Carbon 43 (2005) 734–740

www.elsevier.com/locate/carbon

Preparation and characterization of polyaniline/multi-walled

carbon nanotube composites
a,*
Tzong-Ming Wu , Yen-Wen Lin a, Chien-Shiun Liao b

a
Department of Material Science and Engineering, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 402, Taiwan, ROC
b
Department of Chemical Engineering, Yuan-Ze University, 135 Yuan-Tung Road, Nei-Li, Chung-Li 320, Taiwan, ROC

Received 1 April 2004; accepted 22 October 2004

Available online 8 December 2004

Abstract

This study describes the synthesis of doped polyaniline in its emeraldine salt form (PANI-ES) with carboxylic groups containing
multi-walled carbon nanotubes (c-MWNTs) via in situ polymerization. Both Raman and FTIR spectra indicate that carboxylic acid
groups formed at both ends and on the sidewalls of the MWNTs. Based on the p–p* electron interaction between aniline monomers
and MWNT and hydrogen bonding interaction between the amino groups of aniline monomers and the carboxylic acid group of
c-MWNT, aniline molecules were adsorbed and polymerized on the surface of MWNTs. Structural analysis using FESEM and
HRTEM showed that PANI-ES/c-MWNT composites are core (c-MWNT)-shell (doped-PANI-ES) tubular structures with diam-
eters of several tens to hundreds of nanometers, depending on the PANI content. The conductivities of these PANI-ES/c-MWNT
composites are 50–70% higher than those of PANI without MWNT.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon nanotubes; B. Chemical treatment; C. Raman spectroscopy; D. Microstructure

1. Introduction due to the phase separation between the polymer matrix

and CNTs [12,13]. Recent studies have shown that, be-
Carbon nanotubes (CNTs), discovered by Iijima and sides possibly improving the mechanical and electrical
Ichihashi [1], have attracted considerable interest owing properties of polymers, the formation of polymer/CNT
to their application in fabricating a new classes of ad- composites is considered a useful approach for incorpo-
vanced materials due to their unique structural, mechan- rating CNTs into polymer-based devices [14–17].
ical and electronic properties. They have potential for Among these polymer/CNT composites, many reports
use in field emitters [2], nanoelectronic devices [3,4], have focused on the combination of CNT and conduct-
probe tips for SPMs [5] and nanotube-based composites ing polymers, including poly(p-phenylene venylene)
[6,7]. As expected for theoretical reasons, experimentally (PPV)/CNT [14] or poly(3-octylthiophene)/CNT [15],
introducing CNTs into a polymer matrix improves the for use in highly efficient photovoltaic cells and
electrical conductivity and the mechanical properties poly(3,4-ethylenedioxythiophene) (PEDOT)/CNT for
of the original polymer matrix [8–11]. However, some forming hole-conducting layers in organic light-emitting
reports indicate that the improvements of the mechani- diodes [16].
cal properties of polymer/CNT composites are limit Among various conducting polymers, polyaniline
(PANI) has potential uses in synthesizing polymer/
*
Corresponding author. Tel.: +886 422 872482/840500x806; fax:
CNT composites owing to its environmental stability,
+886 422 857017. good processability and reversible control of conduc-
E-mail address: [email protected] (T.-M. Wu). tivity both by protonation and charge-transfer doping

0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.10.043
 T.-M. Wu et al. / Carbon 43 (2005) 734–740 735

[18,19]. Considerable progress has been made in design- stirring at a reaction temperature of 0–5 °C for 1 h. The
ing and fabricating PANI/CNT composite, with exam- reaction mixture was stirred for a further 2 h at 0–5 °C,
ples including PANI/multi-walled carbon nanotube and then the resulting green suspension, indicating the
(MWNT) composites that exhibit site-selective interac- formation of insoluble polyaniline in its emeraldine salt
tion between the quinoid ring of the polymer and form (designated as PANI-ES), was filtered and rinsed
MWNT [20], the doped PANI/MWNT composite with several times with distilled water and methanol. The
or without protonic acid synthesized via in situ polymer- powder thus obtained was vacuum dried at 60 °C for
ization [21–23], coaxial nanowire of a PANI/MWNT 24 h.
composite prepared by electro-chemical reaction [24]
and the fabrication of PANI/single-wall carbon nano- 2.2. Structural analysis
tube composite [25,26]. Although recent studies indicate
a unique compatibility between PANI and CNT, the The ATR-FTIR spectroscopy, UV–Vis spectroscopy
nature of PANI/CNT remains unclear. and Raman spectroscopy were used to characterize the
This work describes the synthesis and characteriza- structure of PANI-ES/c-MWNT composite. UV–Vis
tion of protonic acid doped PANI with MWNTs fabri- spectra were performed on a Hitachi U-3010 with a
cated by in situ polymerization. The as-prepared scanning speed at 200 nm/min and a bandwidth 0.1 nm.
MWNTs were treated using a 3:1 mixture of concen- The peak position of the UV–Vis spectra was deter-
trated H2SO4:HNO3, as reported by Liu et al. [27], mined using the Peakfit software package. Moreover,
which produced carboxylic acid groups at the defect ATR-FTIR was recorded on a Pike Technologies
sites and thus improved the solubility of the MWNTs ATR 6142, equipped with a ZnSe crystal. Samples in
that contained carboxylic groups (designated as KBr were analyzed at room temperature and undiluted.
c-MWNTs) in HCl solution. Aniline monomers and Furthermore, Raman spectra were recorded with a Ren-
c-MWNTs interact such that nanocomposites of ishaw system 1000 using an Argon ion laser operating at
doped-PANI with c-MWNTs can be synthesized via in 514.5 nm with a CCD detector. The final spectrum pre-
situ chemical oxidation polymerization. The structure, sented is an average of three spectra recorded at different
morphology and conductivity of PANI/c-MWNT com- regions over the entire sample range. Linear h/2h X-ray
posites were characterized: particularly, the tubular intensity scans of these specimens were recorded using a
morphology was first observed and the possible forma- Mac MXT III diffractometer in the reflection mode,
tion mechanism of this nanostructure was also with Ni-filtered CuKa radiation.
discussed.
2.3. Morphological analysis

2. Experimental Field-emission scanning electron microscopy (FES-

EM) and high-resolution transmission electron micros-
2.1. Synthesis of PANI/c-MWNT composites copy (HRTEM) were used to characterize the
morphology of the PANI-ES/c-MWNT composite. An
The MWNTs used in this study were synthesized by ultrathin section of the PANI-ES/c-MWNT sample with
ethylene CVD using Al2O3 supported Fe2O3 catalysts, a thickness of approximate 50 nm was prepared using an
as described in a previous investigation [28]. The purity ultramicrotome equipped with a diamond knife. FES-
of MWNTs was higher than 90% after purification. The EM was conducted at 3 kV using a JEOL JSM-6700F
as-prepared MWNTs were ultrasonically treated using a field-emission instrument and high-resolution transmis-
3:1 mixture of concentrated H2SO4 and HNO3 at 50 °C sion electron microscope (HRTEM), and selected area
for 24 h, producing carboxylic acid groups at the defect electronic diffraction images were recorded on a Hitachi
sites and thus improving the solubility of the c-MWNTs HF-2000 at 200 kV. Due to the high electron density dif-
in HCl solution. ference between carbon nanotuble and polymer matrix,
The composite of protonic acid doped polyaniline sample staining was not required.
(PANI) with c-MWNT was synthesized via in situ
chemical oxidation polymerization. In a typical synthe- 2.4. Electrical properties
sis experiment, various weight ratio of c-MWNTs were
dissolved in 1.0 M HCl solutions and ultrasonicated The samples of c-MWNT, PANI and PANI-ES/c-
over 3 h, then transferred into a 500 ml four-neck flask MWNT composites were pressed into pellet form under
with an ice-bath. Aniline monomer also dissolved in 20 MPa. Moreover, the conductivity at room tempera-
1.0 M HCl solution was added to the above c-MWNTs ture was measured using a programmable DC voltage/
suspension. A 200 ml 1.0 M HCl solution containing current detector (four probe method). The data shown
0.125 M ammonium persulfate (APS) was slowly added here represent the mean measurement values from at
dropwise into the suspension with constant mechanical least three samples.
736 T.-M. Wu et al. / Carbon 43 (2005) 734–740

3. Results and discussion aniline monomers and c-MWNTs causes aniline mole-
cule adsorption on the surface of c-MWNTs. The pro-
Fig. 1 shows the Raman spectrum of the MWNTs tonic acid doped PANI/c-MWNT composites are then
and c-MWNTS. Both spectra have the same pattern, synthesized successfully via in situ chemical oxidation
indicating that treating the surface with a 3:1 mixture polymerization. Fig. 4 presents the X-ray diffraction
of concentrated H2SO4 and HNO3 does not affect the data for c-MWNT, PANI and PANI/c-MWNT com-
graphite structure of the MWNTs and the reaction can posites. For c-MWNTs, the diffraction peaks were ob-
be used to produce carboxylic acid groups at local de- served at 2h = 25.9° and 43°, corresponding to
fects in the curved graphene sheets and tube ends. graphite-like structure, and small amounts of catalytic
First-order Raman spectroscopy shows a strong band particles were encapsulated inside the walls of CNTs,
at 1580 cm 1 (G mode) which is the Raman-allowed respectively [30]. Meanwhile, for PANI samples, the
phonon high-frequency mode and a disordered-induced crystalline peaks appeared at 2h = 9.4°, 15.3°, 20.7°,
peak at 1355 cm 1 (D mode), which may originate from 25.2°, 26.5° and 29.8°, corresponding to (0 0 1), (0 1 1),
the defects in the curved graphene sheets and tube ends. (0 2 0), (2 0 0), (1 2 1) and (0 2 2) reflections of polyaniline
Comparing the IG/ID ratios of the samples, which are in its emeraldine salt form (designated as PANI-ES),
1.72 for MWNTs and 1.58 for c-MWNTs, reveals that respectively [31]. The X-ray data of PANI-ES/c-MWNT
the chemical treatment increases the degree of disorder. composites reveals crystalline peaks similar to those ob-
This finding indicates the presence of defects at both the tained from the pure PANI matrix, indicating that no
ends and the sidewalls of the c-MWNTs. Fig. 2 shows additional crystalline order had been introduced into
the ATR-FTIR spectrum of the MWNTs and c- the composites. The intensity ratio of the crystalline
MWNTs. The peak near 1590 cm 1 corresponds to the peaks for PANI-ES/c-MWNT composites is also close
IR active phonon mode of the MWNTs and the peaks to that for pure PANI. This result reveals that although
at around 1720, 1190 and 1080 cm 1 apparently corre- a very thin amorphous layer exists on the surface of the
spond to the stretching modes of the carboxylic acid c-MWNT, which is probably attributed to the irregular
groups [29]. The above results indicate the formation distribution of the COOH groups on the surface of c-
of carboxylic acid groups at both ends and on the side- MWNTs, and to the interaction between the quinoid
walls of the MWNTs. Fig. 3 presents the TEM image of ring of the polymer and c-MWNT. The c-MWNT fur-
the MWNTs and c-MWNTs. The sidewalls of c-MWNT ther induces the packing of the PANI polymer chains
are very rough and look like leaves that have been eaten along the axis of the c-MWNT, and thus the percentage
by worms. This result reveals the multiple crystalline crystallinity of the outer layer of the PANI-ES/c-
walls with surface defects of c-MWNT, indicating the MWNT composites is almost the same as for pure PANI
possible formation of carboxylic acid groups on the molecules. The mass fraction of c-MWNT in PANI-ES/
sidewalls. The corresponding electron diffraction pattern c-MWNT composites is sufficiently small that the
indicates that this MWNT has a crystalline structure. graphite-like diffraction peaks can hardly be detected
The MWNT modified with carboxylic acid groups for 0.1 wt.% MWNT-containing PANI-ES/c-MWNT
can be used as the self-assembly template for the forma- composites. However, traces of diffraction peaks at
tion of PANI nanostructures. The interaction between 2h = 25.9° were observed as the ratio of c-MWNT

Fig. 1. Raman spectroscopy of MWNT and c-MWNT. Fig. 2. FTIR spectroscopy of MWNT and c-MWNT.
 T.-M. Wu et al. / Carbon 43 (2005) 734–740 737

Fig. 3. HRTEM image of (a) MWNT and (b) c-MWNT (inserted electron diffraction of MWNT).

romolecules encapsulated at the surface of the c-MWNT

(Fig. 5d). This PANI-ES/c-MWNT composite is the typ-
ical core-shell structure, and the c-MWNT serves as the
core and is dispersed individually into the PANI matri-
ces. The aniline monomer is uniformly polymerized on
the surface of the MWNT and forms a tubular shell of
PANI-ES/c-MWNT composites. This tubular morphol-
ogy is first reported for PANI/c-MWNT composites.
Furthermore, the average thickness of the PANI layer
ranges from several tens to hundreds of nanometers,
depending on the PANI content. The inserted in Fig.
5d illustrates the electron diffraction patterns of the
PANI-ES/c-MWNT composites selected from the inter-
face between the PANI and c-MWNT and the outer
area of PANI, indicating that this composite has an
amorphous structure at the interface between the PANI
Fig. 4. X-ray diffraction of (a) c-MWNT, (b) PANI-ES, (c) 0.1 wt.% and c-MWNT and a polycrystalline structure at the out-
MWNT-contained PANI-ES/c-MWNT composite, (d) 0.5 wt.% er layer of PANI. The above data demonstrates the exis-
MWNT-contained PANI-ES/c-MWNT composite and (e) 1 wt.% tence of an amorphous layer in the interface between the
MWNT-contained PANI-ES/c-MWNT composite. PANI polycrystal layer and c-MWNT, which demon-
strates that the aniline monomers were initially absorbed
increased to 1 wt.%, indicating that part of the c-MWNT and randomly polymerized to form the amorphous layer
had not fully interacted with PANI molecules. on the surface of the c-MWNT. After polymerization,
To further confirm the nanostructure of PANI-ES/ they tend to form a regular structure on the surface of
c-MWNT composites, Fig. 5 shows typical FESEM the amorphous layer given increasing aniline monomer
and HRTEM images of the c-MWNTs and 1 wt.% content.
MWNT-containing PANI-ES/c-MWNT composites. Fig. 6 shows the Raman spectra of PANI-ES and
Clearly, a tubular layer of a highly uniformly coated PANI-ES/c-MWNT composites. For comparison, the
PANI film is present on the c-MWNT surface, and the figure also includes the spectrum of c-MWNT, which
diameters of the PANI-ES/c-MWNT composites range contains two strong peaks at 1580 cm 1 and
from several tens to hundreds of nanometers, depending 1355 cm 1. For PANI-ES and PANI-ES/c-MWNT com-
on the PANI content (Fig. 5b). The diameter of the posites, C–H bending of the quinoid ring at 1170 cm 1,
PANI-ES/c-MWNT composites becomes larger than C–H bending of the benzenoid ring at 1260 cm 1, C–
that of the original c-MWNTs after in situ polymeriza- N+, stretching at 1338 cm 1, and C–C stretching of
tion. Closer inspection of HRTEM images (Fig. 5c the benzene ring at 1484 and 1624 cm 1 were observed,
and d) reveals that the resulting PANI-ES/c-MWNT revealing the presence of the doped PANI-ES structures
composites have coaxially tubular structures. These fig- [32,33]. Clearly, these Raman spectra are almost identi-
ures clearly show hollow structure between the two sides cal to those of PANI-ES and PANI-ES/c-MWNT com-
of the multiple crystalline walls and the polyaniline mac- posites, indicating that c-MWNT serves as the core in
738 T.-M. Wu et al. / Carbon 43 (2005) 734–740

Fig. 5. FESEM images of (a) c-MWNT and (b) 1 wt.% MWNT-containing PANI-ES/c-MWNT composite. HRTEM and electron diffraction images
of (c) c-MWNT and (d) 1 wt.% MWNT-containing PANI-ES/c-MWNT composite (insert electron diffraction patterns of the PANI-ES/c-MWNT
composites selected from the interface between the PANI and c-MWNT (pattern i) and the outer area of PANI (pattern ii)).

Fig. 6. Raman spectroscopy of (a) c-MWNT, (b) PANI-ES, (c)

Fig. 7. UV–Vis spectroscopy of (a) PANI-ES, (b) 0.1 wt.% MWNT-
0.1 wt.% MWNT-contained PANI-ES/c-MWNT composite, (d)
contained PANI-ES/c-MWNT composite, (c) 0.5 wt.% MWNT-con-
0.5 wt.% MWNT-contained PANI-ES/c-MWNT composite and (e)
tained PANI-ES/c-MWNT composite and (d) 1 wt.% MWNT-con-
1 wt.% MWNT-contained PANI-ES/c-MWNT composite.
tained PANI-ES/c-MWNT composite and (e) c-MWNT.

the formation of a tubular shell of PANI-ES/c-MWNT teristic absorption peak of the sample of PANI-ES in
composites. N,N-dimethyl formamide (DMF) at approximately
UV–Vis spectroscopy was used to characterize the 450 nm is attributable to polaron-p transition on the
interfacial interaction between polymer and c-MWNT. polyemeraldine chain [34,35], indicating that the result-
Fig. 7 reveals that the c-MWNT sample yields no ing PANI-ES is in the doped state. When the tubular
absorption peak in the 400–800 nm range. The charac- nanostructure of PANI-ES/c-MWNT was formed, the
 T.-M. Wu et al. / Carbon 43 (2005) 734–740 739

Fig. 8. Schematic drawing of the mechanism governing the formation of PANI-ES/c-MWNT composites. The short solid lines and dash line
represents the carboxylic acid group and hydrogen bonding between the carboxylic acid group and aniline hydrochloride, respectively.

characteristic peak assigned to the polaron-p transition PANI matrices. The site-selective interaction between
on the polyemeraldine chain was slightly shifted to a the quinoid ring of the polymer and c-MWNT [20]
smaller wavelength as the c-MWNT content increased, causes PANI polymer chains to be adsorbed at the sur-
revealing the interaction between the quinoid rings of face of the c-MWNT, which thus serves as the core of
PANI-ES and c-MWNT [36]. This result is supported the tubular shell of PANI-ES/c-MWNT composites.
by the data observed from the images of HRTEM. The electrical conductivities of PANI-ES and PANI-
The formation mechanism of PANI-ES/c-MWNT ES/c-MWNT composites were measured using the stan-
composites with the tubular nanostructure is believed dard Van Der Pauw DC four-probe method [37]. The
to involve strong interaction between aniline monomer conductivities of c-MWNT and protonic acid-doped
and c-MWNT. Fig. 8 schematically depicts the forma- PANI in their conductive emeraldine salt form at room
tion mechanism of PANI-ES/c-MWNT composites. temperature were 200 ± 3.4 and 29.6 ± 0.4 S/cm, respec-
The interaction between aniline monomer and c- tively. Meanwhile, the addition of 0.1 wt.% c-MWNT
MWNT is believed to be caused by the presence of the into PANI-ES, the conductivities at room temperature
p–p* electron interaction between MWNT and the ani- dramatically increase from 29.6 ± 0.4 S/cm to
line monomer [31], as well as the hydrogen bond interac- 46.4 ± 0.4 S/cm. With the continuous increase in the
tion between the carboxyl groups of c-MWNT and the content of c-MWNT, the conductivities at room temper-
amino groups of aniline monomers. Such strong interac- ature gradually increase from 46.4 ± 0.4 S/cm for
tion ensures that the aniline monomer is adsorbed on 0.1 wt.% MWNT-containing PANI-ES/c-MWNT com-
the surface of c-MWNTs, which serve as the core and posites to 46.5 ± 0.5, 48 ± 0.4 and 51.8 ± 0.4 S/cm for
self-assembly template during the formation of the tubu- 0.3 wt.%, 0.5 wt.% and 1 wt.% MWNT-containing
lar nanostructure. Although the surface can be treated PANI-ES/c-MWNT composites, respectively. The con-
with a mixture of concentrated H2SO4 and HNO3 to ductivities of PANI-ES/c-MWNT composites with 0.1–
produce carboxylic acid groups at local defect sites of 1 wt.% c-MWNT content at room temperature are 50–
c-MWNTs, and to increase the solubility of c-MWNTs 70% higher than those of PANI-ES without c-MWNT,
in HCl solution, some c-MWNT bundles remain ran- perhaps because MWNTs have a large aspect ratio
domly configured. Consequently, some gaps may exist and surface area, and so may serve as a ‘‘conducting
between individual c-MWNTs to allow the aniline mol- bridge’’ between the PANI-ES conducting domains,
ecules to wriggle into such gaps, followed by in situ increasing the effective percolation.
polymerization due to the strong p–p* electron/hydro-
gen bonding interaction between MWNTs and aniline
monomers. The growing PANI polymer chain would 4. Conclusions
wedge away the MWNT bundles and then break
down the bundles into individual MWNTs. In this case, PANI-ES/c-MWNT composites were prepared via
c-MWNTs are uniformly and individually dispersed into the in situ polymerization. MWNTs that contained
740 T.-M. Wu et al. / Carbon 43 (2005) 734–740

carboxylic acid groups were used as a core in the forma- [15] Kymakis E, Amaratunga GA. Single-wall carbon nanotube/
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Acknowledgments
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