Synthetic Metals 122 (2001) 297–304

Synthesis and characterization of polyaniline nanoparticles

in SDS micellar solutions
Byoung-Jin Kim, Seong-Geun Oh*, Moon-Gyu Han, Seung-Soon Im
Division of Chemical Engineering, Hanyang University, 17 Haendang-dong, Seongdong-gu, Seoul 133-791, South Korea
Received 1 February 2000; received in revised form 7 February 2000; accepted 21 June 2000

Abstract

Polyaniline (PANI) dispersions consisting of 10–20 nm sized nanoparticles were prepared by oxidation with ammonium peroxydisulfate
(APS) in sodium dodecylsulfate (SDS) micellar solutions. Coalescence and coagulation were prevented by electrostatic repulsive
interaction between anionic SDS micelles. Particle morphology was dependent on the initial shape of surfactant aggregates (micelles) and
the molar ratio of SDS to aniline monomer. Spherical particles were obtained at very low monomer concentration and the shape of particles
began to be distorted from the spherical shape as monomer concentration increased at constant 0.2 M SDS concentration. The size of
spherical particles was the same order of the micellar size or slightly larger. UV–VIS spectroscopy, compositions of PANI powder,
morphology, crystalline structure, thermal stability, molecular weight and conductivity of PANI particles synthesized at various monomer
and surfactant concentrations were investigated. # 2001 Elsevier Science B.V. All rights reserved.

Keywords: Polyaniline; Nanoparticles; SDS micelles; Morphology; Solubilization; Thermal stability

1. Introduction poly(N-vinylpyrrolidone), poly(vinyl methyl ether), cellu-

lose ethers or sophisticated tailor-made copolymer architec-
Polyaniline is an electrically conducting polymer with tures [5–8]. Particles are protected from the macroscopic
many features that can be exploited in various applications aggregation by the adsorption of steric stabilizers. PANI
such as microporous electrically conducting materials, particles prepared with these methods showed three distinctive
anticorrosion protection of metals, molecular sensor, sup- morphologies, rice grains, needles and spheres, depending
porting material for catalysts, etc. [1–4]. Among other upon the choice of stabilizers, chemical oxidant and reaction
conducting polymers such as polypyrrole, polythiophene, conditions [9]. Reactive polymeric stabilizers which have
polyacetylene and polyphenylenevinylene, polyaniline has pendant aniline units attached to the main chain and various
been most extensively studied because it exhibits a good kinds of inorganic particles were used as promising alterna-
environmental stability and its electrical properties can be tives resulting in stable polyaniline dispersions [10,11].
modified by the oxidation state of the main chain and degree Microemulsion, which is defined as a thermodynamically
of protonation. However, the poor thermal stability and stable and isotropic transparent solution of two immiscible
difficult processability of polyaniline should be overcome liquids basically consisted of oil, water and surfactant
for the successful application of this electrically conducting molecules, has been employed as a polymerization medium
polymer. to obtain spherical latex particles [12,13]. Microemulsion is
The preparation of polyaniline in colloidal form is one classified into three types, W/O (oil continuous), O/W
of the attractive alternatives to overcome the poor proces- (water continuous) and bicontinuous microemulsion. When
sability of PANI due to its insolubility in common organic polymerization is carried out, monomer molecules are
solvents and infusibility. There have been numerous reports incorporated into the submicron oil or water droplets dis-
on the preparation of PANI dispersions containing 100– persed in the continuous phase. In the case of aniline, W/O
300 nm sized particles. Usually, they are produced with microemulsions were employed exclusively as a reaction
suitable polymeric stabilizers, such as poly(vinyl alcohol), medium. Gan et al. prepared spherical nanoparticles (10–
35 nm) of PANI in water/petroleum ether/NP-5 (nonylphe-
*
Corresponding author. nol ethoxylate (5 mole)) reverse microemulsion [14]. Also,
E-mail address: [email protected] (S.-G. Oh). Tamil et al. obtained highly crystalline nanoparticles of

0379-6779/01/$ – see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 ( 0 0 ) 0 0 3 0 4 - 0
298 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304

PANI using cyclohexane as continuous phase, the mixture of used as an aqueous phase in micellar solution. Compositions
AOT (bis-2-ethylhexyl sulfosuccinate sodium salt) and SDS and characteristics for each reaction medium are shown in
as surfactants [15]. Table 1. In the first set of experiments, aniline concentration
Surfactant aggregates, micelles, have been used for organic was changed from 0.03 to 0.1 M at fixed SDS and HCl
synthesis over the past a few decades. Aliphatic and aromatic concentration, which were kept as 0.2 and 0.1 M concentra-
nucleophilic substitution, hydrolysis of long-chain alkyl sul- tions, respectively. In the second set of experiments, SDS
fates in aqueous solution and reactions involving free radicals concentration was varied at constant aniline concentration.
have been studied mainly focused on the micellar catalysis Before APS was added, total 100 ml of reaction mixtures of
[16]. Siswanto and Rathman reported that the reaction rate different compositions were prepared and purged with nitro-
and the selectivity for N-butyl aniline were improved when N- gen for 10–15 min to remove the dissolved oxygen. The
alkylation of aniline was performed in single-phase aqueous 10 ml of 0.1 M HCl solutions including APS were added
surfactant solution [17]. But in the preparation of PANI dropwise into 100 ml of reaction mixtures for approximately
dispersions, surfactants have been rarely employed as stabi- 20–30 min. After the induction period of about 20–40 min
lizer and micelles as reaction medium. Recently, Kuramoto (including time of APS addition), the homogeneous trans-
et al. successfully prepared stable green colored transparent parent reaction mixtures were turned into bluish tint and the
PANI dispersions using SDS and dodecylbenzene sulfonic coloration was pronounced as polymerization proceeded.
acid (DBSA) [18,19]. They measured UV–VIS spectra of Finally dark green colored PANI dispersions were obtained
PANI dispersions at various pHs to find out insulator–metal without any precipitation. In our experiments, APS was
transition point. And they also investigated effects on the dissolved in a relatively small amount of 0.1M HCl solution
product yield, conductivity of oxidant concentration, reaction not to disturb the initial micellar structure. The molar ratio of
temperature and kinds of dopant anions. Gospodinova APS to aniline was kept as 0.5 through the experiments to
et.al. have reported that they prepared PANI dispersions avoid overoxidation. Since the Krafft point of SDS is around
composed of spherical nanoparticles (5–30 nm) with DBSA 168C, the polymerization was performed at 20
0:1 C in a
and PANI–poly(vinyl alcohol) composites with high electri- two necked round bottom flask mounted in a thermostat for
cal conductivity and transparency at film [20]. 12 h [21]. Reaction mixtures and APS solutions were equi-
In this study, we prepared PANI nanoparticles in anionic librated at experimental temperature before reaction
SDS micelles with ammonium peroxydisulfate (APS) as an initiated.
oxidant, and correlated the PANI morphology formed in
micelles with the size and shape of micelles. This study was 2.2. Precipitation, washing and drying of PANI
focused on the contribution of SDS micelles to the formation of nanoparticles
stable dispersions, morphology and electrical properties of
PANI particles. Preparation of PANI nanoparticles with DBSA Excess amount of methanol was added into the HCl-
as a stabilizer and doping agent may be interpreted with the doped PANI dispersion to precipitate PANI powder by
similar mechanism. Electrical conductivity, molecular weight, breaking the hydrophilic–lyphophilic balance of the system
crystalline structure and thermal stability of PANI powders and to stop the reaction. The precipitates were collected with
synthesized at different compositions were characterized. glass filter and washed two times each with methanol,
ethanol, and pure water to remove unreacted chemicals,
aniline oligomers and SDS. The obtained PANI cakes were
2. Experimental dried in a vacuum oven at 408C for 36 h.

2.1. Synthesis of PANI nanoparticles 2.3. Characterization

The 0.1 M HCl solution was prepared by adding 37 wt.% Before the addition of APS into reaction mixtures, relative
HCl solution into doubly distilled and deionized water and viscosity was measured with an Ubbelohde viscometer to

Table 1
The compositions of the reaction mixtures and characteristics for PANI particles obtained

Aniline SDS pH Relative Inherent Conductivity

concentration concentration viscosity viscosity (S/cm)
(M (g)) (M (g)) (dl/g)

Mix. 1 (1a) 0.03 (0.279) 0.20 (5.768) 0.75 1.03 0.92 6.9
Mix. 2 (1b) 0.05 (0.465) 0.20 (5.768) 0.88 1.71 0.71 5.2
Mix. 3 (1c) 0.08 (0.745) 0.20 (5.768) 1.44 13.52 0.55 8.3
Mix. 4 (1d) 0.10 (0.931) 0.20 (5.768) 3.73 >100 0.60 4.1
Mix. 5 (2a) 0.03 (0.279) 0.05 (1.442) 0.61 8.9
Mix. 6 (2b) 0.03 (0.279) 0.10 (2.884) 0.62 7.1
 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304 299

estimate the concentration at which micellar shape begins to 3.4–4.7 wt.%. If all the detected sulfur were from the SDS,
deviate from the spherical one. 0.2 M SDS solution (0.1 M doping level by SDS was up to 0.21 at maximum (S/N, molar
HCl) was taken as a reference solution and the measurement base). As shown in Table 2, after PANI salt was dedoped,
temperature was 268C. To compare the molecular weight amount of SDS incorporated in the samples was reduced to
indirectly, the inherent viscosity of PANI salt was deter- about one half of that in PANI salt. From that, all SDS
mined at 258C in 0.1% (w/w) solution in concentrated molecules were not seemed to exist as counter-ion of
H2SO4 (97%) using an Ubbelohde viscometer. After 12 h dopants. In our experiments, it was found that SDS mole-
of reaction, 0.5 g of reaction mixtures were taken and diluted cules participated in doping process and could not be
with 20 g of 0.1 M HCl solution for UV–VIS absorption removed perfectly. Amount of SDS remaining PANI salt
spectra (UNICAM 8700 SERIES UV–VIS spectrophot- as both dopant counter-ion and impurity did not show any
ometer). Also dried PANI particles were redispersed in relationship with the used amount of SDS in synthesis.
0.1 M HCl solutions with sonicator (bath type) and UV– Doping level by SDS was considered just to depend on
VIS spectra for those dispersions were measured. The the washing procedure. Although the S/N ratio was around
stability and size of redispersed particles were not measured 0.13 for sample 1d, which meant that major dopant was HCl,
but sedimentation process began within a few hours. Ele- XRD patterns and thermal degradation profiles showed
mental analysis (Eager 200 model, C, H, N, O) was carried typical characteristics of PANI doped with sulfonic and
out to determine the composition of the PANI salt and base sulfuric acid [22,23].
powder. FT-IR spectroscopy (Nicolet, Magna-IR 760) was
used to decide the oxidation state of the PANI base 3.2. FT-IR spectroscopy
powders. PANI base powders were prepared with 5 wt.%
NH4OH solution. X-ray patterns of PANI were taken with Oxidation state of PANI-base was identified with FT-IR
Ni-filtered Cu-Ka radiation using RAD-C X-ray diffract- spectroscopy by comparing two peaks around 1590 (ring
ometer (Rigaku Denki Co.). The detector moved step by stretching in quinoid unit) and 1480 cm1 (ring stretching in
step (D2y ¼ 0:05 ) from 5 to 408 at the speed of 78/min and bezenoid unit) [24]. All samples were in the emeraldine
the X-ray power was 40 KV and 100 mA. The morphology oxidation state and it was also confirmed with the purplish-
of PANI particles was studied by field emission scanning brown coloration upon dissolving PANI in pure concentrated
electron microscopy (FE-SEM, Jeol Model JSM-6340F). sulfuric acid solution [25].
Samples for the electron microscope were sputter-coated
with gold for 60 s. Thermal gravimetric analysis of 3.3. UV–VIS absorption spectra
the PANI–HCl salt was carried out with Shimadzu
TGA-50 at the heating rate of 88C/min up to 8008C in UV–VIS absorption spectra of PANI dispersions and
N2 atmosphere. About 0.05 g of dried PANI salt powders redispersed samples in HCl solution were shown in Figs. 1
were compressed into a disk pellet of 13 mm in diameter and 2. Doped PANI shows three characteristic absorption
with a hydraulic pressure at 3000 psi and conductivity was bands at 320–360, 400–420 and 740–800 nm wavelength.
measured by a four-point probe connected to a Keithley The first absorption band arises from p–p electron transi-
voltmeter-constant current source system. PANI denotes tion within benzenoid segments. The second and third
polyaniline in the emeraldine salt form unless otherwise absorption bands are related to doping level and formation
mentioned. of polaron, respectively [26]. The first two bands are often
combined into a flat or distorted single peak with a local
maximum between 360 and 420 nm. PANI-dispersions
3. Results and discussion synthesized at 0.03, 0.05 M aniline and 0.2 M SDS con-
centration showed maximum at 760 nm wavelength. Max-
3.1. Elemental analysis imum peak of the other two samples (1c, 1d) appeared at
780–800 nm and the amplitude of the peak at 420 nm
The compositions of PANI salt and base were given in increased with increase of monomer concentration in the
Table 2. In all samples, sulfur were detected in the range of initial reaction mixture.

Table 2
Chemical compositions of PANI salt and base powdera

C (wt.%) H (wt.%) N (wt.%) S (wt.%) S/N

Sample 1c 61.5 (69.3) 5.7 (5.7) 10.9 (12.3) 3.8 (1.6) 0.15 (0.06)
Sample 1d 61.6 (70.5) 5.7 (5.6) 10.9 (12.6) 3.4 (1.5) 0.13 (0.05)
Sample 2a 61.5 (68.3) 5.8 (5.6) 10.6 (12.0) 3.7 (1.6) 0.15 (0.06)
Sample 2b 62.3 (67.0) 6.3 (5.9) 9.6 (11.1) 4.7 (2.2) 0.21 (0.08)
a
S/N ratios were given on molar base and values in parenthesis were for the PANI base.
300 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304

Fig. 1. UV–VIS absorption spectra for PANI synthesized at various aniline Fig. 2. UV–VIS absorption spectra for PANI synthesized at various SDS
concentrations in 0.1 M HCl solution; (a) raw samples, (b) redispersed concentrations in 0.1 M HCl solution: (a) raw samples, (b) redispersed
samples, 1a, 1b, 1c, 1d from the top. samples, 2a, 2b, 1a from the top.

Absorption spectra for redispersed samples showed dif- et al. [28]. From the comparison of these UV–VIS absorp-
ferent features from those of the PANI dispersion in SDS tion spectra it is obvious that excess SDS molecules which
micellar solution (taken from the reaction mixtures after a are not involved in doping have negative effects on the
12 h reaction). Overall spectra were a little shifted to a electrical and structural properties of PANI particles. In the
longer wavelength by 10–20 nm with greatly diminished case of PANI dispersion in SDS micellar solution, each
localized polaron band or free carrier tail instead of localized particle is stabilized with the SDS molecules adsorbed on
polaron band around 780 nm, which is observed for the the surface or incorporated in the PANI particles. On the
PANI doped with camphorsulfonic acid exposed to a sec- other hand, redispersed samples consist of the aggregates
ondary dopant such as m-cresol [27]. Appearance of free of primary PANI particles resulting from the removal of
carrier tail has been explained by expanded coil structure by SDS molecules through washing procedure. Adsorbed and
secondary dopant. PANI synthesized in SDS micellar incorporated SDS molecules seemed to affect the intra-
solution showed highly delocalized polaron band without chain and inter-chain conduction process unfavorably
additional doping. Peak at 450 nm was separated and resulting in the decrease of conjugation length and doping
relative intensity of this peak to that of 360 nm band level. PANI dispersions prepared at fixed aniline concen-
was increased. So doping state seemed to be improved tration (0.03 M) varying SDS concentrations showed
by washing. This could be assigned to the removal of the similar spectra to the other samples. Any noticeable
undesired components such as excess SDS, HCl, unreacted change in absorption spectra depending on the SDS con-
aniline monomer. Similar phenomena in emulsion poly- centration was not observed. The spectra of the redispersed
merization process using dinonylnaphthalenesulfonic acid samples could be explained in the same way discussed
as organic dopant and emulsifier were reported by Kinlen before.
 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304 301

Fig. 3. X-ray diffraction patterns for PANI powders prepared (a) at different aniline concentrations, sample 1a, 1b, 1c, 1d and (b) at different SDS
concentrations, sample 2a, 2b, 1a from the top.

3.4. Crystalline structure and molecular weight the viewpoint of acidity of the reaction medium. Sample 1c
polymerized around pH 1.7 showed most well defined
The X-ray diffraction patterns of PANI powders poly- crystalline structure because of the acidity of the reaction
merized at different compositions were represented in Fig. 3. medium and aniline concentration in micellar pseudophase
As mentioned in elemental analysis part, characteristic XRD (discussed later). We also investigated the effect of SDS
patterns of organic sulfonates doped PANI were obtained. concentration on the crystallinity at 0.03 M aniline concen-
All profiles were similar to each other indicating that all tration. Three X-ray diffraction patterns for sample 1a, 2a,
samples were isomorphous, but the relative intensities of the 2b are represented in Fig. 3(b). I20/I17 and I25/I17 increased as
peaks were different. Sample 1a, 1b and 1c showed rela- SDS concentration decreased. Because three samples were
tively the well-developed X-ray diffraction patterns and synthesized at the almost same pH, the difference in the
sample 1d, which was synthesized at the highest monomer crystallinity is not due to the acidity of the reaction med-
concentration (0.1 M), showed a broad amorphous halo ium.and it is also obvious that the micellar shape is spherical
centered at 2y  17 . The ratio of intensity at 20 to 178, at this concentration range. The only possible reason is the
I20/I17, and I25/I17 increased with the increase in the crystal- moles of aniline per SDS micelle. Thus, we can suggest that
linity. Many research groups have reported the relationships crystallinity of the PANI is proportional to the moles of
of crystallinity with reaction temperature, acidity of the aniline per micelle (below solubilization limit), if the other
reaction medium and molecular weight of PANI reaction parameters such as pH of the reaction mixture,
[25,27,29]. According to the reports, low reaction tempera- temperature, addition rate of APS and micellar shape are
ture (below 58C), and low pH (0–2) of the reaction medium controlled to ensure the same reaction conditions.
were favored to obtain highly crystalline PANI having high
molecular weight with less structural defects. As shown in 3.5. Thermal stability
Table 1, pH of the reaction mixtures was in the range
between 0.7 and 3.7. Thus, low crystallinity of PANI Fig. 4 shows the TGA thermograph of the PANI powders.
synthesized at high aniline concentration is interpreted In TGA profile, major losses of weight were observed over
due to the low acidity of reaction medium and this result two temperature periods, beginning around 160 and 4508C.
is well consistent with the literatures [29]. Molecular weight The first decrease of mass was mainly due to the removal of
of PANI estimated by inherent viscosity showed the same dopant molecules, HCl and also the loss of possible impu-
trend as crystallinity and it could be also understood from rities such as remaining monomers. The second weight loss
302 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304

Fig. 4. TGA thermograph for PANI powders polymerized at different aniline and SDS concentrations.

at the higher temperature indicates a structural decomposi-

tion of the polymer. Gradual weight loss over the wide
temperature range could be attributed to the good thermal
stability of the PANI main chain. Higher degradation tem-
perature than HCl-doped PANI indicated that SDS was also
used as dopant counter-ion. PANI powders prepared at the
low aniline concentration, 0.03 M (1a, 2a, 2b), began to
degrade at the 4388C, rather lower than the others and also
showed greater weight loss despite its high molecular weight
and crystallinity. It might be related to the large surface area
per unit mass, which means extremely large thermal con-
tacting area.

3.6. Electrical conductivity of PANI

All samples synthesized at different reaction composi-

tions had the similar electrical conductivity, 4–10 S/cm. It
has been known that PANI of high crystallinity has a higher
conductivity than amorphous one and conductivity is inde-
pendent of molecular weight. As expected from the X-ray
profiles, sample 1c and 2a showed a higher electrical con-
ductivity.

3.7. Particle size and morphology

At low concentration, sample 1a, aniline was polymerized

into the spherical nanoparticles. The size of particles shown
in Fig. 5(a) was 8–15 nm which was the same order of the
initial micellar size or slightly larger. The shape of particles
synthesized at the other concentrations, 1b, 1c, 1d, 2a, 2b,
was expected to slightly deviate from the spherical shape as
shown Fig. 5(b). In the case of SDS, the CMC (critical
micelle concentration) was reported to be 8.0 mM concen-
tration in aqueous solution without any additives at 208C Fig. 5. FE-SEM pictures of the PANI particles: (a) sample 1a, (b) sample
[21]. Micellar size and aggregation number at CMC are 1b, (c) sample 1c, (d) sample 1d.
 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304 303

approximately 6 nm (in diameter) and 62, respectively, at reactants in the micelles, is one of the most important
208C [21]. At this concentration, the shape of micelle is factors, which significantly affects the reaction kinetics,
assumed to be spherical. Generally, as surfactant concentra- selectivity and yield. The site of incorporation of the solu-
tion increases, micellar shape changes from sphere to cylin- bilizate is closely related to its chemical nature. It has been
der, hexagonal and lamellar structure successively. Oh and well accepted that non-polar, highly hydrophobic solubili-
Shah reported that the transition of SDS micelles from zates are located in the hydrocarbon core of the micelles.
spherical to cylindrical shape occurred at 0.2 M surfactant Polar or surface active molecules are solubilized in the
concentration in aqueous solution without any other addi- micelle–water interface. In the case of aniline existing in
tives [30]. If solubilizate, salt, or any other additives are the form of anilinium cation in acidic aqueous solution,
added into the solution, the system becomes so complex that Kuramoto et al. suggested that anilinium cations are
the micellar shape, size and morphology could not be adsorbed on the micellar surface by electrostatic interac-
predicted without experimental investigation. Especially, tion with anionic SDS molecules being fully exposed to the
ionic surfactant micelles are significantly influenced by aqueous phase [19]. But, some portion of Naþ counter-ions
the salt concentration. Salt ions adsorbed onto the micellar would be bound with the micelles and electrical double
surface reduce electric repulsion between hydrophilic head layer might be depressed in acidic aqueous solution lead-
groups of the ionic surfactant, thus increase micellar size and ing to the reduction of the charge density of micelles.
aggregation number and also affect intermicellar interaction Besides, exposure of the aromatic moieties to the aqueous
as depressing electrical double layer. The aggregation num- phase is not acceptable if the transfer free energy change of
ber of SDS at 0.18 M concentration with 0.1 M NaCl was the aniline and anilinium molecules from aqueous phase to
reported to be 92 at 258C, and the size of micelle is assumed micellar pseudophase is considered [31,32]. Thus, we
to be around 15 nm (in diameter) [21]. When hydrochloride assumed, referring to the literatures, that most aniline
is used instead of NaCl, it acts somewhat different way but is monomers were solubilized in the micelle-water interface
expected to show similar influence on micellar behavior. In as shown in Fig. 6. Obviously, some of them adsorb on the
the first set of experiments, SDS and HCl concentrations micellar surface and maybe also exist in the aqueous phase.
were kept at 0.2 and 0.1 M and aniline concentration varied Kandori et al. reported that phenol molecules in dodecyl-
from 0.03 to 0.10 M. At 0.03 M aniline concentration, it is trimethylammonium bromide micellar solution first were
obvious from the viscosity data that micellar shape would be incorporated in the palisade layer and began to adsorb on
spherical or at least spherelike, and this was consistent with the micellar surface when palisade layer had been satu-
SEM photograph of PANI powders. Above 0.03 M aniline rated with solubilized phenol molecules [33]. We assumed
concentration, the micellar shape seemed to be changed into that solubilization locus of aniline-HCl salt was not so
cylindrical or worm like shape, which coincided with the different from that of the phenol, although investigated
sharp increase of relative viscosity up to 13.52. Reaction compositions were not in the same range of our reaction
mixture 4 (0.1 and 0.2 M, aniline, and SDS, respectively) was compositions. Solubilized aniline or anilinium molecules
so viscous such as gel that relative viscosity could not be were polymerized oxidatively by APS existing in the
measured (above 100). Sharp increase of viscosity of surfac- aqueous phase. The reaction took place mainly in the
tant solutions could be thought as the transition of micellar micelle-water interface adjacent to the surfactant head
shape, for example, spherical to cylindrical or, cylindrical to groups, because hydrated APS molecules could not pene-
hexagonal shape. In our experiment, all the reaction mixtures trate into the micellar surface. Here, one must note that the
were not birefringent, which means that the formation of micelles are not static and rigid entities. Micelles are in a
hexagonal and lamella phases could be excluded, but from the dynamic equilibrium state with surfactant monomers in
relative viscosity data, it is certain that the micellar size and
aggregation number increase with increase of aniline con-
centration and also micelle would change from spherical
micelle to cylindrical or worm like micelle followed by
further growth and change of micellar shape to another
one. Exact micellar shape and transition point could not be
revealed with viscosity measurement. Since the reaction takes
place mainly in the micelle–water interface, if the SDS
concentration is high enough to solubilize almost all aniline
and anilinium molecules, morphology of the obtained PANI
particles would be the same as the initial micellar shape.

3.8. Formation of PANI nanoparticles

When organic synthesis or polymerization is carried out Fig. 6. Schematic diagram for the solubilization locus of aniline–HCl salt
within the micelles, solubilization locus, the location of the in SDS micelle.
304 B.-J. Kim et al. / Synthetic Metals 122 (2001) 297–304

solution. Namely, micelles are dissociated into monomers References

and monomers are associated into micelles continuously.
Thus all segments of the surfactant and solubilizates could [1] J. Huang, M. Wan, J. Polym. Sci. A 37 (1999) 151.
[2] S. Sukeerthi, A.Q. Contractor, Anal. Chem. 71 (1999) 2231.
be exposed to the water. The explanation for polymeriza-
[3] W.K. Lu, R.L. Elsenbaumer, B. Wessling, Synth. Met. 71 (1995) 2163.
tion mechanism of aniline in micelles is totally based on [4] A. Drelinkiewicz, M. Hasik, M. Kloc, J. Catal. 186 (1999) 123.
the time-averaged observations. p-Aminodiphenylamine [5] J. Stejskal, P. Kratochvil, Langmuir 12 (1996) 3389.
which is known as an intermediate produced in polymer- [6] S.P. Arms, M. Aldissi, S.F. Agnew, S. Gottesfeld, Lagnmuir 6 (1990)
ization of aniline has very low solubility in pure water, 1745.
[7] P. Banerjee, S.N. Bhattacharyya, B.M. Mandal, Langmuir 11 (1995)
<0.1 g/100 ml. So possible aniline molecules attacked in
2414.
the aqueous phase would be incorporated readily into the [8] D. Chattopadhyay, S. Banerjee, D. Chakravorty, B.M. Mandal,
micelles as they grow into dimer, trimer or tetramer due to Langmuir 14 (1998) 1544.
their increased hydrophobicity. After the reaction is fin- [9] J. Stejskal, M. Spirkova, A. Riede, M. Helmstedt, P. Mokreva, J.
ished, produced PANI nanoparticles are stabilized by Prokes, Polymer 40 (1999) 2487.
[10] C. DeArmitt, S.P. Armes, J. Colloid Interface Sci. 150 (1992) 134.
adsorbed and incorporated SDS molecules by electrostatic
[11] J. Stejskal, P. Kratochvil, et al., Macromolecules 29 (1996) 6814.
repulsive interactions. [12] F. Candau, in: J.M. Asua (Ed.), Polymeric Dispersions: Principles
and Applications, Kluwer Academic Publishers, Amsterdam, 1993,
pp. 127–140.
4. Conclusions [13] C.H. Chew, L.M. Gan, J. Polym. Sci: Polym. Chem. Ed. 23 (1985) 2225.
[14] L.M. Gan, C.H. Chew, S.O. Hardy, L. Ma, Polym. Bull. 31 (1993) 347.
[15] S.T. Selvan, A. Mani, K. Athinarayanasamy, K.L. Phani, S.
In this study, SDS micelles were used as polymerization Pitchumani, Mater. Res. Bull. 30 (1995) 699.
medium to produce PANI nanoparticles. All PANI disper- [16] M.J. Rosen, Surfactants and Interfacial Phenomena, 2nd Edition,
sions prepared at various compositions were highly trans- Wiley, New York, 1989, pp. 196–202,
parent spherical PANI nanoparticles were obtained when [17] C. Siswanto, J.F. Rathman, J. Colloid Interface Sci. 196 (1997) 99.
[18] N. Kuramoto, E.M. Genies, Synth. Met. 68 (1995) 191.
SDS concentration was high enough to solubilize almost all
[19] N. Kuramoto, A. Tomita, Polymer 38 (1997) 3055.
monomer molecules and the micellar shape remained sphe- [20] N. Gospodinova, P. Mokreva, T. Tsanov, L. Terlemezyan, Polymer 38
rical. Small amount of SDS could not be removed after (1997) 743.
washing and also participated in the doping process. XRD [21] N.M. van Os, J.R. Haak, L.A. Rupert, Physico-Chemical Properties
patterns and thermal degradation profiles showed the char- of Selected Anionic, Cationic and Nonionic Surfactants, Elsevier,
Amsterdam, 1993.
acteristics of PANI doped with organic sulfonic or sulfuric
[22] S. Kababya, M. Appel, Y. Haba, et al., Macromolecules 32 (1999) 5357.
acid. More structured PANI particles showed a higher con- [23] V.G. Kulkarni, L.D. Campbell, W.R. Mathew, Synth. Met. 30 (1989) 321.
ductivity. Electrical properties were affected by the presence [24] G.E. Asturias, A.G. Macdiarmid, Synth. Met. 29 (1989) E157.
of the SDS molecules and did not depend on the molecular [25] F. Lux, Polymer 35 (1994) 2915.
weight and morphology as reported in the literatures. [26] J. Stejskal, P. Kratochvil, Synth. Met. 61 (1993) 225.
[27] A.G. Macdiarmid, A.J. Epstein, Mater. Res. Soc. Symp. Proc. 328
Obtained PANI particles were thermally stable inferred from
(1994) 133.
the high decomposition temperature and gradual mass [28] P.J. Kinlen, J. Liu, Y. Ding, C.R. Graham, E.E. Remsen,
decrease. Macromolecules 31 (1998) 1735.
[29] J. Stejskal, A. Riede, et.al., Synth. Met., 96 (1998) 55
[30] S.G. Oh, D.O. Shah, J. Am. Oil Chemists Soc. 70 (1993) 673.
[31] C. Hirose, L. Sepulveda, J. Phys. Chem. 85 (1981) 3689.
Acknowledgements
[32] B.H. Lee, S.D. Christian, E.E. Tucker, J.F. Scamehorn, J. Phys.
Chem. 95 (1991) 360.
This work was supported by the research fund of Hanyang [33] K. Kandori, R.J. McGreevy, R.S. Schechter, J. Phys. Chem. 93 (1989)
University (Project No. HYU-99-015). 1506.