Materials Science and Engineering B 134 (2006) 919

Review
Synthesis and applications of one-dimensional
nano-structured polyaniline: An overview
Donghua Zhang
a,
, Yangyong Wang
b
a
School of Materials and Chemical Engineering, Xian Technological University, Xian 710032, PR China
b
School of Energy and Power Engineering, Xian Jiaotong University, Xian 710049, PR China
Received 9 February 2006; received in revised form 28 July 2006; accepted 28 July 2006
Abstract
This paper summarizes and reviews the various synthesizing approaches of one-dimensional nano-structured polyaniline (PANI) and several
potential applications of the nanomaterial. The synthesizing approaches can be generally categorized into template synthesis and non-template
synthesis according to whether template(s), hard (physical template) or soft (chemical template), is (are) used or not. However, though the various
approaches established, preparation of one-dimensional nano-structured PANI with controllable morphologies and sizes, especially well oriented
arrays on a large scale is still a major challenge. Furthermore, the formation mechanisms of the nanostructures are still unclear. On the other hand,
one-dimensional nano-structured PANI exhibits high surface area, high conductivity, as well as controllable chemical/physical properties and good
environmental stability, rendering the nanomaterial promising candidate for application ranging from sensors, energy storage and ash welding to
digital nonvolatile memory.
2006 Elsevier B.V. All rights reserved.
Keywords: Polyaniline; Synthesis; Template; Nanober; Nanotube; Nanowire; Surface area; Sensor
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.1. Hard template synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2. Soft template synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3. Combined soft and hard template synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.4. Seeding polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5. No-template synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5.1. Interfacial polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5.2. Radiolytic synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.3. Rapid mixing reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.4. Sonochemical synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.5.5. Electrochemical approach. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1. Sensor application. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. Energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.3. Field emission application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.4. Flash welding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.5. Digital nonvolatile memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Corresponding author.
E-mail address: victordhzhang@126.com (D. Zhang).
0921-5107/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.07.037
10 D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919
5. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1. Introduction
Intrinsically conducting polymers, including polyacetylene,
polyaniline (PANI) (Fig. 1), polypyrrole, polythiophene, poly
(p-phenylene-vinylene), etc., are termed organic polymers that
possess the electrical, electronic, magnetic, and optical proper-
ties of a metal while retaining the mechanical property, process-
ability, etc. commonly associated with a conventional polymer,
and more commonly known as synthetic metals [1]. Of these
polymers, PANI has elicited the most interest since its electric
conductivity was found by MacDiarmid et al. [2] in 1985, due
to its wide range of conductivity from insulating to metallic
regime, unique redox tunability, good environmental stability,
low cost, ease of synthesis, and promising applications in var-
ious elds, such as metallic corrosion protection [3,4], electro-
magnetic interference shielding [5], electrostatic discharge [6],
sensors [7], actuators [8], to mention just a few. PANI and its
derivatives are generally synthesized by chemical or electro-
chemical oxidative polymerization of the monomers, although
some other approaches such as plasma polymerization [911],
electroless polymerization [12,13] and solid-state polymeriza-
tion [14,15] were also reported. Note that the intractability, i.e.,
infusibility and insolubility, is the main factor that hampers the
applications of PANI, dispersing of the polymer in conventional
polymers was considered one of the most effective approaches to
address this problem from both the scientic and technological
point of view [3,16]. Accordingly, synthesis of nano-structured
PANI, on one hand, is the key step in preparing highly dispersed
blend of PANI with other processable polymers, and thus to
improve the processability of PANI. On the other hand, some
special physical and chemical properties differing from the bulk
material will be achieved on nano-structured PANI and will ren-
der it for newapplications [17], such as chemical sensors, energy
conversion and storage, light-emitting display devices, micro-
electronics, optical storage, and so on. In comparison with the
PANI nanoparticles, which are mainly synthesized by dispersion
technique and electrochemical method and have been the subject
of a recent review [18], one dimensional nano-structured PANI,
including nanobers, nanowires, nanorods, nanotubes, nanob-
rils, nanobelts and nanoribbons, presents several advantages in
fabricating nano-devices and in preparing nanoscale electrical
Fig. 1. Molecular structure of PANI in emeraldine base (a) and emeraldine salt
(b) form, where A

represents the dopant anion.

connections in highly conducting polymer composites, etc. The
objective of this paper is to reviewthe past works concerning the
synthesis and applications of one-dimensional nano-structured
PANI. It should be emphasized that the paper is only intended
to provide a brief summary of the literature and omissions are
inevitable due to the myriad of investigations carried out on this
subject.
2. Synthesis
Aside from the physical routes like electrospinning [1922]
and mechanical stretching [23], and the doping induced solution
route [24], the chemical approaches adopted for production of
one-dimensional nano-structured PANI can be generally catego-
rized into the chemical oxidative way and the electrochemical
oxidative way, just as that occurred for the synthesis of the
conventional PANI powders. While in this review, the syn-
thesizing approaches used for production of one-dimensional
nano-structured PANI, as detailed below, are divided into two
categories, i.e. the template synthesis and the no-template syn-
thesis, in the light of whether template(s) is (are) used or not.
The former is subdivided into hard template (physical template
[25]) synthesis and soft template (chemical template [25]) syn-
thesis approach according to the solubility of the templates in
the reacting media, while the latter is subdivided into interfacial
polymerization [17,26], radiolytic synthesis [27], rapid mixing
reaction method [28] and sonochemical synthesis [29,30]. Other
approaches like seeding polymerization [31] and combined soft
and hard template synthesis [32] were also reported.
2.1. Hard template synthesis
The hard template synthesis method, which is proposed by
Martin et al. [3337], involves synthesizing the intrinsically
conducting polymers like PANI, polypyrrole, as well as other
materials including metals [38,39], carbons [40,41], in the pores,
channels of hard templates such as membranes [3537], zeolites
[42], anodic aluminum oxide (AAO) [4345], and so on. One
of the interesting and useful features of the method is its effec-
tiveness in preparing one-dimensional micro- or nano-structured
materials with controllable diameter, length and orientation [43].
For example, PANI laments with diameters of 3 nm have been
achieved in the hexagonal channels of mesoporous aluminosili-
cate [42]. However, the disadvantage of the methodis that, rstly,
a rather tedious post-synthesis process is required in order to
remove the templates [46]; secondly, the nano-structured poly-
mers may be destroyed [47] or form undesirable aggregated
structures after released from the templates [48].
Typically, the hard templates were rstly immersed in a pre-
cooled acidic solution of aniline, and the oxidant solution at the
same temperature was added then to start the polymerization.
D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919 11
During the procedure, PANI was produced and deposited within
the pores or channels of the templates. With the templates elim-
inated, partly or completely, one-dimensional nano-structured
PANI was isolated [44]. Occasionally, the templates were not
removed, giving rise to the one-dimensional nano-structured
PANI lled composite materials [42]. In some cases, aniline
was adsorbed from vapor phase into the channels of the tem-
plates, and polymerization was then carried out in an identical
fashion as mentioned above [42]. PANI nanotubules were also
synthesized by placing solutions of aniline and ammonium per-
oxydisulfate (APS), the oxidant, in a two-compartment cell with
the particle track-etched membrane (PTM) as the dividing wall,
which serves as the hard template [49]. The monomer and the
oxidant diffused toward each other through the membrane and
reacted, yielding the PANI nanotubules in the pores of the mem-
brane. In addition to the above-mentioned chemical oxidative
polymerization, PANI nanobers, nanotubules and nanoribbons
were also prepared by electrochemical oxidative polymerization
with hard templates such as PTM [49], AAO [50] and enclosed
nanochannels [51].
With an alumina membrane as the hard-template, PANI nan-
otubules encapsulated nickel nanowires were prepared by Cao
et al. [52] through a two-step process. The nickel nanowires
were protected from corrosion and oxidation in air by the PANI
nanotubules, rendering the nano-structured composite promis-
ing material for some applications such as microelectronics
and magnetic antenna material. Inorganic particles, such as Ni
particles, were also used as templates in synthesizing PANI
nanobers [53].
2.2. Soft template synthesis
The soft template synthesis method, always called the
template-free method [5457] or self-assembly method [58] in
the literatures in that no hard templates is used, entails synthe-
sizing the PANI, as well as polypyrrole [55,59], in the presence
of structure-directing molecules such as surfactants [60,61],
deoxyribonucleic acid (DNA) [62,63], polyelectrolytes [64],
thiolated cyclodextrins [65], sulfonated porphyrin [66], liquid
crystalline [67], and ethanol [68,69], which act as templates for
production of the one-dimensional nanomaterials. The surfac-
tants are often complex acids with bulky side groups, such as the
naphthalenesulfonic acid (NSA) [56,70,71], camphorsulfonic
acid (CSA) [7275], azobenzenesulfonic acid (ABSA) [76],
chiral 2-pyrrolidone-5-carboxylic acid (PCA) [77], 4-(3-(4-((4-
nitrophenyl)azo)phenyloxy)propyl)aminobenzene sulfonic acid
(C3-ABSA) [32], 2-acrylamido-2-methyl-1-propanesulfonic
acid (AMPSA) [78], 5-aminonaphthalene-2-sulfonic acid
(ANSA) [57], etc. The polyelectrolytes include poly(acrylic
acid), poly(styrenesulphonic acid), etc. [64,79]. The method is
simple and cheap in comparison with the hard template method
because it omits the use of the hard templates and therefore
the wearisome post synthesis processing. The formation of the
one-dimensional nano-structured PANI depended on the reac-
tion conditions, such as the concentration of aniline, the molar
ratio of aniline to oxidant or the soft template. Generally, the
lower concentrations of aniline favored the formation of nan-
otubes [77] or nanobers [68], while the higher concentrations
did the granular PANI.
In a typical surfactants based procedure, aniline and surfac-
tants such as CSA, NSA, ANSA, o-aminobenzenesulfonic acid,
etc. with different molar ratios were added to a certain amount of
distilled water. A transparent solution of aniline/surfactant salt
was formed and was brought to a specied temperature. Then
an aqueous solution of oxidant, usually APS, pre-cooled to the
same temperature was added to the above transparent solution to
initiate the polymerization. After a predeterminedperiodof reac-
tion time, the mixture was ltered, washed, and dried to obtain
the one-dimensional nano-structured PANI. For instance, Wans
group prepared both nano- and micro-structured PANI tubes
[56], as well as polypyrrole tubes [55], with various acids by
this method. Yang et al. [77] synthesized chiral PANI nanotubes
with inner diameter of 50130 nm, outer diameter of 80220 nm
and aspect ratio of 610, with chiral PCA as the template. Nick-
els et al. [62] and Ma et al. [63] synthesized nanowires of PANI
with DNAas the template, and the nanowires were immobilized
on silicon surface with pre-stretched strand DNA as the tem-
plate [63]. Very recently, Li et al. [80] prepared PANI nanobers
with diameters of 100120 nm and lengths of several microm-
eters with p-aminobenzenesulfonic acid as the surfactant, and
the diameters of the nanobers decreased with decreasing of the
p-aminobenzenesulfonic acid concentrations. Self-doped PANI
nanobers with a diameter of 120370 nm were synthesized by
Yang et al. [81] with o-aminobenzenesulfonic acid, a self-doping
monomer, as the surfactant.
In another surfactants based procedure, aniline was poly-
merized in acidic solution, including both the inorganic acids
[58] such as hydrochloride acid (HCl), H
2
SO
4
, HBF
4
and
H
3
PO
4
, and organic acids such as AMPSA [82], in the pres-
ence or absence of the surfactants, such as sodium dodecyl-
benzenesulfonate (SDBS) and hexadecyltrimethylammonium
bromide (HTAB) [58], Triton X-100 [82] or Allura Red AC[83]
to prepare one-dimensional nano-structured PANI. Both nan-
otubes/nanorods with average diameter of 150340 nm [58] and
nanobers with average diameter of 56 nm [82] were obtained.
Different dopant anions can be introduced to the nanomaterials
by a dedopingredoping procedure without signicant changing
of the morphologies and diameters of the nanostructures.
Concerning the formation mechanisms of the nanostructures,
it was proposed, but not conrmed [84], that the surfactants self-
assembled with or without their aniline salts into nano- or micro-
structured intermediates [70,76,84,85] due to the hydrophobic
property of aniline and the hydrophilic property of the sur-
factants [70], which played a template role in forming of the
one-dimensional nano-structured PANI [48,54,58,86,87]. The
diameters and lengths of the one-dimensional nano-structured
polymer were depended on the factors such as the soft tem-
plates, molar ratio of surfactant to aniline, reacting temperature
and time and other synthetic conditions. For example, when the
molar ratio of CSA to aniline was xed at 2, granular PANI was
formed, while in decreasing of the ratio from 1 to 0.01, tubular
PANI was produced with diameters decreased from180 to 85 nm
[72]. The same result was obtained with NSA [48] and ANSA
[57] as the soft templates. With decreasing of the molar ratio of
12 D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919
NSA to aniline from 2 to 1 and 0.5, tubular PANI with average
diameters of 650, 154 and 92 nm, respectively, was obtained.
While with further decreasing of the ratio to 0.25, nanobers
with average diameters of 76 nm were produced. In the case
of ANSA [57], irregular granular PANI was obtained when the
molar ratio of ANSA to aniline falls in the range of 0.250.5.
While decreasing of the ratio to 0.1 and 0.02, very short PANI
cylinders andPANI nanotubes withouter diameter of 60100 nm
were observed, respectively, and both coexisted with granu-
lar PANI. Besides, adding of water to the aniline/surfactants
systems before initiation of polymerization decreased also the
diameters of PANI tubes from micrometers to nanometers [54].
In spite of the above-mentioned proposals and results on the for-
mation of PANI nanostructures, Konyushenko et al. [88] pointed
out recently that morphology of PANI depends on the acid-
ity conditions during the reaction rather than on the chemical
nature of the acid adopted. For example, granular PANI was
produced when the polymerization was carried out in solutions
of sulfuric acid, while PANI nanotubes with external diameter
of 100300 nm and internal diameter of 20100 nm, and length
of several micrometres were obtained in solutions of acetic acid.
While in a polyelectrolyte based procedure, the polyelec-
trolyte was rstly dissolved in an organic solvent, such as
tetrahydrofuran, to give a homogeneous solution. Aniline was
then added to the solution to forma gel composed of a molecular
complex of aniline and the polyelectrolyte. After washed with
tetrahydrofuran to eliminate the excess of aniline, the gel com-
plex was re-dissolved in an acidic aqueous solution. Following
the addition of the oxidant solution, polymerization was initi-
ated. Reacted for a specic period of time, PANI nanobers were
collected by ltration. As far as the mechanism is concerned, it
was suggested that aniline was rstly bound onto the polyelec-
trolytes, followed by polymerization of aniline attached to the
polyelectrolyte templates [64,79]. Therefore, PANI nanobers
with diameters of 50 nm were produced when the template
molecule is an extended linear chain of poly(acrylic acid), while
globular morphology was obtained when the random coil con-
formation of poly(styrenesulphonic acid) was used as template.
One-dimensional nano-structured PANI was also reported
during electrochemical polymerization of aniline with thio-
lated cyclodextrins [65], sulfonated porphyrin [66], liquid crys-
talline [67], or ethanol [68], as the soft templates. Modied
the gold electrodes with self-assembled monolayer of thiolated
cyclodextrins, Choi and Park [65] prepared both nanowires of
PANI with diameter of ca. 70 nm and length of 1.5 m, and
nano-rings of PANI with diameter of ca. 85 nm and length
of 3.4 m. The potentiodynamically grown nanowires exhib-
ited much smoother morphology with fewer defects and longer
lengths than those galvanostatically grown ones. When liquid
crystalline was adopted as the template [67], PANI nanowires
with diameter of 5070 nm and lengths of several microns were
obtained. The distance between the working electrode and the
counter electrode played an important role in depositing high
quality nanowires. Generally, reduction of the distance favored
better alignment of the liquid crystalline, and therefore well-
ordered and longer nano-wires of PANI. In the case of ethanol as
the template [68], PANI nanobers with diameters smaller than
100 nm were obtained and it was revealed that both the electric
quantity in electropolymerization and the ethanol affected the
morphology of the nal PANI. For example, 90% (area frac-
tion in SEM images) of nanobers with diameters of 2050 nm
was observed on platinum deposited quartz substrate electrode
with30 minof polymerization, while bers withdiameters larger
than 100 nm were obtained with polymerization time of 15 min.
The reason for the formation of nanobers was, on one hand,
the ethanol molecules wrapped the PANI particles due to the
strong H-bonding between themand prevented thus the aggrega-
tion of PANI particles during their polymerization, on the other
hand, the increased forming rate of crystalline nucleus due to
the presence of ethanol is favorable for electrosynthesizing of
PANI nanobers. Thanks to the one-dimensional aggregation
structures of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin
in water, nanorods of PANI with diameters of 2050 nm and
lengths of 2001000 nm were also prepared by electrochemical
oxidative polymerizationinthe presence of sulfonatedporphyrin
with various porphyrin concentrations [66]. The aspect ratios of
the PANI nanorods were affected by the sweeping potentials and
cycles. The density of the PANI nanorods, i.e. the crowdedness
of the nanorods, increased with the concentrations of porphyrin,
indicating that the aggregated sulfonated porphyrin functioned
as soft template in directing the morphology of PANI.
Additionally, the equilibrium adsorbed surfactant aggregates
can also be used as soft templates for synthesizing nano-
structured PANI, as well as polypyrrole, with controlled mor-
phologyonat surfaces [60]. Aniline andsodiumdodecyl sulfate
(SDS), a kind of surfactant, were allowed to aggregate on highly
oriented pyrolytic graphite surfaces in the rst step, and then the
oxidant was added to start the polymerization. Finally, the sub-
strate was rinsed to remove the excessive ingredients, resulting
well aligned PANI nanowires parallel to the surface, as well as
other morphologies on the substrates.
More importantly, uniform dendritic PANI nanobers, with
diameters and lengths of 6090 nm and several hundreds of
nanometers, respectively, were chemically synthesized with a
special surfactant gel formed by a mixture of hexadecyltrimethy-
lammonium chloride (C
16
TMA), acetic acid, aniline, and water
at 7

C [89]. The lengths of the PANI branches decreased

with decreasing of the C
16
TMA concentration, and nally
PANI nanoparticles were resulted with a C
16
TMA concentra-
tion of 0.05 mol/L. However, when the C
16
TMA was replaced
by cetyltrimethylammonium bromide (CTAB), PANI nanobelts
with thickness, width, and length in the range of 4050,
300400 nm, and about several micrometers, respectively, were
prepared by the same group at 7

C with the concentration

of CTAB vary from 0.05 to 0.25 M [90]. Note that only PANI
nanoparticles with diameters of 70100 nm were obtained with
0.25 M CTAB when the synthesis was carried out at room tem-
perature, it was assumed that the surfactant played a template-
like role in the synthesis of PANI nanobelts.
2.3. Combined soft and hard template synthesis
In order to fabricate highly oriented PANI nanostructures, a
novel method combing the soft and hard template synthesizing
D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919 13
technique was employed [32]. Typically, aniline and the surfac-
tant, e.g. C3-ABSA, was dissolved in deionized water to form a
homogenous emulsion and ultrasonicated for a while. The hard
template, e.g. a porous, hydrophilic Al
2
O
3
, was immersed in the
emulsion and ultrasonicated for another while. Afterwards, the
APS solution was added rapidly to initiate the polymerization.
With different reacting time, the oriented PANI nanotubes and
nanobers were produced within the pores of the hard template.
No oriented nanobers was obtained neither with NSA as the
soft template nor with a hydrophobic Al
2
O
3
as the hard template
solely, revealing that both the dopant and the surface property
of the hard template affect the alignment of PANI nanobers or
nanotubes. The fact that one nanotube or nanober was grown
in a regular hexagon shaped pore, and two or more in a irregular
shaped pore, differing from the fact that one ber or tube in one
pore during the direct use of Al
2
O
3
as the hard template, indi-
cated that both the soft and hard template affected the formation
of the nanobers or nanotubes. The lengths of the nanobers or
nanotubes can be roughly controlled by varying the polymeriza-
tion time.
2.4. Seeding polymerization
By adding a small amount of various nanobers like the PANI
nanobers in diameter of 50 nm, the single-walled carbon nan-
otubes bundles in diameter of 20 nm, nanobrous hexapeptide
in diameter of 12 nm, and the V
2
O
5
nanobers in diameter of
15 nm, into the reacting solution of aniline and APS, Zhang
et al. [31]. invented the so-called nanober seeding method
for preparation of PANI nanobers. Typically, about 14 mg
of these seeding nanobers were added rstly into a stirred
solution of aniline (0.14 M) in hydrochloric acid (1.0 M), and
a solution of 0.04 M APS was added then to the mixture to ini-
tiate the polymerization. The resulting dark-green precipitate of
PANI was isolated after 1.5 h and dried under dynamic vacuum.
The morphology of all the seeded PANI products was bril-
lar with ber diameters in the range of 2060 nm. In contrast,
when the reaction is seeded with spheres, for example, the par-
ticulate PANI and the nanospheres of polypyrrole, nanobrous
morphology was obtained just like that in the unseeded reaction.
One of the advantages of the seeded approach is that bulk quan-
tities of doped PANI nanobers could be produced in one step
without the need of conventional templates, and hence the need
for tedious post-processing. Besides, PANI oligomers [91], Au
nanoparticles with average diameters of 15 nm [92] and carbon
nanotubes [93] were also used as the seeds in preparing PANI
nanobers. Very recently, Zhang et al. [94] conrmed that the
PANI nanobers prepared in chemical oxidative polymerization
with APS as the oxidant were resulted from the rodlike struc-
ture of aniliniumperoxydisulfate ion clusters formed during the
induction period, which acted as the in situ generated seeds in
directing the morphology of the nal product.
2.5. No-template synthesis
To distinguish from the commonly called template-free syn-
thesis of the soft template synthesis method, the phrase no-
template synthesis was coined here to name the method for syn-
thesizing one-dimensional nano-structured PANI without any
templates, hard or soft.
2.5.1. Interfacial polymerization
Initially, PANI or its composite lms were produced via
interfacial polymerization approach in which aniline was co-
dissolved with the surfactant [95] or polymers [96] in the organic
phase, while APS in aqueous acidic phase, giving rise to the
lms at the interface of the two immiscible liquids. However,
both nanobers [17,25] and nano-particles [97] of the polymer
were produced recently, rendering the approach one of the gen-
eral and facile among a variety to synthesize one-dimensional
nano-structured PANI.
In a typical reaction [17,26,93,98,99], aniline was dissolved
in the organic phase, which can either be one with density lower
than water such as hexane, benzene, toluene, etc. or be one
higher, such as carbon tetrachloride, methylene chloride, etc.,
with various concentrations. Meanwhile, APS was dissolved in
an aqueous acid solution, covering a great variety of acids such
as HCl, sulfuric acid, CSA, toluene sulfonic acid, among others.
And then, the two solutions were gently transferred to a reaction
vessel such as a beaker or a vial, generating an interface between
the two layers. Green PANI was formed rstly at the interface as
the reaction proceeds and migrated gradually into the aqueous
phase until the whole aqueous phase is lled homogeneously
with dark-green PANI at last. Finally, the aqueous phase was
collected after sufcient time of reaction by dialysis or ltra-
tion to remove the impurities like excess dopants, etc., yielding
PANI nanobers in the form of a water dispersion or powder.
Dedoped PANI nanobers can be obtained by further washing
or dialyzing with ammonia.
Inconsiderationof the formationmechanisms, it was revealed
that interfacial polymerization suppressed effectively the sec-
ondary growth of PANI, which occurred naturally in the conven-
tional synthesis of PANI, leading thus to the exclusive formation
of nanobers [28]. The monomer and oxidant, separated in two
phases, met only at the interface and reacted there then, forming
PANI nanobers. The nanobers formed moved away rapidly
from the interface and diffused into the water phase due to their
hydrophilicity. As such, the nanobers were continuously with-
drawn from the interface, allowing formation of new nanobers
at the interface.
As far as the synthesizing parameters (such as the solvents,
polymerization temperature, and monomer concentration) are
concerned, it was demonstrated that all aqueous/organic systems
produce similar PANI nanobers, whose morphology was unaf-
fected in the subsequent dedoping process [17,98]. However,
both the diameters and the quality/uniformity of the nanobers
were affected by the acids and their concentrations [98]. For
example, the average diameters of the bers synthesized in HCl,
CSA, perchloric acid, and other acids (such as sulfuric acid,
nitric acid and 4-toluenesulfonic acid) are 30, 50, 120, and
3050 nm, respectively [98]. In the case of strong acids like
HCl and CSA, the lower the concentration of the acid, the lower
the fraction of nanobers in the nal product. While in the case
of medium or weak acids like tartaric acid or pyrrolidone-5-
14 D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919
carboxylic acid, the products were mixtures of nanobers and
particles even at high concentrations. It was therefore stated that
high concentrations of strong acids favored the formation of
PANI nanobers.
The diameters of the nanobers prepared by interfacial poly-
merization can be controlled by using surface active dopants
like AMPSA or CSA, and surfactants in the aqueous phase
[25]. The surfactants cover the single-tailed non-ionic ones like
octylphenol ethoxylate Triton-X 100 and d-Alpha Tocopheryl
Polyethylene Glycol 1000 Succinate (Vitamin E TPGS), the
single-tailed anionic ones like DBSA, and the twin-tailed ones
like potassium cis-1,2-dipentylethene sulfonate (C
5
H
11
-twin-
tailed), potassium cis-1,2-diheptylethene sulfonate (C
7
H
13
-
twin-tailed) andsodiumdi(2-ethylhexyl) sulfosuccinate aerosol-
OT (AOT). Solutions of the surfactants, if used, were gently
syringed into the aqueous phase layer, i.e. bottom phase in
the case, just below the interface. The average diameter of the
bers obtained using 1.0 M AMPSA as the aqueous phase is
23 nm, smaller than the 48 nm for the bers obtained with
1.0 M CSA as the aqueous phase. The reason was expected to
originate from the more efcient packing capability of AMPSA
than that of CSA due to its more linear structure. In the case
of the CSA based nanobers, the single-tailed non-ionic sur-
factants increased the average diameter to 80 nm, while the
single-tailed anionic surfactants seemed to have no any impact
on ber diameter. However, the twin-tailed surfactants increased
the average diameter to 30 nm, and the longer the alkyl chain
length, the smaller the average diameters. For instance, the aver-
age diameters of the CSA based nanobers synthesized with
no surfactant, with C
5
H
11
-twin-tailed and C
7
H
13
-twin-tailed as
surfactants are 48, 35 and 28 nm, respectively. While in the
case of the AMPSA based nanobers, this trend of the alkyl
chain effect was reversed. The average diameters increased
from 23 nm (no surfactant) to 35 nm and 55 nm with C
5
H
11
-
twin-taile and C
7
H
13
-twin-tailed as the surfactants, respectively.
Although these surfactants might be expected to disrupt the
intrinsic packing properties of the AMPSA, the reason for
this reversed alkyl chain effect is not clear up to now. And
aside from the above-mentioned morphological effect, the aver-
age doping percentage of the PANI nanobers was lowered
with addition of the twin-tailed surfactants during interfacial
polymerization.
By placing an Au substrate with self-assembled monolayer
of 4-aminothiolphenol at the interface of an interfacial polymer-
ization, Hopkins and coworkers [100] grafted a two-dimensional
mesh of PANI nanobers with diameters of 4050 nm onto the
Au surface through the covalent bonding between PANI and the
amine created by the 4-aminothiolphenol monolayer. It was of
a great attempt to pattern the one-dimensional nano-structured
PANI onto substrates in an ordered form. In contrast to other
nano-patterning techniques of PANI on Au surfaces, the method
exhibited both improved physical (adhesion) and chemical (lit-
tle changes of conductivity to a series of acid/base exposure)
durability. With sulfonated polystyrene as both the host and the
dopant in interfacial polymerization, the same group [101] pre-
pared transparent conductive nanocomposites with well-dened
two-dimensional PANI nanobers, rendering the procedure a
unique and facile one in preparing robust conductive PANI
nanobers-based composites.
2.5.2. Radiolytic synthesis
In this method, the aqueous solution of aniline and APS
in HCl was irradiated with gamma rays without any template
[27]. In the case of parent solutions with typical concentration
of 0.1 M aniline, 0.3 M HCl, and 0.0020.1 M APS, the mor-
phology of the nal product was predominantly nanobers with
diameters of 50100 nm and length of 13 m, though less than
5vol.% of globular structures were still presented. While with
APS concentrations in the range of 0.050.1 M in the parent
solution, rodlike structures with diameters of 250500 nm and
lengths of 510 m were observed, which represent 5 vol.% of
the total PANI. The selected-area electron-diffraction of the rod-
like structures was comparable to that of the nanobers, which
are poorly ordered. Fourier transform infrared (FTIR) spectrum
agreed well with that of the typically prepared PANI, indicat-
ing that the chemical structure of the bers was not affected
by irradiation. No complete explanation for formation mecha-
nism of the nanobers was provided up to then according to
the authors. However, the authors concluded that PANI self-
assembled when the polymerization was carried out with gamma
irradiation. In addition, four to ve times larger sized spher-
ical aggregates, as compared with the aggregate diameters of
2040 nm without irradiation, and hollow spheres with diame-
ters of 50100 nm were observed with irradiation. The hollow
aggregates tended to stick to and link spheres, which coalesced
then in an anisotropic fashion and resulted then, probably, the
nanobers. PANI nanobers decorated with metal nanoparticles
were also prepared with the same gamma irradiation procedure
[102]. At the same time, thin lms of PANI nanobers were
synthesized by the same group by ultraviolet irradiation of a
spin coated mixture of aniline nitric acid and APS on the sur-
face of a silicon wafer [103]. The nanobers demonstrate typical
diameters of 20150 nm and lengths of microns.
2.5.3. Rapid mixing reaction
With the solution of APS mixed rapidly with that of aniline,
rather than the conventional slow addition of the solution of
APS to that of aniline, PANI nanobers with comparable shapes
and sizes to those of interfacial polymerization [17,98] method
were obtained, rendering this method the simplest one in pro-
ducing PANI nanobers [28]. Owing to the even distribution
of aniline and APS molecules in the solution, all the initiator
molecules were consumed rapidly after the start of the poly-
merization and the secondary growth of PANI was suppressed,
resulting exclusive nanobers in the product. The growth of
the PANI nanobers was related with the polarity of the sol-
vents. For example, in aqueous systems, pure nano-bers were
produced, while in ethanol and isopropanol, mixture of short
nanobers attached with irregular particles and agglomerates of
100300 nm particulates were obtained, respectively. However,
according to Zhang et al. [58], the formation of nano-structured
PANI, which was synthesized in presence of H
3
PO
4
without any
other template, soft or hard, was expected to originate from the
micelles formed by anilinium cations, which acted as the tem-
D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919 15
plates in forming the nanostructures. In another similar study,
chloroaurate acidwas usedas the oxidant [104]. PANI nanobers
with diameters of 35 5 nm and gold nanoparticles in diame-
ters of 3040 nmwere obtained. The formation of the nanobers
was probably owing to the catalytic effect of the gold nanoparti-
cles in directional growth of the PANI, though the exact growth
process of the nanobers was not clear.
Chiou and Epstein [105,106] prepared PANI nanobers by
dilute polymerization, in which a small portion of acid solu-
tion containing aniline was carefully transferred to the solution
of APS in acid and then leave the mixture to react without
any disturbance. The diameters of the bers can be roughly
tuned by appropriate selection of the acids. For instance, when
CSA, methanesulfonic acid and perchloric acid were used, the
diameters of the bers were in the range of 1750, 4270 and
72250 nm, respectively. The formation of the nanobers was,
as explained, owing to the reduced numbers of nucleation sites
on the surface of the nanobers in a dilute condition, which
allowed PANI to grow directionally, differing from that of the
competition between the directional growth and the formation
of additional nucleation centers in the case of high aniline con-
centration, which resulted irregular PANI product.
Very recently, Li and Kaner [107] pointed out that the forma-
tion of PANI nanobers was a result of homogeneous nucleation
during the synthesizing process, differing from the above men-
tioned proposals. At the initial stages, PANI nanobers with
smooth surfaces and uniform sizes were formed in the reaction
system via a homogeneous nucleation. When the system was
mechanical stirred, the primarily formed PANI nanobers were
forced to collide into each other and heterogeneous nucleation
occurs on the surfaces of these particles, causing aggregations
of the primary nanobers; while when the system was left still,
the heterogeneous nucleation was suppressed and nanobers
were produced continuously. The proposed mechanism appears
to hold for other materials such as poly(m-toluidine) and silica
nanoparticles as per the authors. Besides, in absence of stirring,
the higher temperature favors more the homogeneous nucleation
owing to the faster formed embryonic nuclei than the lower tem-
perature. For instance, PANI nanobers formed at 60

Cis more
uniform than that formed at 0

C.
2.5.4. Sonochemical synthesis
By dropwise addition of an acidic APS solution to an acidic
aniline solution, just like the conventional PANI synthesis pro-
cedure, with the aid of ultrasonic irradiation, PANI nanobers
with higher polymer yields were successfully prepared by Jing
et al. [29,30]. It was stated that three possible competitions exist
in the reaction system if more aniline and APS are present
following the formation of the primary PANI nanobers, i.e.
(1) the continuing formation of primary PANI nanobers, (2)
the growth of the primary nanobers into unevenly surfaced
thicker bers, and (3) the growth and agglomeration of the
thicker bers into irregular particles. In the conventional pro-
cedure, irregular PANI particles were obtained owing to the
continually occurring of steps (2) and (3); while in the case of
sonochemical synthesis, the further growth and agglomeration
of the primary nanobers were effectively prevented, even more
Fig. 2. Sonochemically prepared PANI nanobers with secondary addition of
aniline and APS (Reproduced with permission from X.L. Jing, Y.Y. Wang, D.
Wu, L.She, Y. Guo, J. Polym. Sci., Part A: Polym. Chem. 44 (2006) 10141019.
Copyright 2005 Wiley Periodicals, Inc. [29]).
aniline and APS were added into the system [29], resulting to
the formation of more primary PANI nanobers (Fig. 2). One of
the advantages of the approach is its scalability in comparison
with others such as interfacial polymerization or rapid mixing
reaction.
2.5.5. Electrochemical approach
Aside from the above-mentioned chemical no-template
approaches, one-dimensional nano-structured PANI was
also synthesized by electrochemical no-template approaches
[108110]. PANI nanobrils, as well as microbrils or rods,
have been found by Langer et al. [111115] in electrochemi-
cally synthesizing PANI from an aqueous medium at pH 1
without any templates. The nanobrils doped with fullerene
derivatives exhibited diameters of 10100 nm and lengths of
5002000 nm [115]. Both single nanobrils and their networks
were obtained with controlled charge ows [114]. Latterly, large
arrays of uniform and oriented nanowires of PANI with diam-
eters less than 100 nm were synthesized by Liang et al. [116]
and Liu et al. [117] on a variety of substrates by a three-step
electrochemical deposition procedure, also without using any
templates. Typically, a large current density was adopted for a
while (0.08 mA/cm
2
for 0.5 h) to create the nucleation sites on
the substrates in the rst step; in the second step, a reduced cur-
rent density was followed (0.04 mA/cm
2
for 3 h); nally, a much
reduced current was followed (0.02 mA/cm
2
for 3 h). The step-
wise growth produced uniform and oriented nanowires on both
at substrates and particles and textured surfaces. For example,
nanowires with diameters of 5070 nm and lengths of 800 nm
were formed perpendicular to a Pt substrate. When the substrates
were colloidal silica particles, the nanowires produced were ori-
ented perpendicular to the particle surfaces. PANI nanowires
were also fabricated to bridge a sharp scanning tunneling micro-
scope tip and an Au electrode by electrochemical polymeriza-
tion, and the diameter can be reduced by mechanical stretching
of the nanowires [23]. For example, assuming the volume of the
16 D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919
nanowires does not change during stretching, the upper limit
diameter of the PANI nanowires can be reduced from the initial
20 to 6 nm by stretching over a distance of 200 nm. With
porous poly(styrene-block-2-vinylpyridine) diblock copolymer
lms as the templates, which were spin coated to the electrode
and then treated with acetic acid before hand, highly porous
PANI nanober lms were also prepared by electrochemical
approach [118].
3. Properties
As revealed by the FTIR spectra, UVvis spectra, and the
X-ray diffraction, all the PANI nanotubes [57,58], nanobers
[27,31,68,82], nanowires [67], nanorods [58], as well as micro-
tubes [85], have backbone structures similar to that of the
conventional prepared granular PANI. In some cases, the Ein-
stein shifts observed in the FTIR and UVvis spectra were
originated from the interaction between the PANI chains and
some small molecules, such as ethanol [68], not from the
chemical structures. For electrochemical prepared oriented
PANI nanowires [117], polarized infrared spectroscopy sug-
gested that the PANI molecules were aligned perpendicular to
the axis of the nanobers. For the hard-template synthesized
PANI nano- [36] and micro-tubes/bers [119], they exhibited
a highly ordered layer (ca. 5 nm in thickness) on the outer sur-
face, in which the PANI chains are aligned perpendicular to
the axis of the nano- or micro-structures, and progressively
disordered layers toward the center of the nano- or micro-
structures. Conductivity measurement of the hard-template syn-
thesized PANI nanotubules [49,119] showed that the conduc-
tivities decreased with the increasing of the diameters, and
nally reaches the conductivity of the conventional PANI pow-
der. This was resulted from the decreasing proportion of the
highly ordered layer in the materials with increasing of diam-
eters and from the higher conductivity of the highly ordered
layer than that of the disordered inner part of the bers/tubes
[120]. The analogous conductivity decrease was also observed
for electrochemically template-synthesized PANI nanoribbons
[51].
The four-probe conductivity of the PANI pellet consisting
of both granular particles and nanobers [53], or the PANI
nanobers pellet [31,61,91] was similar to their counterpart syn-
thesized by the conventional procedure, and was affected by the
doping acid and doping degree, and so on. The directly mea-
sured electrical conductivity of a single PANI nanotube, which
was synthesized by the soft template method, is ca.30 S/cm
[73,74], far more higher than the 10
2
S/cm order of magnitude
[73,74,76] for the nanotube pellet due to the large intertubular
contact resistance [73,74].
BrunauerEmmettTeller (BET) surface area of the PANI
nanobers decreased with increasing of the ber diameters [98].
For example, BET surface area of dedoped PANI nanobers
with diameters of 30, 50, and 120 nm are 54.6, 49.3, and
37.2 m
2
/g, respectively. In addition, the BET surface area of
doped PANI nanobers was lower than that of the dedoped
ones, which is in consistent with the results of the conventional
PANI.
4. Applications
Apart from the above-mentioned similar properties of the
one-dimensional nano-structured PANI to that of the conven-
tional granular PANI powders, several unique properties, such as
large surface area, were exhibited by the one-dimensional nano-
structured PANI, rendering this important class of newmaterials
promising candidates for applications ranging from sensors to
energy storages and electron eld emissions.
4.1. Sensor application
The electrical conductivity changing of PANI, as well as other
intrinsically conducting polymers [121,122], upon exposure to
acidic or basic vapors and liquids, such as HCl, ammonia gas
[123,124], or ammonia water [125,126], CO
2
[127], as well
as some neutral gases including chloroform [128], alcohols
[129], etc., rendered PANI one of the novel promising mate-
rials for sensor applications, and tremendous works have been
undertaken on the eld. However, poor sensitivity resulted from
the poor diffusion of analyte molecules was observed for the
conventional PANI and the composite lms [130132]. One-
dimensional nano-structured PANI enhanced signicantly the
diffusion [26,110,132] due to its greater exposure area and pen-
etration depth for gas molecules than the conventional PANI,
and became an alternative material to improve the sensitivity
of PANI based sensors, especially for acidic and basic gases.
For example, the resistance response of the interfacial polymer-
ized PANI nanobers based lm was much faster than that of
the conventional PANI based lm on exposure to 100 ppm of
HCl and NH
3
, although the nanobers based lm is more than
twice in thick [17]. In addition, the response and correspond-
ing sensitivity of the nanobers based lm was independent on
the thickness owing to its porous nature which facilitate the
interaction of vapor molecules with all the bers, outside and
inside of the lm. On the other hand, the performance of the
conventional PANI lm was strongly thickness dependent. The
thinner the lm, the better the performance in that only the out-
most surface interacts with the vapor molecules [132]. In the
case of neutral gas molecules, such as hydrazine [26], methanol
[26,110] and water [110], PANI nanobers based lms exhib-
ited faster responses, but lower sensitivity than the conventional
PANI lm. The reason lied in both the relatively open structure
of the polymeric materials as compared with metal or inorganic
materials and the adverse effect from the interbrillar contact
resistance of the nanobers based lms [26,110]. If chirality,
which originate only from the helical conformation of polymer
backbone and/or from the helical packing of the polymer chains
induced by chiral acids due to the absence of asymmetric carbon
in doped PANI, was imparted to the PANI nanobers with high
surface areas, chiral separation and biological sensors would be
the new potential areas for applications of the nanobers [91].
The well-aligned PANI nanowires were also tested as sup-
port materials for sensing applications due to their oriented
microstructure and high surface area [117]. Iron hexacyano-
ferrate, an active ingredient for H
2
O
2
detection, was electro-
chemically deposited in formof nanoparticles on oriented PANI
D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919 17
nanowires to fabricate H
2
O
2
sensors. The presence of the PANI
improved the stability of the iron hexacyanoferrate and lowered
the over-potential of H
2
O
2
, which are of great importance in
practical sensing and detecting of H
2
O
2
. The stable, reliable and
almost linear response of the composite sensor proved the iron
hexacyanoferrate loaded PANI nanowires a useful conguration
for H
2
O
2
sensors.
4.2. Energy storage
PANI nanobers showed higher capacitance values and more
symmetrical charge/discharge cycles due to their increased
available surface area, in spite of their similar redox peaks dis-
played in aqueous electrochemistry to that of the conventional
granular PANI [31]. For example, a capacitance value of 122 F/g
was achieved for HCl doped PANI nanobers, far more higher
than the 33 F/g in the conventional prepared HCl doped PANI
powder. These kinds of specic properties of PANI nanobers
could be benecial to development of the next-generation energy
storage devices [31,61].
4.3. Field emission application
Well-aligned PANI nanobers, in shape of membrane
together with the hard template of AAO, were directly tested as
electron eld emitter [43]. The stable eld emission behavior,
low threshold voltage (56 V/m) and high emission current
density (5 mA/cm
2
) of the membrane suggested the material
an attractive eld-emitting candidate. Furthermore, the easy
preparation, smooth and substantial surface, low cost, and good
mechanical property of the material will be favored in fabrica-
tion of eld emission displays.
4.4. Flash welding
Irradiated by a camera ash, a random network of PANI
nanobers was turned into a smooth and shiny lm [133] due
to the highly efcient photothermal conversion and low thermal
conductivity of PANI, which demonstrated a versatile new tech-
nique for processing polymers into potentially useful structures
[134]. One of the great advantages of the ash welding tech-
nique is that a certain area can be selectively welded by using of
a photomask in fabricating polymer lms into pre-designed pat-
terns, differing from other welding techniques like microwave
welding [135]. In addition, the technique offered a rapid route
in creating asymmetric lms, which are widely used in many
applications such as separation membranes, chemical sensors
and actuators [133].
4.5. Digital nonvolatile memory
PANI nanobers (30 nm in diameters) decorated with Au
nanoparticles (1 nm in diameter) were also attempted for fab-
rication of plastic digital memory device [136]. The device
exhibited very interesting bistable electrical behavior and can
be switched electrically between two states with a conductivity
difference of about three orders of magnitude. The switching
mechanism was attributed to an electric eld-induced charge
transfer from the PANI nanobers to the Au nanoparticles. The
prolonged retention time and good write-read-erase cycle results
suggested the device promising for digital nonvolatile memory.
5. Concluding remarks
One-dimensional nano-structured PANI is one class of the
most promising candidates for development of nano-sized elec-
tronic devices, sensors, supercapacitors, energy storage devices
and others due to their high surface area, versatile synthesis
approaches, high conductivity, as well as the controllable chem-
ical and physical properties by oxidation and protonation, and
the good environmental stability. Although kinds of synthesizing
methods have been established, preparation of one-dimensional
nano-structured PANI with controllable morphologies and sizes,
especially well oriented arrays on a large scale is still a major
challenge. Furthermore, the exact formation mechanisms of the
nanostructures need to be elucidated from a scientic point of
view, which will be of great importance in morphological control
of PANI and other polymers prepared by precipitation polymer-
ization.
Acknowledgment
The project was supported by Open Fund of Shaanxi Province
Key Laboratory of Thin Films Technology and Optical Test,
Xian Technological University (No. ZSKJ200506).
References
[1] A.G. MacDiarmid, Synth. Met. 125 (2001) 1122.
[2] A.G. MacDiarmid, J.C. Chiang, M. Halpern, W.S. Huang, S.L. Mu,
N.L.D. Somasiri, W. Wu, S.I. Yaniger, Mol. Cryst. Liq. Cryst. 121 (1985)
173180.
[3] B. Wessling, Synth. Met. 93 (1998) 143154.
[4] Y.Y. Wang, X.L. Jing, Polym. J. 36 (2004) 374379.
[5] Y.Y. Wang, X.L. Jing, Polym. Adv. Technol. 16 (2005) 344351.
[6] F. Wiznerowicz, Wire 44 (1994) 102108.
[7] K.C. Persaud, Mater. Today 8 (2005) 3844.
[8] W. Lu, E. Smela, P. Adams, G. Zuccarello, B.R. Mattes, Chem. Mater. 16
(2004) 16151621.
[9] M. Millard, in: J.R. Hollahan, A.T. Bell (Eds.), Techniquea and Applica-
tions of Plasma Chemistry, Wiley, New York, 1974 (Chapter 5).
[10] L.G. Paterno, S. Manolache, F. Denes, Synth. Met. 130 (2002) 8597.
[11] G.J. Cruz, J. Morales, M.M. Castillo-Ortega, R. Olayo, Synth. Met. 88
(1997) 213218.
[12] C. Liao, M. Gu, Thin Solid Films 408 (2002) 3742.
[13] Y. Chen, E.T. Kang, K.G. Neoh, Appl. Surf. Sci. 185 (2002) 267276.
[14] J. Gong, X.J. Cui, Z.W. Xie, S.G. Wang, L.Y. Qu, Synth. Met. 129 (2002)
187192.
[15] J.X. Huang, J.A. Moore, J.H. Acquaye, R.B. Kaner, Macromolecules 38
(2005) 317321.
[16] J. Anand, S. Palaniappan, D.N. Sathyanarayana, Prog. Polym. Sci. 23
(1998) 9931018.
[17] J.X. Huang, S. Virji, B.H. Weiller, R.B. Kaner, J. Am. Chem. Soc. 125
(2003) 314315.
[18] D.K. Behera, D.S. Bag, S. Alam, G.N. Mathur, J. Polym. Mater. 21 (2004)
8187.
[19] A.G. MacDiarmid, W.E. Jones Jr., I.D. Norris, J. Gao, A.T. Johnson Jr.,
N.J. Pinto, J. Hone, B. Han, F.K. Ko, H. Okuzaki, M. Llaguno, Synth.
Met. 119 (2001) 2730.
18 D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919
[20] N.J. Pinto, A.T. Johnson Jr., A.G. MacDiarmid, C.H. Mueller, N. The-
ofylaktos, D.C. Robinson, F.A. Miranda, Appl. Phys. Lett. 83 (2003)
42444246.
[21] Y.X. Zhou, M. Freitag, J. Hone, C. Staii, N.J. Pinto, A.T. Johnson Jr.,
A.G. MacDiarmid, Appl. Phys. Lett. 83 (2003) 38003802.
[22] P.K. Kahol, N.J. Pinto, Synth. Met. 140 (2004) 269272.
[23] H.X. He, C.Z. Li, N.J. Tao, Appl. Phys. Lett. 78 (2001) 811813.
[24] C. He, Y.W. Tan, Y.F. Li, J. Appl. Polym. Sci. 87 (2003) 15371540.
[25] X.Y. Zhang, R. Chan-Yu-King, A. Jose, S.K. Manohar, Synth. Met. 145
(2004) 2329.
[26] S. Virji, J.X. Huang, R.B. Kaner, B.H. Weiller, Nano Lett. 4 (2004)
491496.
[27] S.K. Pillalamarri, F.D. Blum, A.T. Tokuhiro, J.G. Story, M.F. Bertino,
Chem. Mater. 17 (2005) 227229.
[28] J.X. Huang, R.B. Kaner, Angew. Chem. Int. Ed. 43 (2004) 58175821.
[29] X.L. Jing, Y.Y. Wang, D. Wu, L. She, Y. Guo, J. Polym. Sci., Part A:
Polym. Chem. 44 (2006) 10141019.
[30] X.L. Jing, Y.Y. Wang, D. Wu, J.P. Qiang, Ultrason. Sonochem. 14 (2007)
7580.
[31] X.Y. Zhang, W.J. Goux, S.K. Manohar, J. Am. Chem. Soc. 126 (2004)
45024503.
[32] H.J. Qiu, J. Zhai, S.H. Li, L. Jiang, M.X. Wan, Adv. Funct. Mater. 13
(2003) 925928.
[33] C.R. Martin, L.S. Van Dyke, Z. Cai, W. Liang, J. Am. Chem. Soc. 112
(1990) 89768977.
[34] R.M. Penner, C.R. Martin, J. Electrochem. Soc. 133 (1986) 22062207.
[35] C.R. Martin, Science 266 (1994) 19611966.
[36] C.R. Martin, Acc. Chem. Res. 28 (1995) 6168.
[37] C.R. Martin, Chem. Mater. 8 (1996) 17391746.
[38] M. Nishizawa, V.P. Menon, C.R. Martin, Science 268 (1995) 700702.
[39] V.P. Menon, C.R. Martin, Anal. Chem. 67 (1995) 19201928.
[40] C.G. Wu, T. Bein, Science 266 (1994) 10131015.
[41] R.V. Parthasarathy, K.L.N. Phani, C.R. Martin, Adv. Mater. 7 (1995)
896897.
[42] C.G. Wu, T. Bein, Science 264 (1994) 17571759.
[43] C.W. Wang, Z. Wang, M.K. Li, H.L. Li, Chem. Phys. Lett. 341 (2001)
431434.
[44] Z. Wang, M.A. Chen, H.L. Li, Mater. Sci. Eng. A 328 (2002) 33
38.
[45] S.M. Yang, K.H. Chen, Y.F. Yang, Synth. Met. 152 (2005) 6568.
[46] Z. Cai, C.R. Martin, J. Am. Chem. Soc. 111 (1989) 41384139.
[47] J. Duchet, R. Legras, S. Demoustier-Champagne, Synth. Met. 98 (1998)
113122.
[48] Z.X. Wei, Z.M. Zhang, M.X. Wan, Langmuir 18 (2002) 917921.
[49] M. Delvaux, J. Duchet, P.Y. Stavaux, R. Legras, S. Demoustier-
Champagne, Synth. Met. 113 (2000) 275280.
[50] Y.C. Zhao, M. Chen, T. Xu, W.M. Liu, Colloids Surf. A 257258 (2005)
363368.
[51] C.Y. Peng, A.K. Kalkan, S.J. Fonash, B. Gu, A. Sen, Nano Lett. 5 (2005)
439444.
[52] H. Cao, C. Tie, Z. Xu, J. Hong, H. Sang, Appl. Phys. Lett. 78 (2001)
15921594.
[53] J. Li, K. Fang, H. Qiu, S.P. Li, W.M. Mao, Q.Y. Wu, Synth. Met. 145
(2004) 191194.
[54] H.J. Qiu, M.X. Wan, B. Matthews, L.M. Dai, Macromolecules 34 (2001)
675677.
[55] J. Liu, M.X. Wan, J. Mater. Chem. 11 (2001) 404407.
[56] Y.Z. Long, Z.J. Chen, P. Zheng, N.L. Wang, Z.M. Zhang, M.X. Wan, J.
Appl. Phys. 93 (2003) 29622965.
[57] Z.X. Wei, M.X. Wan, J. Appl. Polym. Sci. 87 (2003) 12971301.
[58] Z.M. Zhang, Z.X. Wei, M.X. Wan, Macromolecules 35 (2002)
59375942.
[59] Y.S. Yang, J. Liu, M.X. Wan, Nanotechnology 13 (2002) 771773.
[60] A.D.W. Carswell, E.A. ORear, B.P. Grady, J. Am. Chem. Soc. 125 (2003)
1479314800.
[61] X.Y. Zhang, S.K. Manohar, Chem. Commun. (2004) 23602361.
[62] P. Nickels, W.U. Dittmer, S. Beyer, J.P. Kotthaus, F.C. Simmel, Nanotech-
nology 15 (2004) 15241529.
[63] Y.F. Ma, J.M. Zhang, G.J. Zhang, H.X. He, J. Am. Chem. Soc. 126 (2004)
70977101.
[64] J.M. Liu, S.C. Yang, J. Chem. Soc., Chem. Commun. (1991) 15291531.
[65] S.J. Choi, S.M. Park, Adv. Mater. 12 (2000) 15471549.
[66] T. Hatano, M. Takeuchi, A. Ikeda, S. Shinkai, Chem. Lett. 32 (2003)
314315.
[67] L.M. Huang, Z.B. Wang, H.T. Wang, X.L. Cheng, A. Mitra, Y.X. Yan, J.
Mater. Chem. 12 (2002) 388391.
[68] J. Kan, R. Lv, S. Zhang, Synth. Met. 145 (2004) 3742.
[69] J.Q. Kan, S.L. Zhang, G.L. Jing, J. Appl. Polym. Sci. 99 (2006)
18481853.
[70] M.X. Wan, J.C. Li, J. Polym. Sci., Part A: Polym. Chem. 38 (2000)
23592364.
[71] Y.Z. Long, Z.J. Chen, N.L. Wang, Z.M. Zhang, M.X. Wan, Phys. B:
Condens. Matter 325 (2003) 208213.
[72] L.J. Zhang, M.X. Wan, Nanotechnology 13 (2002) 750755.
[73] Y.Z. Long, L.J. Zhang, Y.J. Ma, Z.J. Chen, N.L. Wang, Z. Zhang, M.X.
Wan, Macromol. Rapid Commun. 24 (2003) 938942.
[74] Y.Z. Long, J.L. Luo, J. Xu, Z.J. Chen, L.J. Zhang, J.C. Li, M.X. Wan, J.
Phys. :Condens. Matter 16 (2004) 11231130.
[75] Y.Z. Long, Z.J. Chen, N.L. Wang, Y.J. Ma, Z. Zhang, L.J. Zhang, M.X.
Wan, Appl. Phys. Lett. 83 (2003) 18631865.
[76] K. Huang, M.X. Wan, Chem. Mater. 14 (2002) 34863492.
[77] Y.S. Yang, M.X. Wan, J. Mater. Chem. 12 (2002) 897901.
[78] N.J. Pinto, P.L. Carri on, A.M. Ayala, M. Ortiz-Marciales, Synth. Met.
148 (2005) 271274.
[79] J.H. Hwang, S.C. Yang, Synth. Met. 29 (1989) 271276.
[80] G.C. Li, S.P. Pang, H.R. Peng, Z.B. Wang, Z.L. Cui, Z.K. Zhang, J. Polym.
Sci., Part A: Polym. Chem. 43 (2005) 40124015.
[81] C.H. Yang, Y.K. Chih, H.E. Cheng, C.H. Chen, Polymer 46 (2005)
1068810698.
[82] D.M. Sarno, S.K. Manohar, A.G. MacDiarmid, Synth. Met. 148 (2005)
237243.
[83] H. Xia, J. Narayanan, D. Cheng, C. Xiao, X. Liu, H.S.O. Chan, J. Phys.
Chem. B. 109 (26) (2005) 1267712684.
[84] Z.M. Zhang, Z.X. Wei, L.J. Zhang, W.X. Wan, Acta Mater. 53 (2005)
13731379.
[85] J. Huang, M.X. Wan, J. Polym. Sci., Part A: Polym. Chem. 37 (1999)
151157.
[86] U. Beginn, Adv. Mater. 10 (1998) 13911394.
[87] M. Bockstaller, W. K ohler, G. Wegner, D. Vlassopoulos, G. Fytas, Macro-
molecules 33 (2000) 39513953.
[88] E.N. Konyushenko, J. Stejskal, I. Sedenkova, M. Trchova, I. Sapurina,
M. Cieslar, J. Prokes, Polym. Int. 55 (2006) 3139.
[89] G.C. Li, Z.K. Zhang, Macromolecules 37 (2004) 26832685.
[90] G.C. Li, H.R. Peng, Y. Wang, Y. Qin, Z.L. Cui, Z.K. Zhang, Macromol.
Rapid Commun. 25 (2004) 16111614.
[91] W.G. Li, H.L. Wang, J. Am. Chem. Soc. 126 (2004) 22782279.
[92] X.M. Feng, G. Yang, Q. Xu, W.H. Hou, J.J. Zhu, Macromol. Rapid Com-
mun. 27 (2006) 3136.
[93] R.C.Y. King, F. Roussel, Synth. Met. 153 (2005) 337340.
[94] X. Zhang, H.S. Kolla, X. Wang, K. Raja, S.K. Manohar, Adv. Funct.
Mater. 16 (2006) 11451152.
[95] H.S.O. Chan, P.K.H. Ho, K.L. Tan, B.T.G. Tan, Synth. Met. 35 (1990)
333344.
[96] J.C. Michaelson, A.J. McEvoy, J. Chem. Soc., Chem. Commun. (1994)
7980.
[97] H. Gao, T. Jiang, B. Han, Y. Wang, J. Du, Z. Liu, J. Zhang, Polymer 45
(2004) 30173019.
[98] J.X. Huang, R.B. Kaner, J. Am. Chem. Soc. 126 (2004) 851855.
[99] P.L.B. Ara ujo, E.S. Ara ujo, R.F.S. Santos, A.P.L. Pacheco, Microelectron.
J. 36 (2005) 10551057.
[100] D.D. Sawall, R.M. Villahermosa, R.A. Lipeles, A.R. Hopkins, Chem.
Mater. 16 (2004) 16061608.
[101] A.R. Hopkins, D.D. Sawall, R.M. Villahermosa, R.A. Lipeles, Thin Solid
Films 469470 (2004) 304308.
[102] S.K. Pillalamarri, F.D. Blum, A.T. Tokuhiro, M.F. Bertino, Chem. Mater.
17 (2005) 59415944.
D. Zhang, Y. Wang / Materials Science and Engineering B 134 (2006) 919 19
[103] L.K. Werake, J.G. Story, M.F. Bertino, S.K. Pillalamarri, F.D. Blum, Nan-
otechnology 16 (2005) 28332837.
[104] Y. Wang, Z.M. Liu, B.X. Han, Y. Huang, G.Y. Yang, Langmuir 21 (2005)
833836.
[105] N.R. Chiou, A.J. Epstein, Adv. Mater. 73 (2005) 16791683.
[106] N.R. Chiou, A.J. Epstein, Synth. Met. 153 (2005) 6972.
[107] D. Li, R.B. Kaner, J. Am. Chem. Soc. 128 (3) (2006) 968975.
[108] H. Okamoto, M. Okamoto, T. Kotaka, Polymer 39 (1998) 4359
4367.
[109] J.A. Smith, M. Josowicz, J. Janata, J. Electrochem. Soc. 150 (2003)
E384E388.
[110] G.F. Li, C. Martinez, J. Janata, J.A. Smith, M. Josowicz, S. Semancik,
Electrochem. Solid-State Lett. 7 (2004) H44H47.
[111] J.J. Langer, I. Czajkowski, Adv. Mater. Opt. Electron. 7 (1997) 149156.
[112] J.J. Langer, Adv. Mater. Opt. Electron. 9 (1999) 17.
[113] J.J. Langer, G. Framski, S. Golczak, T. Gibinski, Synth. Met. 119 (2001)
359360.
[114] J.J. Langer, G. Framski, R. Joachimiak, Synth. Met. 121 (2001)
12811282.
[115] J.J. Langer, G. Framski, S. Golczak, Synth. Met. 121 (2001) 13191320.
[116] L. Liang, J. Liu, C.F. Windisch, G.J. Exarhos, Y.H. Lin, Angew. Chem.
Int. Ed. 41 (2002) 36653668.
[117] J. Liu, Y. Lin, L. Liang, J.A. Voigt, D.L. Huber, Z.R. Tian, E. Coker, B.
McKenzie, M.J. McDermott, Chem. Eur. J. 9 (2003) 604611.
[118] X. Li, S. Tian, Y. Ping, D.H. Kim, W. Knoll, Langmuir 21 (2005)
93939397.
[119] R.V. Parthasarathy, C.R. Martin, Chem. Mater. 6 (1994) 16271632.
[120] J.P. Spatz, B. Lorenz, K. Weishaupt, H.D. Hochheimer, Phys. Rev. B 50
(1994) 1488814892.
[121] F. Selampinar, L. Toppare, U. Akbulut, T. Yalcin, S. Suzer, Synth. Met.
68 (1995) 109116.
[122] J.E.G. De Souza, B.B. Neto, F.L. Dos Santos, C.P. De Melo, M.S. Santos,
T.B. Ludermir, Synth. Met. 102 (1999) 12961298.
[123] M. Hirata, L. Sun, Sens. Actuators A 40 (1994) 159163.
[124] K.H. Hong, K.W. Oh, T.J. Kang, J. Appl. Polym. Sci. 92 (2004) 3742.
[125] S.K. Dhawan, D. Kumar, M.K. Ram, S. Chandra, D.C. Trivedi, Sens.
Actuators B 40 (1997) 99103.
[126] S. Koul, R. Chandra, S.K. Dhawan, Sens. Actuators B75 (2001) 151159.
[127] S. Takeda, Thin Solid Films 343344 (1999) 313316.
[128] S. Sharma, C. Nirkhe, S. Pethkar, A.A. Athawale, Sens. Actuators B 85
(2002) 131136.
[129] A.A. Athawale, M.V. Kulkarni, Sens. Actuators B 67 (2000) 173177.
[130] G.E. Collins, L.J. Buckley, Synth. Met. 78 (1996) 93101.
[131] C.P. De Melo, C.G. Dos Santos, A.M.S. Silva, F. Dos Santos, J.E.G. De
Souza, Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A374 (2002) 543548.
[132] J.X. Huang, S. Virji, B.H. Weiller, R.B. Kaner, Chem. Eur. J. 10 (2004)
13141319.
[133] J.X. Huang, R.B. Kaner, Nat. Mater. 3 (2004) 783784.
[134] D. Li, Y.N. Xia, Nat. Mater. 3 (2004) 753754.
[135] C.Y. Wu, A. Benatar, Polym. Eng. Sci. 37 (1997) 738743.
[136] R.J. Tseng, J. Huang, J. Ouyang, R.B. Kaner, Y. Yang, Nano Lett. 5 (2005)
10771080.