Colloids and Surfaces A: Physicochem. Eng.

Aspects 248 (2004) 111120

The preparation of polyaniline waterborne latex nanoparticles and

their films with anti-corrosivity and semi-conductivity
Xin-Gui Lia,b,c, , Mei-Rong Huanga , Jian-Feng Zenga , Mei-Fang Zhub
a

Institute of Materials Chemistry, The Key Laboratory of Concrete Materials Research, College of Materials Science Engineering,
Tongji University, 1239 Siping Road, Shanghai 200092, China
The State Key Laboratory for Modication of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 200051, China
c The Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
Received 16 March 2004; accepted 28 August 2004

Abstract
An emulsion polymerization of aniline was performed in micellar solution of sodium dodecylbenzene sulfonate (SDBS), dodecylbenzene
sulfonic acid (DBSA), or sodium dodecylsulfate (SDS) as both emulsifier and dopant to obtain stable nano-polyaniline (PAN) waterborne
latexes. The direct film formability and anti-corrosivity of PAN latexes were studied. The uniform PANSDS/polyvinyl alcohol (PVA)
composite films were prepared by casting a direct mixture of the PAN latex and PVA aqueous solution. The emulsifier species and concentration,
mixing way of emulsifier with aniline, and polymerization solution acidity, have a remarkable influence on the diameter and stability of PAN
latex particles. The molar ratio of emulsifier over aniline was optimized for the synthesis of the PAN latex with small particle size and good
properties including film formability, anti-corrosivity, and electrical conductivity. The smallest diameters of PANSDBS, PANDBSA, and
PANSDS spherical particles determined by laser particle analyzer and electron microscopes are 2500, 40 and 5 nm, respectively. A good direct
film formability of the PAN latex nanoparticles was found. The film formed by solution-casting method is thin, smooth and metal-lustrous.
The electrochemical impedance spectroscopy was used to evaluate the impedance of the PAN latex films sandwiched between acrylic resin
and iron sheet. It is found that the PAN has excellent anti-corrosivity, implying a possibility of direct application as metal anti-corrosive
coating. A semi-conductive PAN/PVA nanocomposite film containing a very small amount of PAN nanoparticles exhibits low percolation
threshold of PAN concentration of 0.1 wt.%.
2004 Elsevier B.V. All rights reserved.
Keywords: Emulsion polymerization; Polyaniline nanoparticle; Metal anti-corrosion; Polyaniline/polyvinyl alcohol composite film; Semi-conductivity

1. Introduction
Polyaniline (PAN) has been considered as one of the
most important conducting polymers for various electrochemical, electrorheological and electronic applications to
rechargeable batteries, sensors, controlling systems and organic displays [14] because of its facile synthetic process,
good environmental stability, easy conductivity control and
cheap production in large quantities. However, the conductive form of PAN is difficult to be processed because it is

Corresponding author. Tel.: +86 21 65980524; fax: +86 21 65980530.

E-mail address: lixingui@tongji.edu.cn (X.-G. Li).

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.08.077

both insoluble in common organic solvents except for Nmethylpyrrolidone (NMP) and unstable at melt-processing
temperature, which greatly limits its future wide applications.
To solve the intractable processing problem, several modification researches such as introducing side groups [510],
doping with functional dopants [11,12], blend and composite
[13,14], and preparing dispersed particles [1521], have been
done.
PAN dispersion is one of the attractive alternatives to overcome the poor processability, which could also be directly
utilized as a key component of the blend and composite materials exhibiting high performance. Specially, the nano-PAN
waterborne latex not only remains the good property of PAN

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but also greatly improves its processing capability as well

as reduce environmental impact. Furthermore, it possesses
some special properties of the nanoparticles. As to applications, this kind of waterborne latex is suitable to be used as
PAN coating, which is much better than the coatings based
on organic solvent or strong acid because the water in the
PAN coating does not pollute the environment. Therefore,
the nano-PAN waterborne latex has become a hot research
point in materials science.
The synthesis of nanoscopic PAN in colloids form in the
presence of a water-soluble polymers such as poly(vinyl alcohol) (PVA), poly(N-vinylpyrrolidone), poly(vinyl methyl
ether), poly(ethylene oxide) (PEO) or cellulose ethers has
been reported [1517,22]. The water-soluble polymers acted
not only as steric stabilizers but also as co-monomers. However, sometimes the dispersion polymerization still resulted
in macroscopic precipitation and, in certain cases, in a low
yield of small colloidal particles. Thus, it is not easy to get the
pure polymers with these methods and the nanoscopic microspheres obtained are often copolymers or composites because
the separation between the PAN and the water-soluble polymers is very difficult.
One facile method of synthesizing nanoscopic PAN as
a waterborne coating is microemulsion polymerization containing a large amount of nanoscopic micelles. The micelles
can change the local environment by aligning and absorbing the monomer and adjusting polymerization reaction, and
may yield polymer microspheres with improved properties.
Han et al. have prepared PAN nanoparticles in DBSA and
SDS micellar solutions, respectively [18,19]. However, a direct film formability and anti-corrosion property of this kind
of PAN latex have not been investigated. A study on a facile
fabrication of a nanocomposite film of the nano-PAN latex
and PVA exhibiting low percolation threshold is not found
either.
The overall goal of this article is to synthesize nano-PAN
waterborne latexes and investigate their structure, properties
and possible applications. Two series of waterborne latexes,
nano-PANDBSA and nano-PANSDS, were prepared by
emulsion and microemulsion polymerisation, respectively,
in which DBSA and SDS were used both as surfactants and
dopants. The size and shape of PAN micelles were observed
in detail. These two kinds of nano-PAN latexes were directly
cast into homogeneous films and nanocomposite films. The
electrochemical impendence, anti-corrosion ability, and electrical conductivity of the films were characterized for the first
time. The potential application of the PAN latexes is mentioned.

2. Experimental
2.1. Chemicals
Aniline (AN), ammonium persulfate (APS), sodium dodecylbenzene sulfonate (SDBS), dodecylbenzene sulfonic acid

(DBSA), sodium dodecylsulfate (SDS), acrylic resin, and

HCl were of analytical reagent and commercially obtained.
2.2. Preparation of nano-PAN waterborne latexes
2.2.1. Emulsion polymerization in dodecylbenzene
sulfonic acid (DBSA) micellar solution
Aqueous micellar dispersions were prepared by introducing DBSA into distilled water (80 mL) with a slow stirring.
Then AN monomer was added drop-wise to the solution and
a white turbid emulsion of DBSA and AN was formed. After the micellar dispersion was kept stirring for longer than
120 min, an oxidative polymerization was performed at 5 C
for 12 h by a drop-wise addition of APS aqueous solution
(20 mL) into the micellar solution at a fixed total APS/AN
molar ratio of 0.5.
2.2.2. Microemulsion polymerization in sodium
dodecylsulfate (SDS) micellar solution
The 0.1 M HCl solution was used as an aqueous phase in
SDS micellar solution. First, 100 mL 0.1 M HCl was used
to dissolve SDS for the preparation of aqueous micellar dispersions. Then AN monomer was added drop-wise to the
dispersions. After stirring this AN transparent microemulsion for some time, 10 mL 0.1 M HCl solution containing
APS as oxidant was added drop-wise at an adding rate of a
drop (around 60 L) per 3 s into the SDS micellar solution.
After the induction period of about 4060 min, the homogeneous transparent reaction mixtures turned into blue and
its coloration was pronounced as polymerization proceeded.
The molar ratio of APS to AN was kept as 0.5. Since the
Krafft point of SDS is around 16 C, the polymerization was
performed at 20 C.
2.3. Direct lm fabrication from nano-PAN waterborne
latex
The free-standing films were made by casting nano-PAN
waterborne latex on a clean, dry glass with the area of
2 cm 2 cm and drying under an infrared lamp at 60 C to
remove the solvent. After drying for at least 24 h, these films
were immersed in water for 30 min to peel the films from the
glass.
2.4. Preparation of PAN/ACR coating on iron plate
A tinplate containing 99.9% iron with respective area and
thickness of 2 cm 10 cm and 0.8 mm was used as testing
samples. One side of the samples was polished by 100 grit
emery paper. Prior to coating, all samples were degreased
with acetone to remove impurities. The nano-PAN waterborne latex was cast drop-wise on the pretreated iron samples. After drying in oven at 60 C for 24 h, these PAN/iron
samples were coated with acrylic resin as a top layer. These
composite coatings were then dried in the same condition

X.-G. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 248 (2004) 111120

for another 24 h. The other side and edges of the iron samples were sealed with olefin before being characterized by
electrochemical impedance spectroscopy (EIS).
2.5. Preparation of PAN/PVA composite lms
The 5-wt.% PVA solution was obtained by adding 5 g PVA
into 95 g distilled water with vigorous stirring at 85 C. A
mixture of nano-PAN waterborne latex and PVA solution was
prepared by mixing these two solutions directly at room temperature. The resultant volume and solid content of the whole
mixture were controlled to 2 mL and 3%, respectively. The
PAN/PVA composite films were prepared by casting the mixture solutions onto 5 cm 5 cm glass substrates and drying
at 40 C for 48 h prior to measurements.
2.6. Measurements
The size and morphology of PAN particles in their latexes
were observed by HITACHI model H800 transmission electron microscope (TEM) and field emission scanning electron
microscopy (FE-SEM, Jeol Model JSM-6340F). Samples for
TEM observation were prepared by dropping highly diluted
latex onto the carbon-coated copper grid and dried in a desiccator at room temperature. SEM samples were sputter-coated
with gold for 60 s. The size of the PAN latex particles in water
was analyzed using LS230 laser particle size analyzer from
Beckman Coulter Inc. Samples for FT-IR characterization
were made with two different methods. Method 1: original
PAN waterborne latex was directly dried in an oven at 60 C
for 48 h to get solid PAN particles. Method 2: original PAN
waterborne latex was first precipitated by excess amount of
methanol, then washed with ethanol, and finally dried at 60 C
for 48 h. The FT-IR spectra (Nicolet Magna-IRTM 550 spectroscopy) of these two kinds of powders were recorded by
the KBr pellet technique. EIS experiments were carried out
in a three-electrode cell using 1 M NaCl as background electrolyte [23,24]. A saturated calomel electrode (SCE) was used
as reference electrode. The ACR/PAN/iron samples were
used as working electrode and a platinum electrode with a
foil of area 0.8 cm2 as counter electrode. The EIS testing system consists of EG&G Amplifier & Filter model 5208. The
potentiostatic model M273 and the Impedance Spectrum Analyzer with EIS M398 software were employed to measure
and analyze their electrochemical impedance spectra at ambient temperature. In this work, the potential amplitude of
ac was kept at 5 mV and its frequency ranged from 100 kHz
to 10 Hz. In our study, the dried samples were immersed in
the 5% NaCl solution for 10 min before the testing, so that
the open-circuit potential of the coated substrate could be
stable during EIS measurements. The electrical conductivity
of PAN/PVA composite films was measured using a digital
multimeter. The bulk resistance was measured when the film
was clamped tightly between the two electrodes with the area
of 0.785 cm2 . The film thickness was measured with a continuous thickness detector. The DC conductivity () could be

113

calculated according to the following Eq. (1):

=

L
RS

(1)

where R represents bulk resistance; L the film thickness; and

S the electrode area. Therefore, the specific sheet resistance
(Rs ) could be calculated according to Eq. (2):
Rs =

1
L

(2)

3. Results and discussion

3.1. Emulsion polymerization of AN in DBSA and
SDSHCl micellar solutions
The emulsification of AN and surfactants and emulsion
polymerization are followed by the pH values of the reaction
solutions, which might provide an insight into polymerization process. It is seen from Fig. 1 that the emulsification of
ANDBSA aqueous solution is accompanied by a remarkable increase in pH value, suggesting that a strong interaction
between alkaline AN and acidic DBSA occurs, such as the
protonation of AN. As the APS solution was dropped, the
solution pH increased further and then gradually reached up
to 5.4. The solution color also changed from yellow, lightly
green to green at about 8 h. These phenomena strongly imply
an occurrence of the AN oxidative polymerization and the
formation of PAN emeraldine. The variation of the solution
pH with reaction time shows that the oxidative polymerization was substantially finished at 8 h.
As the polymerization proceeded, the color of the
ANSDS solution also changed from yellow, brown, blue,
and finally to green at 5 h, which indicates the formation of
PAN emeraldine salt (ES). Note that the reaction mixture was
transparent from the beginning to the end, which is quite different from turbid emulsion polymerization of AN in DBSA
solution. The pH of this solution in Fig. 1 slightly increased as
the reaction proceeded. Apparently, the enhancement of the
pH value is much lower than that in DBSA micellar solution,
because of the presence of HCl as polymerization medium. It

Fig. 1. The changes of solution pH value with reaction time. (a) In DBSA
micellar solution at 5 C; and (b) in SDS micellar solution at 20 C.

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Fig. 2. FT-IR spectra for PANDBSA and SDS particles of the sample
numbers D3 and S8.

appears that the solution pH is basically constant after oxidative polymerization of 10 h, indicating a completion of the
oxidative polymerization at 10 h. Apparently, the polymerization rate of AN is slower in SDSHCl aqueous solution
than in DBSA aqueous solution.
3.2. Molecular structure and size of PAN latex
nanoparticles

Fig. 3. SEM microphotographs of PANDBSA latex particles of (a) D2

sample and (b) D5 sample.

FT-IR spectra for two kinds of powder samples of

PANDBS A and PANSDS are shown in Fig. 2. The purified samples corresponding to curves b and d exhibit substantially same IR spectra as general PAN [25] except for a
peak at 1125 cm1 assigned to S O stretching mode of sulfonic acid that indicates a doped PAN by DBSA. However,
unpurified original samples illustrate stronger peaks from
2800 to 3000 cm1 due to aliphatic C H stretching mode
on long alkyl tail of DBSA and SDS. Two unpurified samples also illustrate different shapes and wave numbers of the
peaks attributed to C C stretching of benzenoid and quinoid

rings, suggesting their different structures each other, possibly due to the different interactions between the PAN chains
and DBSA or SDS.
Table 1 summarized the size of PAN latex particles formed
at five DBSA/AN molar ratios. Fig. 3 shows the SEM micrographs of PAN latex particles of samples D2 and D5. It can be
seen from Fig. 3(a) that the shape of PAN latex particles is basically globular and their diameter ranges from 80 to 100 nm.
These particles are different from larger needle-like crystals
of polyanilinium-DBSA complex at higher molar ratio of

Table 1
The size and direct film formability of PAN particles obtained by emulsion polymerization of AN in DBSA micellar system at a fixed APS/AN molar ratio of
0.5
Sample numbers

DBS A/AN molar ratio

Particle size determined by SEM (nm)
Film-forming ability
Film appearance
Film color
Film metal luster

D1

D2

D3

D4

D5

0.5
8001000
Fair
Porous, rough
Dark green
No

0.8
80100
Nice
Sparse, slightly smooth
Green
Slight

1.0
6070
Good
Dense, smooth
Green
Evident

1.2
5060
Good
Dense, smooth
Green
Evident

1.5
4050
Good
Dense, smooth
Green
Evident

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115

Table 2
The size of PAN particles obtained by microemulsion polymerization of AN/SDS micellar system at APS/AN molar ratio of 0.5 in 0.1 M HCl
Sample numbers

AN concentration (M)
SDS/AN molar ratio
Particle size determined
by TEM (nm)

S1

S2

S3

S4

S5

S6

S7

S8

S9

0.12
1.7
>2000

0.03
1.7
2000

0.09
2.2
>2000

0.03
2.2
1000

0.06
3.3
>2000

0.03
3.3
300400

0.04
5.0
8001000

0.03
5.0
520

0.03
6.7
1020 [17]

DBSA/AN (1/1), which even could be observed by optical

microscopy [26]. But a few particles are not definitely regular in shape and the their size is up to one micrometer. The
formation of large particles may be ascribed to the aggregation of small particles during the precipitation of the latexes
for SEM observation. The particles of sample D5 shown in
Fig. 3(b) exhibit rice-like shape. The size of some isolated
particles seems to be below 50 nm, which is smaller than that
of sample D2, probably owing to the comparatively higher
DBSA content in sample D5 than D2. At the same time, the
reaction speed is accelerated in lower pH media caused by
relatively higher DBSA content. As a result, the deviation of
latex particle shape from sphere could not be excluded.
TEM microphotographs of PAN latex particles from SDS
micellar system are shown in Fig. 4. PANSDS particles are
clearly observed to be spherical and exhibit much smaller
size and much narrower size distribution than PANDBSA
particles in Fig. 3. In particular, the diameter of PANSDS
particles formed at lower SDS/AN ratio of 5.0 in this study
is 520 nm which is even smaller than that of the PANSDS
particles prepared at higher SDS/AN ratio of 6.7 [19].

the synthesis of nano-PAN waterborne latexes should be 0.8

and 3.9, respectively. That is to say, the DBSA is much more
efficient for the preparation of the nano-PAN waterborne latexes than the SDSHCl. However, the PAN latex particles

3.3. Inuence of polymerization conditions on the

formation of nano-PAN latexes
As can be seen from Tables 1 and 2 and Fig. 5, the molar
ratio of emulsifier to AN has a great affection on the PAN
particle size. The size of both PANDBSA and PANSDS
particles decreased with increasing DBSA/AN or SDS/AN
molar ratio. According to the nucleation mechanism of micelles in emulsion, nucleation plays an important role in the
formation of particles, and the number of the resultant latex particles was controlled by the number of micelles. In
principle, at a fixed AN concentration, the larger the number of micelles, the smaller the size of latex micelles is. So,
as the emulsifier content increases, the number of micelles
increases, leading to a reduced particle size.
On the contrary, it can also be found from Fig. 5 that the
PAN latex particle size increased sharply to one or a few
micrometers at the DBSA/AN molar ratio below 0.8 and
SDS/AN below 5. The reason could be attributed to lower
emulsifier content, resulting in the instability of smaller latex
particles. To stabilize the smaller latex particles, it is necessary for the particles to absorb more emulsifier molecules
from the solution nearby. This suggests that at fixed oxidant
content, the critical DBSA/AN and SDS/AN molar ratios for

Fig. 4. TEM microphotographs of PANSDS latex particles of S8 sample.

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X.-G. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 248 (2004) 111120

revealing a great discrepancy in formation and stabilization

of PAN latex particles caused by DBSA, SDS, and SDBS.
Therefore, it can be concluded that a reduced order of the
size of the PAN latex particles stabilized by three emulsifiers
usually ranks as follows:
SDBSHCl > DBSA > SDSHCl

Fig. 5. The influence of emulsifier/AN molar ratio on dried PAN particle

sizes in the DBSA or SDS micellar system.

Fig. 6. The effect of HCl concentration on the size of PANSDBS latex

particles in water at a fixed SDBS/AN and APS/AN molar ratios of 1 and
0.5, respectively, at 12 C by laser particle size analysis.

formed at the SDS/AN molar ratio of 5 exhibit the smallest

size.
As shown in Fig. 6, the size of PAN latex particles dramatically gets larger with the increase of HCl concentration.
This suggests that the ionization of SDBS molecules in HCl
solution would be depressed with elevating HCl concentration, which weakens the electric repulsion between surfactant
head groups. This weak electric repulsion might prevent the
aggregation of smaller particles with difficulty and then the
formation of larger particles. In addition, at higher HCl concentration, the formation rate of AN radical cations at a fixed
AN concentration becomes slower, resulting in less polymerizing sites or reactive nuclei, and then larger PAN particles.
Figs. 5 and 6 clearly illustrate a great difference in the
sizes of PANDBSA, PANSDS, and PANSDBS particles,

The way of adding the monomer into the micellar solution significantly affected the stability of PAN waterborne
latexes. It is found that the addition of the AN monomer
into the micellar solution in one portion generally resulted
in the formation of big PAN particles that can be seen by
naked eyes. This result may be explained by the followed
two causes. One is that some latex particles aggregated together because of very exquisite polymerization. The other
is that there is not enough time for some AN monomer to
enter into the DBSA or SDS micelles. Therefore, the AN
monomer still stayed in the continuous aqueous phases. Apparently, it is much easier for PAN particles to get together
in the absence of protection from emulsifier molecules. Contrary to the way of adding monomer one time, the way to add
monomer drop-wise could obtain homogeneous and transparent solution-like nano-PAN waterborne latex. Furthermore,
this kind of latex could keep high homogeneity for at least
several months. That is to say, the nano-PAN latexes formed
in this way exhibit much higher stability than those in literature [27]. The way to add AN drop by drop could always
form smaller and more stable nano-PAN latexes because the
AN monomer has enough time to diffuse into micelles homogenously, finally leading to a smooth polymerization in the
micelles.
As listed in Table 3, stirring time of AN emulsion
before adding oxidant strongly influences the stability of
PANDBSA latexes obtained later. It is found that the latexes get more homogeneous and transparent with prolongating stirring time. This is related to the degree of uniformity
extent of AN diffusion into micelles. If the stirring time is
too short, the AN would not have adequate time to uniformly
and sufficiently enter into the micelles, resulting in the polymerization of AN outside the micelles, and finally affecting
the stability of PAN latexes. Approximate stirring time of
AN emulsion before adding oxidant should range from 120
to 150 min for the preparation of homogeneous and semitransparent PAN nano-latexes. Table 3 also shows that the
stability of the PANDBSA and PANSDS latexes exhibits
similar dependency of stirring time.

Table 3
The effect of stirring time of aniline emulsion before polymerization on the stability of PANDBSA micellar system
Stirring time of aniline
emulsion before adding
oxidant (min)

Appearance of PANDBSA latex

after polymerization for 12 h

Appearance of PANDBSA latex on

the 30th day after polymerization

30
60
120
150

Some aggregates
Some floc
Basically homogeneous and semi-transparent
Homogeneous and semi-transparent

Demulsion or precipitation
Demulsion or precipitation
Homogeneous and semi-transparent
Homogeneous and semi-transparent

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117

Table 4
Direct film formability of nano-PAN waterborne latexes obtained using SDSHCl as emulsifier
Sample numbers

Film formability
Film appearance
Film color
Film metal luster

S2

S4

S6

S8

S9

Bad
Porous, rough
Dark green
No

Bad
Porous, rough
Dark green
No

Good
Sparse, slightly smooth
Dark green
Fair

Excellent
Dense, smooth
Dark green
Evident

Excellent
Dense, smooth
Dark green
Evident

3.4. Direct lm formability of nano-PAN waterborne

latexes
Tables 1 and 4 present the apparent characters of the films
formed by directly casting nano-PANDBSA and SDS waterborne latexes. It appears that the film-forming ability of
the latexes becomes better with increasing emulsifier content or decreasing PAN particle size. The films of PAN latexes with smaller size exhibit evident metal luster as well as
dense and homogeneous structure that has been observed by
optical microscope. A possible process of film formation of
latex nanoparticles could be described as follows: the evaporation of water will first result in an appropinquity between
the PAN latex particles. With a further water evaporation,
the latex particles may shrink gradually and then get closer
and closer, leading to a uniform mergence of the adjacent
particles, finally forming homogeneous film. Note that the
emergence of the larger latex particles must accompany with
the formation of some defects, such as microvoids and pinholes between the particles, leading to higher surface roughness. In summary, the smaller the particle size, the stronger
the film formability is, because PAN nanoparticles possess
tremendous specific surface area as well as the surfaces of the
doped PAN nanoparticles are highly charged. These specific
features of PAN nanoparticles provide an original driving
force for the self-assembly of nanomaterials including anticorrosion coating and semi-conducting composite films.

tail demonstrates that the corrosion process has been transformed from electrochemical control to diffusion control, indicating that the coatings have been at the last immersion
stage. Zre and Zim1/2 curves present a characteristic

Fig. 7. The dependency of the modulus of complex number of the impedance

of ACR/iron and ACR/PAN/iron on the testing frequency.

3.5. Inhibition of iron corrosion by PAN/ACR coating

The modulus (|Z|) of complex number of the impedance
of ACR/iron and ACR/PAN/iron shows a dependency of the
testing frequency in Fig. 7. It is seen that ACR/PAN/iron
exhibits much higher |Z| than ACR/iron. Among them,
ACR/PAN(D5)/iron containing the smallest latex particles
(D5) exhibits the highest |Z| value in the higher frequency
range. Figs. 8 and 9 show the electrochemical impedance
spectra of ACR/iron and ACR/PAN/iron. Fig. 8 is a Nyquist
diagram that illustrates the relationship between real part and
imaginary units of impedance (Zre and Zim, respectively).
Fig. 9 displays a relationship between Zre or Zim and 1/2 ,
where represents angle frequency. From the Nyquist diagram, it can be seen that all impedance curves have a semicircle in the high-frequency region and a diffusing tail in
the low-frequency region. This impedance arc is attributable
to the transport resistance through the coating. The diffusing

Fig. 8. Nyquist diagram for ACR and PAN/ACR coatings on iron after
immersed in 1 M NaCl for 120 min. (a) ACR and (b) ACR/PAN(D2) and
ACR/PAN(D5).

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X.-G. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 248 (2004) 111120

Fig. 9. Zre or Zim1/2 diagram for (a) ACR and (b) ACR/PAN(S8)
coatings.

Fig. 10. Equivalent circuits for iron panel coated with ACR or ACR/PAN
coatings.

beeline in the low-frequency region, also verifying the diffusion control. Therefore, it can be deduced that the equivalent
circuit for iron panel coated with PAN/ACR coatings should
be illustrated in Fig. 10.
The electrochemical parameters of corrosion educed by
the electrochemical impedance spectra in Figs. 8 and 9 with
EIS M398 software were summarized in Table 5. Chargetransfer resistance (Rt ), coating resistance (Rc ), and doublelayer capacitance (Cdl ) can be used to jointly represent the
electrochemistry of corrosion at the coating/metal interface
after coating penetration by the corrosion species [28]. It is
found that ACR/S4 and ACR/S6 coatings exhibit basically
similar corrosion parameters as single pure ACR coating, in-

dicative that the insertion of S4 and S6 intermediate layers

could not improve anti-corrosion performance. However, the
insertion of S8, particularly, D2 and D5 coatings, will largely
increase Rt , Rc and impedance coefficient or decrease Cdl ,
suggesting that S8, D2, and D5 coatings indeed offer much
higher anti-corrosive performance than pure ACR layer if
a small difference in thickness is neglected. Therefore, it is
reasonable to infer that there has been a dense passive ironoxide layer formulated on the metal surface. According to
metal corrosion theory, there is an interface capacitance between metal and electrolyte solution. Its value has something
to do with the some factors such as metal surface state or solution components. In a given system, the change of interface
capacitance could reflect the transition of metal surface state.
There is a space charge layer in the passive iron-oxide layer,
which works as a new capacitance. When the passive ironoxide layer came into being, it corresponded to inserting a
new capacitance between metal and electrolyte. At this time,
the interface capacitance is composed of the new capacitance
in series with the double-layer capacitance. Since the space
charge layer exhibits much lower capacitance than the double
layer, the interface capacitance decreases sharply. The formulation of passive layer further approves that nano-PAN waterborne latex film possesses excellent protection properties
and anti-corrosive performance. And a passivation condition
at the coatingmetal interface created by the PAN coating is
also confirmed. Note that both the Rt and Cdl values in this
work are higher than literature value [29] at the analogical
conditions.
Note that the S8 coating gives stronger anti-corrosivity
than S4 and S6 coatings because of its smallest latex particle
size and higher film formability. D2 and D5 coatings show
better anti-corrosive performance than S8 coating because
the D2 and D5 coatings contain much less emulsifier, leading to relatively higher film-forming ability and then more
homogeneous and denser film structure.
3.6. Semi-conductivity of PAN/PVA composite lms
The semi-conductivity and percolation threshold of PANcontaining composite films depend significantly on the size
and morphology of PAN particles. The direct availability of
PAN latex nanoparticles provides the possibility to facilely
prepare semi-conductive composites with low percolation
threshold. The effect of the PANSDS or DBSA loading

Table 5
The best-fitting values of the equivalent circuit element analyzed from Nyquist diagram and Zre or Zim1/2 diagram of the ACR/PAN/tin plate samples
ACR/PAN (layer
thickness, (m)

Coating resistance
Rc (k
/cm2 )

Charge transfer resistance

Rt (k
/cm2 )

Double-layer capacitance
Cdl (F/cm2 )

Warburg impedance
coefficient (k
/cm2 s1/2 )

ACR(217)
ACR/S4(220/10)
ACR/S6(234/10)
ACR/S8(243/10)
ACR/D2(220/10)
ACR/D5(215/10)

1.817
0.250
1.245
375
515.2
607.0

1.482
1.374
3.799
517.2
596.8
628.1

9.831
10.56
25.45
0.102
4.30 106
5.43 106

1.515
2.738
2.225
834
3149
2865

X.-G. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 248 (2004) 111120

119

est PANSDS content (0.1 wt.%). This foreshows that the

PAN/PVA composite films have good antistatic performance.

4. Conclusions

Fig. 11. Effect of PANSDS and DBSA loading on the conductivity and
sheet resistance of PAN/PVA composite films with thickness of 1022 m.

on the room-temperature conductivity of PANSDS(S8) or

DBSA(D5)/PVA composite films is shown in Fig. 11.
As the PANSDS content in the films increased from
0 to 0.1 wt.%, the conductivity sharply increases from
1.65 l015 to 1.10 l07 S/cm for PANSDS(S8)/PVA
film and to 4.93 l012 S/cm for PANDBSA(D5)/PVA
film. With further increasing PAN content to 2.0 wt.%,
the conductivity of the both films gradually increases to
4.4 l05 for PANSDS(S8)/PVA film and 1.2 l08 S/cm
for PANDBSA(D5)/PVA film. Therefore, the percolation
threshold (Pc ) of the PAN concentration for film conductivity was found to be 0.1 wt.%. This Pc value is much lower than
that in composite films containing PAN particles prepared by
dispersion polymerisation [3032]. Note that Banerjee and
Mandal [15] have depressed the Pc to an extremely low value
of 0.043 wt.%. Such a low Pc value should be attributed to the
novel properties of carefully prepared PAN nanoparticles and
is not commonly obtainable through a direct addition of PAN
latex nanoparticles in the present work. It should be noticed
that the PANSDS (2.0 wt.%)/PVA film exhibits higher conductivity of 4.4 105 S/cm than that (5.6 l06 S/cm) of
PAN (7.8 wt.% or higher)/PVA film reported in refs. [32,33].
The establishment and enhancement of conductivity of the
composite films with introducing PAN nanoparticles are attributed to the formation of conductive paths through the
films. The direct addition of PAN latex nanoparticles into
PVA solution is not only simple but also predominant for the
fabrication of PAN nanoparticle composite film exhibiting
higher electrical conductivity.
Specific sheet resistance (Rs ) is defined as the resistance
per unit area, which can be used to evaluate the antistatic performance of materials to some extent. The (Rs ) value has been
calculated based on the electrical conductivity of PANSDS
and DBSA composite films and shown in Fig. 11. It is seen
that the (Rs ) value of the films sharply decreases with inducting PAN. Particularly, the PANSDS/PVA composite film
exhibits much lower specific sheet resistance (7.58 109
)
than the pure PVA film (5.51 1017
) even at the low-

PAN waterborne nano-latexes have been successfully prepared by using DBSA and SDS as surfactant and dopant, respectively. The mean diameter of PANDBSA and PANSDS
spherical particles is 4050 and 520 nm, respectively. The
optimal molar ratios of DBSA and SDS to AN for the synthesis of the PAN latex with nanoscopic particle size and
good properties are 1.5 and 5.0, respectively. The stirring
time of AN emulsion before adding oxidant and the way to
add monomer or oxidant have a great influence on the properties of resultant latex particles. Relatively long stirring time of
resulting AN emulsion and a drop-wise addition of AN into
surfactant solution are preferred. The size of the PAN latex
particles decreases significantly with increasing emulsifier
concentration or decreasing the system acidity. The article
gives a good method of synthesizing very small nanoparticles
with the diameter down to 5 nm that is usually very difficult
to be achieved. The PAN waterborne latex nanoparticles exhibit good direct film formability. The film obtained is smooth
and also metal-lustrous. The PAN nano-latex has better anticorrosivity, which could be directly applied as anti-corrosion
coatings of metals. The PANSDS/PVA composite films containing a very small amount of PAN nanoparticles show semiconductivity with a low percolation threshold of 0.1 wt.%.
As compared with pure PVA film, the PANSDS/PVA composite films show much lower sheet resistance, implying an
ability to dissipate electric charge, and realizing a facile semiconducting functionalization of traditional PVA.

Acknowledgements
The project was supported by (1) the National Natural
Science Foundation of China (20174028); (2) the Foundation of Nano Science and Technology Project of Shanghai
China (0259nm022); (3) the Foundation of Shanghai Leading Academic Discipline, Donghua University, China; and
(4) the Shanghai Key Laboratory of Molecular Catalysis and
Innovative Materials, Fudan University, China. The authors
would like to thank Prof. Dr. Dong-Yuan Zhao and He-Yong
He (Fudan University) for their valuable assistance.

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