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available at www.sciencedirect.com

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

The influence of single-walled carbon nanotube

functionalization on the electronic properties of their
polyaniline composites
E. Lafuentea, M.A. Callejasb, R. Sainza, A.M. Benitoa, W.K. Masera, M.L. Sanjuanb,
D. Saurelc,1, J.M. de Teresab, M.T. Martneza,*
a

Instituto de Carboqumica, CSIC, Miguel Luesma Castan, 4, E-50018 Zaragoza, Spain

Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
c
Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Zaragoza, Spain
b

A R T I C L E I N F O

A B S T R A C T

Article history:

The in situ preparation and characterization of composites of polyaniline (PANI) and sin-

Received 26 April 2008

gle-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and com-

Accepted 30 July 2008

patibility with the polymer matrix the raw SWCNTs were modified following different

Available online 8 August 2008

routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation,
respectively) were subjected to covalent functionalization with octadecylamine (ODA).
SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA
functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultravioletvisible (UVvis), UVvis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements
were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical
conductivity indicating a better interaction with polyaniline than ODA functionalised
SWCNTs. The improvement of conductivity is attributed to the doping effect or charge
transfer of quinoide rings from PANI to SWCNTs.
 2008 Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon nanotubes (CNTs) have unique mechanical, electrical,

magnetic, optical and thermal properties [1,2] and are being
studied for some special applications where high-performance materials are required. Fields of application include
molecular electronics and advanced materials for aerospace,
molecular sensors and biomedical applications [3].

Synthesis and investigation of composites based on conducting polymeric matrices containing carbon nanotubes
are currently very popular topics in the field of materials science and are being considered of theoretical and practical
interest. Polymer/CNT composites are expected to have the
good processability characteristics of the polymer and the
excellent functional properties of the CNTs. Many polymers have been used as matrix materials in carbon

* Corresponding author: Fax: +34 976733318.

E-mail address: mtmartinez@carbon.icb.csic.es (M.T. Martnez).
1
Present address: Nanoscale Superconductivity and Magnetism and Pulsed Fields Group, Institute for Nanoscale Physics and
Chemistry (INPAC), K.U. Leuven, 200D, 3001 Leuven, Belgium.
0008-6223/$ - see front matter  2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2008.07.039

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nanotube/polymer composites for various target applications

[48]. Among them, polyaniline, a conducting polymer, has
achieved widespread importance because of its good processability, electrical conductivity, and environmental stability
[9,10].
The formation of nanotube/polymer composites is considered as a promising approach to effective incorporation
of carbon nanotubes into devices with possible synergetic effects [11,12]. The critical challenge, however, is how to enhance dispersion and alignment of CNTs in the matrix. The
quality of the composites depends on the dispersion of carbon nanotube in the polymer matrix or homogeneity of the
material. Their insolubility and poor compatibility with the
polymer make the uniform dispersion of carbon nanotubes
in the polymer matrix very difficult [13], and the resulting
inhomogeneous nanocomposites often have unsatisfying
properties. To overcome this problem, chemical modification
of the carbon nanotube surface is expected to play an essential role in disrupting the rope structure and adding reactive
species to the nanotube to improve interfacial bonding and
charge transfer in composites. After functionalization, using
functional groups attached to the surfaces, carbon nanotubes could react readily with other chemical reagents to
form homogeneous dispersions or even well aligned
materials.
In the literature [1416], several oxidant reagents can be
found, such as potassium permanganate, HNO3, H2SO4, aqua
regia, superacid HF/BF3, aqueous OsO4, OsO4NaIO4, etc.,
which have been tried to attach functional groups to nanotube surfaces. In our work, the raw material was subjected
to oxidation by refluxing nitric acid and by heating in air
based on the experience acquired in previous studies
[17,18]. The nitric acid treatment introduces defects on the
nanotube surface [19], oxidizing (hole doping) the carbon
nanotubes and producing impurity states at the Fermi level
of nanotubes [20]. Besides, the open ends of SWCNTs become
terminated with carboxylic acid groups [16,21,22]. Further
works have shown that the extent of carboxylic acid incorporation into SWCNTs is much greater than would be anticipated on the basis of end-group functionalization alone; the
extra functionality has been attributed to defect sites in the
walls of SWCNTs [2225].
The carboxylic acid moieties created upon treatment under oxidative conditions (heating in air and/or nitric acid
treatment) are going to allow covalent linkages of oligomers
or polymers with nanotubes [21,23,2633], more precisely carbon nanotubebound carboxylic acids can be used to attach
aminopolymers by means of formation of amide linkages
[3033]. The use of polymers that are structurally and property-wise close to the matrix polymer ensures compatibility
of the dispersed carbon nanotubes with the polymer matrix
to avoid impurities associated with the dispersion agents
and any potential microscopic phase separation in the nanocomposites [34,35].
To this purpose, in the present paper, the material with the
highest concentration of surface oxygen groups was treated
with thionylchloride to reaction with one amine (octadecylamine) in order to reach a better nanotube dispersion and
therefore to get an aniline composite with higher homogene-

ity. The stability of the raw and functionalized CNTs dispersions have been tested in several polar solvents.
The oxidized and functionalizated materials and the final
composites have been characterized by temperature programmed desorption (TPD), ultravioletvisible (UVvis), UV
vis with near infrared (IR), Raman spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and conductivity measurements.

2.

Experimental

2.1.

Raw materials

SWCNT material used in this study has been prepared by arcdischarge using Ni/Y (2/0.5 at.%) as catalyst in the graphite precursor in conditions previously described [36], and it contains
12.8 wt.% Ni and 1.7 wt.% Yof metallic composition. Nitric acid
(37%), thionylchloride, octadecylamine, aniline and ammonium persulphate (99%) were purchased from SigmaAldrich.

2.2.

Oxidation of single-walled carbon nanotubes

SWCNT material was treated in different oxidation conditions: in the gas phase with air at 300 and 350 C for 1 h and
in the liquid phase with 1.5 M nitric acid at reflux for 1 and
2 h. Before being characterized, the materials oxidized in
the liquid phase were subsequently centrifuged (10,000 rpm
for 4 h) and the supernatant acids were decanted off. The sediments were re-suspended in deionized water, three times
centrifuged, decanted and finally vacuum filtered on a 3 lm
pore polycarbonate filter membrane. After this, they were
dried in an oven at 383 K for 1 h.
The original SWCNT material will be named as S1 and the
oxidized samples as follows: S2 are SWNTs oxidized with air
for 1 h at 300 C; S3, SWNTs oxidized with air for 1 h at 350 C;
S4, SWNTs oxidized with 1.5 M nitric acid for 1 h at reflux; S5,
SWNTs oxidized with 1.5 M nitric acid for 2 h at reflux.

2.3.
Functionalization of the oxidized single-walled carbon
nanotubes
We have selected the oxidized single-walled nanotubes (oSWCNTs) with the highest concentration of functional groups
to treat them with thionylchloride in order to convert the carboxylic acid groups into acylchloride ones. The acid chloridefunctionalized SWCNTs were bonded to octadecylamine
(ODA). Chen et al. [21] showed that SWCNTs derivative with
this amine formed stable dispersions in organic solutions
(chloroform, dichloromethane, benzene, toluene, chlorobenzene, 1,2-dichlorobenzene and CS2). A quantitative comparison of the solubility of pristine SWCNTs and f-SWCNTs in
several of these polar solvents; chloroform, dichloromethane,
benzene, toluene and THF was performed. 25 mg of SWCNT
material was dispersed in 200 ml of the selected solvent by
sonication for 2 h; the dispersion was left to settle for 48 h;
then the decanted top 150 ml of the solution was filtered
through a polytetrafluoroethylene membrane of 0.2 lm pore;
finally, the filtered solution, containing soluble SWCNT, was
characterized.

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2.4.

Composites preparation

Polyaniline/nanotube composites from oxidized and

functionalizated material have been synthesized by an
in situ polymerization process, previously reported by the
authors [37]. A 5 wt.% of SWCNT material with respect to aniline monomer was used and the following samples were prepared: C1 composite from amine functionalizated S3 sample
(f-S3); C2 composite from amine functionalizated S5 sample
(f-S5); C3 composite from oxidized sample with air (S3); C4
composite from oxidized sample with nitric acid (S5).

2.5.

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Characterization techniques

Thermogravimetric analysis and the study of the oxygen content were used to confirm the degree of oxygen functionalization in the oxidized materials. Thermogravimetry was
conducted in an inert atmosphere (N2, 90 cc/min) using a
Setaram thermogravimetric analyser, TGADTA 92-16.18, in
the 251250 C range at 6 K/min of heating rate. The surface
oxygen groups were characterized by temperature-programmed desorption (TPDQMS). For the analysis of the gases
evolved during thermolysis (amounts of CO and CO2), the
Setaram thermogravimetric analyzer was coupled to a quadrupolo mass spectrometer (Balzers Omnistar 422).
All materials were further characterized by elemental
analyses with a Carlo Erba 1108 Elemental Analyser. The oxygen content was determined by microanalysis.
The suite of characterization protocols includes UV and
Raman spectroscopy. Raman experiments were performed in
a Dilor XY spectrometer with a liquidnitrogen cooled CCD
detector. Light at 514.5 nm was focused onto the sample
through a 50 microscope objective lens. To avoid sample
damage, the power at the sample was kept lower than 4 mW.
Raman frequencies were calibrated in the region of the radial
breathing modes with the Si line at 520 cm 1 and, in the region
of the tangential modes, with the peak of HOPG at 1582 cm 1.
The estimated accuracy was 1 cm 1. The spectral resolution
was better than 3 cm 1. Several spectra were taken in each
sample, at different points, to test the sample homogeneity.
Solutions stability control was carried out by UVvis with a
Unicam UV4 UVvis spectrometer at 200600 nm range. The
ultravioletvisible and near infrared spectra of solutions were
carried out in a Perkin Elmer UV/vis/NIR spectrometer with a
swept area between 200 and 2260 nm.
The structural characteristics of the materials have been
analyzed by X-ray powder diffraction measurements. These
measurements were carried out in a Bruker D8ADVANCE diffractometer in a qq configuration. The radiation Ka of Cu was
used as source of X-ray, a secondary monochromator of
graphite and a twinkling detector of NaI (Tl). The sweeping
of angles was carried out between 3 and degrees, to 0.5 degrees for step, and the time per step was of 5 s in all experiments carried out.
The qualitative identification of the crystalline phases
present in the sample was carried out using the EVA V 8.0 program of the DIFFRAC plus package of Bruker AXS, for comparison with diffractograms of the powder diffraction database
(PDF) 2002.

To show sidewall modifications, roping interactions and

the obtained dispersion, the materials were analyzed by
TEM in a Philips CM-30 300 kV equipment, after dispersing
the samples in ethanol in an ultrasound bath during 10 min
and by SEM in a HITACHI S3400 N equipment.
The conductivity measurements have been carried out by
means of the four-probe technique and it allows to measure
resistances ranging from 10 3 X to 109 X. The powder samples
were pressed under 1 GPa at room temperature and cut in
pieces with size 10 mm 2 mm 2 mm. Four silver paste contacts were used for the measurements with a U236 keithley
current/voltage source-meter. In order to carry out measurements as a function of temperature, the samples are mounted
in a probe that is placed inside a cryostat of helium flow,
which allows varying temperature in the range of 4.2 K up
to 300 K.

3.

Results and discussion

3.1.
Oxidized (o-SWNTs)
(f-SWNTs) samples

and

ODA

functionalized

The characterization of the o-SWNTs materials indicated

that more severe oxidation conditions (longer time, S5, or
higher temperature, S3), lead to higher oxygen content indicating a higher oxidation degree (Table 1, Supplementary
material). Thermal degradation analyses (TGA) of the oSWCNTs coupled with on-line monitoring of the volatile
products by a mass spectrometer showed different defunctionalizing behavior depending on the oxidation treatment.
The CO2 profile of samples from liquid phase treatment (S4
and S5 samples) presented higher broad desorption bands
at low temperatures while oxidation in the gas phase (S2
and S3) induces a sharp CO2 peak at higher temperatures
indicating different oxygenated groups (Fig. 1, Supplementary material). S5 and S3 samples have the highest number
of oxygenated functional groups of each treatment, liquid
and gas phase, respectively and were selected for further processing with thionyl chloride and ODA to form the corresponding amide bonds.
The o-SWNTs and f-SWCNTs were characterized by Raman
and infrared spectroscopy. The Raman spectra of raw, oxidized
and functionalized SWNTs are presented in Fig. 1. These spectra show the typical features of SWCNTs: tangential modes (or
G-bands), between 1500 and 1600 cm 1, and radial breathing
modes (see upper inset), at wavenumbers ranging from 140
to 200 cm 1 for the catalysts and excitation wavelength used
in this work. Weak D-bands, due to CNT defectivity, are also
observed (see lower inset).
As compared to pristine SWCNTs (sample S1), the main
characteristic of the spectra of oxidized samples (S3 and S5)
is the enhancement of the D-band intensity, relative to that
of the G-band. This effect is slight for the air oxidized sample,
S3, and more pronounced in the spectrum of the HNO3 oxidized sample, S5, indicating that this treatment is more
harmful to the CNT crystallinity. The radial to tangential
mode intensity, however, is approximately constant in all
spectra, and the radial breathing modes (RBM) also preserve
the band structure typical of SWCNT bundles.

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Raman Intensity (arb. units)

RBM

b
f-S3

S1
S3
S5

100

150

200

250

f-S5

S1
100

S3

200

250

S5

S1 1250

150

1300 1350 1400 1450

f -S3

S3

f -S5

S5
1200

1300

1400

1500

1600

1700

18001200

1300

1400

Raman shift (cm-1)

1500

1600

1700

1800

Raman shift (cm-1)

Fig. 1 Raman spectra (kexc = 514.5 nm) of raw SWCNTs material (S1), oxidized with air at 350 C (S3), oxidized with nitric acid
2 h (S5) and functionalized samples (f-S3, f-S5).

(a)

Absorbance (arb. units.)

In f-samples the radial breathing modes appear broader

and with lower resolution than those in oxidized samples.
We also observe that the radial to tangential mode ratios have
decreased in the f-samples. Both effects are attributed to two
possible reasons: (i) a steric one, according to which functionalization or remaining, non-bonded material in the proximity
of the SNWT surface, would hinder the radial vibrations but
not the tangential ones, and (ii) a variation of the resonance
conditions due to a disorder-induced broadening of the electronic transitions involved in the resonant process, that
would affect the radial breathing modes more than the tangential ones. In agreement with this explanation, it can be observed that the D-band increases in relation to the G-band in
the functionalized samples, indicating a higher structural
disorder.
The infrared spectra of SWCNTs (pristine, o-SWCNTs and
f-SWCNTs) as well as the spectrum corresponding to ODA
are shown inFig. 2. The spectrum of raw SWCNTs shows vibrational modes corresponding to C@C bonds at 1580 cm 1,
assigned to the phonon modes of nanotubes [38,39] besides
COR groups at 1190 cm 1. After the air-oxidation treatment
(S3), it is observed that the intensity of the band at 1580 cm 1
increases slightly and that the intensity of the band to
1190 cm 1 remains. It is also possible to observe a small band
at 1720 cm 1 corresponding to the acid carboxylic groups
(C@O), indicating the existence of these functional groups.
The acid treatment (S5) produces a displacement of the band
corresponding to COR groups to 1235 cm 1 and a considerable increase of the intensity of the bands at 1580 cm 1
and 1720 cm 1, indicating an increase of acid carboxylic
(C@O) functional groups.
The functionalization of oxidized samples with octadecylamine (f-S3 and f-S5) produces the appearance of bands corresponding to: CH bonds at 1470 cm 1, 2847 cm 1 and
2921 cm 1, NH bonds at 1574 cm 1 and C@O bonds corresponding to amide carbonyl groups at 1644 cm 1. All these
bands are due to NH(CH17)CH3 group coming from ODA. It
is also possible to observe that the band at 1190 cm 1 corresponding to COR groups stays. All samples present a wide
band at 3450 cm 1 attributed to the presence of OR-H groups
coming from water adsorbed from atmosphere.

S1
S3
S5
f-S3
f-S5
ODA

4000

3500 3000

2500

2000 1500

1000

500

Wavenumber (cm -1 )
Fig. 2 IR spectra of raw, oxidized and functionalizated
SWCNTs material.

The stability of ODA functionalized SWNT samples tested

in five different solvents (chloroform, dichloromethane, benzene, toluene and THF) improved considerably. Functionalized carbon nanotube samples formed dark-coloured
homogeneous solutions being these solutions stable, without
any precipitation over time. Since solutions with pristine
SWCNTs were nearly colourless, the dark solution colour
served as a visual indicator of the improvement of the solubility of these functionalized SWCNTs (Figs. 2 and 3, Supplementary material). Chloroform was found to be the best
solvent for f-SWCNT.
Absorbance measurements of SWNT dispersion in the five
studied solvents using UVvis with near IR spectroscopy were
carried out six months later. The peak positions obtained for
the three samples (S1, f-S3 and f-S5) in chloroform, dichloromethane, benzene, toluene and THF (Table 2, Supplementary
material) are comparable with the electronic transitions of
SWCNTs reported in the literature [40].

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Composites

Raman Intensity (arb. units)

3.2.

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The material balances of composites (Table 3, Supplementary

material) are above 98%, which indicates that in the process of
PANI formation the acid treatment leads to elimination of the
greatest part of metal. They also indicate that the chloride
content is low. On the other hand, the nitrogen percentages
in the prepared composites are between 11.6 and 12.4, what
indicates that the Cl/N relationship is quite lower than the
one existing in PANI. This theoretical Cl/N relationship in PANI
is 1.26 wt.% [41]. The decrease of Cl/N relationship in presence
of carbon nanotubes has been already reported by Zengin et al.
[42] and attributed to the doping effect of CNTs.
The structural characteristics of the four composites have
been analyzed by X-ray powder diffraction measurements
and are shown in Fig. 3. In this figure, the PANI diffractogram,
which shows the highly pronounced oscillation structure
characteristic of the doped form (emeraldine salt) with an
oxidation degree of 0.5 [43] as well as the f-SWCNTs diffractograms are shown.
C1 and C2 composites (Fig. 3a) display the typical peaks of
emeraldine salt as well as the peaks of f-SWCNTs at low angles but not those at higher angles corresponding to Ni and
NiO confirming the decrease of metal content due to the acid
treatment in both the oxidation pre-treatment and the composite formation. The peak of graphitic carbon typical of carbon nanotubes samples at 2h = 26 is also masked. This is
probably due to the low SWCNTs weight percentage used in
the composite. This behavior was observed by the authors
in a previous work [13]. In Fig. 3b it can be observed that the
four composites display similar diffractograms with the typical peaks of emeraldine salt. Besides, in C3 and C4 the peaks
corresponding to NiO and Ni at angles of 45, typical of oSWCNTs, are observed. In conclusion we can state that from
a structural point of view, no additional order due to the presence of CNTs has been introduced.
The composites were also characterized by microRaman
Spectroscopy (Fig. 4) with klaser = 514.5 nm. Reference Raman
spectra for PANI in its different forms at this wavelength were
taken from the literature [44,45]. According to those works,
the most sensitive spectral regions, with bands shifting mark-

160

Lin (Cps)

120

Cg

edly depending on the PANI sate, are a doublet at 11601180,

and the bands around 1330 and at 1485 cm 1.
At the optical microscope, all composite samples looked as
inhomogeneous mixtures of two types of material, with green
and dark grey color, respectively. Green regions gave the spectrum (a), typical of PANI in its EB form [44,45]; no SWCNT
bands were detected in these regions, either in tangential or
RBM ranges. On the contrary, grey-color areas gave spectra
that could be explained as superposition of SWCNT and PANI
bands, with relative intensities varying in different points of
the sample. Spectra (b) and (c), corresponding to composites
C3 and C1, respectively, are examples of that situation. As
shown in Fig. 4, the bands of PANI in the grey areas, i.e. in regions containing a high concentration of SWCNTs, differ from
those found in the green regions, which suggests that the
form of PANI has changed due to interaction with the
SWCNTs. The most remarkable differences are the following:
(i) Enhancement of the high frequency component of the
11601180 doublet.
(ii) Strong decrease of the 1485 cm 1 band.

Ni
NiO

Ni

20

1440 1520 1600 1680

Fig. 4 Raman spectra of: (a) PANI in its EB form; (b) C3 and
(c) C1 composites.

80

40

1280 1360

-1

100

60

(c)

Raman shift (cm )

PANI
f-S3
f-S5
C1
C2

140

(b)

1200

X- ray Intensity (arb. units.)

180

(a)

NiO

b
C4
C3

C2
C1

0
10

20

30

40

50

2-Theta-Scale

60

70

80

10

20

30

40

50

60

70

2-Theta-Scale

Fig. 3 X-ray diffractograms of (a) PANI, f-SWCNTs, C1 and C2 samples, (b) C1, C2, C3 and C4 composites.

80

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(iii) Bands at 13001350 cm 1 seem to increase their relative

intensity, but since they appear superposed to the Dband of SWCNTs, this is difficult to estimate.

Absorbance (arb. units)

These changes indicate that, on bonding to SWCNT, PANI

has adopted the ES form and that green regions arise from
non-SWCNT-bonded PANI-EB.
The infrared spectra of the four composites are shown in
Fig. 5. The IR spectra show the bands characteristics of polyaniline and in the case of the C1 and C2 samples, bands at
2847 cm 1 and 2921 cm 1 corresponding to CH bonds
coming from f-SWCNTs are present. The absorption at
15501600 and 1465 cm 1 is related to C@C groups of quinoide
ring and C@C groups of benzenoide ring respectively and the
band at 1300 cm 1 is assigned to CN bonds of secondary aromatic amines. The band at 1130 cm 1 corresponds to the

4000

C1

C4

C2

(b)
C3

3000

2000

1000
-1

Wavenumber (cm )
Fig. 5 IR spectra of C1, C2, C3 and C4 composites.

N@Q@N bond. It reflects the degree of electronic delocalization and it is characteristic of polyaniline conductivity [46].
This can suggest that strong interaction between f-SWCNTs
and PANI facilitates the effective electronic delocalization,
and is the reason for the increase of the conductivity of the
polymeric chains. The presence of these bands confirms the
presence of the doped form of PANI in composites in spite of
the low content in chlorides that it is deduced from elemental
analysis and confirms the doping effect of the CNTs. Finally,
the absorption at 800820 cm 1 is related with CH bonds outside of the deformation plane of para-di-substituted benzene
rings. The samples present a wide band at 3450 cm 1 typically attributed to the presence of OH groups coming from
water adsorbed from the atmosphere, and for the composites
and they are also attributed to NH bonds.
To examine the nanotube dispersion in the polymer matrix at the nanoscale, the composites were analyzed by SEM
and TEM. The SEM images (Fig. 6), clearly show the presence
of entangled fibrous structures (SWCNTs) at the edge or borders of polymer.
TEM images of C1 and C2 composites are shown in Fig. 7a
and b, respectively where functionalized SWCNTs absorbed in
the polymer matrix can be seen. For composites, TEM analysis is hindered by a lack of sufficient contrast between the dispersed f-SWCNTs and the polyaniline matrix background and
by a large amount of polymer on the nanotube surface that
makes them show bundles of higher size. These TEM images
confirm that the surface of SWCNTs is covered by a great
quantity of polymer, as corresponds to the high polyaniline
content of composites.
PANI/SWCNTs interaction could facilitate the charge
transfer process between them and, in this way, influence
the transport properties of composites. The influence of the
different SWCNTs used on the electric conductivity of composites was determined by performing measurements of

Fig. 6 SEM images of (a) C1, (b) C2, (c) C3, and (d) C4 composites.

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1915

Fig. 7 TEM images of (a) C1 and (b) C2 composites.

Resistivity (ohmcm)

resistivity versus temperature for the four composites, raw

SWCNTs and PANI (Fig. 8). Raw SWCNTs presents the lowest
resistivity, and in consequence, higher conductivity in the
whole range of temperatures between 298 and 5 K. Both polyaniline and as-prepared composites, contrary to what happens in metals [47], present a resistivity increment with
temperature decrease, as it occurs in conductive polymers.
The composites, with a 5% of SWCNTs content, present
higher conductivity than polyaniline in the whole temperature range except C4 that shows lower conductivity at temperatures above 125 K. However, the increase of the
conductivity compared to PANI presents differences due to
characteristics of different types of SWCNTs used. The C4
composite presents the worst conductivity of four composites
obtained by in situ polymerization. This is attributed to the
C4 composite being obtained from the S5 sample (SWNTs oxidized in acid media), which has higher quantity of amorphous carbon or defective CNTs, is more compact and
presents worse dispersion in the polymeric matrix than the
rest of composites. This can hinder the charge transfer between nanotubes and PANI. The C2 composite, obtained from
f-S5 (ODA functionalized S5 sample), presents an improve-

10

10

10

10

10

10

10

10

10

10

10

ment of conductivity in relation to the C4 composite because

ODA functionalization of SWCNTs improves CNTs dispersion
in the polyaniline matrix. The C1 composite presents a similar conductivity to C2 composite (obtained from ODA functionalized S3 sample), because both composites come from
ODA functionalized SWCNTs, although they differ in the oxidation treatment carried out prior to ODA functionalization.
This behavior seems to indicate an improvement of the dispersion of nanotubes in polymeric matrix by ODA functionalization and a good interaction between the polymer and the
nanotube. Nevertheless, C3 composite presents the best conductivity values of four composites. This seems to indicate
that the oxygen functionalized surfaces of nanotubes by air
oxidation provide a better interaction with polyaniline. In
the same way, the negative charge transfer of SWCNT surface
could be favoring the doping of PANI acting in a similar way to
chlorides, allowing a better interaction [42]. The improvement
of conductivity is attributed to the doping effect or charge
transfer of quinoides rings from PANI to CNTs [42]. Carbon
nanotubes act as electron acceptors while PANI is considered
a good electron donor. On the other hand, due to high length/
diameter relationship CNTs can act as conductive bridges
connecting conductive domains of polyaniline and thus
increasing the effective percolation.

4.
PANI
C4

C3

C2

C1

SWNTs

-1

100

200

300

Temperature (K)
Fig. 8 Resistivity dependence with temperature in C1, C2,
C3, C4, SWCNTs and PANI samples.

Conclusions

SWCNTs oxidation leads to an increase in carboxylic acid

groups after nitric acid treatment, whereas gas phase oxidation increases anhydride, lactone, phenol and carboxyl/quinone surface groups. In terms of total oxygen content, the
results obtained by TPD agree well with the elemental analyses of oxidized materials, the acid treatment samples having
the highest oxygen content.
The solubility of f-SWCNTs in common organic solvents,
as revealed by the solution colour and absorption spectra,
has been improved compared to the raw SWCNTs material.
Also, in the UVvis and near IR absorption spectra of these
samples in chloroform and THF, peaks in the range 1127
2258 cm 1 appear, corresponding to electronic transitions of
semiconductor nanotubes. This seems to indicate that the
solutions present semiconductor SWCNTs mainly.

1916

CARBON

4 6 ( 2 0 0 8 ) 1 9 0 9 1 9 1 7

Electrical transport properties of composites based on

functionalizated carbon nanotubes have been measured confirming the formation of a true composite material with enhanced electronic properties. The electric conductivity of
pristine SWCNTs and composites diminishes with the decrease of temperature as occurs in the conductive polymers.
The SWCNT composites prepared with f-SWCNTs present
better conductivity than pure PANI but slightly lower than
the C3 composite prepared with SWCNTs oxidized to air.
The highest conductivity of C3 composite is interpreted to
be a consequence of a better interaction of S3 sample with
the polyaniline. The negative charge of carboxylic functional
groups would be favoring the PANI doping.
The successful fabrication of high-quality composites reflects that the SWCNT functionalization with ODA improves
the solubility and processing of nanotubes, enabling their
incorporation into polymer composite materials through
chemical bonding to the surrounding matrix via terminal
functional groups on nanotubes. Primary functionalization
with carboxylic groups by air oxidation seems to provide the
best interaction with PANI matrix leading to the highest value
of composite conductivity.

Acknowledgements

[9]

[10]
[11]

[12]

[13]

[14]
[15]

[16]
[17]

This work was sponsored by the Spanish DGICYT projects

PETRI 95-0771.OP, MAT2004-03070-C05-03 and Aragon
Government project DGA (BOA, 03.12.04) PM 046.

[18]

Appendix A. Supplementary material

[19]

Supplementary data associated with this article can be found,

in the online version, at doi:10.1016/j.carbon.2008.07.039.
[20]

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