from table 3) follow this evolution
except for some points of PaniNP 1% corresponding to
interactions with methanol vapour which give an overestimated
value for Ar , and PaniNP 5%, which does not show any
peculiar selectivity.
The fact that PaniNP transducers behave totally differently
towards selectivity than classical conductive composite
transducers is a strong indication of the competition between
adsorption/disconnection and swelling/reconnection taking
place during organic vapour diffusion.
Finally these results demonstrate that PaniNP-based
transducer selectivity can be tailored by adjusting the initial
conductivity and addition of MWNT.

with Ar the relative amplitude, a and b constants, and 12 the

interaction parameter.
Thus the smaller 12 , the larger the swelling of the
interphase, inducing an increase of interfiller gap, and
8

Nanotechnology 21 (2010) 255501

J Lu et al

Table 3. 12 FloryHuggins interaction parameter and A r , the relative amplitude of PaniNP-and MWNT-based transducers.

Water
Methanol
Toluene
Chloroform

12[PaniNP]

Ar[PaniNPCNT]

Ar[CNT]

4.906
0.957
0.622
0.295

0.63
0.9
0.28
0.1

0.05
0.1
0.05
0.08

Ar[PaniNP1%]

0.5
0.5
0.2
0.2

Ar[PaniNP2%]

0.4
0.2
0.18
0.1

5. Conclusion

Ar[PaniNP3%]

0.2
0.1
0.18
0.09

Ar[PaniNP4%]

Ar[PaniNP5%]

0.38
0.3
0.05
0.1

0.4
0.5
0.25
0.45

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PaniNP-based chemo-resistive transducers have demonstrated

a high potential for vapour sensing applications. Tailoring the
main chemo-electrical properties, i.e. sensing mode (PVC or
NVC), sensitivity and selectivity toward VOC, can be achieved
by modifying the PaniNP conducting architecture using a
spray LbL process. Simply adjusting PaniNP and MWNT
content in the solution to spray allows us to obtain transducers
with very different characteristics. The most striking features
of PaniNPMWNT hybrids are their NVC/PVC switching
capability, resulting from the intimate association of their
percolated networks well imaged by AFM and their nontraditional selectivity due to the ability of PaniNP to both
coalesce/expand and conduct electrons. Different mechanisms
have been proposed to explain these original behaviours. This
peculiarity makes PaniNPMWNT hybrid transducers good
candidates to be integrated into e-noses, whose principle is
to associate components of very different responsiveness and
selectivity.

Acknowledgments
The authors are grateful to Herve Bellegou for his contribution
to this work. This research was financed by a STAR FrancoKorean collaboration program.

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