2032 Langmuir 1998, 14, 2032-2041

Synthesis and Characterization of Micrometer-Sized,

Polyaniline-Coated Polystyrene Latexes
Christelle Barthet,† Steven P. Armes,*,† Stuart F. Lascelles,† Shen Y. Luk,‡ and
Heather M. E. Stanley†
School of Chemistry, Physics and Environmental Science, University of Sussex,
Falmer, Brighton, BN1 9QJ, U.K., and Analytical Division, Courtaulds Research,
P.O. Box 111, 101 Lockhurst Lane, Coventry, CV6 5RS, U.K.

Received September 25, 1997. In Final Form: January 21, 1998

Poly(N-vinylpyrrolidone)-stabilized polystyrene (PS) latexes have been coated with thin overlayers of
polyaniline (PANi) to produce electrically conductive “core-shell” particles. In this work we focused on
the morphology of the PANi overlayer, the colloid stability of the coated latexes, and electrical conductivity.
PANi-coated particles exhibit a nonuniform morphology as observed by scanning electron microscopy
(SEM), in comparison with the relatively smooth polypyrrole overlayers synthesized in a previous study
(Lascelles, S. F. et al., J. Mater. Chem. 1997, 7, 1339 and 1349). Disk centrifuge photosedimentometry
confirmed that the PANi-coated PS latexes were weakly flocculated. The underlying PS latex “core” was
quantitatively removed by solvent extraction, and SEM observations of the PANi residues revealed a
“broken egg shell” morphology. Vibrational bands due to the PANi component were more intense in both
the FT-IR and Raman spectra of the PANi-coated PS latexes, which is also consistent with the “core-shell”
morphology. No reduction in the surface roughness of the PANi overlayer was observed when the rate
of the aniline polymerization was decreased or if the latex surface was pretreated with either a thin
polypyrrole overlayer or a layer of adsorbed surfactant. Similarly, only rough PANi overlayers were
observed when coating a sulfonated PS latex. However, a more uniform deposition of PANi and a
corresponding improvement of colloid stability were obtained using aniline hydrochloride monomer in the
absence of added acid.

Introduction particles can be made over a much wider size range

In principle, the preparation of colloidal dispersions of
conducting polymers can alleviate the poor processability
characteristics associated with these materials.1 For
example, sterically stabilized polypyrrole (PPy) colloids
can be easily synthesized in aqueous media by chemically
polymerizing pyrrole in the presence of a suitable water-
soluble polymer such as methyl cellulose2 or poly(vinyl
alcohol).3,4 Similarly, polyaniline (PANi) particles can be
synthesized via dispersion polymerization using reactive
polymeric stabilizers.5,6 Sterically stabilized PPy particles
always exhibit a spherical morphology, but PANi disper-
sions can exhibit three distinct morphologies, rice-grains,
needles, or spheres, depending on the choice of steric
stabilizer and chemical oxidant.7
An alternative approach, reported by several research
groups, involves coating preformed latexes with thin
overlayers of conducting polymers to form “core-shell”
particles. If the conducting polymer overlayer is continu-
ous, this can lead to relatively high conductivities even at
very low conducting polymer loadings. Moreover, the latex
† University of Sussex.
‡ Courtaulds Research.
(1) See, for example: Proc. 1992 Int. Conf. Synthetic Metals (ICSM
′92) Synth. Met. 1993, 55-57.
(2) Bjorklund, R. B.; Liedberg, B. J. Chem. Soc., Chem. Commun.
1986, 1293.
(3) Armes, S. P.; Vincent, B. J. Chem. Soc., Chem. Commun. 1987,
288.
(4) Armes, S. P.; Miller, J. F., Vincent, B. J. Colloid Interface Sci.
1987, 118, 410.
(5) Armes S. P. In Handbook of Conducting Polymers; Elsenbaumer,
R., Ed.; M. Dekker: New York, 1997; Vol. II, in press.
(6) DeArmitt, C.; Armes, S. P. J. Colloid Interface Sci. 1992, 150,
134.
(7) Armes S. P.; Aldissi M.; Agnew S.; Gottesfeld S. Langmuir 1990,
6, 1745.
compared to the rather limited size range achieved for
sterically stabilized conducting polymer colloids (30-300
nm).3,4,8 In 1987 Garnier and co-workers9 reported that
sulfonated and carboxylated polystyrene latexes of ca. 130
nm in diameter could be coated with PPy overlayers using
FeCl3. Similarly, Liu et al.10 used a H2O2/Fe3+ catalytic
oxidant11 to coat 200 nm diameter styrene-butadiene-
methacrylate latex particles with PPy. These latter
workers achieved PPy contents of up to 35 wt % with
apparently no colloidal destabilization. This observation
is rather surprising in view of the high Hamaker constant
for PPy reported by Vincent’s group.12 However, no
convincing experimental evidence (e.g., light scattering
or disk centrifuge photosedimentometry) was cited by Liu
et al. to justify their colloid stability claims. Beadle et
al.13 prepared a range of PANi-chlorinated latex compos-
ites and showed that the PANi loading could be easily
controlled by varying the latex concentration in the
syntheses. In this latter study all the composites were
obtained as macroscopic precipitates, as expected. More
recently, Xie et al.14 described the synthesis of colloidal
composites of PANi with poly(butadiene-co-styrene-co-2-
(8) (a) Cawdery, N.; Obey, T. M., Vincent, B. J. Chem. Soc., Chem.
Commun. 1988, 1189. (b) Armes, S. P.; Aldissi, M.; Idzorek, G. C.; Keaton,
P. W.; Rowton, L. J.; Stradling, G. L.; Collopy, M. T.; McColl, D. B. J.
Colloid Interface Sci. 1991, 141, 119.
(9) Yasser, A.; Roncali, J.; Garnier, F. Polym. Commun. 1987, 28,
103.
(10) Liu, C. F.; Maruyama, T.; Yamamoto, T. Polym. J. 1993, 25,
363.
(11) Moon, D. K.; Osakada, K.; Maruyama, T.; Yamamoto, T.
Makromol. Chem. 1992, 193, 829.
(12) Markham, G.; Obey, T. M.; Vincent, B. Colloids Surf. 1990, 51,
239.
(13) Beadle, P.; Armes, S. P.; Gottesfeld, S.; Mombourquette, C.;
Houlton, R.; Andrews, W. D.; Agnew, S. F. Macromolecules 1992, 25,
2526.

S0743-7463(97)01064-0 CCC: $15.00 © 1998 American Chemical Society

Published on Web 03/20/1998
Polyaniline-Coated Polystyrene Latexes
vinylpyridine) latex. Again, a high degree of dispersion
was claimed for the resulting composite particles, but in
this case it is likely that the aniline polymerization occurs
inside the acid-swollen latex. This possibility is admitted
by the authors and is certainly consistent with the
“classical” conductivity percolation threshold behavior
observed for their latex composites; PANi loadings in
excess of 16 wt % were required for high conductivities.
Noncolloidal (macroscopic) polymeric substrates have
also been coated with PPy. For example, Yoshino and
co-workers15 deposited PPy onto 10 µm polyethylene
particles and Omastova et al.16 coated 35 µm polypropylene
particles with PPy (the latter workers also coated 100 nm
poly(methyl methacrylate) latex particles with PPy in the
same study and obtained only macroscopic precipitates).
The Japanese group15 reported conductivities as high as
0.2 S cm-1 for PPy loadings as low as 1 wt %.
Wiersma et al. at DSM Research recently demon-
strated17 that sterically stabilized latexes can be coated
with either PPy or PANi in aqueous media to form
composite particles with good colloid stability. In these
syntheses the presence of a nonionic steric stabilizer, such
as chemically grafted poly(ethylene oxide) or hydroxy-
methyl cellulose, was reported to be critical for producing
stable colloidal dispersions. It was suggested that the
conducting polymer was formed as an ultrathin layer at
the surface of the latex particles, without significantly
interfering with the steric stabilization mechanism con-
ferred by the solvated layer of polymeric stabilizer. The
DSM group utilized several low Tg, film-forming colloidal
substrates such as polyurethane latexes or alkyd resins.
Particle diameters were in the 50-500 nm range, and the
commercial potential of these water-borne antistatic or
anticorrosion coatings (tradename ConQuest) is currently
being explored.18
Lascelles and co-workers19,20 adapted this DSM protocol
in order to coat micrometer-sized poly(N-vinylpyrrolidone)
(PVP)-stabilized polystyrene latexes with PPy. Polysty-
rene (PS) was selected as a model colloidal substrate for
these studies since it has a relatively high Tg of ca. 100
°C (i.e., the particles are rigid and nondeformable) and
PVP-stabilized PS latexes can be easily synthesized with
narrow size distributions via dispersion polymeriza-
tion.21-24 Conductivity measurements on the dried PS-
PPy latexes indicated unexpectedly low percolation thresh-
old of 1-2 vol % similar to those reported by Yoshino et
al.15 Moreover, scanning electron microscopy studies
confirmed that, at PPy loadings of less than 10 wt %, the
conducting polymer overlayer had a relatively smooth and
featureless morphology. Subsequent X-ray photoelectron
spectroscopy (XPS) studies by Perruchot et al.25 confirmed
(14) Xie, H. Q.; Liu, H.; Liu, Z. H.; Guo, J. S. Angew. Makromol.
Chem. 1996, 243, 117.
(15) Yoshino, K.; Yin, X. H.; Morita, S.; Nakayashi, Y.; Nakagawa,
S.; Watanuki, T.; Isla, I. Jpn. J. Appl. Phys. 1993, 32, 979.
(16) Osmatova, M.; Pionteck, J.; Kosina, S. Eur. Polym. J. 1996, 32,
681.
(17) Wiersma A. E.; vd Steeg L. M. A. Eur. Pat. No 589, 529.
(18) Wiersma, A. E.; Van Der Steeg, L. M. A.; Jongeling, T. J. M.
Synth. Met. 1995, 71, 2269.
(19) Lascelles, S. F.; Armes, S. P. Adv. Mater. 1995, 7, 864.
(20) (a) Lascelles, S. F.; Armes, S. P. J. Mater. Chem. 1997, 7, 1339.
(b) Lascelles, S. F.; Armes, S. P.; Zhdan, P. A.; Greaves, S. J.; Brown,
A. M.; Watts, J. F.; Leadley, S. R.; Luk, S. Y. J. Mater. Chem. 1997, 7,
1349.
(21) Goodall, A. R.; Wilkinson, M. C.; Hearn, J. J. Polym. Sci., Polym.
Chem. Ed. 1977, 15, 2193.
(22) Bromley, C. W. A. Colloids Surf. 1986, 17, 1.
(23) Ober, C. K.; Lok, K. P.; Hair, M. L. J. Polym. Sci., Polym. Lett.
1985, 23, 103.
(24) Paine, A. J.; Luymes, W.; McNulty, J. Macromolecules 1990, 23,
3104.
Langmuir, Vol. 14, No. 8, 1998 2033
Table 1. Reaction Conditions for Aniline
Polymerizationsa
oxidant/
polymerization monomer
monomer temperature (°C) pH oxidant ratio
aniline (method 1) 0 0.7 [NH4]2S2O8 1.25
25 0.7 [NH4]2S2O8 1.25
0 0.3 NH4VO3 2
aniline hydrochloride 0 2-4 [NH4]2S2O8 1.25
(method 2)
a The latex solids concentration was 17 wt % and the total solution
volume was 20 mL.
that, for a relatively thick PPy overlayer (ca. 18 nm),
there was very little evidence for the underlying PS latex.
This observation is consistent with a very homogeneous
PPy overlayer and also reflects the highly surface-specific
nature of the XPS technique, which has a sampling depth
of 2-5 nm. This technique has proved particularly useful
in assessing the surface oxidation and degradation
chemistry of conducting polymers.26 The uniform mor-
phology of the PPy coating was also supported by a Raman
study,20b in which only Raman bands due to the PPy
component were observed, even at the lowest PPy loadings.
This was assumed to be due to remarkably efficient
attenuation of the Raman bands due to the PS component
by the highly absorbing PPy overlayer.
In the present work a range of micrometer-sized, PANi-
coated PS latexes have been synthesized and extensively
characterized. Particular attention is given to the uni-
formity of the PANi overlayer, the colloidal stability of
the coated latex, and solid-state conductivities, using FT-
IR and Raman spectroscopy, disk centrifuge photosedi-
mentometry, and scanning electron microscopy. In ad-
dition, various synthetic strategies were explored in order
to try to achieve PANi overlayers of similar uniformity to
that observed for PPy coatings.
Experimental Section
PS Latex Synthesis. The PS latex was prepared by disper-
sion polymerization according to Paine et al.24 The styrene
monomer was purified by passing through an activated neutral
aluminum oxide column. The PVP stabilizer (molecular weight
360 000; 42 g) was dissolved in 2-propanol (2.4 L) in a three-
necked round bottom flask fitted with a condenser and a magnetic
flea. The reaction vessel was then heated to 70 °C under a
nitrogen blanket and purged with nitrogen for 12 h at 70 °C to
remove all traces of oxygen. A solution of azoisobutyronitrile
initiator (3.0 g) predissolved in styrene monomer (300 g) was
added to the reaction vessel, with vigorous stirring. The styrene
polymerization was allowed to proceed for 24 h before cooling to
room temperature. The PS latex particles were then purified by
repeated centrifugation and redispersion cycles, replacing suc-
cessive supernatants with deionized water.
Polyaniline Coating Protocol. The conditions used for the
polymerization of aniline are summarized in Table 1.
Method 1. Aniline (Aldrich) was purified by vacuum distil-
lation over zinc (or magnesium) and stored at -15 °C prior to
use. Either [NH4]2S2O8 or NH4VO3 were dissolved in the PVP-
stabilized PS latex (4 g of dry weight) in a screw-cap bottle with
magnetic stirring. The latex was acidified to pH 0.7 and 0.3 for
[NH4]2S2O8 and NH4VO3, respectively, and the initial oxidant/
monomer molar ratios were fixed at 1.25 and 2. Aniline was
added via syringe, and the polymerization was allowed to proceed
for 24 h at room temperature. The PS latex concentration (and
hence total surface area) was kept constant, and the aniline
monomer was varied from 2 to 60 g L-1. The resulting green
(25) Perruchot, C.; Chehimi, M. M.; Delamar, M.; Lascelles, S. F.;
Armes, S. P. Langmuir 1996, 12, 3245.
(26) Inganas, O.; Erlandsson, R.; Nylander, C.; Lundstrom, I. J. Phys.
Chem. Solids 1984, 45, 427.
2034 Langmuir, Vol. 14, No. 8, 1998
PANi-coated PS latexes were purified by repeated centrifugation/
redispersion cycles (replacing successive supernatants with 1.2
M HCl), to remove the oligomers and the inorganic byproducts
of the aniline polymerization. In the reduced temperature
experiments, the general procedure described for room-temper-
ature syntheses was followed, except that the oxidant/latex
reaction mixture was cooled to 0 °C in an ice bath for at least 60
min prior to addition of the aniline monomer. This temperature
was maintained for the first 5 h of the polymerization, after
which the reaction temperature was allowed to rise to room
temperature.
Method 2. Aniline hydrochloride monomer (Aldrich, 97%)
was dissolved in an aqueous solution containing the PS latex (4
g of dry weight). No external acid was added to this reaction
solution. The monomer/latex reaction mixture was cooled to 0
°C in an ice bath for at least 60 min prior to addition of the
[NH4]2S2O8, and the polymerization temperature was maintained
at 0 °C for the first 5 h of the polymerization. The cleanup
procedure was the same as that described in method 1.
Two further experiments were also carried out, using the same
protocol, but in the presence of (i) 2 × 10-3 M hydroquinone and
(ii) 9.5 × 10-3 M sodium dodecyl sulfate (SDS) (the critical micelle
concentration (cmc) of SDS is ca. 6 × 10-3 M). The polymerization
retarder, hydroquinone,27 was added to the precooled aqueous
solution containing the PS latex and the aniline hydrochloride
monomer, prior to the addition of the [NH4]2S2O8. The SDS was
equilibrated for 12 h with the aqueous latex to allow adsorption
onto the surface of the particles before the addition of the aniline
hydrochloride monomer, followed by the oxidant.
Polypyrrole Coating.19,20 FeCl3‚6H2O oxidant (FeCl3/pyrrole
molar ratio ) 2.33) was dissolved into a stirred aqueous solution
containing the PS latex (5.25 g dry weight) in a screw-cap bottle.
Pyrrole was added via syringe, and the polymerization was
allowed to proceed for 24 h. The resulting PPy-coated PS latex
particles were purified by repeated centrifugation/redispersion
cycles, replacing successive supernatants with deionized water.
Synthesis of the Sulfonated PS Latex. The PVP stabilizer
(molecular weight 360 000; 3.80 g) was dissolved in methanol
(200 mL) in a three-necked round bottom flask fitted with a
condenser and a magnetic flea. The reaction vessel was then
heated to 70 °C under a nitrogen blanket and purged with nitrogen
for 12 h at 70 °C to remove all traces of oxygen. A solution of
azoisobutyronitrile initiator (0.33 g) predissolved in purified
styrene (31.25 g) was added to the reaction vessel, with vigorous
stirring. Sodium 4-styrenesulfonate (NaSS; 1.56 g) dissolved in
50 mL of methanol was immediately added to the previous
mixture. Methanol was used as the synthesis medium instead
of 2-propanol because of its higher dielectric constant. This made
dissolution of the NaSS easier and might be expected to increase
the fraction of sulfonate groups at the surface of the PS particles.
The copolymerization of styrene and NaSS was allowed to proceed
for 24 h before cooling to room temperature. The latex was then
purified by repeated centrifugation and re-dispersion cycles,
replacing successive supernatants with deionized water. Its
polydispersity (Dw/Dn) was found by disk centrifuge photosedi-
mentometry (DCP) to be 1.09. The modified latex was then coated
with PANi according to method 2.
Characterization Techniques. Chemical Composition.
CHN elemental microanalyses of both the dried-coated and
uncoated latexes were carried out at Medac Ltd. at Brunel
University, U.K. The PANi loadings of the coated latexes were
determined by comparing their nitrogen contents to that of the
corresponding uncoated PS latex (this reference material had an
average nitrogen content of 0.19-0.22% due to the PVP stabilizer)
and to that of PANi “bulk powder” synthesized in the absence
of latex particles (average nitrogen content of 10.95%). In the
case of the PPy-PANi bilayer, the PANi content was calculated
by comparing the nitrogen contents of the PPy-PANi-coated
latex, the PPy-coated latex prior to aniline polymerization, and
PANi “bulk powder”.
Conductivity Measurements. The conductivities of com-
pressed pellets of the PANi-coated PS latexes were determined
using standard four-point probe techniques at room temperature.
(27) Wei, Y.; Jang, G. W.; Chan, C. C.; Hsueh, K. F.; Hariharan, R.;
Patel, S. A.; Whitecar, C. K. J. Phys. Chem. 1990, 94, 7716.
Barthet et al.
It is estimated that the random error associated with such
measurements is approximately 10%, with a systematic error of
ca. 5 to 10%.
Disk Centrifuge Photosedimentometry (DCP). This
method was used to obtain the weight-average particle size
distribution of the coated and uncoated latexes. According to
Yamamoto and co-workers,28 PVP chains with a molecular weight
of 360 000 have an adsorbed layer thickness of approximately
20-30 nm. Thus the increase in particle size due to this steric
stabilizer layer is negligible in comparison to the overall diameter
of the PS particles (>1.5 µm). The density of the sterically
stabilized PS latex was therefore assumed to be that of pure
polystyrene, i.e., 1.05 g cm-3. The centrifuge rate was 3000 rpm
and PANi-coated latexes were assumed to have the same
scattering characteristics as carbon black.
Zeta Potential Measurements. Zeta potential vs pH curves
were measured using a Malvern Instruments Zetamaster ap-
paratus. Zeta potentials,29 ζ, were calculated from electrophoretic
mobilities (u) using the Smoluchowsky relationship, ζ ) ηu/,
where it is assumed that κa . 1 (with η and  the viscosity and
dielectric constant of the medium and κ and a the Debye-Hückel
parameter and the radius of the particles, respectively). The
solution pH was adjusted by the addition of HCl.
Fourier Transform Infrared (FT-IR) Spectroscopy. FT-
IR spectra (KBr disk) of PANi “bulk powder” and both coated
and uncoated PANi-PS latexes were recorded using a Nicolet
Magna 550 Series II instrument. Spectra were typically averaged
over 16 scans at 4 cm-1 resolution.
Scanning Electron Microscopy (SEM). Morphology stud-
ies were carried out using a Leica Stereoscan 420 instrument
operating at 20 kV with a probe current of 10 pA. The samples
were mounted on a double-sided adhesive carbon disk and
sputter-coated with a thin layer of gold to prevent sample-
charging problems.
Raman Spectroscopy. Raman spectra were recorded using
a Bruker FRA 106 spectrometer. Excitation was provided by an
Adlas Nd:YAG laser at a wavelength of 1064 nm, operating at
30 mW for the PANi-containing samples and 300 mW for the
uncoated PS latex. Data were acquired at a resolution of 4 cm-1,
and spectra were averaged over 2000 scans.
Solvent Extraction Experiments. Excess THF (10 mL)
was added at room temperature to ca. 50 mg of the dried PANi-
coated PS latexes. This solution was left overnight. The resulting
black residues were filtered, washed with THF, and dried in an
oven at 60 °C. The morphology of the PANi residues was
examined by SEM. FT-IR spectroscopy was used to confirm the
loss of PS.
Results and Discussion
The scanning electron micrographs in Figure 1 cor-
respond to thin overlayers of PPy and PANi on PS latex
at conducting polymer mass loadings of 10 and 8 wt %,
respectively. The PANi overlayer was deposited onto a
1.8 µm PS latex according to method 1. The conditions
used for the PPy coating were those described by Armes
and co-workers.19,20 The morphology of the PANi overlayer
is clearly markedly rougher than that of the PPy. Similar
effects have been reported by Armes et al. for the deposition
of PPy and PANi onto quartz fibers.30 The thickness of
the PPy and PANi overlayers can be calculated using the
following equation
(x( ) )
3
M2F1
δ)R +1 -1 (1)
M1F2
where δ is the conducting polymer overlayer thickness, R
is the radius of the uncoated latex particles, M1 and F1 are
(28) Liu, C. F.; Moon, D. K.; Maruyama, T.; Yamamoto, T. Polym. J.
1993, 25, 775.
(29) Hunter, R. J. Foundations of Colloid Science, Vol. I, 557.
(30) Armes, S. P.; Gottesfeld, S.; Beery, J. G.; Garzon, F.; Mom-
bourquette, C.; Hawley, M.; Kuhn, H. H. J. Mater. Chem. 1991, 1, 525.
Polyaniline-Coated Polystyrene Latexes
Figure 1. Scanning electron micrographs showing (a) a PPy-
coated (10 wt %) PS latex and (b) a PANi-coated (8 wt %) PS
latex. The PS latexes were 1.6 µm diameter for PPy coating and
1.8 µm diameter for PANi coating. The oxidants used were
FeCl3 and (NH4)2S2O8, respectively, for pyrrole and aniline
polymerizations. Deposition of both conducting polymers was
carried out at room temperature. Scale bar ) 2 µm.
the mass fraction and density of the PS component, and
M2 and F2 are the mass fraction and density of the
conducting polymer component. The densities of the PS
latex and PPy and PANi bulk powders were found to be
1.05, 1.46, and 1.40 g cm-3, respectively, by helium
pycnometry. According to eq 1, the PPy and PANi
overlayers thicknesses for the coated latexes depicted in
Figure 1 are close to 21 and 20 nm, respectively. The
calculated PPy thickness is considered to be accurate given
the uniformity of this overlayer. In contrast, the non-
uniform nature of the PANi overlayer suggests that its
calculated thickness of 20 nm is likely to be a lower limit
value. DCP analyses of the uncoated PS latexes used in
this study showed them to be reasonably monodisperse.
In contrast, the presence of multiplets in the DCP traces
of PANi-coated latexes (see later) indicates that the
inhomogeneous PANi overlayer leads to a similar degree
Langmuir, Vol. 14, No. 8, 1998 2035
Figure 2. Variation of conductivity with conducting polymer
loading for PPy-coated latexes ([) (data taken from ref 19),
PANi-coated latexes synthesized using method 1 at 25 °C (O)
and at 0 °C (0) and PANi-coated latexes prepared using method
2 at 0 °C (3).
of flocculation as the PPy coating for these sterically
stabilized particles. Ultrasonic treatment reduces ag-
gregation, but the multiplets are not completely removed.
Effect of Lowering the Polymerization Temper-
ature. Stejskal et al.31 reported that the polymerization
temperature affected the morphology of colloidal PANi-
silica particles. These nanocomposites had an irregular
shape when polymerization proceeded at 25 °C, whereas
particles prepared at 0 °C were more spherical. This may
be due to the reduced rate of aniline polymerization at
this temperature. Although we were coating micrometer-
sized PS latex (rather than ultrafine silica sols), it was
nevertheless envisaged that a reduced polymerization
temperature might also lead to a more controlled poly-
merization. A 1.66 µm PS latex was selected for our
coating experiments at 0 °C and at room temperature.
The conductivities of PANi-coated PS latexes prepared
at room temperature and 0 °C are compared in Figure 2.
The conductivities of the PANi-coated latexes are also
compared to those of PPy-coated PS latexes prepared at
room temperature.20a The somewhat lower conductivities
of the PANi-coated PS latexes prepared at 0 °C compared
to those obtained for PPy-coated latexes synthesized at
25 °C suggest a fundamental difference in either the
quality (i.e., average conjugation length and number of
charge carriers) or morphology (overlayer uniformity)
between the PANi and the PPy overlayers. However, since
the conductivities of the PPy and PANi “bulk powders”
are similar, it is most likely that the decrease in
conductivities is due to a different morphology of the PANi
overlayer. Moreover, the conductivities of the PANi-coated
latexes were not improved by decreasing the polymeri-
zation temperature. Subsequent SEM studies of the
PANi-coated latexes indicated that lowering the poly-
merization temperature had essentially no effect on the
morphology of the PANi overlayer. Moreover, the DCP
traces of PANi-coated latexes prepared at 0 and 25 °C are
(31) Stejskal, J.; Kratochvil, P.; Armes, S. P.; Lascelles, S. F.; Riede,
A.; Helmstedt, M.; Prokes, J.; Krivka, I. Macromolecules 1996, 29, 6814.
2036 Langmuir, Vol. 14, No. 8, 1998
Figure 3. Polymerization yields obtained for PANi syntheses
performed at room temperature ([) and at 0 °C (4). The yields
were calculated assuming that the PANi deposited onto the PS
has a doping level of 50% (i.e., one chloride ion for every two
aniline repeat units).
reasonably similar for a given PANi content. This suggests
a similar degree of flocculation in each case.
It is noteworthy from Figure 3 that much higher
polymerization yields were obtained at 0 °C. The theo-
retical PANi contents were calculated assuming a doping
level of 50% (one chloride anion for every two aniline
residues). The reduced yields obtained for PANi contents
lower than 5 wt % may be explained by the low reagent
concentrations in the reaction medium (and hence slower
polymerization). Reduced polymerization yields and
conductivities were obtained at room temperature for
PANi loadings higher than 17 vol %. This is probably
attributable to the temperature rises caused by the
exothermic polymerization (up to 20-30 °C for the highest
PANi loadings). Boara et al.32 postulated that, under
similar conditions, residual oxidant may cause overoxi-
dation of the PANi chains, forming soluble byproducts.
Shen et al.33 reported the use of solvent extraction to
examine the particle morphology of poly(methyl meth-
acrylate)/PS “core-shell” latexes. Similarly, Lascelles and
co-workers20b treated a dried PPy-coated PS latex (6.5 wt
% PPy loading, corresponding to an overlayer thickness
of 13 nm) with THF to remove the non-cross-linked
underlying PS core. Examination of the PPy residues by
SEM revealed a “broken egg shell” morphology which
confirmed the “core-shell” morphology of the original PPy-
coated PS latex. Similar extraction experiments were
carried out on the PANi-coated PS latex. For relatively
high PANi loadings (11 wt %, 27 nm thickness), SEM
studies of the PANi residues after THF extraction also
revealed a “broken egg shell” morphology (see Figure 4),
with the “egg shell” diameter corresponding to that of the
original coated particles. The FT-IR spectra of the residues
after extraction showed no evidence for the presence of
PS. At lower PANi loadings (6 wt %, 13 nm) rather less
distinct, collapsed egg shells were observed. These
observations are consistent with the less uniform overlayer
morphology observed for PANi in Figure 1. Nevertheless,
(32) Boara, G.; Sparpaglione, M. Synth. Met. 1995, 72, 135.
(33) Shen, S.; El-Aasser, M. S.; Dimonie, V. L.; Vanderhoff, J. W.;
Sudol, E. D. J. Polym. Chem., Part A: Polym. Chem. 1991, 29, 857.
Barthet et al.
these solvent extraction experiments confirm that at
higher loadings PANi coats the PS latex in a continuous
or near-continuous overlayer.
The FT-IR spectrum of a PANi-coated PS latex (PANi
loading 8.8 wt %) was compared to those of three
heterogeneous admixtures of uncoated PS latex with PANi
“bulk powder” containing 5, 10, and 15 wt % PANi,
respectively. (We only show in Figure 5 the spectrum
corresponding to the 15 wt % PANi.) FT-IR spectra of
PANi “bulk powder” and uncoated PS latex reference
materials were also recorded to aid assignment the
characteristic peaks for the PANi and PS components
(Figure 5). For the PANi-coated latex (see spectrum c),
the main peaks due to the PS component are at 1492,
1455, 762, and 695 cm-1. Three strong absorption bands
attributed to PANi are observed at 1295, 1238, and 1140
cm-1. Even allowing for PANi being a strong IR absorber,
these absorption bands seem relatively intense for a PANi
loading of only 8.8 wt %. On the other hand, the FT-IR
spectra of the admixtures only show very weak PANi
bands, even for a PANi content of 15 wt % (see spectrum
d in Figure 5). This observation suggests that the “core-
shell” morphology of the PANi-coated PS latex leads to a
significant enhancement of the IR absorption of the
conducting polymer component. Similar results were
obtained by Lascelles and co-workers for PPy-coated
latexes.20a
Lascelles et al.20b characterized various PPy-coated PS
latexes by Raman spectroscopy. Similar Raman studies
were carried out on the PANi-coated PS latexes. The
Raman spectra for a PANi “bulk powder”, a heterogeneous
admixture of PANi/PS latex (10 wt % PANi loading), and
uncoated and PANi-coated PS latexes are depicted in
Figures 6 and 7. A very strong Raman band at 1003 cm-1,
due to the ν1 ring-breathing mode of the PS component,
is clearly visible in the admixture spectrum (see Figure
6). However, this PS band is absent in the spectrum of
the PANi-coated PS latex (PANi thickness, 23 nm), despite
this composite containing nearly 90% PS latex by mass.
In fact, the spectrum of this “core-shell” latex is essentially
the same as that recorded for PANi bulk powder. It seems
that, as with the PPy-coated PS particles,20b the Raman
signals due to the PS core are completely attenuated by
the PANi overlayer at this loading. Raman spectra of
PANi-coated PS latexes were also recorded at lower PANi
loadings (see Figure 7). The 1003 cm-1 band is present
as a very weak feature in the spectra of the PANi-coated
PS latexes containing between 0.5 and 4.5 wt % PANi
(1-9 nm PANi overlayer). These observations on PANi-
coated latexes are qualitatively different from those
reported for PPy-coated PS latexes, for which uniform
PPy loadings as low as 1 wt % (ca. 2 nm) were sufficient
to completely attenuate the Raman signal arising from
the PS core of the particles.20b We interpret this as
evidence for the inhomogeneous nature of the PANi
overlayer.
In summary, the PANi overlayers have considerable
surface roughness and appear to be discontinuous at low
loadings (<5 wt %) but more uniform at higher loadings.
Variation of the Polyaniline Synthesis Conditions.
Several polymerization parameters were varied in at-
tempts to improve the uniformity of the PANi overlayer.
In particular, three routes were explored to reduce the
polymerization rate: (i) alternative oxidant, (ii) addition
of a polymerization retarder, and (iii) use of aniline
hydrochloride monomer in the absence of added acid. We
also modified the surface of the PS particles prior to the
polymerization of aniline with (1) an ultrathin, smooth
PPy overlayer, (2) a layer of adsorbed surfactant, and (3)
Polyaniline-Coated Polystyrene Latexes
Figure 4. Scanning electron micrographs of the remaining PANi residues, after THF extraction, of a PS latex coated at 0 °C (a)
with 11 wt % PANi and (b) with 6 wt % PANi. Scale bar ) 2 µm.
surface sulfonate groups. All coating experiments were
carried out at 0 °C using the 1.88 µm PS latex. The aniline
polymerization conditions are summarized in Table 2. The
PANi loading was fixed at 10 wt % which, using method
1, had given overlayers with appreciable surface rough-
ness.
The selection of ammonium vanadate as an alternative
oxidant was motivated by a patent disclosure from Kuhn
et al.34 describing the synthesis of PANi-coated textile
fibers. These workers reported that using vanadium(V)-
(34) Kuhn, H. H.; Kimbrell, W. C. European Patent Application 0
352 882.
Langmuir, Vol. 14, No. 8, 1998 2037
based oxidants allowed aniline polymerization at a more
controlled rate, possibly by allowing the adsorption of a
“prepolymer” species onto the textile substrate. This
approach was claimed not only to improve the conductivity
and uniformity of PANi overlayers on textile fibers but
also to minimize the undesirable precipitation of PANi
“bulk powder” during the coating process.
The NH4VO3 oxidant was examined for the deposition
of PANi onto PS latex. Unfortunately, the change of
oxidant did not improve the conductivity of the PANi
overlayer (see Table 2). Moreover, the PANi overlayer
did not appear to be more uniform by SEM. These
2038 Langmuir, Vol. 14, No. 8, 1998 Barthet et al.

Figure 5. FTIR spectra of (a) PANi bulk powder, (b) uncoated

PS latex, (c) PANi-coated PS latex (8.8 wt % PANi), and (d)
admixture of 15 wt % PANi and 85 wt % PS powders.

Figure 7. Raman spectra for PANi-coated PS latexes contain-

ing (a) approximately 0.5 wt % PANi, (b) 4.5 wt % PANi, and
(c) 10.8 wt % PANi. The PS latex was coated with PANi at 25
°C.

Table 2. Aniline Polymerization Yields, PANi Loadings,

and Conductivities of the Coated Latexes Obtained from
Various Aniline Polymerization Conditionsa
PANi polymer-
monomer/ oxidant loading ization σb
additives type (wt %) yield (%) (S cm-1)
aniline NH4VO3 10.1 81 7.5 × 10-2
aniline + PPy underlayer (NH4)2S2O8 8.3 67 0.16
aniline hydrochloride (NH4)2S2O8 9.5 81 0.15
aniline hydrochloride + (NH4)2S2O8 9.4 80 5 × 10-2
SDS
aniline hydrochloride + (NH4)2S2O8 9.4 80 5 × 10-2
SDS
aniline hydrochloride + (NH4)2S2O8 9.3 79 0.17
hydroquinone
Figure 6. Raman spectra for (a) a dried PANi bulk powder, a The polymerizations were all performed at 0 °C. b Average value
(b) a heterogeneous admixture of 10 wt % PANi with 90 wt % obtained by four-point probe method on compressed pellets.
PS, (c) PANi-coated PS latexes containing 10.8 wt % PANi, and
(d) a dried PS latex. The PS latex was coated with PANi at 25
°C.
synthesis of PANi-PS particles (method 2). Reduced
polymerization yields (see Table 2) and slightly lower
observations, together with the inhomogeneous PANi
conductivities were obtained compared to PANi-coated
overlayers obtained at 0 °C, suggest that the uniformity
PS latexes synthesized at 0 °C according to method 1 (see
of the PANi coating does not seem to be directly correlated
to the rate of aniline polymerization. This argument is Figures 2 and 3). However, much smoother, more uniform
supported by our SEM observations, which show smooth PANi coatings were obtained under these conditions (see
PPy overlayers even with the relatively rapid polymer- Figure 8). Further evidence for the homogeneity of the
ization rate produced by the [NH4]2S2O8 oxidant. PANi coating was provided by DCP. The DCP traces of
We also investigated whether surface pretreatment of both coated and uncoated PS latexes are shown in Figure
the PS latex affected the PANi overlayer morphology. 9. The weak flocculation observed after the polymerization
Thus, the PS latex was first coated with a 2 nm overlayer of aniline hydrochloride is significantly reduced compared
of PPy. After cleanup, PANi was deposited onto this PPy- to that found for the polymerization of aniline in 1.2 M
coated latex at 0 °C. However, the adherence and HCl, even though the PANi loading of the former disper-
uniformity of the PANi overlayer remained poor. sion is slightly higher. It is likely that the initial pH of
Stejskal et al.31 reported that the polymerization of the reaction medium influences the morphology of the
aniline hydrochloride on colloidal silica in the absence of PANi overlayer. However, it is emphasized that these
any added acid produced more uniform PANi-silica PANi overlayers are still not as uniform as those obtained
particles. Thus, this protocol was explored for the with PPy (see Figure 1).
Polyaniline-Coated Polystyrene Latexes
Figure 8. Scanning electron micrographs of a PANi-coated PS latex after polymerization of aniline hydrochloride at 0 °C according
to method 2. The PANi content is 9.5 wt %. Scale bar ) 2 µm.
Figure 9. DCP curves of (a) uncoated PS latex, (b) PS latex
coated with 8.8 wt % PANi (method 1), and (c) PS latex coated
with 9.5 wt % PANi (method 2). Both aniline polymerizations
were performed at 0 °C.
The addition of a polymerization retarder, hydro-
quinone, to the reaction medium was also investigated.27
Wei et al. reported that this compound retards both the
chemical and electrochemical oxidation of aniline. How-
ever, no changes in the polymerization yield or conductivity
of the coated latex were observed (see Table 2). Moreover,
the presence of hydroquinone did not improve the uni-
formity of the PANi overlayer, which was identical to that
shown in Figure 8.
We also investigated the adsorption of an anionic
surfactant, SDS, onto the surface of the PS particles prior
to aniline polymerization. It was envisaged that elec-
trostatic binding between the anilinium cation and the
anionic headgroup of the surfactant might aid PANi
Langmuir, Vol. 14, No. 8, 1998 2039
deposition. Moreover, the sulfonate groups of the sur-
factant were expected to act as anionic dopants for the
PANi chains. However, the PANi morphology appeared
to be, if anything, less uniform in the presence of the
surfactant. Similar negative results were obtained with
sodium dodecylbenzenesulfonate.
Finally sulfonated PS particles were synthesized in an
attempt to encourage more uniform PANi deposition
through electrostatic binding between the anilinium cation
and the anionic sulfonate groups at the latex surface.
Better adhesion of the conducting polymer onto the latex
particles was also anticipated because the sulfonate groups
could act as dopants for the PANi. Moreover, according
to Yassar et al.,9 the polymerization reaction onto the
surface of the latex particles is dependent on the pendant
anionic group. Garnier et al.35 claimed that both electronic
and steric factors of the doping anion should be considered
to optimize the dopant-polymer interaction. They re-
ported that the sulfonate anion is particularly suitable
for conducting polyheterocycles.
Before PANi coating, the sulfonated PS latex had a zeta
potential of -21 mV at pH 5.5. In contrast, an unmodified
PS latex had a zeta potential of -1 mV under the same
conditions. This difference confirms the presence of
anionic sulfonate groups on the sulfonated PS latex. By
SEM, the uncoated sulfonated particles are relatively
monodisperse, but some surface imperfections are evident
(see Figure 10a). However, after coating with PANi, the
modified particles have considerable surface roughness.
Thus, the PANi overlayer is still nonuniform despite the
presence of charged groups at the surface of the PS
particles. This suggests that the inhomogeneous mor-
phology of the PANi coating does not result from poor
affinity of the conducting polymer for the PS surface.
Conclusions
This study has confirmed that PANi overlayers on PS
latexes typically have a nonuniform, inhomogeneous
morphology, in contrast to the relatively smooth mor-
(35) Garnier, F.; Tourillon, G.; Barraud, J. Y.; Dexpert, H. J. Mater.
Sci. 1985, 20, 2687.
2040 Langmuir, Vol. 14, No. 8, 1998
Figure 10. Scanning electron micrographs showing an uncoated (a) and PANi-coated (25 wt %) (b) sulfonated PS latex. The average
PANi overlayer thickness is assumed to be around 20 nm.
phologies obtained for the deposition of PPy.20 No
reduction in surface roughness was obtained when the
aniline polymerization was performed at reduced tem-
perature. DCP analysis indicated the weak flocculation
of the PANi-coated PS latexes.
Aniline polymerizations at 0 °C resulted in coated
latexes with conductivities comparable to that of PPy-
coated PS latexes with similar loadings. Extraction of
the soluble PS core using THF revealed a broken “egg
shell” morphology from PANi loadings of 6 wt %, which
strongly suggests complete encapsulation of the PS
particles by the PANi overlayer. FT-IR studies confirmed
enhanced band intensities due to the PANi component,
which is also consistent with a “core-shell” morphology.
Barthet et al.
This enhancement is even more pronounced in the Raman
spectra of the PANi-coated PS latexes, but at lower PANi
loadings the attenuation of the 1003 cm-1 band due to the
underlying PS latex is not as effective as that observed
for PPy-coated PS latexes.20b This spectroscopic evidence
suggests that the thinner PANi overlayers are somewhat
patchy. This point will be further addressed soon in a
detailed X-ray photoelectron spectroscopy study.36
No noticeable improvement in the uniformity of the
PANi overlayer was observed at the lower polymerization
rates which resulted from an alternative oxidant or the
(36) Barthet, C.; Armes, S. P.; Chehimi, M. M.; Bilem, C.; Omastova,
M. Submitted to Langmuir.
Polyaniline-Coated Polystyrene Latexes
presence of a polymerization retarder. Modification of
the latex surface either by a PPy overlayer or by sulfonate
groups or by the preadsorption of an anionic surfactant
also had little effect. More uniform PANi coatings and
better colloid stability were obtained using aniline hy-
drochloride monomer in the absence of added acid.
However, the PANi morphology was still not as smooth
Langmuir, Vol. 14, No. 8, 1998 2041
as that of PPy overlayers deposited onto the same PVP-
stabilized PS latex.
Acknowledgment. This work received the financial
support of the European Community in the form of a TMR
fellowship for Dr. C. Barthet.
LA971064Z