Materials Science and Engineering C 25 (2005) 444 447

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Titanium dioxide doped polyaniline

Ji-Chuan Xua, Wei-Min Liub, Hu-Lin Lia,*
a
Department of Chemistry, Lanzhou University, Lanzhou, Gansu 730000, P.R. China
b
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou, 730000, P.R. China

Received 26 February 2004; received in revised form 16 August 2004; accepted 19 November 2004
Available online 7 January 2005

Abstract

Titanium dioxide doped polyaniline has been prepared by in situ polymerization. TiO2 nanoparticles with an average diameter about
20 nm were used as a dopant of polyaniline. The doping effect of TiO2 was characterized and evaluated by scanning electron
microscopy (SEM), Fourier transformation infrared spectroscopy (FT-IR), energy dispersive spectrometry (EDS) and electrical
conductivity measurement. SEM study shows that TiO2 nanoparticles have a strong effect on the morphology of composites. The FT-IR
spectra reveal that the interaction between TiO2 and polyaniline (PANI) is primarily based on the formation of H-bonding. Electrical
conductivity measurements indicate that the conductivity of composites at low TiO2 content is much higher than that of neat PANI,
while with the increasing contents of TiO2, the conductivity shows an orderly decrease.
D 2004 Published by Elsevier B.V.

Keywords: Titanium dioxide; Polyaniline; Composites

1. Introduction For example, polyaniline/V2O5 nanocomposites showed

Conducting polymers have attracted considerable atten-
tion for their wide applications, such as microelectronic
devices, photodiodes, sensors, batteries, and technological
membranes [13]. Among these polymers, polyaniline
(PANI) is unique primarily due to its high chemical
durability and reversible control of conductivity both by
charge-transfer doping and protonation. Generally, polyani-
line has two forms, the emeraldine base (EB) and
emeraldine salt (ES, both polaronic and/or bipolaronic),
which can be intercharged by treating with acid or base [4].
Its electrical conductivity is considered a result of motions
of polarons and bipolarons [5].
In recent years, much research has been conducted on
polyanilines composites with various nanomaterials [69].
* Corresponding author. Tel.: +86 931 8912517; fax: +86 931 8912582.
E-mail address: lihl@lzu.edu.cn (H.-L. Li).
0928-4931/$ - see front matter D 2004 Published by Elsevier B.V.
doi:10.1016/j.msec.2004.11.003
paramagnetism with a CurieWeiss and a temperature
independent van Vleck contribution [10]. Polyaniline/
MnO3 provided a moderate increase in lithium cell capacity
and improved the reversibility of the Li insertion reaction
[11]. Carbon nanotubes (CNT) doped polyaniline exhibited
an order of magnitude increase in electrical conductivity
over neat PANI [12]. Most recently, polyaniline/TiO2
composites [13,14] with high piezoresistivity [15] and
enhanced conductivity [16] were synthesized and studied
as well. However, less attention has been given to the
interaction between PANI and TiO2, even though it is
essential for a deep understanding of composites physical
and chemical properties.
Here, we report the preparation and characterization of
PANI/TiO2 composites by in situ polymerization. TiO2
nanoparticles with an average diameter about 20 nm were
used as a dopant of polyaniline. Much effort has been put
into the investigation of the interaction between PANI and
TiO2 in order to gain a better understanding of the doping
effect of TiO2. Scanning electron microscopy (SEM),
 J.-C. Xu et al. / Materials Science and Engineering C 25 (2005) 444447
Fig. 1. TEM image of as-prepared TiO2 nanoparticles. The inset is the
selected area electron diffraction pattern.
Fourier transformation infrared spectroscopy (FT-IR) and
energy dispersive spectrometry (EDS) were used for
characterization and analysis.
2. Experimental
Aniline and ammonium peroxidisulfate (APS) at ana-
lytical reagent grade were bought from Beijing Chemical
Factory (Beijing, China). The in situ composites were
Fig. 2. SEM images of PANI/TiO2 composites with different contents of TiO2: (a) 5, (b) 25, (c) 50, and (d) 80 wt.%.
445
synthesized by polymerization of aniline with APS as the
oxidant in the presence of TiO2. TiO2 nanoparticles were
prepared by sol-gel method [17]. The as-prepared nano-
particles were suspended in 1 M HCl and sonicated for 30
min to get well dispersed. Then, a solution of 1 M HCl
containing the aniline monomer was added to the suspen-
sion and sonicated for 30 min. The 0.154 M APS in 1 M
HCl solution was then slowly added dropwise to the well
dispersed suspension mixture with a constant sonication at
0d . After three hours, a good degree of polymerization is
achieved and the suspension was in dark green. The
composite was obtained by filtering and washing the
suspension with distilled water, resulting in the conductive
emeraldine salt (ES) form of PANI/TiO2 composites. The
composites were finally dried under vacuum for 72 h. The
different contents PANI/TiO2 composites were synthesized
using 5, 25, 50, 80 wt.% of TiO2 with respect to aniline
monomer.
The as-prepared TiO2 particles were investigated with a
Hitachi 600 transmission electron microscope (TEM). The
morphology and EDS analysis of the composites were
characterized at 20 kV using a JSM-5600LV scanning
electron microscopy (SEM). The FT-IR spectra were
recorded by using a Nicolet Avatar 360 Fourier transform
infrared spectrometer and samples were dispersed in pressed
KBr disks. Conductivity measurements were carried out by
casting the composites on a glass substrate using the four-
point probe method.
446 J.-C. Xu et al. / Materials Science and Engineering C 25 (2005) 444447

3. Results and discussion Table 1

Elemental analysis results of PANI/TiO2 composites with different contents
of TiO2
3.1. TEM investigation of the dopant morphology
TiO2/aniline Cl N Ti Cl/N
monomer (wt.%) (wt.%) (wt.%) (wt.%)
Fig. 1 is the TEM image of as-prepared TiO2 nano-
0 11.2 13.8 0 0.81
particles. It shows the TiO2 particles were about 20 nm in
5 10.3 13.4 2.4 0.77
diameters. The inset is the selected area electron diffraction 25 9.1 12.7 10.3 0.72
(SAED) pattern and it indicates the nanoparticles were well 50 7.7 11.6 19.5 0.66
crystallized as anatase phase. 80 6.3 10.2 32.1 0.62

3.2. Morphology of titanium dioxide doped polyaniline
composites
Fig. 2 shows the SEM images of composites with
different contents of TiO2. It can be seen that the
morphology of composites at low contents 5 and 25 wt.%
are much similar to that of neat polyaniline (not shown),
especially some fibrous microstructure appears clearly at 5
wt.%, which may be due to the low contents of TiO2
nanoparticles. At higher contents 50 and 80 wt.%, the
composites present as particles with diameters about 500
and 300 nm, respectively. It indicates that the TiO2
nanoparticles have a nucleus effect on the polymerization
and caused a homogeneous PANI shell around them. The
decrease in composite particle diameters might be due to an
increase in TiO2 content, which caused a relative decrease in
PANI contents. The SEM images help us draw a conclusion
that the doping of TiO2 has a strong effect on the PANIs
morphology and with the increase of TiO2 contents, the
composites show a transformation in morphology from
typical fibrous PANI to particles.
3.3. FT-IR study on titanium dioxide doped polyaniline
composites
Fig. 3 shows the FT-IR spectra of PANI/TiO2 composites.
The peaks at 14001600, 700 cm 1, which are common to all
samples, are characteristic of the various vibration modes of
the CH and CC bonds of the aromatic nuclei [18,19]. The
band near 3400 cm 1 corresponds to the stretching of the N
H bonds. The band at 1300 cm 1 is assigned to the stretching
of the CN bonds of the aromatic amines.
There is a remarkable difference from the FT-IR spectra
among the different contents of the composites. The NH
stretching region near 3400 cm 1 is apparent in the neat
PANI yet not clear in the composites, and as the content of
TiO2 increase, the peak intensity decreased. This may be
ascribed to that the interaction of TiO2 and PANI was
followed by the formation of H-bonding between the proton
on NH and the oxygen atom on TiO2 surface. The
prevalence of H-bonding weakened the NH as well as its
stretch intensity [12]. As the content of TiO2 reaches 80
wt.%, a OH peak at 3720 cm 1 appears due to the high
content of TiO2 nanoparticles, which have dangling OH
on its surface.
The strong band at 1130 cm 1 was considered to be a
measure of the degree of electron delocalization and thus it is
a characteristic peak of PANI conductivity [5]. It is obvious
that the intensity of this peak increased with the increasing
content of TiO2. This fact may suggest that the doping of TiO2
can facilitate the effective electron delocalization.
3.4. Elemental analysis results from EDS
The doping effect of TiO2 nanoparticles in the compo-
sites is further observed by the elemental analysis from

0.7

0.6
Conductivity (103S.m-1)

0.5

0.4

0.3

0.2

0.1

0.0
0 20 40 60 80
Weight percent of TiO2

Fig. 3. FT-IR spectra of PANI/TiO2 composites with different contents of Fig. 4. Electrical conductivity versus the contents of TiO2 in PANI/TiO2
TiO2: (a) 0, (b) 5, (c) 25, (d) 50, and (e) 80 wt.%. composites.
 J.-C. Xu et al. / Materials Science and Engineering C 25 (2005) 444447
EDS. The N content is used as a reference because it should
be a constant for any dopant in each sample. If TiO2
nanoparticles compete with Cl ions, the Cl/N ratio should
decrease in the presence of TiO2. That postulation is
subsequently proved by EDS results (shown in Table 1).
The Cl/N ratio is 0.81 in neat PANI, while it decreases
orderly from 0.77 to 0.62 with the increasing content of
TiO2.
3.5. Electrical conductivity measurement
Fig. 4 shows the data measured according to the standard
four-point probe technique at room temperature. Compared
to neat PANI, the conductivity of 5 wt.% TiO2 doped PANI
composite increased remarkably from 0.016 103 to
0.704103 S.m 1. This may be attributed to the doping
effect associated with TiO2 nanoparticles that were believed
to help induce the formation of a more efficient network for
charge transport [20], thus enhancing the conductivity of the
composites. However, with the increasing contents of TiO2,
the relative contents of the conducting polymer PANI
decreased, which caused a decrease from 0.704103 to
0.116103 S.m 1 in the conductivity of composites.
4. Conclusions
TiO2 doped polyaniline has been prepared by in situ
polymerization. SEM study shows that TiO2 nanoparticles
have a strong effect on the morphology of composites. The
FT-IR spectra reveal that the interaction between TiO2 and
PANI is primarily based on the formation of H-bonding.
Electrical conductivity measurements indicate that the
conductivity of composites at low TiO2 content is much
higher than that of neat PANI, while with the increasing
contents of TiO2, the conductivity shows an orderly
decrease.
447
Acknowledgement
This work was supported by the National Natural
Science Foundation of China (Grant No. 60171004).
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